Photosensitive colored resin composition, cured product, color filter and display device

Abstract

The photosensitive coloring resin composition of the present invention contains a colorant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a solvent. The colorant contains a lake colorant of a triarylmethane dye, and the alkali-soluble resin contains an alkali-soluble resin (U). The alkali-soluble resin (U) contains structural units having a benzotriazole backbone and has a weight average molecular weight of 3000 or more.

Description

Technical Field

[0001] This invention relates to a photosensitive coloring resin composition, a cured material, a color filter, and a display device. Prior Technology

[0002] In recent years, with the development of personal computers, especially portable personal computers, the demand for LCD monitors has been increasing. The penetration rate of mobile displays (mobile phones, smartphones, and tablet PCs) is also constantly rising, leading to a rapidly expanding LCD market. Organic light-emitting display devices, such as organic EL (Electroluminescence) displays, which offer higher visibility due to their self-emissive nature, are also attracting attention as next-generation image display devices. These liquid crystal display devices or organic light-emitting display devices use color filters. For example, in the formation of a color image in a liquid crystal display device, light passing through a color filter is directly colored into the colors of each pixel constituting the color filter, and these colored lights are combined to form a color image. As the light source in this case, sometimes white-emitting organic light-emitting elements or white-emitting inorganic light-emitting elements are used. In organic light-emitting display devices, color filters are used for adjusting colors, etc.

[0003] Here, a color filter typically has: a substrate; a color layer formed on the substrate and containing a color pattern of the three primary colors of red, green and blue; and a light-shielding portion formed on the substrate in a manner that divides each color pattern. As a method for forming the colored layer in a color filter, for example, a colored resin composition, formed by adding a binder resin, a photopolymerizable compound, and a photoinitiator to a pigment dispersion prepared by dispersing pigments with a dispersant or the like, is coated onto a glass substrate and dried. Then, it is exposed using a photomask and developed to form a colored pattern. The pattern is then fixed by heating to form the colored layer. These steps are repeated for each color to form a color filter.

[0004] In recent years, the requirements for higher brightness in color filters have increased, and pigment-based color filters are finding it difficult to meet the current requirements for further higher brightness. Therefore, in recent years, the industry has been researching the use of dyes with higher transmittance than pigments, or the use of precipitants to make dyes into insoluble lake pigments as colorants for color filters. However, dyes or lake pigments have the following problems: compared with pigments used in color filters to date, they have poor heat resistance and the colored layer is prone to fading when heated at high temperatures during the color filter manufacturing process.

[0005] In this regard, Patent Document 1 discloses a color filter coloring resin composition that uses lake pigments and is able to suppress the fading of the color layer caused by high-temperature heating in the color filter manufacturing process, forming a high-brightness color layer. The color filter coloring resin composition contains lake pigments, dispersants, hindered phenolic antioxidants, binder components, and solvents, and the dispersant is a specific polymer in which at least a portion of the nitrogen site forms a salt with an acidic organophosphorus compound.

[0006] On the other hand, as a photosensitive coloring composition containing an ultraviolet absorber, Patent Document 2 discloses a coloring resin composition characterized by containing (A) a dye, (B) a solvent, and (C) an adhesive resin, and further containing (D) an antioxidant and (E) an ultraviolet absorber. The object of Patent Document 2 is to provide a coloring resin composition that can maintain and improve the brightness and heat resistance of the obtained pixels, and thereby form contact holes of the desired diameter. Furthermore, Patent Document 3 discloses a photosensitive coloring composition, characterized by comprising a colorant (A); a resin (B); a photopolymerizable monomer (C); a photopolymerization initiator (D) comprising a phosphonium oxychloride organic compound or an oxime ester organic compound; and an ultraviolet absorber (E) selected from at least one of the groups consisting of benzotriazole organic compounds, triazine organic compounds, and benzophenone organic compounds; and the resin (B) comprising a photosensitive resin (B-1), which is configured as follows (b1), (b2), and (b3): (b1): A compound with an alicyclic skeleton and vinyl unsaturated bonds in one molecule. (b2): A compound containing an epoxy group and an vinyl unsaturated bond in one molecule. (b3): ​​A copolymer (b6) is obtained by copolymerizing compounds with ethylene-like unsaturated bonds other than (a1) and (a2), and the obtained copolymer (b6) is reacted with an unsaturated monobasic acid (b4) to obtain a copolymer (b7), and then the obtained copolymer (b7) is reacted with a polybasic anhydride (b5) to obtain a copolymer. The object of Patent Document 3 is to obtain a photosensitive coloring composition with high resolution that can cope with high image quality and low power consumption, especially a photosensitive coloring composition with excellent adhesion that has high resolution even for thick films such as COA (Color Filter on Array) without causing pattern peeling.

[0007] Furthermore, Patent Document 4 discloses a coloring composition for color filters, characterized in that it comprises a colorant (A), a resin (B), a photopolymerizable monomer (C), a photopolymerization initiator (D), and an ultraviolet absorber (E) formed by polymerizing raw material monomers containing benzotriazole monomers and other monomer components, wherein the raw material monomers contain 10.0% to 90.0% by weight of benzotriazole monomers, and the ultraviolet absorber (E) comprises 0.5% to 6.0% by weight of the solid content of the entire coloring composition for color filters. The coloring composition for color filters described in Patent Document 4, by including the ultraviolet absorber (E), exhibits excellent lightfastness and good adhesion. Previous technical documents Patent documents

[0008] Patent Document 1: Japanese Patent Application Publication No. 2014-153569 Patent Document 2: Japanese Patent Application Publication No. 2015-98537 Patent Document 3: Japanese Patent No. 5664299 Patent Document 4: Japanese Patent No. 6578775 Summary of the Invention

[0009] [The problem the invention aims to solve]

[0010] With the increasing sophistication of displays, such as 4K / 8K, pixel sizes are constantly decreasing. This leads to a reduction in the aperture ratio (aperture ratio) of pixels, requiring photoresist with higher brightness and photosensitive coloring resin compositions capable of forming patterns with finer line widths. However, when the dye is dissolved and used as in Patent Document 2, the heat resistance is particularly poor and the brightness of the pixel is not sufficiently improved. Furthermore, in the techniques that use pigments as in Patent Documents 3 and 4, the brightness of the pixel is not sufficiently improved. Triarylmethane-based lake pigments are an example of pigments effective for increasing pixel brightness. However, because the transmittance of triarylmethane-based lake pigments in the UV (Ultra Violet) wavelength region is higher than that of previously used pigments (e.g., CI Pigment Blue 15:6, CI Pigment Violet 23), if the photoinitiator is formulated in the same way as before, the pattern linewidth tends to become coarser. If the photoinitiator dosage is reduced to make the pattern linewidth meet a specific value, or if an antioxidant is added as in Patent Document 1, or if the amount of antioxidant added is increased, the photocuring of the pattern area is insufficient, the film thickness variation from before to after development increases, the residual film yield decreases, and it is difficult to achieve both a finer linewidth design and a higher residual film yield. Patent Document 1 describes a lake pigment containing triarylmethane dyes, but does not address the issue of balancing a finer linewidth design with a higher residual film yield. Patent Document 2 describes a photosensitive coloring resin composition containing triarylmethane dyes. However, since the dyes are dispersed at the molecular level in the photosensitive coloring resin composition, they can easily hinder the curing of photocurable components. If the photoinitiator is formulated in the same way as the pigment, the photocuring is insufficient, the linewidth is easily finer than designed, and the residual film yield is easily reduced. Therefore, in a photosensitive coloring resin composition containing dyes, in order to achieve the desired finer linewidth, it is necessary to increase the photoinitiator or use a photoinitiator with higher sensitivity, thus naturally increasing the residual film yield. Therefore, the issue of the photosensitive coloring resin composition containing dyes being unable to balance a finer linewidth design with a higher residual film yield was not originally present. Furthermore, since Patent Documents 3 and 4 use pigments, the issue of the difficulty in balancing a finer linewidth design with a higher residual film yield was not originally present. As mentioned above, when using lake pigments based on triarylmethane dyes, unlike when using pigments or dyes, there is a challenge in achieving both finer linewidth design and higher residual film yield in the development process.

[0011] On the other hand, the photosensitive coloring resin composition for color filters containing ultraviolet absorbers, as described in Patent Documents 2 and 3, has the following problem: even if it contains ultraviolet absorbers, the final colored layer cannot improve its ultraviolet (UV) resistance. This is believed to be because the low molecular weight ultraviolet absorber volatilizes during high-temperature heating steps such as 230°C, leaving no ultraviolet absorber residue in the final colored layer after the high-temperature heating step. Furthermore, the photosensitive coloring resin composition for color filters described in Patent Document 4, which contains an ultraviolet absorber derived from a polymer formed by polymerizing raw material monomers containing benzotriazole monomers, has the following problem: when it contains ultraviolet absorbers of high molecular weight polymers, it easily remains as developing residue; when it contains ultraviolet absorbers of low molecular weight polymers, it volatilizes during high-temperature heating steps such as 230°C, and the final colored layer cannot improve its ultraviolet (UV) resistance. If the final colored layer cannot improve its UV resistance, problems may arise, such as the following: after the colored layer is formed, during subsequent steps such as the formation of the protective layer, the colored layer will fade after a pre-cleaning step using UV irradiation with a low-pressure mercury lamp. In order to suppress color changes during UV irradiation in this manufacturing process, the UV resistance of the colored layer must also be improved.

[0012] The present invention was made in view of the above-mentioned actual situation, and its object is to provide a photosensitive coloring resin composition containing a lake pigment of triarylmethane dye, which can improve brightness, form a colored layer with a finer linewidth to suppress film thickness changes and development residues before and after development, and has excellent UV resistance. Furthermore, the present invention aims to provide a color filter and display device formed using this photosensitive coloring resin composition. [Technical means to solve the problem]

[0013] The photosensitive coloring resin composition of the present invention contains a colorant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a solvent, and The above-mentioned pigments contain lake pigments of triarylmethane dyes. The above-mentioned alkali-soluble resin contains alkali-soluble resin (U), which contains structural units having a benzotriazole skeleton and has a weight average molecular weight of 3000 or more.

[0014] The color filter of the present invention comprises at least a substrate and a coloring layer disposed on the substrate, and at least one of the coloring layers is a cured form of the photosensitive coloring resin composition of the present invention.

[0015] The display device of the present invention has the color filter of the present invention described above. [Effects of the Invention]

[0016] According to the present invention, a photosensitive coloring resin composition is provided that contains a lake pigment containing a triarylmethane dye, thereby improving brightness and forming a colored layer with a finer linewidth to suppress film thickness changes and development residues before and after development, and exhibiting excellent UV resistance. Furthermore, according to the present invention, a color filter and a display device formed using this photosensitive coloring resin composition are provided. Simple Explanation of the Diagram

[0017] Figure 1 is a schematic diagram showing one example of the color filter of the present invention. Figure 2 is a schematic diagram showing an example of the liquid crystal display device of the present invention. Figure 3 is a schematic diagram showing an example of the organic light-emitting display device of the present invention. Implementation

[0018] The photosensitive coloring resin composition, the cured material, the color filter, and the display device of the present invention will be described in detail below. Furthermore, in this invention, light includes electromagnetic waves of wavelengths in both visible and invisible regions, and is radiated, such as microwaves and electron beams. Specifically, it refers to electromagnetic waves with wavelengths below 5 μm and electron beams. In this invention, (meth)acrylic acid group represents acrylonitrile and methacrylic acid group respectively, (meth)acrylic acid group represents acrylic acid and methacrylic acid group respectively, and (meth)acrylate group represents acrylate and methacrylate group respectively. Furthermore, in this specification, the "~" symbol indicating a numerical range is used to encompass the values ​​before and after it as the lower and upper limits.

[0019] I. Photosensitive coloring resin composition The photosensitive coloring resin composition of the present invention contains a colorant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a solvent, and The above-mentioned pigments contain lake pigments of triarylmethane dyes. The above-mentioned alkali-soluble resin contains alkali-soluble resin (U), which contains structural units having a benzotriazole skeleton and has a weight average molecular weight of 3000 or more.

[0020] The photosensitive coloring resin composition of the present invention contains a pigment, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a solvent. The pigment is a lake pigment of a triarylmethane-based dye. The alkali-soluble resin contains an alkali-soluble resin (U), which comprises structural units having a benzotriazole backbone and has a weight-average molecular weight of 3000 or more. Therefore, it can improve brightness and form a colored layer with a finer linewidth that suppresses film thickness variations and development residues before and after development, and exhibits excellent UV resistance. The mechanism by which this effect is achieved has not yet been determined, but is presumed to be as follows.

[0021] As mentioned above, due to the low ultraviolet transmittance of pigments, the photocurable component in photosensitive coloring resin compositions containing pigments is relatively difficult to cure. Furthermore, dyes tend to hinder the curing of photocurable components, so the photocurable component in photosensitive coloring resin compositions containing dyes is also relatively difficult to cure. In contrast, since lake pigments containing triarylmethane dyes have higher ultraviolet transmittance and do not hinder the curing of photocurable components, their insolubility in the developer after photocuring is greater than that of pigments or dyes, thus the pattern linewidth tends to become thicker. Regarding photosensitive coloring resin compositions containing lake pigments containing triarylmethane dyes, in order to achieve a specific, finer pattern linewidth, the photocuring reaction must be effectively suppressed. If lake pigments with high transmittance triarylmethane dyes are used, and the photoinitiation dose is reduced to achieve a specific pattern linewidth, the generation of free radicals caused by photoreaction will be reduced regardless of the film thickness direction. Therefore, the photocuring property of the patterned area is considered insufficient, resulting in a larger film thickness variation before and after development, and a lower residual film rate. Furthermore, if lake pigments with triarylmethane dyes are used, and antioxidants are added or their amount is increased to achieve a specific pattern linewidth, the free radicals generated during the photoinitiator's photoreaction will be deactivated regardless of the film thickness direction. Therefore, the photocuring property of the patterned area is considered insufficient, resulting in a larger film thickness variation before and after development, and a lower residual film rate. In contrast, in this invention, a base-soluble resin (U) comprising structural units having a benzotriazole backbone and a weight-average molecular weight of 3000 or more is incorporated into the lake pigment of a triarylmethane dye. The base-soluble resin (U) is easily and uniformly dispersed in the coating. The benzotriazole backbone contained in the base-soluble resin (U) has ultraviolet absorption capabilities, preventing UV attenuation and hardening at the film surface. Therefore, the residual film yield does not decrease. It functions according to the film depth by attenuating UV radiation as it penetrates deeper into the film, thereby reducing the generation of free radicals from photoinitiators. Therefore, by including the base-soluble resin (U), the photosensitive coloring resin composition of this invention is believed to suppress the reduction in film thickness after development and decrease linewidth. Furthermore, since the colorant contains lake colorant of triarylmethane dye, the transmittance of the colored layer of the hardened form of the photosensitive coloring resin composition of the present invention is high, and color changes caused by manufacturing steps such as ultraviolet irradiation or post-baking are suppressed. Furthermore, alkali-soluble resins (U) with a weight average molecular weight of 3000 or higher are less likely to become development residues after development because they have ultraviolet absorption function and are alkali-soluble. Furthermore, alkali-soluble resins (U) with a weight average molecular weight of 3000 or higher are not easily volatilized during high-temperature heating steps such as 230°C, thus improving the UV resistance of the final colored layer.

[0022] The photosensitive coloring resin composition of the present invention contains at least a colorant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a solvent, and may further contain other components without impairing the effects of the present invention. For example, in order to improve the dispersibility of the colorant, the photosensitive coloring resin composition of the present invention may further contain a dispersant. Hereinafter, the components of the photosensitive coloring resin composition of the present invention will be described in detail, starting with the alkali-soluble resin.

[0023] [Alkali-soluble resin] The alkali-soluble resin in this invention is one that has an acidic group, can function as an adhesive resin, and can be appropriately selected from those that are soluble in the alkaline developing solution used in pattern formation. In this invention, the alkali-soluble resin can be defined as having an acid value of 40 mgKOH / g or higher. The preferred alkali-soluble resin of the present invention is a resin having an acidic group and generally having a carboxyl group. Specifically, examples include (meth)acrylic resins such as (meth)acrylic copolymers having carboxyl groups and styrene-(meth)acrylic copolymers having carboxyl groups, and epoxy (meth)acrylic ester resins having carboxyl groups.

[0024] (Alkali-soluble resin (U)) The alkali-soluble resin of the present invention contains an alkali-soluble resin (U), wherein the alkali-soluble resin (U) comprises structural units having a benzotriazole skeleton and has a weight average molecular weight of 3000 or more. The alkali-soluble resin (U) used in this invention has the acid value as described above, contains structural units with a benzotriazole skeleton, and has a weight average molecular weight of 3000 or more. The structure of the alkali-soluble resin (U) is not particularly limited as long as it contains structural units with a benzotriazole backbone. It can be a (meth)acrylic resin such as a (meth)acrylic copolymer containing structural units with carboxyl groups, or a styrene-(meth)acrylic copolymer containing carboxyl groups. For example, a (meth)acrylic resin is a copolymer obtained by copolymerizing a carboxyl-containing vinyl unsaturated monomer and other monomers that can be copolymerized as needed, using known methods. Considering the simplicity of the manufacturing process and the ease of controlling the molecular weight, the alkali-soluble resin (U) is preferably a random copolymer.

[0025] The alkali-soluble resin (U) may be a (meth)acrylic copolymer or a styrene-(meth)acrylic copolymer containing structural units having carboxyl groups and structural units having a benzotriazole skeleton. As an ethylene-unsaturated monomer containing a benzotriazole skeleton, examples of monomers having a benzotriazole skeleton represented by the following general formula (A) can be cited.

[0026] [Chemistry 1] General formula (A) (In general formula (A), R1 represents a hydrogen atom or a methyl group, R2 represents an alkyl group or an oxyalkyl group, R3 represents a hydrogen atom, a hydrocarbon group with 1 to 15 carbon atoms, or an alkoxy group with 1 to 15 carbon atoms, and R4 represents a hydrogen atom, a halogen atom, a hydrocarbon group with 1 to 8 carbon atoms, an alkoxy group with 1 to 6 carbon atoms, a cyano group, or a nitro group)

[0027] As R 2, the alkyl group can be an alkyl group with 1 to 10 carbon atoms, or an alkyl group with 1 to 5 carbon atoms. Examples of alkyl groups include: alkyl ethyl, alkyl propyl, alkyl butyl, alkyl hexyl, alkyl octyl, alkyl decyl, etc. As an alkyl group, it can be a straight-chain alkyl group such as methylene, alkyl ethyl, trimethylene, tetramethylene, etc., or a branched alkyl group such as alkyl propyl, 2-methyltrimethylene, 2-methyltetramethylene, etc. As an oxoalkyl group of R 2 (-OR a-, where Ra is an oxoalkyl group), it can be an oxoalkyl group with 1 to 10 carbon atoms or an oxoalkyl group with 1 to 5 carbon atoms. Examples include: oxoethyl, oxopropyl, oxotrimethylene, oxtetramethylene, etc.

[0028] Examples of hydrocarbon groups with 1 to 15 carbon atoms in R 3 include: straight-chain, branched, or cyclic aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and combinations thereof. Specifically, examples of hydrocarbon groups with 1 to 15 carbon atoms include: straight-chain or branched aliphatic hydrocarbon groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tributyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, and pentadecyl; cyclic aliphatic hydrocarbon groups (cycloalkyl) such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl; aromatic hydrocarbon groups such as phenyl, naphthyl, and biphenyl; and combinations thereof such as benzyl, phenylethyl, and 1-methyl-1-phenylethyl. The hydrocarbon group in R3 can be an aliphatic hydrocarbon group, a straight-chain or branched alkyl group, and can be methyl, tributyl, tripentyl, n-octyl, or trioctyl. Examples of alkoxy groups with 1 to 15 carbon atoms in R3 include: methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, tributoxy, pentoxy, hexoxy, heptoxy, octoxy, nonoxy, decoxy, undecoxy, dodecoxy, tridecoxy, tetradecoxy, pentadecoxy, etc.

