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

Abstract

Provided is a photosensitive colored resin composition for color filters that contains a coloring material, a binder resin, a monomer, a photoinitiator, and a solvent, wherein the coloring material is at least one material selected from the group consisting of dyes and lake coloring materials, and the binder resin contains a copolymer that has a polymer structure including 5-25 mass% of a structural unit derived from hydroxyalkyl (meth)acrylate and represented by general formula (A), that has a weight-average molecular weight of not less than 11000, and that has an acid value of 60-130 mgKOH / g. (In general formula (A), RA represents a methyl group or a hydrogen atom, and RB represents a C1-C4 alkylene group.)

Description

[Technical Field]

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

[0002] In recent years, the demand for liquid crystal displays (LCDs) has increased with the development of personal computers, particularly portable personal computers. The penetration rate of mobile displays (mobile phones, smartphones, and tablet PCs) is also rising, further expanding the LCD market. Recently, organic light-emitting displays, such as OLEDs, which offer high visibility due to their self-emissive nature, have also attracted attention as next-generation image display devices. There is a strong desire for further improvements in image quality, such as enhanced contrast and color reproduction, as well as reduced power consumption, in the performance of these image display devices.

[0003] These liquid crystal displays and organic light-emitting displays utilize color filters. For example, in liquid crystal displays, color images are formed when light passing through a color filter is colored according to the color of each pixel constituting the filter, and these colored lights are combined to form a color image. As a light source, in addition to conventional cold cathode tubes, white-emitting organic light-emitting elements and white-emitting inorganic light-emitting elements may be used. Furthermore, organic light-emitting displays use color filters for color adjustment and other purposes. Under these circumstances, there is a growing demand for color filters that offer higher brightness, higher contrast, and improved color reproduction.

[0004] Here, a color filter generally comprises a transparent substrate, a colored layer formed on the transparent substrate consisting of colored patterns of the three primary colors red, green, and blue, and light-shielding portions formed on the transparent substrate to demarcate each colored pattern. One method for forming the colored layer in a color filter involves, for example, adding a binder resin, a photopolymerizable compound, and a photoinitiator to a colorant dispersion liquid, which is made by dispersing colorants with a dispersant, to a photosensitive colored resin composition. This composition is then applied to a glass substrate, dried, exposed 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.

[0005] Photosensitive colored resin compositions for forming color filters require excellent developability to accurately form the colored layer. Patent Document 1 discloses a colored photosensitive resin composition for color filters, comprising a pigment, a binder resin, a polyfunctional monomer, a photoinitiator, a dispersant, and a solvent, wherein the binder resin comprises a copolymer having a main chain structure obtained by copolymerizing at least an alkylcyclohexyl (meth)acrylate having an alkylcyclohexyl group and a monomer having an acid group, and the hydroxyl value of the copolymer is in the range of 15 mg KOH / g to 200 mg KOH / g. Patent Document 1 describes that the colored photosensitive resin composition produces less development residue in unexposed areas and a higher residual film rate in exposed areas.

[0006] Furthermore, the photosensitive colored resin composition for forming color filters is required to be able to form a high-luminosity colored layer. For this reason, the use of finely ground pigments as colorants, or the use of dyes or lake colorants as colorants with higher transmittance, is being considered. [Prior art documents] [Patent Documents]

[0007] [Patent Document 1] Japanese Patent Publication No. 2009-276674 [Overview of the project] [Problems that the invention aims to solve]

[0008] The inventors attempted to use dyes or lake pigments as colorants in a photosensitive colored resin composition to increase the brightness of a color filter. However, it was found that when a photosensitive colored resin composition containing dyes or lake pigments is used to form a colored layer pattern in which two or more colored layers, such as red, green, and blue, are arranged in a predetermined pattern, the distribution of the film thickness inside the pixel becomes non-uniform, impairing the flatness of the pixel. The present invention has been made in view of the above circumstances, and aims to provide a photosensitive colored resin composition for color filters that contains at least one colorant selected from dyes and lake colorants, thereby providing a colored layer that is highly luminous, has excellent flatness, and suppresses the generation of developing residue. The present invention also aims to provide a cured product of the photosensitive colored resin composition, as well as a color filter and display device formed using the photosensitive colored resin composition. [Means for solving the problem]

[0009] The photosensitive colored resin composition for color filters according to the present invention is a photosensitive colored resin composition for color filters comprising a colorant, a binder resin, a monomer, a photoinitiator, and a solvent, The aforementioned colorant includes at least one selected from the group consisting of dyes and lake colorants. The binder resin contains a copolymer having a polymeric structure containing 5 to 25% by mass of constituent units derived from hydroxyalkyl (meth)acrylate represented by the following general formula (A), having a weight-average molecular weight of 11,000 or more, and an acid value of 60 to 130 mgKOH / g.

[0010] [ka] (In general formula (A), R A R represents a methyl group or a hydrogen atom. B (This represents an alkylene group with 1 to 4 carbon atoms.)

[0011] The present invention provides a cured product of the photosensitive colored resin composition for color filters according to the present invention. The present invention provides a color filter comprising a substrate and at least a colored layer provided on the substrate, wherein at least one of the colored layers is a cured product of the photosensitive colored resin composition for color filters according to the present invention.

[0012] The present invention provides a display device having the color filter according to the present invention. [Effects of the Invention]

[0013] The present invention provides a photosensitive colored resin composition for color filters that, by containing at least one colorant selected from dyes and lake colorants, is capable of forming a colored layer that is highly luminous, has excellent flatness, and suppresses the generation of developing residue. Furthermore, the present invention provides a cured product of the photosensitive colored resin composition, as well as a color filter and display device formed using the photosensitive colored resin composition. [Brief explanation of the drawing]

[0014] [Figure 1] Figure 1 is a schematic diagram showing an example of the color filter of the present invention. [Figure 2] Figure 2 is a schematic diagram showing an example of the liquid crystal display device of the present invention. [Figure 3] Figure 3 is a schematic diagram showing an example of the organic light-emitting device of the present invention. [Figure 4] Figure 4 is a schematic diagram showing an example of a conventional method for forming a colored layer of a color filter using a photosensitive colored resin composition containing pigments. [Figure 5] Figure 5 is a schematic diagram showing an example of a conventional method for forming a colored layer of a color filter using a photosensitive colored resin composition containing a dye or lake colorant. [Modes for carrying out the invention]

[0015] The following will describe in detail the photosensitive colored resin composition for color filters and its manufacturing method according to the present invention, as well as the cured product of the photosensitive colored resin composition for color filters according to the present invention, and the color filter and display device formed using the photosensitive colored resin composition for color filters according to the present invention. In this invention, light includes electromagnetic waves with wavelengths in the visible and invisible regions, as well as radiation, and radiation includes, for example, microwaves and electron beams. Specifically, it refers to electromagnetic waves with wavelengths of 5 μm or less, and electron beams. In this invention, (meth)acryloyl refers to acryloyl and methacryloyl respectively, (meth)acrylic refers to acrylic and methacrylic respectively, and (meth)acrylate refers to acrylate and methacrylate respectively. Furthermore, in this specification, the "~" symbol indicating a numerical range is used to mean that the numbers before and after it are included as the lower and upper limits, respectively. In the present invention, the term "solid content" refers to all components of the photosensitive colored resin composition other than the solvent, and includes liquid components such as monomers.

[0016] I. Photosensitive colored resin composition for color filters The photosensitive colored resin composition for color filters according to the present invention (hereinafter sometimes referred to as "photosensitive colored resin composition") is a photosensitive colored resin composition for color filters that contains a colorant, a binder resin, a monomer, a photoinitiator, and a solvent, The aforementioned colorant includes at least one selected from the group consisting of dyes and lake colorants. The binder resin is a photosensitive colored resin composition for color filters, comprising a copolymer having a polymer structure containing 5 to 25% by mass of constituent units derived from hydroxyalkyl (meth)acrylate represented by the general formula (A) described later, having a weight-average molecular weight of 11,000 or more, and an acid value of 60 to 130 mgKOH / g.

[0017] The photosensitive colored resin composition according to the present invention contains at least one colorant selected from the group consisting of dyes and lake colorants. Since dyes and lake colorants have higher transmittance than pigments, a high-luminosity colored layer can be formed by using at least one colorant selected from the group consisting of dyes and lake colorants as the colorant in the photosensitive colored resin composition. However, in a method for forming a colored layer pattern in which two or more colored layers, such as red, green, and blue, are arranged in a predetermined pattern, by sequentially performing a series of steps on a single substrate, in which a photosensitive colored resin composition is applied to a substrate, exposed in a predetermined pattern, and developed, while changing the color of the colorant, it has been found that when a photosensitive colored resin composition containing a dye or lake colorant is used, the film thickness distribution of the second and subsequent colored layers becomes uneven, impairing the flatness of the pixels. The uniformity of the pixel film thickness distribution is related to the uniformity of chromaticity within the pixel and is an important factor in improving image quality. In particular, as the pixel density increases with the resolution of display devices, the impact of the uniformity of the pixel film thickness distribution on image quality becomes greater. The problem of impaired pixel flatness is particularly pronounced when dyes or lake pigments are used as colorants in photosensitive colored resin compositions.

[0018] Figure 4 is a schematic diagram showing an example of a conventional method for forming a colored layer of a color filter using a photosensitive colored resin composition containing pigments. Figure 4 shows the process of forming a red colored layer 3R and a green colored layer 3G in that order on a substrate, followed by the formation of a blue colored layer 3B. Figure 4(a) shows the state in which a blue coating film 3B' is formed using a blue photosensitive colored resin composition on a substrate that has light-shielding portions 2, red colored layer 3R, and green colored layer 3G which serve as boundaries for each colored layer. Because the blue coating film 3B' follows the uneven shape of the coated surface, the height of the coating film surface is relatively low in the region where the blue colored layer is formed, and relatively high in the regions where the red colored layer 3R and green colored layer 3G are provided. Within the region where the blue colored layer is formed, the thickness of the blue coating film 3B' is constant, and its surface becomes flat by following the surface shape of the substrate. Next, this blue coating film 3B' is heat-dried. As shown in Figure 4(b), the blue coating 3B' after heat drying maintains the same shape as before heat drying. After heat drying, the blue coating 3B' is exposed in a predetermined pattern to selectively harden the region where the blue colored layer will form, and then developed to form a flat blue colored layer 3B, as shown in Figure 4(c).

[0019] On the other hand, Figure 5 is a schematic diagram showing an example of a conventional method for forming a colored layer of a color filter using a photosensitive colored resin composition containing a dye or lake colorant. Figure 5 shows the process of forming a red colored layer 3R and a green colored layer 3G in that order on a substrate, and then forming a blue colored layer 3B. Figure 5(a) shows the state in which a blue coating film 3B' is formed using a blue photosensitive colored resin composition on a substrate that has light-shielding portions 2 that form the boundaries of each colored layer, a red colored layer 3R, and a green colored layer 3G. At this stage, the blue coating film 3B' containing a dye or lake colorant, similar to the blue coating film 3B' containing a pigment in Figure 4(a), has a relatively lower surface height in the region where the blue colored layer is formed, and a relatively higher surface height in the regions where the red colored layer 3R and green colored layer 3G are provided. However, within the region where the blue colored layer is formed, the thickness of the blue coating film 3B' is constant, and its surface follows the surface shape of the substrate and becomes flat. Note that the green colored layer 3G shown in Figure 5(a) is the second colored layer formed on the substrate, and unlike the green colored layer 3G containing pigment shown in Figure 4(a), it has a shape with inferior flatness. This point will be explained later. Next, when this blue coating 3B' is heated and dried, the blue coating flows due to the heat. As shown in Figure 5(b), the parts of the blue coating 3B' where the red coloring layer 3R and green coloring layer 3G are provided have a relatively high surface height. These parts flow beyond the boundary between the area with the red coloring layer 3R and the area forming the blue coloring layer, and the boundary between the area with the green coloring layer 3G and the area forming the blue coloring layer, into the parts where the surface height of the coating in the area forming the blue coloring layer is relatively low. As a result, after heating and drying, the blue coating 3B' loses its ability to conform to the surface shape of the substrate. The surface of the coating becomes relatively higher near the boundary between the area with the red coloring layer 3R and the area forming the blue coloring layer, and near the boundary between the area with the green coloring layer 3G and the area forming the blue coloring layer, while the surface of the coating becomes relatively lower in the center, resulting in an overall surface shape that is concave in the center. After heating and drying, the blue coating is exposed in a predetermined pattern to selectively harden the region where the blue colored layer will be formed, and then developed to form a blue colored layer 3B with a concave shape in the center, as shown in 5(c) of Figure 5.

[0020] When forming a second or subsequent colored layer on a substrate using a photosensitive colored resin composition containing a dye or lake colorant, the coating film of the photosensitive colored resin composition softens and flows in the same way as described above during the heat drying process, losing its ability to conform to the surface shape of the substrate. As a result, a colored layer with a relatively high surface is likely to be formed near the boundary adjacent to the previously formed colored layer on the substrate. For example, when a photosensitive colored resin composition containing a dye or lake colorant is used to form a red colored layer, a green colored layer, and a blue colored layer on a substrate in that order, the green colored layer tends to have a shape where the coating height is relatively high at the boundary adjacent to the red colored layer, as shown in 5(a) of Figure 5, and the coating height is relatively low in the central part and in the part far from the red colored layer.

[0021] The reason why the fluidity of a photosensitive colored resin composition during heat drying differs depending on the colorant used is that when a pigment is used as the colorant, the pigment is dispersed in the photosensitive colored resin composition, so even if the coating softens during heat drying, the viscosity does not decrease significantly. On the other hand, when a dye or lake colorant is used as the colorant, the dye or lake colorant is dissolved or dispersed in the photosensitive colored resin composition in a state finer than the pigment particles, so when the coating softens during heat drying, the viscosity decreases and the fluidity increases.

[0022] In the present invention, the above-mentioned problems specific to the use of dyes or lake colorants as colorants in photosensitive colored resin compositions are solved by using a binder resin containing a copolymer (hereinafter sometimes referred to as "hydroxyalkyl (meth)acrylate unit-containing copolymer") having a polymer structure containing 5 to 25% by mass of constituent units derived from hydroxyalkyl (meth)acrylate represented by general formula (A) described later, having a weight-average molecular weight of 11,000 or more, and an acid value of 60 to 130 mgKOH / g. When a binder resin containing a hydroxyalkyl (meth)acrylate unit-containing copolymer is used in a photosensitive colored resin composition containing a dye or lake colorant, the increase in fluidity is suppressed when the coating film of the photosensitive colored resin composition formed on the substrate is heat-dried. As a result, the flatness of the coating film applied to the substrate is easily maintained even after heat-drying, and a colored layer with excellent flatness is formed. The reason why a colored layer with excellent flatness is formed when using the above-mentioned binder resin containing a hydroxyalkyl (meth)acrylate unit copolymer is presumed to be as follows. When a photosensitive colored resin composition coating is heat-dried, the amount of solvent in the coating decreases, reducing the intermolecular distance between binder resin molecules and increasing the influence of hydrogen bonding on the bonding force between binder resin molecules. The above-mentioned hydroxyalkyl (meth)acrylate unit-containing copolymer has an appropriate content of constituent units derived from hydroxyalkyl (meth)acrylate, so when a photosensitive colored resin composition coating is heat-dried, the viscosity of the softened coating is increased by the effect of the hydroxyl groups of the hydroxyalkyl (meth)acrylate unit-containing copolymer promoting hydrogen bonding between binder resin molecules, thereby suppressing the fluidization of the coating. Furthermore, since the weight-average molecular weight of the above-mentioned hydroxyalkyl (meth)acrylate unit-containing copolymer is adjusted to an appropriate range, it is thought that when the coating film of the photosensitive colored resin composition is heat-dried, the viscosity of the softened coating film can be increased by the molecular weight effect, thereby suppressing the fluidization of the coating film. Other methods for suppressing the softening of the coating film of the photosensitive colored resin composition include using other resins with high melt viscosity as binder resins, or using resins with other functional groups that promote hydrogen bonding within the binder resin as binder resins. However, the above-mentioned hydroxyalkyl (meth)acrylate unit-containing copolymer is superior in that it can effectively flatten the shape of the colored layer with a relatively small amount and does not adversely affect the color tone of the colored layer.

[0023] Furthermore, when using a binder resin containing the above-mentioned hydroxyalkyl (meth)acrylate unit-containing copolymer, the acid value of the hydroxyalkyl (meth)acrylate unit-containing copolymer is adjusted to an appropriate range, thus reducing the amount of developing residue. Generally, the higher the acid value of the binder resin, the easier it is for hydrogen bonds to form within the binder resin. Therefore, according to the above explanation, the higher the acid value of the hydroxyalkyl (meth)acrylate unit-containing copolymer, the better the effect of flattening the shape of the colored layer. However, if the acid value of the binder resin is too high, the amount of developing residue on the substrate will increase. In the present invention, by adjusting the weight-average molecular weight of the hydroxyalkyl (meth)acrylate unit-containing copolymer and the content of constituent units derived from hydroxyalkyl (meth)acrylate to an appropriate range, the shape of the colored layer can be effectively flattened. Therefore, the acid value of the hydroxyalkyl (meth)acrylate unit-containing copolymer does not need to be extremely high from the viewpoint of flattening the colored layer, and can be set to an appropriate range from the viewpoint of reducing development residue.

[0024] The components contained in the photosensitive colored resin composition for color filters according to the present invention are described below. [Colorants] <Dyes and lake pigments> In this invention, at least one colorant selected from the group consisting of dyes and lake colorants is used. In this invention, "dye" means a colorant that can be dissolved in a solvent in an effective amount sufficient to exhibit a coloring function. "Lake colorant" refers to a dye that has been laked with a lake agent. Dyes and lake colorants dissolve in a matrix such as a binder resin or are dispersed in the form of extremely fine particles, and do not impair the transparency of the composition. Therefore, by using at least one selected from the group consisting of dyes and lake colorants as a colorant, the brightness of the color filter can be increased.

[0025] The dyes and lake colorants used in this invention are not particularly limited. Examples of dyes include azo dyes, metal complex azo dyes, anthraquinone dyes, triarylmethane dyes, xanthene dyes, cyanine dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, and phthalocyanine dyes. Examples of lake dyes include dyes that have been laked with a lake agent. The lake agent is selected appropriately depending on the dye. For anionic dyes (acid dyes), a compound that generates a countercation of the dye is used as the lake agent, and for cationic dyes (basic dyes), a compound that generates a counteranion of the dye is used as the lake agent. Known lake agents can be used and are not particularly limited, but examples of lake agents used for cationic dyes (basic dyes) include alkali metal salts and alkaline earth metal salts of organic anions, and alkali salts and alkali metal salts of inorganic anions, and examples of lake agents used for anionic dyes (acid dyes) include amine compounds that generate ammonium cations, and metal salts having a desired metal ion. Furthermore, as lake colorants used in the present invention, for example, lake colorants obtained by forming a salt between a monovalent or divalent or higher cationic dye (basic dye) and a divalent or higher polyanion, and lake colorants obtained by forming a salt between a monovalent or divalent or higher anionic dye (acid dye) and a divalent or higher polycation, can be preferably used. Examples of dyes and lake colorants used in the present invention include, for example, the dye described in Japanese Patent Publication No. 2015-96947, the blue dye described in Japanese Patent Publication No. 2016-27149, the lake colorant compound (Aa) described in Japanese Patent Publication No. 2017-16099, and the dye (Ab).

[0026] In particular, the photosensitive colored resin composition of the present invention is preferred when it contains a lake colorant because it easily suppresses the generation of development residue even when the acid value of the hydroxyalkyl (meth)acrylate unit-containing copolymer is relatively high. Because the lake colorant has a salt structure of acid and base, it has a high affinity for hydroxyl groups, and therefore, compared to dyes and pigments, the lake colorant has good compatibility with the hydroxyalkyl (meth)acrylate unit-containing copolymer. For this reason, when the photosensitive colored resin composition of the present invention contains a combination of a lake colorant and a hydroxyalkyl (meth)acrylate unit-containing copolymer, the solubility in the developer solution is made uniform, thereby suppressing the generation of development residue. In particular, when the hydroxyl value of the hydroxyalkyl (meth)acrylate unit-containing copolymer is within the preferred range described later, the compatibility with the lake colorant is further improved, and the effect of suppressing development residue is especially excellent.

[0027] Furthermore, among lake colorants, triarylmethane-based or xanthene-based lake colorants are preferred because they easily improve the brightness and heat resistance of the colored layer. It is particularly preferable to include a lake colorant with a triarylmethane-based dye because it can achieve high brightness when coloring blue and further improves heat resistance. The triarylmethane dyes and xanthene dyes used in lake colorants can be appropriately selected from known dyes and are not particularly limited. Examples of triarylmethane dyes include CI Basic Blue 7, 8, 11, and 26. Examples of xanthene dyes include xanthene acid dyes such as CI Acid Red 50, 51, 52, 87, 92, 94, 289, 388, CI Acid Violet 9, 30, 102, Sulfolhodamine G, Sulfolhodamine B, Sulfolhodamine 101, and Sulfolhodamine 640; and xanthene basic dyes such as CI Basic Violet 11.

[0028] Furthermore, while the lake colorant used in the present invention may have only one color-developing site, it is preferable to have two or more color-developing sites, as this allows for the acquisition of a colored layer with higher brightness and superior heat resistance. Here, a lake colorant having two or more color-developing sites may be a mixture of multiple dye molecules, each having one color-developing site, ionically bonded with a lake agent; a single dye molecule, each having multiple color-developing sites, ionically bonded with a lake agent; or multiple dye molecules, each having multiple color-developing sites, ionically bonded with a lake agent. In particular, from the viewpoint of obtaining a colored layer with high brightness and excellent heat resistance, the colorant used in the present invention preferably contains a lake colorant represented by the following general formula (1) or general formula (2), and more preferably contains a lake colorant represented by the following general formula (1). The lake colorant represented by the following general formula (1) is a lake colorant in which a divalent or higher cationic dye (basic dye) and a divalent or higher polyacid anion form a salt, and the lake colorant represented by the following general formula (2) is a lake colorant in which two or more monovalent cationic dyes and a divalent or higher polyacid anion form a salt. In either lake colorant, dye molecules that do not form a salt with the polyacid anion may be produced, and in particular, when the number of cations and anions differ in the lake colorant represented by the following general formula (1), dye molecules that do not form a salt with the polyacid anion are more likely to be produced. Dye molecules that do not form a salt with the polyacid anion can form a salt with the acidic group in the hydroxyalkyl (meth)acrylate unit-containing copolymer. The lake colorant represented by the following general formula (1) or general formula (2) has a high affinity for the hydroxyalkyl (meth)acrylate units in the copolymer due to the acid-base salt structure. In addition, dye molecules that do not form salts with polyacid anions can form salts with the acidic constituent units in the copolymer. Therefore, it is presumed that the photosensitive colored resin composition of the present invention containing the lake colorant represented by the following general formula (1) or general formula (2) will have improved heat resistance because a composite will be formed in association between the lake colorant and the copolymer, thereby increasing the effect of inhibiting thermal motion. In addition, the lake colorant represented by the following general formula (1) or general formula (2) also has a salt structure of an acid and a base, so that its compatibility with the copolymer containing a hydroxyalkyl (meth) acrylate unit is good. Therefore, even when the acid value of the copolymer containing a hydroxyalkyl (meth) acrylate unit is relatively large, the generation of development residues can be suppressed. Among them, when the hydroxyl value of the copolymer containing a hydroxyalkyl (meth) acrylate unit is within the preferable range described later, the compatibility with the lake colorant represented by the following general formula (1) or general formula (2) is further improved. Therefore, the effect of suppressing development residues is particularly excellent. When the acid value and the hydroxyl value of the copolymer containing a hydroxyalkyl (meth) acrylate unit are within the preferable ranges described later, a complex associated with the lake colorant represented by the following general formula (1) or general formula (2) is likely to be formed. Therefore, the effect of improving heat resistance is particularly excellent.

[0029] (Lake colorant represented by general formula (1)) Hereinafter, the lake colorant represented by general formula (1) preferably used in the present invention will be described in detail.

[0030] [Chemical formula] (In general formula (1), A is an a-valent organic group in which the carbon atom directly bonded to N does not have a π bond. The organic group is an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at least at the terminal directly bonded to N, or an aromatic group having the aliphatic hydrocarbon group, and a heteroatom may be contained in the carbon chain. B c- represents a c-valent polyacid anion. R i ~R v each independently represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent. R ii and R iii , R iv and R v , and R vi and R vii may combine to form a ring structure. R vi and R vii ​​​​​Each independently represents an alkyl group which may have a substituent, an alkoxy group which may have a substituent, a halogen atom or a cyano group. Ar 1 represents a divalent aromatic group which may have a substituent. A plurality of R i ~R vii and Ar 1 may be the same or different from each other. a and c represent integers of 2 or more, b and d represent integers of 1 or more. e is 0 or 1, and when e is 0, the bond does not exist. f and g represent integers of 0 or more and 4 or less, and f + e and g + e are of 0 or more and 4 or less. A plurality of e, f and g may be the same or different from each other. )

[0031] Since the colorant represented by the general formula (1) contains an anion of 2 or more valences and a cation of 2 or more valences, in the aggregate of the colorant, an anion and a cation do not simply form an ionic bond on a one - molecule - to - one - molecule basis, but a molecular aggregate in which a plurality of molecules associate through an ionic bond can be formed. Therefore, the apparent molecular weight is significantly increased compared to the molecular weight of conventional lake colorants. Due to the formation of such a molecular aggregate, the cohesive force in the solid state is further enhanced, the thermal motion is reduced, the dissociation of ion pairs and the decomposition of the cation part can be suppressed, and it is presumed that it is more difficult to fade compared to conventional lake colorants.

[0032] In the general formula (1), A is an a-valent organic group in which the carbon atom directly bonded to N (nitrogen atom) has no π bond, and the organic group represents an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at least at the terminal directly bonded to N, or an aromatic group having the aliphatic hydrocarbon group, and may contain heteroatoms such as O (oxygen atom), S (sulfur atom), N (nitrogen atom), etc. in the carbon chain. That is, the organic group is an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at least at the terminal directly bonded to N and may contain heteroatoms such as O, S, N, etc. in the carbon chain, or represents an aromatic group having an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at the terminal directly bonded to N and may contain heteroatoms such as O, S, N, etc. in the carbon chain. Since the carbon atom directly bonded to N has no π bond, the color characteristics such as the color tone and transmittance of the cationic chromogenic site are not affected by the linking group A or other chromogenic sites, and can retain the same color as the monomer.

[0033] In A, the aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at least at the terminal directly bonded to N may be linear, branched or cyclic as long as the carbon atom at the terminal directly bonded to N has no π bond, the carbon atoms other than the terminal may have an unsaturated bond, may have a substituent, and may contain O, S, N in the carbon chain. For example, a carbonyl group, a carboxy group, an oxycarbonyl group, an amide group, etc. may be contained, and the hydrogen atom may be further substituted with a halogen atom or the like. Further, the aromatic group having the aliphatic hydrocarbon group in A includes a monocyclic or polycyclic aromatic group having an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at least at the terminal directly bonded to N, may have a substituent, and may be a heterocyclic ring containing O, S, N. Among them, from the viewpoint of the robustness of the skeleton, it is preferable that A contains a cyclic aliphatic hydrocarbon group or an aromatic group. Examples of the cyclic aliphatic hydrocarbon group include cyclohexane, cyclopentane, norbornane, bicyclo[2.2.2]octane, tricyclo[5.2.1.0 2,6Examples of groups include those containing decane and adamantane. Aromatic groups include, for example, groups containing benzene rings and naphthalene rings. For example, when A is a divalent organic group, examples include linear, branched, or cyclic alkylene groups having 1 to 20 carbon atoms, or aromatic groups in which two alkylene groups having 1 to 20 carbon atoms, such as xylylene groups, are substituted.

