Colored resin composition and colored film

Abstract

To provide a colored resin composition that achieves low surface-side reflection intensity of a colored film and exhibits excellent recoating property, and to provide a colored film produced using the colored resin composition.SOLUTION: A colored resin composition comprises (A) a colorant, (B) a binder resin, and (C) a polydimethylsiloxane resin, wherein the (C) polydimethylsiloxane resin has a methacryloyl group or an acryloyl group. A colored film is formed by applying the colored resin composition onto a substrate, subjecting it to exposure and development, and forming a pattern.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a colored resin composition and a colored film obtained therefrom. More specifically, the present invention relates to a colored resin composition that is useful in a technology for improving the visibility deterioration of a display device due to reflection, and a colored film using the colored resin composition. [Background technology]

[0002] Conventionally, various devices have been devised to prevent deterioration of visibility due to reflection in display devices, such as anti-reflection films such as moth-eye films and circular polarizing plates, as well as devices that use colored cured films such as color filters.

[0003] In constructing an anti-reflection means for a display device such as a color filter, a colored resin composition in which a colorant is dispersed or dissolved in a binder resin solution is usually used. In particular, a colored resin composition in which a pigment is dispersed in a solution in which a binder resin, a polymerization initiator, a polymerizable compound, etc. are mixed is widely used because it allows fine patterning in a photolithography process of exposure and development.

[0004] However, since the colorants used in colored resin compositions generally have a higher refractive index than the materials constituting display devices such as substrates, films, sealing materials, insulating films, and other structures, the refractive index of a cured film containing a colorant increases as the content of the colorant increases, resulting in an increase in the reflection intensity of light at the boundary with other constituent materials. In other words, the greater the difference in refractive index between the substances forming the boundary, the higher the reflection intensity at the boundary.

[0005] For example, while the refractive index of glass and resin is about 1.5, that of carbon black is about 2.0, and that of copper phthalocyanine is about 1.8, the higher the content of colorant, the greater the difference in refractive index between adjacent layers. Therefore, when the colorant is used as a color filter or the like to transmit light, or when it is used as a light-blocking material, the reflection of light at the surface of the layer containing the colorant becomes strong when light enters the layer, resulting in an inherent problem of poor visibility. Furthermore, with recent changes in panel configuration, there has been a demand for lowering the reflection intensity on the film surface side opposite the substrate.

[0006] Therefore, efforts have been made to reduce reflection by blending particulate silica or the like into a colored resin composition. Patent Document 1 describes that in a colored cured film for a display device, the reflection intensity on the film surface side of the cured film can be reduced by including silica particles and adjusting the Si element content within a specific range in a surface element composition analysis by X-ray photoelectron spectroscopy (XPS).

[0007] Furthermore, Patent Document 2 describes that partition walls with low reflectance can be formed by devising the formulation design of a photosensitive resin composition for black resist, for example, by including an alkali-soluble resin containing an unsaturated group with a specific structure and a surfactant having a fluorine atom and an ethylenically unsaturated bond in the molecule. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] Japanese Patent Application Publication No. 2018-141849 [Patent Document 2] Japanese Patent Publication No. 2022-173086 Summary of the Invention [Problem to be solved by the invention]

[0009] However, the inventors of the present invention have conducted studies and found that when the colored resin composition described in Patent Document 1 contains a large amount of silica particles, the content of the coloring material with light-blocking properties is relatively reduced, and therefore it is not possible to contain a large amount of silica particles for applications that also require light-blocking properties, such as black matrices, and that when a film is formed in which pigments with a high refractive index are scattered near the surface, the effect of reducing the refractive index is hardly obtained.

[0010] Furthermore, Patent Document 2 uses a fluorine-based surfactant, but the use of fluorine-based surfactants is being restricted due to environmental considerations, and there is also the issue that the poor recoatability makes it difficult to handle post-processing, such as processing another layer on top of a layer containing a coloring material.

[0011] Therefore, an object of the present invention is to provide a colored resin composition that has low reflection intensity on the surface side of a colored film and has good recoatability, and to provide a colored film using this colored resin composition. [Means for solving the problem]

[0012] In order to solve the above problems, the present inventors have conducted extensive research and have found that the above problems can be solved by including in a colored resin composition (C) a polydimethylsiloxane resin having a methacryloyl group or an acryloyl group, and have thus completed the present invention.

[0013] That is, the present invention provides the following. (1) A colored resin composition containing (A) a colorant, (B) a binder resin, and (C) a polydimethylsiloxane resin, wherein the (C) polydimethylsiloxane resin has a methacryloyl group or an acryloyl group. (2) The colored resin composition according to (1), wherein the content of the (C) polydimethylsiloxane resin is 0.06% by mass or more and 2% by mass or less, relative to 100% by mass of the total solid content of the colored resin composition. (3) The colored resin composition according to (1) or (2), wherein the polydimethylsiloxane resin (C) is an ether-modified polydimethylsiloxane. (4) The colored resin composition according to (1) or (2), wherein the binder resin (B) is an alkali-soluble resin. (5) The colored resin composition according to (1) or (2), wherein the refractive index of the (C) polydimethylsiloxane resin is 1.430 to 1.460. (6) The colored resin composition according to (1) or (2), wherein the colorant (A) has an average primary particle diameter of 10 nm or more and 25 nm or less. (7) A colored resin composition according to (1) or (2), wherein the colored resin composition is formed into a flat film and the contact angle of propylene glycol monomethyl ether acetate on the film is 13 degrees or less. (8) The colored resin composition according to (1) or (2), wherein the content of the colorant (A) is 15% by mass or more and 55% by mass or less, based on 100% by mass of the total solid content of the colored resin composition. (9) The colored resin composition according to (1) or (2), further comprising (D) a polymerizable compound and (E) a photopolymerization initiator, and all or part of the (E) photopolymerization initiator is an oxime ester-based photopolymerization initiator. (10) A colored film formed by applying the colored resin composition according to (1) or (2) onto a substrate, exposing and developing the composition to form a pattern. (11) The colored film according to (10), having a reflection chromaticity L* value in SCI mode of 24.0 to 28.0. (12) A black matrix formed from the colored film according to (10). [Effects of the Invention]

[0014] By using the colored resin composition of the present invention, the reflection intensity of light incident on the coating film can be reduced, thereby improving the light-blocking properties and jet-blackness of the display device. Furthermore, since the coating film surface itself has high antireflection properties, it is expected that the complicated process of providing an additional antireflection layer can be avoided. Furthermore, it is expected that the reflectance can be reduced due to the reduced refractive index of the (C) polydimethylsiloxane resin. Furthermore, since the colored resin composition of the present invention has excellent recoatability, it is also highly adaptable to subsequent processes. [Brief explanation of the drawings]

[0015] [Figure 1] 1 is an example of a cross-sectional view of a colored film formed from the colored resin composition of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0016] The colored resin composition of the present invention is a colored resin composition containing (A) a colorant, (B) a binder resin, and (C) a polydimethylsiloxane resin, wherein the (C) polydimethylsiloxane resin is a (C) polydimethylsiloxane resin having a methacryloyl group or an acryloyl group. Hereinafter, each component constituting the colored resin composition of the present invention will be described in detail with examples.

[0017] <(A) Coloring material> As the (A) colorant, pigments, dyes, etc. generally used in display devices can be used. To improve the heat resistance, reliability, and light resistance of the coating film, it is preferable to use a pigment. In this case, it is preferable to include a colorant with a small crystallite size, since this can reduce the deterioration of jet black due to scattering.

[0018] The pigment is not particularly limited, and red pigments, blue pigments, yellow pigments, orange pigments, purple pigments, green pigments, black pigments, white pigments, etc. can be appropriately selected and used. These colorants may be used alone or in combination of two or more. Among them, black pigments such as carbon black, titanium black, perylene black, acetylene black, aniline black, and lactam black are preferred in terms of light-blocking properties, and carbon black is more preferred in terms of availability and price. These can be used alone or in combination of multiple types.

[0019] The secondary particle diameter of the (A) colorant is preferably 30 nm to 100 nm. If the secondary particle diameter is 30 nm or more, the storage stability after dispersion is excellent. On the other hand, if the secondary particle diameter is 100 nm or less, the diffuse reflection value when formed into a film is low, allowing for a vivid color, and in the case of a black pigment, excellent jet blackness is achieved.

[0020] The secondary particle size of a pigment is determined as the particle size (D50) at 50% cumulative frequency from the particle size distribution measured by dynamic light scattering (DLS). The secondary particle size is measured at 25°C for a sufficiently diluted colored resin composition (usually diluted to a pigment concentration of about 0.005 to 0.2% by mass; however, if a concentration recommended by the measuring instrument is available, that concentration should be followed).

[0021] It is preferable to use carbon black having an average primary particle size of 10 to 25 nm, a dibutyl phthalate absorption of 30 to 80 cm3 / 100 g, and a pH value of 1.0 to 4.0. By controlling the average primary particle size of the carbon black within the above range, the diffuse reflectance value can be reduced and the jet-black color can be enhanced. Furthermore, by controlling the dibutyl phthalate absorption of the carbon black within the above range, the diffuse reflectance value can be reduced, the jet-black color can be enhanced, and dispersibility can be improved. Furthermore, by controlling the pH value of the carbon black within the above range, dispersibility can be improved.