[0029] R3 can be a hydrogen atom or a hydrocarbon group having 1 to 15 carbon atoms, or a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, or a hydrogen atom or a straight-chain or branched alkyl group having 1 to 8 carbon atoms, or a hydrogen atom, methyl, tert-butyl, tert-pentyl, n-octyl, or tert-octyl.

[0030] Examples of halogen atoms in R4 include fluorine, chlorine, bromine, and iodine atoms. As for the hydrocarbon group with 1 to 8 carbons in R4, examples can be given that are the same as the hydrocarbon groups with 1 to 8 carbons in the hydrocarbon groups of R3 mentioned above. As for the alkoxy group with 1 to 6 carbon atoms in R4, examples can be given that are the same as the alkoxy groups with 1 to 6 carbon atoms in the alkoxy groups of R3 mentioned above.

[0031] R 4 can be a hydrocarbon group with 1 to 4 carbon atoms, such as hydrogen atom, halogen atom, nitro group, cyano group, methoxy group, or tertiary butyl group.

[0032] There are no particular limitations on the monomers having the benzotriazole skeleton represented by the above general formula (A). Specifically, examples include: 2-[2-hydroxy-5-(methacryloyloxymethyl)phenyl]-2H-benzotriazole, 2-[2-hydroxy-5-(propenylooxymethyl)phenyl]-2H-benzotriazole, 2-[2-hydroxy-5-(methacrylooxyethyl)phenyl]-2H-benzotriazole, 2-[2-hydroxy-5-(propenylooxyethyl)phenyl]-2H-benzotriazole, 2-[2-hydroxy-5-(methacrylooxypropyl)phenyl]-2H-benzotriazole, 2-[2-hydroxy-5-(propenylooxyethyl)phenyl]-2H-benzotriazole, 2-[2-hydroxy-5-(propeny ... [2-[2-hydroxy-5-(methacryloyloxybutyl)phenyl]-2H-benzotriazole, 2-[2-hydroxy-5-(methacryloyloxybutyl)phenyl]-2H-benzotriazole, 2-[2-hydroxy-5-(methacryloyloxyethyl)phenyl]-2H-benzotriazole, 2-[2-hydroxy-5-(methacryloyloxyethyl)phenyl]-2H-benzotriazole, 2-[2-hydroxy-3-tert-butyl-5-(methacryloyloxyethyl)phenyl]-2H-benzotriazole, 2-[2-hydroxy-3-tert-butyl-5-(methacryloyloxyethyl)phenyl]-2H-benzotriazole 2H-benzotriazole, 2-[2-hydroxy-5-(methacryloyloxyethyl)phenyl]-5-chloro-2H-benzotriazole, 2-[2-hydroxy-5-(propenylooxyethyl)phenyl]-5-chloro-2H-benzotriazole, 2-[2-hydroxy-5-(methacrylooxyethyl)phenyl]-5-methoxy-2H-benzotriazole, 2-[2-hydroxy-5-(propenylooxyethyl)phenyl]-5-methoxy-2H-benzotriazole, 2-[2-hydroxy-5-(methacrylooxyethyl)phenyl]-5-cyano-2H-benzotriazole, 2-[2-hydroxy-5-(propenylooxyethyl)phenyl] 2-[2-hydroxy-5-(methacryloyloxyethyl)phenyl]-5-tert-butyl-2H-benzotriazole, 2-[2-hydroxy-5-(methacryloyloxyethyl)phenyl]-5-tert-butyl-2H-benzotriazole, 2-[2-hydroxy-5-(methacryloyloxyethyl)phenyl]-5-nitro-2H-benzotriazole, 2-[2-hydroxy-5-(methacryloyloxyethyl)phenyl]-5-nitro-2H-benzotriazole, 2-[2-(2-hydroxy-4-octoxyphenyl)-2H-1,2,3-benzotriazole-5-oxy]ethyl methacrylate, etc.

[0033] Examples of carboxyl-containing vinyl unsaturated monomers include: (meth)acrylic acid, vinylbenzoic acid, maleic acid, monoalkyl maleic acid esters, fumaric acid, itconic acid, butenoic acid, cinnamic acid, and acrylic acid dimers. Additionally, monomers with hydroxyl groups, such as 2-(meth)acrylate hydroxyethyl ester, can be used in addition reactions with cyclic anhydrides such as maleic anhydride, phthalic anhydride, or cyclohexanedicarboxylic anhydride, as well as ω-carboxyl-polycaprolactone mono(meth)acrylate. Furthermore, anhydride-containing monomers such as maleic anhydride, itconic anhydride, and citrate anhydride can also be used as carboxyl precursors. Among these, (meth)acrylic acid is particularly preferred considering copolymerization properties, cost, solubility, and glass transition temperature.

[0034] Among alkali-soluble resins, those with carboxyl groups on the side chains, and further with photopolymerizable functional groups such as vinyl unsaturated groups on the side chains, are particularly preferred. When photopolymerizable functional groups are present, during the curing step of the resin composition in the manufacture of color filters, the alkali-soluble resins can form cross-links with each other, or with photopolymerizable compounds such as polyfunctional monomers. The film strength of the cured film is further improved, resulting in enhanced developability; furthermore, thermal shrinkage of the cured film is suppressed, and adhesion to the substrate becomes excellent. The method for introducing vinyl unsaturated bonds into alkali-soluble resins can be appropriately selected from previously known methods. For example, one can add a compound having both epoxy groups and vinyl unsaturated bonds in its molecule, such as glycidyl (meth)acrylate, to the carboxyl group of the alkali-soluble resin and introduce vinyl unsaturated bonds into the side chain; or pre-introduce a hydroxyl structural unit into the copolymer, add a compound having both isocyanate groups and vinyl unsaturated bonds in its molecule, and introduce vinyl unsaturated bonds into the side chain, etc.

[0035] Furthermore, considering the superior adhesion of the coloring layer, alkali-soluble resins are preferable as they possess hydrocarbon rings. By having hydrocarbon rings as bulky groups in the alkali-soluble resin, shrinkage during curing is suppressed, peeling between substrates is mitigated, and substrate adhesion is improved. Examples of such hydrocarbon rings include: aliphatic hydrocarbon rings that may have substituents, aromatic hydrocarbon rings that may have substituents, and combinations thereof. The hydrocarbon ring may have substituents such as alkyl, carbonyl, carboxyl, oxycarbonyl, amide, hydroxyl, nitro, amino, and halogen atoms. Hydrocarbon rings can be included as monovalent groups or as divalent or higher groups.

[0036] Specific examples of hydrocarbon rings include: aliphatic hydrocarbon rings such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, northoalkyl, isoborneolane, tricyclo[5.2.1.0(2,6)]decane (dicyclopentane), and adamantane; aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, phenanthrene, and fumonisin; chain polycyclic rings such as biphenyl, biphenylene oxide, diphenylmethane, triphenylmethane, and styrene, or Cardo structures (9,9-diarylfumonisin); and groups in which one of these groups is substituted by a substituent. Examples of substituents mentioned above include: alkyl, cycloalkyl, alkylcycloalkyl, hydroxyl, carbonyl, nitro, amino, halogen atom, etc.

[0037] When aliphatic hydrocarbon rings are included as hydrocarbon rings, it is preferable to consider improving the heat resistance or adhesion of the colored layer and increasing the brightness of the obtained colored layer. Furthermore, in cases involving the aforementioned Cardo structure, it is particularly advantageous from the perspectives of improved hardening properties of the coloring layer, suppression of pigment fading, and improved solvent resistance (NMP (N-methyl-2-pyrrolidone) swelling inhibition).

[0038] The alkali-soluble resin (U) of the present invention is preferably a copolymer containing at least one carboxyl-containing group among (meth)acrylic copolymers and styrene-(meth)acrylic copolymers, which contains structural units having carboxyl groups, structural units having benzotriazole skeletons, and structural units having hydrocarbon rings. More preferably, it is a copolymer containing at least one carboxyl-containing group among (meth)acrylic copolymers and styrene-(meth)acrylic copolymers, which contains structural units having carboxyl groups, structural units having benzotriazole skeletons, structural units having hydrocarbon rings, and structural units having ethylene unsaturated bonds in the side chains.

[0039] Examples of vinyl unsaturated monomers with hydrocarbon rings include cyclohexyl methacrylate, dicyclopentyl methacrylate, adamantyl methacrylate, isocyanate methacrylate, benzyl methacrylate, phenoxyethyl methacrylate, and styrene. From the perspective of improving the strength or heat resistance of the coating film, it is preferable to use at least one selected from cyclohexyl methacrylate, dicyclopentyl methacrylate, adamantyl methacrylate, benzyl methacrylate, and styrene.

[0040] The carboxyl-containing copolymer may further contain other structural units with ester groups, such as methyl methacrylate and ethyl methacrylate. These ester-containing structural units function not only to suppress the alkali solubility of the coloring resin composition, but also to improve its solubility in solvents and, consequently, its solvent resolubility.

[0041] The (meth)acrylic acid copolymer can be made into an alkali-soluble resin with the desired properties by appropriately adjusting the amount of each structural unit added. From the perspective of easily and effectively obtaining the effects of the present invention, the amount of vinyl unsaturated monomer containing a benzotriazole skeleton added is preferably 1% by mass or more, and can be 2% by mass or more, relative to the total amount of monomers. On the other hand, since the benzotriazole skeleton contains phenolic hydroxyl groups, although it has reproducibility, it is weakly acidic compared to carboxylic acids, and therefore its reproducibility is weaker. Furthermore, due to its large volume structure, there is a risk that a larger amount introduced may lead to a decrease in reproducibility. Therefore, the amount of vinyl unsaturated monomer containing a benzotriazole skeleton added is preferably 10% by mass or less, and can be less than 10% by mass, and can be 8% by mass or less, relative to the total amount of monomers. That is, relative to all structural units of the alkali-soluble resin (U), it is preferable to include structural units having a benzotriazole skeleton of 1% to 10% by mass, with the lower limit being 2% or more by mass and the upper limit being less than 10% by mass and less than 8% by mass.

[0042] From the perspective of obtaining a good pattern, the amount of carboxyl-containing vinyl unsaturated monomer added is preferably 5% by mass or more, and more preferably 10% by mass or more, relative to the total amount of monomer. On the other hand, from the perspective of suppressing the roughness of the pattern surface after development, the amount of carboxyl-containing vinyl unsaturated monomer added is preferably 50% by mass or less, and more preferably 40% by mass or less, relative to the total amount of monomer.

[0043] Furthermore, in at least one carboxyl-containing copolymer of (meth)acrylic acid copolymers and styrene-(meth)acrylic acid copolymers, which can be more preferably used as alkali-soluble resins and contain structural units having ethylene unsaturated bonds, the amount of the compound having both epoxy groups and ethylene unsaturated bonds added relative to the carboxyl-containing ethylene unsaturated monomer is preferably 5% by mass or more and 95% by mass or less, more preferably 10% by mass or more and 90% by mass or less.

[0044] From the perspective of improving the UV resistance of the final colored layer, the preferred weight-average molecular weight (Mw) of the alkali-soluble resin (U) is 3000 or more. The lower limit is 4000 or more, and 5000 or more. On the other hand, if the weight-average molecular weight (Mw) is too high, the developability of the alkaline developer will decrease, and there is a risk of residue remaining on the substrate. Therefore, the upper limit is preferably 20000 or less, and can be 18000 or less, or 15000 or less.

[0045] Considering both the developability (solubility) in the alkaline aqueous solution used in the developer and the adhesion to the substrate, the acid value of the alkali-soluble resin (U) is preferably 40 mgKOH / g or higher and 300 mgKOH / g or lower. The lower limit can be 50 mgKOH / g or higher, 60 mgKOH / g or higher, or 70 mgKOH / g or higher. On the other hand, if the polarity is higher, considering the decrease in solubility in the solvent, the upper limit can be 150 mgKOH / g or lower, 130 mgKOH / g or lower, or 110 mgKOH / g or lower.

[0046] Considering the effects of improved film strength and developer resistance, as well as excellent adhesion to the substrate, when the side chains of the alkali-soluble resin (U) have vinyl unsaturated groups, the vinyl unsaturated bond equivalent is preferably in the range of 100 to 2000, and more preferably in the range of 140 to 1500. If the vinyl unsaturated bond equivalent is below 2000, the developer resistance or adhesion is excellent. Furthermore, if it is above 100, the ratio of other structural units, such as those with carboxyl groups or hydrocarbon rings, can be relatively increased, thus resulting in excellent developer resistance or heat resistance. Here, the equivalent of vinyl unsaturated bonds is the average molecular weight of vinyl unsaturated bonds per mole in the above-mentioned alkali-soluble resin, expressed by the following formula (1).

[0047] Equation (1) Equivalent amount of ethylene unsaturated bond (g / mol) = W(g) / M(mol) (In formula (1), W represents the mass (g) of alkali-soluble resin, and M represents the number of mol of ethylene unsaturated bonds contained in alkali-soluble resin W (g))

[0048] The equivalent of the aforementioned vinyl unsaturated bonds can also be calculated, for example, by determining the number of vinyl unsaturated bonds per 1 g of alkali-soluble resin according to the iodine value test method described in JIS K 0070:1992.

[0049] The alkali-soluble resin used in the photosensitive coloring resin composition of the present invention includes the specific alkali-soluble resin (U) described above, but may also include alkali-soluble resins that do not conform to the specific alkali-soluble resin (U) described above. As long as the effects of the present invention can be obtained, the content ratio of the specific alkali-soluble resin (U) in the alkali-soluble resin used in the photosensitive coloring resin composition of the present invention is not particularly limited. The content ratio of the specific alkali-soluble resin (U) relative to the total amount of alkali-soluble resin can be 10% by mass or more, 20% by mass or more, 35% by mass or more, 50% by mass or more, 70% by mass or more, or 100% by mass.

[0050] In this invention, there is no particular limitation on the alkali-soluble resin that does not conform to the above-mentioned specific alkali-soluble resin (U), and previously known alkali-soluble resins may be appropriately selected. For example, in the description of the specific alkali-soluble resin (U) mentioned above, there is an alkali-soluble resin that is the same as the alkali-soluble resin (U) mentioned above, except that it does not contain structural units having a benzotriazole skeleton. As an alkali-soluble resin (U) that does not conform to the above-mentioned specific alkali-soluble resin, it may be, for example, a copolymer containing at least one carboxyl-containing group among (meth)acrylic copolymers and styrene-(meth)acrylic copolymers, which contain the above-mentioned structural units having carboxyl groups and the above-mentioned structural units having hydrocarbon rings. Alternatively, it may be a copolymer containing at least one carboxyl-containing group among (meth)acrylic copolymers and styrene-(meth)acrylic copolymers, which contain the above-mentioned structural units having carboxyl groups, the above-mentioned structural units having hydrocarbon rings, and structural units having ethylene unsaturated bonds in the side chains.

[0051] Furthermore, there is no particular limitation on the type of epoxy (meth)acrylate resin containing carboxyl groups; it is suitable to be an epoxy (meth)acrylate compound obtained by reacting an epoxy compound with a reactant containing an unsaturated group of a monocarboxylic acid and an anhydride. Epoxides, monocarboxylic acids containing unsaturated groups, and acid anhydrides may be appropriately selected from those known to the public. As for epoxy (meth)acrylate resins containing carboxyl groups, it is also preferable that they have the above-mentioned hydrocarbon rings in the molecule. In particular, considering the improvement of the curability of the coloring layer, the suppression of pigment fading, and the increase of the residual film rate of the coloring layer, it is preferable that they contain Cardo structures. As an alkali-soluble resin that does not meet the above-mentioned specific requirements (U), it can be used alone or in combination with two or more other resins.

[0052] The alkali-soluble resin used in the photosensitive coloring resin composition may be used alone or in combination with two or more of the above-mentioned specific alkali-soluble resin (U), and there is no particular limitation on its content. Relative to the total solid content of the photosensitive coloring resin composition, the alkali-soluble resin (U) is preferably in the range of 3% by mass or more and 60% by mass or less, more preferably in the range of 5% by mass or more and 50% by mass or less, and even more preferably in the range of 8% by mass or more and 40% by mass or less. If the content of alkali-soluble resin (U) is above the above-mentioned lower limit, sufficient alkaline developability and ultraviolet absorption function can be obtained, sufficient linewidth offset reduction effect can be obtained, and UV resistance is improved. Furthermore, if the content of alkali-soluble resin (U) is below the above-mentioned upper limit, film roughness or pattern defects can be suppressed during development. Relative to the total solid content of the photosensitive coloring resin composition, the alkali-soluble resin content is preferably in the range of 5% by mass or more and 60% by mass or less, and more preferably in the range of 8% by mass or more and 40% by mass or less. If the content of the alkali-soluble resin is at or above the lower limit mentioned above, sufficient alkaline developability can be obtained; and if the content of the alkali-soluble resin is below or above the upper limit mentioned above, film roughness or pattern defects can be suppressed during development.

[0053] [Colorant] In order to produce a photosensitive coloring resin composition that can suppress color changes or brightness reduction before and after the high-temperature heating step, improve the brightness of the final colored layer, and form a colored layer with a finer linewidth to suppress film thickness changes before and after development, the colorant in this invention contains a lake colorant of triarylmethane dyes. <Lake Pigments of Triarylmethane Dyes> Considering the superior heat resistance and lightfastness, and the achievement of high brightness in color filters, the lake pigments of triarylmethane dyes are preferably triarylmethane dyes and polyacid lake pigments. As lake pigments of triarylmethane dyes, it is preferable to select one or more pigments represented by the following general formula (1) and the following general formula (2). Considering the formation of molecular association state and the resulting superior heat resistance, and the achievement of high brightness, the pigment represented by the following general formula (1) is preferred.

[0054] [Chemistry 2] General formula (1) In general formula (1), A is an α-valent organic group that does not have a π bond to a carbon atom directly bonded to N. This organic group represents an aliphatic hydrocarbon group with a saturated aliphatic hydrocarbon group at the end directly bonded to N, or an aromatic group with such aliphatic hydrocarbon group. The carbon chain may contain heteroatoms. Bc- represents a c-valent polyacid anion. Ri~Rv each independently represent a hydrogen atom, an alkyl group that may have a substituent, or an aryl group that may have a substituent. Rii and Riiii, Riv and Rv may be bonded to form a ring structure. Rvi and Rvii each independently represent an alkyl group that may have a substituent, an alkoxy group that may have a substituent, a halogen atom, or a cyano group. Ar1 represents a divalent aromatic group that may have a substituent. Multiple Ri~Rvii and Ar1 may be the same or different. a and c represent integers greater than 2, b and d represent integers greater than 1, and f and g represent integers greater than 0 and less than 4. (There may be multiple f and g values, which may be the same or different.)

[0055] [Chemistry 3] General formula (2) In general formula (2), RI~RVI each independently represent a hydrogen atom, an alkyl group that may have substituents, or an aryl group that may have substituents. RI can bond with RII, RIII with RIV, and RV with RVI to form a ring structure. RVII and RVIII each independently represent an alkyl group that may have substituents, an alkoxy group that may have substituents, a halogen atom, or a cyano group. Ar2 represents a divalent aromatic heterocyclic group that may have substituents. Multiple RI~RVIII and Ar2 may be the same or different. Em- represents an m-valent polyacid anion. m represents an integer greater than 2. k and l represent integers greater than 0 and less than 4. (There may be multiple k and l, which may be the same or different.)

[0056] The pigment represented by the above general formula (1) contains anions with a valence of divalent or higher and cations with a valence of divalent or higher. Therefore, in the aggregate of this pigment, the anions and cations are not simply ionicly bonded one molecule to one molecule, but can form a molecular aggregate of multiple molecules associated through ionic bonds. Thus, the apparent molecular weight is significantly increased compared to the molecular weight of previous lake pigments. It is speculated that by forming such molecular aggregates, the cohesive force in the solid state is further enhanced, thermal motion is reduced, and the dissociation of ion pairs or the decomposition of cations can be suppressed, making it less prone to fading compared to previous lake pigments.

