Colored composition, colored cured film, and display element

Abstract

The present invention provides a colored cured film having excellent adhesion and solvent resistance, a colored composition that provides the cured film, and a display element that includes the cured film. [Solution] A coloring composition comprising (A) a colorant, (B) a binder resin, (C) a radical polymerizable compound, (D) a photoradical generator, and (E) a compound which is an aromatic compound having four benzene rings as a basic skeleton and bonded by an alkylene skeleton, and which has crosslinkable substituents on the benzene rings, wherein the content of the (A) colorant is 5% by mass or more and 80% by mass or less based on the total solid content of the coloring composition.

Description

[Technical field]

[0001] The present invention relates to a coloring composition, a colored cured film, and a display element. More specifically, the present invention relates to a coloring composition used for forming a colored cured film suitable for display elements such as a transmissive or reflective color liquid crystal display element, an organic EL display element, and electronic paper, and a solid-state imaging element such as a CMOS image sensor, a colored cured film formed from the coloring composition, and a display element having the colored cured film. [Background technology]

[0002] To manufacture a color filter using a coloring composition, a method is known in which a pigment-dispersed radiation-sensitive coloring composition is applied to a substrate to form a coating film, and then the coating film is exposed to light in a desired pattern shape and developed to obtain patterned pixels of each color (Patent Documents 1 and 2). As a method for manufacturing a black matrix, a method is known in which a carbon black-dispersed radiation-sensitive coloring composition is used to perform a similar operation to form a patterned black matrix (Patent Document 3). Furthermore, a method is also known in which a pigment-dispersed coloring composition is applied and cured by an inkjet method to form patterned pixels of each color (Patent Document 4). In the above series of operations, the coating film is usually exposed to light in a pattern through a photomask having a desired pattern. At this time, a predetermined proximity gap (exposure gap) is provided between the coating film and the photomask. Ideally, the irradiated light passes directly through the openings of the photomask, and the closed parts block the light. However, since light is diffracted at the edge of the photomask, the coating film near the openings of the closed parts is irradiated with light (leakage light) with an intensity weaker than the predetermined exposure amount. In the coating film, whether the intermediate region irradiated with the leaked light is required to behave in the same manner as the open region (exposed region) or in the closed region (dark region) depends on the process configuration, the purpose of the product, etc. That is, for example, in the case of a negative coloring composition, there are cases where a coloring composition with high photosensitivity in which the intermediate region hardens in the same manner as the exposed region is required, while there are cases where a coloring composition with small mask bias (high mask size reproducibility of the formed pattern) in which the intermediate region does not harden in the same manner as the non-exposed region (i.e., is developed) is required. High photosensitivity and small mask bias are contradictory properties, and it is usually difficult to achieve both at the same time.

[0003] With conventionally known coloring compositions, it is only by trial and error to know whether the coloring composition has high photosensitivity or low mask bias, and it has been difficult to produce a high photosensitivity coloring composition and a low mask bias coloring composition while maintaining the sameness of other properties. By the way, Patent Document 5 describes a coloring composition containing a specific phenolic compound, and explains that the use of the composition makes it possible to form a colored cured film having an excellent pattern shape and high adhesion to a substrate with high precision. This technology is certainly an excellent technology that shows improvements in terms of adhesion and pattern shape, but the inventors' investigations have revealed that the colored cured film formed has insufficient solvent resistance. Therefore, the industry has recognized a need for a colored composition capable of forming a colored cured film having both excellent adhesion and solvent resistance. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 2-144502 [Patent Document 2] Japanese Patent Application Publication No. 3-53201 [Patent Document 3] Japanese Patent Application Publication No. 6-35188 [Patent Document 4] JP 2000-310706 A [Patent Document 5] JP 2009-204895 A Summary of the Invention [Problem to be solved by the invention]

[0005] The present invention has been made to overcome the above-mentioned current situation. Accordingly, an object of the present invention is to provide a colored cured film having both excellent adhesion and solvent resistance, a coloring composition which gives said colored cured film, and a display element comprising said cured film. It is desirable that the coloring composition can be prepared arbitrarily by selecting either a type having high photosensitivity or a type having small mask bias. [Means for solving the problem]

[0006] According to the present invention, the above objects and advantages of the present invention are achieved, firstly, by: (A) a colorant, (B) a binder resin, (C) a radical polymerizable compound, (D) a photoradical generator and (E) A compound having a structure in which a group represented by the following formula (E0) is directly bonded to an aromatic ring: This is achieved by a coloring composition comprising:

[0007] *-(CR II 2) x -OR I (E0)

[0008] [In formula (E0), R I is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R II each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, x is 1 or 2; "*" indicates a bond directly bonded to the aromatic ring.

[0009] The above objects and advantages of the present invention are, secondly, This can be achieved by a colored cured film formed using the above colored composition.

[0010] The above objects and advantages of the present invention are, thirdly, This is achieved by a display device comprising the above-mentioned colored cured film. Effect of the Invention

[0011] According to the present invention, there are provided a colored cured film having excellent adhesion and solvent resistance, a coloring composition which gives said colored cured film, and a display element comprising said cured film. The coloring composition can be made into either a type having high photosensitivity or a type having small mask bias by selecting the compound (E). DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] <(A) Colorant> The colorant (A) contained in the coloring composition of the present invention can be used without any particular limitation. The colorant (A) is appropriately selected and used based on its color, material, etc. according to the application of the coloring composition of the present invention. As the (A) colorant, one or more types selected from pigments and dyes can be used. When the colored composition of the present invention is used for forming each color pixel constituting a color filter, as the colorant (A), pixels having high brightness, contrast and color purity can be easily obtained. It is preferable to use one or more selected from the group consisting of organic pigments and organic dyes. On the other hand, when the coloring composition is used for forming a black matrix or a black spacer, it is preferable to use an inorganic pigment as the colorant (A). The pigments include organic pigments and inorganic pigments.

[0013] Preferred examples of organic pigments include pigments having Color Index (CI) names such as CI Pigment Red 166, CI Pigment Red 177, CI Pigment Red 224, CI Pigment Red 242, CI Pigment Red 254, CI Pigment Green 7, CI Pigment Green 36, CI Pigment Green 58, CI Pigment Blue 15:6, CI Pigment Blue 80, CI Pigment Yellow 83, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 180, CI Pigment Yellow 211, CI Pigment Orange 38, and CI Pigment Violet 23; Examples of the lake pigment include triarylmethane lake pigments obtained by laking a triarylmethane dye with an isopolyacid, a heteropolyacid, or the like, as disclosed in JP-A-2011-186043 and the like; Examples of the xanthene lake pigment include xanthene lake pigments obtained by forming a xanthene dye with an isopolyacid, a heteropolyacid, or the like, as disclosed in JP-A-2010-191304. Preferred examples of inorganic pigments include carbon black and titanium black.

[0014] The pigment may be purified before use, for example, by recrystallization, reprecipitation, solvent washing, sublimation, vacuum heating, or a combination thereof; The particle surface may be modified with a resin before use; For example, the primary particles may be refined by salt milling as disclosed in JP-A-08-179111 before use.

[0015] The pigment may be used together with a dispersant, a dispersing aid, etc., if necessary. As the dispersant, for example, a cationic, anionic, nonionic, or other suitable dispersant may be used, but it is preferable to use a polymer dispersant or a pigment derivative. As the polymer dispersant, for example, an acrylic copolymer (acrylic dispersant), polyurethane (urethane dispersant), polyester dispersant, polyethyleneimine dispersant, polyallylamine dispersant, etc. may be used.

