Photosensitive colored resin composition, color filter, and display device

Abstract

This photosensitive colored resin composition comprises a coloring material, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a solvent, the coloring material containing a diketopyrrolopyrrole pigment, C.I. Pigment Red 202, and C.I. Pigment Red 122.

Description

Technical Field

[0001] The present invention relates to a photosensitive coloring resin composition, a color filter, and a display device.

Background Art

[0002] In recent years, with the development of personal computers, particularly portable personal computers, the demand for liquid crystal displays has been increasing. The penetration rate of mobile displays (mobile phones, smartphones, tablet PCs) has also been rising, and the market for liquid crystal displays is expanding more and more. Organic light-emitting display devices such as organic EL displays with high visibility due to self-emission are also attracting attention as next-generation image display devices. Color filters are used in these liquid crystal display devices and organic light-emitting display devices. For example, in the formation of a color image of a liquid crystal display device, the light passing through the color filter is directly colored into the colors of each pixel constituting the color filter, and the lights of those colors are synthesized to form a color image. As the light source at that time, in addition to a conventional cold cathode tube, a white light-emitting organic light-emitting element or a white light-emitting inorganic light-emitting element may be used in some cases. In an organic light-emitting display device, a color filter is used for color adjustment and the like.

[0003] Here, a color filter generally has a substrate, a coloring layer formed on the substrate and consisting of coloring patterns of the three primary colors of red, green, and blue, and a light-shielding portion formed on the substrate so as to partition each coloring pattern. As a method for forming the coloring layer in a color filter, for example, a coloring resin composition obtained by adding an alkali-soluble resin, a photopolymerizable compound, and a photoinitiator to a colorant dispersion liquid obtained by dispersing a colorant with a dispersant or the like is applied to a glass substrate, dried, exposed using a photomask, developed to form a coloring pattern, and heated to fix the pattern to form a coloring layer. These steps are repeated for each color to form a color filter.

[0004] The red colored layer of color filters has traditionally used a diketopyrrolopyrrole pigment (hereinafter sometimes referred to as DPP) mixed with CI Pigment Red 177 (hereinafter sometimes referred to as R177) as the coloring agent. However, because R177 has a lower transmittance than DPP, when mixed with DPP, the higher the concentration of R177 added, the less the transmittance of DPP can be utilized, resulting in a tendency to lose brightness.

[0005] For example, Patent Document 1 discloses a pigment dispersion composition for color filters (but without Pigment Red 122) that, when prepared based on a pigment dispersion composition for color filters, exhibits excellent high coloring power, high brightness, and stability, and further prevents migration to adjacent areas of other colors such as Green. The objective is to obtain a pigment dispersion resist composition for color filters that is excellent in high coloring power, high brightness, and stability, and further prevents migration to adjacent areas of other colors such as Green.

[0006] Furthermore, Patent Document 2 discloses a colored composition for color filters containing a quinacridone pigment, a dye derivative, a specific basic dispersant, and a binder resin, with the aim of solving problems such as low contrast ratio, low transmittance, dispersion stability, heat resistance, solvent resistance, and precipitation of foreign matter on the coating film when using quinacridone pigments. [Prior art documents] [Patent Documents]

[0007] [Patent Document 1] Japanese Patent Publication No. 6732080 [Patent Document 2] Japanese Patent Publication No. 2019-109487 [Overview of the project] [Problems that the invention aims to solve]

[0008] In recent years, the need for even higher brightness has increased due to factors such as wider color gamuts in color filters, higher pigment densities, smaller patterns resulting from higher resolution, and reduced aperture area. By combining diketopyrrolopyrrole pigments with CI Pigment Red 202 (hereinafter sometimes referred to as R202), which exhibits a bluer hue as a substitute for R177, it is possible to increase the content of diketopyrrolopyrrole pigments and thereby increase brightness. On the other hand, liquid crystal displays (LCDs) have a unique problem: viewing angle dependence due to the refractive index anisotropy of the liquid crystal cells and polarizing plates. This viewing angle dependence problem causes the color and contrast of the image viewed from the front of the LCD to change depending on whether it is viewed from an oblique angle or from a different direction. This problem of viewing angle characteristics has become even more serious with the recent increase in the size of LCD screens. To improve the problem of viewing angle dependence, a method of incorporating a phase difference film into liquid crystal display devices has been widely used. However, since the color filters used in liquid crystal display devices have different phase differences depending on the coloring pattern of each color in the colored layer, when the above-mentioned phase difference film is used, it is not possible to compensate for the differences in phase differences of the coloring patterns of each color, making it difficult to completely solve the problem of viewing angle dependence. In particular, R202 has high crystallinity due to π-π interactions and intermolecular interactions, and adopts a β-type crystal structure, so the colored layer formed by combining diketopyrrolopyrrole pigments and R202 has the problem of high phase difference.

[0009] The present invention has been made in view of the above circumstances, and aims to provide a photosensitive colored resin composition capable of forming a colored layer with high brightness and reduced phase difference. The present invention also aims to provide a color filter and a display device formed using the photosensitive colored resin composition. [Means for solving the problem]

[0010] 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 characterized by containing a diketopyrrolopyrrole pigment, CI Pigment Red 202, and CI Pigment Red 122.

[0011] 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. Furthermore, the present invention provides a display device having the color filter according to the present invention. [Effects of the Invention]

[0012] According to the present invention, it is possible to provide a photosensitive colored resin composition capable of forming a colored layer with high brightness and reduced phase difference. 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]

[0013] [Figure 1] Figure 1 is a schematic cross-sectional view showing an example of the color filter of the present invention. [Figure 2] Figure 2 is a schematic cross-sectional view showing an example of the liquid crystal display device of the present invention. [Figure 3] Figure 3 is a schematic cross-sectional view showing an example of the organic light-emitting device of the present invention. [Modes for carrying out the invention]

[0014] The photosensitive colored resin composition, 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.

[0015] I. Photosensitive colored resin composition The photosensitive colored resin composition of the present invention contains a colorant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a solvent. The aforementioned colorant comprises a diketopyrrolopyrrole pigment, CI Pigment Red 202, and CI Pigment Red 122.

[0016] The photosensitive colored resin composition according to the present invention is capable of forming a colored layer with high brightness and reduced phase difference, by comprising a diketopyrrolopyrrole pigment (DPP), CI pigment red 202 (R202), and CI pigment red 122 (R122) as the colorant. By combining DPP with R202, which exhibits a bluer hue as a substitute for R177, the DPP content can be increased, and thus the brightness can be increased. As mentioned above, R202 has high crystallinity due to π-π interactions and intermolecular interactions, and adopts a β-type crystal structure, so the colored layer formed by combining DPP and R202 had the problem of high phase difference. In contrast, in the present invention, R122 is further used in combination with DPP and R202. Here, R202 and R122 have the following structures.

[0017] [ka]

[0018] By using R202 and R122 together, the steric repulsion of the R122 substituent -CH3 suppresses the crystallization of R202, thereby reducing its crystallinity and enabling the formation of a colored layer with reduced phase difference. Even a small amount of R122 is effective in reducing phase difference, allowing for a reduction in phase difference while maintaining the high brightness achieved by the combination of DPP and R202.

[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, and may further contain other components as long as they do not impair the effects of the present invention. The components of the photosensitive colored resin composition of the present invention will be described in detail below.

[0020] [Colorants] In the present invention, the colorant comprises a diketopyrrolopyrrole pigment, CI Pigment Red 202, and CI Pigment Red 122. Examples of the aforementioned diketopyrrolopyrrole pigments include those represented by the following general formula (i).

[0021] [ka] (In general formula (i), A 1 and A 2 Each of these independently represents a halogen atom, a methyl group, an ethyl group, a tert-butyl group, a phenyl group, an N,N-dimethylamino group, a trifluoromethyl group, or a cyano group, and k and k' each independently represent an integer between 0 and 5, and if k and k' are integers of 2 or more, multiple A 1 and A 2 These may be the same or different.

[0022] Specific examples of diketopyrrolopyrrole pigments include, for example, CI Pigment Red 254, 255, 264, 272, and 291. Among these, those preferred from the viewpoint of high brightness are the diketopyrrolopyrrole pigments represented by the general formula (i) above, in which k and k' are 1, and A1 and A 2 Examples include diketopyrrolopyrrole pigments in which each is independently a 4-chloro group or a 4-bromo group, specifically CI Pigment Red 254 and 291. In particular, in the diketopyrrolopyrrole pigment represented by the above general formula (i), k and k' are 1, and A 1 and A 2 Each of these may be a diketopyrrolopyrrole pigment having a 4-bromo group, and may be CI Pigment Red 291.

[0023] Diketopyrrolopyrrole pigments can be used alone or in combination of two or more types. The content of the diketopyrrolopyrrole pigment is preferably in the range of 50% to 97% by mass, and more preferably 60% to 96% by mass, relative to the total amount of colorant, in order to form a colored layer with high brightness and reduced phase difference.

[0024] The total content ratio of CI Pigment Red 202 and CI Pigment Red 122 is preferably in the range of 3% to 50% by mass, and more preferably 4% to 40% by mass, relative to the total amount of colorant, in order to form a colored layer with high brightness and reduced phase difference. The ratio of CI pigment red 122 to the total content of CI pigment red 202 and CI pigment red 122 may be, for example, 0.0001% to 3% by mass, preferably 0.001% to 3% by mass, and more preferably 0.01% to 3% by mass, in order to form a colored layer with high brightness and reduced phase difference.

[0025] The total content ratio of diketopyrrolopyrrole pigments, CI pigment red 202, and CI pigment red 122 relative to the total amount of colorant may be, for example, 90% by mass or more, preferably 95% by mass or more, more preferably 98% by mass or more, and may also be 100% by mass, in order to form a colored layer with high brightness and reduced phase difference.

[0026] The colorants may include other colorants different from diketopyrrolopyrrole pigments, CI Pigment Red 202, and CI Pigment Red 122, for the purpose of color adjustment and color density adjustment. Other colorants are not particularly limited and can be any material that enables the desired color development when forming the colored layer of the color filter. Various organic pigments, inorganic pigments, dispersible dyes, dye salt-forming compounds, etc., can be used individually or in combination of two or more. The total proportion of other colorants may be, for example, 10% by mass or less, preferably 5% by mass or less, more preferably 2% by mass or less, and may even be 0% by mass, in order to form a colored layer with high brightness and reduced phase difference relative to the total amount of colorants.

[0027] Other colorants include other red colorants, orange colorants, yellow colorants, and so on. Other red and orange pigments include, for example, naphthol-based azo pigments and other azo pigments, quinacridone-based pigments different from Pigment Red 202 and CI Pigment Red 122, dioxazine-based pigments, anthraquinone-based pigments, perinone-based pigments, perylene-based pigments, thioindigo-based pigments, and the like. Examples of yellow pigments include CI Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 55, 60, 61, 65, 71, 73, 74, 81, 83, 93, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 116, 117, 119, 120, 126, and 127. Examples include derivative pigments of CI Pigment Yellow 150, 128, 129, 138, 139, 150, 151, 152, 153, 154, 155, 156, 166, 168, 175, 185, and CI Pigment Yellow 150; and quinophthalone dyes such as CI Disperse Yellow 54, 64, 67, 134, 149, 160, and CI Solvent Yellow 114, 157.

