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

Abstract

The present invention relates to a photosensitive colored resin composition for a color filter, comprising a colorant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a solvent, the colorant comprising a zinc phthalocyanine pigment, the zinc phthalocyanine pigment having a specific surface area in a powder X-ray diffraction spectrum using CuK [alpha] rays independently of the colorant, and having a specific surface area in the powder X-ray diffraction spectrum using CuK [alpha] rays, and a specific surface area in the powder X-ray diffraction spectrum using CuK [alpha] rays independently of the colorant. At least one diffraction peak is present in the range of a diffraction angle (2 [theta]) of 3.00-7.00 DEG.

Description

Technical Field

[0001] This invention relates to a photosensitive coloring resin composition for color filters, a color filter, and a display device. Background Technology

[0002] In recent years, with the development of personal computers, especially portable personal computers, the demand for LCD monitors has been increasing. The penetration rate of mobile displays (mobile phones, smartphones, tablet PCs) is also constantly rising, and the LCD market is expanding rapidly. Organic light-emitting diode (OLED) displays, which offer high visibility due to their self-emissive nature, are also attracting considerable attention as next-generation image display devices.

[0003] Color filters are used in these liquid crystal display devices and organic light-emitting diode (OLED) display devices. For example, in the formation of a color image in a liquid crystal display device, light passing through the color filter directly colors the individual pixels that make up the color filter, and these colors of light are combined to form a color image. As the light source, in addition to conventional cold cathode fluorescent lamps (CCFLs), sometimes white-emitting organic light-emitting elements (OLEDs) and white-emitting inorganic light-emitting elements (INEIs) are also used. In OLED display devices, color filters are used for color adjustment, etc.

[0004] Here, the color filter typically has: a substrate; a color layer formed on the substrate and containing color patterns of the three primary colors of red, green and blue; and a light-shielding portion formed on the substrate in such a way as to divide the color patterns.

[0005] One method for forming the colored layer in a color filter involves, for example, adding an alkali-soluble resin, a photopolymerizable compound, and a photoinitiator to a color material dispersion prepared by dispersing a color material using a dispersant or the like, to form a photosensitive colored resin composition. This photosensitive colored resin composition is then coated onto a glass substrate and dried. The substrate is then exposed to light using a photomask and developed to form a colored pattern. Heating is then applied to fix the pattern and form the colored layer. These processes are repeated for various colors to form a color filter.

[0006] As colorants, pigments are typically used from the perspectives of heat resistance and lightfastness. However, pigments are increasingly unable to meet market demands, especially for high brightness. Therefore, dyes that are soluble in solvents are being extensively researched. Dyes excel in improving the hue and brightness of displayed images due to their inherent color purity and hue vibrancy. On the other hand, dyes are generally considered to have poor heat and solvent resistance, and they are also prone to precipitating foreign matter in the resulting colored layer, thus hindering their practical application. For green coloring layers, the industry is researching the use of specific phthalocyanine dyes (see, for example, Patent Documents 1-2).

[0007] Existing technical documents

[0008] Patent documents

[0009] Patent Document 1: Japanese Patent Application Publication No. 2020-42263

[0010] Patent Document 2: International Publication No. 2020 / 171060 Summary of the Invention

[0011] The problem that the invention aims to solve

[0012] As described in Patent Documents 1-2 above, zinc phthalocyanine halide dyes have good solvent solubility and are therefore used in coloring resin compositions. However, if a coloring resin composition containing zinc phthalocyanine halide dyes dissolved in a solvent is used to form the green coloring layer of a color filter, the zinc phthalocyanine halide dyes easily migrate to the red and blue coloring layers on the substrate, resulting in a decrease in the brightness of the red and blue coloring layers. Even if the brightness of the green coloring layer is increased by using zinc phthalocyanine halide dyes, if the brightness of the red and blue coloring layers decreases, the white brightness of the color filter obtained using the red, green, and blue coloring layers will also decrease.

[0013] It should be noted that, regarding the zinc phthalocyanine halide dye in Patent Document 2, the following is stated: after the zinc phthalocyanine halide dye is heated to form a coating, it exhibits a maximum peak in the X-ray diffraction spectrum within the diffraction angle (2θ) range of 2 to 5°. However, regarding the zinc phthalocyanine halide dye itself used in Patent Document 2, as shown in the comparative example below, in the powder X-ray diffraction spectrum of the dye alone at 25°C before heating, it does not exhibit a diffraction peak within the diffraction angle 2θ range of 2° to 60°.

[0014] The present invention was made in view of the above-mentioned circumstances, and its object is to provide a photosensitive coloring resin composition for color filters capable of forming a color layer that suppresses brightness reduction caused by migration and increases brightness. Furthermore, the present invention aims to provide a color filter and display device formed using this photosensitive coloring resin composition.

[0015] Methods for solving problems

[0016] That is, the present invention relates to the following [1] to [8].

[0017] [1] A photosensitive coloring resin composition for color filters, comprising a colorant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a solvent.

[0018] The aforementioned colorant includes zinc phthalocyanine pigment, which has at least one diffraction peak in the range of 3.00° to 7.00° in the powder X-ray diffraction spectrum of the colorant using CuKα rays alone.

[0019] [2] The photosensitive coloring resin composition for color filters as described in [1] above, wherein the zinc phthalocyanine pigment is the zinc phthalocyanine pigment represented by the following general formula (1).

[0020] [Chemical Formula 1]

[0021]

[0022] (In general formula (1), R) A1 R A2 R A3 R A4 R A5 R A6 R A7 and R A8 Each of these can be independently substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted aralkyl, or substituted or unsubstituted heteroaryl.

[0023] [3] The photosensitive coloring resin composition for color filters as described in [1] or [2] above, wherein the zinc phthalocyanine pigment is the zinc phthalocyanine pigment represented by the following formula (1-1).

[0024] [Chemical Formula 2]

[0025]

[0026] [4] The photosensitive coloring resin composition for a color filter as described in any of [1] to [3] above, wherein the color material further comprises a yellow color material.

[0027] [5] The photosensitive coloring resin composition for a color filter as described in any of [1] to [4] above, wherein the color material further comprises a green color material different from the zinc phthalocyanine pigment described above.

[0028] [6] The photosensitive coloring resin composition for a color filter as described in any of [1] to [5] above, wherein the color material further comprises a blue color material.

[0029] [7] A color filter having at least a substrate and a coloring layer disposed on the substrate, wherein at least one of the coloring layers is a cured product of the photosensitive coloring resin composition described in any one of [1] to [6] above.

[0030] [8] A display device having a color filter as described above [7].

[0031] The effects of the invention

[0032] According to the present invention, a photosensitive coloring resin composition for a color filter can be provided, which can form a coloring layer in which brightness reduction caused by migration is suppressed and brightness is increased. Furthermore, according to the present invention, a color filter and a display device formed using the photosensitive coloring resin composition can be provided.

[0033] The coloring layer of the cured product of the photosensitive coloring resin composition for color filters of the present invention has high brightness and can suppress the decrease in brightness of other coloring layers caused by migration, thereby improving the white brightness of the color filter. Attached Figure Description

[0034] Figure 1 This is a schematic diagram illustrating an example of the color filter of the present invention.

[0035] Figure 2 This is a schematic diagram illustrating an example of the liquid crystal display device of the present invention.

[0036] Figure 3 This is a schematic diagram illustrating an example of the organic light-emitting display device of the present invention. Detailed Implementation

[0037] The photosensitive coloring resin composition, color filter, and display device of the present invention will be described in detail below.

[0038] It should be noted that in this invention, light includes electromagnetic waves with wavelengths in both the visible and non-visible regions, and further includes radiation, such as microwaves and electron beams. Specifically, it refers to electromagnetic waves with wavelengths below 5 μm and electron beams.

[0039] In this invention, (meth)acryloyl group represents either acryloyl group or methacryloyl group, (meth)acrylic acid group represents either acrylic acid group or methacrylic acid group, and (meth)acrylate group represents either acrylate group or methacrylate group.

[0040] In addition, in this specification, the "~" indicating a numerical range is used to mean that the values ​​before and after it are included as the lower limit and upper limit.

[0041] I. Photosensitive coloring resin composition for color filters

[0042] The photosensitive coloring resin composition for color filters of the present invention is characterized in that it contains a colorant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a solvent.

[0043] The aforementioned colorant includes zinc phthalocyanine pigment, which has at least one diffraction peak in the range of 3.00° to 7.00° in the powder X-ray diffraction spectrum of the colorant using CuKα rays alone.

[0044] By including the photosensitive coloring resin composition for color filters of the present invention with a solvent and a zinc phthalocyanine pigment, it is possible to form a coloring layer in which the decrease in brightness caused by migration is suppressed and the brightness is increased. The zinc phthalocyanine pigment has at least one diffraction peak in the powder X-ray diffraction spectrum of the color material alone using CuKα rays before heating, in the range of diffraction angle (2θ) of 3.00° to 7.00°.

[0045] The photosensitive coloring resin composition for color filters of the present invention contains, in the form of particles, a zinc phthalocyanine pigment with specific crystallinity within the colorant itself in a solvent before forming a coating film by heating. Compared to molecular dyes, this zinc phthalocyanine pigment with specific crystallinity consists of larger particles and is a crystal containing molecules. Therefore, when manufacturing a color filter, it is less likely to penetrate into the resin of other color layers when the photosensitive coloring resin composition is coated onto them. In addition, the number of contact points where interactions occur with the various hydrophobic substituents contained in the resin and dispersant of other color layers is reduced. Therefore, with respect to the photosensitive coloring resin composition for color filters of the present invention, it is believed that migration of dye to other color layers is suppressed during the formation of the color filter.

[0046] Furthermore, it is believed that the zinc phthalocyanine pigment used in this invention exhibits at least one diffraction peak in the range of 3.00° to 7.00° in the powder X-ray diffraction spectrum using CuKα rays at 25°C before heating, thus possessing a different crystallinity than conventional pigments. If it is an aggregate (crystal structure) of this fluorinated zinc phthalocyanine, the peak value of the transmitted light undergoes a long wavelength shift, increasing the proportion of the peak wavelength of the color matching function y(λ) in the RGB color system, thereby improving brightness. Additionally, it is speculated that if it is an aggregate (crystal structure) of the zinc phthalocyanine pigment used in this invention, it is less prone to loss of transmitted light due to incident light scattering caused by pigmentation, further enhancing brightness.

[0047] The coloring layer of the cured product of the photosensitive coloring resin composition for color filters of the present invention has high brightness and can suppress the decrease in brightness of other coloring layers caused by migration, thereby improving the white brightness of the color filter.

[0048] According to the coloring layer of the cured product of the photosensitive coloring resin composition for color filters of the present invention, since the white brightness of the color filter can be improved, the required brightness can be obtained in the state of reducing the backlight brightness output setting of the display device, thereby suppressing the power consumption of the display.

[0049] The photosensitive coloring resin composition for color filters of the present invention contains colorant, alkali-soluble resin, photopolymerizable compound, photoinitiator and solvent, and may also contain other components within the range that does not impair the effects of the present invention.

[0050] Hereinafter, each component of the photosensitive coloring resin composition for color filters of the present invention will be described in detail.

[0051] [color material]

[0052] In the photosensitive coloring resin composition for color filters of the present invention, the color material comprises zinc phthalocyanine pigment, which has at least one diffraction peak in the powder X-ray diffraction spectrum of the color material alone using CuKα rays, in the range of diffraction angle (2θ) of 3.00° to 7.00° (hereinafter, the zinc phthalocyanine pigment having the specific diffraction peak is sometimes referred to as "zinc phthalocyanine pigment (P1)").

[0053] The powder X-ray diffraction spectrum of the color material used in this invention was obtained by measuring the diffraction angle (2θ) in the range of 2.00° to 60.00° by passing the color material alone at 25°C through an X-ray diffraction device using CuKα rays, with the θ step set to 0.01°.

[0054] The presence or absence of diffraction peaks 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, peaks with an intensity greater than 1 / 4 Z are identified as diffraction peaks. Then, the presence of at least one diffraction peak in the diffraction angle (2θ) range of 3.00° to 7.00° is used for further determination.

[0055] It should be noted that the background was removed using the Sonnevelt-Visser method. The peak width threshold was set to 0.10, and the intensity threshold to 0.01. Here, the term "background" does not refer to the diffraction peaks originating from crystallinity or their tails, but rather to the superposition of factors such as Compton scattering. The specific method for measuring the powder X-ray diffraction spectra of the colorant used in this invention is the same as in the examples.

[0056] From the perspective of forming a coloring layer that suppresses the decrease in brightness caused by migration and increases the brightness, the aforementioned zinc phthalocyanine pigment (P1) may be one that has at least one diffraction peak in the powder X-ray diffraction spectrum in the range of diffraction angle (2θ) of 4.00° to 7.00°, or one that has at least one diffraction peak in the range of more than 5.00° and less than 7.00°.

[0057] Generally, dyes refer to colorants that are soluble in solvents and are used in this way, while pigments refer to colorants that are insoluble in solvents.

[0058] In this invention, the solubility of the above-mentioned zinc phthalocyanine pigment (P1) relative to acetone at 25°C may be less than 0.1% by mass, less than 0.05% by mass, or less than 0.01% by mass.

[0059] The aforementioned zinc phthalocyanine pigment (P1) is not particularly limited, as long as it has at least one diffraction peak in the powder X-ray diffraction spectrum with a diffraction angle (2θ) of 3.00° to 7.00°. However, from the perspective of being able to form a coloring layer that suppresses the decrease in brightness caused by migration and increases the brightness, it can be a fluorinated zinc phthalocyanine pigment.

[0060] The zinc phthalocyanine pigment (P1) mentioned above is not particularly limited, as long as it has at least one diffraction peak in the powder X-ray diffraction spectrum with a diffraction angle (2θ) of 3.00° to 7.00°. However, from the perspective of being able to form a coloring layer that suppresses the decrease in brightness caused by migration and increases the brightness, it can be the zinc phthalocyanine pigment represented by the following general formula (1).

[0061] [Chemical Formula 3]

[0062]

[0063] (In general formula (1), R) A1 R A2 R A3 R A4 R A5 R A6 R A7 and R A8 Each of these can be independently substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted aralkyl, or substituted or unsubstituted heteroaryl.

[0064] As R A1 ~R A8The substituted or unsubstituted aryl group, preferably an aryl group having 6 to 18 carbon atoms in total, more preferably an aryl group having 6 to 14 carbon atoms in total. As the substituent of the substituted aryl group, for example, the following substituent S can be cited. Here, when the substituent contains carbon atoms, the total carbon number of the aryl group refers to the total number of carbon atoms including the carbon atoms of the substituent.

[0065] As the unsubstituted aryl group (R a ), for example, an aryl group having 6 to 18 carbon atoms can be cited, preferably an aryl group having 6 to 14 carbon atoms. As the unsubstituted aryl group, for example, phenyl, naphthyl, biphenyl, fluorenyl, anthryl, etc. can be cited. As the aryl group, it can be an aryl group having 6 to 10 carbon atoms or a phenyl group.

[0066] As R A1 ~R A8 The substituted or unsubstituted heteroaryl group in, preferably a heteroaryl group having 2 to 12 carbon atoms in total containing oxygen atom, nitrogen atom, sulfur atom, etc. as heteroatoms. As the substituent of the substituted heteroaryl group, for example, the following substituent S can be cited. Here, when the substituent contains carbon atoms, the total carbon number of the heteroaryl group refers to the total number of carbon atoms including the carbon atoms of the substituent.

[0067] As R A1 ~R A8 The unsubstituted heteroaryl group (R b ) in, for example, can be cited: groups such as furan ring, thiophene ring, pyrrole ring, pyridine ring, 1,3-oxazole ring, isoxazole ring, 1,3-thiazole ring, isothiazole ring, imidazole ring, pyrazole ring, furazan ring, pyrazine ring, pyrimidine ring, pyridazine ring, carbazole ring, acridine ring, etc. having 1 free valence (Japanese: 遊離原子価). As the heteroaryl group, it can be a heteroaryl group having 5 to 6 ring-forming atoms.

