Photosensitive colored resin composition for color filters, color filter, and display device

Abstract

The present invention aims to provide a photosensitive colored resin composition for color filters capable of forming a colored layer having improved brightness while suppressing a decrease in brightness due to migration, and also aims to provide a color filter and a display device formed using the photosensitive colored resin composition. [Solution] A photosensitive colored resin composition for color filters comprising a color material, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a solvent, wherein the color material comprises a zinc phthalocyanine pigment having at least one diffraction peak in a diffraction angle (2θ) range of 3.00° to 7.00° in a powder X-ray diffraction spectrum of the color material alone using CuKα radiation.

Description

[Technical field]

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

[0002] In recent years, the demand for liquid crystal displays has increased with the development of personal computers, especially portable personal computers. The penetration rate of mobile displays (mobile phones, smartphones, tablet PCs) is also increasing, and the market for liquid crystal displays is expanding further. Organic light-emitting display devices such as organic electroluminescence displays, which have high visibility due to their self-luminescence, 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, when a color image is formed in a liquid crystal display device, the light passing through the color filter is colored as it is with the color of each pixel that constitutes the color filter, and the light of these colors is combined to form a color image. In this case, in addition to conventional cold cathode fluorescent lamps, white-emitting organic light-emitting elements or white-emitting inorganic light-emitting elements may be used as the light source. In the case of an organic light-emitting display device, a color filter is used for color adjustment and the like.

[0003] Here, a color filter generally comprises a substrate, a colored layer formed on the substrate and consisting of colored patterns of the three primary colors, red, green, and blue, and a light-shielding portion formed on the substrate so as to partition each colored pattern. A method for forming a colored layer in a color filter is, for example, to coat a glass substrate with a photosensitive colored 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, and then drying the composition, exposing the composition using a photomask, developing the composition to form a colored pattern, and heating the composition to fix the pattern to form a colored layer. These steps are repeated for each color to form a color filter.

[0004] Pigments are generally used as coloring materials from the viewpoints of heat resistance, light resistance, etc., but pigments are no longer able to meet market demands, particularly for high brightness. Therefore, dyes that are soluble in solvents have been widely studied. Dyes are excellent in terms of increasing the hue and brightness of a displayed image when an image is displayed, due to the color purity of the dye itself and the vividness of its hue. On the other hand, dyes are generally poor in heat resistance and solvent resistance, and there is a problem that foreign matter is easily precipitated in the resulting colored layer, making it difficult to put them into practical use. Regarding the green colored layer, studies are being conducted on the use of specific phthalocyanine dyes as dyes (see, for example, Patent Documents 1 and 2). [Prior art documents] [Patent documents]

[0005] [Patent Document 1] JP 2020-42263 A [Patent Document 2] International Publication No. 2020 / 171060 Summary of the Invention [Problem to be solved by the invention]

[0006] As described in the above Patent Documents 1-2, the halogenated zinc phthalocyanine dye has good solvent solubility, and is dissolved in a solvent and used in a colored resin composition. However, when a green colored layer of a color filter is formed using a colored resin composition containing a halogenated zinc phthalocyanine dye dissolved in a solvent, the halogenated zinc phthalocyanine dye is likely to migrate to the red colored layer or blue colored layer on the substrate, causing a problem of reduced brightness of the red colored layer or blue colored layer. Even if the brightness of the green colored layer is improved by using the halogenated zinc phthalocyanine dye, if the brightness of the red colored layer or blue colored layer is reduced, the white brightness of the color filter obtained by the red colored layer, green colored layer, and blue colored layer is reduced. It is described that the halogenated zinc phthalocyanine dye of Patent Document 2 has a maximum peak in the diffraction angle (2θ) range of 2 to 5° in the X-ray diffraction spectrum after heating to form a coating film. However, the halogenated zinc phthalocyanine dye used in Patent Document 2 does not have a diffraction peak in the diffraction angle 2θ range of 2 to 60° in the powder X-ray diffraction spectrum of the dye alone at 25°C before heating, as shown in the comparative example described later.

[0007] The present invention has been made in view of the above circumstances, and aims to provide a photosensitive colored resin composition for color filters capable of forming a colored layer with improved brightness and suppressing the decrease in brightness due to migration. Another aim of the present invention is to provide a color filter and a display device formed using the photosensitive colored resin composition. [Means for solving the problem]

[0008] That is, the present invention relates to the following [1] to [8]. [1] A composition comprising a colorant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a solvent; The colorant is a photosensitive colored resin composition for color filters, which contains a zinc phthalocyanine pigment having at least one diffraction peak in a diffraction angle (2θ) range of 3.00° to 7.00° in a powder X-ray diffraction spectrum of the colorant alone using CuKα radiation.

[0009] [2] The photosensitive color resin composition for color filters according to [1] above, wherein the zinc phthalocyanine pigment is a zinc phthalocyanine pigment represented by the following general formula (1):

[0010] [ka] (In general formula (1), R A1 , R A2 , R A3 , R A4 , R A5 , R A6 , R A7 , and R A8are each independently a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted arylalkyl group, or a substituted or unsubstituted heteroarylalkyl group.

[0011] [3] The photosensitive colored resin composition for color filters according to [1] or [2] above, wherein the zinc phthalocyanine pigment is a zinc phthalocyanine pigment represented by the following formula (1-1):

[0012] [ka]

[0013] [4] The photosensitive color resin composition for color filters according to any one of [1] to [3] above, wherein the color material further comprises a yellow color material. [5] The photosensitive color resin composition for color filters according to any one of [1] to [4] above, wherein the color material further contains a green color material different from the zinc phthalocyanine pigment. [6] The photosensitive color resin composition for color filters according to any one of [1] to [5] above, wherein the color material further comprises a blue color material. [7] A color filter comprising at least a substrate and colored layers provided on the substrate, wherein at least one of the colored layers is a cured product of the photosensitive colored resin composition according to any one of [1] to [6] above. [8] A display device comprising the color filter according to [7] above. Effect of the Invention

[0014] According to the present invention, a photosensitive colored resin composition for color filters capable of forming a colored layer having improved brightness and suppressing a decrease in brightness due to migration can be provided. In addition, according to the present invention, a color filter and a display device formed using the photosensitive colored resin composition can be provided. The colored layer, which is a cured product of the photosensitive colored resin composition for color filters of the present invention, has high brightness and can suppress a decrease in brightness of other colored layers due to migration, thereby improving the white brightness of the color filter. [Brief description of the drawings]

[0015] [Figure 1] FIG. 1 is a schematic diagram showing an example of the color filter of the present invention. [Diagram 2] FIG. 2 is a schematic diagram showing an example of the liquid crystal display device of the present invention. [Diagram 3] FIG. 3 is a schematic diagram showing an example of an organic light-emitting display device of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0016] The photosensitive colored resin composition, the color filter, and the display device according to the present invention will be described in detail below. In the present 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 the present invention, (meth)acryloyl refers to each of acryloyl and methacryloyl, (meth)acrylic refers to each of acrylic and methacrylic, and (meth)acrylate refers to each of acrylate and methacrylate. In addition, in this specification, the use of "to" indicating a numerical range is used to mean that the numerical values ​​before and after it are included as the lower limit and upper limit.

[0017] I. Photosensitive colored resin composition for color filters The photosensitive color resin composition for color filters according to the present invention contains a color material, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a solvent, The color material is characterized in that it contains a zinc phthalocyanine pigment having at least one diffraction peak in a diffraction angle (2θ) range of 3.00° to 7.00° in a powder X-ray diffraction spectrum of the color material alone using CuKα rays.

[0018] The photosensitive colored resin composition for color filters according to the present invention contains, together with a solvent, a zinc phthalocyanine pigment having at least one diffraction peak in the range of a diffraction angle (2θ) of 3.00° to 7.00° in the powder X-ray diffraction spectrum of the color material alone using CuKα radiation before heating, thereby making it possible to form a colored layer in which the decrease in brightness due to migration is suppressed and the brightness is improved. The photosensitive colored resin composition for color filters according to the present invention contains a zinc phthalocyanine pigment having a specific crystallinity as a coloring material alone in a solvent as particles before being heated to form a coating film. The zinc phthalocyanine pigment having the specific crystallinity is a particle having a larger size than a molecular dye, and is a crystal containing molecules. Therefore, when the photosensitive colored resin composition is applied onto other colored layers during the production of a color filter, it is difficult for the pigment to penetrate into the resin of the other colored layers, and the number of contact points where interactions occur with various hydrophobic substituents contained in the resin or dispersant in the other colored layers is reduced. For this reason, it is considered that the photosensitive colored resin composition for color filters according to the present invention suppresses migration to other colored layers during the formation of a color filter. In addition, the zinc phthalocyanine pigment used in the present invention has at least one diffraction peak in the range of diffraction angle (2θ) of 3.00° to 7.00° in the powder X-ray diffraction spectrum using CuKα radiation at 25°C of the coloring material alone before heating, and therefore has crystallinity different from that of conventional pigments, and in the case of this zinc phthalocyanine fluoride aggregate (crystal structure), the transmitted light peak wavelength shifts to longer wavelengths, and the proportion of the peak top wavelength of the color matching function y(λ) of the RGB color system increases, which is thought to improve the brightness. In addition, in the case of the zinc phthalocyanine pigment aggregate (crystal structure) used in the present invention, it is presumed that the loss of transmitted light due to incident light scattering caused by pigmentation is less likely to occur, and the brightness is improved.

[0019] The colored layer, which is a cured product of the photosensitive colored resin composition for color filters of the present invention, has high brightness and can suppress a decrease in brightness of other colored layers due to migration, thereby improving the white brightness of the color filter. According to the colored layer which is a cured product of the photosensitive colored resin composition for color filters of the present invention, the white brightness of the color filter can be improved, so that the desired brightness can be obtained even when the backlight brightness output setting of the display device is lowered, and the power consumption of the display can be reduced.

[0020] The photosensitive colored resin composition for color filters 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 within a range that does not impair the effects of the present invention. Hereinafter, each component of the photosensitive colored resin composition for color filters of the present invention will be described in detail in order.

[0021] [Colorant] In the photosensitive colored resin composition for color filters according to the present invention, the colorant contains a zinc phthalocyanine pigment having at least one diffraction peak in a diffraction angle (2θ) range of 3.00° to 7.00° in a powder X-ray diffraction spectrum using CuKα radiation of the colorant alone (hereinafter, the zinc phthalocyanine pigment having the specific diffraction peak may be referred to as "zinc phthalocyanine pigment (P1)"). The powder X-ray diffraction spectrum of the colorant used in the present invention is measured by measuring the colorant alone before heating at 25°C using an X-ray diffractometer with CuKα radiation over a diffraction angle (2θ) range of 2.00° to 60.00° with a θ step of 0.01°. The presence or absence of a diffraction peak is determined after removing the background from the powder X-ray diffraction spectrum. In the obtained powder X-ray diffraction spectrum, when the maximum peak intensity in the diffraction angle (2θ) range of 2.00° to 60.00° is defined as Z, a peak having an intensity of 1 / 4Z (1 / 4 of Z) or more is recognized as a diffraction peak. Then, it is determined whether or not at least one diffraction peak is present in the diffraction angle (2θ) range of 3.00° to 7.00°. The background is removed by the Sonnevelt-Visser method. The peak width threshold is 0.10, and the intensity threshold is 0.01. Here, the "background" does not refer to the diffraction peak caused by crystallinity or the tailing portion of the diffraction peak, but to the superimposed portion caused by Compton scattering, etc. The specific method for measuring the powder X-ray diffraction spectrum of the colorant used in the present invention can be performed in the same manner as in the examples.

[0022] The zinc phthalocyanine pigment (P1) may have at least one diffraction peak in the powder X-ray diffraction spectrum in a diffraction angle (2θ) range of 4.00° to 7.00°, or may have at least one diffraction peak in the range of more than 5.00° to 7.00°, in order to suppress a decrease in brightness due to dye migration and to form a colored layer with improved brightness.

[0023] In general, a dye is a colorant that is soluble in a solvent and is used by dissolving it in the solvent, while a pigment is a colorant that is insoluble in the solvent. In the present invention, the zinc phthalocyanine pigment (P1) may have a solubility in acetone at 25° C. of less than 0.1% by mass, less than 0.05% by mass, or less than 0.01% by mass.

[0024] The zinc phthalocyanine pigment (P1) is not particularly limited as long as it has at least one diffraction peak in the range of a diffraction angle (2θ) of 3.00° to 7.00° in the powder X-ray diffraction spectrum. However, it may be a fluorinated zinc phthalocyanine pigment because it is possible to form a colored layer in which a decrease in luminance due to migration is suppressed and luminance is improved.

[0025] The zinc phthalocyanine pigment (P1) is not particularly limited as long as it has at least one diffraction peak in the diffraction angle (2θ) range of 3.00° to 7.00° in the powder X-ray diffraction spectrum. However, from the viewpoint of suppressing a decrease in luminance due to dye migration and enabling the formation of a colored layer with improved luminance, the zinc phthalocyanine pigment may be represented by the following general formula (1):

[0026] [ka] (In general formula (1), R A1 , R A2 , R A3 , R A4 , R A5 , R A6 , R A7 , and R A8 are each independently a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted arylalkyl group, or a substituted or unsubstituted heteroarylalkyl group.

[0027] R A1 ~R A8 The substituted or unsubstituted aryl group in the formula (I) is preferably an aryl group having a total of 6 to 18 carbon atoms, and more preferably an aryl group having a total of 6 to 14 carbon atoms. An example of the substituent that the substituted aryl group has is the substituent S described below. Here, the total number of carbon atoms in the aryl group means the total number of carbon atoms including the number of carbon atoms in the substituent, when the substituent contains a carbon atom. Unsubstituted aryl group (R a ) may be, for example, an aryl group having 6 to 18 carbon atoms, and preferably an aryl group having 6 to 14 carbon atoms. Examples of the unsubstituted aryl group include a phenyl group, a naphthyl group, a biphenyl group, a fluorenyl group, and an anthracenyl group. The aryl group may be an aryl group having 6 to 10 carbon atoms, or may be a phenyl group.

[0028] R A1 ~R A8 The substituted or unsubstituted heteroaryl group in the above formula is preferably a heteroaryl group containing an oxygen atom, a nitrogen atom, a sulfur atom, or the like as a heteroatom and having a total of 2 to 12 carbon atoms. Examples of the substituent that the substituted heteroaryl group has include the substituent S described below. Here, the total number of carbon atoms in the heteroaryl group means the total number of carbon atoms including the number of carbon atoms in the substituent when the substituent contains a carbon atom. R A1~R A8 The unsubstituted heteroaryl group (R b ) includes, for example, a furan ring, a thiophene ring, a pyrrole ring, a pyridine ring, a 1,3-oxazole ring, an isoxazole ring, a 1,3-thiazole ring, an isothiazole ring, an imidazole ring, a pyrazole ring, a furazan ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, a carbazole ring, an acridine ring, and the like, each having one free valence. The heteroaryl group may be a heteroaryl group having 5 to 6 ring atoms.