[0034] In the present invention, in order to improve heat resistance by achieving both robustness and freedom of molecular motion, it is preferable that A is an aliphatic hydrocarbon group having two or more cyclic aliphatic hydrocarbon groups, having a saturated aliphatic hydrocarbon group at the terminal directly bonded to N, and possibly containing O, S, and N in the carbon chain. It is more preferable that A is an aliphatic hydrocarbon group having two or more cycloalkylene groups, having a saturated aliphatic hydrocarbon group at the terminal directly bonded to N, and possibly containing O, S, and N in the carbon chain, and among these, it is even more preferable that it has a structure in which two or more cyclic aliphatic hydrocarbon groups are linked by a linear or branched aliphatic hydrocarbon group. The two or more cyclic aliphatic hydrocarbon groups may be the same or different, and examples include those similar to the aforementioned cyclic aliphatic hydrocarbon groups, with cyclohexane and cyclopentane being preferred.

[0035] In the present invention, from the viewpoint of heat resistance, it is preferable that A is a substituent represented by the following general formula (1a).

[0036] [ka] (In general formula (1a), R xi R represents an alkylene group having 1 to 3 carbon atoms, which may have an alkyl group having 1 to 4 carbon atoms as a substituent, or an alkoxy group having 1 to 4 carbon atoms. xii and R xiii Each of the following independently represents an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, p is an integer between 1 and 3, and q and r each independently represent an integer between 0 and 4. xi , R xii , R xiiiAnd if there are multiple R's, xi , R xii , R xiii (And r may be the same or different from each other.)

[0037] R xi Examples of alkylene groups having 1 to 3 carbon atoms include methylene groups, ethylene groups, and propylene groups, with methylene groups or ethylene groups being preferred, and methylene groups being more preferred. Examples of alkyl groups having 1 to 4 carbon atoms include methyl, ethyl, propyl, and butyl groups, and they may be linear or branched. Furthermore, examples of alkoxy groups having 1 to 4 carbon atoms include methoxy, ethoxy, propoxy, and butoxy groups, which may be linear or branched.

[0038] R xii and R xiii In the above, the alkyl group having 1 to 4 carbon atoms and the alkoxy group having 1 to 4 carbon atoms are R xi Examples of substituents that may be present include those similar to those that may be present.

[0039] In general formula (1a), it is preferable from the viewpoint of heat resistance that there are two to four cyclohexane (cyclohexylene groups), that is, that p is between 1 and 3, and more preferably that p is between 1 and 2. Furthermore, substituent R of the cyclohexylene group xii and R xiii The number of substitutions is not particularly limited, but from the viewpoint of heat resistance, it is preferably 1 to 3, and more preferably 1 to 2. That is, it is preferable that q and r are integers between 1 and 3, and more preferably that q and r are integers between 1 and 2.

[0040] The following are some preferred examples of such linking group A, but they are not limited to these.

[0041] [ka]

[0042] R i ~R v The alkyl group in is not particularly limited. For example, linear, branched, or cyclic alkyl groups having 1 to 20 carbon atoms are examples, and among these, linear or branched alkyl groups having 1 to 8 carbon atoms are particularly recommended, and linear or branched alkyl groups having 1 to 5 carbon atoms are recommended from the viewpoint of brightness and heat resistance, R i ~R v The alkyl group in the formula may be an ethyl group or a methyl group. The substituents that the alkyl group may have are not particularly limited, but include, for example, an aryl group, a halogen atom, a hydroxyl group, an alkoxy group, etc., and the substituted alkyl group may be an aralkyl group such as a benzyl group. R i ~R v The aryl group in this is not particularly limited. Examples include a phenyl group and a naphthyl group. Examples of substituents that the aryl group may have include alkyl groups, halogen atoms, alkoxy groups, and hydroxyl groups. In particular, from the standpoint of chemical stability, R i ~R v Each of these independently consists of a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group, or R ii and R iii , R iv and R v It is preferable that these elements are bonded together to form a pyrrolidine ring, a piperidine ring, or a morpholine ring.

[0043] From the standpoint of heat resistance, R ii ~R v Preferably, at least one of them is an optionally substituted cycloalkyl group or an optionally substituted aryl group. ii ~R vAmong them, at least one has a cycloalkyl group or an aryl group, so that the intermolecular interaction due to steric hindrance is reduced, and the influence of heat on the chromogenic site can be suppressed. Therefore, it is considered to have excellent heat resistance.

[0044] From the viewpoint of heat resistance, R ii ~R v It is preferable that at least one of them is a substituent represented by the following general formula (1b) or the following general formula (1c).

[0045]

Chemical formula

[0046]

Chemical formula

[0047] R xiv , R xv , R xvi , R xvii , R xviii , and R xix Examples of the alkyl group having 1 to 4 carbon atoms in R Examples of substituents that the alkyl group and alkoxy group may have include halogen atoms and hydroxyl groups.

[0048] When the substituent represented by the general formula (1b) is present, from the viewpoint of heat resistance, R xiv , R xv , and R xvi Preferably, at least one of them is an alkyl group having 1 to 4 carbon atoms which may have substituents, or an alkoxy group having 1 to 4 carbon atoms which may have substituents, R xiv and R xv It is more preferable that at least one of these is an alkyl group having 1 to 4 carbon atoms, which may have substituents, or an alkoxy group having 1 to 4 carbon atoms, which may have substituents.

[0049] Furthermore, if the substituent represented by the general formula (1c) is present, R xvii , R xviii , and R xix Preferably, at least one of them is an alkyl group having 1 to 4 carbon atoms which may have substituents, or an alkoxy group having 1 to 4 carbon atoms which may have substituents, R xvii and R xviii It is more preferable that at least one of these is an alkyl group having 1 to 4 carbon atoms, which may have substituents, or an alkoxy group having 1 to 4 carbon atoms, which may have substituents.

[0050] The following are, but are not limited to, the substituents represented by general formula (1b) and the substituent represented by general formula (1c).

[0051] [ka]

[0052] R vi and R vii Each of these independently represents an alkyl group which may have substituents, an alkoxy group which may have substituents, a halogen atom, or a cyano group. vi and Rvii The alkyl group in is not particularly limited, but is preferably a linear or branched alkyl group having 1 to 8 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms. Examples of alkyl groups having 1 to 4 carbon atoms include methyl, ethyl, propyl, and butyl groups, which may be linear or branched. Substituents that the alkyl group may have are not particularly limited, but examples include aryl groups, halogen atoms, hydroxyl groups, and alkoxy groups. Also, R vi and R vii The alkoxy group in is not particularly limited, but is preferably a linear or branched alkoxy group having 1 to 8 carbon atoms, and more preferably an alkoxy group having 1 to 4 carbon atoms. Examples of alkoxy groups having 1 to 4 carbon atoms include methoxy, ethoxy, propoxy, and butoxy groups, which may be linear or branched. Substituents that the alkoxy group may have are not particularly limited, but examples include aryl groups, halogen atoms, hydroxyl groups, and alkoxy groups. R vi and R vii Examples of halogen atoms in this context include fluorine, chlorine, bromine, and iodine atoms. R vi and R vii The number of substitutions, i.e., f and g, each independently represents an integer between 0 and 4, preferably between 0 and 2, and more preferably between 0 and 1. Multiple f and g may be the same or different. Also, R vi and R vii It may be substituted at either the triarylmethane skeleton or the aromatic ring having a resonance structure within the xanthene skeleton, but among them, -NR ii R iii or -NR iv R v It is preferable that the amino group represented by is substituted at the meta position relative to the substitution position of the amino group.

[0053] Ar1 The divalent aromatic group in [description] is not particularly limited. Ar 1 The aromatic group in [description] may be a heterocyclic group in addition to the aromatic hydrocarbon group consisting of a carbocyclic ring. Examples of the aromatic hydrocarbon in the aromatic hydrocarbon group include, in addition to the benzene ring, condensed polycyclic aromatic hydrocarbons such as naphthalene ring, tetralin ring, indene ring, fluorene ring, anthracene ring, and phenanthrene ring; chain polycyclic hydrocarbons such as biphenyl, terphenyl, diphenylmethane, triphenylmethane, and stilbene. In the chain polycyclic hydrocarbon, O, S, and N may be present in the chain skeleton as in diphenyl ether. On the other hand, examples of the heterocyclic ring in the heterocyclic group include 5-membered heterocyclic rings such as furan, thiophene, pyrrole, oxazole, thiazole, imidazole, and pyrazole; 6-membered heterocyclic rings such as pyran, pyrone, pyridine, pyrone, pyridazine, pyrimidine, and pyrazine; and condensed polycyclic heterocyclic rings such as benzofuran, thionaphthene, indole, carbazole, coumarin, benzo-pyrone, quinoline, isoquinoline, acridine, phthalazine, quinazoline, and quinoxaline. These aromatic groups may further have, as substituents, an alkyl group, an alkoxy group, a hydroxyl group, a halogen atom, and a phenyl group which may be substituted with these.

[0054] A plurality of Rs within one molecule i ~R vii and Ar 1 may be the same or different. R i ~R vii and Ar 1 can be adjusted to a desired color by their combination.

[0055] The valence a in A is the number of chromogenic cation sites constituting the cation, and a is an integer of 2 or more. In this lake colorant, since the valence a of the cation is 2 or more, it has excellent heat resistance. The upper limit of a is not particularly limited, but from the viewpoint of ease of production, it is preferably a is 4 or less, and more preferably 3 or less.

[0056] In the coloring material represented by the general formula (1), the cation part preferably has a molecular weight of 1200 or more, more preferably 1300 or more, because it has excellent heat resistance and is less likely to change color during heating.

[0057] In the coloring material represented by the general formula (1), the anion part (B c- ) is a polyacid anion with a c-valence and is an anion of 2 or more valences, because it has high brightness and excellent heat resistance.

[0058] As the polyacid anion formed by condensation of multiple oxoacids, it may be an isopolyacid anion (M m O n ) c- or a heteropolyacid anion (X l M m O n ) c- . In the above ion formula, M represents a polyatom, X represents a heteroatom, m represents the composition ratio of the polyatom, n represents the composition ratio of oxygen atoms, and l represents the composition ratio of heteroatoms. Examples of the polyatom M include Mo, W, V, Ti, Nb, etc. Examples of the heteroatom X include Si, P, As, S, Fe, Co, etc. Also, counter cations such as Na + and H + may be included in part. Among them, from the point of excellent heat resistance, it is preferably a polyacid having one or more elements selected from tungsten (W) and molybdenum (Mo). Examples of such polyacids include, for example, isopolyacids such as tungstate ion [W 10 O 32 4- , molybdate ion [Mo6O 19 2- , and heteropolyacids such as phosphotungstate ion [PW 12 O 40 3- , [P2W 18 O 62 6- , silicotungstate ion [SiW 12 O 40 4- , phosphomolybdate ion [PMo​​​​12 O 40 ] 3- , silicic molybdate ion [SiMo 12 O 40 ] 4- Phosphate tungstomolybdate ion [PW 12-s Mo s O 40 ] 3- (s is an integer between 1 and 11), [P2W 18-t Mo t O 62 ] 6- (t is an integer between 1 and 17), cytangustmolybdate ion [SiW 12-u Mo u O 40 ] 4- Examples include (where u is an integer between 1 and 11). Among the polyacids containing at least one of tungsten (W) and molybdenum (Mo), heteropolyacids are preferred from the viewpoint of heat resistance and ease of obtaining raw materials, and heteropolyacids containing phosphorus (P) are even more preferred. Furthermore, phosphotungstomolybdate ions [PW 10 Mo2O 40 ] 3- Now PW 11 Mo1O 40 ] 3- Phosphate tungstate ion [PW 12 O 40 ] 3- It is even more preferable from the viewpoint of heat resistance that it be one of the following.

[0059] In general formula (1), b represents the number of cations and d represents the number of anions in the molecular aggregate, where b and d are integers of 1 or more. When b is 2 or more, the multiple cations in the molecular aggregate may be single or in combination of two or more types. Similarly, when d is 2 or more, the multiple anions in the molecular aggregate may be single or in combination of two or more types. It is preferable that b and d in general formula (1) are different integers, as this makes it easier to improve heat resistance when combined with a hydroxyalkyl (meth)acrylate unit-containing copolymer. When b and d in general formula (1) are different integers, the cation dye molecule interacts easily with the hydroxyalkyl (meth)acrylate unit-containing copolymer, and a complex is easily formed in which the colorant and the copolymer associate. This is presumed to increase the effect of inhibiting thermal motion and improve heat resistance.

[0060] In general formula (1), e is an integer of 0 or 1, and when e is 0, no bond exists. e=0 represents a triarylmethane skeleton, and e=1 represents a xanthene skeleton. Multiple e's may be the same or different. In the lake colorant represented by general formula (1) used in the present invention, one containing at least a triarylmethane skeleton is preferably used. The lake colorant represented by general formula (1) can be prepared, for example, by referring to International Publication No. 2012 / 144520 and International Publication No. 2018 / 003706. The lake colorants represented by general formula (1) may be used individually or in combination of two or more types.

[0061] (Lake colorants represented by general formula (2)) Next, a lake colorant represented by general formula (2), which is preferably used in the present invention, will be described in detail.

[0062] [ka] (In general formula (2), R I ~R VI Each independently represents a hydrogen atom, an optionally substituted alkyl group, or an optionally substituted aryl group, and R I and R II , R III and R IV , R V and R VI They may bond to form a ring structure.VII and R VIII Each of these independently represents an optionally substituted alkyl group, an optionally substituted alkoxy group, a halogen atom, or a cyano group. 2 R represents a divalent aromatic heterocyclic group which may have substituents, and there are multiple R I ~R VIII and Ar 2 They may be the same or different. m- This represents a polyacid anion with m-valence. m represents an integer greater than or equal to 2. j is either 0 or 1; when j is 0, no association exists. k and l represent integers between 0 and 4 (inclusive), and k+j and l+j are between 0 and 4 (inclusive). Multiple j, k, and l may be the same or different.

[0063] In general formula (2), R I ~R VI Each independently represents a hydrogen atom, an optionally substituted alkyl group, or an optionally substituted aryl group, and R I and R II , R III and R IV , R V and R VI These may combine to form a ring structure. I ~R VI Each of these is R in the general formula (1) mentioned above. i ~R v It can be the same as that. In general formula (2), R VII and R VIII Each of these independently represents an optionally substituted alkyl group, an optionally substituted alkoxy group, a halogen atom, or a cyano group, but these also represent the R in the general formula (1) mentioned above. vi and R vii It can be the same as that. In general formula (2), Ar 2 This represents a divalent aromatic heterocyclic group which may have substituents, but the Ar 2 This is the Ar of the general formula (1) mentioned above. 1 Among these, it may be the same as an aromatic heterocyclic group. Also, in general formula (2), E m-The symbol represents an m-valent polyacid anion, and this m-valent polyacid anion may be the same as the c-valent polyacid anion in the general formula (1) mentioned above.

[0064] In general formula (2), m represents the number of cations and anions, and is an integer of 2 or more. The multiple cations in general formula (2) may be single, or two or more may be combined. Similarly, the anions may be single, or two or more may be combined. In general formula (2), j is either 0 or 1, and when j is 0, no association exists. The j in general formula (2) may be the same as the e in general formula (1) mentioned above. Also, the k and l in general formula (2) may be the same as the f and g in general formula (1) mentioned above. The lake colorant represented by general formula (2) can be prepared, for example, by referring to Japanese Patent Publication No. 2017-16099. The lake colorants represented by general formula (2) may be used individually or in combination of two or more types.

[0065] The colorant used in this invention may contain multiple types of colorants to adjust the hue. In the present invention, if the colorant used includes a lake colorant represented by general formula (1) or general formula (2), and further includes another colorant to adjust the hue, the other colorant is preferably at least one selected from the group consisting of xanthene dyes, lake colorants of xanthene dyes different from the lake colorant represented by general formula (1) or general formula (2), and CI pigment blue 15:6, in order to obtain a high-luminosity colored layer.

[0066] (Xanthene-based dyes) The xanthene dye used in combination with the lake colorant represented by the general formula (1) or general formula (2) above can be any dye having a xanthene skeleton in its molecule, and known xanthene dyes can be used, and are not particularly limited. Among these, the xanthene dye represented by the following general formula (3) or general formula (4) is preferred because it can produce a highly luminous colored layer.

[0067] In the photosensitive colored resin composition according to the present invention, the brightness and lightfastness of the colored layer can be improved by using a xanthene dye represented by the following general formula (3).

[0068] [ka] (In general formula (3), R 1 and R 2 Each is independently an alkyl group or an aryl group, and R 3 and R 4 Each of these is independently an aryl group or a heteroaryl group.

[0069] The xanthene dye represented by the above general formula (3) has xanthene as its basic skeleton, and also has only one functional group containing SO2, which is bonded to a nitrogen atom. 1 ~R 4 None of them are hydrogen atoms, R 3 and R 4 Since the group is an aryl group or a heteroaryl group, it is characterized by the absence of a saturated hydrocarbon group bonded solely to the nitrogen atom and the absence of alkali metal ions. The effect of using the xanthene dye represented by the above general formula (3) having such characteristics on improving the brightness and lightfastness of the colored layer is thought to be as follows, although there are still some unexplained aspects. The xanthene dye represented by the above general formula (3) consists of a cationic xanthene skeleton and an anionic -SO3 -Because it has one xanthene group, it is electrically stabilized. Therefore, it is presumed to have excellent stability without dissociating even when dispersed in a solvent. Furthermore, because the nitrogen atom has an aromatic substituent such as an aryl group or a heteroaryl group, it is presumed that the lone pair of electrons on the nitrogen atom resonates not only with the xanthene skeleton but also with the aryl group or heteroaryl group, thereby further stabilizing the molecule. Moreover, since the nitrogen atom is not directly bonded to a hydrogen atom, the hydrogen atom will not detach from the nitrogen atom, preventing the colorant from becoming unstable. From these points, the xanthene dye represented by the general formula (3) is stable even under light irradiation and has excellent lightfastness, and by using this colorant, it is possible to form a colored layer with excellent lightfastness. In addition, as a result of suppressing the fading of the colorant, the brightness of the colored layer can be improved. Furthermore, xanthene dyes represented by the above general formula (3) are R 3 and R 4 Because these elements can be made distinct from one another, the range of molecular design is wide, and this also widens the range of adjustment for spectral characteristics, making it easy to bring the colorant closer to the target chromaticity and further improve its brightness. Furthermore, the xanthene dye represented by the above general formula (3) consists of a cationic xanthene skeleton and an anionic -SO3 - Because it has only one group and contains only an intramolecular salt, it does not contain alkali metal ions. As a result, when a colored layer is formed using the xanthene dye represented by the general formula (3) above, the elution of alkali metal ions from the colored layer to the liquid crystal layer can be suppressed when it is used as a liquid crystal panel, thus making it possible to obtain a colored layer with excellent electrical reliability. Furthermore, since the xanthene dye represented by the above general formula (3) has only one functional group containing SO2, it has a high affinity for low-polarity solvents such as PGMEA. In addition, when dissolving the xanthene dye represented by the above general formula (3) in a solvent, a relatively low-polarity solvent can be used, which can improve the stability of the photosensitive colored resin composition.

[0070] In the above general formula (3), R 1 and R 2The alkyl group in this context is not particularly limited, but examples include linear or branched alkyl groups having 1 to 20 carbon atoms, which may have substituents. Among these, linear or branched alkyl groups having 1 to 8 carbon atoms are preferred, and linear or branched alkyl groups having 1 to 5 carbon atoms are more preferred. The substituents that the alkyl group may have are not particularly limited, but examples include halogen atoms, aryl groups, carbamoyl groups, and -CO-OR groups. a The monovalent group represented by -O-CO-R a’ The monovalent group represented by -SO2-R a” A monovalent group represented by -R b -CO-OR c A monovalent group represented by -R b’ -O-CO-R c’ The monovalent group shown by, and -R b” -SO2-R c” Examples include monovalent groups shown as shown. R 1 ~R 4 The aryl group in this context is not particularly limited, but examples include aryl groups having 6 to 20 carbon atoms, which may have substituents, and among these, groups having a phenyl group, a naphthyl group, etc., are preferred. R 3 and R 4 The heteroaryl group in this context is not particularly limited, but may include a heteroaryl group having 5 to 20 carbon atoms, which may have substituents. Preferably, the heteroatom contains, for example, a nitrogen atom, an oxygen atom, or a sulfur atom. Specific examples of heteroaryl groups include furan, thiophene, pyrrole, and pyridine. The substituents that the aryl group or heteroaryl group may have are not particularly limited, but include, for example, alkyl groups, halogen atoms, alkoxy groups, hydroxyl groups, carbamoyl groups, and -CO-OR groups. a The monovalent group represented by -O-CO-R a’ The monovalent group represented by -SO2-R a” A monovalent group represented by -R b -CO-OR c A monovalent group represented by -R b’ -O-CO-R c’A monovalent group represented by -R b” -SO2-R c” Examples include monovalent groups shown as shown. The aforementioned R a , R a’ , R a” , R c , R c’ and R c” R represents an alkyl group, and the R b , R b’ and R b” The substituents represent alkylene groups. These substituents are preferred because they do not adversely affect heat resistance, etc. By adjusting the electron-withdrawing and electron-donating properties of these substituents, it is possible to adjust the spectral characteristics. Note, R 1 ~R 4 In this case, the alkyl group is preferably unsubstituted or substituted with an aryl group, and the substituent of the aryl group or heteroaryl group is preferably an alkyl group. In this case, the polarity of the xanthene dye represented by general formula (3) is reduced, and thus its affinity for low-polarity solvents such as PGMEA is improved. Furthermore, when dissolving the xanthene dye represented by general formula (3) in a solvent, a lower-polarity solvent can be used, and the stability of the photosensitive colored resin composition is improved by using a low-polarity solvent. Also, R 1 ~R 4 These may be the same or different, and R of the xanthene dye represented by the general formula (3) above. 1 ~R 4 It may be symmetric or asymmetric with respect to the xanthene ring. In particular, R 3 and R 4 When these are different from each other, the range of molecular design for the xanthene dye represented by the general formula (3) is broadened, and the range of adjustment for spectral characteristics is also broadened, which is preferable because it makes it easier to bring the colorant closer to the target chromaticity and further improve the brightness. Furthermore, in the general formula (3) above, the benzene ring bonded to the xanthene skeleton has -SO3 -The substitution position of the group is not particularly limited, but it is preferably in the ortho or para position relative to the xanthene skeleton, and -SO3 - It is preferable from the viewpoint of heat resistance and light resistance that the group is substituted in the ortho position relative to the xanthene skeleton. The mechanism of action is not clear, but -SO3 - It is presumed that when the group is in the ortho position, it can resonate with the carbon atoms of the xanthene skeleton to which the benzene ring is bonded, forming a ring structure, thereby improving heat resistance and light resistance.

[0071] Furthermore, the xanthene dye represented by the general formula (3) is -SO3 - The group can be converted to a -SO3H group and used. - The method for converting the group to the -SO3H group is not particularly limited. Examples include acid treatment methods utilizing weak acid liberation reactions and methods utilizing cation exchange resins. As an acid treatment method, for example, the colorant is dissolved in a good solvent such as methanol and in a solvent in which the acid is soluble, and then the acid is added to produce -SO3 - One method is to convert the group to a -SO3H group. The acid used in this acid treatment method is -SO3 - The acid is not particularly limited as long as it is more acidic than the acid obtained by converting the group to a -SO3H group. Examples of commonly used acids include hydrochloric acid, sulfuric acid, nitric acid, p-toluenesulfonic acid (PTS), and trifluoromethanesulfonic acid. On the other hand, examples of ion exchange resins used in methods utilizing cation exchange resins include sulfonic acid-terminated cation exchange resins such as Diaion PK-216H (product name of Mitsubishi Chemical Corporation). Note that the colorant is -SO3 - The sulfone oxidation treatment to convert the group to a -SO3H group may be performed after dissolving the colorant in a good solvent, without removing the colorant containing the sulfo group (-SO3H) as a solid, and may be carried out when preparing the photosensitive colored resin composition by subsequently adding PGMEA or a dispersant. Alternatively, after sulfone oxidation of the colorant, the colorant containing the sulfo group as a solid may be removed by reprecipitation or recrystallization before preparing the photosensitive colored resin composition. Of these, the former method is preferred from the viewpoint of colorant recovery rate.

[0072] The method for producing the xanthene dye represented by the general formula (3) is not particularly limited, but specifically, the following methods can be cited. The sulfofluorane compound and the corresponding amine compound are refluxed in a solvent, and the reaction mixture is filtered at 60°C to remove insoluble matter. After removing part of the solvent, the mixture is poured into 6% hydrochloric acid. Then, a large amount of water is added and the mixture is stirred at room temperature for 30 minutes, after which the wet cake is filtered off. After washing this wet cake with water or hot water and drying it, the colorant of the above general formula (3) is obtained. Also, R 1 and R 3 and R 2 and R 4 To produce a colorant of general formula (3) that differs in some structural aspects and is asymmetric with respect to the xanthene ring, the asymmetric colorant of general formula (3) can be obtained in high yield by adding half of the corresponding amine compound dropwise in small amounts to a highly diluted methanol solution of the sulfofluorane compound, and after the reaction, adding the remaining amine compound dropwise, or by slowly adding a 1:1 solution of each amine compound dropwise to the methanol solution of the sulfofluorane compound. Furthermore, the xanthene dyes represented by the above general formula (3) may be used individually or in combination of two or more types.

[0073] In the photosensitive colored resin composition according to the present invention, by using a xanthene dye represented by the following general formula (4), the generation of foreign matter can be suppressed and a colored layer with improved brightness can be formed.

[0074] [ka] (In general formula (4), R 5 and R 6 Each of these is independently an aliphatic hydrocarbon group or an aromatic hydrocarbon group which may have substituents, and R 7 and R 8 Each of these is independently an aromatic hydrocarbon group or an aromatic heterocyclic group which may have substituents, and R 7 and R 8At least one aromatic hydrocarbon group or aromatic heterocyclic group of R is substituted with an aliphatic hydrocarbon group, 7 and R 8 They are different from each other. L 1 and L 2 Each of these is independently a direct bond, -SO2-, or -CO-, and R 9 (This is a halogenated aliphatic hydrocarbon group.)