[0022] The average primary particle diameter of carbon black can be determined by the following method. First, carbon black is ultrasonically dispersed in chloroform, dropped onto a mesh with a collodion film attached, and dried. A primary particle image of the carbon black is obtained by observation with a transmission electron microscope (TEM). Next, the primary particle diameter of each carbon black particle is converted into the diameter of a circle with the same area, and the particle diameter of each of several carbon black particles (usually around 200 to 300 particles) is determined. Using the obtained primary particle diameter values, the number average value is calculated according to the following formula to determine the average primary particle diameter.

[0023] Particle size of individual pigment particles: X1, X2, X3, X4, , Xi, Xm Average particle size = ΣXi / m

[0024] The dibutyl phthalate absorption of the carbon black was measured in accordance with JIS K 6221. The pH value of the carbon black was measured in accordance with ASTM D1512. Resin-coated carbon black may also be used. Resin-coated carbon black can be obtained by treating known carbon black using the methods described in, for example, JP-A Nos. 9-26571, 9-71733, 9-95625, 9-238863, and 11-60989.

[0025] The content of the (A) colorant is preferably 15% by mass or more and 55% by mass or less, and more preferably 25% by mass or more and 45% by mass or less, based on 100% by mass of the total solid content contained in the colored resin composition. If the content of the (A) colorant is too low, dispersion stability cannot be maintained, and the diffuse reflectance increases. On the other hand, if the content of the (A) colorant is too high, light reflection on the surface of the cured film tends to be strong, and depending on the required level, sufficient jet black may not be obtained. Note that the solid content refers to the non-volatile components of the colored resin composition excluding the (F) solvent described below.

[0026] <(B) Binder resin> The (B) binder resin is a resin material that is soluble in the (F) solvent described below, surrounds the (A) colorant, and gives the colored resin composition of the present invention a viscosity suitable for application, and is a main element in forming a coating film that has the function of forming a solid coating film on a substrate and being patternable. Examples of patterning methods include photolithography, which involves exposing the film with a photomask of the desired pattern and developing it.

[0027] The (B) binder resin is preferably an alkali-soluble resin that undergoes a crosslinking reaction and hardens during the exposure step of photolithography and can be dissolved and removed with an alkaline developer during the development step, and specific examples include cardo resins, acrylic resins, novolac resins, polyimide resins, polyimide precursors, polybenzoxazole resins, polybenzoxazole precursors, polyamide resins, etc. As the alkaline developer, for example, a 0.045% by mass potassium hydroxide aqueous solution or the like is used (see Examples below).

[0028] Among these, from the viewpoints of pattern processability and coating reliability, cardo resins and acrylic resins containing hydroxyl or carboxyl groups, with an acid value of 10 mgKOH / g to 200 mgKOH / g and a weight-average molecular weight (Mw) of 5,000 to 150,000 are preferred. Cardo resins and acrylic resins with an acid value of 70 mgKOH / g to 150 mgKOH / g and a weight-average molecular weight (Mw) of 8,500 to 22,000 are even more preferred. Here, the weight-average molecular weight (Mw) refers to a value measured by gel permeation chromatography using tetrahydrofuran as a carrier and converted using a calibration curve based on standard polystyrene.

[0029] Preferred alkali-soluble cardo resins include cardo resins having two or more, preferably two to four, repeating units of the structure represented by the following general formula (1-A), and containing a photoradical polymerizable group and a carboxyl group or a hydroxyl group as an alkali-soluble group.

[0030] [ka]

[0031] Preferred alkali-soluble acrylic resins include acrylic resins containing a structure having an alkali-soluble group represented by the following general formula (1-B) and a structure having a photoradical polymerizable group represented by the following general formula (1-C).

[0032] [ka]

[0033] (In general formula (1-B), R1 represents hydrogen, a hydroxy group, or a monovalent organic group having 1 to 30 carbon atoms, preferably 1 to 3 carbon atoms. X1 represents an organic group having a hydroxy group or a carboxyl group. n1 represents an integer of 1 or more, preferably an integer of 15 to 650.)

[0034] [ka]

[0035] (In general formula (1-C), R2 represents hydrogen, a hydroxy group, or a monovalent organic group having 1 to 30 carbon atoms, preferably 1 to 3 carbon atoms. X2 represents an organic group having a photoradical polymerizable group. n2 represents an integer of 1 or more, preferably an integer of 15 to 650.)

[0036] <(C) Polydimethylsiloxane resin> The (C) polydimethylsiloxane resin contained in the colored resin composition of the present invention is a siloxane-based resin represented by a repeating unit of the following formula (2) in which the functional groups on both sides of the main chain skeleton are methyl groups, and unlike the (B) binder resin, it is a resin material that has the property of migrating to the surface vicinity of the coating film in the process of applying and drying the colored resin composition to form a coating film, and is generally used as a surfactant mainly composed of siloxane-based resins. In the following, Me is a methyl group.

[0037] [ka]

[0038] Among siloxane-based resins, there are materials in which the functional groups on one or both sides of the main chain skeleton are phenyl groups. However, phenyl groups have a high refractive index and are bulky functional groups, making them somewhat inferior in their ability to migrate to areas near the surface of the coating film. However, methyl groups have a lower refractive index than phenyl groups, and (C) polydimethylsiloxane resins behave like a viscous liquid when the coating film dries, making them excellent at migrating to areas near the surface of the coating film.

[0039] By including such a (C) polydimethylsiloxane resin in the colored resin composition, when the colored resin composition of the present invention is applied and dried to form a coating film, the refractive index of the coating film near the surface can be specifically lowered, thereby exhibiting the effect of reducing the reflection intensity on the coating film surface side. In particular, a (C) polydimethylsiloxane resin having a refractive index of 1.430 to 1.460 is highly effective in reducing the reflection intensity on the coating film surface side. The refractive index of a (C) polydimethylsiloxane resin that achieves this effect is 1.430 to 1.450.

[0040] The weight-average molecular weight of this (C) polydimethylsiloxane resin is preferably 2,000 to 20,000, and more preferably 3,000 to 15,000. If the weight-average molecular weight of the (C) polydimethylsiloxane resin is 2,000 or more, toxicity, persistence, and bioaccumulation are reduced, and if the weight-average molecular weight of the (C) polydimethylsiloxane resin is 20,000 or less, it flows to cover the coating surface, thereby enabling a uniform reduction in the reflectance of the coating surface.

[0041] The content of this (C) polydimethylsiloxane resin is preferably 0.06% by mass or more and 2% by mass or less, and more preferably 0.1% by mass or more and 1% by mass or less, relative to 100% by mass of the total solid content of the colored resin composition of the present invention. When the content of (C) polydimethylsiloxane resin is 0.06% by mass or more, the (C) polydimethylsiloxane resin sufficiently migrates to the coating film surface during drying, thereby reducing reflectance. On the other hand, when the content of (C) polydimethylsiloxane resin is 2% by mass or less, recoatability can be ensured. Furthermore, compatibility between the (C) polydimethylsiloxane resin and the (B) binder resin can be ensured, allowing the coating film to maintain a low diffuse reflectance.

[0042] During the exposure and development steps of forming and patterning a coating film, the methacryloyl or acryloyl groups in the (C) polydimethylsiloxane resin undergo a crosslinking reaction with the (D) polymerizable compound (described below) in the first exposure step, thereby immobilizing and orienting the (C) polydimethylsiloxane resin on the coating film surface. This provides resistance to the developer and prevents the (C) polydimethylsiloxane resin from leaching into the developer during the subsequent development step, thereby maintaining a low refractive index even in the developed coating film. One method for improving the curability of the coating film surface is to reduce the effects of oxygen on curing inhibition by, for example, purging with nitrogen during curing.

[0043] The manner in which methacryloyl or acryloyl groups are incorporated is not particularly limited, but examples include introduction into the terminals of the polysiloxane segments of the main chain or the terminals of some side chains. This terminal includes both one terminal and both terminals. That is, when the polysiloxane segments of the main chain are ABA polymers, examples include a pattern in which a methacryloyl or acryloyl group is introduced into each of the "A"s at both terminals, or a pattern in which a methacryloyl or acryloyl group is introduced into only the "A" at one terminal. The number of methacryloyl or acryloyl groups per polydimethylsiloxane molecule is preferably 1 to 3, and more preferably 1 or 2.

[0044] Commercially available examples of (C) polydimethylsiloxane resins having such methacryloyl groups or acryloyl groups include BYK-UV3500 (manufactured by BYK Japan), X-22-164, X-22-174, X-22-2404, X-22-2426, X-22-2445, and KF-2012 (all manufactured by Shin-Etsu Silicones Co., Ltd.).

[0045] Furthermore, the polydimethylsiloxane resin (C) is preferably an ether-modified compound. Here, the ether group introduced by ether modification is preferably an organic group having an ethylene oxide unit and / or a propylene oxide unit. The manner of ether modification is not particularly limited, but examples include modification in which the ether group is introduced as part of a side chain by covalent bonding with a polydimethylsiloxane segment in the main chain to form a comb polymer, and modification in which the ether group is introduced as part of the main chain by covalent bonding with the end of a polydimethylsiloxane segment in the main chain.

