Pigment dispersions, photosensitive colorings, resin curing films, color filters, and image display elements

Abstract

This invention provides a pigment dispersion composition with good pigment dispersibility or storage stability, and a photosensitive coloring composition that yields a resin-cured film with excellent developability, heat resistance, solvent resistance, and pattern adhesion. The pigment dispersion composition of this invention comprises: a binder resin (A-1) composed of resin (A-1a) or resin (A-1b), a pigment (B), a polymeric dispersant (C), and a solvent (D-1). The aforementioned resin (A-1a) is obtained by adding a portion of the carboxyl group of a copolymer (P) of monomer (M) to a compound (m-4) having an ethylene-containing unsaturated group that is reactive with the carboxyl group. The monomer (M) comprises: a polymeric monomer (m-1) composed of a polymeric monomer (m-1a) having a bridged cyclic hydrocarbon group or a polymeric monomer (m-1b) of the following formula (1), acrylic acid (m-2), and a polymeric monomer (m-3) containing an aromatic ring.

Description

Technical Field

[0001] This invention relates to pigment dispersion compositions and photosensitive coloring compositions. This application asserts priority based on Japanese Patent Application No. 2020-189475 filed in Japan on November 13, 2020, and incorporates the contents of that application herein. Prior Technology

[0002] Currently, from the perspective of saving resources and energy, photosensitive resin compositions that can be cured by active energy lines such as ultraviolet light and electron beams are widely used in various coating, printing, paint, and adhesive fields. In the field of electronic materials such as printed wiring boards, photosensitive resin compositions have been used in solder resists, color filter resists, etc. Color filters are generally composed of: a transparent substrate such as a glass substrate; red, green, and blue pixels formed on the transparent substrate; a black matrix formed at the pixel boundaries; and a protective film formed on the pixels and the black matrix. Color filters with this structure are typically manufactured by sequentially forming a color pattern, called a black matrix or pixel pattern, or a pattern of a protective film, on the transparent substrate. Various methods have been proposed for forming these patterns. Among them, the pigment / dye dispersion method, which uses a photosensitive resin composition as a resist and employs a photolithography process involving repeated coating, exposure, development, and baking, has become the mainstream method because it can produce color patterns with excellent durability and few defects such as pinholes.

[0003] Generally, the photosensitive resin composition used in photolithography contains alkali-soluble resin, reactive diluent, photopolymerization initiator, pigment / dye dispersion (also known as colorant), and solvent. Although the pigment / dye dispersion method has the above advantages, conversely, due to the repeated formation of black matrices, red, green, and blue patterns, it requires: heat resistance to withstand high baking temperatures, or resistance to various solvents exposed during the manufacturing process. Generally, the photosensitive resin composition used in photolithography requires negative resist properties. For example, Patent Document 1 discloses the use of a polymer (A) having an acid group and a bridged cyclic hydrocarbon group with 10 to 20 carbon atoms.

[0004] Furthermore, in recent years, there has been a demand for higher image quality and higher resolution in displays such as liquid crystal displays (LCDs) and organic EL displays. Color filters are also required to achieve higher brightness and a wider color reproduction range. To achieve higher brightness or a wider color reproduction range, there are examples of using dyes instead of pigments as colorants. However, because dyes have lower heat resistance or solvent resistance compared to pigments, and their usage ratio or types are limited, most colorants contain pigments.

[0005] When using pigments to form color filters, the uniform miniaturization of the pigments is essential. By miniaturizing the pigments, the scattering of light passing through the color filter caused by the pigment particles can be reduced, resulting in a high contribution to transmittance and thus achieving high brightness. Furthermore, in order to expand the range of color reproduction, efforts were also made to increase the concentration of colorants. [Previous Technical Documents] [Patent Literature]

[0006] [Patent Document 1] Japanese Patent Application Publication No. 2019-112494 Summary of the Invention

[0007] [The problem that the invention aims to solve]

[0008] However, finely sized pigment particles are prone to aggregation, which leads to a decrease in the storage stability of pigment dispersibility or pigment dispersion compositions. Furthermore, as the concentration of "pigment" increases, the concentration of dispersant or binder resin decreases. Therefore, it is required that a smaller amount of dispersant or binder resin and other components be used to exhibit various inhibitory properties such as pigment dispersibility, storage stability of pigment dispersion components, heat resistance, solvent resistance, and pattern adhesion.

[0009] The present invention is intended to solve the problems described above, and aims to provide a pigment dispersion composition that can achieve sufficient pigment dispersibility or storage stability even when the concentration of dispersant or binder resin is reduced due to the high concentration of pigment. Furthermore, the purpose is to provide: a photosensitive coloring composition that, by using the pigment dispersion composition, produces a resin-cured film with excellent developability, heat resistance, solvent resistance, and pattern adhesion; a color filter having the cured composition; and an image display element having the filter. [Methods for solving problems]

[0010] The present invention includes the following features. [1]. A pigment dispersion composition, characterized in that it contains: Adhesive resin (A-1), Pigment (B) Polymer dispersant (C) and Solvent (D-1), The aforementioned adhesive resin (A-1) is a resin selected from at least one of the group consisting of resins (A-1a) and resin (A-1b). The aforementioned resin (A-1a) is obtained by adding a portion of the carboxyl group of a copolymer (P) of monomer (M) to a compound (m-4) having an ethylene-containing unsaturated group that is reactive with the carboxyl group. The monomer (M) comprises: at least one polymerizable monomer (m-1) selected from the group consisting of a polymerizable monomer (m-1a) having 10 to 20 carbon atoms (excluding polymerizable monomer (m-1b)) and polymerizable monomer (m-1b) represented by the following formula (1), acrylic acid (m-2), and a polymerizable monomer (m-3) containing an aromatic ring. The aforementioned resin (A-1b) is obtained by adding one or more of the hydroxyl groups in the aforementioned resin (A-1a) to a compound (m-5) having an isocyanate group and a polybasic acid anhydride (m-6), wherein the hydroxyl group is generated by ring-opening addition of the aforementioned compound (m-4) having an epoxy group or an oxetyl group in the aforementioned resin (A-1a) to such a monomer. (In formula (1), R1 and R2 independently represent hydrogen atoms or hydrocarbon groups with 1 to 20 carbon atoms. R1 and R2 can also be bonded to form a ring structure. R3 and R4 independently represent hydrogen atoms, or straight-chain or branched hydrocarbon groups with 1 to 4 carbon atoms.) [2]. The pigment dispersion composition as described in [1], wherein the aforementioned pigment (B) comprises a pigment having a halogenated phthalocyanine skeleton. [3]. The pigment dispersion composition as described in [1] or [2], wherein the aforementioned polymeric dispersant (C) has at least one group selected from the group consisting of tertiary amine groups and quaternary ammonium cationic groups. [4]. As described in any of [1] to [3], the aforementioned polymeric dispersant (C) is A monomer selected from at least one monomer from the group consisting of monomers having tertiary amino groups and vinyl unsaturated groups, and monomers having quaternary ammonium cationic groups and vinyl unsaturated groups, and Other monomers with vinyl unsaturated groups Block polymers. [5]. The pigment dispersion composition described in any of [1] to [4], wherein the group that is reactive with the carboxyl group in the aforementioned compound containing an ethylene unsaturated group (m-4) is an epoxy group or an oxobutane group. [6]. The pigment dispersion composition described in any of [1] to [5], wherein when the total of the aforementioned polymeric monomer (m-1), the aforementioned acrylic acid (m-2), and the aforementioned aromatic ring-containing polymeric monomer (m-3) of the aforementioned copolymer (P) is set to 100 mol%, the proportion of the aromatic ring-containing polymeric monomer (m-3) is 9 to 70 mol. [7]. The pigment dispersion composition described in any of [1] to [6], wherein the aforementioned adhesive resin (A-1) is the aforementioned resin (A-1b). [8]. The pigment dispersion composition described in any of [1] to [7] contains, relative to 100 parts by mass of the aforementioned pigment (B), 10 to 50 parts by mass of the aforementioned adhesive resin (A-1) and 10 to 80 parts by mass of the aforementioned polymeric dispersant (C). [9]. A photosensitive coloring composition, characterized in that it contains: The pigment dispersion composition described in any of [1] to [8] Adhesive resin (A-2), Reactive diluent (E) and Photopolymerization initiator (F).

[10] . As described in [9], the photosensitive coloring composition, wherein, relative to 100 parts by mass of the aforementioned pigment (B), The total amount of the aforementioned adhesive resins (A-1) and (A-2) is 50 to 280 parts by weight. Contains 10-80 parts by weight of the aforementioned polymeric dispersant (C), Contains 40-200 parts by weight of the aforementioned reactive diluent (E), It contains 0.1 to 10 parts by weight of the aforementioned photopolymerization initiator (F).

[11] . A resin-cured film, which is formed by curing the photosensitive coloring composition described in [9] or

[10] .

[12] . A color filter having a hardened form of the photosensitive coloring composition described in [0] or

[10] .

[13] . An image display element having the color filter described in

[12] . [The effects of the invention]

[0011] This invention provides a pigment dispersion composition with good pigment dispersibility or storage stability. Furthermore, by using this pigment dispersion composition, a photosensitive coloring composition can be provided that yields a resin-cured film with excellent developability, heat resistance, solvent resistance, and pattern adhesion. Further, a color filter having a cured form of the photosensitive coloring composition and an image display element having the color filter can be provided. Implementation

[0012] [Optimal Form of Invention Implementation]

[0013] The embodiments of the present invention will be described in detail below. However, the present invention is not limited to the embodiments shown below. The embodiments of the present invention will be described in detail below. However, the present invention is not limited to the embodiments shown below. Furthermore, in this specification, the term "(meth)acryloxy" means one or more selected from methacryloxy and acryloxy. "(meth)acrylic acid" and "(meth)acrylate" are also the same.

[0014] <Pigment Dispersion Composition> The pigment dispersion composition of this embodiment contains: binder resin (A-1), pigment (B), polymeric dispersant (C), and solvent (D-1).

[0015] [Adhesive Resin (A-1)] The adhesive resin (A-1) is a resin selected from at least one of the group consisting of resins (A-1a) and resin (A-1b) described below. The resin (A-1a) is obtained by adding a portion of the carboxyl group of the copolymer (P) to a compound (m-4) containing an ethylene unsaturated group. The aforementioned compound (m-4) containing an ethylene unsaturated group has a group that is reactive with the carboxyl group. The aforementioned copolymer (P) is a copolymer of monomer (M), which comprises: at least one polymerizable monomer (m-1) selected from the group consisting of polymerizable monomers (m-1a) having 10 to 20 carbon atoms (excluding polymerizable monomers (m-1b)) and polymerizable monomers (m-1b) represented by the following formula (1), acrylic acid (m-2), and a polymerizable monomer (m-3) containing an aromatic ring. Resin (A-1b) is a resin obtained by adding the aforementioned resin (A-1a) to one or more compounds selected from those containing vinyl unsaturated groups (m-5) and polybasic acid anhydrides (m-6). The aforementioned vinyl unsaturated group compound (m-5) has an isocyanate group. Resin (A-1a) is a resin obtained by adding a portion of the carboxyl group of the aforementioned copolymer (P) to the aforementioned vinyl unsaturated group compound (m-4) having an epoxy group or an oxetyl group. Resin (A-1a) has a plurality of hydroxyl groups resulting from the ring-opening addition. A portion of these hydroxyl groups is added to one or more compounds selected from those containing vinyl unsaturated groups (m-5) and polybasic acid anhydrides (m-6). One form of the adhesive resin (A-1) of this embodiment is a resin (A-1a) obtained by adding a portion of the carboxyl group of a copolymer (P) having a carboxyl group to a compound (m-4) having a reactive, vinyl-containing unsaturated group. The copolymer (P) is a copolymer of monomers (M), which comprises: at least one polymerizable monomer (m-1) selected from the group consisting of polymerizable monomers (m-1a) having 10 to 20 carbon atoms (excluding polymerizable monomers (m-1b)) and polymerizable monomers (m-1b) represented by the following formula (1), acrylic acid (m-2), and a polymerizable monomer (m-3) containing an aromatic ring.