[0028] Specifically, a metal complex can be mentioned as a derivative pigment of CI Pigment Yellow 150, comprising at least one anion selected from the group consisting of mono, di, tri, and tetraanions of an azo compound following the following chemical formula (ii) or one of its tautomerized structures, and at least one metal ion selected from the group consisting of Li, Cs, Mg, Cd, Co, Al, Cr, Sn, Pb, Na, K, Ca, Sr, Ba, Zn, Fe, Ni, Cu, Mn, and La. Particularly preferred as the metal ion is at least one metal ion selected from the group consisting of Na, K, Ca, Sr, Ba, Zn, Fe, Ni, Cu, Mn, and La. The use of such a derivative pigment of CI Pigment Yellow 150 is preferable because it improves brightness.

[0029] [ka] (In the above chemical formulas, R is independently OH, NH2, NH-CN, acylamino, alkylamino, or arylamino, and R' is independently -OH or -NH2.)

[0030] In particular, it is preferable that the yellow colorant contains at least one anion selected from the group consisting of mono, di, tri, and tetraanions of azo compounds represented by the general formula (ii) and tautomerized azo compounds, and at least two metal ions selected from the group consisting of Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Ni, Cu, and Mn, in order to improve brightness and contrast. The at least two metals preferably include at least one metal that forms a divalent or trivalent cation, preferably at least one selected from the group consisting of Ni, Cu, and Zn, and more preferably at least Ni. Furthermore, it is preferable to include Ni and at least one metal selected from the group consisting of Zn, Cu, Al, and Fe. In particular, it is preferable that the at least two metals be Ni and Zn, or Ni and Cu. A detailed description of the derivative pigment of CI Pigment Yellow 150 may be the same as paragraphs 0031 to 0046 of Japanese Patent Application Publication No. 2017-003995, the contents of which are incorporated herein by reference.

[0031] 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.

[0032] 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.

[0033] 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.

[0034] In the photosensitive colored resin composition according to the present invention, the content of the colorant is not particularly limited. The total content of the colorant is preferably in the range of 3% to 65% by mass, more preferably 4% to 60% by mass, relative to the total solid content of the photosensitive colored resin composition, from the viewpoint of dispersibility and dispersion stability. If it is above the lower limit, the colored layer obtained 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 15% to 65% by mass, more preferably 25% to 60% by mass, relative to the total solid content of the photosensitive colored resin composition. In this invention, the solid content refers to everything other than the solvent described later, and includes monomers and the like dissolved in the solvent.

[0035] [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 in 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.

[0036] Among these, those having a carboxyl group in the side chain, and further having a photopolymerizable functional group such as an ethylenically unsaturated group in the side chain, are particularly preferred. When a photopolymerizable functional group is included, crosslinking can be formed between the alkali-soluble resins themselves, or between the alkali-soluble resin and a photopolymerizable compound such as a polyfunctional monomer, during the curing process of the resin composition in the manufacture of color filters. When a photopolymerizable functional group is included, the film strength is improved, so the pigment is less likely to aggregate even after post-baking, and the phase difference can be maintained at a low level. In addition, the film strength of the cured film is improved, development resistance is improved, and the thermal shrinkage of the cured film is suppressed, 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.

[0037] Furthermore, the alkali-soluble resin is preferably further enriched with a hydrocarbon ring, as this provides excellent adhesion to the colored layer. The presence of a bulky 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.

[0038] 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.

[0039] 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).

[0040] (Meth)acrylic resins such as (meth)acrylic copolymers having carboxyl group constituent units and styrene-(meth)acrylic copolymers having carboxyl groups are (meth)polymers obtained by (co)polymerizing, for example, a carboxyl group-containing ethylenically unsaturated monomer and other monomers that can be copolymerized as needed, by known methods. 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.

[0041] The alkali-soluble resin in the present invention is preferably a carboxyl group-containing copolymer such as a (meth)acrylic copolymer and a styrene-(meth)acrylic copolymer having a carboxyl group-containing structural unit and a hydrocarbon ring-containing structural unit, and more preferably a carboxyl group-containing copolymer such as a (meth)acrylic copolymer and a styrene-(meth)acrylic copolymer having a carboxyl group-containing structural unit, a hydrocarbon ring-containing structural unit and an ethylenically unsaturated bond-containing structural unit.

[0042] 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 has a significant effect in maintaining the cross-sectional shape of the colored layer after development even during heat treatment.

[0043] 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.

[0044] The carboxyl group-containing copolymer can be converted into an alkali-soluble resin with desired properties by appropriately adjusting the amount of each constituent unit used. 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.

[0045] Furthermore, in carboxyl group-containing copolymers such as acrylic copolymers and styrene-acrylic copolymers having structural units having ethylenically unsaturated bonds, which are more preferably used as alkali-soluble resins, the compound having both epoxy groups and ethylenically unsaturated bonds is preferably in an amount of 10% to 95% by mass, and more preferably 15% to 90% by mass, relative to the amount of carboxyl group-containing ethylenically unsaturated monomers charged.

[0046] The preferred mass-average molecular weight (Mw) of the carboxyl group-containing copolymer is preferably in the range of 1,000 to 50,000, and more preferably in the range of 3,000 to 20,000. A molecular weight of 1,000 or higher improves the binder function after curing, while a molecular weight of 50,000 or lower results in good pattern formation during development with an alkaline developer. Furthermore, the mass-average molecular weight (Mw) of alkali-soluble resins can be measured using the Shodex GPC System-21H with polystyrene as the standard substance and THF as the eluent.

[0047] 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. Each epoxy (meth)acrylate resin containing a carboxyl group may be used individually or in combination of two or more types.

[0048] For alkali-soluble resins, it is preferable to select and use those with an acid value of 40 mg KOH / g or higher, from the viewpoint of developability (solubility) in alkaline aqueous solutions used in the developing solution. For alkali-soluble resins, it is preferable that the acid value is 40 mg KOH / g or more and 300 mg KOH / g or less, and more preferably 50 mg KOH / g or more and 280 mg KOH / g or less, from the viewpoint of developability (solubility) in alkaline aqueous solutions used in the developing solution and adhesion to the substrate.

[0049] When the alkali-soluble resin has ethylenically unsaturated groups in its side chains, the ethylenically unsaturated bond equivalent is preferably in the range of 100 to 2000, more preferably in the range of 140 to 1500, and may also be in the range of 140 to 1000, in order to obtain effects such as improved film strength of the cured film, easier maintenance of low phase difference, improved development resistance, and excellent adhesion to the substrate. If the ethylenically unsaturated bond equivalent is below the upper limit, it is easier to maintain a low phase difference, and the development resistance and adhesion are excellent. If it is above the lower limit, 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 mass-average molecular weight per mole of ethylenically unsaturated bonds in the alkali-soluble resin described above, and is expressed by the following formula (1).

[0050] 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).)

[0051] 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.

[0052] The alkali-soluble resin used in the photosensitive colored resin composition may be used alone or in combination of two or more types. There are no particular restrictions on the content of the alkali-soluble resin, but it is preferably in the range of 5% to 60% by mass, and more preferably 10% to 40% by mass, relative to the total solid content of the photosensitive colored resin composition. If the content of the alkali-soluble resin is above the lower limit, sufficient alkali developability can be obtained, and if the content of the alkali-soluble resin is below the upper limit, film roughness and pattern defects can be suppressed during development.

[0053] [Photopolymerizable compound] The photopolymerizable compound used in the photosensitive colored resin composition of the present invention is not particularly limited as long as it can be polymerized by a photoinitiator, and is generally a compound having two or more ethylenically unsaturated bonds, and is particularly preferably a polyfunctional (meth)acrylate having two or more acryloyl groups or methacryloyl groups. 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.

[0054] These polyfunctional (meth)acrylates may be used individually or in combination of two or more. Furthermore, since excellent photocurability is required in the photosensitive colored resin composition of the present invention, the polyfunctional (meth)acrylate is preferably a compound having three or more ethylenically unsaturated bonds (trifunctional), more preferably a compound containing 3 to 15 ethylenically unsaturated bonding groups, and even more preferably a compound containing 3 to 6 ethylenically unsaturated bonding groups. In addition, the polymerizable compound is preferably a 3 to 15-functional (meth)acrylate compound, and more preferably a 3 to 6-functional (meth)acrylate compound. As compounds having three or more ethylenically unsaturated bonds (trifunctional), for example, poly(meth)acrylates of trivalent or higher polyhydric alcohols and 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.

[0055] The photopolymerizable compound used in the photosensitive colored resin composition of the present invention may contain a photopolymerizable compound having an acidic group from the viewpoint of developability. Examples of acidic groups include carboxyl groups, sulfo groups, and phosphate groups, with carboxyl groups being preferred. Examples of commercially available photopolymerizable compounds having an acidic group include Arronix M-510, M-520, and Arronix TO-2349 (manufactured by Toagosei Co., Ltd.). In the photopolymerizable compound used in the photosensitive colored resin composition of the present invention, the content of the photopolymerizable compound having an acidic group may be 20% by mass or less, 10% by mass or less, or 5% by mass or less relative to the total amount of the photopolymerizable compound, from the viewpoint of developability, and may be 0% by mass, from the viewpoint of the acid value of the alkali-soluble resin to be combined with it.

[0056] The photopolymerizable compound used in the photosensitive colored resin composition of the present invention may contain a photopolymerizable compound having a caprolactone structure, as it offers good control over curability, facilitates the formation of fine patterns, and easily suppresses chipping. The photopolymerizable compound having a caprolactone structure may contain a ring-opened ε-caprolactone structure, or it may contain a ring-opened ε-caprolactone structure as a repeating unit. Photopolymerizable compounds having a caprolactone structure can be obtained, for example, by esterifying an alcohol with (meth)acrylic acid and ε-caprolactone. Among these, compounds obtained by esterifying a polyhydric alcohol with (meth)acrylic acid and ε-caprolactone are preferably used. As the photopolymerizable compound having a caprolactone structure, commercially available products may be used as appropriate. For example, commercially available products are sold by Nippon Kayaku Co., Ltd. as the KAYARAD DPCA series. In the photopolymerizable compound used in the photosensitive colored resin composition of the present invention, the content of the photopolymerizable compound having a caprolactone structure may be 0% to 70% by mass or 10% to 50% by mass relative to the total amount of the photopolymerizable compound, from the viewpoint of adjusting the curability.

