WO2022034816A1

WO2022034816A1 - Photosensitive colored resin composition for color filter, cured object, color filter, and display device

Info

Publication number: WO2022034816A1
Application number: PCT/JP2021/028530
Authority: WO
Inventors: 裕史大島; 亘田尻; 美嘉境
Original assignee: 株式会社Ｄｎｐファインケミカル
Priority date: 2020-08-11
Filing date: 2021-08-02
Publication date: 2022-02-17
Also published as: JPWO2022034816A1; CN116113649A; TW202219192A

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), R^A represents a methyl group or a hydrogen atom, and R^B represents a C1-C4 alkylene group.)

Description

Photosensitive colored resin compositions for color filters, cured products, color filters, and display devices

The present invention relates to a photosensitive colored resin composition for a color filter, a cured product thereof, a color filter, and a display device.

In recent years, with the development of personal computers, especially portable personal computers, the demand for liquid crystal displays has increased. The penetration rate of mobile displays (mobile phones, smartphones, tablet PCs) is also increasing, and the market for liquid crystal displays is expanding more and more. Recently, organic light emitting display devices such as organic EL displays having high visibility due to self-luminous light have also attracted attention as next-generation image display devices. In terms of the performance of these image display devices, further improvement in image quality and reduction in power consumption such as improvement in contrast and color reproducibility are strongly desired.

Color filters are used in these liquid crystal displays and organic light emitting displays. For example, in the formation of a color image of a liquid crystal display device, the light that has passed through the color filter is colored as it is in the color of each pixel constituting the color filter, and the light of those colors is combined to form a color image. As the light source at that time, in addition to the conventional cold cathode fluorescent lamp, an organic light emitting element that emits white light or an inorganic light emitting element that emits white light may be used. Further, in the organic light emission display device, a color filter is used for color adjustment and the like.
Under such circumstances, there is an increasing demand for color filters as well, such as higher brightness, higher contrast, and improved color reproducibility.

Here, the color filter is generally formed on a transparent substrate, a colored layer formed on the transparent substrate and composed of colored patterns of the three primary colors of red, green, and blue, and on the transparent substrate so as to partition each colored pattern. It has a formed light-shielding portion.
As a method for forming a colored layer in a color filter, for example, a photosensitive colored resin composition obtained by adding a binder resin, a photopolymerizable compound and a photoinitiator to a color material dispersion liquid in which a color material is dispersed with a dispersant or the like. An object is applied to a glass substrate, dried, exposed with a photomask, and developed to form a colored pattern, and heated to fix the pattern to form a colored layer. These steps are repeated for each color to form a color filter.

The photosensitive colored resin composition for forming a color filter is required to have excellent developability capable of accurately forming a colored layer.
Patent Document 1 contains a pigment, a binder resin, a polyfunctional monomer, a photoinitiator, a dispersant, and a solvent, and the binder resin contains an alkylcyclohexyl (meth) acrylate having an alkylcyclohexyl group and an acid group. A colored photosensitive resin composition for a color filter, which comprises a copolymer having a main chain structure obtained by at least copolymerizing a monomer having the same, and the hydroxyl value of the copolymer is in the range of 15 mgKOH / g to 200 mgKOH / g. Is disclosed.
Patent Document 1 describes that the colored photosensitive resin composition has a small amount of development residue in unexposed areas and a high residual film ratio in exposed areas.

Further, the photosensitive coloring resin composition for forming a color filter is required to be able to form a high-luminance coloring layer. Therefore, it is considered to use a finely divided pigment as a coloring material, or to use a dye or a lake coloring material as a coloring material having a higher transmittance.

Japanese Unexamined Patent Publication No. 2009-276674

The present inventors have attempted to use a dye or a lake colorant as the colorant of the photosensitive coloring resin composition in order to increase the brightness of the color filter. However, when a photosensitive coloring resin composition containing a dye or a lake coloring material 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 colored layer pattern is formed. It was found that the in-pixel film thickness distribution became non-uniform and the flatness of the pixels was impaired.
The present invention has been made in view of the above circumstances, and by containing at least one color material selected from dyes and lake color materials, it has high brightness, excellent flatness, and generation of development residue. It is an object of the present invention to provide a photosensitive colored resin composition for a color filter capable of forming a colored layer in which the amount is suppressed. Another object of the present invention is to provide a cured product of the photosensitive coloring resin composition, and a color filter and a display device formed by using the photosensitive coloring resin composition.

The photosensitive coloring resin composition for a color filter according to the present invention is a photosensitive coloring resin composition for a color filter containing a coloring material, a binder resin, a monomer, a light initiator, and a solvent.
The coloring material contains at least one selected from the group consisting of dyes and lake coloring materials.
The binder resin has a polymer structure containing 5 to 25% by mass of a structural unit derived from hydroxyalkyl (meth) acrylate represented by the following general formula (A), has a weight average molecular weight of 11,000 or more, and has an acid value. Contains a copolymer of 60-130 mgKOH / g.

(In the general formula ( ^A ), RA represents a methyl group or a hydrogen atom, and ^RB represents an alkylene group having 1 to 4 carbon atoms.)

The present invention provides a cured product of the photosensitive coloring resin composition for a color filter according to the present invention.
The present invention is a color filter including at least a substrate and a colored layer provided on the substrate, and at least one of the colored layers is a curing of the photosensitive colored resin composition for a color filter according to the present invention. It provides a color filter, which is a thing.

The present invention provides a display device having the color filter according to the present invention.

According to the present invention, by containing at least one color material selected from a dye and a lake color material, it is possible to form a colored layer having high brightness, excellent flatness, and suppressed generation of development residue. A photosensitive colored resin composition for a color filter is provided. Further, according to the present invention, there is provided a cured product of the photosensitive coloring resin composition, and a color filter and a display device formed by using the photosensitive coloring resin composition.

FIG. 1 is a schematic view showing an example of the color filter of the present invention. FIG. 2 is a schematic view showing an example of the liquid crystal display device of the present invention. FIG. 3 is a schematic view showing an example of the organic light emitting display device of the present invention. FIG. 4 is a schematic view showing an example of a conventional method for forming a colored layer of a color filter using a photosensitive colored resin composition containing a pigment. FIG. 5 is a schematic view showing an example of a conventional method for forming a colored layer of a color filter using a photosensitive coloring resin composition containing a dye or a lake coloring material.

Hereinafter, a photosensitive coloring resin composition for a color filter according to the present invention and a method for producing the same, a cured product of the photosensitive coloring resin composition for a color filter according to the present invention, and a photosensitive coloring resin for a color filter according to the present invention. The color filter and the display device formed by using the composition will be described in detail in order.
In the present invention, the light includes electromagnetic waves having wavelengths in the visible and invisible regions, and further includes radiation, and the radiation includes, for example, microwaves and electron beams. Specifically, it refers to an electromagnetic wave having a wavelength of 5 μm or less and an electron beam.
In the present invention, (meth) acryloyl represents each of acryloyl and methacrylic, (meth) acrylic represents each of acrylic and methacrylic, and (meth) acrylate represents each of acrylate and methacrylate.
Further, in the present specification, "-" indicating a numerical range is used in the sense that the numerical values described before and after the numerical range are included as the lower limit value and the upper limit value.
In the present invention, the solid content is all the components other than the solvent among the components contained in the photosensitive coloring resin composition, and also includes liquid components such as monomers.

I. Photosensitive Colored Resin Composition for Color Filters The photosensitive colored resin composition for color filters according to the present invention (hereinafter, may be referred to as “photosensitive colored resin composition”) is a coloring material, a binder resin, a monomer, and the like. A photosensitive coloring resin composition for a color filter containing a light initiator and a solvent.
The coloring material contains at least one selected from the group consisting of dyes and lake coloring materials.
The binder resin has a polymer structure containing 5 to 25% by mass of a structural unit derived from hydroxyalkyl (meth) acrylate represented by the general formula (A) described later, has a weight average molecular weight of 11,000 or more, and is an acid. A photosensitive coloring resin composition for a color filter, which comprises a copolymer having a value of 60 to 130 mgKOH / g.

The photosensitive coloring resin composition according to the present invention contains at least one selected from the group consisting of a dye and a rake coloring material as a coloring material. Since the dye and the rake coloring material have higher transmittance than the pigment, a high-brightness coloring layer is used as the coloring material of the photosensitive coloring resin composition by using at least one selected from the group consisting of the dye and the rake coloring material. Can be formed.
However, by applying a photosensitive colored resin composition on a substrate, exposing it in a predetermined pattern, and developing it to form a colored layer, a series of steps of changing the color of the coloring material are sequentially performed on one substrate. In the method of forming a colored layer pattern in which two or more colored layers such as red, green, and blue are arranged in a predetermined pattern, when a photosensitive colored resin composition containing a dye or a lake coloring material is used, It was found that the film thickness distribution of the second and subsequent colored layers became non-uniform, and the flatness of the pixels was impaired.
The uniformity of the film thickness distribution in the pixel is related to the uniformity of the chromaticity in the pixel and is an important factor for improving the image quality. In particular, as the pixel density increases as the resolution of the display device increases, the effect of the uniformity of the film thickness distribution in the pixel on the image quality increases.
The problem that the flatness of the pixels is impaired is particularly remarkable when a dye or a lake coloring material is used as the coloring material of the photosensitive coloring resin composition.

FIG. 4 is a schematic view showing an example of a conventional method of forming a colored layer of a color filter using a photosensitive colored resin composition containing a pigment. FIG. 4 shows a step of forming the red colored layer 3R and the green colored layer 3G on the substrate in this order, and then forming the blue colored layer 3B. 4 (a) of FIG. 4 shows a blue coating film using a blue photosensitive colored resin composition on a substrate provided with a light-shielding portion 2, a red colored layer 3R, and a green colored layer 3G, which are boundaries of each colored layer. It shows the state in which 3B'is formed. Since 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 forming the blue colored layer, and the region provided with the red colored layer 3R and the green colored layer 3G. Then it will be relatively high. As long as it is limited to the region where the blue colored layer is formed, the thickness of the blue coating film 3B'is constant, and the surface thereof becomes flat according to the surface shape of the base. Next, the blue coating film 3B'is heated and dried. As shown in 4 (b) of FIG. 4, the blue coating film 3B'after heat-drying maintains the same shape as before heat-drying. After heat-drying, the blue coating film 3B'is exposed to a predetermined pattern, the region forming the blue colored layer is selectively cured, and then developed, as shown in 4 (c) of FIG. , A flat blue colored layer 3B is formed.

On the other hand, FIG. 5 is a schematic view showing an example of a conventional method of forming a colored layer of a color filter using a photosensitive colored resin composition containing a dye or a lake coloring material. FIG. 5 shows a step of forming the red colored layer 3R and the green colored layer 3G on the substrate in this order, and then forming the blue colored layer 3B. 5 (a) of FIG. 5 shows a blue coating film using a blue photosensitive colored resin composition on a substrate provided with a light-shielding portion 2, a red colored layer 3R, and a green colored layer 3G, which are boundaries of each colored layer. It shows the state where 3B'is formed. At this stage, the blue coating film 3B'containing the dye or the rake coloring material has a blue-colored layer having a coating film surface height similar to that of the blue coating film 3B'containing the pigment of FIG. 4 (a). It is relatively low in the region forming the blue colored layer, and relatively high in the region provided with the red colored layer 3R and the green colored layer 3G, but the blue coating film 3B'is limited to the region forming the blue colored layer. The thickness is constant, and the surface of the surface follows the surface shape of the base and becomes flat. The green colored layer 3G shown in FIG. 5 (a) is the second colored layer formed on the substrate, and is the green colored layer 3G containing the pigment of FIG. 4 (a). Unlike, it has a shape that is inferior in flatness. This point will be described later.
Next, when the blue coating film 3B'is heated and dried, the blue coating film flows by heating. Therefore, as shown in FIG. 5 (b), of the blue coating film 3B', the red colored layer 3R and the green color are used. The portion where the height of the coating film surface existing in the region provided with the colored layer 3G is relatively high forms the boundary between the region provided with the red colored layer 3R and the region forming the blue colored layer, and the green colored layer 3G. Beyond the boundary between the provided region and the region forming the blue colored layer, it flows into the portion where the height of the coating film surface existing in the region forming the blue colored layer is relatively low. Therefore, the blue coating film 3B'after heat drying loses the ability to follow the surface shape of the base, and is near the boundary between the region provided with the red colored layer 3R and the region forming the blue colored layer, and the green colored layer 3G. The surface of the coating film is relatively high near the boundary between the region where the blue color is formed and the region where the blue colored layer is formed, the surface of the coating film is relatively low in the central portion, and the surface shape is dented in the central portion as a whole. become. After heat-drying, the blue coating film is exposed to a predetermined pattern, the region forming the blue colored layer is selectively cured, and then developed, so that the center is shown in FIG. 5 (c). A blue colored layer 3B having a dented portion is formed.

When the second and subsequent colored layers are formed on the substrate by using the photosensitive coloring resin composition containing a dye or a rake coloring material, the coating film of the photosensitive coloring resin composition is described above in the heating and drying step. In the same way, it softens and flows, and loses its ability to follow the surface shape of the substrate. Therefore, a colored layer having a relatively high coating film surface near the boundary adjacent to the colored layer previously formed on the substrate is formed. Easy to form.
For example, when a red coloring layer, a green coloring layer, and a blue coloring layer are formed in this order on a substrate by using a photosensitive coloring resin composition containing a dye or a lake coloring material, the green coloring layer is shown in FIG. As shown in 5 (a), the height of the coating film at the boundary portion adjacent to the red colored layer is relatively high, and the height of the coating film at the central portion and the portion far from the red colored layer is relatively low. Cheap.

The reason why the fluidity of the photosensitive coloring resin composition when the coating film is heated and dried differs depending on the coloring material used is that when a pigment is used as the coloring material, fine particles of the pigment are contained in the photosensitive coloring resin composition. Since it is dispersed, the viscosity does not decrease so much even if the coating film softens during heating and drying, whereas when a dye or lake coloring material is used as the coloring material, the dye or lake color is added to the photosensitive coloring resin composition. It is presumed that since the material is dissolved or dispersed in a state of being finer than the pigment particles, the viscosity decreases and the fluidity increases when the coating film softens during heating and drying.

In the present invention, the above-mentioned problem peculiar to the case where a dye or a rake coloring material is used as the coloring material of the photosensitive coloring resin composition is solved by a configuration derived from a hydroxyalkyl (meth) acrylate represented by the general formula (A) described later. A copolymer having a polymer structure containing 5 to 25% by mass of units, a weight average molecular weight of 11,000 or more, and an acid value of 60 to 130 mgKOH / g (hereinafter, “hydroxyalkyl (meth) acrylate unit-containing copolymer weight”). It may be referred to as "coalescence"), which can be solved by using a binder resin.
When a binder resin containing a hydroxyalkyl (meth) acrylate unit-containing copolymer is used as the photosensitive coloring resin composition containing a dye or a rake coloring material, the photosensitive coloring resin composition formed on the substrate is coated. Since the increase in fluidity is suppressed when the film is heated and dried, the flatness of the coating film when the photosensitive colored resin composition is applied to the substrate is easily maintained even after heating and drying, and is excellent in flatness. A colored layer having a different shape is formed.
When the binder resin containing the above hydroxyalkyl (meth) acrylate unit-containing copolymer is used, the reason why the colored layer having an excellent flatness is formed is presumed as follows.
When the coating film of the photosensitive colored resin composition is heated and dried, the amount of the solvent in the coating film is reduced and the intermolecular distance between the binder resin molecules is reduced, and the influence of hydrogen bonds on the binding force between the binder resin molecules is affected. Increase. In the above hydroxyalkyl (meth) acrylate unit-containing copolymer, the content of the constituent units derived from hydroxyalkyl (meth) acrylate is adjusted to an appropriate range, so that the coating film of the photosensitive coloring resin composition is heated. When dried, the viscosity of the softened coating film is increased by the effect of promoting hydrogen bonds between the binder resin molecules by the hydroxyl group of the hydroxyalkyl (meth) acrylate unit-containing copolymer, thereby suppressing the fluidization of the coating film. It is thought that it can be done.
Further, since the weight average molecular weight of the above-mentioned hydroxyalkyl (meth) acrylate unit-containing copolymer is adjusted to an appropriate range, the coating film of the photosensitive colored resin composition is softened when the coating film is heated and dried. It is considered that the viscosity of the film can be increased by the molecular weight effect to suppress the fluidization of the coating film.
As another method of suppressing the softening of the coating film of the photosensitive colored resin composition, a method of using another resin having a high melt viscosity as a binder resin and another method of promoting hydrogen bonding in the binder resin have other functional groups. A method of using a resin as a binder resin is also conceivable, but the above-mentioned hydroxyalkyl (meth) acrylate unit-containing copolymer can effectively flatten the shape of the colored layer with a relatively small amount, and is colored. It is excellent in that it does not adversely affect the color tone of the layer.

Further, when the binder resin containing the above-mentioned hydroxyalkyl (meth) acrylate unit-containing copolymer is used, the acid value of the hydroxyalkyl (meth) acrylate unit-containing copolymer is adjusted to an appropriate range. The development residue can be reduced.
In general, the higher the acid value of the binder resin, the easier it is for hydrogen bonds to be formed in the binder resin. Therefore, according to the above explanation, the higher the acid value of the hydroxyalkyl (meth) acrylate unit-containing copolymer, the higher the acid value of the hydroxyalkyl (meth) acrylate unit-containing copolymer. The effect of flattening the shape of the colored layer can be improved. However, if the acid value of the binder resin is too high, the development residue on the substrate increases.
In the present invention, the shape of the colored layer is effective by adjusting the weight average molecular weight of the hydroxyalkyl (meth) acrylate unit-containing copolymer and the content of the constituent units derived from hydroxyalkyl (meth) acrylate to an appropriate range. Therefore, it is not necessary to make the acid value of the hydroxyalkyl (meth) acrylate unit-containing copolymer extremely high from the viewpoint of flattening the colored layer, and it is appropriate from the viewpoint of reducing the development residue. Range can be set.