[0029] R A1 ~R A8 The substituted or unsubstituted arylalkyl group in the formula (I) is preferably an arylalkyl group having a total of 7 to 19 carbon atoms, and more preferably an arylalkyl group having a total of 7 to 15 carbon atoms. An example of a substituent that the substituted arylalkyl group has is the substituent S described below. Here, the total number of carbon atoms in the arylalkyl group means the total number of carbon atoms including the number of carbon atoms in the substituent, when the substituent contains a carbon atom. R A1 ~R A8 The unsubstituted arylalkyl group (R L -R a ) is an alkyl group having the unsubstituted aryl group (R a ) is substituted. The alkyl group may be, for example, a straight-chain, branched, or cyclic alkyl group having 1 to 6 carbon atoms. Examples of the straight-chain or branched alkyl group include a methyl group, an ethyl group, a straight-chain or branched propyl group, a straight-chain or branched butyl group, a straight-chain or branched pentyl group, and a straight-chain or branched hexyl group. Examples of the cyclic alkyl group include a cyclopentyl group, a cyclohexyl group, and the like. The alkyl group in the arylalkyl group may be an alkyl group having 1 to 3 carbon atoms. Examples of the unsubstituted arylalkyl group include a benzyl group, a phenylethyl group, and a naphthylmethyl group.

[0030] R A1 ~R A8The substituted or unsubstituted heteroarylalkyl group in the above formula is preferably a heteroarylalkyl group having a total of 3 to 13 carbon atoms. Examples of the substituent that the substituted heteroarylalkyl group has include the substituent S described below. Here, the total number of carbon atoms in the heteroarylalkyl group means the total number of carbon atoms including the number of carbon atoms in the substituent, when the substituent contains a carbon atom. R A1 ~R A8 The unsubstituted heteroarylalkyl group (R L -R b ) is an alkyl group having the unsubstituted heteroaryl group (R b Examples of the alkyl group include the unsubstituted arylalkyl group (R L -R a ) may be similar to that described above.

[0031] Examples of the substituent S that may be possessed by the aryl group, heteroaryl group, arylalkyl group, or heteroarylalkyl group include a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cyano group, a hydroxy group, a nitro group, an amino group, an alkylamino group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an acylamino group, an arylamino group, a ureido group, an alkylthio group, an arylthio group, a heteroarylthio group, an alkoxycarbonylamino group, a sulfonamide group, a carbamoyl group, an alkoxycarbonyl group, an acyloxy group, a carbamoyloxy group, a silyloxy group, an aryloxycarbonyl group, a heteroaryloxycarbonyl group, an arylcarbonyl group, a heteroarylcarbonyl group, an aryloxycarbonylamino group, an arylalkyloxycarbonyl group, an arylalkyloxycarbonylamino group, an imido group, a phosphoryl group, an acyl group, a carboxy group, and a sulfo group. Each of these groups may further have a substituent.

[0032] The substituent S is preferably one that does not have a substituent that improves the solvent solubility, since it is likely to have at least one diffraction peak in the diffraction angle (2θ) range of 3.00° to 7.00°, and is preferably one that does not have an alkoxycarbonyl group (-COOR c , where R c It is preferred that the group does not contain an alkyl group. Furthermore, the substituent S does not necessarily include an alkoxycarbonylalkyl group, an alkoxycarbonylalkoxy group, an alkylcarbonyl group, an alkoxyalkyl group, or a cyanoalkyl group.

[0033] The substituent S may be at least one type of substituent S1 selected from the group consisting of a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cyano group, a hydroxy group, a nitro group, an aryloxy group, a heteroaryloxy group, an arylamino group, an arylthio group, a heteroarylthio group, an aryloxycarbonyl group, a heteroaryloxycarbonyl group, an arylcarbonyl group, a heteroarylcarbonyl group, an aryloxycarbonylamino group, an arylalkyloxycarbonyl group, and an arylalkyloxycarbonylamino group, an alkyl group, an aryloxy group, a heteroaryloxy group, an aryloxycarbonyl group, and an arylalkyloxycarbonylamino group, or at least one type of substituent S2 selected from the group consisting of an alkyl group, an aryloxy group, a heteroaryloxy group, an aryloxycarbonyl group, and an aryloxycarbonyl group, or at least one type of substituent S3 selected from the group consisting of an alkyl group and an aryloxycarbonyl group, from the viewpoint of being likely to have at least one diffraction peak in the range of a diffraction angle (2θ) of 3.00° to 7.00°. The alkyl group and aryl group in each of these groups may further have a substituent S. The alkyl group contained in the substituent may have 1 to 4 carbon atoms, may have 1 to 3 carbon atoms, or may have 1 or 2 carbon atoms. The alkyl group contained in the substituent may be an unsubstituted alkyl group.

[0034] R A1 , R A2 , R A3 , R A4 , R A5 , R A6, R A7 , and R A8 may be the same or different, but R A1 , R A2 , R A3 , R A4 , R A5 , R A6 , R A7 , and R A8 Of these, R A1 , R A3 , R A5 , and R A7 are the same and R A2 , R A4 , R A6 , and R A8 are preferably identical, and R A1 , R A2 , R A3 , R A4 , R A5 , R A6 , R A7 , and R A8 It is more preferable that all of are identical.

[0035] R A1 , R A2 , R A3 , R A4 , R A5 , R A6 , R A7 , and R A8 are each independently preferably a group represented by the following general formula (2) since they are likely to have at least one diffraction peak in the diffraction angle (2θ) range of 3.00° to 7.00°.

[0036] [ka] (In formula (2), R d1 , R d2 , R d3 , R d4 , and R d5 Each independently represents a hydrogen atom or a monovalent substituent. * indicates the bonding position with the oxygen atom in formula (1).

[0037] R d1 , R d2 , R d3 , R d4 , and R d5 The monovalent substituent in may be the same as the substituent S, but is preferably the substituent S1, or may be the substituent S2 or S3, in that it is likely to have at least one diffraction peak in the diffraction angle (2θ) range of 3.00° to 7.00°. Among them, R d1 , R d2 , R d3 , R d4 , and R d5 The monovalent substituent in is an unsubstituted alkyl group having 1 to 6 carbon atoms, and an aryloxycarbonyl group (-COOR e , where R e may be at least one selected from the group consisting of an unsubstituted alkyl group having 1 to 3 carbon atoms, and an aryloxycarbonyl group (-COOR e , where R e may be at least one selected from the group consisting of an unsubstituted alkyl group having 1 to 2 carbon atoms, and an aryloxycarbonyl group (-COOR e , where R e may be at least one selected from the group consisting of substituted or unsubstituted aryl groups having a total of 6 to 12 carbon atoms. The substituent of the substituted aryl group may be the aforementioned substituent S, and may be a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cyano group, a hydroxy group, a nitro group, an amino group, an alkylamino group, an alkoxy group, an acylamino group, an alkoxycarbonylamino group, a sulfonamide group, an alkoxycarbonyl group, an acyloxy group, an acyl group, a carboxy group, or a sulfo group.

[0038] Since it is likely to have at least one diffraction peak in the range of diffraction angles (2θ) of 3.00° to 7.00°, R d1 , R d2 , R d3 , R d4 , and Rd5 It is preferred that one or two of R are monovalent substituents and the remaining four or three are hydrogen atoms. d1 , R d2 , R d3 , R d4 , and R d5 It is preferable that one of the groups is a monovalent substituent and the remaining four are hydrogen atoms.

[0039] Since it is likely to have at least one diffraction peak in the range of diffraction angles (2θ) of 3.00° to 7.00°, R d1 , R d2 , R d3 , R d4 , and R d5 In R d2 , R d3 , and R d4 It is preferred that one or two of R are monovalent substituents and the remaining four or three are hydrogen atoms. d3 is a monovalent substituent, and R d1 , R d2 , R d4 , and R d5 is preferably a hydrogen atom.

[0040] Preferred specific examples of the group represented by formula (2) include groups represented by the following formulas (2-1) to (2-7), but are not limited thereto.

[0041] [ka] (In formulas (2-1) to (2-7), * indicates the bonding position with the oxygen atom in formula (1).)

[0042] Preferred specific examples of the zinc phthalocyanine pigment (P1) include compounds represented by the following formulas (1-1) to (1-3), but are not limited thereto.

[0043] [ka]

[0044] [ka]

[0045] The zinc phthalocyanine pigment (P1) can be produced by appropriately selecting from conventionally known production methods. For example, a method of cyclizing a phthalonitrile compound with a metal salt in a molten state or in an organic solvent can be preferably used, and can be produced by referring to, for example, JP-A-2005-298491, JP-A-2014-43556, JP-A-2020-42263, etc. The phthalonitrile compound used as the starting material can also be synthesized by appropriately selecting from conventionally known production methods, and commercially available products may be used.

[0046] In the present invention, the coloring material may further contain other coloring materials in addition to the zinc phthalocyanine pigment (P1). The other coloring materials are not particularly limited as long as they can produce the desired color, and various organic pigments, inorganic pigments, dyes, dye salt compounds, etc. can be used alone or in combination of two or more. Among them, organic pigments are preferably used because they have high color development, high heat resistance, and suppressed dye migration. Examples of organic pigments include compounds classified as pigments in the Color Index (CI; published by The Society of Dyers and Colourists), specifically, those assigned the following Color Index (CI) numbers.

[0047] In the present invention, the coloring material may further include a yellow coloring material from the viewpoint of adjusting chromaticity. Examples of yellow colorants 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, 127, 128, and 129. , 138, 139, 150, 151, 152, 153, 154, 155, 156, 166, 168, 175, 185, 231, and derivative pigments thereof; yellow dyes such as coumarin dyes, cyanine dyes, merocyanine dyes, azo dyes, methine dyes, azomethine dyes, and quinophthalone dyes; and salt-forming compounds of the yellow dyes. The coloring material may be any of pigments, dyes, and dye salt-forming compounds. From the viewpoint of suppressing dye migration, however, either pigments or dye salt-forming compounds are preferred, and among them, pigments are preferred.

[0048] As the yellow coloring material, quinophthalone-based coloring materials are preferable because they have good heat resistance and light resistance and high transmittance. Quinophthalone-based coloring materials are also preferable because they have a hue suitable for use in color filters. The quinophthalone coloring material refers to a coloring material synthesized by condensation of a quinoline derivative such as quinaldine with a phthalic anhydride derivative or a naphthalic anhydride derivative. Among the quinophthalone colorants, examples of quinophthalone pigments include CI Pigment Yellow 138. Examples of quinophthalone dyes include CI Disperse Yellow 54, 64, 67, 134, 149, 160, CI Solvent Yellow 114, 157, and the like.

[0049] In the present invention, the coloring material may further contain a green coloring material different from the zinc phthalocyanine pigment from the viewpoint of adjusting chromaticity. Examples of green colorants other than the zinc phthalocyanine pigment include green pigments such as CI Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55, 58, 59, 62, and 63; green dyes such as squarylium, triarylmethane, anthraquinone, coumarin, cyanine, and azo dyes; and salt-forming compounds of the green dyes. From the viewpoint of ease of adjusting the chromaticity, the other green coloring material different from the halogenated phthalocyanine compound is preferably a phthalocyanine green pigment. Examples of the phthalocyanine green pigment include CI Pigment Green 7, 36, 58, 59, 62, and 63. In terms of ease of adjusting the brightness, the phthalocyanine green pigment is preferably CI Pigment Green 7, 58, 59, 62, or 63, more preferably CI Pigment Green 58, 59, 62, or 63, and more preferably CI Pigment Green 59.

[0050] In the present invention, the coloring material may further contain a blue coloring material from the viewpoint of adjusting chromaticity. Examples of blue colorants include blue pigments such as CI Pigment Blue 15, 15:3, 15:4, 15:6, and 60.

[0051] In the photosensitive color resin composition of the present invention, the content ratio of the zinc phthalocyanine pigment (P1) to the entire color material may be appropriately adjusted according to the desired chromaticity, and is not particularly limited, and may be 100 mass% based on the entire color material including the zinc phthalocyanine pigment (P1). In the photosensitive color resin composition for color filters of the present invention, when other color materials are contained, the zinc phthalocyanine pigment (P1) may be contained in an amount of 30 mass% to 95 mass%, 40 mass% to 85 mass%, or 50 mass% to 80 mass% based on the entire color material including the zinc phthalocyanine pigment (P1) from the viewpoint of desired chromaticity adjustment.

[0052] In the photosensitive color resin composition of the present invention, when a yellow coloring material is contained, the yellow coloring material is appropriately selected and used alone or in combination of two or more kinds. In the photosensitive color resin composition of the present invention, the content ratio of the yellow coloring material to the zinc phthalocyanine pigment (P1) of the present invention may be appropriately adjusted according to the desired chromaticity, and is not particularly limited. In particular, from the viewpoint of the desired chromaticity adjustment, the yellow coloring material may be contained in an amount of 5 to 233 parts by mass, 18 to 150 parts by mass, or 25 to 100 parts by mass relative to 100 parts by mass of the zinc phthalocyanine pigment (P1).

[0053] In the photosensitive color resin composition of the present invention, when the green coloring material other than the zinc phthalocyanine pigment (P1) is contained, the green coloring material other than the zinc phthalocyanine pigment (P1) is appropriately selected, and one kind is used alone or two or more kinds are used in combination. In the photosensitive color resin composition of the present invention, the content ratio of the green coloring material different from the zinc phthalocyanine pigment (P1) to the zinc phthalocyanine pigment (P1) is not particularly limited as long as it is appropriately adjusted to a desired chromaticity. In particular, from the viewpoint of desired chromaticity adjustment, brightness adjustment, and color migration suppression, the green coloring material different from the zinc phthalocyanine pigment (P1) may be contained in an amount of 5 parts by mass to 233 parts by mass, 5 parts by mass to 150 parts by mass, or 5 parts by mass to 100 parts by mass, relative to 100 parts by mass of the zinc phthalocyanine pigment (P1).

[0054] In addition, in the photosensitive color resin composition of the present invention, when a green coloring material other than the zinc phthalocyanine pigment (P1) is further contained, the content ratio of the green coloring material including the zinc phthalocyanine pigment (P1) to the entire coloring material is not particularly limited, as long as it is appropriately adjusted according to the desired chromaticity. Among them, from the viewpoint of the desired chromaticity adjustment and brightness adjustment, it is preferable to contain 30 mass% to 95 mass% of the green coloring material including the zinc phthalocyanine pigment (P1) to the entire coloring material, and more preferably to contain 50 mass% to 80 mass%. The content ratio of the yellow colorant to the green colorant containing the zinc phthalocyanine pigment (P1) is not particularly limited, and may be appropriately adjusted according to the desired chromaticity. In particular, from the viewpoint of desired chromaticity adjustment and brightness adjustment, the yellow colorant is preferably contained in an amount of 5 to 70 parts by mass, more preferably 20 to 50 parts by mass, of 100 parts by mass of the green colorant containing the zinc phthalocyanine pigment (P1).

[0055] In addition, in the photosensitive color resin composition of the present invention, when a blue coloring material is contained, the blue coloring material is appropriately selected and used alone or in combination of two or more kinds. In the photosensitive color resin composition of the present invention, the content ratio of the blue coloring material to the zinc phthalocyanine pigment (P1) of the present invention may be appropriately adjusted according to the desired chromaticity, and is not particularly limited. In particular, from the viewpoint of the desired chromaticity adjustment, the blue coloring material may be contained in an amount of 1 to 50 parts by mass, 1 to 20 parts by mass, or 1 to 5 parts by mass with respect to 100 parts by mass of the zinc phthalocyanine pigment (P1).

[0056] In the photosensitive color resin composition of the present invention, the coloring material may further contain other coloring materials other than the green coloring material and the yellow coloring material within the range in which the effects of the present invention are not impaired, but the total content of the green coloring material containing the zinc phthalocyanine pigment (P1) and the yellow coloring material may be 70% by mass to 100% by mass, particularly 80% by mass to 100% by mass, 90% by mass to 100% by mass, or 100% by mass.

