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

Abstract

Provided is a photosensitive colored resin composition comprising a colorant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator and a solvent, in which the colorant comprises a lake colorant comprising a triarylmethane dye, and the alkali-soluble resin comprises an alkali-soluble resin (U) containing a constituent unit having a benzotriazole backbone and having a weight-average molecular weight of 3000 or more.

Description

[Technical Field]

[0001] The present invention relates to a photosensitive colored resin composition, a cured product, a color filter, and a display device. [Background technology]

[0002] In recent years, the demand for liquid crystal displays (LCDs) has increased with the development of personal computers, particularly portable personal computers. The penetration rate of mobile displays (mobile phones, smartphones, and tablet PCs) is also rising, further expanding the LCD market. Organic light-emitting displays, such as OLEDs, which offer high visibility due to their self-illuminating properties, are also attracting attention as next-generation image display devices. These liquid crystal displays and organic light-emitting displays utilize color filters. For example, in liquid crystal displays, a color image is formed when light passing through a color filter is colored according to the color of each pixel constituting the color filter, and these colored lights are combined to form a color image. In this process, white-emitting organic light-emitting elements or white-emitting inorganic light-emitting elements may be used as light sources. Organic light-emitting displays use color filters for color adjustment and other purposes.

[0003] Here, a color filter generally comprises a substrate, a colored layer formed on the substrate consisting of colored patterns of the three primary colors red, green, and blue, and light-shielding portions formed on the substrate to demarcate each colored pattern. One method for forming the colored layer in a color filter involves, for example, adding a binder resin, a photopolymerizable compound, and a photoinitiator to a colorant dispersion liquid, which is made by dispersing colorants with a dispersant, to a colored resin composition. This composition is applied to a glass substrate, dried, exposed using a photomask, and developed to form a colored pattern. The pattern is then fixed by heating to form the colored layer. These steps are repeated for each color to form the color filter.

[0004] In recent years, with increasing demands for higher brightness in color filters, it has become difficult to meet the current demands for even higher brightness using pigment-based color filters. Therefore, in recent years, there has been a growing interest in using dyes, which generally have higher transmittance than pigments, or lake colorants (dyes made insoluble with precipitating agents), as colorants for color filters. However, dyes and lake colorants have poorer heat resistance compared to pigments that have been used as colorants for color filters until now, and there was a problem that the colored layer was prone to fading when heated at high temperatures during the color filter manufacturing process.

[0005] In contrast, Patent Document 1 discloses a colored resin composition for color filters that, while using a lake pigment, can suppress the fading of the colored layer due to high-temperature heating in the color filter manufacturing process and form a high-brightness colored layer. This composition contains a lake pigment, a dispersant, a hindered phenol-based antioxidant, a binder component, and a solvent, wherein the dispersant is a specific polymer in which at least a portion of the nitrogen moiety forms a salt with an acidic organophosphorus compound.

[0006] On the other hand, as a photosensitive colored composition containing an ultraviolet absorber, Patent Document 2 discloses a colored resin composition containing (A) a dye, (B) a solvent, and (C) a binder resin, characterized in that it further contains (D) an antioxidant and (E) an ultraviolet absorber. Patent Document 2 aims to provide a colored resin composition that can form contact holes of a desired diameter while maintaining and improving the brightness and heat resistance of the resulting pixels. Furthermore, Patent Document 3 describes a material comprising a colorant (A), a resin (B), a photopolymerizable monomer (C), a photopolymerization initiator (D) containing an acylphosphine oxide organic compound or an oxime ester organic compound, and an ultraviolet absorber (E) which is at least one selected from the group consisting of benzotriazole organic compounds, triazine organic compounds, and benzophenone organic compounds, wherein the resin (B) is as described in (b1), (b2), and (b3): (b1); Compounds having an alicyclic skeleton and an ethylenically unsaturated bond in one molecule (b2); Compounds having an epoxy group and an ethylenically unsaturated bond in one molecule (b3); A photosensitive coloring composition is disclosed that includes a photosensitive resin (B-1) obtained by copolymerizing a copolymer (b6) with a compound having an ethylenically unsaturated bond other than (a1) and (a2), 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 acid anhydride (b5). Patent Document 3 aims to obtain a photosensitive coloring composition that has high resolution that can be used to improve image quality and reduce power consumption, in particular a photosensitive coloring composition that has high resolution even in thick films such as COA and has excellent adhesion that does not cause pattern peeling.

[0007] Furthermore, Patent Document 4 discloses a colored composition for color filters, characterized by comprising a colorant (A), a resin (B), a photopolymerizable monomer (C), a photopolymerization initiator (D), and an ultraviolet absorber (E) obtained by polymerizing a raw material monomer containing a benzotriazole monomer and other monomer components, wherein the raw material monomer contains 10.0% to 90.0% by mass of the benzotriazole monomer, and the ultraviolet absorber (E) is contained in an amount of 0.5% to 6.0% by weight of the total solid content of the colored composition for color filters. The colored composition for color filters in Patent Document 4 is described as having excellent light resistance and good adhesion due to the inclusion of the ultraviolet absorber (E). [Prior art documents] [Patent Documents]

[0008] [Patent Document 1] Japanese Patent Publication No. 2014-153569 [Patent Document 2] Japanese Patent Publication No. 2015-98537 [Patent Document 3] Patent No. 5664299 [Patent Document 4] Patent No. 6578775 [Overview of the project] [Problems that the invention aims to solve]

[0009] As displays become higher resolution, such as 4K / 8K, pixel sizes are decreasing. To compensate for the decrease in the pixel aperture ratio, there is a need for higher brightness resists, as well as for photosensitive colored resin compositions that can form patterns with narrow line widths. However, when dyes are dissolved and used as in Patent Document 2, the heat resistance is particularly poor and insufficient for improving pixel brightness, and when pigments are used as in Patent Documents 3 and 4, the improvement of pixel brightness is also insufficient. Triarylmethane-based lake colorants are effective colorants for increasing pixel brightness. However, because triarylmethane-based lake colorants have a higher transmittance in the UV wavelength range compared to conventionally used pigments (e.g., CI Pigment Blue 15:6, CI Pigment Violet 23), the pattern line width tends to become thicker when a photoinitiator is added in the same way as before. If the amount of photoinitiator is reduced, or an antioxidant is added as in Patent Document 1, or the amount of antioxidant is increased in order to adjust the pattern line width to a predetermined value, the photocurability of the pattern portion becomes insufficient, the change in film thickness from before to after development becomes large, and the developed film retention rate decreases, making it difficult to achieve both a fine line width design and a high developed film retention rate. Patent Document 1 describes a lake colorant using a triarylmethane dye, but it does not address the challenge of achieving both a fine line width and a high developing film rate. Patent Document 2 describes a photosensitive colored resin composition containing a triarylmethane dye. However, since the dye is dispersed at the molecular level in the photosensitive colored resin composition, it tends to inhibit the curing of the photocurable component, and if a photoinitiator is added as with pigments, the photocurability becomes insufficient, the line width tends to be finer than designed, and the developing film rate tends to decrease. Therefore, in a photosensitive colored resin composition containing a dye, it is necessary to add more photoinitiator or use a more sensitive photoinitiator to achieve the desired fine line width, so the developing film rate naturally improves. Consequently, the challenge of achieving both a fine line width and a high developing film rate does not exist in a photosensitive colored resin composition containing a dye. Furthermore, since Patent Documents 3 and 4 use pigments, the challenge of achieving both a fine line width and a high developing film rate does not exist in those documents either. As described above, when using triarylmethane-based dye lake colorants, there is a challenge in achieving both a fine line width and a high developing film rate, unlike when using pigments or dyes.

[0010] On the other hand, photosensitive colored resin compositions for color filters containing UV absorbers, as described in Patent Documents 2 and 3, had the problem that even if they contained UV absorbers, the resulting colored layer could not improve UV resistance. This is thought to be because the low molecular weight UV absorbers volatilize during high-temperature heating processes such as 230°C, and no UV absorber remains in the colored layer after the high-temperature heating process. Furthermore, photosensitive colored resin compositions for color filters containing polymer UV absorbers obtained by polymerizing raw material monomers including benzotriazole monomers, as described in Patent Document 4, had the problem that if they contained high molecular weight polymer UV absorbers, they tended to remain as development residue, and if they contained low molecular weight polymer UV absorbers, they volatilized during high-temperature heating processes such as 230°C, resulting in the resulting colored layer not being able to improve UV resistance. If the final colored layer does not have improved ultraviolet (UV) resistance, problems can arise, such as the colored layer fading after a pre-cleaning process involving UV irradiation with a low-pressure mercury lamp in a subsequent process, such as forming an overcoat layer after the colored layer has been formed. To suppress such color changes during UV irradiation in the manufacturing process, it is necessary to improve the UV resistance of the colored layer.

[0011] The present invention has been made in view of the above circumstances, and aims to provide a photosensitive colored resin composition that contains a triarylmethane-based dye lake colorant to improve brightness, while forming a colored layer with a fine line width, suppressing changes in film thickness and development residue before and after development, and exhibiting excellent UV resistance. The present invention also aims to provide a color filter and a display device formed using the said photosensitive colored resin composition. [Means for solving the problem]

[0012] The photosensitive colored resin composition according to the present invention contains a colorant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a solvent. The aforementioned colorant contains a triarylmethane-based lake colorant, The alkali-soluble resin contains a constituent unit having a benzotriazole skeleton and an alkali-soluble resin (U) having a weight-average molecular weight of 3000 or more.

[0013] The color filter according to the present invention comprises at least a substrate and a colored layer provided on the substrate, wherein at least one of the colored layers is a cured product of the photosensitive colored resin composition according to the present invention.

[0014] The display device according to the present invention has the color filter according to the present invention. [Effects of the Invention]

[0015] According to the present invention, it is possible to provide a photosensitive colored resin composition that contains a triarylmethane-based dye lake colorant to improve brightness, while forming a colored layer with a fine line width, suppressing changes in film thickness and development residue before and after development, and exhibiting excellent UV resistance. Furthermore, according to the present invention, it is possible to provide a color filter and a display device formed using the photosensitive colored resin composition. [Brief explanation of the drawing]

[0016] [Figure 1] Figure 1 is a schematic diagram showing an example of the color filter of the present invention. [Figure 2] Figure 2 is a schematic diagram showing an example of the liquid crystal display device of the present invention. [Figure 3] Figure 3 is a schematic diagram showing an example of the organic light-emitting device of the present invention. [Modes for carrying out the invention]

[0017] The photosensitive colored resin composition, cured product, color filter, and display device according to the present invention will be described in detail below. In this invention, light includes electromagnetic waves with wavelengths in the visible and invisible regions, as well as radiation, and radiation includes, for example, microwaves and electron beams. Specifically, it refers to electromagnetic waves with wavelengths of 5 μm or less, and electron beams. In this invention, (meth)acryloyl refers to acryloyl and methacryloyl respectively, (meth)acrylic refers to acrylic and methacrylic respectively, and (meth)acrylate refers to acrylate and methacrylate respectively. Furthermore, in this specification, the "~" symbol indicating a numerical range is used to mean that the numbers before and after it are included as the lower and upper limits, respectively.

[0018] I. Photosensitive colored resin composition The photosensitive colored resin composition according to the present invention contains a colorant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a solvent. The aforementioned colorant contains a triarylmethane-based lake colorant, The alkali-soluble resin contains a constituent unit having a benzotriazole skeleton and an alkali-soluble resin (U) having a weight-average molecular weight of 3000 or more.

[0019] The photosensitive colored resin composition according to the present invention contains a colorant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a solvent. The colorant is a lake colorant of a triarylmethane dye, and the alkali-soluble resin contains a structural unit having a benzotriazole skeleton and an alkali-soluble resin (U) with a weight-average molecular weight of 3000 or more. As a result, it is possible to form a colored layer with a fine line width, suppressed changes in film thickness and development residue before and after development, and excellent UV resistance while improving brightness. The mechanism by which these effects are achieved is not yet fully understood, but it is presumed to be as follows.

[0020] As mentioned above, pigments have low ultraviolet light transmittance, so photocurable components in photosensitive colored resin compositions containing pigments are relatively difficult to cure. Also, dyes tend to inhibit the curing of photocurable components, so photocurable components are relatively difficult to cure in photosensitive colored resin compositions containing dyes as well. In contrast, triarylmethane-based dye lake colorants have high ultraviolet light transmittance and do not inhibit the curing of photocurable components, so the effect of becoming insoluble in the developer after photocuring is higher than that of pigments and dyes, making it easier to create thicker pattern lines. In photosensitive colored resin compositions containing triarylmethane-based dye lake colorants, it is necessary to effectively suppress the photocuring reaction in order to achieve a predetermined thin pattern line width. When using a lake colorant with a highly transmittance triarylmethane dye, reducing the amount of photoinitiator to adjust the pattern line width to a predetermined value reduces radical generation due to photoreaction regardless of the film thickness direction. This is thought to result in insufficient photocurability in the pattern area, leading to a large change in film thickness from before to after development and a decrease in the amount of residual film after development. Furthermore, when using a lake colorant with a triarylmethane dye, adding or increasing the amount of antioxidant to adjust the pattern line width to a predetermined value deactivates the radicals generated by the photoreaction of the photoinitiator regardless of the film thickness direction. This is thought to result in insufficient photocurability in the pattern area, leading to a large change in film thickness from before to after development and a decrease in the amount of residual film after development. In contrast, the present invention combines a triarylmethane-based dye lake colorant with an alkali-soluble resin (U) containing a benzotriazole skeleton and having a weight-average molecular weight of 3000 or more. The alkali-soluble resin (U) is easily dispersed uniformly in the coating film. The benzotriazole skeleton contained in the alkali-soluble resin (U) has an ultraviolet absorption function, and since curing proceeds without attenuating ultraviolet rays at the film surface, the development residual film rate does not decrease, and as the film deepens, ultraviolet rays are attenuated, reducing radical generation from the photoinitiator, thus acting according to the depth of the film. Therefore, by including the alkali-soluble resin (U), the photosensitive colored resin composition according to the present invention is thought to be able to reduce the line width while suppressing the decrease in film thickness of the residual film after development. Furthermore, since the colorant contains a lake colorant of a triarylmethane-based dye, the colored layer, which is the cured product of the photosensitive colored resin composition according to the present invention, has high transmittance and suppresses color changes due to manufacturing processes such as ultraviolet irradiation and post-baking. Furthermore, alkali-soluble resins (U) with a weight-average molecular weight of 3000 or more possess both UV absorption capabilities and alkali solubility, making them less likely to develop during development and thus less likely to become development residue. Furthermore, alkali-soluble resins (U) with a weight-average molecular weight of 3000 or more are less likely to volatilize even in high-temperature heating processes such as 230°C, thus improving the UV resistance of the final colored layer.

[0021] The photosensitive colored resin composition according to the present invention contains at least a colorant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a solvent, and may further contain other components as long as they do not impair the effects of the present invention. For example, the photosensitive colored resin composition according to the present invention may further contain a dispersant to improve the dispersibility of the colorant. The components of the photosensitive colored resin composition according to the present invention will be described in detail below, starting with the alkali-soluble resin.

[0022] [Alkali-soluble resin] The alkali-soluble resin in the present invention is one having an acidic group, acting as a binder resin, and is soluble in the alkaline developer used for pattern formation. It can be appropriately selected and used from among these. In this invention, an alkali-soluble resin can be defined as one with an acid value of 40 mgKOH / g or higher. Preferred alkali-soluble resins in the present invention are resins having acidic groups, usually carboxyl groups. Specifically, examples include (meth)acrylic resins such as (meth)acrylic copolymers having carboxyl groups and styrene-(meth)acrylic copolymers having carboxyl groups, and epoxy (meth)acrylate resins having carboxyl groups.

[0023] (Alkali-soluble resin (U)) The alkali-soluble resin of the present invention contains a constituent unit having a benzotriazole skeleton and an alkali-soluble resin (U) having a weight-average molecular weight of 3000 or more. The alkali-soluble resin (U) used in the present invention is a resin having the acid value described above, containing constituent units having a benzotriazole skeleton, and having a weight-average molecular weight of 3000 or more. The structure of the alkali-soluble resin (U) is not particularly limited as long as it includes a structural unit having a benzotriazole skeleton, but it may be a (meth)acrylic resin such as a (meth)acrylic copolymer having a structural unit having a carboxyl group, or a styrene-(meth)acrylic copolymer having a carboxyl group. The (meth)acrylic resin is, for example, a copolymer obtained by copolymerizing a carboxyl group-containing ethylenically unsaturated monomer and other copolymerizable monomers as needed by known methods. The alkali-soluble resin (U) is preferably a random copolymer because the manufacturing process is simple and the molecular weight is easy to control.

[0024] The alkali-soluble resin (U) may be a (meth)acrylic copolymer or styrene-(meth)acrylic copolymer containing a carboxyl group-containing structural unit and a benzotriazole skeleton-containing structural unit, or a (meth)acrylic copolymer or styrene-(meth)acrylic copolymer containing a carboxyl group-containing structural unit derived from an ethylenically unsaturated monomer and a benzotriazole skeleton-containing structural unit derived from an ethylenically unsaturated monomer. Examples of ethylenically unsaturated monomers containing a benzotriazole skeleton include monomers having a benzotriazole skeleton represented by the following general formula (A).

[0025] [ka] (In general formula (A), R 1 R represents a hydrogen atom or a methyl group. 2 R represents an alkylene group or an oxyalkylene group. 3 R represents a hydrogen atom, a hydrocarbon group having 1 to 15 carbon atoms, or an alkoxy group having 1 to 15 carbon atoms. 4 (This represents a hydrogen atom, a halogen atom, a hydrocarbon group with 1 to 8 carbon atoms, an alkoxy group with 1 to 6 carbon atoms, a cyano group, or a nitro group.)

