Photosensitive coloring composition, color filter, and image display device

Abstract

To provide a photosensitive coloring composition which enables formation of a color filter that has a good color tone while being thin, and has good developability, as well as, a good pattern shape and adhesion.SOLUTION: A photosensitive coloring composition contains a coloring agent (A), a binder resin (B), a polymerizable compound (C), and a photopolymerization initiator (D). The coloring agent (A) contains a green pigment, a yellow pigment and a blue pigment. The green pigment contains C.I. pigment green 58. The yellow pigment contains a metal azo pigment (A2) containing a compound represented by the following (a) and (b).SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to a photosensitive coloring composition used in the manufacture of color filters used in liquid crystal display devices, solid-state imaging devices, organic EL display devices, quantum dot display devices, electronic paper, and the like.

Background Art

[0002] With the thinning and weight reduction of smartphones and tablet terminals, there is also a demand for thinning of the color filters incorporated in the liquid crystal display devices. Further, with the increase in brightness and color gamut of liquid crystal display devices, the color filter itself needs to be highly bright, and thinning is required to increase the aperture ratio of the filter segments for higher brightness.

[0003] As photosensitive coloring compositions for forming filter segments, Patent Documents 1 and 2 disclose photosensitive coloring compositions containing zinc phthalocyanine pigments, copper phthalocyanine pigments, and specific dispersants.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0005] However, in order to thin the conventional photosensitive coloring composition while maintaining the color tone of the color filter, it was necessary to contain the coloring agent at a high concentration. On the other hand, it took a long time for development, and there were problems such as the formation of an inverse taper-shaped pattern and a decrease in the adhesion of the pattern.

[0006] An object of the present invention is to provide a photosensitive coloring composition that has a good color tone while being a thin film, has good developability, good pattern shape, adhesion, and chemical resistance, and can form a color filter.

Means for Solving the Problems

[0007] The present invention is a photosensitive coloring composition containing a colorant (A), a binder resin (B), a polymerizable compound (C), and a photopolymerization initiator (D), wherein the colorant (A) includes a green pigment, a yellow pigment, and a blue pigment, the green pigment contains C.I. Pigment Green 58, the yellow pigment contains a metal azo pigment (A2) containing compounds represented by the following (a) and (b), and relates to a photosensitive coloring composition.

[0008] (a) A compound of formula (I) or a tautomeric form thereof

Chemical Formula

[0009] [In formula (I), R 1 and R 2 are each independently OH, NH2, or NHR 5 and R 3 and R 4 are each independently =O or =NR 5 and R 5 is a hydrogen atom or an alkyl group, and Me is Ni 2+ , Zn 2+ , Cu 2+ , Al 3+ 2 / 3 , Fe 2+ , Fe 3+ 2 / 3 , Co 2+ and Co 3+ 2 / 3 are two or more divalent or trivalent metal ions selected from the group consisting of Based on 1 mole of the total of the compounds of (a), Cu 2+ , Zn 2+ and Ni 2+ The total amount of ions is 95 to 100 mol%, and Al 3+ 2 / 3 , Fe 2+ , Fe 3+ 2 / 3 , Co 2+ and Co 3+ The total amount of ions is 0 to 5 mol%, and based on the total amount of the Cu 2+ , Zn 2+ and Ni 2+ ions, the amount of Ni 2+ ions is 10 to 95 mol%.]

[0010] (b) A compound represented by formula (II)

Chemical formula

[0011] [In formula (II), R 6 is each independently a hydrogen atom or an optionally substituted alkyl group.]

[0012] Further, the present invention relates to the photosensitive coloring composition, wherein the blue pigment contains one or more selected from the group consisting of C.I. Pigment Blue 15:3, C.I. Pigment Blue 15:4, and C.I. Pigment Blue 15:6.

[0013] Further, the present invention relates to the photosensitive coloring composition, wherein the total amount of the colorant (A) is 10 to 50% by weight in 100% by weight of the non-volatile components of the photosensitive coloring composition, and the mass ratio of the green pigment, yellow pigment, and blue pigment is 1:0.05 to 1:0.001 to 0.10.

[0014] Further, the present invention relates to the photosensitive coloring composition, wherein the photopolymerization initiator (D) contains an oxime ester compound. The present invention relates to the above photosensitive coloring composition.

[0015] Furthermore, the present invention also relates to the above photosensitive coloring composition containing a thermosetting compound.

[0016] The present invention also relates to a color filter including a substrate and a filter segment formed from the above photosensitive coloring composition.

[0017] The present invention also relates to an image display device including the above color filter. [Effect of the Invention]

[0018] According to the present invention as described above, the present invention can provide a photosensitive coloring composition, a color filter, and an image display device that can form a color filter having good color tone while being a film, having good developability, good pattern shape and adhesion, and further good chemical resistance. [Brief Description of the Drawings]

[0019]

Figure 1

[0020] The terms in this specification are defined. When expressed as "(meth)acryloyl", "(meth)acrylic", "(meth)acrylic acid", "(meth)acrylate", or "(meth)acrylamide", unless otherwise specified, they represent "acryloyl and / or methacryloyl", "acrylic and / or methacrylic", "acrylic acid and / or methacrylic acid", "acrylate and / or methacrylate", or "acrylamide and / or methacrylamide", respectively. "C.I." means Color Index (C.I.). Pixel and filter segment are synonyms. Colorants include pigments and dyes.

[0021] The photosensitive coloring composition of the present invention is preferably used by forming a film by coating. The film can be subjected to ultraviolet exposure, development, etc. by, for example, a photolithography method to form a pattern. The pattern is preferably used as a filter segment constituting a color filter.

[0022] <Colorant (A)> The photosensitive coloring composition of the present invention contains a green pigment, a yellow pigment, and a blue pigment as colorants. Optionally, it may contain a dye and other pigments. The photosensitive coloring composition of the present invention can achieve both high brightness and developability and solvent resistance, particularly even when the pigment concentration is high. Here, a high pigment concentration means 40% by mass or more, preferably 45 - 60% by mass, based on 100% by mass of the non-volatile content of the photosensitive coloring composition. As the pigment, an organic or inorganic pigment can be used alone or in admixture of two or more. The pigment is preferably a pigment having high color developability and high heat resistance, particularly a pigment having high thermal decomposition resistance, and usually an organic pigment is used. Specific examples of the organic pigments that can be used in the photosensitive coloring composition are shown below by Color Index numbers.

[0023] <Green pigment> The green pigment of the present invention C.I. Pigment Green 58 contains. The content of the green pigment is preferably 40 - 95% by mass in 100% by mass of the colorant (A).

[0024] <Yellow pigment> In the present invention, the yellow pigment is a photosensitive coloring composition containing a metal azo pigment (A2) containing the compounds represented by the following (a) and (b). (a) A compound of formula (I) or a tautomeric form thereof

Chemical formula

Chemical formula

[0025] Among other yellow pigments, for example, C.I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 192, 193, 194, 196, 198, 199, 213, 214, 231, 233, and the pigments described in JP-A-2012-226110 may be mentioned. Preferably, they are C.I. Pigment Yellow 138, 139, 150, 185, 231, 233, and the pigments described in JP-A-2012-226110.

[0026] <Blue pigment> The blue pigment of the present invention is not particularly limited as long as the effects of the present invention are not impaired, and known materials can be used.

[0027] Examples of the blue pigment include C.I. Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56:1, 60, 61, 61:1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79, etc. Among these, from the viewpoints of the heat resistance, light resistance, and transmittance of the filter segment, preferably C.I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, or 15:6, and more preferably C.I. Pigment Blue 15:2, 15:3, 15:6.

[0028] The cyan pigment can be used alone or in combination of two or more kinds.

[0029] Examples of the inorganic pigment include titanium oxide, barium sulfate, zinc white, lead sulfate, yellow lead, zinc yellow, red iron oxide (III), cadmium red, ultramarine, cobalt blue, chromium oxide green, cobalt green , amber, synthetic iron black, and the like.

[0030] In addition to being able to suppress the decrease in the ultraviolet curability of a film containing a zinc phthalocyanine halide pigment (A1) that tends to absorb ultraviolet rays by including a metal azo pigment (A2), an unexpected effect of being able to suppress the formation of an inverse taper pattern was found.

[0031] <Fine particle size of pigment> After the organic pigment has been subjected to a fine particle size treatment, it is preferably mixed with other raw materials. Examples of the fine particle size treatment method include wet grinding, dry grinding, solution precipitation method, and the like. Among these, salt milling treatment by a kneader method, which is a kind of wet grinding, is preferable. The average primary particle size of the organic pigment after the fine particle size treatment is preferably 10 to 80 nm, more preferably 15 to 70 nm. With an appropriate particle size, the dispersibility is further improved and the contrast ratio of the film is further improved. The average primary particle size is the average value of about 20 particles arbitrarily selected from the enlarged image of a TEM (transmission electron microscope). When there are a longitudinal axis length and a transverse axis length of the particle, the longitudinal axis length is used.

[0032] Salt milling treatment is a process in which a mixture of a pigment, a water-soluble inorganic salt, and a water-soluble organic solvent is mechanically kneaded while being heated using a batch-type or continuous kneader such as a kneader, a two-roll mill, a three-roll mill, a ball mill, an attritor, a sand mill, a planetary mixer, etc., and then the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water. The water-soluble inorganic salt acts as a crushing aid, and the pigment is crushed by utilizing the high hardness of the inorganic salt during salt milling. By optimizing the conditions for the salt milling treatment of the pigment, it is possible to obtain a pigment having a very fine primary particle diameter, a narrow distribution width, and a sharp particle size distribution.

[0033] Examples of the water-soluble inorganic salt include sodium chloride, potassium chloride, sodium sulfate, etc. Among these, sodium chloride (table salt) is preferable from the viewpoint of price. The amount of the water-soluble inorganic salt used is preferably 50 to 2000 parts by mass, more preferably 300 to 1000 parts by mass, per 100 parts by mass of the pigment, from both the viewpoints of treatment efficiency and production efficiency.

[0034] The water-soluble organic solvent wets the pigment and the water-soluble inorganic salt. The water-soluble organic solvent is a compound that dissolves (mixes) in water and does not substantially dissolve the water-soluble inorganic salt. As the water-soluble organic solvent, a high-boiling solvent having a boiling point of 120°C or higher is preferable in that it is difficult to volatilize due to the temperature rise during salt milling. Examples of the water-soluble organic solvent include 2-methoxyethanol, 2-butoxyethanol, 2-(isopentyloxy)ethanol, 2-(hexyloxy)ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid polypropylene glycol, etc. The amount of the water-soluble organic solvent used is preferably 5 to 1000 parts by mass, more preferably 50 to 500 parts by mass, per 100 parts by mass of the pigment.

[0035] During the salt milling process, resin can be added as needed. Examples of the resin include natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, and the like. The resin is preferably solid at room temperature, water-insoluble, and more preferably partially soluble in a water-soluble organic solvent. The amount of the resin used is preferably 5 to 200 parts by mass with respect to 100 parts by mass of the pigment. <Dye> Examples of the dye include acid dyes, direct dyes, basic dyes, salt-forming dyes, oil-soluble dyes, disperse dyes, reactive dyes, mordant dyes, building dyes, sulfur dyes, and the like. Also included are derivatives of the dye and lake pigments obtained by lake-forming the dye.

[0036] The acid dye preferably has an acidic group such as a sulfonic acid or a carboxylic acid. The direct dye preferably forms a salt-forming compound with an inorganic salt of an acid dye or a salt-forming compound of an acid dye and a nitrogen-containing compound such as a quaternary ammonium salt compound, a tertiary amine compound, a secondary amine compound, or a primary amine compound. Also preferred is a salt-forming compound that is a salt of a resin component having these functional groups and an acid dye. Further, the salt-forming compound can easily obtain a photosensitive coloring composition excellent in resistance (light resistance, solvent resistance) by sulfonamidation and modification into a sulfonic acid amide compound. Also preferred is a salt-forming compound of an acid dye and a compound having an onium base because it is excellent in resistance (light resistance, solvent resistance). The compound having an onium base is preferably a resin having a cationic group.

