Yellow colorant, coloring composition, color filter, sensor using the same, and method for producing yellow colorant

Abstract

To provide a yellow colorant that strikes a balance between high tinting power and high transmittance and also provide a coloring composition that shows excellent stability when blended with another coloring composition, and a color filter and a sensor including the same.SOLUTION: A yellow colorant (A) contains a pigment represented by the following chemical formula (1). The yellow colorant (A) is boiled with distilled water and then filtered, resulting in a filtrate with a pH of 6.0-7.0.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a yellow colorant, a coloring composition, a color filter, a sensor using the same, and a method for producing the yellow colorant.

Background Art

[0002] In recent years, due to the widespread use of digital cameras, mobile phones with cameras, etc., the demand for image sensors such as C-MOS (Complementary Metal Oxide Semiconductor) and CCD (Charge Coupled Device) has been growing significantly. In these image sensors, it is common to perform color separation by disposing color filters each having filter segments of the primary colors of additive mixing of B (blue), G (green), and R (red) on the light receiving elements.

[0003] In color filters for image sensors, there is a demand for thinning, improving color separation properties, and improving color reproducibility. For the coloring compositions used for forming each color filter segment, high coloring power and high transmittance are required. In particular, in order to increase the coloring power of the coloring composition, a high concentration of the colorant or the use of a colorant having high coloring power is carried out.

[0004] Conventionally, for the production of green and red filter segments, colorants containing C.I. Pigment Yellow 139 having high coloring power have been used as colorants for color adjustment (Patent Documents 1 to 3). However, conventional colorants containing C.I. Pigment Yellow 139 have a problem that when the concentration is increased in the coloring composition, the viscosity increases when mixed with other coloring compositions. In addition, in response to the recent strong demand for thinning, there has been a problem that the coloring power is not always satisfactory, and when trying to increase the coloring power, the transmittance decreases.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

[0006] An object of the present invention is to provide a yellow colorant that achieves both high coloring power and high transmittance. Another object is to provide a coloring composition having good stability when mixed with other coloring compositions, a color filter using the same, and a sensor. [Means for Solving the Problems]

[0007] As a result of intensive studies to solve the above problems, the inventors of the present invention have found that a yellow colorant (A) containing a pigment represented by the following chemical formula (1), when the yellow colorant (A) is boiled in distilled water and then filtered, the filtrate has a pH of 6.0 to 7.0. The yellow colorant (A) has both high coloring power and high transmittance, and a coloring composition containing the yellow colorant (A), a binder resin, and a solvent has good stability when mixed with other coloring compositions. The present invention has been made based on this finding.

[0008] Chemical formula (1) [Chemical formula]

[0009] That is, the present invention relates to a yellow colorant (A) containing a pigment represented by the following chemical formula (1), wherein when the yellow colorant (A) is boiled in distilled water and then filtered, the filtrate has a pH of 6.0 to 7.0. Chemical formula (1) [Chemical formula]

[0010] Further, the present invention relates to the yellow colorant (A), characterized in that the content ratio of the pigment represented by the chemical formula (1) is 80% by mass or more and less than 100% by mass in the yellow colorant (A).

[0011] Further, the present invention relates to the yellow colorant (A) containing at least one selected from the group consisting of a dye derivative having an acidic functional group and a resin-type dispersant having an acidic functional group.

[0012] Further, the present invention relates to the yellow colorant (A), characterized in that the acidic functional group is at least one selected from the group consisting of a sulfo group, a carboxyl group, and a phosphate group.

[0013] Further, the present invention relates to a coloring composition characterized by containing the yellow colorant (A), a binder resin, and a solvent.

[0014] Further, the present invention relates to the coloring composition characterized by further containing a red colorant.

[0015] Further, the present invention relates to the coloring composition characterized by further containing a polymerizable compound and / or a photopolymerization initiator.

[0016] Further, the present invention relates to a color filter formed from the coloring composition.

[0017] Further, the present invention relates to a sensor provided with the color filter.

[0018] Further, the present invention relates to a method for producing a yellow colorant (A), comprising subjecting a yellow colorant containing a pigment represented by the following chemical formula (1) and having an average primary particle diameter of 100 nm or more and less than 300 nm to solvent-salt milling to obtain a yellow colorant (A) having an average primary particle diameter of 30 nm or more and less than 100 nm, and characterized in that when the yellow colorant (A) is boiled with distilled water and then filtered, the filtrate has a pH of 6.0 to 7.0. Chemical formula (1)

Chem.

Advantages of the Invention

[0019] According to the present invention, it is possible to provide a yellow colorant that achieves both high coloring power and high transmittance. Further, it is possible to provide a color composition having good stability when mixed with other color compositions, a color filter and a sensor using the same.

Modes for Carrying Out the Invention

[0020] Each component of the present invention will be described below. In the present application, when expressed as “(meth)acryloyl”, “(meth)acrylic”, “(meth)acrylic acid”, “(meth)acrylate”, or “(meth)acrylamide”, unless otherwise specified, they respectively represent “acryloyl and / or methacryloyl”, “acrylic and / or methacrylic”, “acrylic acid and / or methacrylic acid”, “acrylate and / or methacrylate”, or “acrylamide and / or methacrylamide”. In addition, “C.I.” mentioned in this specification means Color Index (C.I.).

[0021] <Yellow colorant (A)> The yellow colorant (A) of the present invention is a yellow colorant (A) containing a pigment represented by the following chemical formula (1), and is characterized in that the filtrate when the yellow colorant (A) is boiled with distilled water and filtered has a pH of 6.0 to 7.0.

[0022] Chemical formula (1)

Chem.

[0023] The pH of the filtrate is evaluated and determined by the following method. Add 100 g of distilled water (purified water for batteries, manufactured by Mishima Sangyo Co., Ltd., pH = 6.12) to 5 g of the colorant, and boil at 200 °C for 40 minutes. After boiling, replenish the distilled water for the evaporated portion and adjust to a total of 105 g. Filter the resulting mixture of the colorant and distilled water, and measure the pH of the filtrate using a pH meter (D-51, manufactured by Horiba, Ltd.).

[0024] The yellow colorant (A) of the present invention can contain a pigment derivative and a resin-type dispersant. Depending on the composition and blending amount of the pigment derivative and resin-type dispersant used for micronization, the pH of the filtrate changes when the colorant is boiled in distilled water and then filtered. By adjusting the composition and blending amount of the pigment derivative and resin-type dispersant used for micronization so that the pH becomes 6.0 to 7.0, decomposition of the pigment represented by Chemical Formula (1) can be suppressed, and a yellow colorant (A) with high coloring power can be obtained.

[0025] (Pigment derivative) A pigment derivative is a compound having an acidic group, a basic group, a neutral group, etc. in an organic pigment residue. Pigment derivatives include, for example, 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 end, and compounds having a neutral substituent such as a phenyl group or a phthalimidalkyl 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, fluorene-based pigments, metal complex-based pigments, and azo-based pigments such as azo, disazo, and polyazo.

[0026] Specifically, diketopyrrolopyrrole-based pigment derivatives are described in JP-A-2001-220520, WO2009 / 081930 pamphlet, WO2011 / 052617 pamphlet, WO2012 / 102399 pamphlet, JP-A-2017-156397; phthalocyanine-based pigment derivatives are described in JP-A-2007-226161, WO2016 / 163351 pamphlet, JP-A-2017-165820, Patent No. 5753266; anthraquinone-based pigment derivatives are described 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 described in JP-A-48-54128, JP-A-03-9961, JP-A-2000-273383; dioxazine-based pigment derivatives are described in JP-A-2011-162662; thiazine indigo-based pigment derivatives are described in JP-A-2007-314785; triazine-based pigment derivatives are described 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; benzoisoindole-based pigment derivatives are described in JP-A-2009-57478; quinophthalone-based pigment derivatives are described in JP-A-2003-167112, JP-A-2006-291194, JP-A-2008-31281, JP-A-2012-226110; naphthol-based pigment derivatives are described in JP-A-2012-208329, JP-A-2014-5439; azo-based pigment derivatives are described in JP-A-2001-172520, JP-A-2012-172092; acidic substituents are described in JP-A-2004-307854; basic substituents are described in JP-A-2002-201377, JP-A-2003-171594, JP-A-2005-181383, JP-A-2005-213404. In these documents, the pigment derivatives may be described as derivatives, pigment derivatives, dispersants, pigment dispersants or simply compounds, etc. However, a compound having a substituent such as an acidic group, a basic group or a neutral group in the above-described organic pigment residue is synonymous with a pigment derivative.

[0027] These dye derivatives can be used alone or in combination of two or more.