Each component contained in the photosensitive coloring resin composition for a color filter according to the present invention will be described below.
[Color material]
<Dyes and rake coloring materials>
In the present invention, at least one selected from the group consisting of dyes and lake coloring materials is used as the coloring material.
In the present invention, the dye means a coloring material capable of dissolving an effective amount capable of exhibiting a coloring function in a solvent. The rake coloring material is a dye that has been raked with a rake agent.
The dye and the rake colorant are at least selected from the group consisting of the dye and the rake colorant because they are dissolved in a matrix such as a binder resin or dispersed in the form of extremely fine particles and do not impair the transparency of the composition. By using one type as a coloring material, the brightness of the color filter can be increased.

The dye and rake coloring material used in the present invention are not particularly limited.
Examples of the dyes include azo dyes, metal complex salt azo dyes, anthraquinone dyes, triarylmethane dyes, xanthene dyes, cyanine dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, phthalocyanine dyes and the like. Can be mentioned.
Examples of the rake coloring material include those obtained by rake-forming the above dyes with a rake agent. The rake agent is appropriately selected and used according to the dye, and the anionic dye (acid dye) is a compound that produces a counter cation of the dye as the rake agent, and the cationic dye (basic dye) is used. , A compound that produces a counter anion of the dye is used as the rake agent. As such a rake agent, known ones can be used, and the rake agent used for the cationic dye (basic dye) is not particularly limited, but the rake agent used is, for example, an alkali metal salt of an organic anion or the like. Examples thereof include alkaline earth metal salts, alkaline salts of inorganic anions, alkali metal salts, and the like, and examples of the rake agent used for anionic dyes (acidic dyes) include amine compounds that generate ammonium cations, and desired ones. A metal salt having a metal ion of the above can be mentioned.
The rake color material used in the present invention includes, for example, a rake color material in which a monovalent or divalent or higher cation dye (basic dye) and a divalent or higher polyanion form a salt, and a monovalent rake color material. Alternatively, a lake color material or the like in which a divalent or higher anionic dye (acidic dye) and a divalent or higher polycation form a salt can be preferably used.
Specific examples of the dye and rake color material used in the present invention include dyes described in JP-A-2015-96947, blue dyes described in JP-A-2016-27149, and JP-A-2017-160099. Examples thereof include a compound (Aa) and a dye (Ab), which are lake coloring materials described in Japanese Patent Publication No.

Above all, when the photosensitive coloring resin composition of the present invention contains a lake coloring material, it is easy to suppress the generation of development residue even if the acid value of the hydroxyalkyl (meth) acrylate unit-containing copolymer is relatively large. preferable. Since the lake color material has a high affinity with hydroxyl groups due to its acid-base salt structure, the lake color material is more compatible with hydroxyalkyl (meth) acrylate unit-containing copolymers than dyes and pigments. Is good. Therefore, when the photosensitive coloring resin composition of the present invention contains a rake coloring material and a hydroxyalkyl (meth) acrylate unit-containing copolymer in combination, the solubility in a developing solution is made uniform, so that the developing material is developed. The generation of residue can be suppressed. Above all, when the hydroxyl value of the hydroxyalkyl (meth) acrylate unit-containing copolymer is within the preferable range described later, the compatibility with the rake coloring material is further improved, so that the effect of suppressing the development residue is particularly excellent.

Further, among the lake coloring materials, triarylmethane-based or xanthene-based lake coloring materials are preferable because they can easily improve the brightness and heat resistance of the colored layer. It is particularly preferable to include a rake coloring material of a triarylmethane dye because high brightness can be achieved at the time of blue toning and heat resistance is easily improved.
The triarylmethane dye and the xanthene dye used for the rake coloring material can be appropriately selected from known dyes, and are not particularly limited. Examples of the triarylmethane dye include C.I. I. Basic blue 7, 8, 11, 26 and the like can be mentioned. Examples of the xanthene dye include C.I. I. Acid Red 50, 51, 52, 87, 92, 94, 289, 388, C.I. I. Xanthene acid dyes such as

Acid Violet

9, 30, 102, Sulforhodamine G, Sulforhodamine B, Sulforhodamine 101, Sulforhodamine 640; C.I. I. Examples thereof include xanthene-based basic dyes such as Basic Violet 11.

Further, the rake coloring material used in the present invention may have only one color-developing portion, but if it has two or more color-developing portions, it is colored with higher luminance and excellent heat resistance. It is preferable because a layer can be obtained. Here, the rake coloring material having two or more color-developing parts may be a material in which a plurality of dye molecules having one color-developing part are ionically bonded to a rake agent, or a plurality of color-developing parts may be formed. One dye molecule having a dye molecule may be ionically bonded to a rake agent, or a plurality of dye molecules having a plurality of color-developing sites may be ionically bonded to the rake agent.
Above all, from the viewpoint of obtaining a colored layer having high brightness and excellent heat resistance, the coloring material used in the present invention preferably contains a rake coloring material represented by the following general formula (1) or general formula (2). It is more preferable to include a rake colorant represented by the following general formula (1). The rake color material represented by the following general formula (1) is a rake color material in which a divalent or higher cationic dye (basic dye) and a divalent or higher polyacid anion form a salt, and the following general formula is used. The rake color material represented by (2) is a rake color material in which two or more monovalent cation dyes and a divalent or more polyacid anion form a salt. In any of the lake coloring materials, a dye molecule that does not form a salt with the polyacid anion may be generated, and particularly when the number of cations and the number of anions are different in the lake coloring material represented by the following general formula (1). , Dye molecules that do not form salts with polyacid anions are likely to occur. Dye molecules that do not form salts with polyacid anions can form salts with acidic groups in hydroxyalkyl (meth) acrylate unit-containing copolymers. In the lake coloring material represented by the following general formula (1) or general formula (2), in addition to the fact that the salt structure of the acid and the base has a high affinity with the hydroxyalkyl (meth) acrylate unit in the above-mentioned copolymer. Since the dye molecule that does not form a salt with the polyacid anion can form a salt with the structural unit having an acidic group in the above-mentioned copolymer, the rake represented by the following general formula (1) or general formula (2). In the photosensitive coloring resin composition of the present invention containing a coloring material, a composite in which the rake coloring material and the copolymer are associated is formed, and the effect of inhibiting thermal motion is increased, so that the heat resistance is improved. It is estimated that.
Further, the lake coloring material represented by the following general formula (1) or general formula (2) also has a salt structure of an acid and a base, so that the compatibility with the hydroxyalkyl (meth) acrylate unit-containing copolymer is high. Since it is good, the generation of development residue can be suppressed even if the acid value of the hydroxyalkyl (meth) acrylate unit-containing copolymer is relatively large.
Above all, when the hydroxyl value of the hydroxyalkyl (meth) acrylate unit-containing copolymer is within the preferable range described later, compatibility with the rake coloring material represented by the following general formula (1) or general formula (2). Is further improved, so that the effect of suppressing the development residue is particularly excellent. When the acid value and the hydroxyl value of the hydroxyalkyl (meth) acrylate unit-containing copolymer were within the preferable ranges described later, they were associated with the lake coloring material represented by the following general formula (1) or general formula (2). Since the complex is easily formed, the effect of improving heat resistance is particularly excellent.

(Rake color material represented by the general formula (1))
Hereinafter, the rake coloring material represented by the general formula (1) preferably used in the present invention will be described in detail.

(In the 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, and the organic group is at least saturated aliphatic hydrocarbon at the terminal directly bonded to N. It represents an aliphatic hydrocarbon group having a hydrogen group 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. Represented. 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 represents R ⁱⁱ and R ii ⁱ , and R ^iv and R. ^v may be bonded to form a ring structure. R ^vi and R ^vii may independently have an alkyl group which may have a substituent, an alkoxy group which may have a substituent, a halogen atom or a cyano. Representing a group. Ar ¹ represents a divalent aromatic group which may have a substituent. A plurality of ^{Ri to R vii} ^and Ar ¹ may be the same or different from each other.
a and c represent integers of 2 or more, and b and d represent integers of 1 or more. e is 0 or 1, and when e is 0, there is no bond. f and g represent integers of 0 or more and 4 or less, and f + e and g + e are 0 or more and 4 or less. The plurality of e, f, and g may be the same or different from each other. )

Since the coloring material represented by the general formula (1) contains a divalent or higher anion and a divalent or higher cation, in the aggregate of the coloring material, the anion and the cation are simply one molecule to one molecule. The apparent molecular weight is significantly increased compared to the molecular weight of the conventional rake coloring material because it is possible to form a molecular assembly in which a plurality of molecules are associated via an ionic bond instead of being ionic bonded in the above. .. The formation of such molecular aggregates further enhances the cohesive force in the solid state, reduces thermal motion, suppresses the dissociation of ion pairs and the decomposition of cations, and is less likely to fade than conventional lake coloring materials. Presumed.

A in the general formula (1) is an a-valent organic group in which the carbon atom directly bonded to N (nitrogen atom) does not have a π bond, and the organic group is saturated at least at the terminal directly bonded to N. Represents an aliphatic hydrocarbon group having an aliphatic hydrocarbon group or an aromatic group having the aliphatic hydrocarbon group, and O (oxygen atom), S (sulfur atom), N (nitrogen atom), etc. in the carbon chain. Heteroatoms may be contained. That is, the organic group has a saturated aliphatic hydrocarbon group at least at the terminal directly bonded to N, and a heteroatom such as O, S, N may be contained in the carbon chain. Alternatively, it represents an aromatic group having an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at the terminal directly bonded to N, and a heteroatom such as O, S, N may be contained in the carbon chain. .. Since the carbon atom directly bonded to N does not have a π bond, the color characteristics such as color tone and transmittance of the cationic color-developing site are not affected by the linking group A and other color-developing sites, and are not affected by the monomer. Similar colors can be retained.

In A, an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at least at the terminal directly bonded to N is linear, branched or cyclic if the carbon atom at the terminal directly bonded to N does not have a π bond. Any of these may be used, carbon atoms other than the terminal may have an unsaturated bond, or may have a substituent, and the carbon chain contains O, S, and N. May be good. For example, a carbonyl group, a carboxy group, an oxycarbonyl group, an amide group and the like may be contained, and a hydrogen atom may be further substituted with a halogen atom or the like.
Further, in A, the aromatic group having an aliphatic hydrocarbon group is a monocyclic or polycyclic aromatic group having an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at a terminal that is directly bonded to at least N. It may be mentioned and may have a substituent, and may be a heterocycle containing O, S, N.
Above all, from the viewpoint of skeletal robustness, A preferably contains a cyclic aliphatic hydrocarbon group or an aromatic group.
Examples of the cyclic aliphatic hydrocarbon group include a group containing cyclohexane, cyclopentane, norbornane, bicyclo [2.2.2] octane, tricyclo [5.2.1.0 ^2,6 ] decane, and adamantane. .. Examples of the aromatic group include a group containing a benzene ring and a naphthalene ring. For example, when A is a divalent organic group, a linear, branched, or cyclic alkylene group having 1 to 20 carbon atoms or an aromatic group in which two alkylene groups having 1 to 20 carbon atoms such as a xylylene group are substituted is substituted. And so on.

In the present invention, A has two or more cyclic aliphatic hydrocarbon groups and is directly bonded to N from the viewpoint of improving heat resistance by achieving both robustness and freedom of molecular movement. It is preferable that the aliphatic hydrocarbon group has a saturated aliphatic hydrocarbon group and O, S, and N may be contained in the carbon chain. A is an aliphatic hydrocarbon having two or more cycloalkylene groups, having a saturated aliphatic hydrocarbon group at the terminal directly bonded to N, and may contain O, S, N in the carbon chain. It is more preferably a group, and more preferably 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 from each other. For example, the same group as the cyclic aliphatic hydrocarbon group can be mentioned, and cyclohexane and cyclopentane are preferable.

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).

(In the general formula (1a), R ^xi has an alkyl group having 1 or more and 4 or less carbon atoms as a substituent, or an alkylene group having 1 or more and 3 or less carbon atoms which may have an alkoxy group having 1 or more and 4 or less carbon atoms. R ^xii and R ^xiii independently represent an alkyl group having 1 or more and 4 or less carbon atoms, or an alkoxy group having 1 or more and 4 or less carbon atoms, p is an integer of 1 or more and 3 or less, and q and r are independent of each other. Represents an integer of 0 or more and 4 or less. When there are a plurality of R ^{xi, R xi, R xiii and r, the plurality of R xi} ^{, R xii} ^{, R xiii} ^and ^r ^may be the same or different from each other. .)

Examples of the alkylene group having 1 or more and 3 or less carbon atoms in R ^xi include a methylene group, an ethylene group, a propylene group and the like from the viewpoint of excellent compatibility between fastness and thermal motion of the colored portion and improvement in heat resistance. Of these, a methylene group or an ethylene group is preferable, and a methylene group is more preferable.
Examples of the alkyl group having 1 or more and 4 or less carbon atoms include a methyl group, an ethyl group, a propyl group and a butyl group, which may be linear or have a branch.
Examples of the alkoxy group having 1 or more and 4 or less carbon atoms include a methoxy group, an ethoxy group, a propoxy group and a butoxy group, which may be linear or have a branch.

Examples of the alkyl group having 1 or more and 4 or less carbon atoms and the alkoxy group having 1 or more and 4 or less carbon atoms in R ^xii and R ^xiii are the same as the substituents that R ^xi may have.

In the general formula (1a), it is preferable that the number of cyclohexane (cyclohexylene group) is 2 or more and 4 or less, that is, p is 1 or more and 3 or less, from the viewpoint of heat resistance, and p is 1 or more and 2 or less. Is more preferable.
The number of substitutions of the substituents R ^xii and R ^xiii contained in the cyclohexylene group is not particularly limited, but is preferably 1 or more and 3 or less, and preferably 1 or more and 2 or less, from the viewpoint of heat resistance. Is more preferable. That is, q and r are preferably integers of 1 or more and 3 or less, and q and r are preferably integers of 1 or more and 2 or less.

Preferable specific examples of such a linking group A include, but are not limited to, the following.

The alkyl group in R ⁱ to R ^v is not particularly limited. For example, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms can be mentioned, and among them, a linear or branched alkyl group having 1 to 8 carbon atoms can be mentioned, and the number of carbon atoms is 1. The linear or branched alkyl group of to 5 is mentioned from the viewpoint of brightness and heat resistance, and the alkyl group in ^{Ri to Rv} ^is an ethyl group or a methyl group. The substituent which the alkyl group may have is not particularly limited, and examples thereof include an aryl group, a halogen atom, a hydroxyl group, an alkoxy group and the like, and the substituted alkyl group is an aralkyl group such as a benzyl group. And so on.
The aryl group in R ⁱ to R ^v is not particularly limited. For example, a phenyl group, a naphthyl group and the like can be mentioned. Examples of the substituent that the aryl group may have include an alkyl group, a halogen atom, an alkoxy group, a hydroxyl group and the like.
Among them, from the viewpoint of chemical stability, R ⁱ to R ^v are independently bonded to a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group, or R ⁱⁱ and R ⁱⁱ , and R ^iv and R ^v . It is preferable to form a pyrrolidine ring, a piperidine ring, and a morpholine ring.

From the viewpoint of heat resistance, it is preferable that at least one of R ⁱⁱ to R ^v is a cycloalkyl group which may have a substituent or an aryl group which may have a substituent. Since at least one of ^Rii to ^Rv has a cycloalkyl group or an aryl group, the intramolecular interaction due to steric hindrance is reduced, and the influence on the heat of the color-developing site can be suppressed. Considered to be excellent.

From the viewpoint of heat resistance, it is preferable that at least one of R ⁱⁱ to R ^v is a substituent represented by the following general formula (1b) or the following general formula (1c).

(In the general formula (1b), R ^xiv , R ^xv , and R ^xvi may each independently have a hydrogen atom, an alkyl group having 1 or more and 4 or less carbon atoms, or a substituent. It represents a good alkoxy group having 1 or more and 4 or less carbon atoms.)

(In the general formula (1c), R ^xvii , R ^xviii , and R ^xix may each independently have a hydrogen atom and a substituent, even if they have an alkyl group having 1 or more and 4 or less carbon atoms, or a substituent. It represents a good alkoxy group having 1 or more and 4 or less carbon atoms.)

Examples of the alkyl group having 1 or more and 4 or less carbon atoms in R ^xiv , R ^xv , R ^xvi , R ^xvii , R ^xviii , and R ^xix include a methyl group, an ethyl group, a propyl group, and a butyl group, and are linear. It may be present or have a branch. Examples of the alkoxy group having 1 or more and 4 or less carbon atoms include a methoxy group, an ethoxy group, a propoxy group and a butoxy group, which may be linear or have a branch.
Examples of the substituent that the alkyl group and the alkoxy group may have include a halogen atom and a hydroxyl group.

When having a substituent represented by the general formula (1b), at least one of R ^xiv , R ^xv , and R ^xvi may have a substituent having 1 or more and 4 or less carbon atoms from the viewpoint of heat resistance. Is preferably an alkoxy group having 1 or more and 4 or less carbon atoms which may have an alkyl group or a substituent, and at least one of R ^xiv and R ^xv may have 1 or more carbon atoms which may have a substituent. More preferably, it is an alkyl group having 4 or less, or an alkoxy group having 1 or more and 4 or less carbon atoms which may have a substituent.

Further, when having a substituent represented by the general formula (1c), at least one of R ^xvii , R ^xviii , and R ^xix may have a substituent having 1 or more carbon atoms 4 from the viewpoint of heat resistance. The following alkyl group or alkoxy group having 1 or more and 4 or less carbon atoms which may have a substituent is preferable, and at least one of R ^xvii and R ^xviii may have a substituent and has 1 carbon number. It is more preferable that the alkyl group has 4 or less or an alkoxy group having 1 or more and 4 or less carbon atoms which may have a substituent.