[0057] In the above general formula (1), A is an α-valent organic group that is directly bonded to the carbon atom of N (nitrogen atom) and does not have a π bond. This organic group is either an aliphatic hydrocarbon group with a saturated aliphatic hydrocarbon group at the end directly bonded to N, or an aromatic group with such an aliphatic hydrocarbon group, and may contain heteroatoms such as O (oxygen atom), S (sulfur atom), and N (nitrogen atom) in the carbon chain. That is, the organic group represents an aliphatic hydrocarbon group with a saturated aliphatic hydrocarbon group at the end directly bonded to N, and may contain heteroatoms such as O, S, and N in the carbon chain; or an aromatic group with an aliphatic hydrocarbon group at the end directly bonded to N, and may contain heteroatoms such as O, S, and N in the carbon chain. Since the carbon atom directly bonded to N does not have a π bond, the color characteristics such as hue or transmittance of the cationic chromogenic site are not affected by the linker A or other chromogenic sites, and can maintain the same color as the monomer.

[0058] In A, at least at the end directly bonded to N, there must be a saturated aliphatic hydrocarbon group. This aliphatic hydrocarbon group can be straight-chain, branched, or cyclic, provided the carbon atom at the end directly bonded to N does not have a π bond. Carbon atoms other than the terminal carbon atom can have unsaturated bonds and can contain substituents. The carbon chain can contain O, S, and N. For example, it can contain carbonyl, carboxyl, oxycarbonyl, amide, etc., and hydrogen atoms can be further substituted by halogen atoms, etc. Furthermore, in A, the aromatic groups having aliphatic hydrocarbon groups mentioned above can be exemplified as monocyclic or polycyclic aromatic groups having aliphatic hydrocarbon groups at least at the end directly bonded to N, and can have substituents, or can be heterocycles containing O, S, and N. In terms of the robustness of the skeleton, A is preferably composed of cyclic aliphatic hydrocarbon groups or aromatic groups. Examples of cyclic aliphatic hydrocarbon groups include cyclohexane, cyclopentane, northane, bicyclo[2.2.2]octane, tricyclo[5.2.1.0 2,6]decane, and adamantane. Examples of aromatic groups include those with benzene rings and naphthyl rings. For example, when A is a divalent organic group, examples include straight-chain, branched, or cyclic alkyl groups with 1 to 20 carbon atoms, or aromatic groups with two alkyl groups having 1 to 20 carbon atoms, such as dimethylbenzene.

[0059] In this invention, considering both robustness and freedom of molecular motion, and improving heat resistance, A preferably has two or more cyclic aliphatic hydrocarbon groups, with a saturated aliphatic hydrocarbon group at the end directly bonded to N, and the carbon chain may contain aliphatic hydrocarbon groups of O, S, and N. A is more preferably a structure having two or more cycloalkyl groups, with a saturated aliphatic hydrocarbon group at the end directly bonded to N, and the carbon chain may contain aliphatic hydrocarbon groups of O, S, and N. Furthermore, it is more preferably a structure in which two or more cyclic aliphatic hydrocarbon groups are linked by straight-chain or branched aliphatic hydrocarbon groups. The presence of two or more cyclic aliphatic hydrocarbon groups can be the same or different. For example, examples with the same cyclic aliphatic hydrocarbon groups as mentioned above can be given, among which cyclohexane and cyclopentane are preferred.

[0060] In this invention, from the perspective of heat resistance, the A mentioned above is preferably a substituent represented by the following general formula (1a).

[0061] [Chemistry 4] General formula (1a) (In general formula (1a), Rxi represents an alkyl group having 1 or more carbon atoms and 3 or less, which may have alkyl groups having 1 or more carbon atoms and 4 or less, or alkoxy groups having 1 or more carbon atoms and 4 or less as substituents; Rxi and Rxiii each independently represent an alkyl group having 1 or more carbon atoms and 4 or less, or alkoxy groups having 1 or more carbon atoms and 4 or less; p represents an integer having 1 or more carbon atoms and 3 or less; q and r each independently represent an integer having 0 or more carbon atoms and 4 or less. When there are multiple Rxi, Rxi, Rxiii and r, the multiple Rxi, Rxi, Rxiii and r may be the same or different from each other.)

[0062] Considering both excellent robustness and thermal motion of the color-developing areas, and to improve heat resistance, it is preferable to use an alkyl group in Rxi with 1 or more but less than 3 carbon atoms. Examples of such alkyl groups include methylene, ethyl, and propyl, among which methylene or ethyl are preferred, and methylene is even more preferred. Examples of alkyl groups with 1 or more but less than 4 carbon atoms include methyl, ethyl, propyl, and butyl. They can be linear or branched. Furthermore, examples of alkoxy groups with 1 or more carbon atoms but less than 4 carbon atoms include methoxy, ethoxy, propoxy, and butoxy. These can be linear or branched.

[0063] The alkyl groups having 1 or more carbon atoms and 4 or fewer carbon atoms, and the alkoxy groups having 1 or more carbon atoms and 4 or fewer carbon atoms in R xii and R xiii can be examples of the same substituents that R xi can have.

[0064] In general formula (1a), from the perspective of heat resistance, it is preferable that there are 2 or more and 4 or less cyclohexane (extrinsic cyclohexyl), that is, p is 1 or more and 3 or less, and more preferably p is 1 or more and 2 or less. Furthermore, the number of substitutions of substituents Rxii and Rxiii in the cyclohexyl group is not particularly limited. From the perspective of heat resistance, it is preferable to have 1 or more and 3 or less, and more preferably 1 or more and 2 or less. That is, q and r are preferably integers of 1 or more and 3 or less, and q and r are preferably integers of 1 or more and 2 or less.

[0065] As suitable specific examples of such a linking base A, the following can be cited, but are not limited to them.

[0066] [Chemistry 5]

[0067] The alkyl group in Ri to Rv is not particularly limited. Examples include straight-chain, branched, or cyclic alkyl groups with 1 to 20 carbon atoms. Among these, straight-chain or branched alkyl groups with 1 to 8 carbon atoms are examples. Considering brightness and heat resistance, straight-chain or branched alkyl groups with 1 to 5 carbon atoms are examples. Examples of alkyl groups in Ri to Rv are ethyl or methyl. The substituents that the alkyl group can have are not particularly limited. Examples include aryl, halogen atoms, hydroxyl, and alkoxy groups. Examples of substituted alkyl groups include aralkyl groups such as benzyl. The aryl group in Ri~Rv is not particularly limited. Examples include phenyl and naphthyl groups. Substituents that can be present on an aryl group include, for example, alkyl groups, halogen atoms, alkoxy groups, and hydroxyl groups. From the perspective of chemical stability, Ri~Rv are preferably each independently composed of a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group, or Rii bonded to Rii and Rii, or Riv bonded to Rv to form a pyrrolidine ring, a piperidine ring, or a morpholine ring.

[0068] From the perspective of heat resistance, it is preferable that at least one of Rii to Rv is a cycloalkyl group that may have substituents, or an aryl group that may have substituents. It is believed that by having at least one of Rii to Rv as a cycloalkyl group or an aryl group, the intermolecular interactions caused by steric hindrance are reduced, thus suppressing the influence of the colorimetric site on heat, resulting in excellent heat resistance.

[0069] From the perspective of heat resistance, it is preferable that at least one of R ii to R v is a substituent represented by the following general formula (1b) or the following general formula (1c).

[0070] [Chemistry 6] General formula (1b) (In general formula (1b), R xiv, R xv, and R xvi each independently represent a hydrogen atom, an alkyl group having 1 or more but less than 4 carbon atoms that may have substituents, or an alkoxy group having 1 or more but less than 4 carbon atoms that may have substituents.)

[0071] [Chemistry 7] General formula (1c) (In general formula (1c), R xvii, R xviii, and R xix each independently represent a hydrogen atom, an alkyl group having 1 or more but less than 4 carbon atoms that may have substituents, or an alkoxy group having 1 or more but less than 4 carbon atoms that may have substituents.)

[0072] Examples of alkyl groups Rxiv, Rxv, Rxvi, Rxvii, Rxviii, and Rxix, which have 1 or more but 4 carbon atoms, include methyl, ethyl, propyl, and butyl. These can be linear or branched. Similarly, examples of alkoxy groups, which have 1 or more but 4 carbon atoms, include methoxy, ethoxy, propoxy, and butoxy. These can be linear or branched. Examples of substituents that can be present in the aforementioned alkyl and alkoxy groups include halogen atoms, hydroxyl groups, etc.

[0073] When the substituents represented by the above general formula (1b) are present, from the viewpoint of heat resistance, it is preferable that at least one of R xiv, R xv, and R xvi is an alkyl group having 1 or more and 4 or less carbon atoms that may have substituents, or an alkoxy group having 1 or more and 4 or less carbon atoms that may have substituents. More preferably, at least one of R xiv and R xv is an alkyl group having 1 or more and 4 or less carbon atoms that may have substituents, or an alkoxy group having 1 or more and 4 or less carbon atoms that may have substituents.

[0074] Furthermore, when the substituents represented by the above general formula (1c) are present, from the perspective of heat resistance, it is preferable that at least one of R xvii, R xviii, and R xix is ​​an alkyl group having 1 or more but less than 4 carbon atoms that may have substituents, or an alkoxy group having 1 or more but less than 4 carbon atoms that may have substituents. More preferably, at least one of R xvii and R xviii is an alkyl group having 1 or more but less than 4 carbon atoms that may have substituents, or an alkoxy group having 1 or more but less than 4 carbon atoms that may have substituents.

[0075] R vi and R vii each independently represent an alkyl group that may have substituents, an alkoxy group that may have substituents, a halogen atom, or a cyano group. The alkyl group in R vi and R vii is not particularly limited, but is preferably a straight-chain alkyl group with 1 to 8 carbon atoms, or a branched alkyl group, and more preferably an alkyl group with 1 to 4 carbon atoms. Examples of alkyl groups with 1 to 4 carbon atoms include methyl, ethyl, propyl, and butyl, which may be straight-chain or branched. The substituents that an alkyl group may have are not particularly limited, and examples include aryl, halogen atoms, hydroxyl, and alkoxy groups. Furthermore, the alkoxy group in Rvi and Rvii is not particularly limited, but it is preferably a straight-chain alkoxy group with 1 or more carbon atoms and 8 or fewer carbon atoms, or a branched alkoxy group, and more preferably an alkoxy group with 1 or more carbon atoms and 4 or fewer carbon atoms. Examples of alkoxy groups with 1 or more carbon atoms and 4 or fewer carbon atoms include: methoxy, ethoxy, propoxy, and butoxy, which can be straight-chain or branched. The substituents that an alkoxy group can have are not particularly limited, and examples include: aryl, halogen atoms, hydroxyl, and alkoxy groups. Examples of halogen atoms in Rvi and Rvii include fluorine, chlorine, bromine, and iodine atoms. The substitution numbers of Rvi and Rvii, i.e., f and g, independently represent integers greater than 0 and less than 4, preferably greater than 0 and less than 2, and more preferably greater than 0 and less than 1. There exist multiple f and g, which may be the same or different. Furthermore, R vi and R vii can be in the triarylmethane skeleton, or 𠮿 Any part of the aromatic ring with resonance structure within the skeleton is substituted, wherein, preferably, substitution is performed at the position of the amino group represented by -NR iiR iii or -NR ivR v.

[0076] The divalent aromatic group in Ar 1 is not particularly limited. Besides aromatic hydrocarbon groups containing a carbocyclic ring, the aromatic group in Ar 1 can also be a heterocyclic group. Aromatic hydrocarbons, in addition to benzene rings, can include: condensed polycyclic aromatic hydrocarbons such as naphthalene rings, naphthalene rings, indene rings, phenanthrene rings, anthracene rings, and phenanthrene rings; and chain polycyclic hydrocarbons such as biphenyl, biphenylene, diphenylmethane, triphenylmethane, and piracene. In these chain polycyclic hydrocarbons, O, S, and N may be present in the chain skeleton, as in diphenyl ethers. On the other hand, examples of heterocyclic groups include: five-membered heterocycles such as furan, thiophene, pyrrole, acetazole, thiazole, imidazole, and pyrazole; six-membered heterocycles such as piperan, piperanone, pyridine, piperanone, pyrazine, pyrimidine, and pyrazine; and condensed polycyclic heterocycles such as benzofuran, benzothiophene, indole, carbazole, coumarin, benzopiperanone, quinoline, isoquinoline, acridine, phthaloline, quinazoline, and quinazonoline. These aromatic groups may further have alkyl, alkoxy, hydroxyl, halogen atoms, and phenyl groups that can be substituted as substituents.

[0077] Within a single molecule, there can be multiple Ri~Rvii and Ar1, which can be the same or different. By combining Ri~Rvii and Ar1, the desired color can be achieved.

[0078] In A, the valence 'a' refers to the number of colorimetric cationic sites constituting the cation, and 'a' is an integer greater than or equal to 2. In this lake pigment, since the valence 'a' of the cation is greater than or equal to 2, it exhibits excellent heat resistance. The valence 'a' of the cation can also be greater than or equal to 3. There is no particular upper limit to 'a', but from the perspective of ease of manufacturing, 'a' is preferably less than or equal to 4, and more preferably less than or equal to 3.

[0079] Considering the excellent heat resistance and the ease with which color changes during heating can be suppressed, the molecular weight of the cation in the pigment represented by general formula (1) is preferably 1200 or more, and preferably 1300 or more.

[0080] In the pigment represented by general formula (1), considering the high brightness and excellent heat resistance, the anionic part (B c-) is a c-valent polyacid anion, and it is an anion with a divalent or higher valence.

[0081] As a polyacid anion formed by the condensation of multiple oxyacids, it can be a homopolyacid anion (M mO n) c- or a heteropolyacid anion (X lM mO n) c-. In the above ionic formula, M represents polyatoms, X represents heteroatoms, m represents the composition ratio of polyatoms, and n represents the composition ratio of oxygen atoms. Examples of polyatoms M include Mo, W, V, Ti, and Nb. Examples of heteroatoms X include Si, P, As, S, Fe, and Co. Furthermore, some may also contain countercations such as Na+ or H+. Among them, considering the excellent heat resistance, it is preferable to have a polyacid containing one or more elements selected from tungsten (W) and molybdenum (Mo). Examples of such polyacids include: tungstate ion [W10O32]4- and molybdate ion [Mo6O19]2-, and heteropolyacids such as phosphotungstate ion [PW12O40]3-, [P2W18O62]6-, silicotttate ion [SiW12O40]4-, phosphotungstate ion [PMo12O40]3-, silicotttate ion [SiMo12O40]4-, phosphotungstate ion [PW12-sMo12O40]3- (s is an integer greater than or equal to 1 and less than 11), [P2W18-tMo12O62]6- (t is an integer greater than or equal to 1 and less than 17), and silicotttate ion [SiW12-sMo12O40]6-. uMo uO 40] 4- (u is an integer of 1 or more and 11 or less). As a polyacid containing at least one of tungsten (W) and molybdenum (Mo), the above-mentioned polyacid is preferably a heteropolyacid from the perspective of heat resistance and ease of obtaining raw materials, and even more preferably a heteropolyacid containing phosphorus (P). Furthermore, considering heat resistance, it is preferable to use any one of phosphotungsticolate ion [PW 10Mo 2O 40] 3-, [PW 11Mo 1O 40] 3-, or phosphotungsticolate ion [PW 12O 40] 3-.

[0082] In general formula (1), b represents the number of cations, d represents the number of anions in the molecular aggregate, and b and d represent integers of 1 or more. When b is 2 or more, the multiple cations present in the molecular aggregate can be a single type or a combination of two or more types. Similarly, when d is 2 or more, the multiple anions present in the molecular aggregate can be a single type or a combination of two or more types.

[0083] Furthermore, the lake pigment represented by general formula (1) can be prepared, for example, with reference to International Publication No. 2012 / 144520 and International Publication No. 2018 / 003706.

[0084] On the other hand, in general formula (2), RI~RVI each independently represent a hydrogen atom, an alkyl group that may have substituents, or an aryl group that may have substituents. RI can be bonded to RII, RIII and RIV, and RV and RVI to form a ring structure. RI~RVI can each be the same as Ri~Rv in the above general formula (1). In general formula (2), R VII and R VIII each independently represent an alkyl group that may have a substituent, an alkoxy group that may have a substituent, a halogen atom or a cyano group, which may also be the same as R vi and R vii in general formula (1) above. In general formula (2), Ar 2 represents a divalent aromatic heterocyclic group that may have substituents, and Ar 2 may be the same as the aromatic heterocyclic group in Ar 1 of the above general formula (1). Furthermore, in general formula (2), E m- represents the m-valent polyacid anion, which can be the same as the c-valent polyacid anion in the above general formula (1).

[0085] In general formula (2), m represents the number of cations and anions, and is an integer greater than or equal to 2. The cations present in general formula (2) can be a single type or a combination of two or more. Similarly, the anions can be a single type or a combination of two or more. Furthermore, k and l in general formula (2) can be the same as f and g in general formula (1) above. Furthermore, the lake pigment represented by formula (2) can be prepared, for example, with reference to Japanese Patent Application Publication No. 2017-16099.

[0086] Furthermore, the lake pigment of the triarylmethane dye used in the photosensitive coloring resin composition of the present invention is not limited to one or more pigments represented by the above general formula (1) and the above general formula (2), and can be used as appropriate. For example, lake pigments containing cationic triarylmethane dyes and various polyacid anions as described above can be used, as described in Japanese Patent Application Publication No. 2015-96947, Japanese Patent Application Publication No. 2016-27149, and Japanese Patent Application Publication No. 2017-16099; or lake pigments containing triarylmethane dyes and polyacids as described in Japanese Patent Application Publication No. 2015-96947, Japanese Patent Application Publication No. 2016-27149, and Japanese Patent Application Publication No. 2017-16099.

[0087] In the photosensitive coloring resin composition of the present invention, the above-mentioned triarylmethane dye lake pigment can be used alone, or two or more can be used in combination.

[0088] <Other colorants> The pigments used in this invention include lake pigments of triarylmethane dyes as essential components, but other pigments may also be used in combination to adjust the hue without compromising the effectiveness of this invention. As other colorants, known pigments, dyes, lake colorants, etc., can be used alone or in combination of two or more.

[0089] Other colorants may be used, including but not limited to, other blue, purple, and red colorants. Other well-known organic blue pigments include CI Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, and 15:6. As a purple pigment, CI pigments purple 1, 14, 15, 19, 23, 29, 32, 33, 36, 37, 38 and other well-known organic purple pigments are commonly known. As a red or purplish-red pigment, it is described in, for example, in International Publication No. 2020 / 071041, Japanese Patent Application Publication No. 2018-100323, and International Publication No. 2014 / 123125, etc. Dyes and tin These are dyes, lake pigments, etc.

[0090] <Content Ratio of Pigments> In the photosensitive coloring resin composition of the present invention, other colorants besides the lake colorant of triarylmethane dyes may be included in the colorant without impairing the effect of the present invention. The content ratio of the lake colorant of triarylmethane dyes is preferably 70% by mass or more and 100% by mass or less relative to the total amount of colorant, more preferably 80% by mass or more and 100% by mass or less, more preferably 90% by mass or more and 100% by mass or less, and even more preferably 95% by mass or more and 100% by mass or less.

[0091] The average primary particle size of the pigments used in this invention, when forming the color layer of a color filter, is not particularly limited as long as it is sufficient to achieve the desired color rendering. It will vary depending on the type of pigment used, but is preferably in the range of 10 to 100 nm, and more preferably 15 to 60 nm. By using the above-mentioned range for the average primary particle size of the pigments, a display device equipped with a color filter manufactured using the photosensitive coloring resin composition of this invention can achieve high contrast and high quality.

[0092] Furthermore, the average dispersed particle size of the pigment in the photosensitive coloring resin composition will vary depending on the type of pigment used, but it is preferably in the range of 10 to 100 nm, and more preferably in the range of 15 to 60 nm. The average dispersed particle size of the pigment in a photosensitive coloring resin composition refers to the dispersed particle size of the pigment particles dispersed in a dispersion medium containing at least a solvent, and is measured using a laser light scattering particle size analyzer. To determine the particle size using a laser light scattering particle size analyzer, the photosensitive coloring resin composition can be appropriately diluted (e.g., 1000 times) to a concentration measurable by a laser light scattering particle size analyzer using the solvent used in the photosensitive coloring resin composition. The measurement is then performed at 23°C using a laser light scattering particle size analyzer (e.g., the Nanotrac particle size analyzer UPA-EX150 manufactured by Nikkiso Corporation) via dynamic light scattering. The average dispersed particle size here refers to the volume average particle size.