[0028] By adding a dye derivative to a pigment and performing a pigmentation treatment such as acid pasting, acid slurry, dry milling, salt milling, solvent salt milling, etc., the dye derivative is adsorbed on the surface of the pigment, and the primary particles of the pigment can be made finer compared to the case where no dye derivative is added.

[0029] The dye derivative can be used not only when the colorant is refined but also when preparing the coloring composition of the present invention described later.

[0030] When used in the refinement of a yellow colorant containing a pigment represented by Chemical Formula (1), it is preferable to add 0 to 30 parts by mass, more preferably 1 to 20 parts by mass, and even more preferably 1 to 10 parts by mass of the dye derivative with respect to 100 parts by mass of the pigment represented by Chemical Formula (1).

[0031] As the dye derivative that may be contained in the yellow colorant (A) of the present invention, a dye derivative having an acidic functional group is preferable, and it is more preferable that the acidic functional group is any one or more of a sulfo group, a carboxyl group, and a phosphate group. Further, when adding a dye derivative having a basic functional group, it is preferable to add a resin type dispersant having an acidic functional group described later.

[0032] (Resin type dispersant) The resin-type dispersant should have a coloring agent affinity site that has the property of adsorbing to the added coloring agent and a site that is compatible with the coloring agent carrier, and it is sufficient if it functions to adsorb to the added coloring agent and stabilize the dispersion in the coloring agent carrier. Specifically, urethane-based dispersants such as polyurethane, polycarboxylic acid esters such as polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, ammonium polycarboxylate salts, alkylamine polycarboxylate salts, polysiloxanes, long-chain polyaminoamidophosphates, hydroxyl group-containing polycarboxylic acid esters, and modified products thereof, 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, (meth)acrylic acid-styrene copolymers, (meth)acrylic acid-(meth)acrylate copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, polyvinyl pyrrolidone and other water-soluble resins and water-soluble polymer compounds, polyester-based, modified polyacrylate-based, ethylene oxide / propylene oxide addition compounds, phosphate ester-based, etc. are used, and these can be used alone or in admixture of two or more kinds.

[0033] Preferable examples of the resin-type dispersant having an acidic functional group include resin-type dispersants having an aromatic carboxylic acid structure, and these can be produced by known methods such as those described 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, etc. Further, rosin-modified maleic acid resins are also mentioned as preferable examples.

[0034] Examples of the resin-type dispersant having a basic functional group include nitrogen atom-containing graft copolymers, nitrogen atom-containing acrylic block copolymers having a functional group containing a tertiary amino group, a quaternary ammonium base, a nitrogen-containing heterocyclic ring, etc. in the side chain, and urethane-based polymer dispersants.

[0035] Also, as disclosed in Japanese Patent Application Laid-Open No. 2009-185277, the combined use of a resin-type dispersant having an aromatic carboxyl group and a vinyl-based resin having a tertiary amino group (having the function of the resin-type dispersant) is also cited as an example.

[0036] The resin-type dispersant can be used not only when the colorant is refined but also when the coloring composition of the present invention is prepared.

[0037] When the resin-type dispersant is used during the refinement of a yellow colorant containing a pigment represented by Chemical Formula (1), it is preferably used in an amount of about 0 to 20% by mass, more preferably about 1 to 10% by mass, based on the total amount of the pigment represented by Chemical Formula (1).

[0038] The resin-type dispersant preferably has at least one functional group selected from the group consisting of a sulfo group, a carboxyl group, and a phosphate group, and more preferably the carboxyl group has an aromatic carboxylic acid structure.

[0039] (Other dyes) The yellow colorant (A) of the present invention can contain other dyes as long as the spectral characteristics of the compound represented by Chemical Formula (1) are not impaired.

[0040] The other dyes may be contained in the yellow colorant (A) or may be added when the coloring composition of the present invention is prepared.

[0041] In the yellow colorant (A) of the present invention, the content ratio of the pigment represented by Chemical Formula (1) is preferably 80% by mass or more and less than 100% by mass.

[0042] <Method for producing yellow colorant (A)> The yellow colorant (A) of the present invention is obtained by subjecting a yellow colorant having an average primary particle diameter of 100 nm or more and less than 300 nm, which contains a pigment represented by Chemical Formula (1), to solvent-salt milling, so that the average primary particle diameter is 30 nm or more and less than 100 nm, and the filtrate when the yellow colorant (A) is boiled in distilled water and then filtered has a pH of 6.0 to 7.0.

[0043] Solvent-salt milling is synonymous with the salt milling treatment described later.

[0044] By refining a yellow colorant having a large average primary particle diameter of 100 nm or more and less than 300 nm by solvent-salt milling, it can be refined more uniformly, and the coloring power, transmittance, and stability of the dispersion can be improved in a well-balanced manner.

[0045] If the average primary particle diameter of the yellow colorant after refinement by solvent-salt milling is 100 nm or more, the coloring power increases, but the transmittance decreases. If the average primary particle diameter is less than 30 nm, the transmittance improves, but the resistance decreases. Further, as the specific surface area of the colorant increases, the cohesive force increases, and the dispersibility and storage stability of the coloring composition deteriorate.

[0046] The above average primary particle diameter was measured by a method of directly measuring the size of primary particles from an electron micrograph using a transmission electron microscope (TEM) H-7650 manufactured by Hitachi High-Technologies Corporation. Specifically, the minor axis diameter and major axis diameter of the primary particles of each pigment were measured, and the average was taken as the particle diameter of the pigment primary particles. Next, for 100 or more pigment particles, the volume (weight) of each particle was approximated by a cube of the obtained particle diameter, and the volume average particle diameter was taken as the average primary particle diameter.

[0047] In order to obtain a suitable average primary particle diameter while suppressing the decomposition of the pigment represented by Chemical Formula (1), it is preferable to add at least one selected from the group consisting of the above-described dye derivative having an acidic functional group and a resin-type dispersant having an acidic functional group during solvent-salt milling.

[0048] As a yellow colorant containing a pigment represented by chemical formula (1) with an average primary particle diameter of 100 nm or more and less than 300 nm, examples include "Cinilex(R) Yellow SY3C" manufactured by CINIC ", "Cinilex(R) Yellow SY3CN" manufactured by CINIC, "Paliotol(R) Yellow L2140HD" manufactured by BASF, "Paliotol(R) Yellow K2142" manufactured by BASF, "Paliotol(R) Yellow L2146HD" manufactured by BASF, and the like.

[0049] <Color Composition> The color composition of the present invention is characterized by containing a yellow colorant (A), a binder resin, and a solvent. If necessary, the above-mentioned pigment derivative, resin type dispersant, and other pigments may be included. By performing dispersion treatment on these raw materials, such as wet dispersion using a two-roll, three-roll, or beads, for example, the pigment derivative is adsorbed on the pigment surface, the pigment surface becomes polar, and the adsorption of the resin type dispersant is promoted. The compatibility between the pigment, pigment derivative, resin type dispersant, solvent, and other additives is improved, and the dispersion stability and viscosity stability over time of the color composition are improved. In addition, due to the improved compatibility, the color composition has excellent coating film stability over time when coated on a glass substrate or the like, and the stability and property dependence of the pattern shape, etc., with respect to the waiting time from coating to exposure (PCD: Post Coating Delay) and the waiting time from exposure to heat treatment (PED: Post Exposure Delay) of the color composition, as well as the line width sensitivity stability, are good. Further, since the pigment surface is adsorbed and coated with the pigment derivative and the resin type dispersant, aggregation of the pigment and crystal precipitation due to sublimation when the coating film is heated and baked can be suppressed. Furthermore, variations in development time and development residues are also suppressed.

[0050] (Binder Resin) The binder resin is a resin having a transmittance of 80% or more in the entire wavelength range of 400 to 700 nm. The transmittance is preferably 95% or more. In terms of curability, examples of the binder resin include thermoplastic resins, thermosetting resins, and active energy ray curable resins. The active energy ray curable resin may have an active energy ray reactive functional group in a thermoplastic resin or a thermosetting resin. In terms of physical properties, examples of the binder resin include alkali-soluble resins. Alkali solubility is for imparting developing solubility in the alkali developing step in the production of a color filter described later, and an acidic group is required.

[0051] The binder resin can be used alone or in combination of two or more.

[0052] Hereinafter, the binder resin that can be used in the coloring composition of the present invention will be described in detail.

[0053] [Thermoplastic resin] Examples of the thermoplastic resin include acrylic resins, butyral resins, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, 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 thermoplastic resin having alkali solubility include resins having an acidic group such as a carboxyl group or a sulfone group. Examples of the thermoplastic resin having alkali solubility include acrylic resins having an acidic group, styrene / styrenesulfonic acid copolymers, and ethylene / (meth)acrylic acid copolymers. Among these, acrylic resins having an acidic group and styrene / styrenesulfonic acid copolymers are preferable in terms of improving developability, heat resistance, and transparency.