[0057] Furthermore, the photopolymerizable compound used in the photosensitive colored resin composition of the present invention may contain an alkylene oxy group, as it offers good control over curability, facilitates the formation of fine patterns, and suppresses chipping. The photopolymerizable compound having an alkylene oxy group is preferably a photopolymerizable compound having an ethylene oxy group and / or a propylene oxy group, more preferably a photopolymerizable compound having an ethylene oxy group, and even more preferably a 3-6 functional (meth)acrylate compound having 4 to 20 ethylene oxy groups. Examples of commercially available photopolymerizable compounds containing alkylene oxy groups include ethoxylated (4) pentaerythritol tetraacrylate (Sartomer, SR-494), trimethylolpropane tripoxy triacrylate (Nippon Kayaku Co., Ltd., KAYARAD TPA-330), ethylene oxide 12 molar modified dipentaerythritol hexaacrylate (Nippon Kayaku Co., Ltd., trade name KAYARAD DPEA-12), and New Frontier MF-001 from Daiichi Kogyo Seiyaku. In the photopolymerizable compound used in the photosensitive colored resin composition of the present invention, the content of the photopolymerizable compound having an alkylene oxy group may be 0% to 50% by mass or 5% to 40% by mass relative to the total amount of the photopolymerizable compound, from the viewpoint of adjusting the curability.

[0058] In the photosensitive colored resin composition of the present invention, the mass-average molecular weight per mole of photopolymerizable groups of the entire photopolymerizable compound used is, for example, the unsaturated bond equivalent, which is preferably 300 or less, more preferably 250 or less, and even more preferably 200 or less, from the viewpoint of curability. The unsaturated bond equivalent may also be 97 or less from the viewpoint of curability. A smaller unsaturated bond equivalent is preferable, but the lower limit may be around 50. Here, the unsaturated bond equivalent refers to the mass-average molecular weight per mole of unsaturated bonds in a photopolymerizable compound, and is expressed by the following formula (2). Formula (2) Unsaturated bond equivalent (g / mol)=W2(g) / M2(mol) (In formula (1), W2 represents the mass (g) of the photopolymerizable compound, and M2 represents the number of moles (mol) of unsaturated bonds contained in W2 (g) of the photopolymerizable compound.)

[0059] 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 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, and the elution of the exposed portion during development can be suppressed. If the content of the photopolymerizable compound is below the upper limit, sufficient alkaline developability is achieved.

[0060] [Photoinitiator] There are no particular limitations on the initiator 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 initiators include polymerization initiators such as thermal polymerization initiators and photopolymerization initiators, and specifically, for example, those described in Japanese Patent Application Publication No. 2013-029832.

[0061] Examples of photoinitiators include aromatic ketones, benzoin ethers, halomethyloxadiazole compounds, α-aminoketones, biimidazoles, N,N-dimethylaminobenzophenone, halomethyl-S-triazine compounds, thioxanthones, and oxime esters. Examples of photoinitiators include those described in International Publication No. 2018 / 062105, and other conventionally known photoinitiators can be appropriately selected and used.

[0062] In the present invention, it is preferable to use an oxime ester-based photoinitiator because it can improve the curability of the coating film, suppress the aggregation of colorant particles during baking, and easily suppress phase differences.

[0063] Examples of the oxime ester-based photoinitiator used in the present invention include, for example, 1,2-octanedione-1-[4-(phenylthio)phenyl]-,2-(o-benzoyloxime), ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-,1-(o-acetoxime), as described in JP-A-2000-80068, JP-A-2001-233842, JP-T-2010-527339, JP-T-2010-527338, JP-A-2013-041153, WO2015 / 152153, JP-A-2010-256891, etc., and can be appropriately selected from among the oxime ester-based photoinitiators described therein.

[0064] Among the oxime ester-based photoinitiators used in the present invention, it is preferable to contain at least one kind of oxime ester compound represented by the following general formula (A) from the viewpoints of improving the curability of the coating film, suppressing the aggregation of colorant particles during baking, and easily suppressing the retardation.

[0065] [Chemical formula] (In general formula (A), Z 1 , Z 3 , Z 4 and Z 5 each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or a phenyl group, and the alkyl group, cycloalkyl group, and phenyl group may each be substituted with a substituent selected from the group consisting of a halogen atom, an alkoxy group having 1 to 6 carbon atoms, and a phenyl group. Z 2 represents an alkyl group having 1 to 20 carbon atoms substituted with a cycloalkyl group.)

[0066] [Compound represented by general formula (A)] In the general formula (A), Z 1 , Z 3 , Z 4 and Z 5Examples of linear or branched alkyl groups having 1 to 12 carbon atoms include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, and n-dodecyl group. Z 1 , Z 3 , Z 4 and Z 5 Examples of the cycloalkyl group having 3 to 20 carbon atoms in the above are cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclooctadecyl group, and the like. Z 2 The cycloalkyl group in may be the same as the cycloalkyl group having 3 to 20 carbon atoms, and a cyclopentyl group or a cyclohexyl group is preferred. Z 2 Examples of the C1-C20 alkyl group in this context include, in addition to the C1-C12 linear or branched alkyl group, n-tetradecyl, n-hexadecyl, n-octadecyl groups, and the like.

[0067] Also, Z 1 , Z 3 , Z 4 and Z 5 Examples of halogen atoms that may be substituted with alkyl groups, cycloalkyl groups, and phenyl groups include fluorine atoms, chlorine atoms, bromine atoms, and the like. Z 1 , Z 3 , Z 4 and Z 5 In this context, examples of the C1-C6 alkoxy group that may be substituted with an alkyl group, a cycloalkyl group, or a phenyl group include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, a t-butoxy group, and the like.

[0068] In general formula (A), Z 1As such, from the standpoint of improving sensitivity, an alkyl group or phenyl group having 1 to 6 carbon atoms is preferred, a methyl group, an ethyl group, or a phenyl group is more preferred, and a methyl group is even more preferred. Furthermore, in general formula (A), Z 3 , Z 4 and Z 5 From the viewpoint of brightness, hydrogen atoms, methyl groups, ethyl groups, n-propyl groups, or i-propyl groups are preferred.

[0069] In general formula (A), Z 2 From the viewpoint of compatibility, alkyl groups having 1 to 14 carbon atoms substituted with cycloalkyl groups having 5 to 6 carbon atoms are preferred, alkyl groups having 1 to 10 carbon atoms substituted with cycloalkyl groups having 5 to 6 carbon atoms are more preferred, cyclohexylmethyl groups or cyclopentylmethyl groups are even more preferred, and cyclohexylmethyl groups are particularly preferred.

[0070] Among the photoinitiators represented by the general formula (A), oxime ester compounds represented by the following chemical formula (A-1) are preferred from the viewpoint of suppressing brightness reduction. Examples of commercially available products include TR-PBG-3057 (manufactured by Changzhou Strong Electronic New Materials Co., Ltd.).

[0071] [ka]

[0072] The photoinitiator represented by the general formula (A) can be synthesized, for example, by using diphenyl sulfide or its derivatives, and by appropriately selecting the solvent, reaction temperature, reaction time, purification method, etc., depending on the materials used, as described in Japanese Patent Publication No. 2012-526185. Alternatively, commercially available products may be obtained and used as appropriate.

[0073] 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 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 and the elution of the exposed portion during development will be suppressed, while if it is below the upper limit, the decrease in brightness due to yellowing of the resulting colored layer can be suppressed. The term "solids" refers to everything except the solvent, and includes liquid polyfunctional monomers, etc.

[0074] If the photoinitiator contains an oxime ester-based photoinitiator, the total content of the oxime ester-based photoinitiator in 100% by mass of the total amount of photoinitiators may be 50% by mass or more, 60% by mass or more, and 100% by mass or less, but may also be 90% by mass or less, or 80% by mass or less, from the viewpoint of improving curability. If the photoinitiator contains one or more compounds selected from the group consisting of compounds represented by the general formula (A), the total content of one or more compounds selected from the group consisting of compounds represented by the general formula (A) in 100% by mass of the total amount of the photoinitiator may be, from the viewpoint of solvent resistance, at a lower limit of 10% by mass or more, at a lower limit of 20% by mass or more, at a lower limit of 30% by mass or more, at a lower limit of 50% by mass or more, at a lower limit of 60% by mass or more, and at an upper limit of 100% by mass.

[0075] [solvent] The solvent used in the present invention is not particularly limited and can be any organic solvent that does not react with the components in the photosensitive colored resin composition but is capable of dissolving or dispersing them. The solvent can be used alone or in combination of two or more types. 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.

[0076] In the photosensitive colored resin composition according to the present invention, the solvent content can be appropriately set within a range that allows for accurate formation of a colored layer. The solvent content is usually preferably in the range of 55% to 95% by mass, and more preferably 65% ​​to 88% by mass, based on 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.

[0077] [Dispersant] In the photosensitive colored resin composition of the present invention, when a colorant is dispersed, a dispersant may be further included from the viewpoint of colorant dispersibility and colorant dispersion stability. 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, polymeric dispersants are preferred because they can disperse uniformly and finely.

[0078] Examples of polymer dispersants include (meth)acrylate copolymer dispersants; polyurethanes; unsaturated polyamides; polysiloxanes; long-chain polyaminoamide phosphates; polyethyleneimine derivatives (amides obtained by the reaction of poly(lower alkyleneimines) 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 having free carboxyl groups, polyamides, or ester-amide cocondensates (polyesteramides)).

[0079] In the present invention, it is preferable to use a (meth)acrylate copolymer-based dispersant as a dispersant from the viewpoint of controlling developability. Since the (meth)acrylate copolymer-based dispersant has good compatibility with the alkali-soluble resin and the photopolymerizable compound, it is presumed that the generation of developing residue is suppressed.

[0080] In the present invention, a (meth)acrylate copolymer-based dispersant means a copolymer that contains at least one constituent unit derived from (meth)acrylate. The (meth)acrylate copolymer dispersant is preferably a copolymer containing constituent units that function as colorant adsorption sites and constituent units that function as solvent affinity sites, and it is preferable that the constituent units that function as solvent affinity sites contain at least constituent units derived from (meth)acrylate.

[0081] The constituent units that function as colorant adsorption sites include constituent units derived from (meth)acrylate and constituent units derived from copolymerizable ethylenically unsaturated monomers. The colorant adsorption sites may be constituent units derived from acidic group-containing ethylenically unsaturated monomers or constituent units derived from basic group-containing ethylenically unsaturated monomers. As a constituent unit derived from a basic group-containing ethylenically unsaturated monomer, the constituent unit represented by the following general formula (I) is preferred because it exhibits excellent dispersibility of the colorant.

[0082] [ka] (In general formula (I), R 1 is a hydrogen atom or a methyl group, A 1 R is a divalent linking group. 2 and R 3 Each of these independently represents a hydrocarbon group which may contain a hydrogen atom or a heteroatom, and R 2 and R 3 They may bond to each other to form a ring structure.

[0083] In general formula (I), A 1 This is a divalent linking group. Examples of divalent linking groups 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 nitrogen atom side of the side chain, or conversely, -NH may be on the carbon atom side of the main chain and -CO on the nitrogen atom side of the side chain. In particular, from the standpoint of dispersion, A in general formula (I) 1 It is preferably a divalent linking group containing a -CONH- group or a -COO- group, and more preferably a divalent linking group containing a -CONH- group or a -COO- group and an alkylene group having 1 to 10 carbon atoms.

