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

Abstract

The present invention provides a photosensitive coloring resin composition for color filters, comprising a colorant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator and a solvent, wherein the photoinitiator comprises a compound represented by the following general formula (1) (the symbols of the general formula (1) are as described in the specification).

Description

Technical Field

[0001] This invention relates to a photosensitive coloring resin composition for color filters, a cured product, a color filter, and a display device. Existing technology

[0002] In recent years, with the development of personal computers, especially portable personal computers, the demand for LCD monitors has increased. The penetration rate of mobile displays (mobile phones, smartphones, and tablet PCs) has also increased, and the LCD market is expanding daily. Organic light-emitting display devices, such as organic EL (electroluminescence) displays that offer high visibility due to their self-emissive nature, are also attracting attention as next-generation image display devices.

[0003] These liquid crystal display devices and organic light-emitting diode (OLED) display devices use color filters. For example, the formation of a color image in a liquid crystal display device involves directly coloring the light passing through the color filter into the colors of the individual pixels constituting the color filter, and then synthesizing these colors of light to form a color image. As the light source, in addition to the previously used cold cathode fluorescent lamp (CCFL), there are cases where white-emitting organic light-emitting elements and white-emitting inorganic light-emitting elements are used. In organic light-emitting diode (OLED) display devices, color filters are used for color adjustment and other purposes.

[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 adding a binder resin, a photopolymerizable compound, and a photoinitiator to a color material dispersion prepared by dispersing a color material using a dispersant or the like. The resulting 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. The pattern is then fixed by heating to form the colored layer. These steps are repeated for each color to form the color filter.

[0006] In recent years, the requirements for high brightness in color filters have increased, and the concentration of colorants in the color layers of color filters has also increased compared to the past. As a result, the amount of components required for photopolymerization has decreased, making patterning increasingly difficult. Consequently, in order to improve the productivity of color filters, it is necessary to reduce the cumulative exposure required for patterning, and ensuring the curing properties required for patterning has become a major challenge.

[0007] To ensure the curability required for patterning of the colored layer, a photoinitiator with a relatively small molecular weight, such as Irgacure 907, is used as a highly sensitive photoinitiator in the coloring resin composition for color filters.

[0008] In recent years, to achieve high sensitivity, the use of oxime ester-based photoinitiators with a diphenyl sulfide or carbazole backbone has been proposed. However, these oxime ester-based photoinitiators are relatively expensive, so cost reduction is desired.

[0009] Patent document 1 states that compared with oxime ester photoinitiators having a diphenyl sulfide skeleton or a carbazole skeleton, fluorene oxime ester photoinitiators with a specific structure are less expensive and have better solubility in the matrix resin.

[0010] Patent document 2 states the following: As a photoinitiator different from oxime ester photoinitiators, fluorene-based multifunctional photoinitiators with specific structures have advantages such as low cost, excellent photoinitiation activity, and low migration.

[0011] Previous technical documents

[0012] Patent Literature

[0013] Patent Document 1: Japanese Patent Publication No. 2018-532851

[0014] Patent Document 2: Japanese Patent Publication No. 2019-507108 Summary of the Invention

[0015] The problem that the invention aims to solve

[0016] The inventors have discovered that when manufacturing color filters, if a coloring resin composition containing a previously developed highly sensitive photoinitiator is used to form a coloring layer, sublimation is easily generated from the coloring resin composition during the drying process before exposure.

[0017] The present invention was made in view of the above-mentioned actual situation, and its object is to provide a photosensitive coloring resin composition for a color filter with good sensitivity and suppressing the generation of sublimation during drying, a cured product of the photosensitive coloring resin composition for a color filter, a color filter having a coloring layer formed using the photosensitive coloring resin composition for a color filter, and a display device having the color filter.

[0018] Technical means for solving problems

[0019] The photosensitive coloring resin composition for color filters of the present invention contains a colorant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a solvent.

[0020] The above photoinitiator contains a compound represented by the following general formula (1).

[0021] [Chemical Formula 1]

[0022] General formula (1)

[0023]

[0024] (In general formula (1), R) a and R b Each is independently an alkyl group having 2 or more but fewer than 8 carbon atoms.

[0025] 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 for color filters of the present invention.

[0026] Furthermore, the present invention provides a display device having the color filter of the present invention described above.

[0027] The effects of the invention

[0028] According to the present invention, a photosensitive coloring resin composition for a color filter with good sensitivity and suppressing the generation of sublimation during drying can be provided, a cured product of the photosensitive coloring resin composition for a color filter, a color filter having a coloring layer formed using the photosensitive coloring resin composition for a color filter, and a display device having the color filter can be provided. Attached Figure Description

[0029] Figure 1 This is a schematic diagram illustrating an example of the color filter of the present invention.

[0030] Figure 2 This is a schematic diagram illustrating an example of the liquid crystal display device of the present invention.

[0031] Figure 3 This is a schematic diagram illustrating an example of the organic light-emitting display device of the present invention.

[0032] Figure 4 This is a partial diagram schematically illustrating an example of the structure of the graft copolymer used in this invention. Detailed Implementation

[0033] The following describes in detail the photosensitive coloring resin composition for color filters, the cured product, the color filter, and the display device of the present invention.

[0034] It should be noted that, in this invention, light includes electromagnetic waves with wavelengths in the visible and invisible light 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.

[0035] In this invention, (meth)acrylate group represents either an acrylic group or a methacrylate group, and (meth)acrylate ester represents either an acrylate ester or a methacrylate ester.

[0036] In this invention, unless otherwise specified, the chromaticity coordinates x and y are the chromaticity coordinates x and y in the XYZ color system of JISZ8701 obtained by colorimetry using a C light source.

[0037] I. Photosensitive coloring resin composition for color filters

[0038] The photosensitive coloring resin composition for color filters of the present invention contains a colorant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a solvent.

[0039] The above photoinitiator contains a compound represented by the following general formula (1).

[0040] [Chemical Formula 2]

[0041] General formula (1)

[0042]

[0043] (In general formula (1), R) a and R b Each is independently an alkyl group having 2 or more but fewer than 8 carbon atoms.

[0044] The photosensitive coloring resin composition for color filters of the present invention uses a compound represented by the above general formula (1) as a photoinitiator, exhibiting good sensitivity and minimizing the formation of sublimation during drying. It is believed that the sublimation formed during drying of previous coloring resin compositions before exposure originates from the photoinitiator within the coloring resin composition. If sublimation is generated from the coloring resin composition during drying before exposure, there is a possibility that the sublimation may adhere to the exhaust pipe, chamber, or other parts of the drying apparatus used in the drying process before exposure and crystallize. If the crystallized sublimation falls onto the coating film of the coloring resin composition before exposure, defects such as black spots occur in the coloring layer, resulting in a deterioration in quality. Furthermore, if the crystallization of sublimation occurs within the drying apparatus, cleaning the drying apparatus becomes difficult, leading to increased cleaning time and reduced production efficiency. Therefore, a coloring resin composition with high sensitivity and suppression of sublimation formation during drying is sought.

[0045] Because the photosensitive coloring resin composition for color filters of the present invention does not easily produce sublimation during drying before exposure, the adhesion of sublimation within the drying apparatus used in the drying process before exposure can be suppressed when a coloring layer is formed using the photosensitive coloring resin composition for color filters of the present invention. Therefore, defects such as black defects caused by sublimation adhering to the drying apparatus can also be suppressed, thereby improving production efficiency by simplifying the cleaning of the drying apparatus. Furthermore, the photosensitive coloring resin composition for color filters of the present invention has good sensitivity, thus enabling the formation of highly fine patterned coloring layers.

[0046] On the other hand, photoinitiators that are less prone to sublimation tend to have higher crystallinity. Therefore, when a coloring layer is formed by curing a photosensitive coloring resin composition containing a photoinitiator that is less prone to sublimation, precipitates may form on the surface of the coloring layer. These precipitates on the surface of the coloring layer can cause problems such as black defects when observed under transmitted light. The inventors have found that the precipitates on the surface of the coloring layer are formed immediately after the coating of the coloring resin composition has dried, before exposure. It is inferred that the precipitates on the surface of the coloring layer are formed due to the concentration and separation of the photoinitiator. In this regard, the photosensitive coloring resin composition for color filters of the present invention can suppress the formation of precipitates when forming the coloring layer. In particular, if a compound represented by the above general formula (1) and other photoinitiators different from the compound represented by the above general formula (1) are used in combination as photoinitiators, the formation of precipitates is easily suppressed. It is inferred that this is because the solvent solubility and solvent resolubility of the photoinitiator are improved, and the compatibility with other components is also improved, thus improving the dispersion stability of the photoinitiator. Furthermore, by using photoinitiators with improved solvent solubility and resolubility, as well as improved compatibility with other components, there are also advantages such as improved linearity of fine line patterns and easier suppression of micropore irregularities.

[0047] Furthermore, the photosensitive coloring resin composition for color filters of the present invention readily suppresses the generation of developing residues, and readily forms the desired micropores in the coloring layer simultaneously during patterning. In cases where a coloring layer with micropores is formed using a highly sensitive photoinitiator, free radicals are generated and migrate to the unexposed areas, making it difficult to maintain the shape of the unexposed areas within the exposed areas and to smoothly cure the periphery of the unexposed areas. Therefore, in previous photosensitive resin compositions, even with good linearity of the fine line patterns, it is difficult to form micropores if a highly sensitive photoinitiator capable of forming fine line patterns is used. In contrast, the photosensitive coloring resin composition for color filters of the present invention readily forms the desired micropores in the coloring layer by using a compound represented by the above general formula (1) as a photoinitiator. In particular, by using an antioxidant in combination with the photoinitiator, well-shaped micropores can be formed more easily. The photosensitive coloring resin composition for color filters of the present invention is suitable for applications such as forming a color layer on a TFT substrate to form a reflective color filter, and simultaneously forming a through-hole for conduction in the color layer, since it is easy to form the desired fine pores in the color layer.

[0048] The photosensitive coloring resin composition for color filters of the present invention contains colorant, alkali-soluble resin, photopolymerizable compound, photoinitiator, and solvent, and optionally also contains other components without impairing the effects of the present invention.

[0049] Hereinafter, each component of the coloring resin composition of the present invention will be described in detail, starting with the photoinitiator, which is characteristic of the present invention.

[0050] [Photoinitiator]

[0051] <Compounds represented by general formula (1)>

[0052] The photoinitiator used in this invention contains a compound represented by the above general formula (1).

[0053] In the above general formula (1), R a and R b Each alkyl group is independently an alkyl group having 2 or more but 8 or fewer carbon atoms. This alkyl group can be any of a straight-chain, branched, cyclic, or combination thereof alkyl group. Examples of such alkyl groups include: ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, n-heptyl, n-octyl, cyclopentyl, methylcyclopentyl, cyclopentylmethyl, cyclohexyl, methylcyclohexyl, cyclohexylmethyl, cyclohexylethyl, etc. From the viewpoint of suppressing the formation of sublimation and precipitates during drying, straight-chain or branched alkyl groups are preferred, and straight-chain alkyl groups are more preferred. Furthermore, the number of carbon atoms in this alkyl group is preferably 2 or more but 6 or fewer, and more preferably 3 or more but 5 or fewer.

[0054] In the above general formula (1), R a and R b Choose either the same or different from each other, if R a and R b If they are identical, they are easy to synthesize and have excellent productivity, making them the preferred choice in this respect.

[0055] Suitable specific examples of compounds represented by the above general formula (1) may be listed, for example, the following compounds (1-1), but are not limited thereto.

[0056] [Chemical Formula 3]

[0057] Compound (1-1)

[0058]

[0059] The compound represented by the above general formula (1) can be synthesized, for example, by a method including the following steps:

[0060] Step 1: Reacting fluorene with chloroisobutyryl chloride in the presence of aluminum trichloride to obtain 2-methyl-1-fluorenyl-2-chloro-1-propanone;

[0061] In a nitrogen atmosphere, 2-methyl-1-fluorenyl-2-chloro-1-propanone obtained in step 1 is epoxidized using sodium methoxide as a catalyst, and then reacted with morpholine to obtain step 2 of 2-methyl-1-fluorenyl-2-morpholinyl-1-propanone; and

[0062] Step 3 involves reacting 2-methyl-1-fluorenyl-2-morpholino-1-propanone obtained in step 2 above with a chloroalkane having 2 or more carbon atoms and 8 or fewer carbon atoms, in the presence of tetrabutylammonium bromide (TBAB), thereby obtaining the compound represented by the above general formula (1).

[0063] It should be noted that in step 3 above, R in the above general formula (1) can be obtained by using two or more chloroalkanes. a and R b Different compounds.

[0064] [Chemical Formula 4]

[0065] Process 1

[0066]

[0067]

[0068] <Other photoinitiators>

[0069] Regarding the suppression of precipitate formation, the coloring resin composition of the present invention preferably contains a photoinitiator that is different from the compound represented by the general formula (1) above. It should be noted that the photoinitiator used in the coloring resin composition of the present invention includes chain transfer agents in addition to photopolymerization initiators.

[0070] Other photoinitiators mentioned above include, for example, α-aminoketone photoinitiators, oxime ester photoinitiators, diimidazole photoinitiators, thioxanone photoinitiators, acylphosphine oxide photoinitiators, and mercapto chain transfer agents, which are different from the compounds represented by the general formula (1) above.

[0071] In terms of the ease with which the generation of precipitates is suppressed or the sensitivity is improved, and in the case of use in combination with the graft copolymer or salt-type graft copolymer described below as a dispersant, the effect of suppressing the generation of developing residues and improving NMP resistance is excellent, other photoinitiators different from the compounds represented by the above general formula (1) are preferably one or more of the group consisting of oxime ester photoinitiators and α-aminoketone photoinitiators.

[0072] It should be noted that, from the viewpoint that when used in combination with the graft copolymer or salt-type graft copolymer described below as a dispersant, the photoinitiator is preferably a compound represented by the above general formula (1) and has excellent effects in suppressing the generation of developing residue and improving NMP resistance.

[0073] Furthermore, in terms of suppressing the generation of precipitates or improving sensitivity, the total content of oxime ester photoinitiators and α-aminoketone photoinitiators in the total amount of the other photoinitiators is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more.

[0074] Furthermore, regarding the suppression of sublimation formation during drying, the molecular weight of the aforementioned other photoinitiators is preferably 350 or more, more preferably 355 or more, and even more preferably 360 or more. There is no particular upper limit to the molecular weight of the aforementioned other photoinitiators; they are typically 1000 or less, but can be 800 or less, or even 600 or less.

[0075] Not particularly limited, but in terms of suppressing the generation of sublimation during drying, the total content of photoinitiators with a molecular weight of 350 or more in the total amount of the other photoinitiators is preferably 50% or more by mass, more preferably 70% or more by mass, and even more preferably 90% or more by mass.

[0076] When using oxime ester-based photoinitiators as other photoinitiators mentioned above, it is easier to suppress the formation of precipitates, and consequently, when forming fine line patterns, it is easier to suppress unevenness in line width within the surface. Furthermore, the use of oxime ester-based photoinitiators tends to improve development resistance and enhance the suppression of water spots. It should be noted that water spots refer to traces resembling water seepage that appear after rinsing with pure water following alkaline development if an ingredient that enhances alkaline developability is used. These water spots disappear after post-baking, so they are not a problem for the finished product. However, during the visual inspection of the patterned surface after development, they are detected as spot abnormalities, making it difficult to distinguish between normal and abnormal products. If the inspection sensitivity of the inspection device is reduced during visual inspection for this reason, it results in a decrease in the yield of the final color filter products, which becomes a problem.

[0077] As an oxime ester photoinitiator, in terms of suppressing the formation of sublimation during drying and suppressing the formation of precipitates, it is preferable to have an aromatic ring, more preferably a fused ring including an aromatic ring, and even more preferably a carbazole skeleton, a diphenyl sulfide skeleton, or a fluorene skeleton. In terms of easily improving sensitivity by combining with compounds represented by the above general formula (1), oxime ester photoinitiators having a carbazole skeleton or a diphenyl sulfide skeleton are also preferred.

[0078] As an oxime ester photoinitiator, an appropriate selection may be made from the oxime ester photoinitiators described in, for example, 1,2-octanedione-1-[4-(phenylthio)phenyl]-,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 with a carbazole backbone include, for example, Irgacure OXE-02 (manufactured by BASF), Adeka ARKLS NCI-831 (manufactured by ADEKA), and TR-PBG-304 (manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.). Commercially available photoinitiators with a diphenyl sulfide backbone include, for example, Adeka ARKLS NCI-930 (manufactured by ADEKA), TR-PBG-345, TR-PBG-3057 (both manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.), and Irgacure OXE-01 (manufactured by BASF). Commercially available photoinitiators with a fluorene backbone include, for example, TR-PBG-365 (manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.).

[0079] As a carbazole skeleton oxime ester photoinitiator, the oxime ester compound represented by the following general formula (2) can be suitably used in terms of suppressing the generation of precipitates and improving sensitivity.

[0080] [Chemical Formula 5]

[0081] General formula (2)

[0082]

[0083] (In general formula (2), R) c R is a hydrocarbon group containing at least one divalent linker selected from thioether (-S-), ether (-O-), and carbonyl (-CO-), having 7 or more carbon atoms and less than 14 carbon atoms. d Z is a hydrogen atom or a hydrocarbon group having 1 or more but less than 4 carbon atoms. 1 (For hydrogen atoms or nitro groups)

[0084] In general formula (2), R c It is a hydrocarbon group with 7 or more carbon atoms and less than 14 carbon atoms that contains at least one divalent linker selected from thioether (-S-), ether (-O-), and carbonyl (-CO-).

[0085] As mentioned above, R cThe hydrocarbon group having 7 or more but less than 14 carbon atoms can be exemplified by alkyl, alkenyl, aryl, aralkyl, etc., with alkyl, aryl, and aralkyl being preferred. The alkyl group can be linear, branched, or cyclic, or a combination of linear and cyclic. Examples of alkyl groups include heptyl, octyl, nonyl, decyl, dodecyl, cyclohexylmethyl, cyclopentylethyl, cyclohexylethyl, borneol, isoborneol, dicyclopentyl, adamantyl, and lower alkyl-substituted adamantyl. Examples of aryl groups include groups where at least one hydrogen atom of the phenyl group is substituted with an alkyl group having 1 or more but less than 6 carbon atoms, biphenyl, naphthyl, and groups where one or two hydrogen atoms of biphenyl and naphthyl are substituted with methyl or ethyl groups. Examples of aralkyl groups include benzyl, phenethyl, naphthylmethyl, naphthylethyl, etc. As R c The hydrocarbon group in the hydrocarbon group is preferably an alkyl, aralkyl, or aryl group with 7 or more but less than 12 carbon atoms, and is particularly preferred to include aliphatic rings such as cyclohexane or aromatic rings such as benzene, as well as straight-chain or branched alkyl or alkylene groups, in order to easily suppress precipitates.

[0086] Furthermore, in the aforementioned R c In this process, the presence of the aforementioned divalent linking group in the hydrocarbon group improves solvent solubility and miscibility, and suppresses the formation of precipitates. As the aforementioned divalent linking group, in terms of improving solvent solubility, a thioether bond (-S-) or an ether bond (-O-) is preferred, and an ether bond (-O-) is more preferred. In the aforementioned R... c In the case where the aforementioned hydrocarbon group contains the aforementioned divalent linking group, the aforementioned hydrocarbon group can bond to the carbon atom of the oxime ester group via the aforementioned divalent linking group, or the carbon atom of the aforementioned hydrocarbon group can directly bond to the carbon atom of the oxime ester group. In the aforementioned R... c In the case where the hydrocarbon group contains the divalent linker and the carbon atom of the hydrocarbon group is directly bonded to the carbon atom of the oxime ester group, examples include the aforementioned R... c This refers to groups formed by bonding hydrocarbon groups together through the aforementioned divalent linking groups. Examples of groups formed by bonding hydrocarbon groups together through the aforementioned divalent linking groups include: structures containing thioether bonds (-S-) such as alkylthioalkyl and arylthioalkyl; structures containing ether bonds (-O-) such as alkoxyalkyl and aryloxyalkyl such as methoxycyclohexyl; and structures containing carbonyl bonds (-CO-) such as benzoylmethyl and acylalkyl.

[0087] In general formula (2), R d It is a hydrogen atom or a hydrocarbon group having 1 or more but 4 or fewer carbon atoms. From the viewpoint of suppressing the generation of precipitates, a hydrocarbon group having 1 or more but 4 or fewer carbon atoms is preferred, an alkyl group having 1 or more but 4 or fewer carbon atoms is more preferred, and a methyl or ethyl group is even more preferred.

[0088] As an oxime ester compound represented by the above general formula (2), for example, the following compound (2-1) may be suitably used.

[0089] [Chemical Formula 6]

[0090] Compound (2-I)

[0091]

[0092] Commercially available examples of the aforementioned compound (2-1) include, for example, Adeka ARKLS NCI-831 (manufactured by ADEKA Corporation).

[0093] It should be noted that the oxime ester compound represented by the above general formula (2) can be synthesized, for example, with reference to Japanese Patent No. 6119922.

[0094] As a photoinitiator of oxime esters with a diphenyl sulfide skeleton, an oxime ester compound represented by the following general formula (3) may be suitably used in terms of suppressing the generation of precipitates and improving sensitivity.

[0095] [Chemical Formula 7]

[0096] General formula (3)

[0097]

[0098] (In general formula (3), R) c′ Z is a hydrocarbon group containing at least one divalent linker selected from thioether (-S-), ether (-O-), and carbonyl (-CO-), having 7 or more carbon atoms and less than 14 carbon atoms. 1′ (It can be a hydrogen atom or a nitro group.)

[0099] R as general formula (3) c′ The optional hydrocarbon group containing at least one divalent linker selected from thioether (-S-), ether (-O-), and carbonyl (-CO-) bonds, having a carbon number of 7 or more and 14 or less, such as R in the above general formula (2). c The same. Furthermore, R in the above general formula (2) c The preferred candidate in general formula (3) is R. c′ It is also a top choice.

[0100] As an oxime ester compound represented by the above general formula (3), for example, the following compound (3-1) may be suitably used.

[0101] [Chemical Formula 8]

[0102] Compound (3-1)

[0103]

[0104] Commercially available examples of the aforementioned compound (3-1) include, for example, TR-PBG-3057 (manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.).

[0105] It should be noted that the oxime ester compound represented by the above general formula (3) can be synthesized, for example, with reference to Japanese Patent Publication No. 2012-526185.

[0106] As a photoinitiator of oxime esters with a fluorene skeleton, an oxime ester compound represented by the following general formula (4) may be suitably used in terms of suppressing the generation of precipitates.

[0107] [Chemical Formula 9]

[0108] General formula (4)

[0109]

[0110] (In general formula (4), R) c″ R is a hydrocarbon group containing at least one divalent linker selected from thioether (-S-), ether (-O-), and carbonyl (-CO-), having 7 or more carbon atoms and less than 14 carbon atoms. e and R f Each is independently a hydrogen atom or a hydrocarbon group having 1 or more but less than 6 carbon atoms, Z 1″ (It can be a hydrogen atom or a nitro group.)

[0111] R as general formula (4) c″ The optional hydrocarbon group containing at least one divalent linker selected from thioether (-S-), ether (-O-), and carbonyl (-CO-) bonds, having a carbon number of 7 or more and 14 or less, such as R in the above general formula (2). c The same. Furthermore, R in the above general formula (2) c The preferred candidate in general formula (4) is R. c″ It is also a top choice.

[0112] In general formula (4), R e and R f Each is independently a hydrogen atom or a hydrocarbon group having 1 or more but 6 or fewer carbon atoms. From the viewpoint of suppressing the generation of precipitates, an alkyl group having 1 or more but 6 or fewer carbon atoms is preferred, and a straight-chain alkyl group having 2 or more but 6 or fewer carbon atoms is more preferred.

[0113] As an oxime ester compound represented by the above general formula (4), for example, the following compound (4-1) may be suitably used.

[0114] [Chemical Formula 10]

[0115] Compound (4-1)

[0116]

[0117] Commercially available examples of the aforementioned compound (4-1) include, for example, TR-PBG-365 (manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.).

[0118] As an oxime ester photoinitiator, in terms of suppressing the generation of precipitates, it is preferable to select one or more from the group consisting of oxime ester compounds represented by the above general formula (2), oxime ester compounds represented by the above general formula (3), and oxime ester compounds represented by the above general formula (4). In terms of suppressing the generation of precipitates and improving sensitivity, it is more preferable to select one or more from the group consisting of oxime ester compounds represented by the above general formula (2) and oxime ester compounds represented by the above general formula (3). It is particularly preferable to select one or more from the above compound (2-1) and the above compound (3-1).

[0119] When using an α-aminoketone photoinitiator that is different from the compound represented by the above general formula (1) as the other photoinitiator, it is preferable that the generation of precipitates is easily suppressed and the crosslinking density in the colored layer is easily made uniform.

[0120] Examples of α-aminoketone photoinitiators include: 2-methyl-1-(4-methylthiophenyl)-2-morpholinylpropane-1-one (e.g., Irgacure 907, manufactured by BASF), 2-benzyl-2-(dimethylamino)-1-(4-morpholinylphenyl)-1-butanone (e.g., Irgacure 369, manufactured by BASF), and 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone (Irgacure 379EG, manufactured by BASF).

[0121] As an α-aminoketone photoinitiator, it can be used alone or in combination of two or more. In terms of suppressing the generation of precipitates, as well as suppressing the reduction of residual film rate and the obstruction of micropores, 2-methyl-1-(4-methylthiophenyl)-2-morpholinylpropane-1-one and 2-benzyl-2-(dimethylamino)-1-(4-morpholinylphenyl)-1-butanone are preferred. In terms of further suppressing the generation of sublimation, 2-benzyl-2-(dimethylamino)-1-(4-morpholinylphenyl)-1-butanone is more preferred.

[0122] Examples of diimidazole-based photoinitiators include: 2,2′-bis(2-chlorophenyl)-4,4′,5,5′-tetra(4-ethoxycarbonylphenyl)-1,2′-diimidazole, 2,2′-bis(2-bromophenyl)-4,4′,5,5′-tetra(4-ethoxycarbonylphenyl)-1,2′-diimidazole, 2,2′-bis(2-chlorophenyl)-4,4′,5,5′-tetraphenyl-1,2′-diimidazole, and 2,2′-bis(2,4-dichlorophenyl)-4,4′,5,5′-tetraphenyl-1,2′-diimidazole. Phenyl-1,2′-diimidazole, 2,2′-bis(2,4,6-trichlorophenyl)-4,4′,5,5′-tetraphenyl-1,2′-diimidazole, 2,2′-bis(2-bromophenyl)-4,4′,5,5′-tetraphenyl-1,2′-diimidazole, 2,2′-bis(2,4-dibromophenyl)-4,4′,5,5′-tetraphenyl-1,2′-diimidazole, 2,2′-bis(2,4,6-tribromophenyl)-4,4′,5,5′-tetraphenyl-1,2′-diimidazole, etc.

[0123] As a diimidazole photoinitiator, it can be used alone or in combination with two or more other types.

[0124] Examples of thioxanthone photoinitiators include: 2,4-isopropylthioxanthone, 2,4-diethylthioxanthone, 1-chloro-4-propoxythioxanthone, and 2,4-dichlorothioxanthone.

[0125] As a thioxanthone-based photoinitiator, it can be used alone or in combination of two or more types. In terms of improving the transfer of free radical generation, 2,4-isopropylthioxanthone and 2,4-diethylthioxanthone are preferred.

[0126] Acylphosphine oxide photoinitiators have the property of less heat-induced yellowing, so although they are suitable for improving brightness, they usually have low sensitivity and cannot achieve sufficient curability. However, when combined with compounds represented by the above general formula (1), the overall curability of the coating film is improved, the non-smoothness at the ends of the pores is suppressed when forming micropores, and micropores with good dimensional accuracy are easily formed, which is preferred in this respect.

[0127] Examples of acylphosphine oxide photoinitiators include: benzoyl-diphenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 2,3,5,6-tetramethylbenzoyl-diphenylphosphine oxide, 3,4-dimethylbenzoyl-diphenylphosphine oxide, 2,4,6-trimethylbenzoyl-phenylethoxyphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide, and bis(2,6-dimethylbenzoyl)-ethylphosphine oxide.

[0128] As an acylphosphine oxide photoinitiator, it can be used alone or in combination of two or more types. In terms of improving the curability of the coating film, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide is preferred.

[0129] Thiol-based chain transfer agents have the property of accelerating reactions by accepting free radicals from slow-reacting free radicals, especially when combined with diimidazole-based photoinitiators, they tend to increase the reaction rate and are preferred in this respect.

[0130] Examples of mercapto-based chain transfer agents 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, 1,4-bis(3-mercaptobutyryloxy)butane, 1,3,5-tris(3-mercaptobutyrylethyl)-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), etc.

[0131] As a thiol-based chain transfer agent, it can be used alone or in combination of two or more, with 2-mercaptobenzothiazole being preferred in terms of improving reaction rate.

[0132] The total content of photoinitiator used in the photosensitive coloring resin composition for color filters of the present invention is not particularly limited as long as it does not impair the effects of the present invention. It is preferably within the range of 0.1% by mass or more and 12.0% by mass or less, and more preferably 1.0% by mass or more and 8.0% by mass or less, relative to the total solid content of the photosensitive coloring resin composition for color filters. If this content is above the lower limit, sufficient photocuring is achieved, suppressing the dissolution of the exposed portion during development. On the other hand, if it is below the upper limit, the reduction in brightness caused by yellowing of the obtained coloring layer can be suppressed.

[0133] It should be noted that the solid component includes all components other than the solvent, including liquid multifunctional monomers, etc.

[0134] When the photoinitiator contains the compound represented by the general formula (1) and the other photoinitiators mentioned above, the content of the compound represented by the general formula (1) in the total amount of 100% by mass of the photoinitiator is preferably 10% by mass or more and 98% by mass or less, more preferably 20% by mass or more and 95% by mass or less, and even more preferably 30% by mass or more and 95% by mass or less, and is particularly preferably 50% by mass or more and 90% by mass or less, in terms of further suppressing the generation of precipitates and easily improving sensitivity.