[0068] As R A1 ~R A8 The substituted or unsubstituted aralkyl group in, preferably an aralkyl group having 7 to 19 carbon atoms in total, more preferably an aralkyl group having 7 to 15 carbon atoms in total. As the substituent of the substituted aralkyl group, for example, the following substituent S can be cited. Here, when the substituent contains carbon atoms, the total carbon number of the aralkyl group refers to the total number of carbon atoms including the carbon atoms of the substituent.

[0069] As R A1 ~R A8 The unsubstituted aralkyl group (R L -R a ), can be cited: the above unsubstituted aryl group (R aThe structure is formed by substituting an alkyl group. The alkyl group can be, for example, a straight-chain, branched, or cyclic alkyl group having 1 to 6 carbon atoms. Examples of straight-chain or branched alkyl groups include: methyl, ethyl, straight-chain or branched propyl, straight-chain or branched butyl, straight-chain or branched pentyl, straight-chain or branched hexyl, etc. Examples of cyclic alkyl groups include cyclopentyl, cyclohexyl, etc.

[0070] As an alkyl group, it can be an alkyl group with 1 to 3 carbon atoms.

[0071] Examples of unsubstituted aralkyl groups include benzyl, phenethyl, naphthylmethyl, etc.

[0072] As R A1 ~R A8 The substituted or unsubstituted heteroaryl group is preferably a heteroaryl group with a total carbon number of 3 to 13. Examples of substituents in the substituted heteroaryl group include the substituent S described below. Here, when the substituent contains a carbon atom, the total carbon number of the heteroaryl group refers to the total number of carbons including the carbon number of the substituent.

[0073] As R A1 ~R A8 Unsubstituted heteroaryl groups (R) L -R b Examples include the aforementioned unsubstituted heteroaryl groups (R...). b The structure is formed by replacing alkyl groups. As an alkyl group, it can be combined with the above-mentioned unsubstituted aralkyl group (R). L -R a The same applies as described in ().

[0074] Examples of substituents S that may be present in the aforementioned aryl, heteroaryl, aralkyl, or heteroaryl groups include: halogen atoms, alkyl groups, cycloalkyl groups, alkenyl groups, cyano groups, hydroxyl groups, nitro groups, amino groups, alkylamino groups, alkoxy groups, aryloxy groups, heteroaryloxy groups, acylamino groups, arylamino groups, ureyl groups, alkylthio groups, arylthio groups, heteroarylthio groups, alkoxycarbonylamino groups, sulfonamide groups, carbamoyl groups, alkoxycarbonyl groups, acyloxy groups, carbamoyloxy groups, silyloxy groups, aryloxycarbonyl groups, heteroaryloxycarbonyl groups, aryloxycarbonylamino groups, arylalkoxycarbonyl groups, arylalkoxycarbonylamino groups, imide groups, phosphoryl groups, acyl groups, carboxyl groups, sulfonyl groups, etc. Each of these groups may further have substituents.

[0075] As for the substituent S, from the perspective of easily having at least one diffraction peak in the diffraction angle (2θ) range of 3.00° to 7.00°, it is preferable that it does not have substituents that improve solvent solubility, and preferably does not contain an alkoxycarbonyl group (-COOR). c R here c (It is an alkyl group).

[0076] Alternatively, the substituent S may not include alkoxycarbonylalkyl, alkoxycarbonylalkoxy, alkylcarbonyl, alkoxyalkyl, or cyanoalkyl.

[0077] As a substituent S, from the perspective of readily having at least one diffraction peak in the diffraction angle (2θ) range of 3.00° to 7.00°, it can be at least one substituent S1 selected from halogen atoms, alkyl, cycloalkyl, alkenyl, cyano, hydroxyl, nitro, aryloxy, heteroaryloxy, arylamino, arylthio, heteroarylthio, aryloxycarbonyl, heteroaryloxycarbonyl, arylcarbonyl, heteroarylcarbonyl, aryloxycarbonylamino, arylalkoxycarbonyl, and arylalkoxycarbonylamino; it can also be at least one substituent S2 selected from alkyl, aryloxy, heteroaryloxy, aryloxycarbonyl, and heteroaryloxycarbonyl; or it can be at least one substituent S3 selected from alkyl and aryloxycarbonyl. The alkyl and aryl groups in these groups may further have substituent S.

[0078] The alkyl group contained in the substituent may have 1 to 4 carbons, or 1 to 3 carbons, or 1 or 2 carbons.

[0079] The alkyl group contained in the substituent may also be an unsubstituted alkyl group.

[0080] R A1 R A2 R A3 R A4 R A5 R A6 R A7 and R A8 They can be the same or different from each other. Starting from the aspect that they are likely to have at least one diffraction peak in the range of diffraction angle (2θ) of 3.00° to 7.00°, R... A1 R A2 R A3 R A4 R A5 R A6 R A7 and R A8 In the middle, R is preferred. A1 R A3 R A5 and R A7 Same and R A2 R A4 R A6 and R A8 The same, more preferably R A1 R A2 R A3 R A4 R A5 R A6 R A7 and RA8 All are the same.

[0081] Starting from the aspect that it is easy to have at least one diffraction peak in the range of diffraction angle (2θ) of 3.00° to 7.00°, R A1 R A2 R A3 R A4 R A5 R A6 R A7 and R A8 Preferably, each group is independently represented by the following general formula (2).

[0082] [Chemical Formula 4]

[0083]

[0084] (In equation (2), R) d1 R d2 R d3 R d4 and R d5 Each symbol represents a hydrogen atom or a monovalent substituent independently. * indicates the position where it bonds to the oxygen atom in formula (1).

[0085] R d1 R d2 R d3 R d4 and R d5 The monovalent substituent can be the same as the substituent S mentioned above, but from the perspective of easily having at least one diffraction peak in the range of diffraction angle (2θ) of 3.00° to 7.00°, the substituent S1 is preferred, but the substituent S2 or S3 can also be used.

[0086] Among them, R d1 R d2 R d3 R d4 and R d5 The monovalent substituent can be an unsubstituted alkyl group selected from carbons 1 to 6, and an aryloxycarbonyl group (-COOR). e R here e It is at least one of substituted or unsubstituted aryl groups having a total carbon number of 6 to 12, and may also be an unsubstituted alkyl group having a carbon number of 1 to 3, and an aryloxycarbonyl group (-COOR). e R here e It is at least one of substituted or unsubstituted aryl groups having a total carbon number of 6 to 12, and may also be an unsubstituted alkyl group having a carbon number of 1 to 2, and an aryloxycarbonyl group (-COOR). e R here eIt is at least one of substituted or unsubstituted aryl groups having a total carbon number of 6 to 12. The substituent for the substituted aryl group may be the substituent S mentioned above, or it may be a halogen atom, alkyl, cycloalkyl, alkenyl, cyano, hydroxyl, nitro, amino, alkylamino, alkoxy, amide, alkoxycarbonylamino, sulfonamide, alkoxycarbonyl, acyloxy, acyl, carboxyl, or sulfonyl.

[0087] From the perspective of easily having at least one diffraction peak in the range of diffraction angle (2θ) of 3.00° to 7.00°, R is preferred. d1 R d2 R d3 R d4 and R d5 One or two of them are monovalent substituents, and the remaining four or three are hydrogen atoms, preferably R. d1 R d2 R d3 R d4 and R d5 One of them is a monovalent substituent and the remaining four are hydrogen atoms.

[0088] From the perspective of easily having at least one diffraction peak in the range of diffraction angle (2θ) of 3.00° to 7.00°, R is preferred. d1 R d2 R d3 R d4 and R d5 In the middle, R d2 R d3 and R d4 One or two of them are monovalent substituents, and the remaining four or three are hydrogen atoms, preferably R. d3 It is a monovalent substituent, and R d1 R d2 R d4 and R d5 It is a hydrogen atom.

[0089] As a preferred example of the group represented by the above formula (2), examples can be given of the groups represented by each of the following formulas (2-1) to (2-7), but are not limited thereto.

[0090] [Chemical Formula 5]

[0091]

[0092] (In equations (2-1) to (2-7), * indicates the position where it bonds with the oxygen atom in equation (1).)

[0093] As preferred examples of the above-mentioned zinc phthalocyanine pigment (P1), compounds represented by each of the following formulas (1-1) to (1-3) can be cited, but are not limited thereto.

[0094] [Chemical Formula 6]

[0095]

[0096] [Chemical Formula 7]

[0097]

[0098] As a method for manufacturing the aforementioned zinc phthalocyanine pigment (P1), conventionally known methods can be appropriately selected. For example, a method in which a cyclization reaction is carried out between a phthalonitrile compound and a metal salt in a molten state or in an organic solvent is preferred, as described in Japanese Patent Application Publication Nos. 2005-298491, 2014-43556, and 2020-42263. Regarding the phthalonitrile compound used in the starting material, conventionally known methods can be appropriately selected for synthesis, or commercially available products can be used.

[0099] In this invention, in addition to the zinc phthalocyanine pigment (P1) mentioned above, the colorant may also contain other colorants.

[0100] Other colorants are not particularly limited, as long as the desired color development can be achieved. Various organic pigments, inorganic pigments, dyes, and dye salts can be used alone or in mixtures of two or more. Among them, organic pigments have higher color development, higher heat resistance, and suppressed migration, so they are preferred. As organic pigments, examples include compounds classified as pigments in the Color Index (CI; published by The Society of Dyers and Colourists). Specifically, those marked with a Color Index (CI) number can be listed below.

[0101] In this invention, from the perspective of color adjustment, the color material may further include yellow color material.

[0102] Examples of yellow pigments include: CI Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 55, 60, 61, 65, 71, 73, 74, 81, 83, 93, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 116, 117, 119, 120, 126, 127. Yellow pigments, including 128, 129, 138, 139, 150, 151, 152, 153, 154, 155, 156, 166, 168, 175, 185, 231, and their derivatives; coumarin dyes; cyanine dyes; quinoline dyes; methylene dyes; azo dyes; methyl alkaloid dyes; quinoline yellow dyes; and salt compounds of these yellow dyes.

[0103] It should be noted that the colorant can be any of pigments, dyes, or salt compounds of dyes, but from the perspective of inhibiting migration, pigments are preferred among the salt compounds of pigments or dyes.

[0104] Among yellow colorants, quinoline yellow colorants are preferred due to their good heat and light resistance and high transmittance. Furthermore, quinoline yellow colorants are also preferred for their hue being suitable for color filter applications.

[0105] Quinoline yellow pigments are pigments synthesized by condensation of quinoline derivatives such as quinazonium with phthalic anhydride derivatives or naphthalic anhydride derivatives.

[0106] Quinoline yellow pigments, such as CI Pigment Yellow 138, are examples of quinoline yellow pigments.

[0107] Examples of quinoline yellow dyes include CI Disperse Yellow 54, 64, 67, 134, 149, 160, CI Solvent Yellow 114, 157, etc.

[0108] In this invention, from the perspective of color adjustment, the color material may further include a green color material that is different from the above-mentioned zinc phthalocyanine pigment.

[0109] Examples of green pigments that differ from the aforementioned zinc phthalocyanine pigments include: 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, 63, etc.; squaric acid, triarylmethane, anthraquinone, coumarin, anthocyanin, or azo dyes, etc.; and salt compounds of these green dyes.

[0110] From the perspective of ease of color adjustment, phthalocyanine green pigment is preferred as an alternative green colorant to the aforementioned halogenated phthalocyanine compounds.

[0111] Examples of phthalocyanine green pigments include CI pigment green 7, 36, 58, 59, 62, and 63. From the perspective of ease of brightness adjustment, CI pigment green 7, 58, 59, 62, or 63 is preferred, CI pigment green 58, 59, 62, or 63 is more preferred, and CI pigment green 59 is even more preferred.

[0112] In this invention, from the perspective of color adjustment, the color material may further include a blue color material.

[0113] Examples of blue pigments include CI pigment blue 15, 15:3, 15:4, 15:6, and 60.

[0114] In the photosensitive coloring resin composition of the present invention, the content ratio of the above-mentioned zinc phthalocyanine pigment (P1) relative to the total color material is not particularly limited, and can be appropriately adjusted according to the desired color. It can be 100% by mass relative to the total color material containing the above-mentioned zinc phthalocyanine pigment (P1). When the photosensitive coloring resin composition for color filters of the present invention contains other color materials, from the perspective of adjusting the desired color, the content of the above-mentioned zinc phthalocyanine pigment (P1) relative to the total color material containing the above-mentioned zinc phthalocyanine pigment (P1) can be 30% to 95% by mass, 40% to 85% by mass, or 50% to 80% by mass.

[0115] When the photosensitive coloring resin composition of the present invention contains a yellow colorant, the yellow colorant may be selected appropriately, and one type may be used alone or two or more types may be used in combination.

[0116] In the photosensitive coloring resin composition of the present invention, the proportion of yellow pigment relative to the zinc phthalocyanine pigment (P1) of the present invention can be adjusted appropriately according to the desired chromaticity, and is not particularly limited. Specifically, from the perspective of adjusting the desired chromaticity, relative to 100 parts by weight of the zinc phthalocyanine pigment (P1), the composition may contain 5 to 233 parts by weight of yellow pigment, 18 to 150 parts by weight, or 25 to 100 parts by weight.

[0117] When the photosensitive coloring resin composition of the present invention contains a green colorant different from the above-mentioned zinc phthalocyanine pigment (P1), a green colorant different from the above-mentioned zinc phthalocyanine pigment (P1) may be appropriately selected, and one type may be used alone or two or more types may be used in combination.

[0118] In the photosensitive coloring resin composition of the present invention, the proportion of a green colorant different from the aforementioned zinc phthalocyanine pigment (P1) relative to the aforementioned zinc phthalocyanine pigment (P1) can be adjusted appropriately to achieve the desired chroma, and there is no particular limitation. Specifically, from the perspective of desired chroma adjustment, brightness adjustment, and inhibition of migration, relative to 100 parts by weight of the aforementioned zinc phthalocyanine pigment (P1), the composition may contain 5 to 233 parts by weight of a green colorant different from the aforementioned zinc phthalocyanine pigment (P1), or 5 to 150 parts by weight, or 5 to 100 parts by weight.

[0119] Furthermore, when the photosensitive coloring resin composition of the present invention also contains a green colorant other than the aforementioned zinc phthalocyanine pigment (P1), the proportion of the green colorant containing the aforementioned zinc phthalocyanine pigment (P1) relative to the total colorant content can be adjusted appropriately according to the desired chromaticity, and is not particularly limited. Specifically, from the perspective of desired chromaticity and brightness adjustment, it is preferable that the composition contains 30% to 95% by mass of the green colorant containing the aforementioned zinc phthalocyanine pigment (P1) relative to the total colorant content, more preferably 50% to 80% by mass.

[0120] Furthermore, the proportion of yellow pigment relative to the green pigment containing zinc phthalocyanine (P1) can be adjusted appropriately according to the desired chromaticity and is not particularly limited. Specifically, from the perspective of adjusting the desired chromaticity and brightness, it is preferable to contain 5 to 70 parts by mass of yellow pigment relative to 100 parts by mass of green pigment containing zinc phthalocyanine (P1), and more preferably 20 to 50 parts by mass.

[0121] Furthermore, when the photosensitive coloring resin composition of the present invention contains a blue colorant, the blue colorant may be selected appropriately, and one type may be used alone or two or more types may be used in combination.

[0122] In the photosensitive coloring resin composition of the present invention, the proportion of blue pigment relative to the zinc phthalocyanine pigment (P1) of the present invention can be adjusted appropriately according to the desired chromaticity, and is not particularly limited. Specifically, from the perspective of adjusting the desired chromaticity, the composition may contain 1 to 50 parts by mass, 1 to 20 parts by mass, or 1 to 5 parts by mass of blue pigment relative to 100 parts by mass of the zinc phthalocyanine pigment (P1).

