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

Abstract

A photosensitive coloring resin composition comprising a colorant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, an ultraviolet absorber, and a solvent, wherein the colorant comprises a lake colorant of a triarylmethane dye.

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 liquid crystal displays (LCDs) has increased. The penetration rate of mobile displays (mobile phones, smartphones, tablet PCs) has also increased, leading to a continuously expanding LCD market. Organic light-emitting diode (OLED) displays, which offer higher visibility due to their self-emissive nature, are also attracting attention as next-generation image display devices. These LCDs or OLEDs use color filters. For example, the formation of a color image in an LCD involves directly coloring the light from a color filter into the colors of each pixel that constitutes the color filter, and then combining these colored lights to form a color image. As the light source, in addition to the previously used cold cathode fluorescent lamp (CCFL), there are cases where white-emitting organic light-emitting elements or white-emitting inorganic light-emitting elements are used. In OLEDs, color filters are used for color adjustment, etc.

[0003] Here, a color filter typically has: a substrate; a color layer formed on the substrate, 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 color material dispersion solution in which color materials are dispersed by a dispersant or the like, is coated onto a glass substrate and dried. The substrate is then exposed to light using a photomask and developed to form a colored pattern. Heating is then applied to fix the pattern, thus forming the colored layer. These steps are repeated for each color to form a color filter.

[0004] In recent years, there has been an increasing demand for higher brightness in color filters, and color filters using pigments are no longer able to meet these demands. Therefore, in recent years, research has been conducted on using dyes with higher transmittance than pigments, or lake pigments made by using precipitants to make dyes insoluble, as pigments for color filters. However, compared with the pigments currently used as color materials for color filters, dyes or lake color materials have the following problems: poor heat resistance, and the color layer is prone to fading when heated at high temperatures during the color filter manufacturing process.

[0005] In contrast, Patent Document 1 discloses a coloring resin composition for color filters that uses lake pigments and suppresses fading of the colored layer caused by high-temperature heating in the color filter manufacturing process, thereby forming a high-brightness colored layer. The coloring resin composition for color filters contains lake pigments, dispersants, hindered phenolic antioxidants, binder components, and solvents. The dispersant is a specific polymer formed by at least a portion of the nitrogen site forming 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 containing (A) a dye, (B) a solvent, and (C) a binder resin, characterized by further containing (D) an antioxidant and (E) an ultraviolet absorber. The object of Patent Document 2 is to provide a method 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) containing a phosphonium oxide organic compound or an oxime ester organic compound, and an ultraviolet absorber (E) selected from the group consisting of benzotriazole organic compounds, triterpenoid organic compounds, and benzophenone organic compounds, wherein the resin (B) comprises a photosensitive resin (B-1), which is obtained by copolymerizing (b1), (b2) and (b3) to obtain a copolymer (b6), reacting the obtained copolymer (b6) with an unsaturated monobasic acid (b4) to obtain a copolymer (b7), and further reacting the obtained copolymer (b7) with a polybasic anhydride (b5) to obtain: (b1): a compound having an alicyclic skeleton and an ethylene unsaturated bond in one molecule; (b2): a compound having an epoxy group and an ethylene unsaturated bond in one molecule; (b3): ​​Compounds containing ethylene-like unsaturated bonds other than (a1) and (a2). Patent Document 3 addresses the issue of obtaining a photosensitive coloring composition with high resolution capable of handling high image quality and low power consumption, particularly a photosensitive coloring composition exhibiting excellent adhesion and high resolution even in thick films such as those using a COA (Color Filter on Array) method, without pattern peeling. Previous Art Documents Patent Documents

[0007] 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 Summary of the Invention

[0008] [The problem the invention aims to solve]

[0009] With the increasing sophistication of displays, such as 4K / 8K, pixel sizes are decreasing, leading to a reduction in the aperture ratio (aperture ratio) of pixels. This necessitates higher brightness resists and photosensitive coloring resin compositions capable of forming patterns with finer linewidths. However, in cases where dyes are dissolved and used, as in Patent Document 2, the increase in pixel brightness is insufficient, especially given the poor heat resistance. Similarly, in techniques using pigments, as in Patent Document 3, the increase in pixel brightness is also insufficient. Triarylmethane-based lake pigments are an example of effective color materials for increasing pixel brightness. However, compared to previously used pigments (such as CI Pigment Blue 15:6 and CI Pigment Violet 23), triarylmethane-based lake pigments have higher transmittance in the UV wavelength region. Therefore, if the photoinitiator is formulated in the same way as before, the pattern linewidth tends to become coarser. If, in order to make the pattern linewidth meet the specified value, the photoinitiator dosage is reduced, or an antioxidant is added as in Patent Document 1, or the amount of antioxidant added is increased, then the photocurability of the patterned area is insufficient, the film thickness variation from before to after development increases, the residual film rate decreases, and it is difficult to simultaneously achieve a finer linewidth design and a higher residual film rate. Although Patent Document 1 describes a lake material containing triarylmethane dyes, it does not address the issue of simultaneously achieving a finer linewidth design and a higher residual film rate. 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, the curing property of the photocurable components is easily suppressed. If the photoinitiator is formulated in the same way as the pigment, the photocurability is insufficient, the linewidth easily becomes finer than designed, and the residual film rate easily decreases. Therefore, in photosensitive coloring resin compositions containing dyes, in order to achieve the desired finer linewidth, it is necessary to increase the amount of photoinitiator or use a photoinitiator with higher sensitivity, thus naturally increasing the residual film yield. Therefore, in photosensitive coloring resin compositions containing dyes, there is inherently no issue of simultaneously achieving a finer linewidth design and a higher residual film yield. Furthermore, Patent Document 3 uses pigments, therefore, there is inherently no issue of simultaneously achieving a finer linewidth design and a higher residual film yield. As mentioned above, when using lake pigments based on triarylmethane dyes, unlike when using pigments or dyes, there is an issue of simultaneously achieving a finer linewidth design and a higher residual film yield.

[0010] 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 form a colored layer that improves brightness and suppresses film thickness changes before and after development by means of a finer linewidth. Furthermore, the present invention aims to provide a color filter and display device formed using the photosensitive coloring resin composition. [Technical means to solve the problem]

[0011] The photosensitive coloring resin composition of the present invention contains a colorant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, an ultraviolet absorber, and a solvent. The above-mentioned color materials contain lake color materials containing triarylmethane dyes.

[0012] The color filter of the present invention comprises at least a substrate and a color layer disposed on the substrate, wherein at least one of the color layers is a cured form of the photosensitive coloring resin composition of the present invention.

[0013] The display device of the present invention has the color filter of the present invention described above. [Effects of the Invention]

[0014] According to the present invention, a photosensitive coloring resin composition is provided that contains a lake pigment containing a triarylmethane dye and is capable of forming a colored layer that improves brightness and suppresses film thickness changes before and after development by means of a finer linewidth. Furthermore, according to the present invention, a color filter and a display device formed using the photosensitive coloring resin composition are provided. Simple Explanation of the Diagram

[0015] Figure 1 is a schematic diagram showing an example of a color filter according to the present invention. Figure 2 is a schematic diagram showing an example of a liquid crystal display device according to the present invention. Figure 3 is a schematic diagram showing an example of an organic light-emitting display device according to the present invention. Implementation

[0016] 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 the present invention, light includes electromagnetic waves of wavelengths in the visible and non-visible light regions, and further includes radiation, such as microwaves and electron beams. Specifically, it refers to electromagnetic waves with wavelengths of 5 μm or less, and electron beams. In this invention, (meth)acrylic acid group represents either acrylonitrile or methacrylic acid group, (meth)acrylic acid group represents either acrylic acid group or methacrylic acid group, and (meth)acrylate group represents either acrylate or methacrylate. Furthermore, in this specification, the "~" symbol indicating a numerical range is used to mean that the values ​​before and after it are the lower and upper limits.

[0017] 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, an ultraviolet absorber, and a solvent. The above-mentioned color materials contain lake color materials containing triarylmethane dyes.

[0018] The photosensitive coloring resin composition of the present invention contains a colorant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, an ultraviolet absorber, and a solvent. The colorant is a lake colorant of a triarylmethane-based dye, thus enabling the formation of a colored layer that enhances brightness and suppresses film thickness variations before and after development through a finer linewidth. The exact mechanism by which this effect is achieved is not yet clear, but is presumed to be as described below.

[0019] As mentioned above, pigments have low ultraviolet transmittance, therefore, in photosensitive coloring resin compositions containing pigments, the photocurable component is relatively difficult to cure. Furthermore, dyes easily inhibit the curing of photocurable components, thus, in photosensitive coloring resin compositions containing dyes, the photocurable component is also relatively difficult to cure. In contrast, lake pigments containing triarylmethane dyes have high ultraviolet transmittance and do not exhibit inhibition of photocurable components. Therefore, after photocuring, they are more insoluble in the developer than pigments or dyes, resulting in thicker pattern linewidths. In photosensitive coloring resin compositions containing lake pigments containing triarylmethane dyes, to achieve a specified finer pattern linewidth, it is necessary to effectively suppress the photocuring reaction. As a colorant, lake colorants using triarylmethane dyes with high transmittance are considered to reduce the photoinitiator dose to meet the specified pattern linewidth. This reduces the generation of free radicals in the photoreaction regardless of the film thickness direction, resulting in insufficient photocurability of the patterned area, increased film thickness variation before and after development, and decreased residual film yield. Furthermore, lake colorants using triarylmethane dyes are considered to add or increase the amount of antioxidants to meet the specified pattern linewidth. This deactivates the free radicals generated by the photoinitiator's photoreaction regardless of the film thickness direction, resulting in insufficient photocurability of the patterned area, increased film thickness variation before and after development, and decreased residual film yield. In contrast, in this invention, an ultraviolet absorber is incorporated into the lake pigment of a triarylmethane-based dye. It is believed that the ultraviolet absorber does not attenuate ultraviolet light on the film surface, thus preventing a decrease in the thickness of the residual film after development. Instead, it attenuates ultraviolet light as it reaches deeper into the film, reducing the generation of free radicals from the initiator. Thus, it functions according to the depth of the film, thereby suppressing the reduction in film thickness after development and decreasing the linewidth. Furthermore, since the colorant contains a lake colorant based on triarylmethane dyes, the color layer of the cured product of the photosensitive coloring resin composition of the present invention has high transmittance, and color changes caused by manufacturing steps such as ultraviolet irradiation or post-baking are suppressed. Therefore, the photosensitive coloring resin composition of the present invention can provide the brightness of the final obtained color layer.

[0020] The photosensitive coloring resin composition of the present invention contains at least a colorant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, an ultraviolet absorber, and a solvent. Without impairing the effects of the present invention, it may further contain other components. For example, to improve the dispersibility of the colorant, the photosensitive coloring resin composition of the present invention may further contain a dispersant. Hereinafter, each component of the photosensitive coloring resin composition of this invention will be described in detail, starting with the ultraviolet absorber.

[0021] [UV absorber] The ultraviolet absorber in this invention refers to a compound that has a maximum absorption wavelength below 400 nm and no absorption under visible light with wavelengths exceeding 420 nm. The ultraviolet absorber used in this invention may be a compound that does not have an absorption wavelength under visible light with wavelengths exceeding 400 nm.

[0022] The structure of the ultraviolet absorber used in this invention is not particularly limited. Examples of ultraviolet absorbers include: benzotriazole-based ultraviolet absorbers, triterpenoid-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, benzoic acid-based ultraviolet absorbers, o-amine benzoic acid-based ultraviolet absorbers, salicylic acid-based ultraviolet absorbers, cinnamic acid-based ultraviolet absorbers, etc.

[0023] For example, as a benzotriazole-based ultraviolet absorber, at least one ultraviolet absorber selected from the group consisting of benzotriazole-based ultraviolet absorbers represented by the following general formula (A) can be cited.

[0024] [Chemistry 1] (In general formula (A), X1, X2, and X3 independently represent a hydrogen atom, a hydroxyl group, -OR a, or a hydrocarbon group with 1 to 15 carbon atoms that may have substituents, Ra represents a hydrocarbon group with 1 to 15 carbon atoms that may have substituents, and at least one of X1, X2, and X3 represents a hydroxyl group, -OR a, or a hydrocarbon group with 1 to 15 carbon atoms that may have substituents. X4 represents a hydrogen atom or a halogen atom.)

[0025] In general formula (A), the hydrocarbon groups with 1 to 15 carbon atoms in X1, X2, X3, and Ra can be linear or branched aliphatic or aromatic hydrocarbon groups, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, dodecyl, phenyl, naphthyl, biphenyl, etc. The number of carbon atoms in the above hydrocarbon groups can be 1 to 12, or 1 to 8. The above hydrocarbon groups can be aliphatic hydrocarbon groups, linear or branched alkyl groups, or methyl, tributyl, tripentyl, n-octyl, trioctyl (1,1,3,3-tetramethylbutyl), 2-ethylhexyl. Examples of substituents include halogen atoms, hydroxyl groups, cyano groups, or groups containing carbonyl, ester, ether, amide, or amideimin groups, such as amide, amide oxy, alkoxy, aryloxy, and glycidyl groups. Furthermore, as substituents for aromatic hydrocarbon groups, alkyl groups can also be used. The substituent hydrocarbon group can be, for example, -C2H3(OH)-CH2-OC8H17, -C2H3(OH)-CH2-OC12H25, -CH(CH3)-CO2-C8H17, methacryloxyethyl, etc., or 4-methylphenyl, 3-chlorophenyl, 4-benzyloxyphenyl, 4-cyanophenyl, 4-phenoxyphenyl, 4-glycidoxyphenyl, 4-isocyanuric phenyl, etc. The -C8H17 and -C12H25 groups can be straight-chain or branched, respectively. In general formula (A), examples of halogen atoms include chlorine atoms, fluorine atoms, and bromine atoms.

[0026] Examples of benzotriazole-based ultraviolet absorbers include: 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-(2-hydroxy-5-tert-butylphenyl)-2H-benzotriazole, a mixture of octyl 3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazole-2-yl)phenyl]propionate and 2-ethylhexyl 3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazole-2-yl)phenyl]propionate, and 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl]propionate]. [Phenyl]-2H-benzotriazole, 2-(3-tert-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3,5-ditertopentyl-2-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole, 2-(2H-benzotriazole-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(2H-benzotriazole-2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3-tetramethylbutyl)phenol, etc.