[0026] R 2The alkylene group may be an alkylene group having 1 to 10 carbon atoms, and may also be an alkylene group having 1 to 5 carbon atoms. Examples of the alkylene group include ethylene group, propylene group, butylene group, hexylene group, octylene group, decylene group, and the like. The alkylene group may be a linear alkylene group such as methylene group, ethylene group, trimethylene group, tetramethylene group, or a branched alkylene group such as propylene group, 2-methyltrimethylene group, 2-methyltetramethylene group. R 2 oxyalkylene group (-O-R a -, wherein R a is an alkylene group) may be an oxyalkylene group having 1 to 10 carbon atoms, and may also be an oxyalkylene group having 1 to 5 carbon atoms. Examples include oxyethylene group, oxypropylene group, oxytrimethylene group, oxytetramethylene group, and the like.

[0027] R 3 Examples of the hydrocarbon group having 1 to 15 carbon atoms include linear, branched or cyclic aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and groups formed by combinations thereof. Specific examples of the hydrocarbon group having 1 to 15 carbon atoms include linear or branched aliphatic hydrocarbon groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group; cyclic aliphatic hydrocarbon groups (cycloalkyl groups) such as cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group; aromatic hydrocarbon groups such as phenyl group, naphthyl group, biphenyl group; and combined groups such as benzyl group, phenylethyl group, 1-methyl-1-phenylethyl group. R 3 The hydrocarbon group may be an aliphatic hydrocarbon group, may be a linear or branched alkyl group, and may specifically be a methyl group, a t-butyl group, a t-pentyl group, an n-octyl group, or a t-octyl group. R 3Examples of alkoxy groups having 1 to 15 carbon atoms in this context include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, tert-butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, tridecyloxy, tetradecyloxy, and pentadecyloxy groups.

[0028] R 3 This may be a hydrogen atom or a hydrocarbon group having 1 to 15 carbon atoms, a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms, or a hydrogen atom, a methyl group, a t-butyl group, a t-pentyl group, an n-octyl group, or a t-octyl group.

[0029] R 4 Examples of halogen atoms include fluorine, chlorine, bromine, and iodine atoms. R 4 As for the carbon-hydrogen group having 1 to 8 carbon atoms, the above R 3 Examples of hydrocarbon groups include those with 1 to 8 carbon atoms. R 4 As for the alkoxy group having 1 to 6 carbon atoms, the above R 3 Examples of alkoxy groups include those with 1 to 6 carbon atoms.

[0030] R 4 This may be a hydrocarbon group having 1 to 4 carbon atoms, such as a hydrogen atom, a halogen atom, a nitro group, a cyano group, a methoxy group, or a t-butyl group.

[0031] The monomer having the benzotriazole skeleton represented by the general formula (A) is not particularly limited, but specifically, 2-[2-hydroxy-5-(methacryloyloxymethyl)phenyl]-2H-benzotriazole, 2-[2-hydroxy-5-(acryloyloxymethyl)phenyl]-2H-benzotriazole, 2-[2-hydroxy-5-(methacryloyloxyethyl)phenyl]-2H-benzotriazole, 2-[2-hydroxy-5-(acryloyloxyethyl)phenyl]-2H-benzotri Azole, 2-[2-hydroxy-5-(methacryloyloxypropyl)phenyl]-2H-benzotriazole, 2-[2-hydroxy-5-(acryloyloxypropyl)phenyl]-2H-benzotriazole, 2-[2-hydroxy-5-(methacryloyloxybutyl)phenyl]-2H-benzotriazole, 2-[2-hydroxy-5-(acryloyloxybutyl)phenyl]-2H-benzotriazole, 2-[2-hydroxy-5-(methacryloyloxyhexyl)phenyl]-2H-benzotriazole 2-[2-hydroxy-5-(acryloyloxyhexyl)phenyl]-2H-benzotriazole, 2-[2-hydroxy-3-t-butyl-5-(methacryloyloxyethyl)phenyl]-2H-benzotriazole, 2-[2-hydroxy-3-t-butyl-5-(acryloyloxyethyl)phenyl]-2H-benzotriazole, 2-[2-hydroxy-5-(methacryloyloxyethyl)phenyl]-5-chloro-2H-benzotriazole, 2-[2-hydroxy-5-(acryloyloxyethyl )phenyl]-5-chloro-2H-benzotriazole, 2-[2-hydroxy-5-(methacryloyloxyethyl)phenyl]-5-methoxy-2H-benzotriazole, 2-[2-hydroxy-5-(acryloyloxyethyl)phenyl]-5-methoxy-2H-benzotriazole, 2-[2-hydroxy-5-(methacryloyloxyethyl)phenyl]-5-cyano-2H-benzotriazole, 2-[2-hydroxy-5-(acryloyloxyethyl)phenyl]-5-cyano-2H-benzotriazole,Examples include 2-[2-hydroxy-5-(methacryloyloxyethyl)phenyl]-5-t-butyl-2H-benzotriazole, 2-[2-hydroxy-5-(acryloyloxyethyl)phenyl]-5-t-butyl-2H-benzotriazole, 2-[2-hydroxy-5-(methacryloyloxyethyl)phenyl]-5-nitro-2H-benzotriazole, 2-[2-hydroxy-5-(acryloyloxyethyl)phenyl]-5-nitro-2H-benzotriazole, and 2-[2-(2-hydroxy-4-octyloxyphenyl)-2H-1,2,3-benzotriazole-5-yloxy]ethyl methacrylate.

[0032] Examples of carboxyl group-containing ethylenically unsaturated monomers include (meth)acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl esters, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, and acrylate dimers. Addition reaction products of monomers having hydroxyl groups, such as 2-hydroxyethyl (meth)acrylate, with cyclic anhydrides such as maleic anhydride, phthalic anhydride, and cyclohexanedicarboxylic acid anhydride, as well as ω-carboxy-polycaprolactone mono(meth)acrylate, can also be used. Furthermore, anhydride-containing monomers such as maleic anhydride, itaconic anhydride, and citraconic anhydride may be used as carboxyl group precursors. Among these, (meth)acrylic acid is particularly preferred in terms of copolymerizability, cost, solubility, and glass transition temperature.

[0033] Among alkali-soluble resins, those having carboxyl groups in their side chains, and further having photopolymerizable functional groups such as ethylenically unsaturated groups in their side chains, are particularly preferred. When photopolymerizable functional groups are present, crosslinking can be formed between the alkali-soluble resins themselves, or between the alkali-soluble resins and photopolymerizable compounds such as polyfunctional monomers, during the curing process of the resin composition in the manufacture of color filters. This improves the film strength of the cured film, enhances development resistance, and suppresses thermal shrinkage of the cured film, resulting in excellent adhesion to the substrate. Methods for introducing ethylenically unsaturated bonds into alkali-soluble resins can be appropriately selected from conventionally known methods. For example, one method involves adding a compound having both an epoxy group and an ethylenically unsaturated bond in its molecule, such as glycidyl (meth)acrylate, to the carboxyl group of the alkali-soluble resin to introduce an ethylenically unsaturated bond to the side chain. Another method involves introducing a structural unit having a hydroxyl group into a copolymer, and then adding a compound having both an isocyanate group and an ethylenically unsaturated bond in its molecule to introduce an ethylenically unsaturated bond to the side chain.

[0034] Furthermore, the alkali-soluble resin preferably has a hydrocarbon ring because it provides excellent adhesion to the colored layer. The presence of a bulky group, such as a hydrocarbon ring, in the alkali-soluble resin suppresses shrinkage during curing, reduces delamination from the substrate, and improves substrate adhesion. Examples of such hydrocarbon rings include aliphatic hydrocarbon rings which may have substituents, aromatic hydrocarbon rings which may have substituents, and combinations thereof, wherein the hydrocarbon ring may have substituents such as alkyl groups, carbonyl groups, carboxyl groups, oxycarbonyl groups, amide groups, hydroxyl groups, nitro groups, amino groups, halogen atoms, etc. The hydrocarbon ring may be included as a monovalent group or as a group with two or more valents.

[0035] Specific examples of hydrocarbon rings include aliphatic hydrocarbon rings such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, norbornane, isobornane, tricyclo[5.2.1.0(2,6)]decane (dicyclopentane), and adamantane; aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, phenanthrene, and fluorene; linear polycyclic structures such as biphenyl, terphenyl, diphenylmethane, triphenylmethane, and stilbene, as well as cardo structures (9,9-diarylfluorene); and groups in which some of these groups are substituted by substituents. Examples of the substituents mentioned above include alkyl groups, cycloalkyl groups, alkylcycloalkyl groups, hydroxyl groups, carbonyl groups, nitro groups, amino groups, halogen atoms, and the like.

[0036] When the hydrocarbon ring includes an aliphatic hydrocarbon ring, it is preferable because it improves the heat resistance and adhesion of the colored layer, as well as the brightness of the resulting colored layer. Furthermore, the inclusion of the aforementioned cardi structure is particularly preferable because it improves the curability of the colored layer, suppresses fading of the colorant, and improves solvent resistance (suppression of NMP swelling).

[0037] In the present invention, the alkali-soluble resin (U) is preferably at least one carboxyl group-containing copolymer of (meth)acrylic copolymers and styrene-(meth)acrylic copolymers having a carboxyl group-containing structural unit, a benzotriazole skeleton-containing structural unit, and a hydrocarbon ring-containing structural unit, and more preferably at least one carboxyl group-containing copolymer of (meth)acrylic copolymers and styrene-(meth)acrylic copolymers having a carboxyl group-containing structural unit, a benzotriazole skeleton-containing structural unit, a hydrocarbon ring-containing structural unit, and a structural unit having an ethylenically unsaturated bond in its side chain.

[0038] Examples of ethylenically unsaturated monomers having a hydrocarbon ring include cyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, adamantyl (meth)acrylate, isobornyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, and styrene. It is preferable to use at least one selected from cyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, adamantyl (meth)acrylate, benzyl (meth)acrylate, and styrene, as this can improve the strength and heat resistance of the coating film.

[0039] The carboxyl group-containing copolymer may further contain other constituent units such as methyl (meth)acrylate, ethyl (meth)acrylate, or other constituent units having ester groups. The constituent units having ester groups not only function as components that suppress the alkali solubility of the colored resin composition, but also as components that improve solubility in solvents and even solvent resolubility.

[0040] The (meth)acrylic copolymer can be made into an alkali-soluble resin with desired properties by appropriately adjusting the amount of each constituent unit used. The amount of benzotriazole skeleton-containing ethylenically unsaturated monomer added is preferably 1% by mass or more, and may be 2% by mass or more, relative to the total amount of monomer, in order to easily obtain the effects of the present invention. On the other hand, although the benzotriazole skeleton contains a phenolic hydroxyl group and is therefore developable, its developability is weaker than that of carboxylic acid because it is weaker in acidity, and on the other hand, because of its bulky structure, a large amount added may lead to a decrease in developability. For these reasons, the amount of benzotriazole skeleton-containing ethylenically unsaturated monomer added is preferably 10% by mass or less, and may be less than 10% by mass, and may be 8% by mass or less, relative to the total amount of monomer. In other words, it is preferable that the alkali-soluble resin (U) contains 1% by mass or more and 10% by mass or less of constituent units having a benzotriazole skeleton relative to all constituent units, the lower limit may be 2% by mass or more, and the upper limit may be less than 10% by mass or 8% by mass or less.

[0041] The amount of carboxyl group-containing ethylenically 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, in order to obtain a good pattern. On the other hand, in order to suppress film roughness on the pattern surface after development, the amount of carboxyl group-containing ethylenically 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.

[0042] Furthermore, in at least one carboxyl group-containing copolymer of a (meth)acrylic copolymer and a styrene-(meth)acrylic copolymer having a constituent unit having an ethylenically unsaturated bond, which is more preferably used as an alkali-soluble resin, the compound having both an epoxy group and an ethylenically unsaturated bond is preferably in an amount of 5% by mass or more and 95% by mass or less, and more preferably 10% by mass or more and 90% by mass or less, relative to the amount of carboxyl group-containing ethylenically unsaturated monomer charged.

[0043] The preferred weight-average molecular weight (Mw) of the alkali-soluble resin (U) is 3000 or higher, from the viewpoint of improving the UV resistance of the final colored layer. The lower limit may be 4000 or higher, or 5000 or higher. On the other hand, if the weight-average molecular weight (Mw) is too high, the developability with the alkaline developer will decrease, and residue may remain on the substrate. Therefore, the upper limit is preferably 20000 or lower, may be 18000 or lower, or 15000 or lower.

[0044] The alkali-soluble resin (U) preferably has an acid value of 40 mg KOH / g or more and 300 mg KOH / g or less, from the viewpoint of developability (solubility) in alkaline aqueous solutions used in the developer and adhesion to the substrate. The lower limit may be 50 mg KOH / g or more, 60 mg KOH / g or more, or 70 mg KOH / g or more. On the other hand, since high polarity reduces solubility in solvents, the upper limit may be 150 mg KOH / g or less, 130 mg KOH / g or less, or 110 mg KOH / g or less.

[0045] When the alkali-soluble resin (U) has ethylenically unsaturated groups in its side chains, the ethylenically unsaturated bond equivalent is preferably in the range of 100 to 2000, and particularly preferably in the range of 140 to 1500, in order to obtain effects such as improved film strength of the cured film, improved development resistance, and excellent adhesion to the substrate. If the ethylenically unsaturated bond equivalent is 2000 or less, the development resistance and adhesion are excellent. Furthermore, if it is 100 or more, the proportion of other constituent units such as the constituent units having carboxyl groups and constituent units having hydrocarbon rings can be relatively increased, resulting in excellent developability and heat resistance. Here, the ethylenically unsaturated bond equivalent refers to the weight-average molecular weight per mole of ethylenically unsaturated bonds in the alkali-soluble resin described above, and is expressed by the following formula (1).

[0046] Formula (1) Ethylene unsaturated bond equivalent (g / mol) = W (g) / M (mol) (In formula (1), W represents the mass (g) of the alkali-soluble resin, and M represents the number of moles (mol) of ethylenically unsaturated bonds contained in the alkali-soluble resin W (g).)

[0047] The above ethylenically unsaturated bond equivalent may be calculated, for example, by measuring the number of ethylenically unsaturated bonds contained in 1 g of alkali-soluble resin in accordance with the iodine value test method described in JIS K 0070:1992.

[0048] The alkali-soluble resin used in the photosensitive colored resin composition of the present invention includes the specific alkali-soluble resin (U), but may further include an alkali-soluble resin that does not fall under the category of the specific alkali-soluble resin (U). The content ratio of the specific alkali-soluble resin (U) in the alkali-soluble resin used in the photosensitive colored resin composition of the present invention is not particularly limited as long as the effects of the present invention are obtained. The content ratio of the specific alkali-soluble resin (U) may be 10% by mass or more, 20% by mass or more, 35% by mass or more, 50% by mass or more, 70% by mass or more, or 100% by mass, based on the total amount of alkali-soluble resin.

[0049] In the present invention, the alkali-soluble resin that does not fall under the specific alkali-soluble resin (U) is not particularly limited, and conventionally known alkali-soluble resins can be appropriately selected and used. For example, in the description of the specific alkali-soluble resin (U) mentioned above, an alkali-soluble resin similar to the alkali-soluble resin (U) can be cited, except that it does not contain a constituent unit having a benzotriazole skeleton. Examples of alkali-soluble resins that do not fall under the specified alkali-soluble resin (U) include at least one carboxyl group-containing copolymer of (meth)acrylic copolymers and styrene-(meth)acrylic copolymers having a carboxyl group-containing structural unit and a hydrocarbon ring-containing structural unit, and at least one carboxyl group-containing copolymer of (meth)acrylic copolymers and styrene-(meth)acrylic copolymers having a carboxyl group-containing structural unit, a hydrocarbon ring-containing structural unit and a structural unit having an ethylenically unsaturated bond in its side chain.

[0050] Furthermore, while there are no particular limitations on the epoxy (meth)acrylate resin having a carboxyl group, epoxy (meth)acrylate compounds obtained by reacting a reaction product of an epoxy compound and an unsaturated group-containing monocarboxylic acid with an acid anhydride are suitable. Epoxy compounds, unsaturated monocarboxylic acids, and acid anhydrides can be appropriately selected from known types. Even as an epoxy (meth)acrylate resin having a carboxyl group, it is preferable that it has the hydrocarbon ring in the molecule, and among these, those containing a cardi structure are preferable because they improve the curability of the colored layer, suppress fading of the colorant, and increase the residual film rate of the colored layer. As for alkali-soluble resins that do not fall under the aforementioned specific alkali-soluble resin (U), one type may be used alone, or two or more types may be used in combination.

[0051] The alkali-soluble resin used in the photosensitive colored resin composition may be used alone or in combination of two or more types, as long as it contains at least the specified alkali-soluble resin (U), and there are no particular restrictions on its content. The alkali-soluble resin (U) in the photosensitive colored resin composition is preferably in the range of 3% to 60% by mass, more preferably 5% to 50% by mass, and even more preferably 8% to 40% by mass, relative to the total solid content. When the alkali-soluble resin (U) content is above the lower limit, sufficient alkali developability and ultraviolet absorption function are obtained, a sufficient line width shift reduction effect is obtained, and UV resistance is improved. When the alkali-soluble resin (U) content is below the upper limit, film roughness and pattern chipping during development can be suppressed. The alkali-soluble resin content of the photosensitive colored resin composition is preferably 5% to 60% by mass, and more preferably 8% to 40% by mass, relative to the total solid content. If the alkali-soluble resin content is above the lower limit, sufficient alkali developability can be obtained, and if the alkali-soluble resin content is below the upper limit, film roughness and pattern defects during development can be suppressed.

[0052] [Colorants] The colorant in this invention contains a triarylmethane-based lake colorant in order to create a photosensitive colored resin composition that suppresses changes in chromaticity and brightness before and after the high-temperature heating process, and that can form a colored layer with a fine line width and suppressed changes in film thickness before and after development, while maintaining good brightness of the final colored layer. <Lake colorants using triarylmethane-based dyes> Lake colorants of triarylmethane dyes are preferable because they have excellent heat resistance and light resistance, and achieve high brightness of color filters. In particular, it is preferable that the lake colorant of a triarylmethane dye and a poly acid be selected from the colorants represented by the following general formula (1) and the colorants represented by the following general formula (2). The colorant represented by the following general formula (1) is preferable because it forms a molecular association state, exhibits better heat resistance, and can achieve high brightness.