[0037] Examples of the basic dye include salt-forming compounds with organic acids, perchloric acid, or metal salts thereof. Among the salt-forming compounds, the salt-forming compounds of basic dyes are preferred because they are excellent in various resistances and compatibility with pigments.

[0038] The chemical structure of the dye includes, for example, azo dyes, disazo dyes, azomethine dyes (such as indoaniline dyes, indophenol dyes, etc.), dipyrromethene dyes, quinone dyes (such as benzoquinone dyes, naphthoquinone dyes, anthraquinone dyes, anthrapyridone dyes, etc.), carbonium dyes (such as diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, acridine dyes, etc.), quinoneimine dyes (such as oxazine dyes, thiazine dyes, etc.), azine dyes, polymethine dyes (such as oxonol dyes, merocyanine dyes, arylidene dyes, styryl dyes, cyanine dyes, squarylium dyes, croconium dyes, etc.), quinophthalone dyes, phthalocyanine dyes, subphthalocyanine dyes, perinone dyes, indigo dyes, thioindigo dyes, quinoline dyes, nitro dyes, nitroso dyes, rhodamine dyes, etc. Among these, from the viewpoints of color characteristics such as hue, color separation property, and color unevenness, azo dyes, xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, squarylium dyes, quinophthalone dyes, phthalocyanine dyes, and subphthalocyanine dyes are preferable, and xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, and phthalocyanine dyes are more preferable. The specific structures of the dyes are described in "New Edition Dye Handbook" (edited by The Society of Synthetic Organic Chemistry, Japan; Maruzen, 1970), "Color Index" (The Society of Dyers and colourists), "Dye Handbook" (edited by Oikawa et al.; Kodansha, 1986), etc.

[0039] <Dye derivative> The photosensitive coloring composition can use a dye derivative as needed. The dye derivative is a compound having an acidic group, a basic group, a neutral group, etc. in an organic dye residue. Examples of the dye derivative include compounds having an acidic substituent such as a sulfo group, a carboxy group, or a phosphoric acid group, and amine salts thereof, compounds having a basic substituent such as a sulfonamide group or a tertiary amino group at the terminal, and compounds having a neutral substituent such as a phenyl group or a phthalimidoalkyl group. Examples of organic pigments include diketopyrrolopyrrole-based pigments, anthraquinone-based pigments, quinacridone-based pigments, dioxazine-based pigments, perinone-based pigments, perylene-based pigments, thiazine indigo-based pigments, triazine-based pigments, benzimidazolone-based pigments, indole-based pigments such as benzisoindole, isoindoline-based pigments, isoindolinone-based pigments, quinophthalone-based pigments, naphthol-based pigments, threne-based pigments, metal complex-based pigments, azo-based pigments such as azo, disazo, and polyazo pigments, and the like.

[0040] Specifically, diketopyrrolopyrrole-based pigment derivatives are disclosed in JP-A-2001-220520, WO2009 / 081930 pamphlet, WO2011 / 052617 pamphlet, WO2012 / 102399 pamphlet, JP-A-2017-156397; phthalocyanine-based pigment derivatives are disclosed in JP-A-2007-226161, WO2016 / 163351 pamphlet, JP-A-2017-165820, Patent No. 5753266; anthraquinone-based pigment derivatives are disclosed in JP-A-63-264674, JP-A-09-272812, JP-A-10-245501, JP-A-10-265697, JP-A-2007-079094, WO2009 / 025325 pamphlet; quinacridone-based pigment derivatives are disclosed in JP-A-48-54128, JP-A-03-9961, JP-A-2000-273383; dioxazine-based pigment derivatives are disclosed in JP-A-2011-162662; thiazine indigo-based pigment derivatives are disclosed in JP-A-2007-314785; triazine-based pigment derivatives are disclosed in JP-A-61-246261, JP-A-11-199796, JP-A-2003-165922, JP-A-2003-168208, JP-A-2004-217842, JP-A-2007-314681; benzisoindole-based pigment derivatives are disclosed in JP-A-2009-57478; quinophthalone-based pigment derivatives are disclosed in JP-A-2003-167112, JP-A-2006-291194, JP-A-2008-31281, JP-A-2012-226110; naphthol-based pigment derivatives are disclosed in JP-A-2012-208329, JP-A-2014-5439; azo-based pigment derivatives are disclosed in JP-A-2001-172520, JP-A-2012-172092; acidic substituents are disclosed in JP-A-2004-307854; basic substituents are disclosed in JP-A-2002-201377, JP-A-2003-171594, JP-A-2005-181383, JP-A-2005-213404. The pigment derivatives described in these documents include derivatives, pigment derivatives, dispersants, pigment dispersants, or Although it may sometimes be simply described as a compound or the like, a compound having a substituent such as an acidic group, a basic group, or a neutral group in the above-described organic dye residue is synonymous with a dye derivative.

[0041] The dye derivatives can be used alone or in admixture of two or more.

[0042] The content of the dye derivative is preferably 1 to 100 parts by mass, more preferably 3 to 70 parts by mass, and still more preferably 5 to 50 parts by mass with respect to 100 parts by mass of the organic pigment.

[0043] When a dye derivative is added to a pigment and subjected to a micronization treatment such as acid pasting, acid slurry, dry milling, salt milling, solvent salt milling, etc., the dye derivative is adsorbed on the pigment surface, and the primary particles of the pigment can be made finer than in the case where no dye derivative is added.

[0044] Also, when a dye derivative is added to a pigment and subjected to a dispersion treatment such as wet dispersion using two-roll, three-roll, or beads, the dye derivative is adsorbed on the pigment surface, the pigment surface becomes polar, and the adsorption of the resin-type dispersant is promoted. The compatibility of the pigment, dye derivative, resin-type dispersant, solvent, and other additives is improved, and the dispersion stability and viscosity stability over time when used as a coloring composition or a colored curable composition are improved.

[0045] <Resin-type dispersant> The photosensitive coloring composition of the present invention can use known resin-type dispersants. Resin-type dispersants have a coloring agent affinity site having a property of adsorbing to a coloring agent and a site compatible with components other than the coloring agent, and adsorb to the coloring agent to function to stabilize the dispersion in the photosensitive coloring composition. Examples of resin types of resin-type dispersants include urethane-based dispersants such as polyurethane; polycarboxylic acid esters such as polyacrylate, unsaturated polyamides, polycarboxylic acids, (partial) amine salts of polycarboxylic acids, ammonium salts of polycarboxylic acids, alkylamine salts of polycarboxylic acids; polysiloxanes; long-chain polyaminoamidophosphates, hydroxyl group-containing polycarboxylic acid esters; oil-based dispersants such as amides and their salts formed by the reaction of poly(lower alkyleneimine) and a polyester having a free carboxyl group; water-soluble resins and water-soluble polymer compounds such as (meth)acrylic acid-styrene copolymers, (meth)acrylic acid-(meth)acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, polyvinylpyrrolidone; polyester-based, modified polyacrylate-based, ethylene oxide / propylene oxide addition compounds, phosphate ester-based, and the like.

[0046] In terms of functional group types, examples of resin-type dispersants include acidic functional group-containing resin-type dispersants, basic functional group-containing resin-type dispersants, and the like.

[0047] Examples of acidic functional group-containing resin-type dispersants include resin-type dispersants having an aromatic carboxylic acid structure. These are described, for example, in WO2008 / 007776, JP-A-2008-029901, JP-A-2009-155406, JP-A-2010-185934, JP-A-2011-157416, JP-A-2009-251481, JP-A-2007-23195, JP-A-1996-143651, and the like.

[0048] Examples of the basic functional group-containing resin type dispersant include nitrogen atom-containing graft copolymers, nitrogen atom-containing acrylic block copolymers having functional groups such as a tertiary amino group, a quaternary ammonium base, and a nitrogen-containing heterocyclic ring in the side chain, and urethane-based polymer dispersants.

[0049] Also, as disclosed in JP-A-2009-185277, a resin type dispersant having an aromatic carboxyl group and a vinyl resin having a tertiary amino group (having the function of the resin type dispersant) can be used in combination.

[0050] The resin type dispersant can be used alone or in combination of two or more.

[0051] The content of the resin type dispersant is preferably about 3 to 200% by mass, more preferably about 5 to 100% by mass, based on 100 parts by mass of the colorant (A). When contained in an appropriate amount, the film-forming property is improved.

[0052] <Binder resin (B)> The binder resin (B) is preferably a resin having a transmittance of 80% or more in the entire wavelength region of 400 to 700 nm when a film having a thickness of 2 μm is formed. In addition, the transmittance is preferably 95% or more. The binder resin (B) is preferably a thermoplastic resin or a photosensitive resin. Further, the binder resin (B) preferably has alkali solubility. Thereby, the film formed from the photosensitive coloring composition can be patterned by photolithography. A photosensitive resin having no alkali solubility and an alkali-soluble resin can have a thermosetting group. Examples of the thermosetting group include an epoxy group and an oxetanyl group.

[0053] The thermoplastic resin does not have alkali solubility. Examples of the thermoplastic resin include acrylic resins, butyral resins, styrene-maleic acid copolymers, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymers, polyvinyl acetate, polyurethane resins, polyester resins, vinyl resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resins. Examples of the alkali-soluble resin having no photosensitivity include resins having acidic groups such as carboxyl groups and sulfone groups. Examples of the alkali-soluble resin having no photosensitivity include acrylic resins having acidic groups, α-olefin / (anhydrous) maleic acid copolymers, styrene / styrene sulfonic acid copolymers, ethylene / (meth)acrylic acid copolymers, or isobutylene / (anhydrous) maleic acid copolymers. Among these, acrylic resins having acidic groups and styrene / styrene sulfonic acid copolymers are preferable in terms of improving developability, heat resistance, and transparency.

[0054] <Alkali-soluble photosensitive resin> The alkali-soluble photosensitive resin has photosensitivity because it has polymerizable unsaturated groups. The alkali-soluble photosensitive resin only needs to have alkali solubility and photosensitivity, and known resins can be used. Resins synthesized by the following methods (i) and (ii) are preferable. When the alkali-soluble photosensitive resin is used, it undergoes three-dimensional crosslinking upon light irradiation, increasing the crosslink density, thereby improving the chemical resistance of the film.

[0055] [Method (i)] Method (i) is, for example, first, synthesizing a polymer of an epoxy group-containing monomer and other monomers. Next, adding a monocarboxyl group-containing monomer to the epoxy group of the polymer, and reacting a polybasic acid anhydride with the generated hydroxyl group to obtain an alkali-soluble photosensitive resin. The monocarboxyl group-containing monomer is a monomer having one carboxyl group.

[0056] Epoxy group-containing monomers include, for example, glycidyl (meth)acrylate, methyl glycidyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, and 3,4-epoxycyclohexyl (meth)acrylate. Among these, from the viewpoint of reactivity, glycidyl (meth)acrylate is preferred.

[0057] Monocarboxyl group-containing monomers include, for example, (meth)acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-haloalkyl, alkoxyl, halogen, nitro, cyano-substituted products of (meth)acrylic acid, and other monocarboxylic acids.

[0058] Polybasic acid anhydrides include, for example, tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, etc. Note that the polybasic acid anhydride may have a carboxyl group that does not form an acid anhydride.

[0059] Other monomers include, for example, (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, or ethoxypolyethylene glycol (meth)acrylate, Alternatively, (meth)acrylamides such as (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, diacetone(meth)acrylamide, or acryloylmorpholine, styrenes such as styrene or α-methylstyrene, vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, or isobutyl vinyl ether, vinyl fatty acids such as vinyl acetate or vinyl propionate, etc. may be mentioned.