[0016] The above polymeric dispersants are commercially available. Specific examples include: Examples of the acrylic dispersant include Disperbyk-2000, Disperbyk-2001, BYK-LPN6919, BYK-LPN21116, and BYK-LPN22102 (all manufactured by BYK); Examples of the urethane dispersants include Disperbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, and Disperbyk-182 (all manufactured by BYK), Solsperse 76500 (manufactured by Lubrizol Japan Co., Ltd.), and the like; Examples of the polyester-based dispersant include Ajisper PB821, Ajisper PB822, Ajisper PB880, and Ajisper PB881 (all manufactured by Ajinomoto Fine-Techno Co., Ltd.); Examples of the polyethyleneimine-based dispersant include Solsperse 24000 (manufactured by Lubrizol Japan Co., Ltd.) and BYK-LPN21324 (manufactured by BYK). Examples of the pigment derivatives include sulfonic acid derivatives of pigments, etc. Specific examples include copper phthalocyanine sulfonic acid derivatives, diketopyrrolopyrrole sulfonic acid derivatives, and sulfonic acid derivatives of quinophthalone.

[0017] The amount of the dispersant used is preferably 60 parts by mass or less, more preferably 5 to 50 parts by mass, and particularly preferably 10 to 40 parts by mass, per 100 parts by mass of the pigment in the colorant (A).

[0018] As the dye, it is preferable to use an organic dye, and for example, xanthene dyes, triarylmethane dyes, cyanine dyes, anthraquinone dyes, azo dyes, etc. can be mentioned as preferred examples. More specifically, for example, organic dyes disclosed in JP2010-32999A, JP2010-254964A, JP2011-138094A, WO2010 / 123071, JP2011-116803A, JP2011-117995A, JP2011-133844A, JP2011-174987A, etc. are suitable. Specifically, for example, compounds represented by the following formulas (A-2-1) to (A-2-9) can be mentioned.

[0019] [ka]

[0020] [ka]

[0021] Among the above, the compounds represented by (A-2-1) and (A-2-3) to (A-2-5) are xanthene dyes; The compounds represented by (A-2-2) and (A-2-6) are triarylmethane dyes; The compounds represented by (A-2-7) and (A-2-8) are cyanine dyes; and The compound represented by (A-2-9) is an anthraquinone dye.

[0022] The pigment and dye as the colorant (A) in the coloring composition of the present invention may each be used alone or in combination of any two or more thereof. Also, the pigment and the dye may be used in combination.

[0023] In the technical field, it is generally recognized that the colored cured film formed using a coloring composition containing a dye has poor solvent resistance.However, even if the coloring composition of the present invention contains a dye as the (A) colorant, it is possible to form a colored cured film having excellent solvent resistance.In this case, the content of the dye in the (A) colorant can be 10% by mass or more, and even 20% by mass or more, and particularly 30% by mass or more, based on the total amount of the (A) colorant, a colored cured film having excellent solvent resistance can be obtained.

[0024] The content of the (A) colorant in the coloring composition of the present invention is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 15% by mass or more, even more preferably 20% by mass or more, and preferably 80% by mass or less, more preferably 60% by mass or less, even more preferably 55% by mass or less, even more preferably 50% by mass or less, even more preferably 45% by mass or less, and even more preferably 40% by mass or less. The content of the (A) colorant in the coloring composition of the present invention is preferably 5 to 80% by mass, more preferably 5 to 60% by mass, even more preferably 10 to 50% by mass, and particularly preferably 15 to 45% by mass, based on the total solid content of the coloring composition. By setting the content ratio of the (A) colorant in the above range, when the colored cured film to be formed is a pixel, the brightness will be high and the color purity and heat resistance will be excellent, and when the colored cured film to be formed is a black matrix or black spacer, the heat resistance and light-shielding properties will be excellent, which is preferable. From the viewpoint of obtaining a colored composition having even more excellent sensitivity, the content of the colorant (A) in the colored composition of the present invention is preferably 10 to 50 mass %, more preferably 15 to 45 mass %, and even more preferably 20 to 40 mass %, based on the total solid content of the colored composition. On the other hand, from the viewpoint of obtaining a colored composition having a smaller mask bias, the content of the (A) colorant in the colored composition of the present invention is preferably 5 to 50 mass %, more preferably 10 to 50 mass %, and even more preferably 15 to 45 mass %, based on the total solid content of the colored composition. The coloring composition of the present invention can form a colored cured film having excellent solvent resistance and adhesion even when the content ratio of the colorant is high. Therefore, the coloring composition of the present invention can be preferably used for forming green pixels and red pixels, which generally tend to have a high content ratio of the colorant, and can be particularly preferably used for forming green pixels.

[0025] <(B) Binder resin> The binder resin (B) in the coloring composition of the present invention is not particularly limited, but is preferably a resin having an acidic functional group, more preferably a resin having a carboxyl group or a phenolic hydroxyl group, and even more preferably a resin having a carboxyl group.

[0026] Particularly preferred examples of the binder resin (B) in the present invention include (b1) an ethylenically unsaturated monomer having one or more carboxyl groups; (b2) with other copolymerizable ethylenically unsaturated monomers (carboxyl group-containing polymer (1)); Examples of the polymer include a polymer having a carboxyl group and a polymerizable unsaturated bond (carboxyl group-containing polymer (2)).

[0027] Examples of the unsaturated monomer (b1) which is the raw material of the carboxyl group-containing polymer (1) include (meth)acrylic acid, maleic acid, maleic anhydride, mono[2-(meth)acryloyloxyethyl] succinate, ω-carboxypolycaprolactone mono(meth)acrylate, and p-vinylbenzoic acid. These unsaturated monomers (b1) can be used alone or in combination of two or more.

[0028] Examples of the unsaturated monomer (b2) include N-substituted maleimides, aromatic vinyl compounds, (meth)acrylic acid esters, vinyl ethers, macromonomers, and the like. Specific examples of these include: Examples of the N-substituted maleimide include N-phenylmaleimide and N-cyclohexylmaleimide; Examples of the aromatic vinyl compound include styrene, α-methylstyrene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, p-vinylbenzyl glycidyl ether, and acenaphthylene; Examples of the (meth)acrylic acid ester include methyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, allyl (meth)acrylate, benzyl (meth)acrylate, polyethylene glycol (degree of polymerization 2 to 10) methyl ether (meth)acrylate, polypropylene glycol (degree of polymerization 2 to 10) methyl ether (meth)acrylate, polyethylene glycol (degree of polymerization 2 to 10) mono(meth)acrylate, polypropylene glycol (degree of polymerization 2 to 10) mono(meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, tricyclo[5.2.1.0] 2,6 ] Deccan -8-yl(meth)acrylate, tricyclo[5.2.1.0 2,6 ]Decen-8-yl (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)acryloyloxymethyl]oxetane, 3-[(meth)acryloyloxymethyl]-3-ethyloxetane, etc.; Examples of the vinyl ether include cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo[5.2.1.0 2,6 ]Decan-8-yl vinyl ether, 3-( (vinyloxymethyl)-3-ethyloxetane,

[0029] [ka]

[0030] Compounds represented by the formula: Examples of the macromonomer include macromonomers having a mono(meth)acryloyl group at the end of the 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 combination of two or more.

[0031] The copolymerization ratio of the unsaturated monomer (b1) in the carboxyl group-containing polymer (1) is The copolymerization ratio is preferably 5 to 50 mass %, more preferably 10 to 40 mass %, based on the total of the unsaturated monomer (b1) and the unsaturated monomer (b2). The coloring composition containing the carboxyl group-containing polymer (1) obtained by copolymerizing the unsaturated monomer (b1) at the above copolymerization ratio is preferred in terms of excellent storage stability and alkaline developability. Specific examples of the carboxyl group-containing polymer (1) are disclosed in, for example, JP-A-7-140654, JP-A-8-259876, JP-A-10-31308, JP-A-10-300922, JP-A-11-174224, JP-A-11-258415, JP-A-2000-56118, and JP-A-2004-101728. As the carboxyl group-containing polymer (2), for example, polymers disclosed in JP-A-5-19467, JP-A-6-230212, JP-A-7-207211, JP-A-9-325494, JP-A-11-140144, JP-A-2008-181095, etc. can be used.