[0123] In the photosensitive coloring resin composition of the present invention, other color materials besides green and yellow color materials may be further included in the color material without impairing the effects of the present invention. The total content of green and yellow color materials containing the above-mentioned zinc phthalocyanine pigment (P1) relative to the color material as a whole may be 70% to 100% by mass, wherein it may be 80% to 100% by mass, 90% to 100% by mass, or 100% by mass.

[0124] In the photosensitive coloring resin composition of the present invention, the content of the colorant is not particularly limited. From the perspective of dispersibility and dispersion stability, the total content of the colorant relative to the total solids of the photosensitive coloring resin composition is preferably in the range of 3% to 65% by mass, more preferably 4% to 60% by mass. If it is above the lower limit, the coloring layer when the photosensitive coloring resin composition is coated to a specified film thickness (typically 1.0 μm to 5.0 μm) has sufficient color concentration. In addition, if it is below the upper limit, a coloring layer with excellent storage stability and sufficient hardness and adhesion to the substrate can be obtained. Especially when forming a coloring layer with a high colorant concentration, the total content of the colorant relative to the total solids of the photosensitive coloring resin composition is preferably in the range of 15% to 65% by mass, more preferably 25% to 60% by mass.

[0125] It should be noted that in this invention, the solid component is the component other than the solvent described below, and also includes monomers dissolved in the solvent.

[0126] [Alkali-soluble resin]

[0127] The alkali-soluble resin used in this invention is one that has acidic groups, and can be appropriately selected from alkali-soluble resins that function as adhesive resins and are soluble in the alkaline developing solution used when forming patterns.

[0128] In this invention, the so-called alkali-soluble resin can be defined as having an acid value of 40 mg KOH / g or higher.

[0129] Examples of acidic groups found in alkali-soluble resins include carboxyl groups. Examples of alkali-soluble resins containing carboxyl groups include carboxyl-containing copolymers and epoxy (meth)acrylate resins. Examples of carboxyl-containing copolymers include (meth)acrylate copolymers and styrene-(meth)acrylate copolymers, etc.

[0130] In addition, two or more of these (meth)acrylic copolymers, such as styrene-(meth)acrylic copolymers with carboxyl groups, and epoxy (meth)acrylic resins can be used in combination.

[0131] (Meth)acrylic copolymers having carboxyl groups and styrene-(meth)acrylic copolymers having carboxyl groups are, for example, (co)polymers obtained by (co)polymerizing a carboxyl-containing olefinic unsaturated monomer and other copolymerizable monomers as needed using known methods.

[0132] Examples of carboxyl-containing olefinic unsaturated monomers include: (meth)acrylic acid, vinylbenzoic acid, maleic acid, monoalkyl maleate, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, and (meth)acrylic acid dimers. Additionally, addition reactions of monomers with hydroxyl groups, such as 2-hydroxyethyl (meth)acrylic acid, with cyclic anhydrides such as maleic anhydride, phthalic anhydride, and cyclohexanedicarboxylic anhydride, can also be used; ω-carboxyl-polycaprolactone mono(meth)acrylic acid esters, etc. Furthermore, anhydride-containing monomers such as maleic anhydride, itaconic anhydride, and citraconic anhydride can be used as precursors for the carboxyl group. Among these, (meth)acrylic acid is particularly preferred from the perspectives of copolymerization, cost, solubility, and glass transition temperature.

[0133] From the perspective of excellent adhesion to the substrate, the alkali-soluble resin is preferably further characterized by having hydrocarbon rings. By having hydrocarbon rings, which are large-volume groups, shrinkage during curing is suppressed, peeling from the substrate is mitigated, and substrate adhesion is improved. Furthermore, by using an alkali-soluble resin with hydrocarbon rings, which are large-volume groups, the solvent resistance of the obtained coloring layer is improved, and this is particularly preferable from the perspective of suppressing swelling of the coloring layer.

[0134] Examples of such hydrocarbon rings include: cyclic aliphatic hydrocarbon rings that may have substituents, aromatic rings that may have substituents, and combinations thereof. Hydrocarbon rings may also have substituents such as carbonyl, carboxyl, oxycarbonyl, and amide groups.

[0135] Specific examples of hydrocarbon rings include: aliphatic hydrocarbon rings such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, norcamphene, tricyclic [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 zirconia, as well as Cardo structures (9,9-diarylfluorene).

[0136] In the case of including an aliphatic hydrocarbon ring as the hydrocarbon ring, it is preferred from the aspects of improving the heat resistance and adhesion of the colored layer, and improving the brightness of the obtained colored layer.

[0137] Furthermore, in the case of a structure containing two benzene rings bonded to a fluorene backbone (Cardo structure), it is particularly preferred from the aspects of improved curability of the coloring layer, improved solvent resistance, and especially the suppression of swelling by NMP.

[0138] Hydrocarbon rings can be contained in the form of monovalent groups or in the form of divalent or higher groups.

[0139] From the perspective of easily adjusting the amount of each structural unit and increasing the amount of structural units with the above-mentioned hydrocarbon rings so as to easily improve the function of the structural unit, it is preferable to use a (meth)acrylic copolymer in the alkali-soluble resin used in the present invention, which contains structural units with the above-mentioned hydrocarbon rings in addition to structural units with carboxyl groups.

[0140] (Meth)acrylic copolymers containing structural units with carboxyl groups and the aforementioned hydrocarbon rings can be prepared by using olefinic unsaturated monomers with hydrocarbon rings as the aforementioned "other copolymerizable monomers".

[0141] As for the alkali-soluble resins containing hydrocarbon rings, preferably used are cyclohexyl methacrylate, dicyclopentyl methacrylate, adamantyl methacrylate, isobornyl methacrylate, phenoxyethyl methacrylate, benzyl methacrylate, styrene, and monomers having the aforementioned Cardo structure and alkene unsaturated groups. From the perspective of having a greater effect in suppressing the precipitation of foreign matter from the colorant even after heat treatment, preferably are cyclohexyl methacrylate, dicyclopentyl methacrylate, adamantyl methacrylate, benzyl methacrylate, styrene, and monomers having the aforementioned Cardo structure and alkene unsaturated groups.

[0142] Furthermore, the alkali-soluble resin used in this invention preferably has olefinically unsaturated bonds in its side chains. When olefinically unsaturated bonds are present, during the curing process of the resin composition in the manufacture of the color filter, the alkali-soluble resin can form cross-links with each other, or with polyfunctional monomers, etc. This further improves the strength of the cured film, enhances its development resistance, suppresses thermal shrinkage, and improves its adhesion to the substrate.

[0143] It should be noted that olefinic unsaturated groups refer to groups containing carbon-carbon double bonds that can undergo free radical polymerization, such as (meth)acryloyl, vinyl, allyl, etc.

[0144] The method for introducing olefin unsaturated bonds into alkali-soluble resins can be appropriately selected from conventionally known methods. Examples include: introducing olefin unsaturated bonds into the side chains of compounds containing both epoxy groups and olefin unsaturated bonds within the molecule, such as glycidyl (meth)acrylate, by adding carboxyl groups to the alkali-soluble resin; or introducing hydroxyl structural units into copolymers beforehand, allowing them to add to compounds containing both isocyanate groups and olefin unsaturated bonds within the molecule, thus introducing olefin unsaturated bonds into the side chains.

[0145] The alkali-soluble resin used in this invention may further contain other structural units such as methyl methacrylate and ethyl methacrylate, which have ester groups. These ester-group structural units not only function as components that suppress the alkali solubility of the photosensitive coloring resin composition, but also as components that enhance the solubility in solvents, thereby improving solvent resolubility.

[0146] The alkali-soluble resin used in this invention is preferably a (meth)acrylic copolymer or a styrene-(meth)acrylic copolymer containing structural units having carboxyl groups and structural units having hydrocarbon rings. More preferably, it is a (meth)acrylic copolymer or a styrene-(meth)acrylic copolymer containing structural units having carboxyl groups, structural units having hydrocarbon rings, and structural units having olefin unsaturated bonds.

[0147] The alkali-soluble resin used in this invention can achieve the desired properties by appropriately adjusting the amount of monomers derived from each structural unit.

[0148] The copolymerization ratio of carboxyl-containing olefinic unsaturated monomers in carboxyl-containing copolymers is typically 5% to 50% by mass, preferably 10% to 40% by mass. In this case, if the copolymerization ratio of carboxyl-containing olefinic unsaturated monomers is 5% by mass or more, the decrease in the solubility of the obtained coating film in alkaline developer can be suppressed, and pattern formation is easier. Furthermore, if the copolymerization ratio is 50% by mass or less, pattern defects and film roughness on the pattern surface are less likely to occur during development with alkaline developer. It should be noted that the above copolymerization ratios are values ​​calculated based on the amount of each monomer added.

[0149] Furthermore, in (meth)acrylic resins such as (meth)acrylic copolymers and styrene-(meth)acrylic copolymers, which are more preferably used as alkali-soluble resins and contain structural units having olefinic unsaturated bonds, the amount of monomers having both epoxy groups and olefinic unsaturated bonds added is preferably 10% to 95% by mass, more preferably 15% to 90% by mass, relative to 100% by mass of the amount of olefinic unsaturated monomer containing carboxyl groups added.

[0150] The preferred weight-average molecular weight (Mw) of the carboxyl-containing copolymer is in the range of 1,000 to 50,000, more preferably 3,000 to 20,000. If the weight-average molecular weight of the carboxyl-containing copolymer is 1,000 or more, sufficient curability of the coating film can be obtained; otherwise, if it is 50,000 or less, it is easy to form patterns when developing with an alkaline developer.

[0151] It should be noted that the weight-average molecular weight (Mw) in this invention is determined by gel permeation chromatography (GPC) in the form of a standard polystyrene conversion value.

[0152] Specific examples of (meth)acrylic acid copolymers having carboxyl groups include those described in Japanese Patent Application Publication No. 2013-029832.

[0153] There are no particular limitations on the type of epoxy (meth)acrylate resin containing carboxyl groups. For example, epoxy (meth)acrylate compounds obtained by reacting an epoxy compound with a reactant of a monocarboxylic acid containing an unsaturated group and an anhydride are more suitable. The epoxy compound, the monocarboxylic acid containing an unsaturated group, and the anhydride can be appropriately selected from those known to the public.

[0154] As an epoxy (meth)acrylate resin containing carboxyl groups, it is preferable that the molecule contains the aforementioned Cardo structure, which improves the effect of suppressing poor display, improves the curability of the coloring layer, and increases the residual film rate of the coloring layer.

[0155] From the perspective of developability (solubility) in the alkaline aqueous solution used in the developer, the acid value of the alkali-soluble resin is more preferably 40 mg KOH / g or more. From the perspective of developability (solubility) in the alkaline aqueous solution used in the developer and adhesion to the substrate, the acid value of the above-mentioned carboxyl-containing copolymer is preferably 50 mg KOH / g or more and 300 mg KOH / g or less, more preferably 60 mg KOH / g or more and 280 mg KOH / g or less, and even more preferably 70 mg KOH / g or more and 250 mg KOH / g or less.

[0156] It should be noted that, in this invention, the acid value can be determined according to JIS K 0070.

[0157] From the perspective of improving the film strength of the cured film and further suppressing the precipitation of pigments, the olefin unsaturated bond equivalent in the case where the side chain of the alkali-soluble resin has olefin unsaturated groups is preferably in the range of 100 or more and 2000 or less, and particularly preferably in the range of 140 or more and 1500 or less. If the olefin unsaturated bond equivalent is 2000 or less, the development resistance and adhesion are excellent. In addition, if it is 100 or more, the proportion of other structural units such as the structural units with carboxyl groups and the structural units with hydrocarbon rings can be relatively increased, thus the development and heat resistance are excellent. Here, the olefin unsaturated bond equivalent refers to the weight-average molecular weight of 1 mole of olefin unsaturated bond in the above-mentioned alkali-soluble resin, which is expressed by the following formula (1).

[0158] Equation (1) Equivalent amount of unsaturated olefinic bond (g / mol) = W (g) / M (mol)

[0159] (In formula (1), W represents the mass (g) of alkali-soluble resin, and M represents the number of moles (mol) of alkali-soluble resin W (g).

[0160] The equivalent of the aforementioned olefinic unsaturated bonds can be calculated, for example, by determining the number of olefinic unsaturated bonds contained in 1g of alkali-soluble resin according to the test method for iodine value described in JIS K 0070:1992.

[0161] The alkali-soluble resin used in the photosensitive coloring resin composition may be used alone or in combination with two or more types. There is no particular limitation on the content of the alkali-soluble resin, but it is preferably in the range of 5% to 60% by mass, more preferably 10% to 40% by mass, relative to the total solid content of the photosensitive coloring resin composition. If the content of the alkali-soluble resin is above the lower limit mentioned above, sufficient alkaline developability can be obtained; conversely, if the content of the alkali-soluble resin is below the upper limit mentioned above, film roughness and pattern defects can be suppressed during development.

[0162] [Photopolymerizable compounds]

[0163] The photopolymerizable compound used in the photosensitive coloring resin composition of the present invention refers to a compound having a photopolymerizable group in its molecule. There are no particular limitations on the photopolymerizable group, as long as it can be polymerized by a photoinitiator; examples include olefinic unsaturated bonds, such as vinyl, allyl, acryloyl, or methacryloyl groups. From the perspective of UV curability, acryloyl or methacryloyl groups are suitable as photopolymerizable groups.

[0164] From the perspective of curability, compounds containing two or more photopolymerizable groups per molecule are preferred, and compounds containing three or more photopolymerizable groups per molecule are more preferred.

[0165] There are no particular limitations on the photopolymerizable compound, as long as it can be polymerized by the following photoinitiators. Compounds with two or more olefinic unsaturated bonds can generally be used, and polyfunctional (meth)acrylates with two or more acryloyl or methacryloyl groups are particularly preferred.

[0166] As for such multifunctional (meth)acrylates, they can be used by appropriately selecting from those already known. Specific examples include those described in Japanese Patent Application Publication No. 2013-029832.

[0167] These photopolymerizable compounds can be used alone or in combination of two or more. Furthermore, when excellent photocurability (high sensitivity) is required for the photosensitive coloring resin composition of the present invention, the photopolymerizable compound is preferably one having three or more polymerizable olefinic unsaturated bonds (trifunctional), preferably poly(meth)acrylates of polyols with three or more tertiary components, or dicarboxylic acid modified forms of these compounds. Specifically, it is preferably trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, succinic acid modified forms of pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, succinic acid modified forms of dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc.

[0168] There is no particular limitation on the content of the aforementioned photopolymerizable compound used in the photosensitive coloring resin composition. Relative to the total solid content of the photosensitive coloring resin composition, it is preferably in the range of 5% to 60% by mass, and more preferably 10% to 40% by mass. If the content of the photopolymerizable compound is above the aforementioned lower limit, photocuring is sufficiently achieved, and the dissolution of the exposed portion during development can be suppressed. Furthermore, if the content of the photopolymerizable compound is below the aforementioned upper limit, alkaline developability is sufficient.

[0169] [Photoinitiator]

[0170] Examples of photoinitiators include: aromatic ketones, benzoin ethers, halomethyl oxadiazole compounds, α-amino ketones, biimidazoles, N,N-dimethylaminobenzophenone, halomethyl-triazine compounds, thioxanthone, etc. Specific examples of photoinitiators include: benzophenone, 4,4'-bis(diethylaminobenzophenone), 4-methoxy-4'-dimethylaminobenzophenone and other aromatic ketones; benzoin ethers such as benzoin methyl ether; benzoin such as ethylbenzoin; biimidazoles such as 2-(o-chlorophenyl)-4,5-phenylimidazolium dimer; halomethyl oxadiazole compounds such as 2-trichloromethyl-5-(p-methoxystyryl)-1,3,4-oxadiazole; and 2-(4-butoxy-naphthalene) -1-yl)-4,6-bis-trichloromethyl-triazine and other halomethyl-triazine compounds, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinoacetone, 1,2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 1-hydroxycyclohexylphenyl ketone, benzoyl, benzoylbenzoic acid, methyl benzoylbenzoate, 4-benzoyl-4'-methyl Benzoyl diphenyl sulfide, benzoyl methyl ketal, dimethyl aminobenzoate, p-dimethylaminobenzoate isoamyl ester, 2-n-butoxyethyl-4-dimethylaminobenzoate, 2-chlorothioxanone, 2,4-diethylthioxanone, 2,4-dimethylthioxanone, isopropylthioxanone, 4-benzoyl-methyl diphenyl sulfide, 1-hydroxy-cyclohexyl-phenyl ketone, 2-benzyl-2-(dimethylamino)-1-[4-(4-morpholinyl)phenyl]-1-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, etc.