[0054] [Active energy ray curable alkali-soluble resin] The active energy ray-curable alkali-soluble resin preferably has an ethylenically unsaturated double bond. The ethylenically unsaturated double bond can be introduced, for example, by the methods (i) and (ii) shown below. Due to the effect of active energy rays, the resin is three-dimensionally crosslinked, resulting in an increase in crosslink density and an improvement in chemical resistance.

[0055] [Method (i)] Method (i) is, for example, a method in which a carboxyl group of an unsaturated monobasic acid having an ethylenically unsaturated double bond is added to the side-chain epoxy group of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having an epoxy group and another monomer. Subsequently, a polybasic acid anhydride is reacted with the generated hydroxyl group to introduce an ethylenically unsaturated double bond and a carboxyl group.

[0056] Examples of the ethylenically unsaturated monomer having an epoxy group include glycidyl (meth)acrylate, methyl glycidyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, and 3,4-epoxycyclohexyl (meth)acrylate. Among these, glycidyl (meth)acrylate is preferred from the viewpoint of reactivity with unsaturated monobasic acids.

[0057] Examples of the unsaturated monobasic acid include monocarboxylic acids such as (meth)acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-haloalkyl, alkoxyl, halogen, nitro, and cyano-substituted products of (meth)acrylic acid.

[0058] Examples of the polybasic acid anhydride include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, etc. In addition, if necessary, such as increasing the number of carboxyl groups, tricarboxylic acid anhydrides such as trimellitic anhydride can be used, or tetracarboxylic dianhydrides such as pyromellitic dianhydride can be used to hydrolyze the remaining anhydride groups.

[0059] Examples of other monomers include the following. 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, or (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, and vinyl fatty acids such as vinyl acetate or vinyl propionate.

[0060] Alternatively, 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 and other N-substituted maleimides, 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 paracumylphenol, EO-modified (meth)acrylate of nonylphenol, PO-modified (meth)acrylate of nonylphenol, etc.

[0061] As a method similar to method (i), for example, an ethylenically unsaturated monomer having an epoxy group is added to a part of the side-chain carboxyl groups of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having a carboxyl group and another monomer, to introduce an ethylenically unsaturated double bond and a carboxyl group.

[0062] [Method (ii)] Method (ii) is a method of reacting the isocyanate group of an ethylenically unsaturated monomer having an isocyanate group with the side-chain hydroxyl group of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having a hydroxyl group and another monomer.

[0063] Examples of the ethylenically unsaturated monomer having a hydroxyl group 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 added with polyγ-butyrolactone, polyε-caprolactone, and / or poly12-hydroxystearic acid, etc. are also included. From the viewpoint of suppressing foreign substances in the coating film, 2-hydroxyethyl methacrylate or glycerol mono(meth)acrylate is preferable, and from the viewpoint of sensitivity, it is preferable to use those having 2 to 6 hydroxyl groups, and glycerol mono(meth)acrylate is more preferable.

[0064] Examples of the ethylenically unsaturated monomer having an isocyanate group include 2-(meth)acryloylethyl isocyanate, 2-(meth)acryloyloxyethyl isocyanate, or 1,1-bis〔methacryloyloxy〕ethyl isocyanate, etc.

[0065] Other monomers that can form an alkali-soluble resin include, in addition to the other ethylenically unsaturated monomers already described, N-substituted maleimides, alkyleneoxy group-containing monomers, phosphoric acid ester group-containing ethylenically unsaturated monomers, carboxyl group-containing ethylenically unsaturated monomers, etc. N-substituted maleimides include, for example, 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 and the like. Alkyleneoxy group-containing monomers include, for example, EO-modified cresol acrylate, n-nonylphenoxypolyethylene glycol acrylate, phenoxyethyl acrylate, ethoxylated phenyl acrylate, ethylene oxide (EO) modification of phenol (meth)acrylate, EO or propylene oxide (PO) modification of paracumylphenol (meth)acrylate, EO modification of nonylphenol (meth)acrylate, PO modification of nonylphenol (meth)acrylate and the like.

[0066] As the carboxyl group-containing ethylenically unsaturated monomer, the monomers already described can be used.

[0067] The phosphoric acid ester group-containing ethylenically unsaturated monomer is, for example, a compound obtained by reacting a phosphoric acid esterifying agent such as phosphorus pentoxide or polyphosphoric acid with the hydroxyl group of the above hydroxyl group-containing ethylenically unsaturated monomer.

[0068] [Alkali-soluble resin having no ethylenically unsaturated double bond] The coloring composition of the present specification can contain an alkali-soluble resin having no ethylenically unsaturated double bond in order to adjust the degree of curing of the film.

[0069] In the present invention, the weight average molecular weight (Mw) of the alkali-soluble resin is 2,000 or more and 40,000 or less, preferably 3,000 or more and 30,000 or less, and more preferably 4,000 or more and 20,000 or less in order to impart alkali developability solubility. Also, the value of Mw / Mn is preferably 10 or less. When the weight average molecular weight (Mw) is less than 2,000, the adhesion to the substrate decreases, and it becomes difficult to leave an exposure pattern. When it exceeds 40,000, the alkali developability solubility decreases, residues are generated, and the linearity of the pattern deteriorates. In the present invention, the acid value of the alkali-soluble resin is 50 or more and 200 or less (KOHmg / g) in order to impart alkali developability solubility, preferably in the range of 70 or more and 180 or less, and more preferably in the range of 90 or more and 170 or less. When the acid value is less than 50, the alkali developability solubility decreases, residues are generated, and the linearity of the pattern deteriorates. When it exceeds 200, the adhesion to the substrate decreases, and it becomes difficult to leave an exposure pattern.

[0070] Each raw material used for the synthesis of the binder resin can be used alone or in combination of two or more.

[0071] [Thermosetting compound] In the present invention, a thermosetting compound can be further included in combination with a thermoplastic resin as the binder resin. When a color filter is produced using the coloring composition of the present invention, by including a thermosetting compound, it reacts during the firing of the filter segment to increase the crosslink density of the coating film. Therefore, the heat resistance of the filter segment is improved, pigment aggregation during the firing of the filter segment is suppressed, and the effect of improving the contrast ratio can be obtained.

[0072] The thermosetting compound may be a low molecular compound or a high molecular weight compound such as a resin. Examples of the thermosetting compound include, but are not limited to, epoxy compounds, oxetane compounds, benzoguanamine compounds, melamine compounds, urea compounds, and phenol compounds. In the coloring composition of the present invention, epoxy compounds and oxetane compounds are preferably used.

[0073] When producing the coloring composition, the dye derivative used is preferably added in an amount of 1 to 30 parts by mass, more preferably 1 to 20 parts by mass, and even more preferably 3 to 10 parts by mass, based on 100 parts by mass of the colorant.

[0074] When the yellow coloring composition containing the pigment represented by Chemical Formula (1) is miniaturized and no dye derivative is used, it is preferable to add a dye derivative when producing the coloring composition.

[0075] When producing the coloring composition, the resin type dispersant used is preferably used in an amount of about 3 to 200% by mass, more preferably about 5 to 100% by mass, based on the total amount of the colorant, from the viewpoint of film forming properties.

[0076] When producing the coloring composition, the content of the binder resin used 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. When contained in an appropriate amount, a film can be easily formed and good color characteristics are easily obtained.

[0077] <Red colorant> The coloring composition of the present invention can further contain a red colorant. The red colorant is not particularly limited as long as it exhibits red, and it can be a pigment or a dye.

[0078] Examples of the red pigment include C.I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52:2, 53, 53:1, 53:2, 53:3, 57, 57:1, 57:2, 58:4, 60, 63, 63:1, 63:2, 64, 64:1, 68, 69, 81, 81:1, 81:2, 81:3, 81:4, 83, 88, 90:1, 101, 101:1, 104, 108, 108:1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276, 277, 278, 279, 280, 281, 282, 283, 284, 285, 286, 287, 291, 295, 296, the pigments described in JP-A-2014-134712, the pigments described in Patent No. 6368844, and the like. Among these, from the viewpoints of the heat resistance, light resistance, and transmittance of the filter segment, preferably C.I. Pigment Red 48:1, 122, 177, 224, 242, 254, 269, 272, 291, 295, 296, the pigments described in JP-A-2014-134712, the pigments described in Patent No. 6368844, and more preferably C.I. Pigment Red 177, 254, 269, 272, 291, 295, 296, the pigments described in JP-A-2014-134712, the pigments described in Patent No. 6368844.

[0079] 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, etc. Further, derivatives of dyes and lake pigments obtained by lake-forming dyes are also included.