[0032] The weight average molecular weight (Mw) of the binder resin (B) in the colored composition of the present invention, measured by gel permeation chromatography (GPC) using tetrahydrofuran as an elution solvent, in terms of polystyrene, is preferably 1,000 to 100,000, more preferably 3,000 to 50,000. By using the binder resin (B) having such Mw, the generation of foreign matter on drying during coating can be suppressed as much as possible, a patterned cured film having a good shape can be formed with high resolution and a high film remaining rate, and the heat resistance, electrical properties, solvent resistance, adhesion, etc. of the obtained cured film can be further improved, which is preferable. The ratio (Mw / Mn) of Mw to number average molecular weight Mn of (B) binder resin is preferably 1.0 to 5.0, more preferably 1.0 to 3.0, where Mn is the polystyrene-equivalent number average molecular weight measured by GPC using tetrahydrofuran as an elution solvent. The binder resin (B) as described above can be produced by a known method using an appropriate unsaturated monomer or a mixture thereof as a raw material. For example, a binder resin having a structure, Mw / Mn, etc. appropriately controlled can be produced by the methods disclosed in JP-A-2003-222717, JP-A-2006-259680, WO 2007 / 029871, etc. As the binder resin (B) in the colored composition of the present invention, the above-mentioned polymers can be used alone or in combination of two or more kinds.

[0033] The content of the (B) binder resin in the coloring composition of the present invention is preferably 10 to 1,000 parts by mass, more preferably 20 to 500 parts by mass, relative to 100 parts by mass of the (A) colorant. A coloring composition containing the (B) binder resin in the above range is preferred in that it has excellent storage stability, good alkali developability of the coating film, and the solvent resistance, adhesion, and chromaticity properties of the resulting cured film are further improved.

[0034] <(C) Radical Polymerizable Compound> The (C) radical polymerizable compound in the coloring composition of the present invention is a compound having two or more radically polymerizable groups in the molecule. Examples of the radically polymerizable group include an ethylenically unsaturated group, an oxiranyl group, an oxetanyl group, and an N-alkoxymethylamino group. The ethylenically unsaturated group is preferably a (meth)acryloyl group. The radically polymerizable compound (C) in the present invention is preferably selected from the group consisting of compounds having two or more (meth)acryloyl groups in the molecule and compounds having two or more N-alkoxymethylamino groups in the molecule.

[0035] Examples of the compound having two or more (meth)acryloyl groups in the molecule include polyfunctional (meth)acrylates obtained by reacting an aliphatic polyhydroxy compound with (meth)acrylic acid, caprolactone-modified polyfunctional (meth)acrylates, and alkylene oxides. Examples of such polyfunctional (meth)acrylates include modified polyfunctional (meth)acrylates, polyfunctional urethane (meth)acrylates obtained by reacting a (meth)acrylate having a hydroxyl group with a polyfunctional isocyanate, and polyfunctional (meth)acrylates having a carboxyl group obtained by reacting a (meth)acrylate having a hydroxyl group with an acid anhydride. Examples of the aliphatic polyhydroxy compound include divalent aliphatic polyhydroxy compounds such as ethylene glycol, propylene glycol, polyethylene glycol, and polypropylene glycol; and trivalent or higher aliphatic polyhydroxy compounds such as glycerin, trimethylolpropane, pentaerythritol, and dipentaerythritol.

[0036] Examples of the (meth)acrylate having a hydroxyl group include 2-hydroxyethyl (meth)acrylate. acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol dipentaerythritol penta(meth)acrylate, dipentaerythritol penta(meth)acrylate, glycerol dimethacrylate, etc.; Examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, and isophorone diisocyanate. Examples of the acid anhydride include anhydrides of dibasic acids and dianhydrides of tetrabasic acids. Specific examples of these include: Examples of the anhydrides of the dibasic acids include succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, and hexahydrophthalic anhydride; Examples of the dianhydride of the tetrabasic acid include pyromellitic anhydride, biphenyltetracarboxylic dianhydride, and benzophenonetetracarboxylic dianhydride.

[0037] Examples of the caprolactone-modified polyfunctional (meth)acrylate include the compounds described in paragraphs

[0015] to

[0018] of JP-A-11-44955. Examples of the alkylene oxide-modified polyfunctional (meth)acrylate include Bisphenol A di(meth)acrylate modified with at least one selected from ethylene oxide and propylene oxide; isocyanuric acid tri(meth)acrylate modified with at least one selected from ethylene oxide and propylene oxide, trimethylolpropane tri(meth)acrylate modified with at least one selected from ethylene oxide and propylene oxide, pentaerythritol tri(meth)acrylate modified with at least one selected from ethylene oxide and propylene oxide; pentaerythritol tetra(meth)acrylate modified with at least one selected from ethylene oxide and propylene oxide; Dipentaerythritol penta(meth)acrylate modified with at least one selected from ethylene oxide and propylene oxide; Examples include dipentaerythritol hexa(meth)acrylate modified with at least one selected from ethylene oxide and propylene oxide.

[0038] Examples of the compound having two or more N-alkoxymethylamino groups in the molecule include compounds having a melamine structure, a benzoguanamine structure, or a urea structure. Here, the melamine structure refers to a chemical structure having one or more triazine rings as a basic skeleton, and the benzoguanamine structure refers to a chemical structure having one or more phenyl-substituted triazine rings as a basic skeleton, and these concepts include melamine, benzoguanamine, and condensates thereof. Specific examples of the compound having two or more N-alkoxymethylamino groups in the molecule include N,N,N Examples of the alkoxymethyl ester include N',N',N",N"-hexa(alkoxymethyl)melamine, N,N,N',N'-tetra(alkoxymethyl)benzoguanamine, and N,N,N',N'-tetra(alkoxymethyl)glycoluril.

[0039] Of the above, preferred compounds of the radical polymerizable compound (C) in the present invention include polyfunctional (meth)acrylates obtained by reacting a trivalent or higher aliphatic polyhydroxy compound with (meth)acrylic acid, caprolactone-modified polyfunctional (meth)acrylates, polyfunctional urethane (meth)acrylates, polyfunctional (meth)acrylates having a carboxyl group, N,N,N',N',N",N"-hexa(alkoxymethyl)melamine, and N,N,N',N'-tetra(alkoxymethyl)benzoguanamine. Of the polyfunctional (meth)acrylates obtained by reacting a trivalent or higher aliphatic polyhydroxy compound with (meth)acrylic and acid, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate are preferred. Among the polyfunctional (meth)acrylates having a carboxyl group, a compound obtained by reacting pentaerythritol triacrylate with succinic anhydride and a compound obtained by reacting dipentaerythritol pentaacrylate with succinic anhydride are particularly preferred, since the colored cured product formed has high strength and excellent surface smoothness, and is less likely to cause background stains, film residues, etc. on the substrate and light-shielding layer in unexposed areas. In the colored composition of the present invention, the radically polymerizable compound (C) may be used alone or in combination of two or more kinds.

[0040] The content of the radical polymerizable compound (C) in the colored composition of the present invention is preferably 10 to 1,000 parts by mass, more preferably 20 to 700 parts by mass, and even more preferably 50 to 500 parts by mass, relative to 100 parts by mass of the colorant (A). The coloring composition containing the radically polymerizable compound (C) in the above range is preferable because it has excellent developability of the coating film, can suppress as much as possible the occurrence of defects such as background stains and film residues on the substrate or light-shielding layer in the unexposed area, and also has excellent curability of the coating film.

[0041] <(D) Photoradical generator> The (D) photoradical generator contained in the coloring composition of the present invention is a compound that generates radicals as active species capable of initiating radical polymerization of the (C) radically polymerizable compound by irradiation with light such as visible light, ultraviolet light, salt ultraviolet light, electron beam, or X-ray. Examples of such (D) photoradical generators include thioxanthone-based compounds, acetophenone-based compounds, biimidazole-based compounds, triazine-based compounds, O-acyloxime-based compounds, onium salt-based compounds, benzoin-based compounds, benzophenone-based compounds, α-diketone-based compounds, polynuclear quinone-based compounds, diazo-based compounds, and imide sulfonate-based compounds. In the colored composition of the present invention, the photoradical generator (D) may be used alone or in combination of two or more kinds.