[0027] For example, as a triterpenoid ultraviolet absorber, at least one ultraviolet absorber selected from the group consisting of triterpenoid ultraviolet absorbers represented by the following general formula (B) can be cited.

[0028] [Chemistry 2] (In general formula (B), Y1, Y2, Y3, Y4, Y5, and Y6 independently represent a hydrogen atom, a hydroxyl group, -ORb, or a hydrocarbon group with 1 to 15 carbon atoms that may have substituents, Rb represents a hydrocarbon group with 1 to 15 carbon atoms that may have substituents, and at least one of Y1, Y2, Y3, Y4, Y5, and Y6 represents a hydroxyl group, -ORb, or a hydrocarbon group with 1 to 15 carbon atoms that may have substituents.)

[0029] The hydrocarbon groups with 1 to 15 carbon atoms that may have substituents in Y1, Y2, Y3, Y4, Y5, Y6, and Rb may be the same as the hydrocarbon groups with 1 to 15 carbon atoms that may have substituents in X1, X2, X3, and Ra mentioned above. At least one of Y2, Y4, and Y6 may be a hydroxyl group or a hydroxyphenyl triterpenoid ultraviolet absorber.

[0030] Examples of triterpenoid ultraviolet absorbers include: 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triterpenoid-2-yl]-5-octoxyphenol, 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triterpenoid-2-yl]-5-[3-(dodecyloxy)-2-hydroxypropoxy]phenol, and 2,4-bis[2-hydroxy-4-butoxyphenyl]-6-(2,4-dibutoxyphenyl)-1,3,5-triterpenoid, etc.

[0031] For example, as a benzophenone-based ultraviolet absorber, a hydroxybenzophenone-based ultraviolet absorber can be cited, and at least one ultraviolet absorber selected from the group consisting of hydroxybenzophenone-based ultraviolet absorbers represented by the following general formula (C) can be cited.

[0032] [Chemistry 3] (In general formula (C), Z1 represents a hydroxyl group, -OR c, or a hydrocarbon group with 1 to 15 carbon atoms that may have substituents; Z2 represents a hydrogen atom, a hydroxyl group, -OR c, or a hydrocarbon group with 1 to 15 carbon atoms that may have substituents; Z3 represents a hydrogen atom or a hydroxyl group; and R c represents a hydrocarbon group with 1 to 15 carbon atoms that may have substituents.)

[0033] In general formula (C), the hydrocarbon groups with 1 to 15 carbon atoms that may have substituents in Z1, Z2, and Rc may be the same as the hydrocarbon groups with 1 to 15 carbon atoms that may have substituents in X1, X2, X3, and Ra mentioned above.

[0034] Examples of benzophenone-based ultraviolet absorbers include: 2,4-dihydroxybenzophenone, 2-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octyloxybenzophenone, and 2,2-dihydroxy-4-methoxybenzophenone.

[0035] The weight-average molecular weight of the ultraviolet absorber used in this invention, in terms of its high efficiency in absorbing ultraviolet light, is typically 80 or higher, preferably 150 or higher, and even more preferably 300 or higher; furthermore, it is typically 2000 or lower, preferably 1500 or lower, and even more preferably 900 or lower. Furthermore, since the polymer of the ultraviolet absorber has a low ultraviolet absorption capacity, it is preferably a non-polymer compound without repeating units.

[0036] The ultraviolet absorber used in this invention is preferably an ultraviolet absorber with a transmittance of less than 45% at a wavelength of 365 nm, which is used in a 0.002% by mass propylene glycol monomethyl ether acetate solution. As described above, combining an ultraviolet absorber with low transmittance at a wavelength of 365 nm with a lake pigment of triarylmethane dyes can effectively reduce the intensity of ultraviolet light, which is weakly absorbed by the triarylmethane lake pigment and has the highest intensity under ultraviolet radiation from an ultra-high pressure mercury lamp. As a result, it is possible to add an amount of initiator sufficient to ensure the curability of the coating surface, suppressing film thickness changes after development residue, and effectively reducing the photocurability within the coating. It is also preferable that the linewidth offset can be easily adjusted in a manner that does not become excessive.

[0037] The transmittance of the ultraviolet absorber at a wavelength of 365 nm can be used to prepare a 0.002% by mass propylene glycol monomethyl ether acetate solution of the ultraviolet absorber. The transmittance of the 0.002% by mass propylene glycol monomethyl ether acetate solution is measured using an ultraviolet-visible-near-infrared spectrophotometer (e.g., the V-7100 from Japan Spectrophotometer Co., Ltd.).

[0038] The transmittance of the ultraviolet absorber used in this invention at a wavelength of 365 nm in a 0.002% by mass propylene glycol monomethyl ether acetate solution is preferably 42% or less, and more preferably 40% or less.

[0039] In terms of achieving the effects of the present invention, the ultraviolet absorber used in the present invention is preferably one that has a solubility of 1% by mass or more in the solvent used in the photosensitive coloring resin composition at 25°C. The ultraviolet absorber used in this invention may be one with a solubility of 1% by mass or more in propylene glycol monomethyl ether acetate at 25°C.

[0040] As ultraviolet absorbers used in this invention, suitable compounds include, for example, 2-(2-hydroxy-5-tert-butylphenyl)-2H-benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole, 2-[4-[(2-hydroxy-3-(2'-ethylhexyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triphenyl, 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3,5-triphenyl, 2 -(2H-benzotriazole-2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2-hydroxy-4-octoxybenzophenone, 2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole, 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole, 2,2'-dihydroxy-4-methoxybenzophenone, 2-(2-hydroxy-5-methylpropenyloxyethylphenyl)-2H-benzotriazole, (2-hydroxy-3-dodecyl-5-methylphenyl)benzotriazole, etc. Commercially available products include, for example: Tinuvin PS, Tinuvin 329, Tinuvin 405, Tinuvin 477, Tinuvin 479, Tinuvin 571, Tinuvin 928 (all manufactured by BASF), Kemisorb 12, Kemisorb 71, Kemisorb 71D, Kemisorb 73, Kemisorb 111 (all manufactured by Chemipro Kasei), RUVA-93 (all manufactured by Otsuka Chemicals), etc.

[0041] In this invention, one type of ultraviolet absorber may be used alone, or two or more types may be used in combination. Furthermore, even when selecting an ultraviolet absorber with a transmittance of 45% or less at 365 nm in a 0.002% by mass propylene glycol monomethyl ether acetate solution, two or more types can be used in combination. That is, even if the ultraviolet absorbers used in this invention include those with a transmittance of more than 45% at 365 nm in a 0.002% by mass propylene glycol monomethyl ether acetate solution, two or more types can be mixed. If the transmittance at 365 nm in a 0.002% by mass propylene glycol monomethyl ether acetate solution is 45% or less, then such a mixture of ultraviolet absorbers can be used.

[0042] The content of the aforementioned ultraviolet absorber, in order to achieve the effect of linewidth suppression and adjust the photocurability in a way that allows for good curing, is typically in the range of 0.2% to 4.0% by mass relative to the total solid content of the photosensitive coloring resin composition, preferably in the range of 0.3% to 3.0% by mass, and even more preferably in the range of 0.5% to 2.0% by mass. Furthermore, the solid components include all components other than the solvent, including liquid photopolymerizable compounds.

[0043] Furthermore, for the purpose of obtaining linewidth suppression effect and adjusting photocurability in a good curing manner, the ratio of the total mass of the ultraviolet absorber to the total mass of the photoinitiator and the ultraviolet absorber is preferably in the range of 2.0% to 20.0% by mass, and more preferably in the range of 4.0% to 18.0% by mass.

[0044] [color material] In order to produce a photosensitive coloring resin composition capable of forming a coloring layer that suppresses color changes or brightness reduction before and after the high-temperature heating step, improves the brightness of the final colored layer, and suppresses film thickness changes before and after development by means of a finer linewidth, the color material in this invention contains a lake color material of triarylmethane dyes. <Lake Pigments for Triarylmethane Dyes> In terms of excellent heat resistance and lightfastness, and achieving high brightness in color filters, lake materials of triarylmethane dyes and polyacids are preferred. As lake materials of triarylmethane dyes, it is preferred to select one or more of the color materials represented by the following general formula (1) and the following general formula (2). In terms of forming a molecular aggregate state, exhibiting better heat resistance, and achieving high brightness, the color material represented by the following general formula (1) is preferred.

[0045] [Chemistry 4] In general formula (1), A is an organic group with an a valence of α and a carbon atom directly bonded to N without a π bond. 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 polyacid anion with a c valence. 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 can 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.)

[0046] [Chemistry 5] 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 a polyacid anion with an m valence. 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.)

[0047] The colorant represented by the above general formula (1) contains divalent or higher anions and divalent or higher cations. Therefore, in the aggregate of this colorant, the anions and cations are not simply ionicly bonded one molecule to one molecule, but can form molecular aggregates of multiple molecules aggregated through ionic bonds. Therefore, the apparent molecular weight is significantly increased compared with the molecular weight of previous lake pigments. It is presumed that by forming such molecular aggregates, the cohesive force in the solid state is further improved, thermal motion is reduced, and the dissociation of ion pairs or decomposition of cations can be suppressed, making it less prone to fading compared with previous lake pigments.

[0048] In the above general formula (1), the A group is an organic group whose carbon atom directly bonded to N (nitrogen atom) does not have a π bond and has an α valence. This 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 such as O (oxygen atom), S (sulfur atom), and N (nitrogen atom). That is, this organic group represents an aliphatic hydrocarbon group with a saturated aliphatic hydrocarbon group at least at the end directly bonded to N and whose carbon chain may contain heteroatoms such as O, S, and N, or an aromatic group with an aliphatic hydrocarbon group at the end directly bonded to N and whose carbon chain may contain heteroatoms such as O, S, and N. 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.

[0049] In A, regarding the aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at least at the end directly bonded to N, as long as the carbon atom at the end directly bonded to N does not have a π bond, it can be any of the following: straight chain, branched chain, or cyclic chain. The carbon atoms other than the end can have unsaturated bonds and can also have 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 with halogen atoms, etc. Furthermore, in A, the aromatic group having an aliphatic hydrocarbon group can be exemplified as a monocyclic or polycyclic aromatic group containing at least an aliphatic hydrocarbon group with a saturated aliphatic hydrocarbon group at the end directly bonded to N, and can have substituents, which can be heterocycles containing O, S, and N. In terms of the strength 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, bicyclic [2.2.2]octane, tricyclic [5.2.1.0 2,6]decane, and adamantane. Examples of aromatic groups include those containing benzene rings and naphthyl rings. For instance, when A is a divalent organogroup, 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.

[0050] In this invention, in terms of balancing robustness and freedom of molecular motion, and improving heat resistance, it is preferable that A has two or more cyclic aliphatic hydrocarbon groups, 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. More preferably, A has two or more cycloalkyl groups, 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 even more preferable that the structure having two or more cyclic aliphatic hydrocarbon groups is formed by straight-chain or branched aliphatic hydrocarbon groups linked together. The presence of two or more cyclic aliphatic hydrocarbon groups can be the same or different. For example, examples of cyclic aliphatic hydrocarbon groups that are the same as those mentioned above can be given, among which cyclohexane and cyclopentane are preferred.

[0051] In this invention, in terms of heat resistance, the A is preferably a substituent represented by the following general formula (1a).

[0052] [Chemistry 6] (In general formula (1a), Rxi represents an alkyl group having 1 to 3 carbon atoms that can have 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms as a substituent; Rxii and Rxiiii each independently represent an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms; p represents an integer of 1 to 3; and q and r each independently represent an integer of 0 to 4. When there are multiple Rxi, Rxii, Rxiiii and r, the multiple Rxi, Rxii, Rxiiii and r may be the same or different from each other.)

[0053] In terms of balancing excellent fastness and thermal motion of the color-developing areas, as well as improved heat resistance, an alkyl group in Rxi with 1 to 3 carbon atoms is preferred. Examples of such alkyl groups include methylene, ethyl, and propyl, with methylene or ethyl being preferred, and methylene being even more preferred. Examples of alkyl groups with 1 to 4 carbon atoms include methyl, ethyl, propyl, and butyl. They can be linear or branched. Furthermore, examples of alkoxy groups with 1 to 4 carbon atoms include methoxy, ethoxy, propoxy, and butoxy, which can be linear or branched.

[0054] Examples of alkyl groups having 1 to 4 carbon atoms and alkoxy groups having 1 to 4 carbon atoms in R xii and R xiii are those with the same substituents as those that R xi may have.

[0055] In general formula (1a), in terms of heat resistance, it is preferred that there are 2 or more but less than 4 cyclohexane (extrinsic cyclohexyl), that is, p is 1 or more but less than 3, and more preferably p is 1 or more but less than 2. Furthermore, the number of substitutions of substituents Rxii and Rxiii in the cyclohexyl group is not particularly limited, but in terms of heat resistance, it is preferably 1 to 3, more preferably 1 to 2. That is, it is preferably q and r to be integers of 1 to 3, and even more preferably q and r to be integers of 1 to 2.

[0056] As suitable specific examples of such a linking base A, the following can be cited, but are not limited to them.

[0057] [Chemistry 7]

[0058] 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 which straight-chain or branched alkyl groups with 1 to 8 carbon atoms are examples. In terms of brightness and heat resistance, straight-chain or branched alkyl groups with 1 to 5 carbon atoms are examples. Furthermore, alkyl groups in Ri to Rv can be ethyl or methyl. The substituents that alkyl groups can have are not particularly limited. Examples include aryl, halogen atoms, hydroxyl, and alkoxy groups. As substituted alkyl groups, examples include benzyl aralkyl groups. 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 alkyl groups, halogen atoms, alkoxy groups, and hydroxyl groups. In terms of chemical stability, Ri~Rv are preferably each independently composed of a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group, or Riii bonded to Riiii, Riv bonded to Rv to form a pyrrolidine ring, a piperidine ring, or a morpholine ring.

[0059] Regarding 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, thereby suppressing the influence of the colorimetric site on heat, and thus resulting in excellent heat resistance.

[0060] In terms of heat resistance, it is preferred 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).

[0061] [Chemistry 8] (In general formula (1b), R xiv, R xv, and R xvi each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms that may have substituents, or an alkoxy group having 1 to 4 carbon atoms that may have substituents.)

[0062] [Chemistry 9] (In general formula (1c), R xvii, R xviii, and R xix each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms that may have substituents, or an alkoxy group having 1 to 4 carbon atoms that may have substituents.)

