Coloring composition, manufacturing method thereof, photosensitive coloring composition, color filter, solid-state photographic element and image display device

Abstract

The present invention aims to provide a coloring composition exhibiting excellent storage stability, foreign matter suppression on coatings, superior filtration properties, and excellent resolubility relative to PGMAc. A coloring composition comprises: a coloring agent containing a pigment, a polyester dispersant, and a solvent. In the coloring composition, the polyester dispersant has a main chain based on an aromatic carboxylic acid ester site having ester bonds and side chains based on vinyl polymer sites. The aromatic carboxylic acid ester site is a reaction formation site of an aromatic compound having two or more anhydride groups and a compound having two or more hydroxyl groups, and the anhydride group is 0.9 to 1.5 mol relative to 1 mol of the hydroxyl group. The main chain based on the aromatic carboxylic acid ester site has a sealing site derived from a monool.

Description

Technical Field

[0001] This invention relates to a coloring composition used in the formation of image display devices such as liquid crystal display devices and organic electroluminescence (EL) display devices, as well as color filters for solid-state photographic elements. Prior Technology

[0002] In recent years, the development of color filters for high color reproduction in image display devices has become increasingly sophisticated. Consequently, the performance requirements for the coloring components used in these filters have become more stringent. Not only have the quality requirements for the final color filter product become more demanding, but the process requirements for pigment dispersions containing a large amount of coloring components have also become more challenging. In particular, improving the resolubility in propylene glycol monomethyl ether acetate (PGMAc) is crucial. If the resolubility of PGMAc is poor, a dry film may form after applying the resist solution using a coating machine. If the resist is not easily redissolved in PGMAc, this dry film may become a foreign object during subsequent processing.

[0003] Examples of methods to achieve good resolubility of PGMAc include: using a grafted dispersant (Patent Document 1) or using an acrylic block polymer (Patent Document 2).

[0004] However, these methods struggle to balance the dispersion stability of the coloring composition with the resolubility of PGMAc. [Existing Technical Documents] [Patent Literature]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 2009-227839 [Patent Document 2] Japanese Patent Application Publication No. 2020-194131 [] Summary of the Invention

[0006] [The problem the invention aims to solve] The purpose of this invention is to provide a coloring composition that exhibits excellent storage stability, foreign matter inhibition on the coating, excellent filtration properties, and excellent resolubility relative to PGMAc. [Technical means to solve the problem]

[0007] The coloring composition of the present invention comprises a coloring agent containing pigment, a polyester dispersant, and a solvent. The polyester dispersant has a main chain based on an aromatic carboxylic acid ester site with ester bonds and side chains based on a vinyl polymer site. The aromatic carboxylic acid ester site with ester bonds is a reaction formation site of an aromatic compound having two or more anhydride groups and a compound having two or more hydroxyl groups. The anhydride group is 0.9 to 1.5 mol relative to the hydroxyl group of 1 mol. The main chain based on the aromatic carboxylic acid ester site has a sealing site derived from a monool.

[0008] In addition, the present invention relates to the coloring composition wherein the monool is a compound having an ether group or a carbonyl group.

[0009] In addition, the present invention relates to the coloring composition wherein the weight average molecular weight of the polyester dispersant is 7,000 to 25,000.

[0010] In addition, the present invention relates to a photosensitive coloring composition comprising: the coloring composition, a photopolymerizable compound, and a photopolymerization initiator.

[0011] In addition, the present invention relates to a color filter, comprising: a substrate, and a filter segment formed of the photosensitive coloring composition.

[0012] In addition, the present invention relates to a solid-state photographic element including the color filter.

[0013] In addition, the present invention relates to an image display device including the color filter.

[0014] Furthermore, the method for manufacturing the coloring composition of the present invention is a method for manufacturing a coloring composition containing a coloring agent comprising a pigment, a polyester dispersant, and a solvent, characterized in that... The polyester dispersant has a main chain based on an aromatic carboxylic acid ester site with ester bonds and side chains based on a vinyl polymer site. The aromatic carboxylic acid ester site with ester bonds is a reaction formation site of an aromatic compound having two or more anhydride groups and a compound having two or more hydroxyl groups. The anhydride group is 0.9 to 1.5 mol relative to the hydroxyl group of 1 mol. The main chain based on the aromatic carboxylic acid ester site has a sealing site derived from a monool. [The effects of the invention]

[0015] According to the present invention, a coloring composition exhibiting excellent storage stability, foreign matter suppression on the coating, excellent filtration properties, and excellent resolubility relative to PGMAc can be provided. Furthermore, the present invention can provide a photosensitive coloring composition, a solid-state photographic element, an image display device, and a method for manufacturing the coloring composition. Implementation

[0016] The terms used in this specification are defined. When expressed as "(meth)acryl," "(meth)acrylate," "(meth)acrylic acid," "(meth)acrylate," or "(meth)acrylamine," unless otherwise specified, they respectively represent "acryl and / or methacryl," "acrylate and / or methacrylate," "acrylic acid and / or methacrylic acid," "acrylate and / or methacrylate," or "acrylamine and / or methacrylamine." Additionally, in this specification, "CI" refers to the Colour Index (CI).

[0017] The coloring composition of the present invention comprises: a coloring agent including a pigment, a polyester dispersant, and a solvent, wherein in the coloring composition, The polyester dispersant has a main chain based on an aromatic carboxylic acid ester site with ester bonds and side chains based on a vinyl polymer site. The aromatic carboxylic acid ester site with ester bonds is the reaction site formed by the reaction of 1 mol of a compound with two or more hydroxyl groups and 0.9 to 1.5 mol of an aromatic compound with two or more anhydride groups. The main chain based on the aromatic carboxylic acid ester site has a sealing site derived from a monool. Polyester dispersants improve dispersibility by forming a backbone based on an aromatic carboxylic acid ester site with ester bonds, thereby increasing the proportion of pigment-adsorbed sites per molecule. The aromatic carboxylic acid ester site with ester bonds is a reaction formation site formed by reacting 1 mol of a compound with two or more hydroxyl groups with 0.9 to 1.5 mol of an aromatic compound with two or more anhydride groups. Furthermore, by sealing the anhydride groups that do not contribute to the reaction formation site with a monool, the stability over time and resolubility relative to PGMAc are improved. Generally speaking, dispersants have sites that adsorb onto pigments and sites that have high affinity for photopolymerizable compounds that serve as pigment carriers, binder resins, and solvents that serve as dispersion media. The performance of a dispersant is determined by the balance between these two sites. In other words, for dispersibility to be observed, the adsorption properties of the dispersant to the pigment and its affinity to the pigment carrier and the solvent as the dispersion medium are both very important. The pigment carrier referred to here includes resins and their precursors or mixtures thereof after the pigment components and dispersants have been removed from the non-volatile components.

[0018] <Polyester Dispersant> The polyester dispersant used in this invention has a main chain based on an aromatic carboxylic acid ester site with ester bonds and side chains based on a vinyl polymer site. The aromatic carboxylic acid ester site with ester bonds is a reaction formation site consisting of 1 mol of a compound having two or more hydroxyl groups and 0.9 to 1.5 mol of an aromatic compound having two or more anhydride groups. The main chain based on the aromatic carboxylic acid ester site has a sealing site derived from a monool. In polyester dispersants, ester bonds are formed through ring-opening reactions between aromatic compounds with two or more anhydride groups as precursors and compounds with two or more hydroxyl groups as precursors, while aromatic carboxylic acids are also generated. The vinyl polymer portion of the polyester dispersant used in this invention can be polymerized, for example, by the following two methods. The first method is a method of polymerizing an vinyl unsaturated monomer in the presence of a compound having two or more hydroxyl groups. The compound having hydroxyl groups is preferably a compound having both hydroxyl and thiol groups within its molecule, more preferably a compound having two hydroxyl groups and one thiol group within its molecule. The second method involves polymerizing ethylene-unsaturated monomers in the presence of a reaction product of an aromatic compound having two or more anhydride groups and the hydroxyl groups of a compound having two or more hydroxyl groups. Preferably, the polymer is formed by polymerizing ethylene-unsaturated monomers in the presence of a reaction product of the hydroxyl groups of a compound having two hydroxyl groups and one thiol group within the molecule and the anhydride groups of an aromatic tetracarboxylic acid dianhydride. The difference between the two methods lies in whether the polymer site formed by the polymerization of ethylene-unsaturated monomers is introduced first or last. Depending on various conditions, the molecular weight and other parameters may vary slightly, but theoretically, they can be the same as long as the raw materials and reaction conditions are identical.

[0019] In the main chain based on the aromatic carboxylic acid ester site, the aromatic carboxylic acid acts as a pigment adsorption group. Furthermore, the aromatic carboxylic acid has a structure where the carboxyl group is directly bonded to the aromatic ring. Additionally, the side chains based on the vinyl polymer site act as pigment carrier affinity sites. This results in suppressed pigment aggregation and excellent dispersion stability. The aromatic carboxylic acid ester backbone is generated by esterification of 1 mol of a compound having two or more hydroxyl groups with 0.9 to 1.5 mol of an aromatic compound having two or more anhydride groups. Furthermore, at least one of the anhydride groups at the end of the aromatic carboxylic acid ester backbone has a sealing site derived from a monool. That is, the anhydride group undergoes ring-opening with a monool to generate an alcohol ester and a carboxyl group. This improves the filterability of the coloring composition, suppresses foreign matter on the coating film formed when the coloring composition is applied, and further improves the resolubility of the cured product derived from the coloring composition formed in the coating apparatus relative to PGMAc during the application of the coloring composition. Moreover, the amount of the aromatic compound having two or more anhydride groups used in the esterification reaction is preferably 1.0 to 1.3 mol. In this invention, the side chains of the vinyl polymer site are formed by the polymerization of vinyl unsaturated monomers. Furthermore, all monomer units constituting the vinyl polymer site refer to the partial structures derived from each vinyl unsaturated monomer after vinyl polymerization. First, the constituent elements of the polyester dispersant of the present invention will be described.

[0020] [Aromatic compounds having two or more anhydride groups] The anhydride groups of the aromatic compounds with two or more anhydride groups used in this invention can be regularly arranged on the main chain of the polyester dispersant by the ring-opening reaction of the anhydride groups with two or more hydroxyl groups as precursors, thereby contributing to the pigment dispersibility.