[0060] In addition, N-substituted maleimides such as cyclohexyl maleimide, phenyl maleimide, methyl maleimide, ethyl maleimide, 1,2-bismaleimide ethane, 1,6-bismaleimide hexane, 3-maleimide propionic acid, 6,7-methylenedioxy-4-methyl-3-maleimide coumarin, 4,4'-bismaleimide diphenylmethane, bis(3-ethyl-5-methyl-4-maleimide phenyl)methane, N,N'-1,3-phenylene dimaleimide, N,N'-1,4-phenylene dimaleimide, N-(1-pyrenyl)maleimide, N-(2,4,6-trichlorophenyl)maleimide, N-(4-aminophenyl)maleimide, N-(4-nitrophenyl)maleimide, N-benzyl maleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimide benzoate, N-succinimidyl-3-maleimide propionate, N-succinimidyl-4-maleimide butyrate, N-succinimidyl-6-maleimide hexanoate, N-[4-(2-benzimidazolyl)phenyl]maleimide, 9-maleimide acridine, EO-modified cresol acrylate, n-nonylphenoxy polyethylene glycol acrylate, phenoxyethyl acrylate, ethoxylated phenyl acrylate, ethylene oxide (EO)-modified (meth)acrylate of phenol, EO or propylene oxide (PO)-modified (meth)acrylate of p-cumylphenol, EO-modified (meth)acrylate of nonylphenol, PO-modified (meth)acrylate of nonylphenol, etc. may be mentioned.

[0061] Method (ii) involves, for example, synthesizing a polymer by synthesizing a hydroxyl group-containing monomer, a carboxyl group-containing monomer, and other monomers. Next, a method of synthesizing an alkali-soluble photosensitive resin by reacting the isocyanate group of an isocyanate group-containing monomer with the hydroxyl group of the polymer can be mentioned.

[0062] Examples of the hydroxyl group-containing monomer include hydroxyalkyl methacrylates such as 2-hydroxyethyl (meth)acrylate, 2- or 3-hydroxypropyl (meth)acrylate, 2- or 3- or 4-hydroxybutyl (meth)acrylate, glycerol mono(meth)acrylate, or cyclohexanedimethanol mono(meth)acrylate. Further, polyether mono(meth)acrylate obtained by addition polymerization of ethylene oxide, propylene oxide, and / or butylene oxide, etc. to hydroxyalkyl (meth)acrylate, and polyester mono(meth)acrylate obtained by adding polyγ-valerolactone, polyε-caprolactone, and / or poly12-hydroxystearic acid, etc. can also be mentioned. Among these, 2-hydroxyethyl methacrylate and glycerol mono(meth)acrylate are preferable, and glycerol mono(meth)acrylate is more preferable.

[0063] Examples of the isocyanate group-containing monomer include 2-(meth)acryloylethyl isocyanate, 2-(meth)acryloyloxyethyl isocyanate, or 1,1-bis〔methacryloyloxy〕ethyl isocyanate.

[0064] In addition to the above monomers, monomers that can be used include, in addition to the other monomers exemplified in the above method (i), phosphate group-containing monomers.

[0065] The phosphate group-containing monomer is, for example, a compound obtained by reacting a phosphate esterifying agent such as phosphorus pentoxide or polyphosphoric acid with the hydroxyl group of a hydroxyl group-containing monomer.

[0066] The above raw materials of the binder resin (B) can be used alone or in combination of two or more. Also, the binder resin (B) can be used alone or in combination of two or more.

[0067] The content of the binder resin (B) is preferably 20 to 400 parts by mass, more preferably 50 to 250 parts by mass, based on 100 parts by mass of the colorant (A). Since the film-forming property and various resistances are good, 20 parts by mass or more is preferable, and since the colorant concentration is high and good color characteristics can be exhibited, 400 parts by mass or less is preferable.

[0068] The weight average molecular weight (Mw) of the binder resin (B) is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and even more preferably 4,000 to 20,000. The value of Mw / Mn is preferably 10 or less. Here, Mn is the number average molecular weight.

[0069] The acid value of the alkali-soluble resin is preferably 50 to 200 mgKOH / g, more preferably 70 to 180 mgKOH / g, and even more preferably 90 to 170 mgKOH / g. With an appropriate acid value, high balance can be achieved among alkali solubility, adhesion, and residue suppression.

[0070] <Polymerizable compound (C)> The polymerizable compound (C) is a monomer (monomer) or oligomer containing a polymerizable unsaturated group. Examples of the polymerizable compound (C) include acid group-containing monomers, urethane bond-containing monomers, and other monomers.

[0071] Examples of the acid group of the acid group-containing monomer include a sulfonic acid group, a carboxyl group, and a phosphoric acid group.

[0072] Examples of the acid group-containing monomer include esterified products of free hydroxyl group-containing poly(meth)acrylates of polyhydric alcohols and (meth)acrylic acid with dicarboxylic acids; esterified products of polyvalent carboxylic acids with monohydroxyalkyl (meth)acrylates, etc. Specific examples include trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate , free carboxyl group-containing monoesterified products of monohydroxyoligoacrylates or monohydroxyoligomethacrylates such as dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate with dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, phthalic acid; free carboxyl group-containing oligoesterified products of tricarboxylic acids such as propane-1,2,3-tricarboxylic acid (tricarballylic acid), butane-1,2,4-tricarboxylic acid, benzene-1,2,3-tricarboxylic acid, benzene-1,3,4-tricarboxylic acid, benzene-1,3,5-tricarboxylic acid with monohydroxymonoacrylates or monohydroxymonomethacrylates such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, etc.

[0073] (Monomer containing urethane bond) Examples of the monomer containing a urethane bond include polyfunctional urethane acrylates obtained by reacting a polyfunctional isocyanate with a (meth)acrylate having a hydroxyl group, and polyfunctional urethane acrylates obtained by reacting a polyfunctional isocyanate with an alcohol and then reacting the resulting product with a (meth)acrylate having a hydroxyl group.

[0074] Examples of (meth)acrylates having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol ethylene oxide-modified penta(meth)acrylate, dipentaerythritol propylene oxide-modified penta(meth)acrylate, dipentaerythritol caprolactone-modified penta(meth)acrylate, glycerol acrylate methacrylate, glycerol dimethacrylate, 2-hydroxy-3-acryloylpropyl methacrylate, reaction products of epoxy group-containing compounds and carboxy(meth)acrylate, hydroxyl group-containing polyol polyacrylate, and the like.

[0075] Examples of polyfunctional isocyanates include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate, polyisocyanate, and the like.

[0076] Other monomers include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, β-carboxyethyl (meth)acrylate, polyethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, triethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, phenoxytetraethylene glycol (meth)acrylate, phenoxyhexaethylene glycol (meth)acrylate, trimethylolpropane PO-modified tri(meth)acrylate, trimethylolpropane EO-modified tri(meth)acrylate, isocyanuric acid EO-modified di(meth)acrylate, isocyanuric acid EO-modified tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, 1,6-hexanediol diglycidyl ether di(meth)acrylate, bisphenol A diglycidyl ether di(meth)acrylate, neopentyl glycol diglycidyl ether di(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, tricyclodecanyl (meth)acrylate, (meth)acrylic acid esters of methylolated melamine, epoxy (meth)acrylate, urethane acrylate and other various acrylic acid esters and methacrylic acid esters, (meth)acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, N-vinylformamide, acrylonitrile and the like.

[0077] The polymerizable compound (C) can be used alone or in combination of two or more.

[0078] The blending amount of the coincidence compound (C) is preferably 1 to 50% by mass, more preferably 2 to 40 parts by mass, per 100% by mass of the non-volatile content of the photosensitive coloring composition. When blended in an appropriate amount, the curability and developability are further improved.

[0079] <Photoinitiator (D)> The photoinitiator (D) is, for example, an acetophenone-based compound such as 4-phenoxydichloroacetophenone, 4-t-butyldichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-(dimethylamino)-1-[4-(4-morpholino)phenyl]-2-(phenylmethyl)-1-butanone, or 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone; a benzoin-based compound such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzyl dimethyl ketal; a benzophenone-based compound such as benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, or 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone; a thioxanthone-based compound such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, or 2,4-diethylthioxanthone; a triazine-based compound such as 2,4,6-trichloros-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-piperonyl-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxy-naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl)-6-triazine, or 2,4-trichloromethyl-(4'-methoxystyryl)-6-triazine;1,2 - octanedione, 1 - [4 - (phenylthio)phenyl]-, 2 - (O - benzoyloxime), or ethanone, 1 - [9 - ethyl - 6 - (2 - methylbenzoyl)-9H - carbazol - 3 - yl]-, 1 - (O - acetyloxime) and other oxime ester compounds; bis(2,4,6 - trimethylbenzoyl)phenylphosphine oxide, or diphenyl - 2,4,6 - trimethylbenzoylphosphine oxide and other phosphine compounds; 9,10 - phenanthrenequinone, camphorquinone, ethylanthraquinone and other quinone compounds; borate compounds; carbazole compounds; imidazole compounds; or titanocene compounds and the like. Among these, oxime ester compounds are preferred.;

[0080] (Oxime ester compound) The photoinitiator preferably contains an oxime ester compound. The oxime ester compound absorbs ultraviolet rays, causing cleavage of the N - O bond of the oxime and generating iminyl radicals and alkyloxy radicals. These radicals further decompose to generate highly active radicals, enabling the formation of patterns with a small exposure amount. When the colorant concentration of the photosensitive coloring composition is high, the ultraviolet transmittance of the coating film may be low and the degree of curing of the coating film may be low. However, since the oxime ester compound has a high quantum efficiency, it can be preferably used.;

[0081] Examples of the oxime ester compound include the oxime ester - type photoinitiators described in JP - A - 2007 - 210991, JP - A - 2009 - 179619, JP - A - 2010 - 037223, JP - A - 2010 - 215575, JP - A - 2011 - 020998, etc.;

[0082] The photoinitiator (D) can be used alone or in combination of two or more.;

[0083] The content of the photoinitiator (D) is preferably 2 to 50 parts by mass, more preferably 2 to 30 parts by mass, per 100 parts by mass of the colorant. When an appropriate amount is blended, the photocurability and developability are further improved.

[0084] The photosensitive coloring composition can further contain a sensitizer. Examples of the sensitizer include chalcone derivatives, unsaturated ketones typified by dibenzalacetone, 1,2-diketone derivatives typified by benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thiophene derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, polymethine dyes such as oxonol derivatives, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, azulene derivatives, azulenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, tetrapyrazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphyllin derivatives, annulene derivatives, spiropyran derivatives, spirooxazine derivatives, thiospiropyran derivatives, metal arene complexes, organoruthenium complexes, or Michler's ketone derivatives, α-acyloxy esters, acylphosphine oxides, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethylanthraquinone, 4,4'-diethylisophthalophenone, 3,3' or 4,4'-tetra(t-butylperoxycarbonyl)benzophenone, 4,4'-bis(diethylamino)benzophenone, and the like. Among these, thioxanthone derivatives, Michler's ketone derivatives, and carbazole derivatives are preferred. Specifically, 2,4 - diethylthioxanthone, 2 - chlorothioxanthone, 2,4 - dichlorothioxanthone, 2 - isopropylthioxanthone, 4 - isopropylthioxanthone, 1 - chloro - 4 - propoxythioxanthone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethylmethylamino)benzophenone, N - ethylcarbazole, 3 - benzoyl - N - ethylcarbazole, 3,6 - dibenzoyl - N - ethylcarbazole, etc. are more preferred.

[0085] The sensitizer can be used alone or in combination of two or more.

[0086] The content of the sensitizer is preferably 3 to 60 parts by mass, more preferably 5 to 50 parts by mass, with respect to 100 parts by mass of the polymerizable initiator (E). When contained in an appropriate amount, the photocurability and developability are further improved.

[0087] <Thermosetting compound> The photosensitive coloring composition can contain a thermosetting compound. When producing a color filter using the photosensitive coloring composition, the thermosetting compound thermosets in the post - bake process to increase the cross - link density of the film and improve the heat resistance. Thereby, pigment aggregation in the post - bake process is suppressed and the contrast ratio is improved.

[0088] The thermosetting compound may be a low - molecular compound or a high - molecular compound such as a resin. Examples of the thermosetting compound include epoxy compounds, oxetane compounds, benzoguanamine compounds, rosin - modified maleic acid compounds, rosin - modified fumaric acid compounds, melamine compounds, urea compounds, and phenol compounds. Among these, epoxy compounds and oxetane compounds are preferred.