[0063] Examples of alkyl groups having 1 to 4 carbon atoms in R xiv, R xv, R xvi, R xvii, R xviii, and R xix include methyl, ethyl, propyl, and butyl, which can be linear or branched. Similarly, examples of alkoxy groups having 1 to 4 carbon atoms include methoxy, ethoxy, propoxy, and butoxy, which 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.

[0064] In the case of having the substituents represented by the above general formula (1b), in terms of heat resistance, it is preferable that at least one of R xiv, R xv, and R xvi is an alkyl group having 1 to 4 carbons or an alkoxy group having 1 to 4 carbons, and more preferably that at least one of R xiv and R xv is an alkyl group having 1 to 4 carbons or an alkoxy group having 1 to 4 carbons.

[0065] Furthermore, when the substituents represented by the above general formula (1c) are present, in terms of heat resistance, it is preferable that at least one of R xvii, R xviii, and R xix is ​​an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and more preferably that at least one of R xvii and R xviii is an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms.

[0066] 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 to 8 carbon atoms or a branched alkoxy group, and more preferably an alkoxy group with 1 to 4 carbon atoms. Examples of alkoxy groups with 1 to 4 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 substitutions of Rvi and Rvii, i.e., f and g, independently represent integers above 0 and below 4, preferably above 0 and below 2, and more preferably above 0 and below 1. There exist multiple f and g, which may be the same or different. Furthermore, Rvi and Rvii can be substituted for compounds with a triarylmethane skeleton, or... Any part of the aromatic ring of the resonance structure within the skeleton, preferably substituted at the meta position based on the substitution position of the amino group represented by -NR iiR iii or -NR ivR v.

[0067] 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. Examples of aromatic hydrocarbon groups, besides benzene rings, 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 oxide, diphenylmethane, triphenylmethane, and piracene. In these chain polycyclic hydrocarbons, O, S, and N may be present in the chain skeleton, as in diphenyl ethers, etc. 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, pyranone, pyridine, pyranone, pyrazine, pyrimidine, and pyrazine; and condensed polycyclic heterocycles such as benzofuran, benzothiophene, indole, carbazole, coumarin, benzopyranone, quinoline, isoquinoline, acridine, thiazoline, quinazolin, and quinazolin. These aromatic groups may further have alkyl, alkoxy, hydroxyl, halogen atoms, and phenyl groups that can be substituted as substituents.

[0068] A molecule contains multiple Ri~Rvii and Ar1, which can be the same or different. By combining Ri~Rvii and Ar1, the desired color can be achieved.

[0069] In A, the valence 'a' represents 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 be greater than or equal to 3. There is no particular upper limit to 'a', but for ease of manufacturing, it is preferable that 'a' is less than or equal to 4, and more preferably less than or equal to 3.

[0070] In terms of excellent heat resistance and easy suppression of color change during heating, the cation in the color material represented by general formula (1) preferably has a molecular weight of 1200 or more, and more preferably 1300 or more.

[0071] In the color material represented by general formula (1), the anionic part (B c-) is a polyacid anion with a c valence, and is an anion with a divalent or higher valence, in terms of high brightness and excellent heat resistance.

[0072] 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 formulas, 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, it may contain countercations such as Na+ or H+ in some of these compounds. In terms of 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-, which are homopolyacids; or phosphotungstate ion [PW12O40]3-, [P2W18O62]6-, silicotttate ion [SiW12O40]4-, phosphotungstate ion [PMo12O40]3-, silicotttate ion [SiMo12O40]4-, phosphotungstate ion [PW12-sMo12O40]3- (where s is an integer between 1 and 11), [P2W18-tMo12O62]6- (where t is an integer between 1 and 17), and silicotttate ion [SiW12-uMouO62]. 40] 4-(u is an integer from 1 to 11) etc. As a polyacid containing at least one of tungsten (W) and molybdenum (Mo), the above-mentioned polyacid is preferably a heteropolyacid in terms of heat resistance and ease of obtaining raw materials, and even more preferably a heteropolyacid containing phosphorus (P). Furthermore, in terms of heat resistance, it is more 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-.

[0073] 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 2 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 2 or more types.

[0074] Furthermore, as a lake pigment represented by general formula (1), it can be prepared, for example, with reference to International Publication No. 2012 / 144520 and International Publication No. 2018 / 003706.

[0075] 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 be the same as Ri~Rv in general formula (1) mentioned above. 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) described 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 general formula (1) mentioned above. Furthermore, in general formula (2), E m- represents a polyacid anion with an m valence, which can be the same as the polyacid anion with a c valence in general formula (1) mentioned above.

[0076] In general formula (2), m represents the number of cations and the number of anions, and represents an integer greater than 2. The multiple cations present in general formula (2) can be a single type or a combination of two or more types. Similarly, the anions can also be a single type or a combination of two or more types. Furthermore, k and l in general formula (2) can be the same as f and g in general formula (1) mentioned above. Furthermore, as a lake pigment represented by general formula (2), it can be prepared, for example, by referring to Japanese Patent Application Publication No. 2017-16099.

[0077] 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 of the pigments represented by the above general formula (1) and the pigments represented by the above general formula (2), and can be appropriately selected. For example, the following can be used: cationic triarylmethane dyes and lake materials containing various polyacid anions 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 materials 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.

[0078] In the photosensitive coloring resin composition of the present invention, the above-mentioned triarylmethane dye lake pigment can be used alone or in combination of two or more.

[0079] <Other Colorants> The color materials used in this invention contain lake color materials of triarylmethane dyes as essential components. In order to adjust the hue, other color materials may be used in combination without compromising the effect of this invention. As other coloring materials, known pigments, dyes, lake coloring materials, etc., can be used alone, or two or more of them can be mixed together.

[0080] Other colorants may include, but are not limited to, other blue, purple, and red colorants. Other blue pigments include well-known organic blue pigments such as CI Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, and 15:6. As a purple pigment, there are well-known organic purple pigments such as CI Pigment Purple 1, 14, 15, 19, 23, 29, 32, 33, 36, 37, and 38. As a red or purplish-red pigment, it is described in, for example, International Publication No. 2020 / 071041, Japanese Patent Application Publication No. 2018-100323, and International Publication No. 2014 / 123125, etc. Dyes and tin It refers to lake pigments and other dyes.

[0081] <Proportion of Colorant> In the photosensitive coloring resin composition of the present invention, without impairing the effects of the present invention, other coloring materials besides the lake coloring material of triarylmethane dyes may be contained in the coloring material. The proportion of the lake coloring material of triarylmethane dyes relative to the total amount of coloring material is preferably 70% by mass or more and 100% by mass, more preferably 80% by mass or more and 100% by mass, more preferably 90% by mass or more and 100% by mass, and more preferably 95% by mass or more and 100% by mass.

[0082] The average primary particle size of the colorant used in this invention, when fabricating the color layer of a color filter, is not particularly limited as long as the desired color rendering can be achieved. It varies depending on the type of colorant 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 colorant, display devices equipped with color filters manufactured using the photosensitive coloring resin composition of this invention can be produced to have high contrast and high quality.

[0083] Furthermore, the average dispersed particle size of the colorant in the photosensitive coloring resin composition varies depending on the type of colorant used, 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 colorant in a photosensitive coloring resin composition refers to the dispersed particle size of the colorant particles dispersed in a dispersion medium containing at least a solvent, and can be measured using a laser light scattering particle size analyzer. As a particle size determination using a laser light scattering particle size analyzer, the photosensitive coloring resin composition can be appropriately diluted (e.g., 1000 times) with the solvent used in the photosensitive coloring resin composition to a concentration measurable by the laser light scattering particle size analyzer. 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.

[0084] The colorant used in this invention can be manufactured by known methods such as recrystallization and solvent salt milling. Alternatively, commercially available colorants can be micronized for use.

[0085] In the photosensitive coloring resin composition of the present invention, the content of the colorant is not particularly limited. In terms of dispersibility and dispersion stability, the content of the colorant, relative to the total solid content of the photosensitive coloring resin composition, is generally in the range of 3% to 65% by mass, preferably in the range of 4% to 60% by mass, and more preferably in the range of 15% to 60% by mass. If it is above the lower limit, the colored layer when the photosensitive coloring resin composition is coated to a specified film thickness (generally 1.0 μm to 5.0 μm) has sufficient color concentration. Furthermore, if it is below the upper limit, a colored layer with excellent storage stability and sufficient hardness or adhesion to the substrate can be obtained. Especially when forming a colored layer with a high colorant concentration, the total content of the colorant relative to the total solid content of the photosensitive coloring resin composition is preferably in the range of 20% to 65% by mass, and more preferably in the range of 30% to 60% by mass.

[0086] [Alkali-soluble resin] The alkali-soluble resin in this invention has an acidic group and can be appropriately selected from those that function as an adhesive resin and are soluble in the alkaline developing solution used during pattern formation. In this invention, the alkali-soluble resin can be defined as having an acid value of 40 mgKOH / g or higher. Preferred alkali-soluble resins in this invention are resins having acidic groups and generally having carboxyl groups. Specifically, examples include: acrylic copolymers having carboxyl groups and acrylic resins such as styrene-acrylic copolymers having carboxyl groups, as well as epoxy (meth)acrylate resins having carboxyl groups.

[0087] Of particular preference are those containing carboxyl groups on the side chains, and further, photopolymerizable functional groups such as vinyl unsaturated groups on the side chains. 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, its development resistance is enhanced, and its thermal shrinkage is suppressed, resulting in excellent adhesion to the substrate. The method for introducing vinyl unsaturated bonds into alkali-soluble resins can be appropriately selected from previously known methods. For example, the following methods can be used: adding a compound with both epoxy groups and vinyl unsaturated bonds in the molecule, such as glycidyl (meth)acrylate, to the carboxyl group of the alkali-soluble resin, and introducing vinyl unsaturated bonds into the side chain; or pre-introducing structural units with hydroxyl groups into the copolymer, adding a compound with both isocyanate groups and vinyl unsaturated bonds in the molecule, and introducing vinyl unsaturated bonds into the side chain. In the following, monomers containing groups with vinyl unsaturated bonds (monomers containing vinyl unsaturated groups) may be simply referred to as vinyl unsaturated monomers.

[0088] Furthermore, in terms of the excellent adhesion of the coloring layer, alkali-soluble resins are preferably those containing hydrocarbon rings. By containing hydrocarbon rings as bulky groups, shrinkage during curing is suppressed, peeling between the resin and the substrate is mitigated, and the adhesion to the substrate 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 contained as monovalent groups or as divalent or higher groups.

[0089] Specific examples of hydrocarbon rings include: aliphatic hydrocarbon rings such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, northane, isothane, tricyclo[5.2.1.0(2,6)]decane (dicyclopentane), and adamantane; aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, phenanthrene, and piracene; chain polycyclic rings such as biphenyl, biphenylene, diphenylmethane, triphenylmethane, and piracene, or Cardo structures (9,9-diarylpiracene); and groups formed by the substitution of one or more of these groups with substituents. Examples of substituents mentioned above include: alkyl, cycloalkyl, alkylcycloalkyl, hydroxyl, carbonyl, nitro, amino, halogen atom, etc.

[0090] When the aliphatic hydrocarbon ring is present as a hydrocarbon ring, it is better in terms of improved heat resistance or adhesion of the colored layer and improved brightness of the obtained colored layer. Furthermore, when the aforementioned Cardo structure is present, it is particularly advantageous in terms of improving the hardening properties of the coloring layer, inhibiting the fading of the coloring material, and improving solvent resistance (NMP (N-methylpyrrolidone) swelling inhibition).

[0091] Acrylic resins, such as acrylic copolymers containing structural units with carboxyl groups and styrene-acrylic copolymers containing carboxyl groups, are, for example, copolymers obtained by known methods of copolymerizing carboxyl-containing vinyl unsaturated monomers and other monomers that can be copolymerized as needed. Examples of vinyl unsaturated monomers containing carboxyl groups include: (meth)acrylic acid, vinylbenzoic acid, maleic acid, monoalkyl maleate, fumaric acid, itconic acid, butenoic acid, cinnamic acid, and acrylic acid dimers. Additionally, monomers with hydroxyl groups, such as 2-hydroxyethyl (meth)acrylic acid), 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)acrylic acid esters. Furthermore, anhydride-containing monomers such as maleic anhydride, itconic anhydride, and citrate anhydride can also be used as carboxyl group precursors. Among these, (meth)acrylic acid is particularly preferred in terms of copolymerization properties, cost, solubility, and glass transition temperature.

[0092] The alkali-soluble resin in this invention is preferably an acrylic copolymer containing carboxyl groups and a hydrocarbon ring structural unit, or a styrene-acrylic copolymer, etc. More preferably, it is an acrylic copolymer containing carboxyl groups, a hydrocarbon ring structural unit, and an ethylene unsaturated bond structural unit, or a styrene-acrylic copolymer, etc.

[0093] Examples of vinyl unsaturated monomers having a hydrocarbon ring include cyclohexyl methacrylate, dicyclopentyl methacrylate, adamantyl methacrylate, isopropyl methacrylate, benzyl methacrylate, phenoxyethyl methacrylate, and styrene. In terms of maintaining the cross-sectional shape of the colored layer after development during heat treatment to a greater extent, it is preferable to use at least one selected from cyclohexyl methacrylate, dicyclopentyl methacrylate, adamantyl methacrylate, benzyl methacrylate, and styrene.

[0094] The copolymer containing carboxyl groups may further contain other structural units such as methyl methacrylate and ethyl methacrylate, which have ester groups. The structural units with ester groups not only function as components that inhibit the alkali solubility of the coloring resin composition, but also function as components that improve solubility relative to the solvent, and further, solvent resolubility.

[0095] The copolymer containing carboxyl groups can be made into an alkali-soluble resin with the desired properties by appropriately adjusting the amount of each structural unit added. Regarding 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, regarding suppressing film roughness on the surface of the pattern 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.

[0096] Furthermore, in acrylic copolymers and styrene-acrylic copolymers containing carboxyl groups, which are better suited as alkali-soluble resins and contain structural units with ethylene unsaturated bonds, the amount of the compound containing both epoxy groups and ethylene unsaturated bonds relative to the ethylene unsaturated monomer containing carboxyl groups is preferably 10% by mass or more and 95% by mass or less, and more preferably 15% by mass or more and 90% by mass or less.