[0042] As the (D) photoradical generator in the present invention, it is preferable to use at least one selected from the group consisting of thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds and O-acyloxime compounds, and it is particularly preferable to use one containing an O-acyloxime compound.

[0043] Specific examples of the (D) photoradical generator are as follows. Examples of the thioxanthone compounds include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-dimethylthioxanthone, 2 , 4-diethylthioxanthone, 2,4-diisopropylthioxanthone, etc.; Examples of the acetophenone compounds include 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, and 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one; As the biimidazole compound, for example, 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, etc.;

[0044] Examples of the triazine-based compounds 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, triazine compounds having halomethyl groups, such as 2-[2-(3,4-dimethoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, and 2-(4-n-butoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine; Examples of the O-acyloxime compounds 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-dioxolanyl)methoxybenzoyl}-9H-carbazol-3-yl]-, 1-(O-acetyloxime), and the like. Examples of commercially available O-acyloxime compounds include NCI-831, NCI-930 (both manufactured by ADEKA CORPORATION), DFI-020, DFI-091 (both manufactured by Daito ChemiX Corporation), and the like.

[0045] When a biimidazole compound is used as the photoradical generator (D) in the present invention, it is preferable to use a hydrogen donor together with the compound in order to increase the photosensitivity. Here, the "hydrogen donor" is a compound that can donate a hydrogen atom to the radical generated from the biimidazole compound by irradiation with light. Examples of such hydrogen donors include mercaptan hydrogen donors such as 2-mercaptobenzothiazole and 2-mercaptobenzoxazole; and 4,4'-bis(dimethylamino)benzoyl benzoate. Amine hydrogen donors such as benzophenone and 4,4'-bis(diethylamino)benzophenone These hydrogen donors can be used alone or in combination of two or more, but it is preferred to use at least one mercaptan hydrogen donor and at least one amine hydrogen donor in combination, since this can extremely increase the photosensitivity.

[0046] On the other hand, when a photoradical generator other than a biimidazole-based compound, preferably at least one selected from the group consisting of a thioxanthone-based compound, an acetophenone-based compound, a triazine-based compound, and an O-acyloxime-based compound, is used as the photoradical generator (D) in the present invention, a sensitizer may be used together with the photoradical generator. Examples of such sensitizers include 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, ethyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,5-bis(4-diethylaminobenzal)cyclohexanone, 7-diethylamino-3-(4-diethylaminobenzoyl)coumarin, and 4-(diethylamino)chalcone. At least one selected from these can be used.

[0047] The content ratio of the photoradical generator (D) in the coloring composition of the present invention is preferably 0.01 to 120 parts by mass, more preferably 1 to 100 parts by mass, relative to 100 parts by mass of the radical polymerizable compound (C). By setting the content ratio of the photoradical generator (D) in the above range, it is preferable in that the curability of the coloring composition can be improved. (D) In ​​the case where a biimidazole-based compound is used as a photoradical generator and a hydrogen donor is used together with the biimidazole-based compound, the content of the hydrogen donor is preferably 500 parts by mass or less, more preferably 50 to 300 parts by mass, relative to 100 parts by mass of the biimidazole-based compound; (D) When a photoradical generator other than a biimidazole-based compound is used as the photoradical generator and a sensitizer is used together with the photoradical generator, the content of the sensitizer is preferably 300 parts by mass or less, and more preferably 50 to 150 parts by mass, per 100 parts by mass of the photoradical generator other than a biimidazole-based compound.

[0048] <(E) compound> The compound (E) in the present invention is a compound having a structure in which the group represented by the above formula (E0) is directly bonded to an aromatic ring. R in the above formula (E0) I Examples of the alkyl group of R include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a sec-butyl group, and a t-butyl group. I is preferably an alkyl group, more preferably a methyl group or an ethyl group. R II each independently represents a hydrogen atom and R I The alkyl group of may be any of the groups exemplified above, but is preferably a hydrogen atom. It is preferred that x is 1.

[0049] The compound (E) in the present invention is preferably a compound having two or more groups represented by the above formula (E0) in the molecule, more preferably a compound having four or more groups, particularly preferably 6 to 10 groups. Two or more groups represented by the above formula (E0) may be bonded to one aromatic ring. The compound (E) in the present invention is preferably a compound having at least one group selected from the group consisting of a monovalent group represented by the following formula (E0-1) and a divalent group represented by the following formula (E0-2).

[0050] [ka]

[0051] [E0 in formulas (E0-1) and (E0-2) is a group represented by the above formula (E0), Each Z is independently a hydroxyl group or a monovalent organic group, Each "+" represents a bond; In formula (E0-1), a1 is an integer of 1 to 5, and b1 is an integer of 0 to 4, provided that the relationship of a1+b1=1 to 5 is satisfied; and In (E0-2), a2 is an integer of 1 to 4, and b2 is an integer of 0 to 3, provided that the relationship of a2+b2=1 to 4 is satisfied.

[0052] a1 in the above formula (E0-1) and a2 in the above formula (E0-2) are each preferably independently 1 or 2, and more preferably 2. Z in the above formulae (E0-1) and (E0-2) is a hydroxyl group or a monovalent organic group. Examples of this organic group include an alkoxy group having 1 to 6 carbon atoms, an alkoxyalkoxy group having 2 to 8 carbon atoms, an acyloxy group having 2 to 6 carbon atoms, a glycidyloxy group, and a 2,3-dihydroxypropoxy group. From the viewpoint of further increasing the stability of the resulting colored composition, Z is preferably a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, an alkoxyalkoxy group having 2 to 6 carbon atoms, or an acyloxy group having 2 to 4 carbon atoms. Specific examples of these include alkoxy groups such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group; Examples of the alkoxyalkoxy group include a 1-methoxyethoxy group, a 2-methoxyethoxy group, a 1-ethoxyethoxy group, a 2-ethoxyethoxy group, a 1-butoxyethoxy group, and the like; and examples of the acyloxy group include an acetyloxy group, and the like. It is preferable that b1 in the above formula (E0-1) and b2 in the above formula (E0-2) are each independently 0 or 1.

[0053] The compound (E) in the present invention having the above-mentioned group is preferably at least one compound selected from the group consisting of compounds represented by each of the following formulas (E-1) to (E-5).

[0054] [ka]

[0055] [ka]

[0056] [E0 and Z in formulae (E-1) to (E-5) are the same as E0 and Z in formulae (E0-1) and (E0-2), respectively. R each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an acyl group having 2 to 6 carbon atoms, a phenyl group, or a naphthyl group; Each A is independently a single bond, -O-, -S-, -CO-, -COO-, -OCO-, -SO-, -SO2-, -CR2- (wherein R has the same meaning as above), or a group represented by the following formula (T-1):

[0057] [ka]

[0058] (In the above formula (T-1), Z has the same meaning as Z in the above formulas (E0-1) and (E0-2), n is an integer of 0 to 4, and "+" represents a bond.) is a group represented by the formula:

[0059] In formula (E-1), c1, c2, d1, and d2 each independently represent an integer of 0 to 5, provided that the conditions of c1+d1=0 to 5 and c2+d2=0 to 5 are satisfied, and at least one of c1 and c2 is not 0; In formula (E-2), e1 to e3 and f1 to f3 each independently represent an integer of 0 to 5, provided that the conditions of e1+f1=0 to 5, e2+f2=0 to 5, and e3+f3=0 to 5 are satisfied, and at least one of e1 to e3 is not 0; In formula (E-3), g1 to g4 and h1 to h4 each independently represent an integer of 0 to 5, provided that the conditions g1+h1=0 to 5, g2+h2=0 to 5, g3+h3=0 to 5, and g4+h4=0 to 5 are satisfied, and at least one of g1 to g4 is not 0; In formula (E-4), i1 to i3 and j1 to j3 each independently represent an integer of 0 to 5, and i4 and j4 each independently represent an integer of 0 to 4, provided that the conditions i1+j1=0 to 5, i2+j2=0 to 5, i3+j3=0 to 5, and i4+J4=0 to 4 are satisfied, and at least one of i1 to i4 is not 0; In formula (E-5), k1, k2, L1, and L2 each independently represent an integer of 0 to 5, and k3 and L3 each independently represent an integer of 0 to 4, provided that the conditions k1+L1=0 to 5, k2+L2=0 to 5, and k3+L3=0 to 4 are satisfied, and at least one of k1 to k3 is not 0; and m is an integer from 1 to 5.