[0053] [ka] (In general formula (1), A is an a-valent organic group in which the carbon atom directly bonded to N does not have a π bond, and the organic group represents an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at least at the terminal directly bonded to N, or an aromatic group having such aliphatic hydrocarbon group, and the carbon chain may contain heteroatoms. B c- R represents a c-valent polyacid anion. i ~R v Each independently represents a hydrogen atom, an optionally substituted alkyl group, or an optionally substituted aryl group, and R ii and R iii , R iv and R v They may bond to form a ring structure. vi and R vii Each of these independently represents an optionally substituted alkyl group, an optionally substituted alkoxy group, a halogen atom, or a cyano group. 1 R represents a divalent aromatic group which may have substituents. i ~R vii and Ar 1 These may be the same or different. a and c represent integers greater than or equal to 2, and b and d represent integers greater than or equal to 1. f and g represent integers between 0 and 4 (exclusive). Multiple instances of f and g may be identical or different.

[0054] [ka] (In general formula (2), R I ~R VI Each independently represents a hydrogen atom, an optionally substituted alkyl group, or an optionally substituted aryl group, and R I and R II , R III and R IV , R V and R VI They may bond to form a ring structure. VII and R VIII Each of these independently represents an optionally substituted alkyl group, an optionally substituted alkoxy group, a halogen atom, or a cyano group. 2 R represents a divalent aromatic heterocyclic group which may have substituents, and there are multiple R I ~R VIII and Ar 2 They may be the same or different. m- This represents a polyacid anion with m-valence. m represents an integer greater than or equal to 2. k and l represent integers between 0 and 4 (exclusive). Multiple k and l values ​​may be the same or different.

[0055] The colorant represented by the general formula (1) contains anions with a valency of 2 or more and cations with a valency of 2 or more. Therefore, in aggregates of this colorant, the anions and cations are not simply ionically bonded one molecule to one, but can form molecular aggregates through ionic bonding, resulting in a significantly increased apparent molecular weight compared to conventional lake pigments. The formation of such molecular aggregates increases the cohesive force in the solid state, reduces thermal motion, suppresses the dissociation of ion pairs and the decomposition of the cation portion, and is presumed to be less prone to fading than conventional lake pigments.

[0056] In the general formula (1) above, A is an a-valent organic group in which the carbon atom directly bonded to N (nitrogen atom) does not have a π bond, and the organic group represents an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at least at the terminal directly bonded to N, or an aromatic group having such aliphatic hydrocarbon group, and the carbon chain may contain heteroatoms such as O (oxygen atom), S (sulfur atom), and N (nitrogen atom). That is, the organic group represents an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at least at the terminal directly bonded to N, and which may contain heteroatoms such as O, S, and N in the carbon chain, or an aromatic group having an aliphatic hydrocarbon group at the terminal directly bonded to N, and which may contain heteroatoms such as O, S, and N in the carbon chain. Because the carbon atom directly bonded to N does not have a π bond, the color properties such as hue and transmittance of the cationic coloring site are not affected by the linking group A or other coloring sites, and can maintain the same color as the monomer.

[0057] In A, the aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at least one terminal directly bonded to N may be linear, branched, or cyclic, as long as the carbon atom at the terminal directly bonded to N does not have a π bond. The carbon atoms other than the terminal may have unsaturated bonds, or they may have substituents, and the carbon chain may contain O, S, and N. For example, it may contain carbonyl groups, carboxyl groups, oxycarbonyl groups, amide groups, etc., and the hydrogen atoms may be further substituted with halogen atoms, etc. Furthermore, in A, the aromatic group having the aliphatic hydrocarbon group mentioned above is a monocyclic or polycyclic aromatic group having an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at least at the terminal directly bonded to N, and may have substituents, and may be a heterocyclic ring containing O, S, and N. In particular, from the viewpoint of structural robustness, A preferably contains a cyclic aliphatic hydrocarbon group or an aromatic group. Examples of cyclic aliphatic hydrocarbon groups include cyclohexane, cyclopentane, norbornane, bicyclo[2.2.2]octane, and tricyclo[5.2.1.0 2,6Examples of groups include those containing decane and adamantane. Aromatic groups include, for example, groups containing benzene rings and naphthalene rings. For example, when A is a divalent organic group, examples include linear, branched, or cyclic alkylene groups having 1 to 20 carbon atoms, or aromatic groups in which two alkylene groups having 1 to 20 carbon atoms, such as xylylene groups, are substituted.

[0058] In the present invention, in order to improve heat resistance by achieving both robustness and freedom of molecular motion, it is preferable that A is an aliphatic hydrocarbon group having two or more cyclic aliphatic hydrocarbon groups, having a saturated aliphatic hydrocarbon group at the terminal directly bonded to N, and possibly containing O, S, and N in the carbon chain. It is more preferable that A is an aliphatic hydrocarbon group having two or more cycloalkylene groups, having a saturated aliphatic hydrocarbon group at the terminal directly bonded to N, and possibly containing O, S, and N in the carbon chain, and among these, it is even more preferable that it has a structure in which two or more cyclic aliphatic hydrocarbon groups are linked by a linear or branched aliphatic hydrocarbon group. The two or more cyclic aliphatic hydrocarbon groups may be the same or different, and examples include those similar to the aforementioned cyclic aliphatic hydrocarbon groups, with cyclohexane and cyclopentane being preferred.

[0059] In the present invention, from the viewpoint of heat resistance, it is preferable that A is a substituent represented by the following general formula (1a).

[0060] [ka] (In general formula (1a), R xi R represents an alkylene group having 1 to 3 carbon atoms, which may have an alkyl group having 1 to 4 carbon atoms as a substituent, or an alkoxy group having 1 to 4 carbon atoms. xii and R xiii Each of the following independently represents an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, p is an integer between 1 and 3, and q and r each independently represent an integer between 0 and 4. xi , R xii , R xiiiAnd if there are multiple R's, xi , R xii , R xiii (And r may be the same or different from each other.)

[0061] R xi It is preferable that the alkylene group has 1 to 3 carbon atoms. Examples of such alkylene groups include methylene groups, ethylene groups, and propylene groups, with methylene groups or ethylene groups being preferred, and methylene groups being more preferred. Examples of alkyl groups having 1 to 4 carbon atoms include methyl, ethyl, propyl, and butyl groups, and they may be linear or branched. Furthermore, examples of alkoxy groups having 1 to 4 carbon atoms include methoxy, ethoxy, propoxy, and butoxy groups, which may be linear or branched.

[0062] R xii and R xiii In the above, the alkyl group having 1 to 4 carbon atoms and the alkoxy group having 1 to 4 carbon atoms are R xi Examples of substituents that may be present include those similar to those that may be present.

[0063] In general formula (1a), it is preferable from the viewpoint of heat resistance that there are two to four cyclohexane (cyclohexylene groups), that is, that p is between 1 and 3, and more preferably that p is between 1 and 2. Furthermore, substituent R of the cyclohexylene group xii and R xiii The number of substitutions is not particularly limited, but from the viewpoint of heat resistance, it is preferable to have 1 to 3 substitutions, and more preferably 1 to 2 substitutions. That is, it is preferable that q and r are integers between 1 and 3, and more preferably that q and r are integers between 1 and 2.

[0064] The following are some preferred examples of such linking group A, but they are not limited to these.

[0065] [ka]

[0066] R i ~R v The alkyl group in is not particularly limited. For example, linear, branched, or cyclic alkyl groups having 1 to 20 carbon atoms are examples, and among these, linear or branched alkyl groups having 1 to 8 carbon atoms are particularly recommended, and linear or branched alkyl groups having 1 to 5 carbon atoms are recommended from the viewpoint of brightness and heat resistance, R i ~R v The alkyl group in the formula may be an ethyl group or a methyl group. The substituents that the alkyl group may have are not particularly limited, but include, for example, an aryl group, a halogen atom, a hydroxyl group, an alkoxy group, etc., and the substituted alkyl group may be an aralkyl group such as a benzyl group. R i ~R v The aryl group in this is not particularly limited. Examples include a phenyl group and a naphthyl group. Examples of substituents that the aryl group may have include alkyl groups, halogen atoms, alkoxy groups, and hydroxyl groups. In particular, from the standpoint of chemical stability, R i ~R v Each of these independently consists of a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group, or R ii and R iii , R iv and R v It is preferable that these elements are bonded together to form a pyrrolidine ring, a piperidine ring, or a morpholine ring.

[0067] From the standpoint of heat resistance, R ii ~R v Preferably, at least one of them is a cyclic alkyl group which may have substituents, or an aryl group which may have substituents. ii ~R vWhen at least one of [the groups] has a cycloalkyl group or an aryl group, intermolecular interactions due to steric hindrance are reduced, whereby the influence of heat on the color-developing site can be suppressed, so that the compound is considered to be excellent in heat resistance.

[0068] From the viewpoint of heat resistance, R ii to R v preferably has at least one substituent represented by the following general formula (1b) or the following general formula (1c).

[0069]

Chemical formula

[0070]

Chemical formula

[0071] R xiv , R xv , R xvi , R xvii , R xviii , and R xix Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, and a butyl group, which may be linear or branched. Examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group, which may be linear or branched. Examples of the substituent which the alkyl group and the alkoxy group may have include a halogen atom, a hydroxyl group and the like.

[0072] When having a substituent represented by the above general formula (1b), from the viewpoint of heat resistance, R xiv , R xv , and R xvi preferably has at least one of an alkyl group having 1 to 4 carbon atoms which may have a substituent, or an alkoxy group having 1 to 4 carbon atoms which may have a substituent, and R xiv and R xv it is more preferred that at least one of these is an alkyl group having 1 to 4 carbon atoms which may have a substituent, or an alkoxy group having 1 to 4 carbon atoms which may have a substituent.

[0073] Further, when having a substituent represented by the above general formula (1c), from the viewpoint of heat resistance, R xvii , R xviii , and R xix preferably has at least one of an alkyl group having 1 to 4 carbon atoms which may have a substituent, or an alkoxy group having 1 to 4 carbon atoms which may have a substituent, and R xvii and R xviii it is more preferred that at least one of these is an alkyl group having 1 to 4 carbon atoms which may have a substituent, or an alkoxy group having 1 to 4 carbon atoms which may have a substituent.

[0074] R vi and R vii each independently represents an alkyl group which may have a substituent, an alkoxy group which may have a substituent, a halogen atom or a cyano group. R vi and R viiThe alkyl group in is not particularly limited, but is preferably a linear or branched alkyl group having 1 to 8 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms. Examples of alkyl groups having 1 to 4 carbon atoms include methyl, ethyl, propyl, and butyl groups, which may be linear or branched. Substituents that the alkyl group may have are not particularly limited, but examples include aryl groups, halogen atoms, hydroxyl groups, and alkoxy groups. Also, R vi and R vii The alkoxy group in is not particularly limited, but is preferably a linear or branched alkoxy group having 1 to 8 carbon atoms, and more preferably an alkoxy group having 1 to 4 carbon atoms. Examples of alkoxy groups having 1 to 4 carbon atoms include methoxy, ethoxy, propoxy, and butoxy groups, which may be linear or branched. Substituents that the alkoxy group may have are not particularly limited, but examples include aryl groups, halogen atoms, hydroxyl groups, and alkoxy groups. R vi and R vii Examples of halogen atoms in this context include fluorine, chlorine, bromine, and iodine atoms. R vi and R vii The number of substitutions, i.e., f and g, each independently represent integers between 0 and 4, preferably between 0 and 2, and more preferably between 0 and 1. Multiple f and g may be the same or different. Also, R vi and R vii It may be substituted at either the triarylmethane skeleton or the aromatic ring having a resonance structure within the xanthene skeleton, but among them, -NR ii R iii or -NR iv R v It is preferable that the amino group represented by is substituted at the meta position relative to the substitution position of the amino group.

[0075] Ar 1The divalent aromatic group in is not particularly limited. 1 The aromatic group in this context may be a heterocyclic group in addition to an aromatic hydrocarbon group consisting of a carbon ring. Examples of aromatic hydrocarbons in the aromatic hydrocarbon group include condensed polycyclic aromatic hydrocarbons such as benzene rings, naphthalene rings, tetralin rings, indene rings, fluorene rings, anthracene rings, and phenanthrene rings; and chain-like polycyclic hydrocarbons such as biphenyl, terphenyl, diphenylmethane, triphenylmethane, and stilbene. In such chain-like polycyclic hydrocarbons, O, S, and N may be present in the chain skeleton, as in diphenyl ether. On the other hand, examples of heterocyclic groups include five-membered heterocyclic groups such as furan, thiophene, pyrrole, oxazole, thiazole, imidazole, and pyrazole; six-membered heterocyclic groups such as pyran, pyrone, pyridine, pyrone, pyridazine, pyrimidine, and pyrazine; and condensed polycyclic heterocyclic groups such as benzofuran, thionaphthene, indole, carbazole, coumarin, benzo-pyrone, quinoline, isoquinoline, acridine, phthalazine, quinazoline, and quinoxaline. These aromatic groups may further have substituents such as alkyl groups, alkoxy groups, hydroxyl groups, halogen atoms, and phenyl groups which may be substituted with these.

[0076] Multiple R molecules within a single molecule i ~R vii and Ar 1 They may be the same or different. i ~R vii and Ar 1 By combining these elements, the desired color can be achieved.

[0077] In A, the valency a is the number of color-developing cationic sites constituting the cation, and a is an integer of 2 or more. In this lake colorant, since the valency a of the cation is 2 or more, it has excellent heat resistance, and in particular, the valency a of the cation may be 3 or more. There is no particular upper limit to a, but from the viewpoint of ease of manufacture, it is preferable that a is 4 or less, and more preferable that it is 3 or less.

[0078] In the colorant represented by general formula (1), the cation is preferably 1200 or more, and more preferably 1300 or more, because it has excellent heat resistance and is less prone to color change during heating.

[0079] In a colorant represented by general formula (1), the anion part (B c- ) is a C-valent polyacid anion with excellent brightness and heat resistance, and is a divalent or higher anion.

[0080] As for polyacid anions formed by the condensation of multiple oxoacids, isopolyacid anions (M m O n ) c- Even if heteropoly acid anion (X l M m O n ) c- It may also be the case. In the above ionic formula, M represents a poly atom, X represents a heteroatom, m represents the composition ratio of poly atoms, and n represents the composition ratio of oxygen atoms. Examples of poly atoms M include Mo, W, V, Ti, Nb, etc. Examples of heteroatoms X include Si, P, As, S, Fe, Co, etc. Also, Na may be used in some cases. + Ya H + It may also contain counter-cations such as the following. In particular, due to its excellent heat resistance, it is preferable to use a polyacid having one or more elements selected from tungsten (W) and molybdenum (Mo). Examples of such polyacids include isopolyacids, such as tungstate ion [W 10 O 32 ] 4- , molybdate ion [Mo6O 19 ] 2- Or, the heteropoly acid, phosphotungstate ion [PW 12 O 40 ] 3- [P2W] 18 O 62 ] 6- , tungstate ion [SiW 12 O 40 ] 4- , phosphomolybdate ion [PMo 12 O40 ] 3- , silicic molybdate ion [SiMo 12 O 40 ] 4- Phosphate tungstomolybdate ion [PW 12-s Mo s O 40 ] 3- (s is an integer between 1 and 11), [P2W 18-t Mo t O 62 ] 6- (t is an integer between 1 and 17), cytangustmolybdate ion [SiW 12-u Mo u O 40 ] 4- Examples include (where u is an integer between 1 and 11). Among the polyacids containing at least one of tungsten (W) and molybdenum (Mo), heteropolyacids are preferred from the viewpoint of heat resistance and ease of obtaining raw materials, and heteropolyacids containing phosphorus (P) are even more preferred. Furthermore, phosphotungstomolybdate ions [PW 10 Mo2O 40 ] 3- Now PW 11 Mo1O 40 ] 3- Phosphate tungstate ions [PW 12 O 40 ] 3- It is even more preferable from the viewpoint of heat resistance that it be either of the above.

[0081] In general formula (1), b represents the number of cations and d represents the number of anions in the molecular aggregate, where b and d are integers of 1 or more. When b is 2 or more, the multiple cations in the molecular aggregate may be single or in combination of two or more types. Similarly, when d is 2 or more, the multiple anions in the molecular aggregate may be single or in combination of two or more types.

[0082] The lake colorant represented by general formula (1) can be prepared, for example, by referring to International Publication No. 2012 / 144520 and International Publication No. 2018 / 003706.

[0083] On the other hand, in general formula (2), R I ~R VI Each independently represents a hydrogen atom, an optionally substituted alkyl group, or an optionally substituted aryl group, and R I and R II , R III and R IV , R V and R VI These may combine to form a ring structure. I ~R VI Each of these is R in the general formula (1) mentioned above. i ~R v It can be the same as that. In general formula (2), R VII and R VIII Each of these independently represents an optionally substituted alkyl group, an optionally substituted alkoxy group, a halogen atom, or a cyano group, but these also represent the R in the general formula (1) mentioned above. vi and R vii It can be the same as that. In general formula (2), Ar 2 This represents a divalent aromatic heterocyclic group which may have substituents, but the Ar 2 This is the Ar of the general formula (1) mentioned above. 1 Among these, it may be the same as an aromatic heterocyclic group. Also, in general formula (2), E m- The symbol represents an m-valent polyacid anion, and this m-valent polyacid anion may be the same as the c-valent polyacid anion in the general formula (1) mentioned above.

[0084] In general formula (2), m represents the number of cations and anions, and is an integer of 2 or more. The multiple cations in general formula (2) may be single, or two or more may be combined. Similarly, the anions may be single, or two or more may be combined. Further, k and l in General Formula (2) may be the same as f and g in General Formula (1) described above. Incidentally, the lake colorant represented by General Formula (2) can be prepared, for example, with reference to Japanese Patent Application Laid-Open No. 2017-16099.

[0085] Further, the lake colorant of triarylmethane dye used in the photosensitive colored resin composition of the present invention is not limited to one or more selected from the colorant represented by General Formula (1) and the colorant represented by General Formula (2), and can be appropriately selected and used. For example, lake colorants formed from cations of triarylmethane dyes described in Japanese Patent Application Laid-Open No. 2015-96947, Japanese Patent Application Laid-Open No. 2016-27149, and Japanese Patent Application Laid-Open No. 2017-16099 and various polyacid anions as described above, or lake colorants formed from triarylmethane dyes and polyacids described in Japanese Patent Application Laid-Open No. 2015-96947, Japanese Patent Application Laid-Open No. 2016-27149, and Japanese Patent Application Laid-Open No. 2017-16099 may also be used.