[0021] Aromatic compounds having two or more anhydride groups include, for example: pyromellitic dianhydride, ethylene glycol diphenyltricarboxylic anhydride ester, propylene glycol diphenyltricarboxylic anhydride ester, butanediol diphenyltricarboxylic anhydride ester, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3 3',4,4'-Biphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-Dimethyldiphenylsilane tetracarboxylic dianhydride, 3,3',4,4'-Tetraphenylsilane tetracarboxylic dianhydride, 1,2,3,4-Furan tetracarboxylic dianhydride, 4,4'-Bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride, 4,4'-Bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride, 4,4'-Bis( 3,4-Dicarboxyphenoxy)diphenylpropane dianhydride, 3,3',4,4'-perfluoroisopropylidene phthalic acid dianhydride, 3,3',4,4'-biphenyltetracarboxylic acid dianhydride, bis(phthalic acid)phenylphosphine oxide dianhydride, p-phenyl-bis(triphenylphthalic acid) dianhydride, m-phenyl-bis(triphenylphthalic acid) dianhydride, bis(triphenylphthalic acid)-4,4'-diphenyl ether Dihydric anhydride, bis(triphenylphthalic acid)-4,4'-diphenylmethane dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, 9,9-bis[4-(3,4-dicarboxyphenoxy)phenyl]fluorene dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthosuccinic anhydride, or 3,4-dicarboxy-1,2,3,4-tetrahydro-6-methyl-1-naphthosuccinic anhydride, etc.

[0022] If an aromatic compound having two or more anhydride groups is represented by a general formula, the following general formulas (2) or (3) can be used to represent aromatic tetracarboxylic acid dianhydrides.

[0023] General formula (2):

[0024] [Chemistry 1] [In general formula (2), k is 1 or 2]

[0025] General formula (3):

[0026] [Chemistry 2] [In general formula (3), Q1 is a direct bond, -O-, -CO-, -COOCH2CH2OCO-, -SO2-, -C(CF3)2-, the base represented by the following general formula (4), or the base represented by the following general formula (5)]

[0027] General formula (4): [Chemistry 3]

[0028] General formula (5): [Chemistry 4]

[0029] From the viewpoint of pigment adsorption, aromatic compounds having two or more anhydride groups are preferably aromatic tetracarboxylic acid dianhydrides, and more preferably pyromellitic dianhydrides.

[0030] Aromatic compounds having two or more anhydride groups can be used in combination with aliphatic compounds having two or more anhydride groups.

[0031] [Compounds having two or more hydroxyl groups] Compounds having two or more hydroxyl groups are as described above, preferably compounds having hydroxyl and thiol groups in the molecule, more preferably compounds having two hydroxyl groups and one thiol group in the molecule.

[0032] Compounds having two hydroxyl groups and one thiol group within their molecule include, for example, 1-mercapto-1,1-methanediol, 1-mercapto-1,1-ethanediol, 3-mercapto-1,2-propanediol (thioglycerol), 2-mercapto-1,2-propanediol, 2-mercapto-2-methyl-1,3-propanediol, 2-mercapto-2-ethyl-1,3-propanediol, 1-mercapto-2,2-propanediol, 2-mercaptoethyl-2-methyl-1,3-propanediol, or 2-mercaptoethyl-2-ethyl-1,3-propanediol, etc.

[0033] Examples of vinyl unsaturated monomers include: methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, isoamyl methacrylate, octyl methacrylate, isooctyl methacrylate, 2-ethylhexyl methacrylate, cetyl methacrylate, decyl methacrylate, isodecyl methacrylate, lauryl methacrylate, tridecyl methacrylate, isomyryl methacrylate, stearyl methacrylate, or isostearyl methacrylate, methoxyethyl methacrylate, methoxy polyethylene glycol (meth)acrylate, methoxy polypropylene glycol (meth)acrylate, methoxy polytetramethylene glycol (meth)acrylate, or methoxy polyethylene glycol polypropylene glycol (meth)acrylate, etc., which are straight-chain or branched alkyl (meth)acrylates; Cyclohexyl methacrylate, tert-butylcyclohexyl methacrylate, dicyclopentyl methacrylate, dicyclopentyloxyethyl methacrylate, dicyclopentenyl methacrylate, dicyclopentenyloxyethyl methacrylate, or isobornyl methacrylate and other cyclic alkyl (meth)acrylates; (Meth)acrylate trifluoroethyl acrylate, (meth)acrylate octafluoropentyl acrylate, (meth)acrylate perfluorooctyl ethyl acrylate, or (meth)acrylate tetrafluoropropyl acrylate, etc., are all fluoroalkyl esters of (meth)acrylate; (Meth)acrylic acid-modified polydimethylsiloxane (silicone macromonomer); (Meth)acrylates such as tetrahydrofurfuryl methacrylate or 3-methyl-3-oxetane butyl methacrylate, which contain heterocyclic (meth)acrylates; (Meth)acrylates containing aromatic rings include benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxy polyethylene glycol (meth)acrylate, p-cumylphenoxyethyl (meth)acrylate, p-cumylphenoxy polyethylene glycol (meth)acrylate, or nonylphenoxy polyethylene glycol (meth)acrylate; (Meth)acrylic acid, acrylic acid dimers, 2-(meth)acrylic acid oxyethyl phthalate, 2-(meth)acrylic acid oxypropyl phthalate, 2-(meth)acrylic acid oxyethyl hexahydrophthalate, 2-(meth)acrylic acid oxypropyl hexahydrophthalate, ethylene oxide modified succinic acid (meth)acrylate, β-carboxyethyl (meth)acrylate, or ω-carboxylated polycaprolactone (meth)acrylate and other (meth)acrylates containing carboxyl groups; Vinyl compounds such as styrene, α-methylstyrene, vinyl acetate, vinyl (meth)acrylate, or allyl (meth)acrylate; N-substituted (meth)acrylamides, such as (meth)acrylamide, N,N-dimethyl (meth)acrylamide, N,N-diethyl (meth)acrylamide, N-isopropyl (meth)acrylamide, diacetone (meth)acrylamide, or acrylamide morpholine; N,N-dimethylaminoethyl methacrylate or N,N-diethylaminoethyl methacrylate, and other amine-containing (meth)acrylates; Nitriles such as (meth)acrylonitrile; or mixtures thereof.

[0034] In addition, examples of monomers that can be used in conjunction with the (meth)acrylic acid monomer include: styrene, α-methylstyrene and other styrene derivatives; vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether and other vinyl ether derivatives; and vinyl esters of fatty acids such as vinyl acetate and vinyl propionate.

[0035] Alternatively, carboxyl-containing vinyl unsaturated monomers can also be used in combination. One or more of the following can be selected as carboxyl-containing vinyl unsaturated monomers: acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, butenoic acid, etc.

[0036] The vinyl polymer site can be formed from a vinyl polymer having two hydroxyl groups in a single-terminal region. In addition to methods involving the free radical polymerization of vinyl unsaturated monomers in the presence of compounds having two hydroxyl groups and one thiol group within the molecule, the following methods can also be used for its synthesis.

[0037] The following methods are available: [1] A method for Michael addition of a resin having a (meth)acrylate group in a single-terminal region with a compound having an amino group and two hydroxyl groups. [2] A method for epoxy addition reaction of a resin having a carboxylic acid group in a single-terminal region with a compound having an epoxy group and a hydroxyl group. [3] A method for adding a resin having a vinyl ether group in a single-terminal region to a compound having a carboxylic acid group and two hydroxyl groups. [4] A method of using a polymerization initiator with two hydroxyl groups to carry out free radical polymerization or atom-moving free radical polymerization (living free radical polymerization). These methods can synthesize resins with two hydroxyl groups in a single-terminal region, but they are mostly multi-stage reactions or difficult to control molecular weight. From a production standpoint, the most preferred method is to carry out free radical polymerization of ethylene unsaturated monomers in the presence of compounds with two hydroxyl groups and one thiol group.

[0038] The vinyl polymer portion can be synthesized by co-polymerizing a compound having two hydroxyl groups and one thiol group with an ethylene unsaturated monomer. The compound having two hydroxyl groups and one thiol group is used at 1% to 10% by mass, more preferably 2% to 9% by mass, and even more preferably 3% to 8% by mass, based on the total monomer mass of the ethylene unsaturated monomer. When the content is 1% by mass or more, the molecular weight of the vinyl polymer portion will not become too high, and as an affinity portion for pigment carriers and solvents, its absolute amount can be suppressed, further improving pigment dispersibility. When the content is 10% by mass or less, the molecular weight of the vinyl polymer portion will not become too low, and as an affinity portion for pigment carriers and solvents, its steric repulsion effect can be fully obtained, further improving pigment dispersibility.

[0039] The polymerization temperature is 40℃~150℃, preferably 50℃~110℃. If the temperature is above 40℃, polymerization is easier to carry out, and if the temperature is below 150℃, molecular weight control becomes easier.

[0040] During polymerization, a polymerization initiator of 0.001% to 5% by mass, based on the total mass of the vinyl unsaturated monomers, can be used. Examples of polymerization initiators include azo compounds and organic peroxides.

[0041] Examples of azo compounds include: 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane-1-formonitrile), 2,2'-azobis(2,4-dimethylpentanonitrile), 2,2'-azobis(2,4-dimethyl-4-methoxypentanonitrile), dimethyl 2,2'-azobis(2-methylpropionate), 4,4'-azobis(4-cyanopentanoic acid), 2,2'-azobis(2-hydroxymethylpropionitrile), or 2,2'-azobis[2-(2-imidazolin-2-yl)propane], etc.

[0042] Examples of organic peroxides include: benzoyl peroxide, tert-butyl peroxide, cumene hydroperoxide, diisopropyl peroxide, di-n-propyl peroxide, di(2-ethoxyethyl) peroxide, tert-butyl peroxyneodecanate, tert-butyl peroxyneodecanate, tert-butyl peroxytrimethylacetate, (3,5,5-trimethylhexyl peroxide), dipropyl peroxide, or diacetyl peroxide, etc.

[0043] Polymerization initiators can be used alone or in combination of two or more.

[0044] The synthesis of vinyl polymers is preferably carried out by bulk polymerization or solution polymerization. Examples of polymerization solvents for solution polymerization include: ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, xylene, acetone, hexane, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, or diethylene glycol monobutyl ether acetate, etc., but are not particularly limited to these. Two or more of these polymerization solvents can be used in combination.

[0045] In addition to vinyl polymer sites, the side chains of polyester dispersants may also have sites based on other polyols.

[0046] [Other polyols] During polymerization, it becomes easy to adjust the density of carboxylic acid groups or the proportion of solvent solubility by using other polyols.