[0060] R in the above formulas (E-2) to (E-5) is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom. A is preferably a single bond, a methylene group, a propane-2,2-diyl group, or a group represented by the above formula (T-1). In the above formulas (E-1) to (E-5), c1, c2, e1 to e3, g1 to g4, i1 to i3, and k1 to k3 each preferably represents 1 or 2, and more preferably represents 2; i4 is preferably 0; Each of d1, d2, f1 to f3, h1 to h4, j1 to j3, and L1 to L3 is preferably 0 or 1, and more preferably 1; It is preferable that j4 is 0.

[0061] Specific examples of such compounds (E) include: As the compound (E-1), for example, compounds represented by each of the following formulae (E-1-1) to (E-1-3) can be used; As the compound (E-2), for example, compounds represented by the following formulae (E-2-1) and (E-2-2) can be used: As the compound (E-3), for example, a compound represented by the following formula (E-3-1) is used: As the compound (E-4), for example, compounds represented by each of the following formulas (E-4-1) to (E-4-8) are used; and Examples of the compound (E-5) include compounds represented by the following formula (E-5-1).

[0062] [ka]

[0063] [ka]

[0064] [ka]

[0065] [ka]

[0066] [In formula (E-5-1), m, n, r, and s each independently represent an integer of 0 to 5; p and q each independently represent an integer of 0 to 4; l is 0 or any natural number representing the number of repeating units, However, m+n and r+s are each in the range of 0 to 5, p+q is in the range of 0 to 4, and at least one of m, r, and p is not 0.

[0067] The amount of the (E) compound used in the colored composition of the present invention is preferably 0.1 to 50 parts by mass, more preferably 1 to 45 parts by mass, and more preferably 3 to 40 parts by mass, relative to 100 parts by mass of the (B) binder resin. As described above, the preferred (E) compound in the present invention has both the group represented by the formula (E0) and the group Z. Here, when a compound in which the group Z is a hydroxyl group is used as the (E) compound, a coloring composition with a small mask bias can be obtained. In this case, the amount of the (E) compound used is preferably 1 part by mass or more, more preferably 2 parts by mass or more, even more preferably 3 parts by mass or more, even more preferably 5 parts by mass or more, and preferably 40 parts by mass or less, more preferably 35 parts by mass or less, and even more preferably 30 parts by mass or less, relative to 100 parts by mass of the (B) binder resin. The content range of the (E) compound in the coloring composition of the present invention is preferably 1 to 40 parts by mass, more preferably 2 to 35 parts by mass, and even more preferably 3 to 30 parts by mass, relative to 100 parts by mass of the (B) binder resin. On the other hand, when a compound in which the group Z is a monovalent organic group is used as the (E) compound, a coloring composition with high photosensitivity can be obtained. In this case, the amount of the (E) compound used is preferably 1 part by mass or more, more preferably 2 parts by mass or more, even more preferably 3 parts by mass or more, and preferably 45 parts by mass or less, more preferably 43 parts by mass or less, even more preferably 40 parts by mass or less, and even more preferably 35 parts by mass or less, relative to 100 parts by mass of the (B) binder resin. The content range of the (E) compound in the coloring composition of the present invention is preferably 1 to 45 parts by mass, more preferably 2 to 40 parts by mass, even more preferably 3 to 35 parts by mass, and can also be 20 to 45 parts by mass, further 25 to 43 parts by mass, and further 30 to 40 parts by mass, relative to 100 parts by mass of the (B) binder resin.

[0068] <Other ingredients> The coloring composition of the present invention contains the above components (A) to (E) as essential components, but may contain other components as long as the effects of the present invention are not impaired. Examples of such other components include fillers such as glass and alumina; Polymeric compounds such as polyvinyl alcohol and poly(fluoroalkyl acrylate); Surfactants such as fluorosurfactants and silicone surfactants; Adhesion promoters such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, and 3-mercaptopropyltrimethoxysilane;

[0069] antioxidants such as 2,2-thiobis(4-methyl-6-t-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, and thiodiethylene bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]; Ultraviolet absorbers such as 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole and alkoxybenzophenones; anti-agglomerating 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 Residue improvers such as 2-amino-1,2-propanediol, 2-amino-1,3-propanediol, and 4-amino-1,2-butanediol; Examples of the developability improvers include mono[2-(meth)acryloyloxyethyl] succinate, mono[2-(meth)acryloyloxyethyl] phthalate, and ω-carboxypolycaprolactone mono(meth)acrylate.

[0070] <Solvent> The colored composition of the present invention contains the above components (A) to (E) as essential components and optionally contains other components, and is preferably prepared as a liquid composition further containing a solvent. The solvent used here is preferably one that disperses or dissolves the above-mentioned components, does not react with these components, and has a suitable degree of volatility. A suitable solvent can be selected from those having such properties and used.

[0071] Examples of the solvent contained in the coloring composition of the present invention include (poly)alkylene glycol monoalkyl ethers such as 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, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, and tripropylene glycol monoethyl 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, and cyclohexanol; ketoalcohols such as diacetone alcohol;

[0072] (poly)alkylene glycol monoalkyl ether acetates such as 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, and 3-methyl-3-methoxybutyl acetate; Other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran, etc.; Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone; Diacetates such as propylene glycol diacetate, 1,3-butylene glycol diacetate, and 1,6-hexanediol diacetate; Alkoxycarboxylic acid esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, and 3-methyl-3-methoxybutylpropionate;

[0073] Other esters such as 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-propyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutanoate, etc.; Aromatic hydrocarbons such as toluene and xylene; Amides or lactams such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone etc. can be mentioned.

[0074] Among these solvents, from the viewpoints of solubility, coating properties, etc., and, when contained, dispersibility of the pigment, (poly)alkylene glycol monoalkyl ethers, lactate alkyl esters, (poly)alkylene glycol monoalkyl ether acetates, other ethers, ketones, diacetates, alkoxycarboxylic acid esters, and other esters are preferred, and in particular propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxyphenyl ether, propylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate ...methyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, It is more preferable to use dibutyl acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 2-heptanone, 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, or the like. In the colored composition of the present invention, the solvents may be used alone or in combination of two or more.

[0075] As the solvent for the coloring composition of the present invention, At least one selected from the group consisting of (poly)alkylene glycol monoalkyl ethers and (poly)alkylene glycol monoalkyl ether acetates, or This is the case when the mixture contains a (poly)alkylene glycol monoalkyl ether and a (poly)alkylene glycol monoalkyl ether acetate.

[0076] The content of the solvent in the coloring composition of the present invention is not particularly limited, but is preferably an amount such that the solid content concentration of the coloring composition (the ratio of the total mass of the components other than the solvent of the coloring composition to the total mass of the coloring composition) is 5 to 50 mass%, more preferably 10 to 40 mass%. A coloring composition containing the solvent in the above amount is preferable in that it has excellent dispersibility of each component contained, therefore has excellent stability as a composition, and also has excellent coatability.

[0077] <Method of preparing coloring composition> The colored composition of the present invention can be prepared by any suitable method, for example, by mixing the above components (A) to (E) and, optionally, other components together with a solvent. For example, when the colorant (A) in the coloring composition of the present invention contains a pigment, the colorant (A) is mixed and dispersed in a solvent, preferably in the presence of a dispersant, and optionally together with a part of the binder resin (B), while being pulverized using, for example, a bead mill, a roll mill, or the like, to prepare a pigment dispersion, and then the remainder of the binder resin (B) and The composition can be prepared by adding and mixing the components (C) to (E) and, optionally, other components.