[0086] In the photosensitive colored resin composition of the present invention, the lake colorant of triarylmethane dye may be used singly or in combination of two or more thereof.

[0087] <Other Colorants> The colorant used in the present invention contains a lake colorant of triarylmethane dye as an essential component, but other colorants may be further used in combination for adjusting color tone within a range that does not impair the effects of the present invention. As other colorants, known pigments, dyes, lake colorants and the like can be used singly or in a mixture of two or more thereof.

[0088] Among other colorants, other blue colorants, purple colorants, and red colorants are preferably used, but are not limited thereto. As other blue colorants, known organic blue pigments such as C.I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, etc. Known organic purple pigments such as CI Pigment Violet 1, 14, 15, 19, 23, 29, 32, 33, 36, 37, and 38 are used as purple colorants. Examples of red to reddish-purple colorants include xanthene dyes and xanthene-based dye lake colorants as described in International Publication No. 2020 / 071041, Japanese Patent Publication No. 2018-100323, International Publication No. 2014 / 123125, etc.

[0089] <Percentage of colorants> In the photosensitive colored resin composition of the present invention, other colorants other than the lake colorant of the triarylmethane dye may be further included in the colorant, to the extent that the effects of the present invention are not impaired. However, the content of the lake colorant of the triarylmethane dye is preferably 70% by mass or more and 100% by mass or less, more preferably 80% by mass or more and 100% by mass or less, more preferably 90% by mass or more and 100% by mass or less, and even more preferably 95% by mass or more and 100% by mass or less, based on the total amount of colorant.

[0090] The average primary particle size of the colorant used in the present invention is not particularly limited and varies depending on the type of colorant used, as long as it enables the desired color development when used as the colored layer of a color filter. However, it is preferably in the range of 10 to 100 nm, and more preferably in the range of 15 to 60 nm. By having the average primary particle size of the colorant within the above range, a display device equipped with a color filter manufactured using the photosensitive colored resin composition according to the present invention can be made high-contrast and of high quality.

[0091] Furthermore, the average dispersed particle size of the colorant in the photosensitive colored resin composition varies depending on the type of colorant used, but is preferably in the range of 10 to 100 nm, and more preferably in the range of 15 to 60 nm. The average dispersed particle size of the colorant in a photosensitive colored resin composition is the dispersed particle size of the colorant particles dispersed in a dispersion medium containing at least a solvent, and is measured by a laser light scattering particle size analyzer. For particle size measurement using a laser light scattering particle size analyzer, the photosensitive colored resin composition is appropriately diluted with the solvent used in the photosensitive colored resin composition to a concentration measurable by the laser light scattering particle size analyzer (e.g., 1000 times), and measured at 23°C using the dynamic light scattering method with a laser light scattering particle size analyzer (e.g., the NanoTrac particle size analyzer UPA-EX150 manufactured by Nikkiso Co., Ltd.). The average dispersed particle size here is the volume average particle size.

[0092] The colorants used in this invention can be manufactured by known methods such as recrystallization or solvent-salt milling. Alternatively, commercially available colorants may be used after being micronized.

[0093] In the photosensitive colored resin composition according to the present invention, the content of the colorant is not particularly limited. From the viewpoint of dispersibility and dispersion stability, the content of the colorant is usually 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, relative to the total solid content of the photosensitive colored resin composition. If it is above the lower limit, the colored layer when the photosensitive colored resin composition is applied to a predetermined film thickness (usually 1.0 μm to 5.0 μm) will have sufficient color density. If it is below the upper limit, a colored layer with excellent storage stability, sufficient hardness, and adhesion to the substrate can be obtained. In particular when forming a colored layer with a high colorant density, the total content of the colorant is preferably in the range of 20% to 65% by mass, more preferably in the range of 30% to 60% by mass, relative to the total solid content of the photosensitive colored resin composition.

[0094] [Photopolymerizable compound] The photopolymerizable compound used in the photosensitive colored resin composition is not particularly limited as long as it can be polymerized by a photoinitiator. Generally, compounds having two or more ethylenically unsaturated bonds are preferred, and polyfunctional (meth)acrylates having two or more acryloyl groups or methacryloyl groups are particularly preferred. Such polyfunctional (meth)acrylates can be appropriately selected from those that are conventionally known. Specific examples include those described in Japanese Patent Application Publication No. 2013-029832.

[0095] These polyfunctional (meth)acrylates may be used individually or in combination of two or more. Furthermore, when excellent photocurability (high sensitivity) is required for the photosensitive colored resin composition of the present invention, it is preferable that the polyfunctional (meth)acrylate has three or more polymerizable ethylenically unsaturated bonds (trifunctional), and poly(meth)acrylates of trivalent or higher polyhydric alcohols or their dicarboxylic acid modified products are preferred. Specifically, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, succinic acid modified product of pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, succinic acid modified product of dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc. are preferred.

[0096] In the present invention, among the photopolymerizable compounds used, those containing alkylene oxides are preferable because they enable both a high development retention rate and a fine line width. Preferably, photopolymerizable compounds containing alkylene oxide include photopolymerizable compounds containing ethylene oxide and / or propylene oxide. When a photopolymerizable compound containing alkylene oxide is included, it is presumed that curability is improved because active radicals are regenerated from peroxy radicals that have lost polymerization activity due to oxygen inhibition. Examples of photopolymerizable compounds containing alkylene oxide include alkylene oxide-modified pentaerythritol tri(meth)acrylate, alkylene oxide-modified pentaerythritol tetra(meth)acrylate, alkylene oxide-modified dipentaerythritol tetra(meth)acrylate, alkylene oxide-modified dipentaerythritol penta(meth)acrylate, alkylene oxide-modified dipentaerythritol hexa(meth)acrylate, alkylene oxide-modified trimethylolpropane tri(meth)acrylate, and alkylene oxide-modified glycerin di(meth)acrylate, and 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 glycerin tri(meth)acrylate, and ethylene oxide-modified diglycerin tetra(meth)acrylate. Among these, it is more preferable to include ethylene oxide-modified diglycerin tetra(meth)acrylate and ethylene oxide-modified dipentaerythritol hexa(meth)acrylate.

[0097] Photopolymerizable compounds can be used individually or in combination of two or more. As the photopolymerizable compound, a mixture of a photopolymerizable compound containing alkylene oxide and a photopolymerizable compound that does not contain alkylene oxide may be used. When a photopolymerizable compound containing alkylene oxide is included, the content is preferably in the range of 3% to 50% by mass, and more preferably in the range of 5% to 30% by mass, relative to the total amount of the photopolymerizable compound.

[0098] The content of the photopolymerizable compound used in the photosensitive colored resin composition is not particularly limited, but is preferably in the range of 5% to 60% by mass, and more preferably in the range of 10% to 40% by mass, relative to the total solid content of the photosensitive colored resin composition. If the content of the photopolymerizable compound is above the lower limit, sufficient photocuring can be achieved, the elution of the exposed portion during development can be suppressed, line width shift can be suppressed, and solvent resistance can be improved. If the content of the photopolymerizable compound is below the upper limit, sufficient alkali developability can be achieved.

[0099] [Photoinitiator] There are no particular limitations on the photoinitiator used in the photosensitive colored resin composition of the present invention, and one or more initiators from among the various initiators known conventionally can be used in combination. Examples of photoinitiators include aromatic ketones such as benzophenone, N,N-dimethylaminobenzophenone, 4,4'-bisdiethylaminobenzophenone (e.g., HyCure ABP, manufactured by Kawaguchi Pharmaceutical), and 4-methoxy-4'-dimethylaminobenzophenone; benzoin ethers such as benzoin methyl ether; benzoins such as ethylbenzoin; biimidazoles such as 2-(o-chlorophenyl)-4,5-phenylimidazole dimer; halomethyloxadiazole compounds such as 2-trichloromethyl-5-(p-methoxystyryl)-1,3,4-oxadiazole; halomethyl-S-triazines such as 2-(4-butoxy-naphtho-1-yl)-4,6-bis-trichloromethyl-S-triazine; 1,2-octadione-1-[4-(phenylthio)-,2-(o-benzoyl oxime)], ethanoone, 1-[9-ethyl-6-(2-methylbenzoyl)-9 Oxime esters such as oxime ester-based photoinitiators described in Japanese Patent Publication No. 2000-80068, Japanese Patent Publication No. 2001-233842, Japanese Patent Publication No. 2010-527339, Japanese Patent Publication No. 2010-527338, Japanese Patent Publication No. 2013-041153, etc.; 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (e.g., Irgacure 907) Examples include α-aminoketones such as 2-benzyl-2-(dimethylamino)-1-(4-morpholinophenyl)-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); and thioxanthones such as diethylthioxanthone. In particular, the photoinitiator used in the present invention preferably contains at least one selected from the group consisting of oxime esters and α-aminoketones, due to its excellent sensitivity, and α-aminoketones are preferred from the viewpoint of line width adjustment during pattern formation and development resistance. α-aminoketones having a tertiary amine structure are preferred because they have a tertiary amine structure that acts as an oxygen quencher within the molecule, making it difficult for radicals generated from the initiator to be deactivated by oxygen, thus improving sensitivity. Furthermore, using α-aminoketones in combination with oxime esters as photoinitiators is preferable because it suppresses water stains and improves sensitivity. Water stains refer to the appearance of water-like marks after rinsing with pure water following alkaline development, which occurs when components that increase alkaline developability are used. While these water stains disappear after post-bake and do not pose a problem for the product, they are detected as unevenness abnormalities during the visual inspection of the patterned surface after development, making it difficult to distinguish between normal and defective products. Therefore, lowering the inspection sensitivity of the inspection device during visual inspection results in a decrease in the yield of the final color filter product, which is problematic. Furthermore, combining thioxanthones with at least one selected from the group consisting of oxime esters and α-aminoketones as a photoinitiator is preferable because it allows for adjustment of sensitivity, suppression of water staining, and improvement of development resistance.

[0100] The total content of the photoinitiator used in the photosensitive colored resin composition of the present invention is not particularly limited as long as the effects of the present invention are not impaired, but is preferably in the range of 0.1% to 12.0% by mass, and more preferably in the range of 1.0% to 8.0% by mass, relative to the total solid content of the photosensitive colored resin composition. If this content is above the lower limit, sufficient photocuring will proceed, suppressing the elution of the exposed portion during development and improving solvent resistance. On the other hand, if it is below the upper limit, the decrease in brightness due to yellowing of the resulting colored layer can be suppressed. Furthermore, regarding the content ratio of the photopolymerizable compound and the photoinitiator used in the photosensitive colored resin composition, from the viewpoints of suppressing line width shift, improving solvent resistance, and further enhancing the effect of suppressing development residues, the total content of the photoinitiator is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and preferably 40 parts by mass or less, more preferably 30 parts by mass or less, relative to 100 parts by mass of the photopolymerizable compound.

[0101] [Solvent] The solvent used in the present invention is not particularly limited as long as it is an organic solvent that does not react with each component in the photosensitive colored resin composition and can dissolve or disperse these components. Solvents may be used alone or in combination of two or more. Specific examples of solvents include, for example, alcohol-based solvents such as methyl alcohol, ethyl alcohol, N-propyl alcohol, i-propyl alcohol, methoxy alcohol, and ethoxy alcohol; carbitol-based solvents such as methoxyethoxyethanol and ethoxyethoxyethanol; ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl methoxypropionate, ethyl ethoxypropionate, ethyl lactate, methyl hydroxypropionate, ethyl hydroxypropionate, n-butyl acetate, isobutyl Ester solvents such as ammonium 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; 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; methoxyethoxyethyl acetate Examples of solvents include carbitol acetate solvents such as ethoxyethoxyethyl acetate and butyl carbitol acetate (BCA); diacetates such as propylene glycol diacetate and 1,3-butylene glycol 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 organic hydrocarbons such as toluene and xylene.Among these solvents, glycol ether acetate solvents, carbitol acetate solvents, glycol ether solvents, and ester solvents are preferably used in terms of their solubility with other components. In particular, the solvent used in the present invention is preferably one or more selected from 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, in terms of solubility with other components and suitability for application.

[0102] In the photosensitive colored resin composition according to the present invention, the solvent content may be appropriately set within a range that allows for accurate formation of a colored layer. The solvent content is usually in the range of 55% to 95% by mass, and preferably in the range of 65% to 88% by mass, relative to the total amount of the photosensitive colored resin composition containing the solvent. By having the solvent content within the above range, excellent coatability can be achieved.

[0103] [Dispersant] In the photosensitive colored resin composition of the present invention, the colorant may be dispersed in a solvent using a dispersant. In the present invention, the dispersant can be appropriately selected from conventionally known dispersants. As dispersants, for example, surfactants such as cationic, anionic, nonionic, amphoteric, silicone, and fluorine-based surfactants can be used. Among surfactants, polymer dispersants are preferred because they can disperse uniformly and finely.

[0104] Examples of polymer dispersants include (co)polymers of unsaturated carboxylic acid esters such as polyacrylic acid esters; (partial)amine salts, (partial) ammonium salts, and (partial) alkylamine salts of (co)polymers of unsaturated carboxylic acid esters such as polyacrylic acid; (co)polymers of hydroxyl group-containing unsaturated carboxylic acid esters such as hydroxyl group-containing polyacrylic acid esters and their modified products; polyurethanes; unsaturated polyamides; polysiloxanes; long-chain polyaminoamide phosphates; polyethyleneimine derivatives (amides obtained by the reaction of poly(lower alkyleneimine) with free carboxyl group-containing polyesters and their bases); and polyallylamine derivatives (reaction products obtained by reacting polyallylamine with one or more compounds selected from three types of compounds: polyesters, polyamides, or ester-amide cocondensates (polyesteramides) having free carboxyl groups). When the polymer dispersant is a copolymer, it may be a block copolymer, a graft copolymer, or a random copolymer, but block copolymers and graft copolymers are preferred from the viewpoint of dispersibility.

[0105] The dispersant can be appropriately selected and used depending on the type of colorant, as long as it provides good dispersibility, and is not particularly limited. When dispersing the lake colorant of the triarylmethane dye, it is preferable to use an acidic dispersant, which is an acidic polymer dispersant. As an acidic dispersant used for dispersing the lake colorant, at least one selected from polymers having a structural unit represented by the general formula (I) described later, and carboxyl group-containing block copolymers can be suitably used. When pigments are used as colorants and dispersed, at least one of the following can be used, selected from the group consisting of acidic or basic polymer dispersants and urethane-based dispersants, depending on the type of pigment; acidic or basic polymer dispersants may be used. When dispersing a basic-treated pigment, it is preferable to use an acidic polymer dispersant, and when dispersing an acid-treated pigment, it is preferable to use a basic polymer dispersant, which is a basic dispersant. As a basic dispersant, at least one selected from the group consisting of polymers containing repeating units having a tertiary amine, and salt-type polymers in which at least a portion of the amino groups in a polymer containing repeating units having a tertiary amine form a salt with an organic acid compound, can be suitably used. Urethane-based dispersants are compounds having one or more urethane bonds (-NH-COO-) in one molecule. Suitable urethane-based dispersants include, for example, reaction products of polyisocyanates having two or more isocyanate groups in one molecule and polyesters having hydroxyl groups at one or both ends.

[0106] <Polymer having a constituent unit represented by general formula (I)> Polymers having the constituent units represented by the following general formula (I) can be preferably used as dispersants for the lake colorants of the triarylmethane-based dyes. Using polymers having the constituent units represented by the following general formula (I) as an acidic dispersant improves the dispersibility and heat resistance of the lake colorants of the triarylmethane-based dyes and suppresses changes in the chromaticity of the lake colorants after heating. Furthermore, when using lake colorants and pigments in combination as colorants, using polymers having the constituent units represented by the following general formula (I) as dispersants improves the dispersibility and storage stability of the pigments and makes it possible to form a colored layer with improved substrate adhesion and coating film uniformity. Polymers having the constituent units represented by the following general formula (I) are ethylenically unsaturated monomer polymers, and therefore have higher heat resistance of the skeleton compared to polyether-based and polyester-based polymers, and also have multiple acidic phosphorus compound groups (-P(=O)(-R) present in the polymer. 12 )(OH)) and its salts (-P(=O)(-R 12 )(O - X + It is presumed that this has a strong adsorption force to the surface of the finely particulated colorant. Furthermore, it is presumed that when the surface of the colorant is coated with at least one of the acidic phosphorus compound group and its salt, attack on the pigment skeleton of the lake colorant by reactive oxygen species such as peroxyl radicals (such as hydrogen abstraction and substitution reactions) is suppressed, and the deterioration (oxidative degradation) of the lake colorant is suppressed.

[0107] [ka] (In general formula (I), L 11 R is a direct bond or a divalent linking group. 11 is a hydrogen atom or a methyl group, R 12 is a hydroxyl group, a hydrocarbon group, -[CH(R 13 )-CH(R 14 )-O] x1 -R 15 ,-[(CH2) y1 -O] z1 -R 15 , or -OR 16 It is a monovalent group represented by R 16 This is a hydrocarbon group, -[CH(R 13 )-CH(R 14 )-O] x1 -R 15 ,-[(CH2) y1 -O] z1 -R 15 -C(R 17 )(R 18 )-C(R 19 )(R 20 )-OH, or -CH2-C(R 21 )(R 22 It is a monovalent group represented by )-CH2-OH. R 13 and R 14 Each is independently a hydrogen atom or a methyl group, and R 15 This refers to a hydrogen atom, a hydrocarbon group, -CHO, -CH2CHO, -CO-CH=CH2, -CO-C(CH3)=CH2, or -CH2COOR 23 It is a monovalent group represented by R 23 R is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. 17 , R 18 , R 19 , R 20 , R 21 and R 22 Each is independently a hydrogen atom, a hydrocarbon group, or a hydrocarbon group having one or more selected from ether bonds and ester bonds, R 17 and R19 These may bond to each other to form a ring structure. When the above ring structure is formed, the ring structure may further have substituents R 24 It may have R 24 (x1 is a hydrocarbon group, or a hydrocarbon group having one or more selected from ether and ester bonds. The hydrocarbon group may have substituents. X represents a hydrogen atom or an organic cation. x1 is an integer between 1 and 18, y1 is an integer between 1 and 5, and z1 is an integer between 1 and 18.)