[0047] Other polyols include, for example, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, neopentanediol, 1,6-hexanediol, 1,4-bis(hydroxymethyl)cyclohexane, bisphenol A, hydrogenated bisphenol A, trimethylolhydroxyacetyltrimethylacetate, trimethylolethane, trimethylolpropane, 2,2,4-trimethyl-1,3-pentanediol, glycerol, or glycerol, etc. Various polyether glycols such as polyethylene glycol, polyoxypropylene glycol, polyoxyethylene ethyl polyoxytetramethylene glycol, polyoxypropylene polyoxytetramethylene glycol, or polyoxyethylene ethyl polyoxypropylene polyoxytetramethylene glycol; Modified polyether polyols obtained by ring-opening polymerization of the aforementioned polyols with various compounds containing (cyclic) ether bonds, such as ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, or allyl glycidyl ether; Polyester polyols obtained by co-condensation of one or more of the aforementioned polyols with polycarboxylic acids, wherein the polycarboxylic acids are particularly representative polycarboxylic acids such as succinic acid, adipic acid, sebacic acid, azelaic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, maleic acid, fumaric acid, citracic acid, itaconic acid, penteneic acid, 1,2,5-hexanetricarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, or 2,5,7-naphthalenetricarboxylic acid; Lactone-based polyester polyols obtained by polycondensation reaction of one or more of the aforementioned polyols with various lactones such as ε-caprolactone, δ-valerolactone, or 3-methyl-δ-valerolactone; or lactone-modified polyester polyols obtained by polycondensation reaction of the aforementioned polyols with polycarboxylic acids or various lactones; In the synthesis of polyester polyols, epoxy-modified polyester polyols are obtained by using one or more bisphenol A type epoxy compounds, hydrogenated bisphenol A type epoxy compounds, monohydric alcohols and / or glycidyl ethers of polyols, or glycidyl esters of monohydric acids and / or polyhydric acids; or polyester polyamide polyols, polycarbonate polyols, polybutadiene polyols, polypentadiene polyols, castor oil, castor oil derivatives, hydrogenated castor oil, hydrogenated castor oil derivatives, hydroxyl-containing acrylic copolymers, hydroxyl-containing fluorinated compounds, or hydroxyl-containing silicone resins, etc.

[0048] Other polyols can be used alone or in combination of two or more. From the viewpoint of compatibility or dispersion stability, a weight average molecular weight of 40 to 10,000 is preferred, more preferably 100 to 2,000, and even more preferably 100 to 1,000. When the weight average molecular weight is 40 or higher, the density of the carboxylic acid groups can be adjusted. When the weight average molecular weight is 10,000 or lower, compatibility with other raw materials becomes good.

[0049] Diols are preferred as other polyols. In particular, by reacting with aromatic compounds having two or more anhydride groups, carboxyl groups that can become pigment adsorbents are regularly arranged in the main chain, which is beneficial for pigment dispersion. If a large amount of polyols with more than two hydroxyl groups are used, the polyester main chain becomes branched and complex, resulting in a large volume and making it difficult to achieve a good dispersion effect. From a design point of view, the amount used should be limited to a minimum to adjust the molecular weight of the polyester dispersant or the viscosity of the dispersion. The dosage will be discussed later.

[0050] [Synthesis of Polyester] For the process of polyester synthesis of the polyester dispersant used in the present invention, the reaction of a compound having two or more hydroxyl groups with an aromatic compound having two or more acid anhydride groups, taking the reaction of a compound having two hydroxyl groups with a tetracarboxylic dianhydride as an example of each preferred compound, will be described.

[0051] The tetracarboxylic dianhydride used in the present invention can react with a hydroxyl group to form an ester bond, and a side carboxyl group remains on the resulting polyester main chain. Let the molar amount of the compound having two hydroxyl groups be a, let the molar amount of the tetracarboxylic dianhydride be b, and the reactions of the tetracarboxylic dianhydride with the compound having two hydroxyl groups when i) a > b, ii) a = b, and iii) a < b are shown in the following general formulas (6), general formula (7), and general formula (8). If the remaining acid anhydride groups in the products of the following general formulas (6) to (8) are hydrolyzed or the acid anhydride is ring-opened with an alcohol, the product obtained by the said reaction has two or three carboxyl groups in the X1 part of the structural formula, and the multiple carboxyl groups are effective as adsorption sites for pigments.

[0052] i) a > b

[0053] General formula (6): [Chemical formula 5]

[0054] ii) a = b

[0055] General formula (7): [Chemical formula 6]

[0056] iii) a < b

[0057] General formula (8): [Chemical formula 7]

[0058] R represents a hydrogen atom when the acid anhydride group is hydrolyzed, and represents the structure of the following monohydric alcohol when the acid anhydride is ring-opened with a monohydric alcohol.

[0059] In this invention, X1 is the reaction residue of tetracarboxylic dianhydride after reaction with a hydroxyl group, and Y is the reaction residue of a compound having two hydroxyl groups after reaction with an acid anhydride group. As the form of X1, it is preferably the reaction residue of tetracarboxylic dianhydride represented by the general formula (2) or general formula (3) after reaction with a compound having two hydroxyl groups.

[0060] Synthesis of polyester dispersants Regarding polyester dispersants, in the description of the synthesis of polyesters represented by general formulas (6) to (8), a preferred method is to introduce the vinyl polymer via the S atom into the Y atom of a compound having two hydroxyl groups. Hereinafter, two preferred synthesis methods are shown.

[0061] Synthesis Mode 1) In the following general formula (9), in the presence of a compound (a1) having two hydroxyl groups and one thiol group at a single end, an ethylene unsaturated monomer is subjected to free radical polymerization to generate a vinyl polymer (a2) having two hydroxyl groups at a single end, and then reacted with tetracarboxylic dianhydride (b1).

[0062] General formula (9):

[0063] [Chemistry 8]

[0064] If the molar ratio of (a1) is set to a (an integer) and the molar ratio of (b) is set to b (an integer), then the preferred molar ratio of the present invention is 2b / 2a = b / a = 0.9 to 1.5. When the molar ratio is less than 1, unreacted anhydride may sometimes remain; this is addressed by sealing the main chain end with a monool. If the molar ratio b / a is 0.9 or higher, the proportion of pigment adsorbed in one molecule is sufficient, and foreign matter generation is suppressed. If it is 1.5 or lower, no anhydride groups remain, resulting in good storage stability. Even if the anhydride ring is opened, there is no excess acidic group, and compatibility with the pigment carrier or solvent becomes good. From the viewpoint of pigment dispersibility and stability, b / a = 1.0 to 1.3 is more preferred.

[0065] Synthesis Mode 2) In the following general formulas (10) and (11), a compound having two hydroxyl groups and one thiol group at a single end can be reacted with a tetracarboxylic acid dianhydride to initially generate a compound without a vinyl polymer site, and then the remaining thiol group can be used as a chain transfer agent for free radical polymerization to introduce a vinyl polymer site.

[0066] General formula (10):

[0067] [Chemistry 9]

[0068] General formula (11)

[0069] [Chemistry 10]

[0070] If the molar ratio of (a1) is set to a (an integer) and the molar ratio of (b) is set to b (an integer), then the preferred molar ratio of the present invention is 2b / 2a = b / a = 0.9 to 1.5. When the molar ratio is less than 1, unreacted anhydride may sometimes remain, and the anhydride can be ring-opened using a monool. The ring-opening reaction of the anhydride using a monool can be carried out before free radical polymerization as in general formula (10), or after free radical polymerization as in general formula (11). If the molar ratio b / a is 0.9 or more, the proportion of the pigment adsorbed in one molecule is sufficient, and the generation of foreign matter is suppressed. If it is 1.5 or less, no anhydride group remains, the storage stability becomes good, and even if the anhydride is ring-opened, the acidic group is not excessive, and the compatibility with the pigment carrier or solvent becomes good. From the viewpoint of pigment dispersibility and stability, b / a = 1.0 to 1.3 is more preferred.

[0071] [Reaction Catalyst] The catalyst used in the synthesis of polyester dispersants is preferably a tertiary amine compound. Examples of tertiary amine compounds include triethylamine, triethyldiamine, N,N-dimethylbenzylamine, N-methylmorpholine, 1,8-diazabicyclo-[5.4.0]-7-undecene, or 1,5-diazabicyclo-[4.3.0]-5-nonene.

[0072] [Reaction Solvent] Solvents can be used in the synthesis of polyester dispersants. Examples of solvents include: acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, ethyl acetate, butyl acetate, toluene, xylene, acetonitrile, and propylene glycol monomethyl ether acetate.

[0073] The main chain of the polyester dispersant based on the aromatic carboxylic acid ester site has a sealing site derived from the monool, obtained by reacting the monool with the anhydride group. Examples of monools include: methanol, ethanol, 1-butanol, 2-butanol, isobutanol, tert-butanol, 1-pentanol, isopentyl alcohol, tert-pentyl alcohol, cyclopentanol, 1-hexanol, cyclohexanol, 1-heptanol, 1-octanol, 2-ethyl-1-hexanol, isononyl alcohol, 1-nonyl alcohol, and amyl alcohol. Monools containing ether groups include: 1) alcohol (such as lauryl alcohol, n-butyl alcohol, isobutyl alcohol, cyclohexanol, benzyl alcohol, methylcyclohexanol, etc.); 2) monools containing carbonyl groups, such as 3-methoxy-3-methyl-1-butanol, 3-methoxybutanol, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monotert-butyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol monophenyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, etc.; 3) monools containing carbonyl groups, such as methyl lactate, ethyl lactate, diacetone alcohol, etc. These can be used individually or in combination.

[0074] The monool is preferably a compound having an ether group or a carbonyl group. The presence of an ether group or a carbonyl group at the end of the dispersant's main chain improves the resolubility of the dispersant's PGMAc. Among these, 3-methoxybutanol, propylene glycol monomethyl ether, and diacetone alcohol are preferred.

[0075] In addition to sealing sites derived from monools, the main chain of aromatic carboxylic acid esters can also have sealing sites obtained by reaction with water.

[0076] Regarding the synthesis of the sealing portion, the amount of monool used relative to the anhydride group remaining in the main chain is preferably 1 to 30 equivalents, more preferably 1.5 to 20 equivalents. At amounts above 1 equivalent, no anhydride group remains, resulting in good storage stability. At amounts below 30 equivalents, transesterification reactions caused by ester bonds between the monool and the dispersant are less likely to occur, thus reducing the molecular weight.

[0077] [Reaction Conditions] Regarding the ring-opening reaction temperature in polyester synthesis, it is carried out in the range of 50℃ to 180℃, preferably 80℃ to 140℃. The reaction proceeds at temperatures above 50℃, while at temperatures below 180℃, the carboxyl and hydroxyl groups do not undergo esterification, and the decrease in acid value or gelation is less likely to occur.

[0078] [Molecular weight] The weight-average molecular weight of the polyester dispersant is preferably 2,000 to 35,000, more preferably 4,000 to 30,000, and even more preferably 4,000 to 25,000. When the molecular weight is 2,000 or higher, the steric repulsion effect generated by the solvent affinity site can suppress pigment aggregation, further improving pigment dispersibility. When the molecular weight is 35,000 or lower, solvent solubility is ensured, maintaining sufficient steric repulsion, and pigment dispersibility is further improved. Within the aforementioned range, the pigment aggregation suppression effect due to steric repulsion becomes even better.