[0097] The preferred mass average molecular weight (Mw) of the copolymer containing carboxyl groups is in the range of 1,000 to 50,000, and more preferably 3,000 to 20,000. If it is above 1,000, the adhesive function after curing is improved; if it is below 50,000, pattern formation becomes better when developing with an alkaline developer.

[0098] There are no particular limitations on the type of epoxy (meth)acrylate resin containing carboxyl groups, but epoxy (meth)acrylate compounds obtained by reacting an epoxy compound with a reactant containing an unsaturated group and an anhydride are suitable. Epoxides, monocarboxylic acids containing unsaturated groups, and acid anhydrides may be appropriately selected from those known to the public. As an epoxy (meth)acrylate resin having a carboxyl group, it is also preferable to have the above-mentioned hydrocarbon ring in the molecule. In terms of improving the curability of the coloring layer, inhibiting the fading of the coloring material, and improving the residual film rate of the coloring layer, it is preferable to contain a Cardo structure. Epoxy (meth)acrylate resins containing carboxyl groups can be used alone or in combination with two or more types.

[0099] Regarding the developability (solubility) of the alkaline aqueous solution used in the developer, it is preferable to select an alkali-soluble resin with an acid value of 30 mgKOH / g or higher. Regarding both the developability (solubility) of the alkaline aqueous solution used in the developer and its adhesion to the substrate, it is preferable to select an alkali-soluble resin with an acid value of 40 mgKOH / g or higher and 300 mgKOH / g or lower, with a more preferably 50 mgKOH / g or higher and 280 mgKOH / g or lower.

[0100] When the side chain of an alkali-soluble resin has 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, to achieve effects such as improved film strength, improved developability, and excellent adhesion to the substrate. If the vinyl unsaturated bond equivalent is less than 2000, the developability or adhesion is excellent. Furthermore, if it is 100 or more, the proportion of other structural units such as those with carboxyl groups or hydrocarbon rings can be relatively increased, thus resulting in excellent developability or heat resistance. Here, the equivalent of the vinyl unsaturated bond is the average molecular weight of the above-mentioned alkali-soluble resin relative to 1 mole of vinyl unsaturated bond, expressed by the following formula (1).

[0101] 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))

[0102] The equivalent of the aforementioned vinyl unsaturated bonds can also be calculated, for example, by determining the number of vinyl unsaturated bonds contained in 1 g of alkali-soluble resin according to the iodine value test method recorded in JIS K 0070:1992.

[0103] The alkali-soluble resin used in the photosensitive coloring resin composition may be used alone or in combination with two or more types. There is no particular limitation on its content. However, relative to the total solid content of the photosensitive coloring resin composition, the alkali-soluble resin content is preferably in the range of 5% to 60% by mass, and more preferably in the range of 8% to 40% by mass. If the content of the alkali-soluble resin is above the lower limit mentioned above, sufficient alkaline developability can be obtained. Furthermore, if the content of the alkali-soluble resin is below the upper limit mentioned above, defects such as film roughness or patterning can be suppressed during development.

[0104] [Photopolymerizable compounds] The photopolymerizable compound used in the photosensitive coloring resin composition is not particularly limited as long as it can be polymerized by a photoinitiator. Generally, compounds having two or more vinyl unsaturated bonds can be used, and polyfunctional (meth)acrylates having two or more acrylonitrile or methacrylonitrile are preferred. As such a multifunctional (meth)acrylate, it is appropriate to select from those previously known. For specific examples, such as those described in Japanese Patent Application Publication No. 2013-029832, etc.

[0105] 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 (trifunctional) polymerizable vinyl unsaturated bonds, preferably a poly(meth)acrylate of a trivalent or higher polyol, or a dicarboxylic acid modified thereof. Specifically, preferably: trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, succinic acid modified pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, succinic acid modified dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc.

[0106] The photopolymerizable compounds used in this invention can achieve both a high residual film yield and a finer linewidth, and preferably contain photopolymerizable compounds comprising epoxides. As photopolymerizable compounds containing alkyl oxides, photopolymerizable compounds containing ethylene oxide and / or propylene oxide are preferably examples. In the case of photopolymerizable compounds containing alkyl oxides as described above, it is presumed that active free radicals are regenerated from peroxide free radicals that have lost their polymerization activity due to oxygen inhibition, thereby improving the curing properties. 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.

[0107] Photopolymerizable compounds can be used alone or in combination of two or more. As a photopolymerizable compound, photopolymerizable compounds containing alkyl epoxides can be used in combination with photopolymerizable compounds that do not contain alkyl epoxides. When the content of the photopolymerizable compound containing epoxide is present, the content relative to the total amount of the photopolymerizable compound is preferably in the range of 3% to 50% by mass, and more preferably in the range of 5% to 30% by mass.

[0108] There is no particular limitation on the content of the aforementioned photopolymerizable compound used in the photosensitive coloring resin composition. Preferably, it is 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, dissolution during development of the exposed portion is suppressed, linewidth shift is suppressed, and solvent resistance becomes good. Furthermore, if the content of the photopolymerizable compound is below the aforementioned upper limit, alkaline developability is sufficient.

[0109] [Photoinitiator] There are no particular limitations on the photoinitiator used in the photosensitive coloring resin composition of the present invention, and one or more initiators can be used in combination from various previously known initiators. 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; methyl-S-triazole compounds such as 2-(4-butoxy-naphthyl-1-yl)-4,6-bis-trichloromethyl-S-triazole; methyl-S-triazole compounds such as 2-(4-butoxy-naphthyl-1-yl)-4,6-bis-trichloromethyl-S-triazole; 1,2-octanedione-1-[4-(phenylthio)-,2-(o-benzoyl oxime)], ethyl ketone, Oxime esters such as 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-,1-(o-acetylated oxime), Japanese Patent Application Publication No. 2000-80068, Japanese Patent Application Publication No. 2001-233842, Japanese Patent Application Publication No. 2010-527339, Japanese Patent Application Publication No. 2010-527338, and Japanese Patent Application Publication No. 2013-041153, which are photoinitiators; 2-methyl-1-(4-methylthiophenyl)-2-morpholinylpropane-1-one (e.g., Irgacure) α-amino ketones such as 907 (manufactured by BASF), 2-benzyl-2-(dimethylamino)-1-(4-morpholinylphenyl)-1-butanone (e.g., Irgacure 369, manufactured by BASF), 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone (Irgacure 379EG, manufactured by BASF); diethyl-9-oxothiophene 9-Oxysulfur kind. In this invention, the photoinitiator is preferably selected from at least one of oxime esters and α-aminoketones for its superior sensitivity. From the viewpoint of linewidth adjustment and development resistance during pattern formation, α-aminoketones are preferred. Since α-aminoketones, which have a tertiary amine structure, possess an intramolecular tertiary amine structure that acts as an oxygen inhibitor, the free radicals generated from the initiator are less likely to be deactivated by oxygen, thus improving sensitivity. Therefore, this method is preferred. Furthermore, as a photoinitiator, it is preferable to use a combination of oxime esters and α-aminoketones to suppress water spots and improve sensitivity. Moreover, water spots refer to the marks that appear after alkaline development and rinsing with pure water, resembling water stains, when using ingredients that enhance alkaline developability. These water spots disappear after baking, so the product itself is not problematic. However, during the visual inspection of the patterned surface after development, they are detected as spot abnormalities, leading to the indistinguishability 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, in terms of adjusting sensitivity, suppressing water spots, and improving development resistance, it is preferable to react at least one of oxime esters and α-aminoketones with 9-oxosulfuron. Classes are combined.

[0110] The total content of photoinitiators used in the photosensitive coloring resin composition of the present invention is not particularly limited as long as it does not impair the effect of the present invention. It is preferably 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 the content is above the lower limit mentioned above, photocuring proceeds sufficiently, the dissolution of the exposed portion during development is suppressed, and solvent resistance becomes good. On the other hand, if it is below the upper limit mentioned above, the reduction in brightness of the obtained colored layer due to yellowing can be suppressed. Furthermore, regarding the improvement in the suppression of linewidth shift and solvent resistance, and further in terms of the enhancement of the suppression effect on developing residues, the total content of the photoinitiator is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and more preferably 40 parts by mass or less, and more preferably 30 parts by mass or less, relative to 100 parts by mass of the photopolymerizable compound. Furthermore, the ratio of the total mass of the aforementioned photoinitiator to the total mass of the aforementioned photoinitiator and the aforementioned ultraviolet absorber is preferably in the range of 80% to 98% by mass, and more preferably in the range of 82% to 96% by mass. If this content is above or below the aforementioned lower limit, photocurability can be sufficiently ensured even in the presence of the ultraviolet absorber. On the other hand, if it is below the aforementioned upper limit, it is easy to obtain the effect of adjusting the linewidth of the ultraviolet absorber.

[0111] [solvent] The solvent used in this invention is not particularly limited as long as it is an organic solvent that does not react with the components of the photosensitive coloring resin composition and can dissolve or disperse them. Two or more solvents may be used alone or in combination. Specific examples of solvents include: alcohol solvents such as methanol, ethanol, N-propanol, isopropanol, methoxy alcohol, and ethoxy alcohol; 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 carbitol acetate, 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, in terms of the solubility of other components, glycol ether acetate-based solvents, carbitol acetate-based solvents, glycol ether-based solvents, and ester-based solvents may be suitably used. Of these, the solvent used in this invention, in terms of 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.

[0112] In the photosensitive coloring resin composition of the present invention, the solvent content can be appropriately set within a range that allows for precise and good formation of the colored layer. Relative to the total amount of the photosensitive coloring resin composition containing the solvent, it 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 above range, its coatability becomes excellent.

[0113] [Dispersant] In the photosensitive coloring resin composition of the present invention, the aforementioned colorant can be dispersed in a solvent using a dispersant. In the present invention, the dispersant can be appropriately selected from previously known dispersants. Examples of dispersants that can be used include cationic, anionic, nonionic, amphoteric, silicone, and fluorinated surfactants. Among surfactants, polymeric dispersants are preferred for their ability to disperse uniformly and finely.

[0114] 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 polyacrylates, or modified forms thereof; polyurethane esters; unsaturated polyamides; polysiloxanes; long-chain polyamide phosphates; polyethylimide derivatives (amides or bases thereof obtained by reacting poly(lower alkylimide) 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.

[0115] The dispersant can be appropriately selected according to the type of color material, and there is no particular limitation. When dispersing the lake color material of the above-mentioned triarylmethane dyes, it is preferable to use an acidic dispersant that is an acidic polymeric dispersant. The acidic dispersant used for dispersing lake pigments may, for example, be at least one selected from polymers having structural units represented by general formula (I) as described below, and block copolymers containing carboxyl groups. When using pigments as colorants and dispersing them, at least one type of dispersant selected from the group consisting of acidic or alkaline polymeric dispersants and carbamate dispersants may be used, depending on the type of pigment. Acidic or alkaline polymeric dispersants may be used. When dispersing alkaline-treated pigments, it is preferable to use an acidic dispersant as an acidic polymeric dispersant; when dispersing acid-treated pigments, it is preferable to use an alkaline dispersant as an alkaline polymeric dispersant. As an alkaline dispersant, for example, at least one type selected from the group consisting of polymers containing repeating units having tertiary amines and salt-type polymers containing at least a portion of the amine groups in polymers having repeating units having tertiary amines forming salts with organic acid compounds may be suitably used. Carbamate-based dispersants are compounds having one or more carbamate bonds (-NH-COO-) within one molecule. For example, reaction products of polyisocyanates having two or more isocyanate groups within one molecule and polyesters having hydroxyl groups at one or both ends can be suitably used as carbamate-based dispersants.

[0116] <Polymers having structural units represented by general formula (I)> Polymers having structural units represented by the following general formula (I) are preferably used as dispersants for the above-mentioned triarylmethane dye lake pigments. When a polymer having structural units represented by the following general formula (I) is used as an acidic dispersant, the dispersibility and heat resistance of the above-mentioned triarylmethane dye lake pigments can be improved, and the color change of the lake pigments after heating can be suppressed. Furthermore, when both lake pigments and pigments are used as pigments, by using a polymer having structural units represented by the following general formula (I) as a dispersant, a colored layer with improved pigment dispersibility and storage stability, improved substrate adhesion, and improved coating uniformity can be formed. Since polymers having the structural units represented by the following general formula (I) are polymers of vinyl unsaturated monomers, it is presumed that their skeletons have higher heat resistance 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 surface of micronized pigments. Additionally, it is presumed that if the pigment surface is coated with at least one of the acidic phosphorus compound groups and their salts, the attack of reactive oxygen species such as peroxide free radicals on the pigment skeleton of the lake pigment (hydrogen abstraction or displacement reactions, etc.) can be suppressed, thereby inhibiting the degradation (oxidative degradation) of the lake pigment.

[0117] [Chemistry 10] (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, or one of the valence groups represented by -CHO, -CH2CHO, -CO-CH=CH2, -CO-C(CH3)=CH2, or -CH2COOR23. R23 is a hydrogen atom or an alkyl group with one to five carbon atoms. R17, R18, R19, R20, R21, and R22 are each independently a hydrogen atom, a hydrocarbon group, or have one or more hydrocarbon groups selected from 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 one or more hydrocarbon groups 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 1 and less than 18, y1 represents an integer greater than 1 and less than 5, and z1 represents an integer greater than 1 and less than 18.

[0118] In general formula (I), L11 is a direct bond or a divalent linker. Here, L11 being a direct bond means that the phosphorus atom is directly bonded to the carbon atom of the main chain backbone without a linker. As a divalent linker in L 11, there are no particular limitations as long as it can link the carbon atoms and phosphorus atoms of the main chain backbone. Examples of divalent linkers in L 11 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 orientation of the bonds in the divalent linker is arbitrary. That is, when the divalent linker contains -CONH-, it can be that -CO is on the carbon atom side of the main chain and -NH is on the phosphorus atom side of the side chain, or conversely, -NH is on the carbon atom side of the main chain and -CO is on the phosphorus atom side of the side chain.

[0119] In terms of dispersibility, L11 in general formula (I) is preferably a divalent linker containing -CONH- or -COO- groups. For example, when L 11 is a divalent linker containing a -COO- group, it is preferable that L 11 is a -COO-L 11'- group (here, L 11' is an alkyl group with 1 to 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 to 18, y represents an integer of 1 to 5, z represents an integer of 1 to 18, and w represents an integer of 1 to 18).