[0075] The xanthene dyes represented by the above general formula (4) have xanthene as their basic structure, as well as specific -L 1 -N - -L 2 -R 9 It has only one functional group containing an anion moiety, and is bonded to a nitrogen atom. 5 ~R 8 None of them are hydrogen atoms, R 7 and R 8 is an aromatic hydrocarbon group or an aromatic heterocyclic group, 7 and R 8 At least one aromatic hydrocarbon group or aromatic heterocyclic group of R is substituted with an aliphatic hydrocarbon group, 7 and R 8 These have the characteristic of being different from each other. The mechanism by which the xanthene dye represented by the above general formula (4), which has such characteristics, can suppress the generation of foreign matter and form a colored layer with improved brightness is thought to be as follows, although there are still some parts that remain unclear. The xanthene dye represented by the above general formula (4) has a monovalent cationic xanthene skeleton and an anionic -L 1 -N - -L 2 -R 9 It has one group and only contains intramolecular salts, making it easily electrically stabilized within a single molecule. On the other hand, it has an anionic -L 1 -N - -L 2 -R 9 In the base, R 9 In this case, the presence of a highly electronegative halogen causes the electrons of the anion moiety to be R 9It is presumed that the ionic bond between molecules is weakened as it is easily attracted to and the anionic properties are weakened. Furthermore, xanthene dyes represented by the above general formula (4) have R that bond with the nitrogen atom. 5 ~R 8 None of them are hydrogen atoms, R 7 and R 8 is an aromatic hydrocarbon group or an aromatic heterocyclic group, 7 and R 8 At least one of them is substituted with an aliphatic hydrocarbon group, R 7 and R 8 Because the elements are different from each other and have an asymmetric structure with respect to the xanthene skeleton, it is presumed that the crystallinity is low, aggregation is difficult, and solvent affinity is high. Due to these synergistic effects, it is presumed that the xanthene dye represented by the above general formula (4) has improved solvent solubility, and when a colored resin composition containing the xanthene dye represented by the above general formula (4) is used to form a colored layer, the generation of foreign matter is suppressed. Furthermore, in the xanthene dye represented by the general formula (4) above, since the nitrogen atom bonded to the xanthene skeleton is not directly bonded to a hydrogen atom, the hydrogen atom does not leave the nitrogen atom and destabilize the colorant. Moreover, because the nitrogen atom has an aromatic substituent such as an aromatic hydrocarbon group or an aromatic heterocyclic group, the lone pair of electrons on the nitrogen atom resonates not only with the xanthene skeleton but also with the aromatic hydrocarbon group or aromatic heterocyclic group, resulting in a highly stable molecular structure. As a result of having such a highly stable molecular structure, the xanthene dye represented by the general formula (4) above has good heat resistance. Furthermore, the xanthene dye represented by the above general formula (4) is R 7 and R 8 At least one aromatic hydrocarbon group or aromatic heterocyclic group of is substituted with an aliphatic hydrocarbon group, 7 and R 8 Because the dyes are different from each other, they are less likely to aggregate, and because they have high solvent solubility, foreign matter is less likely to be generated, and therefore the amount of light transmitted through the colored layer is not reduced. Furthermore, the xanthene dye represented by the above general formula (4) is R 7 and R 8Because these properties differ from one another, and the range of molecular design is wide, the range of adjustment for spectral characteristics, etc., is also wide, making it easy to bring the colorant closer to the target chromaticity and further improve its brightness. As described above, it is estimated that using xanthene dyes represented by the general formula (4) above will suppress the decrease in brightness after baking in the color filter manufacturing process due to their good heat resistance, suppress the aggregation of dyes and the generation of foreign matter in the color filter manufacturing process, and improve the brightness of the colored layer by designing the structure to match the desired chromaticity and adjusting the spectral characteristics, etc.

[0076] In the above general formula (4), R 5 and R 6 The aliphatic hydrocarbon group in this context may be linear, branched, or cyclic, and is not particularly limited. Examples include linear or branched aliphatic hydrocarbon groups having 1 to 20 carbon atoms, or cyclic aliphatic hydrocarbon groups (alicyclic hydrocarbon groups) having 5 to 8 carbon atoms. It is preferable that the number of carbon atoms be 10 or less from the viewpoint of heat resistance. As the aliphatic hydrocarbon group, linear, branched, or cyclic alkyl groups that are saturated aliphatic hydrocarbon groups are preferred. The substituents that the aliphatic hydrocarbon group may have are not particularly limited, but include, for example, halogen atoms, aromatic hydrocarbon groups, carbamoyl groups, and -CO-OR groups. d The monovalent group represented by -O-CO-R d’ The monovalent group represented by -SO2-R d” A monovalent group represented by -R e -CO-OR f A monovalent group represented by -R e’ -O-CO-R f’ The monovalent group shown by, and -R e” -SO2-R f” Examples include monovalent groups shown as shown. R 5 ~R 8 The aromatic hydrocarbon group in this context is not particularly limited, but examples include aromatic hydrocarbon groups having 6 to 20 carbon atoms, which may have substituents, and among these, groups having a phenyl group, a naphthyl group, etc., are preferred. R 7 and R8 The aromatic heterocyclic group in this context is not particularly limited, but may include aromatic heterocyclic groups having 5 to 20 carbon atoms, which may have substituents. Preferably, the heteroatom contains, for example, a nitrogen atom, an oxygen atom, or a sulfur atom. Specific examples of aromatic heterocyclic groups include furan, thiophene, pyrrole, and pyridine. The substituents that an aromatic hydrocarbon group or aromatic heterocyclic group may have are not particularly limited, but include, for example, an aliphatic hydrocarbon group, a halogen atom, an alkoxy group, a hydroxyl group, a carbamoyl group, or a -CO-OR group. d The monovalent group represented by -O-CO-R d’ The monovalent group represented by -SO2-R d” A monovalent group represented by -R e -CO-OR f A monovalent group represented by -R e’ -O-CO-R f’ A monovalent group represented by -R e” -SO2-R f” Examples include monovalent groups shown in R. e , R e’ , R e” , R d , R d’ , R d” , R f , R f’ and R f” R represents an aliphatic hydrocarbon group. These substituents are preferred because they do not adversely affect heat resistance, etc. By adjusting the electron-withdrawing and electron-donating properties of these substituents, it is possible to adjust the spectral characteristics. In this case, the aliphatic hydrocarbon group is R 5 and R 6 It may be similar to the aliphatic hydrocarbon group in [the relevant context].

[0077] Because it suppresses the generation of foreign matter and makes it easier to form a colored layer with improved brightness, R 5 and R 6 At least one of them is preferably an aliphatic hydrocarbon group, R 5 and R 6It is preferable that the group is an aliphatic hydrocarbon group, and more preferably a linear aliphatic hydrocarbon group. The aliphatic hydrocarbon group is preferably one to ten carbon atoms, and more preferably a linear alkyl group with one to six carbon atoms. Because it suppresses the generation of foreign matter and makes it easier to form a colored layer with improved brightness, R 7 and R 8 At least one of them is preferably an aromatic hydrocarbon group, R 7 and R 8 It is preferable that the group is an aromatic hydrocarbon group. The aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 10 carbon atoms, and more preferably a phenyl group. Furthermore, R is an aromatic hydrocarbon group or an aromatic heterocyclic group which may have substituents. 7 and R 8 At least one of them is substituted with an aliphatic hydrocarbon group, R 7 and R 8 These are different things from one another. The aliphatic hydrocarbon group substituted for the hydrogen atom of the aromatic hydrocarbon group or aromatic heterocyclic group is preferably a linear aliphatic hydrocarbon group. The aliphatic hydrocarbon group is preferably a linear alkyl group having 1 to 10 carbon atoms, and more preferably a linear alkyl group having 1 to 6 carbon atoms. 7 and R 8 It is preferable that both of them are substituted with aliphatic hydrocarbon groups as described above. Also, R 7 and R 8 It is preferable that at least one aromatic hydrocarbon group or aromatic heterocyclic group is substituted with two or more aliphatic hydrocarbon groups per aromatic hydrocarbon group or aromatic heterocyclic group, as this suppresses the generation of foreign matter and facilitates the formation of a colored layer with improved brightness. Also, R 5 , R 6 , R 7 and R 8 If any one of the aliphatic hydrocarbon groups contained in the molecule is a linear alkyl group having 2 or more carbon atoms, and furthermore, has 3 or more carbon atoms, it tends to be easier to adjust the electron density in the molecule. R 5 and R 6 In cases where at least one of is substituted with a straight-chain alomethic hydrocarbon group, R 7 and R 8 When at least one aromatic hydrocarbon group or aromatic heterocyclic group is substituted with a linear alkyl group having 2 or more carbon atoms, the generation of foreign matter is easily suppressed, and a colored layer with improved brightness tends to be formed.

[0078] Also, R 5 ~R 8 In this case, the aliphatic hydrocarbon group is preferably unsubstituted, or if it is a branched or linear alkyl group, the substituent is preferably an aromatic hydrocarbon group, and the substituent of the aromatic hydrocarbon group or aromatic heterocyclic group is preferably an aliphatic hydrocarbon group. In such cases, the polarity of the xanthene dye represented by the general formula (4) decreases, and thus its affinity for low-polarity solvents such as PGMEA is improved. Furthermore, when dissolving the colorant in a solvent, a lower-polarity solvent can be used, and the stability of the photosensitive colored resin composition of the present invention is improved by using a low-polarity solvent. In particular, from the viewpoint of improving affinity for low-polarity solvents, it is preferable that the substituent of the aromatic hydrocarbon group or aromatic heterocyclic group consists only of an aliphatic hydrocarbon group.

[0079] -L 1 -N - -L 2 -R 9 In the base, L 1 and L 2 Each of these can be directly bonded, -SO2-, or -CO-, but -SO2- or -CO- is preferred, and -SO2- is even more preferred because it suppresses the generation of foreign matter, has excellent heat resistance, and facilitates the formation of a colored layer with improved brightness.

[0080] -L 1 -N - -L 2 -R 9 In the base, R 9The halogen is a halogenated aliphatic hydrocarbon group, and examples of halogens include fluorine atoms, chlorine atoms, iodine atoms, etc., with fluorine atoms being preferred. 9 The halogenated aliphatic hydrocarbon group is preferably a linear or branched halogenated aliphatic hydrocarbon group having 1 to 8 carbon atoms, more preferably a linear or branched halogenated aliphatic hydrocarbon group having 1 to 5 carbon atoms, and even more preferably a linear or branched halogenated aliphatic hydrocarbon group having 1 to 3 carbon atoms. In particular, the substitution rate of halogen atoms in the aliphatic hydrocarbon group (number of halogen atoms / total number of hydrogen atoms in the aliphatic hydrocarbon group) is preferably 50% or more, more preferably 70% or more, and most preferably 100%. R 9 Among these, a linear or branched perfluoroalkyl group having 1 to 5 carbon atoms is preferred.

[0081] Furthermore, in the general formula (4) above, the benzene ring bonded to the xanthene skeleton has -L 1 -N - -L 2 -R 9 The substitution position of the group is not particularly limited, but it is preferably in the ortho or para position relative to the xanthene skeleton, and -L 1 -N - -L 2 -R 9 The substitution of the group in the ortho position relative to the xanthene skeleton is preferable in terms of the various resistances of the xanthene dye represented by the general formula (4). The mechanism of action is not clear, but -L 1 -N - -L 2 -R 9 When the group is in the ortho position, it can resonate with the carbon atoms of the xanthene skeleton to which the benzene ring is bonded, forming a ring structure. This is thought to increase the molecular stability, thereby improving the various resistances of the colorant.

[0082] The method for producing the xanthene dye represented by the general formula (4) is not particularly limited, but specifically, the following methods can be cited. Sulfofluorane compounds and R 7 and R 8 The corresponding amine compound is refluxed in a solvent at 60°C, and the reaction solution is filtered at 60°C to remove insoluble matter. After removing part of the solvent, the mixture is poured into 6% hydrochloric acid. Then, a large amount of water is added and the mixture is stirred at room temperature for 30 minutes, after which the wet cake is filtered off. After washing this wet cake with water or hot water and drying it, an intermediate of the dye represented by the above general formula (4) is obtained. In this invention, R 7 and R 8 To produce a dye of general formula (4) that is asymmetric with respect to the xanthene ring due to a difference in some of its structure, an intermediate of the asymmetric dye represented by general formula (4) can be obtained in high yield by adding the corresponding half of the amine compound dropwise in small amounts to a highly diluted methanol solution of the sulfofluorane compound, and after the reaction, adding the remaining half of the amine compound dropwise, or by slowly adding a 1:1 solution of each amine compound dropwise to the methanol solution of the sulfofluorane compound. Next, the pigment intermediate represented by general formula (4) is prepared in a polar solvent such as 1-methyl-2-pyrrolidinone in the presence of a base such as potassium carbonate, R 5 and R 6 The reaction is carried out with the corresponding halide at 80°C for 2 hours with stirring. After the reaction is complete, the reaction solution is allowed to cool to room temperature, and then the reaction solution is added dropwise to 17.5% hydrochloric acid at 0-10°C and stirred for 1 hour. After that, the precipitate is filtered off, and the residue is dried at 60°C for 24 hours to obtain a precursor of the dye represented by general formula (4). Next, trifluoromethylsulfonamide is dissolved in chloroform and triethylamine is added dropwise to the asymmetrical colorant precursor of general formula (4) and the reaction is allowed to proceed. After that, the resulting reaction solution is washed with water, and then the organic layer is separated. This organic layer is dried over sodium sulfate, purified by column chromatography, and concentrated under reduced pressure to obtain the xanthene dye represented by the above general formula (4). Also, L 1 When represented by -CO-, a fluorane compound can be used instead of a sulfofluorane compound, and a xanthene dye represented by the above general formula (4) can be obtained in the same manner thereafter.

[0083] The xanthene dye represented by the general formula (4) has high solvent solubility even in low-polarity solvents, and therefore has solvent solubility at the concentration required for colored layer applications without the need to use a solvent containing alcoholic hydroxyl groups. The xanthene dye represented by the general formula (4) preferably has a solubility of 2.0 (g / 100g solvent) or more, and more preferably 2.5 (g / 100g solvent) or more, in at least one of propylene glycol monomethyl ether acetate, 3-methoxy-3-methyl-1-butyl acetate, and diethylene glycol ethyl methyl ether at 23°C. Furthermore, the xanthene dye represented by the general formula (4) may be used alone or in combination of two or more types.

[0084] (xanthene-based dye lake pigment) The lake colorant of a xanthene dye used in combination with the lake colorant represented by the general formula (1) or general formula (2) is not particularly limited, and for example, a lake colorant of a known xanthene dye different from the lake colorant represented by the general formula (1) or general formula (2) can be used. In particular, a metallic lake colorant of a xanthene dye, which is laked with a lake agent containing metal atoms, is preferably used because it has excellent heat resistance and dispersibility of the colorant and can produce a high-brightness colored layer. A metallic lake colorant is a lake colorant to which a metal has been added as a lake agent.

[0085] Among lake colorants of xanthene dyes different from the lake colorants represented by the general formula (1) or general formula (2) above, lake colorants of xanthene dyes having a phenyl group at the 9-position of the xanthene skeleton are preferred. Specifically, lake colorants obtained by lakeping a xanthene dye represented by the following general formula (5) with a lake agent are preferred, and in particular, metallic lake colorants obtained by lakeping a xanthene dye represented by the following general formula (5) with a lake agent containing a metal atom are preferred.

[0086] [ka] (In general formula (5), R 1’ , R 2’ , R 3’ and R 4’ Each of these independently represents a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group, and R 1’ and R 3’ , R 2’ and R 4’ Each of them may bond to form a ring structure, R 1’ and the carbon atom at position 5 of the xanthene ring, R 3’ and the carbon atom at position 7 of the xanthene ring, R 2’ and the carbon atom at position 4 of the xanthene ring, or R 4’ The carbon atoms at position 2 of the xanthene ring may be bonded to each other to form a ring structure. The hydrogen atoms of the above aryl group or heteroaryl group may be substituted with an acidic group or a salt thereof, or a halogen atom. 5’ x represents an acidic group or a salt thereof, and x is an integer between 0 and 5. However, general formula (5) has at least two acidic groups or salts thereof, one of which forms an intramolecular salt.

[0087] R 1’ ~R 4’ The alkyl group in is preferably a linear or branched alkyl group having 1 to 20 carbon atoms, which may have substituents; more preferably a linear or branched alkyl group having 1 to 8 carbon atoms; and even more preferably a linear or branched alkyl group having 1 to 5 carbon atoms. The substituents that the alkyl group may have are not particularly limited, but examples include aryl groups and halogen atoms, and the aryl group may further have halogen atoms, acidic groups or salts thereof as substituents. R 1’ ~R 4’ In this context, the aryl group is preferably an aryl group having 6 to 20 carbon atoms, and more preferably a group having a phenyl group, a naphthyl group, etc. Also, R 1’ ~R 4’In this context, the heteroaryl group is preferably a heteroaryl group which may have substituents with 5 to 20 carbon atoms, and preferably contains a nitrogen atom, an oxygen atom, and a sulfur atom as heteroatoms. Examples of substituents that the aryl group or heteroaryl group may have include C1-C5 alkyl groups, halogen atoms, acidic groups or their salts, hydroxyl groups, alkoxy groups, nitrile groups, carbamoyl groups, carboxylic acid ester groups, and the like.

[0088] R 1’ and R 3’ , R 2’ and R 4’ The fact that they are each bonded together to form a ring structure means that R 1’ and R 3’ , R 2’ and R 4’ This refers to the fact that each element forms a ring structure via a nitrogen atom. The ring structure is not particularly limited, but examples include 5- to 7-membered nitrogen-containing heterocycles, specifically pyrrolidine rings, piperidine rings, morpholine rings, etc. Also, R 1’ and the carbon atom at position 5 of the xanthene ring, R 3’ and the carbon atom at position 7 of the xanthene ring, R 2’ and the carbon atom at position 4 of the xanthene ring, or R 4’ The fact that the carbon atom at position 2 of the xanthene ring is bonded to it and forms a ring structure means that R 1’ ~R 4’ This means that the above combinations with carbon atoms at predetermined positions on the xanthene ring each form a ring structure via a nitrogen atom and a part of the xanthene skeleton. The ring structure is not particularly limited, but examples include nitrogen-containing heterocycles with 5 to 7 members.

[0089] Specific examples of acidic groups or their salts include carboxyl groups (-COOH), carboxylato groups (-COO-), carboxylic acid bases (-COOM, where M represents a metal atom), sulfonate groups (-SO3-), sulfo groups (-SO3H), and sulfonic acid bases (-SO3M, where M represents a metal atom). Among these, it is preferable to have at least one of the sulfonate group (-SO3-), sulfo group (-SO3H), or sulfonic acid base (-SO3M). Examples of metal atoms M include sodium atoms and potassium atoms.

[0090] Specific examples of xanthene dyes represented by the above general formula (5) include Acid Red 50, Acid Red 52, Acid Red 289, Acid Violet 9, Acid Violet 30, Acid Blue 19, and the like.

[0091] <Lake-forming agent> The lake agent used for lake formation of xanthene dyes is any lake agent containing metal atoms. Preferably, the lake agent contains metal atoms that become divalent or higher metal cations. Specifically, examples include barium chloride, calcium chloride, calcium carbonate, aluminum chloride, aluminum sulfate, aluminum acetate, lead acetate, magnesium sulfate, zirconium chloride, zirconium sulfate, zirconium carbonate, polyaluminum chloride, and polyaluminum sulfate. Among these, lake agents containing metal atoms that become trivalent or higher metal cations are more preferable. Furthermore, lake agents containing aluminum are preferable in terms of ease of synthesis of the lake agent and excellent dispersibility of the lake agent. That is, as a xanthene dye metal lake agent, an aluminum lake agent of a xanthene dye is preferred, and an aluminum lake agent of a xanthene dye represented by the above general formula (5) is particularly preferred. By using a lake agent containing aluminum, which forms a trivalent cation, it is estimated that the lake agent exhibits even stronger cohesive force compared to lake agents containing metal atoms that form a divalent metal cation. As a result, the solubility of the laked xanthene dye in solvents is significantly reduced, resulting in properties closer to those of a pigment. This provides advantages such as superior dispersibility and heat resistance of the colorant, as well as the ease of recovering (filtering) the lake colorant during colorant manufacturing.

[0092] Among the aluminum-containing lake agents, polyaluminum chloride represented by the following general formula (6) is preferred because it exhibits excellent heat resistance of the colorant and effectively suppresses sublimation of the colorant.

[0093] [ka] (In general formula (6), n is an integer between 2 and 20, and m is an integer between (n / 2) and (3n-1).)

[0094] In the polyaluminum chloride represented by the general formula (6) above, n represents the number of aluminum atoms, which is between 2 and 20. By using polyaluminum chloride with a relatively small number of aluminum atoms (2 to 20) as a lake agent, the dispersion particle size of the colorant does not become too large, and the dispersibility of the colorant can be improved. In the present invention, it is particularly preferable that n is an integer between 2 and 10.

[0095] Furthermore, in the polyaluminum chloride represented by the above general formula (6), m is a hydroxyl group (OH - This represents the base number and is an integer between (n / 2) and (3n-1). If n is odd, the lower bound of m is the smallest integer within the above range, which is {(n+1) / 2}.

[0096] In polyaluminum chloride, the aluminum has trivalent cationic properties, and the hydroxyl group has monovalent anionic properties; therefore, the polyaluminum chloride as a whole has (3n-m) valent cationic properties. In the present invention, a higher basicity is preferred because it has strong cohesive force, facilitates the recovery of the colorant, and has excellent dispersibility of the colorant, and it is preferable that m is an integer from 2n to (3n-1). In particular, in the polyaluminum chloride represented by the above general formula (6), it is preferable that n is an integer from 2 to 10 and m is an integer from 2n to (3n-1) because this improves the dispersibility of the colorant and the contrast of the coating film.

[0097] Furthermore, polyaluminum chloride represented by general formula (6) is preferable to have a basicity defined as (m / 3n × 100 (%)) of 15 to 99%, more preferably 60 to 97%, and even more preferably 70 to 95%, because it improves the heat resistance of the colorant, suppresses sublimation of the colorant, and improves the dispersibility of the colorant.

[0098] (CI Pigment Blue 15:6) The CI pigment blue 15:6, which is preferably used in the present invention, is a copper phthalocyanine pigment having an ε-type crystalline structure, and is preferred because of its excellent dispersion stability. The CI pigment blue 15:6 used in the present invention may be treated with a basic solution or an acidic solution. In terms of excellent dispersibility and storage stability, it is preferable that the CI pigment blue 15:6 used in combination with an acidic solution be treated with a basic solution, and it is preferable that the CI pigment blue 15:6 used in combination with an acidic solution be treated with an acidic solution.

[0099] In the present invention, a colorant derivative having a basic moiety or a derivative of a colorless compound having a basic moiety is preferably used for the basic treatment. Furthermore, in the present invention, having a basic moiety refers to a form in which a basic group is present as a substituent, or a form in which an acidic group and a basic compound form a salt at the substituent. Examples of basic sites in the colorant derivative or colorless compound derivative of the present invention include an amino group, an ammonium sulfonate salt, or a sulfonamide group having an amino group, an amide group having an amino group, or a basic heterocyclic group.

[0100] The colorant used in the colorant derivative having a basic moiety can be any known colorant as appropriate, but it is preferable that it has a structure that readily adsorbs to CI Pigment Blue 15:6, and preferably has the same or similar pigment skeleton or a structure that readily interacts with it. Furthermore, it is preferable that the colorant does not impair the color of CI Pigment Blue 15:6 used in the basic treatment. Among the colorant derivatives having a basic moiety, blue colorant derivatives are particularly preferred. While phthalocyanine-based colorants, triarylmethane-based colorants, anthraquinone-based colorants, naphthol-based colorants, and benzimidazolon-based colorants can be used as blue colorants in colorant derivatives having a basic moiety, phthalocyanine-based colorants are preferred in terms of color and heat resistance. In particular, phthalocyanine-based colorants having the same structure as CI Pigment Blue 15:6 used in basic treatment are preferred in terms of improved dispersibility and brightness. Furthermore, copper phthalocyanine is preferred as the blue colorant used in colorant derivatives having a basic moiety in terms of improved dispersibility and brightness.

[0101] The colorless compound used as a derivative of a colorless compound having a basic moiety can be defined as a compound that does not change the color of CI Pigment Blue 15:6 before and after basic treatment with the derivative of the colorless compound. Examples of such colorless compounds include condensed ring compounds such as naphthalene-based and triazine-based compounds, and aromatic polycyclic compounds in which multiple aromatic rings are bonded. An example of a triazine-based aromatic polycyclic compound is a structure in which three substituents having aromatic hydrocarbon groups such as phenylamino groups are substituted on the triazine ring. Among these, it is preferable to use a triazine-based aromatic polycyclic compound because it improves dispersibility and brightness.

[0102] As an example of a method for preparing CI Pigment Blue 15:6 having a structure derived from a basic compound, including a colorant derivative having a basic moiety, one method is to dry-grind the colorant derivative having a basic moiety and CI Pigment Blue 15:6, and then further mix in the colorant derivative having a basic moiety. In this case, a ball mill, vibratory mill, attritor, etc., can be used as the dry grinder, and the grinding temperature can be freely set between 20 and 130°C. Furthermore, a method for preparing CI Pigment Blue 15:6 containing a colorant derivative having a basic moiety includes mixing the colorant derivative having a basic moiety, CI Pigment Blue 15:6, a water-soluble inorganic salt such as sodium chloride, calcium chloride, or ammonium sulfate, and a water-soluble organic solvent such as a glycol-based organic solvent, and then kneading the mixture using a kneader-type polishing machine in a solvent-salt milling process. By preparing or creating a basicized CI pigment blue 15:6 solution before dispersing the colorants, the dispersibility of the colorants can be improved.

[0103] In CI Pigment Blue 15:6 containing a colorant derivative having a basic moiety or a derivative of a colorless compound, the content of the colorant derivative having a basic moiety or the derivative of a colorless compound is preferably 0.5 parts by mass or more, more preferably 3 parts by mass or more, even more preferably 5 parts by mass or more, and even more preferably 8 parts by mass or more, per 100 parts by mass of CI Pigment Blue 15:6, from the viewpoint of dispersibility and storage stability. On the other hand, the content of the colorant derivative having a basic moiety or the derivative of a colorless compound is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, and even more preferably 30 parts by mass or less, per 100 parts by mass of CI Pigment Blue 15:6, from the viewpoint of excellent brightness.

[0104] Furthermore, whether the CI pigment blue 15:6 has been treated with a basic or acidic method can be appropriately analyzed using, for example, mass spectrometry, elemental analysis, surface analysis, potentiometric titration, or a combination thereof. Furthermore, examples of acidic dispersants used in combination with basicized CI pigment blue 15:6 include those similar to the acidic dispersants that can be used in the colorant dispersion described later.