[0079] [Acid Value] The acid value of the polyester dispersant is preferably 5 mgKOH / g to 200 mgKOH / g, more preferably 20 mgKOH / g to 180 mgKOH / g, and even more preferably 30 mgKOH / g to 150 mgKOH / g. When the acid value is 5 mgKOH / g or higher, the pigment adsorption capacity is improved, and the pigment dispersibility is further enhanced. On the other hand, when the acid value is 200 mgKOH / g or lower, there is no interaction between the resins, and the viscosity of the pigment dispersion composition can be kept low.

[0080] Regarding the content of polyester dispersant in the coloring composition, based on the mass of the pigment, it is preferably 0.01% to 100% by mass, more preferably 0.01% to 60% by mass, and even more preferably 5% to 40% by mass. When the content of polyester dispersant is 0.01% by mass or more, good dispersion effect can be obtained, and when it is 100% by mass or less, there is no interaction between resins, and the viscosity of the pigment dispersion composition can be kept low.

[0081] <Coloring agent> Colorants include pigments. Examples of pigments include organic pigments and inorganic pigments. Pigments are preferably pigments with high chromaticity and high heat resistance, and particularly with respect to high resistance to thermal decomposition, organic pigments are preferred. Hereinafter, specific examples of organic pigments that can be used in coloring compositions for color filters are indicated using dye index numbers.

[0082] Examples of red pigments include: CI 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, 6 4, 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, 1 84, 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, 2 Pigments described in Japanese Patent Application Publication No. 2014-134712 and Japanese Patent Publication No. 6368844, etc. Among these, from the viewpoint of heat resistance, light resistance and transmittance of the filter segment, the preferred pigments are CI Pigment Red 48:1, 122, 177, 224, 242, 269, 254, 291, 295, 296, the pigments described in Japanese Patent Application Publication No. 2014-134712, and the pigments described in Japanese Patent Application Publication No. 6368844. Further preferred pigments are CI Pigment Red 177, 254, 291, 295, 296, the pigments described in Japanese Patent Application Publication No. 2014-134712, and the pigments described in Japanese Patent Application Publication No. 6368844.

[0083] Examples of orange pigments include: CI Pigment Orange 36, 38, 43, 51, 55, 59, 61, 71, or 73.

[0084] Examples of blue pigments include CI 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, and 79. Among these, from the viewpoint of heat resistance, light resistance, and transmittance of the filter section, CI pigment blue 15, 15:1, 15:2, 15:3, 15:4, or 15:6 is preferred, with CI pigment blue 15:6 being more preferred. Furthermore, purple pigments, described later, may also be used in conjunction with the blue coloring composition.

[0085] Examples of purple pigments include CI 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, and 50. Among these, from the viewpoint of heat resistance, lightfastness, and transmittance of the filter band, CI pigment violet 19 or 23 is preferred, and CI pigment violet 23 is even more preferred.

[0086] Examples of green pigments include: CI 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 the pigments described in Japanese Patent Application Publication No. 2017-111398. Among these, from the viewpoint of transmittance, CI pigment green 36, 58, 59, 62, 63, and the pigments described in Japanese Patent Application Publication No. 2017-111398 are preferred.

[0087] Examples of yellow pigments include: CI 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. Pigments, etc., as described in Japanese Patent Application Publication No. 2012-226110. The preferred pigments are those described in CI Pigment Yellow 138, 139, 150, 185, 231, 233, and Japanese Patent Application Publication No. 2012-226110.

[0088] Examples of blue pigments include: CI Pigment Blue 15:1, 15:2, 15:4, 15:3, 15:6, 16, 81, etc.

[0089] Examples of purple pigments include: CI pigments Violet 1 and 19, CI pigments Red 144, 146, 177, 169, and 81.

[0090] Examples of inorganic pigments include: barium sulfate, zinc white, lead sulfate, chrome yellow, zinc yellow, red iron oxide (red iron oxide (III)), cadmium red, ultramarine, Prussian blue, chromium oxide green, cobalt green, brown earth, titanium black, synthetic iron black, titanium oxide, iron tetroxide, and other metal oxide powders, metal sulfide powders, or metal powders. Inorganic pigments are often used in combination with organic pigments to achieve a balance between chroma and brightness, while ensuring good coatability, sensitivity, and developability.

[0091] The coloring composition of the present invention may contain dyes within a range that does not reduce heat resistance.

[0092] <Adhesive Resins> The adhesive resin is one in which, when a film with a thickness of 2 μm is formed, the transmittance in the entire wavelength region of visible light (400 nm to 700 nm) is preferably 80% or more, more preferably 95% or more. Examples of resins include thermoplastic resins and photosensitive resins.

[0093] Examples of thermoplastic resins include: butadiene acetal resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resins, polyester resins, acrylic resins, alkyd resins, polystyrene, polyamide resins, rubber resins, cyclized rubber resins, cellulose resins, polyethylene, polybutadiene, or polyimide resins, etc. In addition, thermosetting resins include, for example, epoxy resins, benzoguanamine resins, rosin-modified maleic acid resins, rosin-modified fumaric acid resins, melamine resins, urea resins, or phenolic resins.

[0094] Regarding photosensitive resins, a preferred example is a resin in which a (meth)acrylic acid compound or cinnamic acid having reactive substituents such as isocyanate groups, aldehyde groups, or epoxy groups is reacted with a polymer having reactive substituents such as hydroxyl groups, carboxyl groups, or amine groups, thereby introducing photocrosslinking groups such as (meth)acrylic acid groups or styrene groups into the polymer. Alternatively, a resin obtained by half-esterifying a polymer containing anhydride, such as a styrene-maleic anhydride copolymer or an α-olefin-maleic anhydride copolymer, with a (meth)acrylic acid compound having hydroxyl groups, such as a hydroxyl alkyl methacrylate, is also preferred.

[0095] Furthermore, when using the coloring composition of the present invention and forming a filter segment by alkaline development, it is preferable to contain an alkali-soluble non-photosensitive resin. An alkali-soluble non-photosensitive resin refers to a resin that dissolves in an alkaline aqueous solution without cross-linking by free radicals. Examples include resins having an average molecular weight of 1,000 to 500,000, preferably 5,000 to 100,000, with acidic functional groups such as carboxyl and urethane groups. Specific examples of alkali-soluble non-photosensitive resins include: acrylic resins having acidic functional groups, α-olefin / maleic anhydride copolymers, styrene / maleic anhydride copolymers, styrene / styrene sulfonic acid copolymers, ethylene / (meth)acrylic acid copolymers, or isobutylene / maleic anhydride copolymers, etc. Among them, at least one resin selected from the group consisting of acrylic resin having acidic functional groups, α-olefin / maleic acid (anhydride) copolymer, styrene / maleic acid (anhydride) copolymer, and styrene / styrene sulfonic acid copolymer, especially acrylic resin having acidic functional groups, is preferred due to its high heat resistance and transparency.

[0096] The photosensitive coloring composition of the present invention preferably comprises a coloring composition, a photopolymerizable compound, and a photopolymerization initiator. The coloring composition and the photosensitive coloring composition are preferably intended for use in color filters.

[0097] <Photopolymerizable compounds> Photopolymerizable compounds are monomers and oligomers with polymerizable unsaturated groups. Examples of polymerizable unsaturated groups include vinyl, (meth)acryl, and (meth)allyl.