[0120] The alkyl group in L 11' with 1 to 8 carbon atoms can be linear, branched, or cyclic, such as methylene, ethyl, trimethylene, propyl, various butyl, various pentyl, various hexyl, various octyl, etc., and some hydrogens can be replaced by hydroxyl groups. x is an integer between 1 and 18, preferably between 1 and 4, and even more preferably between 1 and 2. y is an integer between 1 and 5, preferably between 1 and 4, and even more preferably 2 or 3. z is an integer between 1 and 18, preferably between 1 and 4, and even more preferably between 1 and 2. w is an integer between 1 and 18, preferably between 1 and 4.

[0121] Suitable specific examples of L 11 in general formula (I) include, for example: -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.

[0122] Examples of hydrocarbon groups in R 12 include alkyl groups with 1 to 18 carbon atoms, alkenyl groups with 2 to 18 carbon atoms, aralkyl groups, and aryl groups. The alkyl groups having 1 to 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 to 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 for the sake of the reactivity of the obtained polymer, it is preferable that the double bond is at the end of the alkenyl group. Examples of aryl groups include phenyl, biphenyl, naphthyl, tolyl, and xylyl, which may further have substituents. The number of carbon atoms in the aryl group is preferably 6 to 24, and more preferably 6 to 12. Furthermore, examples of aralkyl groups include benzyl, phenethyl, naphthylmethyl, and biphenylmethyl, which may further have substituents. The number of carbon atoms in the aralkyl group is preferably 7 to 20, and more preferably 7 to 14. The aforementioned alkyl or alkenyl groups may 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 or branched alkyl groups having one to four carbon atoms, examples include alkenyl, nitro, and halogen atoms. Furthermore, the preferred carbon number mentioned above does not include the carbon number of substituents. In R 12 above, x1 is the same as x above, y1 is the same as y above, and z1 is the same as z above. For example, the hydrocarbon groups in R15 to R22 can be the same as those in R12 mentioned above.

[0123] 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'-OR", -R'-(C=O)-OR", or -R'-O-(C=O)-R" (where R' and R" are hydrocarbon groups, or groups to which a hydrocarbon group is bonded by 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.

[0124] When a ring structure is formed by the bonding of R17 and R19, the number of carbons in the ring structure is preferably 5 to 8, more preferably 6, i.e., 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.

[0125] Regarding the superior 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 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 atoms, 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.

[0126] Furthermore, regarding improving alkali resistance, R12 is preferably a hydrocarbon group, a valence group represented by -[CH(R13)-CH(R14)-O]x1-R15, or -[(CH2)y1-O]z1-R15. In the case of a structure where carbon atoms are directly bonded to phosphorus atoms, it is presumed that due to the difficulty in hydrolysis, a resin layer with excellent alkali resistance can be formed. In terms of excellent alkali resistance and excellent dispersibility and dispersion stability of the dispersed particles, R12 is preferably 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. In terms of dispersibility, R12 is more preferably an aryl group with substituents.

[0127] 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, amidonium cations, piperidinium cations, pyrrolidinium cations, tetraalkylammonium cations and trialkylammonium cations, strontium cations such as trialkylstrontium cations, tetraalkylphosphonium cations, etc. Among these, protonated nitrogen-containing organic cations are preferred in terms of dispersibility and basic reproducibility. In particular, when the organic cation has an ethylene-unsaturated bond, it is better in terms of imparting hardening properties.

[0128] The structural unit represented by general formula (I) may contain one type or more types in the polymer.

[0129] In polymers, the structural units represented by general formula (I) may include two types of structural units: structural units where X is a hydrogen atom and structural units where X is an organic cation. When both types of structural units are included, there are no particular limitations as long as good dispersibility and dispersion stability are achieved. Preferably, the proportion of structural units where X is an organic cation relative to the total number of structural units represented by general formula (I) is 0 to 50 mol%.

[0130] There are no particular limitations on the synthesis method of polymers having structural units represented by general formula (I). For example, polymers having structural units represented by general formula (I) can be synthesized with reference to Japanese Patent Application Publication No. 2017-2191. Preferably, 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 with an acidic phosphorus compound, and is a polymer in which at least a portion of the acidic phosphorus compound groups can form a salt.

[0131] In embodiments of the present invention, polymers having structural units represented by general formula (I) are preferably solvent-affinity sites in terms of dispersibility. Among such polymers, those exhibiting excellent dispersibility and storage stability, and capable of forming high-contrast coatings even after long-term storage, are preferably graft copolymers having structural units represented by general formula (I) and those represented by general formula (II), or block copolymers having structural units represented by general formula (I) and those represented by general formula (III).

[0132] [Chemistry 11] (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, a valence group represented by -[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 represents a monovalent group, where R 30" is an alkyl group with 1 to 18 carbon atoms, and R 31 is a hydrogen atom or an alkyl group with 1 to 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.

[0133] [Chemistry 12] 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 to 18 carbon atoms, and R 39 is a hydrogen atom or an alkyl group with 1 to 5 carbon atoms. The above hydrocarbon groups may have substituents. n represents an integer between 5 and 200. x3 and x4 represent integers between 1 and 18, y3 and y4 represent integers between 1 and 5, and z3 and z4 represent integers between 1 and 18.

[0134] (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 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 derived from an ethylene unsaturated bond to the polymer chain. For example, the same divalent linker as the one in L 11 described above can be cited as a divalent linker in L 21.

[0135] 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 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, or an aryl group. Examples of these are the same as those for R 12 described above.

[0136] R 36 is preferably a hydrogen atom, or an alkyl, aralkyl, aryl, -CHO, -CH 2CHO, or -CH 2COOR 39 group having 1 to 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 to 18 carbon atoms. R 38 is an alkyl group having 1 to 18 carbon atoms, and R 39 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. The alkyl, aralkyl, and aryl groups with 1 to 18 carbon atoms in R 36 and R 37 mentioned above can be examples of those with the same number of carbon atoms as R 12 mentioned above. The alkyl groups in R 38 and R 39 mentioned above may be the same 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 linear, branched, or cyclic alkyl groups having one to five carbon atoms, alkenyl, nitro, halogen atoms such as F, Cl, and Br. Furthermore, the preferred carbon number mentioned above 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.

[0137] Furthermore, R33, R36, R37, R38, and R39, within a range that does not impair the dispersibility of the graft copolymer, can be substituted with substituents such as alkoxy, hydroxyl, carboxyl, amino, epoxy, isocyanate, or hydrogen-bonding groups. Also, after synthesizing the graft copolymer having these substituents, it can be reacted with a compound having functional groups and polymerizable groups that react with the substituents to form a polymerizable group. For example, a graft copolymer having a carboxyl group can be reacted with glycidyl (meth)acrylate, or a graft copolymer having an isocyanate group can be reacted with hydroxyethyl (meth)acrylate to form a polymerizable group.

[0138] The polymer chain having structural units represented by general formula (IV) preferably has structural units derived from the following substances: 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, isopropyl methacrylate, dicyclopentyl methacrylate, adamantyl methacrylate, styrene, α-methylstyrene, vinylcyclohexane, etc. However, it is not limited to these substances.

[0139] In embodiments of the present invention, R33 and R37 are preferably those with excellent solubility in the organic solvents described below, and can be appropriately selected according to the organic solvent used in the colorant dispersion. Specifically, for example, when the organic solvent used is an ether alcohol acetate system, ether system, ester system, or other organic solvent commonly used as an organic solvent in colorant dispersions, methyl, ethyl, isobutyl, n-butyl, 2-ethylhexyl, 2-ethoxyethyl, cyclohexyl, benzyl, etc., are preferred. The reason for setting R33 and R37 in the above manner is that the structural units containing R33 and R37 are soluble in the organic solvents, and the acidic phosphorus compound group and its salt site of the monomer have high adsorption capacity for particles such as colorants, thereby enabling the dispersibility and stability of particles such as colorants to be particularly excellent.

[0140] The weight-average molecular weight of the polymer chains in the polymer is preferably in the range of 500 to 15,000, and more preferably in the range of 1,000 to 8,000. By being in the above range, sufficient stereorepulsion effect as a dispersant can be maintained, and the increase in the dispersion time caused by stereoreactive particles such as colorants can also be suppressed.

[0141] Furthermore, as a standard, it is preferable that the solubility of the polymer chain in the polymer relative to the combined organic solvent at 23°C is 50 (g / 100 g solvent) or more.

[0142] The polymer chains mentioned 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.

[0143] 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 proportion 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 proportion of the affinity sites with the particles in the graft copolymer becomes suitable, and the reduction in solubility in organic solvents can be suppressed. Therefore, the adsorption of particles such as colorants becomes good, and excellent dispersibility and dispersion stability can be obtained. Furthermore, the acidic phosphorus compound groups of the graft copolymer can stably exist locally around the colorant, thus obtaining color filters with excellent heat resistance or contrast. 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 contained in a proportion of 20% to 97% by mass, more preferably 25% to 95% by mass, and even more preferably 40% to 90% by mass. Furthermore, in this invention, the proportion of each structural unit in the copolymer is calculated based on the amount added during the synthesis of the copolymer.

[0144] Furthermore, the weight average molecular weight of the aforementioned graft copolymer is preferably in the range of 1,000 to 500,000, more preferably in the range of 3,000 to 400,000, and even more preferably in the range of 5,000 to 300,000. By falling within the above range, particles such as colorants can be uniformly dispersed.

[0145] 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 appropriately selecting vinyl unsaturated monomers that can copolymerize with vinyl unsaturated monomers that derive structural units from general formula (I).

[0146] (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, in the block portion comprising the structural unit represented by the above general formula (I), the structural unit represented by the above general formula (I) preferably comprises a total of three or more. In terms of improving dispersibility and heat resistance, it is preferable to include three or more but less than 200, more preferably three or more but less than 50, and even more preferably three or more but less than 30. The structural unit represented by the above general formula (I) can function as a color material affinity part, and may include one type or two or more structural units. When there are two or more structural units, the two or more structural units may be randomly arranged in the segment containing the structural unit represented by the above general formula (I).

[0147] 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. If the particle size falls within the aforementioned range, the ratio of the affinity sites to the particles in the block copolymer becomes suitable, and the reduction in solubility in organic solvents can be suppressed. Therefore, the adsorption of particles such as colorants becomes good, resulting in excellent dispersibility and dispersion stability. Furthermore, the acidic phosphorus compound groups of the aforementioned block copolymer can stably exist around the colorant, thus enabling the production of color filters with excellent heat resistance or contrast.

[0148] The block copolymer described above has a block portion comprising the structural unit represented by the general formula (III) above, thereby improving solvent affinity, dispersibility and dispersion stability of the colorant, and heat resistance, and further improving resistance to N-methylpyrrolidone (NMP).

[0149] 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.

[0150] Furthermore, R 30 is a hydrogen atom, a hydrocarbon group, -CHO, -CH 2CHO or -CH 2COOR 31, 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 to 18 carbon atoms, and R 31 is a hydrogen atom or an alkyl group with 1 to 5 carbon atoms. The above hydrocarbon groups may have substituents. The hydrocarbon group in R 30 above can be set to 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.

[0151] As for R 27 and R 30' mentioned above, those that have excellent solubility in the solvents described below are preferred, for example, those that are the same as 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, and hydrogen-bonding groups, within a range that does not impair the dispersibility of the block copolymer. Alternatively, after synthesizing the block copolymer, it can be reacted with a compound having the aforementioned substituents to add the substituents. Furthermore, after synthesizing a block copolymer having these substituents, it can be reacted with a compound having functional groups and polymerizable groups that react with the substituents to add polymerizable groups. For example, a block copolymer having a glycidyl group can be reacted with (meth)acrylic acid, or a block copolymer having an isocyanate group can be reacted with hydroxyethyl (meth)acrylate to add polymerizable groups.

[0152] The number of structural units constituting the block portion comprising the structural unit represented by general formula (III) is not particularly limited. In terms of effectively functioning the solvent affinity portion and the colorant affinity portion to improve the dispersibility of the colorant dispersion, it is preferably 10 to 200, more preferably 20 to 100, and even more preferably 30 to 80.

[0153] In the block copolymers described above, the proportion of the structural unit 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.

[0154] The block portion containing the structural unit represented by general formula (III) can be selected in such a way that it functions as a solvent affinity site. The structural unit represented by general formula (III) may include one type or two or more structural units. In the embodiments of the present invention, when the structural unit represented by general formula (III) includes two or more structural units, the two or more structural units may be randomly arranged in the block portion containing the structural unit represented by the above-mentioned general formula (III).

[0155] In the block copolymer used as a dispersant, the ratio m / n of the number of structural units m comprising the block portion of the structural unit represented by general formula (I) to the number of structural units n comprising the block portion of the structural unit represented by general formula (III) is preferably in the range of 0.01 to 1, and more preferably in the range of 0.1 to 0.7 in terms of the dispersibility and dispersion stability of the colorant.

[0156] As for the bonding sequence of the block copolymer, it is not particularly limited 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), and can stably disperse the colorant. In terms of excellent interaction with the colorant and effective suppression of the aggregation of dispersants, it is preferred that the block portion containing the structural unit represented by the general formula (I) is bonded to only one end of the block copolymer.

[0157] The weight average molecular weight of the block copolymer is not particularly limited, but in terms of improving dispersibility and heat resistance, it is preferably 2,500 to 500,000, more preferably 3,000 to 400,000, and even more preferably 6,000 to 300,000.

[0158] Regarding the dispersibility and storage stability of the aforementioned colorant, the acid value of the polymer having the structural unit represented by the above 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, regarding excellent developability, the acid value of the polymer having the structural unit represented by the above 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.

[0159] On the other hand, the aforementioned block copolymer containing carboxyl groups may include a block copolymer containing an A block comprising a structural unit derived from a carboxyl-containing vinyl unsaturated monomer such as (meth)acrylic acid, and a B block comprising a structural unit derived from an alkyl methacrylate. In the block copolymer containing carboxyl groups, the B block comprising a structural unit derived from an alkyl methacrylate may be identical to the block portion comprising a structural unit represented by the structural unit represented by the aforementioned general formula (I) in a block copolymer having the structural unit represented by the aforementioned general formula (III).

[0160] The proportion (moles%) of each structural unit in the copolymer of the dispersant can be determined based on the amount of raw materials added during manufacturing, and can also be measured using analytical instruments such as NMR. Furthermore, the structure of the dispersant can be determined using NMR, various mass analysis methods, etc. Additionally, the dispersant can be decomposed by thermal decomposition as needed, and the resulting 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).