[0080] <Other colorants> The coloring composition of the present invention can contain other colorants as necessary. The other colorants may be pigments or dyes, and can be used alone or in combination of two or more. Specific examples of usable organic pigments as the other colorants are shown by Color Index numbers, but are not limited thereto.

[0081] (Organic pigment) Examples of the yellow pigment include 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, 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. Preferably, they are C.I. Pigment Yellow 138, 150, 185, 231, 233, and the pigments described in JP-A-2012-226110.

[0082] Examples of the orange pigment include C.I. Pigment Orange 36, 38, 43, 51, 55, 59, 61, or 73.

[0083] Examples of green pigments include C.I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 37, 45, 48, 50, 51, 54, 55, 58, 59, 62, 63, and pigments described in JP-A-2017-111398. Among these, from the viewpoint of transmittance, preferably C.I. Pigment Green 36, 58, 59, 62, 63, and pigments described in JP-A-2017-111398.

[0084] Examples of blue pigments 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, 81, etc. Among these, from the viewpoints of 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 15:6.

[0085] Examples of purple pigments include C.I. Pigment Violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50, etc. Among these, from the viewpoints of heat resistance, light resistance, and transmittance of the filter segment, preferably C.I. Pigment Violet 19 or 23, and more preferably C.I. Pigment Violet 23.

[0086] Examples of inorganic pigments include titanium oxide, barium sulfate, zinc white, lead sulfate, yellow lead, zinc yellow, red iron oxide (III), cadmium red, ultramarine blue, dark blue, chromium oxide green, cobalt green, amber, synthetic iron black, etc. Inorganic pigments are used in combination with organic pigments in order to ensure good coatability, sensitivity, developability, etc. while achieving a balance between chroma and lightness.

[0087] (Fine particle size of pigment) When an organic pigment is used as a colorant, it is preferable to perform a fine particle size treatment and then mix it with other raw materials. Examples of the fine particle size treatment method include wet grinding, dry grinding, solution precipitation method, etc. Among these, salt milling treatment by a kneader method which is a kind of wet grinding, such as a kneader, two-roll mill, three-roll mill, ball mill, attritor, sand mill, planetary mixer, etc., is preferable.

[0088] The salt milling treatment is a treatment in which a mixture of a pigment, a water-soluble inorganic salt, and a water-soluble organic solvent is mechanically kneaded while heating using a batch-type or continuous kneader such as a kneader, two-roll mill, three-roll mill, ball mill, attritor, sand mill, 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 when performing the salt milling treatment on the pigment, a pigment with a very fine primary particle size, a narrow distribution width, and a sharp particle size distribution can be obtained.

[0089] 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 usage amount of the water-soluble inorganic salt is preferably 50 to 2000 parts by mass, more preferably 300 to 1000 parts by mass, based on 100 parts by mass of the pigment, from both the treatment efficiency and the production efficiency.

[0090] 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 for the water-soluble organic solvent, a high-boiling solvent with 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 usage amount of the water-soluble organic solvent is preferably 5 to 1000 parts by mass, more preferably 50 to 500 parts by mass, relative to 100 parts by mass of the pigment.

[0091] During the salt milling treatment, a resin can be added as necessary. Examples of the resin include natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, etc. The resin is preferably solid at room temperature and water-insoluble, and more preferably partially soluble in the water-soluble organic solvent.

[0092] (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, etc. Also included are derivatives of the dye and lake pigments obtained by lake-forming the dye.

[0093] In addition, examples of the dye include acid dyes having acidic groups such as sulfonic acid and carboxylic acid, in the case of direct dyes, inorganic salts of acid dyes; salt-forming compounds of acid dyes with quaternary ammonium salt compounds, tertiary amine compounds, secondary amine compounds, or primary amine compounds; salt-forming compounds of these resin components having amino groups and acid dyes, etc. Salt-forming compounds of acid dyes with compounds having onium bases are also preferable because of their excellent fastness. Note that as the compound having an onium base, a resin having a cationic group in the side chain is preferable.

[0094] Examples of the basic dye include organic acids, or perchloric acid, or salt-forming compounds thereof with metal salts. Among the salt-forming compounds, the salt-forming compounds of basic dyes are preferable because of their excellent various resistances and compatibility with pigments.

[0095] The chemical structures of the dyes include, 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 preferred, and xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, and phthalocyanine dyes are more preferred. Specific structures of the dyes are described in "New Edition Dye Handbook" (edited by The Society of Organic Synthetic Chemistry; Maruzen, 1970), "Color Index" (The Society of Dyers and colourists), "Pigment Handbook" (edited by Ohkawara et al.; Kodansha, 1986), etc.

[0096] <Specific metal element> In the coloring composition of the present invention, a small amount of Li, Na, K, Mg, Ca, Fe, Al, and Cr (hereinafter, also referred to as specific metal elements) may be present in addition to the constituent components of the pigment. When a large amount of these specific metal elements is present, it may inhibit the storage stability, reduce the heat resistance, or cause a decrease in sensitivity when prepared in the form of the photosensitive coloring composition described later. In addition, a color filter prepared using a coloring composition containing a large amount of such a specific metal element may generate foreign matters, and as a result, it is likely to cause a decrease in brightness. The total content of the specific metal element contained in the coloring composition of the present invention is preferably 500 mass ppm or less.

[0097] More preferably, the total amount of the specific metal element contained in the coloring composition of the present invention is 300 mass ppm or less, and particularly preferably 200 mass ppm or less. Also, the lower limit of the total amount of the specific metal element is not particularly limited, but preferably 1 mass ppm or more, and more preferably 5 mass ppm or more. Within the above range, it is possible to obtain a coloring composition that can suppress costs, has excellent storage stability, and can form a color filter with less generation of foreign matters and less decrease in brightness.

[0098] The amount of each specific metal element contained in the coloring composition of the present invention is preferably 100 mass ppm or less for each, and more preferably 50 mass ppm or less for each.

[0099] In addition, when a metal element such as Ni, Zn, Cu, Al, Fe, and Co is contained in a part of the pigment structure, there may be a case where these metal elements that do not constitute a part of the pigment structure are present. It is better that there are also fewer such metal elements, and they can be removed in the same manner as the specific metal element by the following method. Furthermore, those mixed in by materials (such as catalysts) used in the manufacturing process of various raw materials of the coloring composition, such as Mn, Cs, Ti, Co, Si, Pd, etc., are preferably at a low concentration.

[0100] Examples of the method for removing metal elements mixed in from the apparatus during the pigment or the manufacturing process include the method by water washing according to JP-A-2010-83997, JP-A-2018-36521, JP-A-7-198928, JP-A-8-333521, JP-A-2009-7432, etc., and the method for removing magnetic foreign matters by a magnet described in JP-A-2011-48736. These methods can be used alone or in combination as appropriate.

[0101] The content of specific metal elements can be measured by inductively coupled plasma optical emission spectrometry (ICP).

[0102] The coloring composition of the present invention can further contain a polymerizable compound and / or a photoinitiator. Thus, it can be used as a photosensitive coloring composition.

[0103] <Polymerizable compound> The polymerizable compound contained in the coloring composition of the present invention includes monomers or oligomers that are cured by ultraviolet rays, heat, etc. to form a transparent resin.

[0104] Examples of the polymerizable compound include various acrylate esters and methacrylate esters such as 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)acrylate esters of methylolated melamine, epoxy (meth)acrylate, urethane acrylate; (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.

[0105] (Polymerizable compound having an acid group) The polymerizable compound can contain a photopolymerizable monomer having an acid group. Examples of the acid group include a sulfonic acid group, a carboxyl group, a phosphoric acid group, and the like.

[0106] The photopolymerizable monomer having an acid group includes, for example, esterified products of polyhydric alcohols and free hydroxyl group-containing poly(meth)acrylates with (meth)acrylic acid and dicarboxylic acids; esterified products of polyvalent carboxylic acids and monohydroxyalkyl (meth)acrylates, etc. Specific examples include free carboxyl group-containing monoesterified products of monohydroxyoligoacrylates or monohydroxyoligomethacrylates such as trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, etc., and 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, etc., and monohydroxymonoacrylates or monohydroxymonomethacrylates such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, etc.

[0107] (Polymerizable compound having a urethane bond) The polymerizable compound can contain a monomer having an ethylenically unsaturated bond and a urethane bond. The monomer includes, for example, polyfunctional urethane acrylates obtained by reacting a (meth)acrylate having a hydroxyl group with a polyfunctional isocyanate, and polyfunctional urethane acrylates obtained by reacting an alcohol with a polyfunctional isocyanate and then reacting with a (meth)acrylate having a hydroxyl group.