[0098] Examples of photopolymerizable compounds include: methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, isoamyl methacrylate, octyl methacrylate, isooctyl methacrylate, 2-ethylhexyl methacrylate, cetyl methacrylate, decyl methacrylate, isodecyl methacrylate, lauryl methacrylate, tridecyl methacrylate, isomyryl methacrylate, stearyl methacrylate, or isostearyl methacrylate, etc., which are straight-chain or branched alkyl (meth)acrylates. Cyclohexyl methacrylate, tert-butylcyclohexyl methacrylate, dicyclopentyl methacrylate, dicyclopentyloxyethyl methacrylate, dicyclopentenyl methacrylate, dicyclopentenyloxyethyl methacrylate, or isobornyl methacrylate and other cyclic alkyl (meth)acrylates; (Meth)acrylate trifluoroethyl acrylate, (meth)acrylate octafluoropentyl acrylate, (meth)acrylate perfluorooctyl ethyl acrylate, or (meth)acrylate tetrafluoropropyl acrylate, etc., are all fluoroalkyl esters of (meth)acrylate; (Meth)acrylic acid-modified polydimethylsiloxane (silicone macromonomer); (Meth)acrylates such as tetrahydrofurfuryl methacrylate or 3-methyl-3-oxetane butyl methacrylate, which contain heterocyclic (meth)acrylates; (Meth)acrylates containing aromatic rings include benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxy polyethylene glycol (meth)acrylate, p-cumylphenoxyethyl (meth)acrylate, p-cumylphenoxy polyethylene glycol (meth)acrylate, or nonylphenoxy polyethylene glycol (meth)acrylate; 2-Methoxyethyl (meth)acrylate, 2-Ethoxyethyl (meth)acrylate, 3-Methoxybutyl (meth)acrylate, 2-Methoxypropyl (meth)acrylate, diethylene glycol monomethyl ether (meth)acrylate, diethylene glycol monoethyl ether (meth)acrylate, triethylene glycol monomethyl ether (meth)acrylate, triethylene glycol monoethyl ether (meth)acrylate, diethylene glycol mono-2-ethylhexyl ether (meth)acrylate, dipropylene glycol monomethyl ether (meth)acrylate, tripropylene glycol mono(meth)acrylate, polyethylene glycol monolauryl ether (meth)acrylate, or polyethylene glycol monomethyl ether (meth)acrylate, or polyethylene glycol monomethyl ether (meth)acrylate. Alcohol monostearyl ether (meth)acrylates and other (poly)alkyl glycol monoalkyl ether (meth)acrylates; (meth)acrylic acid, acrylic acid dimers, 2-(meth)acrylic acid oxyethyl phthalate, 2-(meth)acrylic acid oxypropyl phthalate, 2-(meth)acrylic acid oxyethyl hexahydrophthalate, 2-(meth)acrylic acid oxypropyl hexahydrophthalate, ethylene oxide modified succinic acid (meth)acrylate, β-carboxyethyl (meth)acrylate, or ω-carboxylated polycaprolactone (meth)acrylate and other (meth)acrylates with carboxyl groups; 2-Hydroxyethyl (meth)acrylate, 2-Hydroxypropyl (meth)acrylate, 2-Hydroxybutyl (meth)acrylate, 4-Hydroxybutyl (meth)acrylate, 2-Acryloyloxyethyl-2-hydroxyethyl (meth)acrylate, diethylene glycol mono(meth)acrylate, dipropylene glycol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate, propylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, polytetramethylene glycol mono(meth)acrylate, poly(ethylene glycol-propylene glycol) mono(meth)acrylate, poly(ethylene glycol-tetramethylene glycol) mono(meth)acrylate, poly(propylene glycol-tetramethylene glycol) mono(meth)acrylate, or glycerol (meth)acrylate and other hydroxyl-containing (meth)acrylates; Ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, poly(ethylene glycol-propylene glycol) di(meth)acrylate, poly(ethylene glycol-tetramethylene glycol) di(meth)acrylate, poly(propylene glycol-tetramethylene glycol) di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, or 2-butyl-propylene glycol di(meth)acrylate, etc. (poly)alkylene glycol di(meth)acrylates; Dimethyloldicyclopentane di(meth)acrylate, neopentyl glycol di(meth)acrylate with trimethylolpropene acetate, stearic acid-modified pentaerythritol di(meth)acrylate, ethylene oxide-modified bisphenol A di(meth)acrylate, propylene oxide-modified bisphenol A di(meth)acrylate, tetrahydrofuran-modified bisphenol A di(meth)acrylate, ethylene oxide-modified bisphenol F di(meth)acrylate, propylene oxide-modified bisphenol F di(meth)acrylate, tetrahydrofuran-modified bisphenol F di(meth)acrylate, zinc diacrylate, ethylene oxide-modified triacrylate phosphate, or glycerol di(meth)acrylate, etc., are all di(meth)acrylates. (Meth)acrylates containing tertiary amino groups include dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, or diethylaminopropyl (meth)acrylate. Glycerol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, or dipentaerythritol hexa(meth)acrylate, etc., are all trifunctional or higher-functional (meth)acrylates. Glycerol triglycidyl ether-(meth)acrylic acid adduct, glycerol diglycidyl ether-(meth)acrylic acid adduct, polyglycerol polyglycidyl ether-(meth)acrylic acid adduct, 1,6-butanediol diglycidyl ether, alkyl glycidyl ether-(meth)acrylic acid adduct, allyl glycidyl ether-(meth)acrylic acid adduct, phenyl glycidyl ether-(meth)acrylic acid adduct, styrene oxide-(meth)acrylic acid adduct, bisphenol A diglycidyl ether-(meth)acrylic acid adduct, propylene oxide modified bisphenol A diglycidyl ether-(meth)acrylic acid adduct, bisphenol F diglycidyl ether-(meth)acrylic acid adduct. Acrylic acid adducts, epichlorohydrin-modified phthalic acid-(meth)acrylic acid adducts, epichlorohydrin-modified hexahydrophthalic acid-(meth)acrylic acid adducts, ethylene glycol diglycidyl ether-(meth)acrylic acid adducts, polyethylene glycol diglycidyl ether-(meth)acrylic acid adducts, propylene glycol diglycidyl ether-(meth)acrylic acid adducts, polypropylene glycol diglycidyl ether-(meth)acrylic acid adducts, phenolic varnish-type epoxy resin-(meth)acrylic acid adducts, cresolic varnish-type epoxy resin-(meth)acrylic acid adducts, or other epoxy resin-(meth)acrylic acid adducts and other epoxy (meth)acrylic acid esters; (Meth)acrylic acid-modified isocyanurate, (meth)acrylic acid-modified polyurethane, (meth)acrylic acid-modified polyester, (meth)acrylic acid-modified melamine, (meth)acrylic acid-modified silicone, (meth)acrylic acid-modified polybutadiene, or (meth)acrylic acid-modified rosin, etc. (meth)acrylic acid-modified resin oligomers; Vinyl compounds such as styrene, α-methylstyrene, vinyl acetate, vinyl (meth)acrylate, or allyl (meth)acrylate; Vinyl ethers such as hydroxyethyl vinyl ether, ethylene glycol divinyl ether, or pentaerythritol trivinyl ether; Acrylamides such as (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, or N-vinylmethacrylamide; or acrylonitrile, etc. Photopolymerizable compounds can be used alone or in combination of two or more.

[0099] <Photopolymerization initiator> Examples of photopolymerization initiators include: 4-phenoxydichloroacetophenone, 4-tert-butyl-dichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butane-1-one, or 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinylpropane-1-one, etc., all of which are acetophenone-based photopolymerization initiators. Benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzoin dimethyl ketal, etc., are benzoin-based photopolymerization initiators. Benzophenone, benzoic acid, methyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, or 4-benzoyl-4'-methyldiphenyl sulfide and other benzophenone-based photopolymerization initiators; Thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, or 2,4-diisopropylthioxanthone are all thioxanthone-based photopolymerization initiators; Triazine-based photopolymerization initiators include 2,4,6-trichloro-triazine, 2-phenyl-4,6-bis(trichloromethyl)-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-triazine, 2-piperyl-4,6-bis(trichloromethyl)-triazine, 2,4-bis(trichloromethyl)-6-styryl-triazine, 2-(naphtho-1-yl)-4,6-bis(trichloromethyl)-triazine, 2-(4-methoxy-naphtho-1-yl)-4,6-bis(trichloromethyl)-triazine, 2,4-trichloromethyl-(piperyl)-6-triazine, or 2,4-trichloromethyl(4'-methoxystyryl)-6-triazine; Borate-based photopolymerization initiators; Carbazole-based photopolymerization initiators; Imidazole-based photopolymerization initiators, etc. Photopolymerization initiators can be used alone or in combination of two or more.

[0100] The content of the photopolymerization initiator relative to 100 parts by weight of the pigment is preferably 5 to 200 parts by weight, more preferably 10 to 150 parts by weight.

[0101] Photosensitive coloring compositions can combine photopolymerization initiators and sensitizers. This improves photoreactivity. Examples of sensitizers include: α-acetylated esters, acetylated phosphine oxides, methyl phenyl glyoxylate, benzodiazepine, 9,10-phenanthroquinone, camphorquinone, ethyl anthraquinone, 4,4'-diethyl isophthalophenone, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, or 4,4'-diethylaminobenzophenone, etc.

[0102] The content of the sensitizer is preferably 0.1 to 60 parts by weight relative to 100 parts by weight of the photopolymerization initiator.

[0103] Solvent To adjust viscosity and other properties, the coloring composition or photosensitive coloring composition of the present invention may contain a solvent.

[0104] Solvents such as: 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butanediol diacetate, 1,4-dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutylacetate, 3-methoxybutanol, 3-methoxybutylacetate, 4-heptanone, m-xylene, m-diethyl Benzene, m-dichlorobenzene, N,N-dimethylacetamide, N,N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, N-methylpyrrolidone, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotert-butyl ether, ethylene glycol monobutyl ether, ethylene glycol... Ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol... Alcohol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methyl cyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, or diesters, etc. Solvents can be used alone or in mixtures of two or more.

[0105] For the coloring composition of the present invention, the coloring composition is prepared by dispersion treatment using pigments, polyester dispersants, and solvents, for example. When the pigment is an organic pigment, if a dispersing aid such as a pigment derivative is used during the dispersion treatment, the organic pigment can be dispersed more finely. Furthermore, when the pigment has high solubility in the solvent, dispersion treatment is sometimes unnecessary. When using two or more pigments, the coloring composition can be prepared separately for each pigment and then mixed. Alternatively, multiple pigments can be used to prepare the coloring composition together. Next, photopolymerizable compounds and photopolymerization initiators are formulated into and mixed with the coloring composition to obtain a photosensitive coloring composition. Furthermore, the timing of formulating each material is, of course, arbitrary.

[0106] The dispersion process may use dispersion devices such as kneaders, two-rod roll mills, three-rod roll mills, ball mills, horizontal sand mills, vertical sand mills, annular type bead mills, or atritors.

[0107] After preparing the coloring composition and the photosensitive coloring composition, it is preferable to remove coarse particles of 5 μm or larger, preferably coarse particles of 1 μm or larger, and even more preferably coarse particles of 0.5 μm or larger, as well as mixed dust, by means of centrifugation, sintering filter, membrane filter, etc.

[0108] <Other Dispersants> In this specification, in addition to using polyester dispersants, other dispersants may also be used. Other dispersants include resin-based dispersants other than polyester dispersants, surfactants, etc.

[0109] Examples of resin-type dispersants other than polyester dispersants include: styrene-maleic anhydride copolymers, olefin-maleic anhydride copolymers, poly(meth)acrylates, styrene-(meth)acrylate copolymers, (meth)acrylate-(meth)acrylate alkyl ester copolymers, (meth)acrylate-polyvinyl macromonomer copolymers, acrylic resins containing phosphate ester groups, acrylic resins containing aromatic carboxyl groups, polystyrene sulfonates, acrylamide-(meth)acrylate copolymers, carboxymethyl cellulose, polyurethane esters containing carboxyl groups, formalin condensates of naphthalene sulfonates, or anionic resin-type pigment dispersants such as sodium alginate; Nonionic resin-based pigment dispersants such as polyvinyl alcohol, polyalkylene polyamine, polyacrylamide, or polymer starch; or Cationic resin-type pigment dispersants such as polyethyleneimine, (meth)acrylate aminoalkyl ester copolymer, polyvinyl imidazoline, amino-containing polyurethane, reaction products of poly(lower alkylimine) and polyesters with free carboxyl groups, or chitosan.

[0110] Commercially available resin-based dispersants include: BYK Chemie (Japan). Disperbyk (Japan) Co., Ltd. manufactures the following products: 101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150, 2155, Anti-Terra-U, 203, 204, BYK-P104, P104S, 220S, 6919, and Lactimon. Lactimon-WS or Bykumen, etc., and SOLSPERSE series manufactured by Lubrizol Corporation of Japan, including models 3000, 9000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500, etc., and BASF of Japan. The following models are manufactured by Japan: EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, and 450. Models 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc., and Ajisper-PA111, PB711, PB821, PB822, PB824, etc., manufactured by Ajinomoto Precision Technology Co., Ltd.

[0111] Examples of surfactants include: polyoxyethylene alkyl ether sulfates, sodium dodecylbenzene sulfonate, alkali salts of styrene-acrylic acid copolymers, sodium alkylnaphthalene sulfonate, sodium alkyl diphenyl ether disulfonate, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymers, or anionic surfactants such as polyoxyethylene alkyl ether phosphates; Nonionic surfactants such as polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate, polyoxyethylene sorbitan monostearate, or polyethylene glycol monolaurate; Cationic surfactants such as alkyl quaternary ammonium salts or their ethylene oxide adducts; or Alkyl betaine and other alkyl betaine, or alkyl imidazoline and other amphoteric surfactants. Other dispersants can be used alone or in combination of two or more.