[0108] In general formula (I), L 11 L is a direct bond or a divalent linking group. 11 A direct bond means that the phosphorus atom is directly bonded to the carbon atom of the main chain skeleton without the need for a linking group. L 11 As for the divalent linking group in L, there are no particular restrictions as long as it can link the carbon atom of the main chain skeleton with the phosphorus atom. 11 Examples of divalent linking groups in this invention include linear, branched, or cyclic alkylene groups, linear, branched, or cyclic alkylene groups having a hydroxyl group, arylene groups, -CONH- groups, -COO- groups, -NHCOO- groups, ether groups (-O- groups), thioether groups (-S- groups), and combinations thereof. In this invention, the orientation of the divalent linking group bond is arbitrary. That is, if the divalent linking group includes -CONH-, -CO may be on the carbon atom side of the main chain and -NH on the phosphorus atom side of the side chain, or conversely, -NH may be on the carbon atom side of the main chain and -CO on the phosphorus atom side of the side chain.

[0109] In particular, from the standpoint of dispersion, L in general formula (I) 11 It is preferable that the linking group is a divalent linking group containing a -CONH- group or a -COO- group. For example, L 11 If is a divalent linking group containing a -COO- group, then L 11 However, -COO-L 11 '-Base (Here, L 11 ' is an alkylene group having 1 to 8 carbon atoms, which may have a hydroxyl group, -[CH(RL11 )-CH(R L12 )-O] x -, or -[(CH2) y -O] z -(CH2) y -O-, -[CH(R L13 )] w -O-, and R L11 , R L12 and R L13 Each of these is independently a hydrogen atom, a methyl group, or a hydroxyl group. x is an integer between 1 and 18, y is an integer between 1 and 5, z is an integer between 1 and 18, and w is an integer between 1 and 18. ) is preferable.

[0110] L 11 The alkylene group in ' having 1 to 8 carbon atoms may be linear, branched, or cyclic, and may be, for example, a methylene group, ethylene group, trimethylene group, propylene group, various butylene groups, various pentylene groups, various hexylene groups, various octylene groups, etc., and some of the hydrogen atoms may be substituted with hydroxyl groups. x is an integer between 1 and 18, preferably between 1 and 4, more preferably between 1 and 2; y is an integer between 1 and 5, preferably between 1 and 4, more preferably 2 or 3; z is an integer between 1 and 18, preferably between 1 and 4, more preferably between 1 and 2; w is an integer between 1 and 18, preferably between 1 and 4.

[0111] L in general formula (I) 11 Suitable specific examples include, but are not limited to, -COO-CH2CH(OH)CH2-O-, -COO-CH2CH2-O-CH2CH(OH)CH2-O-, and -COO-CH2C(CH2CH3)(CH2OH)CH2-O-.

[0112] R 12 Examples of hydrocarbon groups in this context include alkyl groups having 1 to 18 carbon atoms, alkenyl groups having 2 to 18 carbon atoms, aralkyl groups, and aryl groups. The alkyl group having 1 to 18 carbon atoms may be linear, branched, or cyclic. Examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, cyclopentyl, cyclohexyl, bornyl, isobornyl, dicyclopentanyl, adamantyl, and lower alkyl-substituted adamantyl groups. The alkenyl group having 2 to 18 carbon atoms may be linear, branched, or cyclic. Examples of such alkenyl groups include vinyl groups, allyl groups, and propenyl groups. There are no limitations on the position of the double bond of the alkenyl group, but from the viewpoint of the reactivity of the resulting polymer, it is preferable that the double bond be at the end of the alkenyl group. Examples of aryl groups include phenyl groups, biphenyl groups, naphthyl groups, tolyl groups, xylyl groups, etc., and may further have substituents. The number of carbon atoms in the aryl group is preferably 6 to 24, and more preferably 6 to 12. Examples of aralkyl groups include benzyl groups, phenethyl groups, naphthylmethyl groups, and biphenylmethyl groups, and 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 alkyl or alkenyl group may have substituents, and examples of such substituents include halogen atoms such as F, Cl, and Br, and nitro groups. Furthermore, examples of substituents on aromatic rings such as aryl groups and aralkyl groups include linear and branched alkyl groups having 1 to 4 carbon atoms, as well as alkenyl groups, nitro groups, and halogen atoms. Note that the preferred number of carbon atoms mentioned above does not include the number of carbon atoms of substituents. The aforementioned R 12 In this case, x1 is the same as x, y1 is the same as y, and z1 is the same as z. R 15 ~R 22 Examples of hydrocarbon groups in the above R 12 Examples include hydrocarbon groups similar to those in [the relevant context].

[0113] R 17 , R 18 , R 19 , R 20 , R 21 and R 22 In this context, a hydrocarbon group having one or more selected from ether bonds and ester bonds is a group represented as -R'-OR'', -R'-(C=O)-OR'', or -R'-O-(C=O)-R'' (where R' and R'' are hydrocarbon groups, or groups in which a hydrocarbon group is linked by at least one ether bond and an ester bond). A single group may have two or more ether bonds and ester bonds. Examples of monovalent hydrocarbon groups include alkyl groups, alkenyl groups, aralkyl groups, and aryl groups, while examples of divalent hydrocarbon groups include alkylene groups, alkenylene groups, arylene groups, and combinations thereof.

[0114] R 17 and R 19 When atoms bond to form a ring structure, the number of carbon atoms forming the ring structure is preferably 5 to 8, more preferably 6, i.e., a 6-membered ring, and preferably a cyclohexane ring. Substituent R 24 In the above, a hydrocarbon group, or a hydrocarbon group having one or more selected from ether bonds and ester bonds, is R 17 , R 18 , R 19 , R 20 , R 21 and R 22 It can be made to be similar to the one in [location].

[0115] In terms of excellent dispersibility and dispersion stability of the dispersed particles, the R 12 However, hydroxyl group, hydrocarbon group, -[CH(R 13 )-CH(R 14 )-O] x1 -R 15 ,-[(CH2) y1 -O] z1 -R 15 , or -OR 16It is preferably a monovalent group represented by -[CH(R 13 )-CH(R 14 )-O] x1 -R 15 ,-[(CH2) y1 -O] z1 -R 15 , or -OR 16 The monovalent group shown is R 13 and R 14 Each of these is independently a hydrogen atom or a methyl group, and R 15 It is more preferable that -CO-CH=CH2 or -CO-C(CH3)=CH2, and among them, R 12 However, aryl groups, vinyl groups, methyl groups, and hydroxyl groups, which may have substituents, are more preferred.

[0116] Furthermore, R is improved in terms of alkali resistance. 12 This is a hydrocarbon group, -[CH(R 13 )-CH(R 14 )-O] x1 -R 15 , or -[(CH2) y1 -O] z1 -R 15 It is preferable that the group is a monovalent group represented by . If it has a structure in which a carbon atom is directly bonded to a phosphorus atom, it is presumed that it is possible to form a resin layer with excellent alkali resistance because it is less susceptible to hydrolysis. In particular, R 12 This includes a methyl group, an ethyl group, an optionally substituted aryl or aralkyl group, a vinyl group, an allyl group, and -[CH(R 13 )-CH(R 14 )-O] x1 -R 15 , or -[(CH2) y1 -O] z1 -R 15 The monovalent group shown is R 13 and R 14 Each of these is independently a hydrogen atom or a methyl group, and R 15Those in which are -CO-CH=CH2 or -CO-C(CH3)=CH2 are preferred because they have excellent alkali resistance and excellent dispersibility and dispersion stability of the dispersed particles. Among them, R 12 From the viewpoint of dispersibility, an aryl group which may have substituents is more preferable.

[0117] In general formula (I), X represents a hydrogen atom or an organic cation. An organic cation is one in which a carbon atom is contained in the cation portion. Examples of organic cations include imidazolium cation, pyridinium cation, aminidium cation, piperidinium cation, pyrrolidinium cation, ammonium cations such as tetraalkylammonium cation and trialkylammonium cation, sulfonium cations such as trialkylsulfonium cation, and phosphonium cations such as tetraalkylphosphonium cation. Among these, protonated nitrogen-containing organic cations are preferred from the viewpoint of dispersibility and alkali developability. In particular, when the organic cation has an ethylenically unsaturated bond, it is preferable because it can impart curability.

[0118] The constituent units represented by general formula (I) may be present in the polymer as a single unit or as two or more units.

[0119] In a polymer, the constituent units represented by general formula (I) may include both constituent units where X is a hydrogen atom and constituent units where X is an organic cation. When both constituent units are included, there are no particular restrictions as long as good dispersibility and dispersion stability are exhibited, however, it is preferable that the proportion of constituent units where X is an organic cation is 0 to 50 mol% of the total number of constituent units represented by general formula (I).

[0120] The method for synthesizing polymers having structural units represented by general formula (I) is not particularly limited, but for example, polymers having structural units represented by general formula (I) can be synthesized by referring to Japanese Patent Application Publication No. 2017-2191. The polymer having structural units represented by general formula (I) is preferably a polymer that is a reaction product of a polymer having at least one of an epoxy group and a cyclic ether group in its side chains and an acidic phosphorus compound, wherein at least a portion of the acidic phosphorus compound groups may form a salt.

[0121] In embodiments of the present invention, the polymer having the structural unit represented by general formula (I) is preferably further having solvent-affinity moieties from the viewpoint of dispersibility. Among such polymers, a graft copolymer having the structural unit represented by general formula (I) and the structural unit represented by general formula (II) below, or a block copolymer having the structural unit represented by general formula (I) and the structural unit represented by general formula (III) below, is preferred because it has excellent dispersibility and storage stability, and can form a high-contrast coating film even after long-term storage.

[0122] [ka] (In general formula (II), L 21 R is a direct bond or a divalent linking group. 25 is a hydrogen atom or a methyl group, and Polymer represents a polymer chain having a constituent unit represented by the following general formula (IV). In general formula (III), R 26 is a hydrogen atom or a methyl group, R 27 This is a hydrocarbon group, -[CH(R 28 )-CH(R 29 )-O] x2 -R 30 ,-[(CH2) y2 -O] z2 -R 30 ,-[CO-(CH2) y2 -O] z2 -R 30 , -CO-OR 30’ or -O-CO-R 30”The monovalent group shown is R 28 and R 29 Each is independently a hydrogen atom or a methyl group, R 30 This refers to a hydrogen atom, a hydrocarbon group, -CHO, -CH2CHO, or -CH2COOR 31 It is a monovalent group represented by R 30’ This is a hydrocarbon group, -[CH(R 28 )-CH(R 29 )-O] x2’ -R 30 ,-[(CH2) y2’ -O] z2’ -R 30 ,-[CO-(CH2) y2’ -O] z2’ -R 30 It is a monovalent group represented by R 30” R is an alkyl group having 1 to 18 carbon atoms. 31 This is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. The hydrocarbon group may have substituents. x2 and x2' are integers between 1 and 18 (inclusive), y2 and y2' are integers between 1 and 5 (inclusive), and z2 and z2' are integers between 1 and 18 (inclusive).

[0123] [ka] (In general formula (IV), R 32 R is a hydrogen atom or a methyl group, 33 The hydrocarbon group is -[CH(R 34 )-CH(R 35 )-O] x3 -R 36 ,-[(CH2) y3 -O] z3 -R 36 ,-[CO-(CH2) y3 -O] z3 -R 36 , -CO-OR 37 or -O-CO-R 38 The monovalent group shown is R 34 and R 35 Each is independently a hydrogen atom or a methyl group, R 36This refers to a hydrogen atom, a hydrocarbon group, -CHO, -CH2CHO, or -CH2COOR 39 The monovalent group shown is R 37 This is a hydrocarbon group, -[CH(R 34 )-CH(R 35 )-O] x4 -R 36 ,-[(CH2) y4 -O] z4 -R 36 ,-[CO-(CH2) y4 -O] z4 -R 36 The monovalent group shown is R 38 R is an alkyl group having 1 to 18 carbon atoms. 39 This is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and the hydrocarbon group 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.

[0124] (graft copolymer) Examples of graft copolymers preferred as acidic dispersants include graft copolymers having a constituent unit represented by the general formula (I) and a constituent unit represented by the general formula (II). In the above general formula (II), L 21 L is a direct bond or a divalent linking group. 21 The divalent linking group in is not particularly limited as long as it can link the carbon atom derived from the ethylenically unsaturated bond with the polymer chain. 21 Examples of divalent linking groups in the above are, 11 Examples include divalent linking groups similar to those in [the relevant context].

[0125] In the general formula (II) above, Polymer represents a polymer chain having the constituent units represented by the general formula (IV) above. In general formula (IV), R 33The hydrocarbon group in 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. These are, for example, the R mentioned above. 12 Similar examples include the above.

[0126] R 36 This refers to a hydrogen atom, or an alkyl group, aralkyl group, aryl group, -CHO, -CH2CHO, or -CH2COOR group having 1 to 18 carbon atoms. 39 A monovalent group represented by is preferred, R 37 This includes alkyl groups, aralkyl groups, aryl groups, and -[CH(R) 34 )-CH(R 35 )-O] x4 -R 36 ,-[(CH2) y4 -O] z4 -R 36 ,-[CO-(CH2) y4 -O] z4 -R 36 A monovalent group represented by R is preferred. 38 R is an alkyl group having 1 to 18 carbon atoms. 39 This represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. The aforementioned R 36 and R 37 Among these, alkyl groups, aralkyl groups, and aryl groups having 1 to 18 carbon atoms are defined as R 12 Similar examples include the above. The aforementioned R 38 and R 39 Among them, the alkyl group is the aforementioned R 12 Similar examples include the above. The aforementioned R 36 , R 37 and R 39 However, if the group has an aromatic ring, the aromatic ring may have further substituents. Examples of such substituents include linear, branched, or cyclic alkyl groups having 1 to 5 carbon atoms, as well as alkenyl groups, nitro groups, and halogen atoms such as F, Cl, and Br. Note that the preferred number of carbon atoms mentioned above does not include the number of carbon atoms of substituents. The aforementioned R 33 and R 37 In this case, x3 and x4 are the same as x, y3 and y4 are the same as y, and z3 and z4 are the same as z.

[0127] Furthermore, the R 33 , R 36 , R 37 , R 38 and R 39 The graft copolymer may be further substituted with substituents such as alkoxy groups, hydroxyl groups, carboxyl groups, amino groups, epoxy groups, isocyanate groups, and hydrogen bond-forming groups, to the extent that they do not impede the dispersion performance of the graft copolymer. Alternatively, after synthesizing a graft copolymer having these substituents, a polymerizable group may be added by reacting it with a compound having a functional group that reacts with the substituent and a polymerizable group. For example, a polymerizable group can be added by reacting a graft copolymer having a carboxyl group with glycidyl (meth)acrylate, or by reacting a graft copolymer having an isocyanate group with hydroxyethyl (meth)acrylate.

[0128] Polymer chains having structural units represented by general formula (IV) are preferably those having structural units derived from methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, adamantyl (meth)acrylate, styrene, α-methylstyrene, vinylcyclohexane, etc., among the aforementioned structural units. However, they are not limited to these.

[0129] In an embodiment of the present invention, the R 33 and R 37In particular, it is preferable to use one that has excellent solubility with the organic solvent described later, and it should be appropriately selected according to the organic solvent used in the colorant dispersion. Specifically, for example, when the organic solvent used is an organic solvent such as an ether alcohol acetate type, ether type, or ester type, which is commonly used as an organic solvent for colorant dispersions, methyl group, ethyl group, isobutyl group, n-butyl group, 2-ethylhexyl group, 2-ethoxyethyl group, cyclohexyl group, benzyl group, etc. are preferred. Here, the R 33 and R 37 The reason for setting it in this way is the aforementioned R 33 and R 37 This is because the constituent units containing the above are soluble in the organic solvent, and the acidic phosphorus compound group and its salt portion of the monomer have high adsorption properties to particles such as colorants, thereby making the dispersibility and stability of the particles such as colorants particularly excellent.

[0130] The weight-average molecular weight of the polymer chain in the polymer is preferably in the range of 500 to 15000, and more preferably in the range of 1000 to 8000. This range allows for sufficient steric repulsion as a dispersant, and also suppresses the increase in the time required for the dispersion of particles such as colorants due to steric effects.

[0131] Furthermore, as a guideline, the polymer chains in the polymer preferably have a solubility of 50 g / 100g solvent or more at 23°C in the organic solvent used in combination.

[0132] The polymer chain may be a homopolymer or a copolymer. Furthermore, the polymer chain included in the constituent unit represented by general formula (II) may be a single type or a mixture of two or more types in the graft copolymer.

[0133] Preferably, the total amount of the constituent unit represented by general formula (I) is 3% to 80% by mass of all constituent units of the graft copolymer, more preferably 10% to 70% by mass, and even more preferably 20% to 60% by mass. If the total content of the constituent unit represented by general formula (I) in the graft copolymer is within the above range, the proportion of affinity sites with particles in the graft copolymer becomes appropriate, and the decrease in solubility in organic solvents can be suppressed, resulting in good adsorption to particles such as colorants, and excellent dispersibility and dispersion stability. Furthermore, since the acidic phosphorus compound group of the graft copolymer can be stably localized around the colorant, a color filter with excellent heat resistance and contrast can be obtained. On the other hand, with respect to all the structural units of the graft copolymer, the structural unit represented by the 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. In this invention, the content ratio of each constituent unit in the copolymer is calculated from the amount used when synthesizing the copolymer.

[0134] Furthermore, the weight-average molecular weight of the 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. This range allows for uniform dispersion of particles such as colorants.

[0135] The graft copolymer used in the embodiments of the present invention may have other constituent units in addition to the constituent units represented by general formula (I) and general formula (II). For example, other constituent units can be introduced by appropriately selecting and copolymerizing an ethylenically unsaturated monomer that can copolymerize with an ethylenically unsaturated monomer that induces the constituent unit represented by general formula (I).