[0089] <Thiol - based chain transfer agent> The photosensitive coloring composition can contain a chain transfer agent. The chain transfer agent is preferably a thiol-based chain transfer agent. When the thiol-based chain transfer agent is used in combination with a photoinitiator, during radical polymerization after light irradiation, thiyl radicals that are less susceptible to polymerization inhibition by oxygen are generated, improving the sensitivity of the photosensitive coloring composition.

[0090] The thiol-based chain transfer agent is preferably a polyfunctional thiol having two or more thiol groups (SH groups). It is more preferable that the thiol-based chain transfer agent has four or more SH groups. As the number of functional groups increases, it becomes easier for the film to be photocured from the surface to the deepest part.

[0091] Examples of the polyfunctional thiol include hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, tris(2-hydroxyethyl) isocyanurate trimercaptopropionate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2-(N,N-dibutylamino)-4,6-dimercapto-s-triazine, etc. Preferably, ethylene glycol bisthiopropionate, trimethylolpropane tristhiopropionate, and pentaerythritol tetrakisthiopropionate are mentioned.

[0092] The thiol-based chain transfer agent can be used alone or in combination of two or more.

[0093] The content of the thiol-based chain transfer agent is preferably 0.1 to 10% by mass, more preferably 0.1 to 5% by mass, in 100% by mass of the non-volatile content of the photosensitive coloring composition. When contained in an appropriate amount, the photosensitivity and taper shape are improved, and wrinkles are less likely to occur on the film surface.

[0094] <Polymerization inhibitor> The photosensitive coloring composition can contain a polymerization inhibitor. This can suppress the photosensitivity caused by the diffracted light of the mask during the exposure of the photolithography method, making it easier to obtain a pattern with a desired shape.

[0095] Examples of the polymerization inhibitor include alkyl catechol compounds such as catechol, resorcinol, 1,4-hydroquinone, 2-methylcatechol, 3-methylcatechol, 4-methylcatechol, 2-ethylcatechol, 3-ethylcatechol, 4-ethylcatechol, 2-propylcatechol, 3-propylcatechol, 4-propylcatechol, 2-n-butylcatechol, 3-n-butylcatechol, 4-n-butylcatechol, 2-tert-butylcatechol, 3-tert-butylcatechol, 4-tert-butylcatechol, 3,5-di-tert-butylcatechol; alkyl resorcinol compounds such as 2-methylresorcinol, 4-methylresorcinol, 2-ethylresorcinol, 4-ethylresorcinol, 2-propylresorcinol, 4-propylresorcinol, 2-n-butylresorcinol, 4-n-butylresorcinol, 2-tert-butylresorcinol, 4-tert-butylresorcinol; alkyl hydroquinone compounds such as methylhydroquinone, ethylhydroquinone, propylhydroquinone, tert-butylhydroquinone, 2,5-di-tert-butylhydroquinone; phosphine compounds such as tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine, tribenzylphosphine; phosphine oxide compounds such as trioctylphosphine oxide, triphenylphosphine oxide; phosphite compounds such as triphenylphosphite, trisnonylphenylphosphite; pyrogallol, phloroglucin, etc.

[0096] The polymerization inhibitor can be used alone or in combination of two or more.

[0097] The content of the polymerization inhibitor is preferably 0.01 to 0.4 parts by mass in 100 parts by mass of the non-volatile content of the photosensitive coloring composition. In this range, the effect of the polymerization inhibitor becomes great, and the linearity of the taper, the wrinkles of the coating film, the pattern resolution, etc. become good.

[0098] <Ultraviolet absorber> The photosensitive coloring composition can contain an ultraviolet absorber. Examples of the ultraviolet absorber include benzotriazole-based compounds, triazine-based compounds, benzophenone-based compounds, salicylic acid ester-based compounds, cyanoacrylate-based compounds, and salicylate-based compounds. Note that the ultraviolet absorber may be an oligomer or a polymer.

[0099] Examples of the benzotriazole-based compound include 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-(2-hydroxy-5-t-butylphenyl)-2H-benzotriazole, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole, 5% of 2-methoxy-1-methylethyl acetate and 95% of A mixture of benzene propanoic acid, 3-(2H-benzotriazol-2-yl)-(1,1-dimethylethyl)-4-hydroxy, C7-9 side chain and linear alkyl ester, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(2H-benzotriazol-2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3-tetramethylbutyl)phenol, methyl 3-(3-(2H-benzotriazol-2-yl)-5-t-butyl-4-hydroxy Reaction product of (shift phenyl) propionate / polyethylene glycol 300, 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol], 2-(2H-benzotriazol-2-yl)-p-cresol, 2-(5-chloro-2H-benzotriazol-2-yl)-6-t-butyl-4-methylphenol, 2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole, octyl 3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate, 2-ethylhexyl 3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate are mentioned.

[0100] Triazine compounds include, for example, 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-n-octyloxyphenyl)-1,3,5-triazine, 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-[3-(dodecyloxy)-2-hydroxypropoxy]phenol, reaction product of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and (2-ethylhexyl)-glycidic acid ester, 2,4-bis[2-hydroxy-4-butoxyphenyl]-6-(2,4-dibutoxyphenyl)-1,3,5-triazine, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-(hexyloxy)phenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol, 2,4,6-tris(2-hydroxy-4-hexyloxy-3-methylphenyl)-1,3,5-triazine, etc.

[0101] Benzophenone compounds include, for example, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid-3 water temperature, 2-hydroxy-4-n-octoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2,2'dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, and the like.

[0102] Salicylic acid ester compounds include, for example, phenyl salicylate, p-octylphenyl salicylate, p-tert-butylphenyl salicylate, and the like.

[0103] The ultraviolet absorber can be used alone or in combination of two or more.

[0104] The content of the ultraviolet absorber is preferably 5 to 70% by mass in a total of 100% by mass of the photopolymerization initiator and the ultraviolet absorber. When contained in an appropriate amount, the developability after development is further improved.

[0105] Also, the total content of the photopolymerization initiator and the ultraviolet absorber is preferably 1 to 20% by mass in 100% by mass of the non-volatile content of the photosensitive coloring composition. When contained in an appropriate amount, the adhesion between the substrate and the film is further improved, and good developability can be obtained.

[0106] <Antioxidant> The photosensitive coloring composition can contain an antioxidant. The antioxidant can prevent the film formed from the photosensitive coloring composition from yellowing due to oxidation during heat curing or the heat treatment during ITO annealing, and can suppress a decrease in the transmittance of the film. In particular, when the concentration of the colorant in the photosensitive coloring composition is high, since the content of the photopolymerizable compound (D) relatively decreases, if the amount of the photoinitiator is increased or a thermosetting compound is blended for countermeasures, the film is liable to yellow. Therefore, by including an antioxidant, yellowing due to oxidation during the heating process can be prevented, and a decrease in the transmittance of the film can be suppressed.

[0107] Examples of the antioxidant include hindered phenol-based, hindered amine-based, phosphorus-based, sulfur-based, and hydroxylamine-based compounds. In the present specification, the antioxidant is preferably a compound that does not contain a halogen atom.

[0108] Among these, from the viewpoint of achieving both the transmittance and sensitivity of the coating film, hindered phenol-based antioxidants, hindered amine-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants are preferred. preferred.

[0109] The antioxidant can be used alone or in combination of two or more.

[0110] The content of the antioxidant is preferably 0.5 to 5.0% by mass in 100% by mass of the non-volatile content of the photosensitive coloring composition. Thereby, the transmittance, spectral characteristics, and sensitivity are further improved.

[0111] <Leveling agent> The photosensitive coloring composition can contain a leveling agent. Thereby, the wettability with respect to the transparent substrate during film formation and the drying property of the film are further improved. Examples of the leveling agent include silicone-based surfactants, fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and the like.

[0112] The surfactant can be used alone or as a mixture of two or more.

[0113] The content of the surfactant is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass in the non-volatile content of the photosensitive coloring composition. When it is within this range, the balance of the coatability, pattern adhesion, and transmittance of the photosensitive coloring composition is further improved.

[0114] <Storage stabilizer> The photosensitive coloring composition can contain a storage stabilizer to stabilize the viscosity of the composition over time. Examples of the storage stabilizer include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid and their methyl ethers, organic phosphines such as t-butylpyrocatechol, tetraethylphosphine, and tetraphenylphosphine, and phosphites.

[0115] The content of the storage stabilizer is preferably 0.1 to 10% by mass with respect to 100 parts by mass of the colorant (A).

[0116] <Adhesion improver> The photosensitive coloring composition can contain an adhesion improver. Thereby, the adhesion between the film and the substrate is further improved. In addition, it becomes easier to form a pattern with a narrow width by the photolithography method. Examples of the adhesion improver include silane coupling agents.

[0117] Silane coupling agents include, for example, vinyl silanes such as vinyltrimethoxysilane and vinyltriethoxysilane; (meth)acrylic silanes such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane; epoxy silanes such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane; amino silanes such as N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, hydrochloride of N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane; mercapto silanes such as 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane; styryl silanes such as p-styryltrimethoxysilane; ureido silanes such as 3-ureidopropyltriethoxysilane And sulfides such as bis(triethoxysilylpropyl)tetrasulfide, and isocyanates such as 3-isocyanatopropyltriethoxysilane.

[0118] The content of the adhesion improver is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, based on 100 parts by mass of the colorant (A). When contained in an appropriate amount, the photosensitivity of the photosensitive coloring composition is improved, the adhesion of the film is further improved, and the resolution of the pattern is also further improved.

[0119] <Manufacturing method of photosensitive coloring composition> The photosensitive coloring composition is prepared, for example, by performing a dispersion treatment using an organic pigment, a resin-type dispersant, a solvent, etc. to produce a dispersion. When a dispersion aid such as a dye derivative is used in combination during the dispersion treatment, the organic pigment can be dispersed more finely. Also, when the pigment has high solubility in the solvent, the dispersion treatment may not be required. In this specification, since at least three types of pigments are used, dispersions can be prepared for each pigment and then mixed. Also, a dispersion can be prepared collectively using two or more types of pigments. Next, a binder resin (B), a polymerizable compound (C), and a photopolymerization initiator (D) are added to the dispersion and mixed to obtain a photosensitive coloring composition. Needless to say, the timing of adding each material is arbitrary. Also, needless to say, the above production is just an example, and it can be produced by other methods.

[0120] For the above dispersion treatment, for example, apparatuses such as a kneader, a two-roll mill, a three-roll mill, a ball mill, a horizontal sand mill, a vertical sand mill, an annular bead mill, or an attritor can be used.

[0121] The photosensitive coloring composition is preferably prepared as a so-called resist material. Examples of the resist material include a solvent-developable type and an alkali-developable type, and the alkali-developable type is preferred.

[0122] <Solvent> The photosensitive coloring composition can contain a solvent. This makes it easy to adjust the viscosity of the photosensitive coloring composition, so it is easy to form a film with a smooth surface. The solvent can be appropriately selected according to the purpose of use and can contain an appropriate amount.

[0123] Examples of the solvent include ester solvents (solvents containing -COO- in the molecule and not containing -O-), ether solvents (solvents containing -O- in the molecule and not containing -COO-), ether ester solvents (solvents containing -COO- and -O- in the molecule), ketone solvents (solvents containing -CO- in the molecule and not containing -COO-), alcohol solvents (solvents containing OH in the molecule and not containing -O-, -CO-, and -COO-), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide, etc.

[0124] Of the above solvents, from the viewpoint of coatability and drying property, it is preferable to include an organic solvent having a boiling point at 1 atm of 120° C. or more and 180° C. or less. Among them, propylene glycol monomethyl ether acetate, ethyl lactate, butyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 4-hydroxy-4-methyl-2-pentanone, N,N-dimethylformamide, N-methylpyrrolidone, etc. are preferred, and propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, ethyl 3-ethoxypropionate, etc. are more preferred.