[0057] In the photosensitive colored resin composition according to the present invention, the content of the coloring material is not particularly limited. The total content of the coloring material is, for example, preferably 3% by mass to 65% by mass, more preferably 4% by mass to 60% by mass, based on the total solid content of the photosensitive colored resin composition, from the viewpoint of dispersibility and dispersion stability. If it is equal to or more than the above lower limit, the colored layer when the photosensitive colored resin composition is applied to a predetermined film thickness (usually 1.0 μm to 5.0 μm) has sufficient color density. Also, if it is equal to or less than the above upper limit, a colored layer having excellent storage stability, sufficient hardness, and adhesion to the substrate can be obtained. In particular, when a colored layer having a high coloring material concentration is formed, the total content of the coloring material is preferably 15% by mass to 65% by mass, more preferably 25% by mass to 60% by mass, based on the total solid content of the photosensitive colored resin composition. In the present invention, the solid content refers to everything other than the solvent described below, including monomers dissolved in the solvent.

[0058] [Alkali-soluble resin] The alkali-soluble resin used in the present invention has an acidic group, acts as a binder resin, and can be appropriately selected from those that are soluble in an alkaline developer used in forming a pattern. In the present invention, an alkali-soluble resin can be defined as one having an acid value of 40 mgKOH / g or more.

[0059] The acidic group of the alkali-soluble resin may be, for example, a carboxy group. The alkali-soluble resin having a carboxy group may be, for example, a carboxy group-containing copolymer having a carboxy group or an epoxy (meth)acrylate resin having a carboxy group. The carboxy group-containing copolymer may be, for example, a (meth)acrylic copolymer having a carboxy group or a (meth)acrylic copolymer such as a styrene-(meth)acrylic copolymer having a carboxy group. Furthermore, these (meth)acrylic copolymers, (meth)acrylic copolymers such as styrene-(meth)acrylic copolymers having a carboxy group, and epoxy (meth)acrylate resins may be used in combination of two or more kinds.

[0060] (Meth)acrylic copolymers such as a (meth)acrylic copolymer having a carboxy group and a styrene-(meth)acrylic copolymer having a carboxy group are (co)polymers obtained by (co)polymerizing, for example, a carboxy group-containing ethylenically unsaturated monomer and, if necessary, other copolymerizable monomers by a known method.

[0061] Examples of carboxyl group-containing ethylenically unsaturated monomers include (meth)acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, and (meth)acrylic acid dimer. In addition, addition reaction products of monomers having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate with cyclic anhydrides such as maleic anhydride, phthalic anhydride, and cyclohexanedicarboxylic anhydride, and ω-carboxy-polycaprolactone mono(meth)acrylate can also be used. In addition, anhydride-containing monomers such as maleic anhydride, itaconic anhydride, and citraconic anhydride can also be used as precursors of carboxyl groups. Among them, (meth)acrylic acid is particularly preferred in terms of copolymerizability, cost, solubility, glass transition temperature, and the like.

[0062] The alkali-soluble resin preferably further has a hydrocarbon ring in terms of excellent adhesion to the substrate. By having the hydrocarbon ring, which is a bulky group, in the alkali-soluble resin, shrinkage during curing is suppressed, peeling from the substrate is alleviated, and substrate adhesion is improved. In addition, by using an alkali-soluble resin having a hydrocarbon ring, which is a bulky group, the solvent resistance of the obtained colored layer is improved, and in particular, swelling of the colored layer is suppressed, which is also preferable. Examples of such a hydrocarbon ring include an aliphatic hydrocarbon ring which may have a substituent, an aromatic ring which may have a substituent, and a combination thereof, and the hydrocarbon ring may have a substituent such as a carbonyl group, a carboxyl group, an oxycarbonyl group, an amide group, etc.

[0063] Specific examples of hydrocarbon rings include aliphatic hydrocarbon rings such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, norbornane, tricyclo[5.2.1.0(2,6)]decane (dicyclopentane), and adamantane; aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, phenanthrene, and fluorene; chain polycyclic rings such as biphenyl, terphenyl, diphenylmethane, triphenylmethane, and stilbene; and cardo structures (9,9-diarylfluorene).

[0064] Among these, when the hydrocarbon ring contains an aliphatic hydrocarbon ring, the heat resistance and adhesion of the colored layer are improved, and the brightness of the obtained colored layer is also improved, which is preferable. Furthermore, when the colored layer contains a structure in which two benzene rings are bonded to a fluorene skeleton (a cardo structure), the curability of the colored layer is improved, the solvent resistance is improved, and swelling caused by NMP is particularly suppressed, which is particularly preferable. The hydrocarbon ring may be contained as a monovalent group, or may be contained as a divalent or higher valent group.

[0065] In the alkali-soluble resin used in the present invention, it is preferable to use a (meth)acrylic copolymer having a structural unit having a hydrocarbon ring in addition to a structural unit having a carboxy group, since this makes it easy to adjust the amount of each structural unit and to increase the amount of the structural unit having a hydrocarbon ring, thereby improving the function of the structural unit. The (meth)acrylic copolymer having a structural unit having a carboxy group and the above-mentioned hydrocarbon ring can be prepared by using an ethylenically unsaturated monomer having a hydrocarbon ring as the above-mentioned "other copolymerizable monomer".

[0066] Preferred examples of ethylenically unsaturated monomers having a hydrocarbon ring that can be used in the alkali-soluble resin having a hydrocarbon ring include cyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, adamantyl (meth)acrylate, isobornyl (meth)acrylate, phenoxyethyl (meth)acrylate, benzyl (meth)acrylate, styrene, and monomers having a cardo structure and an ethylenically unsaturated group. Among these, cyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, adamantyl (meth)acrylate, benzyl (meth)acrylate, styrene, and monomers having a cardo structure and an ethylenically unsaturated group are preferred because of their high effect of suppressing the precipitation of foreign matter derived from the colorant even after heat treatment.

[0067] The alkali-soluble resin used in the present invention preferably has an ethylenically unsaturated bond in the side chain. When the alkali-soluble resin has an ethylenically unsaturated bond, the alkali-soluble resin may form a cross-linking bond with itself or with a polyfunctional monomer or the like in the curing step of the resin composition during the production of the color filter. The film strength of the cured film is improved, the development resistance is improved, and the heat shrinkage of the cured film is suppressed, resulting in excellent adhesion to the substrate. The ethylenically unsaturated group means a group containing a radically polymerizable carbon-carbon double bond, and examples thereof include a (meth)acryloyl group, a vinyl group, and an allyl group. The method of introducing an ethylenically unsaturated bond into an alkali-soluble resin may be appropriately selected from conventionally known methods. For example, a method of adding a compound having both an epoxy group and an ethylenically unsaturated bond in the molecule, such as glycidyl (meth)acrylate, to a carboxyl group of an alkali-soluble resin, and introducing an ethylenically unsaturated bond into a side chain, or a method of introducing a structural unit having a hydroxyl group into a copolymer, and adding a compound having an isocyanate group and an ethylenically unsaturated bond in the molecule, and introducing an ethylenically unsaturated bond into a side chain, etc. may be mentioned.

[0068] The alkali-soluble resin used in the present invention may further contain other structural units such as structural units having an ester group, such as methyl (meth)acrylate, ethyl (meth)acrylate, etc. The structural unit having an ester group not only functions as a component that suppresses the alkali solubility of the photosensitive colored resin composition, but also functions as a component that improves the solubility in a solvent and further the resolubility in a solvent.

[0069] The alkali-soluble resin used in the present invention is preferably a (meth)acrylic resin such as a (meth)acrylic copolymer or a styrene-(meth)acrylic copolymer having a structural unit having a carboxyl group and a structural unit having a hydrocarbon ring, and more preferably a (meth)acrylic resin such as a (meth)acrylic copolymer or a styrene-(meth)acrylic copolymer having a structural unit having a carboxyl group, a structural unit having a hydrocarbon ring, and a structural unit having an ethylenically unsaturated bond.

[0070] The alkali-soluble resin used in the present invention can be made to have the desired performance by appropriately adjusting the charged amounts of the monomers which derive the respective structural units.

[0071] The copolymerization ratio of the carboxyl group-containing ethylenically unsaturated monomer in the carboxyl group-containing copolymer is usually 5% by mass to 50% by mass, preferably 10% by mass to 40% by mass. In this case, when the copolymerization ratio of the carboxyl group-containing ethylenically unsaturated monomer is 5% by mass or more, the decrease in solubility of the resulting coating film in an alkaline developer can be suppressed, and pattern formation becomes easy. When the copolymerization ratio is 50% by mass or less, chipping of the pattern during development with an alkaline developer and film roughness of the pattern surface are unlikely to occur. The copolymerization ratio is a value calculated from the amount of each monomer charged.

[0072] In addition, in (meth)acrylic resins such as (meth)acrylic copolymers and styrene-(meth)acrylic copolymers having a structural unit having an ethylenically unsaturated bond, which are more preferably used as alkali-soluble resins, the amount of monomer having both an epoxy group and an ethylenically unsaturated bond is preferably 10% by mass to 95% by mass, and more preferably 15% by mass to 90% by mass, relative to 100% by mass of the amount of carboxyl group-containing ethylenically unsaturated monomer.

[0073] The weight average molecular weight (Mw) of the carboxyl group-containing copolymer is preferably in the range of 1,000 to 50,000, and more preferably 3,000 to 20,000. When the weight average molecular weight of the carboxyl group-containing copolymer is 1,000 or more, the coating film has sufficient curability, and when it is 50,000 or less, pattern formation is facilitated during development with an alkaline developer. In the present invention, the weight average molecular weight (Mw) is determined by gel permeation chromatography (GPC) in terms of standard polystyrene.

[0074] Specific examples of the (meth)acrylic copolymer having a carboxy group include those described in JP-A-2013-029832.

[0075] The epoxy (meth)acrylate resin having a carboxyl group is not particularly limited, and for example, an epoxy (meth)acrylate compound obtained by reacting a reaction product of an epoxy compound and an unsaturated group-containing monocarboxylic acid with an acid anhydride is suitable. The epoxy compound, the unsaturated group-containing monocarboxylic acid, and the acid anhydride can be appropriately selected from known ones and used. Among the epoxy (meth)acrylate resins having a carboxy group, those containing the cardo structure in the molecule are preferred, since they have an improved effect of suppressing display defects, improve the curing properties of the colored layer, and increase the remaining film rate of the colored layer.

[0076] The alkali-soluble resin preferably has an acid value of 40 mgKOH / g or more in terms of developability (solubility) in an aqueous alkali solution used in the developer. The carboxyl group-containing copolymer preferably has an acid value of 50 mgKOH / g or more and 300 mgKOH / g or less, more preferably 60 mgKOH / g or more and 280 mgKOH / g or less, and even more preferably 70 mgKOH / g or more and 250 mgKOH / g or less, in terms of developability (solubility) in an aqueous alkali solution used in the developer and adhesion to a substrate. In the present invention, the acid value can be measured in accordance with JIS K 0070.

[0077] When the alkali-soluble resin has an ethylenically unsaturated group in its side chain, the ethylenically unsaturated bond equivalent is preferably in the range of 100 to 2000, particularly 140 to 1500, from the viewpoint of improving the film strength of the cured film and further suppressing the precipitation of the coloring material. If the ethylenically unsaturated bond equivalent is 2000 or less, the development resistance and adhesion are excellent. If the ethylenically unsaturated bond equivalent is 100 or more, the ratio of other structural units such as the structural unit having a carboxyl group and the structural unit having a hydrocarbon ring can be relatively increased, so that the developability and heat resistance are excellent. Here, the ethylenically unsaturated bond equivalent refers to the weight average molecular weight per mole of the ethylenically unsaturated bond in the alkali-soluble resin, and is represented by the following mathematical formula (1).

[0078] Equation (1) Ethylenically 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).)

[0079] The ethylenically unsaturated bond equivalent may be calculated, for example, by measuring the number of ethylenically unsaturated bonds contained in 1 g of the alkali-soluble resin in accordance with the iodine value test method described in JIS K 0070:1992.

[0080] The alkali-soluble resin used in the photosensitive colored resin composition may be used alone or in combination of two or more. The content of the alkali-soluble resin is not particularly limited, but is preferably within the range of, for example, 5% by mass to 60% by mass, more preferably 10% by mass to 40% by mass, based on the total solid content of the photosensitive colored resin composition. When the content of the alkali-soluble resin is equal to or more than the lower limit, sufficient alkali developability is obtained, and when the content of the alkali-soluble resin is equal to or less than the upper limit, film roughness and pattern chipping during development can be suppressed.

[0081] [Photopolymerizable compound] The photopolymerizable compound used in the photosensitive colored resin composition of the present invention refers to a compound having a photopolymerizable group in the molecule. The photopolymerizable group may be any group that can be polymerized by a photoinitiator, and is not particularly limited, but includes an ethylenically unsaturated bond, such as a vinyl group, an allyl group, an acryloyl group, or a methacryloyl group. As the photopolymerizable group, an acryloyl group or a methacryloyl group is preferably used from the viewpoint of ultraviolet curing. From the viewpoint of curability, the photopolymerizable compound preferably contains a compound having two or more photopolymerizable groups in one molecule, and more preferably contains a compound having three or more photopolymerizable groups in one molecule.

[0082] The photopolymerizable compound is not particularly limited as long as it can be polymerized by the photoinitiator described later. Usually, a compound having two or more ethylenically unsaturated bonds is used, and in particular, a polyfunctional (meth)acrylate having two or more acryloyl groups or methacryloyl groups is preferable. Such a polyfunctional (meth)acrylate may be appropriately selected from conventionally known ones, and specific examples thereof include those described in JP-A-2013-029832.

[0083] These photopolymerizable compounds may be used alone or in combination of two or more. In addition, when the photosensitive colored resin composition of the present invention is required to have excellent photocurability (high sensitivity), the photopolymerizable compound is preferably one having three (trifunctional) or more polymerizable ethylenically unsaturated bonds, and poly(meth)acrylates of polyhydric alcohols having a valence of three or more and dicarboxylic acid modified products thereof are preferable, and 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 preferable.

[0084] The content of the photopolymerizable compound used in the photosensitive colored resin composition is not particularly limited, but is preferably 5% by mass to 60% by mass, more preferably 10% by mass to 40% by mass, based on the total solid content of the photosensitive colored resin composition. When the content of the photopolymerizable compound is equal to or more than the lower limit, photocuring proceeds sufficiently, and the exposed part can be suppressed from dissolving during development, and when the content of the photopolymerizable compound is equal to or less than the upper limit, alkaline developability is sufficient.