[0046] This ether modification includes not only cases containing only one ether group, but also polyether modifications with multiple ether groups. This ether modification improves recoatability and developability. It also ensures compatibility between the (C) polydimethylsiloxane resin and the (B) binder resin, allowing the coating film to maintain a low diffuse reflectance. As a result, it is possible to increase the content of the (C) polydimethylsiloxane resin, further lowering the refractive index of the coating film surface.

[0047] <(D) Polymerizable compound> The colored resin composition of the present invention preferably contains a (D) polymerizable compound. The (D) polymerizable compound is a compound containing in its structure a functional group that exhibits polymerization reactivity when irradiated with active energy rays, and does not include the (B) binder resin or (C) polydimethylsiloxane resin. Examples of the polymerizable compound include polymerizable monomers and polymerizable oligomers having a weight average molecular weight (Mw) of less than 5,000.

[0048] Among these, a radically polymerizable compound is preferred. The radically polymerizable compound is a compound that has polymerization activity with respect to radicals generated by the (E) photopolymerization initiator described below. The weight average molecular weight (Mw) of the radically polymerizable compound is preferably 100 to 3,000, more preferably 250 to 1,500. The radically polymerizable compound is more preferably a tri- or higher functional polyfunctional acrylate compound. When the colored resin composition contains a tri- or higher functional polyfunctional acrylate, high polymerization activity can be obtained, thereby improving sensitivity.

[0049] Examples of trifunctional or higher polyfunctional acrylate compounds include trimethylolpropane tri(meth)acrylate, triacrylformal, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, ε-caprolactone-modified dipentaerythritol hexa(meth)acrylate, Examples of the dipentaerythritol hexa(meth)acrylate include δ-valerolactone-modified dipentaerythritol hexa(meth)acrylate, γ-butyrolactone-modified dipentaerythritol hexa(meth)acrylate, β-propiolactone-modified dipentaerythritol hexa(meth)acrylate, dipentaerythritol hexa(meth)acrylate, glycerin triacrylate, ethoxylated glycerin triacrylate, caprolactone-modified isocyanurate acrylate, and ditrimethylolpropane acrylate.

[0050] Furthermore, it is more preferable to use a compound containing a fluorene skeleton as the radical polymerizable compound. Examples of the compound containing a fluorene skeleton include 9,9-bis[4-(3-acryloxy-2-hydroxypropoxy)phenyl]fluorene, 9,9-bis[3-methyl-4-(3-acryloxy-2-hydroxypropoxy)phenyl]fluorene, and a compound having a fluorene skeleton, a fused polycyclic aromatic ring other than a fluorene skeleton, and one or more hydroxyl groups (hereinafter referred to as "component (E-1A)").

[0051] Examples of the (E-1A) component include 9,9-bis[5-(3-(meth)acryloxy-2-hydroxypropoxy)naphthyl]fluorene, 9,9-bis[5-{3-methyl-(3-(meth)acryloxy-2-hydroxypropoxy)}naphthyl]fluorene, 9,9-bis[5-{(3-(meth)acryloxy-2-hydroxypropoxy)ethoxy}-1-naphthyl]fluorene, 9,9-bis[5-{(3-(meth)acryloxy-2-hydroxypropoxy)propoxy}-1-naphthyl]fluorene, and 9,9-bis[5-(3-(meth)acryloxy-2-hydroxypropoxy)anthryl]fluorene.

[0052] Examples of fused polycyclic aromatic rings other than a fluorene skeleton in component (E-1A) include pentalene, indene, naphthalene, heptalene, biphenylene, anthracene, phenanthrene, pentacene, pyrene, tetracene, pentacene, etc. The inclusion of a compound containing a fluorene skeleton crosslinks with polydimethylsiloxane resin (C) during exposure, further preventing dissolution of polydimethylsiloxane resin (C) in the developer during the development step, and playing a role in maintaining a low reflectance more stably.

[0053] Examples of radically polymerizable compounds other than tri- or higher functional polyfunctional acrylate compounds or compounds containing a fluorene skeleton include poly(meth)acrylate carbamate, 1,6-hexanediol adipic acid (meth)acrylic acid ester, phthalic anhydride propylene oxide (meth)acrylic acid ester, tripropylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 2-hydroxy-3-(meth)acryloyloxypropyl methacrylate, 2-hydroxy-3-(meth)acryloyloxypropyl acrylate, 1,6-hexanediylbis(oxy)bis(2-hydroxy-3,1-propanediyl)bis(meth)acrylate, and bisphenol A diglycidyl ether di(meth)acrylate.

[0054] The content of the (D) polymerizable compound is preferably 5% by mass or more and 80% by mass or less, and more preferably 15% by mass or more and 60% by mass or less, relative to the total content of the (B) binder resin and the (D) polymerizable compound (100% by mass). When the content of the (D) polymerizable compound is 5% by mass or more, not only can the developability be improved, but also dissolution of the (C) polydimethylsiloxane resin in the developer can be prevented, thereby maintaining low reflectance. On the other hand, when the content of the (D) polymerizable compound is 80% by mass or less, thickening of the pattern line width relative to the design value can be reduced.

[0055] <(E) Photopolymerization initiator> When the colored resin composition of the present invention contains a polymerizable compound (D), it is preferable to contain a photopolymerization initiator (E). The photopolymerization initiator (E) generates active species such as radicals or cations when exposed to energy such as active energy rays, thereby inducing polymerization of the polymerizable compound (D) and photocuring it. As such a photopolymerization initiator (E), known radical polymerization initiators, cationic polymerization initiators, base generators, etc. can be used alone or in combination of two or more.

[0056] Examples of the (E) photopolymerization initiator include carbazole-based photopolymerization initiators, acylphosphine oxide-based photopolymerization initiators, oxime ester-based photopolymerization initiators, and α-aminoalkylphenone-based photopolymerization initiators. Two or more of these may be contained. Among these, oxime ester-based photopolymerization initiators are preferred because they have high sensitivity to a mixed ray consisting of i-line (365 nm), h-line (405 nm), and g-line (436 nm) in the exposure step described below.

[0057] Examples of oxime ester photopolymerization initiators include 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime, 1,2-octanedione,1-[4-(phenylthio)-2-(o-benzoyloxime)], 1-phenyl-1,2-butadione-2-(o-methoxycarbonyl)oxime, 1,3-diphenylpropanetrione-2-(o-ethoxycarbonyl)oxime, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone(o-acetyloxime), etc. Two or more of these may be contained.

[0058] From the viewpoint of improving sensitivity to light exposure, the content of the (E) photopolymerization initiator is preferably 0.5 to 60 parts by mass, and more preferably 1 to 20 parts by mass, per 100 parts by mass of the (D) polymerizable compound. When the content of the (E) photopolymerization initiator is 0.5 parts by mass or more, not only can development processability be improved, but also dissolution of the (C) polydimethylsiloxane resin in the developer can be prevented, maintaining a lowered refractive index. On the other hand, when the content of the (E) photopolymerization initiator is 60 parts by mass or less, deep curing upon light exposure can be improved, and pattern processability can be improved.

[0059] <(F) Solvent> The colored resin composition of the present invention preferably contains a (F) solvent. Examples of the (F) solvent include ethers, acetates, esters, ketones, aromatic hydrocarbons, amides, and alcohols. From the viewpoint of uniformity in the thickness of the coating film in the coating step, the content of the (F) solvent is preferably 50% by mass or more, and more preferably 70% by mass or more, based on 100% by mass of the colored resin composition. On the other hand, from the viewpoint of suppressing sedimentation of the (A) colorant, the content is preferably 95% by mass or less, and more preferably 90% by mass or less.

[0060] Examples of ethers include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, dipropylene glycol dimethyl ether, dipropylene glycol methyl-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and tetrahydrofuran.

[0061] Examples of acetates include butyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate (hereinafter referred to as BDG-AC), cyclohexanol acetate, propylene glycol diacetate, propylene glycol monomethyl ether acetate (hereinafter referred to as PGMEA), propylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate (hereinafter referred to as DPMA), 3-methoxy-3-methyl-1-butyl acetate, 1,4-butanediol diacetate, 1,3-butylene glycol diacetate, and 1,6-hexanediol diacetate.

[0062] Examples of esters include alkyl lactate esters such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate; ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-pentyl formate, i-pentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, and ethyl 2-oxobutanoate.

[0063] Examples of ketones include methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone. Examples of aromatic hydrocarbons include toluene and xylene. Examples of amides include N-methylpyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide. Examples of alcohols include butyl alcohol, isobutyl alcohol, pentanol, 4-methyl-2-pentanol, 3-methyl-2-butanol, 3-methyl-3-methoxybutanol, and diacetone alcohol. Two or more of these may be contained.

[0064] Among these, acetate solvents are preferred to further stabilize the dispersion of the (A) colorant. The content of acetate solvents in 100% by mass of the total (F) solvent is preferably 40% by mass or more and 100% by mass or less, and more preferably 70% by mass or more and 100% by mass or less.