[0016] (In formula (1), R1 and R2 independently represent hydrogen atoms or hydrocarbon groups with 1 to 20 carbon atoms. R1 and R2 can also be bonded to form a ring structure. R3 and R4 independently represent hydrogen atoms, or straight-chain or branched hydrocarbon groups with 1 to 4 carbon atoms.)

[0017] Furthermore, other forms of the adhesive resin (A-1) of this embodiment are resins (A-1b) obtained by further adding one or more compounds (m-5) containing an isocyanate group and an ethylene-containing unsaturated group and a polybasic acid anhydride (m-6) to the above-mentioned resin (A-1a).

[0018] First, the copolymer (P) of the precursor of the adhesive resin (A-1) corresponding to this embodiment will be described. "Copolymer (P)" The copolymer (P) used in this embodiment contains, as a constituent monomer (M), at least one polymerizable monomer (m-1) selected from the group consisting of polymerizable monomers (m-1a) having a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms and polymerizable monomers (m-1b) represented by the following formula (1), acrylic acid (m-2), and a polymerizable monomer containing an aromatic ring (m-3). Regarding "polymerizable monomer (m-1a) having a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms", "polymerizable monomer (m-1b) represented by the following formula (1)", "polymerizable monomer (m-1)", "acrylic acid (m-2)", and "polymerizable monomer containing an aromatic ring (m-3)", they may be referred to as "monomer (m-1a)", "monomer (m-1b)", "monomer (m-1)", "monomer (m-2)", and "monomer (m-3)" respectively.

[0019] "Single (m-1)" The monomer (m-1) is selected from at least one of the monomers (m-1a) and (m-1b). The monomer (m-1a) has a bridged cyclic hydrocarbon group with 10 to 20 carbon atoms. Here, the so-called bridged cyclic hydrocarbon preferably has the structure represented by the following formula (3) or (4). Examples of bridged cyclic hydrocarbons include adamantane and norcamphene. The so-called bridged cyclic hydrocarbon group refers to the group that is the residue after removing a portion of the hydrogen atoms in the structure. Furthermore, the monomer (m-1a) is defined as excluding the monomer (m-1b) described later.

[0020]

[0021] In formula (3), A and B represent linear or branched alkyl groups with 1 to 10 carbon atoms (including cyclic groups). A and B can be the same or different. The branches of A and B can bond together to form a cyclic structure. R5 represents a hydrogen atom or a methyl group.

[0022]

[0023] In formula (4), A', B' and D each independently represent a straight chain or a branchable alkyl group with 1 to 10 carbon atoms (including cyclic alkyl groups). A', B' and D may be the same or different. The branches of A', B' and D can bond together to form a cyclic structure. R6 represents a hydrogen atom or a methyl group.

[0024] As a monomer (m-1a), it is preferably a (meth)acrylate having a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms, and more preferably a (meth)acrylate adamantane acrylate or a (meth)acrylate having the structure represented by the following formula (5).

[0025]

[0026] In formula (5), R7~R9 represent hydrogen atoms or methyl groups, R10 and R11 represent hydrogen atoms or methyl groups, or can be bonded to form saturated or unsaturated rings, preferably 5-membered or 6-membered rings, and * represents a bond attached to (meth)acryloxy group.

[0027] Specific examples of (meth)acrylates having the structure represented by formula (5) include dicyclopentenyl (meth)acrylate, dicyclopentyl (meth)acrylate, and isocamphenyl (meth)acrylate. These can be used alone or in combination of two or more.

[0028] The monomer (m-1b) is the polymerizable monomer represented by formula (1) above. In formula (1) above, examples of substituents among hydrocarbon groups with 1 to 20 carbon atoms that may have substituents, represented by R1 and R2, include alkoxy, aryl, etc. Specific examples of hydrocarbon groups with 1 to 20 carbon atoms that may have substituents include straight-chain or branched alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, t-pentyl, stearyl, lauryl, 2-ethylhexyl, etc.; alicyclic groups such as cyclohexyl, t-butylcyclohexyl, dicyclopentadienyl, tricyclodecyl, isocamphenyl, adamantyl, 2-methyl-2-adamantyl, etc.; alkyl groups substituted with alkoxy groups such as 1-methoxyethyl, 1-ethoxyethyl, etc.; and alkyl groups substituted with aromatic groups such as phenylaralkyl. Furthermore, specific examples of straight-chain or branchable hydrocarbon groups with 1 to 4 carbon atoms represented by R3 and R4 include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, etc.

[0029] Specific examples of monomers (m-1b) include norcamphene (bicyclo[2.2.1]hept-2-ene), 5-methylbicyclo[2.2.1]hept-2-ene, tetracyclo[4.4.0.1 2,5.1 7,10]dodec-3-ene, 8-ethyltetracyclo[4.4.0.1 2,5.1 7,10]dodec-3-ene, dicyclopentadiene, tricyclo[5.2.1.0 2,6]dec-8-ene, tricyclo[4.4.0.1 2,5]undec-3-ene, tricyclo[6.2.1.0 1,8]undec-9-ene, tetracyclo[4.4.0.1 2,5.1 7,10.0 1,6]dodec-3-ene, and 8-ethyltetracyclo[4.4.0.1 2,5.1 7,10.0 1,6]dodec-3-ene. [7,12]dodecyl-3-ene, pentacyclic [6.5.1.1 3,6.0 2,7.0 9, 13]pentadecan-4-ene, etc. These can be used alone or in combination of two or more.

[0030] By incorporating monomers (m-1a) and / or monomers (m-1b), color filters with high surface hardness and the ability to suppress the exudation of colorants can be provided. At the same time, high resistance to thermal decomposition and high resistance to heat-induced yellowing can reduce color changes in the baked color filters. Furthermore, either monomer (m-1a) or monomer (m-1b) may be used alone, or both may be used. In particular, from the viewpoint of hardness, monomer (m-1) is preferably adamantane methacrylate or a methacrylate having the structure represented by formula (5), and even more preferably dicyclopentyl methacrylate.

[0031] "Single (m-2)" The copolymer (P) of this embodiment contains a monomer (m-2) as a constituent monomer (M). The monomer (m-2) is acrylic acid. The adhesive resin (A-1), by having a carboxyl group from the monomer (m-2), exhibits increased affinity for alkaline developing solutions, resulting in a photosensitive composition with excellent developability, which can provide a high-precision color filter with tight dimensional accuracy. In particular, by using monomer (m-2) as the copolymer (P), compared to other polymerizable monomers containing acidic groups such as carboxyl, sulfonyl, and phosphorus groups, a pigment dispersion composition with excellent pigment dispersibility or storage stability can be obtained. Therefore, an increase in the brightness or transmittance of the color filter can be expected with the improvement in pigment dispersibility. Furthermore, with the improvement in pigment dispersibility, scattering caused by pigment particles during exposure can also be reduced, thus contributing to the improvement of developability as a photosensitive coloring composition. The copolymer (P) of this embodiment may be used as a constituent monomer other than the monomer (m-2) without impairing the effects of the present invention, but for the reasons mentioned above, it is preferred not to use it.

[0032] "Single (m-3)" Monomer (m-3) is any monomer other than monomers (m-1a), (m-1b), and (m-2), and is not particularly limited as long as it is a polymerizable monomer containing an aromatic ring. By including monomer (m-3), the affinity with pigment (B) can be improved, and a pigment dispersion composition with excellent pigment dispersibility or storage stability can be obtained. Furthermore, even if the concentration of dispersant or binder resin is reduced due to the high concentration of pigment, a pigment dispersion composition with sufficient pigment dispersibility or storage stability can still be provided.

[0033] Specific examples of monomers (m-3) include benzyl methacrylate, phenyl methacrylate, triphenyl methyl methacrylate, isophenyl propyl methacrylate, rosin methacrylate, naphthyl methacrylate, anthracene methacrylate, 4-hydroxyphenyl methacrylate, styrene, and α-, O-, M-, P-alkyl, nitro, cyano, acetylamine derivatives of styrene, N-phenylmaleimide, and N-(4-hydroxyphenyl)maleimide. Especially from the viewpoint of ease of copolymerization or ease of obtaining, benzyl methacrylate, phenyl methacrylate, styrene, and α-, O-, M-, P-alkyl derivatives of styrene are preferred. These compounds can be used alone or in combination.

[0034] "The proportions of each monomer in the copolymer (P)" There are no particular limitations on the blending ratio (molar ratio) of the monomers in the copolymer (P) of this embodiment. When the total of monomers (m-1), (m-2), and (m-3) is set to 100 molar%, the proportion of monomer (m-1) is preferably 1 to 40 molar%, more preferably 2 to 20 molar%, and even more preferably 5 to 15 molar%. Furthermore, there are no limitations on the proportion of monomers (m-1a) and / or (m-1b) within monomer (m-1), and any blending ratio can be adopted. When the blending ratio of monomer (m-1) is 1 molar% or more, the desired properties from monomer (m-1) can be obtained. When the blending ratio is 40 molar% or less, other polymerizable monomers can be sufficiently blended, and other properties can be attempted to be obtained.

[0035] When the total percentage of monomers (m-1), (m-2), and (m-3) is set to 100 mol%, the proportion of monomer (m-2) is preferably 10-90 mol%, more preferably 20-85 mol%, and even more preferably 30-70 mol%. When the proportion of monomer (m-2) is 10 mol% or more, good developability of the pigment dispersion can be obtained, while a sufficient amount of vinyl unsaturated groups can be introduced into the side chains of the copolymer (P). On the other hand, when the proportion is 90 mol% or less, other polymerizable monomers can be adequately blended, and other properties can be attempted to be achieved.

[0036] When the total percentage of monomers (m-1), (m-2), and (m-3) is set to 100 mol%, the proportion of monomer (m-3) is preferably 9-70 mol%, more preferably 13-60 mol%, and even more preferably 20-55 mol%. When this proportion is 9 mol% or higher, the desired properties from the aromatic monomers can be obtained. When this proportion is 70 mol% or lower, other polymerizable monomers can be adequately blended, and other properties can be attempted to be obtained.

[0037] Other polymerizable monomers The copolymer (P) of this embodiment may also include constituent units from other polymerizable monomers, provided that the desired properties derived from the aforementioned monomers (m-1), (m-2), and (m-3) are not impaired. That is, it may include other polymerizable monomers besides the aforementioned monomers (m-1a), (m-1b), (m-2), and (m-3). These other polymerizable monomers are generally free radical polymerizable compounds having vinyl unsaturated groups. Specific examples include dienes such as butadiene; methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, amyl methacrylate, neopentyl methacrylate, isoamyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, and others. Non-reactive (meth)acrylates such as dodecyl acrylate, cyclopentyl acrylate, cyclohexyl acrylate, methylcyclohexyl acrylate, ethylcyclohexyl acrylate, allyl acrylate, tetrahydrofurfuryl acrylate, and 3-(N,N-dimethylamino)propyl acrylate; 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 3-hydroxybutyl acrylate, 4-hydroxybutyl acrylate, 3-hydroxypentyl acrylate, and 4-hydroxypentyl acrylate. 5-Hydroxypentyl acrylate, 4-Hydroxyhexyl acrylate, 5-Hydroxyhexyl acrylate, 6-Hydroxyhexyl acrylate, 5-Hydroxy-3-methyl-pentyl acrylate, cyclohexane-1,4-diethanol-mono(meth)acrylate, 2-(2-hydroxyethyloxy)ethyl acrylate, 2,3-dihydroxy acrylate, glycerol mono(meth)acrylate, glycerol mono(meth)acrylate, glycidyl acrylate, 4-hydroxybutyl(meth)acrylate glycidyl ether, 3,4-epoxycyclohexylmethyl(meth)acrylate, (methyl) Reactive (meth)acrylates including (3-ethyloxetane-3-yl)methyl acrylate, 2-isocyanate ethyl acrylate, 2-isocyanate propyl acrylate, 3-isocyanate propyl acrylate, 2-isocyanate-1-methyl ethyl acrylate, 2-isocyanate-1,1-dimethyl ethyl acrylate, 4-isocyanate cyclohexyl acrylate, 1,1-(bisacryloxymethyl)ethyl isocyanate, and compounds with block isocyanate groups obtained by blocking the isocyanate groups of the aforementioned vinyl unsaturated compounds with isocyanate groups using a blocking agent.(Methacrylamide) compounds, including (meth)acrylamide, N,N-dimethylacrylamide, N,N-diethylacrylamide, N,N-dipropylacrylamide, N,N-di-isopropylacrylamide, and anthracene acrylamide; vinyl compounds, including (meth)acrylamide benzene, (meth)acrylonitrile, acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinylpyrrolidone, vinylpyridine, vinyl acetate, and vinyltoluene; maleimides, including N-cyclohexylmaleimide and N-laurylmaleimide; and unsaturated dicarboxylic acid diesters, including diethyl citrate, diethyl maleate, diethyl formanoate, and diethyl itconate. These can be used individually or in combination of two or more, depending on the needs.