[0135] [color material]

[0136] In this invention, the colorant only needs to achieve the desired color development when forming the coloring layer of the color filter, and there are no particular limitations. It can be used alone or in combination with two or more kinds of organic pigments, dyes, dispersible dyes, and inorganic pigments. Among them, organic pigments are preferred because of their high color development and high heat resistance.

[0137] As organic pigments, for example, compounds classified as pigments in the Dye Index (CI; published by The Society of Dyers and Colourists) can be listed, specifically those labeled with the Dye Index (CI) number as follows.

[0138] It should be noted that when listing dye index names below, if only the numbers differ among the dye index names, then only that number may be listed.

[0139] CI Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 55, 60, 61, 65, 71, 73, 74, 81, 83, 93, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 116, 117, 119, 120, 126, 127, 128, 129, 138, 139, 150, 151, 152, 153, 154, 155, 156, 166, 168, 175, 185;

[0140] CI Pigment Orange 1, 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 61, 63, 64, 71, 73;

[0141] CI pigments: purple 1, 19, 23, 29, 32, 36, 38;

[0142] CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48:1, 48:2, 48:3, 48:4, 49:1, 49:2, 50:1, 52:1, 53:1, 57, 57:1, 57:2, 58:2, 58:4, 60:1, 63:1, 63:2, 64:1, 81:1, 83, 88, 90:1, 97, 101, 102, 104 105, 106, 108, 112, 113, 114, 122, 123, 144, 146, 149, 150, 151, 166, 168, 170, 171, 172, 174, 175, 176, 177, 178, 179, 180, 185, 187, 188, 190, 193, 194, 202, 206, 207, 208, 209, 215, 216, 220, 224, 226, 242, 243, 245, 254, 255, 264, 265, 269, 291;

[0143] CI Pigment Blue 15, 15:3, 15:4, 15:6, 60;

[0144] CI Pigment Green 7, 36, 58, 59, 62, 63;

[0145] CI Pigment Brown 23, 25;

[0146] CI Pigment Black 1, 7.

[0147] The aforementioned dyes can be appropriately selected from previously known dyes. Examples of such dyes include: azo dyes, metal complex salt azo dyes, anthraquinone dyes, triarylmethane dyes, xanthones, cyanine dyes, naphthoquinone dyes, quinone imine dyes, methylene dyes, and phthalocyanine dyes. Specifically, examples include: CI Solvent Yellow 4, 14, 15, 24, 82, 88, 94, 98, 162, and 179.

[0148] CI Solvent Red 45, 49;

[0149] CI Solvent Orange 2, 7, 11, 15, 26, 56;

[0150] CI Solvent Blue 35, 37, 59, 67;

[0151] CI Acid Red 50, 52, 289;

[0152] CI Acid Violet 9, 30;

[0153] CI Acid Blue 19, etc.

[0154] Examples of such dispersible dyes include dyes that become dispersible by imparting various substituents to the dye, making it insoluble in solvents; dyes that become dispersible by combining with solvents with low solubility; and lake dyes that insoluble dyes are formed into salts with counterions, thus becoming insoluble (lake-like). By combining such dispersible dyes with dispersants, the dispersibility and dispersion stability of the dye can be improved.

[0155] It should be noted that, as a standard, if the amount of dye dissolved relative to 10g of solvent (or mixed solvent) is less than 100mg, then the dye can be determined to be dispersible in the solvent (or mixed solvent).

[0156] Specific examples of the aforementioned inorganic pigments include: titanium dioxide, barium sulfate, calcium carbonate, zinc white, lead sulfate, litharge, zinc yellow, iron oxide (iron(III) red), cadmium red, ultramarine, iron blue, chromium oxide green, cobalt green, amber, titanium black, synthetic iron black, carbon black, etc.

[0157] When forming a red coloring layer, the colorant used may preferably be one or more selected from CI Pigment Red 177, 254, 269, and 291.

[0158] When forming a green coloring layer, it is preferable to use one or more of CI Pigment Green 62 and CI Pigment Green 63 as the colorant. If one or more of CI Pigment Green 62 and CI Pigment Green 63 are used in combination with the compound represented by the above general formula (1) as a photoinitiator, the effect of suppressing the decrease in brightness of the coloring layer caused by post-baking is greater. It is inferred that this is because CI Pigment Green 62 and CI Pigment Green 63 interact with the compound represented by the above general formula (1) before and after post-baking. It is inferred that since the compound represented by the above general formula (1) has a fluorene skeleton with excellent heat resistance and alkyl groups with 2 or more and 8 or fewer carbon atoms, the steric hindrance of these structures makes it easy to maintain the molecular steric structure of CI Pigment Green 62 and CI Pigment Green 63 before and after post-baking, thus making it easy to maintain the brightness of the coloring layer before and after post-baking.

[0159] When forming a green coloring layer, zinc phthalocyanine polyhalogenated (ZPBA) represented by the following general formula (i) is preferably used as the colorant. If ZPBA represented by the following general formula (i) is also used in combination with the compound represented by the above general formula (1) as a photoinitiator, the effect of suppressing the decrease in brightness of the coloring layer caused by post-baking is greater. This is presumably because ZPBA represented by the following general formula (i) also interacts with the compound represented by the above general formula (1) in the same way as CI Pigment Green 62 and CI Pigment Green 63 before and after post-baking, thereby easily maintaining the three-dimensional structure of the colorant molecules after post-baking, and thus easily maintaining the brightness of the coloring layer before and after post-baking.

[0160] [Chemical Formula 11]

[0161] General formula (i)

[0162]

[0163] (In general formula (i), X) 1 ~X 16 Each molecule consists independently of chlorine, bromine, or hydrogen atoms. The average number of chlorine atoms in one molecule is less than 1, the average number of bromine atoms exceeds 13, and the average number of hydrogen atoms is less than 2.

[0164] From the viewpoint of high brightness, in the mass spectrum of zinc phthalocyanine polyhalogenated represented by the above general formula (i) measured by mass spectrometry, the value obtained by dividing the maximum ion intensity with m / z of 1780 or higher and less than 1820 by the maximum ion intensity with m / z of 1820 or higher and less than 1860 is preferably 1.00 or lower, more preferably less than 1.00, even more preferably 0.9 or lower, and particularly preferably 0.85 or lower. It should be noted that the lower limit of the above value is not particularly limited, and is usually 0.50 or higher.

[0165] Furthermore, when forming a green coloring layer, the color material used may preferably be a green color material formed by combining one or more of CI pigment green 58 and CI pigment green 59, which are zinc phthalocyanine pigments, with a yellow color material.

[0166] As a yellow pigment used in combination with zinc phthalocyanine pigments such as CI pigment green 58 and 59, it is preferably selected from at least one of CI pigment yellow 138, CI pigment yellow 150, and derivative pigments of CI pigment yellow 150.

[0167] As a preferred derivative pigment of CI Pigment Yellow 150, examples of yellow pigments include: at least one anion selected from the group consisting of mono, di, tri, and tetra anions of azo compounds and their tautomers represented by the following general formula (A); ions of at least two metals selected from the group consisting of Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Ni, Cu, and Mn; and compounds represented by the following general formula (B).

[0168] [Chemical Formula 12]

[0169] General formula (A)

[0170]

[0171] (In general formula (A), R) g R is independently -OH, -NH2, -NH-CN, acylamino, alkylamino, or arylamino. h They can be independently -OH or -NH2.

[0172] [Chemical Formula 13]

[0173] General formula (B)

[0174]

[0175] (In general formula (B), R) j Each can be independently a hydrogen atom or an alkyl group.

[0176] Examples of acyl groups in the acylamino group of general formula (A) include: alkyl carbonyl, phenyl carbonyl, alkyl sulfonyl, phenyl sulfonyl; carbamoyl group substituted with alkyl, phenyl, or naphthyl; carbamoyl group substituted with alkyl, phenyl, or naphthyl; and formamidinyl group substituted with alkyl, phenyl, or naphthyl. The alkyl group is preferably substituted with 1 or more carbon atoms and 6 or fewer carbon atoms. Furthermore, the alkyl group may be substituted with at least one of the following: halogens such as F, Cl, Br; -OH, -CN, -NH2; and alkoxy groups with 1 or more carbon atoms and 6 or fewer carbon atoms. Additionally, the phenyl and naphthyl groups may be substituted with, for example, halogens such as F, Cl, Br; -OH, -CN, -NH2, -NO2; alkyl groups with 1 or more carbon atoms and 6 or fewer carbon atoms; and / or alkoxy groups with 1 or more carbon atoms and 6 or fewer carbon atoms.

[0177] The alkyl group in the alkylamino group of general formula (A) is preferably one with 1 or more carbon atoms and 6 or fewer carbon atoms. The alkyl group may be substituted with halogens such as F, Cl, Br, -OH, -CN, -NH2, and / or alkoxy groups having 1 or more carbon atoms and 6 or fewer carbon atoms.

[0178] Aryl groups in the arylamino group of general formula (A) can be phenyl or naphthyl, and these aryl groups can be substituted by halogens such as F, Cl, Br, -OH, alkyl groups with 1 or more carbon atoms and 6 or fewer, alkoxy groups with 1 or more carbon atoms and 6 or fewer, -NH2, -NO2, and -CN.

[0179] Among the azo compounds represented by the above general formula (A) and their tautomers, R g In terms of hue, it is preferable that the two Rs are independently -OH, -NH2, -NH-CN, or alkylamino, respectively. g Choose either the same or different from each other.

[0180] In the above general formula (A), in terms of hue, two Rs are preferred. g The cases are all -OH, all -NH-CN, or one is -OH and the other is -NH-CN, and more preferably, both are -OH.

[0181] Furthermore, among the azo compounds represented by the above general formula (A) and their tautomers, as R h In terms of hue, it is more preferable if both are -OH.

[0182] The metal is selected from the group consisting of Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Ni, Cu and Mn, wherein it preferably contains at least one metal that is a divalent or trivalent cation, preferably contains at least one metal selected from the group consisting of Ni, Cu and Zn, and more preferably contains at least Ni.

[0183] Furthermore, it is preferable to contain Ni and at least one metal selected from the group consisting of Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Cu, and Mn; more preferably, it contains Ni and at least one metal selected from the group consisting of Zn, Cu, Al, and Fe. Among these, Ni and Zn, or Ni and Cu, are particularly preferred as the at least two metals mentioned above.

[0184] In the aforementioned yellow pigment material, which is a derivative pigment of CI Pigment Yellow 150, it is sufficient to prepare it by appropriately containing at least two metals.

[0185] Regarding the hue, in the aforementioned yellow pigment, the proportion of Ni and at least one metal selected from the group consisting of Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Cu and Mn is preferably in a molar ratio of Ni: other at least one of the aforementioned metals of 97:3 to 10:90, and more preferably in a molar ratio of 90:10 to 10:90.

[0186] In terms of hue, it is preferable to contain Ni and Zn in a molar ratio of 90:10 to 10:90, and even more preferably in a molar ratio of 80:20 to 20:80.

[0187] Alternatively, in terms of hue, it is preferable to contain Ni and Cu in a molar ratio of 97:3 to 10:90, and even more preferably in a molar ratio of 96:4 to 20:80.

[0188] The aforementioned yellow pigment, which is a derivative pigment of CI Pigment Yellow 150, may also contain metal ions different from the specific metal ions mentioned above. For example, the aforementioned yellow pigment may optionally contain at least one metal ion selected from the group consisting of Li, Cs, Mg, Na, K, Ca, Sr, Ba, and La.

[0189] As examples of ways in which the aforementioned yellow pigment contains ions of at least two metals, cases where at least two metal ions are contained in a common lattice, and cases where crystallization and aggregation occur where each of the different lattices contains ions of one metal. Of these, the case where the common lattice contains ions of at least two metals is preferred for further enhancing contrast. It should be noted that the cases where the common lattice contains ions of at least two metals, or where crystallization and aggregation occur where each of the different lattices contains ions of one metal, can be appropriately determined using X-ray diffraction, for example, with reference to Japanese Patent Application Publication No. 2014-12838.

[0190] The aforementioned yellow pigment, a derivative of CI Pigment Yellow 150, also contains a compound represented by the following general formula (B). The aforementioned yellow pigment comprises a complex molecule of a metal complex and a compound represented by the following general formula (B), wherein the metal complex comprises an anion of an azo compound represented by the above general formula (A) and its tautomeristic azo compound, and a specific metal ion. These intermolecular bonds can be formed, for example, through intermolecular interactions, Lewis acid-base interactions, or through coordination bonds. Furthermore, it can also be a structure such as an inclusion compound in which guest molecules are incorporated into the crystal lattice constituting the host molecule. Alternatively, it can be a mixed substitution crystallization, such as two substances forming a eutectic where the atoms of the second component are located in regular lattice positions of the first component.

[0191] [Chemical Formula 14]

[0192] General formula (B)

[0193]

[0194] (In general formula (B), R) j Each can be independently a hydrogen atom or an alkyl group.

[0195] As R j The alkyl group in the alkyl group is preferably an alkyl group having 1 or more carbon atoms and 6 or fewer carbon atoms, and more preferably an alkyl group having 1 or more carbon atoms and 4 or fewer carbon atoms. The alkyl group may be substituted with a -OH group.

[0196] Among them, R j Hydrogen atoms are preferred.

[0197] The content of the compound represented by the above general formula (B) is based on 1 mole of the azo compound represented by the above general formula (A) and the azo compound with tautomerism, and is usually 5 moles or more and 300 moles or less, preferably 10 moles or more and 250 moles or less, and even more preferably 100 moles or more and 200 moles or less.

[0198] In addition, the aforementioned yellow pigments, which are derivatives of CI Pigment Yellow 150, may also contain: urea and substituted urea, such as phenylurea, dodecylurea, etc., and their condensation products with aldehydes, especially formaldehyde; heterocyclic compounds, such as barbituric acid, benzimidazolone, benzimidazolone-5-sulfonic acid, 2,3-dihydroxyquinoxaline, 2,3-dihydroxyquinoxaline-6-sulfonic acid, carbazole, carbazole-3,6-disulfonic acid, 2-hydroxyquinoline, 2,4-dihydroxyquinoline, caprolactam, melamine, 6-phenyl-1,3,5-triazine-2,4-diamine, 6-methyl-1,3,5-triazine-2,4-diamine, cyanuric acid, etc.

[0199] In addition, the aforementioned yellow pigment may further contain water-soluble polymers, such as ethylene oxide-propylene oxide block polymers, polyvinyl alcohol, poly(meth)acrylic acid; and modified celluloses such as carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, methyl- and ethyl hydroxyethyl cellulose, etc.

[0200] The aforementioned yellow pigment, which is a derivative pigment of CI Pigment Yellow 150, can be prepared, for example, by referring to Japanese Patent Application Publication No. 2014-12838.

[0201] Furthermore, when forming a green coloring layer, the color material used may preferably be a green color material that is selected from the group consisting of color materials represented by general formula (ii) and general formula (iii) as complementary colors, in terms of heat resistance, light resistance, and high brightness of the color filter.

[0202] When forming a blue coloring layer, a blue coloring material preferably used is a combination of CI pigment blue 15:6, which is a copper phthalocyanine pigment, and CI pigment violet 23, or other purple coloring materials.

[0203] Furthermore, regarding the high brightness of the colorant used to form the blue coloring layer, it is preferable to contain at least one of a triarylmethane dye, a succinate dye, and an indigo dye. In terms of high heat resistance, it is preferable to contain at least one of a triarylmethane dye and a succinate dye, and more preferably a triarylmethane lake colorant. It is also preferable to use the above-mentioned dyes or lake colorants in combination with organic pigments such as CI Pigment Blue 15:6, which is a copper phthalocyanine pigment.

[0204] Regarding the aforementioned triarylmethane lake pigments, which exhibit excellent heat resistance and lightfastness and achieve high brightness in color filters, it is preferable that they contain a triarylmethane basic dye and a polyacid anion. For example, it is preferable to use one or more pigments selected from the group consisting of pigments represented by general formula (ii) and pigments represented by general formula (iii) below, and it is particularly preferable to use pigments represented by general formula (ii).

[0205] The coloring resin composition of the present invention, by combining one or more pigments selected from the group consisting of pigments represented by general formula (ii) and pigments represented by general formula (iii) below, with a compound represented by general formula (1) below as a photoinitiator, can form a coloring layer with particularly improved heat resistance. This is presumably because by using a compound represented by general formula (1) below as a photoinitiator with good sensitivity, the crosslinking density of the coloring layer is increased, and consequently, the pigments represented by general formula (ii) and general formula (iii) interact with the compound represented by general formula (1) above before and after post-baking. It is presumed that because the compound represented by general formula (1) has a fluorene backbone with excellent heat resistance and alkyl groups having 2 or more and 8 or fewer carbon atoms, the pigments represented by general formula (ii) and general formula (iii) easily maintain the aggregated dye molecules after post-baking due to the steric hindrance of these structures, thus reducing the likelihood of color difference in the coloring layer before and after post-baking.

[0206] [Chemical Formula 15]

[0207] General formula (ii)

[0208]

[0209] (In general formula (ii), A is an α-valent organic group whose carbon atom directly bonded to N does not have a π bond, and the organic group represents an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at the end directly bonded to N, or an aromatic group having such aliphatic hydrocarbon group, optionally containing heteroatoms in the carbon chain; B) c- Represents a C-valent polyacid anion; R i ~R v Each of the following groups independently represents a hydrogen atom, an alkyl group optionally with substituents, or an aryl group optionally with substituents; Rii With R iii R iv With R v Optional bonding forms a ring structure; R vi and R vii Each of these can be independently represented as an alkyl group, an alkoxy group, a halogen atom, or a cyano group, optionally with a substituent; Ar 1 Represents an optional divalent aromatic group with substituents; multiple R groups are present. i ~R vii and Ar 1 Choose either the same or different from each other;

[0210] a and c represent integers greater than 2; b and d represent integers greater than 1; e is 0 or 1, and there is no bond when e is 0; f and g represent integers greater than 0 and less than 4, and f+e and g+e are greater than 0 and less than 4; multiple e, f, and g can be chosen to be the same or different.

[0211] [Chemical Formula 16]

[0212] General formula (iii)

[0213]

[0214] (In general formula (iii), R) I ~R VI Each of the following groups independently represents a hydrogen atom, an alkyl group optionally with substituents, or an aryl group optionally with substituents; R I With R II R III With R IV R V With R VI Optional bonding forms a ring structure; R VII and R VIII Each of these can be independently represented as an alkyl group, an alkoxy group, a halogen atom, or a cyano group, optionally with a substituent; Ar 2 This indicates a divalent aromatic heterocyclic group with optional substituents, and the presence of multiple R groups. I ~R VIII and Ar 2 Choose either the same or different from each other; E m- Indicates m-valent polyacid anions;

[0215] m represents an integer greater than 2; j is 0 or 1, and there is no bond when j is 0; k and l represent integers greater than 0 and less than 4, k+j and l+j are greater than 0 and less than 4; multiple j, k, and l can be chosen to be the same or different.

[0216] Since the pigment represented by the above general formula (ii) contains divalent or higher anions and divalent or higher cations, the anions and cations in the aggregate of this pigment are not simply ionicly bonded one molecule to one molecule. Instead, they can form molecular aggregates of multiple molecules gathered through ionic bonds. Therefore, the apparent molecular weight is significantly increased compared to the molecular weight of previous lake pigments. It is inferred that through the formation of such molecular aggregates, the cohesive force in the solid state is further enhanced, which can reduce thermal motion, inhibit the dissociation of ion pairs and the decomposition of cations, and thus make it less prone to fading compared to previous lake pigments.

[0217] In the above general formula (ii), A is an α-valent organic group whose carbon atom directly bonded to N (nitrogen atom) does not have a π bond. This organic group represents an aliphatic hydrocarbon group with a saturated aliphatic hydrocarbon group at least at the end directly bonded to N, or an aromatic group with such an aliphatic hydrocarbon group, and the carbon chain optionally contains heteroatoms such as O (oxygen atom), S (sulfur atom), and N (nitrogen atom). That is, this organic group represents: an aliphatic hydrocarbon group with a saturated aliphatic hydrocarbon group at least at the end directly bonded to N and the carbon chain optionally containing heteroatoms such as O, S, and N, or an aromatic group with an aliphatic hydrocarbon group at the end directly bonded to N and the carbon chain optionally containing heteroatoms such as O, S, and N. Since the carbon atom directly bonded to N does not have a π bond, the color characteristics such as hue or transmittance of the cationic chromogenic site are not affected by the linking group A or other chromogenic sites, and can maintain the same color as the monomer.

[0218] In A, the aliphatic hydrocarbon group at the end directly bonded to N can be any type of aliphatic hydrocarbon group, provided that the carbon atom at the end directly bonded to N does not have a π bond. It can be straight-chain, branched, or cyclic. The carbon atoms other than the terminal carbon atom may optionally have unsaturated bonds or substituents. The carbon chain may also optionally contain O, S, or N. For example, it may optionally contain carbonyl, carboxyl, oxycarbonyl, or amide groups, and hydrogen atoms may be substituted with halogen atoms, etc.

[0219] Furthermore, aromatic groups having the aforementioned aliphatic hydrocarbon groups in A can be listed as follows: monocyclic or polycyclic aromatic groups having aliphatic hydrocarbon groups having at least a saturated aliphatic hydrocarbon group at the end directly bonded to N, optionally having substituents, or heterocycles containing O, S, or N.

[0220] In terms of the robustness of the skeleton, A preferably contains cyclic aliphatic hydrocarbon groups or aromatic groups.

[0221] Examples of cyclic aliphatic hydrocarbon groups include cyclohexane, cyclopentane, norbornene, bicyclic [2.2.2]octane, and tricyclic [5.2.1.0]. 2,6Groups such as those in decane and adamantane. Furthermore, as aromatic groups, examples include groups containing benzene rings and naphthalene rings. For example, when A is a divalent organic group, examples include straight-chain, branched, or cyclic alkylene groups with 1 or more but 20 or fewer carbon atoms, such as dimethylbenzene, which are aromatic groups substituted with two alkylene groups having 1 or more but 20 or fewer carbon atoms.

[0222] In this invention, in terms of balancing strength and freedom of molecular motion, and improving heat resistance, A is preferably an aliphatic hydrocarbon group having two or more cyclic aliphatic hydrocarbon groups, a saturated aliphatic hydrocarbon group at the end directly bonded to N, and optionally containing O, S, or N aliphatic hydrocarbon groups in the carbon chain. A is more preferably an aliphatic hydrocarbon group having two or more cycloalkyl groups, a saturated aliphatic hydrocarbon group at the end directly bonded to N, and optionally containing O, S, or N aliphatic hydrocarbon groups in the carbon chain. Furthermore, a structure having two or more cyclic aliphatic hydrocarbon groups linked by straight-chain or branched aliphatic hydrocarbon groups is preferred.

[0223] The two or more cyclic aliphatic hydrocarbon groups present may be chosen to be the same or different. For example, those that are the same as the above-mentioned cyclic aliphatic hydrocarbon groups can be listed, among which cyclohexane and cyclopentane are preferred.

[0224] In this invention, in terms of heat resistance, the A is preferably a substituent represented by the following general formula (iia).

[0225] [Chemical Formula 17]

[0226] General formula (iia)

[0227]

[0228] (In the general formula (iia), R) xi R represents an alkylene group having 1 or more carbon atoms and 3 or fewer carbon atoms, which may be substituted with an alkyl group having 1 or more carbon atoms and 4 or fewer carbon atoms, or an alkoxy group having 1 or more carbon atoms and 4 or fewer carbon atoms. xii and R xiii Each of the following independently represents an alkyl group having 1 or more carbon atoms and 4 or fewer carbon atoms, or an alkoxy group having 1 or more carbon atoms and 4 or fewer carbon atoms; p represents an integer of 1 or more and 3 or fewer; q and r each independently represent an integer of 0 or more and 4 or fewer; when multiple Rs are present... xi R xii R xiii In the case of r, there exist multiple R. xi R xii R xiii (and r can be either the same as or different from each other.)

[0229] In terms of effectively balancing fastness and thermal motion of the coloring areas, and improving heat resistance, R is preferred. xiThe alkylene group having 1 or more but less than 3 carbon atoms. Examples of such alkylene groups include methylene, ethylene, and propylene, with methylene or ethylene being preferred, and methylene being more preferred.

[0230] Examples of alkyl groups with 1 or more but less than 4 carbon atoms include methyl, ethyl, propyl, and butyl. These can be linear or optionally branched.

[0231] In addition, examples of alkoxy groups with 1 or more carbon atoms but less than 4 carbon atoms include methoxy, ethoxy, propoxy, and butoxy, which can be linear or optionally branched.

[0232] R xii and R xiii Alkyl groups having 1 or more carbon atoms and 4 or fewer carbon atoms, and alkoxy groups having 1 or more carbon atoms and 4 or fewer carbon atoms, can be listed as R above. xi Choose those with the same substituents.

[0233] In the general formula (iia), in terms of heat resistance, the cyclohexane (cyclohexene) is preferably 2 or more and 4 or less, that is, p is 1 or more and 3 or less, and more preferably p is 1 or more and 2 or less.

[0234] Furthermore, the substituent R of the cyclohexylene group xii and R xiii The number of substitutions is not particularly limited, but in terms of heat resistance, it is preferably one or more and three or less, more preferably one or more and two or less. That is, it is preferable that q and r are integers of one or more and three or less, and even more preferably that q and r are integers of one or more and two or less.

[0235] Suitable specific examples of such linking group A include the following groups, but are not limited to these.

[0236] [Chemical Formula 18]

[0237]

[0238] R i ~R v The alkyl group in the text is not particularly limited. Examples include straight-chain, branched, or cyclic alkyl groups having 1 or more but less than 20 carbon atoms. Among these, straight-chain or branched alkyl groups having 1 or more but less than 8 carbon atoms are included. Regarding brightness and heat resistance, straight-chain or branched alkyl groups having 1 or more but less than 5 carbon atoms are included. R is also an example. i ~R v The alkyl group can be ethyl or methyl. The substituents that the alkyl group may have are optional and not particularly limited; examples include aryl, halogen atoms, hydroxyl, alkoxy, etc., and examples of substituted alkyl groups include benzyl aralkyl groups, etc.

[0239] Ri ~R v The aryl group is not particularly limited. Examples include phenyl and naphthyl groups. Substituents that can be present on the aryl group include, for example, alkyl groups, halogen atoms, alkoxy groups, and hydroxyl groups.

[0240] In terms of chemical stability, as R i ~R v Preferably, each is independently a hydrogen atom, an alkyl group having 1 or more but less than 5 carbon atoms, a phenyl group, or an R group. ii With R iii R iv With R v They bond together to form pyrrolidine rings, piperidine rings, and morpholine rings.

[0241] In terms of heat resistance, R is preferred. ii ~R v At least one of them is an optional cycloalkyl group with substituents, or an optional aryl group with substituents. It is believed that due to R... ii ~R v At least one of them has a cycloalkyl or aryl group, and the intermolecular interactions of steric hindrance are reduced, thus suppressing the effect of the colorimetric site on heat, resulting in excellent heat resistance.

[0242] In terms of heat resistance, R is preferred. ii ~R v At least one of them is a substituent represented by the following general formula (iib) or the following general formula (iic).

[0243] [Chemical Formula 19]

[0244] General formula (iib)

[0245]

[0246] (In the general formula (iib), R) xiv R xv and R xvi Each of the following can independently represent a hydrogen atom, an alkyl group having 1 or more but less than 4 carbon atoms optionally having a substituent, or an alkoxy group having 1 or more but less than 4 carbon atoms optionally having a substituent.

[0247] [Chemical Formula 20]

[0248] General formula (iic)

[0249]

[0250] (In the general formula (iic), R) xvii R xviii and R xixEach of the following can independently represent a hydrogen atom, an alkyl group having 1 or more but less than 4 carbon atoms optionally having a substituent, or an alkoxy group having 1 or more but less than 4 carbon atoms optionally having a substituent.

[0251] As R xiv R xv R xvi R xvii R xviii and R xix Alkyl groups having 1 or more but 4 or fewer carbon atoms can be exemplified by methyl, ethyl, propyl, and butyl, and may be linear or optionally branched. Furthermore, alkoxy groups having 1 or more but 4 or fewer carbon atoms can be exemplified by methoxy, ethoxy, propoxy, and butoxy, and may be linear or optionally branched.

[0252] Examples of substituents that may be optionally present in the aforementioned alkyl and alkoxy groups include halogen atoms, hydroxyl groups, etc.

[0253] In the case of substituents represented by the above general formula (iib), R is preferred in terms of heat resistance. xiv R xv and R xvi At least one of them is an alkyl group having 1 or more and 4 or fewer carbon atoms, or an alkoxy group having 1 or more and 4 or fewer carbon atoms, preferably R. xiv and R xv At least one of them is an alkyl group having 1 or more and 4 or fewer carbon atoms, or an alkoxy group having 1 or more and 4 or fewer carbon atoms, optionally having a substituent.

[0254] Furthermore, in cases where the substituents represented by the above general formula (iic) are present, R is preferred in terms of heat resistance. xvii R xviii and R xix At least one of them is an alkyl group having 1 or more and 4 or fewer carbon atoms, or an alkoxy group having 1 or more and 4 or fewer carbon atoms, preferably R. xvii and R xviii At least one of them is an alkyl group having 1 or more and 4 or fewer carbon atoms, or an alkoxy group having 1 or more and 4 or fewer carbon atoms, optionally having a substituent.

[0255] Suitable specific examples of substituents represented by the general formula (iib) and the general formula (iic) may be listed below, but are not limited to these.