[0171] Preferably, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one, 2-benzyl-2-(dimethylamino)-1-(4-morpholinophenyl)-1-butanone, 4,4'-bis(diethylamino)benzophenone, and diethylthioxanone are used. From the perspective of adjusting sensitivity, suppressing water spots, and improving development resistance, it is further preferred to combine α-aminoacetophenone-based initiators such as 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one with thioxanone-based initiators such as diethylthioxanone.

[0172] Regarding the use of α-aminoacetophenone-based initiators and thioxanthone-based initiators, the total content of these, relative to the total solids content of the photosensitive coloring resin composition, is preferably, for example, 5% to 15% by mass. If it is below the upper limit, sublimation during the manufacturing process is reduced, which is therefore preferred. If it is above the lower limit, water spots are suppressed, and development resistance is improved.

[0173] In this invention, from the perspective of improving sensitivity, the photoinitiator preferably comprises an oxime ester-based photoinitiator. Furthermore, by using an oxime ester-based photoinitiator, differences in linewidth within the plane are easily suppressed when forming fine line patterns. In addition, by using an oxime ester-based photoinitiator, there is a tendency to increase the residual film yield and improve the effect of suppressing water spot formation.

[0174] From the perspective of reducing contamination of the photosensitive coloring resin composition and the device caused by decomposition products, the oxime ester photoinitiator is preferably an oxime ester photoinitiator having an aromatic ring, more preferably an oxime ester photoinitiator having a condensed ring containing an aromatic ring, and even more preferably an oxime ester photoinitiator having a fused ring containing a benzene ring and a heterocyclic ring.

[0175] As an oxime ester photoinitiator, an appropriate selection can be made from the oxime ester photoinitiators described in 1,2-octanedione-1-[4-(phenylthio)-,2-(o-benzoyl oxime)], acetone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-,1-(o-acetyl oxime), Japanese Patent Application Publication No. 2000-80068, Japanese Patent Application Publication No. 2001-233842, Japanese Patent Publication No. 2010-527339, Japanese Patent Publication No. 2010-527338, and Japanese Patent Application Publication No. 2013-041153. Commercially available photoinitiators include Irgacure OXE-01 (with a diphenyl sulfide backbone), Adeka Arkls NCI-930, TR-PBG-3057 (with a carbazole backbone), Irgacure OXE-02, Adeka Arkls NCI-831, TR-PBG-304, TR-PBG-345 (with a fluorene backbone), and TR-PBG-365 (with a fluorene backbone). (The Irgacure series is manufactured by BASF, the Adeka Arkls series by ADEKA, and the TR series by Changzhou Qiangli Electronic New Materials Co., Ltd.) From a brightness perspective, oxime ester photoinitiators with a diphenyl sulfide or fluorene backbone are particularly preferred. Furthermore, from a high sensitivity perspective, oxime ester photoinitiators with a carbazole backbone are preferred. From the perspective of sensitivity and brightness, it is preferable to use a combination of oxime ester photoinitiators having a diphenyl sulfide skeleton and oxime ester photoinitiators having a fluorene skeleton. Furthermore, from the perspective of sensitivity and brightness, it is preferable to use a combination of oxime ester photoinitiators having a diphenyl sulfide skeleton and oxime ester photoinitiators having a carbazole skeleton.

[0176] Furthermore, from the perspective of suppressing water spots and improving sensitivity, photoinitiators with tertiary amine structures can be used in combination with oxime ester-based photoinitiators. This is because photoinitiators with tertiary amine structures have an intramolecular tertiary amine structure that acts as an oxygen quencher, thus the free radicals generated by the initiator are less likely to be deactivated by oxygen, thereby improving sensitivity. Commercially available examples of such photoinitiators with tertiary amine structures include: 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropane-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., HicureABP, manufactured by Kawaguchi Pharmaceuticals), etc.

[0177] In addition, from the perspective of adjusting sensitivity, suppressing water spots, and improving development resistance, oxime ester-based photoinitiators can be combined with thioxanthone-based initiators. From the perspective of improving brightness, residual film rate, easy sensitivity adjustment, high suppression of water spot formation, and improving development resistance, two or more oxime ester-based photoinitiators can be combined with thioxanthone-based initiators.

[0178] The content of photoinitiator in the photosensitive coloring resin composition is preferably 0.1% to 15% by mass, more preferably 1% to 10% by mass, relative to the total solid content of the composition. If the content of photoinitiator is above the lower limit, curing is sufficient; if the content of photoinitiator is below the upper limit, side reactions can be suppressed and stability over time can be maintained.

[0179] [solvent]

[0180] The solvents used in this invention are not particularly limited, as long as they are organic solvents that do not react with the components in the photosensitive coloring resin composition and can dissolve or disperse them. Solvents can be used alone or in combination of two or more.

[0181] Specific examples of solvents include: alcohol solvents such as methanol, ethanol, n-propanol, isopropanol, methoxy alcohol, and ethoxy alcohol; carbitol solvents such as methoxyethoxyethanol and ethoxyethoxyethanol; ester solvents such as ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl methoxypropionate, ethyl ethoxypropionate, ethyl lactate, methyl hydroxypropionate, ethyl hydroxypropionate, n-butyl acetate, isobutyl acetate, isobutyl butyrate, n-butyl butyrate, ethyl lactate, and cyclohexyl acetate; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and 2-heptanone; and glycol ether acetate solvents such as methoxyethyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy-3-methyl-1-butyl acetate, 3-methoxybutyl acetate, and ethoxyethyl acetate. Carbitol acetate solvents such as carbitol acetate (BCA), methoxyethoxyethyl acetate, ethoxyethoxyethyl acetate, and butyl carbitol acetate; diacetates such as propylene glycol diacetate and 1,3-butanediol diacetate; glycol ether solvents such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, and dipropylene glycol dimethyl ether; aprotic amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; lactone solvents such as γ-butyrolactone; cyclic ether solvents such as tetrahydrofuran; unsaturated hydrocarbon solvents such as benzene, toluene, xylene, and naphthalene; saturated hydrocarbon solvents such as n-heptane, n-hexane, and n-octane; and aromatic hydrocarbons such as toluene and xylene. Among these solvents, from the perspective of solubility of other components, glycol ether acetate-based solvents, carbitol acetate-based solvents, glycol ether-based solvents, and ester-based solvents are suitable. Specifically, as the solvent used in this invention, from the perspective of solubility of other components and coating adaptability, it is preferably selected from one or more 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.

[0182] Furthermore, in the solvent used in this invention, from the perspectives of colorant dispersibility, solubility of other components, and coating adaptability, the content of propylene glycol monomethyl ether acetate relative to the total amount of solvent in the photosensitive coloring resin composition can be 50% by mass or more, or 70% by mass or more, or 80% by mass or more, or 100% by mass.

[0183] The solvent used in this invention is selected from one or more 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 relative to the total amount of solvent can be 50% by mass or more, or 70% by mass or more.

[0184] In the photosensitive coloring resin composition of the present invention, the solvent content can be appropriately set within a range that allows for the precise formation of the coloring layer. Relative to the total amount of the photosensitive coloring resin composition containing the solvent, the solvent content is generally preferably in the range of 55% to 95% by mass, more preferably 65% ​​to 88% by mass. By keeping the solvent content within the above range, excellent coatability can be achieved.

[0185] Furthermore, in the photosensitive coloring resin composition of the present invention, the water content can 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 water content is within the above range, the aggregation of the colorant caused by the presence of water can be sufficiently suppressed, and the thickening and contrast reduction of the photosensitive coloring resin composition can be suppressed.

[0186] It should be noted that the water content in the photosensitive coloring resin composition was determined using a Karl Fischer titration apparatus (volume titration) at 25°C according to JIS K0113:2005.

[0187] [Add any ingredients]

[0188] In the photosensitive coloring resin composition of the present invention, various additives may be included as needed. Examples of additives include: dispersants, sensitizers, antioxidants, polymerization terminators, chain transfer agents, leveling agents, plasticizers, surfactants, defoamers, silane coupling agents, ultraviolet absorbers, adhesion promoters, etc.

[0189] Specific examples of surfactants and plasticizers include those described in Japanese Patent Application Publication No. 2013-029832.

[0190] The photosensitive coloring resin composition of the present invention may not contain pigment derivatives such as pigment derivatives containing sulfonic acid groups.

[0191] <Dispersant>

[0192] In the photosensitive coloring resin composition of the present invention, a dispersant may be further included to improve the dispersibility and stability of the colorant, in order to disperse the colorant. Preferably, a dispersant is used to disperse the zinc phthalocyanine pigment (P1) described above.

[0193] In this invention, the dispersant can be appropriately selected from conventionally known dispersants. Examples of dispersants include cationic, anionic, nonionic, amphoteric, silicone, and fluorinated surfactants. Among surfactants, polymeric dispersants are preferred from the perspective of uniform and fine dispersion.

[0194] Examples of polymeric dispersants include: (co)polymers of unsaturated carboxylic acid esters such as polyacrylates; (partial) amine salts, (partial) ammonium salts, and (partial) alkylamine salts of (co)polymers of unsaturated carboxylic acid esters such as polyacrylic acid; (co)polymers of hydroxyl-containing unsaturated carboxylic acid esters such as hydroxyl-containing polyacrylates, and their modified forms; polyurethanes; unsaturated polyamides; polysiloxanes; long-chain polyaminoamide phosphates; polyethyleneimine derivatives (amides obtained by reacting poly(lower alkylimine) with polyesters containing free carboxyl groups, and their bases); polyallylamine derivatives (reaction products obtained by reacting polyallylamine with one or more compounds selected from three compounds: polyesters having free carboxyl groups, polyamides, or cocondensates of esters and amides (polyesteramides)).

[0195] As a polymeric dispersant used in the photosensitive coloring resin composition of the present invention, it may be, for example, a polymeric dispersant containing nitrogen atoms in the main chain or side chain and having an amine value, wherein it may be a polymeric dispersant containing repeating units having a tertiary amine.

[0196] As a polymeric dispersant containing nitrogen atoms in the main chain or side chain and having an amine value, the following dispersants can be used, for example, from the perspective of the main chain skeleton not being easily thermally decomposed and having high heat resistance: polymers having structural units represented by the following general formula (I) as described in Japanese Patent Application Publication No. 2016-224447, block copolymers having structural units represented by the following general formula (I) as described in International Patent Publication No. 2016 / 104493, and at least one of salt-type block copolymers.

[0197] [Chemical Formula 8]

[0198]

[0199] (In general formula (I), R) 1 Represents a hydrogen atom or a methyl group, A represents a divalent linker, and R represents a hydrogen atom or a methyl group. 2 and R 3R represents a hydrogen atom or a hydrocarbon group that may contain heteroatoms, respectively. 2 and R 3 They can bond together to form a ring structure.

[0200] In general formula (I), A is a divalent linking group. Examples of divalent linking groups include: straight-chain, branched, or cyclic alkylene groups; straight-chain, branched, or cyclic alkylene groups having hydroxyl groups; aryl groups; -CONH- groups; -COO- groups; -NHCOO- groups; ether groups (-O- groups); thioether groups (-S- groups); and combinations thereof. It should be noted that in this invention, the bonding direction of the divalent linking group is arbitrary. That is, when the divalent linking group contains -CONH-, it can be that -CO is on the carbon atom side of the main chain and -NH is on the nitrogen atom side of the side chain, or conversely, -NH is on the carbon atom side of the main chain and -CO is on the nitrogen atom side of the side chain.

[0201] From the perspective 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.

[0202] Regarding R 2 and R 3 The hydrocarbon group in the form may contain heteroatoms, such as alkyl, aralkyl, aryl, etc.

[0203] Examples of alkyl groups include methyl, ethyl, propyl, butyl, isopropyl, tert-butyl, 2-ethylhexyl, cyclopentyl, and cyclohexyl. The number of carbon atoms in the alkyl group is preferably 1 to 18, and more preferably methyl or ethyl.

[0204] Examples of aralkyl groups include benzyl, phenethyl, naphthylmethyl, and biphenylmethyl. The number of carbon atoms in the aralkyl group is preferably 7 to 20, and more preferably 7 to 14.

[0205] Other examples of aryl groups include phenyl, biphenyl, naphthyl, tolyl, and xylyl. The number of carbon atoms in the aryl group is preferably 6 to 24, more preferably 6 to 12. It should be noted that the preferred carbon numbers mentioned above do not include the number of carbon atoms in the substituents.

[0206] A hydrocarbon group containing a heteroatom has a structure in which the carbon atom in the aforementioned hydrocarbon group is replaced by a heteroatom, or has a structure in which the hydrogen atom in the aforementioned hydrocarbon group is replaced by a substituent containing a heteroatom. Examples of heteroatoms that may be included in a hydrocarbon group include: oxygen atom, nitrogen atom, sulfur atom, silicon atom, etc.

[0207] In addition, hydrogen atoms in hydrocarbon groups can be replaced by halogen atoms such as fluorine, chlorine, and bromine.

[0208] R 2 and R 3 The ring structure formed by mutual bonding refers to R 2 and R 3 A ring structure is formed via nitrogen atoms. R 2 and R 3 The resulting ring structure may contain heteroatoms. There are no particular limitations on the ring structure; examples include pyrrolidine rings, piperidine rings, and morpholine rings.

[0209] In this invention, R is particularly preferred. 2 and R 3 Each is independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group, or an R group. 2 and R 3 They bond together to form pyrrolidine rings, piperidine rings, and morpholine rings.

[0210] Examples of monomers that derive the structural unit represented by the general formula (I) above include: dimethylaminoethyl methacrylate, dimethylaminopropyl methacrylate, diethylaminoethyl methacrylate, diethylaminopropyl methacrylate, and other (meth)acrylates containing alkyl-substituted amino groups; and dimethylaminoethyl (meth)acrylamide, dimethylaminopropyl (meth)acrylamide, and other (meth)acrylamides containing alkyl-substituted amino groups. Among these, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, and dimethylaminopropyl (meth)acrylamide are preferred from the perspective of improving dispersibility and dispersion stability.

[0211] In polymers, the structural unit represented by general formula (I) can be composed of one type or contain two or more structural units.

[0212] In addition, regarding the structural unit that functions as the adsorption site of the colorant, at least a portion of the nitrogen site of the structural unit represented by the above general formula (I) can form a salt with at least one of organic acid compounds and halogenated hydrocarbons (sometimes such copolymers are called salt copolymers).

[0213] As the aforementioned organic acid compound, compounds represented by general formula (A) and general formula (C) are preferred; as the aforementioned halogenated hydrocarbon, compounds represented by general formula (B) are preferred. That is, as at least one of the aforementioned organic acid compounds and halogenated hydrocarbons, one or more compounds selected from general formulas (A), (B) and (C) are preferably used.