[0038] "Proportion of other polymerizable monomers" The proportion of other polymerizable monomers in the copolymer (P) of this embodiment is preferably 10 mol% or less, and more preferably 5 mol% or less, when the total of monomers (m-1), (m-2), (m-3) and other polymerizable monomers is set to 100 mol%.

[0039] "Compounds added to copolymers (P), etc." Next, an adhesive resin (A-1) obtained by adding copolymer (P) to a compound (m-4) having an ethylene-containing unsaturated group that is reactive with a carboxyl group, and further to one or more compounds selected from compounds having an isocyanate group and an ethylene-containing unsaturated group (m-5) and a polybasic acid anhydride (m-6) as arbitrary compounds will be described. Regarding "a compound containing an ethylene-containing unsaturated group that is reactive with a carboxyl group (m-4)", "a compound containing an isocyanate group that is ethylene-containing unsaturated group (m-5)", and "a polyacid anhydride (m-6)", there are instances where they are referred to as "compound (m-4)", "compound (m-5)", and "compound (m-6)" respectively.

[0040] "Compound (m-4)" Compound (m-4) has a "group that is reactive with a carboxyl group" and an "ethylene unsaturated group". Examples of groups that are reactive with a carboxyl group include epoxy, oxetane, isocyanate, hydroxyl, and amino groups. By adding the carboxyl group of monomer (m-2) from the aforementioned copolymer (P) to a group of compound (m-4) that is reactive with the carboxyl group, an ethylene unsaturated group can be introduced into the side chain of the aforementioned copolymer (P). The adhesive resin (A-1) inhibits the exudation of pigment (B) by having an ethylene unsaturated group from compound (m-4), and can provide a pigment dispersion composition that exhibits excellent inhibitory properties such as heat resistance, solvent resistance, pattern adhesion, and developability.

[0041] Specific examples of compound (m-4) include glycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, 3,4-epoxycyclohexyl meth (meth)acrylate, (3-ethyloxetane-3-yl)methyl (meth)acrylate, 2-isocyanoethyl (meth)acrylate, 2-isocyanopropyl (meth)acrylate, 3-isocyanopropyl (meth)acrylate, 2-isocyano-1-methylethyl (meth)acrylate, 2-isocyano-1,1-dimethylethyl (meth)acrylate, 4-isocyanocyclohexyl (meth)acrylate, 1,1-(bisacryloxymethyl)ethyl isocyanate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-(meth)acrylate Hydroxypropyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl methacrylate, 3-hydroxypentyl methacrylate, 4-hydroxypentyl methacrylate, 5-hydroxypentyl methacrylate, 4-hydroxyhexyl methacrylate, 5-hydroxyhexyl methacrylate, 6-hydroxyhexyl methacrylate, 5-hydroxy-3-methylpentyl methacrylate, cyclohexane-1,4-diethanol-mono(meth)acrylate, 2-(2-hydroxyethyloxy)ethyl methacrylate, 2,3-dihydroxy methacrylate, glycerol mono(meth)acrylate, pentaneglycerol mono(meth)acrylate, aminoethyl methacrylate, monomethylaminoethyl methacrylate, dimethylaminoethyl methacrylate, etc. These can be used alone or in combination. From the viewpoint of ease of obtaining or reactivity with copolymer (P) and subsequent addition of the following compound (m-5) or compound (m-6) as any monomer, it is preferred to have an epoxy group or oxetane, and more preferably to be glycidyl methacrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, 3,4-epoxycyclohexyl methacrylate, (3-ethyloxetane-3-yl)methyl methacrylate, and even more preferably glycidyl methacrylate.

[0042] "Compound (m-5)" If a compound having an epoxy group or an oxetyl group is used as compound (m-4), then (m-5) may also be used as needed. Compound (m-5) is a monomer having an isocyanate group and an ethylene unsaturated group, but without a carboxyl group, an epoxy group, or an oxetyl group. By adding one of the plurality of hydroxyl groups of the aforementioned resin (A-1a) to compound (m-5), resin (A-1b) can be obtained. As a result, an ethylene unsaturated group is further introduced into the aforementioned resin (A-1a). By using the aforementioned resin (A-1b), various inhibitor properties such as heat resistance, solvent resistance, pattern adhesion, and developability can be further improved. The aforementioned plurality of hydroxyl groups of the aforementioned resin (A-1a) are generated by ring-opening addition of the carboxyl group from the monomer (m-2) of the aforementioned copolymer (P) to the epoxy group and the oxetyl group of compound (m-4). The aforementioned resin (A-1a) is one form of adhesive resin (A-1), and the aforementioned resin (A-1b) is another form of the aforementioned adhesive resin (A-1).

[0043] Examples of compounds (m-5) include ethyl 2-isocyanate (meth)acrylate, propyl 2-isocyanate (meth)acrylate, propyl 3-isocyanate (meth)acrylate, methyl 1-isocyanate (meth)acrylate, 1,1-dimethyl 2-isocyanate (meth)acrylate, cyclohexyl 4-isocyanate (meth)acrylate, and 1,1-(bisacryloxymethyl)ethyl isocyanate. These can be used alone or in combination. From the viewpoint of ease of acquisition, ethyl 2-isocyanate (meth)acrylate is preferred.

[0044] "Compound (m-6)" Compound (m-6) is a polyacid anhydride. If a compound having an epoxy group or an oxetane group is used as compound (m-4), compound (m-6) may also be used as needed. Compound (m-6) is not particularly limited as long as it has an anhydride structure, but a ring structure that does not produce byproducts after the reaction is preferred. Resin (A-1b) is obtained by adding one of the plural hydroxyl groups of the aforementioned resin (A-1a) to compound (m-6). As a result, a carboxyl group is introduced into the aforementioned resin (A-1a). Using the aforementioned resin (A-1b) contributes to improved developability as a photosensitive coloring component. The aforementioned plural hydroxyl groups of the aforementioned resin (A-1a) are generated by ring-opening addition of the carboxyl group from the monomer (m-2) of the aforementioned copolymer (P) to the epoxy group and oxetane group of compound (m-4). The aforementioned resin (A-1a) is one form of adhesive resin (A-1), and the aforementioned resin (A-1b) is another form of the aforementioned adhesive resin (A-1).

[0045] Examples of compounds (m-6) include 1,2,3,6-tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, bicyclo[2.2.1]heptane-2,3-dicarboxylic anhydride, methylbicyclo[2.2.1]heptane-2,3-dicarboxylic anhydride, succinic anhydride, and octenylsuccinic anhydride. These can be used alone or in combination. From the viewpoint of ease of acquisition, succinic anhydride is preferred.

[0046] "Introduction ratio of compound (m-4)" Regarding the proportion of compound (m-4) introduced relative to the aforementioned copolymer (P), when the total of monomers (m-1) to (m-3) is set to 100 mol%, it is preferably 5 to 90 mol%, more preferably 10 to 70 mol%, and even more preferably 10 to 40 mol%. Furthermore, when acrylic acid (m-2) is set to 100 mol%, it is preferably 5 to 90 mol%, more preferably 10 to 70 mol%, and even more preferably 20 to 50 mol%. By adjusting the proportion of compound (m-4) within the aforementioned range, the effect of introducing ethylene unsaturated groups can be achieved, thereby reducing the residue of unreacted compound (m-4).

[0047] "The combined introduction ratio of compound (m-5) and compound (m-6)" Regarding the total proportion of compounds (m-5) and (m-6) relative to the aforementioned copolymer (P), when the total of monomers (m-1) to (m-3) is set to 100 mol%, it is preferably 3 to 70 mol%, more preferably 5 to 50 mol%, and even more preferably 5 to 25 mol%. Furthermore, when compound (m-4) is set to 100 mol%, it is preferably 5 to 90 mol%, more preferably 20 to 80 mol%, and even more preferably 40 to 70 mol. By bringing the total ratio of the compound containing the ethylene unsaturated group (m-5) and the polybasic acid anhydride (m-6) into the aforementioned range, the effects brought about by the introduction can be achieved, thereby reducing the residue of unreacted monomers.

[0048] Furthermore, there are no restrictions on the proportions of compounds (m-5) and (m-6) used together; any proportion can be chosen according to the desired performance. That is, to improve heat resistance, solvent resistance, and pattern adhesion, simply increase the proportion of compound (m-5); to improve developability, simply increase the proportion of compound (m-6). To improve all properties, simply increase the proportions of compounds (m-5) and (m-6) in equal proportions. By adjusting the introduction ratio of (m-5) and compound (m-6) as described above, the desired performance can be obtained.

[0049] Properties of Adhesive Resin (A-1) The acid value (measured according to the specifications shown in JIS K6901 5.3, etc.) of the adhesive resin (A-1) in this embodiment contains carboxylic acid from acrylic acid (m-2), and is not particularly limited as long as it is 0 mg KOH / g or higher, preferably 10 to 400 mg KOH / g, more preferably 30 to 300 mg KOH / g, and most preferably 50 to 200 mg KOH / g. As long as the acid value of the adhesive resin (A-1) is 10 mg KOH / g or higher, its developability as a photosensitive coloring composition is good. On the other hand, as long as the acid value of the adhesive resin (A-1) is 400 mg KOH / g or lower, it can provide a uniform composition without compromising its affinity with the pigment dispersion composition and other components contained in the photosensitive coloring composition.

[0050] The molecular weight (weight average molecular weight converted from polystyrene) of the adhesive resin (A-1) in this embodiment is not particularly limited, but is preferably 1,000 to 50,000, more preferably 3,000 to 40,000, and most preferably 5,000 to 30,000. If the molecular weight of the adhesive resin (A-1) is 1,000 or higher, excellent heat resistance, solvent resistance, and pattern adhesion can be ensured. On the other hand, if the molecular weight of the adhesive resin (A-1) is 50,000 or lower, the molecular weight and viscosity of the adhesive resin (A-1) can be controlled within an appropriate range during manufacturing, thus providing practical pigment dispersions and photosensitive coloring compositions.

[0051] The vinyl unsaturated group equivalent of the adhesive resin (A-1) in this embodiment is not particularly limited as long as vinyl unsaturated groups are present in the side chains of the aforementioned copolymer (P). A preferred value is 200-5000 g / mol, more preferably 300-2500 g / mol, and most preferably 500-2000 g / mol. If the vinyl unsaturated group equivalent of the adhesive resin (A-1) is 5000 g / mol or less, excellent heat resistance, solvent resistance, and pattern adhesion can be ensured. On the other hand, if the vinyl unsaturated group equivalent of the adhesive resin (A-1) during manufacturing is 200 g / mol or more, practical pigment dispersions and photosensitive coloring compositions that can guarantee the stability of the adhesive resin (A-1) during manufacturing can be provided.