[0125] <Removal of large particles> In the present specification, the colorant dispersion stage or the photosensitive coloring composition is prepared, and then the colorant is added to the photosensitive coloring composition. It is preferable to remove coarse particles that may cause the formation of a fine pattern since foreign matter can be removed from the coating. To remove coarse particles, the photosensitive coloring composition is centrifuged at a gravitational acceleration of 3,000 to 25,000 G. It is preferable to remove coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, and more preferably coarse particles of 0.5 μm or more, and mixed dust by means of filtration using a sintered filter or a membrane filter. In this way, it is preferable that the coloring composition does not substantially contain particles of 0.5 μm or more. More preferably, the particles are 0.3 μm or less.

[0126] <Color filters> In this specification, a color filter includes a base material (also referred to as a transparent substrate) and filter segments formed from a photosensitive coloring composition. By appropriately selecting the type of coloring agent (A) to be used, the color filter can have red filter segments, green filter segments, and blue filter segments. Additionally, if necessary, it can also have magenta filter segments, cyan filter segments, and yellow filter segments. Note that a reflective substrate can be used instead of the transparent substrate. Examples of the transparent substrate include a glass substrate. Examples of the reflective substrate include a substrate that uses an aluminum electrode or a metal thin film as a reflective surface. A transparent electrode such as an ITO film can also be formed on the substrate.

[0127] <Method for manufacturing a color filter> For the color filter, it is preferable to first form a black matrix on the base material and then form the filter segments. Note that a thin film transistor (TFT) can be formed in advance on the base material and then the black matrix can be formed. Examples of the black matrix include inorganic films such as chromium, a multilayer film of chromium / chromium oxide, titanium nitride, and a resin film in which a light-shielding agent is dispersed.

[0128] The formation of the filter segments can be performed, for example, by a printing method, an electrodeposition method, a transfer method, an inkjet method, a photolithography method, etc. In this specification, the most preferable photolithography method will be described.

[0129] In the photolithography method, for example, a photosensitive coloring composition containing a coloring agent of a certain color tone is applied onto a transparent substrate to form a film with a dry film thickness of about 0.2 to 5 μm. The obtained film (hereinafter referred to as the first film) is exposed (irradiated with light) through a mask having a predetermined pattern. Next, development is carried out by immersing it in a solvent or an alkali developer or spraying the developer such as by spraying to remove the uncured portions and obtain a desired pattern. By performing this process in the same manner using a photosensitive coloring composition having a coloring agent of another color tone, a color filter having filter segments of each color can be manufactured. Further, a second film (oxygen barrier film) can be formed on the first film before exposure using polyvinyl alcohol or a water-soluble acrylic resin. Thereby, since the first film does not come into contact with oxygen, the exposure sensitivity is further improved. Also, the color filter can be heated to cure the uncured photopolymerizable compound in the filter segment.

[0130] Examples of the coating apparatus include spray coating, spin coating, slit coating, roll coating, etc. A drying process can be performed during coating. Examples of the drying apparatus include a hot air oven, an infrared heater, etc.

[0131] Examples of the developer as an alkali developer include inorganic alkalis such as sodium carbonate and sodium hydroxide; organic alkalis such as dimethylbenzylamine and triethanolamine. Also, an antifoaming agent and a surfactant can be added to the developer.

[0132] The color filter of the present invention is bonded to a counter substrate using a sealant, liquid crystal is injected through an injection port provided in the seal portion, and then the injection port is sealed. If necessary, a polarizing film or a retardation film is bonded to the outside of the substrate to manufacture a color liquid crystal display device. This color liquid crystal display device can be used in a liquid crystal display mode for colorization using a color filter such as twisted nematic (TN), super twisted nematic (STN), in-plane switching (IPS), vertical alignment (VA), optically compensated bend (OCB).

[0133] In this specification, the color filter can be used for applications such as solid-state image pickup devices, organic EL display devices, quantum dot display devices, electronic paper, and head-mounted displays in addition to liquid crystal display devices.

[0134] <Image display device> An image display device including the color filter of the present invention will be described. The image display device of the present invention includes the color filter of the present invention and a light source. Examples of the light source include a cold cathode tube (CCFL) and a white LED. In the present invention, it is preferable to use a white LED in terms of the expansion of the red reproduction region. FIG. 1 is a schematic cross-sectional view of an image display device 10 including the color filter of the present invention. The device 10 shown in FIG. 1 includes a pair of transparent substrates 11 and 21 arranged to face each other with a gap therebetween, and liquid crystal LC is encapsulated therebetween.

[0135] The liquid crystal LC is aligned according to driving modes such as TN (Twisted Nematic), STN (Super Twisted Nematic), IPS (In-Plane switching), VA (Vertical Alignment), and OCB (Optically Compensated Bifefringence). On the inner surface of the first transparent substrate 11, a TFT (Thin Film Transistor) array 12 is formed, and on top of that, a transparent electrode layer 13 made of, for example, ITO is formed. An alignment layer 14 is provided on the transparent electrode layer 13. Also, a polarizing plate 15 is formed on the outer surface of the transparent substrate 11.

[0136] On the other hand, on the inner surface of the second transparent substrate 21, the color filter 22 of the present invention is formed. The red, green, and blue filter segments that make up the color filter 22 are separated by a black matrix (not shown).

[0137] Covering the color filter 22, a transparent protective film (not shown) is formed as needed, and on top of that, a transparent electrode layer 23 made of, for example, ITO is formed, and an alignment layer 24 is provided covering the transparent electrode layer 23.

[0138] Also, a polarizing plate 25 is formed on the outer surface of the transparent substrate 21. Note that a backlight unit 30 is provided below the polarizing plate 15.

[0139] As white LED light sources, there are those in which a fluorescent filter is formed on the surface of a blue LED, and those in which a phosphor is contained in the resin package of a blue LED. They have a wavelength (λ3) at which the emission intensity is maximized within the range of 430 nm to 485 nm, a wavelength (λ4) at which the emission intensity is maximized within the range of 530 nm to 580 nm, and a wavelength (λ5) at which the emission intensity is maximized within the range of 600 nm to 650 nm. Also, the ratio (I4 / I3) of the emission intensity I3 at wavelength λ3 to the emission intensity I4 at wavelength λ4 is 0.2 or more and 0.4 or less, and the ratio (I5 / I3) of the emission intensity I3 at wavelength λ3 to the emission intensity I5 at wavelength λ5 is 0.1 or more and 1.3 or less. There is a white LED light source (LED1) having such spectral characteristics, or a wavelength (λ1) at which the emission intensity is maximum within the range of 430 nm to 485 nm, and a second emission It is preferable to have a white LED light source (LED2) having spectral characteristics with a peak wavelength (λ2) of the emission intensity within the range of 530 nm to 580 nm, and the ratio (I2 / I1) of the emission intensity I1 at wavelength λ1 to the emission intensity I2 at wavelength λ2 being 0.2 or more and 0.7 or less.

[0140] Specific examples of LED1 include NSSW306D-HG-V1 (manufactured by Nichia Chemical Industries, Ltd.) and NSSW304D-HG-V1 (manufactured by Nichia Chemical Industries, Ltd.).

[0141] Specific examples of LED2 include NSSW440 (manufactured by Nichia Chemical Industries, Ltd.) and NSSW304D (manufactured by Nichia Chemical Industries, Ltd.).

Examples

[0142] Hereinafter, the present invention will be described by way of examples. However, the present invention is not limited to these. Note that "parts" means "parts by mass" and "%" means "% by mass".

[0143] Prior to the examples, the calculation methods for measuring the average molecular weight of the resin and the acid value of the resin will be described. Note that propylene glycol monomethyl ether acetate will be hereinafter referred to as (PGMAc).

[0144] (Average molecular weight of resin) The number average molecular weight (Mn) and mass average molecular weight (Mw) of the resin were measured by gel permeation chromatography (GPC) equipped with an RI detector. HLC-8220GPC (manufactured by Tosoh Corporation) was used as the apparatus. Two separation columns were connected in series, and for both packing materials, two "TSK-GEL SUPER HZM-N" were connected in series and used. The measurement was carried out at an oven temperature of 40°C, using a THF solution as the eluent, and at a flow rate of 0.35 ml / min. The sample was dissolved in a solvent consisting of the above eluent at 1 wt%, and 20 microliters were injected. All molecular weights are in terms of polystyrene conversion values.

[0145] (Acid value of the resin) To 0.5 - 1 g of the resin solution, 80 ml of acetone and 10 ml of water were added and stirred until uniformly dissolved. Using a 0.1 mol / L aqueous KOH solution as the titrant, titration was carried out using an automatic titrator ("COM-555" manufactured by Hiranuma Sangyo Co., Ltd.) to measure the acid value (mgKOH / g) of the resin solution. Then, from the acid value of the resin solution and the non-volatile content concentration of the resin solution, the acid value per non-volatile content of the resin was calculated.

[0146] <Production of Resin-Type Dispersant Solution 1> Into a reaction vessel equipped with a gas inlet tube, a condenser, a stirring blade, and a thermometer, as the first-stage synthesis, 90 parts of methyl methacrylate, 60 parts of ethyl acrylate, 40 parts of t-butyl acrylate, 10 parts of methacrylic acid, and 40 parts of propylene glycol monomethyl ether acetate (hereinafter referred to as PGMAC) were charged and replaced with nitrogen gas. The inside of the reaction vessel was heated to 80°C, and after adding 12 parts of 3-mercapto-1,2-propanediol, 0.2 part of 2,2'-azobisisobutyronitrile was added in 20 portions at 30-minute intervals and reacted at 80°C for 12 hours. It was confirmed by non-volatile content measurement that 95% had reacted. Next, as the second-stage synthesis, 18 parts of pyromellitic dianhydride, 190 parts of PGMAC, and 0.4 part of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were added and reacted at 120°C for 7 hours. It was confirmed by titration that more than 98% of the acid anhydride was half-esterified, and the reaction was terminated. In this way, a resin-type dispersant solution having an acid value of 42 mgKOH / g per non-volatile content and a weight-average molecular weight of 9,800 was obtained. After cooling to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180°C for 20 minutes to measure the non-volatile content, and PGMAC was added so that the non-volatile content became 40% by mass to obtain Resin-type Dispersant Solution 1.

[0147] <Process for Producing Zinc Halide Phthalocyanine Pigment (A1)> (Zinc Halide Phthalocyanine Pigment (A1-1)) 91 parts of sulfuryl chloride, 109 parts of aluminum chloride, 15 parts of sodium chloride, 30 parts of zinc phthalocyanine, and 74 parts of bromine were charged into a 300 mL flask. The temperature was raised to 130 °C over 40 hours, taken out into water, and then filtered to obtain a green crude pigment. 20 parts of the obtained green crude pigment, 140 parts of ground sodium chloride, 32 parts of diethylene glycol, and 1.8 parts of xylene were charged into a 1 L double-arm kneader and kneaded at 100 °C for 6 hours. After kneading, it was taken out into 2 kg of water at 80 °C, stirred for 1 hour, and then filtered, washed with hot water, dried, and pulverized to obtain a zinc phthalocyanine halide pigment (A1-1). The obtained zinc phthalocyanine halide pigment (A1-1) was a zinc phthalocyanine halide pigment in which the average number of halogen atoms in one molecule was 13.97, of which the average number of bromine atoms was 11.46 and the average number of chlorine atoms was 2.51, as determined by fluorescence X-ray analysis using a Rigaku ZSX100E.

[0148] (Zinc phthalocyanine halide pigment (A1-2)) 91 parts of sulfuryl chloride, 109 parts of aluminum chloride, 15 parts of sodium chloride, 30 parts of zinc phthalocyanine, and 59 parts of bromine were charged into a 300 mL flask. The temperature was raised to 130 °C over 40 hours, taken out into water, and then filtered to obtain a green crude pigment. 20 parts of the obtained green crude pigment, 140 parts of ground sodium chloride, 32 parts of diethylene glycol, and 1.8 parts of xylene were charged into a 1 L double-arm kneader and kneaded at 100 °C for 6 hours. After kneading, it was taken out into 2 kg of water at 80 °C, stirred for 1 hour, and then filtered, washed with hot water, dried, and pulverized to obtain a zinc phthalocyanine halide pigment (A1-2). The obtained zinc phthalocyanine halide pigment (A1-2) was a zinc phthalocyanine halide pigment in which the average number of halogen atoms in one molecule was 12.71, of which the average number of bromine atoms was 10.22 and the average number of chlorine atoms was 2.49, as determined by fluorescence X-ray analysis.