[0214] [Chemical Formula 9]

[0215] Formula (A) Formula (B) Formula (C)

[0216] (In general formula (A), R) a It represents a straight-chain, branched, or cyclic alkyl group, vinyl group, phenyl or benzyl group (which may have substituents), or -OR group having 1 to 20 carbon atoms. e R e Represents a straight-chain, branched, or cyclic alkyl, vinyl, phenyl or benzyl group (which may have substituents), or (meth)acryloyl group (with 1 to 20 carbon atoms) via an alkylene group (with 1 to 4 carbon atoms). In general formula (B), R b R b' and R b'' Each of the following can independently represent a hydrogen atom, an acidic group or its ester group, a straight-chain, branched or cyclic alkyl group having 1 to 20 carbon atoms that may have substituents, a vinyl group that may have substituents, a phenyl or benzyl group that may have substituents, or -OR f R f The symbol represents a straight-chain, branched, or cyclic alkyl group having 1 to 20 carbon atoms that may have substituents, a vinyl group having substituents, a phenyl or benzyl group having substituents, or a (meth)acryloyl group via an alkylene group having 1 to 4 carbon atoms, where X represents a chlorine atom, a bromine atom, or an iodine atom. In general formula (C), R c and R d Each of the following can independently represent a hydrogen atom, a hydroxyl group, a straight-chain, branched, or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, a phenyl or benzyl group that may have substituents, or -OR e R e The R group represents a straight-chain, branched, or cyclic alkyl group, vinyl group, phenyl or benzyl group (which may have substituents), or (meth)acryloyl group (which has 1 to 20 carbon atoms) via an alkylene group (1 to 4 carbon atoms). c and R d (At least one of them contains a carbon atom).

[0217] The symbols in the above general formulas (A), (B) and (C) may be the same as those in general formulas (1), (2) and (3) of International Publication No. 2016 / 104493.

[0218] From the perspective of excellent dispersibility and dispersion stability of the colorant, the organic acid compound is preferably an acidic organophosphorus compound such as phenylphosphonic acid or phenylphosphine. Specific examples of the organic acid compound used in such a dispersant include those described in Japanese Patent Application Publication No. 2012-236882, etc.

[0219] Furthermore, from the perspective of excellent dispersibility and dispersion stability of the colorant, at least one of the above-mentioned halogenated hydrocarbons, such as allyl bromide and benzyl chloride, and halogenated aralkyl, is preferred.

[0220] In the salt-type copolymer, regarding the content of at least one selected from organic acid compounds and halogenated hydrocarbons, from the perspective of forming a salt with the terminal nitrogen site of the structural unit represented by general formula (I), the total content of at least one selected from organic acid compounds and halogenated hydrocarbons relative to the terminal nitrogen site of the structural unit represented by general formula (I) is preferably 0.01 mol or more, more preferably 0.05 mol or more, further preferably 0.1 mol or more, and particularly preferably 0.2 mol or more. If the content is at or above the lower limit, it is easy to obtain the effect of improving the dispersibility of the colorant by forming a salt. Similarly, it is preferably 1 mol or less, more preferably 0.8 mol or less, further preferably 0.7 mol or less, and particularly preferably 0.6 mol or less. If the content is at or below the upper limit, it is possible to achieve excellent development adhesion and solvent resolvability.

[0221] It should be noted that at least one of the organic acid compounds and halogenated hydrocarbons may be used alone or in combination of two or more. When two or more are combined, it is preferable that their total content is within the above-mentioned range.

[0222] Examples of methods for preparing salt-type copolymers include adding at least one of the above-mentioned organic acid compounds and halogenated hydrocarbons to a solvent in which the copolymer before salt formation is dissolved or dispersed, stirring, and then heating as needed.

[0223] It should be noted that the terminal nitrogen site of the structural unit represented by the general formula (I) of the copolymer, the salt formation with at least one of the organic acid compounds and halogenated hydrocarbons mentioned above, and the proportion thereof can be confirmed, for example, by known methods such as NMR.

[0224] From the perspective of dispersibility and dispersion stability, the copolymer having the structural unit represented by the above general formula (I) is more preferably at least one of graft copolymer and block copolymer, wherein the graft copolymer has the structural unit represented by the above general formula (I) and has a structural unit derived from (meth)acrylate on the graft polymer chain, and the block copolymer has an A block containing the structural unit represented by the above general formula (I) and a B block containing a structural unit derived from (meth)acrylate.

[0225] In the above-mentioned graft copolymers, the graft polymer chain having structural units derived from (meth)acrylates can be appropriately selected 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 can be used.

[0226] Furthermore, in the aforementioned block copolymers, the B block, which comprises 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 International Publication No. 2016 / 104493 may be used.

[0227] From the perspective of maintaining good substrate adhesion and solvent resistance of the cured film even after low-temperature heating treatment, and suppressing the generation of developing residue, it is preferable that the block copolymer used as a dispersant contains at least one of the following block copolymers and salt-type block copolymers, wherein the acid value of the block copolymer and the at least one of the salt-type block copolymers is 1 mg KOH / g to 18 mg KOH / g, and the glass transition temperature is 30°C or higher. The block copolymer contains an A block comprising a structural unit represented by the above general formula (I), and a B block comprising a structural unit derived from a carboxyl-containing monomer and a structural unit derived from (meth)acrylate. The salt-type block copolymer is a salt-type block copolymer obtained by forming a salt with at least a portion of the nitrogen site of the structural unit represented by the above general formula (I) of the block copolymer and at least one selected from organic acid compounds and halogenated hydrocarbons.

[0228] In this case, the B block contains structural units derived from (meth)acrylates as essential components, and may also be the same as the B block in International Publication No. 2016 / 104493.

[0229] Regarding copolymers having the structural units represented by the above general formula (I), from the perspective of good dispersibility, no precipitation of foreign matter when forming a coating film, and improved brightness and contrast, those with an amine value of 40 mg KOH / g to 120 mg KOH / g are preferred.

[0230] By keeping the amine value within the above-mentioned range, the viscosity exhibits excellent stability over time and heat resistance, as well as excellent alkaline developability and solvent resolubility. In this invention, regarding the amine value of the copolymer having the structural unit represented by the above general formula (I), the amine value can be 50 mg KOH / g or more, preferably 80 mg KOH / g or more, and more preferably 90 mg KOH / g or more. On the other hand, from the perspective of solvent resolubility, the amine value of the copolymer having the structural unit represented by the above general formula (I) is preferably 110 mg KOH / g or less, and more preferably 105 mg KOH / g or less.

[0231] The amine value refers to the number of mg of potassium hydroxide equivalent to perchloric acid required to neutralize the amine component contained in 1 g of the sample, and can be determined by the method defined in JIS-K7237. When determined by this method, even if the amino group forms a salt with an organic acid compound in the dispersant, the organic acid compound will usually dissociate, thus allowing the determination of the amine value of the block copolymer itself (before salt formation) used as the dispersant.

[0232] The proportion (mol%) of each structural unit in the copolymer of the dispersant can be determined based on the amount of raw materials added during manufacturing, and can also be measured using analytical instruments such as NMR. Furthermore, the structure of the dispersant can be determined using NMR, various mass spectrometry analyses, etc. Additionally, the dispersant can be decomposed through thermal decomposition as needed, and the resulting decomposition products can be analyzed using high-performance liquid chromatography, gas chromatography-mass spectrometry, NMR, elemental analysis, XPS / ESCA, and TOF-SIMS.

[0233] In the photosensitive coloring resin composition of the present invention, when a dispersant is used, the content of the dispersant is not particularly limited, as long as it is selected in a manner that provides excellent dispersibility and dispersion stability of the colorant. Relative to the total amount of solid components in the photosensitive coloring resin composition, it can be, for example, within the range of 2% to 30% by mass, or 3% to 25% by mass. If it is above the lower limit, the dispersibility and dispersion stability of the colorant are excellent, and the storage stability of the photosensitive coloring resin composition is even better. Furthermore, if it is below the upper limit, the developability is good.

[0234] In the photosensitive coloring resin composition of the present invention, in order to disperse the above-mentioned zinc phthalocyanine pigment (P1), it is preferable to use a copolymer having the structural unit represented by the above general formula (I) with an amine value of 50 mg KOH / g or more.

[0235] When using a copolymer having structural units represented by the above general formula (I) with an amine value of 50 mg KOH / g or higher to disperse the aforementioned zinc phthalocyanine pigment (P1), from the perspective of improving dispersibility and stability over time, maintaining developability, and minimizing residue formation, the copolymer having structural units represented by the above general formula (I) with an amine value of 50 mg KOH / g or higher is preferably 20 parts by mass or more and less than 50 parts by mass relative to 100 parts by mass of the aforementioned zinc phthalocyanine pigment (P1). From the perspective of lower viscosity, the copolymer having structural units represented by the above general formula (I) with an amine value of 50 mg KOH / g or higher is preferably 25 parts by mass or more and less than 50 parts by mass relative to 100 parts by mass of the aforementioned zinc phthalocyanine pigment (P1). From the perspective of lower viscosity, improved stability over time, and higher contrast, the copolymer having structural units represented by the above general formula (I) with an amine value of 50 mg KOH / g or higher is more preferably 30 parts by mass or more and less than 50 parts by mass.

[0236] <Sensitizer>

[0237] In this invention, the specific zinc phthalocyanine pigment dispersed in the system absorbs the exposed light and easily loses the free radicals generated by the initiator. Therefore, to compensate for this situation, it is preferable to include a sensitizer in combination with the photoinitiator. From the perspective of good reactivity of the (meth)acrylic acid polymerization system, it is preferable to include a thiol-based sensitizer, and more preferably, a thiol-based sensitizer is included in combination with the oxime ester initiator.

[0238] Examples of thiol-based sensitizers include: monofunctional thiol compounds with one thiol group and polyfunctional thiol compounds with two or more thiol groups.

[0239] Examples of monofunctional thiols include: 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-5-methoxybenzothiazole, 2-mercapto-5-methoxybenzimidazole, 3-mercaptopropionic acid, methyl 3-mercaptopropionate, ethyl 3-mercaptopropionate, octyl 3-mercaptopropionate, etc.

[0240] Examples of polyfunctional thiols include 1,4-bis(3-mercaptobutyryloxy)butane, 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetra(3-mercaptobutyrate), pentaerythritol tetra(3-mercaptopropionate), dipentaerythritol hexa(3-mercaptopropionate), and tetraethylene glycol bis(3-mercaptopropionate).

[0241] In the photosensitive coloring resin composition of the present invention, the content of the sensitizer, when it includes a sensitizer, is, from the perspective of improving curability, 0.5% to 10% by mass relative to the total solids content of the photosensitive coloring resin composition. More preferably, the content of the sensitizer, when it includes a sensitizer, is 1% to 6% by mass relative to the total solids content of the photosensitive coloring resin composition, and even more preferably, it is in the range of 2% to 5% by mass.

[0242] <Antioxidants>

[0243] From the perspective of suppressing linewidth offset, the photosensitive coloring resin composition of the present invention preferably further comprises an antioxidant. The photosensitive coloring resin composition of the present invention, combined with the aforementioned specific photoinitiator, contains an antioxidant, thereby enabling control of excessive free radical chain reactions without impairing curability during the formation of the cured film. Therefore, when forming fine line patterns, straightness is further improved, or the ability to form fine line patterns according to the mask linewidth design is enhanced. Furthermore, heat resistance is improved, and brightness reduction after exposure and post-baking is suppressed, thus increasing brightness.

[0244] The antioxidants used in this invention are not particularly limited, and can be appropriately selected from those already known. Specific examples of antioxidants include hindered phenolic antioxidants, amine antioxidants, phosphorus antioxidants, sulfur antioxidants, hydrazine antioxidants, etc. From the viewpoint of improving the ability to form fine line patterns according to the mask linewidth design and from the perspective of heat resistance, hindered phenolic antioxidants are preferred. Latent antioxidants as described in International Publication No. 2014 / 021023 may also be used.

[0245] Examples of hindered phenolic antioxidants include: pentaerythritol tetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (trade name: IRGANOX 1010, manufactured by BASF), 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate (trade name: IRGANOX 3114, manufactured by BASF), 2,4,6-tris(4-hydroxy-3,5-di-tert-butylbenzyl)trimethylbenzylene (trade name: IRGANOX 1330, 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 diethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate (trade name: Irgamod). 195, manufactured by BASF, etc. Among them, from the perspective of heat resistance and light resistance, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (trade name: IRGANOX 1010, manufactured by BASF) is preferred.

[0246] The content of the antioxidant, relative to the total solid content of the photosensitive coloring resin composition, is preferably in the range of 0.1% to 10.0% by mass, more preferably 0.5% to 5.0% by mass. If it is above the lower limit, it exhibits superior performance in terms of the ability to form fine line patterns according to the mask linewidth design, and also in terms of heat resistance. On the other hand, if it is below the upper limit, the photosensitive coloring resin composition of the present invention can be made into a highly sensitive photosensitive coloring resin composition.

[0247] <Method for manufacturing photosensitive coloring resin composition>

[0248] In the method for manufacturing the photosensitive coloring resin composition of the present invention, it can be prepared by mixing the colorant, alkali-soluble resin, photopolymerizable compound, photoinitiator, solvent, and various additives as needed using known mixing methods.

[0249] Examples of methods for preparing the resin composition include: (1) firstly, adding a colorant and a dispersant as needed to a solvent to prepare a colorant dispersion, and then mixing an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and various additives as needed in the colorant dispersion; (2) simultaneously adding a colorant, a dispersant as needed, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and various additives as needed to a solvent and mixing them; (3) adding an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and various additives as needed to a solvent and mixing them, and then further adding a colorant and mixing them; (4) adding a colorant, a dispersant as needed, and an alkali-soluble resin to a solvent to prepare a colorant dispersion, and then further adding an alkali-soluble resin, a solvent, a photopolymerizable compound, a photoinitiator, and various additives as needed to the colorant dispersion and mixing them, etc.

[0250] II. Color Filter

[0251] The color filter of the present invention comprises at least a substrate and a coloring layer disposed on the substrate, wherein at least one of the coloring layers is a cured product of the photosensitive coloring resin composition of the present invention.

[0252] The color filter of this invention will be described with reference to the figures. Figure 1 This is a schematic cross-sectional view showing an example of the color filter of the present invention. According to... Figure 1 The color filter 10 of the present invention has a substrate 1, a light-shielding portion 2, and a coloring layer 3. For example... Figure 1 As shown, the coloring layer 3 may include a red coloring layer 3R, a green coloring layer 3G, and a blue coloring layer 3B formed between the light-shielding portions 2.

[0253] (Substrate)

[0254] As a substrate, transparent substrates, silicon substrates, and substrates on which aluminum, silver, or silver / copper / palladium alloy thin films are formed can be used. Other color filter layers, resin layers, TFTs, and other transistors and circuits can also be formed on these substrates.

[0255] The transparent substrate used in the color filter of this invention is not particularly limited, as long as it is a substrate that is transparent to visible light, and the transparent substrate used in general color filters can be used. Specifically, examples include: rigid transparent materials that are not flexible, such as quartz glass, alkali-free glass, and synthetic quartz plates, or flexible transparent materials that are flexible, such as transparent resin films, optical resin plates, and flexible glass.

[0256] The thickness of the transparent substrate is not particularly limited, and a transparent substrate of about 100μm to 1mm can be used, for example, according to the application of the color filter of the present invention.

[0257] (shading part)

[0258] The light-shielding portion in the color filter of the present invention is formed in a pattern on the substrate described below, and can be the same as the light-shielding portion used in a general color filter.

[0259] The pattern shape of the aforementioned light-shielding portion is not particularly limited; examples include striped or matrix-like shapes. The light-shielding portion can be a thin metal film such as chromium formed by sputtering or vacuum evaporation. Alternatively, the light-shielding portion can be a resin layer containing light-shielding particles such as carbon microparticles, metal oxides, inorganic pigments, or organic pigments in a resin binder. In the case of a resin layer containing light-shielding particles, methods include: patterning using a photosensitive resist and developing; patterning using an inkjet ink containing light-shielding particles; and thermal transfer of the photosensitive resist.

[0260] The thickness of the light-shielding part is set to about 0.2 μm to 0.4 μm in the case of a metal thin film, and to about 0.5 μm to 2 μm in the case of a film formed by dispersing or dissolving black pigment in an adhesive resin.