[0052] "Method for manufacturing adhesive resin (A-1)" A copolymer (P) serving as a precursor to an adhesive resin (A-1) can be obtained by performing a copolymerization reaction using a well-known free radical polymerization method in this technical field. For example, the monomer to be copolymerized can be dissolved in a solvent, and a polymerization initiator can be added to the solution, and the reaction can be carried out at 50-130°C for 1-20 hours. Alternatively, the monomer to be copolymerized and the polymerization initiator can be added dropwise to a solvent adjusted to 50-130°C while the reaction is carried out.

[0053] The solvent that can be used in this copolymerization reaction is not particularly limited, as long as it is inert to free radical polymerization; commonly used organic solvents can be used. Examples include ethylene glycol ether solvents such as propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate; aromatic solvents such as toluene and xylene; and ester solvents such as ethyl acetate, isopropyl acetate, and ethyl lactate. These solvents can be used alone or in combination of two or more. In particular, ethylene glycol ether solvents are preferred.

[0054] The amount of solvent used in this copolymerization reaction is not particularly limited. When the total amount of monomers used in the copolymerization is set to 100 parts by mass, it is generally 30 to 1000 parts by mass, preferably 50 to 800 parts by mass. In particular, by setting the amount of solvent used to 1000 parts by mass or less, the decrease in molecular weight of the copolymer (P) caused by chain transfer can be suppressed, and the viscosity of the copolymer (P) can be controlled within an appropriate range. Furthermore, by setting the amount of solvent used to 30 parts by mass or more, abnormal polymerization reactions can be prevented, and while the polymerization reaction can be carried out stably, the coloring or gelation of the copolymer (P) can also be prevented.

[0055] As a polymerization initiator that can be used in this copolymerization reaction, any initiator capable of initiating free radical polymerization is acceptable and is not particularly limited. Commonly used organic peroxide catalysts or azo compounds can be used. Specific examples include azobisisobutyronitrile, azobisisovalerate, 2,2'-azobis(2,4-dimethylvalerate), azobis(2-methylpropionic acid)dimethyl, benzoyl peroxide, dicumyl peroxide, diisopropyl peroxide, di-t-butyl peroxide, t-butylperoxybenzoate, t-hexylperoxybenzoate, t-butyl-2-ethylhexanoate peroxide, t-hexyl-2-ethylhexanoate peroxide, and 1,1,3,3-tetramethylbutyl-2-ethylhexanoate peroxide. These can be used alone or in combination of two or more, and it is advisable to select a free radical polymerization initiator with an appropriate half-life according to the polymerization temperature.

[0056] The amount of polymerization initiator used in this copolymerization reaction is not particularly limited. When the total amount of monomers used in the copolymerization is set to 100 parts by mass, it is generally 0.5 to 20 parts by mass, and preferably 1.0 to 10 parts by mass.

[0057] As a method for adding a portion of the carboxyl group of the aforementioned copolymer (P) to the compound (m-4), a well-known addition reaction can be used. For example, after adding a polymerization inhibitor and a catalyst to the aforementioned copolymer (P) solution, the compound (m-4) is added, and the addition reaction or dehydration reaction is carried out under conditions of room temperature to 150°C (preferably 50 to 120°C). Here, the polymerization inhibitor is added to prevent side reactions of the introduced unsaturated group. Specific examples of polymerization inhibitors include hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, dibutylhydroxytoluene, etc. Specific examples of catalysts include tertiary amino groups such as triethylamine, quaternary ammonium salts such as triethylbenzylammonium chloride, phosphorus compounds such as triphenylphosphine, organometallic compounds such as chromium or tin, etc.

[0058] A ring-opening addition reaction is performed between a portion of the carboxyl group of the aforementioned copolymer (P) and the epoxy group or oxetane group of compound (m-4) to generate a plurality of hydroxyl groups. If a portion of the aforementioned plurality of hydroxyl groups is then added to one or more compounds selected from those containing vinyl unsaturated groups (m-5) and polybasic anhydrides (m-6), as a method for the addition reaction, compounds (m-5) and (m-6) can be added subsequently after the addition reaction of compound (m-4). The reaction temperature can be adjusted as needed, or the aforementioned catalyst can be added.

[0059] [Pigment(B)] In this embodiment, pigment (B) is not particularly limited to any pixel that can be uniformly dispersed in the composition to form a color filter. It can be pigments of various colors, including those that utilize the so-called three primary colors of light (red, green, and blue), such as yellow, orange, and purple (which can be used as complementary colors), and black and brown (which can be used as black matrices). Furthermore, examples of the chemical structure of pigment (B) include all organic pigments such as isoindolineone, isoindoline, methylimine, anthraquinone, anthrone, dibenzopiperanone, diketopyrrolopyrrole, perylene, violetone, quinacrine, indigo, dioxazine, indigo, phthalocyanine, anthocyanin, and azo dyes, as well as inorganic pigments such as carbon black, titanium black, and titanium dioxide.

[0060] In this embodiment, pigment (B) is preferably a green pigment containing a halogenated phthalocyanine skeleton as represented by the following formula (6).

[0061]

[0062] In formula (6), M represents a divalent or tetravalent metal atom. From the viewpoint of color reproduction, zinc or copper is preferred, and zinc is particularly preferred. X represents any one of hydrogen, chlorine, or bromine atoms, and contains at least one chlorine or bromine atom. Depending on the brightness or color reproduction, the addition ratio of chlorine and bromine atoms will change. When there are more chlorine atoms and fewer bromine atoms, the brightness will be high; conversely, when there are more bromine atoms and fewer chlorine atoms, the color reproduction tends to be good. The chlorine atom ratio is preferably 1 to 10, and even more preferably 1.5 to 8. The bromine atom ratio is preferably 5 to 15, and even more preferably 7 to 14.

[0063] By using the aforementioned pigment (B), binder resin (A-1), and the polymeric dispersant (C) described later, a pigment dispersion composition with excellent pigment dispersibility and storage stability can be obtained, providing a color filter with high brightness and a wide color reproduction range. Simultaneously, it can impart heat resistance, solvent resistance, and pattern adhesion to the colored pattern.

[0064] Halogenated phthalocyanine pigments can be commercially available or prepared at home. Examples of commercially available pigments include CI pigments 7, 36, 58, and 59. Among these, CI pigments 58 and 59 are preferred for their high gloss or color reproduction. When preparing the pigment independently, well-known manufacturing methods are used. Examples include: using phthalic acid or phthalonitrile, where some or all of the hydrogen atoms in the aromatic ring are replaced by halogen atoms, as a starting material, and forming the phthalocyanine skeleton under a catalyst such as ammonium molybdate; or halogenating phthalocyanine with chlorine or bromine gas. The crude pigment obtained by these methods is then dry-milled in a ball mill, vibratory mill, or similar pulverizer, and processed using well-known solvent salt milling methods to obtain the desired green pigment.

[0065] Furthermore, any pigment can be used as long as it contains at least a halogenated phthalocyanine skeleton and can be uniformly dispersed with other components to form pixels of a color filter. There are no particular limitations. Pigments that utilize the so-called red, green, and blue primary colors of light are acceptable, as well as pigments that can utilize complementary colors such as yellow, orange, and purple, and pigments that can utilize black and brown as a black matrix. Moreover, examples of the chemical structures of such pigments include all organic pigments such as isoindolineone, isoindoline, methylimine, anthraquinone, anthrone, dibenzopiperanone, diketopyrrolopyrrole, perylene, violetone, quinacrine, indigo, dioxazine, indigo, anthocyanins, and azo compounds, or inorganic pigments such as carbon black, titanium black, and titanium dioxide.

[0066] Specific examples of other pigments include CI pigments such as Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, and 214; and CI pigments such as Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, and 73. CI pigments include: red pigments such as Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, and 265; blue pigments such as CI Blue 15, 15:3, 15:4, 15:6, and 60; purple pigments such as CI Violet 1, 19, 23, 29, 32, 36, and 38; brown pigments such as CI Brown 23 and 25; and black pigments such as CI Black 1, 7, carbon black, titanium black, and iron oxide. Depending on the desired pixel color, these pigments can be used individually or in combination of two or more.

[0067] Furthermore, as the coloring agent in this embodiment, not only pigments (B) but also dyes can be used in combination. When dyes are used in combination, compared to the case of using pigments, it is expected that high brightness, an expanded color reproduction range, and good developability can be exhibited. On the other hand, when pigments are used in combination, compared to dyes, heat resistance is superior, and color changes are less after the colored pattern is formed. Depending on the color of the pixel as required for the desired performance or purpose, both dyes and pigments can be used in combination.

[0068] From the viewpoints of solubility in the solvent (D-1) or alkaline developing solution (described later), interaction with other components in the resin composition, and heat resistance, it is preferable to use acidic dyes with acidic groups such as carboxyl groups, salts of acidic dyes and nitrogen compounds, or sulfonamide forms of acidic dyes. Specific examples of such dyes include: acid alizarin violet N; acid black 1, 2, 24, 48; acid blue 1, 7, 9, 25, 29, 40, 45, 62, 70, 74, 80, 83, 90, 92, 112, 113, 120, 129, 147; acid chrome violet K; acid fuchsin; acid green 1, 3, 5, 25, 27, 50; acid orange 6, 7, 8, 10, 12, 50, 51, 52, 56, 63, 74, 95; acid red1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 69, 73, 80, 87, 88, 91, 92, 94, 97, 103, 111, 11 4.129,133,134,138,143,145,150,151,158,176,183,198,211,215,216,217,249,252,257,260,266,274;acid violet 6B, 7, 9, 17, 19; acid Yellow 1, 3, 9, 11, 17, 23, 25, 29, 34, 36, 42, 54, 72, 73, 76, 79, 98, 99, 111, 112, 114, 116; food yellow 3 and its derivatives. Among these, azo, dibenzopiperanone, anthraquinone, or phthalocyanine acid dyes are preferred. These dyes can be used alone or in combination of two or more.

[0069] [Polymer Dispersant (C)] The polymeric dispersant (C) is not particularly limited to any substance capable of dispersing the pigment (B). From the viewpoint of pigment dispersibility or storage stability, it is preferably a polymeric compound having at least one substituent selected from the group consisting of tertiary amine groups and quaternary ammonium cationic groups. Examples include: polyamines (or polyammonium cationic salts) obtained by homopolymerization or copolymerization of monomers having tertiary amine groups and vinyl unsaturated groups or monomers having quaternary ammonium cationic groups and vinyl unsaturated groups; polyamines (or polyammonium cationic salts) obtained by copolymerization of such monomers with other monomers having vinyl unsaturated groups; compounds formed by alkylation of polymeric compounds containing one or more primary and / or secondary amine groups to form tertiary amine groups; and compounds formed by further reacting tertiary amine groups with acidic compounds or halogenated alkyl compounds to form quaternary ammonium cationic salts. The aforementioned polymeric dispersant (C) is preferably a block polymer of at least one monomer selected from the group consisting of monomers having tertiary amino groups and vinyl unsaturated groups and monomers having quaternary ammonium cationic groups and vinyl unsaturated groups, and other monomers having vinyl unsaturated groups. As an example of the aforementioned other monomers having vinyl unsaturated groups, (meth)acrylates having alkyl, aryl, aralkyl, cycloalkyl, or alkyldiol groups can be cited.

[0070] In particular, polyamines (or polyammonium cationic salts) obtained by block polymerization of monomers having tertiary amine groups and vinyl unsaturated groups and / or monomers having quaternary ammonium cationic groups and vinyl unsaturated groups, along with other monomers having vinyl unsaturated groups, are preferably used as polymeric dispersants (C). By using polyamines (or polyammonium cationic salts) obtained through block polymerization as polymeric dispersants (C), the tertiary amine groups and / or quaternary ammonium cationic groups will be locally present in the single-terminal regions, thereby enhancing the affinity with the pigment (B). Furthermore, the affinity of the other single-terminal region for other pigment dispersion components (specifically, such as adhesive resins (A-1) or solvents (D-1) described later) will increase, thereby significantly improving the pigment dispersibility or the storage stability of the pigment dispersion component. Furthermore, as an example of other monomers with vinyl unsaturated groups that improve affinity with other pigment dispersion components, (meth)acrylates having alkyl, aryl, aralkyl, cycloalkyl, or alkyldiol groups can be cited.