[0256] [Chemical Formula 21]

[0257]

[0258] R viand R vii Each of these can independently represent an alkyl group, an alkoxy group, a halogen atom, or a cyano group, optionally having a substituent. As R vi and R vii The alkyl group in the alkyl group is not particularly limited, but preferably a straight-chain alkyl group with 1 or more and 8 or less carbon atoms, or a branched alkyl group, more preferably an alkyl group with 1 or more and 4 or less carbon atoms. Examples of alkyl groups with 1 or more and 4 or less carbon atoms include methyl, ethyl, propyl, and butyl, which may be straight-chain or optionally branched. The substituents optionally present in the alkyl group are not particularly limited, and examples include aryl, halogen atoms, hydroxyl, and alkoxy groups.

[0259] In addition, as R vi and R vii The alkoxy group in the alkoxy group is not particularly limited, but preferably a straight-chain alkoxy group with 1 or more and 8 or fewer carbon atoms, or a branched alkoxy group, more preferably an alkoxy group with 1 or more and 4 or fewer carbon atoms. Examples of alkoxy groups with 1 or more and 4 or fewer carbon atoms include methoxy, ethoxy, propoxy, and butoxy, which may be straight-chain or optionally branched. The substituents optionally present in the alkoxy group are not particularly limited, and examples include aryl, halogen atoms, hydroxyl, and alkoxy groups.

[0260] As R vi and R vii Halogen atoms in the atom can be, for example, fluorine, chlorine, bromine, and iodine.

[0261] R vi and R vii The substitution numbers, i.e., f and g, independently represent integers greater than 0 and less than 4, preferably greater than 0 and less than 2, and more preferably greater than 0 and less than 1. Multiple f and g may be chosen to be the same or different.

[0262] In addition, R vi and R vii It can replace any part of the aromatic ring with a resonance structure in the triarylmethane skeleton or zeolite skeleton, wherein -NR is preferred. ii R iii or -NR iv R v The substitution position of the amino group is indicated based on the meta position.

[0263] Ar 1 The divalent aromatic groups in Ar are not particularly limited. 1The aromatic groups in [the text] can be heterocyclic groups in addition to aromatic hydrocarbon groups containing carbocyclic rings. Aromatic hydrocarbons, besides benzene rings, include: fused polycyclic aromatic hydrocarbons such as naphthalene rings, tetrahydronaphthalene rings, indene rings, fluorene rings, anthracene rings, and phenanthrene rings; and chain polycyclic hydrocarbons such as biphenyl, biphenylene oxide, diphenylmethane, triphenylmethane, and piracene. In these chain polycyclic hydrocarbons, groups such as diphenyl ethers may also have O, S, or N atoms in their chain skeleton. On the other hand, examples of heterocyclic groups include: five-membered heterocycles such as furan, thiophene, pyrrole, oxazole, thiazole, imidazole, and pyrazole; six-membered heterocycles such as pyran, pyranone, pyridine, pyranone, pyridazine, pyrimidine, and pyrazine; and fused polycyclic heterocycles such as benzofuran, benzothiophene, indole, carbazole, coumarin, benzopyranone, quinoline, isoquinoline, acridine, phthalazine, quinazoline, and quinoxaline. These aromatic groups may further have alkyl, alkoxy, hydroxyl, halogen atoms, and phenyl groups that can be substituted by these as substituents.

[0264] Multiple R exist within a single molecule. i ~R vii and Ar 1 Choose either the same or different. (via R) i ~R vii and Ar 1 The combination can be adjusted to the desired color.

[0265] In A, the valence 'a' is the number of chromogenic cation sites constituting the cation, and 'a' is an integer of 2 or more. In this lake pigment, since the valence 'a' of the cation is 2 or more, it exhibits excellent heat resistance; preferably, the valence 'a' of the cation is 3 or more. There is no particular upper limit to the value of 'a', but in terms of ease of manufacture, 'a' is preferably 4 or less, and more preferably 3 or less.

[0266] Regarding the cationic portion of the colorant represented by general formula (ii), in terms of excellent heat resistance and ease of suppressing color changes during heating, the molecular weight is preferably 1200 or more, and more preferably 1300 or more.

[0267] In the colorant represented by general formula (ii), the anion portion (B c- In terms of high brightness and excellent heat resistance, it is a C-valent polyacid anion, which is a divalent or higher anion.

[0268] As a polyacid anion formed by the condensation of multiple oxyacids, it can be a homopolyacid anion (M m O n ) c- It can also be a heteropolyacid anion (X). l M m O n ) c-In the above ionic formula, X represents a heteroatom, M represents a polyatom, l represents the composition ratio of heteroatoms, m represents the composition ratio of polyatoms, and n represents the composition ratio of oxygen atoms. Examples of polyatoms M include Mo, W, V, Ti, and Nb. Examples of heteroatoms X include Si, P, As, S, Fe, and Co. Furthermore, some may optionally contain Na. + or H + Counter cations.

[0269] In terms of excellent heat resistance, polyacids containing one or more elements selected from tungsten (W) and molybdenum (Mo) are preferred.

[0270] Examples of such polyacids include: tungstate ions [W], which are homopolyacids. 10 O 32 ] 4- Molybdate ions [Mo6O] 19 ] 2- phosphotungsten ion [PW] as a heteropolyacid 12 O 40 ] 3- [P2W] 18 O 62 ] 6- silicotungstate ions [SiW] 12 O 40 ] 4- phosphomolybdate ion [PMo] 12 O 40 ] 3- SiMo ion 12 O 40 ] 4- phosphotungstic molybdate ion [PW] 12-s Mo s O 40 ] 3- (s is an integer greater than 1 and less than 11), [P2W 18-t Mo t O 62 ] 6- (t is an integer greater than 1 and less than 17), silicotungstic molybdate ion [SiW] 12-u Mo u O 40 ] 4- (u is an integer of 1 or more and 11 or less). As a polyacid containing at least one of tungsten (W) and molybdenum (Mo), the above-mentioned polyacids are preferably heteropolyacids in terms of heat resistance and ease of obtaining raw materials, and more preferably heteropolyacids that also contain phosphorus (P).

[0271] Furthermore, in terms of heat resistance, phosphotungstic molybdate ion [PW] is even more preferred.10 Mo2O 40 ] 3- [PW] 11 Mo1O 40 ] 3- phosphotungsten ion [PW] 12 O 40 ] 3- Either of them.

[0272] In general formula (ii), b represents the number of cations, d represents the number of anions in the molecular aggregate, and b and d are integers greater than or equal to 1. When b is 2 or more, the multiple cations present in the molecular aggregate can be a single type or a combination of two or more types. Similarly, when d is 2 or more, the multiple anions present in the molecular aggregate can be a single type or a combination of two or more types.

[0273] In general formula (ii), e is an integer of 0 or 1, and when e is 0, there is no bonding. e = 0 represents a triarylmethane skeleton, and e = 1 represents a sulfonium skeleton. Multiple e may be the same or different. Among the lake pigments represented by general formula (ii) used in this invention, those containing a triarylmethane skeleton are at least suitably used.

[0274] It should be noted that the lake pigment represented by general formula (ii) can be prepared, for example, with reference to International Publication No. 2012 / 144520 and International Publication No. 2018 / 003706.

[0275] On the other hand, in general formula (iii), R I ~R VI Each of the following groups independently represents a hydrogen atom, an alkyl group optionally with substituents, or an aryl group optionally with substituents; R I With R II R III With R IV R V With R VI Optional bonding forms a ring structure. R I ~R VI R can be compared with the general formula (ii) described above. i ~R v same.

[0276] In general formula (iii), R VII and R VIII Each of these can independently represent an alkyl group optionally having a substituent, an alkoxy group optionally having a substituent, a halogen atom, or a cyano group, which may also be related to R in general formula (ii) described above. vi and R vii same.

[0277] In general formula (iii), Ar2 This indicates an optional divalent aromatic heterocyclic group with substituents, the Ar 2 Ar can be compared with the general formula (ii) described above. 1 The aromatic heterocyclic groups in them are the same.

[0278] Furthermore, in general formula (iii), E m- This represents an m-valent polyacid anion, which may be the same as the c-valent polyacid anion of the general formula (ii) described above.

[0279] In general formula (iii), m represents the number of cations and the number of anions, and is an integer greater than 2. The cations present in general formula (iii) can be a single type or a combination of two or more types. Similarly, the anions can be a single type or a combination of two or more types.

[0280] In formula (iii), j is 0 or 1, and no bonding exists when j is 0. The j in formula (iii) can be the same as e in formula (ii) described above. Furthermore, k and l in formula (iii) can be the same as f and g in formula (ii) described above.

[0281] It should be noted that the lake pigment represented by general formula (iii) can be prepared, for example, by reference to Japanese Patent Application Publication No. 2017-16099.

[0282] The colorants represented by general formula (ii) and general formula (iii) above can also be used in combination with other colorants used for color mixing. From the viewpoint of heat resistance, organic pigments are preferred for use in combination with one or more of the colorants selected from the group consisting of those represented by general formula (ii) and general formula (iii), among which phthalocyanine pigments are preferred. From the viewpoint of improving dispersibility and storage stability, alkali-treated phthalocyanine pigments are preferred. Here, alkali-treated phthalocyanine pigments refer to phthalocyanine pigments having a structure derived from an alkaline compound. Examples of suitable phthalocyanine pigments having a structure derived from an alkaline compound include phthalocyanine pigments containing colorant derivatives having an alkaline site.

[0283] As for the aforementioned phthalocyanine pigment, in terms of its ability to be used in combination with one or more pigments selected from the group consisting of pigments represented by general formula (ii) and general formula (iii), a blue phthalocyanine pigment is preferred, and in terms of superior brightness, a copper phthalocyanine pigment is preferred. The copper phthalocyanine pigment used for alkaline treatment can be a crude copper phthalocyanine pigment or a copper phthalocyanine pigment having α-type, β-type, γ-type, ε-type, or other crystalline structures. Among the copper phthalocyanine pigments used for alkaline treatment, in terms of excellent dispersion stability, one or more pigments selected from the group consisting of copper phthalocyanine pigments having an ε-type crystalline structure and copper phthalocyanine pigments having a β-type crystalline structure are preferred.

[0284] In this invention, a colorant derivative having an alkaline site is suitably used in the alkaline treatment. In this invention, "having an alkaline site" can be exemplified by having an alkaline group as a substituent, or by an alkaline compound forming a salt with an acid in the substituent.

[0285] Examples of alkaline sites in the color material derivatives of this invention include: amino groups, ammonium sulfonate salts, sulfonamide groups with amino groups, amide groups with amino groups, and alkaline heterocyclic groups.

[0286] The basic site of the color material derivative in this invention can be contained in such a way that the hydrogen atoms of the color material are replaced by the aforementioned basic site, or in such a way that the aforementioned basic site is replaced by a linking group in the color material. For example, a method in which the aforementioned basic site is replaced by a linking group in the color material can be described as having a hydrocarbon group having 1 or more but less than 20 carbon atoms substituted on the color material, and the hydrogen atoms of this hydrocarbon group are replaced by the aforementioned basic site.

[0287] The alkaline portion of the colorant derivative is preferably an ammonium sulfonate salt or a sulfonamide group having an amino group, in terms of its tendency to interact with acidic dispersants, and preferably the above-mentioned -SO2NH-(CH2). m -NR′R″ (where R′ and R″ independently represent a hydrogen atom, a hydrocarbon group with 1 or more carbon atoms and 30 or less that can be substituted by the above-mentioned amino group, or a group that forms a basic heterocycle together with adjacent nitrogen atoms bonded to each other, and m represents an integer of 1 or more and 15 or less) group.

[0288] Furthermore, the basic site of the colorant derivative is only required to be at least one per molecule of the colorant, and there is no particular limitation thereto; however, in terms of colorant dispersibility, one or two sites are preferred. The position of the basic site of the colorant derivative on the colorant is not particularly limited.

[0289] The colorant used in the colorant derivative with the alkaline site can be a known colorant, preferably having a structure that readily adsorbs with the phthalocyanine pigment used in the alkaline treatment, and preferably having a structure with the same or similar pigment skeleton that readily interacts with it. Furthermore, it is preferable to exhibit a color close to that of the phthalocyanine pigment used in the alkaline treatment.

[0290] As a color material derivative having an alkaline site, a blue color material derivative is preferred. The blue color material used in the blue color material derivative can be a known blue organic pigment, a blue dye, or a blue lake color material that is a salt-forming compound of a blue dye. Among these, it is preferable to use a pigment having the same pigment skeleton as the blue pigment or cyan pigment shown in the dye index. In terms of improving dispersibility and brightness, it is preferable to use a pigment having a phthalocyanine skeleton, and copper phthalocyanine is particularly preferred.

[0291] Colorant derivatives having a basic site can be manufactured by previously known methods. For example, they can be manufactured by forming a salt using ammonia or an organic amine after sulfonating the colorant, or by sulfonating the substituents of the colorant.

[0292] Regarding methods for preparing phthalocyanine pigments, which are phthalocyanine pigments having a structure derived from a basic compound, for example, a method can be listed as follows: The color material derivative having the basic site is dry-milled with the phthalocyanine pigment, and then the color material derivative having the basic site is mixed. In this case, a ball mill, vibratory mill, or grinding mill can be used as the dry mill, and the milling temperature can be freely set between 20°C and 130°C.

[0293] In addition, as a method for preparing phthalocyanine pigments containing color material derivatives with alkaline sites, the following methods can be listed: mixing color material derivatives with alkaline sites, phthalocyanine pigments, water-soluble inorganic salts such as sodium chloride, calcium chloride, and ammonium sulfate, and water-soluble organic solvents such as glycol-based organic solvents, and kneading them using a kneading mill by solvent salt milling.

[0294] The dispersibility of the pigment is improved by pre-preparing or preparing an alkaline-treated phthalocyanine pigment before dispersing the pigment.

[0295] Regarding dispersibility and storage stability, in phthalocyanine pigments containing a colorant derivative having an alkaline site, the content of the colorant derivative having an alkaline site relative to 100 parts by weight of phthalocyanine pigment is preferably 0.5 parts by weight or more, more preferably 3 parts by weight or more, further preferably 5 parts by weight or more, and even more preferably 8 parts by weight or more. On the other hand, regarding excellent brightness, the content of the colorant derivative having an alkaline site relative to 100 parts by weight of phthalocyanine pigment is preferably 50 parts by weight or less, more preferably 40 parts by weight or less, and even more preferably 30 parts by weight or less.

[0296] It should be noted that phthalocyanine pigments treated with alkaline methods can be appropriately analyzed using, for example, mass spectrometry, elemental analysis, surface analysis, potentiometric titration, and combinations thereof.

[0297] Furthermore, for example, when forming a pattern of a light-shielding layer on a substrate of a color filter using the photosensitive coloring resin composition for color filters of the present invention, a black pigment with high light-shielding properties is formulated into the ink. For example, inorganic pigments such as carbon black and iron oxide, or organic pigments such as phthalocyanine black, can be used as the black pigment with high light-shielding properties.

[0298] The average primary particle size of the colorant used in this invention is not particularly limited when manufacturing the color layer of the color filter, as long as it can achieve the desired color rendering. It varies depending on the type of colorant used, and is preferably in the range of 10 nm or more and 100 nm or less, more preferably 15 nm or more and 60 nm or less. By having the average primary particle size of the colorant within the above range, a display device equipped with a color filter manufactured using the colorant dispersion of this invention can achieve high contrast and high quality.

[0299] Regarding the total content of the colorant, it is preferable to formulate it at a ratio of 3% by mass or more and 65% by mass or less, more preferably 4% by mass or more and 60% by mass or less, relative to the total solid content of the photosensitive coloring resin composition for color filters. If the ratio is above or below the aforementioned lower limit, the color layer has sufficient color concentration when the photosensitive coloring resin composition for color filters is coated to a specified film thickness (typically 1.0 μm or more and 5.0 μm or less). Furthermore, if the ratio is below the aforementioned upper limit, excellent storage stability is achieved, and a color layer with sufficient hardness and good adhesion to the substrate can be obtained. Especially when forming a color layer with a high colorant concentration, the total content of the colorant is preferably formulated at a ratio of 15% by mass or more and 65% by mass or less, more preferably 25% by mass or more and 60% by mass or less, relative to the total solid content of the photosensitive coloring resin composition for color filters.

[0300] [Alkali-soluble resin]

[0301] The alkali-soluble resin of the present invention has acidic groups and can be appropriately selected from resins that function as adhesive resins and are soluble in the alkali developing solution used in pattern formation.

[0302] In this invention, the alkali-soluble resin can be defined as having an acid value of 40 mg KOH / g or higher.

[0303] The preferred alkali-soluble resins in this invention are resins having acidic groups and generally having carboxyl groups. Specifically, examples include: acrylic copolymers having carboxyl groups and acrylic resins such as styrene-acrylic copolymers having carboxyl groups, and epoxy (meth)acrylate resins having carboxyl groups. Among these, those having carboxyl groups on the side chains and, furthermore, photopolymerizable functional groups such as vinyl unsaturated groups on the side chains are particularly preferred. This is because the cured film formed by containing photopolymerizable functional groups has improved film strength. Furthermore, two or more of these acrylic copolymers and acrylic resins such as styrene-acrylic copolymers, as well as epoxy acrylate resins, can be mixed and used.

[0304] Acrylic resins, such as acrylic copolymers containing carboxyl groups and styrene-acrylic copolymers containing carboxyl groups, are (co)polymers obtained, for example, by (co)polymerizing carboxyl-containing vinyl unsaturated monomers and other copolymerizable monomers as desired, using known methods.

[0305] Examples of carboxyl-containing vinyl unsaturated monomers include (meth)acrylic acid, vinylbenzoic acid, maleic acid, monoalkyl maleate, fumaric acid, itaconic acid, butenoic acid, cinnamic acid, and acrylic acid dimers. Additionally, monomers with hydroxyl groups, such as 2-hydroxyethyl (meth)acrylic acid, can be used in addition reactions with cyclic anhydrides such as maleic anhydride, phthalic anhydride, and cyclohexanedicarboxylic anhydride, as well as ω-carboxyl-polycaprolactone mono(meth)acrylic acid esters. Furthermore, anhydride-containing monomers such as maleic anhydride, itaconic anhydride, and methylmaleic anhydride can also be used as precursors for the carboxyl group. Among these, (meth)acrylic acid is particularly preferred in terms of copolymerizability, cost, solubility, and glass transition temperature.

[0306] Regarding the excellent adhesion of the coloring layer, the alkali-soluble resin preferably has a hydrocarbon ring. It has been observed that by having a hydrocarbon ring as a large-volume group in the alkali-soluble resin, the solvent resistance of the obtained coloring layer, especially the swelling of the coloring layer, is suppressed. The exact effect is not yet clear, but it is inferred that by containing a large-volume hydrocarbon ring within the coloring layer, the movement of molecules within the coloring layer is suppressed, resulting in increased coating strength and suppressed solvent-induced swelling.

[0307] Examples of such hydrocarbon rings include: cyclic aliphatic hydrocarbon rings with optional substituents, aromatic rings with optional substituents, and combinations thereof, wherein the hydrocarbon ring may optionally have substituents such as carbonyl, carboxyl, oxycarbonyl, or amide groups. In the case of aliphatic rings, the heat resistance and adhesion of the colored layer are improved, and the brightness of the obtained colored layer is increased.

[0308] Specific examples of hydrocarbon rings include: aliphatic hydrocarbon rings such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, norbornene, tricyclo[5.2.1.0(2,6)]decane (dicyclopentane), and adamantane; aromatic rings such as benzene, naphthalene, anthracene, phenanthrene, and fluorene; chain polycyclic rings or Cardo structures (9,9-diarylfluorene) such as biphenyl, biphenylene, diphenylmethane, triphenylmethane, and zirconia; and groups in which some of these groups are substituted with substituents.

[0309] Examples of substituents mentioned above include: alkyl, cycloalkyl, alkylcycloalkyl, hydroxyl, carbonyl, nitro, amino, and halogen atoms.

[0310] In terms of the ease of adjusting the amount of each structural unit and increasing the amount of structural units with the aforementioned hydrocarbon rings to easily improve the function of the structural unit, it is preferable to use an acrylic copolymer that contains structural units with the aforementioned hydrocarbon rings in addition to structural units with carboxyl groups.

[0311] Acrylic copolymers containing structural units with carboxyl groups and the aforementioned hydrocarbon rings can be prepared by using vinyl unsaturated monomers with hydrocarbon rings as the "other copolymerizable monomers" mentioned above.

[0312] Examples of vinyl unsaturated monomers having a hydrocarbon ring that can be combined with compounds represented by the above general formula (1) include: cyclohexyl methacrylate, dicyclopentyl methacrylate, adamantyl methacrylate, isobornyl methacrylate, benzyl methacrylate, phenoxyethyl methacrylate, styrene, etc. In terms of maintaining the cross-sectional shape of the colored layer after development during heat treatment, cyclohexyl methacrylate, dicyclopentyl methacrylate, adamantyl methacrylate, benzyl methacrylate, styrene are preferred, and styrene is particularly preferred.

[0313] Furthermore, regarding the effect of suppressing developing residue, the preferred monomers as vinyl unsaturated monomers having the aforementioned hydrocarbon rings are monomers having a maleimide structure and styrene, with styrene being particularly preferred.

[0314] Furthermore, the alkali-soluble resin used in this invention preferably has vinyl double bonds in its side chains. When vinyl double 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 photopolymerizable compounds, etc. By combining with the compound represented by the above-described general formula (1) used in this invention, the film strength of the cured film is further improved, the development resistance is improved, and the thermal shrinkage of the cured film is suppressed, resulting in excellent adhesion to the substrate.

[0315] The method for introducing vinyl double bonds into alkali-soluble resins can be appropriately selected from previously known methods. For example, methods can be listed such as: adding compounds with both epoxy groups and vinyl double bonds in the molecule, such as glycidyl (meth)acrylate, to the carboxyl groups of the alkali-soluble resin to introduce vinyl double bonds into the side chain; or introducing hydroxyl structural units into the copolymer in advance, and adding compounds with isocyanate groups and vinyl double bonds in the molecule to introduce vinyl double bonds into the side chain, etc.

[0316] The alkali-soluble resin of the present invention may also contain other structural units such as methyl methacrylate and ethyl methacrylate, which have ester groups. The structural units with ester groups function not only as components that suppress the alkali solubility of the photosensitive coloring resin composition for color filters, but also as components that improve solubility in solvents and, consequently, improve solvent resolubility.

[0317] The alkali-soluble resin in this invention is preferably an acrylic resin containing structural units with carboxyl groups and structural units with hydrocarbon rings, such as acrylic copolymers and styrene-acrylic copolymers. More preferably, it is an acrylic resin containing structural units with carboxyl groups, structural units with hydrocarbon rings, and structural units with vinyl double bonds, such as acrylic copolymers and styrene-acrylic copolymers.

[0318] Alkali-soluble resins can be formulated to have the desired properties by appropriately adjusting the amount of each structural unit added.

[0319] Regarding obtaining a good pattern, the amount of carboxyl-containing vinyl unsaturated monomer added is preferably 5% by mass or more, more preferably 10% by mass or more, relative to the total amount of monomer. On the other hand, regarding suppressing film roughness on the pattern surface after development, the amount of carboxyl-containing vinyl unsaturated monomer added is preferably 50% by mass or less, more preferably 40% by mass or less, relative to the total amount of monomer.

[0320] Furthermore, in acrylic resins such as acrylic copolymers and styrene-acrylic copolymers containing structural units having ethylene double bonds, which can be more preferably used as alkali-soluble resins, the amount of the compound having both epoxy groups and ethylene double bonds relative to the carboxyl-containing ethylene unsaturated monomer is preferably 10% by mass or more and 95% by mass or less, more preferably 15% by mass or more and 90% by mass or less.

[0321] The preferred weight-average molecular weight (Mw) of the carboxyl-containing copolymer is preferably in the range of 1,000 or more and 50,000 or less, and more preferably 3,000 or more and 20,000 or less. If it is less than 1,000, the adhesive function after curing is significantly reduced; if it exceeds 50,000, it is difficult to form a pattern when developing with an alkaline developer.

[0322] It should be noted that the above-mentioned weight-average molecular weight (Mw) of carboxyl-containing copolymers can be determined using polystyrene as a standard substance, THF (tetrahydrofuran) as the eluent, and through the Shodex GPC System-21H.

[0323] There are no particular limitations on the type of epoxy (meth)acrylate resin containing carboxyl groups, but epoxy (meth)acrylate compounds obtained by reacting epoxy compounds with monocarboxylic acids containing unsaturated groups or with acid anhydrides are more suitable.

[0324] Epoxy compounds, monocarboxylic acids containing unsaturated groups, and acid anhydrides may be appropriately selected from those known to the public. Epoxy (meth)acrylate resins containing carboxyl groups may be used alone or in combination with two or more.

[0325] Regarding the developability (solubility) of the alkaline aqueous solution used in the developer, the alkali-soluble resin is preferably selected with an acid value of 50 mg KOH / g or higher. Regarding both the developability (solubility) of the alkaline aqueous solution used in the developer and its adhesion to the substrate, the alkali-soluble resin is preferably with an acid value of 70 mg KOH / g or higher and 300 mg KOH / g or lower, and more preferably 70 mg KOH / g or higher and 280 mg KOH / g or lower.

[0326] It should be noted that, in this invention, the acid value can be determined according to JIS K 0070.

[0327] Regarding the ethylene unsaturated bond equivalent when the side chain of the alkali-soluble resin has ethylene unsaturated groups, in terms of obtaining effects such as improved film strength, improved developability, and excellent adhesion to the substrate of the cured film by combining it with the compound represented by the above-described general formula (1) used in this invention, it 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 ethylene unsaturated bond equivalent is 2000 or less, the developability and adhesion are excellent. Furthermore, if it is 100 or more, the proportion of structural units such as those with carboxyl groups or those with hydrocarbon rings can be relatively increased, thus resulting in excellent developability or heat resistance. It is preferable to use the compound represented by the above-described general formula (1) used in this invention in combination with the content described above.

[0328] Here, the equivalent of ethylene unsaturated bonds is the weight-average molecular weight of 1 mole of ethylene unsaturated bonds in the above-mentioned alkali-soluble resin, expressed by the following mathematical formula (1).

[0329] Mathematical formula (1)

[0330] Equivalent amount of ethylene unsaturated bond (g / mol) = W(g) / M(mol)

[0331] (In mathematical formula (1), W represents the mass (g) of the alkali-soluble resin, and M represents the number of moles (mol) of ethylene double bonds contained in the alkali-soluble resin W (g).)

[0332] The equivalent of the aforementioned vinyl unsaturated bonds can also be calculated, for example, by determining the number of vinyl double bonds per 1g of alkali-soluble resin according to the iodine value test method described in JIS K 0070:1992.

[0333] The alkali-soluble resin used in the photosensitive coloring resin composition for color filters can be used alone or in combination of two or more types. There is no particular limitation on its content. However, relative to the total solid content of the photosensitive coloring resin composition for color filters, the alkali-soluble resin is preferably in the range of 5% by mass or more and 60% by mass or less, and more preferably 10% by mass or more and 40% by mass or less. If the content of the alkali-soluble resin is at or above the aforementioned lower limit, sufficient alkali developability can be obtained. Furthermore, if the content of the alkali-soluble resin is at or below the aforementioned upper limit, film roughness and pattern defects can be suppressed during development.

[0334] [Photopolymerizable compounds]

[0335] The photopolymerizable compound used in the photosensitive coloring resin composition for color filters is not particularly limited as long as it can be polymerized by the aforementioned photoinitiator. Generally, compounds having two or more vinyl unsaturated double bonds can be used, and polyfunctional (meth)acrylates having two or more acryloyl or methacryloyl groups are particularly preferred.

[0336] As such a polyfunctional (meth)acrylate, it is appropriate to select from those previously known. Specific examples include those described in Japanese Patent Application Publication No. 2013-029832.

[0337] These multifunctional (meth)acrylates 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 for color filters of the present invention, the multifunctional (meth)acrylate preferably has three or more polymerizable double bonds (trifunctional), and is preferably a poly(meth)acrylate of a polyol with three or more ternary components, or a dicarboxylic acid modified thereof. Specifically, preferred are: trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, a succinic acid modified version of pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, a succinic acid modified version of dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc.

[0338] There is no particular limitation on the content of the photopolymerizable compound used in the photosensitive coloring resin composition for color filters. However, relative to the total solid content of the photosensitive coloring resin composition for color filters, the photopolymerizable compound is preferably in the range of 5% by mass or more and 60% by mass or less, and more preferably 10% by mass or more and 40% by mass or less. If the content of the photopolymerizable compound is at or above the lower limit, sufficient photocuring can be achieved, suppressing the dissolution of the exposed portion during development. Furthermore, if the content of the photopolymerizable compound is at or below the upper limit, sufficient alkaline developability is achieved.

[0339] Regarding the content of the aforementioned photopolymerizable compound and the ratio of the aforementioned photoinitiator used in the photosensitive coloring resin composition for color filters, in terms of excellent curability, residual film rate, and further in terms of improved electrical reliability, the total content ratio of the aforementioned photoinitiator is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, more preferably 40 parts by mass or less, and more preferably 30 parts by mass or less, relative to 100 parts by mass of the aforementioned photopolymerizable compound.

[0340] [Solvent]

[0341] The solvent used in this invention is not particularly limited, as long as it is an organic solvent that does not react with the components of the photosensitive coloring resin composition for color filters and can dissolve or disperse them. The solvent can be used alone or in combination of two or more.

[0342] 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 cyclohexanol 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, in terms of the solubility of other components, glycol ether acetate-based solvents, carbitol acetate-based solvents, glycol ether-based solvents, and ester-based solvents may be suitably used. Of these, the solvent used in this invention, in terms of the solubility of other components and its suitability for coating, is preferably selected from one or more of the group consisting of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, butyl carbitol acetate (BCA), 3-methoxy-3-methyl-1-butyl acetate, ethyl ethoxypropionate, ethyl lactate, and 3-methoxybutyl acetate.

[0343] In the photosensitive coloring resin composition for color filters of the present invention, the solvent content can be appropriately set within a range that allows for precise and good formation of the coloring layer. Relative to the total amount of the photosensitive coloring resin composition for color filters containing the solvent, it is generally preferably in the range of 55% by mass or more and 95% by mass or less, more preferably in the range of 65% by mass or more and 88% by mass or less. By keeping the solvent content within the aforementioned range, a composition with excellent coatability can be produced.