[0078] <Method of forming colored cured film> The colored composition of the present invention as described above can be used to form a colored cured film. The colored cured film in the present invention is a concept that encompasses pixels of each color, black matrices, black spacers, and the like used in display devices and solid-state imaging devices. In order to form a colored cured film using the colored composition of the present invention, it is preferable to use any one of the following methods. The first method is a method in which the coloring composition of the present invention is applied onto a substrate to form a coating film, and then at least a part of the coating film is irradiated with light, developed, and preferably further heated (post-baked); The second method is a method in which the coloring composition of the present invention is applied in a pattern on a substrate by an inkjet method to form a coating film, and the coating film is optionally irradiated with light, and then preferably further heated (post-baked). In any of the above methods, a color filter can be formed by sequentially forming colored cured films that become pixels of each color using three colored compositions of red, green, and blue or three colored compositions of cyan, magenta, and yellow, while a black matrix or black spacer can be formed by forming a black colored cured film using a black colored composition. Examples of the substrate include substrates made of glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamideimide, polyimide, etc. If necessary, these substrates may be subjected to appropriate pretreatment such as treatment with a chemical (e.g., a silane coupling agent), plasma treatment, ion plating treatment, sputtering treatment, treatment by a gas phase reaction method, treatment by a vacuum deposition method, etc.

[0079] When the coloring composition of the present invention is used to form pixels of a color filter, a black matrix is ​​preferably formed on the substrate to partition the pixel region. The black matrix can be a metal (e.g., chromium, etc.) thin film having a desired pattern, a colored cured film formed from the coloring composition, etc. A patterned metal thin film can be formed, for example, by applying photolithography to a metal thin film formed on a substrate by a sputtering method, a vapor deposition method, etc. A patterned colored cured film formed from the coloring composition can be formed by the same method as the present invention using a black coloring composition. In the second method using the inkjet method, the black matrix not only has a light-shielding function, but also functions as a barrier to prevent the color compositions discharged by the inkjet method from mixing. Therefore, it is preferable that the black matrix in this case has a certain thickness or more, and therefore it is preferable that the black matrix in this case is a black cured film formed using a black coloring composition. When the colored composition of the present invention is used for forming a black matrix, the substrate to be used is preferably a substrate on which a black matrix that partitions pixel regions has not yet been formed. Furthermore, when the colored composition of the present invention is used for forming a black spacer, the substrate used is preferably a substrate on which both a black matrix defining pixel regions and pixels are formed.

[0080] In the first method, examples of the method for applying the coloring composition onto the substrate include spraying, roll coating, rotary coating (spin coating), slit die coating (slit coating), bar coating, etc. Among these, it is preferable to adopt the spin coating or slit die coating. After applying the above method or the inkjet method, the coating is Preferably, the colored composition after coating is heated (prebaked) to remove the solvent. The prebaking conditions are preferably 70 to 110° C. and about 1 to 10 minutes. Prebaking is preferably performed under reduced pressure. The degree of reduced pressure is preferably set so that the ultimate pressure (absolute pressure) is 50 to 200 Pa. The thickness of the coating film after removal of the solvent is preferably 0.6 to 12 μm, more preferably 1.2 to 10 μm.

[0081] Examples of light sources used when irradiating the formed coating film with light include lamp light sources such as xenon lamps, halogen lamps, tungsten lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, medium-pressure mercury lamps, and low-pressure mercury lamps, as well as argon ion lasers, YAG lasers, XeCl excimer lasers, nitrogen lasers, and ultraviolet LEDs. The light to be irradiated is preferably light having an emission line in the range of 190 to 450 nm. The light irradiation amount is 10 to 10,000 J / m 2 is preferably 50 to 5,000 J / m 2 It is more preferable that:

[0082] The development is carried out using an alkaline developer. The unexposed parts of the coating are removed by the development process to form a patterned coating. As the alkaline developer, it is preferable to use an aqueous solution of, for example, sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo-[5.4.0]-7-undecene, 1,5-diazabicyclo-[4.3.0]-5-nonene, etc. If necessary, the aqueous solution may be used by adding, for example, a water-soluble organic solvent such as methanol or ethanol; a surfactant, etc., in an appropriate range. Examples of the developing method include shower developing, spray developing, dip (immersion) developing, and puddle (liquid puddle) developing. The developing conditions are preferably room temperature and 5 to 300 seconds. After development, the coating film is preferably washed with water. The post-baking can be carried out at a temperature of, for example, 180 to 280° C. for, for example, 10 to 60 minutes.

[0083] The thickness of the colored cured film thus formed varies depending on the application as follows: Pixel: preferably 0.5 to 5 μm, more preferably 1 to 3 μm Black matrix: preferably 0.5 to 10 μm, more preferably 0.8 to 5 μm Black spacer: preferably 0.5 to 10 μm, more preferably 1 to 7 μm

[0084] The pixel pattern obtained by forming pixels of each color as described above can be used as a color filter for a display element by forming a protective film thereon as necessary, and then forming a transparent conductive film and spacers in this order.

[0085] <Display element> The display element of the present invention comprises at least one colored cured film selected from the group consisting of the pixels and color filters formed as described above, a black matrix, and a black spacer. 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 can be applied with any suitable known liquid crystal mode, such as TN (Twisted Nematic) type, STN (Super Twisted Nematic) type, IPS (In-Planes Switching) type, VA (Vertical Alignment) type, OCB (Optically Compensated Birefringence) type, etc.

[0086] The color liquid crystal display element may be of a transmission type or a reflection type, and has a liquid crystal cell of an appropriate structure. The liquid crystal cell may have a structure in which a driving substrate on which thin film transistors (TFTs) are arranged and an opposing substrate on which a color filter is formed are used as a pair, and a liquid crystal layer is sandwiched between the pair of substrates; A structure in which a liquid crystal layer is sandwiched between a pair of substrates: one with a thin-film transistor (TFT) and a color filter, and the other with an ITO (tin-doped indium oxide) electrode. The following can be given as examples: The color liquid crystal display device can be equipped with a backlight unit in addition to the above-mentioned liquid crystal cell. Examples of the light source in the backlight unit include a cold cathode fluorescent tube and a white LED. The organic EL display element can have any suitable structure, for example, the structure disclosed in Japanese Patent Application Laid-Open No. 11-307242. The electronic paper can have any suitable structure, such as the structure disclosed in Japanese Patent Application Laid-Open No. 2007-41169. The solid-state imaging device can have any suitable structure, such as the structure disclosed in Japanese Patent No. 4,480,740. EXAMPLES

[0087] The present invention will be described in more detail below with reference to examples, although the present invention is not limited to the following examples. <(B) Synthesis of binder resin> Synthesis Example B1 A flask equipped with a cooling tube and a stirrer was charged with 100 parts by mass of propylene glycol monomethyl ether acetate and purged with nitrogen. The contents of the flask were heated to 80°C, and at the same temperature, a mixture of 100 parts by mass of propylene glycol monomethyl ether acetate, 20 parts by mass of methacrylic acid, 10 parts by mass of styrene, 5 parts by mass of benzyl methacrylate, 15 parts by mass of 2-hydroxyethyl methacrylate, 23 parts by mass of 2-ethylhexyl methacrylate, 12 parts by mass of N-phenylmaleimide, 15 parts by mass of mono(2-acryloyloxyethyl) succinate, and 6 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) was obtained. The solution was added dropwise over 1 hour, and the temperature was maintained for polymerization for 2 hours. The temperature of the reaction solution was then raised to 100°C, and the temperature was maintained for polymerization for another hour, to obtain a solution containing a binder resin (B-1) (solid content concentration 33% by mass). The Mw of the obtained binder resin (B-1) was 12,200, and the Mn was 6,500.

[0088] <Preparation of pigment dispersion> Preparation example P1 A mixture consisting of (A) 9.1 parts by mass of CI Pigment Green 58 and 3.9 parts by mass of CI Pigment Yellow 138 as colorants, 12.5 parts by mass of a solution of BYK-LPN21116 (manufactured by BYK-Chemie KK, solid content concentration 40% by mass) as a dispersant, (B) 15.2 parts by mass of a solution containing the binder resin (B-1) obtained in Synthesis Example B1 as a part of the binder resin, and 59.3 parts by mass of propylene glycol methyl ether acetate as a solvent was mixed and dispersed for 12 hours using a bead mill to prepare a pigment dispersion (A-1-1).