[0093] The pigments used in this invention can be manufactured using known methods such as recrystallization and solvent salt milling. Alternatively, commercially available pigments can be micronized for use.

[0094] In the photosensitive coloring resin composition of the present invention, the content of pigment is not particularly limited. Considering dispersibility and dispersion stability, the pigment content is generally in the range of 3% to 65% by mass relative to the total solid content of the photosensitive coloring resin composition, preferably in the range of 4% to 60% by mass, and more preferably in the range of 15% to 60% by mass. If the content is above the lower limit, the colored layer has sufficient color concentration when the photosensitive coloring resin composition is coated to a specific film thickness (generally 1.0 μm to 5.0 μm). Furthermore, if the content is below the upper limit, excellent storage stability is achieved, and a colored layer with sufficient hardness or adhesion to the substrate can be obtained. Especially when forming a colored layer with a high pigment concentration, the total pigment content is preferably in the range of 20% to 65% by mass relative to the total solid content of the photosensitive coloring resin composition, and more preferably in the range of 30% to 60% by mass.

[0095] [Photopolymerizable compounds] The photopolymerizable compound used in the photosensitive coloring resin composition is not particularly limited as long as it can be polymerized using a photoinitiator. Generally, compounds having two or more vinyl unsaturated bonds are suitable, and polyfunctional (meth)acrylates having two or more acrylonitrile or methacrylonitrile are preferred. As for such multifunctional (meth)acrylates, they can be used by appropriately selecting from those previously known. Specific examples include those described in Japanese Patent Application Publication No. 2013-029832.

[0096] These multifunctional (meth)acrylates can be used alone or in combination of two or more. Furthermore, when excellent photocurability (high sensitivity) is required for the photosensitive coloring resin composition of the present invention, the multifunctional (meth)acrylate is preferably one having three or more polymerizable vinyl unsaturated bonds (trifunctional), preferably a poly(meth)acrylate of a ternary or higher polyol, or a dicarboxylic acid modified thereof. Specifically, it is preferably trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, a succinic acid modified version of pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, a succinic acid modified version of dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc.

[0097] In order to achieve both a high residual film yield and a fine linewidth, the photopolymerizable compound used in this invention is preferably a photopolymerizable compound containing an epoxide. As photopolymerizable compounds containing alkyl oxides, photopolymerizable compounds containing ethylene oxide and / or propylene oxide are preferred examples. It is speculated that in the case of photopolymerizable compounds containing alkyl oxides, the peroxide free radicals that have lost their polymerization activity due to oxygen inhibition are regenerated into active free radicals, thus improving the curing property. Examples of photopolymerizable compounds containing epoxides include: epoxide-modified pentaerythritol tri(meth)acrylate, epoxide-modified pentaerythritol tetra(meth)acrylate, epoxide-modified dipentaerythritol tetra(meth)acrylate, epoxide-modified dipentaerythritol penta(meth)acrylate, epoxide-modified dipentaerythritol hexa(meth)acrylate, epoxide-modified trimethylolpropane tri(meth)acrylate, and epoxide-modified glycerol di(meth)acrylate, etc. More specifically, Examples include: ethylene oxide-modified trimethylolpropane tri(meth)acrylate, ethylene oxide-modified pentaerythritol penta(meth)acrylate, ethylene oxide-modified dipentaerythritol hexa(meth)acrylate, propylene oxide-modified pentaerythritol tri(meth)acrylate, propylene oxide-modified pentaerythritol tetra(meth)acrylate, propylene oxide-modified dipentaerythritol hexa(meth)acrylate, ethylene oxide-modified glycerol tri(meth)acrylate, and ethylene oxide-modified diglycerol tetra(meth)acrylate. Preferably, these include ethylene oxide-modified diglycerol tetra(meth)acrylate and ethylene oxide-modified dipentaerythritol hexa(meth)acrylate.

[0098] Photopolymerizable compounds can be used alone or in combination of two or more. As a photopolymerizable compound, it can also be used by mixing photopolymerizable compounds containing epoxides with those that do not contain epoxides. The content of photopolymerizable compounds, when including photopolymerizable compounds containing epoxides, is preferably in the range of 3% to 50% by mass, and more preferably in the range of 5% to 30% by mass, relative to the total amount of photopolymerizable compounds.

[0099] There is no particular limitation on the content of the aforementioned photopolymerizable compound used in the photosensitive coloring resin composition. It is preferably in the range of 5% to 60% by mass relative to the total solid content of the photosensitive coloring resin composition, and more preferably in the range of 10% to 40% by mass. If the content of the photopolymerizable compound is above or below the aforementioned lower limit, photocuring is sufficiently achieved, leaching of the exposed portion during development is suppressed, linewidth shift is suppressed, and solvent resistance is improved. Furthermore, if the content of the photopolymerizable compound is below the aforementioned upper limit, alkaline developability is more sufficient.

[0100] [Photoinitiator] There are no particular limitations on the photoinitiator used in the photosensitive coloring resin composition of the present invention, and one or more of the various previously known initiators may be used. Examples of photoinitiators include: benzophenone, N,N-dimethylaminobenzophenone, 4,4'-bis(diethylaminobenzophenone) (e.g., Hicure ABP, Kawaguchi Pharmaceutical), 4-methoxy-4'-dimethylaminobenzophenone, and other aromatic ketones; benzoin ethers such as benzoin methyl ether; benzoin compounds such as ethyl benzoin; biimidazoles such as 2-(o-chlorophenyl)-4,5-phenylimidazolium dimer; halomethyl benzoic acid diazole compounds such as 2-trichloromethyl-5-(p-methoxystyryl)-1,3,4-diazole; and 2-(4-butoxy-naphth-1-yl) )-4,6-bis-trichloromethyl-S-triylyl and other halomethyl-S-triylyl derivatives; 1,2-octanedione-1-[4-(phenylthio)-,2-(O-benzoyl oxime)], acetone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-,1-(O-acetyl oxime), Japanese Patent Application Publication No. 2000-80068, Japanese Patent Application Publication No. 2001-233 Oxime esters such as photoinitiators described in Japanese Patent Publication No. 842, Japanese Patent Publication No. 2010-527339, Japanese Patent Publication No. 2010-527338, and Japanese Patent Application Publication No. 2013-041153; α-amino ketones such as 2-methyl-1-(4-methylthiophene)-2-morpholinylpropane-1-one (e.g., Irgacure 907, manufactured by BASF), 2-benzyl-2-(dimethylamino)-1-(4-morpholinylphenyl)-1-butanone (e.g., Irgacure 369, manufactured by BASF), and 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone (Irgacure 379EG, manufactured by BASF); and diethyl-9-oxothiophene. 9-Oxysulfur kind. From the perspective of excellent sensitivity, the photoinitiator used in this invention is preferably selected from at least one of the groups comprising oxime esters and α-aminoketones. From the viewpoint of linewidth adjustment and development resistance during pattern formation, α-aminoketones are preferred. α-aminoketones, having a tertiary amine structure, are preferred because the free radicals generated by the initiator are less likely to be deactivated by oxygen due to the presence of a tertiary amine structure within the molecule, thus improving sensitivity. Furthermore, considering both suppressing water spots and improving sensitivity, it is preferable to use a combination of oxime esters and α-aminoketones as photoinitiators. Additionally, water spots refer to traces that appear as if water has seeped in after alkaline development and rinsing with pure water, when ingredients that enhance alkaline developability are used. These water spots disappear after baking, so they are not a problem for the finished product. However, during visual inspection of the patterned surface after development, they will be detected as abnormal spots, making it difficult to distinguish between normal and abnormal products. Therefore, reducing the inspection sensitivity of the inspection device during visual inspection will result in a decrease in the yield of the final color filter products, thus becoming a problem. Furthermore, as a photoinitiator, considering factors such as adjusting sensitivity, suppressing water spots, and improving development resistance, it is preferable to combine at least one of the groups selected from oxime esters and α-amino ketones with 9-oxosulfuron. Class composition.

[0101] Provided that the effects of the present invention are not impaired, there is no particular limitation on the total content of photoinitiator used in the photosensitive coloring resin composition of the present invention. Preferably, it is in the range of 0.1% to 12.0% by mass relative to the total solid content of the photosensitive coloring resin composition, and more preferably in the range of 1.0% to 8.0% by mass. If this content is above the lower limit, photocuring proceeds sufficiently, leaching of the exposed portion during development is suppressed, and solvent resistance becomes better. On the other hand, if it is below the upper limit, the reduction in brightness caused by yellowing of the obtained colored layer can be suppressed. Furthermore, regarding the content ratio of the aforementioned photopolymerizable compound to the aforementioned photoinitiator used in the photosensitive coloring resin composition, from the perspective of suppressing linewidth shift and improving solvent resistance, and further from the perspective of improving the suppression effect of developing residue, the total content ratio of the aforementioned photoinitiator to 100 parts by mass of the aforementioned photopolymerizable compound is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, more preferably 40 parts by mass or less, and more preferably 30 parts by mass or less.

[0102] [solvent] The solvent used in this invention is any organic solvent that does not react with the components of the photosensitive coloring resin composition and is capable of dissolving or dispersing them; there are no particular limitations. The solvent may be used alone or in combination of two or more. Specific examples of solvents include: alcohol solvents such as methanol, ethanol, n-propanol, isopropanol, methoxyethanol, and ethoxyethanol; carbitol solvents such as methoxyethoxyethanol and ethoxyethoxyethanol; ester solvents such as ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl methoxypropionate, ethyl ethoxypropionate, ethyl lactate, methyl hydroxypropionate, ethyl hydroxypropionate, n-butyl acetate, isobutyl acetate, isobutyl butyrate, n-butyl butyrate, ethyl lactate, and cyclohexanol acetate; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and 2-heptanone; and glycol ether acetate solvents such as methoxyethyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy-3-methyl-1-butyl acetate, 3-methoxybutyl acetate, and ethoxyethyl acetate. Carbitol acetate solvents such as methoxyethoxyethyl ester, ethoxyethoxyethyl acetate, and butyl carbitol acetate (BCA); diacetates such as propylene glycol diacetate and 1,3-butanediol diacetate; glycol ether solvents such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, and dipropylene glycol dimethyl ether; aprotic amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; lactone solvents such as γ-butyrolactone; cyclic ether solvents such as tetrahydrofuran; unsaturated hydrocarbon solvents such as benzene, toluene, xylene, and naphthalene; saturated hydrocarbon solvents such as n-heptane, n-hexane, and n-octane; and aromatic hydrocarbons such as toluene and xylene. Among these solvents, glycol ether acetate-based solvents, carbitol acetate-based solvents, glycol ether-based solvents, and ester-based solvents can be suitably used in terms of the solubility of other components. Of particular, the solvent used in this invention, considering the solubility of other components or the suitability for coating, is preferably selected from one or more of the group consisting of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, butyl carbitol acetate (BCA), 3-methoxy-3-methyl-1-butyl acetate, ethyl ethoxypropionate, ethyl lactate, and 3-methoxybutyl acetate.

[0103] In the photosensitive coloring resin composition of the present invention, the solvent content can be appropriately set within a range that allows for the precise formation of the colored layer. The total amount of the photosensitive coloring resin composition containing the solvent is typically in the range of 55% to 95% by mass, and preferably in the range of 65% to 88% by mass. By keeping the solvent content within the aforementioned range, excellent coatability can be achieved.

[0104] [Dispersant] In the photosensitive coloring resin composition of the present invention, the aforementioned colorant can be used by dispersing it in a solvent using a dispersant. In the present invention, the dispersant can be appropriately selected from previously known dispersants. Examples of dispersants include cationic, anionic, nonionic, amphoteric, polysiloxane, and fluorinated surfactants. Among surfactants, polymeric dispersants are preferred from the viewpoint of being able to disperse uniformly and finely.

[0105] Examples of polymeric dispersants include (co)polymers of unsaturated carboxylic acid esters such as polyacrylates; (partial) amine salts, (partial) ammonium salts, or (partial) alkylamine salts of (co)polymers of unsaturated carboxylic acid esters such as polyacrylic acid; (co)polymers of hydroxyl-containing unsaturated carboxylic acid esters such as hydroxyl-containing polyacrylates or their modifications; polyurethane esters; unsaturated polyamides; polysiloxanes; long-chain polyamide phosphates; polyethyleneimine derivatives (amides or bases thereof obtained by reacting poly(lower alkylimines) with polyesters containing free carboxyl groups); polyallylamine derivatives (reaction products obtained by reacting polyallylamine with one or more compounds selected from polyesters having free carboxyl groups, polyamides, or cocondensates of esters and amides (polyesteramides)). When the polymeric dispersant is a copolymer, it can be any one of block copolymer, graft copolymer or random copolymer. From the point of view of dispersibility, block copolymer and graft copolymer are preferred.

[0106] The dispersant can be selected appropriately based on the type of pigment, and there are no particular limitations. When dispersing lake pigments of the above-mentioned triarylmethane dyes, it is preferable to use an acidic dispersant that is an acidic polymeric dispersant. As an acidic dispersant for dispersing lake pigments, at least one selected from polymers having structural units represented by the following general formula (I) and carboxyl-containing block copolymers may be used. When using pigments as colorants and dispersing them, at least one of the following groups can be used, depending on the type of pigment: acidic or alkaline polymeric dispersants and carbamate-based dispersants. Both acidic and alkaline polymeric dispersants can be used. When dispersing alkaline-treated pigments, it is preferable to use an acidic polymeric dispersant; when dispersing acid-treated pigments, it is preferable to use an alkaline polymeric dispersant. As an alkaline dispersant, at least one of the following can be used, for example: polymers comprising repeating units having tertiary amines and at least a portion of the amine groups in polymers comprising repeating units having tertiary amines, and salt-type polymers that form salts with organic acid compounds. Carbamate dispersants are compounds having one or more carbamate bonds (-NH-COO-) within one molecule. For example, polyisocyanates having two or more isocyanate groups within one molecule and reaction products of polyesters having hydroxyl groups at one or both ends can be used as carbamate dispersants.

[0107] <Polymers having structural units represented by general formula (I)> Polymers having the structural units represented by the following general formula (I) are preferably used as dispersants for the above-mentioned triarylmethane dye lake pigments. As an acidic dispersant, using a polymer having the structural units represented by the following general formula (I) can improve the dispersibility and heat resistance of the above-mentioned triarylmethane dye lake pigments and suppress the color change of the lake pigments after heating. Furthermore, when both lake pigments and pigments are used as pigments, using a polymer having the structural units represented by the following general formula (I) as a dispersant can improve the dispersibility and storage stability of the pigments, forming a colored layer with improved substrate adhesion and coating uniformity. It is speculated that polymers with structural units represented by the following general formula (I) are vinyl unsaturated monomer polymers, thus exhibiting higher heat resistance of the skeleton compared to polyether or polyester polymers. Furthermore, the presence of multiple acidic phosphorus compound groups (-P(=O)(-R 12)(OH)) and their salts (-P(=O)(-R 12)(O -X +)) in this polymer provides stronger adsorption to the micronized pigment surface. Additionally, it is speculated that if the pigment surface is coated with at least one of the acidic phosphorus compound groups and their salts, the attack on the pigment skeleton of the lake pigment caused by reactive oxygen species such as peroxide free radicals (hydrogen abstraction or displacement reactions, etc.) can be suppressed, thereby inhibiting the degradation (oxidative degradation) of the lake pigment.

[0108] [Chemistry 8] (In general formula (I), L 11 is a direct bond or a divalent linker, R 11 is a hydrogen atom or a methyl group, R 12 is a hydroxyl group, a hydrocarbon group, a monovalent group represented by -[CH(R 13)-CH(R 14)-O] x1-R 15, -[(CH 2) y1-O] z1-R 15, or -OR 16, and R 16 is a hydrocarbon group, a monovalent group represented by -[CH(R 13)-CH(R 14)-O] x1-R 15, -[(CH 2) y1-O] z1-R 15, -C(R 17)(R 18)-C(R 19)(R 20)-OH, or -CH 2-C(R 21)(R 22)-CH 2-OH.) R13 and R14 are each independently a hydrogen atom or a methyl group. R15 is a hydrogen atom, a hydrocarbon group, -CHO, -CH2CHO, -CO-CH=CH2, -CO-C(CH3)=CH2, or -CH2COOR23. R23 is a hydrogen atom or an alkyl group with one or more but fewer than five carbon atoms. R17, R18, R19, R20, R21, and R22 are each independently a hydrocarbon group selected from hydrogen atoms, hydrocarbon groups, or ether bonds and ester bonds. R17 and R19 can be bonded to each other to form a ring structure. When the above-mentioned ring structure is formed, the ring structure may further have a substituent R24, which is a hydrocarbon group or has a hydrocarbon group selected from ether bonds and ester bonds. The above-mentioned hydrocarbon group may have substituents. X represents a hydrogen atom or an organic cation. x1 represents an integer greater than or equal to 1 and less than 18, y1 represents an integer greater than or equal to 1 and less than 5, and z1 represents an integer greater than or equal to 1 and less than 18.

[0109] In general formula (I), L11 is a direct bond or a divalent linker. Here, L11 direct bond means that the phosphorus atom is directly bonded to the carbon atom of the main chain backbone without the indirect linker. As a divalent linker in L11, there are no particular limitations as long as it can link the carbon and phosphorus atoms of the main chain backbone. Examples of divalent linkers in L11 include: straight-chain, branched or cyclic alkyl groups, straight-chain, branched or cyclic alkyl groups having hydroxyl groups, aryl groups, -CONH- groups, -COO- groups, -NHCOO- groups, ether groups (-O- groups), thioether groups (-S- groups), and combinations thereof. Furthermore, in this invention, the bonding direction of the divalent linker is arbitrary. That is, when the divalent linker contains -CONH-, -CO can be on the carbon atom side of the main chain and -NH can be on the phosphorus atom side of the side chain; conversely, -NH can be on the carbon atom side of the main chain and -CO can be on the phosphorus atom side of the side chain.

[0110] From the perspective of dispersibility, L 11 in general formula (I) is preferably a divalent linker containing -CONH- or -COO- groups. For example, when L11 is a divalent linker containing a -COO- group, L11 is preferably a -COO-L11'- group (here, L11' is an alkyl group with 1 or more but less than 8 carbon atoms that may have a hydroxyl group, -[CH(R L11)-CH(R L12)-O]x-, or -[(CH 2) yO] z-(CH 2) yO-, -[CH(R L13)] wO-, R L11, R L12 and R L13 are each independently a hydrogen atom, a methyl group, or a hydroxyl group. x represents an integer of 1 or more but less than 18, y represents an integer of 1 or more but less than 5, z represents an integer of 1 or more but less than 18, and w represents an integer of 1 or more but less than 18).

[0111] The alkyl group in L 1 1' with one or more but less than eight carbon atoms can be any of the following: linear, branched, or cyclic, such as methylene, ethyl, trimethylene, propyl, various butyl, various pentyl, various hexyl, various octyl, etc., and some hydrogen atoms can be substituted by hydroxyl groups. x is an integer greater than or equal to 1 and less than 18, preferably greater than or equal to 1 and less than 4, and even more preferably greater than or equal to 1 and less than 2. y is an integer greater than or equal to 1 and less than 5, preferably greater than or equal to 1 and less than 4, and even more preferably greater than or equal to 2 or 3. z is an integer greater than or equal to 1 and less than 18, preferably greater than or equal to 1 and less than 4, and even more preferably greater than or equal to 1 and less than 2. w is an integer greater than or equal to 1 and less than 18, preferably greater than or equal to 1 and less than 4.

[0112] As suitable specific examples of L 1 1 in general formula (I), examples may include: -COO-CH 2CH(OH)CH 2-O-, -COO-CH 2CH 2-O-CH 2CH(OH)CH 2-O-, -COO-CH 2C(CH 2CH 3)(CH 2OH)CH 2-O-, etc., but are not limited to these.