[0149] (Zinc phthalocyanine halide pigment (A1-3)) 91 parts of sulfuryl chloride, 109 parts of aluminum chloride, 15 parts of sodium chloride, 30 parts of zinc phthalocyanine, and 44 parts of bromine were charged into a 300 mL flask. The temperature was raised to 130 °C over 40 hours, and after taking it out in water, a green crude pigment was obtained by filtration. 20 parts of the obtained green crude pigment, 140 parts of pulverized sodium chloride, 32 parts of diethylene glycol, and 1.8 parts of xylene were charged into a 1 L two-arm kneader and kneaded at 100 °C for 6 hours. After kneading, it was taken out in 2 kg of water at 80 °C, stirred for 1 hour, and then filtered, washed with hot water, dried, and pulverized to obtain a zinc phthalocyanine halide pigment (A1-3). The obtained zinc phthalocyanine halide pigment (A1-3) was a zinc phthalocyanine halide pigment in which the average number of halogen atoms in one molecule was 11.98, of which the average number of bromine atoms was 9.00 and the average number of chlorine atoms was 2.98 according to fluorescent X-ray analysis.

[0150] (Zinc phthalocyanine halide pigment (A1-4)) 109 parts of sulfuryl chloride, 131 parts of aluminum chloride, 18 parts of sodium chloride, 30 parts of zinc phthalocyanine, and 52 parts of bromine were charged into a 300 mL flask. The temperature was raised to 130 °C over 40 hours, and after taking it out in water, a green crude pigment was obtained by filtration. 20 parts of the obtained green crude pigment, 140 parts of pulverized sodium chloride, 32 parts of diethylene glycol, and 1.8 parts of xylene were charged into a 1 L two-arm kneader and kneaded at 100 °C for 6 hours. After kneading, it was taken out in 2 kg of water at 80 °C, stirred for 1 hour, and then filtered, washed with hot water, dried, and pulverized to obtain a zinc phthalocyanine halide pigment (A1-4). The obtained zinc phthalocyanine halide pigment (A1-4) was a zinc phthalocyanine halide pigment in which the average number of halogen atoms in one molecule was 12.69, of which the average number of bromine atoms was 8.54 and the average number of chlorine atoms was 4.16 according to fluorescent X-ray analysis.

[0151] (Zinc phthalocyanine halide pigment (A1-5)) A commercially available C.I. Pigment Green 58 (FASTOGEN Green A110 manufactured by DIC Corporation) was used as it was. From fluorescent X-ray analysis, it was a zinc phthalocyanine halide pigment with an average of 15.46 halogen atoms per molecule, among which the average number of bromine atoms was 14.75 and the average number of chlorine atoms was 0.71.

[0152] (Zinc phthalocyanine halide pigment (A1-6)) Into a 300 mL flask, 91 parts of sulfuryl chloride, 72 parts of aluminum chloride, 15 parts of sodium chloride, 30 parts of zinc phthalocyanine, and 29 parts of bromine were charged. It was heated up to 130 °C over 40 hours and then taken out into water and filtered to obtain a green crude pigment. 20 parts of the obtained green crude pigment, 140 parts of ground sodium chloride, 32 parts of diethylene glycol, and 1.8 parts of xylene were charged into a 1 L two-arm kneader and kneaded at 100 °C for 6 hours. After kneading, it was taken out into 2 kg of water at 80 °C, stirred for 1 hour, then filtered, washed with hot water, dried, and pulverized to obtain a zinc phthalocyanine halide pigment (A1-6). From fluorescent X-ray analysis, the obtained zinc phthalocyanine halide pigment (A1-6) was a zinc phthalocyanine halide pigment with an average of 8.88 halogen atoms per molecule, among which the average number of bromine atoms was 6.90 and the average number of chlorine atoms was 1.98.

[0153] <Method for producing yellow micronized pigment> According to the synthesis method described in JP-A-2017-171915, an azobarbituric acid precursor was prepared. (Instruction 1) At 85 °C, 46.2 g of diazobarbituric acid and 38.4 g of barbituric acid were introduced into 1100 g of distilled water. Then, the pH was adjusted to about pH 5 using an aqueous potassium hydroxide solution, and stirring was continued for 90 minutes. (Yellow pigment (Y-1)) The azobarbituric acid (0.3 mol) prepared in Instruction 1 was mixed with 1500 parts of distilled water at 82°C. Then, 10 parts of 30% strength hydrochloric acid was added dropwise to adjust the pH to 2 - 2.5. After that, 79.4 parts of melamine (0.63 mol) was introduced. Next, a 0.3 mol of approximately 25% strength nickel chloride solution was added dropwise. After 3 hours at 82°C, the pH was adjusted to approximately 5.5 using KOH. Subsequently, it was diluted with approximately 100 parts of distilled water at 90°C. Then, 21 parts of 30% strength hydrochloric acid was added dropwise and the temperature of 90°C was maintained for 12 hours. After that, the pH was adjusted to approximately 5 using an aqueous potassium hydroxide solution. Then, the pigment was isolated on a suction filter, washed, dried at 80°C in a vacuum drying cabinet, and ground in a standard laboratory mill for 2 minutes. (Yellow pigment (Y - 1) = adduct of nickel azobarbituric acid and melamine). A yellow pigment (Y - 2) was obtained in the same manner as yellow pigment (Y - 1), except that the "0.3 mol of approximately 25% strength nickel chloride solution" in the production example of yellow pigment (Y - 1) was replaced with a "mixed solution of 0.225 mol of 25% strength nickel chloride + 0.075 mol of 25% strength copper(II) chloride". (Yellow pigment (Y - 2) = melamine adduct of copper / nickel azobarbituric acid, a hybrid compound having components of 25 mol% copper and 75 mol% nickel)

[0154] (Yellow pigment (Y - 2)) A yellow pigment (Y - 3) was obtained in the same manner as yellow pigment (Y - 2), except that the "0.3 mol of approximately 25% strength nickel chloride solution" in the production example of yellow pigment (Y - 1) was replaced with a "mixed solution of 0.150 mol of 25% strength nickel chloride + 0.150 mol of 25% strength zinc chloride". (Yellow pigment (Y - 3) = melamine adduct of zinc / nickel azobarbituric acid, a hybrid compound having components of 25 mol% Zn and 75 mol% nickel)

[0155] (Yellow pigment (Y - 3)) A yellow pigment (Y - 4) was obtained in the same manner as yellow pigment (Y - 3), except that the "0.3 mol of approximately 25% strength nickel chloride solution" in the production example of yellow pigment (Y - 1) was replaced with a "mixed solution of 0.150 mol of 25% strength nickel chloride + 0.150 mol of 25% strength zinc chloride". (Yellow pigment (Y - 4) = melamine adduct of zinc / nickel azobarbituric acid, a hybrid compound having components of 25 mol% Zn and 75 mol% nickel)

[0156] (Yellow pigment (Y - 4)) The yellow pigment (Y-4) was obtained in the same manner as the yellow pigment (Y-2), except that the "nickel chloride solution with a strength of slightly over 25% and a molar amount of 0.3 mol" in the production example of the yellow pigment (Y-1) was replaced with "a mixed solution of nickel chloride with a strength of 25% and a molar amount of 0.075 mol + zinc chloride with a strength of 25% and a molar amount of 0.225 mol". (Yellow pigment (Y-4) = melamine adduct of zinc / nickel azobarbituric acid, a hybrid compound having components of 50 mol% Zn and 50 mol% nickel)

[0157] (Yellow micronized pigment (A2-1)) 100 parts of the yellow pigment (Y-1), 10 parts of the pigment derivative (d-1), 1000 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a 1-gallon stainless steel kneader (manufactured by Inoue Seisakusho), and kneaded at 70 °C for 8 hours. This mixture was poured into 2000 parts of warm water, stirred with a high-speed mixer for about 1 hour while heating to about 80 °C to form a slurry, and after repeating filtration and washing with water to remove sodium chloride and the solvent, it was dried at 80 °C for 24 hours to obtain the yellow micronized pigment (A2-1).

[0158] (Yellow micronized pigment (A2-2)) The yellow micronized pigment (A2-2) was obtained in the same manner as the production of the yellow micronized pigment (A2-1), except that the yellow pigment (Y-1) was changed to the yellow pigment (Y-2).

[0159] (Yellow micronized pigment (A2-3)) The yellow micronized pigment (A2-3) was obtained in the same manner as the production of the yellow micronized pigment (A2-1), except that the yellow pigment (Y-1) was changed to the yellow pigment (Y-3).

[0160] (Yellow micronized pigment (A2-4)) The yellow micronized pigment (A2-4) was obtained in the same manner as the production of the yellow micronized pigment (A2-1), except that the yellow pigment (Y-1) was changed to the yellow pigment (Y-4).

[0161] (Yellow micronized pigment (A2-5)) 100 parts of quinophthalone-based yellow pigment C.I. Pigment Yellow 138 (PY138) ("Parilotol Yellow K0960-HD" manufactured by BASF Japan), 700 parts of sodium chloride, and 180 parts of diethylene glycol were charged into a 1-gallon stainless steel kneader (manufactured by Inoue Seisakusho) and kneaded at 80 °C for 6 hours. This mixture was poured into 2000 parts of warm water, stirred for 1 hour while heating to 80 °C to form a slurry, and filtered and washed with water repeatedly to remove salt and solvent, and then dried at 80 °C for a whole day and night to obtain 95 parts of yellow micronized pigment (A2-5).

[0162] (Blue micronized pigment (A3-1)) 90 parts of crude copper phthalocyanine synthesized by a known method and 10 parts of dye derivative (d-3) were added to 1000 parts of 98% sulfuric acid, stirred at 30 °C for 2 hours, and then mixed with 5000 parts of water using an aspirator to obtain an aqueous solution in which copper phthalocyanine particles were precipitated. After stirring the obtained aqueous solution for 30 minutes, it was filtered, washed with water, dried, and pulverized to obtain 95 parts of blue micronized pigment (A3-1). Regarding the obtained blue micronized pigment (A3-1), when the X-ray diffraction pattern from 2θ = 5 to 35° was confirmed with an X-ray diffractometer (RINT2000 manufactured by Rigaku), characteristic peaks of α-type copper phthalocyanine were confirmed at around 6.94° and around 9.76°, and characteristic peaks of β-type copper phthalocyanine at around 6.9°, around 9.0°, and around 12.4° were not confirmed. Therefore, it was confirmed to be α-type copper phthalocyanine.

[0163] (Blue micronized pigment (A3-2)) 85 parts of crude copper phthalocyanine synthesized by a known method, 15 parts of dye derivative (d-3), 1000 parts of sodium chloride, and 280 parts of diethylene glycol were put into a stainless steel 1 It was charged into a gallon kneader and kneaded at 70 °C for 8 hours. After kneading, it was taken out into 20,000 parts of an acetic acid - sodium acetate buffer aqueous solution (pH 4.0) at 45 °C. After holding and stirring for 1 hour, it was filtered, washed with water, dried, and pulverized to obtain 96 parts of a blue micronized pigment (A3-2). Regarding the obtained blue micronized pigment (A3-2), when the X-ray diffraction pattern from 2θ = 5 to 35° was confirmed with an X-ray diffractometer (RINT2000 manufactured by Rigaku Corporation), characteristic peaks of β-type copper phthalocyanine were confirmed around 6.9°, 9.0°, and 12.4°. Characteristic peaks of α-type copper phthalocyanine around 6.94° and 9.76° were not confirmed, and characteristic peaks of ε-type copper phthalocyanine around 7.5° and 9.1° were not confirmed either. Therefore, it was confirmed to be β-type copper phthalocyanine.