Preferable specific examples of the substituent represented by the general formula (1b) and the substituent represented by the general formula (1c) include, but are not limited to, the following.

R ^vi and R ^vii each represent an alkyl group which may independently have a substituent, an alkoxy group which may have a substituent, a halogen atom or a cyano group. The alkyl group in R ^vi and R ^vii is not particularly limited, but is preferably a linear or branched alkyl group having 1 or more and 8 or less carbon atoms, and an alkyl group having 1 or more and 4 or less carbon atoms. It is more preferable to have. Examples of the alkyl group having 1 or more and 4 or less carbon atoms include a methyl group, an ethyl group, a propyl group and a butyl group, which may be linear or have a branch. The substituent that the alkyl group may have is not particularly limited, and examples thereof include an aryl group, a halogen atom, a hydroxyl group, and an alkoxy group.
The alkoxy group in R ^vi and R ^vii is not particularly limited, but is preferably a linear or branched alkoxy group having 1 or more and 8 or less carbon atoms, and has 1 or more and 4 or less carbon atoms. It is more preferable that it is a group. Examples of the alkoxy group having 1 or more and 4 or less carbon atoms include a methoxy group, an ethoxy group, a propoxy group and a butoxy group, which may be linear or have a branch. The substituent that the alkoxy group may have is not particularly limited, and examples thereof include an aryl group, a halogen atom, a hydroxyl group, and an alkoxy group.
Examples of the halogen atom in R ^vi and R ^vii include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
The number of substitutions of R ^vi and R ^vii , that is, f and g independently represent integers of 0 or more and 4 or less, and among them, 0 or more and 2 or less are preferable, and 0 or more and 1 or less are more preferable. The plurality of f and g may be the same or different from each other.
Further, R ^vi and R ^vii may be substituted with any site of a triarylmethane skeleton or an aromatic ring having a resonance structure in a xanthene skeleton, and among them, -NR ⁱⁱ R ⁱⁱ or -NR ^iv . It is preferable that the amino group is substituted at the meta position based on the substitution position of the amino group represented by ^Rv .

The divalent aromatic group in Ar ¹ is not particularly limited. The aromatic group in Ar ¹ may be a heterocyclic group as well as an aromatic hydrocarbon group composed of a carbon ring. Examples of the aromatic hydrocarbons in the aromatic hydrocarbon group include fused polycyclic aromatic hydrocarbons such as naphthalene ring, tetraline ring, inden ring, fluorene ring, anthracene ring, and phenanthrene ring, in addition to the benzene ring; biphenyl, terphenyl, and the like. Examples thereof include chain polycyclic hydrocarbons such as diphenylmethane, triphenylmethane, and stilben. The chain polycyclic hydrocarbon may have O, S, and N in the chain skeleton like diphenyl ether and the like. On the other hand, the heterocycles in the heterocyclic group include 5-membered heterocycles such as furan, thiophene, pyrrole, oxazole, thiazole, imidazole and pyrazole; and 6-membered heterocycles such as pyran, pyrone, pyridine, pyrone, pyridazine, pyrimidine and pyrazine. ; Condensed polycyclic heterocycles such as benzofuran, thionaphthene, indol, carbazole, coumarin, benzo-pyrone, quinoline, isoquinoline, acridin, phthalazine, quinazoline, quinoxalin and the like can be mentioned. These aromatic groups may further have an alkyl group, an alkoxy group, a hydroxyl group, a halogen atom, a phenyl group which may be substituted with these, or the like as a substituent.

A plurality of R ⁱ to R ^vii and Ar ¹ in one molecule may be the same or different. The desired color can be adjusted by the combination of R ⁱ to R ^vii and Ar ¹ .

The valence a in A is the number of color-developing cation sites constituting the cation, and a is an integer of 2 or more. In this rake coloring material, since the cation valence a is 2 or more, it is excellent in heat resistance. The upper limit of a is not particularly limited, but from the viewpoint of ease of production, a is preferably 4 or less, and more preferably 3 or less.

In the coloring material represented by the general formula (1), the cation portion has excellent heat resistance and color change during heating is easily suppressed. Therefore, the molecular weight is preferably 1200 or more, and preferably 1300 or more. preferable.

In the coloring material represented by the general formula (1), the anion portion (B ^c− ) is a c-valent polyacid anion and is a divalent or higher anion because of its high brightness and excellent heat resistance.

The polyacid anion in which a plurality of oxo acids are condensed may be an _isopolyacid anion ( _MmOn ) ^c- or a heteropolyacid anion ₍ _XlMmOn ₎ ^c- . In the above ionic formula, M represents a poly atom, X represents a hetero atom, m represents a composition ratio of a poly atom, n represents a composition ratio of an oxygen atom, and l represents a composition ratio of a hetero atom. Examples of the poly atom M include Mo, W, V, Ti, Nb and the like. Examples of the heteroatom X include Si, P, As, S, Fe, and Co. Further, a counter cation such as Na ⁺ or H ⁺ may be partially contained.
Among them, a polyacid having one or more elements selected from tungsten (W) and molybdenum (Mo) is preferable from the viewpoint of excellent heat resistance.
Examples of such polyacids include tungstate ion [W ₁₀ O ₃₂ ] ^4- , molybdenum acid ion [Mo ₆ O ₁₉ ] ^2- which is an isopoly acid, and phosphotung acid ion [W 10 O 19] which is a heteropoly acid. PW ₁₂ O ₄₀ ] ^3- , [P ₂ W ₁₈ O ₆₂ ] ^6- , Heteropolymetalate ion [SiW ₁₂ O ₄₀ ] ^4- , Phosphormolybdenum acid ion [PMo ₁₂ O ₄₀ ] ^3- , Heteropolymolybdenum acid ion [ SiMo ₁₂ O ₄₀ ] ^4- , Lintangst molybdenum acid ion [PW _12-s Mo _s O ₄₀ ] ^3- (s is an integer between 1 and 11), [P ₂ W _18-t Mo _t O ₆₂ ] ^6- (T is an integer of 1 or more and 17 or less), Caetangst molybdenum acid ion [SiW _12-u Mo _u O ₄₀ ] ^4- (u is an integer of 1 or more and 11 or less) and the like. The polyacid containing at least one of tungsten (W) and molybdenum (Mo) is preferably a heteropolyacid among the above, from the viewpoint of heat resistance and easy availability of raw materials, and further, phosphorus (P). ) Is more preferable.
Further, it is heat resistant to be one of lintangustomolybdate ion [PW ₁₀ Mo ₂ O ₄₀ ] ^3- , [PW ₁₁ Mo ₁ O ₄₀ ] ^3- , and phosphotungstic acid ion [PW ₁₂ O ₄₀ ] ^3- . It is more preferable from the viewpoint of.

In the general formula (1), b represents the number of cations, d represents the number of anions in the molecular assembly, and b and d represent integers of 1 or more. When b is 2 or more, a plurality of cations in the molecular assembly may be used alone or in combination of two or more. Further, when d is 2 or more, a plurality of anions in the molecular assembly may be used alone or in combination of two or more.
It is preferable that b and d in the general formula (1) are integers different from each other from the viewpoint that the heat resistance can be easily improved by the combination with the hydroxyalkyl (meth) acrylate unit-containing copolymer. When b and d in the general formula (1) are integers different from each other, the dye molecule which is a cation easily interacts with the hydroxyalkyl (meth) acrylate unit-containing copolymer, and the coloring material and the copolymer are separated from each other. Since the associated complex is likely to be formed, it is presumed that the effect of inhibiting thermal motion is increased and the heat resistance is improved.

E in the general formula (1) is 0 or an integer of 1, and when e is 0, there is no combination. e = 0 represents a triarylmethane skeleton and e = 1 represents a xanthene skeleton. A plurality of e may be the same or different. In the rake color material represented by the general formula (1) used in the present invention, a material containing at least a triarylmethane skeleton is preferably used.
The rake color material represented by the general formula (1) can be prepared with reference to, for example, International Publication No. 2012/144520 Pamphlet and International Publication No. 2018/003706 Pamphlet.
The rake coloring material represented by the general formula (1) may be used alone or in combination of two or more.

(Rake color material represented by the general formula (2))
Next, the rake coloring material represented by the general formula (2) preferably used in the present invention will be described in detail.

(In the general formula (2), RI to ^RVI each independently represent a hydrogen atom, an alkyl group which may have a substituent or an aryl group which may have a substituent, and ^RI and R ^represent each. ^II , R ^III and R ^IV , R ^V and R ^VI may be bonded to form a ring structure. R ^VII and R ^VIII may independently have an alkyl group and a substituent which may have a substituent. It represents an alkoxy group, a halogen atom or a cyano group which may have, Ar ² represents a divalent aromatic heterocyclic group which may have a substituent, and a plurality of ^RI to R ^VIII and Ar ² are represented. They may be the same or different. ^Em- represents an m-valent polyacid anion.
m represents an integer of 2 or more. j is 0 or 1, and when j is 0, there is no bond. k and l represent integers of 0 or more and 4 or less, and k + j and l + j are 0 or more and 4 or less. The plurality of j, k, and l may be the same or different. )

In the general formula (2), ^RI to ^RVI each independently represent a hydrogen atom, an alkyl group which may have a substituent or an aryl group which may have a substituent, and ^RI and R ^II . , R ^III and R ^IV , R ^V and R ^VI may be combined to form a ring structure. R ^I to R ^VI may be the same as R ⁱ to R ^v of the above-mentioned general formula (1), respectively.
In the general formula (2), R ^VII and R ^VIII each independently represent an alkyl group which may have a substituent, an alkoxy group which may have a substituent, a halogen atom or a cyano group, and these also represent. It may be the same as R ^vi and R ^vii of the above-mentioned general formula (1).
In the general formula (2), Ar ² represents a divalent aromatic heterocyclic group which may have a substituent, and the Ar ² is an aromatic among Ar ¹ of the above-mentioned general formula (1). It may be the same as the group heterocyclic group.
Further, in the general formula (2), ^Em- represents an m-valent polyacid anion, and the m-valent polyacid anion is the same as the c-valent polyacid anion of the above-mentioned general formula (1). Good.

In the general formula (2), m indicates the number of cations and the number of anions, and represents an integer of 2 or more. The plurality of cations in the general formula (2) may be one type alone or a combination of two or more types. Further, as for the anion, one type may be used alone or two or more types may be combined.
In the general formula (2), j is 0 or 1, and when j is 0, no bond exists. J in the general formula (2) may be the same as e in the above-mentioned general formula (1). Further, k and l in the general formula (2) may be the same as f and g in the above-mentioned general formula (1).
The rake color material represented by the general formula (2) can be prepared, for example, with reference to JP-A-2017-16099.
The rake coloring material represented by the general formula (2) may be used alone or in combination of two or more.

The coloring material used in the present invention may contain a plurality of types of coloring materials in order to adjust the hue.
When the color material used in the present invention contains the rake color material represented by the general formula (1) or the general formula (2) and further contains another color material for adjusting the hue, the other color material is said. As a result, a xanthene dye, a rake color material of a xanthene dye different from the rake color material represented by the general formula (1) or the general formula (2), and C .. I. At least one selected from the group consisting of Pigment Blue 15: 6 is preferred.

(Xanthene dye)
The xanthene-based dye used in combination with the rake coloring material represented by the general formula (1) or the general formula (2) may be any dye having a xanthene skeleton in the molecule, and a known xanthene-based dye is used. It can be, and there is no particular limitation. Among them, the xanthene dye represented by the following general formula (3) or general formula (4) is preferable from the viewpoint of obtaining a high-luminance colored layer.

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

(In the general formula (3), R ¹ and R ² are independently alkyl groups or aryl groups, respectively, and R ³ and R ⁴ are independently aryl groups or hetero aryl groups, respectively.)

The xanthene dye represented by the above general formula (3) has xanthene as a basic skeleton, has only one functional group containing SO ₂ , and is any of R ¹ to R ⁴ bonded to a nitrogen atom. Also, since R ³ and R ⁴ are not hydrogen atoms but are aryl groups or heteroaryl groups, only saturated hydrocarbon groups are not bonded to the nitrogen atoms, and they do not have alkali metal ions. .. The effect of improving the luminance and light resistance of the colored layer by using the xanthene dye represented by the above general formula (3) having such characteristics is considered as follows, although there are some unexplained parts. Be done. Since the xanthene dye represented by the general formula (3) has a cationic xanthene skeleton and one anionic —SO- ₃ ^- group, it is electrically stabilized. Therefore, it is presumed that even if it is dispersed in a solvent, it does not dissociate and is excellent in stability. Further, since the nitrogen atom has an aromatic substituent such as an aryl group or a heteroaryl group, the isolated electron pair of the nitrogen atom resonates not only with the xanthene skeleton but also with the aryl group or the heteroaryl group. Therefore, it is presumed that the molecule becomes more stable. Further, since the nitrogen atom is not directly bonded to the hydrogen atom, the hydrogen atom is not desorbed from the nitrogen atom and the coloring material is not destabilized. From these facts, the xanthene dye represented by the general formula (3) is stable even under light irradiation and has excellent light resistance, and by using the coloring material, a colored layer having excellent light resistance is formed. It will be possible. Further, as a result of suppressing the fading of the coloring material, the brightness of the colored layer can be improved.
Further, since the xanthene dye represented by the above general formula (3) can have R ³ and R ⁴ different from each other, the range of molecular design is wide, and the range of adjustment of spectral characteristics and the like is also wide. Therefore, it is easy to bring the color material closer to the target chromaticity and further improve the brightness.
Further, since the xanthene dye represented by the above general formula (3) has only one cationic xanthene skeleton and one anionic —SO ₃ ⁻ group and has only an intramolecular salt, it is an alkali metal ion. Does not contain. As a result, when the colored layer is formed by using the xanthene dye represented by the general formula (3), it is possible to suppress the elution of alkali metal ions from the colored layer to the liquid crystal layer when the liquid crystal panel is formed. Therefore, a colored layer having excellent electrical reliability can be obtained.
Further, since the xanthene dye represented by the general formula (3) has only one functional group containing SO ₂ , the affinity with a low polar solvent such as PGMEA is high. Further, when the xanthene dye represented by the above general formula (3) is dissolved in a solvent, a solvent having a relatively low polarity can be used, so that the stability of the photosensitive colored resin composition can be improved. can.

In the general formula (3), the alkyl group in R ¹ and R ² is not particularly limited, but for example, a linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent may be used. Among them, a linear or branched alkyl group having 1 to 8 carbon atoms is preferable, and a linear or branched alkyl group having 1 to 5 carbon atoms is more preferable. The substituent that the alkyl group may have is not particularly limited, but for example, a halogen atom, an aryl group, a carbamoyl group, a monovalent group represented by —CO—O—R ^a , —O—CO—R. A monovalent group represented by ^a' , a monovalent group represented by -SO ₂ -R ^{a "} , a monovalent group represented by -R ^b -CO-OR ^c , -R b' ^- O- Examples thereof include a monovalent group represented by CO-R ^c'and a monovalent group represented by -R ^b" -SO ₂ -R ^{c "} .
The aryl group in R ¹ to R ⁴ is not particularly limited, and examples thereof include an aryl group having 6 to 20 carbon atoms which may have a substituent, and among them, a group having a phenyl group, a naphthyl group and the like. Is preferable.
The heteroaryl group in R ³ and R ⁴ is not particularly limited, and examples thereof include a heteroaryl group having 5 to 20 carbon atoms which may have a substituent, and examples of the hetero atom include a nitrogen atom and an oxygen atom. , Those containing a sulfur atom are preferable. Specific examples of the heteroaryl group include furan, thiophene, pyrrole, pyridine and the like.
The substituent which the aryl group or the heteroaryl group may have is not particularly limited, but is, for example, an alkyl group, a halogen atom, an alkoxy group, a hydroxyl group, a carbamoyl group, or ^a monovalent group represented by —CO—O—Ra. Group, a monovalent group represented by -O-CO-R ^a' , a monovalent group represented by _-SO2 -R ^a" , a monovalent group represented by -R ^b -CO-OR ^c . Examples thereof include a monovalent group represented by -R b'-O-CO-R ^c' ^, a monovalent group represented by -R ^b" -SO ₂ -R ^{c "} , and the like.
The R ^a , R ^a' , R ^{a "} , R ^c , R ^c'and R ^c" indicate an alkyl group, and the R ^b , R ^b'and R ^{b "} indicate an alkylene group. It is preferably used because it does not adversely affect heat resistance and the like. It is possible to adjust the spectral characteristics by adjusting the electron attraction and electron donating properties of these substituents.
The alkyl group in R ¹ to R ⁴ is preferably unsubstituted or the substituent is preferably an aryl group, and the substituent of the aryl group or the heteroaryl group is preferably an alkyl group. In such a case, the xanthene dye represented by the general formula (3) has a lower polarity, so that the affinity for a low polar solvent such as PGMEA is improved. Further, a lower polar solvent can be used even when the xanthene dye represented by the general formula (3) is dissolved in a solvent, and the stability of the photosensitive colored resin composition can be improved by using the low polar solvent. improves.
Further, R ¹ to R ⁴ may be the same or different from each other, and R ¹ to R ⁴ of the xanthene dye represented by the general formula (3) are symmetrical with respect to the xanthene ring. It may be asymmetrical. Above all, when R ³ and R ⁴ are different from each other, the range of molecular design of the xanthene dye represented by the general formula (3) is widened, and the range of adjustment of the spectral characteristics is also widened. It is preferable because it is easy to bring the material closer to the target chromaticity and further improve the brightness.
Further, in the above general formula (3) ^, the substitution position of the -SO _3- group of the benzene ring bonded to the xanthene skeleton is not particularly limited, but is preferably the ortho-position or the para-position with respect to the xanthene skeleton. ^, -SO _3- Group is preferably substituted at the ortho position with respect to the xanthene skeleton from the viewpoint of heat resistance and light resistance. Although its mechanism of action is not clear ^, when the -SO _3- group is in the ortho position, it can resonate with the carbon atom of the xanthene skeleton to which the benzene ring is bonded to form a ring structure, and therefore heat resistance and light resistance. Is estimated to improve.