[0084] R 2 and R 3 Examples of hydrocarbon groups in which heteroatoms may be present include alkyl groups, aralkyl groups, and aryl groups. Examples of alkyl groups include methyl, ethyl, propyl, butyl, isopropyl, tert-butyl, 2-ethylhexyl, cyclopentyl, and cyclohexyl groups. The alkyl group preferably has 1 to 18 carbon atoms, and is more preferably a methyl or ethyl group. Examples of aralkyl groups include benzyl, phenethyl, naphthylmethyl, and biphenylmethyl groups. The number of carbon atoms in the aralkyl group is preferably 7 to 20, and more preferably 7 to 14. Examples of aryl groups include phenyl, biphenyl, naphthyl, tolyl, and xylyl groups. The number of carbon atoms in the aryl group is preferably 6 to 24, and more preferably 6 to 12. Note that the number of carbon atoms in substituents is not included in the above preferred number of carbon atoms. A hydrocarbon group containing a heteroatom has a structure in which a carbon atom in the hydrocarbon group is replaced by a heteroatom, or a hydrogen atom in the hydrocarbon group is replaced by a substituent containing a heteroatom. Examples of heteroatoms that the hydrocarbon group may contain include oxygen atoms, nitrogen atoms, sulfur atoms, silicon atoms, and the like. Furthermore, the hydrogen atoms in the hydrocarbon group may be substituted with halogen atoms such as fluorine atoms, chlorine atoms, or bromine atoms.

[0085] R 2 and R 3 The fact that they are bonded to each other and form a ring structure means that R 2 and R 3 This refers to the fact that a ring structure is formed via a nitrogen atom. 2 and R 3 The ring structure formed may contain heteroatoms. The ring structure is not particularly limited, but examples include pyrrolidine rings, piperidine rings, morpholine rings, etc.

[0086] In this invention, in particular, R 2 and R 3 Each of these is independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group, or R 2 and R 3 It is preferable that these elements are bonded together to form a pyrrolidine ring, a piperidine ring, or a morpholine ring.

[0087] Examples of monomers that derive the constituent unit represented by the above general formula (I) include alkyl-substituted amino group-containing (meth)acrylates such as dimethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, diethylaminoethyl (meth)acrylate, and diethylaminopropyl (meth)acrylate, and alkyl-substituted amino group-containing (meth)acrylamides such as dimethylaminoethyl (meth)acrylamide and dimethylaminopropyl (meth)acrylamide. Among these, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, and dimethylaminopropyl (meth)acrylamide can be preferably used because they improve dispersibility and dispersion stability. In a polymer, the constituent units represented by general formula (I) may consist of only one type, or they may contain two or more types of constituent units.

[0088] Furthermore, as a constituent unit that functions as a colorant adsorption site, at least a portion of the nitrogen portion of the constituent unit represented by the general formula (I) may form a salt with at least one selected from the group consisting of organic acid compounds and halogenated hydrocarbons. The aforementioned organic acid compound is preferably an acidic organic phosphorus compound such as phenylphosphonic acid or phenylphosphinic acid, as it exhibits excellent dispersibility and dispersion stability of the colorant. Specific examples of organic acid compounds used as such dispersants include, for example, the organic acid compounds described in Japanese Patent Application Publication No. 2012-236882. Furthermore, it is preferable that the halogenated hydrocarbon is at least one of allyl halides such as allyl bromide and benzyl chloride, and aralkyl halides, from the standpoint of excellent dispersibility and dispersion stability of the colorant.

[0089] From the viewpoint of dispersibility and dispersion stability, the copolymer having the constituent units represented by the general formula (I) is more preferably at least one of the following: a graft copolymer having the constituent units represented by the general formula (I) and having (meth)acrylate-derived constituent units in the graft polymer chain; and a block copolymer having block A containing the constituent units represented by the general formula (I) and block B containing (meth)acrylate-derived constituent units. The graft copolymer and the block copolymer will be described in order below.

[0090] Graft copolymers having a structural unit represented by the general formula (I) and having a structural unit derived from (meth)acrylate in the graft polymer chain include a graft copolymer having a structural unit represented by the general formula (I) and a structural unit represented by the general formula (II) below, and at least one salt-type graft copolymer in which at least a portion of the nitrogen moiety of the structural unit represented by the general formula (I) of the graft copolymer forms a salt with at least one selected from the group consisting of organic acid compounds and halogenated hydrocarbons.

[0091] [ka] (In general formula (II), R 1’ is a hydrogen atom or a methyl group, A 2 (where is a direct bond or a divalent linking group, and Polymer represents a polymer chain, the constituent units of which include (meth)acrylate-derived units.)

[0092] In the above general formula (II), A 2 A is a direct bond or a divalent linking group. 2 As for the divalent linking group in A, there are no particular restrictions as long as it can link the carbon atom derived from the ethylenically unsaturated bond with the polymer chain. 2 Examples of divalent linking groups in A 1 Examples include divalent linking groups similar to those in [the relevant context]. In particular, from the standpoint of dispersion, A in general formula (II)2 It is preferably a divalent linking group containing a -CONH- group or a -COO- group, and more preferably a divalent linking group containing a -CONH- group or a -COO- group and an alkylene group having 1 to 10 carbon atoms.

[0093] In the general formula (II) above, Polymer represents a polymer chain, and the constituent units of the polymer chain include constituent units derived from (meth)acrylate. By having constituent units represented by the general formula (II) above, which have a specific polymer chain, the graft copolymer has good solvent affinity, good dispersibility and dispersion stability of the colorant, and good compatibility with the aforementioned photoinitiator. The constituent units derived from (meth)acrylate contained in the polymer chain are, among the constituent units represented by the following general formula (III), A in general formula (III). 3 One example is a structural unit represented by general formula (III), which is a divalent linking group containing a -COO- group.

[0094] [ka] (In general formula (III), R 4 is a hydrogen atom or a methyl group, A 3 R is a divalent linking group. 10 This is a hydrocarbon group that may contain a hydrogen atom or a heteroatom.

[0095] A 3 For example, the divalent linking group is A 1 Examples include the same divalent linking group as in the present invention. In the present invention, the constituent unit derived from (meth)acrylate is A in general formula (III). 3 It contains at least one constituent unit represented by general formula (III), in which A is a divalent linking group containing a -COO- group. In terms of solubility in organic solvents used for color filter applications, A in general formula (III) 3 This may include a divalent linking group containing a -CONH- group.

[0096] R 10In the hydrocarbon group which may contain a heteroatom, examples of hydrocarbon groups include alkyl groups, alkenyl groups, aryl groups, and combinations thereof such as aralkyl groups and alkyl-substituted aryl groups. 10 Examples of hydrocarbon groups in which heteroatoms may be included include C1-C18 alkyl groups, C2-C18 alkenyl groups, aryl groups, and combinations thereof such as aralkyl groups and alkyl-substituted aryl groups. The C1-C18 alkyl group may be linear, branched, or cyclic. Examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, n-nonyl, n-lauryl, n-stearyl, cyclopentyl, cyclohexyl, bornyl, isobornyl, dicyclopentanyl, adamantyl, and lower alkyl-substituted adamantyl groups. The number of carbon atoms in the alkyl group is preferably 1-12, and more preferably 1-6. The C2-C18 alkenyl group may be linear, branched, or cyclic. Examples of such alkenyl groups include vinyl, allyl, and propenyl groups. There are no limitations on the position of the double bond in 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. The number of carbon atoms in the alkenyl group is preferably 2-12, and more preferably 2-8. Examples of aryl groups include phenyl, biphenyl, naphthyl, tolyl, and xylyl groups. 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. Furthermore, the aromatic rings such as the aryl group and aralkyl group may have linear or branched alkyl groups having 1 to 30 carbon atoms bonded to them as substituents.

[0097] R 10In particular, the hydrocarbon group in is preferably one or more selected from the group consisting of alkyl groups having 1 to 18 carbon atoms, aryl groups having 6 to 12 carbon atoms which may be substituted with alkyl groups, and aralkyl groups having 7 to 14 carbon atoms which may be substituted with alkyl groups, from the viewpoint of dispersion stability. It is also preferably one or more selected from the group consisting of methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, n-nonyl group, n-lauryl group, n-stearyl group, phenyl group which may be substituted with alkyl groups, and benzyl group.

[0098] Examples of heteroatoms that a hydrocarbon group may contain include oxygen atoms, nitrogen atoms, sulfur atoms, silicon atoms, etc. Examples of hydrocarbon groups that may contain heteroatoms include structures in which linking groups such as -CO-, -COO-, -OCO-, -O-, -S-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -OCO-NH-, -NH-COO-, -NH-CO-, -NH-CO-, -NH-O-, and -O-NH- are included in the carbon chain of the hydrocarbon group. Furthermore, the hydrocarbon group may have substituents to the extent that they do not impede the dispersion performance of the graft copolymer, and examples of substituents include halogen atoms, hydroxyl groups, carboxyl groups, alkoxy groups, nitro groups, cyano groups, epoxy groups, isocyanate groups, thiol groups, and the like.

[0099] Also, R 10 The hydrocarbon group that may contain a heteroatom may have a structure in which a polymerizable group such as an alkenyl group is attached to the terminal via a linking group containing a heteroatom in the hydrocarbon group. For example, the constituent unit represented by general formula (III) may be a structure obtained by reacting a constituent unit derived from (meth)acrylic acid with glycidyl (meth)acrylate. That is, -A in general formula (III) 3 -R 10The structure may also be represented by -COO-CH2CH(OH)CH2-OCO-CR=CH2 (where R is a hydrogen atom or a methyl group). Alternatively, the constituent unit represented by general formula (III) may be a structure obtained by reacting a hydroxyalkyl (meth)acrylate-derived constituent unit with a 2-isocyanatoalkyl (meth)acrylate. That is, R in general formula (III) 10 However, the structure may also be represented by -R'-OCONH-R”-OCO-CR=CH2 (where R' and R” are independently alkylene groups, and R is a hydrogen atom or a methyl group).

[0100] Examples of monomers that derive the constituent units represented by general formula (III) include 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, and adamantyl (meth)acrylate. Preferably, the material has constituent units derived from acrylate, (meth)acrylic acid, 2-methacryloyloxyethyl succinate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, phenoxyethyl (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, polyethylene glycol (meth)acrylate, phenoxyethylene glycol (meth)acrylate, etc. However, it is not limited to these.

[0101] In the present invention, the R 10In 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 ether alcohol acetate, ether, ester, or alcohol, which is commonly used as an organic solvent for colorant dispersions, methyl group, ethyl group, isobutyl group, n-butyl group, 2-ethylhexyl group, benzyl group, cyclohexyl group, dicyclopentanyl group, hydroxyethyl group, phenoxyethyl group, adamantyl group, methoxypolyethylene glycol group, methoxypolypropylene glycol group, polyethylene glycol group, etc. are preferred.

[0102] It is preferable that the graft copolymer contains at least one structural unit selected from the group consisting of structural units represented by the following general formula (IV) in the polymer chain structural units of the structural unit represented by the general formula (II), as this makes it easier to reduce the crystallinity of R202, which tends to have a significantly high phase difference, and thus easier to reduce the phase difference. The constituent unit represented by the following general formula (IV) is a constituent unit that is included in the constituent unit represented by the general formula (III) mentioned above.

[0103] [ka] (In general formula (IV), R 4 is a hydrogen atom or a methyl group, A 3 R is a divalent linking group. 5 is an ethylene group or a propylene group, R 6 (where m represents a hydrogen atom or a hydrocarbon group, and m is a number between 2 and 30.)