[0085] [Photoinitiator] Examples of the photoinitiator include aromatic ketones, benzoin ethers, halomethyloxadiazole compounds, α-aminoketones, biimidazoles, N,N-dimethylaminobenzophenone, halomethyl-S-triazine compounds, and thioxanthone.Specific examples of the photoinitiator include aromatic ketones such as benzophenone, 4,4'-bisdiethylaminobenzophenone, and 4-methoxy-4'-dimethylaminobenzophenone, benzoin ethers such as benzoin methyl ether, benzoin such as ethylbenzoin, biimidazoles such as 2-(o-chlorophenyl)-4,5-phenylimidazole dimer, halomethyloxadiazole compounds such as 2-trichloromethyl-5-(p-methoxystyryl)-1,3,4-oxadiazole, and 2-(4-butoxynaphthalene)-2-methylphenyl ether. Halomethyl-S-triazine compounds such as 4,6-bis-trichloromethyl-S-triazine, 2,2-dimethoxy-1,2-diphenylethan-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropanone, 1,2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 1-hydroxy-cyclohexyl-phenyl ketone, benzyl, benzoylbenzoic acid, methyl benzoylbenzoate, 4-benzoyl-4'-methyldiphenyl sulfide, benzyl methyl ketal, dimethylaminobenzoate, p-dimethylaminobenzoic acid isoamyl, 2-n-butoxyethyl-4-dimethylaminobenzoate, 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 4-benzoyl-methyldiphenyl sulfide, 1-hydroxy-cyclohexyl-phenyl ketone, 2-benzyl-2-(dimethylamino)-1-[4-(4-morpholinyl)phenyl]-1-butoxyethyl butanone, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, α-dimethoxy-α-phenylacetophenone, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, 2-methyl-1-[4-(methylthio)phenyl]-2-(4-morpholinyl)-1-propanone, 1-(9,9-dibutyl-9H-fluoren-2-yl)-2-methyl-2-(4-morpholinyl)-1-propanone, and the like. Among them, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-(dimethylamino)-1-(4-morpholinophenyl)-1-butanone, 4,4'-bis(diethylamino)benzophenone, and diethylthioxanthone are preferably used.Furthermore, it is preferable to combine an α-aminoacetophenone initiator such as 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one with a thioxanthone initiator such as diethylthioxanthone, in terms of adjusting sensitivity, suppressing water stains, and improving development resistance. When an α-aminoacetophenone initiator and a thioxanthone initiator are used, the total content of these is, for example, preferably 5% by mass to 15% by mass based on the total solid content of the photosensitive color resin composition. If it is less than the upper limit, it is preferable because the amount of sublimate during the manufacturing process is reduced. If it is more than the lower limit, water stains are suppressed and development resistance is improved.

[0086] In the present invention, the photoinitiator preferably contains an oxime ester photoinitiator, because it can improve the sensitivity. In addition, by using an oxime ester photoinitiator, the variation in the line width in the plane is easily suppressed when forming a fine line pattern. Furthermore, by using an oxime ester photoinitiator, the residual film rate is improved, and the effect of suppressing the occurrence of water stains tends to be enhanced. As the oxime ester photoinitiator, from the viewpoint of reducing contamination of the photosensitive color resin composition and contamination of the device due to decomposition products, it is preferable that the oxime ester photoinitiator has an aromatic ring, more preferably has a condensed ring containing an aromatic ring, and further preferably has a condensed ring containing a benzene ring and a heterocycle. The oxime ester photoinitiator can be appropriately selected from 1,2-octadione-1-[4-(phenylthio)-, 2-(o-benzoyloxime)], ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(o-acetyloxime), and the oxime ester photoinitiators described in JP-A Nos. 2000-80068, 2001-233842, JP-T Nos. 2010-527339, 2010-527338, and 2013-041153. Commercially available products include Irgacure OXE-01, Adeka Arcles NCI-930, and TR-PBG-3057 having a diphenyl sulfide skeleton, Irgacure OXE-02, Adeka Arcles NCI-831, TR-PBG-304, and TR-PBG-345 having a carbazole skeleton, and TR-PBG-365 having a fluorene skeleton (the Irgacure series is manufactured by BASF, the Adeka Arcles series is manufactured by ADEKA, and the TR series is manufactured by Changzhou Strong Electronic New Materials Co., Ltd.). In particular, it is preferable to use an oxime ester photoinitiator having a diphenyl sulfide skeleton or a fluorene skeleton from the viewpoint of brightness. In addition, it is preferable to use an oxime ester photoinitiator having a carbazole skeleton from the viewpoint of high sensitivity. It is preferable to use a combination of an oxime ester photoinitiator having a diphenyl sulfide skeleton and an oxime ester photoinitiator having a fluorene skeleton from the viewpoint of sensitivity and brightness. In addition, it is preferable to use a combination of an oxime ester photoinitiator having a diphenyl sulfide skeleton and an oxime ester photoinitiator having a carbazole skeleton from the viewpoints of sensitivity and brightness.

[0087] In addition, in order to suppress water stains and improve sensitivity, a photoinitiator having a tertiary amine structure may be used in combination with an oxime ester photoinitiator. The photoinitiator having a tertiary amine structure has a tertiary amine structure that is an oxygen quencher in the molecule, so that the radicals generated from the initiator are less likely to be deactivated by oxygen, and the sensitivity can be improved. Examples of commercially available photoinitiators having the above tertiary amine structure include 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (e.g., Irgacure 907, manufactured by BASF), 2-benzyl-2-(dimethylamino)-1-(4-morpholinophenyl)-1-butanone (e.g., Irgacure 369, manufactured by BASF), and 4,4'-bis(diethylamino)benzophenone (e.g., Hi-Cure ABP, manufactured by Kawaguchi Yakuhin). Furthermore, from the viewpoints of adjusting sensitivity, suppressing water stains, and improving development resistance, an oxime ester photoinitiator may be combined with a thioxanthone initiator. From the viewpoints of improving brightness and film remaining rate, facilitating sensitivity adjustment, having a high effect of suppressing the occurrence of water stains, and improving development resistance, two or more types of oxime ester photoinitiators may be combined with a thioxanthone initiator.

[0088] The content of the photoinitiator in the photosensitive colored resin composition is, for example, preferably 0.1% by mass to 15% by mass, more preferably 1% by mass to 10% by mass, based on the total solid content of the photosensitive colored resin composition. When the content of the photoinitiator is equal to or more than the lower limit, curing proceeds sufficiently, and when the content of the initiator is equal to or less than the upper limit, side reactions can be suppressed and stability over time can be maintained.

[0089] [solvent] The solvent used in the present invention is not particularly limited as long as it is an organic solvent that does not react with each component in the photosensitive color resin composition and can dissolve or disperse them. The solvent can be used alone or in combination of two or more kinds. Specific examples of the solvent include 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, and isobutyl acetate. ester solvents such as butyl 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; and methoxyethoxyethyl acetate. 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 aromatic 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 the solubility of other components.Among these, 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, diethylene glycol methyl ethyl ether, butyl carbitol acetate (BCA), 3-methoxy-3-methyl-1-butyl acetate, ethyl ethoxypropionate, ethyl lactate, and 3-methoxybutyl acetate in terms of the solubility of other components and the suitability for application. In addition, in the solvent used in the present invention, from the viewpoint of colorant dispersibility, solubility of other components, and coating suitability, the content of propylene glycol monomethyl ether acetate may be 50 mass% or more, 70 mass% or more, 80 mass% or more, or 100 mass% based on the total amount of the solvent in the photosensitive color resin composition. The solvent used in the present invention is one or more selected from the group consisting of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, diethylene glycol methyl ethyl ether, butyl carbitol acetate (BCA), 3-methoxy-3-methyl-1-butyl acetate, ethyl ethoxypropionate, ethyl lactate, and 3-methoxybutyl acetate, and the content of propylene glycol monomethyl ether acetate may be 50 mass% or more, or 70 mass% or more, based on the total amount of the solvent.

[0090] In the photosensitive colored resin composition according to the present invention, the content of the solvent may be appropriately set within a range that allows the colored layer to be formed with good accuracy. The content of the solvent is usually preferably within a range of 55% by mass to 95% by mass, more preferably 65% ​​by mass to 88% by mass, based on the total amount of the photosensitive colored resin composition containing the solvent. By having the content of the solvent within the above range, it is possible to obtain excellent coating properties.

[0091] In addition, in the photosensitive color resin composition according to the present invention, the content of water may be 2.0% by mass or less, 1.5% by mass or less, 1.0% by mass or less, or 0.5% by mass or less. If the content of water is within the above range, the aggregation of color material caused by the presence of water can be sufficiently suppressed, and the thickening and contrast reduction of the photosensitive color resin composition can be suppressed. The water content in the photosensitive color resin composition is measured at 25° C. using a Karl Fischer titrator (volumetric titration method) in accordance with JIS K0113:2005.

[0092] [Optional addition ingredients] The photosensitive colored resin composition according to the present invention may contain various additives as necessary. Examples of the additives include dispersants, sensitizers, antioxidants, polymerization terminators, chain transfer agents, leveling agents, plasticizers, surfactants, defoamers, silane coupling agents, ultraviolet absorbers, and adhesion promoters. Specific examples of the surfactant and plasticizer include those described in JP2013-029832A. The photosensitive color resin composition according to the present invention may not contain a dye derivative such as a sulfonic acid group-containing dye derivative.

[0093] <Dispersant> In the photosensitive color 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. It is preferable to use a dispersant to disperse the zinc phthalocyanine pigment (P1). In the present invention, the dispersant can be appropriately selected from conventionally known dispersants. For example, cationic, anionic, nonionic, amphoteric, silicone, fluorine-based surfactants can be used as the dispersant. Among the surfactants, polymer dispersants are preferred because they can be uniformly and finely dispersed.

[0094] Examples of polymer dispersants include (co)polymers of unsaturated carboxylic acid esters such as polyacrylic acid esters; (partial) amine salts, (partial) ammonium salts, and (partial) alkylamine salts of (co)polymers of unsaturated carboxylic acids such as polyacrylic acid; (co)polymers of hydroxyl group-containing unsaturated carboxylic acid esters such as hydroxyl group-containing polyacrylic acid esters and modified products thereof; polyurethanes; unsaturated polyamides; polysiloxanes; long-chain polyaminoamide phosphates; polyethyleneimine derivatives (amides obtained by reacting poly(lower alkyleneimine) with polyesters containing free carboxyl groups, or bases thereof); polyallylamine derivatives (reaction products obtained by reacting polyallylamine with one or more compounds selected from the three compounds of polyesters having free carboxyl groups, polyamides, or co-condensates of esters and amides (polyesteramides)).

[0095] The polymer dispersant used in the photosensitive colored resin composition of the present invention may be, for example, a polymer dispersant containing a nitrogen atom in the main chain or side chain and having an amine value, and among them, a polymer dispersant consisting of a polymer containing a repeating unit having a tertiary amine may be used. As the polymer dispersant containing a nitrogen atom in the main chain or side chain and having an amine value, in particular, a polymer having a structural unit represented by the following general formula (I) as described in JP 2016-224447 A, or a dispersant that is at least one of a block copolymer and a salt-type block copolymer having a structural unit represented by the following general formula (I) as described in WO 2016 / 104493 A, may be used because the main chain skeleton is resistant to thermal decomposition and has high heat resistance.

[0096] [ka] (In general formula (I), R 1 is a hydrogen atom or a methyl group, A is a divalent linking group, R 2 and R 3 each independently represents a hydrogen atom or a hydrocarbon group which may contain a heteroatom; R 2 and R3 may be bonded to each other to form a ring structure.

[0097] In general formula (I), A is a divalent linking group. Examples of the divalent linking group 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 the present invention, the direction of the bond of the divalent linking group is arbitrary. That is, when the divalent linking group contains -CONH-, -CO may be on the carbon atom side of the main chain and -NH may be 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 may be on the nitrogen atom side of the side chain. Among these, from the viewpoint of dispersibility, A in general formula (I) 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.

[0098] R 2 and R 3 Examples of the hydrocarbon group in the hydrocarbon group which may contain a heteroatom include an alkyl group, an aralkyl group, and an aryl group. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, a tert-butyl group, a 2-ethylhexyl group, a cyclopentyl group, and a cyclohexyl group. The number of carbon atoms in the alkyl group is preferably 1 to 18, and among these, a methyl group or an ethyl group is more preferable. Examples of the aralkyl group include a benzyl group, a phenethyl group, a naphthylmethyl group, a biphenylmethyl group, etc. The aralkyl group preferably has 7 to 20 carbon atoms, and more preferably has 7 to 14 carbon atoms. Examples of the aryl group include a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, and a xylyl group. The number of carbon atoms in the aryl group is preferably 6 to 24, and more preferably 6 to 12. The above preferred number of carbon atoms does not include the number of carbon atoms of the substituent. The hydrocarbon group containing a heteroatom has a structure in which a carbon atom in the above-mentioned hydrocarbon group is replaced with a heteroatom, or a hydrogen atom in the above-mentioned hydrocarbon group is replaced with a substituent containing a heteroatom. Examples of the heteroatom that may be contained in the hydrocarbon group include an oxygen atom, a nitrogen atom, a sulfur atom, and a silicon atom. Furthermore, a hydrogen atom in the hydrocarbon group may be substituted with a halogen atom such as a fluorine atom, a chlorine atom or a bromine atom.

[0099] R 2 and R 3 are bonded to each other to form a ring structure, R 2 and R 3 forms a ring structure via a nitrogen atom. 2 and R 3 The ring structure formed by may contain a heteroatom. The ring structure is not particularly limited, but examples thereof include a pyrrolidine ring, a piperidine ring, and a morpholine ring.

[0100] In the present invention, among others, R 2 and R 3 are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group, or R 2 and R 3 are preferably bonded to form a pyrrolidine ring, a piperidine ring, or a morpholine ring.

[0101] Examples of monomers that derive the structural unit represented by the general formula (I) include alkyl group-substituted amino group-containing (meth)acrylates such as dimethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, diethylaminoethyl (meth)acrylate, and diethylaminopropyl (meth)acrylate, and alkyl group-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 in terms of improving dispersibility and dispersion stability. In the polymer, the constitutional unit represented by general formula (I) may be composed of one type, or may contain two or more types of constitutional units.

[0102] In addition, as for the structural unit that functions as a colorant adsorption site, at least a portion of the nitrogen site of the structural 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 (such a copolymer may be referred to as a salt-type copolymer). As the organic acid compound, a compound represented by the following general formula (A) and a compound represented by the following general formula (C) are preferable, and as the halogenated hydrocarbon, a compound represented by the following general formula (B) is preferable. That is, as the at least one selected from the group consisting of the organic acid compound and the halogenated hydrocarbon, one or more compounds selected from the group consisting of the following general formulas (A), (B) and (C) can be preferably used.

[0103] [ka] (In the general formula (A), R a represents a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, a phenyl group or a benzyl group which may have a substituent, or -OR e R erepresents a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, a phenyl group or a benzyl group which may have a substituent, or a (meth)acryloyl group connected via an alkylene group having 1 to 4 carbon atoms. b , R b’ , and R b” each independently represents a hydrogen atom, an acidic group or an ester group thereof, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may have a substituent, a vinyl group which may have a substituent, a phenyl group or a benzyl group which may have a substituent, or -OR f R f represents a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may have a substituent, a vinyl group which may have a substituent, a phenyl group or a benzyl group which may have a substituent, or a (meth)acryloyl group connected via an alkylene group having 1 to 4 carbon atoms, and X represents a chlorine atom, a bromine atom or an iodine atom. c and R d each independently represents a hydrogen atom, a hydroxyl group, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, a phenyl group or a benzyl group which may have a substituent, or -OR e R e represents a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, a phenyl group or a benzyl group which may have a substituent, or a (meth)acryloyl group via an alkylene group having 1 to 4 carbon atoms. c and R d At least one of the groups contains a carbon atom.

[0104] The symbols in the general formulae (A), (B), and (C) may be the same as the symbols in the general formulae (1), (2), and (3) in WO 2016 / 104493. The organic acid compound is preferably an acidic organic phosphorus compound such as phenylphosphonic acid or phenylphosphinic acid, because it has excellent dispersibility and dispersion stability of the colorant. Specific examples of the organic acid compound used in such a dispersant include the organic acid compounds described in JP-A-2012-236882 and the like. The halogenated hydrocarbon is preferably at least one of allyl halides, such as allyl bromide and benzyl chloride, and aralkyl halides, from the viewpoint of excellent dispersibility and dispersion stability of the coloring material.