[0105] In the present invention, in order to easily improve the brightness of the colored layer, the total content of dye and lake colorant is preferably 5 parts by mass or more and 100 parts by mass or less, and more preferably 10 parts by mass or more and 100 parts by mass or less, per 100 parts by mass of the total amount of colorant. In particular, in order to obtain a high-brightness colored layer and to improve the development residue suppression effect by improving the compatibility between the colorant and the hydroxyalkyl (meth)acrylate unit-containing copolymer, it is preferable that the content of lake colorant be 20 parts by mass or more and 100 parts by mass or less, and more preferably 30 parts by mass or more and 100 parts by mass or less, per 100 parts by mass of the total amount of colorant. Furthermore, in order to obtain a more luminous colored layer, it is preferable that the total content of the lake colorant represented by general formula (1) or general formula (2) is 20 parts by mass or more and 100 parts by mass or less, and more preferably 30 parts by mass or more and 100 parts by mass or less, per 100 parts by mass of the total amount of colorant. It is also preferable that the total content of the lake colorant represented by general formula (1) or general formula (2) is equal to or greater than the lower limit, as this improves the compatibility between the colorant and the hydroxyalkyl (meth)acrylate unit-containing copolymer, thereby improving the effect of suppressing developing residue and improving heat resistance. When the colorant contains a combination of a lake colorant represented by general formula (1) or general formula (2) and a colorant different from the lake colorant, it is colored to obtain a desired color, and although not particularly limited, the total content of the lake colorant represented by general formula (1) or general formula (2) per 100 parts by mass of the total amount of colorant is preferably 20 parts by mass or more and 98 parts by mass or less, and may be 30 parts by mass or more and 95 parts by mass or less, from the standpoint of obtaining a high-brightness colored layer, improving the development residue suppression effect by improving the compatibility between the colorant and the hydroxyalkyl (meth)acrylate unit-containing copolymer, and improving heat resistance. If the colorant includes a lake colorant represented by general formula (1) or general formula (2), a xanthene dye, and at least one selected from the group consisting of lake colorants of xanthene dyes different from those represented by general formula (1) or general formula (2), the total content of the xanthene dye and the lake colorant of the xanthene dye per 100 parts by mass of the total amount of the colorant may be 2 parts by mass or more, or 5 parts by mass or more, from the viewpoint of obtaining the desired hue, while preferably 30 parts by mass or less, and may also be 25 parts by mass or less, from the viewpoint of suppressing a decrease in heat resistance. Furthermore, when the colorant contains a lake colorant represented by the general formula (1) or general formula (2) and CI pigment blue 15:6, the content of CI pigment blue 15:6 per 100 parts by mass of the total amount of colorant may be 20 parts by mass or more, or 30 parts by mass or more, from the viewpoint of obtaining the desired hue, while it is preferable to be 80 parts by mass or less, and may be 70 parts by mass or less, from the viewpoint of suppressing a decrease in the brightness of the colored layer and suppressing the generation of development residue and a decrease in the heat resistance of the colorant.

[0106] Furthermore, the content of dyes and lake colorants in the photosensitive colored resin composition of the present invention is usually 0.5% by mass or more and 35% by mass or less, preferably 1% by mass or more and 30% by mass or less, and more preferably 2% by mass or more and 25% by mass or less, relative to the total solid content.

[0107] <Other pigments> The photosensitive colored resin composition of the present invention may further use other pigments different from the CI pigment blue 15:6 described above to adjust the color tone, as long as the effects of the present invention are not impaired. These other pigments can be various organic and inorganic pigments conventionally used as colorants for color filters, and are not particularly limited; however, organic pigments are preferred due to their excellent color development and heat resistance.

[0108] For blue applications, other pigments that are preferable due to their excellent dispersion stability include blue pigments such as copper phthalocyanine pigments having an ε-type or β-type crystal structure, and purple pigments such as CI Pigment Violet 23. Among the copper phthalocyanine pigments having an ε-type or β-type crystal structure, at least one selected from the group consisting of CI Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, and 15:5 is preferably used. Furthermore, the other pigments mentioned above may be treated with acid or alkali to improve dispersion stability, similar to CI Pigment Blue 15:6. It is preferable that the other pigments are treated with alkali if the dispersant used in combination is acidic, and preferably with acid if the dispersant used in combination is alkali.

[0109] In the present invention, it is preferable that the above-mentioned other pigments are used in an amount that does not impair the effects of the present invention. Specifically, it is preferable that the content of the above-mentioned other pigments be 25% by mass or less with respect to the total amount of solids in the photosensitive colored resin composition, or that the content of the above-mentioned other pigments be 80 parts by mass or less with respect to 100 parts by mass of the total amount of dye and lake colorant. Furthermore, the smaller of the above two upper limits is considered the more preferable upper limit.

[0110] [Binder resin] <Hydroxyalkyl (meth)acrylate unit-containing copolymer> The binder resin contained in the photosensitive colored resin composition according to the present invention has a polymer structure containing 5 to 25% by mass of constituent units derived from hydroxyalkyl (meth)acrylate represented by general formula (A) described later, and includes a copolymer (hydroxyalkyl (meth)acrylate unit-containing copolymer) having a weight-average molecular weight of 11,000 or more and an acid value of 60 to 130 mgKOH / g. The above-mentioned hydroxyalkyl (meth)acrylate unit-containing copolymer is an alkali-soluble copolymer that contains hydroxyalkyl (meth)acrylate-derived structural units within the chain structure of its polymer backbone. The polymeric structure of a hydroxyalkyl (meth)acrylate unit-containing copolymer may consist only of a main chain, or it may consist of a main chain and side chains. The main chain of a hydroxyalkyl (meth)acrylate unit-containing copolymer typically has a chain structure in which constituent units produced by the addition polymerization of monomers having ethylenically unsaturated bonds are linked, and may further contain constituent units produced by the addition polymerization or condensation polymerization of monomers having functional groups other than ethylenically unsaturated bonds. The side chains of hydroxyalkyl (meth)acrylate unit-containing copolymers are typically attached to the main chain via linking groups formed by the reaction of functional groups on the main chain with functional groups of monomers for forming the side chains, and may also branch off from the main chain via carbon-carbon bonds. As an example of how a side chain is formed by the reaction of a functional group on the main chain with a functional group of a monomer used to form the side chain, if a carboxyl group is present on the main chain, an ester linking group can be formed by reacting this carboxyl group with a monomer having a glycidyl group, and a side chain consisting of structural units derived from the monomer having a glycidyl group can be introduced. Another example is when a hydroxyl group is present on the main chain, a urethane linking group can be formed by reacting this hydroxyl group with a monomer having an isocyanate group, and a side chain consisting of structural units derived from the monomer having an isocyanate group can be introduced. The side chain may be a pendant structure having a single monomer component, or it may have a polymer structure in which two or more component units are linked together. Furthermore, if the side chain has a polymer structure, it may consist only of component units derived from monomers having ethylenically unsaturated bonds, or it may include component units produced by addition polymerization or condensation polymerization of monomers having functional groups other than ethylenically unsaturated bonds. Hydroxyalkyl (meth)acrylate unit-containing copolymers may contain, as needed, atomic groups such as acidic groups that impart alkali solubility, other functional groups such as ethylenically double-bond-containing groups, and groups that modify the molecular structure, such as bulky groups, in addition to the hydroxyl groups derived from hydroxyalkyl (meth)acrylate. These groups may be present in either the main chain or the side chains.

[0111] A suitable example of a hydroxyalkyl (meth)acrylate unit-containing copolymer is a copolymer in which a main chain containing hydroxyalkyl (meth)acrylate-derived structural units, structural units having acidic groups, structural units having bulky groups, and other structural units as needed, is bonded to a side chain containing structural units having photopolymerizable functional groups such as ethylenically unsaturated bonds. Such hydroxyalkyl (meth)acrylate unit-containing copolymers are given alkali solubility by acidic groups on the main chain and crosslinking ability by photopolymerizable functional groups on the side chains. When a hydroxyalkyl (meth)acrylate unit-containing copolymer has photopolymerizable functional groups, crosslinking can be formed between binder resins, or between binder resins and photopolymerizable monomers, etc., during the curing process of the resin composition in the manufacture of color filters. As a result, the film strength of the cured film is further improved, development resistance is enhanced, and thermal shrinkage of the cured film is suppressed, resulting in excellent adhesion to the substrate.

[0112] As a suitable hydroxyalkyl (meth)acrylate unit-containing copolymer, for example, a main chain portion can be synthesized by copolymerizing a hydroxyalkyl (meth)acrylate having an alkylene group having 1 to 4 carbon atoms, an ethylenically unsaturated monomer having an acidic group, an ethylenically unsaturated monomer having a bulky group, and, if necessary, other ethylenically unsaturated monomers. Then, a photopolymerizable functional group-containing monomer having a functional group that reacts with a functional group on the main chain to form a bond and a photopolymerizable functional group can be reacted to produce a hydroxyalkyl (meth)acrylate unit-containing copolymer with a side chain having a photopolymerizable functional group. The constituent units that make up the main chain and side chain of the hydroxyalkyl (meth)acrylate unit-containing copolymer, and the monomers used to form said constituent units, are described below.

[0113] (Constituent units derived from hydroxyalkyl (meth)acrylate represented by general formula (A)) The constituent units derived from hydroxyalkyl (meth)acrylate, represented by the general formula (A) below (hereinafter sometimes referred to as "hydroxyalkyl (meth)acrylate units"), have a chemical structure in which the ethylenic double bond of a hydroxyalkyl (meth)acrylate having an alkylene group with 1 to 4 carbon atoms is cleaved by an addition reaction, resulting in the formation of two single bonds.

[0114] [ka] (In general formula (A), R A R represents a methyl group or a hydrogen atom. B (This represents an alkylene group with 1 to 4 carbon atoms.)

[0115] Among the constituent units derived from hydroxyalkyl (meth)acrylate represented by the general formula (A), R in the general formula (A) is particularly... A A constituent unit derived from hydroxyalkyl methacrylate, in which the group is a methyl group, is preferred. Specific examples of the hydroxyalkyl (meth)acrylate unit represented by the general formula (A) above include, for example, constituent units derived from hydroxyalkyl (meth)acrylates such as hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxy-1-methylethyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, and 2-hydroxyisobutyl (meth)acrylate. Among these, constituent units derived from 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 2-hydroxy-1-methylethyl (meth)acrylate are preferred, and constituent units derived from 2-hydroxyethyl (meth)acrylate are particularly preferred.

[0116] In the present invention, the amount of hydroxyalkyl (meth)acrylate units contained in the hydroxyalkyl (meth)acrylate unit-containing copolymer is 5% by mass or more and 25% by mass or less, based on 100% by mass of the total amount of constituent units constituting the copolymer. By setting the amount of hydroxyalkyl (meth)acrylate units within the above range, a colored layer with excellent flatness and suppressed developing residue can be obtained. If the amount of hydroxyalkyl (meth)acrylate units is less than 5% by mass, the fluidization of the coating film cannot be sufficiently suppressed when the photosensitive colored resin composition coating film is heat-dried, resulting in poor flatness of the resulting colored layer. On the other hand, if the amount of hydroxyalkyl (meth)acrylate units exceeds 25% by mass, the viscosity of the photosensitive colored resin composition increases, leading to poor coatability or a decrease in the solvent resolubility of the photosensitive colored resin composition, making it easier for foreign matter or unevenness to occur in the resulting colored layer. The amount of hydroxyalkyl (meth)acrylate units contained in the hydroxyalkyl (meth)acrylate unit-containing copolymer is preferably 5% by mass or more and 20% by mass or less.

[0117] (Constituent units having acidic groups) In the constituent units having an acidic group, examples of acidic groups include carboxyl groups, phosphoric acid groups, sulfo groups, etc., but among these, the carboxyl group is preferred because it is easy to introduce a side chain having a photopolymerizable functional group. As a constituent unit having an acidic group, for example, a constituent unit derived from an ethylenically unsaturated monomer having a carboxyl group can be preferably used. A constituent unit derived from an ethylenically unsaturated monomer having a carboxyl group has a chemical structure in which the ethylenically unsaturated bond of the ethylenically unsaturated monomer having a carboxyl group is cleaved by an addition reaction, resulting in the formation of two single bonds. In this invention, the constituent units derived from ethylenically unsaturated monomers refer to constituent units in which the radically polymerizable carbon-carbon double bond of an ethylenically unsaturated monomer has been replaced with a carbon-carbon single bond. Examples of ethylenically unsaturated monomers having a carboxyl group include (meth)acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl esters, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, and acrylate dimers. Addition reaction products of monomers having a hydroxyl group, such as 2-hydroxyethyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate, with cyclic anhydrides such as maleic anhydride, succinic anhydride, phthalic anhydride, and cyclohexanedicarboxylic acid anhydride, as well as ω-carboxy-polycaprolactone mono(meth)acrylate, can also be used. Furthermore, anhydride-containing monomers such as maleic anhydride, itaconic anhydride, and citraconic anhydride may be used as precursors for the carboxyl group. Among these, (meth)acrylic acid is particularly preferred in terms of copolymerizability, cost, solubility, and glass transition temperature.

[0118] The amount of acidic constituent units contained in the hydroxyalkyl (meth)acrylate unit-containing copolymer is preferably 8% by mass or more and 30% by mass or less, based on 100% by mass of the total amount of constituent units constituting the copolymer. By keeping the amount of acidic constituent units within the above range, sufficient alkali solubility can be imparted to the coating film of the photosensitive colored resin composition, while suppressing a decrease in solvent solubility. If the amount of constituent units having acidic groups is less than 8% by mass, the acid value may be too low to obtain sufficient alkali solubility. On the other hand, if the amount of constituent units having acidic groups exceeds 30% by mass, the polarity of the photosensitive resin composition may become too high, making it difficult to dissolve in the solvent. The amount of constituent units having acidic groups is more preferably 10% by mass or more and 28% by mass or less, and even more preferably 12% by mass or more and 28% by mass or less.

[0119] (A bulky structural unit) Examples of structural units having bulky groups include structural units derived from ethylenically unsaturated monomers having bulky groups. Structural units derived from ethylenically unsaturated monomers having bulky groups have a chemical structure in which the ethylenically unsaturated bond of the bulky ethylenically unsaturated monomer is cleaved by an addition reaction, resulting in the formation of two single bonds. When a copolymer containing hydroxyalkyl (meth)acrylate units has bulky groups, shrinkage during curing of the binder resin is suppressed, delamination from the substrate is mitigated, and adhesion to the substrate is improved. The bulky groups may be monovalent or divalent or multivalent. Examples of such bulky groups include hydrocarbon rings such as optionally substituted aliphatic hydrocarbon rings, optionally substituted aromatic hydrocarbon rings, and combinations thereof. The hydrocarbon ring may have substituents such as alkyl groups, cycloalkyl groups, alkylcycloalkyl groups, carbonyl groups, carboxyl groups, oxycarbonyl groups, amide groups, hydroxyl groups, nitro groups, amino groups, and halogen atoms. Specific examples of hydrocarbon rings include aliphatic hydrocarbon rings such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, norbornane, isobornane, tricyclo[5.2.1.0(2,6)]decane (dicyclopentane), and adamantane; aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, phenanthrene, and fluorene; linear polycyclic structures such as biphenyl, terphenyl, diphenylmethane, triphenylmethane, and stilbene, as well as cardo structures (9,9-diarylfluorene); and groups in which some of these groups are substituted by substituents. When the hydrocarbon ring includes an aliphatic hydrocarbon ring, it is preferable because it improves the heat resistance and adhesion of the colored layer, as well as the brightness of the resulting colored layer. Furthermore, when the constituent units include the above-mentioned cardo structure, it is particularly preferable because it improves the curability of the colored layer, suppresses fading of the colorant, and improves solvent resistance (suppression of NMP swelling).

[0120] Examples of ethylenically unsaturated monomers having a hydrocarbon ring include cyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, adamantyl (meth)acrylate, isobornyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, and styrene. It is preferable to use at least one selected from cyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, adamantyl (meth)acrylate, benzyl (meth)acrylate, and styrene, as this has a significant effect in maintaining the cross-sectional shape of the colored layer after development even during heat treatment.

[0121] The amount of bulky structural units contained in the hydroxyalkyl (meth)acrylate unit-containing copolymer is preferably 20% by mass or more and 70% by mass or less, relative to 100% by mass of the total amount of structural units constituting the copolymer. By setting the amount of bulky structural units within this range, excellent adhesion of the coating film to the substrate can be achieved. If the amount of bulky group components is less than 20% by mass, the adhesion of the coating film to the substrate may be insufficient. On the other hand, if the amount of bulky group components exceeds 70% by mass, it may not be possible to sufficiently introduce hydroxyalkyl (meth)acrylate units, acidic groups, or photopolymerizable functional groups, which may result in insufficient developability or film-forming properties of the photosensitive colored resin composition, or insufficient flatness of the resulting colored layer. The amount of constituent units having bulky groups is more preferably 20% by mass or more and 60% by mass or less, and even more preferably 20% by mass or more and 55% by mass or less.

[0122] (Other constituent units that make up the main chain) By incorporating structural units that do not have functional groups or bulky groups into the main chain of a hydroxyalkyl (meth)acrylate unit-containing copolymer, it is possible to adjust physical properties such as suppressing alkali solubility, improving solvent solubility, and improving solvent resolubility. As ethylenically unsaturated monomers that derive other constituent units from the main chain of the hydroxyalkyl (meth)acrylate unit-containing copolymer, for example, (meth)acrylates that do not have functional groups and have low molecular weight ester residues, such as methyl (meth)acrylate and ethyl (meth)acrylate, can be used.

[0123] (Constituent units that make up side chains having photopolymerizable functional groups) The side chain having a photopolymerizable functional group may be a pendant structure consisting of only one constituent unit having a photopolymerizable functional group, or it may have a polymer structure in which two or more constituent units are linked together. When the side chain is a pendant structure consisting of a constituent unit equivalent to one monomer, the photopolymerizable functional group-containing monomer has a chemical structure in which the functional group that reacts with the functional group on the main chain to form a bond has formed a linking group that bonds to the main chain. Examples of photopolymerizable functional group-containing monomers having a photopolymerizable functional group and a functional group that reacts with a functional group on the main chain to form a bond include compounds such as glycidyl (meth)acrylate, which has an ethylenically unsaturated bond as the photopolymerizable functional group and an epoxy group as the functional group that reacts with a functional group on the main chain to form a bond, and compounds which have an ethylenically unsaturated bond as the photopolymerizable functional group and an isocyanate group as the functional group that reacts with a functional group on the main chain to form a bond. When using monomers having photopolymerizable functional groups and epoxy groups, side chains having photopolymerizable functional groups can be formed by reacting the monomer with the carboxyl groups on the main chain. In this case, while introducing photopolymerizable functional groups into the hydroxyalkyl (meth)acrylate unit-containing copolymer, the carboxyl groups on the main chain are consumed by the reaction with the epoxy groups, reducing the acid value. As a result, the photocurability and developability of the hydroxyalkyl (meth)acrylate unit-containing copolymer change in conjunction. Therefore, it is necessary to adjust the amount of monomers having carboxyl groups or constituent units derived from such monomers, and the amount of monomers having photopolymerizable functional groups and epoxy groups or constituent units derived from such monomers, taking into consideration the balance between the photocurability and developability of the hydroxyalkyl (meth)acrylate unit-containing copolymer. Furthermore, when using monomers having a photopolymerizable functional group and an isocyanate group, a side chain having a photopolymerizable functional group can be formed by reacting the monomer with the hydroxyl group on the main chain. Among these photopolymerizable functional group-containing monomers, it is preferable to use monomers having both a photopolymerizable functional group and an epoxy group. In the present invention, the amount of hydroxyalkyl (meth)acrylate units in the hydroxyalkyl (meth)acrylate unit-containing copolymer is important from the viewpoint of improving the flatness of the colored layer. Monomers having both a photopolymerizable functional group and an epoxy group have high reactivity with carboxyl groups and consume almost no hydroxyl groups in the hydroxyalkyl (meth)acrylate unit-containing copolymer, making it easy to adjust the amount of hydroxyalkyl (meth)acrylate units.

[0124] When a copolymer containing hydroxyalkyl (meth)acrylate units has ethylenically unsaturated groups in its side chains, the ethylenically unsaturated bond equivalent is preferably in the range of 100 to 2000, and particularly preferably in the range of 140 to 1500, in order to obtain effects such as improved film strength of the cured film, improved development resistance, and excellent adhesion to the substrate. If the ethylenically unsaturated bond equivalent is 100 or more, the development resistance and adhesion are excellent. If it is 2000 or less, the proportion of other constituent units such as constituent units having acidic groups or constituent units having bulky groups can be relatively increased, resulting in excellent developability and heat resistance. Here, the ethylenically unsaturated bond equivalent refers to the weight-average molecular weight per mole of ethylenically unsaturated bonds in a copolymer containing hydroxyalkyl (meth)acrylate units, and is expressed by the following formula (1).

[0125] Formula (1) Ethylene unsaturated bond equivalent (g / mol) = W (g) / M (mol) (In formula (1), W represents the mass (g) of the hydroxyalkyl (meth)acrylate unit-containing copolymer, and M represents the number of moles (mol) of ethylenic double bonds contained in the hydroxyalkyl (meth)acrylate unit-containing copolymer.)

[0126] The above ethylenically unsaturated bond equivalent may be calculated, for example, by measuring the number of ethylenically double bonds contained in 1 g of hydroxyalkyl (meth)acrylate unit-containing copolymer in accordance with the iodine value test method described in JIS K 0070:1992.

[0127] The amount of photopolymerizable functional units contained in the hydroxyalkyl (meth)acrylate unit-containing copolymer is preferably 2.5% by mass or more and 35% by mass or less, based on 100% by mass of the total amount of constituent units constituting the copolymer. By keeping the amount of photopolymerizable functional units within the above range, the photocurability of the hydroxyalkyl (meth)acrylate unit-containing copolymer can be improved. If the amount of constituent units having photopolymerizable functional groups is less than 2.5% by mass, the photocurability of the hydroxyalkyl (meth)acrylate unit-containing copolymer may not be sufficient. On the other hand, if the amount of constituent units having photopolymerizable functional groups exceeds 35% by mass, the acidic groups of the main chain may be consumed too much, and sufficient alkali solubility may not be obtained. The amount of constituent units having photopolymerizable functional groups is more preferably 4% by mass or more and 32% by mass or less, and even more preferably 5% by mass or more and 31% by mass or less.

[0128] In the present invention, the weight-average molecular weight (Mw) of the hydroxyalkyl (meth)acrylate unit-containing copolymer is 11,000 or more. By setting the weight-average molecular weight of the hydroxyalkyl (meth)acrylate unit-containing copolymer to 11,000 or more, when the photosensitive colored resin coating film is heat-dried, the viscosity of the softened coating film can be increased by the molecular weight effect of the hydroxyalkyl (meth)acrylate unit-containing copolymer, thereby suppressing the fluidization of the coating film. If the weight-average molecular weight of the hydroxyalkyl (meth)acrylate unit-containing copolymer is less than 11,000, the fluidization of the coating film cannot be sufficiently suppressed when heat-dried. The weight-average molecular weight of the hydroxyalkyl (meth)acrylate unit-containing copolymer is not particularly limited, but it is preferably 25,000 or less. If the weight-average molecular weight (Mw) of the hydroxyalkyl (meth)acrylate unit-containing copolymer exceeds 25,000, the viscosity of the photosensitive resin composition may become too high, deviating from a viscosity suitable for coating. The weight-average molecular weight of the hydroxyalkyl (meth)acrylate unit-containing copolymer is more preferably 11,000 to 20,000, and even more preferably 11,000 to 19,000.

[0129] In this invention, the weight-average molecular weight (Mw) is a value measured by GPC (gel permeation chromatography). The measurement was performed using a Tosoh HLC-8220GPC, with N-methylpyrrolidone containing 0.01 mol / liter lithium bromide as the eluent, and the polystyrene standard for the calibration curve set to Mw: 8 × 10⁻⁶. 5 (F-80), Mw: 4×10 5 (F-40), Mw: 2×10 5 (F-20), Mw: 1×10 5 (F-10), Mw: 4×10 4 (F-4), Mw: 2×10 4 (F-2), Mw: 5×10 3 (A-5000), Mw: 2.5 × 10 3 (A-2500), Mw: 1×10 3 (A-1000), Mw: 5×10 2 The measurement will be performed using (A-500) (manufactured by Tosoh Corporation) and two TSK-GEL ALPHA-M columns (manufactured by Tosoh Corporation).

[0130] In this invention, the acid value of the hydroxyalkyl (meth)acrylate unit-containing copolymer is set to 60 mg KOH / g or more and 130 mg KOH / g or less. By setting the acid value of the hydroxyalkyl (meth)acrylate unit-containing copolymer to 60 mg KOH / g or more, sufficient alkali solubility can be imparted to the photosensitive colored resin coating film, and the effect of flattening the shape of the colored layer is excellent. On the other hand, by setting the acid value of the hydroxyalkyl (meth)acrylate unit-containing copolymer to 130 mg KOH / g or less, the amount of development residue on the substrate when developing the coating film can be reduced. The acid value of the hydroxyalkyl (meth)acrylate unit-containing copolymer is preferably 65 mg KOH / g or more and 125 mg KOH / g or less, more preferably 65 mg KOH / g or more and 110 mg KOH / g or less, and even more preferably 70 mg KOH / g or more and 100 mg KOH / g or less. When the photosensitive colored resin composition of the present invention contains a lake colorant as a colorant, the effect of suppressing the generation of developing residue is high, so the acid value of the hydroxyalkyl (meth)acrylate unit-containing copolymer may be 100 mg KOH / g or more, 110 mg KOH / g or more, or 120 mg KOH / g or more. The higher the acid value of the hydroxyalkyl (meth)acrylate unit-containing copolymer, the easier it is for the colored layer to be flattened.

[0131] The hydroxyl value of the hydroxyalkyl (meth)acrylate unit-containing copolymer is preferably 50 mg KOH / g or more and 200 mg KOH / g or less. If the hydroxyl value of the hydroxyalkyl (meth)acrylate unit-containing copolymer is less than 50 mg KOH / g, the hydrophobicity of the coating film of the photosensitive colored resin composition may become too high, resulting in poor developability. On the other hand, if the hydroxyl value of the hydroxyalkyl (meth)acrylate unit-containing copolymer exceeds 200 mg KOH / g, the solvent resolubility of the photosensitive colored resin composition may deteriorate, potentially impairing its applicability. The hydroxyl value of the copolymer containing hydroxyalkyl (meth)acrylate units is more preferably 70 mg KOH / g or more and 190 mg KOH / g or less, and even more preferably 80 mg KOH / g or more and 180 mg KOH / g or less.

[0132] The hydroxyalkyl (meth)acrylate unit-containing copolymer is usually added to the photosensitive colored resin composition for color filters of the present invention in the form of a varnish dissolved in a solvent. Although not particularly limited, the hydroxyalkyl (meth)acrylate unit-containing copolymer is preferably dissolved in a solvent in the form of a varnish with a solid content concentration of 60% by mass, and its viscosity when heated to 90°C is preferably 500 mPa·s or more, more preferably 600 mPa·s or more, and even more preferably 700 mPa·s or more, as this makes it easier to obtain a colored layer with excellent flatness. On the other hand, the viscosity may be 10,000 mPa·s or less, or 9,000 mPa·s or less. If the viscosity is below the above upper limit, the photosensitive colored resin composition dries more easily, which can improve the productivity of color filters. The solvent used to dissolve the hydroxyalkyl (meth)acrylate unit-containing copolymer is not particularly limited, and for example, a solvent similar to that contained in the photosensitive resin composition for color filters of the present invention can be used.

[0133] <Other binder resins> The photosensitive colored resin composition of the present invention may contain other binder resins in combination with the hydroxyalkyl (meth)acrylate unit-containing copolymer. As the other binder resins, photosensitive or non-photosensitive polymers obtained by polymerizing ethylenically unsaturated bond-containing monomers such as acrylic resins having a structure obtained by removing the hydroxyalkyl (meth)acrylate units from the structure of the above-mentioned hydroxyalkyl (meth)acrylate unit-containing copolymer, acrylic resins containing other constituent units and side chains, styrene-acrylic resins, and polyolefin resins can be used. Furthermore, polymers conventionally used as binder resins for forming the colored layer of color filters, such as photosensitive or non-photosensitive resins like epoxy resins, urethane resins, polyester resins, polyimide resins, and novolac resins, may also be used as the other binder resins.