[0113] Examples of hydrocarbon groups in R12 include alkyl groups with 1 or more but less than 18 carbon atoms, alkenyl groups with 2 or more but less than 18 carbon atoms, aralkyl groups, and aryl groups. The alkyl groups having 1 or more but less than 18 carbon atoms can be linear, branched, or cyclic. Examples include: methyl, ethyl, n-propyl, isopropyl, n-butyl, cyclopentyl, cyclohexyl, alkyl, isoalkyl, dicyclopentyl, adamantyl, and lower alkyl-substituted adamantyl. The alkenyl groups with 2 or more but less than 18 carbon atoms can be linear, branched, or cyclic. Examples of such alkenyl groups include vinyl, allyl, and propenyl. The position of the double bond in the alkenyl group is not limited, but from the perspective of the reactivity of the obtained polymer, it is preferable that the double bond is present at the end of the alkenyl group. Examples of aryl groups include phenyl, biphenyl, naphthyl, tolyl, and xylyl, and they may also have substituents. The number of carbon atoms in the aryl group is preferably 6 or more and 24 or less, and more preferably 6 or more and 12 or less. Furthermore, examples of aralkyl groups include benzyl, phenethyl, naphthylmethyl, and biphenylmethyl, and they may also have substituents. The number of carbon atoms in the aralkyl group is preferably 7 or more and 20 or less, and more preferably 7 or more and 14 or less. The aforementioned alkyl or alkenyl groups may also have substituents, such as halogen atoms like F, Cl, and Br, and nitro groups. Furthermore, as substituents for the aromatic rings of the aforementioned aryl or aralkyl groups, in addition to straight-chain and branched alkyl groups having one or more but four or fewer carbon atoms, examples include alkenyl, nitro, and halogen atoms. Furthermore, the aforementioned preferred carbon number does not include the carbon number of substituents. In R12 above, x1 is the same as x above, y1 is the same as y above, and z1 is the same as z above. As for the hydrocarbon groups in R15 to R22, examples can be given that are the same as the hydrocarbon groups in R12 mentioned above.

[0114] The groups R17, R18, R19, R20, R21, and R22 are groups having one or more hydrocarbon groups selected from ether bonds and ester bonds, represented by -R'-O-R'', -R'-(C=O)-O-R'', or -R'-O-(C=O)-R'' (where R' and R'' are hydrocarbon groups, or groups formed by linking hydrocarbon groups using at least one of ether bonds and ester bonds). A single group may have two or more ether bonds and ester bonds. Examples of monovalent hydrocarbon groups include alkyl, alkenyl, aralkyl, and aryl groups; examples of divalent hydrocarbon groups include alkylene, alkenyl, aryl, and combinations thereof.

[0115] When a ring structure is formed by the bonding of R17 and R19, the number of carbons in the ring structure is preferably 5 or more and 8 or less, more preferably 6, that is, a 6-membered ring, and preferably a cyclohexane ring. The hydrocarbon group in substituent R 24, or the hydrocarbon group having one or more selected from ether bonds and ester bonds, may be the same as those in R 17, R 18, R 19, R 20, R 21 and R 22 above.

[0116] Considering the excellent dispersibility and dispersion stability of the dispersed particles, R12 is preferably a hydroxyl, hydrocarbon, -[CH(R13)-CH(R14)-O]x1-R15, -[(CH2)y1-O]z1-R15, or -OR16 valence group, more preferably the following: R12 is a hydroxyl, methyl, ethyl, vinyl, aryl or aralkyl group with substituents, vinyl, allyl, -[CH(R13)-CH(R14)-O]x1-R15, -[(CH2)y1-O]z1-R15, or -OR16 valence group, where R13 and R14 are independently hydrogen atoms or methyl groups, and R15 is -CO-CH=CH2 or -CO-C(CH3)=CH2; wherein, R 12 is preferably aryl, vinyl, methyl, or hydroxyl groups that may have substituents.

[0117] Furthermore, considering improved alkali resistance, R12 is preferably a hydrocarbon group, or a valence group represented by -[CH(R13)-CH(R14)-O]x1-R15, or -[(CH2)y1-O]z1-R15. It is speculated that in the case of a structure where carbon atoms are directly bonded to phosphorus atoms, it is less susceptible to hydrolysis, thus enabling the formation of a resin layer with excellent alkali resistance. From the perspective of excellent alkali resistance and excellent dispersibility and dispersion stability of the dispersed particles, the following is preferred: R12 is a methyl, ethyl, aryl or aralkyl group with substituents, vinyl, allyl, -[CH(R13)-CH(R14)-O]x1-R15, or -[(CH2)y1-O]z1-R15, where R13 and R14 are independently hydrogen atoms or methyl groups, and R15 is -CO-CH=CH2 or -CO-C(CH3)=CH2. From the perspective of dispersibility, R12 is more preferably an aryl group with substituents.

[0118] Furthermore, in general formula (I), X represents a hydrogen atom or an organic cation. An organic cation refers to one whose cation portion contains a carbon atom. Examples of organic cations include: imidazolium cations, pyridinium cations, amidine cations, piperidinium cations, pyrrolidine cations, tetraalkylammonium cations, trialkylammonium cations, strontium cations, and tetraalkylphosphonium cations. Among these, protonated nitrogen-containing organic cations are preferred from the perspectives of dispersibility and basic reproducibility. In cases where the organic cation has ethylene-unsaturated bonds, it is preferable to consider the ability to impart hardening properties.

[0119] The structural unit represented by general formula (I) may be a single unit or two or more units in the polymer.

[0120] The polymer may contain two types of structural units, namely, structural units in which X is a hydrogen atom and structural units in which X is an organic cation, as represented by general formula (I). When both types of structural units are included, there are no particular restrictions as long as good dispersibility and dispersion stability are achieved. Preferably, the ratio of the number of structural units in which X is an organic cation to the total number of structural units represented by general formula (I) is 0 or more and less than 50 mol%.

[0121] There are no particular limitations on the synthesis method of polymers having structural units represented by general formula (I). For example, Japanese Patent Application Publication No. 2017-2191 can be referred to for the synthesis of polymers having structural units represented by general formula (I). The polymer having structural units represented by general formula (I) is a reaction product of a polymer having at least one of epoxy groups and cyclic ether groups in its side chains and an acidic phosphorus compound, preferably a polymer in which at least a portion of the acidic phosphorus compound groups can form a salt.

[0122] In embodiments of the present invention, from the perspective of dispersibility, polymers having structural units represented by general formula (I) are preferably further having solvent-affinity sites. Among such polymers, from the perspective of excellent dispersibility and storage stability, and the ability to form high-contrast coatings even after long-term storage, graft copolymers having structural units represented by general formula (I) and those represented by general formula (II) are preferred; or block copolymers having structural units represented by general formula (I) and those represented by general formula (III).

[0123] [Chemistry 9] (In general formula (II), L 21 represents a direct bond or a divalent linker, R 25 represents a hydrogen atom or a methyl group, and Polymer represents a polymer chain having the structural units represented by the following general formula (IV). In general formula (III), R26 is a hydrogen atom or a methyl group, R27 is a hydrocarbon group, -[CH(R28)-CH(R29)-O]x2-R30, -[(CH2)y2-O]z2-R30, -[CO-(CH2)y2-O]z2-R30, -CO-OR30' or -O-CO-R30'', R28 and R29 are independently hydrogen atoms or methyl groups, R30 is a hydrogen atom, a hydrocarbon group, -CHO, -CH2CHO or -CH2COOR31, R30' is a hydrocarbon group, -[CH(R28)-CH(R29)-O]x2'-R30, -[(CH2)y2'-O]z2'-R30, -[CO- ... 2) The y2'-O] z2'-R 30 group represents a monovalent group, where R 30'' is an alkyl group with 1 or more but less than 18 carbon atoms, and R 31 is a hydrogen atom or an alkyl group with 1 or more but less than 5 carbon atoms. The above hydrocarbon group may have substituents. x2 and x2' represent integers greater than 1 and less than 18, y2 and y2' represent integers greater than 1 and less than 5, and z2 and z2' represent integers greater than 1 and less than 18.

[0124] [Chemistry 10] In general formula (IV), R 32 is a hydrogen atom or a methyl group; R 33 is a hydrocarbon group, a valence group represented by -[CH(R 34)-CH(R 35)-O] x3-R 36, -[(CH 2) y3-O] z3-R 36, -[CO-(CH 2) y3-O] z3-R 36, -CO-OR 37, or -O-CO-R 38; R 34 and R 35 are independently hydrogen atoms or methyl groups; R 36 is a hydrogen atom, a hydrocarbon group, -CHO, -CH 2CHO, or -CH 2COOR 39; R 37 is a hydrocarbon group, -[CH(R 34)-CH(R 35)-O] x4-R 36, -[(CH 2) y4-O] z4-R 36, -[CO-(CH 2) The y4-O] z4-R 36 represents a monovalent group, R 38 is an alkyl group with 1 or more but less than 18 carbon atoms, and R 39 is a hydrogen atom or an alkyl group with 1 or more but less than 5 carbon atoms. The above hydrocarbon groups may have substituents. n represents an integer greater than 5 and less than 200. x3 and x4 represent integers greater than 1 and less than 18, y3 and y4 represent integers greater than 1 and less than 5, and z3 and z4 represent integers greater than 1 and less than 18.

[0125] (graft copolymer) Graft copolymers that are preferred as acidic dispersants include, for example, graft copolymers having structural units represented by the above general formula (I) and structural units represented by the above general formula (II). In the above general formula (II), L 21 is a direct bond or a divalent linker. As a divalent linker in L 21, there are no particular restrictions as long as it can link a carbon atom from an ethylene unsaturated bond to the polymer chain. For example, the same divalent linker as in L 11 can be cited as a divalent linker in L 21.

[0126] In the above general formula (II), Polymer represents a polymer chain having the structural unit represented by the above general formula (IV). In general formula (IV), the hydrocarbon group in R 33 is preferably an alkyl group having 1 or more but less than 18 carbon atoms, an alkenyl group having 2 or more but less than 18 carbon atoms, an aralkyl group, or an aryl group. Examples of these are the same as those for R 12 described above.

[0127] R 36 is preferably a hydrogen atom, or an alkyl, aralkyl, aryl, -CHO, -CH 2CHO, or -CH 2COOR 39 group having 1 or more but less than 18 carbon atoms. R 37 is preferably an alkyl, aralkyl, aryl, -[CH(R 34)-CH(R 35)-O] x4-R 36, -[(CH 2) y4-O] z4-R 36, or -[CO-(CH 2) y4-O] z4-R 36 group having 1 or more but less than 18 carbon atoms. R 38 is an alkyl group having 1 or more but less than 18 carbon atoms, and R 39 represents a hydrogen atom or an alkyl group having 1 or more but less than 5 carbon atoms. The alkyl, aralkyl, and aryl groups with one or more but less than 18 carbon atoms in R 36 and R 37 mentioned above can be exemplified as those in R 12 mentioned above. The alkyl groups in R 38 and R 39 mentioned above can be exemplified as those in R 12 mentioned above. When R 36, R 37, and R 39 are groups having an aromatic ring, the aromatic ring may further have substituents. Examples of such substituents include, in addition to straight-chain, branched, and cyclic alkyl groups having one or more but less than five carbon atoms, alkenyl, nitro, halogen atoms such as F, Cl, and Br. Furthermore, the aforementioned preferred carbon number does not include the carbon number of substituents. In R 33 and R 37 above, x3 and x4 are the same as x above, y3 and y4 are the same as y above, and z3 and z4 are the same as z above.

[0128] Furthermore, R33, R36, R37, R38, and R39 can be substituted with substituents such as alkoxy, hydroxyl, carboxyl, amino, epoxy, isocyanate, or hydrogen-bonding groups, within a range that does not impair the dispersion properties of the graft copolymer. Alternatively, after synthesizing the graft copolymer having these substituents, a compound having a functional group that reacts with the substituent and a polymerizable group can be reacted to form a polymerizable group. For example, glycidyl (meth)acrylate can be reacted with a graft copolymer having a carboxyl group, or hydroxyethyl (meth)acrylate can be reacted with a graft copolymer having an isocyanate group to form a polymerizable group.

[0129] Polymer chains having structural units represented by general formula (IV) are preferably those having structural units derived from methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tributyl methacrylate, 2-ethylhexyl methacrylate, 2-ethoxyethyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, phenyl methacrylate, isobutyl methacrylate, dicyclopentyl methacrylate, adamantyl methacrylate, styrene, α-methylstyrene, vinylcyclohexane, etc. However, they are not limited to these.

[0130] In embodiments of the present invention, R33 and R37 are preferably those with excellent solubility in the following organic solvents, which can be appropriately selected according to the organic solvent used in the pigment dispersion. Specifically, for example, when the above-mentioned organic solvent is a commonly used organic solvent for pigment dispersions, such as ether alcohol acetate, ether, or ester solvents, it is preferred to use methyl, ethyl, isobutyl, n-butyl, 2-ethylhexyl, 2-ethoxyethyl, cyclohexyl, benzyl, etc. The reason for setting R33 and R37 in this way is that the structural units containing R33 and R37 have solubility in the organic solvent, and the acidic phosphorus compound group of the monomer and its salt site have high adsorption capacity for pigment particles, which can make the dispersibility and stability of pigment particles particularly excellent.

[0131] The weight-average molecular weight of the polymer chains in the polymer is preferably in the range of 500 or more and 15,000 or less, and more preferably in the range of 1,000 or more and 8,000 or less. Within the above range, sufficient stereorepulsion effect as a dispersant can be maintained, and the increased time required for the dispersion of particles such as pigments caused by stereorepulsion can also be suppressed.

[0132] Furthermore, as a standard, the solubility of the polymer chain in the polymer relative to the combined organic solvent at 23°C is preferably 50 (g / 100 g solvent) or higher.

[0133] The polymer chains described above can be homopolymers or copolymers. Furthermore, the polymer chains contained in the structural unit represented by general formula (II) in the graft copolymer can be a single type or a mixture of two or more types.

[0134] Relative to all structural units of the graft copolymer described above, the structural units represented by the general formula (I) are preferably contained in a ratio of 3% to 80% by mass, more preferably 10% to 70% by mass, and even more preferably 20% to 60% by mass. If the total content of the structural units represented by the general formula (I) in the graft copolymer is within the above range, the ratio of the particle-affinity sites in the graft copolymer becomes appropriate, and the decrease in solubility in organic solvents can be suppressed. Therefore, the adsorption of pigments and other particles becomes better, and excellent dispersibility and dispersion stability can be obtained. Furthermore, since the acidic phosphorus compound groups of the graft copolymer can stably exist locally around the pigment, color filters with excellent heat resistance or contrast can be obtained. On the other hand, relative to all the structural units of the above-mentioned graft copolymer, the structural unit represented by the above-mentioned general formula (II) is preferably included in a ratio of more than 20% by mass and less than 97% by mass, more preferably more than 25% by mass and less than 95% by mass, and even more preferably more than 40% by mass and less than 90% by mass. Furthermore, in this invention, the content ratio of each structural unit in the copolymer is calculated based on the amount added during the synthesis of the copolymer.

[0135] Furthermore, the weight average molecular weight of the aforementioned graft copolymer is preferably in the range of 1,000 or more and 500,000 or less, more preferably in the range of 3,000 or more and 400,000 or less, and even more preferably in the range of 5,000 or more and 300,000 or less. Within the above range, pigments and other particles can be uniformly dispersed.

[0136] In addition to the structural units represented by general formula (I) and general formula (II) above, the graft copolymers used in the embodiments of the present invention may further have other structural units. For example, other structural units may be introduced by copolymerizing with vinyl unsaturated monomers that can copolymerize with vinyl unsaturated monomers that derive structural units from general formula (I).

[0137] (block copolymer) Preferred block copolymers as acidic dispersants include, for example, block copolymers having a block portion comprising the structural unit represented by the above general formula (I) and a block portion comprising the structural unit represented by the above general formula (III). In the block copolymer, the block portion comprising the structural unit represented by the above general formula (I) preferably comprises a total of three or more structural units represented by the above general formula (I). From the perspective of improving dispersibility and heat resistance, it is preferable to include three or more and less than 200 structural units, more preferably three or more and less than 50 structural units, and even more preferably three or more and less than 30 structural units. The structural unit represented by the above general formula (I) only needs to function as a pigment affinity site, and may contain one type or more types of structural units. In the case where more than two types of structural units are included, the two or more types of structural units may be arranged randomly within the block portion containing the structural unit represented by the above general formula (I).

[0138] In the block copolymer described above, the total percentage of the structural units represented by the general formula (I) relative to all the structural units of the block copolymer is preferably 5% by mass or more and 80% by mass or less, more preferably 10% by mass or more and 70% by mass or less, and even more preferably 20% by mass or more and 60% by mass or less. Within the aforementioned range, the ratio of particle-affinity sites in the block copolymer becomes appropriate, and the decrease in solubility in organic solvents can be suppressed. Therefore, the adsorption of pigments and other particles becomes better, resulting in excellent dispersibility and dispersion stability. Furthermore, since the acidic phosphorus compound groups of the aforementioned block copolymer can stably exist around the pigment, color filters with excellent heat resistance or contrast can be obtained.

[0139] The block copolymers described above, by having block portions comprising the structural units represented by the above general formula (III), have good solvent affinity, good pigment dispersibility and dispersion stability, good heat resistance, and excellent resistance to N-methylpyrrolidone (NMP).

[0140] In general formula (III), R 27 is a hydrocarbon group, -[CH(R 28)-CH(R 29)-O] x2-R 30, -[(CH 2) y2-O] z2-R 30, -[CO-(CH 2) y2-O] z2-R 30, -CO-OR 30', or -O-CO-R 30''. As for the hydrocarbon group in R 27, it can be set to be the same as that represented by R 12 above.

[0141] Furthermore, R 30 is a hydrogen atom, a hydrocarbon group, -CHO, -CH 2CHO or -CH 2COOR 31, and R 30' is a hydrocarbon group, -[CH(R 28)-CH(R 29)-O] x2'-R 30, -[(CH 2) y2'-O] z2'-R 30, -[CO-(CH 2) y2'-O] z2'-R 30. R 30'' is an alkyl group with 1 or more but less than 18 carbon atoms, and R 31 is a hydrogen atom or an alkyl group with 1 or more but less than 5 carbon atoms. The above hydrocarbon groups may have substituents. The hydrocarbon group in R 30 above can be the same as that represented by R 12 above. In R 27 and R 30' above, x2 and x2' are the same as x above, y2 and y2' are the same as y above, and z2 and z2' are the same as z above. Furthermore, the R 27 in the structural units represented by the above general formula (III) can be the same or different from each other.

[0142] Of the aforementioned R 27 and R 30', those with excellent solubility in the solvents described below are preferred, for example, those similar to R 33 and R 37 mentioned above. Furthermore, R27, R30, R30', R30'', and R31 in the above general formula (IV) can be substituted with substituents such as alkoxy, hydroxyl, carboxyl, amino, epoxy, isocyanate, or hydrogen-bonding groups, within a range that does not impair the dispersion properties of the block copolymer. Alternatively, after synthesizing the block copolymer, the substituents can be added by reacting with a compound having the aforementioned substituents. Alternatively, after synthesizing a block copolymer having these substituents, a compound having a functional group that reacts with the substituent and a polymerizable group can be reacted to add a polymerizable group. For example, (meth)acrylic acid can be reacted with a block copolymer having a glycidyl group, or hydroxyethyl (meth)acrylic acid can be reacted with a block copolymer having an isocyanate group to add a polymerizable group.

[0143] There is no particular limitation on the number of structural units constituting the block portion containing the structural units represented by general formula (III). From the perspective of effectively functioning the solvent affinity site and the pigment affinity site to improve the dispersibility of the pigment dispersion, it is preferably 10 or more and 200 or less, more preferably 20 or more and 100 or less, and even more preferably 30 or more and 80 or less.

[0144] In the block copolymers described above, the proportion of the structural units represented by general formula (III) relative to all structural units of the block copolymers is preferably 30% by mass or more and 95% by mass or less, and more preferably 40% by mass or more and 90% by mass or less.