[0089] Preparation examples P2~P6 Pigment dispersions (A-1-2) to (A-1-6) were each prepared in the same manner as in Preparation Example P1, except that in Preparation Example P1, the type and amount of pigment shown in Table 1 was used as the colorant (A).

[0090] [Table 1]

[0091] The pigment abbreviations in Table 1 have the following meanings: G58: CI Pigment Green 58 Y138: CI Pigment Yellow 138 G7: CI Pigment Green 7 Y129: CI Pigment Yellow 129 Y185: CI Pigment Yellow 185 R254: CI Pigment Red 254 R177: CI Pigment Red 177 B15:6:CI Pigment Blue 15:6

[0092] <Dye synthesis> Synthesis example SD1 According to Synthesis Example 1 of JP2013-190776A, a compound represented by the above formula (A-2-1) (compound (A-2-1)) was synthesized.

[0093] Synthesis example SD2 According to the method described in Colorant Synthesis Example 3 of JP2012-108469A, a compound represented by the above formula (A-2-2) (compound (A-2-2)) was synthesized.

[0094] <Preparation of dye solution> Preparation example SD1 A dye solution (A-2-1) was prepared by dissolving 10 parts by mass of the compound (A-2-1) obtained in the above Synthesis Example SD1 in 90 parts by mass of propylene glycol monomethyl ether.

[0095] Preparation example SD2 A dye solution (A-2-2) was prepared by dissolving 10 parts by mass of the compound (A-2-2) obtained in the above Synthesis Example SD2 in 90 parts by mass of propylene glycol monomethyl ether.

[0096] Example 1 <Preparation of Coloring Composition> A mixture of 100 parts by mass of the pigment dispersion (A-1-1) obtained in Preparation Example P1 above, 15 parts by mass of the solution containing the binder resin (B-1) obtained in Synthesis Example B1 above as the binder resin (B), and KAYARAD DPHA (trade name, manufactured by Nippon Kayaku Co., Ltd., dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate) as the radical polymerizable compound (C) was used. (D) 13 parts by mass of a mixture of 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1) as a photoradical generator, 0.7 parts by mass of IRGACURE 369 (trade name, manufactured by BASF, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1) and 0.6 parts by mass of ADEKA ARCLES NCI-831 (trade name, O-acyloxime compound, manufactured by ADEKA Corporation), (E) 1.0 parts by mass of the compound represented by the above formula (E-4-1) as a compound, and 0.05 parts by mass of Megafac F-554 (trade name, manufactured by DIC Corporation) as a fluorine-based surfactant were mixed, and 3-methoxybutyl acetate (MBA) and propylene glycol monomethyl ether acetate (PGMEA) were added to prepare a colored composition (S-1) having a solvent composition of MBA:PGMEA = 15:85 (parts by mass) including the amount carried over from the pigment dispersion, and a solids concentration of 17% by mass. This colored composition was evaluated according to the following procedures. The evaluation results are shown in Table 5.

[0097] <Evaluation of Coloring Composition> (1) Evaluation of solvent resistance The colored composition (S-1) was applied onto a glass substrate using a spin coater, and then prebaked on a hot plate at 90° C. for 100 seconds to form a coating film having a thickness of 2.5 μm. The substrate with the coating film was allowed to cool to room temperature, and then the coating film was exposed to light at an exposure dose of 400 J / m through a photomask having a line and space pattern with a slit width of 90 μm and a space width of 210 μm. 2 The substrate was irradiated with a high-pressure mercury lamp at 1000 nm (exposure gap = 300 μm). Next, a potassium aqueous solution with a concentration of 0.04 mass% was used as a developer at a temperature of 23°C, and shower development was performed for 60 seconds under the conditions of a development pressure of 110 kPa and a developer flow rate of 1.2 L / min. After the development, the substrate with the coating was washed with ultrapure water and air-dried, and then post-baked for 30 minutes in a clean oven at 230°C to form a pixel pattern consisting of a line and space pattern on the substrate. The substrate on which the pixel pattern was formed as described above was immersed in N-methylpyrrolidone at 25° C. for 30 minutes, and the pixel pattern shape and film thickness before and after immersion were observed with a scanning electron microscope and evaluated according to the following criteria.

[0098] Evaluation criteria If no chipping is found in the pixel pattern and the film thickness after immersion is 95% or more of the film thickness before immersion: Solvent resistance "Good" If a part of the pixel pattern is chipped or the film thickness after immersion is 80% or more but less than 95% of the film thickness before immersion: Solvent resistance "poor" If some chipping is found in the pixel pattern and the film thickness after immersion is less than 80% of the film thickness before immersion: Solvent resistance "Fail"

[0099] (2) Evaluation of sensitivity and mask bias A pixel pattern consisting of a line and space pattern was formed on a glass substrate by the same procedure as in "(1) Evaluation of solvent resistance" above. The pixel pattern obtained above was observed using an optical microscope to check for the presence or absence of chipping at the pattern edge, and was evaluated according to the following criteria.

[0100] Evaluation criteria If no defects are found in the pattern: Sensitivity "Excellent" If slight defects are found in the pattern: Sensitivity is "Good" If many defects are found in the pattern: Sensitivity is "poor"

[0101] In addition, the line width of the pixel pattern obtained above was measured, and the slit width (90 μm) of the photomask was subtracted from the line width measurement value to obtain a value, and the mask bias property was evaluated based on this value. Ta. The mask bias property can be roughly evaluated according to the following criteria.

[0102] Evaluation criteria If the subtraction value is negative: curing is poor and sensitivity is significantly poor When the subtraction value is 0 μm or more and less than 10 μm: Mask bias is small (excellent mask bias) If the subtraction value is 10 μm or more: Mask bias is large (Poor mask bias)

[0103] Here, if the photosensitivity of the colored composition is sufficiently high, a pattern (colored cured film) having excellent curability and adhesion to the substrate is formed, and therefore no chipping or peeling is observed in the formed pattern. On the other hand, if the mask bias property is small, a pattern having a size that reproduces the photomask size is formed. Therefore, as long as the colored composition is excellent in either one of the above-mentioned photosensitivity and mask bias property, it can be suitably used after selecting the process design to be adopted, the application of the liquid crystal display device, and the like.

[0104] Examples 2 to 4, 8 to 10 and 12 to 15 Colored compositions were prepared in the same manner as in Example 1 above, except that the types and amounts of the components (A) to (E) were as shown in Table 2, and various evaluations were carried out. The evaluation results are shown in Table 5.

[0105] Example 5 85 parts by mass of the pigment dispersion (A-1-5) obtained in Preparation Example P5 above (containing 11 parts by mass of pigment and 4.2 parts by mass of binder resin (B-1)), 20 parts by mass of the dye solution (A-2-1) obtained in Preparation Example SD1 above (containing 2 parts by mass of dye), 31 parts by mass of the solution containing binder resin (B-1) as the binder resin (B) obtained in Synthesis Example B1 above (corresponding to 10.2 parts by mass of binder resin (B-1)), (C) 19 parts by mass of KAYARAD DPHA (trade name, manufactured by Nippon Kayaku Co., Ltd., a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate) as a radical polymerizable compound, (D) IRGACURE as a photoradical generator, 369 (trade name, BASF, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1) 1.0 parts by mass and ADEKA ARCLES NCI-831 (trade name, O-acyloxime compound, ADEKA Corporation) 0.9 parts by mass, (E) compound 1.5 parts by mass of the compound represented by the above formula (E-4-1), and fluorine-based surfactant Megafac F-554 (trade name, DIC Corporation) 0.05 parts by mass were mixed, and MBA, PGMEA and propylene glycol monomethyl ether (PGME) were added to prepare a colored composition having a solvent composition of MBA:PGMEA:PGME = 15:75:10 (parts by mass) including the amount carried over from the pigment dispersion, and a solids concentration of 17% by mass. This colored composition was used to carry out various evaluations in the same manner as in Example 1. The evaluation results are shown in Table 5.