[0134] In the photosensitive colored resin composition of the present invention, the binder resin content is usually 4% by mass or more and 25% by mass or less, preferably 5% by mass or more and 22% by mass or less, and more preferably 5% by mass or more and 20% by mass or less, based on the total amount of solids of the photosensitive colored resin composition. Furthermore, in the photosensitive colored resin composition of the present invention, the content of the hydroxyalkyl (meth)acrylate unit-containing copolymer per 100 parts by mass of the total amount of binder resin is usually 50 parts by mass or more and 95 parts by mass or less, preferably 60 parts by mass or more and 92 parts by mass or less, and more preferably 65 parts by mass or more and 90 parts by mass or less.

[0135] [Monomers (photopolymerizable compounds)] The monomer, which is a photopolymerizable compound used in the photosensitive colored resin composition of the present invention, is not particularly limited as long as it is polymerizable by a photoinitiator, but it is preferable to include a polyfunctional monomer having two or more polymerizable double bonds. As the polyfunctional monomer, a polyfunctional monomer having two or more ethylenically unsaturated double bonds is preferred, and a polyfunctional (meth)acrylate having two or more acryloyl groups or methacryloyl groups is particularly preferred. As the polyfunctional (meth)acrylate, it may be appropriately selected from those that are conventionally known. Specific examples include those described in Japanese Patent Application Publication No. 2013-029832. Furthermore, when excellent photocurability (high sensitivity) is required for the photosensitive colored resin composition of the present invention, the polyfunctional monomer is preferably one having three or more polymerizable double bonds (trifunctional). For example, poly(meth)acrylates of trivalent or higher polyhydric alcohols and their dicarboxylic acid modified products can be preferably used. Specifically, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, succinic acid modified product of pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, succinic acid modified product of dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tri(2-(meth)acryloyloxyethyl)phosphate, etc. are preferred. Using a phosphorus atom-containing polyfunctional (meth)acrylate such as tri(2-(meth)acryloyloxyethyl)phosphate is preferable because it helps suppress fading of the lake colorant and improves brightness after post-baking. These polyfunctional (meth)acrylates may be used individually or in combination of two or more types.

[0136] In the photosensitive colored resin composition of the present invention, the viscosity of the coating film of the photosensitive colored resin composition tends to be appropriate, and the flatness of the resulting colored layer is improved. Therefore, the content of polyfunctional monomers per 100 parts by mass of the total amount of monomers is preferably 90 parts by mass or more, more preferably 95 parts by mass or more, and particularly preferably 100 parts by mass.

[0137] In the photosensitive colored resin composition of the present invention, the monomer content is not particularly limited, but it is preferably 5% by mass or more and 60% by mass or less, and more preferably 10% by mass or more and 50% by mass or less, based on the total solid content of the photosensitive colored resin composition. If the monomer content is above the lower limit, the photocuring reaction proceeds more easily, which can suppress the elution of the exposed area during development, and if the monomer content is below the upper limit, the alkali developability can be improved.

[0138] [Photoinitiator] There are no particular limitations on the photoinitiator used in the photosensitive colored resin composition of the present invention, and one or more conventionally known initiators can be used in combination. Examples of photoinitiators include aromatic ketones such as benzophenone, N,N-dimethylaminobenzophenone, 4,4'-bisdiethylaminobenzophenone (e.g., HyCure ABP, manufactured by Kawaguchi Pharmaceutical), and 4-methoxy-4'-dimethylaminobenzophenone; benzoin ethers such as benzoin methyl ether; benzoins such as ethylbenzoin; biimidazoles such as 2-(o-chlorophenyl)-4,5-phenylimidazole dimer; halomethyloxadiazole compounds such as 2-trichloromethyl-5-(p-methoxystyryl)-1,3,4-oxadiazole; halomethyl-S-triazines such as 2-(4-butoxy-naphtho-1-yl)-4,6-bis-trichloromethyl-S-triazine; 1,2-octadione-1-[4-(phenylthio)-,2-(o-benzoyl oxime)], ethanoone, 1-[9-ethyl-6-(2-methylbenzoyl)-9 Oxime esters such as oxime ester-based photoinitiators described in Japanese Patent Publication No. 2000-80068, Japanese Patent Publication No. 2001-233842, Japanese Patent Publication No. 2010-527339, Japanese Patent Publication No. 2010-527338, Japanese Patent Publication No. 2013-041153, etc.; 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (e.g., Irgacure 907) Examples include α-aminoketones such as 2-benzyl-2-(dimethylamino)-1-(4-morpholinophenyl)-1-butanone (e.g., Irgacure 369, manufactured by BASF), 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone (Irgacure 379EG, manufactured by BASF); and thioxanthones such as diethylthioxanthone. In particular, the photoinitiator used in the present invention preferably contains at least one selected from oxime esters and α-aminoketones, due to its excellent sensitivity, and α-aminoketones are preferred from the viewpoint of line width adjustment during pattern formation and development resistance. α-aminoketones having a tertiary amine structure are preferred because they have a tertiary amine structure that acts as an oxygen quencher within the molecule, making it difficult for radicals generated from the initiator to be deactivated by oxygen, thus improving sensitivity. Furthermore, using α-aminoketones in combination with oxime esters as photoinitiators is preferable because it suppresses water stains and improves sensitivity. Water stains refer to the appearance of water-like marks after rinsing with pure water following alkaline development, which occurs when components that increase alkaline developability are used. While these water stains disappear after post-bake and do not pose a problem for the product, they are detected as unevenness abnormalities during the visual inspection of the patterned surface after development, making it difficult to distinguish between normal and defective products. Therefore, lowering the inspection sensitivity of the inspection device during visual inspection results in a decrease in the yield of the final color filter product, which is problematic. Furthermore, combining thioxanthones with at least one selected from oxime esters and α-aminoketones as a photoinitiator is preferable because it allows for adjustment of sensitivity, suppression of water staining, and improvement of development resistance.

[0139] The total content of the photoinitiator used in the photosensitive colored resin composition of the present invention is not particularly limited as long as the effects of the present invention are not impaired, but is preferably in the range of 0.1% 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 amount of solids in the photosensitive colored resin composition. If this content is above the lower limit, sufficient photocuring will proceed and the elution of the exposed portion during development will be suppressed, while if it is below the upper limit, yellowing of the resulting colored layer can be suppressed, thereby preventing a decrease in brightness.

[0140] [Antioxidant] The photosensitive colored resin composition of the present invention is preferably further enriched with an antioxidant, as this improves heat resistance, suppresses fading of the colorant, and enhances brightness. The inclusion of an antioxidant in the photosensitive colored resin composition of the present invention allows for the control of excessive radical chain reactions within the micropores without impairing curability when forming micropores in the cured film, thus making it easier to form micropores of a desired shape. Furthermore, the antioxidant is preferably used in combination with an oxime ester-based photoinitiator, as this facilitates the acquisition of the above-mentioned effects. The antioxidant used in the present invention is not particularly limited and may be appropriately selected from those conventionally known. Specific examples of antioxidants include, for example, hindered phenol antioxidants, amine antioxidants, phosphorus antioxidants, sulfur antioxidants, and hydrazine antioxidants. Hindered phenol antioxidants are preferred in terms of heat resistance and the ability to improve the shape of micropores. Latent antioxidants, such as those described in International Publication No. 2014 / 021023, may also be used.

[0141] Examples of hindered phenol antioxidants include pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (trade name: IRGANOX 1010, manufactured by BASF), 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate (trade name: Irganox 3114, manufactured by BASF), and 2,4,6-tris(4-hydroxy-3,5-di-tert-butylbenzyl Examples include methylene (product name: Irganox 1330, manufactured by BASF), 2,2'-methylenebis(6-tert-butyl-4-methylphenol) (product name: Sumirizer MDP-S, manufactured by Sumitomo Chemical), 6,6'-thiobis(2-tert-butyl-4-methylphenol) (product name: Irganox 1081, manufactured by BASF), and 3,5-di-tert-butyl-4-hydroxybenzylphosphonate diethyl (product name: Irgamod 195, manufactured by BASF). In particular, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (trade name: IRGANOX1010, manufactured by BASF) is preferred in terms of heat resistance and light resistance.

[0142] The antioxidant content is preferably 0.1% to 10.0% by mass, and more preferably 0.5% to 5.0% by mass, relative to the total solid content of the photosensitive colored resin composition. If the antioxidant content is above the lower limit, the heat resistance and light resistance are excellent. On the other hand, if the antioxidant content is below the upper limit, the photosensitive resin composition can be made highly sensitive.

[0143] When an antioxidant is used in combination with the oxime ester-based photoinitiator, the antioxidant content is preferably 1 to 250 parts by mass, more preferably 3 to 80 parts by mass, and even more preferably 5 to 65 parts by mass, per 100 parts by mass of the total amount of the oxime ester-based photoinitiator. Within the above range, the effect of the above combination is excellent.

[0144] [Optional addition ingredients] The photosensitive colored resin composition of the present invention may contain various additives as needed. Examples of additives include mercapto compounds, polymerization inhibitors, chain transfer agents, leveling agents, plasticizers, surfactants, defoamers, silane coupling agents, ultraviolet absorbers, adhesion promoters, and the like. Specific examples of surfactants and plasticizers include, for example, those described in Japanese Patent Publication No. 2013-029832.

[0145] [solvent] The solvent used in the present invention is not particularly limited and can be any organic solvent that does not react with the components of the photosensitive colored resin composition but is capable of dissolving or dispersing them. The solvent can be used alone or in combination of two or more. Specific examples of solvents include, for example, alcohol-based solvents such as methyl alcohol, ethyl alcohol, N-propyl alcohol, i-propyl alcohol, methoxy alcohol, and ethoxy alcohol; carbitol-based solvents such as methoxyethoxyethanol and ethoxyethoxyethanol; ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl methoxypropionate, ethyl ethoxypropionate, ethyl lactate, methyl hydroxypropionate, ethyl hydroxypropionate, n-butyl acetate, and isobutyl acetate. Ester solvents such as tate, isobutyl butyrate, n-butyl butyrate, ethyl lactate, and cyclohexanol acetate; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and 2-heptanone; glycol ether acetate solvents such as methoxyethyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy-3-methyl-1-butyl acetate, 3-methoxybutyl acetate, and ethoxyethyl acetate; methoxyethoxyethyl acetate, ethoxyethyl acetate Examples of solvents include carbitol acetate solvents such as toxicethyl acetate, butyl carbitol acetate (BCA), and carbitol acetate; diacetates such as propylene glycol diacetate and 1,3-butylene glycol diacetate; glycol ether solvents such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, and dipropylene glycol dimethyl ether; aprotic amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; lactone solvents such as γ-butyrolactone; cyclic ether solvents such as tetrahydrofuran; unsaturated hydrocarbon solvents such as benzene, toluene, xylene, and naphthalene; saturated hydrocarbon solvents such as N-heptane, N-hexane, and N-octane; and organic hydrocarbons such as toluene and xylene.Among these solvents, glycol ether acetate solvents, carbitol acetate solvents, glycol ether solvents, and ester solvents are preferred in terms of their solubility of other components. In particular, the solvent used in the present invention is preferably one or more selected from the group consisting of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, butyl carbitol acetate (BCA), carbitol acetate, 3-methoxy-3-methyl-1-butyl acetate, ethyl ethoxypropionate, ethyl lactate, and 3-methoxybutyl acetate, from the viewpoint of solubility of other components and suitability for application.

[0146] The solvent content is not particularly limited, but is preferably 75% to 95% by mass, and more preferably 80% to 90% by mass, based on the total amount of the photosensitive colored resin composition. A solvent content above the lower limit of the above-mentioned value in the photosensitive colored resin composition improves the solubility and applicability of other components, while a solvent content below the upper limit of the above-mentioned value reduces the amount of photosensitive colored resin composition used when forming the color filter.

[0147] II. Method for producing a photosensitive colored resin composition for color filters The method for producing the photosensitive colored resin composition of the present invention is not particularly limited. For example, the photosensitive colored resin composition may be produced by mixing the above-mentioned components such as colorants, binder resins, monomers, and photoinitiators in a solvent and dissolving or dispersing them. However, it is preferable to prepare in advance a colorant dispersion or a colorant solution by dissolving the colorant in a solvent using a dispersant, and then produce the photosensitive colored resin composition by mixing the colorant dispersion or solution, and the components of the photosensitive colored resin composition other than the colorants, such as binder resins, monomers, and photoinitiators, in a solvent using known dispersion methods and dissolving or dispersing them. Furthermore, when using two or more colorants, a colorant dispersion or solution may be prepared for each colorant, and then the respective colorant dispersion or solution, along with components of the photosensitive colored resin composition other than the colorants, such as binder resin and photoinitiator, may be mixed in a solvent and dissolved or dispersed to produce the photosensitive colored resin composition. Colorant dispersions and colorant solutions are used as preliminary preparations for preparing colored resin compositions. That is, colorant dispersions and colorant solutions are pre-prepared in the step before preparing the colored resin composition, and have a high P / V ratio, i.e., the ratio of (mass of colorant component in the composition) / (mass of solid content other than colorant component in the composition). Specifically, the P / V ratio of colorant dispersions and colorant solutions is usually 1.0 or higher.

[0148] The photosensitive colored resin composition of the present invention, manufactured using a colorant dispersion, contains a dispersant. Since the photosensitive colored resin composition of the present invention, which contains a lake colorant or pigment, is preferably manufactured using a colorant dispersion in which the lake colorant or pigment is dispersed, it is preferable that it contains a dispersant. The following describes in detail the colorant dispersion used in the production of the photosensitive colored resin composition of the present invention. The colorant dispersion used in the present invention comprises a solvent, a dispersant, and the colorant dispersed in the solvent by the dispersant, and may further contain other components such as dispersion aids as needed.

[0149] [Dispersant] As a dispersant, one can be appropriately selected from those conventionally used as dispersants. Examples of dispersants that can be used include cationic, anionic, nonionic, amphoteric, silicone, and fluorine-based surfactants. Among surfactants, polymeric surfactants (polymeric dispersants) are preferred because they can disperse uniformly and finely. Examples of polymer dispersants include (co)polymers of unsaturated carboxylic acid esters such as polyacrylic acid esters; (partial)amine salts, (partial) ammonium salts, and (partial) alkylamine salts of (co)polymers of unsaturated carboxylic acid esters such as polyacrylic acid; (co)polymers of hydroxyl group-containing unsaturated carboxylic acid esters such as hydroxyl group-containing polyacrylic acid esters and their modified products; polyurethanes; unsaturated polyamides; polysiloxanes; long-chain polyaminoamide phosphates; polyethyleneimine derivatives (amides obtained by the reaction of poly(lower alkyleneimine) with free carboxyl group-containing polyesters and their bases); and polyallylamine derivatives (reaction products obtained by reacting polyallylamine with one or more compounds selected from three types of compounds: polyesters, polyamides, or ester-amide cocondensates (polyesteramides) having free carboxyl groups).

[0150] The dispersant can be appropriately selected and used depending on the type of colorant to ensure good dispersibility, and is not particularly limited. However, when dispersing a lake colorant represented by the above general formula (1) or (2), or a metal lake colorant of a xanthene dye represented by the above general formula (5), and when co-dispersing these lake colorants with dyes such as xanthene dyes or pigments such as CI Pigment Blue 15:6, it is preferable to use an acidic dispersant, which is an acidic polymer dispersant. In this invention, the dye may also be used after being dissolved in a solvent. When dispersing pigments, it is preferable to use at least one selected from the group consisting of acidic or basic polymer dispersants and urethane-based dispersants, depending on the type of pigment, and it is more preferable to use an acidic or basic polymer dispersant. When dispersing a basic treated pigment, it is preferable to use an acidic polymer dispersant, and when dispersing an acid treated pigment, it is preferable to use a basic polymer dispersant, which is a basic dispersant. For the dispersion of lake colorants, at least one of the following can be suitably used as an acidic dispersant: for example, a polymer having a structural unit represented by general formula (I) described later, and a carboxyl group-containing block copolymer described later. For the dispersion of pigments, for example, a carboxyl group-containing block copolymer can be suitably used as an acidic dispersant. As a basic dispersant, at least one selected from the group consisting of polymers containing repeating units having a tertiary amine, and salt-type polymers in which at least a portion of the amino groups in a polymer containing repeating units having a tertiary amine form a salt with an organic acid compound, can be suitably used. Urethane-based dispersants are compounds having one or more urethane bonds (-NH-COO-) in one molecule. Suitable urethane-based dispersants include, for example, reaction products of polyisocyanates having two or more isocyanate groups in one molecule and polyesters having hydroxyl groups at one or both ends.

[0151] <Polymer having a constituent unit represented by general formula (I)> Polymers having the constituent units represented by the following general formula (I) can be preferably used as dispersants for lake colorants, and in particular, can be preferably used as dispersants for lake colorants represented by the above general formula (1) or general formula (2). When polymers having the constituent units represented by the following general formula (I) are used as acidic dispersants, the dispersibility and heat resistance of lake colorants can be improved, and changes in the chromaticity of lake colorants after heating can be suppressed. Furthermore, when lake colorants and pigments are used in combination as colorants, using polymers having the constituent units represented by the following general formula (I) as dispersants can improve the dispersibility and storage stability of pigments, and it is possible to form a colored layer with improved substrate adhesion and coating film uniformity. Polymers having the constituent units represented by the following general formula (I) are ethylenically unsaturated monomer polymers, and therefore have higher heat resistance of the skeleton compared to polyether-based and polyester-based polymers, and also have multiple acidic phosphorus compound groups (-P(=O)(-R) present in the polymer. 12 )(OH)) and its salts (-P(=O)(-R 12 )(O- X + It is presumed that this has a strong adsorption force to the surface of the finely particulated colorant. Furthermore, it is presumed that when the surface of the colorant is coated with at least one of the acidic phosphorus compound group and its salt, attack on the pigment skeleton of the lake colorant by reactive oxygen species such as peroxyl radicals (such as hydrogen abstraction and substitution reactions) is suppressed, and the deterioration (oxidative degradation) of the lake colorant is suppressed.

[0152] [ka] (In general formula (I), L 11 R is a direct bond or a divalent linking group. 11 is a hydrogen atom or a methyl group, R 12 is a hydroxyl group, a hydrocarbon group, -[CH(R 13 )-CH(R 14 )-O] x1 -R 15 ,-[(CH2) y1 -O] z1 -R 15 , or -OR 16 It is a monovalent group represented by R 16 The hydrocarbon group is -[CH(R 13 )-CH(R 14 )-O] x1 -R 15 ,-[(CH2) y1 -O] z1 -R 15 , -C(R 17 )(R 18 )-C(R 19 )(R 20 )-OH, or -CH2-C(R 21 )(R 22 It is a monovalent group represented by )-CH2-OH. R 13 and R 14 Each is independently a hydrogen atom or a methyl group, and R 15 This refers to a hydrogen atom, a hydrocarbon group, -CHO, -CH2CHO, -CO-CH=CH2, -CO-C(CH3)=CH2, or -CH2COOR 23 It is a monovalent group represented by R 23R is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. 17 , R 18 , R 19 , R 20 , R 21 and R 22 Each is independently a hydrogen atom, a hydrocarbon group, or a hydrocarbon group having one or more selected from ether bonds and ester bonds, R 17 and R 19 These may bond to each other to form a ring structure. When the above ring structure is formed, the ring structure may further have substituents R 24 It may have R 24 (x1 is a hydrocarbon group, or a hydrocarbon group having one or more selected from ether and ester bonds. The hydrocarbon group may have substituents. X represents a hydrogen atom or an organic cation. x1 is an integer between 1 and 18, y1 is an integer between 1 and 5, and z1 is an integer between 1 and 18.)

[0153] In general formula (I), L 11 L is a direct bond or a divalent linking group. 11 A direct bond means that the phosphorus atom is directly bonded to the carbon atom of the main chain skeleton without the need for a linking group. L 11 As for the divalent linking group in L, there are no particular restrictions as long as it can link the carbon atom of the main chain skeleton with the phosphorus atom. 11 Examples of divalent linking groups in this invention include linear, branched, or cyclic alkylene groups, linear, branched, or cyclic alkylene groups having a hydroxyl group, arylene groups, -CONH- groups, -COO- groups, -NHCOO- groups, ether groups (-O- groups), thioether groups (-S- groups), and combinations thereof. In this invention, the orientation of the divalent linking group bond is arbitrary. That is, if the divalent linking group includes -CONH-, -CO may be on the carbon atom side of the main chain and -NH on the phosphorus atom side of the side chain, or conversely, -NH may be on the carbon atom side of the main chain and -CO on the phosphorus atom side of the side chain.

[0154] In particular, from the standpoint of dispersion, L in general formula (I)11 It is preferable that the linking group is a divalent linking group containing a -CONH- group or a -COO- group. For example, L 11 If is a divalent linking group containing a -COO- group, then L 11 However, -COO-L 11 '-Base (Here, L 11 ' is an alkylene group having 1 to 8 carbon atoms, which may have a hydroxyl group, -[CH(R L11 )-CH(R L12 )-O] x -, or -[(CH2) y -O] z -(CH2) y -O-, -[CH(R L13 )] w -O-, and R L11 , R L12 and R L13 Each of these is independently a hydrogen atom, a methyl group, or a hydroxyl group. x is an integer between 1 and 18, y is an integer between 1 and 5, z is an integer between 1 and 18, and w is an integer between 1 and 18. ) is preferable.

[0155] L 11 The alkylene group in ' having 1 to 8 carbon atoms may be linear, branched, or cyclic, and may be, for example, a methylene group, ethylene group, trimethylene group, propylene group, various butylene groups, various pentylene groups, various hexylene groups, various octylene groups, etc., and some of the hydrogen atoms may be substituted with hydroxyl groups. x is an integer between 1 and 18, preferably between 1 and 4, more preferably between 1 and 2; y is an integer between 1 and 5, preferably between 1 and 4, more preferably 2 or 3; z is an integer between 1 and 18, preferably between 1 and 4, more preferably between 1 and 2; w is an integer between 1 and 18, preferably between 1 and 4.

[0156] L in general formula (I) 11Suitable specific examples include, but are not limited to, -COO-CH2CH(OH)CH2-O-, -COO-CH2CH2-O-CH2CH(OH)CH2-O-, and -COO-CH2C(CH2CH3)(CH2OH)CH2-O-.

[0157] R 12 Examples of hydrocarbon groups in this context include alkyl groups having 1 to 18 carbon atoms, alkenyl groups having 2 to 18 carbon atoms, aralkyl groups, and aryl groups. The alkyl group having 1 to 18 carbon atoms may be linear, branched, or cyclic. Examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, cyclopentyl, cyclohexyl, bornyl, isobornyl, dicyclopentanyl, adamantyl, and lower alkyl-substituted adamantyl groups. The alkenyl group having 2 to 18 carbon atoms may be linear, branched, or cyclic. Examples of such alkenyl groups include vinyl groups, allyl groups, and propenyl groups. There are no limitations on the position of the double bond of the alkenyl group, but from the viewpoint of the reactivity of the resulting polymer, it is preferable that the double bond be at the end of the alkenyl group. Examples of aryl groups include phenyl groups, biphenyl groups, naphthyl groups, tolyl groups, xylyl groups, etc., and may further have substituents. The number of carbon atoms in the aryl group is preferably 6 to 24, and more preferably 6 to 12. Examples of aralkyl groups include benzyl groups, phenethyl groups, naphthylmethyl groups, and biphenylmethyl groups, and may further have substituents. The number of carbon atoms in the aralkyl group is preferably 7 to 20, and more preferably 7 to 14. The alkyl or alkenyl group may have substituents, and examples of such substituents include halogen atoms such as F, Cl, and Br, and nitro groups. Furthermore, examples of substituents on aromatic rings such as aryl groups and aralkyl groups include linear and branched alkyl groups having 1 to 4 carbon atoms, as well as alkenyl groups, nitro groups, and halogen atoms. Note that the preferred number of carbon atoms mentioned above does not include the number of carbon atoms of substituents. The aforementioned R 12 In this case, x1 is the same as x, y1 is the same as y, and z1 is the same as z. R 15 ~R 22 Examples of hydrocarbon groups in the above R 12 Examples include hydrocarbon groups similar to those in [the relevant context].

[0158] R 17 , R 18 , R 19 , R 20 , R 21 and R 22 In this context, a hydrocarbon group having one or more selected from ether bonds and ester bonds is a group represented as -R'-OR'', -R'-(C=O)-OR'', or -R'-O-(C=O)-R'' (where R' and R'' are hydrocarbon groups, or groups in which a hydrocarbon group is linked by at least one ether bond and an ester bond). A single group may have two or more ether bonds and ester bonds. Examples of monovalent hydrocarbon groups include alkyl groups, alkenyl groups, aralkyl groups, and aryl groups, while examples of divalent hydrocarbon groups include alkylene groups, alkenylene groups, arylene groups, and combinations thereof.

[0159] R 17 and R 19 When atoms bond to form a ring structure, the number of carbon atoms forming the ring structure is preferably 5 to 8, more preferably 6, i.e., a 6-membered ring, and preferably a cyclohexane ring. Substituent R 24 In the above, a hydrocarbon group, or a hydrocarbon group having one or more selected from ether bonds and ester bonds, is R 17 , R 18 , R 19 , R20 , R 21 and R 22 It can be made to be similar to the one in [location].

[0160] In terms of excellent dispersibility and dispersion stability of the dispersed particles, the R 12 However, hydroxyl group, hydrocarbon group, -[CH(R 13 )-CH(R 14 )-O] x1 -R 15 ,-[(CH2) y1 -O] z1 -R 15 , or -OR 16 It is preferably a monovalent group represented by -[CH(R 13 )-CH(R 14 )-O] x1 -R 15 ,-[(CH2) y1 -O] z1 -R 15 , or -OR 16 The monovalent group shown is R 13 and R 14 Each of these is independently a hydrogen atom or a methyl group, and R 15 It is more preferable that -CO-CH=CH2 or -CO-C(CH3)=CH2, and among them, R 12 However, aryl groups, vinyl groups, methyl groups, and hydroxyl groups, which may have substituents, are more preferred.

[0161] Furthermore, R is improved in terms of alkali resistance. 12 The hydrocarbon group is -[CH(R 13 )-CH(R 14 )-O] x1 -R 15 , or -[(CH2) y1 -O] z1 -R 15 It is preferable that the group is a monovalent group represented by . If it has a structure in which a carbon atom is directly bonded to a phosphorus atom, it is presumed that it is possible to form a resin layer with excellent alkali resistance because it is less susceptible to hydrolysis. In particular, R 12This includes a methyl group, an ethyl group, an optionally substituted aryl or aralkyl group, a vinyl group, an allyl group, and -[CH(R 13 )-CH(R 14 )-O] x1 -R 15 , or -[(CH2) y1 -O] z1 -R 15 The monovalent group shown is R 13 and R 14 Each of these is independently a hydrogen atom or a methyl group, and R 15 Those in which are -CO-CH=CH2 or -CO-C(CH3)=CH2 are preferred because they have excellent alkali resistance and excellent dispersibility and dispersion stability of the dispersed particles. Among them, R 12 From the viewpoint of dispersibility, an aryl group which may have substituents is more preferable.