[0108] The (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, the reaction product of an epoxy group-containing compound and carboxy (meth)acrylate, hydroxyl group-containing polyol polyacrylate, and the like.

[0109] Moreover, the polyfunctional isocyanates include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate, polyisocyanate, and the like.

[0110] The polymerizable compounds can be used alone or in combination of two or more.

[0111] The blending amount of the polymerizable compound is preferably 1 to 50% by mass, more preferably 2 to 40 parts by mass, in 100% by mass of the non-volatile content of the coloring composition. When an appropriate amount is blended, the curability and developability are further improved.

[0112] <Photoinitiator> The photoinitiator 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, benzoyl benzoic acid, methyl benzoyl benzoate, 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.;

[0113] The photoinitiator can be used alone or in combination of two or more kinds.;

[0114] (Oxime ester compound) Oxime ester compounds absorb ultraviolet rays, causing the cleavage of the N - O bond of the oxime to generate iminyl radicals and alkyloxy radicals. These radicals further decompose to generate highly active radicals, so that patterns can be formed with a small exposure amount. When the colorant concentration of the 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, oxime ester compounds have a high quantum efficiency and are therefore preferably used.;

[0115] Examples of the oxime ester compounds include oxime ester - type photoinitiators described in JP - A No. 2007 - 210991, JP - A No. 2009 - 179619, JP - A No. 2010 - 037223, JP - A No. 2010 - 215575, JP - A No. 2011 - 020998, etc.;

[0116] The content of the photoinitiator is preferably 2 to 50 parts by mass, more preferably 2 to 30 parts by mass, based on 100 parts by mass of the colorant. When blended in an appropriate amount, the photocurability and developability are further improved.;

[0117] <Sensitizer> Furthermore, a sensitizer can be contained in the coloring composition of the present invention. 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, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, polymethine dyes such as cyanine derivatives, merocyanine derivatives, 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.

[0118] Among the above sensitizers, particularly preferred sensitizers that can sensitize suitably include thioxanthone derivatives, Michler's ketone derivatives, and carbazole derivatives. More 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 used.

[0119] More specifically, sensitizers described in Noboru Okawara et al. (ed.), "Dye Handbook" (1986, Kodansha), Noboru Okawara et al. (ed.), "Chemistry of Functional Dyes" (1981, CMC), Chuuzou Ikemori et al. (ed.), and "Special Functional Materials" (1986, CMC) are included, but not limited to these. In addition, other sensitizers that show absorption against light from ultraviolet to near-infrared regions can also be contained.

[0120] The sensitizer can be used alone or in combination of two or more.

[0121] The content of the sensitizer is preferably 3 to 60 parts by mass, more preferably 5 to 50 parts by mass, based on 100 parts by mass of the photopolymerization initiator. When contained in an appropriate amount, the curability and developability are further improved.

[0122] <Thiol-based chain transfer agent> The colored composition of the present invention preferably contains a thiol-based chain transfer agent as a chain transfer agent. By using a thiol together with a photopolymerization initiator, in the radical polymerization process after light irradiation, a thiyl radical that acts as a chain transfer agent and is less susceptible to polymerization inhibition by oxygen is generated, so that the resulting colored composition has high sensitivity.

[0123] In addition, polyfunctional aliphatic thiols in which a thiol group is bonded to an aliphatic group such as methylene or ethylene group having two or more thiol groups are preferred. More preferably, it is a polyfunctional aliphatic thiol having four or more thiol groups. By increasing the number of functional groups, the polymerization initiation function is improved, and it is possible to cure from the surface to the vicinity of the substrate in the pattern.

[0124] 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.

[0125] The thiol-based chain transfer agent can be used alone or in combination of two or more.

[0126] The content of the thiol-based chain transfer agent is preferably 0.1 to 10% by mass, more preferably 0.1 to 3% by mass, in 100% by mass of the non-volatile content of the 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.

[0127] <Polymerization inhibitor> The coloring composition can contain a polymerization inhibitor. This can suppress the photosensitivity due to the diffracted light of the mask during the exposure of the photolithography method, so that it becomes easier to obtain a pattern having a desired shape.

[0128] Examples of the polymerization inhibitor include alkylcatechol 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; alkylresorcinol 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; alkylhydroquinone 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, and the like.

[0129] The content of the polymerization inhibitor is preferably 0.01 to 0.4 parts by mass in 100 parts by mass of the nonvolatile content of the coloring composition. In this range, the effect of the polymerization inhibitor becomes significant, and the linearity of the taper, the wrinkles of the coating film, the pattern resolution, etc. become good.

[0130] <Ultraviolet absorber> The coloring composition of the present invention may contain an ultraviolet absorber. The ultraviolet absorber in the present invention is an organic compound having an ultraviolet absorption function, and examples thereof include benzotriazole compounds, triazine compounds, benzophenone compounds, salicylic acid ester compounds, cyanoacrylate compounds, and salicylate compounds.

[0131] 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.

[0132] Further, 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 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.

[0133] Examples of benzotriazole compounds 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, a mixture of 5% 2-methoxy-1-methylethyl acetate and 95% benzenepropanoic 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, the reaction product of methyl 3-(3-(2H-benzotriazol-2-yl)-5-t-butyl-4-hydroxyphenyl)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. Other oligomer-type and polymer-type compounds having a benzotriazole structure can also be used.

[0134] Examples of the triazine compound include 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, the 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. Other oligomer-type and polymer-type compounds having a triazine structure can also be used.

[0135] Examples of the benzophenone compound include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octyloxybenzophenone, 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, etc. Other oligomer-type and polymer-type compounds having a benzophenone structure can also be used.

[0136] Examples of the salicylic acid ester compounds include phenyl salicylate, p-octylphenyl salicylate, p-tert-butylphenyl salicylate, etc. In addition, oligomer-type and polymer-type compounds having a salicylic acid ester structure can also be used.

[0137] <Antioxidant> The colored composition of the present invention can contain an antioxidant. The antioxidant can prevent the photoinitiator and thermosetting compound contained in the colored composition from being oxidized and yellowed by the heat treatment during thermosetting or ITO annealing, thereby improving the transmittance of the coating film. In particular, when the colorant concentration of the colored composition is high, since the amount of the coating film crosslinking component is small, a phenomenon of stronger yellowing in the heat treatment is observed due to measures such as using a highly sensitive crosslinking component or increasing the amount of the photoinitiator. Therefore, by containing an antioxidant, yellowing due to oxidation during the heating process can be prevented, and a high transmittance of the coating film can be obtained.

[0138] Examples of the antioxidant include compounds of the hindered phenol type, hindered amine type, phosphorus type, sulfur type, and hydroxylamine type. In this specification, the antioxidant is preferably a compound that does not contain a halogen atom.

[0139] Among these, from the viewpoint of achieving both the transmittance and sensitivity of the coating film, hindered phenol type antioxidants, hindered amine type antioxidants, phosphorus type antioxidants, and sulfur type antioxidants are preferred.

[0140] The antioxidant can be used alone or in combination of two or more.

[0141] In addition, when the content of the antioxidant is 0.5 to 5.0% by mass in 100% by mass of the solid content of the colored composition, it is more preferable because the transmittance, spectral characteristics, and sensitivity are good.

[0142] <Leveling agent> In the coloring composition of the present invention, it is preferable to add a leveling agent for the purpose of improving the coatability of the composition on a transparent substrate and the drying property of the colored film. As the leveling agent, various surfactants such as silicone-based surfactants, fluorine-based surfactants, nonionic surfactants, cationic surfactants, and anionic surfactants can be used.

[0143] When the coloring composition of the present invention contains a surfactant, the addition amount of the surfactant is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass, based on the total solid content of the composition of the present invention. By being within this range, the balance between the coatability, pattern adhesion, and transmittance of the coloring composition becomes good. The coloring composition of the present invention may contain only one type of surfactant or may contain two or more types. When two or more types are contained, it is preferable that the total amount thereof is within the above range.

[0144] <Storage stabilizer> The coloring composition of the present invention can contain a storage stabilizer in order 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. The storage stabilizer can be used in an amount of 0.1 to 10% by mass based on the total amount of the colorant (100% by mass).

[0145] <Adhesion improver> The coloring composition of the present invention can contain an adhesion improver such as a silane coupling agent to enhance the adhesion to the substrate. By improving the adhesion with the adhesion improver, the reproducibility of fine lines becomes good and the resolution is improved.