[0071] The amine content of the polymeric dispersant (C) can be quantitatively determined by measuring the amine value (the value measured according to the specifications shown in JIS K7237, etc.). The amine content of the polymeric dispersant (C) in this embodiment is not particularly limited, but is preferably 10 mg KOH / g to 200 mg KOH / g, and more preferably 30 mg KOH / g to 160 mg KOH / g. When the amine value is 10 mg KOH / g or higher, the affinity with the aforementioned pigment (B) can be improved, resulting in sufficient pigment dispersibility or storage stability of the pigment dispersion composition. On the other hand, when the amine value is 200 mg KOH / g or lower, yellowing caused by the amine's chromogenic pattern can be suppressed.

[0072] Furthermore, the molecular weight (weight average molecular weight converted from polystyrene) of the polymeric dispersant (C) in this embodiment is not particularly limited, but is preferably 1,000 to 50,000, and more preferably 3,000 to 30,000. Moreover, the molecular weight distribution of the polymeric dispersant (C) (the value obtained by dividing the weight average molecular weight converted from polystyrene by the number average molecular weight) is preferably 1.0 to 2.0, more preferably 1.0 to 1.7, and even more preferably within the range of 1.0 to 1.5. When the molecular weight or molecular weight distribution of the polymeric dispersant (C) is within the above range, the viscosity of the pigment dispersion composition can be controlled within an appropriate range, thereby obtaining sufficient pigment dispersibility or storage stability of the pigment dispersion composition. In particular, the narrower the molecular weight distribution, the more effectively pigment dispersibility or storage stability of the pigment dispersion composition can be obtained with a smaller dispersant dosage.

[0073] The polymeric dispersant (C) can be commercially available or prepared in-house. Furthermore, commercially available products and polyamines obtained using well-known block polymer manufacturing methods can be arbitrarily modified or functionalized. Examples of suitable commercially available polymeric compounds include the DISPERBYK series manufactured by BYK, the Solsperse series manufactured by Lubrizol, and the EFKA-PX series manufactured by BASF. These polymeric dispersants (C) can be used alone or in combination of two or more, depending on the requirements.

[0074] When preparing the polymeric dispersant (C) yourself, the polyamine shown above is synthesized using a well-known block polymer manufacturing method. Specific examples of monomers having tertiary amino groups and vinyl unsaturated groups include dimethylaminoethyl methacrylate, dimethylaminopropyl methacrylate, dimethylaminobutyl methacrylate, diethylaminoethyl methacrylate, diethylaminopropyl methacrylate, diethylaminobutyl methacrylate, pentamethylpiperidin methacrylate, tetramethylpiperidin methacrylate, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, dimethylaminoethyl(meth)acrylamide, dimethylaminopropyl(meth)acrylamide, diacetone(meth)acrylamide, or acrylamide-modalin, etc. These monomers can be used alone or in combination with two or more. Specific examples of monomers having quaternary ammonium cationic groups and vinyl unsaturated groups include organohalogen salts of monomers having tertiary amino groups. There are no particular limitations on organohalogen salts; from the viewpoint of ease of acquisition, specific examples include chloromethane, chloroethane, chloropropane, chlorobutane, benzyl chloride, ethyl chloride, bromomethane, bromoethane, bromopropane, bromobutane, benzyl bromide, ethyl bromide, iodomethane, iodomethane, iodopropane, iodobutane, benzyl iodide, and ethyl iodide. Furthermore, the introduction of quaternary ammonium cationic groups can also be achieved without using the aforementioned monomers. Instead, a monomer having tertiary amino groups can be block polymerized with other monomers having vinyl unsaturated groups, and then, under arbitrary temperature and in the presence of a catalyst, the organohalogen salt can be added to a tertiary amine, thereby introducing the quaternary ammonium cationic group by partially or completely replacing one or more of the tertiary amine with a quaternary ammonium cationic group. On the other hand, monomers with vinyl unsaturated groups that enhance affinity with other pigment dispersions can include, for example, (meth)acrylates with alkyl, aryl, aralkyl, cycloalkyl, or (poly)oxyalkyl backbones. There are no particular limitations as long as they do not impair affinity with other pigment dispersions. Specific examples include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isocamphene (meth)acrylate, phenyl (meth)acrylate, etc. The monomers include (meth)acrylates such as benzyl acrylate, phenoxyethyl acrylate, phenoxydiethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, or ethoxypolyethylene glycol (meth)acrylate; styrene-based monomers such as styrene or α-methylstyrene; vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, or isobutyl vinyl ether; and aliphatic vinyl esters such as vinyl acetate or vinyl propionate. These monomers may be used alone or in combination.

[0075] [solvent (D-1))] The solvent (D-1) is not particularly limited, as long as it does not react with the components contained in the pigment dispersion or photosensitive coloring composition of this embodiment and can dissolve or disperse them. As the solvent (D-1), the same solvent used in the manufacture of the adhesive resin (A-1) or the polymeric dispersant (C) can be used. The solvent contained after the reaction can be used directly, or further solvent can be added. Furthermore, when adding other components, the solvent can coexist with the other components.

[0076] Specific examples of solvents (D-1) include propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, ethyl acetate, butyl acetate, isopropyl acetate, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethylene glycol monoethyl ether acetate, and diethylene glycol ethyl ether acetate. These can be used alone or in combination of two or more. Among these, ethylene glycol ether solvents such as propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate are preferred for use in the manufacture of color filters.

[0077] [Composition of Pigment Dispersions] The appropriate mixing amounts of each component in the pigment dispersion composition of this embodiment are as follows.

[0078] The content of the adhesive resin (A-1) relative to 100 parts by weight of pigment (B) is preferably 10 to 50 parts by weight, more preferably 15 to 40 parts by weight, and even more preferably 20 to 30 parts by weight. When the content of the adhesive resin (A-1) is 10 parts by weight or more, a photosensitive coloring composition with good developability can be obtained, as well as a resin-cured film with excellent heat resistance, solvent resistance, and pattern adhesion. When the content of the adhesive resin (A-1) is 50 parts by weight or less, the content of pigment (B) can be sufficiently ensured, and a resin-cured film with excellent color reproduction can be obtained.

[0079] The content of the polymeric dispersant (C) relative to 100 parts by mass of pigment (B) is preferably 10 to 50 parts by mass, more preferably 15 to 40 parts by mass, and even more preferably 20 to 30 parts by mass. When the content of polymeric dispersant (C) is 10 parts by mass or more, a pigment dispersion composition with excellent pigment dispersibility or storage stability can be obtained. When the content of polymeric dispersant (C) is 50 parts by mass or less, sufficient content of pigment (B) can be ensured, and a photosensitive coloring composition with excellent color reproduction can be obtained.

[0080] The amount of solvent (D-1) prepared, when the total amount of the pigment dispersion components other than solvent (D-1) is set to 100 parts by mass, is preferably 100 to 900 parts, more preferably 120 to 600 parts, and even more preferably 150 to 400 parts. As long as the content of solvent (D-1) is within the above range, a pigment dispersion component with appropriate viscosity can be obtained.

[0081] [Manufacturing method of pigment dispersion composition] In this embodiment of the pigment dispersion composition, a specified amount of binder resin (A-1), pigment (B), polymeric dispersant (C), and solvent (D-1) are weighed, and the pigment (B) is micronized and dispersed using a known dispersion treatment process. This dispersion treatment process typically utilizes devices such as paint shakers, bead mills, ball mills, roller mills, stone mills, jet mills, homogenizers, planetary mixers, and rotation-revolutionary mixers. Furthermore, using beads with a diameter of 0.01 to 10 mm in this dispersion treatment process allows for efficient and uniform micronization of the pigment (B). The material of the beads is not limited; however, considering hardness and potential contamination of the pigment dispersion composition, glass beads or zirconia beads are preferred. The appropriate time, temperature, bead diameter, and dosage for the dispersion treatment will vary depending on the composition of the pigment dispersion composition and the size of the apparatus; these conditions can be adjusted appropriately. Finally, for the purpose of removing fine impurities and coarse particles or agglomerates of pigment (B) from the pigment dispersion, it is preferable to use a glass filter or the like to filter the pigment dispersion.

[0082] <Photosensitive coloring composition> The photosensitive coloring composition of this embodiment contains: the above-mentioned pigment dispersion composition, binder resin (A-2), reactive diluent (E), and photopolymerization initiator (F). The photosensitive coloring composition of this embodiment may also contain solvent (D-2). Preferably, the photosensitive coloring composition of this embodiment contains, relative to 100 parts by weight of pigment (B): 50 to 280 parts by weight of the binder resin (A) and the binder resin (A-2), 40 to 200 parts by weight of the reactive diluent (E), and 0.1 to 10 parts by weight of the photopolymerization initiator (F). The solvent (D-2) can be the same as the solvent (D-1) contained in the above-mentioned pigment dispersion composition, or different solvents may be added.

[0083] [Adhesive Resin (A-2)] The binder resin (A-2) used in the photosensitive coloring composition is not particularly limited, but resins such as (meth)acrylic resin, epoxy (meth)acrylic resin, and vinyl ester resin commonly used in negative resists are preferred. As the specific skeleton, a resin containing vinyl unsaturated double bonds such as vinyl or (meth)acrylic groups, and substituents such as carboxylic acid, phosphoric acid, or sulfonic acid that contribute to alkali solubility, is more preferably provided. By using such resins, a photosensitive coloring composition with excellent pattern adhesion or developability can be provided.

[0084] Among these resins, especially from the viewpoint of readily providing a wide range of properties, (meth)acrylic resins having (meth)acryloxy and carboxyl groups are preferred. Commercially available resins can be used, or they can be prepared in-house. When preparing in-house, the same resin as the adhesive resin (A-1) can be used. Furthermore, in order to control the molecular weight within an appropriate range during synthesis, and to adjust the viscosity after synthesis to an appropriate range, a solvent (D-2) can be added.

[0085] There are no particular limitations on the physical properties of the adhesive resin (A-2). However, from the viewpoint of ease of manufacturing the photosensitive coloring composition or compatibility with other components, the following are preferred: weight average molecular weight: 1000~50000; solid fraction acid value: 10~200mgKOH / mg; double bond equivalent: 100~3000g / mol; and viscosity of the adhesive resin (A-2) solution: 0.1~1000dPa·s.

[0086] The total content of adhesive resin (A) of the aforementioned adhesive resin (A-1) and adhesive resin (A-2) is preferably 50 to 280 parts by weight, more preferably 75 to 230 parts by weight, and even more preferably 100 to 200 parts by weight, relative to 100 parts by weight of pigment (B).

[0087] [Reactive diluent (E)] The reactive diluent (E) can be any low-molecular-weight compound containing vinyl unsaturated double bonds such as vinyl or (meth)acryloxy groups, and is not particularly limited. Specific examples of reactive diluents (E) include aromatic vinyl monomers such as styrene, α-methylstyrene, α-chloromethylstyrene, vinyltoluene, divinylbenzene, diallyl phthalate, and diallyl phenylphosphonate; polycarboxylic acid monomers such as vinyl acetate and vinyl adipate; (meth)acrylate monomers such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, β-hydroxyethyl methacrylate, hydroxypropyl methacrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and tri(meth)acrylate of tri(hydroxyethyl)isocyanurate; and triallyl cyanurate, etc. These compounds can be used alone or in combination of two or more. Among them, compounds having a plurality of (meth)acryloxy groups are preferred, and compounds having three or more (meth)acryloxy groups are even more preferred, such as trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and tri(hydroxyethyl)isocyanurate tri(meth)acrylate.

[0088] The amount of reactive diluent (E) relative to 100 parts by weight of pigment (B) is preferably 40 to 200 parts by weight, more preferably 60 to 180 parts by weight, and even more preferably 80 to 160 parts by weight.