Further, the xanthene dye represented by the general formula (3) can be used by converting the —SO ₃ ⁻ group into the −SO ₃ H group. The method for converting the -SO ₃ ^-group to the -SO ₃ H group is not particularly limited. For example, an acid treatment method using a weak acid liberation reaction, a method using a cation exchange resin, and the like can be mentioned.
As an acid treatment method, for example, a method of dissolving the coloring material in a good solvent such as methanol and a solvent in which the acid dissolves and adding an acid to convert -SO ₃ ^- groups into -SO ₃ H groups is used. Can be mentioned. The acid used in the acid treatment method is not particularly limited as long as it is an acid having a higher acidity than the acid obtained by converting the -SO _3- group ^to the -SO ₃ H group. Examples of the highly versatile acid include hydrochloric acid, sulfuric acid, nitric acid, p-toluenesulfonic acid (PTS), trifluoromethanesulfonic acid and the like.
On the other hand, examples of the ion exchange resin used in the method using a cation exchange resin include sulfonic acid-terminated cation exchange resins such as Diaion PK-216H (trade name manufactured by Mitsubishi Chemical Corporation).
The sulfone oxidation treatment for converting the -SO _3- group of the coloring material into the -SO ₃ H group is performed after the coloring material is dissolved in a good solvent, ^and the coloring material having a sulfo group (-SO ₃ H) as a solid is used. It may be carried out when preparing a photosensitive colored resin composition, such as adding PGMEA or a dispersant without taking it out. Alternatively, after performing sulfonic oxidation of the coloring material, the coloring material having a sulfo group as a solid may be taken out by a reprecipitation method or a recrystallization method, and then a photosensitive colored resin composition may be prepared. Above all, the former method is preferable from the viewpoint of the recovery rate of the coloring material.

The method for producing the xanthene dye represented by the general formula (3) is not particularly limited, and specific examples thereof include the following methods.
The sulfofluorane compound and the corresponding amine compound are refluxed in a solvent, and the reaction solution is filtered at 60 ° C. to remove insoluble matter, and then a part of the solvent is removed and poured into 6% hydrochloric acid. Then, after adding a large amount of water and stirring at room temperature for 30 minutes, the wet cake is collected by filtration. By washing this wet cake with water or hot water and then drying it, the coloring material of the above general formula (3) can be obtained. Further, when producing a coloring material of the general formula (3) in which the structures of some of R ¹ and R ³ and R ² and R ⁴ are different and asymmetric with respect to the xanthene ring, the corresponding half of the amine compound is used. , A small amount is added dropwise to a highly diluted sulfofluorane compound methanol solution, and after the reaction, the remaining amine compound is added dropwise, or a 1: 1 solution of each amine compound is slowly added dropwise to the sulfofluorane compound methanol solution. By doing so, it is possible to obtain a coloring material of the general formula (3) with high yield and asymmetry.
The xanthene dye represented by the general formula (3) may be used alone or in combination of two or more.

In the photosensitive coloring resin composition according to the present invention, by using the xanthene dye represented by the following general formula (4), the generation of foreign substances can be suppressed and a colored layer having improved brightness is formed. be able to.

(In the general formula (4), R ⁵ and R ⁶ are each independently an aliphatic hydrocarbon group or an aromatic hydrocarbon group which may have a substituent, and R ⁷ and R ⁸ are independent of each other. , An aromatic hydrocarbon group or an aromatic heterocyclic group which may have a substituent, wherein at least one aromatic hydrocarbon group or aromatic heterocyclic group of R ⁷ and R ⁸ is an aliphatic hydrocarbon. Substituentally substituted, R ⁷ and R ⁸ are different from each other. L ¹ and L ² are independently directly bonded, -SO _2- , or -CO-, and R ⁹ is a halogenated aliphatic hydrocarbon. Is the basis.)

The xanthene dye represented by the above general formula ( ⁴ ) has xanthene as a basic skeleton and also has only one functional group containing a specific anion moiety of ^−L1 −N ^－－L2 ^- R9. None of R ⁵ to R ⁸ having and bonded to a nitrogen atom is a hydrogen atom, and R ⁷ and R ⁸ are aromatic hydrocarbon groups or aromatic heterocyclic groups, and at least one of R ⁷ and R ⁸ is used. The two aromatic hydrocarbon groups or aromatic heterocyclic groups are substituted with aliphatic hydrocarbon groups and are characterized in that R ⁷ and R ⁸ are different from each other. By using the xanthene dye represented by the above general formula (4) having such characteristics, the action of suppressing the generation of foreign substances and forming a colored layer having improved brightness has not been clarified yet. However, it can be considered as follows. The xanthene-based dye represented by the above general formula (4) has a monovalent cationic xanthene skeleton and an anionic −L ¹ − N ^{－－} L ² −R ⁹ groups and one intramolecular. Since it has only a salt, it is easy to be electrically stabilized within one molecule. On the other hand, in the anionic -L ¹ ^- N --L ² -R ⁹ groups, the halogen having a high electronegativity is bonded to R ⁹ , so that the electrons at the anionic site are easily attracted to R ⁹ . It is presumed that the weakening of the anionic property weakens the ionic bond between the molecules. Further, in the xanthene dye represented by the above general formula ⁽ ⁴ ), none of R5 to R8 bonded to the nitrogen atom is a hydrogen atom, and ^R7 and ^R8 are aromatic hydrocarbon groups or aromatic heterocycles. Of the ring groups, at least one of R ⁷ and R ⁸ is substituted with an aliphatic hydrocarbon group, and since R ⁷ and R ⁸ are different from each other and have an asymmetric structure with respect to the xanthene skeleton, the crystallinity is high. It is presumed that it is low, difficult to aggregate, and has high solvent affinity. Due to these synergistic effects, the xanthene dye represented by the general formula (4) has improved solvent solubility, and a colored resin composition containing the xanthene dye represented by the general formula (4) is used. When the colored layer is formed, it is presumed that the generation of foreign matter is suppressed.
Further, in the xanthene dye represented by the above general formula (4), since the nitrogen atom bonded to the xanthene skeleton is not directly bonded to the hydrogen atom, the hydrogen atom is desorbed from the nitrogen atom and the coloring material is unstable. Since the nitrogen atom has an aromatic substituent such as an aromatic hydrocarbon group or an aromatic heterocyclic group, the lone electron pair of the nitrogen atom is not only the xanthene skeleton but also the said one. It has a highly stable molecular structure by resonating with an aromatic hydrocarbon group or an aromatic heterocyclic group. The xanthene dye represented by the general formula (4) has a highly stable molecular structure as described above, and therefore has good heat resistance.
Further, in the xanthene dye represented by the above general formula (4), at least one aromatic hydrocarbon group or aromatic heterocyclic group of R ⁷ and R ⁸ is replaced with an aliphatic hydrocarbon group, and R ^{Since 7} and R ⁸ are different from each other, the dyes are less likely to aggregate with each other, and foreign matter is less likely to be generated because the dyes are highly soluble in the solvent, so that the amount of transmitted light in the colored layer is not attenuated.
In addition, the xanthene dye represented by the above general formula ( ⁴ ) has different ^R7 and R8, and has a wide range of molecular design. Therefore, a wide range of adjustments such as spectral characteristics is possible. It is easy to bring it closer to chromaticity and further improve the brightness.
As described above, when the xanthene dye represented by the general formula (4) is used, the heat resistance is good, so that the decrease in brightness after baking in the color filter manufacturing process is suppressed, and in the color filter manufacturing process. It is presumed that the brightness of the colored layer can be improved by suppressing the aggregation of dyes and the generation of foreign substances, and by designing the structure according to the desired chromaticity and adjusting the spectral characteristics and the like.

^In the general formula ( ⁴ ), the aliphatic hydrocarbon group in R5 and R6 may be linear, branched or cyclic, and is not particularly limited, but for example, it has 1 or more carbon atoms and 20 carbon atoms. Examples thereof include the following linear or branched aliphatic hydrocarbon groups, or cyclic aliphatic hydrocarbon groups having 5 or more and 8 or less carbon atoms (aliphatic hydrocarbon groups), and the number of carbon atoms is 10 or less. , Preferred from the viewpoint of heat resistance. As the aliphatic hydrocarbon group, a linear, branched or cyclic alkyl group which is a saturated aliphatic hydrocarbon group is preferable.
The substituent that the aliphatic hydrocarbon group may have is not particularly limited, but is, for example, a halogen atom, an aromatic hydrocarbon group, a carbamoyl group, or a monovalent group represented by —CO—O—R ^d . , -O-CO-R ^d' , a monovalent group, -SO ₂ -R ^{d "} , a -R ^e -CO-O-R ^f , a monovalent group, Examples thereof include a monovalent group represented by -R e'-O-CO-R ^f' ^, and a monovalent group represented by -R ^{e "} -SO ₂ -R ^f" .
The aromatic hydrocarbon group ⁱⁿ R5 to R8 is not particularly limited, and examples thereof include an aromatic hydrocarbon group having ⁶ or more and 20 or less carbon atoms which may have a substituent, and among them, a phenyl group. , A group having a naphthyl group or the like is preferable.
The aromatic heterocyclic group ⁱⁿ ^R7 and R8 is not particularly limited, and examples thereof include an aromatic heterocyclic group having 5 or more and 20 or less carbon atoms which may have a substituent, and examples of the heteroatom include, for example. Those containing a nitrogen atom, an oxygen atom and a sulfur atom are preferable. Specific examples of the aromatic heterocyclic group include furan, thiophene, pyrrole, and pyridine.
The substituent which the aromatic hydrocarbon group or the aromatic heterocyclic group may have is not particularly limited, but for example, an aliphatic hydrocarbon group, a halogen atom, an alkoxy group, a hydroxyl group, a carbamoyl group, -CO-O. -R ^d is a monovalent group, -O-CO-R ^d' is a monovalent group, -SO ₂ -R ^{d "} is a monovalent group, -R ^e -CO-O- The monovalent group represented by R ^f , the monovalent group represented by -R e'-O-CO-R ^f' ^, the monovalent group represented by -R ^{e "} -SO ₂ -R ^f" , etc. The above-mentioned R ^e , Re ^e' , Re ^{e "} , R ^d , R ^d' , R ^d" , R ^f , R ^f'and R ^{f "} indicate an aliphatic hydrocarbon group. These substituents are preferably used because they do not adversely affect heat resistance and the like. It is possible to adjust the spectral characteristics by adjusting the electron-withdrawing property and the electron-donating property of these substituents. Further, the aliphatic hydrocarbon group here may be the ^same as the aliphatic hydrocarbon group in R5 and ^R6 .

^At ^least one of R5 and ^R6 is preferably an aliphatic hydrocarbon group, and R5 and ^R6 are aliphatics, from the viewpoint that the generation of foreign substances is suppressed and a colored layer having improved brightness is easily formed. It is preferably a hydrocarbon group, and more preferably a linear aliphatic hydrocarbon group. The aliphatic hydrocarbon group preferably has 1 or more and 10 or less carbon atoms, and more preferably 1 or more and 6 or less carbon atoms.
At least one of R ⁷ and R ⁸ is preferably an aromatic hydrocarbon group, and R ⁷ and R ⁸ are aromatic, from the viewpoint that the generation of foreign substances is suppressed and a colored layer having improved brightness is easily formed. It is preferably a hydrocarbon group. The aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 or more carbon atoms and 10 or less carbon atoms, and more preferably a phenyl group.
Further, at least one of R ⁷ and R ⁸ which are aromatic hydrocarbon groups or aromatic heterocyclic groups which may have a substituent is substituted with an aliphatic hydrocarbon group, and R ⁷ and R ⁸ are substituted. Are different from each other.
The aliphatic hydrocarbon group substituted with the hydrogen atom of the aromatic hydrocarbon group or the aromatic heterocyclic group is preferably a linear aliphatic hydrocarbon group. The aliphatic hydrocarbon group preferably has 1 or more and 10 or less carbon atoms, and more preferably 1 or more and 6 or less carbon atoms. Further, it is preferable that both R ⁷ and R ⁸ are substituted with the above-mentioned aliphatic hydrocarbon group.
Further, at least one aromatic hydrocarbon group or aromatic heterocyclic group of R ⁷ and R ⁸ is replaced with two or more aliphatic hydrocarbon groups per aromatic hydrocarbon group or aromatic heterocyclic group. This is preferable because the generation of foreign substances is suppressed and it is easy to form a colored layer having improved brightness.
When any one of the aliphatic hydrocarbon groups contained in R ⁵ , R ⁶ , R ⁷ and R ⁸ is a linear alkyl group having 2 or more carbon atoms and 3 or more carbon atoms, it is contained in the molecule. It tends to be easy to adjust the electron density of.
When at least one of R ⁵ and R ⁶ is substituted with a linear aliphatic hydrocarbon group, at least one aromatic hydrocarbon group or aromatic heterocyclic group of R ⁷ and R ⁸ has a carbon number of carbon atoms. When substituted with two or more linear alkyl groups, the generation of foreign substances tends to be suppressed, and a colored layer with improved brightness tends to be easily formed.

Further, ⁱⁿ ^R5 to R8, the aliphatic hydrocarbon group is preferably unsubstituted, or in the case of a branched or linear alkyl group, the substituent is preferably an aromatic hydrocarbon group, and is aromatic. The substituent of the hydrocarbon group or the aromatic heterocyclic group is preferably an aliphatic hydrocarbon group. In such a case, the xanthene dye represented by the general formula (4) has a lower polarity, so that the affinity for a low polar solvent such as PGMEA is improved. Further, a lower polar solvent can be used even when the coloring material is dissolved in a solvent, and the use of the low polar solvent improves the stability of the photosensitive colored resin composition of the present invention. Above all, from the viewpoint of improving the affinity for a low-polarity solvent, it is preferable to have only an aliphatic hydrocarbon group as a substituent of the aromatic hydrocarbon group or the aromatic heterocyclic group.

-L ¹ -N ^--- L ² -R In ⁹ units, L ¹ and L ² are independently directly bonded, -SO _2- , or -CO-, and among them, -SO _2- or-. It is preferably CO-, and more preferably -SO _2- because it suppresses the generation of foreign substances, has excellent heat resistance, and easily forms a colored layer having improved brightness.

-L ¹ -N ^--- L ² -R ⁹ in ⁹ groups is a halogenated aliphatic hydrocarbon group, and examples of the halogen include a fluorine atom, a chlorine atom, an iodine atom and the like, and among them, a fluorine atom. Is preferable. The halogenated aliphatic hydrocarbon group of R9 is preferably a linear or branched halogenated aliphatic hydrocarbon group having 1 or more and ⁸ or less carbon atoms, and a linear or branched halogenated aliphatic hydrocarbon group having 1 or more and 5 or less carbon atoms. It is more preferably a branched halogenated aliphatic hydrocarbon group, and even more preferably a linear or branched halogenated aliphatic hydrocarbon group having 1 or more and 3 or less carbon atoms. Above all, the substitution rate of halogen atoms in the aliphatic hydrocarbon group (the number of halogen atoms / the total number of hydrogen atoms of the aliphatic hydrocarbon group) is preferably 50% or more, more preferably 70% or more. Above all, it is preferably 100%.
The R ⁹ is preferably a linear or branched perfluoroalkyl group having 1 or more and 5 or less carbon atoms.

Further, in the above general formula ( ⁴ ), the substitution position of the -L ¹ -N ^--- L ² -R9 group of the benzene ring bonded to the xanthene skeleton is not particularly limited, but the ortho position with respect to the xanthene skeleton. Alternatively, it is preferably in the para position, and the fact that the -L ¹ ^- N --L ² -R ⁹ groups are substituted in the ortho position with respect to the xanthene skeleton is the xanthene system represented by the general formula (4). It is preferable from the viewpoint of various resistances of dyes. The mechanism of action is not clear, but when the -L ¹ ^- N --L ² -R ⁹ groups are in the ortho position, a ring structure can be formed by resonating with the carbon atom of the xanthene skeleton to which the benzene ring is bonded. It is presumed that the stability of the molecule is increased, and therefore the resistance of various coloring materials is improved.

The method for producing the xanthene dye represented by the general formula (4) is not particularly limited, and specific examples thereof include the following methods.
The sulfofluorane compound and the amine compound corresponding to ^R7 and R8 were refluxed ⁱⁿ a solvent at 60 ° C., and the reaction solution was filtered at 60 ° C. to remove insoluble matter, and then a part of the solvent was removed. Pour into% hydrochloric acid. Then, after adding a large amount of water and stirring at room temperature for 30 minutes, the wet cake is collected by filtration. By washing this wet cake with water or hot water and then drying it, an intermediate of the dye represented by the above general formula (4) can be obtained. In the present invention, in order to produce the dye of the general formula (4), which has a partially different structure of R ⁷ and R ⁸ and is asymmetric with respect to the xanthene ring, the corresponding half of the amine compound is largely diluted. By dropping a small amount into the sulfofluorane compound methanol solution of the above, and after the reaction, the remaining amine compound is added dropwise, or a 1: 1 solution of each amine compound is slowly added dropwise to the sulfofluorane compound methanol solution. , A high yield and asymmetric dye intermediate represented by the general formula (4) can be obtained.
Next, the intermediate of the dye represented by the general ^formula ( ⁴ ) was prepared with a halide corresponding to R5 and R6 in the presence of a base such as potassium carbonate in a polar solvent such as 1-methyl-2-pyrrolidinone, and 80. The reaction is carried out at ° C. for 2 hours with stirring. After completion of the reaction, 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 to 10 ° C. and stirred for 1 hour. Then, the precipitate is collected by filtration and the residue is dried at 60 ° C. for 24 hours to obtain a precursor of the dye represented by the general formula (4).
Next, trifluoromethylsulfonamide is dissolved in chloroform in the precursor of the asymmetric colorant of the general formula (4), and triethylamine is added dropwise to cause a reaction. Then, the obtained reaction solution is washed with water, and then the organic layer is separated. The xanthene dye represented by the above general formula (4) can be obtained by drying this organic layer with sodium sulfate, purifying it by column chromatography, and concentrating it under reduced pressure.
When L ¹ is represented by —CO—, a fluorane compound is used instead of the sulfofluorane compound, and the xanthene dye represented by the above general formula (4) can be obtained in the same manner thereafter.