[0105] In the salt type copolymer, the content of at least one selected from the group consisting of organic acid compounds and halogenated hydrocarbons is a salt formed with the terminal nitrogen moiety of the structural unit represented by general formula (I), so the total of at least one selected from the group consisting of organic acid compounds and halogenated hydrocarbons is preferably 0.01 mol or more, more preferably 0.05 mol or more, even more preferably 0.1 mol or more, and particularly preferably 0.2 mol or more, relative to the terminal nitrogen moiety of the structural unit represented by general formula (I). If it is more than the above lower limit, the effect of improving the colorant dispersibility due to salt formation is easily obtained. Similarly, it is preferably 1 mol or less, more preferably 0.8 mol or less, even more preferably 0.7 mol or less, and particularly preferably 0.6 mol or less. If it is less than the above upper limit, it can be excellent in development adhesion and solvent resolubility. The at least one selected from the group consisting of organic acid compounds and halogenated hydrocarbons may be used alone or in combination of two or more. When two or more types are combined, the total content is preferably within the above range.

[0106] Examples of a method for preparing the salt-type copolymer include a method in which at least one selected from the group consisting of the organic acid compounds and halogenated hydrocarbons described above is added to a solvent in which the copolymer before salt formation is dissolved or dispersed, and the mixture is stirred and, if necessary, heated. The fact that the terminal nitrogen moiety of the structural unit represented by the general formula (I) of the copolymer forms a salt with at least one selected from the group consisting of the organic acid compound and the halogenated hydrocarbon, and the ratio thereof can be confirmed by a known method such as NMR.

[0107] From the viewpoints of dispersibility and dispersion stability, the copolymer having a structural unit represented by the general formula (I) is more preferably at least one of a graft copolymer having a structural unit represented by the general formula (I) and having a structural unit derived from a (meth)acrylate in the graft polymer chain, and a block copolymer having an A block containing a structural unit represented by the general formula (I) and a B block containing a structural unit derived from a (meth)acrylate. In the graft copolymer, the graft polymer chain having a (meth)acrylate-derived structural unit can be appropriately selected and used from conventionally known structures. For example, at least one of the graft copolymers and salt-type graft copolymers described in International Publication No. 2021 / 006077 may be used. In the block copolymer, the B block containing a structural unit derived from (meth)acrylate may be appropriately selected from conventionally known structures. For example, at least one of the block copolymers and salt-type block copolymers described in WO 2016 / 104493 may be used.

[0108] Among the block copolymers used as dispersants, preferred are block copolymers containing an A block including a constituent unit represented by the general formula (I) and a B block including a constituent unit derived from a carboxy group-containing monomer and a constituent unit derived from a (meth)acrylate, and at least one salt-type block copolymer in which at least a portion of the nitrogen moieties 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 an organic acid compound and a halogenated hydrocarbon, and the block copolymer and at least one of the salt-type block copolymers have an acid value of 1 mgKOH / g to 18 mgKOH / g and a glass transition temperature of 30°C or higher, from the viewpoints of improving the substrate adhesion and solvent resistance of the cured film even in a low-temperature heat treatment and suppressing the generation of development residues. In this case, the B block contains a structural unit derived from a (meth)acrylate as an essential component, and may be similar to the B block in WO 2016 / 104493.

[0109] As the copolymer having a constitutional unit represented by the general formula (I), a copolymer having an amine value of 40 mgKOH / g to 120 mgKOH / g is preferred, since it has good dispersibility, does not precipitate foreign matter during coating film formation, and improves brightness and contrast. By the amine value being within the above range, the copolymer has excellent stability over time of viscosity and heat resistance, and is also excellent in alkali developability and solvent resolubility. In the present invention, the amine value of the copolymer having the constitutional unit represented by the general formula (I) may be 50 mgKOH / g or more, preferably 80 mgKOH / g or more, and more preferably 90 mgKOH / g or more. On the other hand, from the viewpoint of solvent resolubility, the amine value of the copolymer having the constitutional unit represented by the general formula (I) is preferably 110 mgKOH / g or less, and more preferably 105 mgKOH / g or less. The amine value refers to the amount of potassium hydroxide (mg) equivalent to the amount of perchloric acid required to neutralize the amine components contained in 1 g of sample, and can be measured by the method defined in JIS-K 7237. 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 that the amine value of the block copolymer itself (before salt formation) used as a dispersant can be measured.

[0110] The content (mol%) of each structural unit in the copolymer of the dispersant can be determined from the amount of raw materials charged during production, and can be measured using an analytical device such as NMR. The structure of the dispersant can be measured using NMR, various mass analyses, etc. The dispersant can be decomposed by pyrolysis or the like as necessary, and the obtained decomposition product can be determined using high performance liquid chromatography, gas chromatograph mass spectrometer, NMR, elemental analysis, XPS / ESCA, TOF-SIMS, etc.

[0111] In the photosensitive colored resin composition according to the present invention, the content of the dispersant when used may be selected so as to provide excellent dispersibility and dispersion stability of the colorant, and is not particularly limited, but may be, for example, 2% by mass to 30% by mass, and may be within the range of 3% by mass to 25% by mass, based on the total amount of solids in the photosensitive colored resin composition. If it is equal to or more than the above lower limit, the dispersibility and dispersion stability of the colorant are excellent, and the storage stability of the photosensitive colored resin composition is more excellent. Also, if it is equal to or less than the above upper limit, the developability is good. In the photosensitive colored resin composition according to the present invention, it is preferable to use a copolymer having a constitutional unit represented by the general formula (I) having an amine value of 50 mgKOH / g or more in order to disperse the zinc phthalocyanine pigment (P1). When using a copolymer having a constitutional unit represented by the general formula (I) having an amine value of 50 mgKOH / g or more for dispersing the zinc phthalocyanine pigment (P1), the copolymer having a constitutional unit represented by the general formula (I) having an amine value of 50 mgKOH / g or more is preferably 20 parts by mass or more and less than 50 parts by mass, since dispersibility and stability over time are good, and the developability is not deteriorated and residue is not easily generated. The copolymer having a constitutional unit represented by the general formula (I) having an amine value of 50 mgKOH / g or more is preferably 25 parts by mass or more and less than 50 parts by mass, since viscosity is low, and 30 parts by mass or more and less than 50 parts by mass is more preferable, since viscosity is low, stability over time is good, and contrast is high.

[0112] <Sensitizer> In the present invention, since the specific zinc phthalocyanine pigment dispersed in the system absorbs exposure light and is prone to lose radical generation from the photoinitiator, it is preferable to include a sensitizer in combination with the photoinitiator in order to compensate for this. Among them, it is preferable to include a thiol-based sensitizer in order to improve the reactivity of the (meth)acrylic polymerization system, and it is more preferable to include a thiol-based sensitizer in combination with the oxime ester-based initiator.

[0113] Examples of the thiol-based sensitizer include monofunctional thiol compounds having one thiol group and polyfunctional thiol compounds having two or more thiol groups. Examples of monofunctional thiol compounds include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-5-methoxybenzothiazole, 2-mercapto-5-methoxybenzimidazole, 3-mercaptopropionic acid, methyl 3-mercaptopropionate, ethyl 3-mercaptopropionate, and octyl 3-mercaptopropionate. Examples of polyfunctional thiol compounds include 1,4-bis(3-mercaptobutyryloxy)butane, 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutyrate), pentaerythritol tetrakis(3-mercaptopropionate), dipentaerythritol hexakis(3-mercaptopropionate), and tetraethylene glycol bis(3-mercaptopropionate).

[0114] In the photosensitive colored resin composition of the present invention, the content of the sensitizer when it is included can be, for example, 0.5% by mass to 10% by mass based on the total solid content of the photosensitive colored resin composition from the viewpoint of curability improvement effect. The content of the sensitizer when it is included is more preferably 1% by mass to 6% by mass, and even more preferably 2% by mass to 5% by mass based on the total solid content of the photosensitive colored resin composition.

[0115] <Antioxidants> The photosensitive colored resin composition of the present invention preferably further contains an antioxidant in terms of suppressing the amount of line width shift. The photosensitive colored resin composition of the present invention contains an antioxidant in combination with the specific photoinitiator, so that excessive radical chain reaction can be controlled without impairing the curability when forming a cured film, and therefore, when forming a fine line pattern, linearity is improved and the ability to form a fine line pattern according to the design of the mask line width is improved. In addition, heat resistance can be improved, and brightness reduction after exposure and post-baking can be suppressed, so brightness can be improved. The antioxidant used in the present invention is not particularly limited, and may be appropriately selected from conventionally known ones.Specific examples of the antioxidant include hindered phenol-based antioxidants, amine-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, and hydrazine-based antioxidants.It is preferable to use a hindered phenol-based antioxidant in terms of improving the ability to form a fine line pattern according to the design of the mask line width and heat resistance.It may also be a latent antioxidant as described in International Publication No. 2014 / 021023.

[0116] Examples of the hindered phenol-based antioxidant include pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (trade name: IRGANOX 1010, manufactured by BASF), 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate (trade name: IRGANOX 3114, manufactured by BASF), 2,4,6-tris(4-hydroxy-3,5-di-tert-butylbenzene Examples of the tert-butyl-4-hydroxyphenyl ester include pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (trade name: IRGANOX 1010, manufactured by BASF), 2,2'-methylenebis(6-tert-butyl-4-methylphenol) (trade name: Sumilizer MDP-S, manufactured by Sumitomo Chemical), 6,6'-thiobis(2-tert-butyl-4-methylphenol) (trade name: IRGANOX 1081, manufactured by BASF), and 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid diethyl (trade name: Irgamod 195, manufactured by BASF). Among these, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (trade name: IRGANOX 1010, manufactured by BASF) is preferred from the viewpoint of heat resistance and light resistance.

[0117] The content of the antioxidant is preferably 0.1% by mass to 10.0% by mass, more preferably 0.5% by mass to 5.0% by mass, based on the total solid content of the photosensitive colored resin composition. If it is equal to or more than the lower limit, the ability to form a fine line pattern according to the design of the mask line width is improved, and heat resistance is excellent. On the other hand, if it is equal to or less than the upper limit, the photosensitive colored resin composition of the present invention can be a highly sensitive photosensitive colored resin composition.

[0118] <Method for producing 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 additive components that are used as desired using a known mixing means. Examples of methods for preparing the resin composition include: (1) a method of first preparing a colorant dispersion by adding a colorant and, if necessary, a dispersant to a solvent, and then mixing an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and various additive components used as desired into the colorant dispersion; (2) a method of simultaneously adding a colorant, if necessary, a dispersant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and various additive components used as desired into a solvent and mixing them; (3) a method of adding an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and various additive components used as desired into a solvent, mixing them, and then adding a colorant and mixing them; (4) a method of adding a colorant, if necessary, a dispersant, and an alkali-soluble resin to a solvent to prepare a colorant dispersion, and then adding an alkali-soluble resin, a solvent, a photopolymerizable compound, a photoinitiator, and various additive components used as desired into the colorant dispersion, and mixing them; and the like.

[0119] II. Color filters The color filter according to the present invention is a color filter comprising at least a substrate and a colored layer provided on the substrate, and at least one of the colored layers is a cured product of the photosensitive colored resin composition according to the present invention.

[0120] The color filter according to the present invention will be described with reference to the drawings. Fig. 1 is a schematic cross-sectional view showing an example of the color filter according to the present invention. According to Fig. 1, the color filter 10 according to the present invention has a substrate 1, a light-shielding portion 2, and a colored layer 3. As shown in Fig. 1, the colored layer 3 may include a red colored layer 3R, a green colored layer 3G, and a blue colored layer 3B formed between the light-shielding portions 2.

[0121] (substrate) The substrate may be a transparent substrate, a silicon substrate, or a transparent or silicon substrate on which an aluminum, silver, or silver / copper / palladium alloy thin film is formed, as described below. On these substrates, other color filter layers, resin layers, transistors such as TFTs, circuits, etc. may be formed.

[0122] The transparent substrate in the color filter of the present invention is not particularly limited as long as it is a base material transparent to visible light, and a transparent substrate used in general color filters can be used. Specifically, examples of the transparent substrate include transparent rigid materials with no flexibility, such as quartz glass, non-alkali glass, and synthetic quartz plate, and transparent flexible materials with flexibility, such as transparent resin films, optical resin plates, and flexible glass. The thickness of the transparent substrate is not particularly limited, but may be, for example, about 100 μm to 1 mm depending on the application of the color filter of the present invention.

[0123] (Light shielding part) The light-shielding portion in the color filter of the present invention is formed in a pattern on a substrate 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 part is not particularly limited, and examples thereof include stripe-like and matrix-like shapes. The light-shielding part may be a thin metal film such as chromium formed by a sputtering method, a vacuum deposition method, or the like. Alternatively, the light-shielding part may be a resin layer containing light-shielding particles such as carbon fine particles, metal oxides, inorganic pigments, and organic pigments in a resin binder. In the case of a resin layer containing light-shielding particles, there are a method of patterning by development using a photosensitive resist, a method of patterning using an inkjet ink containing light-shielding particles, a method of thermally transferring a photosensitive resist, and the like.

[0124] The film thickness of the light-shielding portion is set to about 0.2 μm to 0.4 μm in the case of a metal thin film, and is set to about 0.5 μm to 2 μm in the case of a black pigment dispersed or dissolved in a binder resin.

[0125] (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 of the present invention. The colored layer is usually formed in the opening of the light-shielding part on the substrate described later, and usually consists of a colored pattern of three or more colors. The colored layer which is the cured product of the photosensitive colored resin composition according to the present invention may be a green colored layer. The arrangement of the colored layers is not particularly limited, and may be, for example, a common arrangement such as a stripe type, a mosaic type, a triangle type, a four-pixel arrangement type, etc. The width, area, etc. of the colored layers may be set arbitrarily. The thickness of the colored layer is appropriately controlled by adjusting the coating method, the solid content concentration and the viscosity of the photosensitive colored resin composition, etc., but it is usually preferably in the range of 1 μm to 5 μm.

[0126] The manufacturing method of the colored layer is not particularly limited, and a manufacturing method of the colored layer in a conventionally known manufacturing method of a color filter can be appropriately selected and used. In addition, the photosensitive colored resin composition for other colored layers, such as a red photosensitive resin composition and a blue photosensitive resin composition, can be appropriately selected and used from conventionally known photosensitive colored resin compositions. The colored layer can be formed, for example, by the following method. First, a photosensitive colored resin composition of any one color (for example, red) is applied onto the substrate using a coating method such as spray coating, dip coating, bar coating, roll coating, or spin coating to form a wet coating film. Next, the wet coating film is dried using a hot plate or oven, and then exposed to light through a mask having a predetermined pattern to photopolymerize the alkali-soluble resin and the polyfunctional monomer, etc., to form a photosensitive coating film. Examples of light sources used for exposure include ultraviolet light from a low-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, etc., and electron beams. The amount of exposure is appropriately adjusted depending on the light source used and the thickness of the coating film. In order to promote the polymerization reaction after the exposure, a heat treatment may be carried out. The heating conditions are appropriately selected depending on the blending ratio of each component in the photosensitive color resin composition used, the thickness of the coating film, etc.

[0127] Next, the coating is developed using a developer to dissolve and remove the unexposed parts, forming a coating film in a desired pattern. As the developer, a solution in which an alkali is dissolved in water or a water-soluble solvent is usually used. A suitable amount of a surfactant or the like may be added to this alkaline solution. A general method may be used as the development method.