[0161] In this invention, the content of the dispersant can be appropriately selected according to the type of colorant used, and further, the concentration of solid components in the photosensitive coloring resin composition described below. The content of the dispersant relative to the total solid content of the photosensitive coloring resin composition is preferably in the range of 2% to 30% by mass, 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 colorant 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 good.

[0162] [Antioxidants] In terms 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 antioxidant used in this invention is 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, and hydrazine antioxidants. In terms of improving the ability to form fine line patterns, such as in linewidth masking linewidth designs, and in terms of 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 the compound exhibits antioxidant function by removing the protecting group. Preferably, the protecting group is easily removed by heating at 150°C or above. 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 formed by replacing the hydrogen atom of the phenolic hydroxyl group of hindered phenolic antioxidants with a tert-butoxycarbonyl urethane protecting group are suitable examples.

[0163] Examples of hindered phenolic antioxidants include: pentaerythritol tetra[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)trimethylbenzyl (trade name: Irganox 1330, manufactured by BASF), 2,2'-methylenebis(6-tert-butyl-4-methylphenol) (trade name: Sumilizer MDP-S, manufactured by Sumitomo Chemical), and 6,6'-thiobis(2-tert-butyl-4-methylphenol) (trade name: Irganox). Among these, pentaerythritol tetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (trade name: Irgamod 195, manufactured by BASF) is preferred in terms of heat resistance and lightfastness.

[0164] The content of the antioxidant relative to the total solid content of the photosensitive coloring resin composition 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. If it is above the lower limit of the above, it is excellent in terms of improving heat resistance and brightness. On the other hand, if it is below the upper limit of the above, the coloring resin composition of the present invention can be made into a highly sensitive photosensitive resin composition.

[0165] [Thiols] In terms of improving the inhibition effect of film thickness change before and after development by means of a finer linewidth, the photosensitive coloring resin composition of the present invention preferably contains a thiol compound. Thiol compounds exhibit excellent surface hardening properties due to the fact that the enthiol reaction is not inhibited by oxygen-induced polymerization, thus improving the residual film yield in development. Thiol compounds also have the effect of coarsening linewidth, but by combining them with ultraviolet absorbers, a synergistic effect of achieving both finer linewidth and improved residual film yield in development can be achieved. Examples of thiol compounds include monofunctional thiol compounds with one thiol group and polyfunctional thiol compounds with two or more thiol groups. In terms of improving the suppression of film thickness variation before and after development by using 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, pentaerythritol tetra(3-mercaptobutyrate) is preferred in terms of improving the inhibition effect of film thickness change before and after development by means of finer linewidth. 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, 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, it is easy to produce the photocurable red resin composition of the present invention with good developability and suppressed linewidth shift.

[0166] [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, etc. Specific examples of surfactants and plasticizers include those described in Japanese Patent Application Publication No. 2013-029832.

[0167] <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 colorant, alkali-soluble resin, photopolymerizable compound, photoinitiator, ultraviolet absorber, solvent, and dispersant or various additives as needed using a known mixing method. Examples of methods for preparing the resin composition include: (1) preparing a color material dispersion by first adding a color material and a dispersant to a solvent, and then mixing an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, an ultraviolet absorber, and various additives as needed in the dispersion; (2) simultaneously adding and mixing a color material, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, an ultraviolet absorber, and various additives as needed to a solvent; (3) adding and mixing an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, an ultraviolet absorber, and a dispersant as needed, or various additives, to a solvent, and then adding the color material to disperse it; (4) preparing a color material dispersion by adding a color material, a dispersant, and an alkali-soluble resin to a solvent, and then further adding and mixing an alkali-soluble resin, a solvent, a photopolymerizable compound, a photoinitiator, an ultraviolet absorber, and various additives as needed to the dispersion; etc. Of these methods, the methods described in (1) and (4) above are preferred in terms of effectively preventing the aggregation of the color material and dispersing it evenly.

[0168] The method for preparing the color material dispersion 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 paint conditioners, continuous disc bead mills, and continuous annular bead mills. For optimal dispersion conditions in bead mills, the bead diameter used is preferably 0.03 mm to 2.00 mm, and more preferably 0.10 mm to 1.0 mm.

[0169] [use] The photosensitive coloring resin composition of the present invention is a lake coloring material containing triarylmethane dyes and can form a colored layer that improves brightness and suppresses film thickness changes before and after development by means of finer linewidth. Therefore, it can be suitable for use as a color filter.

[0170] [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, for example, be the same as the method used in forming the colored layer of the color filter of the present invention described below. Furthermore, the hardened material of the present invention is a lake color material containing triarylmethane dyes, which improves brightness and suppresses film thickness changes before and after development by means of finer linewidth, and can be suitable as a color layer for color filters.

[0171] III. Color Filters The color filter of the present invention comprises at least a substrate and a color layer disposed on the substrate, wherein at least one of the color layers is a cured form of the photosensitive coloring resin composition of the present invention.

[0172] 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.

[0173] [Shading layer] The color filter of the present invention uses at least one of the coloring layers as the curing layer 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 described 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 can be 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 1~5 μm.

[0174] The colored layer can be formed, for example, by the following method. First, the photosensitive coloring resin composition of the present invention described above is coated onto the substrate described below using coating methods such as spraying, dip coating, rod coating, roller coating, spin coating, and die coating to form a wet coating film. Among these methods, spin coating and die coating can be used appropriately. Next, after the wet coating is dried using a heating plate or oven, it is exposed to light through a mask with a specified 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 can be adjusted appropriately according to the light source used or the thickness of the coating. Furthermore, after exposure, a heat treatment can be performed to promote the polymerization reaction. The heating conditions can be appropriately selected according to the mixing ratio of the components in the photosensitive coloring resin composition used or the thickness of the coating film.

[0175] 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 alkali solution. Furthermore, conventional methods can be used for development. After development, the coating is typically washed with the developer and dried to form a hardened film of the photosensitive coloring resin composition. Furthermore, after development, a heat treatment may be performed to ensure sufficient hardening of the coating. There are no particular limitations on the heating conditions; they can be appropriately selected based on the intended use of the coating.

[0176] [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 the light-shielding portion in a conventional color filter. The shape of the pattern in this light-shielding part is not particularly limited; for example, it can be a striped or matrix-like shape. The light-shielding part can be a thin film of metal such as chromium obtained by 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 a photosensitive resist by development, patterning using inkjet ink containing light-shielding particles, and heat transfer of the photosensitive resist.

[0177] The thickness of the light-shielding portion is set to approximately 0.2 to 0.4 μm in the case of a metal thin film, and approximately 0.5 to 2 μm in the case of a film formed to disperse or dissolve black pigment in an adhesive resin.

[0178] [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 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. The transparent substrate commonly used in color filters can be used. Specifically, examples include: rigid transparent materials that are not flexible, such as quartz glass, alkali-free glass, and synthetic quartz plates, or flexible transparent materials that are flexible, such as transparent resin films, optical resin plates, and flexible glass. The thickness of the transparent substrate is not particularly limited, and can be, for example, around 100 μm to 1 mm, depending on the application of the color filter according to the present invention. Furthermore, in addition to the aforementioned substrate, light-shielding portion and coloring layer, the color filter of the present invention may also be, for example, an outer coating layer or a transparent electrode layer, and may be formed with an alignment film or columnar spacers.

[0179] 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.

[0180] Liquid crystal display device As a liquid crystal display device of the present invention, an example may be a liquid crystal display device having the color filter, the opposing substrate, and the liquid crystal layer formed between the color filter and the opposing substrate as described above. The liquid crystal display device of the present invention will be described with reference to the 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 including a TFT array substrate, 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.

[0181] The driving method for the liquid crystal display device of the present invention is not particularly limited, and a driving method commonly used in liquid crystal display devices can be adopted. Examples of such driving methods include: TN (Twisted Nematic), IPS (In-Plane Switching), OCB (optically compensated bend), 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.

[0182] As a method for forming the liquid crystal layer, methods commonly used in the fabrication of liquid crystal cells can be used, such as vacuum injection or liquid crystal droplet application. After forming the liquid crystal layer by the above method, the liquid crystal cell is slowly cooled to room temperature, thereby allowing the encapsulated liquid crystal to align.

[0183] Organic light-emitting display device As an organic light-emitting display device of the present invention, an organic light-emitting display device having the color filter and organic light-emitting body described above can be cited as an example. The organic light-emitting display device of the present invention will be described with reference to the figures. Figure 3 is a schematic diagram showing an example of the organic light-emitting display device of the present invention. As illustrated in Figure 3, 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 be provided between the color filter 10 and the organic light emitter 80.

[0184] 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 an OLED 80 formed on another substrate onto 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, and 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, for example, to a passively driven OLED display or an actively driven OLED display. 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

[0185] The present invention will be specifically described below with reference to embodiments. These descriptions are not intended to limit the scope of the invention. The mass-average molecular weight (Mw) of the copolymer before salt formation can be determined by GPC (gel permeation chromatography) in the form of a standard polystyrene equivalent, according to the determination method described in the specification of this invention above.

[0186] [Solubility test of UV absorber in PGMEA] The solubility test of the UV absorber in PGMEA was conducted by measuring 0.5 g of each UV absorber at 25°C and adding it to 9.5 g of PGMEA. After stirring for 1 hour, the mixture was visually evaluated. 〇: No dissolved residue ×: Residual dissolution remains.

[0187] [Determination of transmittance of ultraviolet absorbers at a wavelength of 365 nm] The transmittance of the ultraviolet absorber at a wavelength of 365 nm was determined by preparing a 0.002% by mass propylene glycol monomethyl ether acetate solution of each ultraviolet absorber and measuring the 0.002% by mass propylene glycol monomethyl ether acetate solution using an ultraviolet-visible-near-infrared spectrophotometer (e.g., the V-7100 from Japan Spectrophotometer Co., Ltd.). The results of the transmittance measurement of the ultraviolet absorber at a wavelength of 365 nm are shown in Table 1.

[0188] [Table 1] Table 1. UV absorber PGMEA solubility 365 nm transmittance UV absorber U1 〇 38.8% UV absorber U2 〇 77.9% UV absorber U3 〇 14.9% UV absorber U4 〇 16.0% UV absorber U5 〇 29.4% UV absorber U6 〇 34.5% UV absorber U7 〇 65.8% UV absorber U8 〇 46.9% UV absorber U9 〇 30.2% UV absorber U10 〇 16.5% UV absorber U11 〇 39.1% UV absorber (U1): Kemisorb71, manufactured by Chemipro Kasei Ultraviolet absorber (U2): Kemisorb12, manufactured by Chemipro Kasei UV absorber (U3): Kemisorb111, manufactured by Chemipro Kasei UV absorber (U4): Kemisorb73, manufactured by Chemipro Kasei UV absorber (U5): Tinuvin PS, manufactured by BASF UV absorber (U6): Tinuvin 928, manufactured by BASF UV absorber (U7): Tinuvin 405, manufactured by BASF UV absorber (U8): Tinuvin 479, manufactured by BASF UV absorber (U9): Tinuvin 329, manufactured by BASF UV absorber (U10): Tinuvin 477, manufactured by BASF UV absorber (U11): RUVA-93, manufactured by Otsuka Chemical.

[0189] (Synthesis Example 1: Synthesis of Lake Colorant 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%). Based on the following analytical results, the obtained compound was confirmed to be the target compound. MS(ESI) (m / z): 677(+), divalent • Elemental analysis values: Measured values ​​of CHN (Carbon-Hydrogen-Nitrogen) (81.81%, 7.31%, 5.85%); Theoretical values ​​(81.77%, 7.36%, 5.90%)

[0190] [Chemistry 13]

[0191] (2) Synthesis of lake pigment 1 2.59 g (0.76 mmol) of 12-tungsten phosphate-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 off 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%). Based on the following analytical results, the obtained compound was confirmed to be the target compound. ·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%)

[0192] [Chemistry 14]

[0193] (Synthesis Example 2: Synthesis of Lake Pigment 2) (1) Preparation of K 6 (P 2MoW 17O 62) 44.0 g of NaWO₄·2H₂O (manufactured by Wako Pure Chemical Industries) and 1.90 g of Na₂MoO₄·2H₂O (manufactured by Kanto Chemical) were dissolved in 230 g of purified water. 64.9 g of 85% phosphoric acid was added to the solution while stirring using a dropping funnel. 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. After stirring for another hour, the precipitate was filtered off. The obtained solid was dried at 90°C to obtain 29.4 g of K₆ (P₂MoW₁₇O₆₂). (2) Synthesis of lake pigment 2 5.30 g of Basic Blue 7 (BB7) (manufactured by Tokyo Kasei Corporation) was dissolved in 350 ml of purified water and stirred at 40°C to prepare a BB7 solution. Separately, 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 raised to 80°C and stirred for another 1 hour to achieve lake coloring. 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 material 2 with an average primary particle size of 40 nm as a triarylmethane dye and polyacid lake material, in the form of a blackish-blue solid.

[0194] (Synthesis Example 3: Synthesis of acidic dispersant A1 (a polymer having at least one of the structural units selected from the structural units represented by 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 flow while being heated to 90°C. After 1.5 hours, 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, and the reaction was further carried out for 3 hours. Subsequently, the nitrogen flow was stopped, and the reaction solution was cooled to 80°C. 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 showed a mass-average molecular weight (Mw) of 4010, a number-average molecular weight (Mn) of 1910, and a molecular weight distribution (Mw / Mn) of 2.10.

[0195] (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 stirred under a nitrogen flow while the temperature was raised to 90°C. After 1.5 hours, a mixed solution of the above-mentioned macromonomer MM-1 solution (33.33 parts by weight of solids), 16.67 parts by weight of glycidyl methacrylate (GMA), 1.24 parts by weight of n-dodecyl mercaptan, 25.0 parts by weight of PGMEA, and 0.5 parts by weight of AIBN was added dropwise. 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 further 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 determined by GPC to have a mass average molecular weight (Mw) of 10570, a number average molecular weight (Mn) of 4370, and a molecular weight distribution (Mw / Mn) of 2.42.

[0196] (3) Manufacturing of a polymer (acidic dispersant A1) having at least one of the structural units selected from those represented by 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 while the temperature was raised 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 structural units represented by the above general formula (I). The esterification reaction of GMA and PPA of the obtained acidic dispersant A1 was confirmed by acid value determination and 1H-NMR determination (the disappearance of the peak originating from the epoxy group was confirmed). The acid value of the obtained acidic dispersant A1 was 98 mgKOH / g.