[0162] In general formula (I), X represents a hydrogen atom or an organic cation. An organic cation is one in which a carbon atom is contained in the cation portion. Examples of organic cations include imidazolium cation, pyridinium cation, aminidium cation, piperidinium cation, pyrrolidinium cation, ammonium cations such as tetraalkylammonium cation and trialkylammonium cation, sulfonium cations such as trialkylsulfonium cation, and phosphonium cations such as tetraalkylphosphonium cation. Among these, protonated nitrogen-containing organic cations are preferred from the viewpoint of dispersibility and alkali developability. In particular, when the organic cation has an ethylenically unsaturated double bond, it is preferable because it can impart curability.

[0163] The constituent unit represented by general formula (I) may be present in the polymer as a single unit or as two or more units.

[0164] In a polymer, the constituent units represented by general formula (I) may include both constituent units where X is a hydrogen atom and constituent units where X is an organic cation. When both constituent units are included, there are no particular restrictions as long as good dispersibility and dispersion stability are exhibited, however, it is preferable that the proportion of constituent units where X is an organic cation is 0 mol% or more and 50 mol% or less relative to the total number of constituent units represented by general formula (I).

[0165] The method for synthesizing polymers having structural units represented by general formula (I) is not particularly limited, but for example, polymers having structural units represented by general formula (I) can be synthesized by referring to Japanese Patent Application Publication No. 2017-2191. The polymer having structural units represented by general formula (I) is preferably a polymer that is a reaction product of a polymer having at least one of an epoxy group and a cyclic ether group in its side chains and an acidic phosphorus compound, wherein at least a portion of the acidic phosphorus compound groups may form a salt.

[0166] In embodiments of the present invention, the polymer having the structural unit represented by general formula (I) is preferably further having solvent-affinity moieties from the viewpoint of dispersibility. Among such polymers, a graft copolymer having the structural unit represented by general formula (I) and the structural unit represented by general formula (II) below, or a block copolymer having the structural unit represented by general formula (I) and the structural unit represented by general formula (III) below, is preferred because it has excellent dispersibility and storage stability, and can form a high-contrast coating film even after long-term storage.

[0167] [ka] (In general formula (II), L 21 R is a direct bond or a divalent linking group. 25 ' is a hydrogen atom or a methyl group, and 'polymer' represents a polymer chain having a constituent unit represented by the following general formula (IV). In general formula (III), R 26 is a hydrogen atom or a methyl group, R 27The hydrocarbon group is -[CH(R 28 )-CH(R 29 )-O] x2 -R 30 ,-[(CH2) y2 -O] z2 -R 30 ,-[CO-(CH2) y2 -O] z2 -R 30 , -CO-OR 30’ or -O-CO-R 30” The monovalent group shown is R 28 and R 29 Each is independently a hydrogen atom or a methyl group, R 30 This refers to a hydrogen atom, a hydrocarbon group, -CHO, -CH2CHO, or -CH2COOR 31 It is a monovalent group represented by R 30’ The hydrocarbon group is -[CH(R 28 )-CH(R 29 )-O] x2’ -R 30 ,-[(CH2) y2’ -O] z2’ -R 30 ,-[CO-(CH2) y2’ -O] z2’ -R 30 It is a monovalent group represented by R 30” R is an alkyl group having 1 to 18 carbon atoms. 31 This is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. The hydrocarbon group may have substituents. x2 and x2' are integers between 1 and 18 (inclusive), y2 and y2' are integers between 1 and 5 (inclusive), and z2 and z2' are integers between 1 and 18 (inclusive).

[0168] [ka] (In general formula (IV), R 32 R is a hydrogen atom or a methyl group, 33 The hydrocarbon group is -[CH(R 34 )-CH(R 35 )-O] x3 -R 36 ,-[(CH2) y3 -O]z3 -R 36 ,-[CO-(CH2) y3 -O] z3 -R 36 , -CO-OR 37 or -O-CO-R 38 The monovalent group shown is R 34 and R 35 Each is independently a hydrogen atom or a methyl group, R 36 This refers to a hydrogen atom, a hydrocarbon group, -CHO, -CH2CHO, or -CH2COOR 39 The monovalent group shown is R 37 The hydrocarbon group is -[CH(R 34 )-CH(R 35 )-O] x4 -R 36 ,-[(CH2) y4 -O] z4 -R 36 ,-[CO-(CH2) y4 -O] z4 -R 36 The monovalent group shown is R 38 R is an alkyl group having 1 to 18 carbon atoms. 39 This is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and the hydrocarbon group may have substituents. n represents an integer between 5 and 200. x3 and x4 represent integers between 1 and 18, y3 and y4 represent integers between 1 and 5, and z3 and z4 represent integers between 1 and 18.

[0169] (graft copolymer) Examples of graft copolymers preferred as acidic dispersants include graft copolymers having a constituent unit represented by the general formula (I) and a constituent unit represented by the general formula (II). In the above general formula (II), L 21 L is a direct bond or a divalent linking group. 21 As for the divalent linking group in L, there are no particular restrictions as long as it can link the carbon atom derived from the ethylenically unsaturated double bond to the polymer chain. 21 Examples of divalent linking groups in the above L 11Examples include divalent linking groups similar to those in [the relevant context].

[0170] In the general formula (II) above, Polymer represents a polymer chain having the constituent units represented by the general formula (IV) above. In general formula (IV), R 33 The hydrocarbon group in is preferably an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, or an aryl group. These are, for example, the R mentioned above. 12 Similar examples include the above.

[0171] R 36 This refers to a hydrogen atom, or an alkyl group, aralkyl group, aryl group, -CHO, -CH2CHO, or -CH2COOR group having 1 to 18 carbon atoms. 39 A monovalent group represented by R is preferred, 37 This includes alkyl groups, aralkyl groups, aryl groups, and -[CH(R) 34 )-CH(R 35 )-O] x4 -R 36 ,-[(CH2) y4 -O] z4 -R 36 ,-[CO-(CH2) y4 -O] z4 -R 36 A monovalent group represented by R is preferred. 38 R is an alkyl group having 1 to 18 carbon atoms. 39 This represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. The aforementioned R 36 and R 37 Among these, alkyl groups, aralkyl groups, and aryl groups having 1 to 18 carbon atoms are defined as R 12 Similar examples include the above. The aforementioned R 38 and R 39 Among them, the alkyl group is the R mentioned above. 12 Similar examples include the above. The aforementioned R 36 , R 37 and R 39However, if the group has an aromatic ring, the aromatic ring may have further substituents. Examples of such substituents include linear, branched, or cyclic alkyl groups having 1 to 5 carbon atoms, as well as alkenyl groups, nitro groups, and halogen atoms such as F, Cl, and Br. Note that the preferred number of carbon atoms mentioned above does not include the number of carbon atoms of substituents. The aforementioned R 33 and R 37 In this case, x3 and x4 are the same as x, y3 and y4 are the same as y, and z3 and z4 are the same as z.

[0172] Furthermore, the R 33 , R 36 , R 37 , R 38 and R 39 The graft copolymer may be further substituted with substituents such as alkoxy groups, hydroxyl groups, carboxyl groups, amino groups, epoxy groups, isocyanate groups, and hydrogen bond-forming groups, to the extent that they do not impede the dispersion performance of the graft copolymer. Alternatively, after synthesizing a graft copolymer having these substituents, a polymerizable group may be added by reacting it with a compound having a functional group that reacts with the substituent and a polymerizable group. For example, a polymerizable group can be added by reacting a graft copolymer having a carboxyl group with glycidyl (meth)acrylate, or by reacting a graft copolymer having an isocyanate group with hydroxyethyl (meth)acrylate.

[0173] Polymer chains having structural units represented by general formula (IV) are preferably those having structural units derived from methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, adamantyl (meth)acrylate, styrene, α-methylstyrene, vinylcyclohexane, etc., among the aforementioned structural units. However, they are not limited to these.

[0174] In an embodiment of the present invention, the R 33 and R 37 In particular, it is preferable to use one that has excellent solubility with organic solvents, and it should be appropriately selected according to the organic solvent used in the colorant dispersion. Specifically, for example, when using organic solvents such as ether alcohol acetate, ether, or ester, which are commonly used as organic solvents for colorant dispersions, methyl groups, ethyl groups, isobutyl groups, n-butyl groups, 2-ethylhexyl groups, 2-ethoxyethyl groups, cyclohexyl groups, benzyl groups, etc., are preferred. Here, the R 33 and R 37 The reason for setting it in this way is the aforementioned R 33 and R 37 This is because the constituent units containing the above are soluble in the organic solvent, and the acidic phosphorus compound group and its salt portion of the monomer have high adsorption properties to particles such as colorants, thereby making the dispersibility and stability of the particles such as colorants particularly excellent.

[0175] The weight-average molecular weight of the polymer chain in the polymer is preferably in the range of 500 to 15000, and more preferably in the range of 1000 to 8000. This range allows for sufficient steric repulsion as a dispersant, and also suppresses the increase in the time required for the dispersion of particles such as colorants due to steric effects.

[0176] Furthermore, as a guideline, the polymer chains in the polymer preferably have a solubility of 50 g / 100g solvent or more at 23°C in the organic solvent used in combination.

[0177] The polymer chain may be a homopolymer or a copolymer. Furthermore, the polymer chain included in the constituent unit represented by general formula (II) may be a single type or a mixture of two or more types in the graft copolymer.

[0178] Preferably, the total amount of the constituent unit represented by general formula (I) is 3% to 80% by mass of all constituent units of the graft copolymer, more preferably 10% to 70% by mass, and even more preferably 20% to 60% by mass. If the total content of the constituent unit represented by general formula (I) in the graft copolymer is within the above range, the proportion of affinity sites with particles in the graft copolymer becomes appropriate, and the decrease in solubility in organic solvents can be suppressed, resulting in good adsorption to particles such as colorants, and excellent dispersibility and dispersion stability. Furthermore, since the acidic phosphorus compound group of the graft copolymer can be stably localized around the colorant, a color filter with excellent heat resistance and contrast can be obtained. On the other hand, with respect to all the structural units of the graft copolymer, the structural unit represented by the general formula (II) is preferably contained in a proportion of 20% to 97% by mass, more preferably 25% to 95% by mass, and even more preferably 40% to 90% by mass. In this invention, the content ratio of each constituent unit in the copolymer is calculated from the amount used when synthesizing the copolymer.

[0179] Furthermore, the weight-average molecular weight of the graft copolymer is preferably in the range of 1,000 to 500,000, more preferably in the range of 3,000 to 400,000, and even more preferably in the range of 5,000 to 300,000. This range allows for uniform dispersion of particles such as colorants.

[0180] The graft copolymer used in the embodiments of the present invention may have other constituent units in addition to the constituent units represented by general formula (I) and general formula (II). For example, other constituent units can be introduced by appropriately selecting and copolymerizing an ethylenically unsaturated monomer that can copolymerize with an ethylenically unsaturated monomer that induces the constituent unit represented by general formula (I).

[0181] (Block copolymer) Examples of block copolymers preferred as acidic dispersants include block copolymers having a block portion containing a structural unit represented by the general formula (I) and a block portion containing a structural unit represented by the general formula (III). In the block copolymer, it is preferable that the block portion containing the constituent unit represented by the general formula (I) contains a total of 3 or more of the constituent unit represented by the general formula (I). In particular, from the viewpoint of good dispersibility and improved heat resistance, it is preferable to contain 3 to 200 units, more preferably 3 to 50 units, and even more preferably 3 to 30 units. The constituent unit represented by the general formula (I) above only needs to function as a colorant affinity part, and may consist of one type or may contain two or more types of constituent units. If it contains two or more types of constituent units, the two or more types of constituent units may be randomly arranged within the block containing the constituent unit represented by the general formula (I).

[0182] In the block copolymer, the total content of the constituent units represented by the general formula (I) is preferably 5% by mass or more and 80% by mass or less, more preferably 10% by mass or more and 70% by mass or less, and even more preferably 20% by mass or more and 60% by mass or less, relative to the total constituent units of the block copolymer. If the values ​​are within the aforementioned range, the proportion of affinity sites with particles in the block copolymer becomes appropriate, and the decrease in solubility in organic solvents can be suppressed, resulting in good adsorption to particles such as colorants, and excellent dispersibility and dispersion stability. Furthermore, since the acidic phosphorus compound groups of the block copolymer can be stably localized around the colorants, a color filter with excellent heat resistance and contrast can be obtained.

[0183] The block copolymer, by having a block portion containing the constituent unit represented by the general formula (III), exhibits good solvent affinity, good dispersibility and dispersion stability of the colorant, good heat resistance, and further excellent resistance to N-methylpyrrolidone (NMP) (NMP resistance).

[0184] In general formula (III), R 27 The hydrocarbon group is -[CH(R 28 )-CH(R 29 )-O] x2 -R 30 ,-[(CH2) y2 -O] z2 -R 30 ,-[CO-(CH2) y2 -O] z2 -R 30 , -CO-OR 30’ or -O-CO-R 30” It is a monovalent group represented by [this symbol]. R 27 The hydrocarbon group in is the aforementioned R 12 It can be the same as the one shown.

[0185] Furthermore, the R 30 This refers to a hydrogen atom, a hydrocarbon group, -CHO, -CH2CHO, or -CH2COOR 31It is a monovalent group represented by R 30’ The hydrocarbon group is -[CH(R 28 )-CH(R 29 )-O] x2’ -R 30 ,-[(CH2) y2’ -O] z2’ -R 30 ,-[CO-(CH2) y2’ -O] z2’ -R 30 It is a monovalent group represented by R 30” R is an alkyl group having 1 to 18 carbon atoms. 31 This is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and the hydrocarbon group may have substituents. The aforementioned R 30 The hydrocarbon group in R 12 It can be the same as the one shown. The aforementioned R 27 and R 30’ In this case, x2 and x2' are the same as x, y2 and y2' are the same as y, and z2 and z2' are the same as z. Furthermore, R in the constituent unit represented by the general formula (III) 27 These may be the same as or different from each other.

[0186] The aforementioned R 27 and R 30’ In particular, it is preferable to use one that has excellent solubility with organic solvents, for example, the R 33 and R 37 Similar examples include the above. Furthermore, R in the general formula (IV) 27 , R 30 , R 30’ , R 30” and R 31The constituent groups may be substituted with substituents such as alkoxy groups, hydroxyl groups, carboxyl groups, amino groups, epoxy groups, isocyanate groups, and hydrogen bond-forming groups, to the extent that they do not impede the dispersion performance of the block copolymer. Alternatively, the substituents may be added after the synthesis of the block copolymer by reacting it with a compound having the substituents. Furthermore, polymerizable groups may be added after the synthesis of the block copolymer having these substituents by reacting it with a compound having a functional group that reacts with the substituent and a polymerizable group. For example, polymerizable groups can be added by reacting a block copolymer having a glycidyl group with (meth)acrylic acid, or by reacting a block copolymer having an isocyanate group with hydroxyethyl (meth)acrylate.

[0187] The number of constituent units constituting the block portion, which includes the constituent unit represented by general formula (III), is not particularly limited. However, from the viewpoint of enabling the solvent affinity portion and the colorant affinity portion to work effectively and improve the dispersibility of the colorant dispersion, it is preferably 10 to 200, more preferably 20 to 100, and even more preferably 30 to 80.

[0188] In the block copolymer, the content of the constituent unit represented by general formula (III) is preferably 30% by mass or more and 95% by mass or less, and more preferably 40% by mass or more and 90% by mass or less, relative to the total constituent units of the block copolymer.

[0189] The block portion containing the constituent unit represented by general formula (III) should be selected to function as a solvent affinity site, and the constituent unit represented by general formula (III) may consist of one type or may contain two or more types of constituent units. In embodiments of the present invention, when the constituent unit represented by general formula (III) contains two or more types of constituent units, the two or more types of constituent units may be randomly arranged within the block portion containing the constituent unit represented by general formula (III).

[0190] In block copolymers used as dispersants, the ratio m / n of the number of constituent units m in the block portion containing the constituent unit represented by general formula (I) to the number of constituent units n in the block portion containing the constituent unit represented by general formula (III) is preferably in the range of 0.01 to 1, and more preferably in the range of 0.1 to 0.7 from the viewpoint of dispersibility and dispersion stability of the colorant.

[0191] The bonding order of the block copolymer is not particularly limited, as long as it has a block portion containing the structural unit represented by general formula (I) and a block portion containing the structural unit represented by general formula (III), and can stably disperse the colorant. However, it is preferable that the block portion containing the structural unit represented by general formula (I) is bonded only to one end of the block copolymer, as this provides excellent interaction with the colorant and effectively suppresses aggregation of the dispersants.

[0192] The weight-average molecular weight of the block copolymer is not particularly limited, but is preferably 2,500 to 500,000, more preferably 3,000 to 400,000, and even more preferably 6,000 to 300,000, in order to ensure good dispersibility and excellent heat resistance.

[0193] The acid value of the polymer having the constituent units represented by the general formula (I) is preferably 20 mg KOH / g or more, more preferably 30 mg KOH / g or more, and even more preferably 40 mg KOH / g or more, from the viewpoint of the dispersibility and storage stability of the colorant. On the other hand, from the viewpoint of excellent developability, the acid value of the polymer having the constituent units represented by the general formula (I) is preferably 150 mg KOH / g or less, more preferably 120 mg KOH / g or less, and even more preferably 100 mg KOH / g or less. In this invention, the acid value refers to the number of milligrams of potassium hydroxide required to neutralize the acidic components contained in 1 g of the sample, and can be measured according to JIS K 0070:1992.

[0194] <Other acidic dispersants> The colorant dispersion of the present invention may further contain other acidic dispersants different from the polymer having the constituent units represented by the general formula (I). Other acidic dispersants include dispersants having an acidic group. Examples of acidic groups include carboxyl groups, sulfol groups, or phosphate groups, but among the acidic groups included in the dispersants of other acidic dispersants, carboxyl groups are preferred due to their excellent dispersibility.

[0195] The acid value of the other acidic dispersants is preferably in the range of 30 mg KOH / g to 250 mg KOH / g, from the viewpoint of excellent dispersibility, and more preferably 40 mg KOH / g or more, more preferably 50 mg KOH / g or more, and even more preferably 70 mg KOH / g or more. On the other hand, from the viewpoint of suppressing developing residue, the acid value of the other acidic dispersants is preferably 200 mg KOH / g or less, more preferably 190 mg KOH / g or less, and even more preferably 180 mg KOH / g or less.

[0196] In the present invention, other acidic dispersants are preferably polymeric dispersants having carboxyl groups, as this improves the suppression of developing residue when used in combination with a polymer having the constituent units represented by the general formula (I). In particular, it is preferable to include a block copolymer comprising block A, which contains constituent units derived from a carboxyl group-containing ethylenically unsaturated monomer, and block B, which contains constituent units derived from an alkyl (meth)acrylate, as this improves the suppression of developing residue and provides better uniformity of the coating film when used in combination with a polymer having the constituent units represented by the general formula (I). Hereinafter, a block copolymer comprising block A, which contains structural units derived from a carboxyl group-containing ethylenically unsaturated monomer, and block B, which contains structural units derived from an alkyl (meth)acrylate, may simply be referred to as a "carboxyl group-containing block copolymer." This carboxyl group-containing block copolymer is suitably used, for example, as a metal lake colorant for xanthene dyes and as a dispersant for pigments.

[0197] (Carboxylate-containing block copolymer) {Block A} In a carboxyl group-containing block copolymer, block A is a polymer block containing constituent units derived from a carboxyl group-containing ethylenically unsaturated monomer. Examples of carboxyl group-containing ethylenically unsaturated monomers used in Block A include those similar to those used in hydroxyalkyl (meth)acrylate unit-containing copolymers, which have a carboxyl group. If block A contains two or more constituent units, each constituent unit within block A may be included in any manner, such as random copolymerization or block copolymerization, but from the viewpoint of uniformity, it is preferable that it be included in the manner of random copolymerization. Block A preferably contains 40% by mass or more, more preferably 70% by mass or more, of the constituent units derived from carboxyl group-containing ethylenically unsaturated monomers relative to the total constituent units of Block A, and even more preferably is a polymer block composed solely of constituent units derived from carboxyl group-containing ethylenically unsaturated monomers.

[0198] Block A may consist solely of structural units derived from carboxyl group-containing ethylenically unsaturated monomers, or it may contain structural units derived from ethylenically unsaturated monomers other than carboxyl group-containing ethylenically unsaturated monomers, to the extent that the acidity of Block A is stronger than that of Block B. If Block A contains structural units derived from ethylenically unsaturated monomers other than carboxyl group-containing ethylenically unsaturated monomers, it is preferable that the amount is 60% by mass or less, and more preferably 30% by mass or less, relative to the total structural units of Block A. Examples of ethylenically unsaturated monomers other than carboxyl group-containing ethylenically unsaturated monomers include structural units used in Block B, which will be described later.

[0199] From the viewpoint of dispersibility and dispersion stability, the content of Block A is preferably 5% by mass or more, more preferably 10% by mass or more, relative to the total constituent units of the block copolymer, while it is preferably 95% by mass or less, and more preferably 40% by mass or less.

[0200] {Block B} In a carboxyl group-containing block copolymer, block B is a polymer block containing constituent units derived from alkyl (meth)acrylate. The alkyl (meth)acrylate monomer used in block B may be the same as the alkyl (meth)acrylate monomer used in the polymer chain having the constituent unit represented by the general formula (IV), and one or more types may be used in combination. Block B may contain structural units derived from other ethylenically unsaturated monomers in addition to structural units derived from alkyl (meth)acrylate. Examples of structural units derived from other ethylenically unsaturated monomers include structural units represented by the general formula (III) that are different from the structural units derived from alkyl (meth)acrylate.

[0201] If block B contains two or more constituent units, each constituent unit within block B may be included in any manner, such as random copolymerization or block copolymerization, but from the viewpoint of uniformity, it is preferable that it be included in the manner of random copolymerization.

[0202] In Block B, it is preferable that the constituent units derived from ethylenically unsaturated monomers having acidic groups are 10% by mass or less, more preferably 5% by mass or less, and even more preferably 2% by mass or less, relative to the total constituent units of Block B. In the present invention, it is even more preferable that Block B is a polymer block that does not contain constituent units derived from ethylenically unsaturated monomers having acidic groups.

[0203] The carboxyl group-containing block copolymer may be an AB block copolymer or a BAB block copolymer. When the block copolymer is a BAB block copolymer, the ratio of the two B blocks to each other is preferably adjusted within the range of 50:50 to 70:30 by mass ratio from the viewpoint of dispersibility.

[0204] The acid value of the carboxyl group-containing block copolymer is preferably in the range of 30 mg KOH / g to 250 mg KOH / g from the viewpoint of dispersibility, and it is preferable that block A contains constituent units derived from carboxyl group-containing ethylenically unsaturated monomers so that the acid value of the block copolymer is in this range. The acid value is preferably 50 mg KOH / g or more, and more preferably 70 mg KOH / g or more. The acid value is preferably 200 mg KOH / g or less, and more preferably 150 mg KOH / g or less.

[0205] The weight-average molecular weight of the carboxyl group-containing block copolymer is preferably 5,000 or more and 100,000 or less from the viewpoint of dispersibility. The weight-average molecular weight of the carboxyl group-containing block copolymer is more preferably 8,000 or more, even more preferably 10,000 or more, while it is more preferably 80,000 or less and even more preferably 70,000 or less.

[0206] The molecular weight distribution of the carboxyl group-containing block copolymer is preferably less than 2, more preferably less than 1.5, and even more preferably less than 1.3. In this invention, the molecular weight distribution is determined by (weight-average molecular weight (Mw)) / (number-average molecular weight (Mn)). A larger molecular weight distribution means that the polymer contains molecules with lower and higher molecular weights compared to the designed polymer, which tends to worsen the dispersibility of the colorant. Therefore, a smaller molecular weight distribution is preferable.

[0207] As a method for producing the carboxyl group-containing block copolymer, conventionally known methods for producing block copolymers can be appropriately selected and used. It is preferable to use a living polymerization method because it facilitates the production of polymers with a uniform composition. Examples of living polymerization methods include methods using an organic acid catalyst and a silyl initiator (GTP method), methods using a transition metal catalyst (ATRP method), methods using a sulfur-based reversible chain transfer agent (RAFT method), and methods using an organotellurium compound (TERP method).

[0208] The amount of dispersant in the colorant dispersion can be adjusted as appropriate, but from the viewpoint of dispersibility and storage stability, it is preferable to use 5 parts by mass or more and 80 parts by mass or less per 100 parts by mass of colorant, and more preferably 20 parts by mass or more and 70 parts by mass or less.

[0209] [Other ingredients] The colorant dispersion may further contain dispersion-enhancing resins and other components as needed, provided that the effects of the present invention are not impaired. Examples of dispersion-enhancing resins include alkali-soluble resins. The steric hindrance of alkali-soluble resins makes it difficult for colorant particles to come into contact with each other, thus stabilizing the dispersion of the colorant. In some cases, this dispersion-stabilizing effect can reduce the amount of dispersant used. Other components include, for example, surfactants to improve wettability, silane coupling agents to improve adhesion, defoaming agents, anti-repellent agents, anti-coagulation agents, and UV absorbers.

[0210] [solvent] The solvent contained in the colorant dispersion can be the same as the solvent contained in the photosensitive colored resin composition of the present invention described above. The amount of solvent is usually preferably in the range of 55% to 95% by mass, more preferably in the range of 65% to 90% by mass, and more preferably in the range of 70% to 88% by mass, relative to the total amount of the colorant dispersion. If there is too little solvent, the viscosity will increase and dispersibility will decrease. Conversely, if there is too much solvent, the colorant concentration will decrease, making it difficult to achieve the target chromaticity coordinate.

[0211] [Method for manufacturing a colorant dispersion] The method for producing a colorant dispersion is not particularly limited as long as it is a method that yields a colorant dispersion in which colorants are dispersed in a solvent by a dispersant. For example, a production method can be applied that includes the steps of preparing colorants, preparing a dispersant, and dispersing the colorants in a solvent in the presence of the dispersant. Two or more colorants may be codispersed in a solvent in the presence of a dispersant, or one or more colorants may be dispersed or codispersed and then two or more colorant dispersions may be mixed. The dispersion of colorants can be carried out using conventionally known dispersion machines. Specific examples of dispersion machines include roll mills such as 2-roll and 3-roll mills, ball mills such as ball mills and vibrating ball mills, paint conditioners, continuous disc-type bead mills, and continuous annular-type bead mills. Preferred dispersion conditions for bead mills are that the bead diameter used is preferably 0.03 mm to 3.0 mm, and more preferably 0.05 mm to 2.0 mm.