[0128] After the development process, the developer is usually washed off and the cured coating film of the photosensitive color resin composition is dried to form a colored layer of one color (for example, red). After the development process, a heat treatment may be performed to sufficiently cure the coating film. The heating conditions are not particularly limited, but may be, for example, 200°C to 250°C.

[0129] Next, a colored layer is formed in the same manner as described above using a photosensitive colored resin composition of another color (e.g., blue), and then a colored layer is formed in the same manner as described above using the photosensitive colored resin composition of the present invention as yet another color (e.g., green), thereby producing a color filter having three colored layers, for example, a green colored layer, a blue colored layer, and a red colored layer. The colored layer (green colored layer) which is a cured product of the photosensitive colored resin composition for color filters of the present invention has high brightness and can suppress a decrease in brightness of other colored layers due to migration, thereby improving the white brightness of the color filter.

[0130] In addition to the above-mentioned substrate, light-shielding portion, and colored layer, the color filter of the present invention may also include, for example, an overcoat layer, a transparent electrode layer, an alignment film for aligning a liquid crystal material, columnar spacers, etc. The color filter of the present invention is not limited to the above-mentioned configurations, and any known configuration generally used in color filters may be appropriately selected and used.

[0131] 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 according to the present invention is not particularly limited, and can be appropriately selected from conventionally known display devices, for example, liquid crystal display devices and organic light-emitting display devices.

[0132] [Liquid crystal display device] A liquid crystal display device of the present invention is characterized by comprising 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. Such a liquid crystal display device of the present invention will be described with reference to the drawings. FIG. 2 is a schematic diagram showing an example of a liquid crystal display device of the present invention. As illustrated in FIG. 2, a 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 15 located between the color filter 10 and the counter substrate 20. FIG. 2 shows an example in which an alignment film 13a is located on the colored layer 3 side of the color filter 10 and an alignment film 13b is located on the counter substrate 20 side, and the liquid crystal layer 15 is located between the two alignment films 13a and 13b. Furthermore, FIG. 2 shows an example in which the liquid crystal display device 40 has a polarizing plate 25a located on the outside of the color filter 10, a polarizing plate 25b located on the outside of the counter substrate 20, and a backlight 30 located outside the polarizing plate 25b located on the counter substrate 20 side of the liquid crystal display device 40. The liquid crystal display device of the present invention is not limited to the configuration shown in FIG. 2, but may have any known configuration as a liquid crystal display device that generally uses color filters.

[0133] The driving method of the liquid crystal display device of the present invention is not particularly limited, and any driving method generally used for liquid crystal display devices can be adopted. Examples of such driving methods include the TN method, the IPS method, the OCB method, and the MVA method. Any of these methods can be suitably used in the present invention. The counter substrate can be appropriately selected depending on the driving method of the liquid crystal display device of the present invention. Furthermore, as the liquid crystal constituting the liquid crystal layer, various liquid crystals having different dielectric anisotropy and mixtures thereof can be used depending on the driving method of the liquid crystal display device of the present invention.

[0134] The liquid crystal layer can be formed by any method generally used for producing liquid crystal cells, such as a vacuum injection method or a liquid crystal dropping method. In the vacuum injection method, for example, a liquid crystal cell is prepared in advance using a color filter and an opposing substrate, the liquid crystal is heated to make it an isotropic liquid, the liquid crystal is injected into the liquid crystal cell in the isotropic liquid state using the capillary effect, and the liquid crystal layer is formed by sealing with an adhesive. The liquid crystal cell is then gradually cooled to room temperature to align the enclosed liquid crystal. In the liquid crystal dropping method, for example, a sealant is applied to the periphery of a color filter, the color filter is heated to a temperature at which the liquid crystal becomes isotropic, the liquid crystal is dropped in an isotropic liquid state using a dispenser or the like, the color filter and the opposing substrate are superimposed under reduced pressure, and bonded together via the sealant, thereby forming a liquid crystal layer. The liquid crystal cell is then gradually cooled to room temperature, whereby the enclosed liquid crystal can be aligned.

[0135] The backlight used in the liquid crystal display device of the present invention can be appropriately selected depending on the application of the liquid crystal display device. For example, the backlight can include a cold cathode fluorescent lamp (CCFL), a white LED, or a backlight unit using a white organic EL as a light source. Examples of white LEDs include a white LED that obtains white light by mixing a red LED, a green LED, and a blue LED, a white LED that obtains white light by mixing a blue LED, a red LED, and a green phosphor, a white LED that obtains white light by mixing a blue LED, a red light-emitting phosphor, and a green light-emitting phosphor, a white LED that obtains white light by mixing a blue LED and a YAG phosphor, and a white LED that obtains white light by mixing an ultraviolet LED, a red light-emitting phosphor, a green light-emitting phosphor, and a blue light-emitting phosphor, etc. Quantum dots may be used as the phosphor.

[0136] [Organic light-emitting display device] The organic light-emitting display device according to the present invention includes the color filter according to the present invention described above and an organic light-emitting body. Such an organic light-emitting display device of the present invention will be described with reference to the drawings. Fig. 3 is a schematic diagram showing an example of an organic light-emitting display device of the present invention. As illustrated in Fig. 3, an organic light-emitting display device 100 of the present invention has a color filter 10 and an organic light-emitting body 80. An organic protective layer 50 and an inorganic oxide film 60 may be provided between the color filter 10 and the organic light-emitting body 80.

[0137] Examples of the method for laminating the organic light-emitting body 80 include a method for 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, and a method for bonding an organic light-emitting body 80 formed on a separate substrate onto an inorganic oxide film 60. The transparent anode 71, the hole injection layer 72, the hole transport layer 73, the light-emitting layer 74, the electron injection layer 75, the cathode 76, and other components of the organic light-emitting body 80 may be appropriately selected from known components. The organic light-emitting display device 100 thus fabricated can be applied to, for example, a passive-drive organic EL display and an active-drive organic EL display. The organic light-emitting display device of the present invention is not limited to the configuration shown in FIG. 3, but may have any known configuration as an organic light-emitting display device that generally uses color filters. EXAMPLES

[0138] The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. The intermediates of zinc phthalocyanine coloring materials (pigments or dyes) were analyzed by LC-MS (Agilent Technologies, quadrupole LC / MS, Agilent 1260 Infinity). The zinc phthalocyanine coloring material (pigment or dye) was analyzed by MALDI-TOF-MS (Shimadzu Corporation, MALDI-8020).

[0139] (Synthesis Example 1: Synthesis of Zinc Phthalocyanine Pigment 1) In a 200 mL three-neck flask, 10 g of tetrafluorophthalonitrile, 6.95 g of potassium fluoride, and 36 mL of acetone were placed and dissolved with stirring at 25° C. Then, the internal temperature was cooled, and a solution of 10.8 g of p-cresol dissolved in 24 mL of acetone was added dropwise in the range of −11° C. to −5° C., and the solution was added dropwise while increasing the temperature to 25° C., and the reaction was carried out for 5 hours. The insoluble matter in the reaction solution was filtered off, and the filtrate was concentrated and purified by silica gel chromatography to obtain intermediate 1. Next, 3.88 g of zinc iodide, 15.4 g of intermediate 1, and 40 mL of benzonitrile were placed in a 200 mL recovery flask and reacted for 5 hours at 160° C. under a nitrogen atmosphere. The recovery flask was cooled to 25° C., and the reaction liquid was poured into 600 mL of methanol for reprecipitation. The precipitated crystals were purified by silica chromatography to obtain zinc phthalocyanine pigment 1 having the following structure. MALDI-TOF-MS: 1571.8 ([M+1] + )

[0140] [ka]

[0141] (Synthesis Example 2: Synthesis of Zinc Phthalocyanine Pigment 2) In a 200 mL three-neck flask, 15 g of tetrafluorophthalonitrile, 10.45 g of potassium fluoride, and 54 mL of acetone were placed and dissolved with stirring at 25° C. Then, the internal temperature was cooled, and a solution of 28.8 g of p-ethylphenol dissolved in 36 mL of acetone was added dropwise in the range of −11° C. to −5° C., and the solution was added dropwise while increasing the temperature to 25° C., and the reaction was carried out for 5 hours. The insoluble matter in the reaction solution was filtered off, and the filtrate was concentrated and purified by silica gel chromatography to obtain intermediate 2. Zinc phthalocyanine pigment 2 having the following structure was obtained in the same manner as in Synthesis Example 1, except that 16.5 g of Intermediate 2 was used instead of 15.4 g of Intermediate 1 in Synthesis Example 1. MALDI-TOF-MS: 1684.0 ([M+1] + )

[0142] [ka]

[0143] (Synthesis Example 3: Synthesis of Zinc Phthalocyanine Pigment 3) Zinc phthalocyanine pigment 3 having the following structure was obtained in the same manner as in Synthesis Example 1, except that 24.0 g of 3,6-difluoro-4,5-bis[4-(phenoxycarbonyl)phenoxy)phthalonitrile] was used instead of 15.4 g of Intermediate 1 in Synthesis Example 1. MALDI-TOF-MS: 2420.5 ([M+1] + )

[0144] [ka]

[0145] (Comparative Synthesis Example 1: Synthesis of Zinc Phthalocyanine Dye C1) With reference to the synthesis of dye A in Synthesis Example 1 of Patent Document 2 (WO 2020 / 171060), a zinc phthalocyanine dye C1 having the following structure was synthesized. MALDI-TOF-MS: 2036.1 ([M+1] + )

[0146] [ka]

[0147] (Comparative Synthesis Example 2: Synthesis of Zinc Phthalocyanine Dye C2) In the synthesis of dye A in Synthesis Example 1 of Patent Document 2 (WO 2020 / 171060), instead of using ethyl p-hydroxybenzoate, an equimolar amount of methyl p-hydroxybenzoate was used. In the same manner as in the synthesis of dye A, a zinc phthalocyanine dye C2 having the following structure was synthesized. MALDI-TOF-MS: 1923.9 ([M+1] + )

[0148] [ka]

[0149] (Comparative Synthesis Example 3: Synthesis of Zinc Phthalocyanine Dye C3) With reference to the synthesis of dye B in Synthesis Example 2 of Patent Document 2 (WO 2020 / 171060), a zinc phthalocyanine dye C3 having the following structure was synthesized. MALDI-TOF-MS: 2148.3 ([M+1] + )

[0150] [ka]

[0151] [Evaluation of color materials] As coloring materials, the zinc phthalocyanine pigments 1 to 3 obtained in Synthesis Examples 1 to 3, the zinc phthalocyanine dyes C1 to C3 obtained in Comparative Synthesis Examples 1 to 3, and commercially available Pigment Green 58 (FASTOGEN GREEN A350, manufactured by DIC Corporation) were used and evaluated as follows.

[0152] (Powder X-ray diffraction measurement of color materials) A standard glass sample plate with a bottom was used, in which the sample filling area was etched to 2.0 mm × 2.0 mm × 0.2 mm depth. The glass sample plate with a bottom, a 20 × 20 glass sample plate with a bottom 0.2 manufactured by Rigaku Corporation, was used. The colorant alone before heating was placed in the sample filling section, and the colorant was pressed and spread with another glass plate or the like to fill it evenly. In order to reduce error, the colorant surface and the glass sample plate were made to be on the same plane to prepare the measurement sample.

[0153] The above measurement sample (bottomed glass sample plate with a coloring material filled in the sample filling section) was subjected to powder X-ray diffraction measurement using a powder X-ray diffractometer (Rigaku Corporation, SmartLab) at 25° C. A powder X-ray diffraction spectrum was obtained using CuKα radiation as the X-ray source, with X-ray output of 45 kV, 200 mA, fixed incidence angle (θ) of 0.20°, diffraction angle (2θ) of 2.00° to 60.00°, θ step of 0.01°, and scan speed of 3.0° / min. The presence or absence of a diffraction peak was judged after removing the background from the powder X-ray diffraction spectrum. The background was removed using the Sonnevelt-Visser method. The peak width threshold was 0.10, and the intensity threshold was 0.01. In the obtained powder X-ray diffraction spectrum, when the maximum peak intensity in the range of diffraction angles (2θ) of 2.00° to 60.00° is Z, a peak having an intensity of 1 / 4Z (1 / 4 of Z) or more was recognized as a diffraction peak. Then, it was judged whether or not at least one diffraction peak was present in the range of diffraction angles (2θ) of 3.00° to 7.00°.

[0154] (Solubility of coloring material in solvent) At 25° C., 100 g of acetone was stirred with a stirrer (stirring speed: 50 rpm) in a 200 mL sample bottle, and the coloring material was added until undissolved matter was produced, and the dissolved mass concentration was determined. First, 0.01 g of coloring material was added, and if any undissolved matter was generated, the solvent solubility in acetone was evaluated to be less than 0.01% by mass. <Evaluation criteria> Pigment: Solubility in acetone at 25°C is less than 0.1% by mass Dye: Solubility in acetone at 25°C is 0.1% by mass or more

[0155] [Table 1]

[0156] (Synthesis Example 4: Synthesis of Basic Dispersant 1) As a dispersant, a basic dispersant 1 (salt-type block copolymer) solution was prepared in the same manner as in the production of dispersant b in Synthesis Example II-2 described in paragraph 0302 of WO 2016 / 104493 (solid content 40 mass%, amine value before salt formation 95 mg KOH / g, amine value after salt formation 57 mg KOH / g, acid value 8 mg KOH / g).

[0157] (Synthesis Example 5: Synthesis 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 azobisisobutyronitrile (AIBN) was added dropwise to a polymerization tank containing 150 parts by mass of propylene glycol monomethyl ether acetate (PGMEA) at 100°C over 3 hours under a nitrogen gas flow. After the dropwise addition was completed, the mixture was further heated at 100°C for 3 hours to obtain a polymer solution. The weight 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 solution was heated at 110° C. for 10 hours to react the carboxylic acid group of the main chain methacrylic acid with the epoxy group of the glycidyl methacrylate. During the reaction, air was bubbled into the reaction solution to prevent polymerization of the glycidyl methacrylate. The reaction was monitored by measuring the acid value of the solution. The obtained alkali-soluble resin A was a resin in which a side chain having an ethylenically unsaturated bond was introduced using GMA to the main chain formed by copolymerization of BzMA, MMA, and MAA, and had an acid value of 74 mgKOH / g and a weight-average molecular weight of 12,000. The alkali-soluble resin A solution had a solid content of 40% by mass.

[0158] (Synthesis Example 6: Synthesis of Basic Treated Phthalocyanine Pigment 1) In a reaction vessel, 300 parts by mass of chlorosulfonic acid and 30 parts by mass of copper phthalocyanine were added and completely dissolved, after which 24 parts by mass of thionyl chloride was added and the temperature was gradually raised to 101°C for 3 hours to react. The reaction liquid was poured into 9000 parts by mass of ice water, stirred, filtered, and washed with water. The obtained press cake was made into a slurry with 300 parts by mass of water, and 13 parts by mass of 1,1-diethyl-1,5-diazapentane was added, stirred at 65°C for 4 hours, filtered, washed with water, and dried to obtain blue colorant derivative 1 having a basic site for use in surface treatment. The obtained blue colorant derivative 1 having a basic site was confirmed to have the structure of the following chemical formula. (TOF-MS: 768.35)

[0159] [ka]

[0160] 100 parts by mass of commercially available CI Pigment Blue 15:6 (ε-type copper phthalocyanine pigment, FASTOGEN BLUE A510 manufactured by DIC) and 5 parts by mass of the blue colorant derivative 1 having a basic site were dry-ground in an attritor at 60° C. for 1.5 hours. The ground product was further mixed with 5 parts by mass of the blue colorant derivative 1 having a basic site to obtain the target basic-treated phthalocyanine pigment, basic-treated phthalocyanine pigment 1.