[0089] [Photopolymerization initiator (F)] Photopolymerization initiator (F), preferably a photoradical generator, includes, as specific examples, benzoin and its alkyl ethers such as benzoin, benzoin methyl ether, and benzoin ethyl ether; acetophenones such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, and 4-(1-t-butyldioxy-1-methylethyl)acetophenone; anthraquinones such as 2-methylanthraquinone, 2-pentylanthraquinone, 2-t-butylanthraquinone, and 1-chloroanthraquinone; and 2,4-dimethylthioxanthone and 2,4-diisopropylthioxanthone. Thioxanones such as ketones and 2-chlorothioxanone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenones such as 4-(1-t-butyldioxy-1-methylethyl)benzophenone and 3,3',4,4'-tetra(t-butyldioxycarbonyl)benzophenone; 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propane-1-one; 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1; oxyphosphine oxides; and thioxanones, etc. These can be used alone or in combination of two or more.

[0090] The content of photopolymerization initiator (F) relative to 100 parts by weight of adhesive resin (A-1), adhesive resin (A-2), and reactive diluent (E) is preferably 0.02 to 11 parts by weight, more preferably 0.24 to 6.7 parts by weight, and even more preferably 0.56 to 4.4 parts by weight.

[0091] In addition to the components described above, to impart the specified properties, the photosensitive coloring composition of this embodiment may also be formulated with known additives, fillers, etc., such as photoacid generators, photoalkali generators, coupling agents, and leveling agents. The amount of these components is not particularly limited without affecting the effects of the present invention.

[0092] [Manufacturing method of photosensitive coloring composition] The photosensitive coloring composition of this embodiment can be manufactured by mixing the above-mentioned components using a well-known mixing apparatus. For example, the pigment dispersion composition can be adjusted first, and then the binder resin (A-2), reactive diluent (E), photopolymerization initiator (F), etc., can be mixed in sequence. Furthermore, depending on the requirements, a solvent (D-2) can be added in addition to the solvent (D-1) contained in the pigment dispersion composition. In this case, the solvent (D) contained in the photosensitive coloring composition will include both solvent (D-1) and solvent (D-2). Moreover, the solvent (D-2) can be the same as solvent (D-1) or a different one.

[0093] The photosensitive coloring composition obtained through the above-described operation, even when the concentration of the colorant is increased while the concentration of the dispersant or binder resin is reduced, still maintains sufficient pigment dispersion or stability of the pigment dispersion composition. This results in high brightness and exhibits various inhibitory properties such as heat resistance, solvent resistance, pattern adhesion, and developability. Consequently, a color pattern with excellent reliability can be formed. In other words, by using the aforementioned photosensitive coloring composition, a color filter with excellent reliability can be provided.

[0094] <Color Filter> Next, a color filter having a color pattern composed of a hardened form of the photosensitive coloring composition of the present invention will be described. The color filter of the present invention has a color pattern formed using the aforementioned photosensitive coloring composition. Generally, a color filter is composed of the following components: a substrate; RGB pixels formed on the substrate; black matrices formed at the boundaries of the respective pixels; and protective films formed on the pixels and the black matrices. In this configuration, except that the pixels and the black matrices (color pattern) are formed using the aforementioned photosensitive coloring composition, other components can be those known to the public.

[0095] Next, one embodiment of the manufacturing method for a color filter will be described. First, a color pattern is formed on a substrate. Specifically, a black matrix and RGB pixels are sequentially formed on the substrate. The material of the substrate is not particularly limited, and glass substrates, silicon substrates, polycarbonate substrates, polyester substrates, polyamide substrates, polyamide-imide substrates, polyimide substrates, aluminum substrates, printed wiring substrates, array substrates, etc., can be used appropriately.

[0096] The colored pattern can be formed by photolithography. Specifically, after coating the above-mentioned photosensitive coloring composition onto a substrate to form a coating film, the coating film is exposed through a photomask with a specified pattern to photocur the exposed portion. Next, the unexposed portion is developed with an alkaline aqueous solution and then baked to form the specified colored pattern.

[0097] The coating method for the photosensitive coloring composition is not particularly limited; methods such as screen printing, roller coating, curtain coating, spraying, and spin coating can be used. Furthermore, after coating, the photosensitive coloring composition can be heated using methods such as circulating ovens, infrared heaters, or heating plates to evaporate the solvent (D-1) or solvent (D-2), as needed. Heating conditions are not particularly limited and can be appropriately set according to the type of photosensitive coloring composition used. Generally, heating at 50°C to 120°C for 30 seconds to 30 minutes is sufficient.

[0098] Next, through a negative mask, the formed coating is partially exposed by irradiating it with active energy lines such as ultraviolet light or excimer laser light. The amount of irradiated energy line can be appropriately selected according to the composition of the photosensitive colorant, for example, preferably 30~2000 mJ / cm2. There are no particular limitations on the light source used for exposure, and low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, xenon lamps, metal halide lamps, etc. can be used.

[0099] The alkaline aqueous solution used for developing is not particularly limited, and aqueous solutions of sodium carbonate, potassium carbonate, calcium carbonate, sodium hydroxide, potassium hydroxide, etc., can be used; aqueous solutions of amine compounds such as ethylamino, diethylamino, and dimethylethanolamino; aqueous solutions of p-phenylenediamine compounds such as tetramethylammonium, 3-methyl-4-amino-N,N-diethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamide ethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline, and their sulfates, hydrochlorides, or p-toluenesulfonates are also acceptable. Furthermore, defoamers or surfactants may be added to these aqueous solutions as needed. After developing with the above-mentioned alkaline aqueous solution, it is preferable to perform water washing and drying.

[0100] Furthermore, there are no particular limitations on the baking conditions; the heating process can be adjusted according to the type of photosensitive coloring agent used. Generally, heating at 130-250°C for 10-60 minutes is sufficient.

[0101] Using photosensitive coloring compositions for the black matrix and for red, green, and blue pixels, the coating, exposure, development, and baking processes described above are repeated sequentially to form the desired colored pattern. Then, a protective film is formed on the colored pattern (each pixel of the RGB matrix and the black matrix). The protective film is not particularly limited and can be formed using methods known to the public.

[0102] Color filters manufactured using this method achieve excellent pigment dispersion due to the uniform micronization of the pigments, and also achieve high brightness, excellent heat resistance, solvent resistance, adhesion, and developability, resulting in high precision.

[0103] <Image display element> The image display element of this embodiment includes the aforementioned color filter. Examples of such elements include solid-state imaging elements such as liquid crystal display elements, organic EL display elements, CCD elements, or CMOS elements. The manufacturing of the image display element of this embodiment can be performed using conventional methods, except for the use of the aforementioned color filter. For example, when manufacturing a liquid crystal display element, the aforementioned color filter is formed on a substrate, followed by the sequential formation of electrodes, spacers, etc. Then, after forming electrodes on another substrate, the two substrates are bonded together, a specified amount of liquid crystal is injected, and the substrate is sealed. [Example]

[0104] The present invention will now be described in detail with reference to embodiments, but the present invention is not limited to these embodiments. Furthermore, unless otherwise specified, in these embodiments, parts and percentages are based on mass.

[0105] <Method for measuring weight-average molecular weight> The weight-average molecular weights described below refer to the weight-average molecular weights of standard polystyrene obtained by gel permeation chromatography (GPC) under the following conditions. Tube String: Shodex (registered trademark) LF-804 + LF-804 (manufactured by Showa Denko Co., Ltd.) Column temperature: 40℃ Sample: 0.2% tetrahydrofuran solution of adhesive resin (A-1) Solvent: Tetrahydrofuran Detector: Differential refractometer (Shodex RI-71S) (manufactured by Showa Denko Co., Ltd.) Flow rate: 1 mL / min

[0106] <Methods for measuring acid value> According to JIS K6901 5.3.2, measure the number of mg of potassium hydroxide required to neutralize the acidic components contained in 1 g of the solids of adhesive resin (A-1). Measuring instrument: 776 Dosimat (Metrohm) Mixed indicator: A mixed indicator of bromothymol blue and phenol red.

[0107] <Method for measuring unsaturated basis equivalent> The mass of adhesive resin (A-1) per mole of vinyl unsaturated groups is a calculated value based on the amount of monomer used.

[0108] <Methods for measuring amine value> This refers to the mass of the polymeric dispersant (C) per mole of tertiary amine and quaternary ammonium cationic groups, calculated based on the amount of monomer used. The calculation is based on the definition of amine value (measured according to specifications shown in JIS K7237, etc.), representing the number of mg of potassium hydroxide required to neutralize the amine component contained in 1 g of the polymeric dispersant (C) in solid form.

[0109] Examples of the synthesis of adhesive resin (A-1) and comparative synthesis examples are presented below.

[0110] <Synthesis example 1> In a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer, and a gas inlet tube, 67.2 g of propylene glycol monomethyl ether acetate (50.0 parts by mass relative to a total of 100 parts by mass of monomers (m-1a), (m-2), and (m-3)) was added. The mixture was then stirred while replacing the gas with nitrogen and heated to 120°C. Next, 8.0 g of t-butyl-2-ethylhexanoate peroxide (8.4 parts by mass relative to a total of 100 parts by mass of monomers (m-1a), (m-2), and (m-3)) was added dropwise to the aforementioned flask as a polymerization initiator from a monomer mixture consisting of 16.2 g of dicyclopentyl methacrylate (m-1a), 26.5 g of acrylic acid (m-2), and 51.8 g of benzyl methacrylate (m-3). After the dripping process is complete, the mixture is stirred at 120°C for 2 hours to carry out a copolymerization reaction, thereby obtaining copolymer (P). Next, after replacing the aforementioned flask with dry air, 15.7 g of glycidyl methacrylate (m-4), 0.3 g of triphenylphosphine (0.3 parts by mass relative to a total of 100 parts by mass of monomers (m-1a), (m-2), (m-3), and (m-4)) as catalysts, and 0.2 g of hydroquinone monomethyl ether (0.2 parts by mass relative to a total of 100 parts by mass of monomers (m-1a), (m-2), (m-3), and (m-4)) as polymerization inhibitors were added. The mixture was stirred at 120°C for 5 hours to carry out the addition reaction with copolymer (P). Subsequently, propylene glycol monomethyl ether acetate was added as a solvent to achieve a solid fraction of 40.0%, resulting in a solution of adhesive resin (A-1) having ethylene unsaturated double bonds and carboxyl groups as alkali-soluble groups, which was designated as Sample No. 1. The mixing ratio of each monomer, the weight average molecular weight, acid value, and unsaturated group equivalent of the adhesive resin (A-1) are shown in Table 1 when the total of monomers (m-1a), (m-2) and (m-3) is set to 100 moles.

[0111] <Synthetic Examples 2, 5, 6; Comparative Synthetic Examples 1-4> Except for the monomer blending ratios listed in Table 1, the adhesive resin (A-1) was obtained in the same manner as in Synthesis Example 1, and these were designated as Sample No. 2, Sample No. 5 to 10. The blending ratios of each monomer, and the weight average molecular weight, acid value, and unsaturated group equivalent of the adhesive resin (A-1) are shown in Table 1.

[0112] <Synthesis example 3> The copolymer (P) was obtained in the same manner as in Synthesis Example 1. Next, after replacing the aforementioned flask with dry air, 15.7 g of glycidyl methacrylate (m-4), 0.3 g of triphenylphosphine as a catalyst (0.3 parts by mass relative to a total of 100 parts by mass of monomers (m-1a), (m-2), (m-3) and (m-4)), and 0.2 g of hydroquinone monomethyl ether as a polymerization inhibitor (0.2 parts by mass relative to a total of 100 parts by mass of monomers (m-1a), (m-2), (m-3) and (m-4)) were added, and the mixture was stirred at 120°C for 5 hours to carry out the addition reaction of copolymer (P). Then, 10.4 g of ethyl 2-isocyanate acrylate (m-5) was added, and the mixture was stirred at 100°C for 1 hour to carry out the addition reaction with copolymer (P). Propylene glycol monomethyl ether acetate was added as a solvent to achieve a solid fraction of 40.0%, resulting in a solution of adhesive resin (A-1) with ethylene unsaturated double bonds and carboxyl groups as alkali-soluble groups. This solution was designated as sample No. 3. The mixing ratio of each monomer, the weight average molecular weight, acid value, and unsaturated group equivalent of the adhesive resin (A-1) are shown in Table 1 when the total of monomers (m-1a), (m-2) and (m-3) is set to 100 moles.