[0065] Furthermore, it is preferable to use a solvent (F) with a vapor pressure of 0.01 Pa or more and 1000 Pa or less at 20°C. This is because using a solvent with a low vapor pressure reduces the drying rate, making it easier for the polydimethylsiloxane resin (C) to precipitate on the surface, further reducing the reflective intensity of the coating film surface. Examples of acetate solvents with a vapor pressure of 0.01 Pa or more and 600 Pa or less at 20°C include PGMEA (vapor pressure at 20°C: 500 Pa), DPMA (vapor pressure at 20°C: 10 Pa), and BDG-AC (vapor pressure at 20°C: 5 Pa).

[0066] The content of the (F) solvent, which has a vapor pressure of 0.01 to 600 Pa at 20°C, is preferably 10% by mass or more, and more preferably 20% by mass or more, based on 100% by mass of the total solvent, from the viewpoint of suppressing the observation rate. On the other hand, from the viewpoint of ultimately drying the coating film and minimizing the amount of residual solvent, the content is preferably 95% by mass or less, and more preferably 90% by mass or less. <Other ingredients that can be used optionally>

[0067] The colored resin composition of the present invention may contain a polymeric dispersant. A polymeric dispersant is a compound having both a pigment-affinity group that chemically bonds to or adsorbs to the pigment surface and a polymer chain or group that is solvent-philic. In a wet media dispersion process, the polymeric dispersant improves the pigment's wettability with the dispersion medium, promoting deagglomeration of the pigment, stabilizing particle size and viscosity through steric hindrance and / or electrostatic repulsion, and further suppressing color separation during storage or application of the colored resin composition.

[0068] Commercially available polymer dispersants can be used as polymer dispersants. Examples include polyester-based polymer dispersants, acrylic-based polymer dispersants, polyurethane-based polymer dispersants, polyallylamine-based polymer dispersants, and carbodiimide-based dispersants. Polymer dispersants are classified into polymer dispersants with an amine value of 1 mgKOH / g or more and an acid value of less than 1 mgKOH / g, polymer dispersants with an acid value of 1 mgKOH / g or more and an amine value of less than 1 mgKOH / g, polymer dispersants with an amine value of 1 mgKOH / g or more and an acid value of 1 mgKOH / g or more, and polymer dispersants with an amine value less than 1 mgKOH / g and an acid value less than 1 mgKOH / g. Two or more of these may be used.

[0069] Among these, polymer dispersants with an amine value of 1 mgKOH / g or more are preferred. The content of the polymer dispersant is preferably 5% by mass or more and 50% by mass or less, and more preferably 10% by mass or more and 30% by mass or less, relative to 100% by mass of the colorant. A polymer dispersant content of 5% by mass or more can improve dispersion stability. On the other hand, a polymer dispersant content of 50% by mass or less can improve the heat resistance and adhesion of the coating film.

[0070] The colored resin composition of the present invention may contain a blocked isocyanate. A blocked isocyanate is a compound having two or more isocyanate groups blocked with a blocking agent. The blocking agent dissociates upon heating, and the isocyanate groups are regenerated. Therefore, the blocked isocyanate has a long pot life, and a colored resin composition containing the blocked isocyanate has excellent viscosity stability. In the colored resin composition of the present invention, the blocked isocyanate can be used as a curing agent for the (B) binder resin.

[0071] The blocked isocyanate dissociates (deprotects) the blocking agent when heated at a relatively low temperature, regenerating the isocyanate group. The regenerated isocyanate group thermally reacts with the hydroxyl groups and / or carboxyl groups in the (B) binder resin, thereby curing the (B) binder resin. The type of blocked isocyanate is not particularly limited, and commercially available products can be used. The content of the blocked isocyanate is preferably 1% by mass or more and 300% by mass or less per 100 parts by mass of the (B) binder resin.

[0072] The colored resin composition of the present invention may contain an adhesion improver. Examples of the adhesion improver include silane coupling agents such as vinyltrimethoxysilane, vinyltriethoxysilane, epoxycyclohexylethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and N-phenyl-3-aminopropyltrimethoxysilane, titanium chelating agents, aluminum chelating agents, and compounds obtained by reacting an aromatic amine compound with an alkoxy group-containing silicon compound. Two or more of these may be contained.

[0073] The inclusion of these adhesion promoters can improve adhesion to underlying substrates such as silicon wafers, ITO, SiO2, and silicon nitride when developing the coating film. It can also improve resistance to oxygen plasma and UV ozone treatments used in cleaning. The content of the adhesion promoter is preferably 0.1% by mass or more and 10% by mass or less relative to 100% by mass of the (B) binder resin.

[0074] The colored resin composition of the present invention may contain a surfactant other than the (C) polydimethylsiloxane resin, if necessary, for the purposes of improving wettability with the substrate or improving the uniformity of the coating film thickness. Therefore, even if the (C) polydimethylsiloxane resin exhibits surface activity in the coating film, it is not included in the surfactants referred to here. Commercially available surfactants can be used. The content of the (C) surfactant other than the polydimethylsiloxane resin is preferably 0.001% by mass or more and 0.1% by mass or less relative to 100% by mass of the (B) binder resin.

[0075] <Method for preparing colored resin composition> The method for preparing the colored resin composition of the present invention will be described below with reference to an example. However, it goes without saying that the following explanation is merely an example to aid in the implementation, and the present invention is not to be construed as being limited to this example.

[0076] A preferred method for producing the colored resin composition of the present invention is to use a disperser to disperse a resin solution containing (A) the colorant, a portion of (B) the binder resin, and optionally a dispersant and (F) the solvent to prepare a dispersion with a high colorant concentration, and then add the remaining (B) the binder resin, (C) the polydimethylsiloxane resin, (D) the polymerizable compound, (E) the photopolymerization initiator, and optionally additional (F) the solvent and other components, followed by stirring. Filtration may also be performed as necessary.

[0077] Examples of dispersing machines include ball mills, bead mills, sand grinders, three-roll mills, and high-speed impact mills. Among these, bead mills are preferred for improving dispersion efficiency and achieving fine dispersion. Examples of bead mills include co-ball mills, basket mills, pin mills, and dyno mills. Examples of beads used in bead mills include titania beads, zirconia beads, and zircon beads. The bead diameter of the bead mill is preferably 0.03 mm to 3.0 mm.

[0078] When the primary particle size of the (A) colorant and the secondary particle size formed by aggregation of the primary particles are small, it is preferable to use minute beads with a diameter of 0.03 mm to 0.10 mm. In this case, a bead mill equipped with a centrifugal separator capable of separating the minute beads from the dispersion liquid is preferable. On the other hand, when dispersing (A) colorant containing coarse particles on the submicron scale, it is preferable to use beads with a diameter of 0.10 mm or more to obtain sufficient crushing power.

[0079] Next, a method for forming a coating film and patterning by applying the colored resin composition of the present invention will be described in detail. The method for forming a coating film and patterning by applying the colored resin composition includes the steps of applying the colored resin composition to the surface of a substrate to form a coating film, drying the coating film, exposing the coating film to light, developing the exposed coating film, and curing the coating film. FIG. 1 shows a colored film 1 formed by these steps. The colored film 1 is a coating film formed on (A) substrate 2. The colored film 1 contains (A) colorant 3 and (C) polydimethylsiloxane resin 5 in (B) binder resin 4. The (A) colorant 3 is dispersed almost uniformly throughout the (B) binder resin 4, while the (C) polydimethylsiloxane resin 5 is concentrated on the surface of the colored film 1 (see FIG. 1).

[0080] First, the step of applying a colored resin composition to form a coating film will be described. In this step, the colored resin composition of the present invention is applied to a substrate by a method such as spin coating, slit coating, dip coating, spray coating, or printing to form a coating film. Among these, the slit coating method is preferably used. The coating speed in the slit coating method is generally in the range of 10 mm / sec to 400 mm / sec.

[0081] (A) Examples of the substrate 2 include transparent substrates such as soda glass, alkali-free glass, and quartz glass, silicon wafers, ceramics, and gallium arsenide substrates. Other resin layers, inorganic films, pixels, wiring, and the like may be present on the substrate 2. Prior to application, the substrate to which the colored resin composition is to be applied may be subjected to pretreatment such as UV treatment or plasma treatment.

[0082] Next, the step of drying the coating film will be described. In this step, after applying the colored resin composition, the formed coating film is dried. Typical drying methods in this step are vacuum drying or heat drying. Both vacuum drying and heat drying may be performed, or only one of them may be used. Heat drying may be performed using a hot plate, oven, infrared rays, or the like. The heating temperature varies depending on the type and purpose of the coating film, and is preferably in the range of 50°C to 180°C for 1 minute to several hours. In the drying step, volatile components such as solvents are removed.

[0083] The thickness of the coating film after drying varies depending on the solid content concentration, viscosity, etc. of the colored resin composition, but it is usually advisable to apply the colored resin composition so that the thickness becomes 0.1 μm to 10 μm, preferably 0.5 μm to 3 μm. Here, the solid content concentration refers to the ratio of the mass of components other than (F) the solvent to the mass of all components at the time of preparing the composition, expressed as a percentage.