[0161] (Synthesis Example 7: Synthesis of Acidic Dispersant 2 (a block copolymer including an A block containing a structural unit derived from a carboxyl group-containing ethylenically unsaturated monomer and a B block containing a structural unit derived from a (meth)acrylic acid alkyl ester) A triblock copolymer having a block of 20 parts by mass of MMA and 40 parts by mass of BMA, a block of 20 parts by mass of acrylic acid (MAA) and 20 parts by mass of BMA, and a block of 20 parts by mass of MMA and 40 parts by mass of BMA was synthesized with reference to Example 1 described in International Publication WO 2016 / 132863. The obtained block copolymer had a weight average molecular weight (Mw) of 11,000, a molecular weight distribution (Mw / Mn) of 1.50, and an acid value of 130 mgKOH / g.

[0162] (Synthesis Example 8: Synthesis of Alkali-Soluble Resin B) A polymerization tank was charged with 150 parts by mass of PGMEA and heated to 100°C under a nitrogen atmosphere, and then 22 parts by mass of methacrylic acid (MAA), 64 parts by mass of cyclohexyl methacrylate (CHMA), 6 parts by mass of Perbutyl O (NOF Corporation), and 2 parts by mass of a chain transfer agent (n-dodecyl mercaptan) were continuously added dropwise over 1.5 hours. The reaction was then continued while maintaining the temperature at 100°C, and 2 hours after the completion of the dropwise addition of the main chain forming mixture, 0.1 parts by mass of p-methoxyphenol was added as a polymerization inhibitor to terminate the polymerization. Next, while blowing in air, 14 parts by mass of glycidyl methacrylate (GMA) was added as an epoxy group-containing compound, and the temperature was raised to 110°C. After that, 0.8 parts by mass of triethylamine was added and an addition reaction was carried out at 110°C for 15 hours to obtain an alkali-soluble resin B solution (weight average molecular weight (Mw) 9,000, acid value 90 mgKOH / g, solid content 40% by mass).

[0163] (Synthesis Example 9: Synthesis of Y138 sulfonic acid derivative) A monosulfonic acid derivative of CI Pigment Yellow 138 was synthesized in the same manner as in the synthesis of a monosulfonic acid derivative of CI Pigment Yellow 138 in Synthesis Example 2 of WO 2014 / 069416.

[0164] (Preparation Example 1: Preparation of Photosensitive Binder Component CR-1) To 19.13 parts by mass of the alkali-soluble resin A solution (solid content 40% by mass), 17.85 parts by mass of dipentaerythritol hexaacrylate (DPHA) (Aronix M403, manufactured by Toa Gosei) as a photopolymerizable compound, 2.25 parts by mass of an oxime ester photoinitiator (PBG-3057, manufactured by Changzhou Strong Electronic New Materials Co., Ltd.) as a photoinitiator, 2.25 parts by mass of an oxime ester photoinitiator (NCI-831E, manufactured by ADEKA), and 58.53 parts by mass of PGMEA were added to obtain a photosensitive binder component CR-1.

[0165] (Preparation Example 2: Preparation of Photosensitive Binder Component CR-2) To 36.5 parts by mass of the alkali-soluble resin B solution (solid content 40% by mass), 21.9 parts by mass of dipentaerythritol hexaacrylate (DPHA) (Aronix M402, manufactured by Toa Gosei) as a photopolymerizable compound, 1.1 parts by mass of an α-aminoacetophenone-based photoinitiator (Irgacure 907, manufactured by BASF) as a photoinitiator, 1.3 parts by mass of an oxime ester-based photoinitiator having a fluorene skeleton (SPI-04, manufactured by Sanyo), 0.3 parts by mass of a thioxanthone-based photoinitiator (Kayacure DETX-S, manufactured by Nippon Kayaku), 0.8 parts by mass of an antioxidant (IRGANOX1010, manufactured by BASF), and 38.1 parts by mass of PGMEA were added to obtain a photosensitive binder component CR-2.

[0166] (Preparation Example 3: Preparation of Photosensitive Binder Component CR-3) To 13.80 parts by mass of the alkali-soluble resin A solution (solid content 40% by mass), 22.08 parts by mass of dipentaerythritol hexaacrylate (DPHA) (Aronix M403, manufactured by Toa Gosei) as a photopolymerizable compound, 2.40 parts by mass of an oxime ester-based photoinitiator (PBG-3057, manufactured by Changzhou Strong Electronic New Materials Co., Ltd.) as a photoinitiator, and 61.72 parts by mass of PGMEA were added to obtain a photosensitive binder component CR-3.

[0167] Example 1 (1) Manufacture of pigment dispersion G1 8.75 parts by weight (3.5 parts by weight of solids) of the basic dispersant 1 solution as a dispersant, 10.00 parts by weight of the zinc phthalocyanine pigment 1 obtained in Synthesis Example 1, 16.25 parts by weight of the alkali-soluble resin A, 65.00 parts by weight of PGMEA, and 100 parts by weight of zirconia beads with a particle size of 2.0 mm were placed in a mayonnaise bottle and shaken for 1 hour using a paint shaker (manufactured by Asada Iron Works Co., Ltd.) as a preliminary crushing. Next, the zirconia beads with a particle size of 2.0 mm were removed, 200 parts by weight of zirconia beads with a particle size of 0.1 mm were added, and similarly, dispersion was performed for 10 hours using a paint shaker as a main crushing to obtain pigment dispersion liquid G1.

[0168] (2) Preparation of Y138 dispersion 13.00 parts by mass of the basic dispersant 1 solution as a dispersant, 13.00 parts by mass of Chromofine Yellow 6206EC (manufactured by Dainichi Seikagaku Kogyo Co., Ltd.) as a colorant, 13.00 parts by mass of the alkali-soluble resin A solution, 61.00 parts by mass of PGMEA, and 100 parts by mass of zirconia beads with a particle size of 2.0 mm were placed in a mayonnaise bottle and shaken for 1 hour with a paint shaker (manufactured by Asada Iron Works Co., Ltd.) as a preliminary crushing. Next, the zirconia beads with a particle size of 2.0 mm were removed and 200 parts by mass of zirconia beads with a particle size of 0.1 mm were added, and similarly dispersed for 4 hours with a paint shaker as main crushing, to obtain Y138 dispersion.

[0169] (3) Preparation of Photosensitive Colored Resin Composition G1 A photosensitive colored resin composition (green composition) G1 was obtained by adding 35.07 parts by mass of the pigment dispersion G1 obtained in (1) above, 17.60 parts by mass of the Y138 dispersion obtained in (2) above, 18.97 parts by mass of the photosensitive binder component CR-1, 0.114 parts by mass of a sensitizer (pentaerythritol tetrakis(3-mercaptobutyrate), trade name Karenz MT-PE1, manufactured by Showa Denko), 0.03 parts by mass of a fluorine-based surfactant (trade name Megafac F559, manufactured by DIC Corporation), 0.34 parts by mass of a silane coupling agent (trade name KBM503, manufactured by Shin-Etsu Silicones), and 27.88 parts by mass of PGMEA.

[0170] (Examples 2 to 3) (1) Production of pigment dispersions G2 to G3 Pigment dispersions G2 to G3 were obtained in the same manner as in Example 1(1), except that in Example 1(1), the zinc phthalocyanine pigment 2 obtained in Synthesis Example 2 or the zinc phthalocyanine pigment 3 obtained in Synthesis Example 3 was used in an equimolar amount instead of the zinc phthalocyanine pigment 1 obtained in Synthesis Example 1. (2) Production of Photosensitive Colored Resin Compositions G2 to G3 Photosensitive colored resin compositions (green compositions) G2 to G3 were obtained in the same manner as in Example 1(3), except that the pigment dispersion G2 or G3 was used instead of the pigment dispersion G1 in Example 1(3).

[0171] Comparative Example 1 (1) Preparation of comparative coloring solutions CG1 to CG3 Comparative coloring solutions CG1 to CG3 were obtained in the same manner as in Example 1(1), except that in Example 1(1), the zinc phthalocyanine pigment 1 obtained in Synthesis Example 1 was replaced with an equimolar amount of the zinc phthalocyanine dye C1 obtained in Comparative Synthesis Example 1, the zinc phthalocyanine dye C2 obtained in Comparative Synthesis Example 2, or the zinc phthalocyanine dye C3 obtained in Comparative Synthesis Example 3. (2) Preparation of Comparative Photosensitive Colored Resin Compositions CG1 to CG3 Comparative photosensitive colored resin compositions (green compositions) CG1 to CG3 were obtained in the same manner as in Example 1(3), except that the comparative colored liquids CG1 to CG3 were used instead of the pigment dispersion G1 in Example 1(3).

[0172] Comparative Example 4 (1) Preparation of comparative pigment dispersion CG4 9.75 parts by weight of the basic dispersant 1 solution, 13.00 parts by weight of CI Pigment Green 58 (FASTOGEN GREEN A350, manufactured by DIC Corporation) as a colorant, 16.25 parts by weight of the alkali-soluble resin A, 61.00 parts by weight of PGMEA, and 100 parts by weight of zirconia beads with a particle size of 2.0 mm were placed in a mayonnaise bottle and shaken for 1 hour with a paint shaker (manufactured by Asada Iron Works Co., Ltd.) as pre-crushing, then the zirconia beads with a particle size of 2.0 mm were removed and 200 parts by weight of zirconia beads with a particle size of 0.1 mm were added, and similarly dispersed for 3 hours with the paint shaker as main crushing, to obtain comparative pigment dispersion CG4. (2) Preparation of Comparative Photosensitive Colored Resin Composition CG4 A comparative photosensitive colored resin composition (green composition) CG4 was obtained in the same manner as in Example 1(3), except that the comparative pigment dispersion CG4 was used instead of the pigment dispersion G1 in Example 1(3).

[0173] (Production of Blue Composition B1) (1) Preparation of colorant dispersion of basic-treated phthalocyanine pigment 1 10 parts by mass of the basic treated phthalocyanine pigment 1, 16.7 parts by mass of the acidic dispersant 2 solution (effective solids content 5.0 parts by mass), 7.5 parts by mass of the alkali soluble resin B (effective solids content 3.0 parts by mass), and 65.8 parts by mass of PGMEA were mixed, and the mixture was dispersed in a paint shaker (manufactured by Asada Iron Works) for 1 hour using 2 mm zirconia beads as pre-dispersion, and further for 6 hours using 0.1 mm zirconia beads as main dispersion, thereby obtaining a colorant dispersion of basic treated phthalocyanine pigment 1. (2) Preparation of Co-Dispersion Colorant Dispersion 1 of Base-Treated Phthalocyanine Pigment 1 and CI Pigment Violet 23 9 parts by weight of the basic treated phthalocyanine pigment 1, 1 part by weight of CI Pigment Violet 23 (Sigma-Aldrich Japan), 16.7 parts by weight (effective solids content 5.0 parts by weight) of the acidic dispersant 2 solution, 7.5 parts by weight (effective solids content 3.0 parts by weight) of the alkali-soluble resin B, and 65.8 parts by weight of PGMEA were mixed together, and the mixture was dispersed in a paint shaker (Asada Iron Works) for 1 hour using 2 mm zirconia beads as a preliminary dispersion, and further dispersed for 6 hours using 0.1 mm zirconia beads as a main dispersion, to obtain a co-dispersed colorant dispersion liquid 1. (3) Preparation of blue composition B1 18.95 parts by mass of the colorant dispersion of the basic-treated phthalocyanine pigment 1, 17.49 parts by mass of the co-dispersed colorant dispersion 1, 34.78 parts by mass of the photosensitive binder component CR-2, 0.03 parts by mass of surfactant F559 (manufactured by DIC), and 28.75 parts by mass of PGMEA were mixed together to obtain a blue composition B1.

[0174] (Production of Red Composition R1) (1) Preparation of colorant dispersion R254 A mixture of 12.4 parts by weight of a colorant (CI Pigment Red 254), 16.2 parts by weight of a PGMEA solution of the basic block copolymer 1 (solid content 40% by weight) as a dispersant, 0.7 parts by weight of the Y138 sulfonic acid derivative, 9.8 parts by weight of the alkali-soluble resin A, 61.0 parts by weight of PGMEA, and 100 parts by weight of zirconia beads with a particle size of 2.0 mm was placed in a mayonnaise bottle and shaken for 1 hour with a paint shaker (manufactured by Asada Iron Works Co., Ltd.) as pre-crushing. The zirconia beads with a particle size of 2.0 mm were then removed and 200 parts by weight of zirconia beads with a particle size of 0.1 mm were added, and the mixture was similarly dispersed for 8 hours with a paint shaker as main crushing, to obtain colorant dispersion liquid R254. (2) Preparation of colorant dispersion R177 A colorant dispersion R177 was obtained in the same manner as in the preparation of the colorant dispersion R254, except that CI Pigment Red 177 was used instead of CI Pigment Red 254 as the colorant in the preparation of the colorant dispersion R254. (3) Preparation of Red Composition R1 2.77 parts by mass of colorant dispersion R254, 19.89 parts by mass of colorant dispersion R177, 31.69 parts by mass of the photosensitive binder component CR-3, 0.03 parts by mass of a fluorine-based surfactant (product name Megafac F559, manufactured by DIC Corporation), 0.34 parts by mass of a silane coupling agent (product name KBM503, manufactured by Shin-Etsu Silicones), and 45.27 parts by mass of PGMEA were added to obtain a red composition R1.

[0175] [Evaluation method] <Formation of Color Filter Substrate 1> The red composition 1, the blue composition 1, and one of the photosensitive colored resin compositions (green compositions) G1 to G3 of the present invention and the comparative photosensitive colored resin compositions (green compositions) CG1 to CG4 as the green composition were used in the order of red, blue, and green as shown in Table 2 to form colored layers, thereby forming a color filter substrate 1. (In the following table, the zinc phthalocyanine pigments 1 to 3 used in the examples of the present invention are represented as "pigments 1 to 3", the zinc phthalocyanine dyes C1 to C3 used in the comparative examples are represented as "dyes C1 to C3", and Pigment Green 58 is represented as "PG58".) First, a curable resin composition for black matrix was prepared in the same manner as in Example 1 of Japanese Patent No. 4833777, and a black matrix (10 μm wide) was formed on a 0.7 mm thick glass substrate ("NA35" manufactured by NH Technoglass Co., Ltd.) in the same manner as in paragraph 0085 of Japanese Patent No. 4833777. The red composition R1 was applied using a spin coater so that the film thickness after post-baking would be 2.3 μm. Then, the composition was dried by heating on a hot plate at 80° C. for 3 minutes. A 40 mJ / cm 2 super-high pressure mercury lamp was used through a pattern photomask (chrome mask) in which a chrome mask with an opening dimension of 80 μm×250 μm was arranged. 2A post-exposure coating film was formed on a glass substrate by exposing the substrate to ultraviolet light of 1000 nm. The substrate was then spin-developed using a 0.05 wt% potassium hydroxide aqueous solution as the developer, and developed by incubating the substrate in the developer for 60 seconds and then washing with pure water to obtain a red coating film in an independent fine line pattern. The substrate was then post-baked in a clean oven at 230°C for 25 minutes to form a red colored layer in an independent fine line pattern. On the glass substrate on which the red colored layer was formed, the blue colored layer B1 was used instead of the red colored layer R1, and was applied by a spin coater so that the film thickness after post-baking was 2.3 μm. In the same manner as above, a pattern photomask (chrome mask) was used to obtain an independent thin line patterned blue colored layer at a specified position different from the part where the red colored layer was formed. On the glass substrate on which the red and blue colored layers were formed, the green composition shown in Table 2 was used instead of the red composition R1, and the green composition was applied by a spin coater so that the film thickness after post-baking was 2.3 μm. In the same manner as above, a pattern photomask (chrome mask) was used to obtain an independent thin line patterned green colored layer at a specified position different from the portion where the red and green colored layers were formed. In this manner, a color filter substrate 1 having colored layers of three colors, RGB, was manufactured.