[0164] (Blue micronized pigment (A3-3)) 95 parts of ε-type copper phthalocyanine pigment "LIONOL BLUE E" manufactured by Toyo Color Co., 5 parts of a dye derivative (d-3), 1000 parts of sodium chloride, and 280 parts of diethylene glycol were charged into a 1-gallon stainless steel kneader manufactured by Inoue Manufacturing Co., Ltd. and kneaded at 80 °C for 10 hours. After kneading, it was taken out into 20,000 parts of an acetic acid - sodium acetate buffer aqueous solution (pH 4.0) at 30 °C. After holding and stirring for 1 hour, it was filtered, washed with water, dried, and pulverized to obtain 96 parts of a blue micronized pigment (A3-3). Regarding the obtained blue micronized pigment (A3-3), when the X-ray diffraction pattern from 2θ = 5 to 35° was confirmed with an X-ray diffractometer (RINT2000 manufactured by Rigaku Corporation), characteristic peaks of ε-type copper phthalocyanine around 7.5° and 9.1° were confirmed. Characteristic peaks of α-type copper phthalocyanine around 6.94° and 9.76° were not confirmed, and characteristic peaks of β-type copper phthalocyanine around 6.9°, 9.0°, and 12.4° were not confirmed either. Therefore, it was confirmed to be ε-type copper phthalocyanine.

[0165] <Method for manufacturing a pigment dispersion> (Pigment dispersion (PG-1)) After stirring and mixing the following mixture to make it uniform, it was dispersed for 5 hours using a 0.5 mm diameter zirconia bead in an Eiger mill (Mini Model M-250 MKII manufactured by Eiger Japan Co., Ltd.), and then filtered through a 5.0 μm filter to prepare a yellow pigment dispersion (PG-1). Zinc phthalocyanine halide pigment (A1-1): 14.0 parts Resin type dispersant solution 1: 15.0 parts PGMAC: 71.0 parts

[0166] (Pigment dispersions (PG-2 to 6, DY-1 to 5, DB-1 to 3)) Hereinafter, except that the types and blending amounts (parts by mass) of the micronized pigment, pigment derivative, resin type dispersant solution, and solvent were changed as shown in Table 1, pigment dispersions (PG-2 to 6, DY-1 to 5, DB-1 to 3) were prepared in the same manner as the pigment dispersion (PG-1).

[0167]

Table 1

[0168] The pigment derivatives in Table 1 are shown in Table 2.

[0169]

Table 2

[0170] The abbreviations in Table 2 are described below. Et: Ethyl group

[0171] <Preparation of binder resin (B) solution> (Preparation of binder resin solution (B1-1)) A separable four-necked flask equipped with a thermometer, a condenser, a nitrogen gas inlet tube, a dropping funnel, and a stirrer was charged with 196 parts of cyclohexanone, heated to 80 °C, and the atmosphere in the reaction vessel was replaced with nitrogen. Then, a mixture of 37.2 parts of n-butyl methacrylate, 12.9 parts of 2-hydroxyethyl methacrylate, 12.0 parts of methacrylic acid, 20.7 parts of para-cumylphenol ethylene oxide-modified acrylate (“Aronix M110” manufactured by Toagosei Co., Ltd.), and 1.1 parts of 2,2’-azobisisobutyronitrile was added dropwise through the dropping funnel over 2 hours. After completion of the addition, the reaction was continued for an additional 3 hours to obtain a solution of the acrylic resin. After cooling to room temperature, about 2 parts of the resin solution were sampled, heated and dried at 180 °C for 20 minutes to measure the nonvolatile content, and PGMAc was added to the previously synthesized resin solution so that the nonvolatile content became 20% to prepare a non-photosensitive binder resin solution (B1-1). The weight average molecular weight (Mw) was 26,000.

[0172] (Preparation of Binder Resin Solution (B1-2)) A separable four-necked flask equipped with a thermometer, a condenser, a nitrogen gas inlet tube, a dropping funnel, and a stirrer was charged with 207 parts of cyclohexanone, heated to 80 °C, and the atmosphere in the reaction vessel was replaced with nitrogen. Then, 20 parts of methacrylic acid, 20 parts of para-cumylphenol ethylene oxide-modified acrylate (“Aronix M110” manufactured by Toagosei Co., Ltd.), 45 parts of methyl methacrylate, 8.5 parts of 2-hydroxyethyl methacrylate, and 2,2'-azobis A mixture of 1.33 parts of isobutyronitrile was added dropwise over 2 hours. After the addition was completed, the reaction was continued for another 3 hours to obtain a copolymer resin solution. Next, with respect to the total amount of the obtained copolymer solution, nitrogen gas was stopped, and while injecting dry air for 1 hour with stirring, it was cooled to room temperature. Then, a mixture of 6.5 parts of 2-methacryloyloxyethyl isocyanate (Karenz MOI manufactured by Showa Denko K.K.), 0.08 part of dibutyltin laurate, and 26 parts of cyclohexanone was added dropwise at 70°C over 3 hours. After the addition was completed, the reaction was continued for another 1 hour to obtain a solution of an acrylic resin. After cooling to room temperature, about 2 parts of the resin solution was sampled and heated and dried at 180°C for 20 minutes to measure the non-volatile content. Cyclohexanone was added to the previously synthesized resin solution so that the non-volatile content became 20% to prepare a photosensitive binder resin solution (B1-2). The weight average molecular weight (Mw) was 18,000.

[0173] (Preparation of Binder Resin Solution (B1-3)) 370 parts of cyclohexanone was charged into a separable four-necked flask equipped with a thermometer, a condenser, a nitrogen gas inlet tube, a dropping tube, and a stirring device, and the temperature was raised to 80°C. After replacing the inside of the flask with nitrogen, a mixture of 18 parts of dicyclopentanyl methacrylate, 10 parts of benzyl methacrylate, 18.2 parts of glycidyl methacrylate, 25 parts of methyl methacrylate, and 2.0 parts of 2,2'-azobisisobutyronitrile was added dropwise from the dropping tube over 2 hours. After the addition, the reaction was further carried out at 100°C for 3 hours. Then, a solution prepared by dissolving 1.0 part of azobisisobutyronitrile in 50 parts of cyclohexanone was added, and the reaction was continued at 100°C for 1 hour. Next, the inside of the container was replaced with air, 9.3 parts of acrylic acid (100% of the glycidyl group), 0.5 part of tris(dimethylamino)phenol, and 0.1 part of hydroquinone were added into the above container, and the reaction was continued at 120°C for 6 hours until the non-volatile acid value reached 0.5, and then the reaction was terminated to obtain a solution of an acrylic resin. Further, 19.5 parts of tetrahydrophthalic anhydride (100% of the generated hydroxyl group) and 0.5 part of triethylamine were added and reacted at 120°C for 3.5 hours to obtain a solution of an acrylic resin. After cooling to room temperature, about 2 g of the resin solution was sampled and heated and dried at 180 °C for 20 minutes to measure the non-volatile content. PGMAc was added to the previously synthesized resin solution so that the non-volatile content became 20% by mass, and the binder resin solution (B1-3) of (I) was prepared. The weight average molecular weight (Mw ) was 19,000.

[0174] (Preparation of Binder Resin Solution (B1-4)) Into a 1 L flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a gas inlet tube , 333 g of PGMAc was introduced. Then, nitrogen gas was introduced into the flask through the gas inlet tube. Then, the temperature of the solution in the flask was raised to 100 °C, and a mixture consisting of 22.0 g of dicyclopentanyl methacrylate, 70.5 g of benzyl methacrylate, 43.0 g of methacrylic acid, 3.6 g of azobisisobutyronitrile and 164 g of PGMAc was added dropwise to the flask using the dropping funnel over 2 hours. After completion of the dropping, stirring was continued at 100 °C for 5 hours. After completion of stirring, air was introduced into the flask through the gas inlet tube, 35.5 g of glycidyl methacrylate, 0.9 g of tris(dimethylaminomethyl)phenol and 0.145 g of hydroquinone were added into the flask, and the reaction was continued at 110 °C for 6 hours to obtain a resin solution having a non-volatile content and an acid value of 80 mg KOH / g. After cooling to room temperature, about 2 g of the resin solution was sampled and heated and dried at 180 °C for 20 minutes to measure the non-volatile content. PGMAc was added to the previously synthesized resin solution so that the non-volatile content became 20% by mass, and the binder resin solution (B1-4) of (II) was prepared.

[0175] <Method for Producing Photosensitive Coloring Composition for Color Filter> [Example 1] (Photosensitive Coloring Composition (R-1)) The following mixture was stirred and mixed uniformly and then filtered through a 1.0 μm filter to prepare a photosensitive coloring composition (R-1) for a color filter. Pigment Dispersion (PG-1): 26.42 parts Pigment Dispersion (PY-2): 11.57 parts Pigment Dispersion (PB-1): 0.58 parts Binder Resin Solution (B1-1): 30.64 parts Photopolymerizable Compound (C-1): 2.70 parts Photoinitiator (D-1): 0.31 parts Thermosetting Compound (E-1): 0.05 parts Sensitizer (F): 0.14 parts Thiol-based Chain Transfer Agent (G): 0.18 parts Polymerization Inhibitor (H): 0.18 parts UV Absorbent (I): 0.18 parts Antioxidant (J): 0.18 parts Leveling Agent (K: Non-volatile content 3%): 0.30 parts Storage Stabilizer (L): 0.09 parts Silane Coupling Agent (M): 0.18 parts Solvent (N): 26.31 parts

[0176] [Examples 2 to 32, Comparative Examples 1 to 4] (Photosensitive Coloring Composition (R-2 to 32) Hereinafter, except that the types and blending amounts (parts by mass) of the pigment dispersion, alkali-soluble resin solution, photopolymerizable compound, photoinitiator, chain transfer agent, UV absorbent, and solvent are changed as shown in Table 3, the photosensitive Coloring Composition (R-1) was used to prepare photosensitive coloring compositions (R-2 to 36) for color filters in the same manner. Note that Examples 1 to 4 in this specification are reference examples.

[0177] [Table 3-1]

[0178] [Table 3-2]

[0179] [Table 3-3]

[0180] <Photopolymerizable Compound (C)> (C-1) Trimethylolpropane Triacrylate [Aronix M309 (manufactured by Toagosei Co., Ltd.)] (C-2) Dipentaerythritol Penta and Hexaacrylate [Aronix M402 (manufactured by Toagosei Co., Ltd.)] (C-3) Polybasic Acid Acrylic Oligomer [Aronix M520 (manufactured by Toagosei Co., Ltd.)] (C-4) Caprolactone-Modified Dipentaerythritol Hexaacrylate [KAYARAD DPCA-30 (manufactured by Nippon Kayaku Co., Ltd.)]

[0181] (C-5) Polyfunctional Urethane Acrylate According to the Following Into a 1-liter five-necked reaction vessel, pentaerythritol triacrylate (432 parts) and hexamethylene diisocyanate (84 parts) were charged and reacted at 60°C for 8 hours to obtain a product containing polyfunctional urethane acrylate (C-5) having a (meth)acryloyl group. In the product, the proportion of polyfunctional urethane acrylate (C-5) was 70% by mass, and the balance was occupied by other photopolymerizable monomers. It was confirmed by IR analysis that no isocyanate group was present in the reaction product.

[0182] (C-6) Bifunctional Bisphenol A-Type (Meth)acrylate [ABE-300 (manufactured by Shin-Nakamura Chemical Co., Ltd.)] (C-7) Ethoxylated Triacryloyl Isocyanurate [A-9300 (manufactured by Shin-Nakamura Chemical Co., Ltd.)] The above (C-1) to (C-7) were each mixed in the same amount to obtain a photopolymerizable compound (C).

[0183] <Photopolymerization Initiator (D)> (D-1) 2-Methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one [Omnirad 907 (manufactured by IGM Resins)] (D-2) 2-(Dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone [Omnirad 379EG (manufactured by IGM Resins)] (D-3) 2,4,6-Trimethylbenzoyl-diphenyl-phosphine oxide [Omnirad TPO (manufactured by IGM Resins)] (D-4) 2,2’-Bis(o-chlorophenyl)-4,5,4’,5’-tetraphenyl-1,2’-biimidazole [Biimidazole (manufactured by Kinkinka Kasei Co., Ltd.)] (D-5) p-Dimethylaminoacetophenone [DMA (manufactured by Daiki Fine Co., Ltd.)] (D-6) Ethan-1-one, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl], 1-(O-acetoxyoxime) [Irgacure OXE02 (manufactured by BASF Japan Ltd.)] (D-7) 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one [Omnirad 2959 (manufactured by IGM Resins)] (D-8) Bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide [Omnirad 819 (manufactured by IGM Resins)] The above (D-1) to (D-8) were each mixed in the same amount to obtain the photoinitiator (D).