[0136] (Block copolymer) Examples of block copolymers preferred as acidic dispersants include block copolymers having a block portion containing a structural unit represented by the general formula (I) and a block portion containing a structural unit represented by the general formula (III). In the block copolymer, it is preferable that the block portion containing the constituent unit represented by the general formula (I) contains a total of 3 or more of the constituent unit represented by the general formula (I). In particular, from the viewpoint of good dispersibility and improved heat resistance, it is preferable to contain 3 to 200 units, more preferably 3 to 50 units, and even more preferably 3 to 30 units. The constituent unit represented by the general formula (I) above only needs to function as a colorant affinity part, and may consist of one type or may contain two or more types of constituent units. If it contains two or more types of constituent units, the two or more types of constituent units may be randomly arranged within the block containing the constituent unit represented by the general formula (I).

[0137] In the block copolymer, the total content of the constituent units represented by the general formula (I) 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, relative to the total constituent units of the block copolymer. If the values ​​are within the aforementioned range, the proportion of affinity sites with particles in the block copolymer becomes appropriate, and the decrease in solubility in organic solvents can be suppressed, resulting in good adsorption to particles such as colorants, and excellent dispersibility and dispersion stability. Furthermore, since the acidic phosphorus compound groups of the block copolymer can be stably localized around the colorants, a color filter with excellent heat resistance and contrast can be obtained.

[0138] The block copolymer, by having a block portion containing the constituent unit represented by the general formula (III), exhibits good solvent affinity, good dispersibility and dispersion stability of the colorant, good heat resistance, and further excellent resistance to N-methylpyrrolidone (NMP) (NMP resistance).

[0139] In general formula (III), R 27 This is a hydrocarbon group, -[CH(R 28 )-CH(R 29 )-O] x2 -R 30 ,-[(CH2) y2 -O] z2 -R 30 ,-[CO-(CH2) y2 -O] z2 -R 30 , -CO-OR 30’ or -O-CO-R 30” It is a monovalent group represented by [this symbol]. R 27 The hydrocarbon group in is the aforementioned R 12 It can be the same as the one shown.

[0140] Furthermore, the R 30 This refers to a hydrogen atom, a hydrocarbon group, -CHO, -CH2CHO, or -CH2COOR 31 It is a monovalent group represented by R 30’ This is a hydrocarbon group, -[CH(R 28 )-CH(R 29 )-O] x2’ -R 30 ,-[(CH2) y2’ -O] z2’ -R 30 ,-[CO-(CH2) y2’ -O] z2’ -R 30 It is a monovalent group represented by R 30” R is an alkyl group having 1 to 18 carbon atoms. 31 This is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and the hydrocarbon group may have substituents. The aforementioned R 30 The hydrocarbon group in R 12 It can be the same as the one shown. The aforementioned R 27 and R 30’ In this case, x2 and x2' are the same as x, y2 and y2' are the same as y, and z2 and z2' are the same as z. Furthermore, R in the constituent unit represented by the general formula (III) 27 These may be the same as or different from each other.

[0141] The aforementioned R 27 and R 30’ In particular, it is preferable to use one that has excellent solubility with solvents, as described later, for example, R 33 and R 37 Similar examples include the above. Furthermore, R in the general formula (IV) 27 , R 30 , R 30’ , R 30” and R 31 The constituent groups may be substituted with substituents such as alkoxy groups, hydroxyl groups, carboxyl groups, amino groups, epoxy groups, isocyanate groups, and hydrogen bond-forming groups, to the extent that they do not impede the dispersion performance of the block copolymer. Alternatively, the substituents may be added after the synthesis of the block copolymer by reacting it with a compound having the substituents. Furthermore, polymerizable groups may be added after the synthesis of the block copolymer having these substituents by reacting it with a compound having a functional group that reacts with the substituent and a polymerizable group. For example, polymerizable groups can be added by reacting a block copolymer having a glycidyl group with (meth)acrylic acid, or by reacting a block copolymer having an isocyanate group with hydroxyethyl (meth)acrylate.

[0142] The number of constituent units constituting the block portion, which includes the constituent unit represented by general formula (III), is not particularly limited. However, from the viewpoint of enabling the solvent affinity portion and the colorant affinity portion to work effectively and 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.

[0143] In the block copolymer, the content of the constituent unit represented by general formula (III) 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, relative to the total constituent units of the block copolymer.

[0144] The block portion containing the constituent unit represented by general formula (III) should be selected to function as a solvent affinity site, and the constituent unit represented by general formula (III) may consist of one type or may contain two or more types of constituent units. In embodiments of the present invention, when the constituent unit represented by general formula (III) contains two or more types of constituent units, the two or more types of constituent units may be randomly arranged within the block portion containing the constituent unit represented by general formula (III).

[0145] In block copolymers used as dispersants, the ratio m / n of the number of constituent units m in the block portion containing the constituent unit represented by general formula (I) to the number of constituent units n in the block portion containing the constituent 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 from the viewpoint of dispersibility and dispersion stability of the colorant.

[0146] The bonding order of the block copolymer is not particularly limited, as long as it has a block portion containing the structural unit represented by general formula (I) and a block portion containing the structural unit represented by general formula (III), and can stably disperse the colorant. However, it is preferable that the block portion containing the structural unit represented by general formula (I) is bonded only to one end of the block copolymer, as this provides excellent interaction with the colorant and effectively suppresses aggregation of the dispersants.

[0147] The weight-average molecular weight of the block copolymer is not particularly limited, but is preferably 2,500 to 500,000, more preferably 3,000 to 400,000, and even more preferably 6,000 to 300,000, in order to ensure good dispersibility and excellent heat resistance.

[0148] The acid value of the polymer having the constituent units represented by the general formula (I) is preferably 20 mg KOH / g or more, more preferably 30 mg KOH / g or more, and even more preferably 40 mg KOH / g or more, from the viewpoint of the dispersibility and storage stability of the colorant. On the other hand, from the viewpoint of excellent developability, the acid value of the polymer having the constituent units represented by the general formula (I) is preferably 150 mg KOH / g or less, more preferably 120 mg KOH / g or less, and even more preferably 100 mg KOH / g or less. In this invention, the acid value refers to the number of milligrams of potassium hydroxide required to neutralize the acidic components contained in 1 g of the sample, and can be measured according to JIS K 0070:1992.

[0149] On the other hand, the carboxyl group-containing block copolymer may include a block copolymer comprising block A containing structural units derived from a carboxyl group-containing ethylenically unsaturated monomer such as (meth)acrylic acid, and block B containing structural units derived from an alkyl (meth)acrylate. In the carboxyl group-containing block copolymer, block B containing structural units derived from an alkyl (meth)acrylate may be the same as that of a block copolymer having structural units represented by the general formula (I).

[0150] The content percentage (mol%) of each constituent unit in the copolymer of the dispersant can be determined from the amount of raw materials used during manufacturing, and can also be measured using analytical instruments such as NMR. Furthermore, the structure of the dispersant can be measured using NMR, various mass spectrometers, etc. Additionally, the dispersant can be decomposed by thermal decomposition as needed, and the resulting decomposition products can be analyzed using high-performance liquid chromatography, gas chromatography-mass spectrometry, NMR, elemental analysis, XPS / ESCA, and TOF-SIMS, etc.

[0151] In the present invention, the amount of dispersant can be appropriately selected depending on the type of colorant used, and further, the solid content concentration in the photosensitive colored resin composition described later. The dispersant content is preferably in the range of 2% to 30% by mass, and more preferably in the range of 3% to 25% by mass, relative to the total solid content of the photosensitive colored resin composition. If the content is above the lower limit, the dispersibility and dispersion stability of the colorant are excellent, and the storage stability of the photosensitive colored resin composition is excellent. If the content is below the upper limit, the developability is good.

[0152] [Antioxidant] The photosensitive colored resin composition of the present invention preferably further contains at least one antioxidant and a latent antioxidant, in order to improve heat resistance and brightness. The antioxidant used in the present invention is not particularly limited and may be appropriately selected from those conventionally known. Specific examples of antioxidants include hindered phenol antioxidants, amine antioxidants, phosphorus antioxidants, sulfur antioxidants, and hydrazine antioxidants. Hindered phenol antioxidants are preferred because they improve the ability to form fine line patterns according to the mask line width design and offer heat resistance. The latent antioxidant used in the present invention is a compound having a protecting group that can be removed by heating, and which exhibits antioxidant function upon removal of the protecting group. Among these, compounds in which the protecting group is easily removed by heating at 150°C or higher are preferred. Examples of latent antioxidants used in the present invention include those described in International Publication No. 2014 / 021023 and International Publication No. 2017 / 170263. Among these, latent antioxidants in which the phenolic hydroxyl group of a hindered phenolic antioxidant is protected by a protecting group are preferred, and more specifically, structures in which the hydrogen atoms of the phenolic hydroxyl group of a hindered phenolic antioxidant are substituted with a carbamate protecting group such as a t-butoxycarbonyl group are preferred.

[0153] Examples of hindered phenol antioxidants include pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (trade name: IRGANOX 1010, manufactured by BASF), 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate (trade name: Irganox 3114, manufactured by BASF), and 2,4,6-tris(4-hydroxy-3,5-di-tert-butylbenzyl Examples include 2,2'-methylenebis(6-tert-butyl-4-methylphenol) (product name: Sumirizer MDP-S, manufactured by Sumitomo Chemical), 6,6'-thiobis(2-tert-butyl-4-methylphenol) (product name: Irganox 1081, manufactured by BASF), and 3,5-di-tert-butyl-4-hydroxybenzylphosphonate diethyl (product name: Irgamod 195, manufactured by BASF). Among these, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (product name: IRGANOX 1010, manufactured by BASF) is preferred in terms of heat resistance and light resistance.

[0154] The antioxidant content is preferably in the range of 0.1% to 10.0% by mass, and more preferably in the range of 0.5% to 5.0% by mass, relative to the total solid content of the photosensitive colored resin composition. If it is above the lower limit, it is excellent in improving heat resistance and brightness. On the other hand, if it is below the upper limit, the colored resin composition of the present invention can be made into a highly sensitive photosensitive resin composition.

[0155] [Thiol compounds] The photosensitive colored resin composition of the present invention preferably further contains a thiol compound, in order to improve the effect of suppressing changes in film thickness before and after development, while maintaining a fine line width. Thiol compounds exhibit excellent surface hardening properties and improve the rate of residual film after development because the enethiol reaction is not inhibited by polymerization by oxygen. While thiol compounds also have the effect of increasing line width, when used in combination with UV absorbers, they have a synergistic effect that achieves both fine line width and improved residual film after development. Examples of thiol compounds include monofunctional thiol compounds with one thiol group and polyfunctional thiol groups with two or more thiol groups. Using polyfunctional thiols is more preferable in terms of achieving a fine line width and improving the suppression of film thickness changes before and after development. Examples of monofunctional thiol compounds include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-5-methoxybenzothiazole, 2-mercapto-5-methoxybenzimidazole, 3-mercaptopropionic acid, methyl 3-mercaptopropionate, ethyl 3-mercaptopropionate, and octyl 3-mercaptopropionate. Examples of polyfunctional thiol compounds include 1,4-bis(3-mercaptobutyryloxy)butane, 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutyrate), pentaerythritol tetrakis(3-mercaptopropionate), dipentaerythritol hexakis(3-mercaptopropionate), and tetraethylene glycol bis(3-mercaptopropionate). The thiol compound may be used alone or in combination of two or more, and among them, pentaerythritol tetrakis(3-mercaptobutyrate) is preferred because it has a fine line width and improves the effect of suppressing changes in film thickness before and after development. The thiol compound content is typically in the range of 0.5% to 10% by mass, preferably 1% to 5% by mass, relative to the total solid content of the photosensitive colored resin composition. If the content is above the lower limit, it exhibits excellent suppression of film thickness changes before and after development. On the other hand, if the content is below the upper limit, the photocurable red resin composition of the present invention tends to have good developability and suppressed line width shift.

[0156] [Other ingredients] The photosensitive colored resin composition of the present invention may contain various additives as needed. Examples of additives include polymerization inhibitors, chain transfer agents, leveling agents, plasticizers, surfactants, defoamers, silane coupling agents, adhesion promoters, ultraviolet absorbers, and the like. Specific examples of surfactants and plasticizers include, for example, those described in Japanese Patent Publication No. 2013-029832.

[0157] <Method for producing a photosensitive colored resin composition> The photosensitive colored resin composition of the present invention can be prepared by mixing a colorant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, a solvent, and optionally a dispersant and various additive components using known mixing methods. Examples of methods for preparing the resin composition include: (1) first adding a colorant and a dispersant to a solvent to prepare a colorant dispersion, and then mixing an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and various optional additives into the dispersion; (2) simultaneously adding and mixing a colorant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and various optional additives into a solvent; (3) adding an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and various optional dispersants and additives to a solvent, mixing them, and then adding and dispersing the colorant; (4) preparing a colorant dispersion by adding a colorant, a dispersant, and an alkali-soluble resin to a solvent, and then further adding an alkali-soluble resin, a solvent, a photopolymerizable compound, a photoinitiator, and various optional additives to the dispersion and mixing them; and so on. Among these methods, methods (1) and (4) above are preferred because they effectively prevent aggregation of the colorant and allow for uniform dispersion. In addition, in method (4), the alkali-soluble resin added to the colorant dispersion may or may not contain the alkali-soluble resin (U) used in the present invention.

[0158] The method for preparing the colorant dispersion can be appropriately selected from conventionally known dispersion methods. Examples of dispersers for dispersion processing include roll mills such as 2-roll and 3-roll mills, ball mills such as ball mills and vibrating ball mills, paint conditioners, continuous disc-type bead mills, and continuous annular-type bead mills. Preferred dispersion conditions for bead mills are that the bead diameter used is preferably 0.03 mm to 2.00 mm, and more preferably 0.10 mm to 1.0 mm.

[0159] [Application] The photosensitive colored resin composition according to the present invention contains a triarylmethane-based dye lake colorant, which improves brightness while forming a colored layer with a fine line width and suppressed changes in film thickness before and after development. Therefore, it can be suitably used for color filter applications.

[0160] [Cured product of photosensitive colored resin composition] The cured product according to the present invention is a cured product of the photosensitive colored resin composition according to the present invention. The cured product according to the present invention can be obtained by forming a coating film of the photosensitive colored resin composition according to the present invention, drying the coating film, and then exposing and developing it. The method for forming the coating film, exposure, and development can be, for example, the same method used in forming the colored layer of the color filter according to the present invention, which will be described later. Furthermore, the cured product according to the present invention contains a triarylmethane-based dye lake colorant, improving brightness while having a fine line width and suppressing changes in film thickness before and after development, making it suitable for use as a colored layer for color filters.

[0161] PRO Color Filters The color filter according to the present invention comprises at least a substrate and a colored layer provided on the substrate, wherein at least one of the colored layers is a cured product of the photosensitive colored resin composition according to the present invention.

[0162] The color filter according to 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 colored layer 3.

[0163] [Colored layer] The colored layer used in the color filter of the present invention is a colored layer in which at least one of the layers is a cured product of the photosensitive colored resin composition according to the present invention. The colored layer is typically formed in the openings of the light-shielding portion on the substrate, as described later, and usually consists of a colored pattern of three or more colors. Furthermore, the arrangement of the colored layer is not particularly limited and can be a general arrangement such as a stripe pattern, mosaic pattern, triangle pattern, or 4-pixel arrangement. The width and area of ​​the colored layer can also be set arbitrarily. The thickness of the colored layer can be appropriately controlled by adjusting the coating method, the solid content concentration and viscosity of the photosensitive colored resin composition, etc., but it is generally preferable to have a thickness in the range of 1 μm to 5 μm.

[0164] The colored layer can be formed, for example, by the following method. First, the photosensitive colored resin composition of the present invention described above is applied to a substrate, described later, using coating methods such as spray coating, dip coating, bar coating, roll coating, spin coating, and die coating to form a wet coating film. Among these, spin coating and die coating are preferably used. Next, the wet coating is dried using a hot plate or oven, and then exposed to light through a mask with a predetermined pattern to cause a photopolymerization reaction of alkali-soluble resin and polyfunctional monomers, etc., to form a cured coating. Examples of light sources used for exposure include ultraviolet light from low-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, electron beams, etc. The amount of exposure is adjusted as appropriate depending on the light source used and the thickness of the coating. Furthermore, heat treatment may be performed after exposure to promote the polymerization reaction. The heating conditions are appropriately selected depending on the mixing ratio of each component in the photosensitive colored resin composition used, the thickness of the coating film, etc.

[0165] Next, the film is developed using a developing solution to dissolve and remove the unexposed areas, thereby forming a coating with the desired pattern. Typically, a solution of alkali dissolved in water or a water-soluble solvent is used as the developing solution. A suitable amount of surfactant may be added to this alkaline solution. Furthermore, a general development method can be employed. After the developing process, the developing solution is usually washed off and the cured coating film of the photosensitive colored resin composition is dried to form the colored layer. Alternatively, heat treatment may be performed after the developing process to sufficiently cure the coating film. There are no particular limitations on the heating conditions, and they can be appropriately selected depending on the application of the coating film.

[0166] [Light-blocking part] The light-shielding portion in the color filter of the present invention is formed in a pattern on a substrate, as described later, and can be the same as that used as a light-shielding portion in a general color filter. The pattern shape of the light-shielding portion is not particularly limited, and examples include stripe-like and matrix-like shapes. The light-shielding portion may be a thin metal film such as chromium produced by sputtering or vacuum deposition. Alternatively, the light-shielding portion may be a resin layer containing light-shielding particles such as carbon nanoparticles, metal oxides, inorganic pigments, or organic pigments in a resin binder. In the case of a resin layer containing light-shielding particles, methods include patterning by developing with a photosensitive resist, patterning with an inkjet ink containing light-shielding particles, or thermal transfer of a photosensitive resist.

[0167] The film thickness of the light-shielding portion is set to approximately 0.2 μm to 0.4 μm for thin metal films, and approximately 0.5 μm to 2 μm for films in which black pigment is dispersed or dissolved in a binder resin.