Since the xanthene dye represented by the general formula (4) has high solvent solubility even in a low-polarity solvent, the concentration required for the colored layer application can be obtained without using a solvent having an alcoholic hydroxyl group. Has solvent solubility. The xanthene-based dye represented by the general formula (4) is at 23 ° C. with respect to at least one of propylene glycol monomethyl ether acetate, 3-methoxy-3-methyl-1-butyl acetate, and diethylene glycol ethyl methyl ether. The solubility of the xanthene dye represented by the general formula (4) is preferably 2.0 (g / 100 g solvent) or more, and more preferably 2.5 (g / 100 g solvent) or more.
The xanthene dye represented by the general formula (4) may be used alone or in combination of two or more.

(Rake color material of xanthene dye)
The rake coloring material of the xanthene dye used in combination with the rake coloring material represented by the general formula (1) or the general formula (2) is not particularly limited, and is, for example, the general formula (1) or the general formula. A known xanthene-based dye rake color material different from the rake color material represented by the formula (2) can be used. Among them, a metal lake colorant of a xanthene dye obtained by laking a xanthene dye with a rake agent containing a metal atom is preferably used because the colorant has excellent heat resistance and dispersibility and a high-brightness colored layer can be obtained. be able to. The metal lake color material is a lake color material to which a metal is added as a lake agent.

As a lake color material of a xanthene dye different from the lake color material represented by the general formula (1) or the general formula (2), among them, the lake color of a xanthene dye having a phenyl group at the 9-position of the xanthene skeleton. The material is preferred. Specifically, a rake coloring material obtained by laking a xanthene dye represented by the following general formula (5) with a rake agent is preferably used, and in particular, a xanthene dye represented by the following general formula (5). A metal rake coloring material raked by a rake agent containing a metal atom is preferably used.

(In the general formula (5), R ^1' , R ^2' ^, R ^3'and R 4'independently represent a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group, respectively, and R ^1'and R ^3' ^, R ^2'and R ^4'may be bonded to each other to form a ring structure, and R 1'and the 5-position carbon atom of the xanthene ring, R ^3'and the 7-position carbon atom of the xanthene ring, respectively. R ^2'and the 4-position carbon atom of the xanthene ring, or R ^4'and the 2-position carbon atom of the xanthene ring may be bonded to each other to form a ring structure. The above aryl group or heteroaryl group may form a ring structure. The hydrogen atom to have may be substituted with an acidic group or a salt thereof, or a halogen atom. R ^5'represents an acidic group or a salt thereof, and x is an integer of 0 to 5. However, the general formula ( 5) has at least two acidic groups or salts thereof, one of which forms an intramolecular salt.)

As the alkyl group in R 1'to R ^4' ^, a linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent is preferable, and a linear or branched alkyl group having 1 to 8 carbon atoms is preferable. It is more preferable that the alkyl group is a linear or branched alkyl group having 1 to 5 carbon atoms. The substituent that the alkyl group may have is not particularly limited, and examples thereof include an aryl group and a halogen atom. The aryl group further has a halogen atom, an acidic group or a salt thereof as a substituent. You may be doing it.
As the aryl group in R 1'to R ^4' ^, an aryl group which may have a substituent having 6 to 20 carbon atoms is preferable, and a group having a phenyl group, a naphthyl group and the like is more preferable.
Further, as the heteroaryl group in R 1'to R ^4' ^, a heteroaryl group which may have a substituent having 5 to 20 carbon atoms is preferable, and the hetero atom includes a nitrogen atom, an oxygen atom and a sulfur atom. Is preferable.
Examples of the substituent that the aryl group or the heteroaryl group may have include an alkyl group having 1 to 5 carbon atoms, a halogen atom, an acidic group or a salt thereof, a hydroxyl group, an alkoxy group, a nitrile group, a carbamoyl group, and a carboxylic acid. Examples include an ester group.

R ^1'and R ^3' ^, R 2'and R ^4'are bonded to form a ring structure, respectively, that R ^1'and R ^3'and R ^2'and R ^4'have nitrogen atoms, respectively. It means that a ring structure is formed through the ring. The ring structure is not particularly limited, and examples thereof include a nitrogen-containing heterocycle having a 5- to 7-membered ring, and specific examples thereof include a pyrrolidine ring, a piperidine ring, and a morpholine ring.
Further, R ^1'and the carbon atom at the 5-position of the xanthene ring, R ^3'and the carbon atom at the 7-position of the xanthene ring, R ^2'and the carbon atom at the 4-position of the xanthene ring, or R ^4'and the xanthene ring. The fact that the carbon atom at the 2-position is bonded to form a ring structure means that the above combination of R ^1'to R ^4'and the carbon atom at the predetermined position of the xanthene ring is one of a nitrogen atom and a xanthene skeleton, respectively. It means that a ring structure is formed through the portions. The ring structure is not particularly limited, and examples thereof include a nitrogen-containing heterocycle having a 5- to 7-membered ring.

Specific examples of the acidic group or a salt thereof include a carboxy group (-COOH), a carboxylato group (-COO-), a carboxylic acid base (-COOM, where M represents a metal atom), and a sulfonate group (-SO). _3- ), sulfo group (-SO ₃ H), sulfonic acid base (-SO ₃ M, where M represents a metal atom), etc., among others, sulfonato group (-SO _3- ), sulfo group. It is preferable to have at least one of (-SO ₃ H) or a sulfonic acid base (-SO ₃ M). Examples of the metal atom M include a sodium atom and a potassium atom.

Specific examples of the xanthene dye represented by the general formula (5) include acid red 50, acid red 52, acid red 289, acid violet 9, acid violet 30, and acid blue 19.

<Rake agent>
The rake agent used for rake formation of the metal rake coloring material of the xanthene dye may be any rake agent containing a metal atom. As the rake agent containing a metal atom, a rake agent containing a metal atom having a divalent or higher valent metal cation is preferable, and specifically, barium chloride, calcium chloride, calcium carbonate, aluminum chloride, aluminum sulfate, and aluminum acetate. , Lead acetate, magnesium sulfate, zirconium chloride, zirconium sulfate, zirconium carbonate, polyaluminum chloride, polyaluminum sulfate and the like, and among them, a rake agent containing a metal atom which becomes a trivalent or higher metal cation is more preferable. Further, a rake agent containing aluminum is preferable because it is easy to synthesize the rake color material and is excellent in the dispersibility of the rake color material. That is, as the metal lake color material of the xanthene dye, the aluminum lake color material of the xanthene dye is preferable, and the aluminum lake color material of the xanthene dye represented by the above general formula (5) is particularly preferable.
By using a rake agent containing aluminum as a trivalent cation, it is presumed that the cohesive force is stronger as a rake agent as compared with the rake agent containing a metal atom as a divalent metal cation. .. Therefore, the solubility of the raked xanthene dye in the solvent is greatly reduced, and the properties are closer to those of the pigment. Therefore, the dispersibility and heat resistance of the coloring material are excellent, and there is also an advantage that the rake coloring material can be easily recovered (filtered) at the time of manufacturing the coloring material.

As the rake agent containing aluminum, among them, polyaluminum chloride represented by the following general formula (6) is preferable because the heat resistance of the coloring material is excellent and the sublimation of the coloring material is easily suppressed. ..

(In the general formula (6), n is an integer of 2 to 20, and m is an integer of (n / 2) to (3n-1).)

In the polyaluminum chloride represented by the above general formula (6), n represents the number of aluminum atoms, which is 2 to 20. By using polyaluminum chloride, which has a relatively small aluminum atom of 2 to 20, as a rake agent, the dispersed particle size of the coloring material does not become too large, and the dispersibility of the coloring material can be improved. In the present invention, n is preferably an integer of 2 to 10.

Further, in the polyaluminum chloride represented by the general formula (6), m represents the number of hydroxy groups (OH ⁻ groups) and is an integer of (n / 2) to (3n-1). When n is an odd number, the lower limit of m is {(n + 1) / 2}, which is the smallest integer in the above range.

Since the aluminum in the polyaluminum chloride has a trivalent cationic property and the hydroxy group has a monovalent anionic property, the polyaluminum chloride as a whole has a (3 nm) valent cationic property. In the present invention, from the viewpoints of strong cohesive force, easy recovery of the coloring material, and excellent dispersibility of the coloring material, it is preferable that the basicity is high, and m is an integer of 2n to (3n-1). Is preferable.
Above all, in the polyaluminum chloride represented by the above general formula (6), n is an integer of 2 to 10 and m is an integer of 2n to (3n-1). This is preferable because the contrast of the coating film is improved.

Further, the polyaluminum chloride represented by the general formula (6) has higher heat resistance of the coloring material, is likely to suppress sublimation of the coloring material, and is likely to improve the dispersibility of the coloring material. The basicity defined by m / 3n × 100 (%)) is preferably 15 to 99%, more preferably 60 to 97%, and even more preferably 70 to 95%.

(CI Pigment Blue 15: 6)
C.I., preferably used in the present invention. I. Pigment Blue 15: 6 is a copper phthalocyanine pigment having an ε-type crystal structure, and is preferable because it is excellent in dispersion stability.
C.I. used in the present invention. I. Pigment Blue 15: 6 may be subjected to basic treatment or acid treatment, and from the viewpoint of excellent dispersibility and storage stability, when the dispersant used in combination is acidic, it shall be basic treatment. When the dispersant used in combination is basic, it is preferably acid-treated. Above all, C.I. I. Pigment Blue 15: 6 is preferably basic-treated, and the basic-treated C.I. I. Pigment Blue 15: 6 is preferably used in combination with an acidic dispersant.

In the present invention, a color material derivative having a basic moiety and a colorless compound derivative having a basic moiety are preferably used for the basic treatment. Further, in the present invention, the embodiment having a basic moiety includes an embodiment having a basic group as a substituent, an embodiment in which an acidic group and a basic compound are salt-formed in the substituent, and the like.
In the present invention, the basic moiety of the colorant derivative or the derivative of the colorless compound includes, for example, an amino group, an ammonium sulfonic acid salt, a sulfonamide group having an amino group, an amide group having an amino group, and a basic heterocycle. The group etc. can be mentioned.

As the color material used for the color material derivative having a basic moiety, a known color material can be appropriately selected and used. I. It is preferable to have a structure that easily adsorbs to Pigment Blue 15: 6, and it is preferable that it has the same or similar pigment skeleton or a structure that easily interacts with it. In addition, C.I. I. A coloring material that does not impair the color of Pigment Blue 15: 6 is preferable.
As the color material derivative having a basic moiety, a blue color material derivative is preferable. As the blue color material used for the color material derivative having a basic moiety, a phthalocyanine color material, a triarylmethane color material, an anthraquinone color material, a naphthol color material, a benzimidazolone color material, or the like may be used. However, it is preferable to use a phthalocyanine-based coloring material from the viewpoint of color and heat resistance. Among them, C.I. I. It is preferable to use a phthalocyanine-based coloring material having the same skeleton as Pigment Blue 15: 6. Further, among them, copper phthalocyanine is preferably used as the blue color material used for the color material derivative having a basic portion from the viewpoint of improving dispersibility and brightness.

The colorless compound used for the derivative of the colorless compound having a basic moiety is C.I. I. Even if Pigment Blue 15: 6 was basicly treated with the derivative of the colorless compound, C.I. I. A compound that does not change the color of Pigment Blue 15: 6 can be used as a guide. As the colorless compound, for example, a condensed ring compound such as a naphthalene type or a triazine type or an aromatic polycyclic compound to which a plurality of aromatic rings are bonded can be used. Examples of the triazine-based aromatic polycyclic compound include a structure in which a triazine ring is substituted with three substituents having an aromatic hydrocarbon group such as a phenylamino group. Above all, it is preferable to use a triazine-based aromatic polycyclic compound from the viewpoint of improving dispersibility and brightness.

C.I. with a structure derived from a basic compound. I. Pigment Blue 15: 6, for example, C.I. I. As a method for preparing Pigment Blue 15: 6, for example, a coloring material derivative having a basic moiety and C.I. I. Examples thereof include a method in which Pigment Blue 15: 6 and Pigment Blue 15: 6 are dry-ground and then mixed with a coloring material derivative having a basic moiety. In this case, a ball mill, a vibration mill, an attritor, or the like can be used as the dry crusher, and the crushing temperature can be freely set at 20 to 130 ° C.
In addition, C.I. I. Pigment Blue 15: 6 can be prepared by using a coloring material derivative having a basic moiety and C.I. I. Pigment Blue 15: 6, water-soluble inorganic salts such as sodium chloride, calcium chloride, and ammonium sulfate, and water-soluble organic solvents such as glycol-based organic solvents are mixed and kneaded with a kneader-type polishing machine by the solvent salt milling method. How to do it, etc.
C.I. I. By preparing or preparing Pigment Blue 15: 6 and dispersing the coloring material, the dispersibility of the coloring material can be improved.

C. including a colorant derivative having a basic moiety or a derivative of a colorless compound. I. In Pigment Blue 15: 6, the content of the colorant derivative having a basic moiety or the derivative of the colorless compound is C.I. I. Pigment Blue 15: 6 With respect to 100 parts by mass, it is preferably 0.5 parts by mass or more, more preferably 3 parts by mass or more, further preferably 5 parts by mass or more, and 8 parts by mass or more. Is even more preferable. On the other hand, the content of the color material derivative having a basic moiety or the derivative of the colorless compound is excellent in luminance, and thus C.I. I. Pigment Blue 15: 6 It is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, and further preferably 30 parts by mass or less with respect to 100 parts by mass.

In addition, C.I. I. Pigment Blue 15: 6 can be appropriately analyzed using, for example, mass spectrometry, elemental analysis, surface analysis, potentiometric titration, and combinations thereof.
In addition, the basic-treated C.I. I. Examples of the acid dispersant used in combination with Pigment Blue 15: 6 include the same acid dispersants that can be used in the colorant dispersion liquid described later.

In the present invention, the total content of the dye and the rake coloring material is preferably 5 parts by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the total amount of the coloring material from the viewpoint that the brightness of the colored layer is easily improved. It is more preferably 10 parts by mass or more and 100 parts by mass or less.
Above all, the total amount of the coloring material is obtained from the viewpoint that a high-brightness colored layer can be obtained and the effect of suppressing the development residue is improved by improving the compatibility between the coloring material and the hydroxyalkyl (meth) acrylate unit-containing copolymer. The content of the rake coloring material is preferably 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 with respect to 100 parts by mass.
From the viewpoint of obtaining a brighter colored layer, the total content of the rake coloring material represented by the general formula (1) or the general formula (2) is 20 parts by mass with respect to 100 parts by mass of the total amount of the coloring material. It is preferably 100 parts by mass or less, and more preferably 30 parts by mass or more and 100 parts by mass or less. When the total content of the rake coloring material represented by the general formula (1) or the general formula (2) is at least the above lower limit value, the compatibility between the coloring material and the hydroxyalkyl (meth) acrylate unit-containing copolymer It is also preferable from the viewpoint that the effect of suppressing the development residue is improved and the heat resistance is improved.
When the coloring material contains a rake coloring material represented by the general formula (1) or the general formula (2) in combination with a coloring material different from the rake coloring material, a desired color can be obtained. The color is adjusted to, but the effect of suppressing the development residue is improved by obtaining a high-brightness colored layer and improving the compatibility between the coloring material and the hydroxyalkyl (meth) acrylate unit-containing copolymer. The total content of the rake coloring material represented by the general formula (1) or the general formula (2) is 20 parts by mass or more and 98 parts by mass with respect to 100 parts by mass of the total amount of the coloring material. It is preferably 30 parts by mass or less, and may be 30 parts by mass or more and 95 parts by mass or less.
The coloring material is a rake coloring material represented by the general formula (1) or the general formula (2), a xanthene dye, and a rake coloring material represented by the general formula (1) or the general formula (2). When containing at least one selected from the group consisting of rake coloring materials of different xanthene dyes, the total content of the xanthene dye and the rake coloring material of the xanthene dye is 100 parts by mass of the total amount of the coloring material. From the viewpoint of obtaining a desired hue, it may be 2 parts by mass or more, 5 parts by mass or more, and on the other hand, from the viewpoint of suppressing deterioration of heat resistance, it is preferably 30 parts by mass or less. , 25 parts by mass or less.
Further, the coloring material is the rake coloring material represented by the general formula (1) or the general formula (2), and C.I. I. When Pigment Blue 15: 6 is included, C.I. I. The content of Pigment Blue 15: 6 may be 20 parts by mass or more or 30 parts by mass or more from the viewpoint of obtaining a desired hue, while suppressing a decrease in brightness of the colored layer. , And, from the viewpoint of suppressing the generation of development residue and the deterioration of the heat resistance of the coloring material, it is preferably 80 parts by mass or less, and may be 70 parts by mass or less.

Further, the content of the dye and the rake coloring material is usually 0.5% by mass or more and 35% by mass or less, and 1% by mass or more and 30% by mass with respect to the total solid content of the photosensitive coloring resin composition of the present invention. It is preferably 2% by mass or more and 25% by mass or less.