[0344] [Dispersant]

[0345] In the photosensitive coloring resin composition for color filters of the present invention, the aforementioned colorant is preferably used by dispersing it in a solvent using a dispersant. In the present invention, the dispersant can be appropriately selected from previously known dispersants. For example, cationic, anionic, nonionic, amphoteric, silicone, and fluorinated surfactants can be used as dispersants. Among surfactants, polymeric dispersants are preferred in terms of their ability to disperse uniformly and finely.

[0346] Examples of polymeric dispersants include: (co)polymers of unsaturated carboxylic acid esters such as polyacrylates; (partial) amine salts, (partial) ammonium salts, or (partial) alkylamine salts of (co)polymers of unsaturated carboxylic acids such as polyacrylic acid; (co)polymers of hydroxyl-containing unsaturated carboxylic acid esters such as hydroxyl-containing polyacrylates, or modified versions thereof; polyurethanes; unsaturated polyamides; polysiloxanes; long-chain polyaminoamide phosphates; polyethyleneimine derivatives (amides obtained by reacting poly(lower alkylimines) with polyesters containing free carboxyl groups, and bases thereof); polyallylamine derivatives (reaction products obtained by reacting polyallylamine with one or more compounds selected from three compounds having free carboxyl groups, polyesters, polyamides, or cocondensates of esters and amides (polyesteramides), etc.

[0347] When the polymeric dispersant is a copolymer, it can be any of a block copolymer, a graft copolymer, or a random copolymer. From the point of view of dispersibility, block copolymers and graft copolymers are preferred.

[0348] As a polymeric dispersant, in terms of enabling the above-mentioned color material to be appropriately dispersed and having good dispersion stability, a polymeric dispersant containing nitrogen atoms in the main chain or side chain and having an amine value is preferred. In terms of good dispersibility, not precipitating foreign matter during film formation, and improving brightness and contrast, a polymeric dispersant containing a polymer comprising repeating units having tertiary amines is preferred.

[0349] The repeating unit containing the tertiary amine is a site with affinity for the aforementioned colorant and functions as an adsorption site for the colorant. Polymer dispersants containing polymers comprising repeating units with tertiary amines typically include repeating units that form sites with solvent affinity. Among polymers comprising repeating units with tertiary amines, block copolymers having both block portions containing repeating units with tertiary amines and block portions with solvent affinity are preferred in terms of excellent heat resistance and the ability to form high-gloss coatings. Furthermore, graft copolymers as described below are also preferred as polymers comprising repeating units with tertiary amines.

[0350] The repeating unit having a tertiary amine only needs to have a tertiary amine. In block copolymers, the tertiary amine may optionally be contained in the side chain of the block polymer or may be a component of the main chain.

[0351] Among them, as a block copolymer, it is preferred to have repeating units with tertiary amines in the side chains, and in terms of the main chain backbone being less prone to thermal decomposition and having high heat resistance, it is more preferred to have a structure represented by the following general formula (I).

[0352] [Chemical Formula 22]

[0353]

[0354] (In general formula (I), R) 1 A represents a hydrogen atom or a methyl group. 1 R represents a divalent linker group. 2 and R 3 Each can independently represent a hydrogen atom, or optionally a hydrocarbon group containing a heteroatom, R 2 and R 3 (The elements can be arbitrarily bonded together to form a ring structure.)

[0355] In general formula (I), A 1 This refers to 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.

[0356] In terms of dispersion, A in general formula (I) 1 Preferably, it is a divalent linker containing a -CONH- group or a -COO- group, more preferably a divalent linker containing a -CONH- group or a -COO- group and an alkylene group having 1 to 10 carbon atoms.

[0357] R 2 and R 3 The hydrocarbon groups that can be selected to contain heteroatoms include, for example, alkyl, aralkyl, aryl, etc.

[0358] 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.

[0359] Examples of aralkyl groups include benzyl, phenethyl, naphthylmethyl, and biphenylmethyl. The number of carbon atoms in an aralkyl group is preferably 7 to 20, and more preferably 7 to 14.

[0360] In addition, 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, and more preferably 6 to 12. It should be noted that the preferred carbon number does not include the number of carbon atoms in the substituents.

[0361] A hydrocarbon group containing heteroatoms is a structure in which the carbon atom in the aforementioned hydrocarbon group is replaced by a heteroatom, or in which the hydrogen atom in the aforementioned hydrocarbon group is replaced by a substituent containing a heteroatom. The heteroatoms that can be arbitrarily contained in the hydrocarbon group can be, for example, oxygen atoms, nitrogen atoms, sulfur atoms, silicon atoms, etc.

[0362] In addition, hydrogen atoms in hydrocarbon groups can be replaced by halogen atoms such as fluorine, chlorine, and bromine.

[0363] R 2 With R 3 The mutual bonding to form a ring structure refers to R 2 With R 3 A ring structure is formed via nitrogen atoms. R 2 and R 3 The resulting ring structure may contain heteroatoms at will. There are no particular limitations on the ring structure; examples include pyrrolidine rings, piperidine rings, and morpholine rings.

[0364] In this invention, R is preferred. 2 With 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 With R 3 They bond together to form pyrrolidine rings, piperidine rings, and morpholine rings.

[0365] It should be noted that the structure represented by the above general formula (I) can also be represented by the following general formula (I′).

[0366] [Chemical Formula 23]

[0367] General formula (1′)

[0368]

[0369] (In general formula (I′), R) 1″ A represents a hydrogen atom or a methyl group. 1′ A represents a divalent linker group. 1″ Indicates alkylene groups with 1 or more carbon atoms and 8 or fewer carbon atoms, -[CH(R A1 )-CH(R A2 )-O]x -CH(R A1 )-CH(R A2 - or - [(CH2)] y -O] z -(CH2) y - indicates a divalent organic group, R 2′ and R 3′ Each can be independently represented by a substituted chain or cyclic hydrocarbon group, R 2′ and R 3′ They bond together to form a ring structure; R A1 and R A2 Each can be independently a hydrogen atom or a methyl group;

[0370] x represents an integer greater than or equal to 1 and less than 18, y represents an integer greater than or equal to 1 and less than 5, and z represents an integer greater than or equal to 1 and less than 18.

[0371] As the divalent linker A of the above general formula (I′) 1′ Examples include: alkylene groups with 1 or more but less than 10 carbon atoms, aryl groups, -CONH- groups, -COO- groups, ether groups with 1 or more but less than 10 carbon atoms (-R′-OR″-: R′ and R″ are each independently alkylene groups), and combinations thereof. Among these, A... 1′ Preferably, it is a -COO- group or a -CONH- group.

[0372] The divalent organic group A of the above general formula (I′) 1″ It is an alkylene group with 1 or more carbon atoms and less than 8 carbon atoms, -[CH(R A1 )-CH(R A2 )-O] x -CH(R A1 )-CH(R A2 - or - [(CH2)] y -O] z -(CH2) y - The alkylene groups having 1 or more but less than 8 carbon atoms can be either straight-chain or branched, for example: methylene, ethylene, trimethylene, propylene, various butylenes, various pentylenes, various hexylenes, various octylenes, etc.

[0373] R A1 and R A2 Each can be a hydrogen atom or a methyl group, independently.

[0374] As for the above A 1″In terms of dispersibility, it is preferred to be an alkylene group having 1 or more and 8 or fewer carbon atoms, wherein A1″ is more preferably methylene, ethylene, propylene, or butylene, and more preferably methylene and ethylene.

[0375] R, as the above general formula (I′) 2′ R 3′ The ring structure formed by mutual bonding includes, for example, a nitrogen-containing heterocyclic monocyclic ring with 5 to 7 members, or a fused ring formed by two of these. The nitrogen-containing heterocyclic ring is preferably non-aromatic, and more preferably saturated.

[0376] Examples of monomers that derive the repeating unit represented by the above general formula (I) include: dimethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, diethylaminoethyl (meth)acrylate, diethylaminopropyl (meth)acrylate, 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 (meth)acrylate, diethylaminoethyl (meth)acrylate, and dimethylaminopropyl (meth)acrylamide are preferred for improving dispersibility and dispersion stability.

[0377] It should be noted that in polymers containing structural units represented by the above general formula (I), the structural units represented by the above general formula (I) may include one type or more types of structural units.

[0378] In the block portion comprising repeating units having tertiary amines, it is preferable to include three or more structural units represented by general formula (I). In terms of improving dispersibility and dispersion stability, it is preferable to include three or more but less than 100 units, more preferably three or more but less than 50 units, and even more preferably three or more but less than 30 units.

[0379] Regarding good solvent affinity and improved dispersibility, the solvent-affinity block portion in a block copolymer containing a repeating unit having a tertiary amine (hereinafter sometimes referred to as A block) and a solvent-affinity block portion (hereinafter sometimes referred to as B block) has a solvent-affinity block portion that does not have the structural unit represented by the above general formula (I) and has a structural unit that can copolymerize with the above general formula (I). In this invention, the configuration of each block of the block copolymer is not particularly limited, and for example, AB block copolymers, ABA block copolymers, BAB block copolymers, etc., can be made. Among these, AB block copolymers or ABA block copolymers are preferred in terms of excellent dispersibility.

[0380] The above B-section may be the same as the B-section in International Publication No. 2016 / 104493.

[0381] The number of structural units constituting the solvent-affinity block portion can be appropriately adjusted within the range of improving the dispersibility of the colorant. Specifically, in terms of effectively interacting with the colorant-affinity portion and improving the dispersibility of the colorant, the number of structural units constituting the solvent-affinity block portion is preferably 10 or more and 200 or less, more preferably 10 or more and 100 or less, and even more preferably 10 or more and 70 or less.

[0382] The solvent-affinity block can be selected in a manner that functions as a solvent-affinity site, and the repeating unit constituting the solvent-affinity block can include one type or two or more repeating units.

[0383] In the block copolymer used as the dispersant of the present invention, the ratio m / n of the number of structural units m, which is the structural unit represented by the above general formula (I), to the number of other structural units n constituting the solvent-affinity block portion is preferably in the range of 0.01 or more and 1 or less, and more preferably in the range of 0.05 or more and 0.7 or less in terms of the dispersibility and dispersion stability of the colorant.

[0384] Furthermore, in this invention, regarding good dispersibility, no precipitation of foreign matter during film formation, and improved brightness and contrast, the dispersant is preferably a polymer containing the structure represented by the above general formula (I′) and having an amine value of 40 mg KOH / g or more and 120 mg KOH / g or less. Furthermore, in this invention, as a dispersant, regarding good dispersibility and improved brightness and contrast, it is also preferred to be a non-salt-forming polymer containing the structure represented by the above general formula (I) and having an amine value of 40 mg KOH / g or more and 140 mg KOH / g or less, and a salt-type polymer containing the structure represented by the above general formula (I) and having an amine value of 0 mg KOH / g or more and 130 mg KOH / g or less. It should be noted that in this invention, there are cases where polymers containing repeating units having tertiary amines that form salts with organic acid compounds or halogenated hydrocarbons are referred to as salt-type polymers.

[0385] With an amine value within the above-mentioned range, the viscosity exhibits excellent stability over time and heat resistance, as well as excellent alkali developability and solvent resolubility. A higher amine value in the dispersant improves dispersibility and dispersion stability, further enhances solvent solubility and resolubility, improves compatibility with other components, increases the straightness of the fine line pattern in the colored layer, and makes it easier to suppress micropore irregularities.

[0386] It should be noted that the amine value of the salt-form polymer decreases the degree of salt formation compared to the polymer before salt formation. However, the salt-forming site becomes the same as, or even reinforced by, the nitrogen-terminal site corresponding to the amino group, which is the pigment adsorption site. Therefore, there is a tendency for pigment dispersibility and dispersion stability to improve through salt formation. Furthermore, if there are too many salt-forming sites that are identical to the amino group, it will adversely affect solvent resolubility. Therefore, the amine value of the polymer before salt formation can be used as an indicator to improve pigment dispersion stability and solvent resolubility.

[0387] The amine value of the non-salt-forming polymer used as a dispersant is preferably 50 mg KOH / g or more, more preferably 60 mg KOH / g or more, even more preferably 80 mg KOH / g or more, and even more preferably 90 mg KOH / g or more. On the other hand, regarding solvent resolubility, the amine value of the non-salt-forming polymer used as a dispersant is preferably 130 mg KOH / g or less, more preferably 120 mg KOH / g or less, even more preferably 110 mg KOH / g or less, and particularly preferably 105 mg KOH / g or less.

[0388] The amine value of the salt polymer used as a dispersant is preferably 10 mg KOH / g or more, more preferably 20 mg KOH / g or more, and in terms of solvent resolubility, it is preferably 120 mg KOH / g or less, more preferably 110 mg KOH / g or less, and even more preferably 105 mg KOH / g or less.

[0389] The amine value refers to the number of mg of potassium hydroxide required to neutralize the amine content in 1 g of the sample, equivalent to the amount of perchloric acid, and can be determined by the method defined in JIS-K7237:1995. When determined by this method, even if the amino group forms a salt with an organic acid compound in the dispersant, the amine value of the block copolymer itself used as a dispersant can be determined since the organic acid compound usually dissociates.

[0390] It should be noted that, in salt-type polymers, the amine value of salt-type graft copolymers in which salts are formed by compounds represented by general formula (VI) as described below can be set as the value determined by the method described in JIS K 7237:1995. This is because, since compounds of general formula (VI) form salts by the terminal nitrogen site of the structural unit represented by general formula (I) with a halogen atom-side hydrocarbon, the amine value can be determined using this method without altering the state of salt formation.

[0391] On the other hand, in salt-type polymers, the amine value of salt-type graft copolymers in which salts are formed by compounds represented by general formulas (V) or (VII) as described below can be calculated from the amine value of the polymer before salt formation, as described below. This is because, since the compounds represented by general formulas (V) or (VII) form salts by the terminal nitrogen sites of the structural units represented by general formula (I) with acidic groups, if the amine value of such salt-type graft copolymers is determined using the method described in JIS K 7237:1995 above, the state of salt formation will change, making it impossible to determine an accurate value.

[0392] First, the amine value of the polymer before salt formation is determined using the method described above. Second, the amine value of the salt-form polymer is determined using nuclear magnetic resonance (NMR). 13 In the C-NMR (nuclear magnetic resonance) spectrum obtained, the ratio of the integral values ​​of the carbon atom peak adjacent to the nitrogen atom that does not form a salt to the carbon atom peak adjacent to the nitrogen atom that forms a salt in the terminal nitrogen site of the structural unit represented by the above general formula (I) is determined. The reaction rate (salt-forming terminal nitrogen site ratio) of one or more compounds selected from the group consisting of general formula (V) or (VII) relative to the terminal nitrogen site of the structural unit represented by general formula (I) of the salt-type polymer is measured. Regarding the terminal nitrogen site of the structural unit represented by general formula (I) that forms a salt from one or more compounds selected from the group consisting of general formula (V) or (VII), assuming an amine value of 0, the value of the polymer before salt formation is subtracted from the amine value of the polymer before salt formation by subtracting the amine value of the polymer before salt formation from (amine value of the polymer before salt formation as determined by the method described in JIS K 7237:1995) × (ratio of terminal nitrogen sites of salt formation calculated from 13C-NMR spectrum (%) / 100), which is the amine value consumed in the formation of the salt.

[0393] The amine value of the salt-type polymer = {amine value of the polymer before salt formation, determined by the method described in JIS K 7237:1995} - {amine value of the polymer before salt formation, determined by the method described in JIS K 7237:1995} × {ratio of nitrogen sites at the salt-forming end calculated from the 13C-NMR spectrum (%) / 100}

[0394] Regarding improving development adhesion and solvent resolubility, the acid value of the dispersant used in this invention may be less than 1 mg KOH / g, but for the purpose of suppressing development residue, a lower limit is preferably 1 mg KOH / g or more. For even better suppression of development residue, the acid value of the dispersant is more preferably 2 mg KOH / g or more. Furthermore, regarding the acid value of the dispersant used in this invention, for preventing deterioration of development adhesion or solvent resolubility, improving the straightness of the fine line pattern in the colored layer, and easily suppressing the unevenness of micropores, an upper limit is preferably 18 mg KOH / g or less. For better development adhesion and solvent resolubility, the acid value of the dispersant is more preferably 16 mg KOH / g or less, more preferably 14 mg KOH / g or less, and particularly preferably 12 mg KOH / g or less.

[0395] In salt-type block copolymers or salt-type graft copolymers, the acid value before salt formation can be less than 1 mg KOH / g, preferably 1 mg KOH / g or more, and even more preferably 2 mg KOH / g or more, in terms of improving developer adhesion and solvent resolvability. This is because the suppression effect on developer residue is improved. Furthermore, as an upper limit for the acid value before salt formation, it is preferably 18 mg KOH / g or less, more preferably 16 mg KOH / g or less, even more preferably 14 mg KOH / g or less, and particularly preferably 12 mg KOH / g or less. This is because developer adhesion and solvent resolvability become better.

[0396] The acid value represents the mass (mg) of potassium hydroxide required to neutralize the acidic components contained in 1g of the sample, and is the value determined by the method described in JISK 0070:1992.

[0397] Furthermore, in this invention, in terms of solvent resolubility, the hydroxyl value of the dispersant is preferably 120 mg KOH / g or less, more preferably 60 mg KOH / g or less, even more preferably 30 mg KOH / g or less, and preferably 0 mg KOH / g.

[0398] On the other hand, in terms of developability, the hydroxyl value of the dispersant is preferably 5 mg KOH / g or more, and more preferably 15 mg KOH / g or more.

[0399] It should be noted that, in this invention, the hydroxyl value represents the mass (mg) of KOH required to neutralize the acetic acid bonded to the acetylated compound obtained from 1g of solid component, and refers to the value obtained by potentiometric titration in accordance with JIS K 0070:1992.

[0400] Furthermore, in this invention, regarding the improvement of development adhesion, the glass transition temperature of the dispersant is preferably 30°C or higher. That is, regardless of whether the dispersant is a pre-salt-forming block copolymer or a salt-type block copolymer, its glass transition temperature is preferably 30°C or higher. If the glass transition temperature of the dispersant is low, especially if it is close to the developer temperature (usually around 23°C), there is a concern that the development adhesion may decrease. The reason for this is that if the glass transition temperature is close to the developer temperature, the movement of the dispersant increases during development, resulting in poorer development adhesion. It is inferred that by setting the glass transition temperature to 30°C or higher, the molecular movement of the dispersant during development is suppressed, thus suppressing the decrease in development adhesion.

[0401] Regarding the glass transition temperature of the dispersant, from the perspective of developing adhesion, it is preferably 32°C or higher, more preferably 35°C or higher. On the other hand, from the viewpoint of ease of use and operability during application, such as easy and accurate weighing, it is preferably 200°C or lower.

[0402] The glass transition temperature of the dispersant in this invention can be determined by differential scanning calorimetry (DSC) in accordance with JIS K7121.

[0403] Furthermore, the glass transition temperature (Tg) of the block portion and the block copolymer can be calculated using the following formula.

[0404] 1 / Tg=Σ(Xi / Tgi)

[0405] Here, the block copolymer is defined as the copolymerization of n monomer components from i = 1 to n. Xi is the weight fraction of the i-th monomer (ΣXi = 1), and Tgi is the glass transition temperature (absolute temperature) of the homopolymer of the i-th monomer. Σ is the sum of i = 1 to n. It should be noted that the values ​​of the glass transition temperature (Tgi) of the homopolymer of each monomer can be adopted from the Polymer Handbook (3rd edition) (J. Brandrup, E. Himmergut, Wiley-Interscience, 1989).

[0406] Increasing the colorant concentration and dispersant content reduces the amount of binder, making the colored resin layer easier to peel off from the substrate during development. In block copolymers used as dispersants, the development adhesion is improved by including B blocks containing structural units derived from carboxyl-containing monomers and possessing the aforementioned specific acid value and glass transition temperature. It is inferred that if the acid value is too high, although the developability is excellent, the excessive polarity will make peeling during development less likely.

[0407] As the dispersant used in this invention, the following dispersant is preferred: it has excellent color material dispersion stability, which improves contrast; when a coloring resin composition containing the compound represented by the above general formula (1) is prepared, the generation of developing residue is suppressed; and it has excellent solvent resolubility, which in turn provides high developing adhesion. Furthermore, it is preferred to form well-shaped micropores and suppress the non-flow of micropores and developing residue. The dispersant is a polymer containing the structure represented by the above general formula (I′) with an amine value of 40 mg KOH / g or more and 120 mg KOH / g or less, an acid value of 1 mg KOH / g or more and 18 mg KOH / g or less, and a glass transition temperature of 30°C or more.

[0408] Furthermore, as the dispersant used in this invention, in terms of excellent colorant dispersion stability and improved contrast, and in terms of suppressing the generation of developing residues and excellent solvent resolubility when preparing a coloring resin composition containing the compound represented by the above general formula (I), the following dispersant is preferred: a non-salt-forming polymer containing the structure represented by the above general formula (I) with an amine value of 40 mg KOH / g or more and 140 mg KOH / g or less, and an acid value of 1 mg KOH / g or more and 18 mg KOH / g or less; and a salt-type polymer containing the structure represented by the above general formula (I) with an amine value of 0 mg KOH / g or more and 130 mg KOH / g or less, and an acid value of 1 mg KOH / g or more and 18 mg KOH / g or less.

[0409] As the aforementioned carboxyl-containing monomer, monomers containing unsaturated double bonds and carboxyl groups that can copolymerize with monomers having structural units represented by general formula (I) can be used. Examples of such monomers include: (meth)acrylic acid, vinylbenzoic acid, maleic acid, monoalkyl maleate, fumaric acid, itaconic acid, butenoic acid, cinnamic acid, and acrylic acid dimers. Furthermore, monomers with hydroxyl groups, such as 2-hydroxyethyl (meth)acrylic acid, and cyclic anhydrides such as maleic anhydride, phthalic anhydride, and cyclohexanedicarboxylic anhydride, as well as ω-carboxyl-polycaprolactone mono(meth)acrylic acid esters, can also be used. Additionally, anhydride-containing monomers such as maleic anhydride, itaconic anhydride, and methylmaleic anhydride can also be used as precursors for the carboxyl group. Among these, (meth)acrylic acid is particularly preferred in terms of copolymerizability, cost, solubility, and glass transition temperature.

[0410] In the block copolymer before salt formation, the proportion of structural units derived from carboxyl-containing monomers can be appropriately set such that the acid value of the block copolymer is within the range of the aforementioned specific acid values, and there is no particular limitation. Relative to the total mass of all structural units of the block copolymer, it is preferably 0.05% by mass or more and 4.5% by mass or less, more preferably 0.07% by mass or more and 3.7% by mass or less.

[0411] When the proportion of structural units derived from carboxyl monomers is above the lower limit mentioned above, a suppressive effect on developing residue can be achieved; when it is below the upper limit mentioned above, a decrease in developing adhesion and a decrease in solvent resolubility can be prevented.

[0412] It should be noted that the structural units derived from carboxyl-containing monomers only need to have the specific acid value mentioned above, and can contain one type of structural unit or two or more structural units.

[0413] Furthermore, regarding the improvement of development adhesion by setting the glass transition temperature of the dispersant used in this invention to a specific value or above, in the B block, it is preferable that the monomers with a glass transition temperature (Tgi) of 10°C or above in the homopolymer of the monomers be 75% or more by mass, and more preferably 85% or more by mass.

[0414] In the block copolymer described above, the ratio m / n of the number of structural units m of the A block to the number of structural units n of the B block is preferably in the range of 0.05 or more and 1.5 or less, and more preferably in the range of 0.1 or more and 1.0 or less in terms of the dispersibility and dispersion stability of the colorant.

[0415] The weight-average molecular weight Mw of the block copolymer is not particularly limited, but in terms of improving the dispersibility and dispersion stability of the colorant, it is preferably 1,000 or more and 20,000 or less, more preferably 2,000 or more and 15,000 or less, and even more preferably 3,000 or more and 12,000 or less.

[0416] Here, the weight-average molecular weight (Mw) is determined as a standard polystyrene conversion value using gel permeation chromatography (GPC). It should be noted that the macromonomers, salt-type block copolymers, and graft copolymers used as raw materials for block copolymers are also analyzed under the above conditions.

[0417] As a specific example of such a block copolymer having a block portion containing repeating units with tertiary amines and a block portion having solvent affinity, the block copolymer described in Japanese Patent No. 4911253 can be cited as an example.

[0418] When using the polymer containing repeating units with tertiary amines as a dispersant to disperse the colorant, the content of the polymer containing repeating units with tertiary amines is preferably 15 parts by mass or more and 300 parts by mass or less, more preferably 20 parts by mass or more and 250 parts by mass or less, relative to 100 parts by mass of the colorant. Within these ranges, the dispersibility and dispersion stability are excellent, and the effect of improving contrast is enhanced.

[0419] In this invention, in terms of the dispersibility and dispersion stability of the colorant, it is also preferable to use a salt-type polymer that contains at least a portion of the amino groups in the polymer having repeating units of tertiary amines and forms a salt with an organic acid compound or a halogenated hydrocarbon as a dispersant.

[0420] In terms of excellent dispersibility and dispersion stability of the colorant, it is preferable that the polymer containing repeating units having tertiary amines is a block copolymer, and that the organic acid compound is an acidic organophosphorus compound such as phenylphosphonic acid or phenylphosphine. Specific examples of the organic acid compound used in this dispersant include, for instance, those described in Japanese Patent Application Publication No. 2012-236882.

[0421] Furthermore, in terms 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 groups, is preferred.

[0422] Furthermore, as a polymeric dispersant, it can suppress the generation of developing residues, thereby improving the resistance (NMP resistance) to N-methylpyrrolidone (NMP), which is used as a solvent in the fabrication of color filters. It is also preferred to be a graft copolymer having structural units represented by the above general formula (I) and structural units represented by the following general formula (II), and at least one salt-type graft copolymer in which at least a portion of the nitrogen site of the structural unit represented by the general formula (I) of the graft copolymer forms a salt with at least one of the organic acid compounds and halogenated hydrocarbons.

[0423] [Chemical Formula 24]

[0424] General formula (11)

[0425]

[0426] (In general formula (II), R) 1′ A represents a hydrogen atom or a methyl group. 2 (This indicates a directly bonded or divalently linked group. The polymer indicates a polymer chain whose structural units include at least one structural unit selected from the group consisting of structural units represented by general formula (III) and general formula (III′).)

[0427] [Chemical Formula 25]

[0428] General formula (111)

[0429]

[0430] General formula (III′)

[0431]

[0432] (In general formula (III), R) 4 A is a hydrogen atom or a methyl group. 3 R is a divalent linker group. 5 It is ethylene or propylene, R 6 It can be a hydrogen atom or a hydrocarbon group, and s represents a number greater than 3 and less than 80;

[0433] In general formula (III′), R 4′ A is a hydrogen atom or a methyl group. 3′ R is a divalent linker group. 7 R is an alkylene group having 1 to 10 carbon atoms. 8 R is an alkylene group having 3 to 7 carbon atoms. 9 (This represents a hydrogen atom or a hydrocarbon group; t represents a number greater than 1 and less than 40.)

[0434] The aforementioned specific graft copolymers contain structural units of polyethylene oxide chains, polypropylene oxide chains, or ester chains within the grafted polymer chains. It is inferred that because the multiple grafted polymer chains in these specific graft copolymers act as solvent-affinity parts of the dispersant, the specific surface area of ​​the solvent-affinity parts of the dispersant increases, thus inhibiting solvent penetration into the coating film and reaching the colorant. It is also inferred that by including structural units of polyethylene oxide chains, polypropylene oxide chains, or ester chains within the structural units of the grafted polymer chains, the oxygen atoms in these structural units interact with acidic groups such as carboxyl groups of the alkali-soluble resin contained in the photosensitive coloring resin composition through hydrogen bonds, thereby further inhibiting the penetration of solvent (NMP) into the cured coating film. Furthermore, it is anticipated that the sublimation of the photosensitive coloring resin composition of the present invention during pre-exposure drying is suppressed by the compound represented by the above-described general formula (1) contained as a photoinitiator, and that in the dried coating film of the photosensitive coloring resin composition of the present invention, the residual compound represented by the above-described general formula (1) and the colorant dispersed in the above-described specific graft copolymer with higher performance are formed into a dense coating film. It is inferred that through these synergistic effects, the resistance of the cured product of the photosensitive coloring resin composition of the present invention, which combines the above-described specific graft copolymer and the compound represented by the above-described general formula (1) as a photoinitiator, to N-methylpyrrolidone (NMP), used as a solvent in the fabrication of the orientation film of the color filter, can be improved (NMP resistance).

[0435] Furthermore, the photosensitive coloring resin composition of the present invention, by containing the aforementioned specific graft copolymer, suppresses the generation of developing residue. It is believed that the aforementioned specific graft copolymer, through the oxygen atoms contained in the polyethylene oxide chain, polyethylene oxide chain, or ester chain, interacts with the OH and CH groups of the carboxyl groups, etc., of the alkali-soluble resin contained in the photosensitive resin composition via hydrogen bonds. During development, only the alkali-soluble resin dissolves, and the colorant and dispersant are less likely to remain as residue. On the other hand, if the number of repeating units in the polyethylene oxide chain, polyethylene oxide chain, or ester chain becomes too large, the effect of suppressing developing residue is not easily improved. The reason for this is likely as follows: if the number of repeating units in the polyethylene oxide chain, polyethylene oxide chain, or ester chain becomes too large, the affinity for the alkaline developing solution becomes excessively greater than the adsorption force of the colorant, and only the graft copolymer dissolves in the alkaline developing solution, leaving the colorant remaining on the substrate.

[0436] The structural units represented by the above general formula (I) constituting the main chain of the graft copolymer are alkaline and function as adsorption sites for colorants.

[0437] The structural unit represented by the above general formula (I) constituting the main chain of the graft copolymer is the same as the structural unit represented by the above general formula (I) in the above block copolymer, and therefore is omitted here.