[0112] The amount of other dispersants used is preferably 0.1 to 40 parts by mass relative to 100 parts by mass of pigment, more preferably 0.1 to 30 parts by mass. When the amount of other dispersants is less than 0.1% by mass, it is difficult to obtain the desired effect. When the amount is more than 40% by mass, the dispersion may be affected by the excess dispersant.

[0113] <Pigment Derivatives> To improve the dispersibility of pigments, pigment derivatives may be used in coloring compositions as needed. Pigment derivatives are compounds that contain acidic, basic, or neutral groups in the organic pigment residues. Examples of pigment derivatives include: compounds with acidic substituents such as sulfonyl, carboxyl, or phosphate groups (hereinafter referred to as acidic derivatives), and their amine salts; compounds with basic substituents such as sulfonamide groups or tertiary amino groups at the end (hereinafter referred to as basic derivatives); and compounds with neutral substituents such as phenyl or phthalimide alkyl groups. Examples of organic pigments include: diketopyrrole-based pigments, anthraquinone-based pigments, quinacridone-based pigments, dioxazine-based pigments, violet ketone-based pigments, perylene-based pigments, thiazine-indigo-based pigments, triazine-based pigments, benzimidazolone-based pigments, benzidisoindole and other indole-based pigments, isoindoline-based pigments, isoindolineone-based pigments, quinoline ketone-based pigments, naphthol-based pigments, reduction-based pigments, metal complex-based pigments, azo, diazo, polyazo and other azo-based pigments, etc. Among these, basic derivatives are preferred.

[0114] In the coloring composition of the present invention, the amount of the basic derivative is based on the mass of the pigment, preferably 1 to 50 parts by mass, more preferably 3 to 30 parts by mass, and even more preferably 5 to 25 parts by mass. When the amount of the pigment derivative having a basic group is 1% or more by mass, the effect of addition can be obtained, and the pigment dispersibility is improved. When it is 50% or less by mass, it is less likely to have an adverse effect on heat resistance and lightfastness.

[0115] Specific examples of pigment derivatives having basic groups used in this invention are assigned compound numbers and shown below, but are not limited to these.

[0116] Compound 1 General formula (27): [Chemistry 11]

[0117] Compound 2 General formula (28): [Chemistry 12]

[0118] Compound 3 General formula (29): [Chemistry 13]

[0119] Compound 4 General formula (30): [Chemistry 14]

[0120] Compound 5 General formula (31): [Chemistry 15]

[0121] <Storage Stabilizer> The coloring composition of the present invention may contain a storage stabilizer to stabilize the viscosity of the coloring composition over time.

[0122] Storage stabilizers, for example, include quaternary ammonium chloride such as benzyltrimethylammonium chloride or diethylhydroxyamine hydrochloride; Organic acids such as lactic acid or oxalic acid; The methyl ester of the organic acid; tert-butylcatechol and other catechols; Organophosphines such as tetraethylphosphine or tetraphenylphosphine; phosphites, etc.

[0123] <Color Filter> Next, the color filter of the present invention will be described.

[0124] The color filter of the present invention includes filter segments or a black matrix formed by the coloring composition of the color filter of the present invention on a transparent substrate. A typical color filter includes at least one red filter segment, at least one green filter segment, and at least one blue filter segment. Alternatively, it may include at least one magenta filter segment, at least one cyan filter segment, and at least one yellow filter segment.

[0125] The color filter of the present invention can be manufactured by forming various colored filter segments on a substrate using photolithography with the coloring composition of the present invention. Examples of substrates include glass plates with high transmittance for visible light, or resin plates such as polycarbonate, polymethyl methacrylate, and polyethylene terephthalate.

[0126] The formation of each color filter segment using photolithography is carried out by the following method. The color filter composition is coated onto a transparent substrate such as glass using coating methods such as spray coating, spin coating, slot coating, or roller coating, with a dried film thickness of 0.2 μm to 10 μm, more preferably 0.2 μm to 5 μm. When drying the coated film, a vacuum dryer, convection oven, infrared ray (IR) oven, or heated plate can be used. For films that need to be dried as required, ultraviolet light exposure is performed via a screen with a predetermined pattern, positioned in contact or non-contact with the film. Then, the uncured portions are removed by immersion in a solvent or alkaline developer, or by spraying the developer using a sprayer, thereby forming the desired pattern and manufacturing the color filter.

[0127] Furthermore, heating can be applied as needed to promote the polymerization of the coloring components used in the color filter. If photolithography is used, color filters with higher precision than those produced by printing can be manufactured.

[0128] During development, aqueous solutions of sodium carbonate, sodium hydroxide, etc., can be used as alkaline developing solutions. Alternatively, organic bases such as dimethylbenzylamine and triethanolamine can also be used. Additionally, defoamers or surfactants can be added to the developing solution.

[0129] If a black matrix is ​​pre-formed before forming the color filter segments on the transparent or reflective substrate, the contrast of the liquid crystal display panel can be further improved. As the black matrix, a multilayer film of chromium or chromium / chromium oxide, an inorganic film such as titanium nitride, or a resin film with dispersed light-blocking agents can also be used. Alternatively, a thin film transistor (TFT) can be pre-formed on the transparent or reflective substrate, and then the filter segments can be formed. By forming the filter segments on the TFT substrate, the aperture ratio of the liquid crystal display panel can be increased, thereby improving the brightness.

[0130] On the color filter of the present invention, an overcoat film, columnar spacers, transparent conductive film, liquid crystal alignment film, etc., may be formed as needed.

[0131] A color filter is bonded to an opposing substrate using a sealant. Liquid crystal is injected through an injection port located in the sealing part. The injection port is then sealed. If necessary, a polarizing film or a phase retardation film is bonded to the outside of the substrate, thereby manufacturing a liquid crystal display panel.

[0132] The liquid crystal display panel can be used for liquid crystal display modes that use color filters for colorization, such as twisted nematic (TN), super twisted nematic (STN), in-plane switching (IPS), vertical alignment (VA), and optically compensated bend (OCB).

[0133] <Solid-state photographic elements> The solid-state imaging element of the present invention includes the color filter of the present invention. The structure of the solid-state imaging element of the present invention is not particularly limited to the structure including the color filter for the solid-state imaging element of the present invention; for example, the following structures can be listed. The structure is as follows: a substrate has multiple photodiodes constituting the light-receiving region of a solid-state photographic element (charge-coupled device (CCD) sensor, complementary metal oxide semiconductor (CMOS) sensor, organic CMOS sensor, etc.) and a transmission electrode containing polysilicon, etc. The photodiodes and the transmission electrodes have a light-shielding film containing tungsten, etc., which opens only to the light-receiving portion of the photodiodes. The light-shielding film has a device protective film containing silicon nitride, etc., formed in such a way that it covers the entire surface of the light-shielding film and the light-receiving portion of the photodiodes. The solid-state photographic element color filter of the present invention is on the device protective film. Furthermore, the structure may have a light-gathering unit (e.g., a microlens; the same applies below) on the protective layer of the device and below the color filter (on the side closer to the substrate), or a structure with a light-gathering unit on the color filter, etc. Furthermore, the organic CMOS sensor is composed of a panchromatic photosensitive organic photoconversion film, which serves as a photoconversion layer, and a CMOS signal readout substrate. It is a hybrid structure with two layers, in which organic materials capture light and convert it into electrical signals, and inorganic materials extract the electrical signals to the outside. In principle, the aperture ratio can be 100% relative to the incident light. Since organic photoelectric conversion films are structurally free continuous films that can be laid on CMOS signal readout substrates, they do not require expensive microfabrication processes and are suitable for miniaturizing filter segments. There are no particular restrictions on the configuration of the color filter segments; well-known methods can be used. [Example]

[0134] The present invention will now be described based on embodiments, but the invention is not limited to these embodiments. Furthermore, "parts" refers to "parts by mass", and "%" refers to "% by mass".

[0135] (Weight-average molecular weight of the resin (Mw)) The weight-average molecular weight (Mw) of the resin was determined using a gel permeation chromatograph (GPC) (Tosoh HLC-8120GPC) with a TSK gel column (manufactured by Tosoh Corporation) and equipped with a refractive index (RI) detector, and tetrahydrofuran (THF) as the developing solvent. This was the weight-average molecular weight (Mw) of polystyrene.

[0136] (Acid value of the resin) To a resin solution of 0.5 to 1.0 parts, add 80 ml of acetone and 10 ml of water and stir until homogeneous. Use a 0.1 mol / L potassium hydroxide (KOH) aqueous solution as the titrant and perform titration using an automatic titration apparatus ("COM-555", manufactured by Hiranuma Sangyo Co., Ltd.) to determine the acid value of the resin solution. Furthermore, calculate the acid value per unit of non-volatile component of the resin based on the acid value and the concentration of non-volatile components in the resin solution.

[0137] The acid value (mgKOH / g) is calculated using the following formula, which is the value of the dispersant in its dry state. Acid value (mgKOH / g) = {(5.611×α×F) / S} / (concentration of non-volatile components / 100) Where S: sample collection amount (g) α: Consumption volume (ml) of 0.1 mol / L potassium hydroxide-ethanol solution F: Potency of 0.1 mol / L potassium hydroxide-ethanol solution

[0138] (The non-volatile components of the resin) As a condition for determining the non-volatile components of the resin, the sample mass was approximately 1 gram, and the drying conditions were set at 200°C for 10 minutes.

[0139] (Example of manufacturing dispersant X1) In a reaction vessel including a gas inlet tube, thermometer, condenser, and stirrer, 50.0 parts of tert-butyl acrylate, 50.0 parts of methyl methacrylate, and 25.0 parts of propylene glycol monomethyl ether acetate were added, and the mixture was purged with nitrogen gas. The reaction vessel was heated to 50°C, and 6.0 parts of 3-mercapto-1,2-propanediol were added. The temperature was then raised to 90°C, and a solution prepared by dissolving 0.1 parts of 2,2'-azobisisobutyronitrile in 45.7 parts of propylene glycol monomethyl ether acetate was added. The reaction was allowed to proceed for 10 hours. Determination of non-volatile components confirmed that 95% of the reaction had occurred. Next, 14.5 parts of pyromellitic dianhydride (manufactured by Daicel Chemical Industries, Ltd.), 38.0 parts of PGMAc, and 0.2 parts of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were added, and the reaction was carried out at 120°C for 5 hours. Then, 12.1 g of 3-methoxybutanol was added, and the reaction was carried out at 120°C for 3 hours. The reaction was terminated after confirming that more than 98% of the anhydride had undergone half-esterification by measuring the acid value. After the reaction was completed, propylene glycol monomethyl ether acetate was added at a non-volatile content of 50% by mass to prepare a dispersant X1 solution with an acid value of 95 mgKOH / g and a weight average molecular weight of 9500.