[0146] Examples of the adhesion promoter include silane coupling agents such as vinyl silanes such as vinyltrimethoxysilane and vinyltriethoxysilane; (meth)acrylic silanes such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acryloxypropyltrimethoxysilane; epoxy silanes such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltriethoxysilane; aminosilanes 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, and hydrochloride of N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane; mercaptans such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane; styryls such as p-styryltrimethoxysilane; ureides such as 3-ureidopropyltriethoxysilane; sulfides such as bis(triethoxysilylpropyl)tetrasulfide; and isocyanates such as 3-isocyanatopropyltriethoxysilane. The adhesion promoter can be used in an amount of 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass, per 100 parts by mass of the colorant in the coloring composition. Using it within this range results in a greater effect and is more preferable because it provides a good balance of adhesion, resolution, and sensitivity.

[0147] <Solvent> The coloring composition of the present invention contains a solvent in order to facilitate the formation of a colored film by coating it on a substrate such as glass so that the dry film thickness becomes 0.2 to 5 μm. The solvent is selected in consideration of the good coatability of the coloring composition, the solubility of each component of the coloring composition, and further the safety.

[0148] As the solvent, solvents commonly used in the art can be used, and in consideration of performances such as boiling point, SP value, evaporation rate, and viscosity, they are used alone or in combination as appropriate according to the coating conditions (such as speed and drying conditions).

[0149] Examples of the solvents used 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, and the like.

[0150] Among the above solvents, from the viewpoints of coatability and drying property, it is preferable to contain an organic solvent having a boiling point at 1 atm of 120°C or higher and 180°C or lower. 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 preferable, and propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, ethyl 3-ethoxypropionate, etc. are more preferable.

[0151] <Method for producing a photosensitive coloring composition> The coloring composition of the present invention can be produced by finely dispersing a colorant in a colorant carrier such as a dispersant, a binder resin, and / or a solvent, preferably together with a dispersion aid (such as a dye derivative or a surfactant), using various dispersion means 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 (colorant dispersion). At this time, two or more colorants or the like may be dispersed in the colorant carrier simultaneously, or those dispersed separately in the colorant carrier may be mixed. When the solubility of the colorant such as a dye is high, specifically, when the solubility in the solvent to be used is high and there is no foreign matter confirmed by dissolution by stirring, it is not necessary to produce it by finely dispersing as described above.

[0152] When used as a photosensitive coloring composition (resist material), it can be prepared as a solvent-developable or alkali-developable coloring composition. The solvent-developable or alkali-developable coloring composition can be prepared by mixing the above-mentioned colorant dispersion, a photopolymerizable monomer and / or a photoinitiator, and, if necessary, a solvent, other dispersion aids, and additives. The photoinitiator may be added at the stage of preparing the coloring composition, or may be added later to the prepared coloring composition.

[0153] <Removal of Coarse Particles> The coloring composition of the present invention is preferably subjected to removal of coarse particles of 5 μm or more, preferably 1 μm or more, more preferably 0.5 μm or more, and mixed dust by means such as centrifugation at a gravitational acceleration of 3000 to 25000 G, filtration with a sintered filter or a membrane filter. Thus, the coloring composition preferably does not substantially contain particles of 0.5 μm or more. More preferably, it is 0.3 μm or less.

[0154] <Water Content in the Coloring Composition> The coloring composition of the present invention preferably has a water content of 2% by mass or less based on the total amount of the coloring composition.

[0155] When the water content is within the above range, the dispersion stability and sensitivity are excellent even after the coloring composition is stored over time.

[0156] The water content is preferably 1.8% by mass or less, more preferably 1.6% by mass or less, based on the total amount of the coloring composition. With such a sufficiently small amount of water in this range, problems are less likely to occur in the dispersion stability and sensitivity of the coloring composition even after storage over time.

[0157] The method for controlling the water content is not particularly limited, and known methods can be used. For example, a method of manufacturing the coloring composition while blowing in a dried inert gas, or a method of adding molecular sieves for dehydration after manufacturing, etc. can be mentioned. Among them, a method of manufacturing while blowing in a dried inert gas is preferred.

[0158] The water content can be measured by a known method such as the Karl Fischer method.

[0159] <Color Filter> Next, the color filter of the present invention will be described. The color filter of the present invention includes a red filter segment, a green filter segment, and a blue filter segment. Further, the color filter may further include a magenta filter segment, a cyan filter segment, and a yellow filter segment.

[0160] (Method for manufacturing a color filter) The color filter can be manufactured by a printing method or a photolithography method. The formation of filter segments by the printing method can be patterned simply by repeating the printing and drying of the coloring composition prepared as printing ink. Therefore, as a manufacturing method of color filters, it is low-cost and excellent in mass productivity. Furthermore, due to the development of printing technology, it is possible to print fine patterns having high dimensional accuracy and smoothness. In order to perform printing, it is preferable to have a composition such that the ink does not dry or solidify on the printing plate or on the blanket. Also, the control of the fluidity of the ink on the printing machine is important, and it is also possible to adjust the ink viscosity with a dispersant or an extender pigment.

[0161] When forming filter segments by the photolithography method, the coloring composition prepared as the above solvent-developable or alkali-developable coloring resist material is applied onto a transparent substrate by a coating method such as spray coating, spin coating, slit coating, roll coating, etc. so that the dry film thickness becomes 0.2 to 5 μm. If necessary, the dried film is exposed (irradiated with radiation) through a mask having a predetermined pattern provided in contact or non-contact with this film. Thereafter, it is immersed in a solvent or an alkali developer or the developer is sprayed by spraying or the like to remove the uncured portion to form a desired pattern, and then the same operation can be repeated for other colors to manufacture a color filter. Furthermore, heating can be applied as necessary to accelerate the polymerization of the coloring resist material. According to the photolithography method, a color filter with higher accuracy than the above printing method can be manufactured.

[0162] At the time of development, an aqueous solution such as sodium carbonate or sodium hydroxide is used as the alkali developer, and organic alkalis such as dimethylbenzylamine or triethanolamine can also be used. Also, an antifoaming agent or a surfactant can be added to the developer. In addition, in order to increase the exposure sensitivity, after applying and drying the above coloring resist, a water-soluble or alkali-water-soluble resin, for example, polyvinyl alcohol or a water-soluble acrylic resin, etc. is applied and dried to form a film that prevents polymerization inhibition by oxygen, and then exposure can be performed.

[0163] The color filter of the present invention can be manufactured by an electrodeposition method, a transfer method, an inkjet method, etc. in addition to the above method, and the coloring composition of the present invention can be used in any method. The electrodeposition method is a method of manufacturing a color filter by electrodepositing each color filter segment on a transparent conductive film by electrophoresis of colloidal particles using the transparent conductive film formed on a substrate. The transfer method is a method of forming a filter segment in advance on the surface of a peelable transfer base sheet and transferring this filter segment to a desired substrate.

[0164] Before forming each color filter segment on a transparent substrate or a reflective substrate, a black matrix can be formed in advance. As the black matrix, an inorganic film such as chromium, a multilayer film of chromium / chromium oxide, titanium nitride, or a resin film in which a light-shielding agent is dispersed is used, but it is not limited thereto. Also, a thin film transistor (TFT) can be formed in advance on the above transparent substrate or reflective substrate, and then each color filter segment can be formed. Further, an overcoat film, a transparent conductive film, etc. are formed on the color filter of the present invention as necessary.

[0165] The color filter of the present invention can also be used in the manufacture of color liquid crystal display devices, color solid-state imaging devices, organic EL display devices, quantum dot display devices, and electronic paper, etc.

[0166] <Sensor> The sensor of the present invention includes the color filter segment of the present invention. The configuration of the sensor of the present invention is a configuration including the color filter segment of the present invention, and there is no particular limitation as long as it functions as a sensor. For example, the following configurations can be mentioned. On a substrate, there are a plurality of photodiodes that constitute the light-receiving area of a solid-state imaging device (such as a CCD sensor, a CMOS sensor, an organic CMOS sensor, etc.) and transfer electrodes made of polysilicon or the like. There is a light-shielding film made of tungsten or the like with an opening only in the light-receiving part of the photodiode on the photodiodes and the transfer electrodes. There is a device protection film made of silicon nitride or the like formed so as to cover the entire surface of the light-shielding film and the light-receiving part of the photodiode on the light-shielding film. On the device protection film, there is a configuration having the color filter of the present invention. Furthermore, a configuration having condensing means (for example, a microlens or the like. The same applies hereinafter) on the device protection layer and under the color filter (the side closer to the substrate), or a configuration having condensing means on the color filter may be employed. Note that an organic CMOS sensor is a two-layer hybrid structure including a thin-film panchromatic photosensitive organic photoelectric conversion film as a photoelectric conversion layer and a CMOS signal readout substrate. An organic material plays a role of capturing light and converting it into an electrical signal, and an inorganic material plays a role of extracting the electrical signal to the outside. In principle, the aperture ratio can be set to 100% with respect to incident light. Since the organic photoelectric conversion film is a structure-free continuous film that can be laid on the CMOS signal readout substrate, it does not require an expensive microfabrication process and is suitable for miniaturization of filter segments. The arrangement of the color filter is not particularly limited, and known methods can be used.