<Other pigments>
The photosensitive colored resin composition of the present invention has the above-mentioned C.I. I. Other pigments different from Pigment Blue 15: 6 may be further used. As the other pigment, various organic pigments and inorganic pigments conventionally used as colorants of color filters can be used, and the organic pigment is not particularly limited, but is excellent in color development and heat resistance. preferable.

In the case of blue applications, the other pigments include blue pigments such as copper phthalocyanine pigments having an ε-type or β-type crystal structure, and C.I. I. A purple pigment such as Pigment Violet 23 is preferably used. Among the copper phthalocyanine pigments having an ε-type or β-type crystal structure, C.I. I. At least one selected from the group consisting of Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4 and 15: 5 is preferably used.
The other pigments mentioned above are C.I. I. Similar to Pigment Blue 15: 6, it may be acid-treated or basic-treated in order to improve the dispersion stability. When the dispersant used in combination is acidic, the other pigments are preferably treated with a basic treatment, and when the dispersant used in combination is basic, they are preferably treated with an acid.

In the present invention, the above-mentioned other pigments are preferably used in an amount within a range that does not impair the effects of the present invention. Specifically, the content of the other pigment is 25% by mass or less with respect to the total solid content of the photosensitive coloring resin composition, or the above is made with respect to 100 parts by mass of the total amount of the dye and the rake coloring material. The content of other pigments is preferably 80 parts by mass or less. Further, the smaller of the above two upper limit amounts is set as a more preferable upper limit amount.

[Binder resin]
<Polymer containing hydroxyalkyl (meth) acrylate unit>
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 a structural unit derived from a hydroxyalkyl (meth) acrylate represented by the general formula (A) described later. A copolymer having a weight average molecular weight of 11,000 or more and an acid value of 60 to 130 mgKOH / g (hydroxyalkyl (meth) acrylate unit-containing copolymer) is contained.
The hydroxyalkyl (meth) acrylate unit-containing copolymer is an alkali-soluble copolymer containing a structural unit derived from hydroxyalkyl (meth) acrylate in the chain structure of the polymer skeleton.
The polymer structure of the hydroxyalkyl (meth) acrylate unit-containing copolymer may have a structure having only a main chain or a structure having a main chain and a side chain. The main chain of the hydroxyalkyl (meth) acrylate unit-containing copolymer typically has a chain structure in which the structural units generated by the addition polymerization of the monomer having an ethylenically unsaturated bond are linked, and further, the ethylenically unsaturated bond is obtained. It may contain a structural unit generated by addition polymerization or depolymerization of a monomer having a functional group other than the saturated bond.
The side chains of hydroxyalkyl (meth) acrylate unit-containing copolymers are typically via linking groups resulting from the reaction of functional groups on the backbone with the functional groups of the monomers to form the side chains. It is bonded to the main chain and may be branched from the main chain via a carbon-carbon bond.
As an example of the reaction of the functional group on the main chain with the functional group of the monomer for forming the side chain to form the side chain, for example, when a carboxy group is present on the main chain, the carboxy group may be used. An ester linking group is formed by reacting a monomer having a glycidyl group, and a side chain composed of a structural unit derived from the monomer having a glycidyl group can be introduced. As another example, when a hydroxyl group is present on the main chain, a urethane linking group is formed by reacting the hydroxyl group with a monomer having an isocyanate group, and the side consisting of a structural unit derived from the monomer having an isocyanate group is formed. Chains can be introduced.
The side chain may have a pendant structure having one structural unit of a monomer, or may have a polymer structure in which two or more structural units are connected. When the side chain has a polymer structure, it may consist only of a structural unit derived from a monomer having an ethylenically unsaturated bond, or addition polymerization of a monomer having a functional group other than the ethylenically unsaturated bond. It may contain a structural unit generated by the condensation polymerization.
In addition to the hydroxyl group derived from hydroxyalkyl (meth) acrylate, the hydroxyalkyl (meth) acrylate unit-containing copolymer includes an acidic group that imparts alkali solubility and other functional groups such as an ethylenically double bond-containing group. It has, if necessary, atomic groups such as groups that regulate the molecular structure, such as bulky groups, which may be present in either the main chain or the side chains.

Suitable examples of hydroxyalkyl (meth) acrylate unit-containing copolymers include hydroxyalkyl (meth) acrylate-derived structural units, structural units with acidic groups, bulky groups, and optionally other components. Examples thereof include a copolymer in which a side chain containing a structural unit having a photopolymerizable functional group such as an ethylenically unsaturated bond is bonded to a main chain containing a structural unit.
In such a hydroxyalkyl (meth) acrylate unit-containing copolymer, alkali solubility is imparted by an acidic group on the main chain, and crosslinkability is imparted by a photopolymerizable functional group of the side chain. When the hydroxyalkyl (meth) acrylate unit-containing copolymer has a photopolymerizable functional group, the binder resins or the binder resin and the photopolymerizable compound are used in the curing step of the resin composition at the time of producing a color filter. Certain monomers and the like can form crosslinked bonds. As a result, the film strength of the cured film is further improved, the development resistance is improved, the thermal shrinkage of the cured film is suppressed, and the adhesion to the substrate is excellent.

Examples of the suitable hydroxyalkyl (meth) acrylate unit-containing copolymer include hydroxyalkyl (meth) acrylate having an alkylene group having 1 to 4 carbon atoms, an ethylenically unsaturated monomer having an acidic group, and a bulky group. After synthesizing the main chain portion by copolymerizing the ethylenically unsaturated monomer and other ethylenically unsaturated monomers as necessary, the functional group reacts with the functional group on the main chain to form a bond. By reacting a photopolymerizable functional group-containing monomer having a photopolymerizable functional group, a hydroxyalkyl (meth) acrylate unit-containing copolymer having a side chain having a photopolymerizable functional group introduced can be produced. ..
The structural units constituting the main chain and side chains of the hydroxyalkyl (meth) acrylate unit-containing copolymer and the monomers used to form the structural units will be described below.

(Constituent unit derived from hydroxyalkyl (meth) acrylate represented by the general formula (A))
The structural unit derived from hydroxyalkyl (meth) acrylate represented by the following general formula (A) (hereinafter, may be referred to as “hydroxyalkyl (meth) acrylate unit”) is an alkylene group having 1 to 4 carbon atoms. It has a chemical structure in which the ethylenic double bond of the hydroxyalkyl (meth) acrylate to be contained is cleaved by an addition reaction to form two single bonds.

As the structural unit derived from the hydroxyalkyl (meth) acrylate represented by the general formula (A), the structural unit derived from hydroxyalkyl methacrylate in which RA in the general formula ( ^A ) is a methyl group is preferable.
Specific examples of the hydroxyalkyl (meth) acrylate unit represented by the general formula (A) include hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 2-hydroxypropyl (meth) acrylate. Examples thereof include structural units derived from hydroxyalkyl (meth) acrylates such as 2-hydroxy-1-methylethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 2-hydroxyisobutyl (meth) acrylate. Of these, a structural unit derived from 2-hydroxyethyl (meth) acrylate, a structural unit derived from 2-hydroxypropyl (meth) acrylate, and a structural unit derived from 2-hydroxy-1-methylethyl (meth) acrylate are preferable. Building blocks derived from ethyl (meth) acrylate are particularly preferred.

In the present invention, the amount of the hydroxyalkyl (meth) acrylate unit contained in the hydroxyalkyl (meth) acrylate unit-containing copolymer is 5% by mass or more and 25% by mass or more with respect to 100% by mass of the total amount of the constituent units constituting the copolymer. It shall be mass% or less. By setting the amount of the hydroxyalkyl (meth) acrylate unit within the above range, a colored layer having excellent flatness and suppressed development residue can be obtained.
When the amount of the hydroxyalkyl (meth) acrylate unit is less than 5% by mass, the fluidization of the coating film cannot be sufficiently suppressed when the coating film of the photosensitive colored resin composition is heated and dried. The flatness of the obtained colored layer is deteriorated. On the other hand, when the amount of the hydroxyalkyl (meth) acrylate unit exceeds 25% by mass, the coatability is deteriorated due to the increase in the viscosity of the photosensitive colored resin composition or the solvent resolubility of the photosensitive colored resin composition is deteriorated. As a result, foreign matter or unevenness is likely to occur in the obtained colored layer.
The amount of the hydroxyalkyl (meth) acrylate unit contained in the hydroxyalkyl (meth) acrylate unit-containing copolymer is preferably 5% by mass or more and 20% by mass or less.

(Constituent unit having an acidic group)
In the structural unit having an acidic group, examples of the acidic group include a carboxy group, a phosphoric acid group, a sulfo group and the like, but among them, a side chain having a photopolymerizable functional group can be easily introduced. A carboxy group is preferred. As the structural unit having an acidic group, for example, a structural unit derived from an ethylenically unsaturated monomer having a carboxy group can be preferably used. The structural unit derived from the ethylenically unsaturated monomer having a carboxy group has a chemical structure in which the ethylenically unsaturated bond of the ethylenically unsaturated monomer having a carboxy group is cleaved by an addition reaction to form two single bonds. There is.
In the present invention, the structural unit derived from the ethylenically unsaturated monomer means a structural unit in which a radically polymerizable carbon-carbon double bond of the ethylenically unsaturated monomer becomes a carbon-carbon single bond.
Examples of the ethylenically unsaturated monomer having a carboxy group include (meth) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, katsura acid, and acrylic acid dimer. Can be mentioned. Further, a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate or 4-hydroxybutyl (meth) acrylate and maleic anhydride, succinic anhydride, phthalic anhydride, cyclohexanedicarboxylic acid anhydride, etc. Additive reactants with cyclic anhydride, ω-carboxy-polycaprolactone mono (meth) acrylate and the like can also be used. Further, as a precursor of the carboxy group, an anhydride-containing monomer such as maleic anhydride, itaconic anhydride, and citraconic anhydride may be used. Among them, (meth) acrylic acid is particularly preferable from the viewpoints of copolymerizability, cost, solubility, glass transition temperature and the like.

The amount of the structural unit having an acidic group contained in the hydroxyalkyl (meth) acrylate unit-containing copolymer is 8% by mass or more and 30% by mass or less with respect to 100% by mass of the total amount of the constituent units constituting the copolymer. It is preferable to have. By setting the amount of the structural unit having an acidic group within the above range, sufficient alkali solubility can be imparted to the coating film of the photosensitive colored resin composition, and deterioration of solvent solubility can be suppressed.
When the amount of the structural unit having an acidic group is less than 8% by mass, the acid value may be too low to obtain sufficient alkali solubility. On the other hand, when the amount of the structural unit having an acidic group exceeds 30% by mass, the polarity of the photosensitive resin composition becomes too high, and it may be difficult to dissolve in the solvent.
The amount of the structural unit having an acidic group is more preferably 10% by mass or more and 28% by mass or less, and further preferably 12% by mass or more and 28% by mass or less.

(Constituent unit having a bulky group)
Examples of the structural unit having a bulky group include a structural unit derived from an ethylenically unsaturated monomer having a bulky group. The structural unit derived from the ethylenically unsaturated monomer having a bulky group has a chemical structure in which the ethylenically unsaturated bond of the ethylenically unsaturated monomer having a bulky group is cleaved by an addition reaction to form two single bonds. is doing.
When the hydroxyalkyl (meth) acrylate unit-containing copolymer has a bulky group, shrinkage of the binder resin during curing is suppressed, peeling from the substrate is alleviated, and adhesion to the substrate is improved. The bulky group may be contained as a monovalent group or may be contained as a divalent or higher valent group.
Examples of such bulky groups include an aliphatic hydrocarbon ring which may have a substituent, an aromatic hydrocarbon ring which may have a substituent, and a hydrocarbon ring such as a combination thereof. Can be mentioned. The hydrocarbon ring has a substituent such as an alkyl group, a cycloalkyl group, an alkylcycloalkyl group, a carbonyl group, a carboxy group, an oxycarbonyl group, an amide group, a hydroxyl group, a nitro group, an amino group and a halogen atom. May be good.
Specific examples of the hydrocarbon ring include aliphatic compounds such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, norbornan, isobornane, tricyclo [5.2.1.0 (2,6)] decane (dicyclopentane), and adamantane. Hydrocarbon rings; aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, phenanthrene, and fluorene; chain polycycles such as biphenyl, terphenyl, diphenylmethane, triphenylmethane, and stilben, and cardo structures (9,9-diarylfluorene). ); Examples include groups in which some of these groups are substituted with substituents.
When the hydrocarbon ring contains an aliphatic hydrocarbon ring, it is preferable because the heat resistance and adhesion of the colored layer are improved and the brightness of the obtained colored layer is improved.
Further, when the structural unit includes the cardo structure, it is particularly preferable because the curability of the colored layer is improved, the fading of the coloring material is suppressed, and the solvent resistance (suppression of NMP swelling) is improved.

Examples of the ethylenically unsaturated monomer having a hydrocarbon ring include cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, adamantyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, and phenoxyethyl. Examples thereof include (meth) acrylate and styrene, and cyclocarbonate (meth) acrylate, dicyclopentanyl (meth) acrylate, and adamantyl (adamantyl) because the cross-sectional shape of the colored layer after development has a great effect of being maintained even in heat treatment. It is preferable to use at least one selected from meta) acrylate, benzyl (meth) acrylate, and styrene.

The amount of the structural unit having a bulky group contained in the hydroxyalkyl (meth) acrylate unit-containing copolymer is 20% by mass or more and 70% by mass or less with respect to 100% by mass of the total amount of the structural units constituting the copolymer. Is preferable. By setting the amount of the structural unit having a bulky group within this range, the adhesion of the coating film to the substrate can be improved.
When the amount of the structural unit having a bulky group is less than 20% by mass, the adhesion of the coating film to the substrate may be insufficient. On the other hand, when the amount of the structural unit having a bulky group exceeds 70% by mass, the hydroxyalkyl (meth) acrylate unit, the acidic group or the photopolymerizable functional group cannot be sufficiently introduced, and the photosensitive coloring is performed. The developability or film-forming property of the resin composition, or the flatness of the obtained colored layer may be insufficient.
The amount of the structural unit having a bulky group is more preferably 20% by mass or more and 60% by mass or less, and further preferably 20% by mass or more and 55% by mass or less.

(Other building blocks that make up the main chain)
By including a structural unit having neither a functional group nor a bulky group in the main chain of the hydroxyalkyl (meth) acrylate unit-containing copolymer, alkali solubility is suppressed, solvent solubility is improved, and solvent resolubility is achieved. It is possible to adjust physical properties such as improvement of.
Examples of the ethylenically unsaturated monomer for deriving other structural units constituting the main chain of the hydroxyalkyl (meth) acrylate unit-containing copolymer include functional groups such as methyl (meth) acrylate and ethyl (meth) acrylate. (Meta) acrylates that do not have and have low molecular weight ester residues can be used.

(Constituent unit constituting a side chain having a photopolymerizable functional group)
The side chain having a photopolymerizable functional group may have a pendant structure consisting of only one structural unit having a photopolymerizable functional group, or may have a polymer structure in which two or more structural units are linked. When the side chain has a pendant structure having a structural unit equivalent to one monomer, the functional group of the photopolymerizable functional group-containing monomer that reacts with the functional group on the main chain to form a bond is the main chain. It has a chemical structure that yields a linking group to be attached.
As the photopolymerizable functional group-containing monomer having a photopolymerizable functional group and a functional group that reacts with a functional group on the main chain to form a bond, for example, the photopolymerizable functional group has an ethylenically unsaturated bond. It has a compound such as glycidyl (meth) acrylate having an epoxy group as a functional group that reacts with a functional group on the main chain to form a bond, and an ethylenically unsaturated bond as a photopolymerizable functional group. Examples of the functional group that reacts with the functional group on the chain to form a bond include a compound having an isocyanate group.
When a monomer having a photopolymerizable functional group and an epoxy group is used, a side chain having a photopolymerizable functional group can be formed by reacting the monomer with a carboxy group on the main chain. In this case, a photopolymerizable functional group is introduced into the hydroxyalkyl (meth) acrylate unit-containing copolymer, and at the same time, the carboxy group on the main chain is consumed by the reaction with the epoxy group to reduce the acid value. The photocurability and developability of the (meth) acrylate unit-containing copolymer change in conjunction with each other. Therefore, in consideration of the balance between the photocurability and the developability of the hydroxyalkyl (meth) acrylate unit-containing copolymer, the amount of the monomer having a carboxy group or the structural unit derived from the monomer and the photopolymerizable functional group And it is necessary to adjust the amount of the monomer having an epoxy group or the structural unit derived from the monomer.
When a monomer having a photopolymerizable functional group and an isocyanate group is used, a side chain having a photopolymerizable functional group can be formed by reacting the monomer with a hydroxyl group on the main chain.
Among these photopolymerizable functional group-containing monomers, it is preferable to use a monomer having a photopolymerizable functional group and an epoxy group. In the present invention, the amount of the hydroxyalkyl (meth) acrylate unit in the hydroxyalkyl (meth) acrylate unit-containing copolymer is important from the viewpoint of improving the flatness of the colored layer, but the photopolymerizable functional group and the epoxy Since the monomer having a group has high reactivity with the carboxy group and hardly consumes the hydroxyl group in the hydroxyalkyl (meth) acrylate unit-containing copolymer, the amount of the hydroxyalkyl (meth) acrylate unit can be easily adjusted.

When the hydroxyalkyl (meth) acrylate unit-containing copolymer has an ethylenically unsaturated group in the side chain, the ethylenically unsaturated bond equivalent increases the film strength of the cured film, improves the development resistance, and is different from the substrate. From the viewpoint of obtaining an effect such as excellent adhesion, the range is preferably in the range of 100 to 2000, and particularly preferably in the range of 140 to 1500. When the ethylenically unsaturated bond equivalent is 100 or more, the development resistance and adhesion are excellent. Further, if it is 2000 or less, the ratio of other structural units such as the structural unit having an acidic group and the structural unit having a bulky group can be relatively increased, so that the developability and heat resistance are excellent. There is.
Here, the ethylenically unsaturated bond equivalent is the weight average molecular weight per mol of the ethylenically unsaturated bond in the hydroxyalkyl (meth) acrylate unit-containing copolymer, and is represented by the following mathematical formula (1). ..