[0212] III. Cured products of photosensitive colored resin compositions Since the photosensitive colored resin composition of the present invention contains a monomer that is a photopolymerizable compound as a photocurable component, a cured product of the present invention can be obtained by photopolymerizing the photosensitive colored resin composition of the present invention. For example, a cured product of the present invention can be obtained by forming a coating film of the photosensitive colored resin composition of the present invention, drying the coating film, exposing it to light, and developing it as necessary. The methods for forming the coating film, exposure, and development can be, for example, the same methods used in forming the colored layer of the color filter according to the present invention, which will be described later. In a preferred embodiment, the photosensitive colored resin composition of the present invention also has polymerizable functional groups in the binder resin, such as a hydroxyalkyl (meth)acrylate unit-containing copolymer. In such a preferred embodiment, the cured product of the photosensitive colored resin composition of the present invention is a cured product in which a colorant, comprising at least one selected from the group consisting of dyes and lake colorants, is dissolved or dispersed in a matrix produced by a photopolymerization reaction of a binder resin containing a hydroxyalkyl (meth)acrylate unit-containing copolymer and monomers. The cured product according to the present invention is formed by dissolving or dispersing a colorant, which includes at least one selected from the group consisting of dyes and lake colorants, in a matrix containing a binder resin containing a hydroxyalkyl (meth)acrylate unit-containing copolymer. As a result, it exhibits high brightness, excellent flatness, and suppresses the generation of development residue when developed, making it suitable for use as a colored layer in color filters.

[0213] IV. Color Filters The color filter according to the present invention comprises at least a transparent substrate and a colored layer provided on the transparent substrate, wherein at least one of the colored layers is a cured product of the photosensitive colored resin composition according to the present invention. The color filter according to the present invention has a color layer that is highly luminous, has excellent flatness, and suppresses the generation of developing residue, as at least one of the color layers is formed by a cured product obtained by dissolving or dispersing a colorant, which is selected from the group consisting of dyes and lake colorants, in a matrix containing a binder resin containing a hydroxyalkyl (meth)acrylate unit-containing copolymer.

[0214] Figure 1 is a schematic cross-sectional view showing an example of the color filter of the present invention. The color filter 10 of the present invention shown in Figure 1 comprises a transparent substrate 1, a light-shielding portion 2, and a colored layer 3 consisting of a red colored layer 3R, a green colored layer 3G, and a blue colored layer 3B. In the color filter of the present invention, the colored layer is usually formed in the opening of the light-shielding portion on the transparent substrate described later, and is composed of a coloring pattern of three or more colors. In the example in Figure 3, a red colored layer 3R, a green colored layer 3G, and a blue colored layer 3B are formed and arranged in a predetermined order. The colored layers of each color are formed in the order of red colored layer 3R, green colored layer 3G, and blue colored layer 3B. The arrangement method of the colored layer is not particularly limited and can be a general arrangement such as a stripe pattern, mosaic pattern, triangle pattern, or 4-pixel arrangement. Furthermore, the width and area of ​​the colored layer can be set arbitrarily. The thickness of the colored layer can be appropriately controlled by adjusting the application method, the solid content concentration and viscosity of the colored resin composition, etc., but it is generally preferable that it be in the range of 1 μm to 5 μm.

[0215] The individual colored layers can be formed by the following procedure. First, a photosensitive colored resin composition is applied to a transparent substrate that has a pre-formed light-shielding area using a coating method such as spray coating, dip coating, bar coating, roll coating, or spin coating to form a wet coating film. Next, the wet coating is dried using a hot plate or oven, and then exposed to light through a mask with a predetermined pattern to cause a photopolymerization reaction of the binder resin and monomers, etc., to form a photosensitive coating. Examples of light sources used for exposure include ultraviolet light from low-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, electron beams, etc. The amount of exposure is adjusted as appropriate depending on the light source used and the thickness of the coating. Furthermore, heat treatment may be performed after exposure to promote the polymerization reaction. The heating conditions are appropriately selected depending on the mixing ratio of each component in the colored resin composition used, the thickness of the coating film, etc.

[0216] Next, the film is developed using a developing solution to dissolve and remove the unexposed areas, thereby forming a coating with the desired pattern. Typically, a solution of alkali dissolved in water or a water-soluble solvent is used as the developing solution. A suitable amount of surfactant may be added to this alkaline solution. Furthermore, a general development method can be employed. After the developing process, the developing solution is usually washed off and the cured coating film of the colored resin composition is dried to form the colored layer. Alternatively, heat treatment may be performed after the developing process to fully cure the coating film. There are no particular limitations on the heating conditions, and they can be appropriately selected depending on the application of the coating film.

[0217] [Light-blocking part] The light-shielding portion in the color filter of the present invention is formed in a pattern on the substrate and can be the same as that used as a light-shielding portion in a general color filter. The pattern shape of the light-shielding portion is not particularly limited, and examples include stripe-like and matrix-like shapes. The light-shielding portion may be a thin metal film such as chromium produced by sputtering or vacuum deposition. Alternatively, the light-shielding portion may be a resin layer containing light-shielding particles such as carbon nanoparticles, metal oxides, inorganic pigments, or organic pigments in a resin binder. In the case of a resin layer containing light-shielding particles, methods include patterning by developing with a photosensitive resist, patterning with an inkjet ink containing light-shielding particles, or thermal transfer of a photosensitive resist. The film thickness of the light-shielding portion is set to approximately 0.2 μm to 0.4 μm in the case of a thin metal film, and to approximately 0.5 μm to 2 μm in the case of a black pigment dispersed or dissolved in a binder resin.

[0218] [Transparent substrate] The transparent substrate can be any substrate that is transparent to visible light, and is not particularly limited; transparent substrates commonly used in color filters can be used. Specifically, examples include rigid transparent materials that do not allow flexibility, such as quartz glass, alkali-free glass, and synthetic quartz plates, or flexible transparent materials that have flexibility, such as transparent resin films, optical resin plates, and flexible glass. Transparent substrates used in such color filters usually have polar groups on their surface. From the viewpoint of improving the adhesion of the photosensitive colored resin composition of the present invention to the substrate, the transparent substrate is preferably a substrate containing silicon dioxide, such as quartz glass, alkali-free glass, or synthetic quartz plate. The thickness of the transparent substrate is not particularly limited, but depending on the application of the color filter, for example, a thickness of 50 μm to 1 mm can be used. Furthermore, the color filter of the present invention may have, in addition to the transparent substrate, light-shielding portion, and colored layer described above, an overcoat layer, a transparent electrode layer, an alignment film for aligning liquid crystal material, a columnar spacer, and the like formed thereon. The color filter of the present invention is not limited to the configuration described above, and known configurations commonly used in color filters can be appropriately selected and used.

[0219] V.Display device The display device according to the present invention is characterized by having the color filter according to the present invention. The configuration of the display device in the present invention is not particularly limited and can be appropriately selected from conventionally known display devices, such as liquid crystal display devices and organic light-emitting display devices.

[0220] [Liquid crystal display device] The liquid crystal display device of the present invention is characterized by comprising the color filter according to the present invention described above, a counter substrate, and a liquid crystal layer formed between the color filter and the counter substrate. Figure 2 is a schematic diagram showing an example of a liquid crystal display device belonging to the present invention. As illustrated in Figure 2, the liquid crystal display device 40 of the present invention has a color filter 10, a counter substrate 20 having a TFT array substrate or the like, and a liquid crystal layer 30 formed between the color filter 10 and the counter substrate 20. It should be noted that the liquid crystal display device of the present invention is not limited to the configuration shown in Figure 2, and can be configured in a way that is generally known as a liquid crystal display device using a color filter.

[0221] The driving method for the liquid crystal display device of the present invention is not particularly limited, and any driving method commonly used in liquid crystal display devices can be employed. Examples of such driving methods include the TN method, IPS method, OCB method, and MVA method. Any of these methods can be suitably used in the present invention. Furthermore, the opposing substrate can be appropriately selected and used depending on the driving method of the liquid crystal display device of the present invention. As for the method of forming the liquid crystal layer, methods generally used for manufacturing liquid crystal cells can be used, such as the vacuum injection method and the liquid crystal drop method.

[0222] [Organic light-emitting display device] The organic light-emitting display device according to the present invention is characterized by comprising the color filter according to the present invention described above and an organic light-emitting element. Figure 3 is a schematic diagram showing an example of an organic light-emitting display device belonging to the present invention. As illustrated in Figure 3, the organic light-emitting display device 100 of the present invention has a color filter 10 and an organic light-emitting element 80. An organic protective layer 50 or an inorganic oxide film 60 may be provided between the color filter 10 and the organic light-emitting element 80.

[0223] Examples of methods for laminating the organic light-emitting element 80 include sequentially forming a transparent anode 71, a hole injection layer 72, a hole transport layer 73, a light-emitting layer 74, an electron injection layer 75, and a cathode 76 on the upper surface of a color filter, or laminating an organic light-emitting element 80 formed on a separate substrate onto an inorganic oxide film 60. The transparent anode 71, hole injection layer 72, hole transport layer 73, light-emitting layer 74, electron injection layer 75, cathode 76, and other components of the organic light-emitting element 80 can be those of known origin or design. The organic light-emitting display device 100 thus fabricated can be applied to both passively driven organic EL displays and actively driven organic EL displays, for example. It should be noted that the organic light-emitting display device of the present invention is not limited to the configuration shown in Figure 3, and can be configured in a way that is generally known as an organic light-emitting display device using a color filter. [Examples]

[0224] The present invention will be described in detail below with reference to examples. These descriptions are not intended to limit the present invention. The weight-average molecular weight (Mw) was determined as a standard polystyrene equivalent value by GPC (gel permeation chromatography) according to the measurement method of the present invention described above. The acid value and hydroxyl value were determined according to the method specified in JIS K 0070:1992. The viscosity of the binder resin produced in each manufacturing example was determined by drying the obtained binder resin solution (40% solids by mass) under reduced pressure at a pressure of 20-30 hPa and a temperature of 80°C, concentrating it until the solids content reached 60% by mass, and then circulating and heating it in a 90°C water bath, using a B-type viscometer.

[0225] (Synthesis Example 1: Synthesis of Lake Colorant 1) (1) Synthesis of intermediate 1 Referring to the methods for producing intermediates A-2, B-1, and compound 1-3 described in Japanese Patent Publication No. 2018-3013, intermediate 1 represented by the following chemical formula (a) was obtained (yield 87%). The obtained compound was confirmed to be the target compound based on the analysis results below. ·MS(ESI) (m / z):677(+), bivalent • Elemental analysis values: CHN measured values ​​(81.81%, 7.31%, 5.85%); theoretical values ​​(81.77%, 7.36%, 5.90%)

[0226] [ka]

[0227] (2) Synthesis of Lake Colorant 1 2.59 g (0.76 mmol) of Kanto Chemical's 12-tungst phosphate n-hydrate was heated and dissolved in a mixture of 40 mL of methanol and 40 mL of water. 1.6 g (1.19 mmol) of the aforementioned intermediate 1 was added, and the mixture was stirred for 1 hour. The precipitate was filtered and washed with water. The obtained precipitate was dried under reduced pressure to obtain lake colorant 1 represented by the following chemical formula (b) (yield 95%). The obtained compound was confirmed to be the target compound based on the analysis results below. ·31P NMR(d-DMSO, ppm)δ-15.15 MS (MALDI) (m / z): 1355 (M + ), 2879 (MH2 - ) • Elemental analysis values: CHN measured values ​​(35.55%, 3.24%, 2.61%); theoretical values ​​(35.61%, 3.20%, 2.57%) • X-ray fluorescence analysis: MoW measurement ratio (0%, 100%); theoretical value (0%, 100%)

[0228] [ka]

[0229] (Synthesis Example 2: Synthesis of Xanthene Dye 1) In a 500 ml four-necked flask, 40.2 parts by mass of a sulfofluorane compound represented by the following chemical formula (c), 312 parts by mass of methanol, 6.8 parts by mass of 2,6-xylidine, and 6.0 parts by mass of N-methyl-o-toluidine were charged and refluxed for 30 hours. The reaction mixture was filtered at 60°C to remove insoluble matter, and then the solvent was removed under reduced pressure until the reaction mixture was approximately 70 ml, and then poured into 200 parts by mass of 6% hydrochloric acid. Next, 600 parts by mass of water was added and the mixture was stirred at room temperature for 30 minutes, after which the wet cake was filtered off. The wet cake was suspended in 100 parts by mass of water and stirred at 60°C for 2 hours, filtered again, washed with hot water at 60°C, and dried to obtain 27.4 parts by mass of xanthene dye 1 represented by the following chemical formula.

[0230] [ka]

[0231] [ka]

[0232] (Synthesis Example 3: Synthesis of Xanthene Dye 2) In a 500 ml four-necked flask, 18.0 parts by mass of the sulfofluorane compound represented by the above chemical formula (c), 312 parts by mass of methanol, 5.4 parts by mass of 2,6-xylidine, and 4.8 parts by mass of o-toluidine were charged and refluxed for 30 hours. The reaction mixture was filtered at 60°C to remove insoluble matter, and then the solvent was removed under reduced pressure until the reaction mixture was reduced to approximately 70 ml, and then poured into 200 parts by mass of 6% hydrochloric acid. Next, 600 parts by mass of water was added and the mixture was stirred at room temperature for 30 minutes, after which the wet cake was filtered off. The wet cake was suspended in 100 parts by mass of water and stirred at 60°C for 2 hours, filtered again, washed with hot water at 60°C, and dried to obtain 21.9 parts by mass of intermediate I-1 represented by the following chemical formula.

[0233] [ka]

[0234] Next, a mixture of 20 parts by mass of intermediate I-1, 135.3 parts by mass of 1-methyl-2-pyrrolidinone, 7.8 parts by mass of potassium carbonate, and 16.2 parts by mass of methyl iodide was stirred at 80°C for 2 hours. After the reaction was complete, the reaction solution was allowed to cool to room temperature, and then the reaction solution was added dropwise to 541.2 parts by mass of 17.5% hydrochloric acid at 0-10°C and stirred for 1 hour. After that, the precipitate was filtered off, and the residue was dried at 60°C for 24 hours to obtain 20.4 parts by mass of crystals. 20 parts by mass of the obtained crystals and 106 parts by mass of phosphorus oxychloride were placed in a flask and stirred at 60°C for 2 hours. The resulting reaction solution was allowed to cool to room temperature, and the reaction solution was added dropwise to 1500 parts by mass of ice water and stirred for 30 minutes. The obtained crystals were filtered off, washed with 200 parts by mass of water, and dried for 10 hours. 7 parts by mass of these crystals and 1.8 parts by mass of trifluoromethylsulfonamide were dissolved in 40 parts by mass of chloroform, and 1.55 parts by mass of triethylamine was added dropwise and stirred at room temperature for 1 hour. Then, 100 parts by mass of water was added to the resulting reaction solution and washed with water, and the organic layer was separated. The organic layer was dried and purified over sodium sulfate, and concentrated under reduced pressure to obtain 6.8 parts by mass of xanthene dye 2 represented by the following chemical formula (yield 80%).

[0235] [ka]

[0236] (Synthesis Example 4: Synthesis of xanthene-based metallic lake colorant 3) 5.0 parts by mass of Acid Red 289 was added to 500 ml of water and dissolved at 80°C to prepare a dye solution. 3.85 parts by mass of polyaluminum chloride ("Takibain #1500", manufactured by Taki Chemical Co., Ltd., Al2(OH)5Cl, basicity 83.5% by mass, alumina content 23.5% by mass) was added to 200 ml of water and stirred at 80°C to prepare an aqueous solution of polyaluminum chloride. The prepared aqueous solution of polyaluminum chloride was added dropwise to the dye solution over 15 minutes at 80°C and stirred for 1 hour at 80°C. The resulting precipitate was filtered and washed with water. The obtained cake was dried to obtain 6.30 parts by mass (yield 96.2%) of xanthene-based metal lake colorant 3, which is a xanthene-based dye metal lake colorant.

[0237] (Synthesis Example 5: Synthesis of Basic-treated PB15:6) In a reaction vessel, 300 parts by mass of chlorosulfonic acid and 30 parts by mass of copper phthalocyanine were added and completely dissolved. Then, 24 parts by mass of thionyl chloride were added, and the temperature was gradually increased, reacting at 101°C for 3 hours. The reaction solution was poured into 9000 parts by mass of ice water, stirred, filtered, and washed with water. The resulting press cake was made into a slurry with 300 parts by mass of water, then 13 parts by mass of 1,1-diethyl-1,5-diazapentane was added, stirred at 65°C for 4 hours, filtered, washed with water, and dried to obtain blue colorant derivative 1 having a basic moiety for surface treatment. The structure of the obtained blue colorant derivative 1 having a basic moiety was confirmed to be that of the following chemical formula (d). TOF-MS: 768.35

[0238] [ka]

[0239] 100 parts by mass of commercially available CI pigment blue 15:6 (ε-type copper phthalocyanine pigment, DIC FASTOGEN BLUE A510) and 5 parts by mass of the blue pigment derivative 1 having the basic moiety were dry-ground in an attritor at 60°C for 1.5 hours. By further mixing 5 parts by mass of the blue pigment derivative 1 having the basic moiety with this pulverized product, a basic-treated CI pigment blue 15:6, or basic-treated PB15:6, was obtained.

[0240] (Synthesis Example 6: Synthesis of Acidic Dispersant A1 (a polymer having the constituent units represented by the general formula (I) above)) (1) Synthesis of macromonomer MM-1 In a reactor equipped with a condenser, an additive funnel, a nitrogen inlet, a mechanical stirrer, and a digital thermometer, 80.0 parts by mass of propylene glycol monomethyl ether acetate (PGMEA) was charged and heated to 90°C while stirring under a nitrogen atmosphere. A mixed solution of 50.0 parts by mass of methyl methacrylate, 30.0 parts by mass of n-butyl methacrylate, 20.0 parts by mass of benzyl methacrylate, 4.0 parts by mass of 2-mercaptoethanol, 30 parts by mass of PGMEA, and 1.0 part by mass of α,α'-azobisisobutyronitrile (AIBN) was added dropwise over 1.5 hours, and the reaction was continued for a further 3 hours. Next, the nitrogen gas flow was stopped, and the reaction solution was cooled to 80°C. 8.74 parts by mass of currant MOI (Showa Denko), 0.125 parts by mass of dibutyltin dilaurate, 0.125 parts by mass of p-methoxyphenol, and 10 parts by mass of PGMEA were added, and the mixture was stirred for 3 hours to obtain a 49.5% by mass solution of macromonomer MM-1. GPC measurements of the obtained macromonomer MM-1 showed a weight-average molecular weight (Mw) of 4010, a number-average molecular weight (Mn) of 1910, and a molecular weight distribution (Mw / Mn) of 2.10.

[0241] (2) Synthesis of graft copolymer A1 In a reactor equipped with a condenser, an additive funnel, a nitrogen inlet, a mechanical stirrer, and a digital thermometer, 85.0 parts by mass of PGMEA were charged, and the mixture was heated to 90°C while stirring under a nitrogen atmosphere. A mixed solution of 67.34 parts by mass (33.33 parts by mass of solids) of the macromonomer MM-1 solution, 16.67 parts by mass of glycidyl methacrylate (abbreviated as GMA), 1.24 parts by mass of n-dodecyl mercaptan, 25.0 parts by mass of PGMEA, and 0.5 parts by mass of AIBN was added dropwise over 1.5 hours, and the mixture was heated and stirred for 3 hours. Then, a mixed solution of 0.10 parts by mass of AIBN and 10.0 parts by mass of PGMEA was added dropwise over 10 minutes, and the mixture was aged at the same temperature for 1 hour to obtain a 25.0% by mass solution of graft copolymer A1. The obtained graft copolymer A1 was measured by GPC and found to have a weight-average molecular weight (Mw) of 10570, a number-average molecular weight (Mn) of 4370, and a molecular weight distribution (Mw / Mn) of 2.42.

[0242] (3) Production of a polymer (acidic dispersant A1) having a constituent unit represented by the general formula (I) above. In a reactor equipped with a condenser, an additive funnel, a nitrogen inlet, a mechanical stirrer, and a digital thermometer, 27.80 parts by mass of PGMEA and 9.27 parts by mass of phenylphosphonic acid (product name "PPA," manufactured by Nissan Chemical) were charged, and the mixture was heated to 90°C while stirring under a nitrogen atmosphere. 100.0 parts by mass of the graft copolymer A1 was added dropwise over 30 minutes, and the mixture was heated and stirred for 2 hours to obtain a polymer solution (acidic dispersant A1) having the constituent units represented by the general formula (I) (solid content 25.0% by mass). The progress of the esterification reaction between GMA and PPA in the obtained acidic dispersant A1 was measured by acid value measurement and 1 This was confirmed by 1H-NMR measurement (confirming the disappearance of peaks derived from epoxy). The acid value of the obtained acidic dispersant A1 was 98 mgKOH / g.

[0243] (Synthesis Example 7: Synthesis of Acidic Dispersant B1 (a block copolymer containing a block A with structural units derived from a carboxyl group-containing ethylenically unsaturated monomer and a block B with structural units derived from an alkyl (meth)acrylate)) Referring to Example 1 described in International Publication No. 2016 / 132863, a triblock copolymer was synthesized comprising a block containing 20 parts by mass of methyl methacrylate (MMA) and 40 parts by mass of n-butyl methacrylate (BMA), a block containing 20 parts by mass of methacrylic acid (MAA) and 20 parts by mass of BMA, and a block containing 20 parts by mass of MMA and 40 parts by mass of BMA. The obtained block copolymer had a weight-average molecular weight (Mw) of 11000, a molecular weight distribution (Mw / Mn) of 1.50, and an acid value of 130 mgKOH / g.

[0244] (Synthesis Example 8: Synthesis of alkali-soluble resin A) 150 parts by mass of PGMEA were charged into a polymerization tank, and the temperature was raised to 100°C under a nitrogen atmosphere. Then, 22 parts by mass of methacrylic acid (MAA), 64 parts by mass of cyclohexyl methacrylate (CHMA), 6 parts by mass of perbutyl O (manufactured by NOF Corporation) as a photoinitiator, and 2 parts by mass of a chain transfer agent (n-dodecyl mercaptan) were added dropwise over 1.5 hours. The reaction was then continued at 100°C, and 2 hours after the completion of the dropwise addition of the main chain forming mixture, 0.1 parts by mass of p-methoxyphenol was added as a polymerization inhibitor to stop the polymerization. Next, while blowing air in, 14 parts by mass of glycidyl methacrylate (GMA) as an epoxy group-containing compound was added, the temperature was raised to 110°C, and then 0.8 parts by mass of triethylamine was added and the addition reaction was carried out at 110°C for 15 hours to obtain alkali-soluble resin A solution (weight-average molecular weight (Mw) 9,000, acid value 90 mg KOH / g, solid content 40% by mass).

[0245] (Synthesis Example 9: Synthesis of Lake Colorant 4) (1) K6(P2MoW 17 O 62 Preparation of ) 44.0 g of NaWO4·2H2O (manufactured by Wako Pure Chemical Industries, Ltd.) and 1.90 g of Na2MoO4·2H2O (manufactured by Kanto Chemical Co., Ltd.) were dissolved in 230 g of purified water. 64.9 g of 85% phosphoric acid was added to this solution dropwise using a funnel while stirring. The resulting solution was heated under reflux for 8 hours. The reaction mixture was cooled to room temperature, 1 drop of bromine water was added, and 45 g of potassium chloride was added while stirring. After stirring for another hour, the precipitate was filtered off. The resulting solid was dried at 90°C to obtain 29.4 g of K6(P2MoW 17 O 62 ) was obtained. (2) Synthesis of Lake Colorant 4 5.30 g of CI Basic Blue 7 (BB7) (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to 350 ml of purified water and stirred at 40°C to dissolve it, and a BB7 solution was prepared. Separately, the K6 (P2MoW) prepared in (1) above was used. 17 O 62 ) 10.0g was dissolved in 40ml of purified water. K6(P2MoW) was added to the BB7 solution. 17 O 62The solution was added and stirred at 40°C for 1 hour. Next, the internal temperature was raised to 80°C and stirred for another hour to perform lake formation. After cooling, the mixture was filtered and washed three times with 300 ml of purified water. By drying the obtained solid at 90°C, 10.4 g of lake colorant 4, a blackish-blue solid with an average primary particle size of 40 nm, consisting of a triarylmethane dye and a polyacid anion, was obtained.

[0246] (Manufacturing Example 1: Manufacturing of Binder Resin 1) 150 parts by mass of PGMEA were charged into a polymerization vessel, and the temperature was raised to 100°C under a nitrogen atmosphere. Then, 26.9 parts by mass of methacrylic acid (MAA), 38.9 parts by mass of benzyl methacrylate (BzMA), 5 parts by mass of 2-hydroxyethyl methacrylate (HEMA), and 1.4 parts by mass of perbutyl O (manufactured by NOF Corporation) as a photoinitiator, and 2.5 parts by mass of a chain transfer agent (n-dodecyl mercaptan) were added dropwise over 1.5 hours. The reaction was then continued while maintaining the temperature at 100°C, and 2 hours after the completion of the dropwise addition of the main chain forming mixture, 0.1 parts by mass of p-methoxyphenol was added as a polymerization inhibitor to stop the polymerization. Next, while blowing air in, 29.2 parts by mass of glycidyl methacrylate (GMA) as an epoxy group-containing compound was added, the temperature was raised to 110°C, and then 0.8 parts by mass of triethylamine was added and the addition reaction was carried out at 110°C for 15 hours to obtain binder resin solution 1 (weight-average molecular weight (Mw) 14,900, acid value 67 mg KOH / g, hydroxyl value 129 mg KOH / g, solid content 40% by mass).

[0247] (Manufacturing examples 2-9, comparative manufacturing examples 1-9: Manufacturing of binder resins 2-9 and comparative binder resins C1-C9) In Production Example 1, the binder resin solutions 2-9 of Production Examples 2-9 and comparative binder resin solutions C1-C9 of Comparative Production Examples 1-9 were obtained in the same manner as in Production Example 1, except that the amounts of monomer, photoinitiator, and chain transfer agent added were changed according to Table 1. (Each binder resin solution had a solid content of 40% by mass.)

[0248] (Comparative manufacturing example 10: Manufacturing of comparative binder resin C10) 150 parts by mass of PGMEA was placed in a polymerization tank, and the temperature was raised to 110°C under a nitrogen atmosphere. Then, 81.5 parts by mass of t-butylcyclohexyl methacrylate (t-BuCHMA), 15.0 parts by mass of methacrylic acid (MAA), 3.5 parts by mass of 2-hydroxyethyl methacrylate (HEMA), and 3.0 parts by mass of AIBN as a photoinitiator were added dropwise, one by one, over 1.5 hours. After that, the mixture was stirred at 110°C for 2 hours to obtain a comparative binder resin C10 solution (solid content 40% by mass).

[0249] [Table 1]

[0250] (Preparation Example 1: Preparation of Lake Colorant Dispersion) 10 parts by mass of Lake Colorant 1 from Synthesis Example 1, 20 parts by mass of Acid Dispersant A1 Solution from Synthesis Example 6 (effective solids content 5.0 parts by mass), 7.5 parts by mass of Alkali-Soluble Resin A Solution from Synthesis Example 8 (effective solids content 3.0 parts by mass), and 62.5 parts by mass of PGMEA were mixed and dispersed in a paint shaker (manufactured by Asada Iron Works) using 2 mm zirconia beads for 1 hour as a preliminary dispersion, and then with 0.1 mm zirconia beads for 4 hours as a final dispersion to obtain Lake Colorant 1 dispersion.