[0106] Example 6 Colored compositions were prepared in the same manner as in Example 5 above, except that the type and amount of the component (A) were as shown in Table 2, and various evaluations were carried out. The evaluation results are shown in Table 5.

[0107] Example 7 130 parts by mass of the dye solution (A-2-2) obtained in Preparation Example SD2 above (containing 13 parts by mass of dye), 62 parts by mass of the solution containing the binder resin (B-1) obtained in Synthesis Example B1 above (corresponding to 20.5 parts by mass of the binder resin (B-1)), (C) 27 parts by mass of KAYARAD DPHA (trade name, manufactured by Nippon Kayaku Co., Ltd., a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate) as a radical polymerizable compound, (D) IRGACURE as a photoradical generator, 369 (trade name, BASF, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1) 2.5 parts by mass and ADEKA ARCLES NCI-831 (trade name, O-acyloxime compound, ADEKA Corporation) 2.2 parts by mass, (E) compound 2.0 parts by mass of the compound represented by the above formula (E-4-1), and fluorine-based surfactant Megafac F-554 (trade name, DIC Corporation) 0.05 parts by mass were mixed, and MBA, PGMEA and PGME were added to prepare a colored composition having a solvent composition of MBA:PGMEA:PGME = 15:40:45 (parts by mass) including the amount carried over from the pigment dispersion, and a solids concentration of 17% by mass. This colored composition was used to carry out various evaluations in the same manner as in Example 1. The evaluation results are shown in Table 5.

[0108] Example 11 Colored compositions were prepared in the same manner as in Example 7 above, except that the type and amount of the component (E) were as shown in Table 2, and various evaluations were carried out. The evaluation results are shown in Table 5.

[0109] Examples 16, 17, and 20 to 24 and Comparative Examples 1 and 4 Colored compositions were prepared in the same manner as in Example 1 above, except that the types and amounts of the components (A) to (E) were as shown in Table 3, and various evaluations were carried out. The evaluation results are shown in Table 6.

[0110] Examples 18 and 25 and Comparative Examples 2 and 5 Colored compositions were prepared in the same manner as in Example 5 above, except that the types and amounts of the components (A) to (E) were as shown in Table 3, and various evaluations were carried out. The evaluation results are shown in Table 6.

[0111] Example 19 and Comparative Examples 3 and 6 A colored composition was prepared in the same manner as in Example 7 above, except that the types and amounts of the components (A) to (E) were as shown in Table 3, and various evaluations were carried out. The evaluation results are shown in Table 6.

[0112] Examples 26, 27, 33 and 34 and Comparative Examples 7, 8, 11 and 12 Colored compositions were prepared in the same manner as in Example 1 above, except that the types and amounts of the components (A) to (E) were as shown in Table 4, and various evaluations were carried out. The evaluation results are shown in Table 7.

[0113] Examples 30 to 32, 35 and 36 and Comparative Examples 10, 13 and 14 Colored compositions were prepared in the same manner as in Example 5 above, except that the types and amounts of the components (A) to (E) were as shown in Table 4, and various evaluations were carried out. The evaluation results are shown in Table 7.

[0114] Examples 28, 29 and Comparative Example 9 A colored composition was prepared in the same manner as in Example 7 above, except that the types and amounts of the components (A) to (E) were as shown in Table 4, and various evaluations were carried out. The evaluation results are shown in Table 7.

[0115] [Table 2]

[0116] [Table 3]

[0117] [Table 4]

[0118] The abbreviations of the components in Tables 2 to 4 above have the following meanings. [(C) Radical polymerizable compound] C-1: KAYARAD DPHA (trade name, manufactured by Nippon Kayaku Co., Ltd., a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate) [(D) Photoradical generator] D-1: IRGACURE 369 (trade name, manufactured by BASF, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1) D-2: ADEKA ARCLES NCI-831 (trade name, O-acyloxime compound, manufactured by ADEKA Corporation) [(E) Compound] E-1-1: Compound represented by the above formula (E-1-1) E-2-1: Compound represented by the above formula (E-2-1) E-2-2: Compound represented by the above formula (E-2-2) E-3-1: Compound represented by the above formula (E-3-1) E-4-1: Compound represented by the above formula (E-4-1) E-4-2: Compound represented by the above formula (E-4-2) E-4-3: Compound represented by the above formula (E-4-3) E-4-4: Compound represented by the above formula (E-4-4) E-4-5: Compound represented by the above formula (E-4-5) E-5-1: Compound represented by the above formula (E-5-1) [Other compounds] R-1: A compound represented by the following formula (R-1):

[0119] [ka]

[0120] The compounds represented by the above formula (R-1) used in Comparative Examples 1 to 3 do not fall under the category of (E) compounds defined in the present invention, but are listed in the column for (E) compounds in Table 3 for convenience.

[0121] [Table 5]

[0122] [Table 6]

[0123] [Table 7]

Claims

1. (A) a colorant, (B) a binder resin, (C) a radical polymerizable compound, (D) a photoradical generator, and (E) A compound shown in (E-2-1) or (E-2-2) below. Contains the radical polymerizable compound (C) is a polyfunctional (meth)acrylate obtained by reacting a trivalent or higher aliphatic polyhydroxy compound with (meth)acrylic acid, A method for producing a negative colored composition, characterized in that the content ratio of the (E) compound is 3 to 30 parts by mass relative to 100 parts by mass of the (B) binder resin, A method for producing a negative colored composition, comprising the following steps (1) or (2): (1) A step of selecting the compound shown in the following (E-2-1) as the compound (E) for producing a negative colored composition for low mask bias. (2) A step of selecting the compound shown in the following (E-2-2) as the compound (E) in order to produce a negative-tone colored composition for high photosensitivity. 【Chemistry 1】

2. (A) a colorant, (B) a binder resin, (C) a radical polymerizable compound, (D) a photoradical generator, and (E) A compound shown in (E-2-1) or (E-2-2) below. Contains the (D) photoradical generator contains an O-acyloxime compound, A method for producing a negative colored composition, characterized in that the content ratio of the (E) compound is 3 to 30 parts by mass relative to 100 parts by mass of the (B) binder resin, A method for producing a negative colored composition, comprising the following steps (1) or (2): (1) A step of selecting the compound shown in the following (E-2-1) as the compound (E) for producing a negative colored composition for low mask bias. (2) A step of selecting the compound shown in the following (E-2-2) as the compound (E) in order to produce a negative-tone colored composition for high photosensitivity. 【Chemistry 2】

3. The method for producing a negative colored composition according to claim 1, wherein the photoradical generator (D) contains an O-acyloxime compound.

4. The method for producing a negative colored composition according to any one of claims 1 to 3, wherein the content of the colorant (A) is 15 to 45 mass% based on the total solid content of the colored composition.

5. The method for producing a negative colored composition according to any one of claims 1 to 4, wherein the colorant (A) contains a dye.

6. A method for producing a colored cured film, comprising the following steps (A) or (B): (A) A step including a step of applying a negative colored composition obtained by the manufacturing method according to any one of claims 1 to 5 onto a substrate to form a coating film, and then irradiating at least a part of the coating film with light and then developing the coating film. (B) A step including a step of applying the negative colored composition obtained by the manufacturing method according to any one of claims 1 to 5 on a substrate in a pattern shape by an inkjet method to form a coating film, and then irradiating the coating film with light.

7. A method for producing a colored cured film as described in claim 6, wherein the colored cured film is a pixel, a black matrix, or a black spacer.

8. A method for manufacturing a display element, comprising the following steps (C) or (D): (C) A step including a step of applying the negative colored composition obtained by the manufacturing method according to any one of claims 1 to 5 onto a substrate of a display element to form a coating film, and then irradiating at least a part of the coating film with light and then developing the coating film. (D) A step including a step of applying the negative colored composition obtained by the manufacturing method according to any one of claims 1 to 5 on a substrate of a display element in a pattern shape by an inkjet method to form a coating film, and then irradiating the coating film with light.

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