[0104] A 3 The divalent linking group may be the same as that of general formula (III). In particular, from the viewpoint of solubility in organic solvents used for color filter applications, A in general formula (IV) 3It is preferably a divalent linking group containing a -CONH- group or a -COO- group, more preferably a -CONH- group or a -COO- group, and even more preferably a -COO- group.

[0105] The aforementioned m represents the number of repeating units of the ethylene oxide chain or propylene oxide chain, and may be 2 or more, 4 or more, and in particular, 19 or more, or 21 or more, from the standpoint of reducing the phase difference. In the case where the aforementioned m is 19 or more and the graft copolymer contains a structural unit represented by general formula (IV), the graft copolymer contains a main chain portion having a structural unit represented by general formula (I) and a structural unit represented by general formula (II), and the structural unit represented by general formula (II) includes a structural unit represented by general formula (IV) that has a specific number of repeating polyethylene oxide chains or polypropylene oxide chains in the polymer chain. In the specific graft copolymer used in the present invention, the structural units of the grafted polymer chain thus include structural units having a specific number of repeating polyethylene oxide chains or polypropylene oxide chains, and the grafted polymer chain itself has a branched structure. Since the multiple grafted polymer chains spread three-dimensionally in the film and the specific surface area increases, it is presumed that the pigment, which has been finely dispersed, is easier to maintain with low crystallinity.

[0106] R 6 The hydrocarbon group in is the aforementioned R 10 It may be similar to the hydrocarbon group in the above. R 6In particular, the hydrocarbon group in is preferably one or more selected from the group consisting of C1-C18 alkyl groups, C6-C12 aryl groups which may be alkyl groups substituted with alkyl groups, and C7-C14 aralkyl groups which may be alkyl groups substituted with alkyl groups, from the viewpoint of dispersion stability and compatibility. It is also preferably one or more selected from the group consisting of methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, n-nonyl group, n-lauryl group, n-stearyl group, phenyl group which may be alkyl groups substituted with alkyl groups, and benzyl group.

[0107] In the polymer chain, at least one constituent unit selected from the group consisting of constituent units represented by the general formula (IV) may be a single unit or a mixture of two or more units.

[0108] When the polymer chain components in the component unit represented by the general formula (II) contain at least one component selected from the group consisting of the component units represented by the general formula (IV), the total proportion of the component units represented by the general formula (IV) is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 30% by mass or more, when the total proportion of the component units in the polymer chain is set to 100% by mass. On the other hand, from the viewpoint of dispersion stability and compatibility (resolubility) with solvents and resists, it is preferably 80% by mass or less, more preferably 70% by mass or less, and even more preferably 60% by mass or less.

[0109] In the polymer chain, the constituent unit represented by general formula (III), which includes the constituent unit represented by general formula (IV), may be a single unit or a mixture of two or more types. From the viewpoint of the dispersibility and dispersion stability of the colorant, the total proportion of the constituent units represented by the general formula (III) is preferably 70% by mass or more, and more preferably 90% by mass or more, when the total constituent units of the polymer chain are set to 100% by mass. On the other hand, from the viewpoint of dispersion stability, the total proportion of the constituent units represented by the general formula (III) in the polymer chain may be 100% by mass when the total constituent units of the polymer chain are set to 100% by mass. In particular, the total proportion of constituent units derived from (meth)acrylate is preferably 60% by mass or more, and more preferably 80% by mass or more, when the total constituent units of the polymer chain are set to 100% by mass, from the viewpoint of dispersion stability, solvent resistance, and compatibility with the initiator. On the other hand, from the viewpoint of simultaneously satisfying dispersion stability and excellent solvent resistance, the total proportion of constituent units derived from (meth)acrylate in the polymer chain may be 100% by mass when the total constituent units of the polymer chain are set to 100% by mass.

[0110] The polymer chain components in the graft copolymer represented by the general formula (II) may include other components in addition to the components represented by the general formula (III). Other constituent units include monomer-derived units having unsaturated bonds that can copolymerize with monomers that derive the constituent unit represented by the general formula (III). Examples of monomers that can be used to derive other constituent units include styrenes such as styrene and α-methylstyrene, and vinyl ethers such as phenyl vinyl ether.

[0111] In the polymer chain of the graft copolymer represented by the general formula (II), the total proportion of other constituent units is preferably 30% by mass or less, and more preferably 10% by mass or less, when the total constituent units of the polymer chain are considered to be 100% by mass, from the viewpoint of the effects of the present invention.

[0112] In polymers, the mass-average molecular weight Mw of the polymer chain is preferably 2000 or more, more preferably 3000 or more, even more preferably 4000 or more, more preferably 15000 or less, and even more preferably 12000 or less, from the viewpoint of dispersibility and dispersion stability of the colorant. By staying within the aforementioned range, sufficient steric repulsion effect as a dispersant can be maintained, and the specific surface area of ​​the solvent-affinity portion of the dispersant becomes larger, making it easier to suppress the penetration of solvent into the coating film and its reach to the colorant.

[0113] Furthermore, as a guideline, the polymer chains in the polymer preferably have a solubility of 20 g / 100g solvent or more at 23°C in the organic solvent used in combination. The solubility of the polymer chain can be determined by whether the raw material into which the polymer chain is introduced during the preparation of the graft copolymer has the aforementioned solubility. For example, when a polymerizable oligomer (macromonomer) containing a polymer chain and a group having an ethylenically unsaturated bond at its end is used to introduce a polymer chain into a graft copolymer, it is sufficient if the polymerizable oligomer has the aforementioned solubility. Alternatively, when a copolymer is formed using a monomer containing a group having an ethylenically unsaturated bond, and then a polymer chain containing a reactive group that can react with the reactive group contained in the copolymer is used to introduce the polymer chain, it is sufficient if the polymer chain containing the reactive group has the aforementioned solubility.

[0114] In the graft copolymer, when the total amount of structural units in the main chain containing the structural unit represented by the general formula (I) is taken as 100% by mass, the structural unit represented by the general formula (I) is preferably present in a proportion of 3% to 60% by mass, more preferably 6% to 45% by mass, and even more preferably 9% to 30% by mass. If the structural unit represented by the general formula (I) in the graft copolymer is within the above range, the proportion of the affinity portion with the colorant in the graft copolymer becomes appropriate, and the decrease in solubility in organic solvents can be suppressed, resulting in good adsorption to the colorant, and making it easier to obtain excellent dispersibility and dispersion stability. On the other hand, in the graft copolymer, when the total amount of structural units in the main chain including the structural unit represented by general formula (I) is taken as 100% by mass, the structural unit represented by general formula (II) is preferably contained in a proportion of 40% to 97% by mass, more preferably 55% to 94% by mass, and even more preferably 70% to 91% by mass. If the structural unit represented by general formula (II) in the graft copolymer is within the above range, the proportion of the solvent affinity portion in the graft copolymer becomes appropriate, allowing for sufficient steric repulsion as a dispersant, and the specific surface area of ​​the solvent affinity portion of the dispersant becomes larger, making it easier to suppress the penetration of solvent into the coating film and its reach to the colorant. In the graft copolymer, when the total number of structural units in the main chain including the structural unit represented by general formula (I) is set to 100% by mass, the total proportion of the structural unit represented by general formula (I) and the structural unit represented by general formula (II) is preferably 70% by mass or more, more preferably 90% by mass or more, and may be 100% by mass.

[0115] The graft copolymer used in the present invention may have other constituent units in addition to the constituent units represented by general formula (I) and general formula (II), as long as the effects of the present invention are not impaired. As other constituent units, an ethylenically unsaturated bond-containing monomer that can be copolymerized with an ethylenically unsaturated bond-containing monomer that induces the constituent unit represented by general formula (I) can be appropriately selected and copolymerized to introduce other constituent units. Other constituent units copolymerized with the constituent unit represented by the general formula (I) include, for example, the constituent unit represented by the general formula (III). The content ratio of the aforementioned constituent units is calculated during manufacturing from the amount of monomers used to derive the constituent units represented by general formula (I), general formula (II), and general formula (III) when synthesizing the graft copolymer.

[0116] Furthermore, the mass-average molecular weight Mw of the graft copolymer is preferably 4000 or more, more preferably 6000 or more, and even more preferably 8000 or more, from the viewpoint of dispersibility and dispersion stability. On the other hand, from the viewpoint of solvent resolubility, it is preferably 50000 or less, and more preferably 30000 or less. In this invention, the mass-average molecular weight Mw is a value measured by GPC (gel permeation chromatography). The measurement can be performed using a Tosoh HLC-8120GPC, with N-methylpyrrolidone with 0.01 mol / liter lithium bromide added as the eluent, and polystyrene standards for calibration curves of Mw 377400, 210500, 96000, 50400, 20650, 10850, 5460, 2930, 1300, and 580 (all from Polymer Laboratories' Easi PS-2 series) and Mw 1090000 (Tosoh). The measurement column can be two TSK-GEL ALPHA-M tubes (Tosoh).

[0117] Next, a block copolymer having a block A containing a constituent unit represented by the general formula (I) and a block B containing a constituent unit derived from (meth)acrylate will be described. In the present invention, the arrangement of each block in the block copolymer is not particularly limited, and can be, for example, AB block copolymer, ABA block copolymer, BAB block copolymer, etc. Among these, AB block copolymer or ABA block copolymer is preferred in terms of excellent dispersibility.

[0118] Block A is a block that functions as a colorant adsorption site and includes at least one constituent unit represented by the general formula (I). It may also be a salt-type block copolymer in which at least a portion of the nitrogen moiety of the constituent unit represented by the general formula (I) of the block copolymer forms a salt with at least one selected from the group consisting of organic acid compounds and halogenated hydrocarbons. Block A may have constituent units other than those represented by general formula (I) to the extent that the objectives of the present invention are achieved, and may contain any constituent units that are copolymerizable with the constituent units represented by general formula (I). Specifically, examples include the constituent units represented by general formula (III). In the block copolymer before salt formation, the content of the constituent unit represented by general formula (I) in block A is preferably 50% to 100% by mass, more preferably 80% to 100% by mass, and most preferably 100% by mass, when the total content of all constituent units in block A is set to 100% by mass. This is because a higher proportion of the constituent unit represented by general formula (I) improves the adsorption capacity to the colorant, resulting in better dispersibility and dispersion stability of the block copolymer. The content of the above constituent unit is calculated from the initial mass when synthesizing block A having the constituent unit represented by general formula (I).

[0119] In the block copolymer before salt formation, the total content of all constituent units of block A, including the constituent units represented by general formula (I), is preferably 5% to 60% by mass, and more preferably 10% to 50% by mass, when the total constituent units of the block copolymer are considered to be 100% by mass, in order to obtain good dispersibility and dispersion stability. Furthermore, in the block copolymer before salt formation, the content of the constituent units represented by general formula (I) is preferably 5% to 60% by mass, and more preferably 10% to 50% by mass, when the total content of the block copolymer is set to 100% by mass, in order to obtain good dispersibility and dispersion stability. The content of each constituent unit in the block copolymer is calculated from the initial mass when synthesizing the block copolymer before salt formation. Furthermore, the constituent units represented by general formula (I) only need to have affinity with the colorant, and may consist of only one type or may contain two or more constituent units.