[0113] <Synthesis example 4> The copolymer (P) was obtained in the same manner as in Synthesis Example 1. Next, after replacing the contents of the aforementioned flask with dry air, 15.7 g of glycidyl methacrylate (m-4), 0.3 g of triphenylphosphine (0.3 parts by mass relative to a total of 100 parts by mass of monomers (m-1a), (m-2), (m-3), and (m-4)) as catalysts, and 0.2 g of hydroquinone monomethyl ether (0.2 parts by mass relative to a total of 100 parts by mass of monomers (m-1a), (m-2), (m-3), and (m-4)) as polymerization inhibitors were added. The mixture was stirred at 120°C for 5 hours to carry out the addition reaction with copolymer (P). Then, 7.4 g of succinic anhydride (m-6) was added, and the mixture was stirred at 120°C for 1 hour to carry out the addition reaction with copolymer (P). Subsequently, propylene glycol monomethyl ether acetate was added as a solvent in a solid fraction of 40.0% to obtain a solution of adhesive resin (A-1) having ethylene unsaturated double bonds and carboxyl groups as alkali-soluble groups, and this was taken as sample No.4. The mixing ratio of each monomer, the weight average molecular weight, acid value, and unsaturated group equivalent of the adhesive resin (A-1) are shown in Table 1 when the total of monomers (m-1a), (m-2) and (m-3) is set to 100 moles.

[0114]

[0115] An example of manufacturing a polymeric dispersant (C) is shown below.

[0116] <Synthesis Example 7> In a flask equipped with a stirrer, dropping funnel, condenser, thermometer, and gas inlet tube, 133 g of propylene glycol monomethyl ether acetate, 80.5 g of isoborneol methacrylate, and 13.2 g of tetramethylethylenediamine as a catalyst were added to replace nitrogen in the flask, and the mixture was stirred at 50 °C for 1 hour. Then, 9.3 g of ethyl bromoisobutyrate and 5.6 g of copper(I) chloride as a catalyst were added, and the flask was heated to 110 °C for 4 hours for polymerization. After the reaction, the solution was sampled to measure the non-volatile matter. Once the polymerization conversion rate, calculated from the non-volatile matter, was confirmed to be above 98%, 61 g of propylene glycol monomethyl ether acetate and 19.5 g of dimethylaminoethyl methacrylate, a monomer with tertiary amine groups, were added, and the reaction was carried out at 110 °C for 2 hours. After the reaction, the solution was sampled again to measure the non-volatile content. Once the polymerization conversion rate calculated from the non-volatile content was confirmed to be above 98%, the solution was cooled. Finally, propylene glycol monomethyl ether acetate was added as a solvent with a solid content of 40.0%, resulting in sample No. 11 (amine value 70 mg KOH / g, weight average molecular weight 5500) as a solution of a polymeric dispersant (C) with tertiary amine groups.

[0117] <Synthesis example 8> In a flask equipped with a stirrer, dropping funnel, condenser, thermometer, and gas inlet tube, 133 g of propylene glycol monomethyl ether acetate, 70.0 g of isoborneol methacrylate, and 13.2 g of tetramethylethylenediamine as a catalyst were added to replace nitrogen in the flask, and the mixture was stirred at 50 °C for 1 hour. Then, 9.3 g of ethyl bromoisobutyrate and 5.6 g of copper(I) chloride as a catalyst were added, and the flask was heated to 110 °C for 4 hours for polymerization. After the reaction, the solution was sampled to measure the non-volatile matter. Once the polymerization conversion rate, calculated from the non-volatile matter, was confirmed to be above 98%, 61 g of propylene glycol monomethyl ether acetate and 30.0 g of methacryloxyethyl benzyl dimethyl ammonium chloride (a monomer with quaternary ammonium cationic groups) were added, and the reaction was carried out at 110 °C for 2 hours. After the reaction, the solution was sampled again to measure the non-volatile content. Once the polymerization conversion rate calculated from the non-volatile content was confirmed to be above 98%, the solution was cooled. Finally, propylene glycol monomethyl ether acetate was added as a solvent with a solid content of 40.0%, resulting in sample No. 12 (amine value 60 mg KOH / g, weight average molecular weight 5000) as a solution of a polymeric dispersant (C) with quaternary ammonium cationic groups.

[0118] An example of manufacturing a pigment dispersion composition is shown below.

[0119] <Examples 1-7, Comparative Examples 1-4> In an SUS container (50 mm inner diameter × 100 mm height) filled with 200 g of zirconia beads (NIKKATO YTZ balls) with a diameter of 0.1 mm, the following components were mixed according to the composition shown in Table 2: 7.5 g of CI Pigment Green 58 (Fastogen Green A110 manufactured by DIC Corporation) as pigment (B), either sample No. 11 with tertiary amine groups or sample No. 12 with quaternary ammonium cationic groups as polymeric dispersant (C), and any of the aforementioned samples No. 1 to No. 10 as adhesive resin (A-1), and as solvent (D-1), propylene glycol monomethyl ether acetate was added to a solid content excluding zirconia beads of 24%, and the mixture was dispersed by mixing at room temperature for 2 hours using a paint shaker (Red Devil 5400 manufactured by Red Devil Equipment). The contents were then filtered using a glass filter to obtain pigment dispersions No. 1-7 and 10-13.

[0120] <Examples 8-9, Comparative Example 5> Except for the following: mixing according to the composition shown in Table 2: 9.4 g of CI Pigment Green 58 as pigment (B), EFKA-PX4300 as polymeric dispersant (C), and any one of the aforementioned samples No.1, No.6, or No.10 as adhesive resin (A-1), the remaining components were mixed in the same manner as in Example 1 to obtain pigment dispersion compositions No.8-9 and 14.

[0121] <Evaluation of Pigment Dispersion> The viscosity of the freshly prepared pigment dispersion was measured using an E-type viscometer (RE-80L, manufactured by Toki Sangyo Co., Ltd., measuring temperature 25°C, cone type No. 3, rotation speed 20 rpm) for evaluation. Furthermore, based on the viscosity measurement results, the pigment dispersibility and storage stability of the pigment dispersion were evaluated using three stages (◎, ○, ×) according to the following criteria, with ◎ and ○ designated as acceptable. The evaluation results are shown in Table 2. ◎: Less than 6.0 mPa·s ○: 6.0 mPa·s or higher but less than 10.0 mPa·s ×: 10.0 mPa·s or higher

[0122] <Evaluation of the storage stability of pigment dispersions> The viscosity of the prepared pigment dispersion was measured using an E-type viscometer after being stored at room temperature for two weeks for evaluation. The rate of increase in viscosity of the pigment dispersion after two weeks of storage at room temperature was compared with that of the freshly prepared dispersion. The evaluation was conducted using three stages (○, △, ×) according to the following criteria, with ○ and △ being considered acceptable. The evaluation results are shown in Table 2. ○: Less than 10% △: 10% or more (less than 10% after one week of storage at room temperature) ×: Above 10% (After being stored at room temperature for one week, it has reached above 10%)

[0123]

[0124] An example of manufacturing adhesive resin (A-2) is shown below.

[0125] <Synthesis Example 9> In the above Synthesis Example 1, except that 11.9 g of dicyclopentyl methacrylate was used to replace 16.2 g of dicyclopentyl methacrylate (m-1a); 42.7 g of benzyl methacrylate was used to replace 51.8 g of benzyl methacrylate (m-3); 20.9 g of methacrylic acid was used to replace 26.5 g of acrylic acid (m-2); 1.6 g of t-butyl-2-ethylhexanoate peroxide was used to replace 8.0 g of t-butyl-2-ethylhexanoate peroxide as a polymerization initiator; and 11.5 g of glycidyl methacrylate was used to replace 15.7 g of glycidyl methacrylate (m-4), the same method as in Synthesis Example 1 was used to obtain Sample No. 13 (molecular weight 32000, solid fraction acid value 104 mg KOH / g, vinyl unsaturated group equivalent 1100 g / mol) as an adhesive resin (A-2).

[0126] An example of manufacturing a photosensitive coloring composition is shown below.

[0127] <Examples 10-18, Comparative Examples 6-10> When the solid fractions of the aforementioned pigment dispersions No. 1 to 13 are divided into 100 parts by weight, the following are mixed: 80 parts by weight of the aforementioned sample No. 13 as an adhesive resin (A-2), 80 parts by weight of dipentaerythritol hexaacrylate as a reactive diluent (E), 4 parts by weight of 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl-]-,-1-(O-acetyloxime) as a photopolymerization initiator (F), and propylene glycol monomethyl ether acetate as a solvent (D-2) are added in such a manner that the total solid fraction is 30%, thereby preparing photosensitive coloring compositions No. 1 to 14. Furthermore, as relative to 100 parts by mass of pigment (B), for photosensitive coloring compositions No. 1-7 and No. 10-13, the amounts of each component are: 120 parts by mass of binder resin (A-2), 120 parts by mass of reactive diluent (E), and 6 parts by mass of photopolymerization initiator (F). For photosensitive coloring compositions No. 8, No. 9, and No. 14, the amounts of binder resin (A-2) are: 112 parts by mass of binder resin (A-2), 112 parts by mass of reactive diluent (E), and 5.6 parts by mass of photopolymerization initiator (F).

[0128] <Evaluation of the storage stability of photosensitive coloring compositions> The viscosity of the prepared photosensitive coloring composition and that of the adjusted photosensitive coloring composition after being stored at room temperature for 2 weeks were measured using an E-type viscometer (RE-80L, Toki Sangyo Co., Ltd., measuring temperature 25°C, cone type No. 3, rotation speed 20 rpm) for evaluation. The rate of increase in viscosity of the photosensitive coloring composition after 2 weeks of storage at room temperature was compared with that of the freshly prepared composition, and the evaluation was carried out in two stages according to the following criteria: ○ (pass) and × (fail). The evaluation results are shown in Tables 3 and 4. ○: Less than 10% ×:10% or more

[0129] <Preparation of Green Color Inhibitor (1)> Photosensitive coloring components No. 1-7 and No. 10-13 were spin-coated onto a 5 cm square glass substrate (alkali-free glass substrate) with an average thickness of 2.0 μm for the final hardened coating. The substrate was then heated at 100°C for 3 minutes to evaporate the solvent. Next, the entire surface of the coating was exposed (Ushio Electric Co., Ltd. USH-250BY lamp was used with an exposure dose of 40 mJ / cm²), and then baked at 230°C for 30 minutes to obtain a green color resist as a hardened coating (1).

[0130] <Preparation of Green Color Inhibitor (2)> Photosensitive coloring components No. 1-7 and No. 10-13 were spin-coated onto a 5 cm square glass substrate (alkali-free glass substrate) with an average final hardened coating thickness of 2.0 μm. The substrate was then heated at 100°C for 3 minutes to evaporate the solvent. Next, a line and space or dot pattern photomask was set on the substrate, and the coating was exposed (Ushio Electric Co., Ltd. USH-250BY lamp with an exposure dose of 40 mJ / cm²) for photocuring. Afterward, development was performed using a 0.2% by mass potassium hydroxide aqueous solution. Finally, the substrate was baked at 230°C for 30 minutes to obtain a green color resist as a hardened coating (2).