[0197] (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 of International Publication No. 2016 / 132863, a triblock copolymer comprising 20 parts by weight of methyl methacrylate (MMA), 40 parts by weight of n-butyl methacrylate (BMA), 20 parts by weight of methacrylic acid (MAA), 20 parts by weight of BMA, and 20 parts by weight of MMA and 40 parts by weight of BMA was synthesized. 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.

[0198] (Synthesis Example 5: Synthesis of a Potential Antioxidant) 0.01 mol of the phenolic compound represented by chemical formula (c) below, 0.05 mol of dibutyl dicarbonate, and 30 g of pyridine were mixed. 0.025 mol of 4-dimethylaminopyridine was added under nitrogen atmosphere and at room temperature, and the mixture was stirred at 60°C for 3 hours. 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 resulting white powdery crystals were dried under reduced pressure at 60°C for 3 hours to obtain a potential antioxidant (compound A). Furthermore, the structure of the obtained potential antioxidant was confirmed by IR and NMR.

[0199] [Chemistry 15]

[0200] (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, as described in Example 1 of Japanese Patent Application Publication No. 2011-133844, (toluenesulfonyl)trifluoromethanesulfonylimine triethylamine salt was synthesized. Subsequently, 5 g of Basic Blue CI 7 (N-[4-[[4-(diethylamino)phenyl][4-(ethylamino)-1-naphthyl]methylene]-2,5-cyclohexadiene-1-ylidene]-N-ethylethaneammonium-chloride) (manufactured by Tokyo Kasei) was dissolved in 30 mL of methanol. While stirring, 3.93 g of (toluenesulfonyl)trifluoromethanesulfonylimine 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, 100 mL of water was added, and the precipitate was filtered off and washed with water. The filter cake was dried under reduced pressure to obtain triarylmethane dye 1.

[0201] (Preparation Example 1: Preparation of Alkali-Soluble Resin P1) 300 parts by weight of PGMEA were added to the polymerization tank, and the temperature was raised to 100°C under nitrogen atmosphere. Then, over 1.5 hours, 67.6 parts by weight of benzyl methacrylate (BzMA), 67.6 parts by weight of MMA, 36.4 parts by weight of methacrylic acid (MAA), 3 parts by weight of PERBUTYL O (Nippon Oil Manufacturing Co., Ltd.), and 9 parts by weight of chain transfer agent (n-dodecyl mercaptan) were added dropwise. The reaction was then maintained 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. Subsequently, while blowing in air, 28.4 parts by mass of glycidyl methacrylate (GMA), a compound containing epoxy groups, were added. After heating to 110°C, 0.8 parts by mass of triethylamine were added, and the addition reaction was carried out at 110°C for 15 hours to obtain an alkali-soluble resin P1 solution (weight average molecular weight (Mw) 9000, 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 the 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.

[0202] (Example 1: Preparation of photosensitive coloring resin composition 1) (1) Preparation of color material dispersion 1 61 parts by weight of PGMEA, 5 parts by weight of the alkali-soluble resin P1 solution (40% by weight of solids) from Preparation Example 1, and 24 parts by weight of the acidic dispersant A1 solution (25.0% by weight of solids) from Synthesis Example 3 were added to a 225 mL mayonnaise bottle and stirred. Ten parts by mass of the triarylmethane-based lake pigment 1 of Synthesis Example 1 and 100 parts by mass of zirconia beads with a particle size of 2.0 mm were added to the mixture. The mixture was shaken for 1 hour using a paint shaker (manufactured by Asada Iron Works Co., Ltd.) as a pre-disintegration. Then, 200 parts of zirconia beads with a particle size of 0.1 mm were added and dispersed for 4 hours using a paint shaker as a formal disintegration, thus obtaining pigment dispersion 1.

[0203] (2) Preparation of photosensitive adhesive component B1 The following were added: 26.5 parts by weight of the alkali-soluble resin P1 solution (solid content 40% by mass) obtained in Preparation Example 1; 17.7 parts by weight of the photopolymerizable compound (trade name ARONIX M-403, pentaerythritol pentaacrylate and pentaerythritol hexaacrylate, manufactured by Toa Synthetic); 7.06 parts by weight of the photopolymerizable compound (trade name ARONIX M-305, pentaerythritol triacrylate and pentaerythritol tetraacrylate, manufactured by Toa Synthetic); 1.96 parts by weight of photoinitiator 1 (I1): Irgacure 907 (manufactured by BASF, α-aminoacetophenone-based photoinitiator); 1.96 parts by weight of photoinitiator 2 (I2): OXE-02 (manufactured by BASF, oxime ester-based photoinitiator with a carbazole skeleton); and ultraviolet absorber (ultraviolet absorber 1 (U1): Kemisorb 71, Chemipro). The photosensitive adhesive component B1 is obtained by combining 0.392 parts by weight of Kasei-manufactured, 0.392 parts by weight of IRGANOX1010 (manufactured by BASF) as an antioxidant, and 44.1 parts by weight of PGMEA. (3) Preparation of photosensitive coloring resin composition 1 The photosensitive coloring resin composition of Example 1 was prepared by mixing 3.44 parts by weight of the above-obtained color material dispersion 1, 3.50 parts by weight of the photosensitive adhesive component B1, and 3.06 parts by weight of PGMEA.

[0204] (Examples 2-27: Manufacturing of photosensitive coloring resin compositions 2-27) In Example 1, each photosensitive adhesive component B2 to B27 was prepared and used as shown in Table 2, in place of photosensitive adhesive component B1. Otherwise, photosensitive coloring resin compositions 2 to 27 were obtained in the same manner as photosensitive coloring resin composition 1 in Example 1.

[0205] (Example 28: Manufacturing of photosensitive coloring resin composition 28) In Example 2, the colorant in the colorant dispersion 1 was changed from the triarylmethane-based lake colorant 1 of Synthesis Example 1 to the triarylmethane-based lake colorant 2 of Synthesis Example 2. Otherwise, the photosensitive coloring resin composition 28 was obtained in the same manner as in Example 2.

[0206] (Comparative Examples 1-5: Manufacturing of Comparative Photosensitive Coloring Resin Compositions 1-5) In Example 1, each photosensitive adhesive component CB1 to CB5 was prepared and used as shown in Table 3, replacing photosensitive adhesive component B1. Otherwise, comparative photosensitive coloring resin compositions 1 to 5 were obtained in the same manner as photosensitive coloring resin composition 1 in Example 1.

[0207] (Comparative Examples 6-8: Comparative manufacturing of photosensitive coloring resin compositions 6-8) (1) Preparation of color material dispersion C1 65 parts by weight of PGMEA, 15 parts by weight of the alkali-soluble resin P1 solution (40% by weight of solids) of Preparation Example 1, and 10 parts by weight of the PGMEA solution (20.0% by weight of acidic dispersant A2) of Synthesis Example 4 were added to a 225 mL mayonnaise bottle and stirred. 8.8 parts by weight of PB15:6, 1.2 parts by weight of PV23, and 100 parts by weight of zirconia beads with a particle size of 2.0 mm were added to the mixture. The mixture was shaken for 1 hour using a paint shaker (manufactured by Asada Iron Works Co., Ltd.) as a pre-crushing process. Then, 200 parts of zirconia beads with a particle size of 0.1 mm were added and dispersed for 4 hours using a paint shaker as a formal crushing process, thus obtaining the color material dispersion C1. (2) Comparison of the preparation of photosensitive coloring resin compositions 6-8 In Example 1, photosensitive adhesive components CB6 to CB8 were prepared in place of photosensitive adhesive component B1 as shown in Table 3. 2.56 parts by weight of colorant dispersion C1, 3.58 parts by weight of photosensitive adhesive component, and 3.85 parts by weight of PGMEA were mixed to obtain comparative photosensitive coloring resin compositions 6-8.

[0208] (Comparative Examples 9-11: Manufacturing of Comparative Photosensitive Coloring Resin Compositions 9-11) In Example 1, photosensitive adhesive components CB9~CB11 were prepared in place of photosensitive adhesive component B1 as shown in Table 3. 0.333 parts by weight of dye (triarylmethane dye 1 of Comparative Synthesis Example 1), 4.17 parts by weight of photosensitive adhesive component, and 5.50 parts by weight of PGME were mixed to obtain comparative photosensitive coloring resin compositions 9-11.

[0209] [Evaluation Method] Using a spin coater, 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, "NA35") with a film thickness of 2.2 μm after baking. The substrates were then heated and dried at 80°C for 3 minutes. Subsequently, a photomask with 40 μm lines was formed, and the substrate was irradiated with 60 mJ / cm² ultraviolet light using an ultra-high pressure mercury lamp. Then, a 0.05% (w / w) potassium hydroxide aqueous solution was used as an alkaline developer, and the substrate was sprayed and developed for 60 seconds. Afterward, the substrate was baked in a clean oven at 230°C for 30 minutes, thereby creating a patterned substrate with a colored layer formed on the glass substrate using a 40 μm line pattern.

[0210] <Suppressing Linewidth Increase in Shading Layers> The width of the fine line pattern of the colored layer in the portion of the chromium mask used during exposure, which is equivalent to an opening width of 40 μm, was measured at 5 locations using an optical microscope. The line width offset was evaluated based on the difference between the average line width and the target line width. (Increased linewidth suppresses evaluation criteria) AA: The difference relative to the target linewidth is within 5.0 μm; A: The difference relative to the target linewidth is greater than 5.0 μm but less than 7.0 μm; B: The difference relative to the target linewidth exceeds 7.0 μm but is within 10.0 μm; C: The difference relative to the target linewidth exceeds 10.0 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.

[0211] <Evaluation of Residual Film Rate> After baking, the film thickness was 2.2 μm. Using a spin coater, 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, "NA35"), and then dried at 80°C for 3 minutes using a heating plate. Subsequently, without a photomask, the substrate was irradiated with 60 mJ / cm² ultraviolet light using an ultra-high pressure mercury lamp. The film thickness T1 of the resist coating was then measured using a film thickness gauge. Next, the substrate was 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 is above 97% but below 98%; B: The residual film rate is above 94% but below 97%; C: The residual film rate after development did not reach 94%. If the evaluation result is A, the residual film rate is good; if the evaluation result is AA, the residual film rate is excellent.

[0212] <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, "NA35") using a spin coater. Subsequently, the substrate was heated and dried on a hot plate at 80°C for 3 minutes. Without a light shield, it was irradiated with 60 mJ / cm² ultraviolet light using an ultra-high pressure mercury lamp, and then 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. Subsequently, the substrate with the hardened film formed was baked in a clean oven at 230°C for 30 minutes, then cooled for 30 minutes. This process was repeated three times, and the L, a, and b (L1, a1, b1) values ​​of the resulting colored substrate were measured. Based on the measured values, the color difference (ΔEab) before and after the treatment was calculated using the following formula. Color difference (ΔEab) = {(L₁ - L₀)² + (a₁ - a₀)² + (b₁ - b₀)²}¹ / ²

[0213] (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: Brightness (Y) is 9.5 or higher but less than 10.0; C: Brightness (Y) did not reach 9.5. If the evaluation result is A, the brightness is good; if the evaluation result is AA, the brightness is excellent.

[0214] (Heat resistance evaluation criteria) AA: ΔEab did not reach 3.0; A: ΔEab is 3.0 or higher but less than 5.0; B: ΔEab is 5.0 or higher but less than 8.0; C: ΔEab is above 8.0. If the evaluation result is A, the heat resistance is good; if the evaluation result is AA, the heat resistance is excellent.

[0215] [Table 2] Table 2. Adhesive components Photoinitiator UV absorber antioxidants resin P1 M1 M2 M3 M4 Thiols solvent I1 I2 U1 U2 U3 U4 U5 U6 U7 U8 U9 U10 U11 A1 LA1 EO modification B1 1.96 1.96 0.392 0.392 26.5 17.7 7.06 44.1 B2 1.94 1.94 0.388 0.388 0.388 26.2 17.5 6.99 44.3 B3 1.92 1.92 0.769 0.385 0.385 26.0 17.3 6.92 44.4 B4 2.31 2.31 0.769 0.385 0.385 25.4 16.9 6.77 44.8 B5 1.92 1.92 0.769 0.385 0.385 26.0 17.3 6.92 44.4 B6 2.31 2.31 0.769 0.385 0.385 25.4 16.9 6.77 44.8 B7 1.92 1.92 0.769 0.385 0.385 26.0 17.3 6.92 44.4 B8 2.31 2.31 0.769 0.385 0.385 25.4 16.9 6.77 44.8 B9 1.92 1.92 0.769 0.385 0.385 26.0 17.3 6.92 44.4 B10 2.31 2.31 0.769 0.385 0.385 25.4 16.9 6.77 44.8 B11 1.92 1.92 0.769 0.385 0.385 26.0 17.3 6.92 44.4 B12 2.31 2.31 0.769 0.385 0.385 25.4 16.9 6.77 44.8 B13 1.92 1.92 0.769 0.385 0.385 26.0 17.3 6.92 44.4 B14 2.31 2.31 0.769 0.385 0.385 25.4 16.9 6.77 44.8 B15 1.92 1.92 0.769 0.385 0.385 26.0 17.3 6.92 44.4 B16 2.31 2.31 0.769 0.385 0.385 25.4 16.9 6.77 44.8 B17 1.92 1.92 0.769 0.385 0.385 26.0 17.3 6.92 44.4 B18 2.31 2.31 0.769 0.385 0.385 25.4 16.9 6.77 44.8 B19 1.92 1.92 0.769 0.385 0.385 26.0 17.3 6.92 44.4 B20 2.31 2.31 0.769 0.385 0.385 25.4 16.9 6.77 44.8 B21 1.92 1.92 0.769 0.385 0.385 26.0 17.3 6.92 44.4 B22 2.31 2.31 0.769 0.385 0.385 25.4 16.9 6.77 44.8 B23 1.92 1.92 0.769 0.385 0.385 26.0 17.3 6.92 44.4 B24 2.31 2.31 0.769 0.385 0.385 25.4 16.9 6.77 44.8 B25 2.31 2.31 0.769 0.385 0.385 25.4 16.9 6.77 44.8 B26 2.31 2.31 0.769 0.385 0.385 25.4 16.9 6.77 44.8 B27 1.91 1.91 0.762 0.381 0.381 25.7 17.1 6.86 0.381 44.6