Example

[0167] Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. In the examples, "parts" and "%" represent "parts by weight" and "weight %", respectively.

[0168] The weight-average molecular weight (Mw) of the resin-type dispersant having an acidic functional group was measured by GPC (HLC-8120GPC manufactured by Tosoh Corporation) equipped with an RI detector using a TSKgel column (manufactured by Tosoh Corporation), and is the weight-average molecular weight (Mw) in terms of polystyrene measured using THF as the eluent. The solid content is the value of the solid content measurement determined from the weight loss on drying when 0.5 g of the solution of the resin-type dispersant was precisely weighed and placed in a dryer at 180 °C for 20 minutes.

[0169] The acid value of the resin-type dispersant having an acidic functional group was determined by potentiometric titration using a 0.1 N potassium hydroxide-ethanol solution. The acid value of the resin indicates the acid value of the non-volatile matter.

[0170] The weight-average molecular weight (Mw) of the resin-type dispersant having a basic functional group was measured by GPC (HLC-8120GPC manufactured by Tosoh Corporation) equipped with an RI detector using a TSKgel column (manufactured by Tosoh Corporation), and is the weight-average molecular weight (Mw) in terms of polystyrene measured using an N,N-dimethylformamide solution containing 3 mM triethylamine and 10 mM LiBr as the eluent.

[0171] The amine value of the resin-type dispersant having a basic functional group was determined by potentiometric titration using a 0.1 N hydrochloric acid aqueous solution and then converted to the equivalent of potassium hydroxide. The amine value of the resin indicates the amine value of the non-volatile matter.

[0172] The quaternary ammonium salt value of the resin-type dispersant having a basic functional group was determined by titration with a 0.1 N silver nitrate aqueous solution using a 5% potassium chromate aqueous solution as an indicator and then converted to the equivalent of potassium hydroxide. The quaternary ammonium salt value of the resin indicates the quaternary ammonium salt value of the non-volatile matter.

[0173] First, the dye derivatives used in the examples and comparative examples have the following structures.

[0174] (Dye Derivative (C1))

Chemical Formula

[0175] (Pigment Derivative (C2))

Chem.

[0176] (Pigment Derivative (C3))

Chem.

[0177] (Pigment Derivative (C4))

Chem.

[0178] (Pigment Derivative (C5))

Chem.

[0179] (Pigment Derivative (C6))

Chem.

[0180] (Pigment Derivative (C7))

Chem.

[0181] Next, the production methods of the resin-type dispersant, binder resin, red colorant, and red color composition used in the examples and comparative examples will be described.

[0182] <Production Method of Binder Resin or Resin-Type Dispersant> (Preparation of Binder Resin (B1)) 370 parts of cyclohexanone was charged into a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas inlet tube, a dropping tube and a stirring device, and the temperature was raised to 80 °C. After purging 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, 1.0 part of azobisisobutyronitrile dissolved 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, 0.5 part of tris(dimethylamino)phenol and 0.1 part of hydroquinone were added to 9.3 parts of acrylic acid (100% of glycidyl groups) in the above container, and the reaction was continued at 120 °C for 6 hours until the solid 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 groups) 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. Propylene glycol monomethyl ether acetate was added to the previously synthesized resin solution so that the non-volatile content became 20% by mass to prepare a binder resin (B1). The weight average molecular weight (Mw) was 19,000.

[0183] (Preparation of resin type dispersant (B2) having acidic functional groups) 10 parts of methacrylic acid, 100 parts of methyl methacrylate, 70 parts of i-butyl methacrylate, 20 parts of benzyl methacrylate, and 50 parts of propylene glycol monomethyl ether acetate were charged into a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser and a stirrer, and purged with nitrogen gas. The reaction vessel was heated and stirred at 50 °C, and 12 parts of 3-mercapto-1,2-propanediol were added. The temperature was raised to 90 °C, and a solution prepared by adding 0.1 part of 2,2'-azobisisobutyronitrile to 90 parts of propylene glycol monomethyl ether acetate was added while reacting for 7 hours. It was confirmed by solid content measurement that 95% of the reaction had occurred. 19 parts of pyromellitic dianhydride, 50 parts of propylene glycol monomethyl ether acetate, 50 parts of cyclohexanone, and 0.4 part of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were added, and the mixture was reacted at 100 °C for 7 hours. It was confirmed by acid value measurement that 98% or more of the acid anhydride had been half-esterified, and the reaction was terminated. Propylene glycol monomethyl ether acetate was added for dilution so that the solid content became 40% by solid content measurement, and a resin-type dispersant (B2) having an acidic functional group with an acid value of 70 mgKOH / g and a weight average molecular weight of 8500 was obtained.

[0184] (Preparation of resin-type dispersant (B3) having a basic functional group) In a reactor equipped with a gas inlet tube, a condenser, a stirring blade, and a thermometer, 40 parts of methyl methacrylate, 10 parts of n-butyl methacrylate, and 13.2 parts of tetramethylethylenediamine as a catalyst were charged. While flowing nitrogen, the mixture was stirred at 50 °C for 1 hour, and the system was purged with nitrogen. Next, 9.3 parts of ethyl bromoisobutyrate as an initiator, 5.6 parts of cuprous chloride as a catalyst, and 133 parts of methoxypropyl acetate were charged. Under a nitrogen stream, the temperature was raised to 110 °C to initiate the polymerization of the first block (B block). After 4 hours of polymerization, the polymerization solution was sampled for solid content measurement, and it was confirmed that the polymerization conversion rate was 98% or more in terms of non-volatile content. Next, 61 parts of methoxypropyl acetate, 40 parts of dimethylaminoethyl methacrylate as the second block (A block) monomer, and 10 parts of methacryloyloxyethylbenzyldimethylammonium chloride were added to this reactor, and stirring was continued while maintaining the temperature at 110 °C in a nitrogen atmosphere. Two hours after the addition, the polymerization solution was sampled for solid content measurement, and it was confirmed that the polymerization conversion rate of the second block (A block) was 98% or more in terms of non-volatile content, and the reaction solution was cooled to room temperature to stop the polymerization. As a result of GPC measurement, the polymer had a mass average molecular weight of 20,000 and a molecular weight distribution Mw / Mn of 1.4, and the reaction conversion rate was 98.5%. In this way, a resin solution having an amine value of 169.8 mgKOH / g per solid content was obtained. 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, and propylene glycol monomethyl ether acetate was added so that the non-volatile content became 40 mass% to prepare a resin-type dispersant (B3) having a basic functional group.

[0185] [Production Example 1-1] <Production of Red Colorant> 95 parts of diketopyrrolopyrrole-based red pigment PR254 ("Irgaphor Red S 3610 CF" manufactured by BASF), 5 parts of a pigment derivative (C5), 1000 parts of ground salt, and 180 parts of diethylene glycol were charged into a 1-gallon stainless steel kneader (manufactured by Inoue Seisakusho) and kneaded at 60 °C for 8 hours. This mixture was poured into 2000 parts of warm water and stirred with a high-speed mixer for about 1 hour while heating to about 60 °C to form a slurry. After repeating filtration and washing with water to remove salt and the solvent, it was dried at 80 °C for 24 hours to obtain 100 parts of a red colorant (PR-1).

[0186] [Production Example 2-1] <Method for Producing Red Color Composition> A mixture of 91 parts of a red colorant (PR-1), 9 parts of a pigment derivative (C5), 60 parts of a resin-type dispersant (B2) having an acidic functional group, and 460 parts of propylene glycol monomethyl ether acetate was uniformly stirred and mixed, and then dispersed with an Eiger mill for 2 hours using zirconia beads with a diameter of 0.5 mm, and then filtered through a 5-μm filter to prepare a red color composition (DR-1).

[0187] [Example 1-1] <Production of Yellow Colorant> 100 parts of an isoindoline-based yellow pigment PY139 ("Cinilex(R) Yellow SY3C" manufactured by CINIC), 1000 parts of ground salt, and 180 parts of diethylene glycol were charged into a 1-gallon stainless steel kneader (manufactured by Inoue Seisakusho) and kneaded at 60 °C for 8 hours. This mixture was poured into 2000 parts of warm water and stirred with a high-speed mixer for about 1 hour while heating to about 60 °C to form a slurry. After repeating filtration and washing with water to remove salt and the solvent, it was dried at 80 °C for 24 hours to obtain 100 parts of a yellow colorant (PY-1).