[0131] <Preparation of Green Color Inhibitor (3)> Except for adjusting the photosensitive coloring components No.1, No.7~9, and No.14 to the average thickness described later and placing them on a 5cm square glass substrate (alkali-free glass substrate), the rest were prepared in the same manner as the green color resist (1) to obtain the green color resist (3) as a hardened coating. The aforementioned average thickness was achieved using a Shimadzu UV-1650PC spectrophotometer to ensure that the final hardened coating had an average thickness of x=0.26±0.005 and y=0.45±0.005 in the color coordinates.

[0132] <Coloring strength test> The film thickness of the green color resist (3) was measured using a step gauge (ET4000M manufactured by Kosaka Labs Co., Ltd.). The film thickness was evaluated in three stages (◎, ○, ×) according to the following criteria, with ◎ and ○ being considered acceptable. The evaluation results are shown in Table 4. ◎: Film thickness less than 1.9μm ○: Film thickness 1.9~2.1μm ×: Film thickness 2.1μm or more

[0133] <Penetration Test> The transmittance of the green color resists (1) and (3) at 525 nm was measured using a Shimadzu UV-1650PC spectrophotometer. A transmittance of 95.0% or higher was set as ○ (pass), and a transmittance of 94.9% or lower was set as × (fail). The measurement results are shown in Tables 3 and 4.

[0134] <Soluble Resistance Test> The entire surface of the green color resist (1) was immersed in N-methylpyrrolidone at 60°C or 80°C for 3 minutes. Afterwards, the green color resist was removed and air-dried. The degree of peeling of the entire surface of the green color resist was visually assessed. Based on the presence or absence of peeling, the solvent resistance of the photosensitive coloring composition was evaluated using three stages (◎, ○, ×) according to the following criteria, with ◎ and ○ designated as acceptable. The evaluation results are shown in Table 3. ◎: No peeling occurred at 60℃ and 80℃. ○: More than one instance of peeling was observed at 80℃, but no peeling was observed at 60℃. ×: More than one instance of peeling was observed at 60℃ and 80℃.

[0135] <Reflectivity Test> The developability test evaluates two aspects: developing speed and pattern shape. Regarding the development speed, in the development step of the green color resist (2) described above, the time required until the pattern is no longer visible in the development using a 0.2% by mass potassium hydroxide aqueous solution was measured. The evaluation was conducted according to the following criteria using three stages: ◎, ○, and ×, with ◎ and ○ being considered acceptable. The evaluation results are shown in Table 3. ◎: Less than 40 seconds ○: 40 seconds or more but less than 80 seconds ×: Over 80 seconds

[0136] Regarding the pattern shape, the procedure was performed under the condition that the development speed was acceptable. The shape of the pattern end face of the hardened coating of the green color resist (2) was confirmed using a scanning electron microscope (S-3400N manufactured by Hitachi-High Technologies Co., Ltd.). The evaluation was conducted in two stages, ○ (acceptable) and × (unacceptable), according to the following criteria. The evaluation results are shown in Table 3. ○: The end face shape is preferred (not an inverted cone shape). ×: The end face becomes an inverted cone shape.

[0137]

[0138]

[0139] As can be seen from the results in Tables 2 and 3, Examples 1-16 generally exhibit excellent pigment dispersibility and storage stability of the pigment dispersion compositions, as well as excellent transmittance and solvent resistance of the photosensitive coloring compositions. Furthermore, they confirm that the pigment dispersion compositions provide high brightness and suppress colorant exudation. This results in excellent development speed and pattern shape, and demonstrates the ability to provide color filters with excellent processability. In particular, Examples 4 and 13, compared to Examples 1 and 10, used an adhesive resin (A-1) with more vinyl unsaturated groups incorporated into its side chain, thus achieving very excellent solvent resistance in the photosensitive coloring composition. However, on the other hand, Examples 5 and 14, compared to Examples 1 and 10, used an adhesive resin (A-1) with more carboxylic acids incorporated into its side chain, thus achieving very excellent developability in the photosensitive coloring composition.

[0140] Furthermore, the results in Tables 2 and 4 show that, compared to Examples 1 and 10, Examples 8 and 17, even with reduced concentrations of dispersant or binder resin due to the high concentration of pigment, still exhibited sufficient pigment dispersibility and storage stability. This indicates that, even in a thin film state, the photosensitive coloring composition possesses sufficient tinting strength due to the high pigment concentration, and exhibits excellent solvent resistance due to the reduced concentration of dispersant or binder resin, which inhibits colorant exudation.

[0141] Conversely, in Comparative Examples 1 and 6, the pigment dispersion composition exhibited good pigment dispersibility and storage stability. However, on the other hand, the curing properties of the photosensitive coloring composition were poor because the binder resin (A-1) lacked constituent units derived from the compound (m-4) containing vinyl unsaturated groups. As a result, peeling of the green color resist or the inverted conical shape of the developing pattern was confirmed in the solvent resistance test.

[0142] Furthermore, in Comparative Examples 2 and 7, the pigment dispersion composition exhibits superior pigment dispersibility and storage stability. However, on the other hand, since the binder resin (A-1) lacks constituent units derived from the polymerizable monomer (m-1), the transmittance and solvent resistance of the photosensitive coloring composition are poor. Consequently, it is impossible to achieve high brightness and suppress colorant exudation.

[0143] Furthermore, in Comparative Examples 3-4 and 8-9, since the adhesive resin (A-1) lacks constituent units derived from acrylic acid (m-2) and polymerizable monomers containing aromatic rings (m-3), the pigment dispersion and storage stability of the pigment dispersion composition are significantly poor. Consequently, the storage stability, transmittance, and developability of the photosensitive coloring composition are also poor, making it a composition that is difficult to use practically.

[0144] Furthermore, the results from Tables 2 and 4 reveal the following: In Comparative Examples 5 and 10, since the adhesive resin (A-1) does not contain constituent units from the aromatic-ring-containing polymeric monomer (m-3), similar to Comparative Examples 4 and 9, even in pigment dispersion compositions with high pigment concentrations, the pigment dispersibility is insufficient, and the storage stability or penetration rate is also poor, making practical use difficult. The aforementioned aromatic-ring-containing polymeric monomer (m-3) has a high affinity for the pigment (B). When considering the results of Examples 8 and 17, and Examples 9 and 18 together, the following situation emerges: Adhesive resin (A-1) with a low content of aromatic-ring-containing polymeric monomer (m-3), as in Examples 7 and 16, can be used in pigment dispersion compositions with low pigment concentrations, but in cases of high pigment concentrations, the storage stability tends to decrease.

[0145] Based on the above, it can be understood that the present invention provides a pigment dispersion composition that achieves high brightness due to sufficient pigment dispersibility or preservation stability, and suppresses colorant exudation, thereby exhibiting excellent heat resistance, solvent resistance, pattern adhesion, and reliability. Furthermore, a photosensitive coloring composition comprising the pigment dispersion composition and a color filter comprising the photosensitive coloring composition can be provided. [Industrial Utilization]

[0146] According to the present invention, a pigment dispersion composition with good pigment dispersibility or storage stability can be provided. Furthermore, by using this pigment dispersion composition, a photosensitive coloring composition capable of producing a cured material with excellent solvent resistance can be provided. Moreover, a color filter having a cured material having the photosensitive coloring composition and an image display element having the color filter can be provided.

Claims

1. A pigment dispersion composition, characterized in that it comprises: a binder resin (A-1), a pigment (B), a polymeric dispersant (C), and a solvent (D-1), wherein the binder resin (A-1) is a resin selected from the group consisting of resin (A-1a) and resin (A-1b), wherein the resin (A-1a) is a resin obtained by adding a portion of the carboxyl group of a copolymer (P) of monomer (M) to a compound (m-4) having an ethylene-containing unsaturated group having a group reactive with the carboxyl group, wherein the monomer (M) comprises: a polymerizable monomer (m-1a) selected from a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms (but excluding the monomers of the following formula (1)). The polymerizable monomers (m-1b), acrylic acid (m-2), and aromatic ring-containing polymerizable monomers (m-3) are represented. The polymerizable monomer (m-1a) is a (meth)acrylate having the structure represented by formula (5). The resin (A-1b) is obtained by adding one or more of the hydroxyl groups in the resin (A-1a) to a compound (m-5) containing an isocyanate group and a polyacid anhydride (m-6). The hydroxyl group is generated by ring-opening addition of the compound (m-4) containing an isocyanate group in the resin (A-1a) to a monomer having an epoxy group or an oxetane.

1. (In formula (1), R1 and R2 independently represent hydrogen atoms or hydrocarbon groups with 1 to 20 carbon atoms, and R1 and R2 can also be bonded to form a ring structure, and R3 and R4 independently represent hydrogen atoms, or straight-chain or branched hydrocarbon groups with 1 to 4 carbon atoms, respectively.) 1. (In formula (5), R7~R9 represent hydrogen atoms or methyl groups respectively, R10 and R11 represent hydrogen atoms or methyl groups, or can be bonded to form saturated or unsaturated rings, which are 5-membered or 6-membered rings, and * represents the bond attached to (meth)acryloxy group).

2. The pigment dispersion composition as claimed in claim 1, wherein, The aforementioned pigment (B) includes pigments having a halogenated phthalocyanine skeleton.

3. The pigment dispersion composition as claimed in claim 1 or 2, wherein, The aforementioned polymeric dispersant (C) has at least one group selected from the group consisting of tertiary amine groups and quaternary ammonium cationic groups.

4. The pigment dispersion composition as claimed in claim 1 or 2, wherein, The aforementioned polymeric dispersant (C) is a block polymer of at least one monomer selected from the group consisting of monomers having tertiary amino groups and vinyl unsaturated groups, and monomers having quaternary ammonium cationic groups and vinyl unsaturated groups, and other monomers having vinyl unsaturated groups.

5. The pigment dispersion composition as claimed in claim 1 or 2, wherein, The aforementioned compound (m-4) containing an ethylene-containing unsaturated group has an epoxy or oxobutyric group that is reactive with the carboxyl group.

6. The pigment dispersion composition as claimed in claim 1 or 2, wherein, When the total of the aforementioned polymerizable monomer (m-1), the aforementioned acrylic acid (m-2), and the aforementioned aromatic ring-containing polymerizable monomer (m-3) of the aforementioned copolymer (P) is set to 100 mol%, the proportion of the aforementioned aromatic ring-containing polymerizable monomer (m-3) is 9 to 70 mol.

7. The pigment dispersion composition as claimed in claim 1 or 2, wherein, The aforementioned adhesive resin (A-1) is the aforementioned resin (A-1b).

8. The pigment dispersion composition as claimed in claim 1 or 2, wherein, Relative to 100 parts by weight of the aforementioned pigment (B), it contains 10 to 50 parts by weight of the aforementioned adhesive resin (A-1) and 10 to 80 parts by weight of the aforementioned polymeric dispersant (C).

9. The pigment dispersion composition as claimed in claim 8, wherein, The product contains 10 to 50 parts by mass of the aforementioned polymeric dispersant (C) relative to 100 parts by mass of the aforementioned pigment (B).

10. A photosensitive coloring composition, characterized in that it comprises: a pigment dispersion composition of any one of claims 1 to 9, a binder resin (A-2), a reactive diluent (E), and a photopolymerization initiator (F), wherein the binder resin (A-2) is a (meth)acrylic resin having (meth)acryloxy and carboxyl groups.

11. The photosensitive coloring composition as claimed in claim 10, wherein, Relative to 100 parts by weight of the aforementioned pigment (B), the total amount of the aforementioned adhesive resins (A-1) and (A-2) is 50 to 280 parts by weight, the amount of the aforementioned polymeric dispersant (C) is 10 to 80 parts by weight, the amount of the aforementioned reactive diluent (E) is 40 to 200 parts by weight, and the amount of the aforementioned photopolymerization initiator (F) is 0.1 to 10 parts by weight.

12. A resin-cured film formed by curing a photosensitive coloring composition as claimed in claim 10 or 11.

13. A color filter having a hardened form of the photosensitive coloring composition as claimed in claim 10 or 11.

14. An image display element comprising a color filter as claimed in claim 13.