[0145] The block portion containing the structural unit represented by general formula (III) can be selected in a manner that functions as a solvent affinity site. The structural unit represented by general formula (III) may include one type or more types of structural units. In the embodiments of the present invention, when the structural unit represented by general formula (III) includes two or more types of structural units, the two or more types of structural units may be arranged randomly within the block portion containing the structural unit represented by the above-mentioned general formula (III).

[0146] In the block copolymer used as a dispersant, the ratio m / n of the number of structural units m of the block portion containing the structural units represented by general formula (I) and the number of structural units n of the block portion containing the structural units represented by general formula (III) is preferably in the range of 0.01 or more and 1 or less. From the perspective of the dispersibility and dispersion stability of the pigment, it is more preferably in the range of 0.1 or more and 0.7 or less.

[0147] As for the bonding sequence of the block copolymer, as long as it has a block portion containing the structural unit represented by the general formula (I) and a block portion containing the structural unit represented by the general formula (III), the pigment can be stably dispersed, and there is no particular limitation. Considering the excellent interaction with the pigment and the ability to effectively suppress the aggregation of dispersants, it is preferable that the block portion containing the structural unit represented by the general formula (I) is only bonded to one end of the block copolymer.

[0148] The weight average molecular weight of the block copolymer is not particularly limited, but from the perspective of achieving good dispersibility and excellent heat resistance, it is preferably 2,500 or more and 500,000 or less, more preferably 3,000 or more and 400,000 or less, and even more preferably 6,000 or more and 300,000 or less.

[0149] From the perspective of the dispersibility and storage stability of the pigments, the acid value of the polymer having the structural unit represented by the general formula (I) is preferably 20 mgKOH / g or more, more preferably 30 mgKOH / g or more, and even more preferably 40 mgKOH / g or more. On the other hand, from the perspective of excellent developability, the acid value of the polymer having the structural unit represented by the general formula (I) is preferably 150 mgKOH / g or less, more preferably 120 mgKOH / g or less, and even more preferably 100 mgKOH / g or less. Furthermore, in this invention, the acid value refers to the number of mg of potassium hydroxide required to neutralize the acidic components contained in 1 g of the sample, which can be determined according to JIS K 0070:1992.

[0150] On the other hand, the aforementioned carboxyl-containing block copolymer may be a block copolymer comprising an A block containing structural units derived from carboxyl-containing vinyl unsaturated monomers such as (meth)acrylic acid, and a B block containing structural units derived from alkyl (meth)acrylates. In the carboxyl-containing block copolymer, the B block containing structural units derived from alkyl (meth)acrylates may be the same as in block copolymers having structural units represented by the aforementioned general formula (I).

[0151] The content ratio (moles%) of each structural unit in the copolymer of the dispersant can be determined during manufacturing based on the amount of raw materials added, and can also be measured using analytical instruments such as NMR (Nuclear Magnetic Resonance). Furthermore, the structure of the dispersant can be determined using NMR, various mass spectrometry analyses, etc. Additionally, if necessary, the dispersant can be decomposed by thermal decomposition, and the obtained decomposition products can be determined using high-performance liquid chromatography, gas chromatography-mass spectrometry, NMR, elemental analysis, XPS / ESCA (X-ray photoelectron spectroscopy / Electron Spectroscopy for Chemical Analysis), and TOF-SIMS (Time-Of-Flight Secondary Ion Mass Spectrometry).

[0152] In this invention, the content of the dispersant can be appropriately selected based on the type of pigment used and, consequently, the concentration of the solid components in the following photosensitive coloring resin composition. The content of dispersant is preferably in the range of 2% to 30% by mass relative to the total solids content of the photosensitive coloring resin composition, and more preferably in the range of 3% to 25% by mass. If it is above the lower limit of the above values, the dispersibility and dispersion stability of the pigment are excellent, and the storage stability of the photosensitive coloring resin composition is even better. Furthermore, if it is below the upper limit of the above values, the developability becomes better.

[0153] [Antioxidants] From the perspective of improving heat resistance and brightness, the photosensitive coloring resin composition of the present invention preferably contains at least one of an antioxidant and a potential antioxidant. The antioxidants used in this invention are not particularly limited, and can be appropriately selected from those previously known. Specific examples of antioxidants include hindered phenolic antioxidants, amine antioxidants, phosphorus antioxidants, sulfur antioxidants, hydrazine antioxidants, etc. Considering the improved ability to form fine line patterns such as photomask linewidth design and heat resistance, hindered phenolic antioxidants are preferred. The potential antioxidants used in this invention are compounds having a protecting group that can be removed by heating, and which exhibit antioxidant function by removing the protecting group. Preferably, the protecting group is easily removed by heating above 150°C. Examples of potential antioxidants used in this invention include those described in International Publications No. 2014 / 021023 and No. 2017 / 170263. Among these, potential antioxidants in which the phenolic hydroxyl group of hindered phenolic antioxidants is protected by a protecting group are suitable examples. More specifically, structures in which an aminocarbamate protecting group, such as a tert-butoxycarbonyl group, replaces the hydrogen atom of the phenolic hydroxyl group in the hindered phenolic antioxidant are suitable examples.

[0154] Examples of hindered phenolic antioxidants include: pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (trade name: IRGANOX 1010, manufactured by BASF), 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate (trade name: Irganox 3114, manufactured by BASF), 2,4,6-tris(4-hydroxy-3,5-di-tert-butylbenzyl)trimethylbenzylene (trade name: Irganox 1330, manufactured by BASF), and 2,2'-methylenebis(6-tert-butyl-4-methylphenol) (trade name: Sumilizer). MDP-S (manufactured by Sumitomo Chemical), 6,6'-thiobis(2-tert-butyl-4-methylphenol) (trade name: Irganox 1081, manufactured by BASF), and diethyl 3,5-ditert-butyl-4-hydroxybenzylphosphonate (trade name: Irgamod 195, manufactured by BASF), etc. Among them, considering heat resistance and lightfastness, pentaerythritol tetratetra[3-(3,5-ditert-butyl-4-hydroxyphenyl)propionate] (trade name: IRGANOX 1010, manufactured by BASF) is preferred.

[0155] The antioxidant content is preferably in the range of 0.1% to 10.0% by mass, and more preferably in the range of 0.5% to 5.0% by mass, relative to the total solid content of the photosensitive coloring resin composition. If the content is above the lower limit, it is superior in improving heat resistance and brightness. On the other hand, if the content is below the upper limit, the coloring resin composition of the present invention can be made into a highly sensitive photosensitive resin composition.

[0156] [Thiols] From the perspective of improving the effect of suppressing film thickness changes before and after development with a finer linewidth, the photosensitive coloring resin composition of the present invention preferably contains a thiol compound. Regarding thiol compounds, since the reaction of enthiols is not inhibited by polymerization caused by oxygen, they exhibit excellent surface hardening properties, thus improving the residual film yield in development. Thiol compounds also have the effect of coarsening linewidth, but by combining them with ultraviolet absorbers, they achieve a synergistic effect that balances finer linewidth with improved residual film yield in development. Examples of thiol compounds include monofunctional thiol compounds with one thiol group and polyfunctional thiol compounds with two or more thiol groups. From the perspective of improving the effect of suppressing film thickness changes before and after development with a finer linewidth, polyfunctional thiools are preferable. Examples of monofunctional thiols include: 2-mercaptobenzothiazole, 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercapto-5-methoxybenzothiazole, 2-mercapto-5-methoxybenzimidazole, 3-mercaptopropionic acid, methyl 3-mercaptopropionic acid, ethyl 3-mercaptopropionic acid, octyl 3-mercaptopropionic acid, etc. Examples of polyfunctional thiols include 1,4-bis(3-mercaptobutoxy)butane, 1,3,5-tris(3-mercaptobutoxyethyl)-1,3,5-tris(2,4,6(1H,3H,5H)-trione, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetra(3-mercaptobutyrate), pentaerythritol tetra(3-mercaptopropionate), dipentaerythritol hexa(3-mercaptopropionate), and tetraethylene glycol bis(3-mercaptopropionate). As a thiol compound, it can be used alone or in combination of two or more. Among them, from the perspective of improving the effect of suppressing film thickness changes before and after development with a finer linewidth, pentaerythritol tetra(3-mercaptobutyrate) is preferred. The content of thiol compounds, relative to the total solid content of the photosensitive coloring resin composition, is typically in the range of 0.5% to 10% by mass, and preferably in the range of 1% to 5% by mass. If the content is above the lower limit, the effect of suppressing film thickness changes before and after development is excellent. On the other hand, if the content is below the upper limit, the photocurable red resin composition of the present invention is more likely to have good developability and suppressed linewidth shift.

[0157] [Other ingredients] The photosensitive coloring resin composition of the present invention may contain various additives as needed. Examples of additives include: polymerization terminators, chain transfer agents, leveling agents, plasticizers, surfactants, defoamers, silane coupling agents, adhesion promoters, and ultraviolet absorbers. Specific examples of surfactants and plasticizers include those described in Japanese Patent Application Publication No. 2013-029832.

[0158] <Method for manufacturing photosensitive coloring resin composition> The method for manufacturing the photosensitive coloring resin composition of the present invention can be prepared by mixing pigments, alkali-soluble resins, photopolymerizable compounds, photoinitiators, solvents, and dispersants or various additives as needed using a known mixing method. Examples of methods for preparing the resin composition include: (1) firstly, adding a pigment and a dispersant to a solvent to prepare a pigment dispersion, and then mixing an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and various additives as needed in the dispersion; (2) simultaneously adding a pigment, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and various additives as needed to a solvent and mixing them; (3) adding an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a dispersant as needed or various additives to a solvent and mixing them, and then adding a pigment for dispersion; (4) adding a pigment, a dispersant, and an alkali-soluble resin to a solvent to prepare a pigment dispersion, and then adding an alkali-soluble resin, a solvent, a photopolymerizable compound, a photoinitiator, and various additives as needed to the dispersion and mixing them. Of these methods, the methods described in (1) and (4) above are preferred in terms of effectively preventing pigment aggregation and dispersing it evenly. Furthermore, in the method of (4), the alkali-soluble resin added to the pigment dispersion may or may not contain the alkali-soluble resin (U) used in this invention.

[0159] The method for preparing pigment dispersions can be appropriately selected from previously known dispersion methods. Examples of dispersers used for dispersion processing include: roller mills such as two-roll mills and three-roll mills; ball mills such as ball mills and vibratory ball mills; and bead mills such as coating conditioners, continuous disc bead mills, and continuous ring bead mills. For optimal dispersion conditions in bead mills, the bead diameter used is preferably 0.03 mm to 2.00 mm, more preferably 0.10 mm to 1.0 mm.

[0160] [use] The photosensitive coloring resin composition of the present invention contains a lake pigment of triarylmethane dye, which can improve brightness and form a colored layer with a finer linewidth to suppress film thickness changes before and after development. Therefore, it can be suitable for use as a color filter.

[0161] [Curing of photosensitive coloring resin composition] The cured product of the present invention is the cured product of the photosensitive coloring resin composition of the present invention described above. The cured product of the present invention can be obtained by forming a coating of the photosensitive coloring resin composition of the present invention described above, drying the coating, and then exposing and developing it. The method for forming, exposing, and developing the coating can be, for example, the same method used in forming the colored layer of the color filter of the present invention described below. Furthermore, the hardened material of this invention is a lake pigment containing triarylmethane dyes to improve brightness, and a colored layer with a finer linewidth to suppress film thickness changes before and after development, making it suitable for use as a colored layer for color filters.

[0162] III. Color Filters The color filter of the present invention comprises at least a substrate and a coloring layer disposed on the substrate, and at least one of the coloring layers is a cured form of the photosensitive coloring resin composition of the present invention.

[0163] The color filter of the present invention will be described with reference to the figures. Figure 1 is a schematic cross-sectional view showing an example of the color filter of the present invention. According to Figure 1, the color filter 10 of the present invention has a substrate 1, a light-shielding portion 2, and a coloring layer 3.

[0164] [Shading layer] At least one of the color layers used in the color filter of the present invention is a color layer of the hardened form of the photosensitive coloring resin composition of the present invention. The coloring layer is usually formed in the opening of the light-shielding part on the substrate below, and usually contains a coloring pattern of three or more colors. Furthermore, there are no particular limitations on the arrangement of the color layers; for example, they can be arranged in a striped, mosaic, triangular, or 4-pixel configuration, among other common arrangements. Also, the width and area of ​​the color layers can be set arbitrarily. The thickness of the coloring layer is appropriately controlled by adjusting the coating method, the concentration or viscosity of the solid components in the photosensitive coloring resin composition, etc., and is usually preferably in the range of 1 μm to 5 μm.

[0165] The colored layer can be formed, for example, by the following method. First, the photosensitive coloring resin composition of the present invention is coated onto the substrate using coating methods such as spraying, dip coating, rod coating, roller coating, spin coating, and die coating to form a wet coating film. Spin coating and die coating are preferred methods. Subsequently, after the wet coating is dried using a heating plate or oven, it is exposed to light through a photomask with a specific pattern, causing the alkali-soluble resin and multifunctional monomers to undergo a photopolymerization reaction to form a hardened coating. Examples of light sources used for exposure include low-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, ultraviolet light, and electron beams. The exposure amount is adjusted appropriately according to the light source used or the thickness of the coating. Furthermore, after exposure, heat treatment can be performed to promote the polymerization reaction. The heating conditions are appropriately selected based on the mixing ratio of the components in the photosensitive coloring resin composition used, or the thickness of the coating film.

[0166] Next, a developing solution is used to develop the coating, dissolving and removing the unexposed areas to form the desired pattern. The developing solution is typically a solution made by dissolving an alkali in water or a water-soluble solvent. An appropriate amount of surfactant may also be added to this alkaline solution. Furthermore, conventional methods can be used for development. After development, the coating is typically washed with the developer and dried to form a colored layer. Alternatively, after development, a heat treatment may be performed to ensure the coating is fully cured. There are no particular limitations on the heating conditions; they are selected appropriately based on the intended use of the coating.

[0167] [Light shielding part] The light-shielding portion of the color filter of the present invention is formed in a pattern on the substrate described below, and can be configured to be the same as that used as a light-shielding portion in a conventional color filter. The shape of the pattern in the light-shielding part is not particularly limited; for example, stripes or matrices can be used. The light-shielding part can also be a thin film of metal such as chromium formed using sputtering or vacuum evaporation. Alternatively, the light-shielding part can be a resin layer containing light-shielding particles such as carbon microparticles, metal oxides, inorganic pigments, or organic pigments in the resin binder. When using a resin layer containing light-shielding particles, methods include patterning using photosensitive photoresist by development, patterning using inkjet ink containing light-shielding particles, and heat transfer of photosensitive photoresist.

[0168] The thickness of the light-shielding portion is set to approximately 0.2 μm to 0.4 μm for metal films and approximately 0.5 μm to 2 μm for films formed to disperse or dissolve black pigment in adhesive resins.

[0169] [Substrate] As a substrate, transparent substrates, silicon substrates, and substrates on which aluminum, silver, silver / copper / palladium alloy thin films are formed can be used. Other color filter layers, resin layers, TFT (Thin Film Transistor) transistors, circuits, etc., can also be formed on such substrates. As for the transparent substrate in the color filter of the present invention, it is not particularly limited as long as it is a substrate that is transparent to visible light, and the transparent substrate used in conventional color filters can be used. Specifically, examples include: non-flexible transparent rigid materials such as quartz glass, alkali-free glass, and synthetic quartz plates; or flexible transparent materials such as transparent resin films, optical resin plates, and flexible glass. The thickness of the transparent substrate is not particularly limited and can be around 100 μm to 1 mm, depending on the application of the color filter according to the present invention. Furthermore, in addition to forming the aforementioned substrate, light-shielding portion and coloring layer, the color filter of the present invention may also form, for example, a protective layer or a transparent electrode layer, and further an alignment film or columnar spacer.

[0170] IV. Display Device The display device of the present invention is characterized by having the color filter of the present invention described above. In the present invention, the configuration of the display device is not particularly limited, and can be appropriately selected from previously known display devices, such as liquid crystal displays or organic light-emitting displays.

[0171] Liquid crystal display device As a liquid crystal display device of the present invention, an example of such a liquid crystal display device may be given, which has the color filter, the opposing substrate, and the liquid crystal layer formed between the color filter and the opposing substrate of the present invention. The liquid crystal display device of the present invention will be described with reference to the reference figures. FIG2 is a schematic diagram showing an example of the liquid crystal display device of the present invention. As illustrated in FIG2, the liquid crystal display device 40 of the present invention includes: a color filter 10, a counter substrate 20 having a TFT array substrate, etc., and a liquid crystal layer 30 formed between the color filter 10 and the counter substrate 20. Furthermore, the liquid crystal display device of the present invention is not limited to the configuration shown in FIG2, and can be configured as a configuration commonly known as a liquid crystal display device using a color filter.

[0172] The driving method for the liquid crystal display device of the present invention is not particularly limited, and a driving method commonly used in devices can be adopted. Examples of such driving methods include: TN (Twisted nematic), IPS (In-Plane Switching), OCB (Optically Compensated Birefringence), and MVA (Multi-Domain Vertical Alignment). In the present invention, any of these methods can be suitably used. Furthermore, as a counter substrate, it can be appropriately selected according to the driving method of the liquid crystal display device according to the present invention. Furthermore, as the liquid crystal constituting the liquid crystal layer, various liquid crystals with different dielectric anisotropy and mixtures thereof can be used according to the driving method of the liquid crystal display device of the present invention.

[0173] As a method for forming the liquid crystal layer, methods commonly used for fabricating liquid crystal cells can be used, such as vacuum injection or liquid crystal droplet application. After forming the liquid crystal layer using the above methods, the liquid crystal cell is slowly cooled to room temperature, thereby enabling the encapsulated liquid crystal to align.

[0174] Organic light-emitting display device As an organic light-emitting display device of the present invention, an example of such an organic light-emitting display device is provided, which has the color filter and organic light-emitting body of the present invention described above. The organic light-emitting display device of the present invention will be described with reference to the accompanying drawings. FIG3 is a schematic diagram showing an example of the organic light-emitting display device of the present invention. As illustrated in FIG3, the organic light-emitting display device 100 of the present invention includes a color filter 10 and an organic light emitter 80. An organic protective layer 50 or an inorganic oxide film 60 may also be provided between the color filter 10 and the organic light emitter 80.

[0175] Examples of methods for stacking the organic light-emitting diode (OLED) 80 include: sequentially forming a transparent anode 71, a hole injection layer 72, a hole transport layer 73, a light-emitting layer 74, an electron injection layer 75, and a cathode 76 on the upper surface of a color filter; or bonding the OLED 80 formed on another substrate to an inorganic oxide film 60. The transparent anode 71, hole injection layer 72, hole transport layer 73, light-emitting layer 74, electron injection layer 75, cathode 76, and other components of the OLED 80 can be appropriately made using known methods. The OLED display device 100 manufactured in the above manner can be applied to both passively driven OLED displays and actively driven OLED displays. Furthermore, the organic light-emitting display device of the present invention is not limited to the configuration shown in FIG3, but can be configured as is commonly known as an organic light-emitting display device using a color filter. Example

[0176] The present invention will now be specifically described with reference to embodiments. The present invention is not limited to these descriptions. The weight-average molecular weight (Mw) of the copolymer before salt formation was determined by GPC (gel permeation chromatography) in the form of a standard polystyrene equivalent, according to the determination method described in the specification of the present invention.