[0084] Next, the step of exposing the coating film will be described. In this step, to form a pattern from the resulting coating film, a photomask having a desired pattern is placed on the coating film, and the coating film is exposed to actinic radiation through the photomask. Actinic radiation used for exposure includes ultraviolet light, visible light, electron beams, and X-rays. However, it is preferable to use monochromatic light such as i-rays (365 nm), h-rays (405 nm), and g-rays (436 nm) from a mercury lamp, or a UV-LED light source.

[0085] Next, the process of developing the exposed coating film will be described. In this process, after exposure, the unexposed areas are removed using a developer to form the desired pattern. The developer is preferably an aqueous solution of an alkaline compound such as tetramethylammonium hydroxide (TMAH), diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine, or hexamethylenediamine.

[0086] In some cases, polar solvents such as N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, γ-butyrolactone, and dimethylacrylamide; alcohols such as methanol, ethanol, and isopropanol; esters such as ethyl lactate and PGMEA; and ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, and methyl isobutyl ketone may be added alone or in combination to these alkaline aqueous solutions.

[0087] Possible development methods include spray, paddle, immersion, and ultrasonic. Next, it is preferable to rinse the pattern formed by development with distilled water. Here, too, the rinsing treatment may be carried out by adding alcohols such as ethanol and isopropyl alcohol, or esters such as ethyl lactate and PGMEA to the distilled water.

[0088] Finally, the coating film curing process will be described. A patterned coating film obtained through the development process is subjected to a heat treatment (post-baking) to obtain a cured coating film (colored film 1). The heat treatment may be carried out in air, in a nitrogen atmosphere, or in a vacuum. The heating temperature is preferably 85 to 300°C, and the heating time is preferably 0.25 to 5 hours. The heating temperature may be changed continuously or in steps.

[0089] The resulting colored film 1 is unevenly distributed on the surface of the colored film 1 due to the mass transfer properties of the (C) polydimethylsiloxane resin 5 (see Figure 1), resulting in low reflection intensity on the surface of the colored film 1. The reason for this mass transfer is presumably due to the low surface tension of the (C) polydimethylsiloxane resin 5. This mass transfer can be determined by the fact that when mass analysis is performed in the thickness direction of the coating film using time-of-flight secondary ion mass spectrometry (TOF-SIMS) using sputtered ions, the intensity profile of substances derived from the (C) polydimethylsiloxane resin tends to be higher near the coating surface. Furthermore, when composition analysis is performed in the depth direction using X-ray photoelectron spectroscopy (XPS), the intensity of the (C) polydimethylsiloxane resin tends to be higher near the coating surface.

[0090] In addition, it is preferable that the colored film formed from the colored resin composition in the form of a flat film as described above has a contact angle of propylene glycol monomethyl ether acetate on the colored film of 13 degrees or less, in order to improve recoatability and interlayer adhesion when another film is laminated on the colored film. This contact angle of 13 degrees or less can be achieved by using an ether-modified polydimethylsiloxane resin as the (C) polydimethylsiloxane resin, and / or by making the content of the (C) polydimethylsiloxane resin 2% by mass or less, more preferably 1% by mass or less, relative to 100% by mass of the total solid content of the colored resin composition of the present invention.

[0091] Furthermore, it is preferable that the formed colored film has a reflection chromaticity L* value of 24.0 to 28.0 in SCI mode, as this suppresses external light reflection from the colored film surface and improves design when used as a black matrix of a color filter, etc. Here, the reflection chromaticity L* value in SCI mode can be measured as follows. The method for measuring the reflection chromaticity L* value in SCI mode is specifically described in the Examples. Furthermore, achieving a reflection chromaticity L* value measured in this manner in the range of 24.0 to 28.0 can be achieved by forming a colored resin composition containing (A) a colorant, (B) a binder resin, and (C) a polydimethylsiloxane resin having a methacryloyl group or an acryloyl group into a flat film. [Example]

[0092] EXAMPLES The present invention will be described in detail below with reference to examples and comparative examples, but the present invention is not limited to these examples.

[0093] <Evaluation method> [Light blocking property] The sample colored resin composition was applied to an alkali-free glass substrate (AN100) manufactured by AGC Corporation using a spinner (MS-A150) manufactured by Mikasa Corporation so that the coating film would have a thickness of 1.5 μm after coating and drying. The resulting coating film was then heated and dried on a hot plate at 90°C for 3 minutes. The coating film was exposed to ultraviolet light at 200 mJ / cm2 and developed for 80 seconds using an alkaline developer of 0.045% by mass potassium hydroxide aqueous solution. The resulting substrate was heated and dried in an oven at 170°C for 30 minutes. The OD value per unit film thickness of 1 μm was calculated for the resulting coating film using an optical densitometer 361T Visual manufactured by X-Rite Corporation.

[0094] [Total reflected light brightness, diffuse reflected light brightness] The sample colored resin composition was applied to an alkali-free glass substrate (AN100) using a spinner (MS-A150) manufactured by Mikasa Co., Ltd., so that the coating film thickness after coating and drying would be 1.5 μm, and the resulting coating film was heated and dried on a hot plate at 90°C for 3 minutes. This coating film was exposed to ultraviolet light at 200 mJ / cm2 and developed for 80 seconds with an alkaline developer of 0.045 mass% potassium hydroxide aqueous solution. The resulting substrate was heated and dried in an oven at 170°C for 30 minutes.

[0095] The resulting coating film was calibrated with a Konica Minolta, Inc. white calibration plate "CM-A145" and measured using a Konica Minolta, Inc. spectrophotometer "CM-2600d" under the following measurement conditions: standard illuminant D65 (color temperature 6504K), viewing angle 10° (CIE1976), atmospheric pressure, 20°C, with light incident on the surface of the coating film, using both the SCI method (detecting all reflected light including specular reflected light) and the SCE method (detecting only diffuse reflected light). The lightness (L* value) was calculated for each measurement method and evaluated according to the following criteria, with A being the best.

[0096] (L* value measured using the SCI method) A: Less than 28.0 B: 28.0 or more and less than 29.2 C: 29.2 or more and less than 29.6 D: 29.6 or more and less than 30.0 E: 30.0 or higher (L* value measured using the SCE method) A: Less than 0.8 B: 0.8 or more and less than 2.0 C:2.0 or higher

[0097] [Development processability] The sample colored resin composition was applied to an alkali-free glass substrate (AN100) using a spinner (MS-A150) manufactured by Mikasa Co., Ltd., so that the thickness of the coating film after coating and drying would be 1.5 μm, and the resulting coating film was heated and dried on a hot plate at 90° C. for 3 minutes. This coating film was then irradiated with ultraviolet light at 200 mJ / cm 2 using a mask aligner (PEM-6M) manufactured by Union Optical Co., Ltd., through a negative mask (design line & space: four locations of 5, 10, 15, and 20 μm) manufactured by HOYA Corporation. 2 The patterned substrate was then exposed to light and developed for 80 seconds with an alkaline developer of 0.045% by mass potassium hydroxide aqueous solution, followed by heating and drying in an oven at 170°C for 30 minutes.

[0098] Each line and space pattern was observed at 100 locations per size at 50x magnification using an optical microscope (Olympus Sales Co., Ltd., "BH3-MJL (trade name)"), and the developability was evaluated according to the following criteria, starting from the smallest opening pattern with 90 or more patterns remaining. A is the best.

[0099] A: The minimum pattern is less than 15 μm B: Minimum pattern is 15 μm or more and less than 25 μm C: Minimum pattern is 25 μm or more and less than 50 μm D: Minimum pattern is 50 μm or more

[0100] [Recoatability] The sample colored resin composition was applied onto an alkali-free glass substrate (AN100) using a spinner (MS-A150) manufactured by Mikasa Co., Ltd., so that the coating film would have a thickness of 1.5 μm after coating and drying, and the resulting coating film was heated and dried for 3 minutes on a hot plate at 90° C. The coating film was exposed to ultraviolet light at 200 mJ / cm2, developed for 80 seconds with an alkaline developer of 0.045 mass% potassium hydroxide aqueous solution, and heated and dried for 30 minutes in an oven at 170° C.

[0101] 1 μL of PGMEA was dropped onto the surface of the resulting coating film, and the contact angle was measured. Measurements were performed using a contact angle measuring device (DMs-401; manufactured by Kyowa Interface Science Co., Ltd.) in accordance with JIS-R3257 using the sessile drop method at 23°C. Recoatability was evaluated based on the contact angle value according to the following criteria, with A being the best.

[0102] A: Contact angle is 13 degrees or less B: Contact angle is between 13 degrees and 15 degrees C: Over 15 degrees

[0103] In many cases, a coating film of another composition containing a solvent such as PGMEA is formed on the resulting coating film in a subsequent process. If the contact angle of the solvent on the coating film is high, it becomes difficult to form a coating film of another composition in the subsequent process.

[0104] [Refractive Index] (C) The refractive index of polydimethylsiloxane resin was measured by the critical angle method using an Abbe refractometer (DR-A1-Plus, manufactured by Atago Co., Ltd.) in accordance with JIS K 0062:1992. A sodium lamp (D line) was used as the light source. A is the best in terms of reducing reflectance.