[0251] (Preparation Example 2: Preparation of a dispersion of xanthene-based metal lake colorants) Ten parts by mass of xanthene-based metal lake colorant 3 from Synthesis Example 4, 16.7 parts by mass of acidic dispersant B1 solution from Synthesis Example 7 (effective solids content 5.0 parts by mass), 7.5 parts by mass of alkali-soluble resin A solution from Synthesis Example 8 (effective solids content 3.0 parts by mass), and 65.8 parts by mass of PGMEA were mixed and dispersed in a paint shaker (manufactured by Asada Iron Works) with 2 mm zirconia beads for 1 hour as a preliminary dispersion, and then with 0.1 mm zirconia beads for 4 hours as a final dispersion to obtain a dispersion of xanthene-based metal lake colorant 3.

[0252] (Preparation Example 3: Preparation of a xanthene dye solution) 5.0 parts by mass of xanthene dye 1 from Synthesis Example 2 was dissolved in 45 parts by mass of diacetone alcohol to obtain xanthene dye 1 solution.

[0253] (Preparation Example 4: Preparation of two xanthene dye solutions) 5.0 parts by mass of xanthene dye 2 from Synthesis Example 3 was dissolved in 45 parts by mass of diacetone alcohol to obtain a solution of xanthene dye 2.

[0254] (Preparation Example 5: Preparation of PB15:6 dispersion) 10 parts by mass of the basic treatment PB15:6 from Synthesis Example 5, 16.7 parts by mass of the acidic dispersant B1 solution from Synthesis Example 7 (effective solids content 5.0 parts by mass), 7.5 parts by mass of the alkali-soluble resin A solution from Synthesis Example 8 (effective solids content 3.0 parts by mass), and 65.8 parts by mass of PGMEA were mixed and dispersed using a paint shaker (manufactured by Asada Iron Works) with 2 mm zirconia beads for 1 hour as a preliminary dispersion, and then with 0.1 mm zirconia beads for 6 hours as a final dispersion to obtain a PB15:6 dispersion.

[0255] (Preparation Example 6: Preparation of PV23 dispersion) In a 30ml mayonnaise bottle, 10 parts by weight of commercially available CI pigment violet 23 (PV23), 16.7 parts by weight of acidic dispersant B1 solution from Synthesis Example 7 (effective solids content 5.0 parts by weight), 7.5 parts by weight of alkali-soluble resin A solution from Synthesis Example 8 (effective solids content 3.0 parts by weight), 65.8 parts by weight of PGMEA, and 30 parts by weight of 2mm diameter zirconia beads were added. After pre-disintegrating for 1 hour using a paint shaker (manufactured by Asada Steel), the mixture was transferred to another 30ml mayonnaise bottle, 30 parts by weight of 0.1mm diameter zirconia beads were added, and the mixture was shaken in a paint shaker for 5 hours to obtain a PV23 dispersion.

[0256] (Preparation Example 7: Preparation of a four-dispersion of lake colorant) A dispersion of lake colorant 4 was prepared in the same manner as in Preparation Example 1, except that, as in Preparation Example 1, 10 parts by mass of lake colorant 4 from Synthesis Example 6 was used instead of 10 parts by mass of lake colorant 1 from Synthesis Example 1 as the colorant.

[0257] (Preparation Example I: Preparation of Photosensitive Binder Component 1) To 26.5 parts by mass of binder resin solution 1 of Production Example 1 (solid content 40% by mass), 24.7 parts by mass of dipentaerythritol hexaacrylate (DPHA) (Aronics M402 (manufactured by Toagosei)) as a photopolymerizable compound, 3.53 parts by mass of Irgacure 907 (manufactured by BASF, α-aminoketone-based photoinitiator) and 0.39 parts by mass of Kayacure DETX-S (manufactured by Nippon Kayaku, thioxanthone-based photoinitiator, 2,4-diethylthioxanthone) were added as photoinitiators, 0.78 parts by mass of IRGANOX1010 (manufactured by BASF) as antioxidants, and 44.1 parts by mass of PGMEA were added to obtain photosensitive binder component 1.

[0258] (Preparation Examples II-IX, Comparative Preparation Examples I-X: Preparation of photosensitive binder components 2-9, comparative photosensitive binder components 1-10) In the preparation of photosensitive binder component 1 in Preparation Example I, the binder resin solutions 2 to 9 from Production Examples 2 to 9 were used in place of binder resin solution 1 from Production Example 1 in Preparation Examples II to IX, and comparative binder resin solutions C1 to C10 from Comparative Production Examples C1 to C10 were used in Comparative Preparation Examples I to X. Otherwise, the process was the same as in Preparation Example I, yielding photosensitive binder components 2 to 9 in Preparation Examples II to IX and comparative photosensitive binder components C1 to C10 in Comparative Preparation Examples I to X.

[0259] (Example 1) 23.2 parts by mass of the lake colorant dispersion of Preparation Example 1, 32.1 parts by mass of the photosensitive binder component 1 of Preparation Example I, 0.03 parts by mass of the surfactant Megafac R08MH (manufactured by DIC), and 44.7 parts by mass of PGMEA were mixed to obtain the photosensitive colored resin composition of Example 1.

[0260] (Examples 2-9, Comparative Examples 1-10) In preparing the photosensitive colored resin composition of Example 1, the photosensitive binder components 2 to 9 were used in place of photosensitive binder component 1 in Examples 2 to 9, and comparative photosensitive binder components C1 to C10 were used in Comparative Examples 1 to 10. Otherwise, the photosensitive colored resin compositions of Examples 2 to 9 and Comparative Examples 1 to 10 were obtained in the same manner as in Example 1.

[0261] (Comparative Examples 11-12) In preparing the photosensitive colored resin composition of Example 1, 25.5 parts by mass of PB15:6 dispersion and 4.0 parts by mass of PV23 dispersion were used instead of 23.2 parts by mass of lake colorant 1 dispersion, so that the mass ratio of basic treated PB15:6 to PV23 (basic treated PB15:6 :PV23) was 86.4:13.6. Furthermore, instead of 32.1 parts by mass of photosensitive binder component 1, 29.2 parts by mass of photosensitive binder component 2 was used in Comparative Example 11, and 29.2 parts by mass of comparative photosensitive binder component C5 was used in Comparative Example 12. The amount of PGMEA added was changed from 44.7 parts by mass to 41.3 parts by mass. Otherwise, the photosensitive colored resin compositions of Comparative Examples 11 and 12 were obtained in the same manner as in Example 1.

[0262] (Example 10, Comparative Examples 13-15) In preparing the photosensitive colored resin composition of Example 1, instead of 23.2 parts by mass of lake colorant 1 dispersion, 17.6 parts by mass of lake colorant 1 dispersion and 1.32 parts by mass of xanthene-based metal lake colorant 3 dispersion were used, such that the mass ratio of lake colorant 1 to xanthene-based metal lake colorant 3 (lake colorant 1: xanthene-based metal lake colorant 3) was 93.0:7.0. Furthermore, instead of 32.1 parts by mass of photosensitive binder component 1, 34.0 parts by mass of photosensitive binder component 2 was used in Example 10, 34.0 parts by mass of comparative photosensitive binder component C1 was used in Comparative Example 13, 34.0 parts by mass of comparative photosensitive binder component C4 was used in Comparative Example 14, and comparative photosensitive binder component C6 was used in Comparative Example 15. Except for using 34.0 parts by mass and changing the amount of PGMEA added from 44.7 parts by mass to 47.1 parts by mass, the photosensitive colored resin compositions of Example 10 and Comparative Examples 13-15 were obtained in the same manner as in Example 1.

[0263] (Example 11, Comparative Examples 16-18) In preparing the photosensitive colored resin composition of Example 1, instead of 23.2 parts by mass of lake colorant 1 dispersion, 17.3 parts by mass of lake colorant 1 dispersion and 1.06 parts by mass of xanthene dye 1 solution were used, such that the mass ratio of lake colorant 1 to xanthene dye 1 (lake colorant 1: xanthene dye 1) was 94.2:5.8. Furthermore, instead of 32.1 parts by mass of photosensitive binder component 1, 34.4 parts by mass of photosensitive binder component 2 was used in Example 11, 34.4 parts by mass of comparative photosensitive binder component C1 was used in Comparative Example 16, 34.4 parts by mass of comparative photosensitive binder component C4 was used in Comparative Example 17, and comparative photosensitive binder component C6 was used in Comparative Example 18. Except for using 34.4 parts by mass and changing the amount of PGMEA added from 44.7 parts by mass to 47.2 parts by mass, the photosensitive colored resin compositions of Example 11 and Comparative Examples 16-18 were obtained in the same manner as in Example 1.

[0264] (Example 12, Comparative Examples 19-21) In preparing the photosensitive colored resin composition of Example 1, instead of 23.2 parts by mass of lake colorant 1 dispersion, 17.3 parts by mass of lake colorant 1 dispersion and 1.06 parts by mass of xanthene dye 2 solution were used, such that the mass ratio of lake colorant 1 to xanthene dye 2 (lake colorant 1: xanthene dye 2) was 94.2:5.8. Furthermore, instead of 32.1 parts by mass of photosensitive binder component 1, 34.4 parts by mass of photosensitive binder component 2 was used in Example 12, 34.4 parts by mass of comparative photosensitive binder component C1 was used in Comparative Example 19, 34.4 parts by mass of comparative photosensitive binder component C4 was used in Comparative Example 20, and comparative photosensitive binder component C6 was used in Comparative Example 21. Except for using 34.4 parts by mass and changing the amount of PGMEA added from 44.7 parts by mass to 47.2 parts by mass, the photosensitive colored resin compositions of Example 12 and Comparative Examples 19-21 were obtained in the same manner as in Example 1.

[0265] (Comparative Examples 22-23) In preparing the photosensitive colored resin composition of Example 1, 17.4 parts by mass of PB15:6 dispersion and 5.35 parts by mass of PV23 dispersion were used instead of 23.2 parts by mass of lake colorant 1 dispersion, so that the mass ratio of basic treated PB15:6 to PV23 (basic treated PB15:6 :PV23) was 76.5:23.5. Furthermore, instead of 32.1 parts by mass of photosensitive binder component 1, 32.2 parts by mass of photosensitive binder component 2 were used in Comparative Example 22, and 32.2 parts by mass of comparative photosensitive binder component C5 were used in Comparative Example 23. The amount of PGMEA added was changed from 44.7 parts by mass to 44.9 parts by mass. Otherwise, the photosensitive colored resin compositions of Comparative Examples 22 and 23 were obtained in the same manner as in Example 1.

[0266] (Example 13, Comparative Examples 24-26) In preparing the photosensitive colored resin composition of Example 1, instead of 23.2 parts by mass of lake colorant 1 dispersion, 18.3 parts by mass of lake colorant 1 dispersion and 12.4 parts by mass of PB15:6 dispersion were used so that the mass ratio of lake colorant 1 to basic-treated PB15:6 (lake colorant 1: basic-treated PB15:6) was 59.6:40.4. Furthermore, instead of 32.1 parts by mass of photosensitive binder component 1, 28.7 parts by mass of photosensitive binder component 2 was used in Example 13, 28.7 parts by mass of comparative photosensitive binder component C1 was used in Comparative Example 24, 28.7 parts by mass of comparative photosensitive binder component C4 was used in Comparative Example 25, and comparative photosensitive binder component C6 was used in Comparative Example 26. Except for using 28.7 parts by mass and changing the amount of PGMEA added from 44.7 parts by mass to 40.6 parts by mass, the photosensitive colored resin compositions of Example 13 and Comparative Examples 24-26 were obtained in the same manner as in Example 1.

[0267] (Comparative Examples 27-28) In preparing the photosensitive colored resin composition of Example 1, 34.8 parts by mass of PB15:6 dispersion and 2.82 parts by mass of PV23 dispersion were used instead of 23.2 parts by mass of lake colorant 1 dispersion, so that the mass ratio of basic treated PB15:6 to PV23 (basic treated PB15:6 :PV23) was 92.5:7.5. Furthermore, instead of 32.1 parts by mass of photosensitive binder component 1, 25.6 parts by mass of photosensitive binder component 2 was used in Comparative Example 27, and 25.6 parts by mass of comparative photosensitive binder component C5 was used in Comparative Example 28. The amount of PGMEA added was changed from 44.7 parts by mass to 36.8 parts by mass. Otherwise, the photosensitive colored resin compositions of Comparative Examples 27 and 28 were obtained in the same manner as in Example 1.

[0268] (Examples 1-2 to 9-2, Comparative Examples 1-2 to 10-2) In preparing the photosensitive colored resin compositions of Examples 1-9 and Comparative Examples 1-10, the photosensitive colored resin compositions of Examples 1-2 to 9-2 and Comparative Examples 1-2 to 10-2 were obtained in the same manner as in Examples 1-9 and Comparative Examples 1-10, except that the lake colorant dispersion 4 of Preparation Example 7 was used instead of the lake colorant dispersion 1 of Preparation Example 1.

[0269] [Evaluation Method] <Colored layer shape> The photosensitive colored resin composition of Example 1 was applied to a 0.7 mm thick glass substrate ("NA35" manufactured by NH Techno Glass Co., Ltd.) using a spin coater to achieve a post-baking film thickness of 2.5 μm, and then heated and dried on a hot plate at 80°C for 3 minutes. Subsequently, a photomask forming a 60 μm line and space was used to apply a pressure of 60 mJ / cm using an ultra-high pressure mercury lamp. 2 The substrate was irradiated with ultraviolet light, and then shower-developed for 60 seconds using a 0.05% by mass potassium hydroxide aqueous solution as an alkaline developer. Subsequently, a pattern-forming substrate was fabricated on the glass substrate by post-baking in a clean oven at 230°C for 30 minutes, resulting in a colored layer with a 60 μm line and space pattern. On the pattern-forming substrates thus prepared, the photosensitive colored resin compositions of each example and comparative example were applied using a spin coater to a post-baking film thickness of 2.5 μm, and then heated and dried at 90°C for 3 minutes using a hot plate. After that, a pressure of 60 mJ / cm² was applied using an ultra-high pressure mercury lamp without using a photomask. 2 After irradiation with ultraviolet light, a colored layer, which is a cured film of the photosensitive colored resin composition of each example or comparative example, was formed between 60 μm patterns by post-baking in a clean oven at 230°C for 30 minutes. After forming the colored layer, the pattern profile was measured using a KLA-Tencor P-17 stylus profiler. Using the center of the base pattern as a reference, the difference in film thickness between the center and a point 15 μm away from the center was determined and evaluated according to the following evaluation criteria. (Evaluation criteria for the shape of the colored layer) A: Film thickness difference is less than 0.05 μm B: Film thickness difference of 0.05 μm or more and less than 0.1 μm C: Film thickness difference of 0.1 μm or more

[0270] <Developing residue evaluation> The photosensitive colored resin compositions of the examples and comparative examples were each applied to a 0.7 mm thick glass substrate ("NA35" manufactured by NH Techno Glass Co., Ltd.) using a spin coater, and then dried on a hot plate at 60°C for 3 minutes to form a 2.5 μm thick colored layer. The glass plate on which the colored layer was formed was shower-developed for 60 seconds using a 0.05% by mass potassium hydroxide aqueous solution as the alkaline developer. After visually observing the area where the colored layer was formed after development, it was thoroughly wiped with a lens cleaner containing ethanol (manufactured by Toray Industries, Inc., product name Toraysee MK Clean Cloth), and the degree of coloration of the lens cleaner was visually observed and evaluated according to the following evaluation criteria. (Developing residue evaluation criteria) A: No development residue was visible to the naked eye, and the lens cleaner did not leave any discoloration. B: No development residue was detected visually, and slight discoloration from the lens cleaner was observed. C: A small amount of development residue was observed visually, and discoloration from the lens cleaner was confirmed. D: Visual inspection revealed development residue and discoloration from the lens cleaner.

[0271] <Brightness> The photosensitive colored resin compositions of the examples and comparative examples were each applied to a 0.7 mm thick glass substrate ("NA35" manufactured by NH Techno Glass Co., Ltd.) using a spin coater so that the chromaticity after post-baking was y = 0.099. Then, they were heated and dried on an 80°C hot plate for 3 minutes, and then subjected to a high-pressure mercury lamp at 60 mJ / cm² without a photomask. 2 A cured film (colored film) was obtained by irradiating the substrate with ultraviolet light and then post-baking it in a clean oven at 230°C for 30 minutes. The brightness (Y) of the obtained colored substrate was measured using an Olympus OSP-SP200 microspectroscopy analyzer and evaluated according to the following evaluation criteria. (Brightness evaluation) A: Brightness (Y) is 13.0 or higher B: Brightness (Y) is between 12.0 and 13.0 C: Brightness (Y) is less than 12.0

[0272] <Heat resistance> After obtaining a cured film (colored film) using the same method as described above for brightness evaluation, the obtained colored film was further post-baked in a clean oven at 240°C for 25 minutes, and the chromaticity (L0, a0, b0) of the colored film was measured. Then, it was further post-baked in a clean oven at 240°C for 50 minutes, and the chromaticity (L1, a1, b1) of the obtained colored film was measured again. The change in chromaticity of the colored film from 25 minutes to 75 minutes after 240°C was evaluated using the following formula. ΔEab={(L1-L0) 2 +(a1-a0) 2 +(b1-b0) 2} 1 / 2 A smaller ΔEab value indicates better heat resistance. A ΔEab value of less than 3.0 is considered acceptable for practical use. (Heat resistance evaluation criteria) A: ΔEab is less than 2.0 B: ΔEab is between 2.0 and 3.0 C:ΔEab is 3.0 or higher

[0273] In Tables 2-5 below, "metal lake colorant 3" refers to the xanthene-based metal lake colorant 3 obtained in Synthesis Example 4, "PB15:6" refers to the basic-treated PB15:6 obtained in Synthesis Example 5, and "PV23" refers to the commercially available CI pigment violet 23. Furthermore, "dispersant A1" refers to the acidic dispersant A1 obtained in Synthesis Example 6, and "dispersant B1" refers to the acidic dispersant B1 obtained in Synthesis Example 7.

[0274] [Table 2]

[0275] [Table 3]

[0276] [Table 4]

[0277] [Table 5]

[0278] [Summary of results] The results in Tables 2-5 show that the colored layers formed using the photosensitive colored resin compositions of Examples 1-13 and 1-2-9-2, which combine a colorant containing at least one selected from the group consisting of dyes and lake colorants, and a binder resin containing a copolymer (hydroxyalkyl (meth)acrylate unit-containing copolymer) having a polymer structure containing 5-25% by mass of constituent units derived from hydroxyalkyl (meth)acrylate represented by general formula (A), a weight-average molecular weight of 11,000 or more, and an acid value of 60-130 mgKOH / g, exhibited high brightness, excellent flatness, and suppressed development residue generation. Furthermore, a comparison between Examples 1-9 and Comparative Examples 1-10 shown in Table 2, and a comparison between Examples 1-2-9-2 and Comparative Examples 1-2-10-2 shown in Table 5, showed that in a photosensitive colored resin composition containing Lake Colorant 1, which is a lake colorant represented by the general formula (1), or Lake Colorant 4, which is a lake colorant represented by the general formula (2), the heat resistance is improved when a hydroxyalkyl (meth)acrylate unit-containing copolymer is used as the binder resin.

[0279] On the other hand, in Comparative Examples 1-4, 13-14, 16-17, 19-20, 24-25, and 1-2-4-2, the inhibitory effect on developing residue was inferior because one of the comparative binder resins C1-C4, which does not contain hydroxyalkyl (meth)acrylate units, was used. In particular, Comparative Examples 4, 14, 17, 20, 25, and 4-2, which used comparative binder resin C4, which does not contain hydroxyalkyl (meth)acrylate units, has a weight-average molecular weight of less than 11,000, and has an acid value exceeding 130 mgKOH / g, showed a particularly poor inhibitory effect on developing residue. In Comparative Examples 1-4, 13-14, 16-17, 19-20, 24-25, and 1-2-4-2, the excellent flatness of the colored layer was observed despite the copolymer used as the binder resin not containing hydroxyalkyl (meth)acrylate units. This is thought to be due to the relatively high acid value of the copolymer, which was 108-147 mgKOH / g. On the other hand, in the photosensitive colored resin composition of the present invention, the hydroxyalkyl (meth)acrylate unit-containing copolymer used as the binder resin contains hydroxyalkyl (meth)acrylate units in the specified amount mentioned above. As long as the acid value is within the range of 60-130 mgKOH / g, the generation of developing residue is suppressed even if the acid value is relatively high. For example, in Examples 8 and 9, although the acid values ​​of the binder resins 8 and 9 used were as high as those in Comparative Examples 1-3, the generation of developing residue was suppressed. In the photosensitive colored resin composition of the present invention, the hydroxyalkyl (meth)acrylate unit-containing copolymer used as the binder resin contains hydroxyalkyl (meth)acrylate units in the specified amount. This allows components with low developability other than the binder resin in the resin composition to interact with the hydroxyalkyl (meth)acrylate units, leading to the development of these components and thus suppressing the generation of residue. If the binder resin does not contain sufficient hydroxyalkyl (meth)acrylate units and has a high acid value, the developability of the binder resin alone becomes too high, leaving the components with low developability behind, which is thought to easily generate residue. In comparative examples using comparative binder resins C1 to C3, since they do not contain hydroxyalkyl (meth)acrylate units, the generation of development residue is easily affected by the acid value, and it is thought that development residue occurred when the acid value was 108 mg KOH / g or higher.

[0280] In Comparative Examples 5 and 5-2, comparative binder resin C5, which does not contain hydroxyalkyl (meth)acrylate units and has a weight-average molecular weight of less than 11,000, was used. Similarly, in Comparative Examples 6-10, 15, 18, 21, 26, and 6-2-10-2, comparative binder resins C6-C10, which also have a weight-average molecular weight of less than 11,000, were used. As a result, the flatness of the colored layer was inferior in each of these cases. In Comparative Examples 11-12, 22-23, and 27-28, the brightness of the colored layer was inferior because only pigments were used as colorants. However, in Comparative Examples 12, 23, and 28, the same comparative binder resin C5 as in Comparative Example 5 was used, and the flatness of the colored layer was excellent. This demonstrates that when pigments are used as colorants, the problem of impaired flatness of the colored layer is less likely to occur. [Explanation of Symbols]

[0281] 1 circuit board 2. Light-shielding part 3 Colored layer 3R red colored layer 3G green colored layer 3B Blue colored layer 3B' Blue coating 10 Color Filters 20 Opposing substrate 30 liquid crystal layers 40 LCD display device 50 Organic protective layer 60 Inorganic oxide film 71 Transparent anode 72 Hole injection layer 73 Hole transport layer 74. Emitting layer 75 Electron injection layer 76 Cathode 80 Organic light-emitting materials 100 Organic Light-Emitting Display Devices

Claims

1. A photosensitive colored resin composition for color filters, comprising a colorant, a binder resin, a monomer, a photoinitiator, and a solvent, The aforementioned colorant does not contain dyes, but contains lake colorants. A photosensitive colored resin composition for color filters, comprising a copolymer in which the binder resin has a polymer structure containing 5 to 25% by mass of constituent units derived from hydroxyalkyl (meth)acrylate represented by the following general formula (A), the polymer structure contains constituent units having a carboxyl group, the constituent units having a carboxyl group are (meth)acrylic acid units, the weight-average molecular weight is 11,000 or more, and the acid value is 60 to 130 mgKOH / g. 【Chemistry 1】 (In general formula (A), R Ａ R represents a methyl group or a hydrogen atom. Ｂ (This represents an alkylene group with 1 to 4 carbon atoms.)

2. The photosensitive colored resin composition for color filters according to claim 1, wherein the colorant comprises a lake colorant represented by the following general formula (1) or general formula (2). 【Chemistry 2】 In general formula (1), A is an a-valent organic group in which the carbon atom directly bonded to N has no π bond, and the organic group is an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at least at the terminal directly bonded to N, or an aromatic group having the aliphatic hydrocarbon group, and a hetero atom may be contained in the carbon chain. B ｃ－ represents a c-valent polyacid anion. R ｉ to R ｖ each independently represents a hydrogen atom, an alkyl group which may have a substituent or an aryl group which may have a substituent, and R ｉｉ and R ｉｉｉ , R ｉｖ and R ｖ may combine to form a ring structure. R ｖｉ and R ｖｉｉ each independently represents an alkyl group which may have a substituent, an alkoxy group which may have a substituent, a halogen atom or a cyano group. Ar １ represents a divalent aromatic group which may have a substituent. A plurality of R ｉ to R ｖｉｉ and Ar １ may be the same or different from each other. a and c represent integers greater than or equal to 2, and b and d represent integers greater than or equal to 1. e is either 0 or 1, and when e is 0, no association exists. f and g represent integers between 0 and 4 (inclusive), and f + e and g + e are between 0 and 4 (inclusive). Multiple e, f, and g may be the same or different. 【Transformation 3】 (In general formula (2), R Ｉ ~R ＶＩ Each independently represents a hydrogen atom, an optionally substituted alkyl group, or an optionally substituted aryl group, R Ｉ and R ＩＩ , R ＩＩＩ and R ＩＶ , R Ｖ and R ＶＩ They may bond to form a ring structure. ＶＩＩ and R ＶＩＩＩ Each of these independently represents an optionally substituted alkyl group, an optionally substituted alkoxy group, a halogen atom, or a cyano group. ２ R represents a divalent aromatic heterocyclic group which may have substituents, and there are multiple R Ｉ ~R ＶＩＩＩ and Ar ２ These may be the same or different. E ｍ－ This represents a polyacid anion with m-valence. m represents an integer greater than or equal to 2. j is either 0 or 1, and when j is 0, no association exists. k and l represent integers between 0 and 4 (inclusive), and k+j and l+j are between 0 and 4 (inclusive). Multiple j, k, and l may be the same or different.

3. The photosensitive colored resin composition for color filters according to claim 2, wherein the colorant further comprises a lake colorant of a xanthene dye different from the lake colorant represented by general formula (1) or general formula (2), and at least one selected from the group consisting of C.I. Pigment Blue 15:

6.

4. The photosensitive colored resin composition for color filters according to claim 3, wherein the xanthene dye lake colorant is a metal lake colorant of a xanthene dye represented by the following general formula (5). 【Chemistry 4】 (In general formula (5), R １’ , R ２’ , R ３’ and R ４’ Each of these independently represents a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group, and R １’ and R ３’ , R ２’ and R ４’ Each of them may bond together to form a ring structure, R １’ and the carbon atom at position 5 of the xanthene ring, R ３’ and the carbon atom at position 7 of the xanthene ring, R ２’ and the carbon atom at position 4 of the xanthene ring, or R ４’ The carbon atoms at position 2 of the xanthene ring may be bonded to each other to form a ring structure. The hydrogen atoms of the above aryl group or heteroaryl group may be substituted with an acidic group or a salt thereof, or a halogen atom. ５’ x represents an acidic group or a salt thereof, and x is an integer from 0 to 5. However, general formula (5) has at least two acidic groups or salts thereof, one of which forms an intramolecular salt.

5. The photosensitive colored resin composition for color filters according to any one of claims 1 to 4, further comprising a dispersant.

6. A cured product of a photosensitive colored 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 colored layer provided on the substrate, wherein at least one of the colored layers is a cured product of the photosensitive colored resin composition for color filters described in any one of claims 1 to 5.

8. A display device having the color filter described in claim 7.

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