[0177] (Manufacturing Example 1: Preparation of Alkali-Soluble Resin U1) 150 parts by weight of PGMEA were added to the polymerization tank, and the temperature was raised to 100°C under a nitrogen atmosphere. Then, over a period of 1.5 hours, 34 parts by weight of methyl methacrylate (MMA), 35 parts by weight of benzyl methacrylate (BzMA), 1 part by weight of 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole (RUVA-93, trade name, manufactured by Otsuka Chemicals), 18 parts by weight of methacrylic acid (MAA), 3 parts by weight of PERBUTYL O (manufactured by Nippon Oil Co., Ltd.), and 9 parts by weight of chain transfer agent (n-dodecyl mercaptan) were added dropwise. The reaction was then continued at 100°C. Two hours after the addition of the above main chain forming mixture was completed, 0.1 parts by weight of p-methoxyphenol, as a polymerization inhibitor, was added to stop the polymerization. Secondly, while blowing air, 12 parts by mass of glycidyl methacrylate (GMA), an epoxy-containing compound, were added. After heating to 110°C, 0.8 parts by mass of triethylamine were added, and an addition reaction was carried out at 110°C for 15 hours to obtain an alkali-soluble resin U1 solution (weight average molecular weight (Mw) 8000, acid value 75 mgKOH / g, solid content 40% by mass). Furthermore, the above-mentioned method for determining the weight-average molecular weight uses polystyrene as a standard substance and THF (tetrahydrofuran) as a dissolution solution, and determines the weight-average molecular weight using the Shodex GPC System-21H. Also, the method for determining the acid value is based on JIS K 0070.

[0178] (Manufacturing Examples 2-12: Preparation of Alkali-Soluble Resins U2-U12) In Manufacturing Example 1, except that the mass ratio of the monomers used was changed to the amounts recorded in Table 1, alkali-soluble resins U2 to U12 were prepared in the same manner as in Manufacturing Example 1. Furthermore, the adjustment of the weight average molecular weight in manufacturing examples 7-12 was achieved by changing the amount of PERBUTYL O and chain transfer agent (n-dodecyl mercaptan). The weight-average molecular weight and acid value of the obtained alkali-soluble resin are also shown in Table 1.

[0179] (Comparative Manufacturing Example 1: Preparation of Alkali-Soluble Resin P1) In Manufacturing Example 1, except that RUVA-93 was not used and the mass ratio of the other monomers used was changed to the amounts recorded in Table 1, the alkali-soluble resin P1 was prepared in the same manner as in Manufacturing Example 1. The weight-average molecular weight and acid value of the obtained alkali-soluble resin are also shown in Table 1.

[0180] (Comparative manufacturing examples 2-4: Preparation of alkali-soluble resin P2, and resins P3 and P4) In Manufacturing Example 1, except that the mass ratio of the monomers used was changed to the amounts recorded in Table 1, and the amounts of PERBUTYL O and chain transfer agent (n-dodecyl mercaptan) were changed, alkali-soluble resin P2, as well as resins P3 and P4, were prepared in the same manner as in Manufacturing Example 1. The weight-average molecular weight and acid value of the obtained resins are also shown in Table 1.

[0181] [Table 1] Table 1 acid value Weight average molecular weight MMA BzMA BMA RUVA-93 MAA GMA mgKOH / g wt% wt% wt% wt% wt% wt% Manufacturing Example 1 U1 75 8000 34 35 1 18 12 Manufacturing Example 2 U2 75 8000 33 35 2 18 12 Manufacturing Example 3 U3 75 8000 30 35 5 18 12 Manufacturing Example 4 U4 75 8000 27 35 8 18 12 Manufacturing Example 5 U5 75 8000 25 35 10 18 12 Manufacturing Example 6 U6 75 8000 20 35 15 18 12 Manufacturing Example 7 U7 75 4000 30 35 5 18 12 Manufacturing Example 8 U8 75 6000 30 35 5 18 12 Manufacturing Example 9 U9 75 11000 30 35 5 18 12 Manufacturing Example 10 U10 75 15000 30 35 5 18 12 Manufacturing Example 11 U11 75 20000 30 35 5 18 12 Manufacturing Example 12 U12 75 30000 30 35 5 18 12 Comparative Manufacturing Example 1 P1 75 8000 35 35 18 12 Comparative Manufacturing Example 2 P2 75 2000 30 35 5 18 12 Comparative Manufacturing Example 3 P3 0 40000 23.7 76.3 Comparative Manufacturing Example 4 P4 37 1500 6.6 66.2 21.5 5.7 Furthermore, the abbreviations for the monomers used in the table are as follows. MMA: Methyl methacrylate BzMA: Benzyl methacrylate RUVA-93: 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole (trade name, manufactured by Otsuka Chemicals) MAA: Methacrylic acid GMA: Glycidyl methacrylate BMA: n-Butyl methacrylate

[0182] (Synthesis Example 1: Synthesis of Lake Pigment 1) (1) Synthesis of intermediate 1 Referring to the manufacturing methods of intermediate A-2, intermediate B-1, and compounds 1-3 described in Japanese Patent Application Publication No. 2018-3013, intermediate 1 represented by the following chemical formula (a) was obtained (yield 87%). The obtained compound was confirmed as the target compound based on the following analytical results. MS (ESI) (m / z): 677 (+), divalent • Elemental analysis values: Measured values ​​of CHN (81.81%, 7.31%, 5.85%); Theoretical values ​​(81.77%, 7.36%, 5.90%)

[0183] [Chemistry 11] Chemical formula (a)

[0184] (2) Synthesis of Lake Pigment 1 2.59 g (0.76 mmol) of 12-phosphotungstic acid·n hydrate manufactured by Kanto Chemical was dissolved by heating in a mixture of 40 mL methanol and 40 mL water. 1.6 g (1.19 mmol) of the above intermediate 1 was added, and the mixture was stirred for 1 hour. The precipitate was filtered and washed with water. The obtained precipitate was dried under reduced pressure to obtain lake pigment 1 represented by the following chemical formula (b) (yield 95%). The obtained compound was confirmed as the target compound based on the following analytical results. ·31P NMR (d-dmso, ppm) δ-15.15 ·MS (MALDI) (m / z): 1355 (M +), 2879 (MH 2 -) • Elemental analysis values: Measured values ​​of CHN (35.55%, 3.24%, 2.61%); Theoretical values ​​(35.61%, 3.20%, 2.57%) • Fluorescence X-ray analysis: MoW measured ratio (0%, 100%); theoretical value (0%, 100%)

[0185] [Chemistry 12] Chemical formula (b)

[0186] (Synthesis Example 2: Synthesis of Lake Pigment 2) (1) Preparation of K6(P2MoW17O62) 44.0 g of NaWO₄·2H₂O (manufactured by Wako Pure Chemical Industries, Ltd.) and 1.90 g of Na₂MoO₄·2H₂O (manufactured by Kanto Chemical Co., Ltd.) were dissolved in 230 g of purified water. 64.9 g of 85% phosphoric acid was added to this solution using a dropping funnel while stirring. The resulting solution was heated under reflux for 8 hours. The reaction solution was cooled to room temperature, and 1 drop of bromine water was added, followed by the addition of 45 g of potassium chloride while stirring. The mixture was stirred for another hour, after which the precipitate was filtered off. 29.4 g of K₆(P₂MoW₁₇O₆₂) was obtained by drying the resulting solid at 90°C. (2) Synthesis of Lake Pigment 2 5.30 g of Basic Blue 7 (BB7) (manufactured by Tokyo Chemical Co., Ltd.) was dissolved in 350 ml of purified water and stirred at 40°C to prepare a BB7 solution. In addition, 10.0 g of K6 (P2MoW17O62) prepared in (1) above was dissolved in 40 ml of purified water. The K6 (P2MoW17O62) solution was added to the BB7 solution and stirred directly at 40°C for 1 hour. Then, the internal temperature was increased to 80°C and stirred for another hour to perform lake formation. After cooling, the solution was filtered and washed three times with 300 ml of purified water. The obtained solid was dried at 90°C to obtain 10.4 g of lake pigment, which is a blue-black solid with an average primary particle size of 40 nm, used as a lake pigment for triarylmethane dyes and polyacids.

[0187] (Synthesis Example 3: Synthesis of acidic dispersant A1 (a polymer having at least one of the structural units selected from the above general formula (I))) (1) Synthesis of the giant monomer MM-1 80.0 parts by weight of propylene glycol monomethyl ether acetate (PGMEA) were added to a reactor equipped with a condenser, a funnel for adding, a nitrogen inlet, a mechanical stirrer, and a digital thermometer. The mixture was stirred under a nitrogen atmosphere and heated to 90°C. A mixed solution of 50.0 parts by weight of methyl methacrylate, 30.0 parts by weight of n-butyl methacrylate, 20.0 parts by weight of benzyl methacrylate, 4.0 parts by weight of 2-mercaptoethanol, 30 parts by weight of PGMEA, and 1.0 part by weight of α,α'-azobisisobutyronitrile (AIBN) was added dropwise over 1.5 hours, and the reaction was carried out for 3 hours. Next, the nitrogen flow was stopped, and the reaction solution was cooled to 80°C. Then, 8.74 parts by mass of Karenz MOI (manufactured by Showa Denko), 0.125 parts by mass of dibutyltin dilaurate, 0.125 parts by mass of p-methoxyphenol, and 10 parts by mass of PGMEA were added, and the mixture was stirred for 3 hours to obtain a 49.5% by mass solution of the macromonomer MM-1. GPC analysis of the obtained macromonomer MM-1 yielded the following results: weight average molecular weight (Mw) 4010, number average molecular weight (Mn) 1910, and molecular weight distribution (Mw / Mn) 2.10.

[0188] (2) Synthesis of graft copolymer A1 85.0 parts by weight of PGMEA were added to a reactor equipped with a condenser, a funnel for adding, a nitrogen inlet, a mechanical stirrer, and a digital thermometer. The reactor was heated to 90°C while being stirred under a nitrogen flow. A mixed solution of the above-mentioned macromonomer MM-1 solution (33.33 parts by weight of solids), glycidyl methacrylate (GMA), n-dodecyl mercaptan, 25.0 parts by weight of PGMEA, and 0.5 parts by weight of AIBN was added dropwise over 1.5 hours. After heating and stirring for 3 hours, a mixed solution of 0.10 parts by weight of AIBN and 10.0 parts by weight of PGMEA was added dropwise over 10 minutes. The mixture was then matured at the same temperature for 1 hour to obtain a 25.0% by weight solution of graft copolymer A1. The obtained graft copolymer A1 was subjected to GPC analysis, and the results were: weight average molecular weight (Mw) 10570, number average molecular weight (Mn) 4370, and molecular weight distribution (Mw / Mn) 2.42.

[0189] (3) Manufacturing of a polymer (acidic dispersant A1) having at least one of the structural units selected from the above general formula (I). 27.80 parts by weight of PGMEA and 9.27 parts by weight of phenylphosphonic acid (product name "PPA", manufactured by Nissan Chemical) were added to a reactor equipped with a condenser, a funnel for adding, a nitrogen inlet, a mechanical stirrer, and a digital thermometer. The mixture was stirred under a nitrogen flow and heated to 90°C. 100.0 parts by weight of the above-mentioned graft copolymer A1 were added dropwise over 30 minutes, and the mixture was heated and stirred for 2 hours to obtain a polymer (acidic dispersant A1) solution (solid content 25.0% by weight) having at least one structural unit selected from the above general formula (I). The esterification reaction of the obtained acidic dispersant A1 with GMA and PPA was confirmed by acid value determination and 1H-NMR (Nuclear Magnetic Resonance) determination (confirmed until the peak from the epoxy group disappeared). The acid value of the obtained acidic dispersant A1 was 98 mgKOH / g.

[0190] (Synthesis Example 4: Synthesis of acidic dispersant A2 (a block copolymer containing A blocks comprising structural units derived from carboxyl-containing vinyl unsaturated monomers and B blocks comprising structural units derived from (meth)acrylate alkyl esters)) Referring to Example 1 described in International Publication No. 2016 / 132863, a triblock copolymer was synthesized comprising: 20 parts by weight of methyl methacrylate (MMA) and 40 parts by weight of n-butyl methacrylate (BMA); 20 parts by weight of methacrylic acid (MAA) and 20 parts by weight of BMA; and 20 parts by weight of MMA and 40 parts by weight of BMA. The obtained block copolymer had a weight average molecular weight (Mw) of 11,000, a molecular weight distribution (Mw / Mn) of 1.50, and an acid value of 130 mgKOH / g.

[0191] (Synthesis Example 5: Synthesis of a Potential Antioxidant) 0.01 mol of the phenolic compound represented by chemical formula (c), 0.05 mol of dibutyl dicarbonate, and 30 g of pyridine were mixed and stirred at 60°C for 3 hours under a nitrogen atmosphere at room temperature with the addition of 0.025 mol of 4-dimethylaminopyridine. After cooling to room temperature, the reaction solution was injected into 150 g of deionized water, and 200 g of chloroform was added for oil-water separation. The organic layer was dried using anhydrous sodium sulfate, and the solvent was removed by distillation. 100 g of methanol was added to the residue for crystallization. The obtained white powder crystals were dried under reduced pressure at 60°C for 3 hours to obtain the potential antioxidant (AO1). Furthermore, the structure of the obtained potential antioxidant was confirmed using IR (Infrared Radiation) and NMR.

[0192] [Chemistry 13] Chemical formula (c)

[0193] (Comparative Synthesis Example 1: Synthesis of Triarylmethane Dye 1) Triarylmethane dye 1 was synthesized in the same manner as dye A described in Example 1 of Japanese Patent Application Publication No. 2011-133844. First, (toluenesulfonyl)trifluoromethanesulfonylaminoimino acid triethylamine salt was synthesized as described in Example 1 of Japanese Patent Application Publication No. 2011-133844. Next, 5 g of Basic Blue CI 7 (N-[4-[[4-(diethylamino)phenyl][4-(ethylamino)-1-naphthyl]methylene]-2,5-cyclohexadiene-1-ylidene]-N-ethylethane ammonium chloride) (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 30 mL of methanol. While stirring, 3.93 g of (toluenesulfonyl)trifluoromethanesulfonyl imine triethylamine salt was added, and the mixture was stirred at room temperature for 1 hour. The methanol in the solution was concentrated using an evaporator, and 100 mL of water was added to filter out the precipitate, which was then washed with water. The filter cake was dried under reduced pressure to obtain triarylmethane dye 1.

[0194] (Example 1: Preparation of photosensitive coloring resin composition 1) (1) Preparation of pigment dispersion D1 In a 225 mL mayonnaise bottle, add 61 parts by weight of PGMEA, 5 parts by weight of the alkali-soluble resin P1 solution (40% by weight of solids) from Comparative Manufacturing Example 1, and 24 parts by weight of the acidic dispersant A1 solution (25.0% by weight of solids) from Synthetic Example 3, and stir. 110 parts by weight of triarylmethane lake pigment from Synthesis Example 1 and 100 parts by weight of zirconia beads with a particle size of 2.0 mm were added to the mixture. The mixture was pre-crushed by shaking for 1 hour using a paint shaker (manufactured by Asada Iron Works). Then, the mixture was changed to 200 parts by weight of zirconia beads with a particle size of 0.1 mm and dispersed for 4 hours using a paint shaker to obtain pigment dispersion D1.

[0195] (2) Preparation of photosensitive adhesive component B1 By adding 26.4 parts by mass of the alkali-soluble resin U1 solution (solid content 40% by mass) obtained in Manufacturing Example 1, 12.3 parts by mass of the photopolymerizable compound (trade name ARONIX M-403, pentaerythritol penta- and hexaacrylates, manufactured by Dong-A Synthetic Co., Ltd.), 12.3 parts by mass of the photopolymerizable compound (trade name ARONIX M-305, pentaerythritol tri- and tetraacrylates, manufactured by Dong-A Synthetic Co., Ltd.), 2.4 parts by mass of photoinitiator 1: Irgacure907 (manufactured by BASF, α-aminoacetophenone-based photoinitiator), and 2.4 parts by mass of photoinitiator 2: OXE-02 (manufactured by BASF, oxime ester-based photoinitiator with a carbazole skeleton), 0.8 parts by mass of the potential antioxidant (AO1) from Synthesis Example 5, and 45.4 parts by mass of PGMEA, the photosensitive adhesive component B1 is obtained. (3) Preparation of photosensitive coloring resin composition 1 The photosensitive coloring resin composition of Example 1 was prepared by mixing 3.33 parts by weight of the pigment dispersion D1 obtained above, 35.0 parts by weight of the photosensitive adhesive component B1, 0.2 parts by weight of the fluorinated surfactant (trade name MEGAFAC F559, manufactured by DIC Corporation), 2 parts by weight of the silane coupling agent (trade name KBM503, manufactured by Shin-Etsu Silicones), and 61.67 parts by weight of PGMEA.

[0196] (Examples 2-18, 20-22: Manufacturing of photosensitive coloring resin compositions 2-18, 20-22) In the photosensitive adhesive component B1 of Example 1, as an alkali-soluble resin, as shown in Table 2, at least one of the alkali-soluble resin solutions U2 to U12 was added, and alkali-soluble resin solution P1 was added instead of alkali-soluble resin solution U1, depending on the situation. Furthermore, the type of antioxidant, the type of polymerizable compound, and the addition of thiol were changed as appropriate to prepare photosensitive adhesive components B2 to B18 and B20 to B22 for use. Otherwise, photosensitive coloring resin compositions 2 to 18 and 20 to 22 were obtained in the same manner as photosensitive coloring resin composition 1 of Example 1.

[0197] (Example 19: Preparation of photosensitive coloring resin composition 19) (1) Preparation of pigment dispersion D2 In a 225 mL mayonnaise bottle, add 61 parts by weight of PGMEA, 5 parts by weight of the alkali-soluble resin P1 solution (40% by weight of solids) from Comparative Manufacturing Example 1, and 24 parts by weight of the acidic dispersant A1 solution (25.0% by weight of solids) from Synthetic Example 3, and stir. 10 parts by weight of triarylmethane lake pigment 2 from Synthetic Example 2 and 100 parts by weight of zirconia beads with a particle size of 2.0 mm were added to the mixture. The mixture was pre-crushed by shaking for 1 hour using a paint shaker (manufactured by Asada Iron Works). Then, the mixture was changed to 200 parts by weight of zirconia beads with a particle size of 0.1 mm and dispersed for 4 hours using a paint shaker to obtain pigment dispersion D2. (2) Preparation of photosensitive coloring resin composition 19 In Example 6, except that pigment dispersion D1 was replaced with pigment dispersion D2, photosensitive coloring resin composition 19 was obtained in the same manner as photosensitive coloring resin composition 6 in Example 6.

[0198] (Comparative Examples 1-2, 6-7: Comparative manufacture of photosensitive coloring resin compositions 1-2, 6-7) In the photosensitive adhesive component B1 of Example 1, the alkali-soluble resin was changed to an alkali-soluble resin P1 solution instead of an alkali-soluble resin U1 solution. In Comparative Examples 2 and 6-7, as shown in Table 2, photosensitive adhesive components CB1-CB2 and CB6-CB7 were prepared using alkali-soluble resin P2 solution, resin P3 solution, or resin P4 solution. Otherwise, comparative photosensitive coloring resin compositions 1-2 and 6-7 were obtained in the same manner as photosensitive coloring resin composition 1 of Example 1.

[0199] (Comparative Examples 3-5: Comparative manufacturing of photosensitive coloring resin compositions 3-5) In the photosensitive adhesive component B1 of Example 1, the alkali-soluble resin was changed to an alkali-soluble resin P1 solution instead of an alkali-soluble resin U1 solution. As shown in Table 2, photosensitive adhesive components CB3 to CB5 were prepared using ultraviolet absorbers and used. Otherwise, comparative photosensitive coloring resin compositions 3 to 5 were obtained in the same manner as photosensitive coloring resin composition 1 of Example 1.