[0105] A: 1.430 or more and less than 1.450 B: 1.450 or more and less than 1.460 C: 1.460 or more and less than 1.465 D;1.465 or more

[0106] (Production Example 1: Production of Colorant Dispersion Liquid (A-1)) 75 g of carbon black “#1000” (manufactured by Mitsubishi Chemical Corporation) as a black pigment having an average primary particle size of 18 nm, a dibutyl phthalate absorption of 56 cm / 100 g, and a pH of 3.5, 43 g of a 35 mass % PGMEA solution of binder resin (B-1) obtained in Synthesis Example 1 described below, 25 g of an amine-based polymer dispersant DISPER BYK21116 (a PGMEA solution with a solids concentration of 40%, manufactured by BYK-Chemie KK; hereinafter referred to as “BYK-21116”) as a dispersant, 257 g of PGMEA, and 100 g of 3-methoxybutyl acetate (hereinafter referred to as MBA) were charged into a tank and stirred for 20 minutes with a homomixer to obtain a preliminary dispersion.

[0107] The resulting preliminary dispersion was then fed into a Kotobuki Industries Ultra Apex Mill UAM015 disperser equipped with a centrifugal separator filled with 75% by volume of 0.30mm diameter zirconia beads, and dispersed for 20 minutes at a rotation speed of 9m / s. The dispersed liquid was then fed into another Ultra Apex Mill UAM015 disperser filled with 75% by volume of 0.05mm diameter zirconia beads, and dispersed for 120 minutes at a rotation speed of 9m / s, yielding a colorant dispersion (A-1) with a colorant concentration of 15%. The secondary particle diameter of the black pigment contained in (A-1) was 61nm. The secondary particle diameter was measured using a dynamic light scattering particle size distribution analyzer (SZ-100; manufactured by HORIBA, Ltd.) by diluting (A-1) with PGMEA and measuring at 25°C, and the secondary particle diameter of the pigment particles at a cumulative frequency of 50% (D50) was calculated as the average secondary particle diameter.

[0108] (Production Example 2: Production of Colorant Dispersion Liquid (A-2)) A colorant dispersion (A-2) having a colorant concentration of 15% was obtained in the same manner as in Production Example 1, except that "Irgaphor" (registered trademark) Black S0100CF (manufactured by BASF Ltd.) was used as the black pigment. The secondary particle diameter of the black pigment contained in (A-2) was 58 nm.

[0109] (Production Example 3: Production of Colorant Dispersion Liquid (A-3)) 46 g of red pigment PR264 (manufactured by BASF Japan Ltd.), 19 g of PB15:6 (manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd.), 9 g of PY139 (manufactured by Zeya Chemicals), 25 g of polymer dispersant BYK-21116, 42 g of a 35 mass % PGMEA solution of binder resin (B-2) obtained in Synthesis Example 2 described below, and 257 g of PGMEA were mixed and dispersed using a mill-type disperser filled with zirconia beads, and further PGMEA was added to obtain a colorant dispersion (A-3) with a colorant concentration of 15%.

[0110] (Synthesis Example 1 (B) Synthesis of Binder Resin (B-1)) A 500 mL three-neck flask was charged with 33 g of methyl methacrylate (0.33 mol), 32 g of styrene (0.32 mol), 35 g of methacrylic acid (0.39 mol), 3 g of 2,2'-azobis(2-methylbutyronitrile) (0.02 mol), and 150 g of PGMEA, and the mixture was stirred at 90°C for 2 hours, after which the internal temperature was raised to 100°C and the mixture was allowed to react for another 1 hour.

[0111] To the resulting reaction solution, 32 g of glycidyl methacrylate, 1.3 g of dimethylbenzylamine, and 0.2 g of p-methoxyphenol were added and stirred at 90°C for 4 hours. At the end of the reaction, 50 g of PGMEA was added to obtain a PGMEA solution (solid concentration 40%) of alkali-soluble binder resin (B-1). The acid value of this binder resin (B-1) was 81.5 mgKOH / g, and the weight average molecular weight measured by GPC was 21,000.

[0112] The acid value was measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of binder resin (unit: mgKOH / g), and the weight-average molecular weight was measured in terms of polystyrene using a gel permeation chromatography (GPC) "HLC-8220GPC" (a test device manufactured by Tosoh Corporation) with tetrahydrofuran as the carrier.

[0113] (Synthesis Example 2 (B) Synthesis of Binder Resin (B-2)) To 250 parts by weight of a PGMEA solution (solids concentration 35%) of methyl methacrylate / methacrylic acid / styrene copolymer (mass ratio 30 / 40 / 30), 90 parts by weight of a PGMEA solution (solids concentration 30%) of glycidyl methacrylate was added, reprecipitated with purified water, filtered, dried, and then 200 g of PGMEA was added to obtain a PGMEA solution (solids concentration 35%) of alkali-soluble binder resin (B-2). The acid value of this binder resin (B-2) was 110 mg KOH / g and the weight-average molecular weight was 15,000.

[0114] (Synthesis Example 3 (C) Synthesis of Polydimethylsiloxane Resin (C-1)) 70 g of an ether-modified polydimethylsiloxane compound represented by the following average composition formula (3), 45.1 g of ethyl acrylate, 3.7 g of zirconium acetylacetonate, 0.51 g of diethylhydroxyamine, 0.06 g of 2,6-di-tert-butyl-4-methylphenol, and 93.5 g of toluene were placed in a 300 mL three-neck flask and heated with stirring at 85°C for 24 hours while removing the by-product ethanol.

[0115] The reaction solution was filtered and then evaporated under reduced pressure at 85°C and 20 mmHg for 2 hours to obtain an ether-modified polydimethylsiloxane having acryloyl groups represented by the following average composition formula (3): In the formula, Me represents a methyl group and A represents an acryloyl group. The refractive index was measured and found to be 1.430.

[0116] [ka]

[0117] [ka]

[0118] (Synthesis Example 4 (C) Synthesis of Polydimethylsiloxane Resin (C-2)) 80.9 g of an epoxy-ether-modified polydimethylsiloxane compound represented by the following average composition formula (5), 0.95 g of 1,4-diazabicyclo[2.2.2]octane, 0.06 g of 2,6-di-tert-butyl-4-methylphenol, and 95 g of toluene were added and heated to 50°C. Once the temperature reached 50°C, a mixture of 37.2 g of methacrylic acid and 6.6 g of methacrylic anhydride was added dropwise from the dropping funnel. After the dropwise addition was completed, the temperature was raised to 90-100°C and the mixture was heated and stirred for 40 hours.

[0119] The mixture was then subjected to vacuum distillation at 120°C and 20 mmHg for 3 hours, followed by filtration to obtain an ether-modified polydimethylsiloxane having methacryloyl groups, represented by the following average composition formula (6): where Me is a methyl group and M is a methacryloyl group. The refractive index was measured and found to be 1.432.

[0120] [ka]

[0121] [ka]

[0122] (Synthesis Example 5 (B) Synthesis of Binder Resin (B-3)) Nitrogen was supplied at a rate of 0.02 L / min into a 1 L flask equipped with a reflux condenser, a dropping funnel, and a stirrer to form a nitrogen atmosphere, and 150 g of diethylene glycol methyl ethyl ether was charged and heated to 70° C. with stirring. Next, 66 g of the following composition formula (7) and a mixture of composition formula (7) (molar ratio 50:50), 68 g of phenyl methacrylate, 66 g of glycidyl methacrylate, and 22 g of methacrylic acid were dissolved in 150 g of diethylene glycol methyl ethyl ether to prepare a solution.

[0123] [ka]

[0124] [ka]

[0125] Next, the above solution was added dropwise to the flask using a dropping funnel, followed by the addition of a solution of 28 g of 2,2'-azobis(2,4-dimethylvaleronitrile) dissolved in 200 g of diethylene glycol methyl ethyl ether using another dropping funnel over 4 hours. After the addition was completed, the mixture was held at 70°C for 4 hours and then cooled to room temperature to obtain a copolymer binder resin (B-3) with a solids content of 42% by mass. The acid value of this binder resin (B-3) was 56 mgKOH / g and the weight-average molecular weight Mw was 8060.

[0126] (Synthesis Example 5 (B) Synthesis of Binder Resin (B-4)) A 500 mL three-neck flask was charged with 33 g of methyl methacrylate (0.33 mol), 32 g of styrene (0.32 mol), 3 g of 2,2'-azobis(2-methylbutyronitrile) (0.02 mol), and 150 g of PGMEA. The mixture was stirred at 90°C for 2 hours, then the internal temperature was raised to 100°C and the mixture was allowed to react for an additional hour. At the end of the reaction, 50 g of PGMEA was added to obtain a PGMEA solution (solids concentration 40%) of the alkali-insoluble binder resin (B-4). The acid value of this binder resin (B-4) was 0 mgKOH / g, and the weight-average molecular weight measured by GPC was 21,000.