[0176] <Formation of Color Filter Substrate 2> In forming the color filter substrate 1, the red composition 1, the blue composition 1, and one of the photosensitive colored resin compositions (green compositions) G1 to G3 of the present invention and the comparative photosensitive colored resin compositions (green compositions) CG1 to CG4 as the green composition were used as shown in Table 3, and the colored layers were formed in the order of red → green → blue. A color filter substrate 2 having colored layers of three colors, RGB, was manufactured in the same manner as the color filter substrate 1, except that the colored layers were formed in the order of red → green → blue.

[0177] <Formation of Color Filter Substrate 3> In forming the color filter substrate 1, the red composition 1, the blue composition 1, and one of the photosensitive colored resin compositions (green compositions) G1 to G3 of the present invention and the comparative photosensitive colored resin compositions (green compositions) CG1 to CG4 as the green composition were used as shown in Table 4, and the colored layers were formed in the order of blue → green → red. A color filter substrate 3 having colored layers of three colors, RGB, was manufactured in the same manner as the color filter substrate 1, except that the colored layers were formed in the order of blue → green → red.

[0178] <Formation of Color Filter Substrate 4> In forming the color filter substrate 1, the red composition 1, the blue composition 1, and one of the photosensitive colored resin compositions (green compositions) G1 to G3 of the present invention and the comparative photosensitive colored resin compositions (green compositions) CG1 to CG4 as the green composition were used as shown in Table 5, and the colored layers were formed in the order of green → red → blue. A color filter substrate 4 having colored layers of three colors, RGB, was manufactured in the same manner as the color filter substrate 1, except that the colored layers were formed in the order of green → red → blue.

[0179] <Optical performance> In each of the examples and comparative examples, the optical performance was evaluated using the obtained color filter substrate. The central positions of the red, green, and blue colored layers in the width direction (80 μm) were measured by a spectroscopic characteristic measuring device LCF (manufactured by Otsuka Electronics Co., Ltd.), and the chromaticity (x, y) and luminance (Y) of each color were calculated. The measured values ​​of each color were used to calculate the white chromaticity and luminance. The chromaticity coordinates are expressed in the JIS Z8701 XYZ color system measured using a C light source. As a reference luminance for the decrease in luminance of the first and second coated color layers, the luminance of the color layer formed by the final (third) coating using the same composition combination was used. The luminance decrease of each of the first and second coated red colored layers was determined based on the luminance of the red colored layer of the same composition combination of color filter substrate 3 (Table 4) on which the red colored layer was finally coated, as the reference luminance. The decrease in luminance of each of the first and second coated green colored layers was determined based on the luminance of the green colored layer of the same composition combination of color filter substrate 1 (Table 2) on which the green colored layer was finally coated. The decrease in luminance of each of the first and second coated blue colored layers was determined based on the luminance of the blue colored layer of the same composition combination on color filter substrate 2 (Table 3) on which the blue colored layer was finally coated, as the reference luminance. (Evaluation criteria for brightness reduction due to stain migration, etc.) A: Luminance reduction is less than 1.0% compared to the reference luminance. B: Luminance reduction is 1.0% or more and less than 2.0% compared to the reference luminance. C: Luminance reduction of 2.0% or more compared to the reference luminance Furthermore, for the green colored layer, 63.0 was set as the reference luminance, and luminance of 63.0 or more was rated as OK, and luminance of less than 63.0 was rated as NG.

[0180] <Evaluation of development residue> The development residues on the red and blue colored layers were evaluated when the layers were coated in the order of red, blue, and green. The red composition was applied to a 100 mm x 100 mm glass substrate (manufactured by NH Techno Glass Co., Ltd., "NA35") with a thickness of 0.7 mm using a spin coater, and then dried for 3 minutes at 60°C using a hot plate to form a coating layer with a thickness of 2.5 μm. Next, the glass plate on which the coating layer was formed was exposed to light at a specified position with an opening of 90 mm x 30 mm using a dedicated mask, and then shower-developed for 60 seconds using a 0.05 mass% potassium hydroxide aqueous solution as an alkaline developer, and washed with ion-exchanged water. The substrate on which the red colored layer was formed was then baked at 230°C for 30 minutes. A blue composition was applied onto the substrate on which the red colored layer was formed using a spin coater, and an opening of 90 mm x 30 mm was exposed using a dedicated mask at a specified position different from the part on which the red colored layer was formed, and then the substrate was shower-developed for 60 seconds using a 0.05 mass% potassium hydroxide aqueous solution as an alkaline developer, and washed with ion-exchanged water.Then, the substrate on which the red and blue colored layers were formed was baked at 230°C for 30 minutes. A green composition was applied onto the substrate on which the red and blue colored layers were formed using a spin coater, and an opening of 90 mm x 30 mm was exposed using a dedicated mask at a specified position different from the part on which the red and blue colored layers were formed, and then the composition was shower-developed for 60 seconds using a 0.05 mass% potassium hydroxide aqueous solution as an alkaline developer, and washed with ion-exchanged water. At this stage, the residue on the red and blue colored layers was evaluated. After that, the substrate on which the red, green, and blue colored layers were formed was baked at 230°C for 30 minutes. To evaluate the residues on the red and blue colored layers, the monochrome exposed area (90 mm x 30 mm) of the glass substrate after the development of the green colored layer was visually observed, then thoroughly wiped with a lens cleaner (manufactured by Toray Industries, Inc., product name: Toraysee MK Clean Cloth) soaked in ethanol, and the degree of coloring of the lens cleaner was visually observed. Similarly, evaluation was made on development residues on the red colored layer and the green colored layer when the layers were coated in the order of red→green→blue. Similarly, evaluation was made on development residues on the blue colored layer and the green colored layer when the layers were coated in the order of blue→green→red. Similarly, development residues on the green colored layer and the red colored layer when coated in the order of green→red→blue were evaluated. (Development Residue Evaluation Criteria) A: No development residue was found by visual inspection, and the lens cleaner was not colored at all. B: No development residue was found by visual inspection, and only slight coloring of the lens cleaner was found. C: A small amount of developing residue was visually confirmed, and coloring of the lens cleaner was confirmed.

[0181] [Table 2]

[0182] [Table 3]

[0183] [Table 4]

[0184] [Table 5]

[0185] [Summary of results] As shown in Comparative Examples 1 to 3, it was revealed that when a green colored layer of a color filter is formed using a photosensitive resin composition containing a halogenated zinc phthalocyanine dye dissolved in a solvent, the halogenated zinc phthalocyanine dye is likely to migrate to the red colored layer or blue colored layer on the substrate, and the luminance of the red colored layer or blue colored layer is likely to decrease. In Comparative Examples 1 to 3, even if the luminance of the green colored layer is improved by using a halogenated zinc phthalocyanine dye as a green coloring material, the luminance of the red colored layer or blue colored layer decreases, and the white luminance of the color filter decreases. As shown in Comparative Example 4, when a green colored layer of a color filter was formed using a photosensitive resin composition containing the conventional green pigment Pigment Green 58, migration was suppressed, but the brightness of the green colored layer was low and the white brightness of the color filter was reduced. In contrast, as shown in Examples 1 to 3, when the photosensitive colored resin composition for color filters of the present invention is used to form a green colored layer of a color filter, the brightness of the green colored layer is high and the decrease in brightness of the red colored layer and blue colored layer due to migration can be suppressed, so that the white brightness of the color filter can be improved (see Table 2).

[0186] Furthermore, even in Table 3 where the order of forming the colored layers was changed to red → green → blue, in Comparative Examples 5 to 7 in which the green colored layer of the color filter was formed using a photosensitive resin composition containing a halogenated zinc phthalocyanine dye dissolved in a solvent, the halogenated zinc phthalocyanine dye was easily transferred to the red colored layer on the substrate, and development residues of the blue colored layer were easily generated on the green colored layer, resulting in a decrease in the brightness of the red colored layer and the green colored layer, and a decrease in the white brightness of the color filter. As shown in Comparative Example 8, when a green colored layer of a color filter was formed using a photosensitive resin composition containing the conventional green pigment Pigment Green 58, migration was suppressed, but the brightness of the green colored layer was low and the white brightness of the color filter was reduced. In contrast, as shown in Examples 4 to 6, when the photosensitive color resin composition for color filters of the present invention is used to form a green color layer of a color filter, the brightness of the green color layer is high and the decrease in brightness of the red color layer due to migration is suppressed, development residues of the blue color layer are unlikely to occur on the green color layer, and the white brightness of the color filter can be improved.

[0187] Furthermore, even in Table 4, where the order of forming the colored layers was changed to blue → green → red, in Comparative Examples 9 to 11, in which the green colored layer of the color filter was formed using a photosensitive resin composition containing a halogenated zinc phthalocyanine dye dissolved in a solvent, the halogenated zinc phthalocyanine dye was easily transferred to the blue colored layer on the substrate, and development residues of the red colored layer were easily generated on the green colored layer, resulting in a decrease in the brightness of the blue colored layer and a decrease in the white brightness of the color filter. As shown in Comparative Example 12, when a green colored layer of a color filter was formed using a photosensitive resin composition containing the conventional green pigment Pigment Green 58, migration was suppressed, but the brightness of the green colored layer was low and the white brightness of the color filter was reduced. In contrast, as shown in Examples 7 to 9, when the photosensitive color resin composition for color filters of the present invention is used to form a green color layer of a color filter, the brightness of the green color layer is high and the decrease in brightness of the red color layer due to migration is suppressed, development residues of the blue color layer are less likely to occur on the green color layer, and the white brightness of the color filter can be improved.

[0188] Furthermore, even in Table 5, where the order of forming the colored layers was changed to green → red → blue, in Comparative Examples 13 to 15, in which the green colored layer of the color filter was formed using a photosensitive resin composition containing a halogenated zinc phthalocyanine dye that was dissolved in a solvent, development residues of the red colored layer were likely to occur on the green colored layer, reducing the brightness of the green colored layer and decreasing the white brightness of the color filter. As shown in Comparative Example 16, when a green colored layer of a color filter was formed using a photosensitive resin composition containing the conventional green pigment Pigment Green 58, the luminance reduction rate of the green colored layer was low, but the luminance of the green colored layer was originally low, and the white luminance of the color filter was reduced. In contrast, as shown in Examples 10 to 12, when the green colored layer of a color filter is formed using the photosensitive colored resin composition for color filters of the present invention, development residues of the red colored layer are less likely to be generated on the green colored layer, the decrease in brightness of the green colored layer is suppressed, and the white brightness of the color filter can be improved. [Explanation of symbols]

[0189] 1 Board 2 Light shielding section 3 Colored layer 10 Color Filters 20 Opposing substrate 30 Liquid crystal layer 40 LCD display device 50 Organic protective layer 60 Inorganic oxide film 71 Transparent anode 72 Hole injection layer 73 Hole transport layer 74 Light-emitting layer 75 Electron injection layer 76 Cathode 80 Organic Light Emitting Materials 100 Organic light-emitting display device

Claims

1. The composition contains a color material, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a solvent, the colorant contains a zinc phthalocyanine fluoride pigment that has at least one diffraction peak in a diffraction angle (2θ) range of 3.00° to 7.00° in a powder X-ray diffraction spectrum of the colorant alone using CuKα radiation, and has a solubility in acetone at 25° C. of less than 0.1% by mass; A photosensitive colored resin composition for color filters (excluding the case of an inkjet ink) that does not contain a sulfonic acid group-containing colorant derivative.

2. 2. The photosensitive color resin composition for color filters according to claim 1, wherein the fluorinated zinc phthalocyanine pigment is a zinc phthalocyanine pigment represented by the following general formula (1): 【Chemistry 1】 (In general formula (1), R Ａ１ , R Ａ２ , R Ａ３ , R Ａ４ , R Ａ５ , R Ａ６ , R Ａ７ , and R Ａ８ are each independently a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted arylalkyl group, or a substituted or unsubstituted heteroarylalkyl group, and the substituent that the substituted aryl group, the substituted heteroaryl group, the substituted arylalkyl group, or the substituted heteroarylalkyl group may have is a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cyano group, a hydroxy group, a nitro group, an amino group, an alkylamino group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an acylamino group, an arylamino group, a ureido group, an alkylthio group, an arylthio group, At least one selected from the group consisting of an aryl group, a heteroarylthio group, an alkoxycarbonylamino group, a sulfonamide group, a carbamoyl group, an alkoxycarbonyl group, an acyloxy group, a carbamoyloxy group, a silyloxy group, an aryloxycarbonyl group, a heteroaryloxycarbonyl group, an arylcarbonyl group, a heteroarylcarbonyl group, an aryloxycarbonylamino group, an arylalkyloxycarbonyl group, an arylalkyloxycarbonylamino group, an imido group, a phosphoryl group, an acyl group, a carboxy group, and a sulfo group, and the alkyl group and the aryl group in each of these groups may further have the above-mentioned substituent.

3. The photosensitive colored resin composition for color filters according to claim 1 or 2, wherein the fluorinated zinc phthalocyanine pigment is a zinc phthalocyanine pigment represented by the following formula (1-1): 【Chemistry 2】

4. The photosensitive color resin composition for color filters according to claim 1 or 2, wherein the color material further comprises a yellow color material.

5. 3. The photosensitive color resin composition for color filters according to claim 1, wherein the coloring material further comprises a green coloring material different from the zinc phthalocyanine fluoride pigment.

6. The photosensitive colored resin composition for color filters according to claim 1 or 2, wherein the color material further comprises a blue color material.

7. 3. The photosensitive colored resin composition for color filters according to claim 1, wherein the water content is 2.0 mass % or less.

8. 3. The photosensitive colored resin composition for color filters according to claim 1, wherein the photoinitiator comprises an oxime ester-based photoinitiator having a diphenyl sulfide skeleton or a fluorene skeleton.

9. The photosensitive colored resin composition for color filters according to claim 1 or 2, further comprising, as a dispersant, a copolymer having a constitutional unit represented by the following general formula (I) having an amine value of 50 mg KOH / g or more and 110 mg KOH / g or less. 【Chemistry 3】 (In general formula (I), R １ is a hydrogen atom or a methyl group, A is a divalent linking group, R ２ and R ３ each independently represents a hydrogen atom or a hydrocarbon group which may contain a heteroatom; R ２ and R ３ may be bonded to each other to form a ring structure.)

10. 3. The photosensitive colored resin composition for color filters according to claim 1, wherein the photoinitiator comprises an oxime ester-based initiator and further comprises a thiol-based sensitizer.

11. A color filter comprising at least a substrate and colored layers provided on the substrate, wherein at least one of the colored layers is a cured product of the photosensitive colored resin composition according to claim 1 or 2.

12. A display device comprising the color filter according to claim 11.

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