[0200] (Comparative Example 8: Manufacturing of Comparative Photosensitive Coloring Resin Composition 8) (1) Preparation of pigment dispersion CD1 In a 225 mL mayonnaise bottle, add 57.5 parts by weight of PGMEA, 7.5 parts by weight of the alkali-soluble resin P1 solution (solid content 40% by weight) of Comparative Manufacturing Example 1, and 25 parts by weight of the PGMEA solution (solid content 20.0% by weight) of the acidic dispersant A2 of Synthetic Example 4, and stir. Add 68.8 parts by weight of PB15, 1.2 parts by weight of PV23, and 100 parts by weight of zirconia beads with a particle size of 2.0 mm. Use a paint shaker (manufactured by Asada Iron Works) to shake for 1 hour as pre-crushing. Then change to 200 parts by weight of zirconia beads with a particle size of 0.1 mm and use a paint shaker to disperse for 4 hours as formal crushing to obtain pigment dispersion CD1. (2) Comparison of the preparation of photosensitive coloring resin composition 8 In the photosensitive adhesive component B1 of Example 1, the alkali-soluble resin P1 solution was used instead of the alkali-soluble resin U1 solution, and the content of each component was changed as shown in Table 2. Otherwise, the photosensitive adhesive component CB8 was prepared in the same manner as the photosensitive adhesive component B1 of Example 1. A comparative photosensitive coloring resin composition 8 was obtained by mixing 3.33 parts by weight of colorant dispersion CD1, 35.0 parts by weight of photosensitive adhesive component CB8, 0.2 parts by weight of fluorinated surfactant (trade name MEGAFAC F559, manufactured by DIC Corporation), 2 parts by weight of silane coupling agent (trade name KBM503, manufactured by Shin-Etsu Silicones), and 61.67 parts by weight of PGMEA.

[0201] [Evaluation Method] After baking, the film thickness was 2.2 μm. The photosensitive coloring resin compositions of the examples and comparative examples were coated onto a 0.7 mm thick glass substrate (manufactured by NH TECHNO GLASS Co., Ltd., "NA35") using a spin coater. The substrates were then heated and dried at 80°C for 3 minutes. A 40 μm line photomask was then formed, and the substrate was irradiated with 60 mJ / cm² ultraviolet light using an ultra-high pressure mercury lamp. Subsequently, a 0.05% (w / w) potassium hydroxide aqueous solution was used as an alkaline developer for 60 seconds of spray development. The substrates were then baked in a clean oven at 230°C for 30 minutes to create a patterned substrate with a 40 μm line pattern of coloring layer formed on the glass substrate.

[0202] <Suppressing Linewidth Increase in Shading Layers> The width of the fine line pattern of the colored layer at five locations in contact with the 40 μm opening of the chromium photomask used during exposure was measured using an optical microscope. The line width offset was evaluated by the difference between the average line width and the line width that became the target. (Increased linewidth suppresses evaluation criteria) AA: The difference between the linewidth and the target linewidth is within 5.0 μm. A: The difference between the linewidth relative to the target linewidth and the linewidth within 5.0 μm is greater than 5.0 μm but less than 5.5 μm. B: The difference between the linewidth relative to the target linewidth and the linewidth within 7.0 μm exceeds 5.5 μm. C: The difference between the linewidth and the target linewidth exceeds 7.0 μm. If the evaluation result is A, the suppression of linewidth increase is good; if the evaluation result is AA, the suppression of linewidth increase is excellent.

[0203] <Evaluation of Residual Film Rate> After baking, the film thickness was 2.2 μm. The photosensitive coloring resin compositions of the examples and comparative examples were then coated onto a 0.7 mm thick glass substrate (manufactured by NH TECHNO GLASS Co., Ltd., "NA35") using a spin coater. The substrates were then heated and dried at 80°C for 3 minutes. Subsequently, the substrates were irradiated with 60 mJ / cm² ultraviolet light using an ultra-high pressure mercury lamp without a photomask. The film thickness T1 of the photoresist coating was then measured using a film thickness gauge. Next, the substrates were developed using a 0.05% (w / w) potassium hydroxide aqueous solution as an alkaline developer for 60 seconds, and the film thickness T2 after development was measured. It is calculated in the form of residual film rate = T2 / T1 [%). (Evaluation Criteria for Residual Film Rate After Development) AA: The residual film rate after development is over 98%. A: The residual film rate after development is above 97% but below 98%. B: The residual film rate after development is above 94% but below 97%. C: The residual film rate after development did not reach 94%.

[0204] <Brightness and Heat Resistance Evaluation> After baking, the color was set to y=0.088. The photosensitive coloring resin compositions of the examples and comparative examples were coated onto a 0.7 mm thick glass substrate (manufactured by NH TECHNO GLASS Co., Ltd., "NA35") using a spin coater. Subsequently, the substrate was heated and dried on a hot plate at 80°C for 3 minutes, then irradiated with 60 mJ / cm² ultraviolet light using an ultra-high pressure mercury lamp without a light shield, and finally baked in a clean oven at 230°C for 30 minutes to obtain a hardened film (coloring film). The brightness (Y), L, a, and b (L 0, a 0, b 0) of the obtained colored substrate were measured using an Olympus OSP-SP200 microspectrophotometer, and evaluated according to the following evaluation criteria. Next, the process of baking the substrate with the hardened film formed above in a clean oven at 230°C for 30 minutes and then cooling it for 30 minutes was repeated three times, and the L, a, and b (L1, a1, b1) of the obtained colored substrate were measured. Based on the measured values, the color difference (ΔEab) before and after the treatment was calculated according to the following formula. Color difference (ΔEab) = {(L₁ - L₀)² + (a₁ - a₀)² + (b₁ - b₀)²}¹ / ²

[0205] (Brightness Evaluation Criteria) AA: Luminance (Y) is 10.6 or higher. A: Luminance (Y) is 10.0 or higher but less than 10.6. B: Luminance (Y) is 9.5 or higher but less than 10.0. C: Brightness (Y) did not reach 9.5

[0206] (Heat resistance evaluation criteria) AA: ΔEab did not reach 1.5 A: ΔEab is 1.5 or higher but less than 2.0. B: ΔEab is 2.0 or higher but less than 3.0. C: ΔEab is 3.0 or higher.

[0207] <UV Resistance Evaluation> After baking, the color was set to y=0.088. The photosensitive coloring resin compositions of the examples and comparative examples were coated onto a 0.7 mm thick glass substrate (manufactured by NH TECHNO GLASS Co., Ltd., "NA35") using a spin coater. Subsequently, the substrate was heated and dried on a hot plate at 80°C for 3 minutes, then irradiated with 60 mJ / cm² ultraviolet light using an ultra-high pressure mercury lamp without a photomask, and finally baked in a clean oven at 230°C for 30 minutes to obtain a hardened film (coloring film). The brightness (Y), L, a, and b (L 0, a 0, b 0) of the obtained colored substrate were measured using an Olympus OSP-SP200 microspectrophotometer, and evaluated according to the following evaluation criteria. Next, the substrate with the aforementioned hardened film was irradiated with 20 mJ / cm² ultraviolet light for 15 minutes using a low-pressure mercury lamp, and the L, a, and b (L², a², b²) values ​​of the resulting colored substrate were measured. Based on the measured values, the color difference (ΔEab) before and after treatment was calculated using the following formula. Color difference (ΔEab) = {(L² - L₀)² + (a² - a₀)² + (b² - b₀)²}¹ / ² (UV resistance evaluation criteria) AA: ΔEab did not reach 1.5 A: ΔEab is 1.5 or higher but less than 2.0. B: ΔEab is 2.0 or higher but less than 3.0. C: ΔEab is 3.0 or higher.

[0208] <Evaluation of Developer Residue> After baking, the film thickness was 2.2 μm. The photosensitive coloring resin compositions of the examples and comparative examples were then coated onto a 0.7 mm thick glass substrate (manufactured by NH TECHNO GLASS Co., Ltd., "NA35") using a spin coater. The substrates were then heated and dried at 80°C for 3 minutes. Subsequently, a photomask with a 40 μm line was formed, and the substrate was irradiated with 60 mJ / cm² ultraviolet light using an ultra-high pressure mercury lamp. Following this, a 0.05% (w / w) potassium hydroxide aqueous solution was used as an alkaline developer for 60 seconds of spray development. The pattern of the colored layer in contact with the 80 μm opening of the chromium photomask used during exposure was then observed using an optical microscope, and the presence of residue was visually evaluated. (Residue Evaluation Criteria) AA: No developer residue A: Some contain tiny residues. B: Tiny residues exist across the entire surface. C: Residue exists on the entire surface.

[0209] [Table 2] Table 2. Photosensitive adhesives solvent Alkali-soluble resins resin Photopolymers Photoinitiator Thiols antioxidants UV absorber PGMEA U1 U2 U3 U4 U5 U6 U7 U8 U9 U10 U11 U12 P1 P2 P3 P4 M1 M2 M3 M4 I1 I2 AO1 AO2 U1 U2 U3 B1 45.4 26.4 12.3 12.3 2.4 2.4 0.8 B2 45.4 13.2 13.2 12.3 12.3 2.4 2.4 0.8 B3 45.4 26.4 12.3 12.3 2.4 2.4 0.8 B4 45.4 26.4 12.3 12.3 2.4 2.4 0.4 0.4 B5 45.4 26.4 12.3 12.3 2.4 2.4 0.4 B6 45.4 10.5 15.9 12.3 12.3 2.4 2.4 0.8 B7 45.4 14 12.4 12.3 12.3 2.4 2.4 0.8 B8 45.4 6.5 19.9 12.3 12.3 2.4 2.4 0.8 B9 45.4 8.7 17.7 12.3 12.3 2.4 2.4 0.8 B10 45.4 5.2 21.2 12.3 12.3 2.4 2.4 0.8 B11 45.4 7 19.4 12.3 12.3 2.4 2.4 0.8 B12 45.4 3.5 22.9 12.3 12.3 2.4 2.4 0.8 B13 45.4 10.5 15.9 12.3 12.3 2.4 2.4 0.8 B14 45.4 10.5 15.9 12.3 12.3 2.4 2.4 0.8 B15 45.4 10.5 15.9 12.3 12.3 2.4 2.4 0.8 B16 45.4 10.5 15.9 12.3 12.3 2.4 2.4 0.8 B17 45.4 10.5 15.9 12.3 12.3 2.4 2.4 0.8 B18 45.4 10.5 15.9 12.3 12.3 2.4 2.4 0.8 B19 45.4 10.5 15.9 12.3 12.3 2.4 2.4 0.8 B20 45.4 10.5 15.9 12.3 12.3 2.4 2.4 0.8 B21 45.4 10.5 15.9 12.3 12.3 2.4 2.4 0.8 B22 46.6 10.5 15.9 12.3 12.3 2.4 2.4 0.8 0.8 CB1 45.4 26.4 12.3 12.3 2.4 2.4 0.8 CB2 45.4 15.9 10.5 12.3 12.3 2.4 2.4 0.8 CB3 46.2 26.4 12.3 12.3 2.4 2.4 0.8 0.525 CB4 46.2 26.4 12.3 12.3 2.4 2.4 0.8 0.525 CB5 46.2 26.4 12.3 12.3 2.4 2.4 0.8 0.525 CB6 45.4 23.4 3 12.3 12.3 2.4 2.4 0.8 CB7 45.4 21.4 5 12.3 12.3 2.4 2.4 0.8 CB8 46.4 24.6 11.5 11.5 3.6 3.6 0.8

[0210] [Table 3] Table 3. (A) Dispersion Photosensitive adhesives surfactants Silane coupling agent solvent Line width Residual film rate brightness Heat resistance (ΔEab) UV resistance (ΔEab) Developing residue D1 D2 CD1 type Quality F559 KBM503 PGMEA determination determination determination determination determination determination Example 1 3.33 B1 35.0 0.2 2 61.67 A AA AA AA A AA Example 2 3.33 B2 35.0 0.2 2 61.67 A AA AA AA A AA Example 3 3.33 B3 35.0 0.2 2 61.67 AA AA AA AA AA AA Example 4 3.33 B4 35.0 0.2 2 61.67 AA AA AA AA AA AA Actual example 5 3.33 B5 35.0 0.2 2 61.67 AA AA AA AA AA AA Actual example 6 3.33 B6 35.0 0.2 2 61.67 AA AA AA AA AA AA Actual example 7 3.33 B7 35.0 0.2 2 61.67 AA AA AA AA AA AA Actual example 8 3.33 B8 35.0 0.2 2 61.67 AA AA AA AA AA AA Actual example 9 3.33 B9 35.0 0.2 2 61.67 AA AA AA AA AA AA Actual example 10 3.33 B10 35.0 0.2 2 61.67 AA AA AA AA AA AA Actual example 11 3.33 B11 35.0 0.2 2 61.67 AA AA AA AA AA AA Actual example 12 3.33 B12 35.0 0.2 2 61.67 AA A AA AA AA A Actual example 13 3.33 B13 35.0 0.2 2 61.67 AA AA AA AA AA AA Actual example 14 3.33 B14 35.0 0.2 2 61.67 AA AA AA AA AA AA Actual example 15 3.33 B15 35.0 0.2 2 61.67 AA AA AA AA AA AA Actual example 16 3.33 B16 35.0 0.2 2 61.67 AA AA AA AA AA AA Actual example 17 3.33 B17 35.0 0.2 2 61.67 AA AA AA AA AA AA Actual example 18 3.33 B18 35.0 0.2 2 61.67 AA AA AA AA AA A Actual example 19 3.33 B19 35.0 0.2 2 61.67 AA AA AA A AA AA Actual example 20 3.33 B20 35.0 0.2 2 61.67 AA AA AA AA AA AA Actual example 21 3.33 B21 35.0 0.2 2 61.67 AA AA AA AA AA AA Actual example 22 3.33 B22 35.0 0.2 2 61.67 AA AA AA AA AA AA Comparative Example 1 3.33 CB1 35.0 0.2 2 61.67 B AA AA AA C AA Comparative Example 2 3.33 ​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​ Comparative Example 5 3.33 CB5 35.0 0.2 2 61.67 AA AA AA AA C AA Comparative Example 6 3.33 CB6 35.0 0.2 2 61.67 C AA AA AA AA C Comparative Example 7 3.33 CB7 35.0 0.2 2 61.67 AA C AA AA C B Comparative Example 8 3.33 CB8 35.0 0.2 2 61.67 AA AA C AA AA AA

[0211] The abbreviations in the table are as follows. Resins U1~U12: Alkali-soluble resins U1~U12 from Examples 1~12 Resins P1~P2: Comparative alkali-soluble resins P1~P2 from manufacturing examples 1~2 Resins P3~P4: Comparative manufacturing examples 3~4 use resins P3~P4 M1: Photopolymerizable compound, ARONIX M-403, dipentaerythritol penta- and hexaacrylates, manufactured by Dong-A Synthetic Co., Ltd. M2: Photopolymerizable compound, ARONIX M-305, pentaerythritol tri and tetraacrylate, manufactured by Dong-A Synthetic Co., Ltd. M3: Photopolymerizable compound, ARONIX M-460, diglyceride ethylene oxide modified acrylate, manufactured by Dong-A Synthetic Co., Ltd. M4: Photopolymerizable compound, Kayarad DPEA-12, ethylene oxide modified (12) dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd. Photoinitiator 1 (I1): Irgacure 907, manufactured by BASF, α-aminoacetophenone-based photoinitiator Photoinitiator 2 (I2): OXE-02, manufactured by BASF, is an oxime ester photoinitiator with a carbazole backbone. Thiols: Karenz MT PE1, manufactured by Showa Denko Antioxidant (AO1): Potential antioxidant from Synthetic Example 5 Antioxidant (AO2): IRGANOX 1010, manufactured by BASF UV absorber (U1): Tinuvin 928, manufactured by BASF UV absorber (U2): Tinuvin 405, manufactured by BASF UV absorber (U3): Tinuvin 479, manufactured by BASF

[0212] [Results Summary] The photosensitive coloring resin compositions of Examples 1-22, which combine alkali-soluble resins (U) containing structural units with a benzotriazole backbone and a weight average molecular weight of 3000 or more in lake pigments of triarylmethane dyes, show that they can improve brightness, form a coloring layer with a finer linewidth that suppresses film thickness changes and development residues before and after development, and have excellent UV resistance. In contrast, the photosensitive coloring resin composition of Comparative Example 1, which does not contain UV absorbers, shows that even though it contains antioxidants in the same way as the examples, the linewidth offset is larger, the linewidth is thicker, and it is impossible to form a colored layer with the required finer linewidth, resulting in poorer UV resistance. Regarding Comparative Example 2, which uses alkali-soluble resin P2 containing structural units with a benzotriazole backbone but with a weight average molecular weight of 2000, the molecular weight of alkali-soluble resin P2 is relatively small. Alkali-soluble resin P2 volatilizes during the high-temperature heating step at 230°C, which cannot improve the UV resistance of the final colored layer, resulting in poor UV resistance. Comparative Examples 3-5, which use ultraviolet absorbers as low molecular weight compounds, show that the ultraviolet absorbers volatilize during the high-temperature heating step at 230°C, failing to improve the UV resistance of the final colored layer, resulting in poor UV resistance. Furthermore, regarding Comparative Example 6, which uses resin P3 containing structural units with a benzotriazole backbone but with an acid value of 0 mgKOH / g and a high molecular weight, development residue remained near the pattern, resulting in a seemingly larger linewidth offset. Regarding Comparative Example 7, which uses resin P4 containing structural units with a benzotriazole backbone but with a weight-average molecular weight of 1500, the molecular weight of resin P4 is relatively small. Resin P4 volatilizes during the high-temperature heating step at 230°C, failing to improve the UV resistance of the final colored layer, resulting in poor UV resistance. Furthermore, in Comparative Example 7, a decrease in the thickness of the residual film was observed after development, and development residue was generated. On the other hand, regarding the photosensitive coloring resin composition of Comparative Example 8, which uses pigments instead of lake pigments with triarylmethane dyes, in order to achieve the same linewidth offset as the examples using lake pigments with triarylmethane dyes, a large amount of photoinitiation dose must be used. In this case, the residual film rate after development will not be a problem, but the display brightness will be lower.

[0213] 1:Substrate 2:Light shielding part 3: Coloring layer 5: Micropores 10: Color Filter 20: Opposing substrate 30: Liquid Crystal Layer 40: Liquid crystal display device 50: Organic protective layer 60: Inorganic oxide film 71: Transparent Anode 72: Hole Injection Layer 73: Hole Transport Layer 74: Emissive Layer 75: Electron Injection Layer 76: Cathode 80: Organic light-emitting body 100: Organic light-emitting display device

Claims

1. A photosensitive coloring resin composition comprising a colorant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a solvent, wherein the colorant comprises a lake colorant of a triarylmethane dye, the alkali-soluble resin comprises an alkali-soluble resin (U), the alkali-soluble resin (U) comprising structural units having a benzotriazole backbone, and having a weight average molecular weight of 3000 or more.

2. The photosensitive coloring resin composition of claim 1, further comprising a dispersant.

3. The photosensitive coloring resin composition of claim 1 or 2, wherein the alkali-soluble resin (U) comprises, relative to all the structural units of the alkali-soluble resin (U), the aforementioned structural units having a benzotriazole skeleton being 1% by mass or more and 10% by mass or less.

4. The photosensitive coloring resin composition of claim 1 or 2, further comprising at least one of an antioxidant and a potential antioxidant.

5. The photosensitive coloring resin composition of claim 1 or 2, wherein the lake pigment of the above-mentioned triarylmethane dye contains a pigment represented by the following general formula (1), [Chemical 1] General formula (1) (In general formula (1), A is an a-valent organic group that does not have a π bond to a carbon atom directly bonded to N. The organic group represents an aliphatic hydrocarbon group with a saturated aliphatic hydrocarbon group at least at the end directly bonded to N, or an aromatic group with such aliphatic hydrocarbon group. The carbon chain may contain heteroatoms; Bc- represents a c-valent polyacid anion; Ri to Rv each independently represent a hydrogen atom, an alkyl group that may have a substituent, or an aryl group that may have a substituent. Ri and Riii, and Riv and Rv may be bonded to form a ring structure; Rvi and Rvii each independently represent an alkyl group that may have a substituent, an alkoxy group that may have a substituent, a halogen atom, or a cyano group; Ar1 ​​represents a divalent aromatic group that may have a substituent. There may be multiple Ri to Rvii and Ar1, which may be the same or different; a and c represent integers of 2 or more, b and d represent integers of 1 or more; f and g represent integers of 0 or more and 4 or less. There may be multiple f and g, which may be the same or different.) 6. A cured product, which is a cured product of the photosensitive coloring resin composition of any one of claims 1 to 5.

7. A color filter comprising at least a substrate and a coloring layer disposed on the substrate, wherein at least one of the coloring layers is a cured form of the photosensitive coloring resin composition as claimed in claim 6.

8. A display device having a color filter as claimed in claim 7.

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