[0261] (Coloring layer)

[0262] At least one of the coloring layers used in the color filter of the present invention is a cured product of the photosensitive coloring resin composition of the present invention described above.

[0263] The coloring layer is typically formed at the opening of the light-shielding portion on the substrate described below, and typically includes a coloring pattern of three or more colors. The coloring layer of the cured product of the photosensitive coloring resin composition of the present invention may be a green coloring layer.

[0264] Furthermore, there are no particular limitations on the arrangement of this color layer; for example, it can be set to a striped, mosaic, triangular, or four-pixel configuration, etc. Additionally, the width and area of ​​the color layer can be set arbitrarily.

[0265] The thickness of the coloring layer is appropriately controlled by adjusting the coating method, the concentration of solid components in the photosensitive coloring resin composition, viscosity, etc., and is usually preferably in the range of 1μm to 5μm.

[0266] There are no particular limitations on the manufacturing method of the coloring layer, and a coloring layer manufacturing method from a conventionally known method for manufacturing color filters can be appropriately selected. Furthermore, other photosensitive coloring resin compositions for coloring layers, such as red and blue photosensitive resin compositions, can be conventionally known photosensitive coloring resin compositions.

[0267] The aforementioned coloring layer can be formed, for example, by the following method.

[0268] First, a photosensitive coloring resin composition of any color (e.g., red) is applied to the substrate using coating methods such as spraying, dip coating, rod coating, roller coating, and spin coating to form a wet coating film.

[0269] Next, the wet coating is dried using a heating plate, oven, etc., and then exposed through a mask with a specific pattern. This causes the alkali-soluble resin and multifunctional monomers to undergo a photopolymerization reaction, forming a photosensitive coating. Examples of light sources used for exposure include low-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, ultraviolet light, and electron beams. The exposure amount is adjusted appropriately based on the light source used and the thickness of the coating.

[0270] In addition, heat treatment can be performed after exposure to promote the polymerization reaction. The heating conditions are appropriately selected based on the mixing ratio of each component in the photosensitive coloring resin composition used, the thickness of the coating film, etc.

[0271] Further, a developing solution is used to develop the film, dissolving and removing the unexposed areas, thereby forming a coating with the desired pattern. The developing solution is typically a solution made by dissolving an alkali in water or a water-soluble solvent. Appropriate amounts of surfactants may also be added to this alkaline solution. Alternatively, conventional methods can be used for development.

[0272] After development, the coating is typically cleaned with the developer, cured, and dried to form a color layer of any color (e.g., red). It should be noted that heat treatment can also be performed after development to ensure complete curing of the coating. The heating conditions are not particularly limited, but can be, for example, 200°C to 250°C.

[0273] Next, a coloring layer is formed in the same manner as described above using a photosensitive coloring resin composition of another color (e.g., blue), and then a coloring layer is formed in the same manner as described above using a photosensitive coloring resin composition of the present invention of another color (e.g., green), thereby enabling the manufacture of a color filter having a coloring layer of, for example, a green coloring layer, a blue coloring layer, and a red coloring layer.

[0274] The green coloring layer, which is a cured product of the photosensitive coloring resin composition for color filters according to the present invention, has a high brightness and can suppress the decrease in brightness of other coloring layers caused by migration, thereby improving the white brightness of the color filter.

[0275] It should be noted that, in addition to the substrate, light-shielding portion, and coloring layer described above, the color filter of the present invention may also have, for example, an outer coating layer, a transparent electrode layer, and further may have an alignment film for aligning the liquid crystal material, columnar spacers, etc. The color filter of the present invention is not limited to the configuration illustrated above, and may be used with appropriately selected known configurations commonly used in color filters.

[0276] III. Display Device

[0277] The display device of the present invention is characterized by having the color filter described above. In the present invention, the configuration of the display device is not particularly limited, and can be appropriately selected from conventionally known display devices, such as liquid crystal displays and organic light-emitting displays.

[0278] Liquid crystal display device

[0279] The liquid crystal display device of the present invention is characterized in that it has the color filter, the opposing substrate, and the liquid crystal layer formed between the color filter and the opposing substrate as described above.

[0280] The liquid crystal display device of the present invention will be described with reference to the figures. Figure 2 This is a schematic diagram illustrating an example of the liquid crystal display device of the present invention. (As shown) Figure 2 As illustrated, the liquid crystal display device 40 of the present invention includes: 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. Figure 2 The diagram shows an example where alignment film 13a is located on the side of the color layer 3 of the color filter 10, alignment film 13b is located on the side of the opposing substrate 20, and liquid crystal layer 15 is located between the two alignment films 13a and 13b. Further, Figure 2 The diagram shows an example of a liquid crystal display device 40 having a polarizing plate 25a located outside the color filter 10, a polarizing plate 25b located outside the opposing substrate 20, and a backlight 30 located further outward than the polarizing plate 25b located on the opposing substrate 20 side of the liquid crystal display device 40.

[0281] It should be noted that the liquid crystal display device of the present invention is not limited to this. Figure 2 The configuration shown can be configured as commonly known in liquid crystal display devices that use color filters.

[0282] There is no particular limitation on the driving method of the liquid crystal display device of the present invention, and a driving method commonly used in liquid crystal display devices can be adopted. Examples of such driving methods include TN, IPS, OCB, and MVA. In the present invention, any of these methods can be used appropriately.

[0283] Furthermore, the opposing substrate can be appropriately selected and used according to the driving method of the liquid crystal display device according to the present invention.

[0284] Furthermore, as the liquid crystal constituting the liquid crystal layer, various liquid crystals with different dielectric anisotropy and mixtures thereof can be used, depending on the driving method of the liquid crystal display device according to the present invention.

[0285] As a method for forming the liquid crystal layer, methods commonly used for manufacturing liquid crystal cells can be used, such as vacuum injection and liquid crystal droplet methods.

[0286] Regarding vacuum injection, a liquid crystal layer can be formed, for example, by: pre-fabricating a liquid crystal cell using a color filter and a counter substrate; creating an isotropic liquid by heating the liquid crystal; injecting the isotropic liquid liquid into the liquid crystal cell using capillary effect; and sealing it with an adhesive. Subsequently, the sealed liquid crystal can be aligned by slowly cooling the liquid crystal cell to room temperature.

[0287] In addition, regarding the liquid crystal dropping method, the liquid crystal layer can be formed, for example, by applying a sealant around the periphery of a color filter, heating the color filter to a temperature at which the liquid crystal becomes an isotropic phase, dropping the liquid crystal as an isotropic liquid using a dispenser or the like, overlapping the color filter with an opposing substrate under reduced pressure, and bonding them together using a sealant. Subsequently, the encapsulated liquid crystal can be aligned by slowly cooling the liquid crystal cell to room temperature.

[0288] Furthermore, the backlight used in the liquid crystal display device of the present invention can be appropriately selected according to the application of the liquid crystal display device. As a backlight, for example, in addition to a backlight unit using a cold cathode fluorescent lamp (CCFL) as a light source, a backlight unit using a white LED or a white organic EL as a light source can also be provided.

[0289] Examples of white LEDs include: white LEDs that combine red, green, and blue LEDs and obtain white light through color mixing; white LEDs that combine blue, red, and green phosphors and obtain white light through color mixing; white LEDs that combine blue, red, and green phosphors and obtain white light through color mixing; white LEDs that obtain white light through color mixing of blue LEDs and YAG phosphors; and white LEDs that combine ultraviolet LEDs, red phosphors, green phosphors, and blue phosphors and obtain white light through color mixing. Quantum dots can also be used as the phosphors mentioned above.

[0290] Organic light-emitting display device

[0291] The organic light-emitting display device of the present invention includes the color filter and organic light-emitting element described above.

[0292] The organic light-emitting display device of the present invention will be described with reference to the accompanying drawings. Figure 3 This is a schematic diagram illustrating an example of the organic light-emitting display device of the present invention. (As shown) Figure 3 As illustrated, the organic light-emitting display device 100 of the present invention includes a color filter 10 and an organic light-emitting element 80. An organic protective layer 50 and an inorganic oxide film 60 may also be provided between the color filter 10 and the organic light-emitting element 80.

[0293] Examples of methods for stacking the organic light-emitting element 80 include: sequentially forming a transparent anode 71, a hole injection layer 72, a hole transport layer 73, an emissive layer 74, an electron injection layer 75, and a cathode 76 on the upper surface of a color filter; and attaching the organic light-emitting element 80, formed on another substrate, to an inorganic oxide film 60. The transparent anode 71, hole injection layer 72, hole transport layer 73, emissive layer 74, electron injection layer 75, cathode 76, and other components of the organic light-emitting element 80 can be appropriately derived from known methods. An organic light-emitting display device 100 manufactured in this manner can be applied, for example, to a passively driven organic EL display or an actively driven organic EL display.

[0294] It should be noted that the organic light-emitting display device of the present invention is not limited to this. Figure 3 The configuration shown can be configured as is commonly known in organic light-emitting display devices that use color filters.

[0295] Example

[0296] The present invention will now be specifically described with reference to the embodiments shown. The present invention is not limited to these descriptions.

[0297] Zinc phthalocyanine pigment (pigment or dye) intermediates were analyzed by LC-MS (manufactured by Agilent Technologies, quadrupole LC / MS, Agilent 1260 Infinity).

[0298] Zinc phthalocyanine pigments (pigments or dyes) were analyzed using MALDI-TOF-MS (manufactured by Shimadzu Corporation, MALDI-8020).

[0299] (Synthesis Example 1: Synthesis of Zinc Phthalocyanine Pigment 1)

[0300] Add 10 g of tetrafluorophthalonitrile, 6.95 g of potassium fluoride, and 36 mL of acetone to a 200 mL three-necked flask and stir at 25 °C until dissolved. Then, cool the flask and add dropwise a solution of 10.8 g of p-cresol dissolved in 24 mL of acetone within a temperature range of -11 °C to -5 °C, while simultaneously heating to 25 °C. The reaction is carried out for 5 hours.

[0301] The insoluble matter obtained by filtration and separation of the reaction solution and concentration of the filtrate was purified by silica gel column chromatography to obtain intermediate 1.

[0302] Next, 3.88 g of zinc iodide, 15.4 g of intermediate 1, and 40 mL of benzonitrile were added to a 200 mL round-bottom flask. The mixture was reacted at 160 °C for 5 hours under a nitrogen atmosphere. The inside of the round-bottom flask was cooled to 25 °C, and the reaction solution was added to 600 mL of methanol for reprecipitation. The precipitated crystals were purified by silica chromatography to obtain zinc phthalocyanine pigment 1 with the following structure.

[0303] MALDI-TOF-MS: 1571.8 ([M+1]) + )

[0304] [Chemical Formula 10]

[0305]

[0306] (Synthesis Example 2: Synthesis of Zinc Phthalocyanine Pigment 2)

[0307] Add 15 g of tetrafluorophthalonitrile, 10.45 g of potassium fluoride, and 54 mL of acetone to a 200 mL three-necked flask and stir at 25 °C until dissolved. Then, cool the flask and add dropwise a solution containing 28.8 g of p-ethylphenol dissolved in 36 mL of acetone within a temperature range of -11 °C to -5 °C, while simultaneously heating to 25 °C. The reaction proceeds for 5 hours.

[0308] The insoluble matter obtained by filtering and separating the reaction solution and concentrating the filtrate was purified by silica gel column chromatography to obtain intermediate 2.

[0309] Except that 16.5g of intermediate 2 was used instead of 15.4g of intermediate 1 in Synthesis Example 1, zinc phthalocyanine pigment 2 having the following structure was obtained in the same manner as in Synthesis Example 1.

[0310] MALDI-TOF-MS: 1684.0 ([M+1]) + )

[0311] [Chemical Formula 11]

[0312]

[0313] (Synthesis Example 3: Synthesis of Zinc Phthalocyanine Pigment 3)

[0314] 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, zinc phthalocyanine pigment 3 having the following structure was obtained in the same manner as in Synthesis Example 1.

[0315] MALDI-TOF-MS: 2420.5 ([M+1]) + )

[0316] [Chemical Formula 12]

[0317]

[0318] (Comparative Synthesis Example 1: Synthesis of Zinc Phthalocyanine Dye C1)

[0319] Referring to the synthesis of dye A in Synthesis Example 1 of Patent Document 2 (International Publication No. 2020 / 171060), zinc phthalocyanine dye C1 having the following structure was synthesized.

[0320] MALDI-TOF-MS: 2036.1 ([M+1]) + )

[0321] [Chemical Formula 13]

[0322]

[0323] (Comparative Synthesis Example 2: Synthesis of Zinc Phthalocyanine Dye C2)

[0324] Except for using an equimolar amount of methylparaben to replace ethylparaben used in the synthesis of dye A in Synthesis Example 1 of Patent Document 2 (International Publication No. 2020 / 171060), zinc phthalocyanine dye C2 having the following structure was synthesized in the same manner as the synthesis of dye A.

[0325] MALDI-TOF-MS: 1923.9 ([M+1]) + )

[0326] [Chemical Formula 14]

[0327]

[0328] (Comparative Synthesis Example 3: Synthesis of Zinc Phthalocyanine Dye C3)

[0329] Referring to the synthesis of dye B in Synthesis Example 2 of Patent Document 2 (International Publication No. 2020 / 171060), zinc phthalocyanine dye C3 having the following structure was synthesized.

[0330] MALDI-TOF-MS: 2148.3 ([M+1]) + )

[0331] [Chemical Formula 15]

[0332]

[0333] [Evaluation of Colorant]

[0334] The following evaluation was conducted using zinc phthalocyanine pigments 1-3 obtained from self-synthesized Examples 1-3, zinc phthalocyanine dyes C1-C3 obtained from self-comparative synthesized Examples 1-3, and commercially available pigment green 58 (FASTOGEN GREEN A350, manufactured by DIC Corporation) as color materials.

[0335] (Powder X-ray diffraction determination of color materials)

[0336] A standard glass specimen plate with a base was used, which was etched to fill the specimen area with a diameter of 2.0 mm × 2.0 mm × a depth of 0.2 mm. A 20 × 20 mm glass specimen plate with a base and a depth of 0.2 mm manufactured by Rigaku Corporation was used as the glass specimen plate.

[0337] Before heating, the colorant is placed separately into the sample filling section and pressed and spread evenly using other glass plates. To reduce errors, the colorant surface is made to be on the same plane as the glass sample plate to prepare the test sample.

[0338] For the above-mentioned test sample (a bottomed glass sample plate with a colored material filling the sample filling part), powder X-ray diffraction was performed at 25°C using a powder X-ray diffraction apparatus (manufactured by Rigaku Corporation, SmartLab). CuKα rays were used as the X-ray source, and the settings were as follows: X-ray output 45 kV, 200 mA, fixed incident angle (θ) 0.20°, diffraction angle (2θ) 2.00°~60.00°, θ step 0.01°, and scanning speed 3.0° / min, to obtain the powder X-ray diffraction spectrum.

[0339] The presence or absence of diffraction peaks was determined after background removal from the powder X-ray diffraction (PXRD) spectra. Background removal was performed using the Sonnevelt-Visser method. The peak width threshold was set to 0.10, and the intensity threshold to 0.01. In the obtained PXRD spectra, peaks with an intensity greater than or equal to 1 / 4 of Z (1 / 4 of Z) were identified as diffraction peaks when the maximum peak intensity within the diffraction angle (2θ) range of 2.00° to 60.00° was defined as Z. Then, it was determined whether at least one diffraction peak was present within the diffraction angle (2θ) range of 3.00° to 7.00°.

[0340] (Solvent solubility of colorant)

[0341] At 25°C, in a 200mL sample vial, 100g of acetone was stirred with a stirrer (stirring speed 50rpm) while the colorant was added until undissolved matter was produced, and the mass concentration of the dissolved substance was determined.

[0342] First, when 0.01g of colorant is added and undissolved matter is produced, the solvent solubility in acetone is rated as less than 0.01g by mass.

[0343] <Evaluation Criteria>

[0344] Pigment: Solubility in acetone at 25°C is less than 0.1% by mass.