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

The ethylenically unsaturated bond equivalent is, for example, an ethylenically double bond contained in 1 g of a hydroxyalkyl (meth) acrylate unit-containing copolymer according to a test method for iodine value as described in JIS K0070: 1992. It may be calculated by measuring the number of bonds.

The amount of the constituent unit having a photopolymerizable functional group contained in the hydroxyalkyl (meth) acrylate unit-containing copolymer is 2.5% by mass or more with respect to 100% by mass of the total amount of the constituent units constituting the copolymer. It is preferably 35% by mass or less. By setting the amount of the constituent unit having a photopolymerizable functional group within the above range, the photocurability of the hydroxyalkyl (meth) acrylate unit-containing copolymer can be improved.
When the amount of the constituent unit having a photopolymerizable functional group is less than 2.5% by mass, the photocurability of the hydroxyalkyl (meth) acrylate unit-containing copolymer may not be sufficiently obtained. On the other hand, when the amount of the structural unit having a photopolymerizable functional group exceeds 35% by mass, the acidic group of the main chain may be consumed too much and sufficient alkali solubility may not be obtained.
The amount of the structural unit having a photopolymerizable functional group is more preferably 4% by mass or more and 32% by mass or less, and further preferably 5% by mass or more and 31% by mass or less.

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, the viscosity of the softened coating film is increased by hydroxyalkyl (meth) when the coating film of the photosensitive coloring resin is heated and dried. ) It can be increased by the molecular weight effect of the acrylate unit-containing copolymer to suppress the fluidization of the coating film. When 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 it is heated and dried.
The weight average molecular weight of the hydroxyalkyl (meth) acrylate unit-containing copolymer is not particularly limited, but is preferably 25,000 or less. When the weight average molecular weight (Mw) of the hydroxyalkyl (meth) acrylate unit-containing copolymer exceeds 25,000, the viscosity of the photosensitive resin composition becomes too high, and the viscosity deviates from the viscosity suitable for coating. There is.
The weight average molecular weight of the hydroxyalkyl (meth) acrylate unit-containing copolymer is more preferably 11,000 or more and 20,000 or less, and further preferably 11,000 or more and 19,000 or less.

In the present invention, the weight average molecular weight (Mw) is a value measured by GPC (gel permeation chromatography). For the measurement, HLC-8220GPC manufactured by Tosoh was used, the elution solvent was N-methylpyrrolidone to which 0.01 mol / liter of lithium bromide was added, and the polystyrene standard for calibration curve was Mw: ⁸ × 105 (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 (A-500) (all manufactured by Tosoh), and the measurement column is TSK-GEL ALPHA-M × 2 (manufactured by Tosoh).

In the present invention, the acid value of the hydroxyalkyl (meth) acrylate unit-containing copolymer is 60 mgKOH / g or more and 130 mgKOH / g or less. By setting the acid value of the hydroxyalkyl (meth) acrylate unit-containing copolymer to 60 mgKOH / g or more, sufficient alkali solubility can be imparted to the coating film of the photosensitive coloring resin, and the shape of the colored layer is flattened. Excellent effect. On the other hand, by setting the acid value of the hydroxyalkyl (meth) acrylate unit-containing copolymer to 130 mgKOH / g or less, it is possible to reduce the development residue on the substrate when developing the coating film.
The acid value of the hydroxyalkyl (meth) acrylate unit-containing copolymer is preferably 65 mgKOH / g or more and 125 mgKOH / g or less, more preferably 65 mgKOH / g or more and 110 mgKOH / g or less, and 70 mgKOH / g or more and 100 mgKOH or less. It is more preferably less than / g.
When the photosensitive coloring resin composition of the present invention contains a lake coloring material as a coloring material, the acid value of the hydroxyalkyl (meth) acrylate unit-containing copolymer is 100 mgKOH because it is highly effective in suppressing the generation of development residues. It may be / g or more, 110 mgKOH / g or more, or 120 mgKOH / 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.

The hydroxyl value of the hydroxyalkyl (meth) acrylate unit-containing copolymer is preferably 50 mgKOH / g or more and 200 mgKOH / g or less. When the hydroxyl value of the hydroxyalkyl (meth) acrylate unit-containing copolymer is less than 50 mgKOH / g, the hydrophobicity of the coating film of the photosensitive colored resin composition may become too high and the developability may deteriorate. .. On the other hand, when the hydroxyl value of the hydroxyalkyl (meth) acrylate unit-containing copolymer exceeds 200 mgKOH / g, the solvent resolubility of the photosensitive colored resin composition may deteriorate and the coatability may be impaired.
The hydroxyl value of the hydroxyalkyl (meth) acrylate unit-containing copolymer is more preferably 70 mgKOH / g or more and 190 mgKOH / g or less, and further preferably 80 mgKOH / g or more and 180 mgKOH / g or less.

The hydroxyalkyl (meth) acrylate unit-containing copolymer is usually added to the photosensitive coloring resin composition for a color filter 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 a varnish dissolved in a solvent so that the solid content concentration is 60% by mass because a colored layer having excellent flatness can be easily obtained. In this state, the 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. On the other hand, the viscosity may be 10,000 mPa · s or less, or 9,000 mPa · s or less. When the viscosity is not more than the upper limit value, the photosensitive colored resin composition is easily dried, so that the productivity of the color filter can be improved.
The solvent used to dissolve the hydroxyalkyl (meth) acrylate unit-containing copolymer is not particularly limited, and for example, the same solvent as that contained in the photosensitive resin composition for a color filter of the present invention may be used. Can be used.

<Other binder resins>
The photosensitive coloring resin composition of the present invention may contain other binder resins in combination with the hydroxyalkyl (meth) acrylate unit-containing copolymer. Other binder resins include acrylic resins having a structure obtained by removing the hydroxyalkyl (meth) acrylate units from the structure of the hydroxyalkyl (meth) acrylate unit-containing copolymer, and acrylics containing other structural units and side chains. A photosensitive or non-photosensitive polymer obtained by polymerizing an ethylenically unsaturated bond-containing monomer such as a based resin, a styrene-acrylic resin, or a polyolefin-based resin can be used. Further, a polymer conventionally used as a binder resin for forming a colored layer of a color filter, for example, photosensitive or non-photosensitive such as an epoxy resin, a urethane resin, a polyester resin, a polyimide resin, and a novolak resin. The photosensitive resin may be used as another binder resin.

In the photosensitive coloring resin composition of the present invention, the content of the binder resin is usually 4% by mass or more and 25% by mass or less, and 5% by mass or more and 22% by mass with respect to the total solid content of the photosensitive coloring resin composition. It is preferably 5% by mass or more and 20% by mass or less.
Further, in the photosensitive colored resin composition of the present invention, the content of the hydroxyalkyl (meth) acrylate unit-containing copolymer with respect to 100 parts by mass of the total amount of the binder resin is usually 50 parts by mass or more and 95 parts by mass or less, 60. It is preferably 5 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.

[Monomer (photopolymerizable compound)]
The monomer, which is a photopolymerizable compound used in the photosensitive colored resin composition of the present invention, may be any as long as it can be polymerized by a photoinitiator, and is not particularly limited, but has two or more polymerizable double bonds. It is preferable to contain the polyfunctional monomer having. As the polyfunctional monomer, a polyfunctional monomer having two or more ethylenically unsaturated double bonds is preferable, and a polyfunctional (meth) acrylate having two or more acryloyl groups or methacryloyl groups is particularly preferable.
As the polyfunctional (meth) acrylate, a conventionally known one may be appropriately selected and used. Specific examples include those described in Japanese Patent Application Laid-Open No. 2013-029832.
Further, when the photosensitive colored resin composition of the present invention is required to have excellent photocurability (high sensitivity), the polyfunctional monomer has three or more polymerizable double bonds (trifunctional). Those are preferable, and for example, poly (meth) acrylates of trivalent or higher-valent polyvalent alcohols and dicarboxylic acid-modified products thereof can be preferably used. Specifically, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate succinic acid-modified product, 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 and the like are preferable.
It is preferable to use a phosphorus atom-containing polyfunctional (meth) acrylate such as tri (2- (meth) acryloyloxyethyl) phosphate because the fading of the rake coloring material is easily suppressed and the brightness after post-baking is easily improved. ..
These polyfunctional (meth) acrylates may be used alone or in combination of two or more.

In the photosensitive coloring resin composition of the present invention, the viscosity of the coating film of the photosensitive coloring resin composition tends to be appropriate, and the flatness of the obtained colored layer is improved. The content of the functional monomer is preferably 90 parts by mass or more, more preferably 95 parts by mass or more, and particularly preferably 100 parts by mass.

In the photosensitive coloring resin composition of the present invention, the content of the monomer is not particularly limited, but is preferably 5% by mass or more and 60% by mass or less with respect to the total solid content of the photosensitive coloring resin composition. It is more preferably 10% by mass or more and 50% by mass or less. When the content of the monomer is at least the above lower limit value, the photocuring reaction is likely to proceed, so that the exposed portion can suppress elution during development, and when the content of the monomer is at least the above upper limit value, it is alkaline. Developability can be improved.

[Light initiator]
The photoinitiator used in the photosensitive colored resin composition of the present invention is not particularly limited, and one or a combination of two or more of various conventionally known initiators can be used.
Examples of the photoinitiator include benzophenone, N, N-dimethylaminobenzophenone, 4,4'-bisdiethylaminobenzophenone (for example, Hycure ABP, manufactured by Kawaguchi Pharmaceutical Co., Ltd.), 4-methoxy-4'-dimethylaminobenzophenone and the like. Group Ketones; Benzoin Ethers such as Benzoin Methyl Ether; Benzoins such as Ethylbenzoin; Biimidazoles such as 2- (o-chlorophenyl) -4,5-phenylimidazole dimer; 2-Trichloromethyl-5- Halomethyl oxadiazole compounds such as (p-methoxystyryl) -1,3,4-oxadiazole; 2- (4-butoxy-naphtho-1-yl) -4,6-bis-trichloromethyl-S- Halomethyl-S-triazines such as triazine; 1,2-octadion-1- [4- (phenylthio)-, 2- (o-benzoyloxime)], etanone, 1- [9-ethyl-6- (2-) Methylbenzoyl) -9H-carbazole-3-yl]-, 1- (o-acetyloxime), JP-A-2000-80068, JP-A-2001-233842, JP-A-2010-527339, JP-A-2010 Oxime esters such as oxime ester-based photoinitiators described in Japanese Patent Laid-Open No. 527338, Japanese Patent Application Laid-Open No. 2013-041153; 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one. (For example, Irgacure 907, manufactured by BASF), 2-benzyl-2- (dimethylamino) -1- (4-morpholinophenyl) -1-butanone (for example, Irgacure 369, manufactured by BASF), 2- (dimethylamino) Α-Aminoketones such as -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone (Irgacure 379EG, manufactured by BASF); thioxanthones such as diethylthioxanthone Can be mentioned.
Among them, the photoinitiator used in the present invention preferably contains at least one selected from oxime esters and α-aminoketones from the viewpoint of excellent sensitivity, and line width adjustment and development resistance during pattern formation are preferable. From the viewpoint of, α-aminoketones are preferable. Since α-aminoketones having a tertiary amine structure have a tertiary amine structure which is an oxygen quencher in the molecule, radicals generated from the initiator are not easily deactivated by oxygen, and the sensitivity can be improved. preferable.
Further, it is preferable to use a combination of α-aminoketones and oxime esters as the photoinitiator from the viewpoint of suppressing water stains and improving sensitivity. In addition, water stain means that when a component that enhances alkaline developability is used, traces of water stain are generated after alkaline development and rinsing with pure water. Such water stains disappear after post-baking, so there is no problem as a product, but there is a problem that it is detected as unevenness abnormality in the visual inspection of the patterning surface after development, and it is not possible to distinguish between normal products and abnormal products. Occurs. Therefore, if the inspection sensitivity of the inspection device is lowered in the visual inspection, the yield of the final color filter product is lowered as a result, which becomes a problem.
Further, it is preferable to combine thioxanthones with at least one selected from oxime esters and α-aminoketones as the photoinitiator from the viewpoint of adjusting the sensitivity, suppressing water stains, and improving the development resistance. ..

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 effect of the present invention is not impaired, but the total content of the solid content of the photosensitive colored resin composition is not particularly limited. It 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. When this content is at least the above lower limit value, photocuring is sufficiently promoted and the exposed portion is suppressed from elution during development, while when it is at least the above upper limit value, yellowing of the obtained colored layer is suppressed. It is possible to suppress the decrease in brightness.

[Antioxidant]
It is preferable that the photosensitive coloring resin composition of the present invention further contains an antioxidant because the heat resistance is improved, the fading of the coloring material is suppressed, and the brightness is improved. Since the photosensitive coloring resin composition of the present invention contains an antioxidant, it is possible to control an excessive radical chain reaction in the micropores without impairing the curability when forming the micropores in the cured film, which is desired. It is possible to more easily form micropores in the shape of. Further, it is preferable that the antioxidant is used in combination with the oxime ester-based photoinitiator from the viewpoint that the above-mentioned effects can be easily obtained.
The antioxidant used in the present invention is not particularly limited, and may be appropriately selected from conventionally known ones. Specific examples of the antioxidant include hindered phenol-based antioxidants, amine-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, hydrazine-based antioxidants, and the like, and have heat resistance. It is preferable to use a hindered phenolic antioxidant from the viewpoint of improving the shape of the dots and the micropores. It may be a latent antioxidant as described in WO 2014/021023.

Examples of the hindered phenol-based antioxidant include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (trade name: IRGANOX1010, manufactured by BASF), 1,3. , 5-Tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate (trade name: Irganox 3114, manufactured by BASF), 2,4,6-Tris (4-hydroxy-3,5-) Di-tert-butylbenzyl) mecitylene (trade name: Irganox 1330, manufactured by BASF), 2,2'-methylenebis (6-tert-butyl-4-methylphenol) (trade name: Sumilyzer MDP-S, manufactured by Sumitomo Chemical) ), 6,6'-thiobis (2-tert-butyl-4-methylphenol) (trade name: Irganox 1081, manufactured by BASF), diethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate (trade name: Irganox 1081, manufactured by BASF). Product name: Irgamod 195, manufactured by BASF) and the like.
Among them, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (trade name: IRGANOX1010, manufactured by BASF) is preferable from the viewpoint of heat resistance and light resistance.

The content of the antioxidant is preferably 0.1% by mass or more and 10.0% by mass or less, preferably 0.5% by mass, based on the total amount of solids in the photosensitive colored resin composition. More preferably, it is% or more and 5.0% by mass or less. If it is at least the above lower limit value, it is excellent in heat resistance and light resistance. On the other hand, if it is not more than the above upper limit value, the photosensitive resin composition can be made highly sensitive.

When the antioxidant is used in combination with the oxime ester-based photoinitiator, the content of the antioxidant is 1 part by mass of the antioxidant with respect to 100 parts by mass of the total amount of the oxime ester-based photoinitiator. It is preferably 250 parts by mass or less, more preferably 3 parts by mass or more and 80 parts by mass or less, and further preferably 5 parts by mass or more and 65 parts by mass or less. If it is within the above range, the effect of the above combination is excellent.

[Optional additive ingredients]
The photosensitive colored resin composition of the present invention may contain various additives, if necessary. Examples of the additive include a mercapto compound, a polymerization inhibitor, a chain transfer agent, a leveling agent, a plasticizer, a surfactant, a defoaming agent, a silane coupling agent, an ultraviolet absorber, an adhesion accelerator and the like.
Specific examples of the surfactant and the plasticizer include those described in JP2013-029832A.

[solvent]
The solvent used in the present invention is not particularly limited as long as it is an organic solvent that does not react with each component of the photosensitive coloring resin composition and can dissolve or disperse them. The solvent can be used alone or in combination of two or more.
Specific examples of the solvent include alcohol-based solvents such as methyl alcohol, ethyl alcohol, N-propyl alcohol, i-propyl alcohol, methoxy alcohol and ethoxy alcohol; carbitol solvents such as methoxyethoxyethanol and ethoxyethoxyethanol; Ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl methoxypropionate, ethyl ethoxypropionate, ethyl lactate, methyl hydroxypropionate, ethyl hydroxypropionate, n-butyl acetate, isobutyl acetate, isobutyl butyrate, n-butyl butyrate, Ester solvents such as ethyl lactate and cyclohexanol acetate; Ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and 2-heptanone; methoxyethyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy-3-methyl-1 -Glycol ether acetate solvents such as butyl acetate, 3-methoxybutyl acetate and ethoxyethyl acetate; carbitol acetate solvents such as methoxyethoxyethyl acetate, ethoxyethoxyethyl acetate, butyl carbitol acetate (BCA) and carbitol acetate; Diacetates such as propylene glycol diacetate and 1,3-butylene glycol diacetate; 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 , Glycol ether solvent such as dipropylene glycol dimethyl ether; aprotonic amide solvent such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone; lactone solvent such as γ-butyrolactone; Cyclic ether solvent; unsaturated hydrocarbon solvent such as benzene, toluene, xylene, naphthalene; saturated hydrocarbon solvent such as N-heptane, N-hexane, N-octane; aromatic hydrocarbons such as toluene, xylene Organic solvents such as. Among these solvents, glycol ether acetate-based solvents, carbitol acetate-based solvents, glycol ether-based solvents, and ester-based solvents are preferably used in terms of the solubility of other components.
Among them, the solvent used in the present invention includes propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, butyl carbitol acetate (BCA), carbitol acetate, 3-methoxy-3-methyl-1-butyl acetate, and ethyl ethoxypropionate. , Ethyl lactate, and 3-methoxybutyl acetate are preferably one or more selected from the group, from the viewpoint of solubility of other components and suitability for application.