[0168] [substrate] As substrates, transparent substrates, silicon substrates, and substrates on which aluminum, silver, silver / copper / palladium alloy thin films are formed are used, as described later. Other color filter layers, resin layers, transistors such as TFTs, circuits, etc. may be formed on these substrates. The transparent substrate in the color filter of the present invention is not particularly limited and can be any substrate that is transparent to visible light; a transparent substrate commonly used in color filters can be used. Specifically, examples include rigid transparent materials that do not allow flexibility, such as quartz glass, alkali-free glass, or synthetic quartz plates, or flexible transparent materials that allow flexibility, such as transparent resin films, optical resin plates, or flexible glass. The thickness of the transparent substrate is not particularly limited, but depending on the application of the color filter of the present invention, for example, a thickness of about 100 μm to 1 mm can be used. Furthermore, the color filter of the present invention may have, in addition to the substrate, light-shielding portion, and colored layer described above, also an overcoat layer, a transparent electrode layer, or even an alignment film or columnar spacer formed on it.

[0169] IV.Display device The display device according to the present invention is characterized by having the color filter according to the present invention. The configuration of the display device in the present invention is not particularly limited and can be appropriately selected from conventionally known display devices, such as liquid crystal display devices and organic light-emitting display devices.

[0170] [Liquid crystal display device] Examples of liquid crystal display devices of the present invention include a liquid crystal display device having the color filter according to the present invention described above, a counter substrate, and a liquid crystal layer formed between the color filter and the counter substrate. The liquid crystal display device of the present invention will be described with reference to the figures. Figure 2 is a schematic diagram showing an example of the liquid crystal display device of the present invention. As illustrated in Figure 2, the liquid crystal display device 40 of the present invention has a color filter 10, a counter substrate 20 having a TFT array substrate or the like, and a liquid crystal layer 30 formed between the color filter 10 and the counter substrate 20. It should be noted that the liquid crystal display device of the present invention is not limited to the configuration shown in Figure 2, and can be configured in a way that is generally known as a liquid crystal display device using a color filter.

[0171] The driving method for the liquid crystal display device of the present invention is not particularly limited, and any driving method commonly used in liquid crystal display devices can be employed. Examples of such driving methods include the TN method, IPS method, OCB method, and MVA method. Any of these methods can be suitably used in the present invention. Furthermore, the opposing substrate can be appropriately selected and used depending on the driving method of the liquid crystal display device of the present invention. Furthermore, as the liquid crystals constituting the liquid crystal layer, various liquid crystals with different dielectric anisotropy, and mixtures thereof, can be used depending on the driving method of the liquid crystal display device of the present invention.

[0172] As for the method of forming the liquid crystal layer, methods generally used for manufacturing liquid crystal cells can be used, such as the vacuum injection method or the liquid crystal drop method. After forming the liquid crystal layer by the above method, the sealed liquid crystal can be aligned by slowly cooling the liquid crystal cell to room temperature.

[0173] [Organic light-emitting display device] Examples of organic light-emitting devices of the present invention include an organic light-emitting device having the color filter and organic light-emitting element described above. 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 has a color filter 10 and an organic light-emitting element 80. An organic protective layer 50 or an inorganic oxide film 60 may be provided between the color filter 10 and the organic light-emitting element 80.

[0174] Examples of methods for laminating the organic light-emitting element 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 laminating an organic light-emitting element 80 formed on a separate 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, cathode 76, and other components of the organic light-emitting element 80 can be those of known origin or design. The organic light-emitting display device 100 thus fabricated can be applied to both passively driven organic EL displays and actively driven organic EL displays, for example. It should be noted that the organic light-emitting display device of the present invention is not limited to the configuration shown in Figure 3, and can be configured in a way that is generally known as an organic light-emitting display device using a color filter. [Examples]

[0175] The present invention will be described in detail below with reference to examples. These descriptions are not intended to limit the present invention. The weight-average molecular weight (Mw) of the copolymer before salt formation was determined as a standard polystyrene equivalent value by GPC (gel permeation chromatography) according to the measurement method described in the specification of the present invention.

[0176] (Manufacturing Example 1: Preparation of alkali-soluble resin U1) 150 parts by mass of PGMEA were charged into the polymerization tank, and after raising the temperature to 100°C under a nitrogen atmosphere, 34 parts by mass of methyl methacrylate (MMA), 35 parts by mass of benzyl methacrylate (BzMA), 1 part by mass of 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole (RUVA-93, trade name, manufactured by Otsuka Chemical Co., Ltd.), 18 parts by mass of methacrylic acid (MAA), 3 parts by mass of perbutyl O (manufactured by NOF Corporation), and 9 parts by mass of a chain transfer agent (n-dodecyl mercaptan) were added. The mixture was added dropwise continuously over 1.5 hours. The reaction was then continued at 100°C, and 2 hours after the completion of the addition of the main chain forming mixture, 0.1 parts by mass of p-methoxyphenol was added as a polymerization inhibitor to stop the polymerization. Next, while blowing air in, 12 parts by mass of glycidyl methacrylate (GMA) as an epoxy group-containing compound was added, the temperature was raised to 110°C, and then 0.8 parts by mass of triethylamine was added and the addition reaction was carried out at 110°C for 15 hours to obtain an alkali-soluble resin U1 solution (weight-average molecular weight (Mw) 8000, acid value 75 mg KOH / g, solid content 40% by mass). The weight-average molecular weight was measured using the Shodex GPC System-21H, with polystyrene as the standard substance and THF as the eluent. The acid value was measured according to JIS K 0070.

[0177] (Manufacturing Examples 2-12: Preparation of alkali-soluble resins U2-U12) Alkali-soluble resins U2 to U12 were prepared in the same manner as in Production Example 1, except that the mass ratio of the monomers used was changed to the amounts listed in Table 1. In addition, the weight-average molecular weight in production examples 7-12 was adjusted by changing the amounts of perbutyl O and the chain transfer agent (n-dodecyl mercaptan). The weight-average molecular weight and acid value of the obtained alkali-soluble resin are also shown in Table 1.

[0178] (Comparative manufacturing example 1: Preparation of alkali-soluble resin P1) Alkali-soluble resin P1 was prepared in the same manner as in Production Example 1, except that RUVA-93 was not used and the mass ratio of the other monomers used was changed to the amounts listed in Table 1. The weight-average molecular weight and acid value of the obtained alkali-soluble resin are also shown in Table 1.

[0179] (Comparative manufacturing examples 2-4: Preparation of alkali-soluble resin P2, and resins P3 and P4) Alkali-soluble resin P2, and resins P3 and P4 were prepared in the same manner as in Production Example 1, except that the mass ratio of the monomers used was changed to the amounts listed in Table 1, and the amounts of perbutyl O and the chain transfer agent (n-dodecyl mercaptan) were also changed. The weight-average molecular weight and acid value of the obtained resin are also shown in Table 1.

[0180] [Table 1] The abbreviations for the monomers used in the table are as follows: MMA: Methyl methacrylate BzMA: Benzyl methacrylate RUVA-93:2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole (trade name, manufactured by Otsuka Chemical Co., Ltd.) MAA: Methacrylic acid GMA: Glycidyl methacrylate BMA: n-butyl methacrylate

[0181] (Synthesis Example 1: Synthesis of Lake Colorant 1) (1) Synthesis of intermediate 1 Referring to the methods for producing intermediates A-2, B-1, and compound 1-3 described in Japanese Patent Publication No. 2018-3013, intermediate 1 represented by the following chemical formula (a) was obtained (yield 87%). The obtained compound was confirmed to be the target compound based on the analysis results below. ·MS(ESI) (m / z):677(+), bivalent • Elemental analysis values: CHN measured values ​​(81.81%, 7.31%, 5.85%); theoretical values ​​(81.77%, 7.36%, 5.90%)

[0182] [ka]

[0183] (2) Synthesis of Lake Colorant 1 2.59 g (0.76 mmol) of Kanto Chemical's 12-tungst phosphate n-hydrate was heated and dissolved in a mixture of 40 mL of methanol and 40 mL of water. 1.6 g (1.19 mmol) of the aforementioned intermediate 1 was added, and the mixture was stirred for 1 hour. The precipitate was filtered and washed with water. The obtained precipitate was dried under reduced pressure to obtain lake colorant 1 represented by the following chemical formula (b) (yield 95%). The obtained compound was confirmed to be the target compound based on the analysis results below. ·31P NMR(d-DMSO, ppm)δ-15.15 MS (MALDI) (m / z): 1355 (M + ), 2879 (MH2 - ) • Elemental analysis values: CHN measured values ​​(35.55%, 3.24%, 2.61%); theoretical values ​​(35.61%, 3.20%, 2.57%) • X-ray fluorescence analysis: MoW measurement ratio (0%, 100%); theoretical value (0%, 100%)

[0184] [ka]

[0185] (Synthesis Example 2: Synthesis of Lake Colorant 2) (1) K6(P2MoW 17 O 62 Preparation of ) 44.0 g of NaWO4·2H2O (manufactured by Wako Pure Chemical Industries, Ltd.) and 1.90 g of Na2MoO4·2H2O (manufactured by Kanto Chemical Co., Ltd.) were dissolved in 230 g of purified water. 64.9 g of 85% phosphoric acid was added to this solution dropwise using a funnel while stirring. The resulting solution was heated under reflux for 8 hours. The reaction mixture was cooled to room temperature, 1 drop of bromine water was added, and 45 g of potassium chloride was added while stirring. After stirring for another hour, the precipitate was filtered off. The resulting solid was dried at 90°C to obtain 29.4 g of K6(P2MoW 17 O 62 ) was obtained. (2) Synthesis of Lake Colorant 2 5.30 g of CI Basic Blue 7 (BB7) (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to 350 ml of purified water and stirred at 40°C to dissolve it and prepare the BB7 solution. Separately, the K6 (P2MoW) prepared in (1) above was used. 17 O 62 ) 10.0g was dissolved in 40ml of purified water. K6(P2MoW) was added to the BB7 solution. 17 O 62 The solution was added and stirred at 40°C for 1 hour. Next, the internal temperature was raised to 80°C and stirred for another hour to induce lake formation. After cooling, the mixture was filtered and washed three times with 300 ml of purified water. By drying the obtained solid at 90°C, 10.4 g of lake colorant 2, a blackish-blue solid with an average primary particle size of 40 nm, consisting of a triarylmethane dye and a polyacid, was obtained.

[0186] (Synthesis Example 3: Synthesis of Acidic Dispersant A1 (a polymer having at least one component selected from the constituent units represented by the general formula (I) above)) (1) Synthesis of macromonomer MM-1 In a reactor equipped with a condenser, an additive funnel, a nitrogen inlet, a mechanical stirrer, and a digital thermometer, 80.0 parts by mass of propylene glycol monomethyl ether acetate (PGMEA) was charged and heated to 90°C while stirring under a nitrogen atmosphere. A mixed solution of 50.0 parts by mass of methyl methacrylate, 30.0 parts by mass of n-butyl methacrylate, 20.0 parts by mass of benzyl methacrylate, 4.0 parts by mass of 2-mercaptoethanol, 30 parts by mass of PGMEA, and 1.0 part by mass of α,α'-azobisisobutyronitrile (AIBN) was added dropwise over 1.5 hours, and the reaction was continued for a further 3 hours. Next, the nitrogen gas flow was stopped, and the reaction solution was cooled to 80°C. 8.74 parts by mass of currant MOI (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 macromonomer MM-1. GPC measurements of the obtained macromonomer MM-1 showed a weight-average molecular weight (Mw) of 4010, a number-average molecular weight (Mn) of 1910, and a molecular weight distribution (Mw / Mn) of 2.10.

[0187] (2) Synthesis of graft copolymer A1 In a reactor equipped with a condenser, an additive funnel, a nitrogen inlet, a mechanical stirrer, and a digital thermometer, 85.0 parts by mass of PGMEA were charged and heated to 90°C while stirring under a nitrogen stream. A mixed solution of 67.34 parts by mass (33.33 parts by mass of solids) of the macromonomer MM-1 solution, 16.67 parts by mass of glycidyl methacrylate (abbreviated as GMA), 1.24 parts by mass of n-dodecyl mercaptan, 25.0 parts by mass of PGMEA, and 0.5 parts by mass of AIBN was added dropwise over 1.5 hours, and after heating and stirring for 3 hours, a mixed solution of 0.10 parts by mass of AIBN and 10.0 parts by mass of PGMEA was added dropwise over 10 minutes, and the mixture was further aged at the same temperature for 1 hour to obtain a 25.0% by mass solution of graft copolymer A1. The obtained graft copolymer A1 was measured by GPC and found to have a weight-average molecular weight (Mw) of 10570, a number-average molecular weight (Mn) of 4370, and a molecular weight distribution (Mw / Mn) of 2.42.

[0188] (3) Production of a polymer (acidic dispersant A1) having at least one selected from the constituent units represented by the general formula (I) above. In a reactor equipped with a condenser, an additive funnel, a nitrogen inlet, a mechanical stirrer, and a digital thermometer, 27.80 parts by mass of PGMEA and 9.27 parts by mass of phenylphosphonic acid (product name "PPA," manufactured by Nissan Chemical) were charged, and the mixture was heated to 90°C while being stirred under a nitrogen atmosphere. 100.0 parts by mass of the graft copolymer A1 was added dropwise over 30 minutes, and the mixture was heated and stirred for 2 hours to obtain a polymer solution (acidic dispersant A1) having at least one constituent unit selected from the general formula (I) (solid content 25.0% by mass). The progress of the esterification reaction between GMA and PPA of the obtained acidic dispersant A1 was measured by acid value measurement and 1 This was confirmed by 1H-NMR measurement (confirming the disappearance of the epoxy-derived peak). The acid value of the obtained acidic dispersant A1 was 98 mgKOH / g.

[0189] (Synthesis Example 4: Synthesis of Acidic Dispersant A2 (a block copolymer containing a block A with structural units derived from a carboxyl group-containing ethylenically unsaturated monomer and a block B with structural units derived from an alkyl (meth)acrylate)) Referring to Example 1 described in International Publication No. 2016 / 132863, a triblock copolymer was synthesized comprising a block containing 20 parts by mass of methyl methacrylate (MMA) and 40 parts by mass of n-butyl methacrylate (BMA), a block containing 20 parts by mass of methacrylic acid (MAA) and 20 parts by mass of BMA, and a block containing 20 parts by mass of MMA and 40 parts by mass of BMA. The obtained block copolymer had a weight-average molecular weight (Mw) of 11000, a molecular weight distribution (Mw / Mn) of 1.50, and an acid value of 130 mgKOH / g.

[0190] (Synthesis Example 5: Synthesis of Latent Antioxidants) 0.01 mol of the phenol compound represented by the following chemical formula (c), 0.05 mol of di-tert-butyl dicarbonate, and 30 g of pyridine were mixed. Under a nitrogen atmosphere, at room temperature, 0.025 mol of 4-dimethylaminopyridine was added, and the mixture was stirred at 60°C for 3 hours. After cooling to room temperature, the reaction mixture was poured into 150 g of deionized water, and 200 g of chloroform was added to separate the oil and water. The organic layer was dried over anhydrous sodium sulfate, the solvent was removed by distillation, and 100 g of methanol was added to the residue to perform crystallization. The obtained white powdery crystals were dried under reduced pressure at 60°C for 3 hours to obtain a latent antioxidant (AO1). The structure of the obtained latent antioxidant was confirmed by IR and NMR.

[0191] [ka]

[0192] (Comparative synthesis example 1: Synthesis of triarylmethane dye 1) Triarylmethane-based dye 1 was synthesized in the same manner as dye A described in Example 1 of Japanese Patent Publication No. 2011-133844. First, (tosyl)trifluoromethanesulfonylimidate triethylamine salt was synthesized as described in Example 1 of Japanese Patent Publication No. 2011-133844. Next, 5 g of CI Basic Blue 7 (N-[4-[[4-(diethylamino)phenyl][4-(ethylamino)-1-naphthyl]methylene]-2,5-cyclohexadiene-1-ylidene]-N-ethylethaneaminium chloride) (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 30 mL of methanol, and 3.93 g of (tosyl)trifluoromethanesulfonylimidate triethylamine salt was added while stirring, 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, the precipitate was filtered off and washed with water. The cake was dried under reduced pressure to obtain triarylmethane dye 1.

[0193] (Example 1: Production of photosensitive colored resin composition 1) (1) Preparation of colorant dispersion D1 In a 225 mL mayonnaise bottle, 61 parts by mass of PGMEA, 5 parts by mass of alkali-soluble resin P1 solution (40% solids by mass) from Comparative Production Example 1, and 24 parts by mass of acidic dispersant A1 solution (25.0% solids by mass) from Synthesis Example 3 were added and stirred. To this, 10 parts by mass of the triarylmethane-based lake colorant 1 from Synthesis Example 1 and 100 parts by mass of 2.0 mm particle size zirconia beads were added, and the mixture was shaken for 1 hour using a paint shaker (manufactured by Asada Iron Works Co., Ltd.) as a preliminary crushing. Then, 200 parts of 0.1 mm particle size zirconia beads were added, and the mixture was dispersed for 4 hours using a paint shaker as a final crushing to obtain colorant dispersion D1.

[0194] (2) Preparation of photosensitive binder component B1 26.4 parts by mass of the alkali-soluble resin U1 solution (40% solids by mass) obtained in Production Example 1, 12.3 parts by mass of a photopolymerizable compound (trade name Arronix M-403, dipentaerythritol penta-hexaacrylate, manufactured by Toagosei Co., Ltd.), 12.3 parts by mass of a photopolymerizable compound (trade name Arronix M-305, pentaerythritol tri-tetraacrylate, manufactured by Toagosei Co., Ltd.), 2.4 parts by mass of photoinitiator 1: Irgacure 907 (manufactured by BASF, α-aminoacetophenone-based photoinitiator) and 2.4 parts by mass of photoinitiator 2: OXE-02 (manufactured by BASF, oxime ester-based photoinitiator having a carbazole skeleton), 0.8 parts by mass of the latent antioxidant (AO1) from Synthesis Example 5, and 45.4 parts by mass of PGMEA were added to obtain photosensitive binder component B1. (3) Preparation of photosensitive colored resin composition 1 The above-mentioned colorant dispersion D1 was mixed with 3.33 parts by mass of photosensitive binder component B1, 35.0 parts by mass of fluorine-based surfactant (product name Megafac F559, manufactured by DIC Corporation), 0.2 parts by mass of silane coupling agent (product name KBM503, manufactured by Shin-Etsu Silicone), and 61.67 parts by mass of PGMEA to prepare the photosensitive colored resin composition of Example 1.