[0345] Dye: Solubility in acetone at 25°C is ≥0.1% by mass.

[0346] [Table 1]

[0347]

[0348] (Synthesis Example 4: Synthesis of Basic Dispersant 1)

[0349] As a dispersant, an alkaline dispersant 1 (salt-type block copolymer) solution (solid content 40% by 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) was prepared in the same manner as the dispersant b in Synthesis Example II-2 described in paragraph 0302 of International Publication No. 2016 / 104493.

[0350] (Synthesis Example 5: Synthesis of Alkali-soluble Resin A)

[0351] A mixture of 40 parts by weight of benzyl methacrylate (BzMA), 15 parts by weight of methyl methacrylate (MMA), 25 parts by weight of methacrylic acid (MAA), and 3 parts by weight of azobisisobutyronitrile (AIBN) was added dropwise to a polymerization tank containing 150 parts by weight of propylene glycol monomethyl ether acetate (PGMEA) over a nitrogen stream at 100°C for 3 hours. After the addition was complete, 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.

[0352] Next, 20 parts by weight of glycidyl methacrylate (GMA), 0.2 parts by weight of triethylamine, and 0.05 parts by weight of p-methoxyphenol were added to the obtained polymer solution, and the mixture was heated at 110°C for 10 hours, thereby allowing the carboxylic acid groups of the main chain methacrylic acid to react with the epoxy groups of glycidyl methacrylate. During the reaction, air was bubbled into the reaction solution to prevent the polymerization of glycidyl methacrylate.

[0353] It should be noted that the reaction was tracked by measuring the acid value of the solution. The obtained alkali-soluble resin A is a resin formed by introducing side chains with olefinic unsaturated bonds into the main chain through copolymerization of BzMA with MMA and MAA using GMA. It has an acid value of 74 mgKOH / g and a weight-average molecular weight of 12000. The solid content of the alkali-soluble resin A solution is 40% by mass.

[0354] (Synthesis Example 6: Synthesis of Alkali-treated Phthalocyanine Pigment 1)

[0355] 300 parts by mass of chlorosulfonic acid and 30 parts by mass of copper phthalocyanine were added to a reaction vessel and completely dissolved. Then, 24 parts by mass of thionyl chloride were added, and the mixture was slowly heated to 101°C and reacted for 3 hours. The reaction solution was then poured into 9000 parts by mass of ice water, stirred, filtered, and washed with water. The obtained filter cake was slurried with 300 parts by mass of water, and 13 parts by mass of 1,1-diethyl-1,5-diazapentane were added. After stirring at 65°C for 4 hours, the mixture was filtered, washed with water, and dried to obtain a blue pigment derivative 1 with alkaline sites for surface treatment. The obtained blue pigment derivative 1 with alkaline sites was confirmed to have the following chemical formula. (TOF-MS: 768.35)

[0356] [Chemical Formula 16]

[0357]

[0358] Using a grinder, 100 parts by weight of commercially available CIPigment Blue 15:6 (ε-type copper phthalocyanine pigment, FASTOGEN BLUE A510 manufactured by DIC) and 5 parts by weight of the aforementioned blue pigment derivative 1 with an alkaline portion were dry-milled at 60°C for 1.5 hours. Further, 5 parts by weight of the aforementioned blue pigment derivative 1 with an alkaline portion were mixed into the milled product, thereby obtaining the target alkaline-treated phthalocyanine pigment, i.e., alkaline-treated phthalocyanine pigment 1.

[0359] (Synthesis Example 7: Synthesis of acidic dispersant 2 (a block copolymer comprising A block and B block, wherein the A block comprises a structural unit derived from a carboxyl-containing olefinic unsaturated monomer and the B block comprises a structural unit derived from an alkyl methacrylate))

[0360] Referring to Example 1 described in International Publication No. 2016 / 132863, a triblock copolymer was synthesized having: blocks of 20 parts by mass of MMA and 40 parts by mass of BMA; blocks of 20 parts by mass of acrylic acid (MAA) and 20 parts by mass of BMA; and blocks of 20 parts by mass of MMA and 40 parts by mass of BMA. The obtained block copolymer had a weight-average molecular weight (Mw) of 11,000, a molecular weight distribution (Mw / Mn) of 1.50, and an acid value of 130 mg KOH / g.

[0361] (Synthesis Example 8: Synthesis of Alkali-soluble Resin B)

[0362] 150 parts by weight of PGMEA were added to the polymerization tank. After heating to 100°C under a nitrogen atmosphere, 22 parts by weight of methacrylic acid (MAA), 64 parts by weight of cyclohexyl methacrylate (CHMA), 6 parts by weight of PERBUTYL O (manufactured by Nippon Oil Co., Ltd.), and 2 parts by weight of chain transfer agent (n-dodecyl mercaptan) were continuously added dropwise over 1.5 hours. The reaction was then continued at 100°C. Two hours after the addition of the above main chain forming mixture was completed, 0.1 parts by weight of p-methoxyphenol was added as a polymerization inhibitor to terminate the polymerization.

[0363] Next, while blowing in air, 14 parts by mass of glycidyl methacrylate (GMA), an epoxy-containing compound, were added. After heating to 110°C, 0.8 parts by mass of triethylamine were 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 mg KOH / g, solid content 40% by mass).

[0364] (Synthetic Example 9: Synthesis of Y138 sulfonic acid derivative)

[0365] The monosulfonic acid derivative of CI Pigment Yellow 138 was synthesized in the same manner as the synthesis of the monosulfonic acid derivative of CI Pigment Yellow 138 in Synthesis Example 2 of International Publication No. 2014 / 069416.

[0366] (Preparation Example 1: Preparation of CR-1, a photosensitive adhesive component)

[0367] Compared to the above-mentioned alkali-soluble resin A solution (solid content 40% by mass) 19.13 parts by mass, 17.85 parts by mass of dipentaerythritol hexaacrylate (DPHA) (ARONIX M403, manufactured by Toa Synthetic) as a photopolymerizable compound, 2.25 parts by mass of oxime ester photoinitiator (PBG-3057, manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.) as a photoinitiator, 2.25 parts by mass of oxime ester photoinitiator (NCI-831E, manufactured by ADEKA), and 58.53 parts by mass of PGMEA were added to obtain the photosensitive adhesive component CR-1.

[0368] (Preparation Example 2: Preparation of CR-2, a photosensitive adhesive component)

[0369] Compared to the above-mentioned alkali-soluble resin B solution (40% by mass of solids), 36.5 parts by mass of dipentaerythritol hexaacrylate (DPHA) (ARONIX M402, manufactured by Toa Synthetic) as a photopolymerizable compound were added, along with 21.9 parts by mass of α-aminoacetophenone-based photoinitiator (Irgacure 907, manufactured by BASF) as a photoinitiator, 1.3 parts by mass of oxime ester-based photoinitiator with a fluorene skeleton (SPI-04, manufactured by Sanyang), 0.3 parts by mass of thioxanone-based photoinitiator (kayacure DETX-S, manufactured by Nippon Kayaku), 0.8 parts by mass of antioxidant (IRGANOX1010, manufactured by BASF), and 38.1 parts by mass of PGMEA, to obtain the photosensitive adhesive component CR-2.

[0370] (Preparation Example 3: Preparation of CR-3, a photosensitive adhesive component)

[0371] Compared with the above-mentioned alkali-soluble resin A solution (solid content 40% by mass) 13.80 parts by mass, 22.08 parts by mass of dipentaerythritol hexaacrylate (DPHA) (ARONIX M403, manufactured by Dong-A Synthetic) as a photopolymerizable compound, 2.40 parts by mass of oxime ester photoinitiator (PBG-3057, manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.) as a photoinitiator, and 61.72 parts by mass of PGMEA were added to obtain the photosensitive adhesive component CR-3.

[0372] (Example 1)

[0373] (1) Preparation of pigment dispersion G1

[0374] 8.75 parts by mass of the above-mentioned alkaline dispersant 1 solution (3.5 parts by mass of solid component), 10.00 parts by mass of zinc phthalocyanine pigment 1 obtained in Synthesis Example 1, 16.25 parts by mass of the above-mentioned alkali-soluble resin A, 65.00 parts by mass of PGMEA, and 100 parts by mass of zirconia beads with a particle size of 2.0 mm were added to a mayonnaise bottle. As a pre-crushing process, the mixture was shaken for 1 hour using a paint shaker (manufactured by Asada Tetsuko Co., Ltd.). Next, 200 parts by mass of zirconia beads with a particle size of 0.1 mm were added, and the mixture was dispersed for 10 hours using a paint shaker as a formal crushing process to obtain pigment dispersion G1.

[0375] (2) Preparation of Y138 dispersion

[0376] 13.00 parts by weight of the above-mentioned alkaline dispersant 1 solution as a dispersant, 13.00 parts by weight of Chromofine Yellow 6206EC (manufactured by Dai Nippon Seika Kogyo Co., Ltd.) as a colorant, 13.00 parts by weight of the above-mentioned alkali-soluble resin A solution, 61.00 parts by weight of PGMEA, and 100 parts by weight of zirconia beads with a particle size of 2.0 mm were added to a mayonnaise bottle. As a pre-crushing process, the mixture was shaken for 1 hour using a paint shaker (manufactured by Asada Tetsuko Co., Ltd.). Next, 200 parts by weight of zirconia beads with a particle size of 0.1 mm were added, and the mixture was dispersed for 4 hours using a paint shaker as a formal crushing process to obtain Y138 dispersion.

[0377] (3) Preparation of photosensitive coloring resin composition G1

[0378] Add 35.07 parts by weight of pigment dispersion G1 obtained in (1) above, 17.60 parts by weight of Y138 dispersion obtained in (2) above, 18.97 parts by weight of the above photosensitive adhesive component CR-1, 0.114 parts by weight of sensitizer (pentaerythritol tetrakis(3-mercaptobutyric acid), trade name Karenz MT-PE1, manufactured by Showa Denko), 0.03 parts by weight of fluorinated surfactant (trade name MEGAFAC F559, manufactured by DIC Co., Ltd.), 0.34 parts by weight of silane coupling agent (trade name KBM503, manufactured by Shin-EtsuSilicones), and 27.88 parts by weight of PGMEA to obtain a photosensitive coloring resin composition (green composition) G1.

[0379] (Examples 2-3)

[0380] (1) Preparation of pigment dispersions G2 to G3

[0381] Except for using equimolar amounts of zinc phthalocyanine pigment 2 obtained in Synthesis Example 2 or zinc phthalocyanine pigment 3 obtained in Synthesis Example 3 instead of zinc phthalocyanine pigment 1 obtained in Synthesis Example 1 (1), pigment dispersions G2 to G3 were obtained in the same manner as in Example 1 (1).

[0382] (2) Preparation of photosensitive coloring resin compositions G2 to G3

[0383] Except for using the above-mentioned pigment dispersion G2 or G3 instead of pigment dispersion G1 in Example 1 (3), the photosensitive coloring resin composition (green composition) G2 to G3 were obtained in the same manner as in Example 1 (3).

[0384] (Comparative Example 1)

[0385] (1) Compare the manufacturing processes of coloring solutions CG1 to CG3

[0386] Except for replacing the zinc phthalocyanine pigment 1 obtained in synthesis example 1 of example 1 with equimolar amounts of zinc phthalocyanine dye C1 obtained in comparative synthesis example 1, zinc phthalocyanine dye C2 obtained in comparative synthesis example 2, or zinc phthalocyanine dye C3 obtained in comparative synthesis example 3, comparative coloring solutions CG1 to CG3 were obtained in the same manner as in example 1 (1).

[0387] (2) Comparison of the manufacturing processes of photosensitive coloring resin compositions CG1 to CG3

[0388] Except that comparative coloring liquids CG1 to CG3 were used instead of pigment dispersion G1 in Example 1 (3), comparative photosensitive coloring resin compositions (green compositions) CG1 to CG3 were obtained in the same manner as in Example 1 (3).

[0389] (Comparative Example 4)

[0390] (1) Comparison of the manufacturing of pigment dispersion CG4

[0391] 9.75 parts by weight of the above-mentioned alkaline dispersant 1 solution, 13.00 parts by weight of CI pigment green 58 (FASTOGEN GREENA350, manufactured by DIC Co., Ltd.) as a colorant, 16.25 parts by weight of the above-mentioned 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 added to a mayonnaise bottle. As a pre-crushing process, the mixture was shaken for 1 hour using a paint shaker (manufactured by Asada Tetsuko Co., Ltd.). Next, 200 parts by weight of zirconia beads with a particle size of 0.1 mm were added and dispersed for 3 hours using a paint shaker as a formal crushing process to obtain the comparative pigment dispersion CG4.

[0392] (2) Comparison of the manufacturing of photosensitive coloring resin composition CG4

[0393] The comparative photosensitive coloring 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).

[0394] (Preparation of blue composition B1)

[0395] (1) Preparation of the pigment dispersion of phthalocyanine pigment 1 under alkaline treatment

[0396] 10 parts by weight of the above-mentioned alkaline-treated phthalocyanine pigment 1, 16.7 parts by weight of the above-mentioned acidic dispersant 2 solution (5.0 parts by weight of effective solids), 7.5 parts by weight of the above-mentioned alkali-soluble resin B (3.0 parts by weight of effective solids), and 65.8 parts by weight of PGMEA were mixed. The mixture was dispersed for 1 hour using 2 mm zirconia beads as a pre-dispersion using a paint shaker (manufactured by Asada Iron Works), and further dispersed for 6 hours using 0.1 mm zirconia beads as a formal dispersion to obtain a color material dispersion of alkaline-treated phthalocyanine pigment 1.

[0397] (2) Preparation of co-dispersible pigment dispersion 1 of phthalocyanine pigment 1 and CI pigment violet 23 under alkaline treatment

[0398] Nine parts by weight of the above-mentioned alkaline-treated phthalocyanine pigment 1, one part by weight of CI pigment violet 23 (manufactured by Sigma-Aldrich Japan), 16.7 parts by weight of the above-mentioned acidic dispersant 2 solution (5.0 parts by weight of effective solids), 7.5 parts by weight of the above-mentioned alkali-soluble resin B (3.0 parts by weight of effective solids), and 65.8 parts by weight of PGMEA were mixed. The mixture was dispersed for 1 hour using 2 mm zirconia beads as a pre-dispersion using a paint shaker (manufactured by Asada Tetsuko), and further dispersed for 6 hours using 0.1 mm zirconia beads as a formal dispersion to obtain co-dispersed colorant dispersion 1.

[0399] (3) Preparation of blue composition B1

[0400] 18.95 parts by weight of the above-mentioned alkaline-treated phthalocyanine pigment 1 dispersion, 117.49 parts by weight of the above-mentioned co-dispersed pigment dispersion, 34.78 parts by weight of the above-mentioned photosensitive adhesive component CR-2, 0.03 parts by weight of surfactant F559 (manufactured by DIC), and 28.75 parts by weight of PGMEA were mixed to obtain blue composition B1.

[0401] (Preparation of red composition R1)

[0402] (1) Preparation of colorant dispersion R254

[0403] 12.4 parts by weight of pigment (CI Pigment Red 254), 16.2 parts by weight of the above-mentioned basic block copolymer 1 PGMEA solution (40% by weight of solids) as a dispersant, 0.7 parts by weight of the above-mentioned Y138 sulfonic acid derivative, 9.8 parts by weight of the above-mentioned 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 were added to a mayonnaise bottle. As a pre-crushing process, the mixture was shaken for 1 hour using a paint shaker (manufactured by Asada Tetsuko Co., Ltd.). Next, 200 parts by weight of zirconia beads with a particle size of 0.1 mm were added, and the mixture was dispersed for 8 hours using a paint shaker as a formal crushing process to obtain pigment dispersion R254.

[0404] (2) Preparation of colorant dispersion R177

[0405] Except for using CI Pigment Red 177 instead of CI Pigment Red 254 as the pigment material in the preparation of pigment dispersion R254, pigment dispersion R177 is obtained in the same manner as pigment dispersion R254.