[0120] Block B is a block that functions as a solvent affinity site and contains at least one constituent unit derived from (meth)acrylate. The constituent units derived from (meth)acrylate may be the same as those derived from (meth)acrylate described in the graft copolymer. As the B block, it is preferable to appropriately select and use a monomer having an unsaturated bond that can copolymerize with the monomer that derives the constituent unit represented by general formula (I), depending on the solvent, so as to have solvent affinity. As a guideline, it is preferable to introduce the B block so that the solubility of the copolymer at 23°C is 20 (g / 100g solvent) or more in the solvent used in combination. The constituent unit constituting the B block portion may consist of one type, or it may contain two or more types of constituent units. Examples of constituent units included in block B include the constituent unit represented by the general formula (III) mentioned above.

[0121] In the block copolymer used as a dispersant of the present invention, the ratio m / n of the number of units m of the constituent unit represented by the general formula (I) to the number of units n of other constituent units constituting the solvent-affinity block portion is preferably in the range of 0.01 to 1, and more preferably in the range of 0.05 to 0.7 from the viewpoint of dispersibility and dispersion stability of the colorant.

[0122] It is preferable that the block copolymer contains at least one structural unit selected from the group consisting of structural units represented by the general formula (IV) in the structural units included in block B, as this makes it easier to reduce the crystallinity of R202, which tends to have a significantly high phase difference, and thus easier to reduce the phase difference. The at least one constituent unit included in the block copolymer, selected from the group consisting of constituent units represented by the general formula (IV), may be the same as that described in the graft copolymer. When m contains 19 or more constituent units represented by the general formula (IV), the block copolymer has long polyalkylene chains, which causes it to spread sterically within the film and increase its specific surface area. Therefore, it is presumed that the pigment, which has been finely dispersed, is more likely to maintain its low crystallinity.

[0123] In the block copolymer, the content of at least one constituent unit selected from the group consisting of constituent units represented by the general formula (IV) is preferably 2.0% by mass or more, and more preferably 5.0% by mass or more, when the total constituent units of the block copolymer are considered to be 100% by mass. A value above the lower limit is preferable for suppressing phase differences. Similarly, a value of 40% by mass or less is preferable, and more preferably 30% by mass or less. A value below the upper limit is preferable because it allows for an increase in the introduction ratio of other useful monomers. The content of the above constituent units is calculated from the initial mass when synthesizing the block copolymer before salt formation.

[0124] The mass-average molecular weight Mw of the block copolymer is not particularly limited, but is preferably 1,000 to 20,000, more preferably 2,000 to 15,000, and even more preferably 3,000 to 12,000, from the viewpoint of good colorant dispersibility and dispersion stability. Here, the mass-average molecular weight (Mw) can be measured in the same manner as described above.

[0125] Furthermore, from the viewpoint of dispersion stability, solvent resistance, and compatibility with photoinitiators, the total proportion of constituent units derived from (meth)acrylate is preferably 60% by mass or more, more preferably 80% by mass or more, and even more preferably 90% by mass or more, when the total proportion of constituent units in block B of the block copolymer is set to 100% by mass. On the other hand, from the viewpoint of simultaneously satisfying dispersion stability and excellent solvent resistance, the total proportion of constituent units derived from (meth)acrylate may be 100% by mass when the total proportion of constituent units in block B is set to 100% by mass. If the B block contains constituent units derived from the carboxyl group-containing monomer, the total proportion of constituent units derived from (meth)acrylate may be 100% by mass when the total proportion of constituent units in block B that are different from the constituent units derived from the carboxyl group-containing monomer is set to 100% by mass.

[0126] In the block copolymer before salt formation, the total content of all constituent units of block B is preferably 40% to 95% by mass, and more preferably 50% to 90% by mass, when the total constituent units of the block copolymer are set to 100% by mass, in order to obtain good dispersibility and dispersion stability. Furthermore, in the block copolymer before salt formation, the content of the constituent units represented by the above general formula (III) is preferably 40% to 95% by mass, and more preferably 50% to 90% by mass, when the total content of the block copolymer is set to 100% by mass, in order to improve the dispersibility of the colorant. The content of the above constituent units is calculated from the initial mass when synthesizing the block copolymer before salt formation.

[0127] Among the (meth)acrylate copolymers containing the constituent units represented by the general formula (I), copolymers with an amine value of 40 mg KOH / g to 120 mg KOH / g are preferred because they have good dispersibility, do not precipitate foreign matter during coating film formation, and improve brightness and contrast. By having an amine value within the above range, the viscosity exhibits excellent stability over time and heat resistance, as well as excellent alkali developability and solvent resolubility. In the present invention, the amine value of the (meth)acrylate copolymer containing the constituent unit represented by the general formula (I) is preferably 80 mg KOH / g or higher, and more preferably 90 mg KOH / g or higher. On the other hand, from the viewpoint of solvent resolubility, the amine value of the (meth)acrylate copolymer containing the constituent unit represented by the general formula (I) is preferably 110 mg KOH / g or lower, and more preferably 105 mg KOH / g or lower. The amine value refers to the number of milligrams of perchloric acid equivalent to potassium hydroxide required to neutralize the amine components contained in 1 g of sample, and can be measured by the method defined in JIS-K7237. When measured by this method, even if an amino group forms a salt with an organic acid compound in the dispersant, the organic acid compound usually dissociates, so the amine value of the block copolymer used as the dispersant can be measured.

[0128] In the present invention, the method for producing the graft copolymer or block copolymer is not particularly limited and can be produced by appropriately selecting and using known polymerization methods.

[0129] The content percentage (mol%, mass%) 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.

[0130] In the photosensitive colored resin composition according to the present invention, the content of the dispersant is not particularly limited, but should be selected to provide excellent dispersibility and dispersion stability of the colorant. For example, it is preferably in the range of 2% to 30% by mass, more preferably 3% to 25% by mass, based on the total amount of solids in the photosensitive colored resin composition. If it 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 it is below the upper limit, the developability is good. In particular, when forming a cured film with a high colorant concentration, the content of the dispersant is preferably in the range of 2% to 25% by mass, more preferably 3% to 20% by mass, based on the total amount of solids in the photosensitive colored resin composition.

[0131] [Dye derivatives] In the photosensitive colored resin composition of the present invention, when a colorant is dispersed, a dye derivative in which a functional group is conjugated to the dye skeleton may be further included from the viewpoint of colorant dispersibility and colorant dispersion stability. Examples of functional groups in dye derivatives include basic groups, acidic groups, and phthalimidomethyl groups, which may have substituents. The dye derivative may be a dye derivative having an acidic group, or a dye derivative having a sulfonic acid group (-SO3H). Alternatively, it may be a metal salt or amine salt of the aforementioned dye derivative having a sulfonic acid group.

[0132] In a dye derivative having a sulfonic acid group, the sulfonic acid group may be directly bonded to the dye skeleton, or for example, -SO2NH-(CH2) m The sulfonic acid group may be bonded to the pigment skeleton via a linking group such as -SO3H (where m is an integer from 1 to 6). From the standpoint of ease of action on the target component, the sulfonic acid group may be directly bonded to the pigment skeleton. Furthermore, in a dye derivative having a sulfonic acid group, the number of substituted sulfonic acid groups may be 1 to 4 per molecule, preferably 1 to 2, and most preferably 1, as this does not easily reduce brightness.

[0133] The pigment skeleton of the pigment derivative used in the present invention can be appropriately selected, but in terms of interaction with the diketopyrrolopyrrole pigments, R202, and R122 used as colorants, and in terms of color, examples include the quinophthalone skeleton, xanthene skeleton, coumarin skeleton, naphthol azo skeleton, diketopyrrolopyrrole skeleton, quinacridone skeleton, etc., and may be the quinophthalone skeleton or the diketopyrrolopyrrole skeleton.

[0134] Examples of pigments having a quinophthalone skeleton include quinophthalone pigments such as CI Pigment Yellow 138, and quinophthalone dyes such as CI Disperse Yellow 54, 64, 67, 134, 149, 160, and CI Solvent Yellow 114, 157. As the dye having a quinophthalone skeleton, CI Pigment Yellow 138 or Pigment Yellow 231 is preferred due to its high transmittance and high brightness, and CI Pigment Yellow 138 is also acceptable. Examples of dyes having a diketopyrrolopyrrole skeleton include CI Pigment Red 254, 255, 264, and 272, with CI Pigment Red 254 and 272 being preferred due to their high transmittance.

[0135] The pigment derivative used in the present invention may be a pigment derivative having a quinophthalone skeleton with one sulfonic acid group, or a pigment derivative having a diketopyrrolopyrrole skeleton, from the viewpoint of good dispersibility and reduction of phase difference, and may be a monosulfonic acid derivative of CI Pigment Yellow 138, a monosulfonic acid derivative of CI Pigment Yellow 231, or a monosulfonic acid derivative of CI Pigment Red 254, or a monosulfonic acid derivative of CI Pigment Yellow 138.

[0136] The dye derivative can be used individually or in combination of two or more types. In the photosensitive colored resin composition according to the present invention, the content of the dye derivative may be, for example, 0.03% to 9.75% by mass, 0.12% to 9.0% by mass, preferably 1.0% to 5.0% by mass, and more preferably 2.5% to 3.5% by mass, relative to the total amount of solids of the photosensitive colored resin composition, in order to achieve both transmittance and dispersibility.

[0137] [Optional addition ingredients] The photosensitive colored resin composition may contain various additives as needed. Examples of additives include antioxidants, polymerization inhibitors, chain transfer agents, leveling agents, plasticizers, surfactants, defoamers, silane coupling agents, ultraviolet absorbers, adhesion promoters, and the like. Specific examples of surfactants and plasticizers include, for example, those described in Japanese Patent Publication No. 2013-029832.

[0138] The photosensitive colored resin composition of the present invention may further contain an antioxidant from the viewpoint of suppressing line width shift. 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, for example, 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 because they offer good heat resistance. Latent antioxidants, such as those described in International Publication No. 2014 / 021023, may also be used.

[0139] 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.

[0140] The antioxidant content is preferably in the range of 0.1% to 10.0% by mass, more preferably 0.5% to 5.0% by mass, relative to the total solid content of the photosensitive colored resin composition. If the content is above the lower limit, the ability to form fine line patterns according to the mask line width design is improved, and heat resistance is excellent. On the other hand, if the content is below the upper limit, the photosensitive colored resin composition of the present invention can be made into a highly sensitive photosensitive resin composition.

[0141] <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 various optional 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 and mixing an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and various optional additives into a solvent, 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 and mixing an alkali-soluble resin, a solvent, a photopolymerizable compound, a photoinitiator, and various optional additives into the dispersion; 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.

[0142] 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.

[0143] II. 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.

[0144] 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.

[0145] (colored layer) At least one of the colored layers used in the color filter of the present invention 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 application 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.

[0146] 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 heated and 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 photopolymerizable compounds 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, and electron beams. 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.