[0438] It should be noted that in graft copolymers, the structural unit represented by general formula (I) may contain one type or more than two types of structural units.

[0439] (Structural unit represented by general formula (II))

[0440] The graft copolymer described above exhibits good solvent affinity, good dispersibility and dispersion stability of the colorant by containing structural units represented by the above general formula (II) having specific polymer chains. Furthermore, the graft copolymer includes at least one structural unit selected from the group consisting of structural units represented by the above general formula (III) and the above general formula (III′) in the structural units represented by the above general formula (II). Therefore, as mentioned above, the development time of the photosensitive resin composition is shortened, and the solvent resistance of the cured photosensitive coloring resin composition is improved.

[0441] In the above general formula (II), A 2 It is a directly bonded or divalent linkage group. As A 2 The divalent linking group in the polymer chain is not particularly restricted as long as it can link a carbon atom derived from an ethylene unsaturated double bond to the polymer chain. As an A... 2 The divalent linker in it, for example, can be listed with the above A 1 Those with the same divalent linker group.

[0442] In terms of dispersion, A in general formula (II) 2 Preferably, it is a divalent linker containing a -CONH- group or a -COO- group, more preferably a divalent linker containing a -CONH- group or a -COO- group and an alkylene group having 1 to 10 carbon atoms.

[0443] In the above general formula (II), polymer represents a polymer chain, the structural unit of which includes at least one structural unit selected from the group consisting of the structural units represented by the above general formula (III) and the structural units represented by the above general formula (III′).

[0444] In the above general formula (III), R 4 A is a hydrogen atom or a methyl group. 3 R is a divalent linker group. 5 It is ethylene or propylene, R 6 It represents a hydrogen atom or a hydrocarbon group, and s represents a number greater than 3 and less than 80.

[0445] As A 3 The divalent linker, for example, can be listed with the above A 1 Those with the same divalent linking group. Among them, regarding solubility in organic solvents used in color filter applications, A in general formula (III) 3 Preferably, it contains a divalent linker group containing a -CONH- group or a -COO- group, more preferably a -CONH- group or a -COO- group.

[0446] The 's' above indicates the number of repeating units in the ethylene oxide or propylene oxide chain, and is a number of 3 or more, preferably 19 or more, and more preferably 21 or more, in terms of suppressing water spot formation. Water spots in the cured film of the photosensitive resin composition can be attributed to water absorption into the cured film. The alkali-soluble resin in the cured film readily absorbs water due to the presence of acidic groups such as carboxyl groups. Furthermore, it is believed that the water absorption is further enhanced when these acidic groups form metal salts with alkali metals typically contained in alkaline developing solutions during development. The oxygen atoms contained in the polyethylene oxide or polypropylene oxide chain can be captured by complexing with metals such as alkali metals. It is speculated that as the number of repeating units in the polyethylene oxide or polypropylene oxide chain increases, the complexation constant increases, and the metal molecule capture ability increases, thus suppressing the formation of alkali metal salts in the alkali-soluble resin, thereby suppressing water absorption into the cured film. Furthermore, it is speculated that the oxygen atoms contained in the polyethylene oxide chain or polyethylene oxide chain interact with the acidic groups such as the carboxyl groups of the alkali-soluble resin contained in the photosensitive resin composition through hydrogen bonds, thereby inhibiting the formation of alkali metal salts of acidic groups and thus inhibiting water absorption into the cured film.

[0447] When s is 19 or more, such as Figure 4As shown, the graft copolymer 110 contains a main chain portion 113 having structural units 111 represented by general formula (I) and structural units 112 represented by general formula (II). At least a portion of the nitrogen sites of the structural unit 111 represented by general formula (I) can form a salt with at least one 114 selected from the group consisting of organic acid compounds and halogenated hydrocarbons. The structural unit 112 represented by general formula (II) includes structural units 116 represented by general formula (III) in the polymer chain 115. The structural unit 116 contains polyethylene oxide chains or polypropylene oxide chains with a specific number of repetitions 117. In the specific graft copolymer used in this invention, the structural units of the polymer chain 115 grafted in the above manner include structural units 116, which contain polyethylene oxide chains or polypropylene oxide chains with a specific number of repetitions. The grafted polymer chain 115 itself has a branched structure. The conclusion is that, in conjunction with the increased specific surface area of ​​the metal-capturing portion of the dispersant, the metal-capturing effect of the oxygen atoms contained in the polyethylene oxide or polypropylene oxide chains becomes more significant, improving the water absorption inhibition effect and thus suppressing the formation of water spots caused by water absorption. It is speculated that by inhibiting water absorption into the cured film, the formation of water spots caused by water absorption can be suppressed.

[0448] On the other hand, the upper limit of s is 80 or less, and in terms of solubility in organic solvents used for color filter applications, it is preferably 50 or less.

[0449] As R 6 Hydrocarbon groups, for example, include alkyl groups with 1 to 18 carbon atoms, alkenyl groups with 2 to 18 carbon atoms, aryl groups, and combinations of aralkyl groups, alkyl-substituted aryl groups, etc.

[0450] The alkyl groups having 1 to 18 carbon atoms can be linear, branched, or cyclic, and examples include: methyl, ethyl, n-propyl, isopropyl, n-butyl, n-nonyl, n-lauryl, n-stearyl, cyclopentyl, cyclohexyl, borneol, isoborneol, dicyclopentyl, adamantyl, and lower alkyl-substituted adamantyl. The alkyl group preferably has 1 to 12 carbon atoms, and more preferably 1 to 6.

[0451] The alkenyl group with 2 to 18 carbon atoms can be linear, branched, or cyclic. Examples of such alkenyl groups include vinyl, allyl, and propenyl. The position of the double bond in the alkenyl group is not limited, but from the perspective of the reactivity of the obtained polymer, it is preferable that the double bond is at the end of the alkenyl group. The alkenyl group preferably has 2 to 12 carbon atoms, and more preferably 2 to 8 carbon atoms.

[0452] 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, and more preferably 6 to 12.

[0453] Furthermore, examples of aralkyl groups include benzyl, phenethyl, naphthylmethyl, and biphenylmethyl, which may further have substituents. The number of carbon atoms in the aralkyl group is preferably 7 to 20, and more preferably 7 to 14.

[0454] In addition, a straight-chain or branched alkyl group with 1 to 30 carbon atoms may be optionally bonded to the aromatic ring of the aryl or aralkyl group as a substituent.

[0455] As R 6 The hydrocarbon group in the hydrocarbon group, in terms of dispersion stability, is preferably one or more selected from the group consisting of alkyl groups having 1 to 18 carbon atoms, aryl groups having 6 to 12 carbon atoms that can be substituted by alkyl groups, and aralkyl groups having 7 to 14 carbon atoms that can be substituted by alkyl groups, and preferably one or more selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, n-nonyl, n-lauryl, n-stearyl, alkyl-substituted phenyl and benzyl groups.

[0456] Furthermore, in the above general formula (III′), as A 3′ The divalent linker, for example, can be listed with the above A 1 Those with the same divalent linking group. Among them, regarding solubility in organic solvents used for color filter applications, A in general formula (III′) 3′ Preferably, it contains a divalent linker group containing a -CONH- group or a -COO- group, more preferably a -CONH- group or a -COO- group.

[0457] In the above general formula (III′), in terms of solvent resolubility, R 7 Preferably, it is an alkylene group having 1 to 10 carbon atoms, and more preferably an alkylene group having 2 to 8 carbon atoms.

[0458] R 8 The alkylene group having 3 to 7 carbon atoms is preferred in terms of substrate adhesion, and more preferably an alkylene group having 3 to 5 carbon atoms.

[0459] R 9 It is a hydrogen atom or a hydrocarbon group, as the above R 9 The hydrocarbon group in it can react with the above R 6 The hydrocarbon groups are the same.

[0460] In the above general formula (III′), t represents the number of repeating units of the ester chain, which is 1 or more, and is preferably 2 or more, and more preferably 3 or more, in terms of simultaneously satisfying the aspects of shortening the development time and excellent solvent resistance.

[0461] On the other hand, the upper limit of t is 40 or less, and in terms of solubility in organic solvents used for color filter applications, it is preferably 20 or less.

[0462] In the polymer chain described above, at least one structural unit selected from the group consisting of the structural unit represented by the above general formula (III) and the structural unit represented by the following general formula (III′) may be a single unit or a mixture of two or more units.

[0463] In the polymer chain described above, it is preferable to include the structural unit represented by the general formula (III) above, in terms of making the role of the solvent affinity of oxygen atoms more significant.

[0464] In terms of improving the NMP resistance and development residue suppression effect of the photosensitive coloring resin composition of the present invention, it is more preferable to combine at least one of the structural units of the polymer chain in the structural unit represented by the above general formula (II) containing at least one of the structural units of the above general formula (III) with s selected as 19 or more and 80 or less, and at least one of the structural units of the above general formula (III) with s selected as 3 or more and 10 or less. More preferably, it is more preferable to combine at least one of the structural units of the above general formula (III) containing at least one of the structural units of the above general formula (III) with s selected as 19 or more and 50 or less, and at least one of the structural units of the above general formula (III) with s selected as 3 or more and 8 or less.

[0465] When the structural units of the polymer chain in the structural unit represented by the above general formula (II) include at least one type selected from the group consisting of structural units represented by the above general formula (III) with s being 19 or more and 80 or less, when all structural units of the above polymer chain are set to 100% by mass, the total proportion of the structural units represented by the above general formula (III) with s being 19 or more and 80 or less is preferably 1% by mass or more, more preferably 2% by mass or more, and even more preferably 4% by mass or more. On the other hand, it is preferably 75% by mass or less, more preferably 65% ​​by mass or less, and even more preferably 50% by mass or less. If the total proportion of the structural units represented by the above general formula (III) with s being 19 or more and 80 or less is within the above range, it is easy to improve the NMP resistance and development residue suppression effect of the photosensitive coloring resin composition of the present invention.

[0466] In the case where the structural units of the polymer chain in the structural unit represented by the above general formula (II) are combined with at least one of the group consisting of structural units of the above general formula (III) selected from those with s of 19 or more and 80 or less, and at least one of the group consisting of structural units of the above general formula (III) selected from those with s of 3 or more and 10 or less, when all structural units of the above polymer chain are set to 100% by mass, the total proportion of structural units of the above general formula (III) with s of 3 or more and 10 or less is preferably 20% by mass or more. On the other hand, in terms of solvent resolubility, in the above polymer chain, when all structural units of the polymer chain are set to 100% by mass, the total proportion of structural units of the above general formula (III) with s of 3 or more and 10 or less is preferably 80% by mass or less, more preferably 60% by mass or less.

[0467] Furthermore, regarding the improvement of the effect of suppressing developer residue, in the polymer chain described above, the mixing ratio of the structural unit represented by the above general formula (III) with s of 19 or more and 80 or less to the structural unit represented by the above general formula (III) with s of 3 or more and 10 or less is preferably 3 or more by mass, more preferably 6 or more by mass, and preferably 80 or less by mass, more preferably 60 or less by mass, in order to improve the effect of suppressing developer residue.

[0468] Regarding the simultaneous satisfaction of dispersion stability, high contrast, shortened development time, and excellent solvent resistance, when all structural units of the polymer chain are set to 100% by mass, the total proportion of at least one structural unit selected from the group consisting of structural units represented by general formula (III) and general formula (III′) is preferably 1% by mass or more, more preferably 2% by mass or more, and even more preferably 4% by mass or more. Regarding the total proportion of at least one structural unit selected from the group consisting of structural units represented by general formula (III) and general formula (III′), in terms of solvent resolubility, when all structural units of the polymer chain are set to 100% by mass, it is preferably 80% by mass or less, more preferably 70% by mass or less, and even more preferably 60% by mass or less.

[0469] In terms of the dispersibility and dispersion stability of the colorant, it is preferable that the structural unit of the polymer chain in the structural unit represented by the above general formula (II) of the above graft copolymer further includes the structural unit represented by the following general formula (IV), which is different from the structural unit represented by the above general formula (III) and the structural unit represented by the above general formula (III′).

[0470] [Chemical Formula 26]

[0471]

[0472] (In general formula (IV), R) 4″ A is a hydrogen atom or a methyl group. 4 R is a divalent linker group. 10 (The atom is a hydrogen atom, or optionally a hydrocarbon group containing a heteroatom.)

[0473] As A 4 The divalent linker, for example, can be listed with the above A 1 Those with the same divalent linking group. Among them, regarding solubility in organic solvents used for color filter applications, A in general formula (IV) 4 Preferably, it contains a divalent linker group containing a -CONH- group or a -COO- group, more preferably a -CONH- group or a -COO- group.

[0474] R 10 The hydrocarbon groups that can be selected to contain heteroatoms include, for example, alkyl, alkenyl, aryl, and combinations of aralkyl, alkyl-substituted aryl, etc. As R 10 The hydrocarbon groups in any of the hydrocarbon groups containing heteroatoms can be listed as R above. 6 Those with the same hydrocarbon group.

[0475] The heteroatoms that can be optionally contained in a hydrocarbon group include, for example, oxygen atoms, nitrogen atoms, sulfur atoms, silicon atoms, etc. The hydrocarbon group that can optionally contain heteroatoms may have structures in which the carbon chain contains linking groups such as -CO-, -COO-, -OCO-, -O-, -S-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -OCO-NH-, -NH-COO-, -NH-CO-NH-, -NH-O-, and -O-NH-.

[0476] Furthermore, the hydrocarbon group may optionally have substituents within a range that does not impair the dispersion properties of the graft copolymer, etc. Examples of substituents include: halogen atoms, hydroxyl groups, carboxyl groups, alkoxy groups, nitro groups, cyano groups, epoxy groups, isocyanate groups, thiol groups, etc.

[0477] In addition, as R 10The optional hydrocarbon group containing heteroatoms can also be a structure in which a polymerizable group such as an alkenyl group is added to the end of the hydrocarbon group via a linking group containing heteroatoms. For example, the structural unit represented by general formula (IV) can be a structure in which glycidyl (meth)acrylate reacts with a structural unit derived from (meth)acrylic acid. That is, -A in general formula (IV) 4 -R 10 The structure can be represented by -COO-CH2CH(OH)CH2-OCO-CR=CH2 (where R is a hydrogen atom or a methyl group). Furthermore, the structural unit represented by general formula (IV) can also be a structure formed by reacting a 2-isocyanate alkyl ester of (meth)acrylate with a structural unit derived from a hydroxyalkyl ester of (meth)acrylate. That is, R in general formula (IV) 10 It can be represented by the structure -R′-OCONH-R″-OCO-CR=CH2 (where R′ and R″ are alkylene groups, and R is a hydrogen atom or a methyl group).

[0478] Monomers representing structural units of the derived general formula (IV) are preferably those having structural units derived from the following substances: methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, 2-ethylhexyl methacrylate, 2-ethoxyethyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, phenyl methacrylate, isobornyl methacrylate, and dicyclopentyl methacrylate. Esters, adamantyl methacrylate, methacrylic acid, 2-methacryloyloxyethyl succinate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 4-hydroxybutyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, phenoxyethyl methacrylate, methoxy polyethylene glycol (meth)acrylates and polyethylene glycol (meth)acrylates with fewer than 19 repeating units in the ethylene oxide chain, phenoxy polyethylene glycol (meth)acrylates, etc. However, it is not limited to these.

[0479] In this invention, R is described above. 10 Preferably, the organic solvent used has excellent solubility with the organic solvents described below, and the organic solvent used in the colorant dispersion can be appropriately selected. Specifically, for example, when the organic solvent used is an ether-alcohol-acetic acid ester, ether-based, ester-based, or alcohol-based organic solvent commonly used as an organic solvent for colorant dispersions, the preferred solvents are: methyl, ethyl, isobutyl, n-butyl, 2-ethylhexyl, benzyl, cyclohexyl, dicyclopentyl, hydroxyethyl, phenoxyethyl, adamantyl, methoxy polyethylene glycol, methoxy polyethylene glycol, polyethylene glycol, etc.

[0480] In the polymer chain described above, the structural unit represented by the general formula (IV) may be a single type or a mixture of two or more types.

[0481] Regarding the dispersibility and dispersion stability of the colorant, in the aforementioned polymer chain, when all structural units of the polymer chain are set to 100% by mass, the total proportion of structural units represented by the aforementioned general formula (IV) is preferably 25% by mass or more, more preferably 35% by mass or more. On the other hand, regarding simultaneously satisfying dispersion stability, high contrast, shortened development time, and excellent solvent resistance, in the aforementioned polymer chain, when all structural units of the polymer chain are set to 100% by mass, the total proportion of structural units represented by the aforementioned general formula (IV) is preferably 99% by mass or less, more preferably 98% by mass or less.

[0482] In addition to the structural units represented by the structural units of the polymer chains in the structural units of the above-mentioned graft copolymers represented by general formula (II), other structural units may also be included.

[0483] Other structural units can be listed as structural units derived from monomers having unsaturated double bonds that can be copolymerized with monomers that can derive structural units represented by the above general formula (III), monomers that derive structural units represented by the above general formula (III′), or monomers that derive structural units represented by the above general formula (IV).

[0484] Monomers that derive other structural units include, for example, styrene, α-methylstyrene and other styrene derivatives; phenyl vinyl ethers and other vinyl ether derivatives.

[0485] In the polymer chain of the structural unit represented by the above general formula (II) of the above-mentioned graft copolymer, in terms of the effect of the present invention, when all structural units of the polymer chain are set to 100% by mass, the total proportion of other structural units is preferably 30% by mass or less, more preferably 10% by mass or less.

[0486] Regarding the dispersibility and dispersion stability of the colorant, the weight-average molecular weight Mw of the polymer chain in the polymer is preferably 2,000 or more, more preferably 3,000 or more, even more preferably 4,000 or more, and even more preferably 15,000 or less, and even more preferably 12,000 or less.

[0487] By defining the above range, sufficient stereorepulsion effect as a dispersant can be maintained, and the specific surface area of ​​the solvent-affinity portion of the dispersant becomes larger. As a result, the interaction of oxygen atoms contained in the polyethylene oxide chain, polypropylene oxide chain, or ester chain becomes significant, thereby improving the effect of suppressing developing residue, shortening developing time, and improving solvent resistance.

[0488] Furthermore, regarding the polymer chains in the polymer, as a standard, the solubility of the organic solvent used in combination at 23°C is preferably 20 (g / 100g solvent) or more.

[0489] The solubility of the polymer chain can be assessed by using the aforementioned solubility of the raw material introduced into the polymer chain during the preparation of the graft copolymer. For example, when a polymeric oligomer (macromonomer) containing a polymer chain and a group having an ethylene unsaturated double bond at its terminal is used to introduce the polymer chain into the graft copolymer, the polymeric oligomer simply needs to have the aforementioned solubility. Furthermore, when a copolymer is formed from a monomer containing a group having an ethylene unsaturated double bond, and a polymer chain containing a reactive group that can react with the reactive groups contained in the copolymer is used to introduce the polymer chain, the polymer chain containing the reactive group simply needs to have the aforementioned solubility.

[0490] In the above-mentioned graft copolymer, the structural unit represented by the general formula (I) is preferably contained in a proportion of 3 to 60% by mass, more preferably 6 to 45% by mass, and even more preferably 9 to 30% by mass. If the structural unit represented by the general formula (I) in the graft copolymer is within the above range, the proportion of the affinity portion with the colorant in the graft copolymer becomes suitable, and the reduction in solubility in organic solvents can be suppressed. Therefore, the adsorption of the colorant becomes good, and excellent dispersibility and dispersion stability can be obtained.

[0491] On the other hand, in the above-mentioned graft copolymer, the structural unit represented by the general formula (II) is preferably contained in a proportion of 40 to 97% by mass, more preferably 55 to 94% by mass, and even more preferably 70 to 91% by mass. If the structural unit represented by the general formula (II) in the graft copolymer is within the above range, the proportion of the solvent-affinity portion in the graft copolymer becomes suitable, sufficient stereorepulsion effect as a dispersant can be maintained, and the specific surface area of ​​the solvent-affinity portion of the dispersant becomes larger. As a result, the interaction of oxygen atoms contained in the polyethylene oxide chain, polyethylene oxide chain, or ester chain becomes significant, and the effects of shortening the development time and improving solvent resistance become better.

[0492] The graft copolymers used in this invention may further have other structural units besides those represented by general formula (I) and general formula (II) without impairing the effects of this invention. As other structural units, monomers containing ethylene-unsaturated double bonds that can be copolymerized with monomers that derive structural units from general formula (I) may be appropriately selected and copolymerized to introduce other structural units.

[0493] Other structural units that are copolymerized with the structural unit represented by the above general formula (I) may include, for example, the structural unit represented by the above general formula (IV) and structural units with polymer chains that are different from the structural unit represented by the above general formula (II). The structural unit with polymer chains that is different from the structural unit represented by the above general formula (II) is a structural unit whose polymer chain does not contain at least one structural unit selected from the group consisting of the structural unit represented by the above general formula (III) and the structural unit represented by the above general formula (III′), and contains the structural unit represented by the above general formula (IV).

[0494] It should be noted that the proportion of the above-mentioned structural units is calculated by the amount of monomers added during the synthesis of the graft copolymer to derive the structural units represented by the above-mentioned general formula (I), the above-mentioned general formula (II), the above-mentioned general formula (III), and the above-mentioned general formula (III′).

[0495] Furthermore, regarding dispersibility and dispersion stability, the weight-average molecular weight (Mw) of the graft copolymer is preferably 4000 or more, more preferably 6000 or more, and even more preferably 8000 or more. On the other hand, regarding solvent resolubility, it is preferably 50000 or less, more preferably 30000 or less.

[0496] It should be noted that in this invention, the weight-average molecular weight Mw is a value determined by GPC (gel permeation chromatography). The determination was performed using a Tosoh-manufactured HLC-8120 GPC, with the dissolution solvent being N-methylpyrrolidone containing 0.01 mol / L lithium bromide. The calibration curves were performed using polystyrene standards Mw377400, 210500, 96000, 50400, 20650, 10850, 5460, 2930, 1300, and 580 (all from the Polymer Laboratories Easi PS-2 series) and Mw1090000 (manufactured by Tosoh). The measurement column was set to two TSK-GEL ALPHA-M tubes (manufactured by Tosoh).

[0497] In this invention, any method for manufacturing the graft copolymer described above is acceptable as long as it can produce a graft copolymer having structural units represented by general formula (I) and general formula (II) as described above, and there is no particular limitation. When manufacturing a graft copolymer having structural units represented by general formula (I) and general formula (II), for example, the following method can be used: A polymeric oligomer (macromonomer) containing a monomer represented by general formula (Ia) and a polymeric oligomer containing the polymer chain and a group having ethylene-unsaturated double bonds at its ends is copolymerized as a copolymer component to produce the graft copolymer.

[0498] Other monomers may also be used as needed to produce graft copolymers using known polymerization methods.

[0499] [Chemical Formula 27]

[0500]

[0501] (In general formula (Ia), R) 1 、A 1 R 2 and R 3 Same as general formula (I).

[0502] Furthermore, when manufacturing graft copolymers having structural units represented by general formula (I) and general formula (II) above, optionally after forming a copolymer by addition polymerization of a monomer represented by general formula (Ia) with other monomers containing groups having vinyl unsaturated double bonds, a polymer chain containing reactive groups that can react with reactive groups contained in the copolymer is introduced into the polymer chain. Specifically, for example, optionally after synthesizing a copolymer having substituents such as alkoxy, hydroxyl, carboxyl, amino, epoxy, isocyanate, or hydrogen-bonding groups, it is reacted with a polymer chain containing functional groups that react with the substituents to introduce the polymer chain.

[0503] For example, a polymer chain with a carboxyl group at the end can be reacted with a copolymer with a glycidyl group on the side chain, or a polymer chain with a hydroxyl group at the end can be reacted with a copolymer with an isocyanate group on the side chain to introduce the polymer chain.

[0504] It should be noted that additives commonly used in polymerization, such as polymerization initiators, dispersion stabilizers, and chain transfer agents, can also be used in the above polymerization process.

[0505] In terms of improving the dispersibility of the colorant, the above-mentioned graft copolymer may also be a salt-type graft copolymer in which at least a portion of the nitrogen site of the structural unit represented by the above general formula (I) forms a salt with at least one of the organic acid compounds and halogenated hydrocarbons selected from the group consisting of organic acid compounds and halogenated hydrocarbons.

[0506] As the aforementioned organic acid compound, compounds represented by general formula (V) and general formula (VII) are preferred; as the aforementioned halogenated hydrocarbon, compounds represented by general formula (VI) are preferred. That is, as at least one of the above-mentioned compounds selected from the group consisting of organic acid compounds and halogenated hydrocarbons, one or more compounds selected from the group consisting of general formulas (V) to (VII) are preferably used.

[0507] [Chemical Formula 28]

[0508]

[0509] (In the general formula (V), R) 11 Describing a straight-chain, branched, or cyclic alkyl, vinyl, optionally substituted phenyl or benzyl, or -OR group having 1 to 20 carbon atoms. 15 R 15 Represents a straight-chain, branched, or cyclic alkyl, vinyl, optionally substituted phenyl or benzyl, or (meth)acryloyl group separated by an alkylene group having 1 to 20 carbon atoms; in general formula (VI), R 12 R 12′ and R 12” Each of the following can independently represent a hydrogen atom, an acidic group or its ester group, an alkyl group having 1 to 20 carbon atoms that is either straight-chain, branched or cyclic, optionally with a substituent, a vinyl group that is optionally with a substituent, a phenyl or benzyl group that is optionally with a substituent, or -OR 16 R 16 The symbol represents a straight-chain, branched, or cyclic alkyl group having 1 to 20 carbon atoms, optionally a substituted vinyl group, optionally a substituted phenyl or benzyl group, or a (meth)acryloyl group separated by an alkylene group having 1 to 4 carbon atoms; X represents a chlorine atom, a bromine atom, or an iodine atom; in general formula (VII), R 13 and R 14 Each of the following independently represents a hydrogen atom, a hydroxyl group, a straight-chain, branched, or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, an optional phenyl or benzyl group with substituents, or -OR 15 R 15 Represents a straight-chain, branched, or cyclic alkyl, vinyl, optionally substituted phenyl or benzyl, or (meth)acryloyl group separated by an alkylene group having 1 to 20 carbon atoms; wherein, R c and R d (At least one of them contains a carbon atom.)

[0510] In the above general formulas (V) to (VII), as R 11 R 12 R 12′ R 12” R13 R 14 R 15 and R 16 The alkyl group having 1 to 20 carbon atoms can be either straight-chain or branched, and optionally contains a cyclic structure. Examples include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, dodecyl, cyclopentyl, cyclohexyl, tetradecyl, octadecyl, etc. Preferably, the alkyl group having 1 to 15 carbon atoms can be straight-chain, branched, or cyclic, and more preferably, the alkyl group having 1 to 8 carbon atoms can be straight-chain, branched, or cyclic.

[0511] Furthermore, in R 11 R 13 R 14 and R 15 In this context, the phenyl or benzyl substituents that are optionally substituted can be, for example, alkyl, acyl, acyloxy, etc., having 1 to 5 carbon atoms.

[0512] In R 12 R 12′ R 12″ and R 16 In this context, the phenyl or benzyl substituents that are optionally substituted can be, for example, acidic groups or their ester groups, alkyl groups having 1 to 5 carbon atoms, acyl groups, acyloxy groups, etc.

[0513] Furthermore, in R 12 R 12′ R 12″ and R 16 Among them, the substituents that are straight-chain, branched or cyclic alkyl or vinyl groups having 1 to 20 carbon atoms can be listed as acid groups or their ester groups, phenyl groups, acyl groups, acyloxy groups, etc.

[0514] In R 12 R 12′ R 12″ and R 16 In this context, an acidic group refers to a group that releases a proton in water and exhibits acidic properties. Specific examples of acidic groups include: carboxyl groups (-COOH), sulfonyl groups (-SO3H), phosphonic acid groups (-P(=O)(OH)2), phosphonite groups (>P(=O)(OH)), borate groups (-B(OH)2), dihydroboronic acid groups (>BOH), and carboxylic acid groups (-COO). - Anions formed by the dissociation of hydrogen atoms, such as sodium ions, potassium ions, etc., can also be acidic salts that form salts with alkali metal ions such as sodium ions and potassium ions.

[0515] Furthermore, examples of ester groups that are acidic include: carboxylic acid esters (-COOR), sulfonates (-SO3R), phosphate esters (-P(=O)(OR)2), (>P(=O)(OR)), borate esters (-B(OR)2), and dihydroboronates (>BOR). Among these, carboxylic acid esters (-COOR) are preferred in terms of dispersibility and dispersion stability. It should be noted that R is a hydrocarbon group and is not particularly limited, but in terms of dispersibility and dispersion stability, an alkyl group with 1 to 5 carbon atoms is preferred, and methyl or ethyl groups are more preferred.

[0516] In terms of dispersibility, dispersion stability, alkali developability, and inhibitory effect on developing residue, the compound of the above general formula (VI) is preferably having one or more functional groups selected from carboxyl, borate, dihydroboronic acid, their anions, their alkali metal salts, and their esters, and more preferably having functional groups selected from carboxyl, carboxylate, carboxylate salt, and carboxylic acid ester.

[0517] When the compound of the above general formula (VI) has an acidic group and its ester group (hereinafter referred to as acidic group, etc.), either the acidic group or the halogen atom-side hydrocarbon of the compound can form a salt with the terminal nitrogen site. However, it is inferred that, compared with the case where the terminal nitrogen site forms a salt with the acidic group, the terminal nitrogen site will stably form a salt with the halogen atom-side hydrocarbon. Furthermore, it is inferred that by adsorbing the colorant onto the stably existing salt-forming site, the dispersibility and dispersion stability are improved.

[0518] When the compound of the above general formula (VI) has the aforementioned acidic groups, it may optionally have two or more of the aforementioned acidic groups. When it has two or more of the aforementioned acidic groups, the multiple acidic groups may optionally be the same or different. The number of the aforementioned acidic groups in the compound of the above general formula (VI) is preferably 1 to 3, more preferably 1 to 2, and even more preferably 1.