[0195] (Examples 2-18, 20-22: Production of photosensitive colored resin compositions 2-18, 20-22) In addition to changing the alkali-soluble resin in the photosensitive binder component B1 of Example 1, by replacing the alkali-soluble resin U1 solution with at least one of the alkali-soluble resin U2 to U12 solutions, and optionally further adding alkali-soluble resin P1 solution, as shown in Table 2, and optionally changing the type of antioxidant, the type of polymerizable compound, or the addition of thiols, photosensitive colored resin compositions 2 to 18 and 20 to 22 were obtained in the same manner as photosensitive colored resin composition 1 of Example 1.

[0196] (Example 19: Production of photosensitive colored resin composition 19) (1) Preparation of colorant dispersion D2 In a 225 mL mayonnaise bottle, 61 parts by mass of PGMEA, 5 parts by mass of alkali-soluble resin P1 solution (40% solids by mass) from Comparative Production Example 1, and 24 parts by mass of acidic dispersant A1 solution (25.0% solids by mass) from Synthesis Example 3 were added and stirred. To this, 10 parts by mass of the triarylmethane-based lake colorant 2 from Synthesis Example 2 and 100 parts by mass of 2.0 mm particle size zirconia beads were added, and the mixture was shaken for 1 hour using a paint shaker (manufactured by Asada Iron Works Co., Ltd.) as a preliminary crushing. Then, 200 parts of 0.1 mm particle size zirconia beads were added, and the mixture was dispersed for 4 hours using a paint shaker as a final crushing to obtain colorant dispersion D2. (2) Preparation of photosensitive colored resin composition 19 In Example 6, a photosensitive colored resin composition 19 was obtained in the same manner as the photosensitive colored resin composition 6 of Example 6, except that the colorant dispersion D1 was changed to colorant dispersion D2.

[0197] (Comparative Examples 1-2, 6-7: Production of comparative photosensitive colored resin compositions 1-2, 6-7) In the photosensitive binder component B1 of Example 1, the alkali-soluble resin was changed from the alkali-soluble resin U1 solution to the alkali-soluble resin P1 solution. In Comparative Examples 2, 6, and 7, as shown in Table 2, the photosensitive binder components CB1 to CB2 and CB6 to CB7 were prepared and used using the alkali-soluble resin P2 solution, resin P3 solution, or resin P4 solution. Other than these differences, comparative photosensitive colored resin compositions 1 to 2 and 6 to 7 were obtained in the same manner as the photosensitive colored resin composition 1 of Example 1.

[0198] (Comparative Examples 3-5: Manufacturing of Comparative Photosensitive Colored Resin Compositions 3-5) Comparative photosensitive colored resin compositions 3 to 5 were obtained in the same manner as photosensitive colored resin composition 1 of Example 1, except that in the photosensitive binder component B1 of Example 1, the alkali-soluble resin was changed from the alkali-soluble resin U1 solution to the alkali-soluble resin P1 solution, and further, as shown in Table 2, photosensitive binder components CB3 to CB5 were prepared and used using an ultraviolet absorber.

[0199] (Comparative Example 8: Production of Comparative Photosensitive Colored Resin Composition 8) (1) Preparation of colorant dispersion CD1 In a 225 mL mayonnaise bottle, 57.5 parts by mass of PGMEA, 7.5 parts by mass of alkali-soluble resin P1 solution (40% solids by mass) from Comparative Production Example 1, and 25 parts by mass of PGMEA solution of acidic dispersant A2 (20.0% solids by mass) from Synthesis Example 4 were added and stirred. To this, 8.8 parts by mass of PB15:6, 1.2 parts by mass of PV23, and 100 parts by mass of 2.0 mm particle size zirconia beads were added. As a preliminary crushing, the mixture was shaken for 1 hour using a paint shaker (manufactured by Asada Iron Works Co., Ltd.). Then, 200 parts of 0.1 mm particle size zirconia beads were added, and the mixture was dispersed for 4 hours using a paint shaker as the main crushing to obtain the colorant dispersion CD1. (2) Preparation of comparative photosensitive colored resin composition 8 Photosensitive binder component CB8 was prepared in the same manner as photosensitive binder component B1 of Example 1, except that in the photosensitive binder component B1 of Example 1, an alkali-soluble resin P1 solution was used instead of an alkali-soluble resin U1 solution, and the content of each component was changed as shown in Table 2. A comparative photosensitive colored resin composition 8 was obtained by mixing 3.33 parts by mass of colorant dispersion CD1, 35.0 parts by mass of photosensitive binder component CB8, 0.2 parts by mass of fluorine-based surfactant (product name Megafac F559, manufactured by DIC Corporation), 2 parts by mass of silane coupling agent (product name KBM503, manufactured by Shin-Etsu Silicone), and 61.67 parts by mass of PGMEA.

[0200] [Evaluation Method] The photosensitive colored resin compositions of the examples and comparative examples were each applied to a 0.7 mm thick glass substrate ("NA35" manufactured by NH Techno Glass Co., Ltd.) using a spin coater to achieve a post-bake film thickness of 2.2 μm, and then heated and dried on a hot plate at 80°C for 3 minutes. Subsequently, a photomask forming a 40 μm line was used to apply a pressure of 60 mJ / cm² using an ultra-high pressure mercury lamp. 2 The substrate was irradiated with ultraviolet light, and then shower-developed for 60 seconds using a 0.05% by mass potassium hydroxide aqueous solution as an alkaline developer. Subsequently, a pattern-forming substrate was fabricated on the glass substrate by post-baking in a clean oven at 230°C for 30 minutes, resulting in a colored layer with a 40 μm line pattern.

[0201] <Suppression of line width increase in the colored layer> The width of the fine line pattern in the colored layer corresponding to the 40 μm aperture width of the chrome mask used during exposure was measured at five locations using an optical microscope. The amount of line width shift was evaluated by the difference between the average line width and the target line width. (Evaluation criteria for suppressing line width increase) AA: Difference from the target line width is within 5.0 μm. A: The difference from the target line width is between 5.0 μm and 5.5 μm. B: Difference from the target line width is between 5.5 μm and 7.0 μm. C: Difference from the target line width exceeds 7.0 μm. An evaluation result of A indicates good suppression of line width increase, while an evaluation result of AA indicates excellent suppression of line width increase.

[0202] <Evaluation of residual film after development> The photosensitive colored resin compositions of the examples and comparative examples were each applied to a 0.7 mm thick glass substrate ("NA35" manufactured by NH Techno Glass Co., Ltd.) using a spin coater to achieve a post-baking film thickness of 2.2 μm, and then heated and dried on a hot plate at 80°C for 3 minutes. Subsequently, without using a photomask, a pressure of 60 mJ / cm² was applied using an ultra-high pressure mercury lamp. 2 The resist coating was irradiated with ultraviolet light, and then the film thickness T1 was measured using a film thickness gauge. Next, the film was shower-developed for 60 seconds using a 0.05 mass% potassium hydroxide aqueous solution as the alkaline developer, and the film thickness T2 after development was measured. The developing residue rate was calculated as T2 / T1 [%]. (Development residual film rate evaluation criteria) AA: Development residue rate of 98% or higher A: Development residue rate is 97% or more but less than 98% B: Development residue rate is 94% or more but less than 97% C: Development residue rate is less than 94%

[0203] <Brightness and heat resistance evaluation> The photosensitive colored resin compositions of the examples and comparative examples were each applied to a 0.7 mm thick glass substrate ("NA35" manufactured by NH Techno Glass Co., Ltd.) using a spin coater so that the chromaticity after post-baking was y = 0.088. Then, they were heated and dried on an 80°C hot plate for 3 minutes, and then subjected to a high-pressure mercury lamp at 60 mJ / cm² without a photomask. 2 A cured film (colored film) was obtained by irradiating the substrate with ultraviolet light and then post-baking it in a clean oven at 230°C for 30 minutes. The brightness (Y), L, a, and b (L0, a0, b0) of the obtained colored substrate were measured using an Olympus OSP-SP200 microspectroscopy analyzer and evaluated according to the following evaluation criteria. Next, the substrates on which the cured film described above was formed were post-baked in a clean oven at 230°C for 30 minutes, followed by a 30-minute cooling period. This process was repeated three times, and the L, a, and b (L1, a1, b1) values ​​of the resulting colored substrates were measured. The color difference (ΔEab) before and after treatment was calculated from the measured values ​​according to the following formula. Color difference (ΔEab) ={(L1-L0)2 +(a1-a0) 2 +(b1-b0) 2} 1 / 2

[0204] (Brightness evaluation criteria) AA: Brightness (Y) is 10.6 or higher A: Brightness (Y) is between 10.0 and less than 10.6 B: Brightness (Y) is between 9.5 and less than 10.0 C: Brightness (Y) is less than 9.5

[0205] (Heat resistance evaluation criteria) AA:ΔEab is less than 1.5 A: ΔEab is between 1.5 and 2.0 B: ΔEab is between 2.0 and 3.0 C:ΔEab is 3.0 or higher

[0206] <UV resistance evaluation> The photosensitive colored resin compositions of the examples and comparative examples were each applied to a 0.7 mm thick glass substrate ("NA35" manufactured by NH Techno Glass Co., Ltd.) using a spin coater so that the chromaticity after post-baking was y = 0.088. Then, they were heated and dried on an 80°C hot plate for 3 minutes, and then subjected to a high-pressure mercury lamp at 60 mJ / cm² without a photomask. 2 A cured film (colored film) was obtained by irradiating the substrate with ultraviolet light and then post-baking it in a clean oven at 230°C for 30 minutes. The brightness (Y), L, a, and b (L0, a0, b0) of the obtained colored substrate were measured using an Olympus OSP-SP200 microspectroscopy analyzer and evaluated according to the following evaluation criteria. Next, the substrate on which the above-mentioned cured film was formed was subjected to a low-pressure mercury lamp treatment of 20 mJ / cm². 2 The substrate was irradiated with ultraviolet light for 15 minutes, and the L, a, and b (L2, a2, b2) of the resulting colored substrate were measured. From the measured values, the color difference before and after treatment (ΔEab) was calculated according to the following formula. Color difference (ΔEab) ={(L2-L0) 2 +(a2-a0) 2 +(b2-b0) 2} 1 / 2 (UV resistance evaluation criteria) AA:ΔEab is less than 1.5 A: ΔEab is between 1.5 and 2.0 B: ΔEab is between 2.0 and 3.0 C:ΔEab is 3.0 or higher

[0207] <Developing residue evaluation> The photosensitive colored resin compositions of the examples and comparative examples were each applied to a 0.7 mm thick glass substrate ("NA35" manufactured by NH Techno Glass Co., Ltd.) using a spin coater to achieve a post-bake film thickness of 2.2 μm, and then heated and dried on a hot plate at 80°C for 3 minutes. Subsequently, a photomask forming a 40 μm line was used to apply a pressure of 60 mJ / cm² using an ultra-high pressure mercury lamp. 2 The images were irradiated with ultraviolet light, and then shower-developed for 60 seconds using a 0.05% by mass potassium hydroxide aqueous solution as the alkaline developer. Afterwards, the pattern of the colored layer in the area corresponding to the 80 μm aperture width of the chrome mask used during exposure was observed with an optical microscope, and the presence or absence of residue was visually evaluated. (Residue Evaluation Criteria) AA: No development remaining A: There is some fine residue. B: Fine residue is present throughout. C: Residue is present throughout.

[0208] [Table 2]

[0209] [Table 3]

[0210] In the table, the abbreviations are as follows: Resins U1-U12: Alkali-soluble resins U1-U12 from manufacturing examples 1-12 Resins P1-P2: Alkali-soluble resins P1-P2 from comparative manufacturing examples 1-2 Resin P3~P4: Resin P3~P4 of comparative manufacturing examples 3~4 M1: Photopolymerizable compound, Aronics M-403, dipentaerythritol penta and hexaacrylate, manufactured by Toagosei Co., Ltd. M2: Photopolymerizable compound, Arronix M-305, pentaerythritol tritetraacrylate, manufactured by Toagosei Co., Ltd. M3: Photopolymerizable compound, Aronics M-460, diglycerin ethylene oxide modified acrylate, manufactured by Toagosei Co., Ltd. M4: Photopolymerizable compound, Kayarad DPEA-12, ethylene oxide-modified (12) dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd. Photoinitiator 1(I1): Irgacure 907, manufactured by BASF, α-aminoacetophenone-based photoinitiator Photoinitiator 2(I2): OXE-02, manufactured by BASF, oxime ester photoinitiator with a carbazole skeleton. Thiol: Karens MT PE1, manufactured by Showa Denko. Antioxidant (AO1): Latent antioxidant in Synthesis Example 5 Antioxidant (AO2): IRGANOX1010, manufactured by BASF UV absorber (U1): Tinuvin928, manufactured by BASF UV absorber (U2): Tinuvin 405, manufactured by BASF UV absorber (U3): Tinuvin 479, manufactured by BASF.

[0211] [Summary of results] The photosensitive colored resin compositions of Examples 1 to 22, which combine a triarylmethane-based dye lake colorant with a constituent unit having a benzotriazole skeleton and an alkali-soluble resin (U) with a weight-average molecular weight of 3000 or more, were shown to be able to form a colored layer with a fine line width, suppressed changes in film thickness and development residue before and after development, and excellent UV resistance while improving brightness. In contrast, the photosensitive colored resin composition of Comparative Example 1, which does not contain an ultraviolet absorber, showed that even though it contained an antioxidant in the same way as in the examples, the line width shift was large, the line width became thicker, and it was not possible to form a colored layer with the desired thin line width, and furthermore, its UV resistance was inferior. In Comparative Example 2, which used alkali-soluble resin P2 containing a benzotriazole skeleton but with a weight-average molecular weight of 2000, the low molecular weight of alkali-soluble resin P2 caused it to volatilize during the high-temperature heating process at 230°C. As a result, the UV resistance of the final colored layer could not be improved, and the resulting layer exhibited poor UV resistance. In Comparative Examples 3-5, which used low-molecular-weight UV absorbers, the low-molecular-weight UV absorbers volatilized during the high-temperature heating process at 230°C, resulting in poor UV resistance of the final colored layer. Furthermore, in Comparative Example 6, which used resin P3 containing a benzotriazole skeleton but with an acid value of 0 mgKOH / g and high molecular weight, development residue remained near the pattern, resulting in a large apparent line width shift. In Comparative Example 7, which used resin P4 containing a benzotriazole skeleton but with a weight-average molecular weight of 1500, the low molecular weight of resin P4 caused it to volatilize during the high-temperature heating process at 230°C. As a result, the UV resistance of the final colored layer could not be improved, and it exhibited poor UV resistance. Furthermore, in Comparative Example 7, a decrease in the thickness of the residual film after development was observed, and development residue was generated. On the other hand, in Comparative Example 8, a photosensitive colored resin composition that used pigments instead of a triarylmethane-based lake colorant, it was shown that a large amount of photoinitiator was required to achieve the same line width shift as in the example using a triarylmethane-based lake colorant. In this case, the developing residue rate was not a problem, but the brightness was low. [Explanation of Symbols]

[0212] 1 circuit board 2. Light-shielding part 3 Colored layer 5 Micropore 10 Color Filters 20 Opposing substrate 30 liquid crystal layers 40 LCD display device 50 Organic protective layer 60 Inorganic oxide film 71 Transparent anode 72 Hole injection layer 73 Hole transport layer 74. Emitting layer 75 Electron injection layer 76 Cathode 80 Organic light-emitting materials 100 Organic Light-Emitting Display Devices

Claims

1. It contains a colorant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a solvent. The aforementioned colorant contains a triarylmethane-based lake colorant, A photosensitive colored resin composition comprising an alkali-soluble resin (U) having a weight-average molecular weight of 3000 or more, wherein the alkali-soluble resin contains a constituent unit having a benzotriazole skeleton.

2. Furthermore, the photosensitive colored resin composition according to claim 1 further contains a dispersant.

3. The photosensitive colored resin composition according to claim 1 or 2, wherein the alkali-soluble resin (U) contains 1% by mass or more and 10% by mass or less of constituent units having a benzotriazole skeleton with respect to all constituent units of the alkali-soluble resin (U).

4. Furthermore, the photosensitive colored resin composition according to claim 1 or 2 further contains at least one antioxidant and a latent antioxidant.

5. The photosensitive colored resin composition according to claim 1 or 2, wherein the lake colorant of the triarylmethane dye contains a colorant represented by the following general formula (1). 【Chemistry 1】 In general formula (1), A is an a-valent organic group in which the carbon atom directly bonded to N has no π bond, said organic group represents an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at the terminal end directly bonded to at least N, or an aromatic group having said aliphatic hydrocarbon group, and a hetero atom may be contained in the carbon chain. B ｃ－ represents a c-valent polyacid anion. R ｉ to R ｖ each independently represent a hydrogen atom, an optionally substituted alkyl group or an optionally substituted aryl group, R ｉｉ and R ｉｉｉ , R ｉｖ and R ｖ may be bonded to each other to form a ring structure. R ｖｉ and R ｖｉｉ each independently represent an optionally substituted alkyl group, an optionally substituted alkoxy group, a halogen atom or a cyano group. Ar １ represents an optionally substituted divalent aromatic group. When there are plural groups, R ｉ to R ｖｉｉ and Ar １ may each be the same or different from each other. a and c represent integers greater than or equal to 2, and b and d represent integers greater than or equal to 1. f and g represent integers between 0 and 4 (exclusive). Multiple instances of f and g may be identical or different.

6. A cured product of the photosensitive colored resin composition according to claim 1 or 2.

7. A color filter comprising at least a substrate and a colored layer provided on the substrate, wherein at least one of the colored layers is a cured product of the photosensitive colored resin composition described in claim 6.

8. A display device having the color filter described in claim 7.

Images