[0147] Next, the coating 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 or other additives may be added to this alkaline solution. Furthermore, a standard development method can be used. 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. The colored layer may be a colored layer with a fine pattern having a line width of 40 μm or less, or a colored layer with a fine pattern having a line width of 20 μm or less.

[0148] (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.

[0149] 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.

[0150] (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.

[0151] 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, alignment protrusions, columnar spacers, etc.

[0152] III.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.

[0153] [Liquid crystal display device] The liquid crystal display device according to the present invention comprises 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.

[0154] 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.

[0155] 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.

[0156] [Organic light-emitting display device] The organic light-emitting display device according to the present invention comprises the color filter according to the present invention described above and an organic light-emitting element. 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.

[0157] 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]

[0158] The present invention will be described in detail below with reference to examples. These descriptions are not intended to limit the present invention. The acid value was determined by a method in accordance with the method described in JIS K 0070:1992. The mass-average molecular weight (Mw) 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.

[0159] (Preparation Example 1: Preparation of alkali-soluble resin A) A mixture of 40 parts by mass of benzyl methacrylate (BzMA), 15 parts by mass of methyl methacrylate (MMA), 25 parts by mass of methacrylic acid (MAA), and 3 parts by mass of azoisobutyronitrile (AIBN) was added dropwise to a polymerization vessel containing 150 parts by mass of propylene glycol monomethyl ether acetate (PGMEA) under a nitrogen stream at 100°C over 3 hours. After the addition was complete, the mixture was heated at 100°C for another 3 hours to obtain a polymer solution. The mass-average molecular weight of this polymer solution was 7000. Next, 20 parts by mass of glycidyl methacrylate (GMA), 0.2 parts by mass of triethylamine, and 0.05 parts by mass of p-methoxyphenol were added to the obtained polymer solution, and the mixture was heated at 110°C for 10 hours to react the carboxylic acid groups of the main chain methacrylic acid with the epoxy groups of glycidyl methacrylate, thereby obtaining alkali-soluble resin solution A. During the reaction, air was bubbled into the reaction solution to prevent polymerization of glycidyl methacrylate. The reaction was monitored by measuring the acid value of the solution. The obtained alkali-soluble resin solution A was a resin in which side chains having ethylenically unsaturated bonds were introduced using GMA to a main chain formed by copolymerization of BzMA, MMA, and MAA. It had a solid content of 40% by mass, an acid value of 74 mgKOH / g, an ethylenically unsaturated bond equivalent of 711, and a mass-average molecular weight of 12000.

[0160] (Preparation Example 2: Preparation of Compound IA) (1) Synthesis of intermediate IA1 In a 500 ml four-necked flask, 0.2 mol of diphenylthioether, 30.22 mol of pulverized AlCl, and 150 ml of dichloroethane were added and stirred. Argon gas was then passed through the mixture and cooled in an ice bath until the temperature dropped to 0°C. At this point, a solution consisting of 0.22 mol of cyclohexylpropionyl chloride and 42 g of dichloroethane was added dropwise, gradually increasing the temperature to below 10°C over approximately 1.5 hours. The temperature was then raised to 15°C and stirred for another 2 hours before the reaction mixture was drained. The reaction mixture was gradually added to a dilute hydrochloric acid solution containing 400g of ice and 65ml of concentrated hydrochloric acid under stirring. The lower layer was separated using a separatory funnel, and the upper layer was extracted with 50ml of dichloroethane. The extract and the lower layer were then combined. The mixture was then washed with a NaHCO3 solution containing 100g of NaHCO3 and 200g of water, and further washed three times with 200ml of water until the pH was neutral. After drying with 60g of anhydrous MgSO4 to remove moisture, the dichloroethane was evaporated by rotary evaporation. The solid powder remaining in the rotary evaporator was placed in 200ml of petroleum ether, filtered by suction, and then added to 150ml of anhydrous ethanol, heated, and refluxed. After cooling to room temperature, it was further cooled with ice for 2 hours, filtered by suction, and dried in a 50°C oven for 2 hours to obtain the intermediate IA1 described below.

[0161] [ka]

[0162] (2) Synthesis of intermediate IA2 42 g of the intermediate IA1, 400 g of tetrahydrofuran, 200 g of concentrated hydrochloric acid, and 24.2 g of isoamyl nitrite were added to a 500 ml four-necked flask, and the mixture was stirred at room temperature for 5 hours before the reaction solution was drained. The reaction mixture was placed in a large beaker, 1000 ml of water was added and stirred, then allowed to stand overnight to separate into layers, yielding a yellow, viscous liquid. The viscous liquid was extracted with dichloroethane, 50 g of anhydrous MgSO4 was added and dried, then suction filtration was performed, and the filtrate was rotated and evaporated to remove the solvent, yielding an oily viscosity. Subsequently, this viscosity was placed in 150 ml of petroleum ether, stirred, precipitated, and suction filtration was performed to obtain a white powdery solid. After that, it was dried at 60°C for 5 hours to obtain the intermediate IA2 described below.

[0163] [ka]

[0164] (3) Synthesis of compound IA In a 1000 ml four-necked flask, 34 g of the intermediate IA2, 350 ml of dichloroethane, and 12.7 g of triethylamine were added and stirred. The mixture was cooled in an ice bath, and when the temperature dropped to 0°C, a solution consisting of 15.7 g of acetate chloride and 15 g of dichloroethane was added dropwise, over approximately 1.5 hours. After stirring for another hour, 500 ml of cold water was added dropwise, and the mixture was separated using a separatory funnel. The mixture was washed once with 200 ml of 5% NaHCO3 solution, then twice with 200 ml of water until the pH was neutral, then once with dilute hydrochloric acid (20 g of concentrated hydrochloric acid and 400 ml of water), followed by three washes with 200 ml of water. The mixture was then dried over 100 g of anhydrous MgSO4, and the solvent was removed by rotary evaporation to obtain a viscous liquid. An appropriate amount of methanol was added to the viscous liquid, and the resulting white solid was filtered and dried to obtain compound IA. The molecular weight of compound IA is 395.51.

[0165] [ka]

[0166] (Preparation Example 3: Preparation of Y138 sulfonic acid derivative) 374.76 parts by mass of 11% fuming sulfuric acid was stirred while cooling to 10°C, and 74.96 parts by mass of 138 CI pigment yellow were added. The mixture was then stirred at 90°C for 6 hours. The reaction mixture was added to 1600 parts by mass of ice water and stirred for 15 minutes, after which the precipitate was filtered. The resulting wet cake was washed three times with 800 ml of water. The wet cake was vacuum-dried at 80°C to obtain 81.55 parts by mass of the yellow product. The TOF-MS mass spectrometry results of this yellow product (Y138 sulfonic acid derivative) were consistent with the molecular weight (Mw=774.0) of the Y138 monosulfonic acid derivative having the following structure.

[0167] [ka]

[0168] (Preparation Example 4: Preparation of Dispersant 1 (Basic Block Copolymer 1)) A 500 ml four-neck separable flask was dried under reduced pressure and then purged with argon (Ar). While flowing Ar, 100 g of anhydrous THF, 2.0 g of methyltrimethylsilyldimethylketene acetal, 0.15 ml of 1 M acetonitrile solution of tetrabutylammonium-3-chlorobenzoate (TBACB), and 0.2 g of mesitylene were added. Using a dropping funnel, 7.8 parts by mass of n-butyl methacrylate (BMA), 48.9 parts by mass of methyl methacrylate (MMA), and 25.7 parts by mass of diethylene glycol monobutyl ether methacrylate (trade name: Light Ester BC, Kyoeisha Chemical Co., Ltd.) were added dropwise over 45 minutes. As the reaction proceeded, the temperature was kept below 40°C by cooling with ice. After 1 hour, 17.6 parts by mass of dimethylaminoethyl methacrylate (DMMA) were added dropwise over 15 minutes. After reacting for 1 hour, 5 g of methanol was added to stop the reaction. The solvent was removed under reduced pressure to obtain basic block copolymer 1. The mass-average molecular weight determined by GPC measurement (NMP LiBr 10 mM) was 8,000, and the amine value was 70 mgKOH / g.

[0169] (Preparation Example 5: Preparation of Dispersant 2 (Basic Block Copolymer 2)) In Preparation Example 4, instead of 7.8 parts by mass of n-butyl methacrylate (BMA), 48.9 parts by mass of methyl methacrylate (MMA), and 25.7 parts by mass of diethylene glycol monobutyl ether methacrylate (trade name: Light Ester BC, Kyoeisha Chemical Co., Ltd.), 9.8 parts by mass of n-butyl methacrylate (BMA), 62.6 parts by mass of methyl methacrylate (MMA), and methoxypolyethylene glycol monomethacrylate (polyethylene glycol chain repeat count n≈23, trade name: Bremmer PME-1000, manufactured by NOF Corporation) Basic block copolymer 2 was obtained in the same manner as in Preparation Example 4, except that 6.6 parts by mass of the basic copolymer and 21.0 parts by mass of dimethylaminoethyl methacrylate (DMMA) were used. The mass-average molecular weight determined by GPC measurement (NMP LiBr 10 mM) was 7,800 and the amine value was 70 mgKOH / g.

[0170] (Preparation Example 6: Preparation of Dispersant 3 (Basic Graft Copolymer 3)) (1) Synthesis of macromonomer A In a reactor equipped with a condenser, an additive funnel, a nitrogen inlet, a mechanical stirrer, and a digital thermometer, 70.0 parts by mass of propylene glycol methyl ether acetate (PGMEA) was charged and heated to 90°C while stirring under a nitrogen stream. A mixed solution consisting of 6.0 parts by mass of methoxypolyethylene glycol monomethacrylate (polyethylene glycol chain repeat count n≈23, trade name Bremmer PME-1000, manufactured by NOF Corporation), 41.0 parts by mass of methoxypolyethylene glycol monomethacrylate (polyethylene glycol chain repeat count n≈4, trade name Bremmer PME-200, manufactured by NOF Corporation), 53.0 parts by mass of methyl methacrylate (MMA), 4.0 parts by mass of 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 Karenz MOI (manufactured by Showa Denko K.K.), 0.125 g of dioctyl tin dilaurate, 0.125 parts by mass of p-methoxyphenol, and 30 parts by mass of PGMEA were added, and the mixture was stirred for 3 hours to obtain a 50% solution of macromonomer A. The obtained macromonomer A was examined by GPC (gel permeation chromatography) under conditions of N-methylpyrrolidone, 0.01 mol / L lithium bromide addition, and polystyrene standard, and was found to have a mass-average molecular weight (Mw) of 4700 and a molecular weight distribution (Mw / Mn) of 1.6. (2) Synthesis of basic graft copolymer 3 In a reactor equipped with a condenser, an additive funnel, a nitrogen inlet, a mechanical stirrer, and a digital thermometer, 63.1 parts by mass of PGMEA were charged and heated to 85°C while stirring under a nitrogen stream. A mixed solution of 165.4 parts by mass of a 50% solution of macromonomer A (82.7 parts by mass of effective solids), 17.3 parts by mass of 2-(dimethylamino)ethyl methacrylate (DMMA), 1.24 parts by mass of n-dodecyl mercaptan, 49.4 parts by mass of PGMEA, and 1.0 part by mass of AIBN was added dropwise over 1.5 hours, and the mixture was heated and stirred for 3 hours. Then, a mixed solution of 0.10 parts by mass of AIBN and 6.0 parts by mass of PGMEA was added dropwise over 10 minutes, and the mixture was aged at the same temperature for 1 hour to obtain a 35.0% by mass solution of graft copolymer 3. The obtained basic graft copolymer 3 had a mass-average molecular weight (Mw) of 16000 as determined by GPC measurement. The amine value was 105 mgKOH / g.