[0188] [Example 1-2] to [Example 1-63], [Comparative Example 1-1] to [Comparative Example 1-9] A yellow colorant (PY-2) to (PY-72) was obtained by kneading, purifying, and drying under the same conditions as in Example 1-1, except that a pigment, a pigment derivative C, a binder resin B, or a resin type dispersant B was added at the ratios shown in Table 1. Note that the parts by weight of the binder resin B or the resin type dispersant B in Table 1 are the parts by weight of the solid content.

[0189] In Table 1, Markid 32 represents a rosin-modified maleic acid resin (Markid No. 32, acid value 130, weight average molecular weight 1000, manufactured by Arakawa Chemical Industries, Ltd.) which is a resin type dispersant having an acidic functional group, and D1155 represents Paliotol(R) Yellow D1155 manufactured by BASF.

[0190] Also, the pigments represented by Chemical Formula (1) in Table 1 are as follows. SY3CN: "Cinilex(R) Yellow SY3CN" manufactured by CINIC, average primary particle diameter 150 to 200 nm L2140HD: "Paliotol(R) Yellow L2140HD" manufactured by BASF, average primary particle diameter 150 to 200 nm K2142: "Paliotol(R) Yellow K2142" manufactured by BASF, average primary particle diameter 150 to 200 nm L2146HD: "Paliotol(R) Yellow L2146HD" manufactured by BASF, average primary particle diameter 200 to 250 nm D1819: "Paliotol(R) Yellow D1819" manufactured by BASF, average primary particle diameter 50 to 80 nm K1841: "Paliotol(R) Yellow K1841" manufactured by BASF, average primary particle diameter 50 to 80 nm H2R: "Graphtol(R) Yellow H2R" manufactured by CLARIANT, average primary particle diameter 50 to 80 nm

[0191] [Measurement of pH of yellow colorant] After boiling the yellow colorants (PY-1) to (PY-72) in distilled water and filtering, the pH of the filtrate was measured under the following conditions (X).

[0192] Condition (X) Add 100 g of distilled water to 5 g of the colorant and boil at 200 °C for 40 minutes. After boiling, replenish the distilled water for the evaporated portion and adjust to a total of 105 g. Filter the resulting mixture of the colorant and distilled water using No. 5C filter paper (manufactured by Toyo Roshi Kaisha, Ltd.), and measure the pH of the filtrate using a pH meter (D-51, manufactured by Horiba, Ltd.).

[0193]

Table 1

[0194] [Example 2-1] to [Example 2-66], [Comparative Example 2-1] to [Comparative Example 2-9] <Method for producing yellow coloring composition> After uniformly stirring and mixing the mixture of the composition (parts by weight) shown in Table 2, disperse it for 2 hours using an Igarashi mill with zirconia beads having a diameter of 0.5 mm, and then filter it through a 5-μm filter to prepare yellow coloring compositions (DY-1) to (DY-66), (DY-67) to (DY-75). In Table 2, the parts by weight of resin type dispersant B represent the parts by weight of the solid content, and the parts by weight of PGMAc represent the total parts by weight including the PGMAc contained in resin type dispersant B.

[0195] PGMAc in Table 2 represents propylene glycol monomethyl ether acetate.

[0196] [Example 2-67] to [Example 2-69] <Method for producing red coloring composition> After uniformly stirring and mixing the mixture of the composition (parts by weight) shown in Table 2, disperse it for 2 hours using an Igarashi mill with zirconia beads having a diameter of 0.5 mm, and then filter it through a 5-μm filter to prepare red coloring compositions (DYR-1) to (DYR-3).

[0197]

Table 2

[0198] [Example 3-1] to [Example 3-69], [Comparative Example 3-1] to [Comparative Example 3-9] <Method for Producing Photosensitive Coloring Composition> After uniformly stirring and mixing the mixture of the composition (parts by weight) shown in Table 3, it was filtered through a 1-μm filter to prepare photosensitive coloring compositions (RR-1) to (RR-78). In addition, the parts by weight other than PGMAc in Table 3 represent the parts by weight of the solid content excluding PGMAc. Also, for Coloring Compositions 1 and 2, when the transmittance at 400 nm was 5%, the mixing ratio was changed so that the transmittance at 530 nm was 5%, and they were mixed so that the total was 14.88 parts by mass.

[0199] PGMAc in Table 3 represents propylene glycol monomethyl ether acetate. Also, the photopolymerizable monomer M-402 is dipentaerythritol hexaacrylate ("Aronix M-402" manufactured by Toagosei Co., Ltd.), and the photoinitiator OXE-01 is 1,2-octanedione, 1-[4-(phenylthio)phenyl]-, 2-(O-benzoyloxime) (IRGACURE OXE-01 manufactured by BASF Japan Ltd.).

[0200] <Evaluation> [Mixing Stability] The mixing stability of the obtained photosensitive coloring composition was evaluated in three grades according to the following criteria. ○: The viscosity increase rate when stored at 40°C for 1 week is less than 103% △: The viscosity increase rate when stored at 40°C for 1 week is 103% or more and less than 105% ×: The viscosity increase rate when stored at 40°C for 1 week is 105% or more

[0201] [Color Strength Evaluation] The obtained photosensitive coloring composition was applied onto a 6-inch silicon wafer by spin coating with a resist solution for planarization film (HL-18s, manufactured by Nippon Steel Chemical Co., Ltd.), and as pre-baking, heat treatment was performed at 100 °C on a hot plate for 6 minutes. Further, treatment was carried out in an oven at 230 °C for 1 hour to cure the coating film and form a 1.0-μm planarization film, thereby obtaining a wafer with a planarization film. Next, the obtained resist material was applied onto the silicon wafer with a planarization film by a spin coater, and as pre-baking, heat treatment was performed at 100 °C on a hot plate for 1 minute. Then, using an i-line stepper exposure apparatus FPA-3000i5+ (manufactured by Canon Inc.), pattern exposure was performed at an exposure amount of 150 mJ / cm2 through a photomask for forming a 1.0-μm square pixel at a wavelength of 365 nm. The coated film after exposure was paddle-developed with an organic alkali developer for 1 minute. After paddle development, rinsing was performed with pure water by spin shower for 20 seconds, and further, water washing was performed with pure water for 20 seconds. Thereafter, the water droplets remaining on the wafer were blown off with high-pressure air, and the substrate was naturally dried to form a square pixel pattern. Then, heat drying was performed at 230 °C for 60 minutes to prepare an evaluation substrate. At the time of preparation, the rotation speed of spin coating was changed and adjusted so that the transmittance at 530 nm became 5%. Regarding the coloring power of this coating film, three-level evaluation was performed according to the following criteria. ○: Film thickness is less than 0.55 μm △: Film thickness is 0.55 μm or more and less than 0.60 μm ×: Film thickness is 0.60 μm or more

[0202] [Transmittance evaluation] Regarding the transmittance of the previous coating film, three-level evaluation was performed according to the following criteria. ○: Transmittance at 600 nm is 90% or more △: Transmittance at 600 nm is 85% or more and less than 90% ×: Transmittance at 600 nm is less than 85%

[0203]

Table 3

[0204] As described above, by using a yellow coloring composition containing a pigment represented by chemical formula (1) and having a filtrate with a pH of 6.0 to 7.0 when boiled with distilled water and filtered, a photosensitive coloring composition having good mixing stability with a red coloring composition and good coloring power and transmittance can be obtained.

[0205] Furthermore, by using these photosensitive coloring compositions, color filters and sensors for image sensors with improved thin film formation, improved color separation properties, and improved color reproducibility can be provided.

Claims

1. A yellow colorant (A) comprising at least one selected from the group consisting of a pigment represented by the following chemical formula (1), a dye derivative having an acidic functional group, and a resinous dispersant having an acidic functional group, wherein when 100 g of distilled water is added to 5 g of the yellow colorant (A), boiled at 200 °C for 40 minutes, and then the evaporated portion of the distilled water is replenished to make a total of 105 g, the filtrate when the resulting mixture of the colorant (A) and distilled water is filtered has a pH of 6.0 to 7.

0. Chemical formula (1) 【Chemical Formula 1】

2. The yellow colorant (A) according to Claim 1, wherein the content of the pigment represented by the chemical formula (1) is 80% by mass or more and less than 100% by mass in the yellow colorant (A).

3. The yellow colorant (A) according to Claim 1, wherein the acidic functional group is at least one selected from the group consisting of a sulfo group, a carboxyl group, and a phosphate group.

4. A coloring composition comprising the yellow colorant (A) according to any one of Claims 1 to 3, a binder resin, and a solvent.

5. The coloring composition according to Claim 4, further comprising a red colorant.

6. The coloring composition according to Claim 4 or 5, further comprising a polymerizable compound and / or a photoinitiator.

7. A color filter formed from the coloring composition according to any one of Claims 4 to 6.

8. A sensor comprising the color filter according to Claim 7.

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