[0519] In the above general formula (V), R 11 R in the above general formula (VI) 12 R 12′ and R 12″ At least one of them, and R in the above general formula (VII) 13 and R 14 When at least one of them has an aromatic ring, the affinity between it and the color material skeleton described below is improved, the dispersibility and dispersion stability of the color material become excellent, and a coloring composition with excellent contrast can be obtained, which is preferred in this respect.

[0520] In terms of improving the dispersibility of the colorant, the molecular weight of one or more compounds selected from the group consisting of the above general formulas (V) to (VII) is preferably 1000 or less, preferably 50 to 800, more preferably 50 to 400, more preferably 80 to 350, and most preferably 100 to 330.

[0521] Examples of compounds represented by the above general formula (V) include: benzenesulfonic acid, vinylsulfonic acid, methanesulfonic acid, p-toluenesulfonic acid, monomethylsulfuric acid, monoethylsulfuric acid, mono-n-propylsulfuric acid, etc. It should be noted that hydrates of, for example, p-toluenesulfonic acid monohydrate can also be used. Examples of compounds represented by the above general formula (VI) include: chloromethane, bromomethane, chloroethane, bromoethane, iodomethane, iodoethane, chlorobutane, chlorohexane, chlorooctane, chlorododecane, chlorotetradecane, chlorohexadecane, chlorophenylethane, benzyl chloride, benzyl bromide, benzyl iodide, chlorobenzene, α-chlorophenylacetic acid, α-bromophenylacetic acid, α-iodophenylacetic acid, 4-chloromethylbenzoic acid, 4-bromomethylbenzoic acid, 4-iodophenylbenzoic acid, chloroacetic acid, bromoacetic acid, iodoacetic acid, methyl α-bromophenylacetate, 3-(bromomethyl)phenylboronic acid, etc. Examples of compounds represented by the above general formula (VII) include: monobutylphosphoric acid, dibutylphosphoric acid, methylphosphoric acid, dibenzylphosphoric acid, diphenylphosphoric acid, phenylphosphonic acid, phenylphosphonic acid, dimethylacryloyloxyethyl phosphate, etc.

[0522] With regard to particularly excellent dispersion stability, it is preferably selected from one or more of the group consisting of phenylphosphine, phenylphosphonic acid, dimethyl methacrylate, dibutyl phosphate, chloromethane, bromomethane, iodomethane, benzyl chloride, benzyl bromide, vinyl sulfonic acid, and p-toluenesulfonic acid monohydrate, wherein it is more preferably selected from one or more of the group consisting of phenylphosphine, phenylphosphonic acid, benzyl chloride, benzyl bromide, and p-toluenesulfonic acid monohydrate.

[0523] Furthermore, in terms of improving the suppression effect of developing residue by combining with the aforementioned specific graft copolymer, compounds of general formula (VI) having acidic groups and their ester groups may also be suitably used, wherein one or more selected from the group consisting of α-chlorophenylacetic acid, α-bromophenylacetic acid, α-iodophenylacetic acid, 4-chloromethylbenzoic acid, 4-bromomethylbenzoic acid, and 4-iodophenylbenzoic acid may also be suitably used.

[0524] In salt-type graft copolymers, regarding the content of at least one selected from the group consisting of organic acid compounds and halogenated hydrocarbons, in terms 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 the group consisting of organic acid compounds and halogenated hydrocarbons 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, relative to the terminal nitrogen site of the structural unit represented by general formula (I). If it is at or above the above lower limit, it is easy to obtain the effect of improving the dispersibility of the colorant through salt formation. 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 it is at or below the above upper limit, it can achieve excellent development adhesion and solvent resolvability.

[0525] It should be noted that at least one of the compounds selected from the group consisting of organic acid compounds and halogenated hydrocarbons may be used alone or in combination of two or more. When two or more compounds are combined, it is preferable that their total content is within the range mentioned above.

[0526] As a method for preparing salt-type graft copolymers, the following methods can be listed: adding at least one of the above-mentioned organic acid compounds and halogenated hydrocarbons to a solvent in which the graft copolymer before salt formation is dissolved or dispersed, stirring, and then heating as needed.

[0527] It should be noted that the terminal nitrogen site of the structural unit represented by the general formula (I) of the graft copolymer forms a salt with at least one of the above-mentioned organic acid compounds and halogenated hydrocarbons, and the proportion thereof can be confirmed, for example, by known methods such as NMR.

[0528] The proportion (mol%) of each structural unit in the copolymer of the dispersant can be determined from 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 if necessary, and the resulting decomposition products can be determined using high-performance liquid chromatography, gas chromatography-mass spectrometry, NMR, elemental analysis, XPS / ESCA (X-ray photoelectron spectroscopy / Electron Spectroscopy for Chemical Analysis), and TOF-SIMS (Time-of-Flight Secondary Ion Mass Spectrometry).

[0529] When using a dispersant, the content is not particularly limited as long as it allows for uniform dispersion of the colorant. For example, it can be used at 1% by mass or more and 40% by mass or less relative to the total solid content of the photosensitive coloring resin composition for color filters. Furthermore, it is preferable to formulate at 2% by mass or more and 30% by mass or less relative to the total solid content of the photosensitive coloring resin composition for color filters, and particularly preferably at 3% by mass or more and 25% by mass or less. If the content is above the lower limit, the dispersibility and dispersion stability of the colorant are excellent, and the storage stability of the photosensitive coloring resin composition for color filters is even better. In addition, if the content is below the upper limit, the developability becomes good. Especially when forming a coloring layer with a high concentration of colorant, the content of the dispersant is preferably formulated at 2% by mass or more and 25% by mass or less, more preferably 3% by mass or more and 20% by mass or less relative to the total solid content of the photosensitive coloring resin composition for color filters.

[0530] [Antioxidants]

[0531] The photosensitive coloring resin composition for color filters of the present invention may further include an antioxidant. By including an antioxidant in combination with the compound represented by the above general formula (1), the photosensitive coloring resin composition for color filters of the present invention can improve heat resistance, suppress the decrease in brightness after exposure and post-baking, and thus improve brightness. In addition, when the cured film forms micropores, excessive free radical chain reaction within the micropores can be controlled without compromising curability, thus making it easier to form micropores of the desired shape.

[0532] The antioxidant used in this invention is not particularly limited and can be appropriately selected from those previously known. Specific examples of antioxidants include hindered phenolic antioxidants, amine antioxidants, phosphorus antioxidants, sulfur antioxidants, hydrazine antioxidants, etc. In terms of heat resistance and improving the shape of micropores, hindered phenolic antioxidants are preferred.

[0533] Hindered phenolic antioxidants refer to antioxidants that contain at least one phenolic structure and have a substituent having four or more carbon atoms at at least one of the 2- or 6-positions of the hydroxyl group in the phenolic structure.

[0534] Specific examples of hindered phenolic antioxidants include: butylated hydroxytoluene (BHT), 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)trimethylbenzyl (trade name: Irganox 1330, manufactured by BASF), and 6-(4-hydroxy-3,5-di-tert-butylphenylamino)-2,4-bis(octylthio)-1,3,5-triazine (trade name: Irganox). 565 (manufactured by BASF), 2,2′-thiodiethylbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (trade name: Irganox 1035, manufactured by BASF), 1,2-bis[3-(4-hydroxy-3,5-di-tert-butylphenyl)propionyl]hydrazine (trade name: Irganox MD1024, manufactured by BASF), octyl 3-(4-hydroxy-3,5-diisopropylphenyl)propionate (trade name: Irganox 1135, manufactured by BASF), 4,6-bis(octylthiomethyl)-o-cresol (trade name: Irganox 1520L, manufactured by BASF), N,N′-hexamethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide] (trade name: Irganox) 1098 (manufactured by BASF), 1,6-hexanediol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (trade name: Irganox 259, manufactured by BASF), 1-dimethyl-2-[(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl]2,4,8,10-tetraoxazolo[5.5] Undecane (trade name: ADK STABAO-80, manufactured by ADEKA), Ethylenebis(oxyvinyl)bis(3-tert-butyl-4-hydroxy-5-methylphenylpropionate) (trade name: Irganox 245, manufactured by BASF), 1,3,5-tris[[4-(1,1-dimethylethyl)-3-hydroxy-2,6-dimethylphenyl]methyl]-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (trade name: Irganox 1790, 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), diethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate (trade name: Irgamod 195, manufactured by BASF), 2-tert-butyl-4-methyl-6-(2-hydroxy-3-tert-butyl-5-methylbenzyl)phenyl acrylate (trade name: Sumilizer GM, manufactured by Sumitomo Chemical), 4,4′-thiobis(6-tert-butyl-m-cresol) (trade name: Sumilizer WX-R, manufactured by Sumitomo Chemical), 6,6′-di-tert-butyl-4,4′-butylidene di-m-cresol (trade name: Adekastab AO-40, manufactured by ADEKA), etc. In addition, oligomer and polymeric compounds with hindered phenolic structures can also be used.

[0535] When using antioxidants, there is no particular limitation on the content of antioxidants. For example, relative to the total amount of solids in the photosensitive coloring resin composition for color filters, it can be set to 0.1% by mass or more and 20% by mass or less, preferably 0.2% by mass or more and 10% by mass or less. In terms of fully utilizing the combined effect with the above-mentioned photoinitiator, it is particularly preferred to be 0.3% by mass or more and 5% by mass or less.

[0536] Furthermore, when the photosensitive coloring resin composition for color filters of the present invention further includes an antioxidant, in order to fully utilize the combined effect with the aforementioned photoinitiator, the content of the antioxidant is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, and even more preferably 30 parts by mass or more, relative to the total 100 parts by mass of the photoinitiator.

[0537] On the other hand, in terms of maintaining appropriate sensitivity, the content of antioxidant is preferably 300 parts by mass or less, more preferably 200 parts by mass or less, relative to a total of 100 parts by mass of photoinitiator.

[0538] [Add any ingredients]

[0539] Various additives may be included in the photosensitive coloring resin composition for color filters as needed. Examples of such additives include: polymerization terminators, chain transfer agents, leveling agents, plasticizers, surfactants, defoamers, silane coupling agents, ultraviolet absorbers, and adhesion promoters.

[0540] Specific examples of surfactants and plasticizers include those described in Japanese Patent Application Publication No. 2013-029832.

[0541] Regarding the ratio of the mass (P) of the colorant used in this invention to the mass (V) of the solid components other than the colorant (hereinafter sometimes referred to as the "P / V ratio"), when making the coloring layer of a color filter, there is no particular limitation as long as the desired color development can be achieved. Preferably, it is in the range of 0.05 or more and 1.00 or less, more preferably in the range of 0.10 or more and 0.80 or less, further preferably in the range of 0.15 or more and 0.75 or less, and particularly preferably in the range of 0.20 or more and 0.70 or less. With the P / V ratio in the above range, a photosensitive coloring resin composition for a color filter can be made that can form a coloring layer that can achieve the desired color development, and can be uniformly dispersed in the above photosensitive coloring resin composition for a color filter.

[0542] When preparing a red-colored resin composition, from the viewpoint of the desired color development, the P / V ratio is preferably 0.50 or more, more preferably 0.60 or more, and even more preferably 0.74 or more. Furthermore, it is preferably 1.0 or less.

[0543] When preparing a green-colored resin composition, from the viewpoint of the desired color development, the P / V ratio is preferably 0.46 or higher, more preferably 0.56 or higher, and even more preferably 0.68 or higher. Furthermore, it is preferably 1.0 or lower.

[0544] When preparing a blue-colored resin composition, from the viewpoint of desired color rendering, the P / V ratio is preferably 0.24 or higher, more preferably 0.34 or higher, and even more preferably 0.41 or higher. Furthermore, it is preferably 1.0 or lower. If the values ​​are all above the lower limit, the color concentration of the photosensitive colored resin composition for color filters can be increased, resulting in higher color rendering of the color filter pixels and a thinner film thickness. Furthermore, if the values ​​are all below the upper limit, excellent storage stability is achieved, and a colored layer with sufficient hardness and good adhesion to the substrate can be obtained.

[0545] <Method for manufacturing photosensitive coloring resin composition for color filters>

[0546] Regarding the method for manufacturing the photosensitive coloring resin composition for color filters of the present invention, in terms of improving contrast, it is preferable to include a colorant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, a solvent, and preferably a dispersant, an antioxidant, and various additives as needed. The colorant can be uniformly dispersed in the solvent by the dispersant, and can be prepared by mixing using a known mixing method.

[0547] Examples of methods for preparing the resin composition include: (1) first adding a colorant and a dispersant to a solvent to prepare a colorant dispersion, and then mixing an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and various additives as needed in the dispersion; (2) simultaneously adding and mixing a colorant, a dispersant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and various additives as needed to a solvent; (3) adding and mixing a dispersant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and various additives as needed to a solvent, and then adding a colorant for dispersion; (4) preparing a colorant dispersion by adding a colorant, a dispersant, and an alkali-soluble resin to a solvent, and then adding and mixing an alkali-soluble resin, a solvent, a photopolymerizable compound, a photoinitiator, and various additives as needed to the dispersion.

[0548] Of these methods, the methods described in (1) and (4) above are preferred in terms of effectively preventing the aggregation of the colorant and dispersing it evenly.

[0549] The method for preparing a colorant dispersion can be appropriately selected from previously known dispersion methods. For example, the following methods can be listed: (1) Preparing a dispersion solution by mixing the dispersant in a solvent and stirring it, and then mixing an organic acid compound as needed, so that the amino group of the dispersant forms a salt with the organic acid compound. Mixing it with the colorant and other components as needed, and dispersing it using a known mixer or disperser; (2) Preparing a dispersion solution by mixing the dispersant in a solvent and stirring it, and then mixing the colorant and organic acid compound as needed, and then other components as needed, and dispersing it using a known mixer or disperser; (3) Preparing a dispersion solution by mixing the dispersant in a solvent and stirring it, and then mixing the colorant and other components as needed, and then adding an organic acid compound as needed after preparing a dispersion using a known mixer or disperser, etc.

[0550] Examples of dispersers used for dispersion processing include: roller mills such as two-roll mills and three-roll mills, ball mills such as vibrating ball mills, paint conditioners, continuous disc bead mills, and continuous ring bead mills. As preferred dispersion conditions for bead mills, the diameter of the beads used is preferably 0.03 mm or more and 2.00 mm or less, more preferably 0.10 mm or more and 1.0 mm or less.

[0551] II. Cured product

[0552] The cured product of the present invention is the cured product of the photosensitive coloring resin composition for color filters of the present invention described above.

[0553] The cured product of the present invention can be obtained, for example, by forming a coating film of the photosensitive coloring resin composition for color filters of the present invention described above, drying the coating film, exposing it, and developing it as needed. The methods for forming, exposing, and developing the coating film can, for example, be the same as those used to form the color layer of the color filter of the present invention described below.

[0554] The generation of sublimation products in the cured product of the present invention is suppressed. In addition, the generation of precipitates and developing residues is easily suppressed, achieving high-precision patterning and forming the required micropores, making it suitable as a coloring layer for color filters.

[0555] III. Color Filter

[0556] 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 for color filters of the present invention.

[0557] The color filter of this invention will be described with reference to the accompanying drawings. 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 part 2, and a coloring layer 3.

[0558] (Coloring layer)

[0559] 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 for color filters of the present invention described above.

[0560] The coloring layer is typically formed in the opening of the light-shielding portion of the substrate described below, and typically contains a coloring pattern of three or more colors.

[0561] Furthermore, there are no particular limitations on the arrangement of the color layers; for example, they can be set to common arrangements such as stripes, mosaics, triangles, or 4-pixel configurations. Additionally, the width and area of ​​the color layers can be set arbitrarily.

[0562] The thickness of the coloring layer can be appropriately controlled by adjusting the coating method, the concentration of solid components in the photosensitive coloring resin composition for the filter, viscosity, etc., and is generally preferably in the range of 1 μm or more and 5 μm or less.

[0563] The aforementioned coloring layer can be formed, for example, by the following method.

[0564] First, the photosensitive coloring resin composition for color filters of the present invention described above is applied to the substrate described below using coating methods such as spraying, dip coating, rod coating, roller coating, spin coating, and die coating to form a wet coating film. Spin coating and die coating are preferred methods.

[0565] Next, the wet coating is heated and dried using a heating plate, oven, etc., and then exposed to a mask with a specified pattern. This allows the alkali-soluble resin and photopolymerizable compounds to undergo a photopolymerization reaction, resulting in a cured coating. Examples of light sources used for exposure include ultraviolet light from low-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, and electron beams. The exposure amount is adjusted appropriately based on the light source used and the thickness of the coating.

[0566] In addition, heat treatment can be performed after exposure to promote the polymerization reaction. The heating conditions can be appropriately selected according to the mixing ratio of each component in the photosensitive coloring resin composition for the color filter used, the thickness of the coating film, etc.

[0567] Next, a developing solution is used to develop the coating, dissolving and removing the unexposed areas, thereby forming a film with the desired pattern. The developing solution is typically a solution made by dissolving an alkali in water or a water-soluble solvent. Optionally, a suitable amount of surfactant may be added to the alkaline solution.

[0568] In addition, conventional methods can be used for development.

[0569] After development, the coating is typically cleaned with the developer, cured with the photosensitive coloring resin composition for the filter, and then dried to form a colored layer. It should be noted that after development, heat treatment may also be performed to ensure complete curing of the coating. There are no particular limitations on the heating conditions; they can be appropriately selected depending on the intended use of the coating.

[0570] Furthermore, according to the application of the color filter of the present invention, micropores can be formed in the above-described coloring layer during the development process. In the present invention, since the above-described photosensitive coloring resin composition for color filters is used, it is easy to form the desired micropores in the coloring layer. The shape of the micropores can be appropriately selected according to the application and is not particularly limited. In the present invention, for example, micropores with a size of about 10 μm × 10 μm to 30 μm × 30 μm can be formed. In addition, the shape of the micropores is not particularly limited, and examples include circular, elliptical, and polygonal shapes.

[0571] As a method for forming micropores in a colored layer, one example is a method that uses a patterned photomask, in which a tiny mask for forming micropores is disposed within the opening pattern of a patterned photomask capable of forming fine line patterns, as the photomask used when forming the colored layer.

[0572] (shading part)

[0573] 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 configured to be the same as that used as the light-shielding portion in a conventional color filter.

[0574] The shape of the light-shielding part is not particularly limited; for example, striped or matrix-like shapes can be used. The light-shielding part can be a thin film of metal such as chromium formed using sputtering or vacuum evaporation. Alternatively, the light-shielding part 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 through development, patterning using inkjet ink containing light-shielding particles, and heat transfer of the photosensitive resist.

[0575] The thickness of the light-shielding part is set to approximately 0.2 μm or more and 0.4 μm or less in the case of a metal thin film, and approximately 0.5 μm or more and 2 μm or less in the case of a film formed by dispersing or dissolving black pigment in an adhesive resin.

[0576] (Substrate)

[0577] As a substrate, transparent substrates, silicon substrates, and substrates on which aluminum, silver, or silver / copper / palladium alloy thin films are formed, as described below, can be used. Other color filter layers, resin layers, TFTs, and other transistors and circuits can also be formed on these substrates.

[0578] As the transparent substrate in the color filter of the present invention, any substrate that is transparent to visible light is acceptable and there are no particular limitations. The transparent substrate commonly used in color filters can be used. Specifically, examples include: rigid materials that are inflexible and transparent, such as quartz glass, alkali-free glass, and synthetic quartz plates, or flexible materials that are flexible, such as transparent resin films, optical resin plates, and flexible glass.

[0579] The thickness of the transparent substrate is not particularly limited. For example, a thickness of 100 μm or more and about 1 mm or less can be used for the application of the color filter according to the present invention.

[0580] It should be noted that, in addition to the substrate, light-shielding part and coloring layer described above, the color filter of the present invention may also have an outer coating layer or a transparent electrode layer, and may further have an alignment film, alignment protrusions, columnar spacers, etc.

[0581] IV. Display Device

[0582] 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 previously known display devices, such as liquid crystal displays and organic light-emitting displays.

[0583] Liquid crystal display device

[0584] The liquid crystal display device of the present invention includes the color filter, the opposing substrate, and the liquid crystal layer formed between the color filter and the opposing substrate as described above.

[0585] The liquid crystal display device of the present invention will be described with reference to the accompanying drawings. 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, etc., and a liquid crystal layer 30 formed between the color filter 10 and the counter substrate 20.

[0586] 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 is commonly known in liquid crystal display devices that use color filters.

[0587] As the driving method for the liquid crystal display device of the present invention, a driving method commonly used in liquid crystal display devices may be used without particular limitation. Examples of such driving methods include TN, IPS, OCB, and MVA. Any of these methods may be used appropriately in the present invention.

[0588] Furthermore, the opposing substrate can be appropriately selected based on the driving method of the liquid crystal display device according to the present invention.

[0589] Furthermore, as the liquid crystal constituting the liquid crystal layer, various liquid crystals with different dielectric anisotropy and mixtures thereof can be used in the driving mode of the liquid crystal display device according to the present invention.

[0590] As a method for forming the liquid crystal layer, methods commonly used in the fabrication of liquid crystal cells can be used, such as vacuum injection and liquid crystal droplet methods. After forming the liquid crystal layer using the above methods, the liquid crystal cell is slowly cooled to room temperature, thereby aligning the sealed liquid crystal.

[0591] Organic light-emitting display device

[0592] The organic light-emitting display device of the present invention includes the color filter and organic light-emitting element described above.

[0593] 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. Optionally, an organic protective layer 50 and an inorganic oxide film 60 are provided between the color filter 10 and the organic light-emitting element 80.

[0594] 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 sources. The organic light-emitting display device 100 manufactured in the above manner can be applied, for example, to a passively driven organic EL display or an actively driven organic EL display.

[0595] 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 set to the configuration commonly known as an organic light-emitting display device that uses a color filter.

[0596] Example

[0597] The present invention will be specifically described below with reference to embodiments. The present invention is not limited to these descriptions.

[0598] The structures of the obtained compounds were confirmed by 1H- and 13C-NMR spectra obtained by nuclear magnetic resonance (Bruker BioSpin, AVANCEIII HD 500MHz), mass spectrometry analysis by liquid chromatography-mass spectrometry (Shimadzu Corporation, LC-30A; Bruker Daltonics, microTOFQ2), and MALDI-TOF / MS.

[0599] (Synthesis Example 1: Synthesis of Compound A)

[0600] 35.5 g of fluorene, 120 g of dichloromethane, and 30.1 g of chloroisobutyryl chloride were mixed and cooled to a temperature above -5°C and below 0°C. Aluminum trichloride was added in 10 portions, and the mixture was reacted at 10°C for 6 hours. The resulting reaction solution was injected into a mixture of 50 g of hydrochloric acid and 150 g of ice, followed by the addition of 150 g of dichloromethane and stirring for 3 hours. The resulting organic phase was then concentrated, and 150 g of methanol was added. After solidification, the solid phase was cooled to crystallize, filtered, and dried to obtain 2-methyl-1-fluorenyl-2-chloro-1-propanone.

[0601] 27 g of the obtained 2-methyl-1-fluorenyl-2-chloro-1-propanone was added to a 250 mL three-necked flask, followed by 1.76 g of calcium oxide and 7.0 g of sodium methoxide. The mixture was reacted at 68 °C for 6 hours for epoxidation. Afterward, the mixture was cooled to 50 °C, and 68 g of morpholine was added, followed by reaction for 14 hours. The mixture was then decolorized using activated carbon and filtered, and refluxed using a mixed solvent of toluene and methanol to obtain 2-methyl-1-fluorenyl-2-morpholinyl-1-propanone.

[0602] 20 g of the obtained 2-methyl-1-fluorenyl-2-morpholino-1-propanone, 0.6 g of tetrabutylammonium bromide (TBAB), and 34 g of chlorobutane were mixed and heated to 78 °C. 72 g of 50% NaOH aqueous solution was added dropwise, and the reaction was maintained at 82 °C for 4 hours. Subsequently, the temperature was lowered, 50 g of water and 58 g of toluene were added, and the mixture was stirred for 0.5 hours. The obtained organic phase was decolorized with activated carbon and filtered. Then, it was crystallized using a mixed solvent of toluene and methanol. The precipitate was filtered and dried to obtain compound A. It should be noted that the molecular weight of compound A is 433.63.

[0603] [Chemical Formula 29]

[0604] Compound A

[0605]

[0606] (Synthesis Example 2: Synthesis of Compound B)

[0607] (1) Synthesis of intermediate B1

[0608] In a 500 ml four-necked flask, 0.2 mol of diphenyl sulfide, 0.22 mol of pulverized AlCl3, and 150 ml of dichloroethane were added and stirred. Argon gas was introduced, and the mixture was cooled in an ice bath. When the temperature dropped to 0 °C, a solution containing 0.22 mol of cyclohexylpropionyl chloride and 42 g of dichloroethane was added dropwise over approximately 1.5 hours while maintaining the temperature below 10 °C. The temperature was then raised to 15 °C, and stirring was continued for 2 hours before the reaction mixture was drained.

[0609] The reaction mixture was slowly added to a solution of dilute hydrochloric acid prepared with 400g of ice and 65ml of concentrated hydrochloric acid under stirring. The lower layer was separated using a separatory funnel. The upper layer was extracted with 50ml of dichloroethane, and the extract was combined with the lower layer. The mixture was then washed with a NaHCO3 solution prepared with 10g of NaHCO3 and 200g of water, followed by three washes with 200ml of water until the pH was neutral. The mixture was dried with 60g of anhydrous MgSO4 to remove moisture, and then the dichloroethane was evaporated by rotary evaporation. The remaining solid powder in the rotary evaporator was added to 200ml of petroleum ether, filtered under vacuum, and then added to 150ml of anhydrous ethanol for heating and reflux. The mixture was then cooled to room temperature and then cooled with ice for 2 hours. After filtration under vacuum, the mixture was dried in an oven at 50°C for 2 hours to obtain intermediate B1.

[0610] [Chemical Formula 30]

[0611] Intermediate B1

[0612]

[0613] (2) Synthesis of intermediate B2

[0614] Add 42g of the above intermediate B1, 400g of tetrahydrofuran, 200g of concentrated hydrochloric acid, and 24.2g of isoamyl nitrite to a 500ml four-necked flask. Stir at room temperature for 5 hours, then drain the reaction solution.

[0615] The reaction solution was placed in a large beaker, 1000 ml of water was added, and the mixture was stirred and allowed to stand overnight. This resulted in layering, yielding a yellow, viscous liquid. The viscous liquid was extracted with dichloroethane, dried in 50 g of anhydrous MgSO4, and then filtered under vacuum. The filtrate was then evaporated by rotary evaporation to remove the solvent, yielding an oily, viscous substance. This substance was then added to 150 ml of petroleum ether, stirred, precipitated, and filtered under vacuum to obtain a white, powdery solid. This powder was then dried at 60°C for 5 hours to obtain intermediate B2.

[0616] [Chemical Formula 31]

[0617] Intermediate B2

[0618]

[0619] (3) Synthesis of compound B

[0620] 34 g of the above intermediate B2, 350 ml of dichloroethane, and 12.7 g of triethylamine were added to a 1000 ml four-necked flask and stirred. The mixture was cooled in an ice bath, and when the temperature dropped to 0 °C, a solution containing 15.7 g of acetyl chloride and 15 g of dichloroethane was added dropwise over approximately 1.5 hours. After stirring for another hour, 500 ml of cold water was added dropwise, and the mixture was separated into layers using a separatory funnel. The mixture was washed once with 200 ml of 5% NaHCO3 solution, followed by two washes with 200 ml of water until the pH was neutral. Then, it was washed once with dilute hydrochloric acid prepared by mixing 20 g of concentrated hydrochloric acid with 400 ml of water, followed by three washes with 200 ml of water. The mixture was then dried with 100 g of anhydrous MgSO4, and the solvent was removed by rotary evaporation to obtain a viscous liquid. An appropriate amount of methanol was added to this viscous liquid, and the precipitated white solid was filtered and dried to obtain compound B. It should be noted that the molecular weight of compound B is 395.51.

[0621] [Chemical Formula 32]

[0622] Compound B

[0623]

[0624] Compound C is represented by the following chemical formula. It should be noted that the molecular weight of compound C is 503.55.

[0625] [Chemical Formula 33]

[0626] Compound C

[0627] (Synthesis Example 3: Synthesis of Compound D)

[0628] (1) Synthesis of intermediate D1

[0629] 0.60 mol of fluorene, 2.4 mol of potassium hydroxide, and 0.06 mol of potassium iodide were dissolved in 500 mL of anhydrous dimethyl sulfoxide under a nitrogen atmosphere. The mixture was kept at 15 °C, and 1.33 mol of bromobutane was slowly added over 2 hours. The reaction product was stirred at 15 °C for 1 hour. Subsequently, 2 L of distilled water was added to the reaction product and stirred for approximately 30 minutes. The product was then extracted with 2 L of dichloromethane, and the extracted organic layer was washed twice with 2 L of distilled water. The recovered organic layer was then dried with anhydrous MgSO4, and the solvent was removed by vacuum distillation. The product was purified by silica gel column chromatography (developing solvent: ethyl acetate: n-hexane = 1:20) to obtain intermediate D1.

[0630] [Chemical Formula 34]

[0631] Intermediate D1

[0632]

[0633] (2) Synthesis of intermediate D2

[0634] Intermediate D1 (0.11 mol) was dissolved in 500 mL of dichloromethane. After cooling to -5 °C, 0.13 mol of AlCl3 was slowly added. A solution containing 15 mL of dichloromethane and 0.13 mol of cyclohexylpropionyl chloride was slowly added dropwise over 1 hour without raising the temperature of the reaction product. The mixture was stirred at -5 °C for 1 hour. The reaction product was then slowly injected into 500 mL of ice water and stirred for 30 minutes. The organic layer was washed with 200 mL of distilled water. Next, the recovered organic layer was subjected to vacuum distillation, and the product was purified by silica gel column chromatography (developing solvent: ethyl acetate: n-hexane = 1:4) to obtain intermediate D2.