[0216] [Table 3] Table 3. Adhesive components Photoinitiator UV absorber antioxidants resin P1 M1 M2 M3 M4 Thiols solvent I1 I2 U1 U2 U3 U4 U5 U6 U7 U8 U9 U10 U11 A1 LA1 EO modification CB1 1.96 1.96 0.392 0.392 26.5 17.7 7.06 44.1 CB2 1.57 1.57 0.392 0.392 27.1 18.0 7.22 43.8 CB3 1.18 1.18 0.392 0.392 27.7 18.4 7.37 43.4 CB4 1.96 1.96 0.784 26.5 17.7 7.06 44.1 CB5 1.92 1.92 1,538 26.0 17.3 6.92 44.4 CB6 2.00 2.00 27.0 18.0 7.20 43.8 CB7 3.60 3.60 24.6 16.4 6.56 45.2 CB8 3.53 3.53 0.784 24.1 16.1 6.43 45.5 CB9 1.98 1.98 0.396 26.4 17.8 7.13 44.3 CB10 3.96 3.96 0.396 23.8 15.8 6.34 45.7 CB11 3.92 3.92 0.392 0.392 23.5 15.7 6.27 45.9

[0217] In the table, the abbreviations are as follows. Photoinitiator 1 (I1): Irgacure 907, manufactured by BASF, an α-aminoacetophenone-based photoinitiator. Photoinitiator 2 (I2): OXE-02, manufactured by BASF, is an oxime ester photoinitiator with a carbazole backbone. UV absorber (U1): Kemisorb71, manufactured by Chemipro Kasei Ultraviolet absorber (U2): Kemisorb12, manufactured by Chemipro Kasei UV absorber (U3): Kemisorb111, manufactured by Chemipro Kasei UV absorber (U4): Kemisorb73, manufactured by Chemipro Kasei UV absorber (U5): Tinuvin PS, manufactured by BASF UV absorber (U6): Tinuvin 928, manufactured by BASF UV absorber (U7): Tinuvin 405, manufactured by BASF UV absorber (U8): Tinuvin 479, manufactured by BASF UV absorber (U9): Tinuvin 329, manufactured by BASF UV absorber (U10): Tinuvin 477, manufactured by BASF UV absorber (U11): RUVA-93, manufactured by Otsuka Chemical. Antioxidant (A1): IRGANOX 1010, manufactured by BASF Potential antioxidant (LA1): Potential antioxidant in Synthesis Example 5 Resin P1: Preparation of Alkali-Soluble Resin P1 from Example 1 M1: Photopolymerizable compound, ARONIX M-403, dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, manufactured by Dong-A Synthetic. M2: Photopolymerizable compound, ARONIX M-305, pentaerythritol triacrylate and pentaerythritol tetraacrylate, manufactured by Dong-A Synthetic. M3: Photopolymerizable compound, ARONIX M-460, diglycerol ethylene oxide modified acrylate, manufactured by Dong-A Synthetic. M4: Photopolymerizable compound, Kayarad DPEA-12, ethylene oxide modified (12) dipentaerythritol hexaacrylate, Nippon Kayaku Manufacturing Co., Ltd. Thiols: Karenz MT PE1, manufactured by Showa Denko

[0218] [Table 4] Table 4. Percentage of the adhesive component [weight %] color material Adhesive components Photoinitiator UV absorber antioxidants EO modified / thiol Line width offset Residual film rate brightness Heat resistance color difference ΔEab U1 U2 U3 U4 U5 U6 U7 U8 U9 U10 U11 A1 LA1 determination determination determination determination Example 1 L1 B1 10 1 1 4.8 AA 97.4 A 10.4 A 3.3 A Example 2 L1 B2 10 1 1 1 4.7 AA 97.4 A 10.7 AA 2.7 AA Example 3 L1 B3 10 2 1 1 3.3 AA 97.3 A 10.7 AA 2.3 AA Example 4 L1 B4 12 2 1 1 3.7 AA 98.3 AA 10.7 AA 2.4 AA Example 5 L1 B5 10 2 1 1 4.2 AA 97.4 A 10.6 AA 2.8 AA Example 6 L1 B6 12 2 1 1 4.8 AA 98.5 AA 10.6 AA 2.6 AA Example 7 L1 B7 10 2 1 1 2.9 AA 97.5 A 10.7 AA 2.6 AA Example 8 L1 B8 12 2 1 1 3.3 AA 98.4 AA 10.6 AA 2.5 AA Example 9 L1 B9 10 2 1 1 3.5 AA 97.2 A 10.6 AA 2.6 AA Actual example 10 L1 B10 12 2 1 1 3.9 AA 98.1 AA 10.6 AA 2.5 AA Actual example 11 L1 B11 10 2 1 1 3.5 AA 97.3 A 10.6 AA 2.5 AA Example 12 L1 B12 12 2 1 1 3.9 AA 98.4 AA 10.6 AA 2.6 AA Example 13 L1 B13 10 2 1 1 2.7 AA 97.2 A 10.7 AA 2.7 AA Example 14 L1 B14 12 2 1 1 3.4 AA 98.1 AA 10.7 AA 2.6. AA Example 15 L1 B15 10 2 1 1 4.1 AA 97.0 A 10.6 AA 2.5 AA Example 16 L1 B16 12 2 1 1 4.4 AA 98.0 AA 10.6 AA 2.5 AA Example 17 L1 B17 10 2 1 1 4.2 AA 97.3 A 10.6 AA 2.5 AA Example 18 L1 B18 12 2 1 1 4.7 AA 98.4 AA 10.6 AA 2.6 AA Actual example 19 L1 B19 10 2 1 1 3.0 AA 97.5 A 10.7 AA 2.6 AA Actual example 20 L1 B20 12 2 1 1 3.7 AA 98.7 AA 10.7 AA 2.5 AA Example 21 L1 B21 10 2 1 1 3.3 AA 97.7 A 10.6 AA 2.7 AA Example 22 L1 B22 12 2 1 1 3.9 AA 98.7 AA 10.6 AA 2.6 AA Example 23 L1 B23 10 2 1 1 3.5 AA 97.5 A 10.7 AA 2.8 AA Example 24 L1 B24 12 2 1 1 3.9 AA 98.4 AA 10.7 AA 2.7 AA Example 25 L1 B25 12 2 1 1 M3 2.4 AA 98.0 AA 10.6 AA 2.7 AA Example 26 L1 B26 12 2 1 1 M4 2.7 AA 98.2 AA 10.6 AA 2.7 AA Example 27 L1 B27 10 2 1 1 Thiols 4.1 AA 98.1 AA 10.7 AA 2.5 AA Example 28 L2 B2 10 1 1 1 5.4 A 97.3 A 10.2 A 3.2 A

[0219] [Table 5] Table 5. Percentage of the adhesive component [weight %] color material Adhesive components Photoinitiator UV absorber antioxidants EO modified / thiol Line width offset Residual film rate brightness Heat resistance color difference ΔEab U1 U2 U3 U4 U5 U6 U7 U8 U9 U10 U11 A1 LA1 determination determination determination determination Comparative Example 1 L1 BC1 10 1 1 7.8 B 97.5 A 10.7 AA 2.7 AA Comparative Example 2 L1 BC2 8 1 1 6.9 A 95.4 B 10.7 AA 2.8 AA Comparative Example 3 L1 BC3 6 1 1 6.3 A 93.9 C 10.6 AA 3.0 AA Comparative Example 4 L1 BC4 10 2 6.1 A 95.9 B 10.5 A 2.6 AA Comparative Example 5 L1 BC5 10 4 5.4 A 93.1 C 10.5 A 2.7 AA Comparative Example 6 pigment BC6 10 1.2 AA 93.5 C 9.3 C 1.0 AA Comparative Example 7 pigment BC7 18 4.8 AA 99.5 AA 9.2 C 0.5 AA Comparative Example 8 pigment BC8 18 2 3.8 AA 99.3 AA 9.4 C 0.6 AA Comparative Example 9 dye BC9 10 1 0.3 AA 91.4 C 8.9 C 15.9 C Comparative Example 10 dye BC10 20 1 4.7 AA 98.2 AA 9.3 C 14.3 C Comparative Example 11 dye BC11 20 1 1 4.3 AA 97.5 A 9.6 B 14.2 C

[0220] Furthermore, the values ​​for photoinitiator, ultraviolet absorber, antioxidant, and thiol are the solids content ratios. L1 (Lake Colorant 1): Lake Colorant 1 of Triarylmethane Dyes in Synthesis Example 1 L2 (Lake Colorant 2): Lake Colorant 2 of Triarylmethane Dye Synthesis Example 2 Pigments: PB15:6 (CI Pigment Blue 15:6) and PV23 (CI Pigment Violet 23) Dyes: Comparative Synthesis Example 1 - Triarylmethane Dyes

[0221] [Results Summary] The photosensitive coloring resin compositions of Examples 1-28, which combine triarylmethane-based dye lake pigments with ultraviolet absorbers, can form a colored layer that improves brightness and suppresses film thickness changes before and after development by using finer linewidths. Furthermore, in the embodiments, if the lake pigment of the triarylmethane dye is used in combination with the ultraviolet absorber, the linewidth offset can be adjusted to a target value of less than 5 μm by using the initial dose while maintaining the residual film rate. Furthermore, in the embodiments, if an ultraviolet absorber with a transmittance of less than 40% at a wavelength of 365 nm is used in a 0.002% by mass propylene glycol monomethyl ether acetate solution, it is less likely to increase the linewidth offset. Furthermore, in the embodiments, when the product contains a photopolymerizable compound comprising an epoxide, it is easy to achieve both a higher residual film yield and a finer linewidth. In contrast, in the photosensitive coloring resin composition of Comparative Example 1, which does not contain ultraviolet absorbers, even though it contains antioxidants and potential antioxidants in the same way as in the examples, the line width offset is larger and the line width is thicker, making it impossible to form a colored layer with the required finer line width. In the photosensitive coloring resin composition of Comparative Example 1, which does not contain ultraviolet absorbers, and in the photosensitive coloring resin compositions of Comparative Examples 2 and 3, which reduced the photoinitiation dose in order to make the linewidth thinner, although the linewidth offset was reduced to some extent, the residual film rate deteriorated. In the photosensitive coloring resin composition of Comparative Example 1, which does not contain ultraviolet absorbers, and in the photosensitive coloring resin compositions of Comparative Examples 4 and 5, where the antioxidant dosage was increased to make the linewidth thinner, although the linewidth offset was reduced, the residual film yield deteriorated. On the other hand, in the photosensitive coloring resin compositions of Comparative Examples 6 to 8, which use pigments instead of lake materials with triarylmethane dyes, a large amount of photoinitiation dose is required in order to achieve the same linewidth offset as in the examples using lake materials with triarylmethane dyes. In this case, the residual film rate is not a problem, but the brightness is low. Furthermore, in the photosensitive coloring resin compositions of Comparative Examples 9 to 11, which use triarylmethane dyes instead of lake pigments, a large amount of photoinitiation dose is required in order to achieve the same linewidth offset as in the examples using lake pigments with triarylmethane dyes. In this case, the residual film rate after development is not a problem, but the color difference increases and the brightness decreases after heating.

[0222] 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, an ultraviolet absorber, and a solvent, wherein the colorant comprises a triarylmethane dye and a lake colorant of a polyacid, wherein the polyacid contains one or more elements selected from tungsten and molybdenum, and further, the photosensitive coloring resin composition comprises an acidic dispersant selected from at least one polymer having a structural unit represented by general formula (I) and a block copolymer, wherein the block copolymer comprises an A block containing a structural unit derived from an ethylene unsaturated monomer containing a carboxyl group and a B block containing a structural unit derived from an alkyl methacrylate, [Chemical 1] (In general formula (I), L11 is a direct bond or a divalent linker, R11 is a hydrogen atom or a methyl group, R12 is a hydroxyl group, a hydrocarbon group, -[CH(R13)-CH(R14)-O]x1-R15, -[(CH2)y1-O]z1-R15, or -O-R16, which represents a monovalent group, and R16 is a hydrocarbon group, -[CH(R13)-CH(R14)-O]x1-R15, -[(CH2)y1-O]z1-R15, -C(R17)(R18)-C(R19)(R20)-OH, or -CH2-C(R21)(R22)-CH2-OH, which represents a monovalent group; R13 and R14 are each independently a hydrogen atom or a methyl group; R15 is a hydrogen atom, a hydrocarbon group, or a valence group represented by -CHO, -CH2CHO, -CO-CH=CH2, -CO-C(CH3)=CH2, or -CH2COOR23; R23 is a hydrogen atom or an alkyl group with 1 to 5 carbon atoms; R17, R18, R19, R20, R21, and R22 are each independently a hydrogen atom, a hydrocarbon group, or have bonds selected from ether bonds and ester bonds. One or more hydrocarbon groups, 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, R24 is a hydrocarbon group, or has one or more hydrocarbon groups 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 of 1 to 18, y1 represents an integer of 1 to 5, and z1 represents an integer of 1 to 18.

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

3. The photosensitive coloring resin composition of claim 1 or 2, further comprising a thiol compound.

4. The photosensitive coloring resin composition of claim 1 or 2, wherein the lake pigment of the above-mentioned triarylmethane dye contains the pigment represented by the following general formula (1), [Chemical 2] (In general formula (1), A is an organic group with an a valence of α that does not have a π bond to the carbon atom directly bonded to N, the organic group being an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at least at the end directly bonded to N, or an aromatic group having the aliphatic hydrocarbon group, the carbon chain may contain heteroatoms; Bc- represents a polyacid anion with a c valence; 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, Rii and Riii, 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 are multiple Ri to Rvii and Ar1 that may be the same or different. a and c represent integers greater than 2, b and d represent integers greater than 1; f and g represent integers greater than 0 and less than 4; there may be multiple f and g, which may be the same or different.

5. The photosensitive coloring resin composition of claim 1 or 2, wherein the transmittance of the ultraviolet absorber in a 0.002% by mass propylene glycol monomethyl ether acetate solution at a wavelength of 365 nm is less than 40%.

6. The photosensitive coloring resin composition of claim 1 or 2, wherein the photopolymerizable compound comprises a photopolymerizable compound containing an epoxy alkane.

7. A cured product, which is a cured product of the photosensitive coloring resin composition of any one of claims 1 to 6.

8. 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 7.

9. A display device having a color filter as described in claim 8 above.

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