[0140] (Manufacturing examples of dispersants X2 to X14, and comparative dispersants Y1 to Y3) Except for the raw materials and loading amounts listed in Table 1, the same synthesis was carried out as in the manufacturing example of dispersant X1 to obtain solutions of dispersant X2 to dispersant X14 and comparative dispersant Y1 to comparative dispersant Y3.

[0141] [Table 1-1] Table 1-1 dispersant X1 X2 X3 X4 X5 X6 X7 X8 X9 X10 monomer t-BA 50 50 20 10 90 50 50 50 50 t-BMA 50 MMA 50 50 45 45 90 10 50 50 50 50 EA 30 MAA 5 5 2-MTA Compounds having two or more hydroxyl groups Thiopropyltriol 6 6 6 6 6 6 6 6 6 6 Polymerization initiator AIBN 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 reaction solvent PGMAc 70.7 70.7 70.7 70.7 70.7 70.7 70.7 70.7 70.7 70.7 total 176.8 176.8 176.8 176.8 176.8 176.8 176.8 176.8 176.8 176.8 Aromatic compounds having two or more anhydride groups PMA 14.5 14.5 14.5 14.5 14.5 14.5 14.5 14.5 14.5 10.9 reaction catalyst DBU 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 reaction solvent PGMAc 38.0 38.0 38.0 38.0 38.0 38.0 38.0 38.0 38.0 34.7 3MB 12.1 12.1 12.1 12.1 12.1 12.1 6.0 11.7 PGME 12.1 DAA 12.1 water 6.0 total 241.6 241.6 241.6 241.6 241.6 241.6 241.6 241.6 241.6 234.4 Weight average molecular weight 9500 9300 9000 9400 9700 9500 9700 9200 8800 10100 Acid value (mgKOH / g) 95 98 110 105 93 95 97 98 100 85 Anhydride / OH equivalent ratio 1.20 1.20 1.20 1.20 1.20 1.20 1.20 1.20 1.20 0.90 [Table 1-2] Table 1-2 dispersant Comparison of dispersants X11 X12 X13 X14 Y1 Y2 Y3 monomer t-BA 50 50 50 20 50 50 50 t-BMA MMA 50 50 50 45 50 50 50 EA MAA 5 2-MTA 30 Compounds having two or more hydroxyl groups Thiopropyltriol 6 2 9 6 6 6 6 Polymerization initiator AIBN 0.1 0.1 0.1 0.1 0.1 0.1 0.1 reaction solvent PGMAc 70.7 68.1 72.7 70.7 70.7 70.7 70.7 total 176.8 170.2 181.8 176.8 176.8 176.8 176.8 Aromatic compounds having two or more anhydride groups PMA 18.1 4.8 21.8 14.5 6.0 21.8 14.5 reaction catalyst DBU 0.2 0.2 0.2 0.2 0.2 0.2 0.2 reaction solvent PGMAc 41.3 28.4 45.2 38.0 41.6 44.5 50.1 3MB 12.4 10.7 13.1 12.1 12.8 PGME DAA water total 248.9 214.3 262.1 241.6 224.7 256.1 241.6 Weight average molecular weight 8000 24000 7200 9000 6800 7400 9500 Acid value (mgKOH / g) 130 55 132 108 55 160 95 Anhydride / OH equivalent ratio 1.50 1.20 1.20 1.20 0.50 1.80 1.20

[0142] (Example of manufacturing dispersant X15) In a reaction vessel including a gas inlet pipe, thermometer, condenser, and stirrer, 6 parts of 3-mercapto-1,2-propanediol, 14.5 parts of PMA, and 70.8 parts of propylene glycol monomethyl ether acetate were added, and the mixture was purged with nitrogen gas. The reaction vessel was heated to 100°C and reacted for 5 hours. Then, 12.1 g of 3-methoxybutanol was added, and the reaction was carried out at 120°C for 3 hours. After confirming that more than 98% of the anhydride had undergone half-esterification by acid value determination, the system was cooled to 70°C, and 50.0 parts of tert-butyl acrylate and 50.0 parts of methyl methacrylate were added, along with 38.0 parts of propylene glycol monomethyl ether acetate containing 0.1 parts of 2,2'-azobisisobutyronitrile. The reaction was carried out for 10 hours. The reaction was terminated when the polymerization was confirmed to be 95% complete by non-volatile component determination. After the reaction was completed, propylene glycol monomethyl ether acetate was added in a manner with 50% by mass of non-volatile components to prepare a solution of dispersant X15 with an acid value of 93 mgKOH / g and a weight average molecular weight of 10800.

[0143] (Example of manufacturing dispersant X16) Except for the raw materials and loading amounts listed in Table 2, the same synthesis as the manufacturing example of dispersant X15 was carried out to obtain a solution of dispersant X16.

[0144] [Table 2] Table 2 dispersant X15 X16 Compounds having two or more hydroxyl groups Thiopropyltriol 6 6 Aromatic compounds having two or more anhydride groups PMA 14.5 10.9 reaction catalyst DBU 0.2 0.2 reaction solvent PGMAc 70.8 56.6 3MB 12.1 11.7 total 91.5 73.7 monomer t-BA 50 50 t-BMA MMA 50 50 EA MAA n-BA i-BA Polymerization initiator AIBN 0.1 0.1 reaction solvent PGMAc 38.0 48.8 total 241.6 234.4 Weight average molecular weight 10800 10000 Acid value (mgKOH / g) 93 82 Anhydride / OH equivalent ratio 1.20 0.90

[0145] The following lists the materials used in the table. [Ethylene-unsaturated monomers] ·t-BA: tert-butyl acrylate ·t-BMA: tert-butyl methacrylate MMA: Methyl methacrylate ·EA: Ethyl acrylate MAA: Methacrylic acid

[0146] [Compounds containing two hydroxyl groups and one thiol group] ·Thiopropanetriol: 3-mercapto-1,2-propanediol

[0147] [Free radical polymerization initiator] AIBN: 2,2'-Azobisisobutyronitrile

[0148] [Organic solvents] PGMAC: Propylene Glycol Monomethyl Ether Acetate ·3MB: 3-Methoxybutanol ·PGME: Propylene Glycol Monomethyl Ether ·DAA: Diacetone alcohol [Tetracarboxylic acid dianhydride] • PMA: Pyromellitic dianhydride (manufactured by Daicel Chemical Industries)

[0149] [Esterification catalyst] • DBU: 1,8-diazabicyclo-[5.4.0]-7-undecene (manufactured by San-Apro)

[0150] <Manufacturing Method of Adhesive Resin> (Preparation of acrylic resin solution 1) 70.0 parts of propylene glycol monomethyl ether acetate were added to a reaction vessel equipped with a thermometer, cooling pipe, nitrogen gas inlet pipe, and stirrer in a separable four-necked flask. The mixture was heated to 80°C, and after purging the reaction vessel with nitrogen, a mixture of 13.3 parts of n-butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 4.3 parts of methacrylic acid, 7.4 parts of p-cumylphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toa Synthetic Co., Ltd.), and 0.4 parts of 2,2'-azobisisobutyronitrile was added dropwise over a period of 2 hours. After the addition was completed, the reaction was continued for another 3 hours to obtain a solution of acrylic resin with a weight average molecular weight (Mw) of 26,000. After cooling to room temperature, take about 2 g of the resin solution, heat and dry it at 180°C for 20 minutes, and determine the non-volatile components. Add propylene glycol monoethyl ether acetate to make the non-volatile components 20% by mass, thereby preparing acrylic resin solution 1.

[0151] <Methods for manufacturing pigment dispersions> (Example of manufacturing pigment dispersion 1) After the following mixture was stirred and mixed in a uniform manner, it was dispersed for 3 hours using 0.5 mm diameter zirconia beads in an Eiger mill (Mini model M-250 MKII manufactured by Eiger Japan) and then filtered using a 5.0 μm pore size filter to prepare pigment dispersion 1 with 20% by mass of non-volatile components. PR254 (CI Pigment Red 254, Irgaphor Red B-CF manufactured by BASF Japan): 15.2 parts Basic derivative 1:0.8 parts Dispersant X1: 8.0 parts Propylene glycol monomethyl ether acetate (PGMAc): 60.0 parts 3-Methoxybutanol (3MB): 16.0 parts

[0152] (Examples of manufacturing pigment dispersions 2 to 26) Except for using the raw materials and loading amounts listed in Table 3, the process was carried out in the same manner as the manufacturing example of pigment dispersion 1 to obtain pigment dispersion 2 to pigment dispersion 26.

[0153] Basic derivative 1:

[0154] [Chemistry 16]

[0155] Basic derivative 2:

[0156] [Chemistry 17]

[0157] Basic derivative 3:

[0158] [Chemistry 18]

[0159] [Table 3] Table 3 dispersant pigment Basic derivatives solvent type Mixing amount type Mixing amount type Mixing amount type Mixing amount Pigment Dispersion 1 X1 8 PR254 15.2 Basic derivative 1 0.8 PGMAc 76 Pigment dispersion 2 X2 8 PR254 15.2 Basic derivative 1 0.8 PGMAc 76 Pigment dispersion 3 X3 8 PR254 15.2 Basic derivative 1 0.8 PGMAc 76 Pigment dispersion 4 X4 8 PR254 15.2 Basic derivative 1 0.8 PGMAc 76 Pigment dispersion 5 X5 8 PR254 15.2 Basic derivative 1 0.8 PGMAc 76 Pigment dispersion 6 X6 8 PR254 15.2 Basic derivative 1 0.8 PGMAc 76 Pigment Dispersion 7 X7 8 PR254 15.2 Basic derivative 1 0.8 PGMAc 76 Pigment dispersion 8 X8 8 PR254 15.2 Basic derivative 1 0.8 PGMAc 76 Pigment Dispersion 9 X9 8 PR254 15.2 Basic derivative 1 0.8 PGMAc 76 Pigment dispersion 10 X10 8 PR254 15.2 Basic derivative 1 0.8 PGMAc 76 Pigment dispersion 11 X11 8 PR254 15.2 Basic derivative 1 0.8 PGMAc 76 Pigment dispersion 12 X12 8 PR254 15.2 Basic derivative 1 0.8 PGMAc 76 Pigment dispersion 13 X13 8 PR254 15.2 Basic derivative 1 0.8 PGMAc 76 Pigment dispersion 14 X14 8 PR254 15.2 Basic derivative 1 0.8 PGMAc 76 Pigment dispersion 15 X15 8 PR254 15.2 Basic derivative 1 0.8 PGMAc 76 Pigment dispersion 16 X16 8 PR254 15.2 Basic derivative 1 0.8 PGMAc 76 Pigment dispersion 17 X1 8 PB15:6 15.2 Basic derivative 2 0.8 PGMAc 76 Pigment dispersion 18 X1 8 PG36 15.2 Basic derivative 2 0.8 PGMAc 76 Pigment dispersion 19 X1 8 PY138 15.2 Basic derivative 3 0.8 PGMAc 76 Pigment dispersion 20 X1 8 PR177 15.2 Basic derivative 1 0.8 PGMAc 76 Pigment dispersion 21 Y1 8 PR254 15.2 Basic derivative 1 0.8 PGMAc 76 Pigment dispersion 22 Y2 8 PR254 15.2 Basic derivative 1 0.8 PGMAc 76 Pigment dispersion 23 Y3 8 PR254 15.2 Basic derivative 1 0.8 PGMAc 76

[0160] [Example 1] (Photosensitive coloring component 1) The mixture of the following components was stirred and mixed in a homogeneous manner, and then filtered using a filter with a pore size of 1 μm to prepare photosensitive coloring composition 1. Pigment dispersion 1:50.0 parts Acrylic resin solution 1:7.5 parts Photopolymerizable compound (Aronix M-402 manufactured by Dong-A Synthetic Co., Ltd.): 2.0 parts Photopolymerization initiator (Omnirad 907, manufactured by IGM Resins): 1.2 parts Sensitizer (EAB-F, manufactured by Hodogaya Chemical Co., Ltd.): 0.3 parts Propylene glycol monomethyl ether acetate (PGMAc): 39.0 parts

[0161] [Photopolymerizable compounds] Aronix M-402: Dipentaerythritol pentaacrylate / Dipentaerythritol hexaacrylate (manufactured by Dong-A Synthetic Chemical Co., Ltd.)