[0171] (Preparation Example 7: Preparation of Dispersant 4 (Basic Block Copolymer 4)) Basic block copolymer 4 was obtained in the same manner as in Preparation Example 4, except that in Preparation Example 4, 13.4 parts by mass of n-butyl methacrylate (BMA), 47.5 parts by mass of methyl methacrylate (MMA), 7.5 parts by mass of benzyl methacrylate (BzMA), and 9.0 parts by mass of 2-ethylhexyl methacrylate (EHMA) were used instead of 7.8 parts by mass of n-butyl methacrylate (BMA), 48.9 parts by mass of methyl methacrylate (MMA), and 25.7 parts by mass of diethylene glycol monobutyl ether methacrylate (trade name: Light Ester BC, Kyoeisha Chemical Co., Ltd.), and 22.6 parts by mass of dimethylaminoethyl methacrylate (DMMA). The mass-average molecular weight determined by GPC measurement (NMP LiBr 10 mM) was 7,000 and the amine value was 90 mgKOH / g.

[0172] (Manufacturing Example 1: Manufacturing of colorant dispersion R-1) 12.4 parts by mass of colorant (CI Pigment Red 202), 10.8 parts by mass of a PGMEA solution (60% solids) of basic block copolymer 1 obtained in Preparation Example 4 as a dispersant, 0.7 parts by mass of Y138 sulfonic acid derivative, 9.8 parts by mass of alkali-soluble resin A obtained in Preparation Example 1, 66.4 parts by mass of PGMEA, and 100 parts by mass of 2.0 mm particle size zirconia beads were placed in a mayonnaise bottle. For preliminary crushing, the mixture was shaken for 1 hour using a paint shaker (manufactured by Asada Iron Works Co., Ltd.). Then, the 2.0 mm particle size zirconia beads were removed, and 200 parts by mass of 0.1 mm particle size zirconia beads were added. The mixture was similarly dispersed for 8 hours using a paint shaker to obtain colorant dispersion R-1.

[0173] (Manufacturing Examples 2-5: Manufacturing of colorant dispersions R-2-R-5) Colorant dispersions R-2 to R-5 were manufactured in the same manner as in Manufacturing Example 1, except that CI Pigment Red 122, CI Pigment Red 254, CI Pigment Red 291, or CI Pigment Red 177 were used instead of CI Pigment Red 202 as the colorant.

[0174] (Manufacturing Example 6: Manufacturing of Colorant Dispersion R-6) In Production Example 1, colorant dispersion R-6 was obtained in the same manner as in Production Example 1, except that instead of 10.8 parts by mass of the PGMEA solution of basic block copolymer 1 obtained in Preparation Example 4 (60% solids by mass), 16.3 parts by mass of the PGMEA solution of basic block copolymer 2 obtained in Preparation Example 5 (40% solids by mass) was used, and instead of 66.4 parts by mass of PGMEA, 61.0 parts by mass of PGMEA was used.

[0175] (Manufacturing examples 7-9: Manufacturing of colorant dispersions R-7-R-9) In addition to using CI Pigment Red 122, CI Pigment Red 254, or CI Pigment Red 291 as the colorants in Production Example 6, colorant dispersions R-7 to R-9 were manufactured in the same manner as in Production Example 6, except that CI Pigment Red 122, CI Pigment Red 254, or CI Pigment Red 291 were used instead of CI Pigment Red 202 as the colorants.

[0176] (Manufacturing Example 10: Manufacturing of colorant dispersion R-10) In Production Example 1, colorant dispersion R-10 was obtained in the same manner as in Production Example 1, except that instead of 10.8 parts by mass of the PGMEA solution of basic block copolymer 1 obtained in Preparation Example 4 (60% solids by mass), 18.6 parts by mass of the PGMEA solution of basic graft copolymer 3 obtained in Preparation Example 6 (35% solids by mass) was used, and instead of 66.4 parts by mass of PGMEA, 58.7 parts by mass of PGMEA was used.

[0177] (Manufacturing Examples 11-13: Manufacturing of colorant dispersions R-11-R-13) In addition to using CI Pigment Red 122, CI Pigment Red 254, or CI Pigment Red 291 as the colorants in Production Example 10, colorant dispersions R-11 to R-13 were produced in the same manner as in Production Example 10, except that CI Pigment Red 122, CI Pigment Red 254, or CI Pigment Red 291 were used instead of CI Pigment Red 202 as the colorants.

[0178] (Manufacturing Example 14: Manufacturing of colorant dispersion R-14) In Production Example 1, colorant dispersion R-14 was obtained in the same manner as in Production Example 1, except that instead of 10.8 parts by mass of the PGMEA solution of basic block copolymer 1 obtained in Preparation Example 4 (60% solids by mass), 13.0 parts by mass of the PGMEA solution of basic block copolymer 4 obtained in Preparation Example 7 (50% solids by mass) was used, and instead of 66.4 parts by mass of PGMEA, 64.3 parts by mass of PGMEA was used.

[0179] (Manufacturing examples 15-17: Manufacturing of colorant dispersions R-15-R-17) In addition to using CI Pigment Red 122, CI Pigment Red 254, or CI Pigment Red 291 as the colorants in Production Example 14, colorant dispersions R-15 to R-17 were produced in the same manner as in Production Example 14, except that CI Pigment Red 122, CI Pigment Red 254, or CI Pigment Red 291 were used instead of CI Pigment Red 202 as the colorants.

[0180] (Example 1: Production of photosensitive colored resin composition 1) The photosensitive colored resin composition 1 was obtained by adding the colorant dispersions in the amounts by mass shown in Table 1, 4.6 parts by mass of the alkali-soluble resin A of Preparation Example 1, 2.8 parts by mass of M-403 (trade name: Aronix M-403, manufactured by Toagosei Co., Ltd., unsaturated bond equivalent: 98.8 to 99.6) as a photopolymerizable compound, 0.2 parts by mass of Compound IA of Preparation Example 2 as a photoinitiator, 0.30 parts by mass of a leveling agent (trade name: Megafac R-08MH, manufactured by DIC Corporation), and 48.6 parts by mass of PGMEA.

[0181] (Examples 2 to 20: Production of Photosensitive Colored Resin Compositions 2 to 20) In Example 1, the colorant dispersions, the alkali-soluble resin A of Preparation Example 1, M-403 as a photopolymerizable compound, and PGMEA were changed to the amounts by mass shown in Table 1 or Table 2, and photosensitive colored resin compositions 2 to 20 were obtained.

[0182] (Comparative Examples 1 to 8: Production of Comparative Photosensitive Colored Resin Compositions C1 to C8) In Example 1, the colorant dispersions, the alkali-soluble resin A of Preparation Example 1, M-403 as a photopolymerizable compound, and PGMEA were changed to the amounts by mass shown in Table 3, and comparative photosensitive colored resin compositions C1 to C8 were obtained.

[0183] [Table 1]

[0184] [Table 2]

[0185] [Table 3]

[0186] [Evaluation Method] [Optical Properties] The colored resin compositions of the examples and comparative examples were each applied onto a glass substrate (manufactured by NH Techno Glass Co., Ltd., "NA35") with a thickness of 0.7 mm using a spin coater so that the chromaticity after post-baking would be y = 0.653 (film thickness = 2.2 μm). Thereafter, heat drying was performed on a hot plate at 80 °C for 3 minutes. Ultraviolet rays of 60 mJ / cm 2 were irradiated using an ultra-high pressure mercury lamp without passing through a photomask, and then post-baking was carried out in a clean oven at 230 °C for 30 minutes to obtain a cured film (red colored layer). The chromaticity (x, y) and luminance (Y) of the obtained colored substrate were measured using an "Optical Microscopic Spectrophotometer OSP-SP200" manufactured by Olympus Corporation.

[0187] <Phase difference> Using a cured film (red colored layer) similar to that for the optical performance evaluation, phase difference measurement was performed. The phase difference of the colored layer was indicated by the retardation (Rth) in the thickness direction calculated by the following formula. The retardation (Rth) was measured using a phase difference layer measuring device (AxoscanTM Mueller Matrix Polarimeter manufactured by AXOMETRICS). The measurement wavelength of the red colored layer was measured at 620 nm. Rth was rounded to an integer by rounding the first decimal place. Rth = ((Nx + Ny) / 2 - Nz)d Nx: Refractive index in the in-plane slow axis direction Ny: Refractive index in the in-plane fast axis direction Nz: Refractive index in the thickness direction d: Film thickness (nm) (Phase difference evaluation criteria) A: Rth is 10 or less B: Rth is 11 or more and 15 or less C: Rth is 16 or more

[0188] [Table 4]

[0189] [Table 5]

[0190] [Table 6]

[0191] [Summary of Results] In Comparative Photosensitive Coloring Resin Compositions of Comparative Examples 5 to 8 in which a conventional diketopyrrolopyrrole-based pigment and R177 were combined, although the retardation was suppressed, a colored layer with insufficient luminance Y was obtained at each y value. In Comparative Photosensitive Coloring Resin Compositions of Comparative Examples 1 to 4 in which R202 was used instead of R177 as a combination of diketopyrrolopyrrole-based pigments, it was revealed that although the content ratio of the diketopyrrolopyrrole-based pigment could be increased and the luminance Y was improved at each y value, the retardation became high. On the other hand, it was revealed that all of the photosensitive coloring resin compositions of Examples 1 to 20 were capable of forming a colored layer with reduced retardation while improving the luminance at each y value. Among the examples, when the content ratio of C.I. Pigment Red 122 with respect to the total content of C.I. Pigment Red 202 and C.I. Pigment Red 122 was a predetermined amount, a high retardation suppressing effect was shown. Also, among the examples, when a dispersant of a (meth)acrylate copolymer having a polyethylene glycol chain was combined and used with respect to the pigment containing C.I. Pigment Red 202 and C.I. Pigment Red 122, a high retardation suppressing effect was shown. [Explanation of Signs]

[0192] 1 Substrate 2 Light-Shielding Portion<00​​​​​​​​​​​​​​​ 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. A photosensitive colored resin composition comprising, as the colorant, at least one diketopyrrolopyrrole pigment selected from the group consisting of C.I. Pigment Red 254 and C.I. Pigment Red 291, C.I. Pigment Red 202, and C.I. Pigment Red 122.

2. The photosensitive colored resin composition according to claim 1, wherein the content ratio of C.I. Pigment Red 122 to the total content of C.I. Pigment Red 202 and C.I. Pigment Red 122 is 0.01% by mass to 3% by mass.

3. 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 1 or 2.

4. A display device having the color filter described in claim 3.

Images