[0127] (Synthesis Example 6: Synthesis of polydiphenylsiloxane resin (C-3)) 70 g of an ether-modified polyphenylsiloxane compound represented by the following average composition formula (9), 45.1 g of ethyl acrylate, 3.7 g of zirconium acetylacetonate, 0.51 g of diethylhydroxyamine, 0.06 g of 2,6-di-tert-butyl-4-methylphenol, and 93.5 g of toluene were placed in a 300 mL three-neck flask, and the mixture was heated and stirred at 85°C for 24 hours while removing the by-product ethanol.

[0128] The reaction solution was filtered and then evaporated under reduced pressure at 85°C and 20 mmHg for 2 hours to obtain an ether-modified polydiphenylsiloxane having acryloyl groups represented by the following average composition formula (10): Ph represents a phenyl group, Me represents a methyl group, and A represents an acryloyl group. The refractive index was measured and found to be 1.480.

[0129] [ka]

[0130] [ka]

[0131] (Synthesis Example 7: Synthesis of polydiphenylsiloxane resin (C-4)) 70 g of an ether-modified polydimethylsiloxane compound represented by the following average composition formula (11), 45.1 g of ethyl acrylate, 3.7 g of zirconium acetylacetonate, 0.51 g of diethylhydroxyamine, 0.06 g of 2,6-di-tert-butyl-4-methylphenol, and 93.5 g of toluene were placed in a 300 mL three-neck flask, and the mixture was heated and stirred at 85°C for 24 hours while removing the by-product ethanol.

[0132] The reaction solution was filtered and then evaporated under reduced pressure at 85°C and 20 mmHg for 2 hours to obtain an ether-modified polydimethylsiloxane having acryloyl groups represented by the following average composition formula (12): Ph represents a phenyl group, Me represents a methyl group, and A represents an acryloyl group. The refractive index was measured and found to be 1.455.

[0133] [ka]

[0134] [ka]

[0135] (Synthesis Example 8: Synthesis of polydiphenylsiloxane resin (C-5)) 70 g of an ether-modified polydimethylsiloxane compound represented by the following average composition formula (12), 45.1 g of ethyl acrylate, 3.7 g of zirconium acetylacetonate, 0.51 g of diethylhydroxyamine, 0.06 g of 2,6-di-tert-butyl-4-methylphenol, and 93.5 g of toluene were placed in a 300 mL three-neck flask, and the mixture was heated and stirred at 85°C for 24 hours while removing the by-product ethanol.

[0136] The reaction solution was filtered and then evaporated under reduced pressure at 85°C and 20 mmHg for 2 hours to obtain an ether-modified polydimethylsiloxane having acryloyl groups represented by the following average composition formula (13): Ph represents a phenyl group, Me represents a methyl group, and A represents an acryloyl group. The refractive index was measured and found to be 1.462.

[0137] [ka]

[0138] [ka]

[0139] Example 1 33.33 g of the colorant dispersion (A-1) was mixed with 18.91 g of a 35 mass % PGMEA solution of (B-1) as a binder resin, 5.08 g of DPHA (a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (manufactured by Nippon Kayaku Co., Ltd.) as a polymerizable compound, 0.63 g of the oxime ester initiator Adeka Arcles NCI-831E (manufactured by Adeka Corporation) as a photopolymerization initiator, and BYK-UV as a polydimethylsiloxane resin. 1.00 g of BYK-UV3500 (manufactured by BYK Japan) and PGMEA were added to the mixture to a solids concentration of 20.0%, yielding a colored resin composition (PB-1). The polydimethylsiloxane resin content of the resulting colored resin composition (PB-1) was 1.00% by mass based on 100% by mass of the total solids. The colorant content was 25% by mass based on 100% by mass of the total solids. The refractive index of BYK-UV3500 was measured and found to be 1.443.

[0140] Example 2 A colored resin composition (PB-2) having a solids concentration of 20% was obtained in the same manner as in Example 1, except that 3.33 g of a 30 mass % PGMEA solution of the polydimethylsiloxane resin (C-1) obtained in Synthesis Example 3 was used as the polydimethylsiloxane resin. The content of the polydimethylsiloxane resin in the obtained colored resin composition (PB-2) was 1.00 mass % relative to 100 mass % of the total solids.

[0141] Example 3 A colored resin composition (PB-3) having a solids concentration of 20% was obtained in the same manner as in Example 1, except that 3.33 g of a 30 mass % PGMEA solution of the polydimethylsiloxane resin (C-2) obtained in Synthesis Example 4 was used as the polydimethylsiloxane resin. The content of the polydimethylsiloxane resin in the obtained colored resin composition (PB-3) was 1.00 mass % relative to 100 mass % of the total solids.

[0142] Example 4 A colored resin composition (PB-4) having a solids concentration of 20% was obtained in the same manner as in Example 1, except that the amount of polydimethylsiloxane resin added was changed from 1.00 g to 0.06 g. The content of polydimethylsiloxane resin in the obtained colored resin composition (PB-4) was 0.06 mass% relative to 100 mass% of the total solids.

[0143] Example 5 A colored resin composition (PB-5) having a solid content concentration of 20% was obtained in the same manner as in Example 1, except that the amount of polydimethylsiloxane resin added was changed from 1.00 g to 2.00 g. The content of polydimethylsiloxane resin in the obtained colored resin composition (PB-5) was 2.00 mass% relative to 100 mass% of the total solid content.

[0144] Example 6 A colored resin composition (PB-6) having a solid content concentration of 20% was obtained in the same manner as in Example 2, except that the amount of 30 mass% PGMEA solution of polydimethylsiloxane resin was changed from 3.33 g to 0.20 g. The content of polydimethylsiloxane resin in the obtained colored resin composition (PB-6) was 0.06 mass% relative to the total solid content of 100 mass%.

[0145] Example 7 A colored resin composition (PB-7) having a solids concentration of 20% was obtained in the same manner as in Example 2, except that the amount of 30 mass% PGMEA solution of polydimethylsiloxane resin was changed from 3.33 g to 6.67 g. The content of polydimethylsiloxane resin in the obtained colored resin composition (PB-7) was 2.00 mass% relative to 100 mass% of the total solids.

[0146] Example 8 A colored resin composition (PB-8) having a solids concentration of 20% was obtained in the same manner as in Example 3, except that the amount of 30 mass% PGMEA solution of polydimethylsiloxane resin was changed from 3.33 g to 0.20 g. The content of polydimethylsiloxane resin in the obtained colored resin composition (PB-8) was 0.06 mass% relative to 100 mass% of the total solids.

[0147] Example 9 A colored resin composition (PB-9) having a solids concentration of 20% was obtained in the same manner as in Example 3, except that the amount of 30 mass% PGMEA solution of polydimethylsiloxane resin was changed from 3.33 g to 6.67 g. The content of polydimethylsiloxane resin in the obtained colored resin composition (PB-9) was 2.00 mass% relative to 100 mass% of the total solids.

[0148] Example 10 A colored resin composition (PB-10) having a solids concentration of 20% was obtained in the same manner as in Example 1, except that X-22-2445 (manufactured by Shin-Etsu Silicones Co., Ltd.) was used as the polydimethylsiloxane resin. The content of the polydimethylsiloxane resin in the obtained colored resin composition (PB-10) was 1.00% by mass relative to 100% by mass of the total solids. The refractive index of X-22-2445 was 1.407.

[0149] Example 11 A colored resin composition (PB-11) having a solid content concentration of 20% was obtained in the same manner as in Example 10, except that the amount of polydimethylsiloxane resin added was changed from 1.00 g to 0.06 g. The content of polydimethylsiloxane resin in the obtained colored resin composition (PB-11) was 0.06 mass% relative to 100 mass% of the total solid content.

[0150] Example 12 A colored resin composition (PB-12) having a solid content concentration of 20% was obtained in the same manner as in Example 10, except that the amount of polydimethylsiloxane resin added was changed from 1.00 g to 2.00 g. The content of polydimethylsiloxane resin in the obtained colored resin composition (PB-12) was 2.00 mass% relative to 100 mass% of the total solid content.

[0151] (Examples 13 to 24) Colored resin compositions (PB-13) to (PB-24) were obtained in the same manner as in Examples 1 to 12, except that the binder resin was changed to (B-2).

[0152] (Examples 25 to 36) Colored resin compositions (PB-25) to (PB-36) were obtained in the same manner as in Examples 1 to 12, except that the binder resin was changed to (B-3).

[0153] (Examples 37 to 48) Colored resin compositions (PB-37) to (PB-48) were obtained in the same manner as in Examples 1 to 12, except that the colorant dispersion was changed to (A-2) and the colorant dispersion (A-2) was added so that the content of the colorant in the colored resin composition was 35% by mass relative to 100% by mass of the total amount of solids.

[0154] (Examples 49 to 60) Colored resin compositions (PB-49) to (PB-60) were obtained in the same manner as in Examples 1 to 12, except that the colorant was changed to (A-3) and the colorant dispersion (A-3) was added so that the content of the colorant in the colored resin composition was 45% by mass relative to 100% by mass of the total solid content.

[0155] (Examples 61 to 72) Colored resin compositions (PB-61) to (PB-72) were obtained in the same manner as in Examples 37 to 48, except that the binder resin was changed to (B-3).