[0162] [Photopolymerization initiator] Irgacure OXE02: Ethane-1-one, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl], 1-(O-acetylgoxime) (manufactured by BASF Japan)

[0163] [Sensitizer] • EAB-F: 4,4'-Bis(diethylamino)benzophenone (manufactured by Hodogaya Chemical Co., Ltd.)

[0164] [Examples 2-21, Comparative Examples 1-3] (Examples of manufacturing photosensitive coloring compositions 2 to 26) Except that the pigment dispersion described in Table 4 was used instead of the pigment dispersion 1 in Example 1, the same procedure as in the manufacturing example of photosensitive coloring composition 1 was followed to obtain photosensitive coloring composition 2 to photosensitive coloring composition 26.

[0165] (Viscosity stability) The viscosity stability of the obtained photosensitive coloring composition was evaluated using the following method. Using an E-type viscometer ("ELD type viscometer" manufactured by Toki Sangyo Co., Ltd.), the initial viscosity on the second day after preparation of the photosensitive coloring composition and the viscosity after one week of acceleration at 40°C were measured at 25°C and 50 rpm. Based on the initial viscosity and the viscosity over time, the rate of change of viscosity over time was calculated using the following formula, and viscosity stability was evaluated in three stages. [Percentage change in viscosity over time] = |([Initial viscosity] - [Viscosity over time]) / [Initial viscosity]| × 100 ○: Change rate less than 5% (good) △: The rate of change is 5% or more but less than 10% (practical). ×: Change rate is above 10% (unfavorable)

[0166] (Foreign Object Evaluation) The obtained photosensitive coloring composition was applied onto a glass substrate on which a black matrix had been previously formed by spin coating, and then dried in a clean oven at 70 °C for 20 minutes. Next, after cooling the substrate to room temperature, ultraviolet light exposure was performed using an ultra-high pressure mercury lamp through a photomask. Then, the substrate was spray-developed with a 0.2 mass% aqueous sodium carbonate solution at 23 °C for 30 seconds, and then washed and dried with ion-exchanged water. Further, a heat treatment was performed in a clean oven at 230 °C for 30 minutes to form a striped coloring pixel layer on the substrate. After the heat treatment of the produced coloring pixel layer at 230 °C, the film thickness was adjusted to 2.0 μm. Using the obtained substrate, the number of foreign matters in the coloring pixels was measured. The evaluation was performed by surface observation using a metal microscope "BX60" manufactured by Olympus System Corporation. The magnification was set to 500 times, and the number of foreign matters observable in any five fields of view during transmission was measured. ◎: The number of foreign matters is less than 3: Excellent ○: The number of foreign matters is 3 or more and less than 20: Good △: The number of foreign matters is 21 or more and less than 100: Practicable ×: The number of foreign matters is 100 or more: Poor

[0167] (Filterability) As an evaluation method for filterability, 60 g of the obtained photosensitive coloring composition was applied with a pressure of 0.05 MPa·s for a certain period of time using a 1.5 μm disk filter Titan 3 polytetrafluoroethylene filter (Titan3PTFEFILTER) manufactured by Tomsic Corporation, and the liquid volume passing through the filter during that time was evaluated. It can be said that the more the liquid volume, the more excellent the filterability. ○: The liquid volume passing through the filter is 45 g or more (Good) △: The liquid volume passing through the filter is 30 g or more and less than 45 g (Practicable) ×: The liquid volume passing through the filter is less than 30 g (Poor)

[0168] <PGMAc Re-dissolvability> The obtained photosensitive coloring composition was applied onto a glass substrate by spin coating, pre-baked at 100 °C for 3 minutes, and then the produced substrate was immersed in PGMAc, and the dissolution state was visually evaluated. ○: Dissolved (Good) ×: Peeled off (Poor)

[0169] [Table 4] Table 4 Photosensitive coloring composition Pigment dispersion viscosity stabilizer foreign body Filterability PGMAc Resolubility Pigment dispersion pigment dispersant Example 1 Photosensitive coloring composition 1 Pigment Dispersion 1 PR254 X1 ○ ◎ ○ ○ Example 2 Photosensitive coloring composition 2 Pigment dispersion 2 PR254 X2 ○ ○ ○ ○ Example 3 Photosensitive coloring composition 3 Pigment dispersion 3 PR254 X3 ○ ◎ ○ ○ Example 4 Photosensitive coloring composition 4 Pigment dispersion 4 PR254 X4 ○ ○ ○ ○ Example 5 Photosensitive coloring composition 5 Pigment dispersion 5 PR254 X5 △ ○ ○ ○ Example 6 Photosensitive coloring composition 6 Pigment dispersion 6 PR254 X6 ○ ○ ○ ○ Example 7 Photosensitive coloring composition 7 Pigment Dispersion 7 PR254 X7 ○ ○ ○ ○ Example 8 Photosensitive coloring composition 8 Pigment dispersion 8 PR254 X8 ○ ○ ○ ○ Example 9 Photosensitive coloring composition 9 Pigment Dispersion 9 PR254 X9 ○ ○ △ ○ Example 10 Photosensitive coloring composition 10 Pigment dispersion 10 PR254 X10 △ ○ ○ ○ Example 11 Photosensitive coloring composition 11 Pigment dispersion 11 PR254 X11 ○ ○ △ ○ Example 12 Photosensitive coloring composition 12 Pigment dispersion 12 PR254 X12 ○ ○ ○ ○ Example 13 Photosensitive coloring composition 13 Pigment dispersion 13 PR254 X13 △ ○ ○ ○ Example 14 Photosensitive coloring composition 14 Pigment dispersion 14 PR254 X14 ○ ○ ○ ○ Example 15 Photosensitive coloring composition 15 Pigment dispersion 15 PR254 X15 ○ ○ ○ ○ Example 16 Photosensitive coloring composition 16 Pigment dispersion 16 PR254 X16 ○ ○ ○ ○ Example 18 Photosensitive coloring composition 17 Pigment dispersion 17 PB15:6 X1 ○ ○ ○ ○ Example 19 Photosensitive coloring composition 18 Pigment dispersion 18 PG36 X1 ○ ○ ○ ○ Example 20 Photosensitive coloring composition 19 Pigment dispersion 19 PY138 X1 ○ ○ ○ ○ Example 21 Photosensitive coloring composition 20 Pigment dispersion 20 PR177 X1 ○ ○ ○ ○ Comparative Example 1 Photosensitive coloring composition 21 Pigment dispersion 21 PR254 Y1 × × △ ○ Comparative Example 2 Photosensitive coloring composition 22 Pigment dispersion 22 PR254 Y2 × △ × × Comparative Example 3 Photosensitive coloring composition 23 Pigment dispersion 23 PR254 Y3 × × × △

[0170] As shown in Table 4, the coloring compositions of the present invention using dispersants X1 to X16 exhibit excellent storage stability, foreign matter suppression on the coating film, filterability, and PGMAc resolubility. In Comparative Example 1, because the molar ratio of anhydride to hydroxyl groups in the dispersant is less than 0.9, the number of anhydride residues in one molecule is reduced, resulting in insufficient adsorption of the pigment, poor viscosity stability, and the generation of foreign matter. In Comparative Example 2, because the molar ratio of anhydride to hydroxyl groups exceeds 1.5, the viscosity stability is poor, and the compatibility with the solvent is reduced. In Comparative Example 3, because water or alcohol is not used in the dispersant, anhydride groups remain at the ends of the main chain, resulting in poor viscosity stability and poor filterability.

[0171] none

Claims

1. A coloring composition comprising: a coloring agent containing a pigment, a polyester dispersant, and a solvent, wherein the polyester dispersant has a main chain based on an aromatic carboxylic acid ester site having an ester bond and side chains based on a vinyl polymer site, wherein the aromatic carboxylic acid ester site having an ester bond is a reaction formation site of an aromatic compound having two or more anhydride groups and a compound having two or more hydroxyl groups, and the anhydride group is 1.0 mol to 1.5 mol relative to 1 mol of the hydroxyl group, and the main chain based on the aromatic carboxylic acid ester site has a sealing site derived from a monool.

2. The coloring composition as described in claim 1, wherein, The monool is a compound having an ether group or a carbonyl group.

3. The coloring composition as described in claim 1, wherein, The polyester dispersant has a weight average molecular weight of 7,000 to 25,000.

4. A photosensitive coloring composition comprising: a coloring composition as described in any one of claims 1 to 3, a photopolymerizable compound, and a photopolymerization initiator.

5. A color filter, comprising: The substrate and the filter segment formed from the photosensitive coloring composition as described in claim 4.

6. A solid-state photographic element comprising a color filter as described in claim 5.

7. An image display device comprising a color filter as described in claim 5.

8. A method for manufacturing a coloring composition, comprising: A colored composition is obtained by mixing a pigment-containing colorant, a polyester dispersant, and a solvent, characterized in that the polyester dispersant has a main chain based on an aromatic carboxylic acid ester site having ester bonds and side chains based on a vinyl polymer site formed by polymerizing an ethylene unsaturated monomer, wherein the main chain of the aromatic carboxylic acid ester site having ester bonds is generated by reacting an aromatic compound having two or more anhydride groups with a compound having two or more hydroxyl groups at a ratio of 1.0 mol to 1.5 mol relative to 1 mol of the hydroxyl groups, and the main chain based on the aromatic carboxylic acid ester site has a sealing site derived from a monool.