[0635] [Chemical Formula 35]

[0636] Intermediate D2

[0637]

[0638] (3) Synthesis of intermediate D3

[0639] Intermediate D2 (0.042 mol) was dissolved in 200 mL of tetrahydrofuran (THF). Then, 25 mL of 4N HCl dissolved in 1,4-dioxane and 0.063 mol of isobutyl nitrite were added sequentially. The reaction mixture was stirred at 25 °C for 6 hours. Subsequently, 200 mL of ethyl acetate was added to the reaction solution and stirred for 30 minutes to separate the organic layer. The organic layer was then washed with 200 mL of distilled water. The recovered organic layer was then dried with anhydrous MgSO4, and the solvent was removed by vacuum distillation. The product was purified by silica gel column chromatography (developing solvent: ethyl acetate: n-hexane = 1:4) to obtain intermediate D3.

[0640] [Chemical Formula 36]

[0641] Intermediate D3

[0642]

[0643] (4) Synthesis of compound D

[0644] Intermediate D3 (0.056 mol) was dissolved in 200 mL of N-methyl-2-pyrrolidone (NMP) under a nitrogen atmosphere and maintained at -5°C. Triethylamine (0.068 mol) was added, and the reaction solution was stirred for 30 minutes. Subsequently, a solution containing 0.068 mol acetyl chloride and 10 mL of N-methyl-2-pyrrolidone was slowly added over 30 minutes, and the mixture was stirred for 30 minutes without raising the temperature. Then, 200 mL of distilled water was slowly added to the reaction product, and the mixture was stirred for 30 minutes to separate the organic layer. The recovered organic layer was then dried using anhydrous MgSO4, the solvent was removed by vacuum distillation, and the product was recrystallized using 1 L of ethanol and dried to obtain compound D. It should be noted that the molecular weight of compound D is 487.67.

[0645] [Chemical Formula 37]

[0646] Compound D

[0647]

[0648] Compound E is represented by the following chemical formula. It should be noted that the molecular weight of compound E is 569.60.

[0649] [Chemical Formula 38]

[0650] Compound E

[0651]

[0652] (Synthesis Example 4: Synthesis of Compound F)

[0653] (1) Synthesis of intermediate F1

[0654] In Synthesis Example 3(1), the same molar amount of bromoethane was used instead of bromobutane, and purification by silica gel column chromatography was not performed. Otherwise, intermediate F1 was obtained in the same manner as in Synthesis Example 3(1).

[0655] [Chemical Formula 39]

[0656] intermediate F1

[0657]

[0658] (2) Synthesis of intermediate F2

[0659] In Synthesis Example 3 (2), the same molar amount of the above intermediate F1 was used instead of intermediate D1, and the same molar amount of propionyl chloride was used instead of cyclohexylpropionyl chloride. Otherwise, intermediate F2 was obtained in the same manner as in Synthesis Example 3 (2).

[0660] [Chemical Formula 40]

[0661] intermediate F2

[0662]

[0663] (3) Synthesis of intermediate F3

[0664] In Synthesis Example 3 (3), the same molar amount of the above intermediate F2 was used instead of intermediate D2, and silica gel column chromatography was not used. Instead, the intermediate was purified by recrystallization and drying using a mixed solvent of ethyl acetate: n-hexane (1:6). Otherwise, intermediate F3 was obtained in the same manner as in Synthesis Example 3 (3).

[0665] [Chemical Formula 41]

[0666] intermediate F3

[0667]

[0668] (4) Synthesis of compound F

[0669] In synthesis example 3(4), the same molar amount of the above intermediate F3 was used instead of intermediate D3, and the following compound F was obtained in the same manner as in synthesis example 3(4). It should be noted that the molecular weight of the following compound F is 349.42.

[0670] [Chemical Formula 42]

[0671] Compound F

[0672]

[0673] (Synthesis Example 5: Preparation of Dispersant (Block Copolymer A))

[0674] In a 500 mL round-bottom four-necked separable flask equipped with a condenser, adding funnel, nitrogen inlet, mechanical stirrer, and digital thermometer, add 250 parts by weight of THF and 0.6 parts by weight of lithium chloride, and purge thoroughly with nitrogen. After cooling the reaction flask to -60°C, inject 4.9 parts by weight of butyllithium (15% hexane solution), 1.1 parts by weight of diisopropylamine, and 1.0 parts by weight of methyl isobutyrate using a syringe. Using the adding funnel, dropwise add the following B-block monomers over 60 minutes: 2.2 parts by weight of 1-ethoxyethyl methacrylate (EEMA), 18.7 parts by weight of 2-hydroxyethyl methacrylate (HEMA), 12.8 parts by weight of 2-ethylhexyl methacrylate (EHMA), 13.7 parts by weight of n-butyl methacrylate (BMA), 9.5 parts by weight of benzyl methacrylate (BzMA), and 17.5 parts by weight of methyl methacrylate (MMA). After 30 minutes, 26.7 parts by mass of dimethylaminoethyl methacrylate (DMMA), the monomer for block A, were added dropwise over a period of 20 minutes. After another 30 minutes of reaction, 1.5 parts by mass of methanol were added to stop the reaction. The obtained precursor block copolymer THF solution was redeprecipitated in hexane, purified by filtration and vacuum drying, and diluted with PGMEA to prepare a 30% by mass solution of solids. 32.5 parts by mass of water were added, the temperature was raised to 100°C, and the reaction was carried out for 7 hours to deprotect the structural units from EEMA, yielding structural units derived from methacrylic acid (MAA). The obtained block copolymer PGMEA solution was redeprecipitated in hexane, purified by filtration and vacuum drying, to obtain block copolymer A (acid value 8 mg KOH / g, Tg 38°C) containing block A with structural units represented by general formula (I) and block B with structural units derived from carboxyl-containing monomers and exhibiting solubility. The block copolymer A obtained in the above manner was confirmed by GPC (gel permeation chromatography), and the weight-average molecular weight Mw was 7730. Furthermore, the amine value was 95 mg KOH / g.

[0675] (Synthesis Example 6: Synthesis of Alkali-Soluble Resin A Solution)

[0676] A mixture of 40 parts by weight of styrene, 15 parts by weight of MMA, 25 parts by weight of MAA, and 3 parts by weight of azobisisobutyronitrile (AIBN) was dropwise added to a polymerization tank containing 150 parts by weight of PGMEA under a nitrogen gas flow and at 100°C for 3 hours. After the dropwise addition was completed, the mixture was heated at 100°C for 3 hours to obtain a polymer solution. The weight-average molecular weight of this polymer solution was 7000.

[0677] Subsequently, 20 parts by mass of glycidyl methacrylate (GMA), 0.2 parts by mass of triethylamine, and 0.05 parts by mass of p-methoxyphenol were added to the obtained polymer solution, and the mixture was heated at 110°C for 10 hours, with air purged into the reaction solution. The resulting alkali-soluble resin A was a resin formed by introducing side chains with vinyl double bonds into the main chain of styrene copolymerized with MMA and MAA using GMA. The solid content was 42.6% by mass, the acid value was 74 mg KOH / g, and the weight-average molecular weight was 12000. It should be noted that the weight-average molecular weight was determined using polystyrene as a standard, THF as the eluent, and the measurement was performed using the Shodex GPC System-21H. Furthermore, the acid value was determined based on JIS K 0070.

[0678] (Synthesis Example 7: Synthesis of Lake Pigment 1)

[0679] (1) Synthesis of intermediate 1

[0680] Referring to the manufacturing methods of intermediate A-2, intermediate B-1 and compound 1-3 as described in Japanese Patent Application Publication No. 2018-3013, intermediate 1 represented by the following chemical formula (a) was obtained (yield 87%).

[0681] The obtained compound was confirmed as the target compound based on the following analytical results.

[0682] MS(ESI)(m / z): 677(+), divalent

[0683] • Elemental analysis values: Measured CHN values ​​(81.81%, 7.31%, 5.85%); Theoretical values ​​(81.77%, 7.36%, 5.90%)

[0684] [Chemical Formula 43]

[0685] Chemical formula (a)

[0686]

[0687] (2) Synthesis of lake pigment 1

[0688] 2.59 g (0.76 mmol) of 12-tungsten phosphate-n hydrate manufactured by Kanto Chemical was dissolved by heating in a mixture of 40 mL methanol and 40 mL water. 1.6 g (1.19 mmol) of the above intermediate 1 was added and the mixture was stirred for 1 hour. The precipitate was filtered off and washed with water. The obtained precipitate was dried under reduced pressure to obtain lake pigment 1 represented by the following chemical formula (b) (yield 95%).

[0689] The obtained compound was confirmed as the target compound based on the following analytical results.

[0690] • 31P NMR (d-dmso, ppm) δ-15.15

[0691] MS(MALDI)(m / z): 1355(M + ), 2879 (MH2-)

[0692] • Elemental analysis values: Measured values ​​of CHN (35.55%, 3.24%, 2.61%); Theoretical values ​​(35.61%, 3.20%, 2.57%)

[0693] • Fluorescence X-ray analysis: Measured MoW ratio (0%, 100%); Theoretical value (0%, 100%)

[0694] [Chemical Formula 44]

[0695] Chemical formula (b)

[0696]

[0697] (Synthesis Example 8: Synthesis of Pigment G)

[0698] A mixture was prepared by mixing 270g of sulfonyl chloride (manufactured by Wako Pure Chemical Industries, Ltd.), 315g of anhydrous aluminum chloride (manufactured by Kanto Chemical Co., Ltd.), 43g of sodium chloride (manufactured by Tokyo Chemical Co., Ltd.), and 43g of bromine. Meanwhile, zinc phthalocyanine was prepared using phthalonitrile, ammonia, and zinc chloride as raw materials, and 65g of zinc phthalocyanine was added to the above mixture. 407g of bromine (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise, and the mixture was heated to 80°C for 22 hours, followed by the addition of 72g of bromine. Then, the mixture was heated to 130°C for 3 hours, and the reaction mixture was poured into water, precipitating crude zinc phthalocyanine polyhalogenated pigment. This aqueous slurry was filtered, washed with hot water at 60°C, and then decoagulated in water. The resulting slurry was filtered again, washed with water at 60°C, and dried at 90°C to obtain 173g of crude zinc phthalocyanine polyhalogenated pigment. 3g of the crude zinc phthalocyanine polyhalogenated pigment, 30g of pulverized sodium chloride, and 3g of diethylene glycol were added to a double-arm kneader and kneaded at 100°C for 8 hours. After kneading, the mixture was placed in 300g of water at 80°C, stirred for 1 hour, filtered, washed, dried, and pulverized to obtain the zinc phthalocyanine polyhalogenated pigment. The structure of the obtained zinc phthalocyanine polyhalogenated pigment was confirmed by MALDI-TOF / MS. The results showed that the average number of chlorine atoms per molecule was greater than 0 and less than 0.1, the average number of bromine atoms was 14.3, and the average number of hydrogen atoms was 1.7. It should be noted that the above average number of bromine atoms and average number of hydrogen atoms were obtained according to Rule B of JIS Z8401:1999, rounded to one decimal place.

[0699] Furthermore, mass spectrometry analysis of the obtained zinc phthalocyanine polyhalogenated pigments showed that the maximum ion intensity in the range of m / z ≥ 1780 and < 1820 divided by the maximum ion intensity in the range of m / z ≥ 1820 and < 1860 yielded a value of 0.71. The delay time was 310 ns, and the resolving power value for the peaks in the range of m / z ≥ 1820 and < 1860 was 42004.

[0700] (Synthetic Example 9: Synthesis of Azo Derivative 1)

[0701] 23.1 g of diazobarbituric acid and 19.2 g of barbituric acid were added to 550 g of distilled water. Then, the mixture was adjusted to azobarbituric acid (0.3 mol) using potassium hydroxide aqueous solution and mixed with 750 g of distilled water. 5 g of 30% hydrochloric acid was added dropwise. Subsequently, 38.7 g of melamine was added. Then, 0.39 mol of nickel chloride solution and 0.21 mol of zinc chloride solution were added together, and the mixture was stirred at 80°C for 8 hours. The pigment was isolated by filtration, washed, dried at 120°C, and ground using a mortar and pestle to obtain azo derivative 1 (azo pigment with a Ni:Zn ratio of 65:35).

[0702] (Example 1)

[0703] (1) Manufacturing of colorant dispersion 1

[0704] 5.1 parts by mass of the block copolymer A from Synthesis Example 5 (as a dispersant), 11.6 parts by mass of CI pigment blue 15:6 (trade name FASTOGEN BLUE A510, manufactured by DIC Corporation) and 1.4 parts by mass of CI pigment violet 23 (trade name Hostaperm Violet RL-NF, manufactured by Clariant Corporation) (as colorants), 5.1 parts by mass of the alkali-soluble resin A solution obtained from Synthesis Example 6 (converted to solids content), 76.8 parts by mass of PGMEA, and 100 parts by mass of 2.0 mm zirconia beads were placed in a mayonnaise bottle for pre-crushing. The mixture was shaken for 1 hour using a paint shaker (manufactured by Asada Iron Works Co., Ltd.). Then, the 2.0 mm zirconia beads were removed, and 200 parts by mass of 0.1 mm zirconia beads were added for formal crushing. The mixture was also dispersed for 4 hours using a paint shaker to obtain colorant dispersion 1.

[0705] (2) Preparation of photosensitive coloring resin composition 1 for color filters

[0706] By adding 286.1 parts by mass of the color material dispersion 1 obtained in (1) above, 8.6 parts by mass of the alkali-soluble resin A solution obtained in Synthesis Example 6 (based on solid content), 18.2 parts by mass of the photopolymerizable compound (trade name ARONIX M-520D, manufactured by Toa Synthetic Co., Ltd.), 5.1 parts by mass of the compound A obtained in Synthesis Example 1 as a photoinitiator, and 42.2 parts by mass of PGMEA, a photosensitive coloring resin composition 1 for color filters is obtained.

[0707] (Examples 2-15)

[0708] In Example 1, colorants were used according to the types shown in Table 1. Otherwise, photosensitive coloring resin compositions 2 to 15 for color filters were obtained in the same manner as in Example 1.

[0709] It should be noted that in each embodiment and comparative example, the total amount of colorant added to the colorant dispersion was set to 13 parts by mass.

[0710] In Example 4, 4.0 parts by weight of CI Pigment Blue 15:6 and 9.0 parts by weight of Lake Pigment 1 were used as color materials.

[0711] In Example 12, 5.0 parts by weight of CI pigment green 58 and 8.0 parts by weight of CI pigment yellow 138 were used as color materials.

[0712] In Example 13, 5.0 parts by weight of CI pigment green 58 and 8.0 parts by weight of azo derivative 1 obtained in Synthesis Example 9 were used as colorants.

[0713] In Example 14, 5.0 parts by weight of CI pigment green 59 and 8.0 parts by weight of CI pigment yellow 138 were used as color materials.

[0714] In Example 15, 5.0 parts by weight of CI pigment green 59 and 8.0 parts by weight of azo derivative 1 obtained in Synthesis Example 9 were used as colorants.

[0715] (Examples 16-19)

[0716] In Example 1, photoinitiators and colorants were used according to the types and amounts shown in Table 1. Furthermore, 2.0 parts by weight of bisphenol-based antioxidant (Adekastab AO-40, manufactured by ADEKA) as an antioxidant was added to the coloring resin composition. Otherwise, 16 to 19 photosensitive coloring resin compositions for color filters were obtained in the same manner as in Example 1.

[0717] It should be noted that in Example 17, the colorant is prepared in the same way as in Example 1, and in Examples 16, 18, and 19, the colorant is prepared in the same way as in Example 4.

[0718] Furthermore, in each embodiment and comparative example, the total amount of photoinitiator added to the coloring resin composition was set to 5.1 parts by weight.

[0719] The percentages (%) of photoinitiators listed in Tables 1 and 2 refer to the percentages (by mass) of the total amount of photoinitiators per 100% mass. For example, in Example 18, 2.55 parts by mass (50% by mass) of compound A and 2.55 parts by mass (50% by mass) of Irg907 were used.

[0720] (Comparative Examples 1-2)

[0721] In Example 1, 5.1 parts by mass of the photoinitiator shown in Table 1 were used instead of 5.1 parts by mass of compound A obtained in Synthesis Example 1. Otherwise, comparative coloring resin compositions 1 to 2 were obtained in the same manner as in Example 1.

[0722] It should be noted that the Irg907 used as a photoinitiator in Example 18 and Comparative Example 1 is an α-aminoketone photoinitiator (trade name Irgacure 907, manufactured by BASF, molecular weight 279.40), which is a compound represented by the following chemical formula (c).

[0723] [Chemical Formula 45]

[0724] Chemical formula (c)

[0725]

[0726] (Examples 20-49)

[0727] In Example 1, photoinitiators were used according to the types and amounts shown in Table 2. Otherwise, photosensitive coloring resin compositions for color filters 20-49 were obtained in the same manner as in Example 1.

[0728] The Irg369 used as a photoinitiator in Examples 38-43 is an α-aminoketone photoinitiator (trade name Irgacure369, manufactured by BASF, molecular weight 366.50), and is a compound represented by the following chemical formula (d).

[0729] [Chemical Formula 46]

[0730] Chemical formula (d)

[0731]

[0732] In Examples 44 and 45, OXE-01 used as a photoinitiator is an oxime ester photoinitiator (trade name Irgacure OXE-01, manufactured by BASF, molecular weight 445.57), which is the compound represented by the following chemical formula (e).

[0733] [Chemical Formula 47]

[0734] Chemical formula (e)

[0735]

[0736] In Examples 46 and 47, OXE-02 used as a photoinitiator is an oxime ester photoinitiator (trade name Irgacure OXE-02, manufactured by BASF, molecular weight 412.48), which is the compound represented by the following chemical formula (f).

[0737] [Chemical Formula 48]

[0738] Chemical formula (f)

[0739]

[0740] [evaluate]

[0741] <Sublimation>

[0742] Using a spin coater, the photosensitive coloring resin compositions obtained in each example and comparative example were coated onto one side of a 5 cm square glass substrate (manufactured by NH TECHNO GLASS Co., Ltd., "NA35") to achieve a film thickness of 2.5 μm after heat drying. The coating was then dried under reduced pressure at a maximum pressure of 40 Pa. The glass substrate with the coating on one side was placed on a heating plate with its side in contact with the heating plate. A 10 cm square glass substrate on the upper surface was positioned 0.7 mm from the surface of the coating, covering the entire coating. With the heating plate, glass substrate, photosensitive coloring resin composition coating, and upper glass substrate sequentially arranged, the heating plate was heated to 100°C and maintained for 10 minutes to heat dry the coating. After heat drying, the surface of the upper glass substrate was observed visually and under an optical microscope (100x magnification), and evaluated according to the following evaluation criteria. It should be noted that 10 samples were evaluated in each embodiment and each comparative example. The evaluation results for the samples with the highest adhesion of sublimation to the glass substrate on the upper surface are shown in Table 1 or Table 2.

[0743] (Elevation Evaluation Criteria)

[0744] ◎: No sublimation material was observed adhering to the glass substrate on the upper surface through both visual and microscopic observation;

[0745] ○: No sublimation was observed adhering to the glass substrate on the upper surface by visual inspection, but adhering to the glass substrate on the upper surface was observed by microscopic inspection;

[0746] ×: Both visual and microscopic observations revealed the adhesion of sublimation material to the glass substrate on the upper surface.

[0747] <Optical Properties>

[0748] The photosensitive coloring resin compositions obtained in the various examples and comparative examples were coated onto a glass substrate (manufactured by NH TECHNO GLASS Co., Ltd., "NA35") using a spin coater. After vacuum drying at a maximum pressure of 40 Pa, the substrate was dried at 100°C for 10 minutes using a heating plate to form a coating film on the glass substrate. The entire surface was then irradiated with an ultra-high pressure mercury lamp at 60 mJ / cm² without a photomask. 2 Ultraviolet light is applied to form an exposed coating. Then, a 0.05% (w / w) potassium hydroxide aqueous solution is used as the developer for spin development. After contact with the developer for 60 seconds, the coating is rinsed with pure water, thus forming a developed coating. Subsequently, it is baked in a clean oven at 230°C for 25 minutes, and a cured coating (colored layer) is formed with the y-coordinate of the colorimetric coordinates as shown in Table 1 or Table 2. The colorimetric (x, y) and luminance (Y) of the colored layer are measured using an OSP-SP200 microspectrometry apparatus manufactured by Olympus Corporation.

[0749] <Sensitivity>

[0750] When forming the colored layer for which the above optical properties have been evaluated, the film thickness (E) after exposure and the film thickness (D) after development were measured using a stylus-type profilometer P-16 (manufactured by KLA-Tencor). The residual film rate (%) was calculated as film thickness after development (D) / film thickness after exposure (E) × 100, and evaluated according to the following evaluation criteria. It should be noted that the higher the residual film rate, the higher the sensitivity of the photosensitive colored resin composition. If the residual film rate is 90% or higher, it is within the range suitable for practical use.

[0751] (Sensitivity evaluation criteria)

[0752] ◎◎: Residual film rate is over 98%;

[0753] ◎: The residual film rate is above 95% and less than 98%;

[0754] ○: The residual film rate is above 90% and less than 95%;

[0755] ×: Residual film rate is less than 90%.

[0756] <Extraction>

[0757] For the colored layer that underwent the above optical property evaluation, a 1cm × 1cm area on the surface of the colored layer was observed using an optical microscope (100x magnification), and the number of precipitates present within this area was counted. Similarly, the number of precipitates within a 1cm × 1cm area was counted at 10 random locations on the surface of the colored layer. The average number of precipitates at these 10 locations was taken as the average number of precipitates per unit area, and the evaluation was performed according to the following evaluation criteria. It should be noted that precipitates identified as foreign matter during observation using an optical microscope (100x magnification) were considered precipitates.

[0758] (Evaluation Criteria)

[0759] ◎◎: No precipitates were observed.

[0760] ◎: The average number of precipitates per unit area is less than 0.1;

[0761] ○: The average number of precipitates per unit area is more than 0.1 and less than 0.2;

[0762] △: The average number of precipitates per unit area is more than 0.2 and less than 0.3;

[0763] ×: The average number of precipitates per unit area is more than 0.3.

[0764] <Developer residue>

[0765] Using a spin coater, the photosensitive coloring resin compositions obtained in each example and comparative example were coated onto a glass substrate (manufactured by NH TECHNO GLASS Co., Ltd., "NA35") to achieve a cured film thickness of 3.0 μm. After vacuum drying at an ultimate pressure of 40 Pa, the substrate was dried at 100°C for 10 minutes using a heating plate to form a coating film on the glass substrate. Using an ultra-high pressure mercury lamp, a patterned photomask (chromium mask) with a 20 μm × 20 μm chromium mask centrally arranged within independent fine lines with an aperture size of 90 μm × 300 μm was used at 40 mJ / cm². 2The coating was exposed to ultraviolet light, thus forming an exposed coating on the glass substrate. Subsequently, spin development was performed using a 0.05% (w / w) potassium hydroxide aqueous solution as the developer. After contact with the developer for 60 seconds, the coating was rinsed with pure water, resulting in a coating with an independent fine-line pattern of micropores. This was then baked in a clean oven at 230°C for 25 minutes, forming a colored layer with an independent fine-line pattern of micropores. The obtained colored layer was observed using an optical microscope (100x magnification), and the development residue inside the micropores was evaluated according to the following evaluation criteria. It should be noted that the less development residue inside the micropores, the easier it is to form the desired micropores.

[0766] (Developer residue evaluation criteria)

[0767] ◎◎: Observation using an optical microscope revealed no coloring inside the micropores formed in the colored layer, nor any transparent material at the periphery of the micropores;

[0768] ◎: Observation using an optical microscope revealed no coloring inside the micropores formed in the colored layer, but some transparent material was observed around the periphery of the micropores;

[0769] ○: Observation using an optical microscope revealed no coloring inside the micropores formed in the colored layer, but colored residue was observed at the periphery of the micropores;

[0770] △: Observation using an optical microscope revealed no coloring inside the micropores formed in the colored layer, but some transparent material was observed inside the micropores;

[0771] ×: By using an optical microscope, colored residues were observed inside the micropores formed in the colored layer.

[0772] The abbreviations in the table are as follows.

[0773] • Irg907: α-Aminoketone photoinitiator (Irgacure 907, manufactured by BASF)

[0774] • Irg369: α-aminoketone photoinitiator (Irgacure 369, manufactured by BASF)

[0775] • OXE01: Oxime ester photoinitiator (trade name Irgacure OXE-01, manufactured by BASF)

[0776] • OXE02: Oxime ester photoinitiator (trade name Irgacure OXE-02, manufactured by BASF)

[0777] • B15:6:CI Pigment Blue 15:6 (Trade name FASTOGEN BLUE A510, manufactured by DIC Corporation)

[0778] • V23: CI Pigment Violet 23 (trade name Hostaperm Violet RL-NF, manufactured by Clariant)

[0779] • R254: CI Pigment Red 254 (trade name Hostaperm Red D2B-COF LV3781, manufactured by Clariant)

[0780] R291: CI Pigment Red 291

[0781] R269: CI Pigment Red 269

[0782] • R177: CI Pigment Red 177 (trade name Cromophtal Red A2B, manufactured by BASF)

[0783] G62: CI Pigment Green 62

[0784] G63: CI Pigment Green 63

[0785] • G58: CI Pigment Green 58 (trade name FASTOGEN GREEN A110, manufactured by DIC Corporation)

[0786] • G59: CI Pigment Green 59 (trade name FASTOGEN GREEN C100, manufactured by DIC Corporation)

[0787] Y138: CI Pigment Green 59 (trade name Chromofine Yellow 6206EC, manufactured by Daihatsu Seika Kogyo)

[0788] • AO-40: Bisphenol-based antioxidant (Adekastab AO-40, manufactured by ADEKA)

[0789] [Table 1]

[0790] [Table 2]

[0791]

[0792] <Summary of Results>

[0793] The results in the table show that the photosensitive coloring resin compositions of Examples 1-49, containing compounds represented by the above general formula (1) as photoinitiators, exhibited suppressed sublimation formation immediately after coating drying and suppressed sublimation formation during drying before exposure. Furthermore, the photosensitive coloring resin compositions of Examples 1-49 showed high residual film yield and good sensitivity during coloring layer formation.

[0794] In particular, the formation of sublimation during drying was suppressed in the photosensitive coloring resin compositions of Examples 1-17 and 20-49. The photosensitive coloring resin compositions of Examples 16-19 also contain antioxidants, thus the development residue formed inside the micropores within the coloring layer is particularly suppressed.

[0795] Furthermore, the photosensitive coloring resin compositions of Examples 18-49 contain compounds represented by the above general formula (1) and other photoinitiators as photoinitiators, thus further suppressing the formation of precipitates. Among them, the photosensitive coloring resin compositions of Examples 18-47 use oxime ester-based photoinitiators or α-aminoketone-based photoinitiators as other photoinitiators, thus exhibiting excellent effects in suppressing precipitate formation, improving sensitivity, or both.

[0796] The photosensitive coloring resin compositions of Examples 20-31 and 44-47 use oxime ester photoinitiators with carbazole or diphenyl sulfide skeletons as other photoinitiators, thus the sensitivity is particularly improved and the generation of sublimation during drying is easily suppressed.

[0797] The photosensitive coloring resin compositions of Examples 20-43 use compound B, which is an oxime ester compound represented by the above general formula (3), compound C, which is an oxime ester compound represented by the above general formula (2), compound D, which is an oxime ester compound represented by the above general formula (4), or Irg369, which is a preferred α-aminoketone photoinitiator, as other photoinitiators. Therefore, it is easy to suppress the generation of sublimation during drying, and it is also particularly easy to suppress the generation of precipitates. The photosensitive coloring resin compositions of Examples 20-31, which use compound B, which is an oxime ester compound represented by the above general formula (3), or compound C, which is an oxime ester compound represented by the above general formula (2), as other photoinitiators, have further improved sensitivity. Among them, the photosensitive coloring resin compositions of Examples 22, 23, 28, and 29, in which the proportion of the compound represented by the above general formula (1) is set to 50% or more and 90% or less of the total amount of photoinitiator, have further improved sensitivity, and the effect of suppressing the generation of precipitates is also particularly excellent.

[0798] On the other hand, the comparative photosensitive coloring resin compositions of Comparative Examples 1 and 2 do not contain the compounds represented by the above general formula (1) as photoinitiators, so the generation of sublimation during drying is not suppressed.

[0799] <Changes in heat resistance caused by the presence or absence of compound A>

[0800] Using the photosensitive coloring resin compositions obtained in Examples 3 and 4, a coloring layer was formed in the same manner as when evaluating the optical properties described above. During the formation of the coloring layer, the L, a, b (L0, a0, b0) of the coating after development and the L, a, b (L1, a1, b1) after post-baking were measured, and the color difference (ΔEab) before and after post-baking was calculated according to the following formula.

[0801] ΔEab={(L1-L0) 2 +(a1-a0) 2 +(b1-b0) 2}1 / 2

[0802] It should be noted that colorimetry was measured using an OSP-SP200 microspectrophotometer manufactured by Olympus Corporation. A C-type light source was used. This was for heat resistance evaluation.

[0803] On the other hand, in Examples 3 and 4, Irg907 was used instead of compound A obtained in Synthesis Example 1 as the photoinitiator. Otherwise, comparative resin compositions 3′ and 4′ (Comparative Examples 3′ and 4′) were prepared in the same manner as in Examples 3 and 4, differing only in the photoinitiator. For comparative resin compositions 3′ and 4′, colored layers were also formed in the same manner as described above. The L, a, b (L0, a0, b0) of the coating after development and the L, a, b (L1, a1, b1) after post-baking were measured, and the color difference (ΔEab) before and after post-baking was calculated as a heat resistance evaluation.

[0804] The difference in heat resistance (ΔEab2 - ΔEab1) was calculated by subtracting ΔEab(ΔEab1) from ΔEab(ΔEab2) in Comparative Examples 3' and 4' corresponding to each example. The change in heat resistance caused by the presence or absence of compound A was evaluated according to the following evaluation criteria. The evaluation results are shown in Table 3.