[0156] (Examples 73 to 84) Colored resin compositions (PB-73) to (PB-84) were obtained in the same manner as in Examples 1 to 12, except that the colorant dispersion (A-1) was added so that the content of the colorant in the colored resin composition was 55% by mass relative to 100% by mass of the total solid content.

[0157] (Examples 85 to 96) Colored resin compositions (PB-73) to (PB-84) were obtained in the same manner as in Examples 1 to 12, except that the colorant dispersion (A-1) was added so that the content of the colorant in the colored resin composition was 15% by mass relative to 100% by mass of the total amount of solids.

[0158] (Examples 97 to 102) Colored resin compositions (PB-97) to (PB-102) were obtained in the same manner as in Examples 4 to 9, except that the content of (C) polydimethylsiloxane was changed as shown in Table 6.

[0159] (Examples 103 to 108) Colored resin compositions (PB-103) to (PB-108) were obtained in the same manner as in Examples 16 to 21, except that the content of (C) polydimethylsiloxane was changed as shown in Table 6.

[0160] (Examples 109 to 110) Colored resin compositions (PB-109) to (PB-110) were obtained in the same manner as in Example 1, except that (C) polydimethylsiloxane was changed to C-4 or C-5.

[0161] (Examples 111 to 112) Colored resin compositions (PB-111) to (PB-112) were obtained in the same manner as in Examples 109 to 110, except that the colorant dispersion was changed to A-2 and the colorant content was added so as to be 35% by mass relative to 100% by mass of the total solid content.

[0162] (Examples 113 to 114) Colored resin compositions (PB-113) to (PB-114) were obtained in the same manner as in Examples 109 to 110, except that the colorant dispersion was changed to A-3 and the colorant content was added so as to be 45% by mass relative to 100% by mass of the total solid content.

[0163] Example 115 A colored resin composition (PB-115) was obtained in the same manner as in Example 1, except that the binder resin (B) was changed to B-4, which does not exhibit alkali solubility.

[0164] (Examples 116 to 117) Colored resin compositions (PB-116) to (PB-117) were obtained in the same manner as in Example 1, except that the colorant content was added so that it was 13% by mass or 57% by mass relative to 100% by mass of the total solid content.

[0165] (Comparative Example 1) Except for not containing a binder resin, a colored resin composition (HB-1) was obtained in the same manner as in Example 1. The content of the polydimethylsiloxane resin in the obtained colored resin composition (HB-1) was 1.00 mass% relative to 100 mass% of the total amount of solids.

[0166] (Comparative Example 2) A colored resin composition (HB-2) was obtained in the same manner as in Comparative Example 1, except that the colorant dispersion liquid (A-1) was changed to the colorant dispersion liquid (A-2) and the colorant dispersion liquid (A-2) was added so that the content of the colorant in the colored resin composition was 35% by mass relative to 100% by mass of the total solid content.

[0167] (Comparative Example 3) A colored resin composition (HB-3) was obtained in the same manner as in Comparative Example 1, except that the colorant dispersion (A-1) was changed to the colorant dispersion (A-3), and the colorant dispersion (A-3) was added so that the content of the colorant in the colored resin composition was 45% by mass relative to 100% by mass of the total solid content.

[0168] (Comparative Examples 4 to 6) Colored resin compositions (HB-4) to (HB-6) were obtained in the same manner as in Comparative Examples 1 to 3, except that 3.33 g of a 30 mass % PGMEA solution of the polydimethylsiloxane resin (C-1) obtained in Synthesis Example 3 was used as the polydimethylsiloxane resin. The content of the polydimethylsiloxane resin in the obtained colored resin compositions (HB-4) to (HB-6) was 1.00 mass % relative to 100 mass % of the total solid content.

[0169] (Comparative Examples 7 to 9) Colored resin compositions (HB-7) to (HB-9) were obtained in the same manner as in Comparative Examples 1 to 3, except that 3.33 g of a 30 mass % PGMEA solution of the polydimethylsiloxane resin (C-2) obtained in Synthesis Example 4 was used as the polydimethylsiloxane resin. The content of the polydimethylsiloxane resin in the obtained colored resin compositions (HB-7) to (HB-9) was 1.00 mass % relative to 100 mass % of the total solid content.

[0170] (Comparative Example 10) A colored resin composition (HB-10) was obtained in the same manner as in Example 1, except that the polydimethylsiloxane resin was changed to 3.33 g of a 30 mass % PGMEA solution of the polydiphenylsiloxane resin (C-3) obtained in Synthesis Example 5. The content of the polydiphenylsiloxane resin in the obtained colored resin composition (HB-10) was 1.00 mass % relative to 100 mass % of the total solid content.

[0171] (Comparative Example 11) A colored resin composition (HB-11) was obtained in the same manner as in Comparative Example 10, except that the colorant dispersion (A-1) was changed to the colorant dispersion (A-2), and the colorant dispersion (A-2) was added so that the content of the colorant in the colored resin composition was 35% by mass relative to 100% by mass of the total solid content.

[0172] (Comparative Example 12) A colored resin composition (HB-12) was obtained in the same manner as in Comparative Example 10, except that the colorant dispersion (A-1) was changed to the colorant dispersion (A-3), and the colorant dispersion (A-3) was added so that the content of the colorant in the colored resin composition was 45% by mass relative to 100% by mass of the total solid content.

[0173] (Comparative Examples 13 to 15) Colored resin compositions (HB-13) to (HB-15) were obtained in the same manner as in Comparative Examples 10 to 12, except that the binder resin was changed to (B-2).

[0174] (Comparative Examples 16 to 18) Colored resin compositions (HB-16) to (HB-18) were obtained in the same manner as in Comparative Examples 10 to 12, except that the binder resin was changed to (B-3).

[0175] (Comparative Examples 19 to 27) Colored resin compositions (HB-19) to (HB-27) were obtained in the same manner as in Comparative Examples 10 to 18, except that 1.00 g of BYK-333 (manufactured by BYK Japan) was added as a polydimethylsiloxane resin having no methacryloyl groups or acryloyl groups instead of the 30 mass% PGMEA solution of polydiphenylsiloxane resin (C-3).

[0176] The colored resin compositions of the examples and comparative examples were evaluated by the evaluation methods described above, and the results are shown in Tables 1 to 5.

[0177] [Table 1]

[0178] [Table 2]

[0179] [Table 3]

[0180] [Table 4]

[0181] [Table 5]

[0182] [Table 6]

[0183] The colored resin compositions of each example have low L* values ​​measured by the SCI method and low L* values ​​measured by the SCE method on the film surface, and are excellent in low reflectivity and jet black. In addition, they have low PGMEA contact angles and are excellent in recoatability.

[0184] On the other hand, the colored resin composition of the comparative example has a high L* value measured by the SCI method and a high L* value measured by the SCE method on the film surface, and is inferior in low reflectivity and jet blackness. Furthermore, when no binder resin is contained, the development processability is inferior. [Industrial Applicability]

[0185] The colored resin composition and cured film of the present invention can be suitably used for light-shielding images such as black matrices of color filters provided in liquid crystal display devices and the like, colored partition walls inside organic EL displays, and light-shielding images such as black matrices inside mini LED displays and micro LED displays. [Explanation of symbols]

[0186] 1 Colored film 2 boards 3 Coloring material 4. Binder resin 5 Polydimethylsiloxane resin

Claims

1. A colored resin composition comprising (A) a colorant, (B) a binder resin, and (C) a polydimethylsiloxane resin, wherein the (C) polydimethylsiloxane resin has a methacryloyl group or an acryloyl group.

2. The colored resin composition according to claim 1, wherein the content of the (C) polydimethylsiloxane resin is 0.06% by mass or more and 2% by mass or less, relative to 100% by mass of the total solid content of the colored resin composition.

3. 3. The colored resin composition according to claim 1, wherein the polydimethylsiloxane resin (C) is an ether-modified polydimethylsiloxane.

4. 3. The colored resin composition according to claim 1, wherein the binder resin (B) is an alkali-soluble resin.

5. 3. The colored resin composition according to claim 1, wherein the refractive index of the (C) polydimethylsiloxane resin is 1.430 to 1.

460.

6. 3. The colored resin composition according to claim 1, wherein the colorant (A) has an average primary particle diameter of 10 nm or more and 25 nm or less.

7. 3. The colored resin composition according to claim 1, wherein the colored resin composition is formed into a flat film, and the contact angle of propylene glycol monomethyl ether acetate on the film is 13 degrees or less.

8. 3. The colored resin composition according to claim 1, wherein the content of the colorant (A) is 15% by mass or more and 55% by mass or less, relative to 100% by mass of the total solid content of the colored resin composition.

9. 3. The colored resin composition according to claim 1 or 2, further comprising (D) a polymerizable compound and (E) a photopolymerization initiator, and all or a part of (E) the photopolymerization initiator is an oxime ester-based photopolymerization initiator.

10. 3. A colored film formed by applying the colored resin composition according to claim 1 or 2 onto a substrate, exposing and developing the composition to form a pattern.

11. 11. The colored film according to claim 10, wherein the reflected chromaticity L* value in SCI mode is 24.0 to 28.

0.

12. A black matrix formed from the colored film according to claim 10.

Images