[0184] <Thermosetting compound (E)> ·Epoxy compound (E-1) (E-1-1) 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2’-bis(hydroxymethyl)-1-butanol [EHPE-3150 (manufactured by Daicel Corporation)], (E-1-2) Glycidyl etherified epoxy compound of sorbitol [Denacol EX6 11 (manufactured by Nagase ChemteX Corporation) (E-1-3) Triglycidyl isocyanurate (E-1-1) to (E-1-3) were each mixed in the same amount to obtain an epoxy compound (E-1). · Oxetane compound (E-2): 3-Ethyl-3-[(3-ethyloxetan-3-yl)methoxymethyl]oxetane [Aron Oxetane OXT-221 (manufactured by Toagosei Co., Ltd.)]

[0185] <Sensitizer (F)> (F-1) 2,4-Diethylthioxanthone [Kayacure DETX-S (manufactured by Nippon Kayaku Co., Ltd.)] (F-2) 4,4’-Bis(diethylamino)benzophenone [Chemark DEABP (manufactured by Chemark Chemical Co., Ltd.)] The above (F-1) and (F-2) were each mixed in the same amount to obtain a sensitizer (F).

[0186] <Thiol-based chain transfer agent (G)> (G-1) Trimethylolethane tris(3-mercaptobutyrate) [TEMB (manufactured by Showa Denko K.K.)] (G-2) Trimethylolpropane tris(3-mercaptobutyrate) [TPMB (manufactured by Showa Denko K.K.)] (G-3) Pentaerythritol tetrakis(3-mercaptopropionate) [PEM P (manufactured by Sakai Chemical Industry Co., Ltd.)] (G-4) Trimethylolpropane tris(3-mercaptopropionate) [TMMP (manufactured by Sakai Chemical Industry Co., Ltd.)] (G-5) Tris[(3-mercaptopropionyloxy)-ethyl]-isocyanurate [TEMPIC (manufactured by Sakai Chemical Industry Co., Ltd.)] The above (G-1) to (G-5) were each mixed in the same amount to obtain a thiol-based chain transfer agent (G).

[0187] <Coincidence inhibitor (H)> (H-1) 3-Methylcatechol (H-2) Methylhydroquinone (H-3) t-Butylhydroquinone The above (H-1) to (H-3) were each mixed in the same amount to obtain the polymerization inhibitor (H).

[0188] <Ultraviolet absorber (I)> (I-1) 2-[4-[(2-Hydroxy-3-(dodecyl and tridecyl)oxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine [TINUVIN 400 (manufactured by BASF Japan Ltd.)] (I-2) 2-(2H-Benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol [TINUVIN 900 (manufactured by BASF Japan Ltd.)] The above (I-1) to (I-2) were each mixed in the same amount to obtain the ultraviolet absorber (I).

[0189] <Antioxidant (J)> (J-1) Pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate (J-2) Dioctadecyl 3,3'-thiodipropionate (J-3) Tris[2,4-di-(t)-butylphenyl]phosphine (J-4) Bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate (J-5) p-Octylphenyl salicylate The above (J-1) to (J-5) were each mixed in the same amount to obtain the antioxidant (J).

[0190] <Leveling agent (K)> 1 part of "BYK-330" manufactured by BYK-Chemie GmbH, 1 part of "Megafac F-551" manufactured by DIC Corporation, and A mixed solution in which 1 part of "Emulgen 103" manufactured by Kao Corporation was dissolved in 97 parts of PGMAc.

[0191] <Storage stabilizer (L)> (L-1) 2,6-Bis(1,1-dimethylethyl)-4-methylphenol (manufactured by Honshu Chemical Industry Co., Ltd. "BHT") (L-2) Triphenylphosphine (manufactured by Kitakyo Chemical Industry Co., Ltd. "TPP") The above (L-1) to (L-2) were mixed in the same amount respectively to obtain the storage stabilizer (L).

[0192] <Adhesion improver (M)> (M-1) 3-Glycidoxypropyltriethoxysilane [Shin-Etsu Silicone Silane Coupling Agent KBM-403 (manufactured by Shin-Etsu Chemical Co., Ltd.)] (M-2) 3-Methacryloxypropyltriethoxysilane [Shin-Etsu Silicone Silane Coupling Agent KBE-503 (manufactured by Shin-Etsu Chemical Co., Ltd.)] (M-3) N-2-(Aminoethyl)-3-aminopropyltrimethoxysilane [Shin-Etsu Silicone Silane Coupling Agent KBM-603 (manufactured by Shin-Etsu Chemical Co., Ltd.)] (M-4) 3-Mercaptopropyltrimethoxysilane [Shin-Etsu Silicone Silane Coupling Agent KBM-803 (manufactured by Shin-Etsu Chemical Co., Ltd.)] The above (M-1) to (M-4) were mixed in the same amount respectively to obtain the silane coupling agent (M).

[0193] <Evaluation of photosensitive coloring composition> The developability, film thickness, pattern adhesion, pattern shape, and chemical resistance of the obtained photosensitive coloring compositions (R-1 to R-36) were evaluated by the following methods. The results are shown in Tables 4 and 5.

[0194] (Developability) A photosensitive coloring composition obtained on a glass substrate with a length of 100 mm, a width of 100 mm, and a thickness of 0.7 mm was applied with a spin coater at a rotational speed so that the film thickness after drying would be 2.0 μm. Next, , it was dried at 90 °C for 90 seconds to remove the solvent, and a coated film substrate was obtained. Next, it was spray-developed with an alkaline developer composed of a 0.2 mass% aqueous sodium carbonate solution, and the time until the coated film was completely dissolved was defined as the development dissolution time and evaluated according to the following criteria. 〇: The development dissolution time is 20 seconds or more and less than 40 seconds, and it is good. △: The development dissolution time is 40 seconds or more and less than 60 seconds, and it is practical. ×: The development dissolution time is 60 seconds or more, and it is not practical.

[0195] <Formation of Filter Segment> A black matrix was pattern-processed on a glass substrate with a length of 100 mm, a width of 100 mm, and a thickness of 0.7 mm. Next, the obtained photosensitive coloring composition was applied with a spin coater at a rotational speed such that y in the XYZ color system would be 0.597 for the film after firing (heating at 230 °C for 20 minutes), dried at 90 °C for 90 seconds to remove the solvent, and a coated film substrate was obtained. Next, ultraviolet rays of 100 mJ / cm 2 were irradiated using an ultra-high pressure mercury lamp through a mask having a stripe pattern with a width of 10 to 50 μm and a pattern of 400 μm × 400 μm. Next, it was spray-developed with an alkaline developer composed of a 0.2 mass% aqueous sodium carbonate solution to remove the uncured portion and form a desired pattern. Then, a filter segment was formed by heating the coated film substrate in an oven at 230 °C for 20 minutes. Note that the transmission spectrum was measured using a microspectrophotometer ("OSP-SP100" manufactured by Olympus Optical Co., Ltd.), and x was calculated.

[0196] (Film Thickness) Regarding the obtained filter segment, the film thickness of the 400 μm × 400 μm pattern portion was measured using a Dektak 3030 (manufactured by Nippon Vacuum Technology Co., Ltd.). The evaluation was performed according to the following criteria as follows. 〇: When y is 0.597, the thickness is less than 2.2 μm, which is a good film thickness. △: When y is 0.597, the thickness is 2.2 μm or more and less than 2.6 μm, which is a practically applicable film thickness. ×: When y is 0.597, the thickness is 2.7 μm or more, which is a non - practically applicable film thickness.

[0197] (Pattern adhesion) Regarding the obtained filter segment, using an optical microscope of Nikon's ECLIPSE LV100POL Model in transmission mode, the presence or absence of disappearance of patterns with a size of 10 μm to 50 μm was confirmed. The evaluation of pattern adhesion was based on the following criteria according to how thin the pattern remained on the glass substrate. ○: All patterns of 10 μm or more remained, indicating good pattern adhesion. △: All patterns of 50 μm or more remained, indicating practically applicable pattern adhesion. ×: There were places where patterns of 50 μm or more disappeared, indicating non - practically applicable pattern adhesion.

[0198] (Pattern cross - sectional shape) Regarding the obtained filter segment, the pattern cross - sectional shape was confirmed using a scanning electron microscope (Hitachi High - Tech Corporation's "S - 3000H"). The evaluation was carried out by taking SEM images of stripe - type patterns with a width of 50 μm and evaluating as follows. 〇: The taper angle is 60° or more and less than 70°, indicating a good cross - sectional shape. △: The taper angle is 30° or more and less than 60°, or 70° or more and less than 90°, indicating a cross - sectional shape with no practical problems. ×: The taper angle is 90° or more, with an inverse taper, indicating a non - practically applicable cross - sectional shape.

[0199] (Chemical resistance) Regarding the 400 μm × 400 μm pattern of the obtained filter segment, the chromaticity ([L*(1), a*(1), b*(1)]) under a C light source was measured using a micro spectrophotometer ("OSP-SP100" manufactured by Olympus Optical Co., Ltd.). Then, it was immersed in N-methylpyrrolidone for 30 minutes, washed with ion-exchanged water, and air-dried. Next, regarding the 400 μm × 400 μm pattern, the chromaticity ([L*(2), a*(2), b*(2)]) under a C light source was measured, and the color difference ΔE*a*b* was obtained using the following calculation formula. ΔE*a*b* = {(L*(2) - L*(1)) 2 +(b*(2) - b*(1)) 2 +(a*(2) - a*(1)) 2} 0.5 The evaluation criteria are as follows. ○: ΔE*a*b* is less than 2.0, indicating extremely good chemical resistance. △: ΔE*a*b* is 2.0 or more and less than 3.0, indicating practical chemical resistance. ×: ΔE*a*b* is 3.0 or more, indicating impractical chemical resistance.

[0200]

Table 4

Claims

1. A photosensitive coloring composition containing a colorant (A), a binder resin (B), a polymerizable compound (C), and a photopolymerization initiator (D), wherein the colorant (A) includes a green pigment, a yellow pigment, and a blue pigment, the green pigment contains C.I. Pigment Green 58, the blue pigment, includes one or more selected from the group consisting of α-type copper phthalocyanine, β-type copper phthalocyanine, and ε-type copper phthalocyanine, the yellow pigment includes a metal azo pigment (A2) containing compounds represented by the following (a) and (b), and the mass ratio of the green pigment, the yellow pigment, and the blue pigment is 1:0.06 to 0.98:0.003 to 0.

09. A photosensitive coloring composition. (a) A compound of formula (I) or a tautomeric form thereof 【Chemical 1】 [In formula (I), R １ and R ２ are OH, R ３ and R ４ are each independently =O, Me is Ni ２＋ , Zn ２＋ , Cu ２＋ and is two or more divalent metal ions selected from the group consisting of Based on 1 mol of the total of the compound of (a), Cu ２＋ , Zn ２＋ and Ni ２＋ The total amount of ions is 95 to 100 mol%, and said Cu ２＋ , Zn ２＋ and Ni ２＋ Based on the total amount of ions, the amount of Ni ２＋ ions is 10 to 95 mol%. ] (b) A compound represented by formula (II) 【Chemical 2】 [In formula (II), R ６ is a hydrogen atom.]

2. The photosensitive coloring composition according to claim 1, wherein the total amount of the colorant (A) is 10 to 50% by weight in 100% by weight of the non-volatile content of the photosensitive coloring composition.

3. The photosensitive coloring composition according to claim 1 or 2, wherein the photopolymerization initiator (D) contains an oxime ester compound.

4. Furthermore, the photosensitive coloring composition according to any one of claims 1 to 3, which contains a thermosetting compound.

5. A color filter comprising a substrate and a filter segment formed from the photosensitive coloring composition according to any one of claims 1 to 4.

6. An image display device comprising the color filter according to claim 5.

Images