[0805] (Evaluation criteria for changes in heat resistance caused by the presence or absence of compound A)

[0806] ◎: The difference between ΔEab and ΔEab is greater than or equal to 1;

[0807] ○: The difference in ΔEab is greater than 0.5 and less than 1;

[0808] △: The difference between ΔEab and ΔEab is greater than 0 and less than 0.5.

[0809] [Table 3]

[0810] Table 3

[0811]

[0812] Comparing Examples 3 and 4, which form a blue coloring layer using lake pigment 1 represented by the above general formula (ii), with Comparative Examples 3' and 4', the color difference ΔEab before and after baking is significantly reduced in Examples 3 and 4, which use compound A as a photoinitiator, compared to Comparative Examples 3' and 4', which do not use compound A as a photoinitiator. Therefore, it can be seen that in the photosensitive coloring resin composition of the present invention containing a compound represented by the above general formula (1) as a photoinitiator, if the pigment represented by the above general formula (ii) is used as the pigment, a coloring layer with improved heat resistance can be formed. It should be noted that, as described above, the pigment represented by the above general formula (iii) exhibits the same behavior in its interaction with the compound represented by the above general formula (1) as the pigment represented by the above general formula (ii). Therefore, it is inferred that in the photosensitive coloring resin composition of the present invention, using the pigment represented by the above general formula (iii) as the pigment can also form a coloring layer with improved heat resistance.

[0813] <Brightness changes caused by the presence or absence of compound A>

[0814] Using the photosensitive coloring resin compositions obtained in Examples 9, 10, and 11, a coloring layer was formed in the same manner as when evaluating the optical properties described above. The brightness (Y0) of the coating after development and the brightness (Y1) after baking were measured, and the brightness difference (ΔY) before and after baking was calculated according to the following formula.

[0815] ΔY = Y0 - Y1

[0816] It should be noted that the brightness was measured using an OSP-SP200 microspectrophotometer manufactured by Olympus Corporation. A C-type light source was used.

[0817] On the other hand, in Examples 9, 10, and 11, Irg907 was used instead of compound A obtained in Synthesis Example 1 as the photoinitiator. Otherwise, comparative resin compositions 9′, 10′, and 11′ (Comparative Examples 9′, 10′, and 11′) were prepared in the same manner as in Examples 9, 10, and 11, differing only in the photoinitiator. For the comparative resin compositions 9′, 10′, and 11′, a coloring layer was formed in the same manner as described above, and the brightness (Y0) of the coating after development and the brightness (Y1) after baking were measured. The brightness difference (ΔY) before and after baking was calculated.

[0818] The brightness difference (ΔY2 - ΔY1) of the coloring layers in Comparative Examples 9′, 10′, and 11′ was subtracted from the brightness difference (ΔY1) of the corresponding coloring layers in Examples 9′, 10′, and 11′ to calculate the ΔY difference. The brightness change caused by the presence or absence of compound A was evaluated according to the following evaluation criteria. The evaluation results are shown in Table 4.

[0819] (Evaluation criteria for brightness changes caused by the presence or absence of compound A)

[0820] ◎: ΔY difference is 0.5 or higher;

[0821] ○: The difference in ΔY is greater than 0.1 and less than 0.5;

[0822] △: ΔY difference is less than 0.1.

[0823] [Table 4]

[0824] Table 4

[0825]

[0826] Compared with Comparative Examples 9', 10', and 11, which use CI Pigment Green 62, CI Pigment Green 63, or Zinc Phthalocyanine Polyhalogenated Residue G represented by General Formula (i) to form a green coloring layer, Examples 9', 10', and 11, which use Compound A as a photoinitiator, show a significant reduction in brightness difference ΔY before and after baking compared to Comparative Examples 9', 10', and 11', which do not use Compound A as a photoinitiator. Therefore, it can be seen that in the photosensitive coloring resin composition of the present invention containing a compound represented by the above general formula (i) as a photoinitiator, if one or more selected from CI Pigment Green 62 and CI Pigment Green 63, or Zinc Phthalocyanine Polyhalogenated Residue G represented by the above general formula (i) is used as the colorant, a coloring layer in which brightness reduction due to baking is suppressed can be formed.

[0827] (Synthesis Example 10: Production of Macromonomer A)

[0828] 70.0 parts by weight of propylene glycol methyl ether acetate (PGMEA) were added to a reactor equipped with a condenser, a funnel for adding, a nitrogen inlet, a mechanical stirrer, and a digital thermometer. The temperature was raised to 90°C under a nitrogen flow while stirring. After 1.5 hours, monomers with PEG chains and derived from the structural unit represented by general formula (III) (manufactured by Evonik, trade name: VISIOMER MPEG 1005 MA W, R in general formula (III)) were added dropwise. 4 For CH3, A 3 For COO, R 5 It is ethylene, R 6A mixed solution of 1.0 parts by mass of CH3(s=22), 99.0 parts by mass of methyl methacrylate (MMA), 4.0 parts by mass of mercaptoethanol, 30 parts by mass of PGMEA, and 1.0 parts by mass of α,α′-azobisisobutyronitrile (AIBN) was prepared and reacted for 3 hours. Then, the nitrogen flow was stopped, the reaction solution was cooled to 80°C, and 8.74 parts by mass of Karenz MOI (manufactured by Showa Denko Co., Ltd.), 0.125 g of dioctyltin dilaurate, 0.125 parts by mass of p-methoxyphenol, and 30 parts by mass of PGMEA were added, followed by stirring for 3 hours to obtain a 50% solution of macromonomer A. The obtained macromonomer A was confirmed by GPC (gel permeation chromatography) under conditions of N-methylpyrrolidone / polystyrene standard with 0.01 mol / L lithium bromide. The results showed a weight-average molecular weight (Mw) of 4500 and a molecular weight distribution (Mw / Mn) of 1.6.

[0829] (Synthetic Examples 11-20: Production of macromonomers B-M)

[0830] In the production of macromonomer A in Synthesis Example 10, at least one of the monomer types and mass ratios was changed as shown in Table 5 to replace 1.0 parts by mass of monomer and 99.0 parts by mass of MMA, which are structural units represented by the derived general formula (III). Otherwise, macromonomers B to M were produced in the same manner as in Synthesis Example 10. The weight-average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the obtained macromonomers are shown in Table 5.

[0831] (Synthesis Example 21: Production of the macromonomer N)

[0832] 30.0 parts by mass of PGMEA were added to a reactor equipped with a condenser, a funnel for adding, a nitrogen inlet, a mechanical stirrer, and a digital thermometer. The temperature was raised to 90°C under a nitrogen flow while stirring. After 1.5 hours, a mixed solution of 25.0 parts by mass of MMA, 75.0 parts by mass of caprolactone-modified hydroxyethyl methacrylate (trade name: PLACEL FM5, manufactured by Daicel Inc., caprolactone chain repeat number t=5) (PCL-FM5), 7.0 parts by mass of mercaptopropionic acid, and 1.0 part by mass of AIBN was added dropwise, and the reaction was continued for 3 hours. After cooling, the reaction solution was diluted with 200 parts by mass of tetrahydrofuran (THF) and then reprecipitated with 3000 parts by mass of hexane, yielding 106.0 parts by mass of a white powder. Subsequently, 50.0 parts by weight of PGMEA, 3.7 parts by weight of glycidyl methacrylate (GMA), 0.15 parts by weight of N,N-dimethyldodecylamine, and 0.1 parts by weight of p-methoxyphenol were added to 50.0 parts by weight of the white powder. The mixture was stirred at 110°C for 24 hours while air was introduced. After cooling, the reaction solution was redeprecipitated using 3000 parts by weight of hexane to obtain 52.0 parts by weight of the macromonomer N.

[0833] The weight-average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the obtained macromonomers are shown in Table 5.

[0834] (Synthetic Examples 22-23: Production of macromonomers O-P)

[0835] In the production of macromonomer A in Synthesis Example 10, as shown in Table 5, at least one of the monomer types and mass ratios was changed to replace 1.0 parts by mass of monomer and 99.0 parts by mass of MMA, which are structural units represented by the derived general formula (III). Otherwise, macromonomers O to P were produced in the same manner as in Synthesis Example 10. The weight-average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the obtained macromonomers are shown in Table 5.

[0836] As the macromonomer Q, it is prepared as a commercial name for Nippon Oil Manufacturing, which is a monomer with PEG chains: Blemmer PME-4000 (PEG chain repeat number s = 90).

[0837] [Table 5]

[0838]

[0839] It should be noted that the abbreviations in the table are as follows.

[0840] Monomers with PEG chains (s=30): manufactured by Nippon Oil, trade name: Blemmer PSE-1300, R in general formula (III) 4 For CH3, A3 For COO, R 5 It is ethylene, R 6 C 18 H 37 The number of repeats in the PEG chain is s = 30.

[0841] Monomer with PEG chain (s=45): manufactured by Evonik, trade name: VISIOMER MPEG 2005 MA W, R in general formula (III) 4 For CH3, A 3 For COO, R 5 It is ethylene, R 6 For CH3, the repeat number of PEG chains is s = 45.

[0842] Monomer with PEG chains (s=17): Manufactured by Evonik, trade name: VISIOMER MPEG 750 MA W, PEG chain repeat number s=17

[0843] Monomer with PEG chains (s=9): manufactured by Nippon Oil, trade name: Blemmer PME-400, PEG chain repeat number s=9

[0844] Monomer with PEG chains (s=3): Manufactured by Tokyo Chemical Industry Co., Ltd., trade name: Triethylene Glycol Monoethyl Ether Methacrylate, PEG chain repeat number s=3

[0845] Caprolactone-modified hydroxyethyl methacrylate (t=5): Manufactured by Daicel Inc., trade name: PLACEL FM5, caprolactone chain repeat number t=5

[0846] Monomers with PEG chains (s=90): manufactured by Nippon Oil, trade name: Blemmer PME-4000, PEG chain repeat number s=90

[0847] BMA: n-Butyl methacrylate

[0848] 2-EHMA: 2-Ethylhexyl methacrylate

[0849] BzMA: Benzyl methacrylate

[0850] (Manufacturing Example 1: Manufacturing of Graft Copolymer A)

[0851] 63.1 parts by mass of PGMEA were added to a reactor equipped with a condenser, a funnel for adding polymers, a nitrogen inlet, a mechanical stirrer, and a digital thermometer. The temperature was raised to 85°C under a nitrogen flow while stirring. After 1.5 hours, a mixed solution of 141 parts by mass of macromonomer A solution (70.5 parts by mass of effective solids), 29.5 parts by mass of 2-(dimethylamino)ethyl methacrylate (DMMA), 1.24 parts by mass of n-dodecyl mercaptan, 49.4 parts by mass of PGMEA, and 1.0 part by mass of AIBN was added dropwise. After heating and stirring for 3 hours, a mixture of 0.10 parts by mass of AIBN and 6.0 parts by mass of PGMEA was added dropwise over 10 minutes, and then matured at the same temperature for 1 hour, thereby obtaining a 35.0% by mass solution of graft copolymer A. The GPC determination of the obtained graft copolymer A showed a weight-average molecular weight (Mw) of 10,000. It should be noted that the amine value is 105 mg KOH / g.

[0852] (Manufacturing Examples 2-15: Manufacturing of Graft Copolymers B-Q)

[0853] In Manufacturing Example 1, as shown in Table 6, the type of macromonomer and the mass ratio of macromonomer to DMMA were changed to replace 70.5 parts by mass of effective solids component of macromonomer A and 29.5 parts by mass of DMMA. Otherwise, graft copolymers B to Q were manufactured in the same manner as in Manufacturing Example 1. The weight-average molecular weight (Mw) and amine value before modification of the obtained graft copolymers B to Q are shown in Table 6.

[0854] [Table 6]

[0855]

[0856] (Preparation Example 1: Preparation of Alkali-Soluble Resin B)

[0857] 300 parts by weight of PGMEA were added to the polymerization tank, and the temperature was raised to 100°C under nitrogen atmosphere. Then, over 1.5 hours, 90 parts by weight of 2-phenoxyethyl methacrylate (PhEMA), 54 parts by weight of MMA, 36 parts by weight of methacrylic acid (MAA), 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 added dropwise. The reaction was then maintained 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 stop the polymerization.

[0858] Subsequently, while blowing air in, 20 parts by mass of glycidyl methacrylate (GMA), an epoxy-containing compound, were added. The temperature was raised to 110°C, and then 0.8 parts by mass of triethylamine were added. The addition reaction was carried out at 110°C for 15 hours to obtain alkali-soluble resin B solution (weight-average molecular weight (Mw) 8500, acid value 75 mg KOH / g, solid content 40% by mass). It should be noted that the weight-average molecular weight and acid value were determined using the same method as for alkali-soluble resin A.

[0859] (Example 50)

[0860] (1) Manufacturing of colorant dispersion 50

[0861] 9.29 parts by mass of the graft copolymer A from Manufacturing Example 1 (used as a dispersant), 11.7 parts by mass of CI pigment blue 15:6 (trade name FASTOGEN BLUE A510, manufactured by DIC Co., Ltd.) (used as a colorant), 1.3 parts by mass of CI pigment violet 23 (trade name Hostaperm Violet RL-NF, manufactured by Clariant Co., Ltd.) (used as a colorant), 14.63 parts by mass (5.85 parts by mass based on solid content) of the alkali-soluble resin B solution obtained in Preparation Example 1, 63.09 parts by mass of PGMEA, and 100 parts by mass of zirconia beads with a particle size of 2.0 mm were placed into a mayonnaise bottle for pre-crushing. The mixture was shaken for 1 hour using a paint shaker (manufactured by Asada Iron Works Co., Ltd.). Then, the zirconia beads with a particle size of 2.0 mm were removed, and 200 parts by mass of zirconia beads with a particle size of 0.1 mm were added for formal crushing. The mixture was also dispersed for 4 hours using a paint shaker to obtain a colorant dispersion 50.

[0862] (2) Preparation of photosensitive coloring resin composition 1 for color filters

[0863] By adding 9.77 parts by mass of the color material dispersion 50 obtained in (1) above, 0.28 parts by mass (0.11 parts by mass based on solid content) of the alkali-soluble resin B solution obtained in Preparation Example 1, 0.99 parts by mass of the photopolymerizable compound (trade name ARONIX M-403, manufactured by Toa Synthetic Co., Ltd.), 0.12 parts by mass of the compound A obtained in Synthesis Example 1 as a photoinitiator, 0.07 parts by mass of the fluorinated surfactant (trade name MEGAFAC R-08MH, manufactured by DIC Co., Ltd.), and 8.73 parts by mass of PGMEA, a photosensitive coloring resin composition 50 for color filters is obtained.

[0864] (Examples 51-74, Comparative Examples 3 and 4)

[0865] In Example 50, as a dispersant, graft copolymers B to Q obtained in Manufacturing Examples 2 to 15 or block copolymer A obtained in Synthesis Example 5 were used instead of graft copolymer A obtained in Manufacturing Example 1, according to Table 7. Furthermore, in Examples 58 to 65, as a photoinitiator, 0.06 parts by mass of each of the two photoinitiators were used instead of 0.12 parts by mass of compound A obtained in Synthesis Example 1, according to Table 7. In Comparative Examples 3 and 4, as a photoinitiator, 0.12 parts by mass of Irg907 (trade name Irgacure 907, manufactured by BASF, molecular weight 279.40) were used instead of 0.12 parts by mass of compound A obtained in Synthesis Example 1. Otherwise, the photosensitive coloring resin compositions 51 to 74 for color filters of Examples 51 to 74 and the comparative coloring resin compositions 3 to 4 of Comparative Examples 3 to 4 were obtained in the same manner as in Example 50.

[0866] (Example 75)

[0867] In Example 50, as the colorant, 13.0 parts by weight of CI Pigment Red 254 (trade name HostapermRed D2B-COF LV3781, manufactured by Clariant) was used instead of 11.7 parts by weight of CI Pigment Blue 15:6 and 1.3 parts by weight of CI Pigment Violet 23. Otherwise, the photosensitive coloring resin composition 75 for the color filter of Example 75 was obtained in the same manner as in Example 50.

[0868] (Examples 76-99, Comparative Examples 5-6)

[0869] In Example 75, as a dispersant, graft copolymers B to Q obtained in Manufacturing Examples 2 to 15 or block copolymer A obtained in Synthesis Example 5 were used instead of graft copolymer A obtained in Manufacturing Example 1, according to Table 8. Furthermore, in Examples 83 to 90, as a photoinitiator, 0.06 parts by mass of each of the two photoinitiators were used instead of 0.12 parts by mass of compound A obtained in Synthesis Example 1, according to Table 8. In Comparative Examples 5 to 6, as a photoinitiator, 0.12 parts by mass of Irg907 (trade name Irgacure 907, manufactured by BASF, molecular weight 279.40) were used instead of 0.12 parts by mass of compound A obtained in Synthesis Example 1. Otherwise, the photosensitive coloring resin compositions 76 to 99 for color filters and the comparative coloring resin compositions 5 to 6 for Comparative Examples 5 to 6 were obtained in the same manner as in Example 75.

[0870] (Example 100)

[0871] In Example 50, as colorants, 9.10 parts by weight of CI pigment green 59 (trade name FASTOGENGREEN C100, manufactured by DIC Corporation) and 3.90 parts by weight of CI pigment yellow 150 (LEVASCREEN YELLOWTP LXS 51084, manufactured by Sanyo Pigment Corporation) were used instead of 11.7 parts by weight of CI pigment blue 15:6 and 1.3 parts by weight of CI pigment violet 23. Otherwise, the photosensitive coloring resin composition 100 for color filters of Example 100 was obtained in the same manner as in Example 50.

[0872] (Examples 101-124, Comparative Examples 7-8)

[0873] In Example 100, as a dispersant, graft copolymers B to Q obtained in Manufacturing Examples 2 to 15 or block copolymer A obtained in Synthesis Example 5 were used instead of graft copolymer A obtained in Manufacturing Example 1, according to Table 9. Furthermore, in Examples 108 to 115, as a photoinitiator, 0.06 parts by mass of each of the two photoinitiators were used instead of 0.12 parts by mass of compound A obtained in Synthesis Example 1, according to Table 9. In Comparative Examples 7 and 8, as a photoinitiator, 0.12 parts by mass of Irg907 (trade name Irgacure 907, manufactured by BASF, molecular weight 279.40) were used instead of 0.12 parts by mass of compound A obtained in Synthesis Example 1. Otherwise, the photosensitive coloring resin compositions 101 to 124 for color filters and the comparative coloring resin compositions 7 to 8 of Comparative Examples 7 and 8 were obtained in the same manner as in Example 100.

[0874] [evaluate]

[0875] <Evaluation of Solvent Resistance (NMP Resistance)>

[0876] The photosensitive coloring resin compositions obtained in the examples and comparative examples shown in Tables 7-9 were coated onto glass substrates (manufactured by NH TECHNO GLASS Co., Ltd., "NA35") using a spin coater to form a colored layer with a thickness of 2.0 μm after baking. The substrates were then dried at 80°C for 3 minutes using a heating plate, thereby forming a colored layer on the glass substrate. The colored layer was irradiated with an ultra-high pressure mercury lamp at 60 mJ / cm². 2 Ultraviolet rays.

[0877] Subsequently, the colored substrate was baked in a clean oven at 230°C for 30 minutes to produce the colored substrate. After measuring the film thickness of the obtained colored substrate, it was immersed in NMP for 30 minutes and then air-dried, and the film thickness was measured again. It should be noted that the film thickness was measured using a stylus-type step film thickness gauge "P-15Tencor" (manufactured by Instruments).

[0878] (NMP resistance evaluation criteria)

[0879] ◎◎◎: When the NMP immersion time is set to 60 minutes, the change rate of film thickness before and after NMP immersion is less than 2%;

[0880] ◎◎: The change rate of film thickness before and after NMP impregnation is less than 2%;

[0881] ◎: The change rate of film thickness before and after NMP impregnation is greater than 2% and less than 5%;

[0882] △: The change rate of film thickness before and after NMP impregnation is greater than 5% and less than 8%;

[0883] ×: The change rate of film thickness before and after NMP impregnation is more than 8%.

[0884] If the evaluation result is ◎, the resistance to NMP is good; if the evaluation result is ◎◎ or even ◎◎◎, the resistance to NMP is excellent.

[0885] Furthermore, the above-mentioned evaluations of sublimation and development residue were also performed on the photosensitive coloring resin compositions obtained in the various examples and comparative examples shown in Tables 7-9.

[0886] [Table 7]

[0887]

[0888] [Table 8]

[0889]

[0890] [Table 9]

[0891]

[0892] [Results Summary]

[0893] Examples 50-70 shown in Table 7, Examples 75-95 shown in Table 8, and Examples 100-120 shown in Table 9 used compounds represented by the above general formula (1) as photoinitiators and graft copolymers or salt-type graft copolymers having structural units represented by the above general formula (I) and structural units represented by the above general formula (II) as dispersants. Compared with Examples 71-73 shown in Table 7, Examples 96-98 shown in Table 8, and Examples 121-123 shown in Table 9, which used graft copolymers or salt-type graft copolymers with graft chains whose structures are different from those of polymer chains specified by the above general formula (II) as dispersants, the generation of developing residue was suppressed and the NMP resistance was improved. It can be seen that in the photosensitive coloring resin composition for color filters of the present invention, if graft copolymers or salt-type graft copolymers having structural units represented by the above general formula (I) and structural units represented by the above general formula (II) are used as dispersants, a photosensitive coloring resin composition with suppressed developing residue and excellent NMP resistance can be obtained.

[0894] Furthermore, the development residue suppression and NMP resistance improvement effects are particularly excellent in Examples 57-63 and 65-66 shown in Table 7, Examples 82-88 and 90-91 shown in Table 8, and Examples 107-113 and 115-116 shown in Table 9, which use only the compound represented by the above general formula (1) or in combination with one or more of the group consisting of oxime ester photoinitiators and α-aminoketone photoinitiators and use graft copolymer H or graft copolymer K as dispersants. Therefore, it can be seen that when using the compound represented by the above general formula (1), and further including other photoinitiators, using one or more photoinitiators selected from the group consisting of oxime ester photoinitiators and α-aminoketone photoinitiators, and using a graft copolymer or salt-type graft copolymer, such as graft copolymer H and graft copolymer K, in the structural unit of the polymer chain in the structural unit represented by the above general formula (II) containing at least one of the group consisting of the structural unit represented by the above general formula (III) with s of s of 19 or more and 80 or less, and at least one of the group consisting of the structural unit represented by the above general formula (III) with s of s of 3 or more and 10 or less, the effect of suppressing development residue and improving NMP resistance is more significant. It should be noted that in the cases where the compound represented by the above general formula (1) and the above compound E are used as photoinitiators, it is believed that the above compound E leads to a decrease in sensitivity, and therefore it is difficult to improve NMP resistance.

[0895] On the other hand, if we compare Comparative Examples 3 and 4 shown in Table 7, Comparative Examples 5 and 6 shown in Table 8, and Comparative Examples 7 and 8 shown in Table 9, which use only Irg907 as a photoinitiator, we find that, compared with the case where block copolymers are used as dispersants, the NMP resistance is not improved when using the above-mentioned specific graft copolymers, although the developing residue is suppressed. Therefore, it can be seen that by using a graft copolymer or salt-type graft copolymer containing at least one of the group consisting of structural units of the above general formula (I) and structural units of the above general formula (II) and the polymer chain in the structural unit of the above general formula (II) and at least one of the group consisting of structural units of the above general formula (III) with s of 19 or more and 80 or less, and at least one of the group consisting of structural units of the above general formula (III) with s of 3 or more and 10 or less as a dispersant, the effect of significantly improved NMP resistance can be obtained. This effect is unique to the case where only the compound of the above general formula (1) is used as a photoinitiator and the case where the compound of the above general formula (1) is used as a photoinitiator along with one or more of the group consisting of oxime ester photoinitiators and α-aminoketone photoinitiators as other photoinitiators. Attached Figure Description

[0897] 1:Substrate

[0898] 2:Light shielding part

[0899] 3: Coloring layer

[0900] 10: Color Filter

[0901] 20: Opposing substrate

[0902] 30: Liquid Crystal Layer

[0903] 40: Liquid crystal display device

[0904] 50: Organic protective layer

[0905] 60: Inorganic oxide film

[0906] 71: Transparent Anode

[0907] 72: Hole Injection Layer

[0908] 73: Hole transport layer

[0909] 74: Emissive Layer

[0910] 75: Electron Injection Layer

[0911] 76: Cathode

[0912] 80: Organic light-emitting body

[0913] 100: Organic light-emitting display device

[0914] 110: Graft copolymer

[0915] 111: Structural unit represented by general formula (I)

[0916] 112: Structural unit represented by general formula (II)

[0917] 113: Main chain section

[0918] 114: Select at least one from the group consisting of organic acid compounds and halogenated hydrocarbons.

[0919] 115: Polymer chain

[0920] 116: Structural unit represented by general formula (III)

[0921] 117: Polyethylene oxide chain or polypropylene oxide chain

Claims

1. A photosensitive coloring resin composition for color filters, comprising: Colorants, alkali-soluble resins, photopolymerizable compounds, photoinitiators, and solvents. The photoinitiator contains a compound represented by the following general formula (1), and other photoinitiators different from the compound represented by the general formula (1). The other photoinitiators contain one or more selected from the group consisting of oxime ester photoinitiators and α-aminoketone photoinitiators. Of the total amount of the other photoinitiators (100% by mass), the total content of photoinitiators with a molecular weight of 350 or higher is 70% by mass or higher. In general formula (1), R a and R b Each is an alkyl group having 2 or more carbon atoms and 8 or fewer carbon atoms.

2. The photosensitive coloring resin composition for color filters according to claim 1, wherein, The colorant contains one or more selected from CI Pigment Green 62 and CI Pigment Green 63.

3. The photosensitive coloring resin composition for color filters according to claim 1, wherein, The colorant contains zinc polyhalogenated phthalocyanine, represented by the following general formula (i). In general formula (i), X 1 ~X 16 Each molecule consists independently of chlorine, bromine, or hydrogen atoms. The average number of chlorine atoms in one molecule is less than 1, the average number of bromine atoms is more than 13, and the average number of hydrogen atoms is less than 2.

4. The photosensitive coloring resin composition for color filters according to claim 1, wherein, The colorant contains one or more selected from the group consisting of colorants represented by general formula (ii) and colorants represented by general formula (iii). In general formula (ii), A is an α-valent organic group whose carbon atom directly bonded to N does not have a π bond, and the organic group represents an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at the end directly bonded to N, or an aromatic group having such aliphatic hydrocarbon group, optionally containing heteroatoms in the carbon chain. B c- Indicates a C-valent polyacid anion; R i ~R v Each of the following groups independently represents a hydrogen atom, an alkyl group optionally with substituents, or an aryl group optionally with substituents; R ii With R iii R iv With R v Ring structures are formed by optional bonding; R vi and R vii Each of the following can be independently represented: an alkyl group with optional substituents, an alkoxy group with optional substituents, a halogen atom, or a cyano group; Ar 1 Represents an optional divalent aromatic group with substituents; multiple R groups are present. i ~R vii and Ar 1 Choose either the same or different from each other; a and c represent integers greater than 2, b and d represent integers greater than 1; e is 0 or 1, and there is no bond when e is 0; f and g represent integers greater than 0 and less than 4, f+e and g+e are greater than 0 and less than 4; multiple e, f, and g can be chosen to be the same or different. In general formula (iii), R I ~R VI Each of the following groups independently represents a hydrogen atom, an alkyl group optionally with substituents, or an aryl group optionally with substituents; R I With R II R III With R IV R V With R VI Ring structures are formed by optional bonding; R VII and R VIII Each of the following can be independently represented: an alkyl group with optional substituents, an alkoxy group with optional substituents, a halogen atom, or a cyano group; Ar 2 This indicates a divalent aromatic heterocyclic group with optional substituents, and the presence of multiple R groups. I ~R VIII and Ar 2 Choose either the same or different from each other; E m- Indicates m-valent polyacid anions; m represents an integer greater than 2; j is 0 or 1, and there is no bond when j is 0; k and l represent integers greater than 0 and less than 4, k+j and l+j are greater than 0 and less than 4; multiple j, k and l can be chosen to be the same or different.

5. The photosensitive coloring resin composition for color filters according to any one of claims 1 to 4, further comprising a dispersant. The dispersant contains at least one of the following: graft copolymers having structural units represented by general formula (I) and general formula (II) below, and salt-type graft copolymers. The salt-type graft copolymer is formed by at least a portion of the nitrogen site of the structural unit represented by the general formula (I) of the graft copolymer forming a salt with at least one of the compounds selected from the group consisting of organic acid compounds and halogenated hydrocarbons. In general formula (I), R 1 A represents a hydrogen atom or a methyl group. 1 R represents a divalent linker group. 2 and R 3 Each can independently represent a hydrogen atom, or optionally a hydrocarbon group containing a heteroatom, R 2 and R 3 They can be selectively bonded together to form a ring structure; In general formula (II), R 1' A represents a hydrogen atom or a methyl group. 2 The term "polymer" indicates a directly bonded or divalently linked group, and "polymer" indicates a polymer chain. The structural units of this polymer chain include at least one structural unit selected from the group consisting of structural units represented by general formula (III) and general formula (III'). In general formula (III), R 4 A is a hydrogen atom or a methyl group. 3 R is a divalent linker group. 5 It is ethylene or propylene, R 6 It can be a hydrogen atom or a hydrocarbon group, and s represents a number greater than 3 and less than 80; In general formula (III'), R 4' A is a hydrogen atom or a methyl group. 3' R is a divalent linker group. 7 R is an alkylene group having 1 to 10 carbon atoms. 8 R is an alkylene group having 3 to 7 carbon atoms. 9 It represents a hydrogen atom or a hydrocarbon group, and t represents a number greater than 1 and less than 40.

6. A cured product, which is a cured product of the photosensitive coloring resin composition for color filters according to any one of claims 1 to 5.

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 for color filters according to any one of claims 1 to 5.

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

Images