[0406] (3) Preparation of red composition R1

[0407] Add 2.77 parts by weight of color material dispersion R254, 19.89 parts by weight of color material dispersion R177, 31.69 parts by weight of the above-mentioned photosensitive adhesive component CR-3, 0.03 parts by weight of fluorinated surfactant (trade name MEGAFAC F559, manufactured by DIC Co., Ltd.), 0.34 parts by weight of silane coupling agent (trade name KBM503, manufactured by Shin-Etsu Silicones), and 45.27 parts by weight of PGMEA to obtain red composition R1.

[0408] [Evaluation Method]

[0409] <Formation of Color Filter Substrate 1>

[0410] As shown in Table 2, the above-described red composition 1, the above-described blue composition 1, and any one of the photosensitive coloring resin compositions (green compositions) G1 to G3 and comparative photosensitive coloring resin compositions (green compositions) CG1 to CG4 of the present invention, as green compositions, are used to form a coloring layer in the order of red → blue → green, thereby forming a color filter substrate 1. (In the following table, the zinc phthalocyanine pigments 1 to 3 used in the embodiments of the present invention are referred to as "pigment 1 to 3", the zinc phthalocyanine dyes C1 to C3 used in the comparative examples are referred to as "dyes C1 to C3", and pigment green 58 is referred to as "PG58".)

[0411] First, a curable resin composition for a black matrix was prepared in the same manner as the curable resin composition for a black matrix in Example 1 of Japanese Patent No. 4833777. A black matrix (10 μm wide) was formed on a glass substrate (NA35 manufactured by NH TECHNO GLASS Co., Ltd.) with a thickness of 0.7 mm, in the same manner as paragraph 0085 of Japanese Patent No. 4833777.

[0412] The red composition R1 was coated using a spin coater to a thickness of 2.3 μm after baking. It was then heat-dried on a hot plate at 80°C for 3 minutes. A patterned photomask (chromium mask) with an aperture size of 80 μm × 250 μm was used, and an ultra-high pressure mercury lamp at 40 mJ / cm² was applied. 2 The substrate is exposed to ultraviolet light to form an exposed coating. Next, a 0.05 wt% potassium hydroxide aqueous solution is used as the developer for spin development. After contact with the developer for 60 seconds, the substrate is rinsed with pure water, resulting in a red coating with individual fine line patterns. This red coating is then baked in a clean oven at 230°C for 25 minutes to form a red coloring layer with individual fine line patterns.

[0413] Using blue composition B1 instead of red composition R1, a spin coater was used to coat the glass substrate on which the red coloring layer was formed, with the resulting film thickness of blue composition B1 after baking being 2.3 μm. In the same manner as above, a patterned photomask (chromium mask) was used to obtain a blue coloring layer with independent fine line patterns at predetermined locations different from the area where the red coloring layer was formed.

[0414] Using the green composition shown in Table 2 instead of the red composition R1, the green composition, after baking, was applied to a glass substrate on which the above-mentioned red and blue colored layers were formed using a spin coater to achieve a film thickness of 2.3 μm. In the same manner as above, a patterned photomask (chromium mask) was used to obtain a green colored layer with an independent fine line pattern at predetermined locations different from the areas where the red and green colored layers were formed.

[0415] Thus, a color filter substrate 1 with an RGB 3-color coloring layer is manufactured.

[0416] <Formation of color filter substrate 2>

[0417] In addition to using any one of the above-mentioned red composition 1, blue composition 1, and the photosensitive coloring resin compositions (green compositions) G1 to G3 and comparative photosensitive coloring resin compositions (green compositions) CG1 to CG4 of the present invention as green compositions, as shown in Table 3, and forming the color layer in the order of red→green→blue, a color filter substrate 2 having an RGB 3-color color layer is manufactured in the same manner as the color filter substrate 1.

[0418] <Forming of color filter substrate 3>

[0419] In addition to using any one of the above-mentioned red composition 1, blue composition 1, and the photosensitive coloring resin compositions (green compositions) G1 to G3 and comparative photosensitive coloring resin compositions (green compositions) CG1 to CG4 of the present invention as green compositions, as shown in Table 4, and forming the color layer in the order of blue → green → red, a color filter substrate 3 having an RGB 3-color color layer is manufactured in the same manner as the color filter substrate 1.

[0420] <Formation of color filter substrate 4>

[0421] In addition to using any one of the above-mentioned red composition 1, blue composition 1, and the photosensitive coloring resin compositions (green compositions) G1 to G3 and comparative photosensitive coloring resin compositions (green compositions) CG1 to CG4 of the present invention as green compositions, as shown in Table 5, and forming the coloring layer in the order of green→red→blue, a color filter substrate 4 having an RGB 3-color coloring layer is manufactured in the same manner as the color filter substrate 1.

[0422] <Optical Performance>

[0423] In both the embodiments and comparative examples, the optical performance of the obtained color filter substrate was evaluated.

[0424] The central positions along the width direction (80 μm) of the red, green, and blue coloring layers were measured using a spectrophotometer LCF (manufactured by Otsuka Electronics). The chromaticity (x, y) and luminance (Y) of each color were calculated. The chromaticity and luminance of white were then calculated using the measured values ​​for each color. It should be noted that the chromaticity coordinates are expressed using the XYZ color table of JIS Z8701, which measures color using a C light source.

[0425] As a reference brightness for the decrease in brightness of the coloring layer formed by the first and second coatings, the brightness of the coloring layer formed by the final (third) coating with the same composition is used.

[0426] Regarding the decrease in brightness of each red coloring layer applied in the first and second coats, the brightness of the red coloring layer of the same composition combination of the color filter substrate 3 (Table 4) formed by the final coating of the red coloring layer is set as the reference brightness.

[0427] Regarding the decrease in brightness of each green coloring layer formed by the first and second coating processes, the brightness of the green coloring layer of the same composition of the filter substrate 1 (Table 2) formed by the final coating of the green coloring layer is set as the reference brightness.

[0428] Regarding the decrease in brightness of each blue coloring layer formed by the first and second coating processes, the brightness of the blue coloring layer of the same composition of the filter substrate 2 (Table 3) formed by the final coating of the blue coloring layer is set as the reference brightness.

[0429] (Evaluation criteria for brightness reduction caused by staining, etc.)

[0430] A: The brightness reduction is less than 1.0% compared to the reference brightness.

[0431] B: Compared to the reference brightness, the brightness reduction is greater than 1.0% but less than 2.0%.

[0432] C: The brightness is reduced by more than 2.0% compared to the reference brightness.

[0433] In addition, regarding the green coloring layer, 63.0 is set as the baseline brightness, brightness above 63.0 is rated OK, and brightness below 63.0 is rated NG.

[0434] <Evaluation of Developing Residue>

[0435] Evaluation of development residue on red and blue colored layers when coating in the order of red→blue→green.

[0436] The red composition was coated to a thickness of 0.7 mm onto a 100 mm × 100 mm glass substrate (manufactured by NHTECHNO GLASS Co., Ltd., "NA35") using a spin coater, and then dried at 60°C for 3 minutes using a heated plate to form a coating layer with a thickness of 2.5 μm. Next, the glass substrate with the above coating layer was exposed to a 90 mm × 30 mm opening at a specified position using a special mask, and then sprayed with a 0.05% by mass potassium hydroxide aqueous solution as an alkaline developer for 60 seconds, followed by rinsing with deionized water. Subsequently, the substrate with the red coloring layer was baked at 230°C for 30 minutes.

[0437] A blue composition was applied to a substrate with a red coloring layer using a spin coater. At a predetermined location different from the area with the red coloring layer, an opening of 90mm × 30mm was exposed using a special mask. Then, a 0.05% (w / w) potassium hydroxide aqueous solution was used as an alkaline developer for 60 seconds of spray development, followed by rinsing with deionized water. Subsequently, the substrate with both red and blue coloring layers was baked at 230°C for 30 minutes.

[0438] A green composition was applied to a substrate with red and blue coloring layers using a spin coater. At a predetermined location different from the areas with red and blue coloring layers, an opening of 90mm × 30mm was exposed using a dedicated photomask. Then, a 60-second spray development was performed using a 0.05% (w / w) potassium hydroxide aqueous solution as an alkaline developer, followed by rinsing with deionized water. Residue on the red and blue coloring layers was evaluated during this stage. Subsequently, the substrate with red, green, and blue coloring layers was baked at 230°C for 30 minutes.

[0439] The evaluation of residues on the red and blue coloring layers was carried out as follows: After visually observing the monochrome exposure area (90mm×30mm) of the glass substrate after the green coloring layer was developed, the substrate was thoroughly wiped with a lens cleaning cloth containing ethanol (manufactured by Toray Industries, Inc., trade name Toraysee MK Clean Cloth), and the degree of coloring of the lens cleaning cloth was observed visually.

[0440] Similarly, the development residue on the red and green colored layers was evaluated when the coating was applied in the order of red → green → blue.

[0441] Similarly, the development residue on the blue and green colored layers was evaluated when the coating was applied in the order of blue → green → red.

[0442] Similarly, the development residue on the green and red colored layers was evaluated when the coating was applied in the order of green → red → blue.

[0443] (Developer residue evaluation criteria)

[0444] A: No developer residue was visually detected, and the lens cleaning cloth was completely unstained.

[0445] B: No developer residue was visually detected, but slight staining of the lens cleaning cloth was observed.

[0446] C: Slight developer residue was observed visually, and the lens cleaning cloth was also found to be stained.

[0447] [Table 2]

[0448]

[0449] [Table 3]

[0450]

[0451] [Table 4]

[0452]

[0453] [Table 5]

[0454]

[0455] [Results Summary]

[0456] As shown in Comparative Examples 1-3, it is clear that if a photosensitive resin composition containing a zinc phthalocyanine dye dissolved in a solvent is used to form the green coloring layer of the color filter, the zinc phthalocyanine dye easily migrates to the red and blue coloring layers on the substrate, and the brightness of the red and blue coloring layers easily decreases. In Comparative Examples 1-3, even if the brightness of the green coloring layer is increased by using a zinc phthalocyanine dye as the green colorant, the brightness of the red and blue coloring layers decreases, and the white brightness of the color filter decreases.

[0457] As shown in Comparative Example 4, if a photosensitive resin composition containing Pigment Green 58, a conventional green pigment, is used to form the green coloring layer of the color filter, migration is suppressed, but the brightness of the green coloring layer is low, and the white brightness of the color filter is reduced.

[0458] In contrast, as shown in Examples 1 to 3, if the green coloring layer of the color filter is formed using the photosensitive coloring resin composition for color filters of the present invention, the brightness of the green coloring layer is high and the reduction in brightness of the red and blue coloring layers caused by migration can be suppressed, thereby improving the white brightness of the color filter (see Table 2).

[0459] In addition, in Table 3, where the formation order of the coloring layer is changed to red→green→blue, in Comparative Examples 5 to 7, where a green coloring layer of the color filter is formed using a photosensitive resin composition containing zinc phthalocyanine dye dissolved in a solvent, the zinc phthalocyanine dye migrates to the red coloring layer on the substrate, or blue coloring layer development residue is easily generated on the green coloring layer, resulting in a decrease in the brightness of the red and green coloring layers and a decrease in the white brightness of the color filter.

[0460] As shown in Comparative Example 8, if a photosensitive resin composition containing Pigment Green 58, a conventional green pigment, is used to form the green coloring layer of the color filter, migration is suppressed, but the brightness of the green coloring layer is low, and the white brightness of the color filter is reduced.

[0461] In contrast, as shown in Examples 4 to 6, if the green coloring layer of the color filter is formed using the photosensitive coloring resin composition for color filters of the present invention, the brightness of the green coloring layer is high and the reduction in brightness of the red coloring layer caused by migration is suppressed. The development residue of the blue coloring layer is not easily generated on the green coloring layer, and the white brightness of the color filter can be improved.

[0462] In addition, in Table 4, where the formation order of the coloring layer is changed to blue→green→red, in Comparative Examples 9 to 11, where a green coloring layer of the color filter is formed using a photosensitive resin composition containing zinc phthalocyanine dye dissolved in a solvent, the zinc phthalocyanine dye migrates to the blue coloring layer on the substrate, or red coloring layer development residue is easily generated on the green coloring layer, resulting in a decrease in the brightness of the blue coloring layer and a decrease in the white brightness of the color filter.

[0463] As shown in Comparative Example 12, if a photosensitive resin composition containing Pigment Green 58, a conventional green pigment, is used to form the green coloring layer of the color filter, migration is suppressed, but the brightness of the green coloring layer is low, and the white brightness of the color filter is reduced.

[0464] In contrast, as shown in Examples 7-9, if the green coloring layer of the color filter is formed using the photosensitive coloring resin composition for color filters of the present invention, the brightness of the green coloring layer is high and the reduction in brightness of the red coloring layer caused by migration is suppressed. The development residue of the blue coloring layer is not easily generated on the green coloring layer, and the white brightness of the color filter can be improved.

[0465] In addition, in Table 5, where the formation order of the coloring layer is changed to green→red→blue, in Comparative Examples 13 to 15, where a green coloring layer of the filter is formed using a photosensitive resin composition containing a zinc phthalocyanine dye dissolved in a solvent, red coloring layer development residue is easily generated on the green coloring layer, resulting in a decrease in the brightness of the green coloring layer and a decrease in the white brightness of the filter.

[0466] As shown in Comparative Example 16, if a photosensitive resin composition containing Pigment Green 58, which is a conventional green pigment, is used to form the green coloring layer of the color filter, the brightness reduction rate of the green coloring layer is low, but the brightness of the green coloring layer is originally low, and the white brightness of the color filter is reduced.

[0467] In contrast, as shown in Examples 10-12, if the green coloring layer of the color filter is formed using the photosensitive coloring resin composition for color filters of the present invention, the development residue of the red coloring layer is not easily generated on the green coloring layer, the decrease in brightness of the green coloring layer is suppressed, and the white brightness of the color filter can be improved.

[0468] Explanation of reference numerals in the attached figures

[0469] 1 substrate

[0470] 2 shading part

[0471] 3. Coloring layer

[0472] 10 Color Filters

[0473] 20 Opposing substrates

[0474] 30 liquid crystal layers

[0475] 40 Liquid Crystal Display Device

[0476] 50 Organic protective layer

[0477] 60 Inorganic oxide film

[0478] 71 Transparent Anode

[0479] 72 Hole Injection Layer

[0480] 73 Hole Transport Layer

[0481] 74 Emissive Layer

[0482] 75 Electron Injection Layer

[0483] 76 Cathode

[0484] 80 Organic light-emitting materials

[0485] 100 Organic Light Emitting Display Devices

Claims

1. A photosensitive coloring resin composition for color filters, comprising a colorant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a solvent. The colorant comprises zinc phthalocyanine pigment, which has at least one diffraction peak in the range of 3.00° to 7.00° in the powder X-ray diffraction spectrum of the colorant using CuKα rays alone.

2. The photosensitive coloring resin composition for color filters according to claim 1, wherein, The zinc phthalocyanine pigment is the zinc phthalocyanine pigment represented by the following general formula (1). In general formula (1), R A1 R A2 R A3 R A4 R A5 R A6 R A7 and R A8 Each can be independently substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted aralkyl, or substituted or unsubstituted heteroaryl.

3. The photosensitive coloring resin composition for color filters according to claim 1 or 2, wherein, The zinc phthalocyanine pigment is the zinc phthalocyanine pigment represented by the following formula (1-1). 。 4. The photosensitive coloring resin composition for color filters according to claim 1 or 2, wherein, The colorant further includes a yellow colorant.

5. The photosensitive coloring resin composition for color filters according to claim 1 or 2, wherein, The colorant further comprises a green colorant that is different from the zinc phthalocyanine pigment.

6. The photosensitive coloring resin composition for color filters according to claim 1 or 2, wherein, The colorant further includes a blue colorant.

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

8. A display device having the color filter of claim 7.

Images