The content of the solvent is not particularly limited, but is preferably 75% by mass or more and 95% by mass or less, and preferably 80% by mass or more and 90% by mass or less, based on the total amount of the photosensitive colored resin composition. More preferred. When the content of the solvent in the photosensitive colored resin composition is not less than the above lower limit value, the solubility and coating suitability of other components can be improved, while when it is not more than the above upper limit value, the color filter can be improved. The amount of the photosensitive colored resin composition used at the time of formation can be reduced.

II. Method for Producing Photosensitive Colored Resin Composition for Color Filter The method for producing the photosensitive colored resin composition of the present invention is not particularly limited, and for example, each component such as the above-mentioned coloring material, binder resin, monomer, and light initiator can be used. A photosensitive colored resin composition may be produced by mixing with a solvent and dissolving or dispersing it, but a coloring material dispersion liquid in which the coloring material is dispersed in the solvent using a dispersant, or a coloring material in the solvent. A color material solution dissolved in is prepared in advance, and the components of the color material dispersion or the color material solution and the components of the photosensitive coloring resin composition other than the color material such as the binder resin, the monomer, and the photoinitiator are known. It is preferable to produce a photosensitive colored resin composition by mixing it with a solvent using a dispersing means and dissolving or dispersing it.
When two or more kinds of coloring materials are used, after preparing a coloring material dispersion or a coloring material solution for each coloring material, each coloring material dispersion or a coloring material solution, a binder resin, and light are used. A photosensitive coloring resin composition may be produced by mixing components of a photosensitive coloring resin composition other than a coloring material such as an initiator with a solvent and dissolving or dispersing them.
The colorant dispersion and the colorant solution are used as preparatory preparations for preparing the colored resin composition. That is, the coloring material dispersion liquid and the coloring material solution are pre-prepared in the stage before preparing the coloring resin composition, and the P / V ratio, that is, (mass of the coloring material component in the composition) / (coloring material in the composition). The ratio of solid content (mass other than components) is high. Specifically, the P / V ratio of the color material dispersion liquid and the color material solution is usually 1.0 or more.

The photosensitive coloring resin composition of the present invention produced by using the colorant dispersion liquid contains a dispersant. Since the photosensitive coloring resin composition of the present invention containing a rake coloring material or a pigment is preferably produced using a coloring material dispersion liquid in which a rake coloring material or a pigment is dispersed, it is preferable to contain a dispersant. ..
Hereinafter, the color material dispersion liquid used for producing the photosensitive coloring resin composition of the present invention will be described in detail.
The color material dispersion liquid used in the present invention contains a solvent, a dispersant, and the above-mentioned color material dispersed in the solvent by the dispersant, and further contains other components such as a dispersion aid, if necessary. You may.

[Dispersant]
As the dispersant, those conventionally used as a dispersant can be appropriately selected and used. As the dispersant, for example, a cationic, anionic, nonionic, amphoteric, silicone-based, or fluorine-based surfactant can be used. Among the surfactants, a polymer surfactant (polymer dispersant) is preferable because it can be dispersed uniformly and finely.
Examples of the polymer dispersant include (co) polymers of unsaturated carboxylic acid esters such as polyacrylic acid esters; (partial) amine salts of (co) polymers of unsaturated carboxylic acids such as polyacrylic acid. (Partial) ammonium salts and (partial) alkylamine salts; (co) polymers of hydroxyl group-containing unsaturated carboxylic acid esters such as hydroxyl group-containing polyacrylic acid esters and their modifications; polyurethanes; unsaturated polyamides; polysiloxane Classes; long-chain polyaminoamide phosphates; polyethylene imine derivatives (amides obtained by the reaction of poly (lower alkylene imine) with free carboxy group-containing polyesters and their bases); polyallylamine derivatives (polyallylamine and free carboxy). Examples thereof include a reaction product obtained by reacting one or more compounds selected from three kinds of compounds of a polyester having a group, a polyamide, or a cocondensate of an ester and an amide (polyester amide)).

As the dispersant, one having good dispersibility can be appropriately selected and used depending on the type of coloring material, and the dispersant is not particularly limited, but is a rake color represented by the above general formula (1) or (2). When the material or the metal lake color material of the xanthene dye represented by the above general formula (5) is dispersed, and these lake color materials and the dye such as the xanthene dye or C.I. I. When co-dispersing with a pigment such as Pigment Blue 15: 6, it is preferable to use an acidic dispersant, which is an acidic polymer dispersant, as the dispersant. In the present invention, the dye may be used by dissolving it in a solvent.
When dispersing the pigment, it is preferable to use at least one selected from the group consisting of an acidic or basic polymer dispersant and a urethane-based dispersant, depending on the type of the pigment, and it is preferable to use an acidic or basic polymer. It is more preferable to use a dispersant. When dispersing a basic-treated pigment, it is preferable to use an acidic dispersant which is an acidic polymer dispersant, and when dispersing an acid-treated pigment, a base which is a basic polymer dispersant is used. It is preferable to use a sex dispersant.
As the acidic dispersant used for the dispersion of the rake colorant, for example, at least one selected from a polymer having a structural unit represented by the general formula (I) described later and a carboxy group-containing block copolymer described later will be used. It can be suitably used. As the acidic dispersant used for dispersing the pigment, for example, a carboxy group-containing block copolymer can be preferably used.
Examples of the basic dispersant include a polymer containing a repeating unit having a tertiary amine and at least a part of amino groups in a polymer containing a repeating unit having a tertiary amine and an organic acid compound. At least one selected from the group consisting of salt-type polymers forming a salt can be preferably used.
The urethane-based dispersant is a compound having one or more urethane bonds (-NH-COO-) in one molecule. As the urethane-based dispersant, for example, a reaction product of polyisocyanates having two or more isocyanate groups in one molecule and polyesters having hydroxyl groups at one end or both ends can be preferably used.

<Polymer having a structural unit represented by the general formula (I)>
The polymer having the structural unit represented by the following general formula (I) can be preferably used as a dispersant for the rake coloring material, and in particular, the rake represented by the above general formula (1) or general formula (2). It can be preferably used as a dispersant for coloring materials. When a polymer having a structural unit represented by the following general formula (I) is used as the acidic dispersant, the dispersibility and heat resistance of the rake color material are improved, and the change in chromaticity of the rake color material after heating is suppressed. It is possible. When a lake coloring material and a pigment are used in combination as a coloring material, a polymer having a structural unit represented by the following general formula (I) is used as a dispersant to improve the dispersibility and storage stability of the pigment. It is possible to form a colored layer with improved substrate adhesion and improved coating film uniformity.
Since the polymer having the structural unit represented by the following general formula (I) is an ethylenically unsaturated monomer polymer, the heat resistance of the skeleton is higher than that of the polyether-based or polyester-based polymer, and the polymer has higher heat resistance. Multiple acidic phosphorus compound groups (-P (= O) (-R ¹² ) (OH)) and salts thereof (-P (= O) (-R ¹² ) (O ^- X ⁺ )) present in the polymer. However, it is presumed that the finely divided coloring material has a strong adsorption force on the surface. In addition, when the surface of the coloring material is coated with at least one of an acidic phosphorus compound group and a salt thereof, active oxygen such as peroxy radicals attacks the pigment skeleton of the rake coloring material (hydrogen extraction, substitution reaction, etc.). It is presumed that the deterioration of the rake color material (oxidative deterioration) is suppressed.

(In the general formula (I), L ¹¹ is a direct bond or a divalent linking group, R ¹¹ is a hydrogen atom or a methyl group, R ¹² is a hydroxyl group or a hydrocarbon group, and-[CH (R ¹³ ) -CH. (R ¹⁴ ) -O] _x1 -R ¹⁵ ,-[(CH ₂ ) _y1 -O] _z1 -R ¹⁵ or -OR ¹⁶ is a monovalent group, and R ¹⁶ is a hydrocarbon group. ,-[CH (R ¹³ ) -CH (R ¹⁴ ) -O] _x1 -R ¹⁵ ,-[(CH ₂ ) _y1 -O] _z1 -R ¹⁵ , -C (R ¹⁷ ) (R ¹⁸ ) -C ( It is a monovalent group represented by R ¹⁹ ) (R ²⁰ ) -OH or -CH ₂ -C (R ²¹ ) (R ²² ) -CH ₂ -OH.
R ¹³ and R ¹⁴ are each independently a hydrogen atom or a methyl group, and R ¹⁵ is a hydrogen atom, a hydrocarbon group, -CHO, -CH ₂ CHO, -CO-CH = CH ₂ , -CO-C ( CH ₃ ) = CH ₂ or -CH ₂ COOR ²³ is a monovalent group, and R ²³ is a hydrogen atom or an alkyl group having 1 or more and 5 or less carbon atoms. R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ and R ²² are each independently a hydrogen atom, a hydrocarbon group, or a hydrocarbon group having one or more selected from an ether bond and an ester bond. Yes, R ¹⁷ and R ¹⁹ may be coupled to each other to form a ring structure. When the cyclic structure is formed, the cyclic structure may further have a substituent R ²⁴ , ^which is a hydrocarbon group or a hydrocarbon having one or more selected from an ether bond and an ester bond. It is a hydrogen group. The hydrocarbon group may have a substituent. X represents a hydrogen atom or an organic cation. x1 is an integer of 1 or more and 18 or less, y1 is an integer of 1 or more and 5 or less, and z1 is an integer of 1 or more and 18 or less. )

In the general formula (I), L ¹¹ is a direct coupling or a divalent linking group. Here, when L ¹¹ is directly bonded, it means that the phosphorus atom is directly bonded to the carbon atom of the main chain skeleton without interposing a linking group.
The divalent linking group in L ¹¹ is not particularly limited as long as the carbon atom of the main chain skeleton and the phosphorus atom can be linked. Examples of the divalent linking group in L ¹¹ include a linear, branched or cyclic alkylene group, a linear, branched or cyclic alkylene group having a hydroxyl group, an arylene group, a —CONH— group, and a —COO— group. -NHCOO- group, ether group (-O- group), thioether group (-S- group), combinations thereof and the like can be mentioned. In the present invention, the direction of bonding of the divalent linking group is arbitrary. That is, when -CONH- is contained in the divalent linking group, -CO may be on the carbon atom side of the main chain and -NH may be on the phosphorus atom side of the side chain, and conversely, -NH may be on the main chain. -CO may be on the phosphorus atom side of the side chain on the carbon atom side of.

Above all, from the viewpoint of dispersibility, L ¹¹ in the general formula (I) is preferably a divalent linking group containing a —CONH— group or a —COO— group.
For example, if L ¹¹ is a divalent linking group containing a -COO- group, then L ¹¹ is a -COO-L ^11' -group (where L ^11'may have a hydroxyl group. An alkylene group having 1 or more and 8 or less,-[CH ( ^{RL11) -CH (RL12} ⁾ -O] _x- , or-[(CH ₂ ) _y -O] _z- (CH ₂ ) _y- O-,-[CH ( ^RL13 )] _w -O-, and ^{RL11, RL12 and RL13} ^are ^{independently} hydrogen atoms, methyl groups or hydroxyl groups. X is 1 or more and 18 or less. It is preferable that y is an integer of 1 or more and 5 or less, z is an integer of 1 or more and 18 or less, and w is an integer of 1 or more and 18 or less.

The alkylene group having 1 or more and 8 or less carbon atoms in L ^11'may be linear, branched, or cyclic, and may be, for example, a methylene group, an ethylene group, a trimethylene group, a propylene group, or various types. It is a butylene group, various pentylene groups, various hexylene groups, various octylene groups, etc., and a part of hydrogen may be substituted with a hydroxyl group.
x is an integer of 1 or more and 18 or less, preferably an integer of 1 or more and 4 or less, more preferably an integer of 1 or more and 2 or less, and y is an integer of 1 or more and 5 or less, preferably an integer of 1 or more and 4 or less, more preferably. Is 2 or 3. z is an integer of 1 or more and 18 or less, preferably an integer of 1 or more and 4 or less, and more preferably an integer of 1 or more and 2 or less. w is an integer of 1 or more and 18 or less, preferably an integer of 1 or more and 4 or less.

Suitable specific examples of L ¹¹ in the general formula (I) include, for example, -COO-CH ₂ CH (OH) CH ₂ -O-, -COO-CH ₂ CH ₂ -O-CH ₂ CH (OH) CH. ₂ -O-, -COO-CH ₂ C (CH ₂ CH ₃ ) (CH ₂ OH) CH ₂ -O- and the like can be mentioned, but the present invention is not limited thereto.

Examples of the hydrocarbon group in R ¹² include an alkyl group having 1 or more and 18 or less carbon atoms, an alkenyl group having 2 or more and 18 or less carbon atoms, an aralkyl group, and an aryl group.
The alkyl group having 1 or more and 18 or less carbon atoms may be linear, branched or cyclic, and may be, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group or n-butyl. Examples thereof include a group, a cyclopentyl group, a cyclohexyl group, a bornyl group, an isobornyl group, a dicyclopentanyl group, an adamantyl group, a lower alkyl group substituted adamantyl group and the like.
The alkenyl group having 2 or more and 18 or less carbon atoms may be linear, branched or cyclic. Examples of such an alkenyl group include a vinyl group, an allyl group, a propenyl group and the like. The position of the double bond of the alkenyl group is not limited, but from the viewpoint of the reactivity of the obtained polymer, it is preferable that the double bond is at the end of the alkenyl group.
Examples of the aryl group include a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, a xylyl group and the like, and may further have a substituent. The aryl group preferably has 6 or more and 24 or less carbon atoms, and more preferably 6 or more and 12 or less carbon atoms.
Examples of the aralkyl group include a benzyl group, a phenethyl group, a naphthylmethyl group, a biphenylmethyl group and the like, and may further have a substituent. The number of carbon atoms of the aralkyl group is preferably 7 or more and 20 or less, and more preferably 7 or more and 14 or less.
The alkyl group or alkenyl group may have a substituent, and examples of the substituent include halogen atoms such as F, Cl and Br, a nitro group and the like.
Further, as the substituent of the aromatic ring such as the aryl group or the aralkyl group, a linear or branched alkyl group having 1 or more and 4 or less carbon atoms, an alkenyl group, a nitro group, a halogen atom and the like can be used. Can be mentioned.
The preferable carbon number does not include the carbon number of the substituent.
In the R ¹² , x1 is the same as the x, y1 is the same as the y, and z1 is the same as the z.
Examples of the hydrocarbon group in R ¹⁵ to R ²² include the same group as the hydrocarbon group in R ¹² .

The hydrocarbon groups having one or more selected from the ether bond and the ester bond in R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ and R ²² are -R'-OR ", -R. "-(C = O) -OR" or -R'-O- (C = O) -R "(R'and R" is a hydrocarbon group or an ether bond and ester of a hydrocarbon group. A group represented by a group bonded by at least one of the bonds). One group may have two or more ether bonds and ester bonds. Examples of the monovalent hydrocarbon group include an alkyl group, an alkenyl group, an aralkyl group, and an aryl group. When the hydrocarbon group is divalent, an alkylene group, an alkenylene group, an arylene group, and a combination thereof are used. The basis of is mentioned.

When R ¹⁷ and R ¹⁹ are bonded to form a ring structure, the number of carbon atoms forming the ring structure is preferably 5 or more and 8 or less, and is 6, that is, a 6-membered ring. More preferably, it is preferable to form a cyclohexane ring.
The hydrocarbon group in the substituent R ²⁴ or the hydrocarbon group having one or more selected from the ether bond and the ester bond is described in R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ and R ²² . It can be similar to the one.

From the viewpoint of excellent dispersibility and dispersion stability of the dispersed particles, the R ¹² is a hydroxyl group, a hydrocarbon group,-[CH (R ¹³ ) -CH (R ¹⁴ ) -O] _x1 -R ¹⁵ ,-[ (CH ₂ ) _y1 -O] It is preferably a monovalent group represented by _z1 -R ¹⁵ or -OR ¹⁶ , and has a hydroxyl group, a methyl group, an ethyl group, a vinyl group and a substituent. Also good aryl group or aralkyl group, vinyl group, allyl group,-[CH (R ¹³ ) -CH (R ¹⁴ ) -O] _x1 -R ¹⁵ ,-[(CH ₂ ) _y1 -O] _z1 -R ¹⁵ , Or, the monovalent group represented by -OR ¹⁶ and R ¹³ and R ¹⁴ are independently hydrogen atoms or methyl groups, and R ¹⁵ is -CO-CH = CH ₂ or -CO-C (CH ₃ ). = CH ₂ is more preferable, and among them, an aryl group, a vinyl group, a methyl group and a hydroxyl group, in which R ¹² may have a substituent, are more preferable.

Further, from the viewpoint of improving alkali resistance, R ¹² has a hydrocarbon group,-[CH (R ¹³ ) -CH (R ¹⁴ ) -O] _x1 -R ¹⁵ or-[(CH ₂ ) _y1 -O. ] It is preferably a monovalent group represented by _z1 - ^R15 . When it has a structure in which a carbon atom is directly bonded to a phosphorus atom, it is presumed that a resin layer having excellent alkali resistance can be formed because it is difficult to be hydrolyzed. Among them, R ¹² has a methyl group, an ethyl group, an aryl group which may have a substituent or an aralkyl group, a vinyl group, an allyl group, and-[CH (R ¹³ ) -CH (R ¹⁴ ) -O] _x1 . -R ¹⁵ or-[(CH ₂ ) _y1 -O] The monovalent groups represented by _z1 -R ¹⁵ , R ¹³ and R ¹⁴ are independently hydrogen atoms or methyl groups, and R ¹⁵ is -CO. Those having -CH = CH ₂ or -CO-C (CH ₃ ) = CH ₂ are preferable from the viewpoint of excellent alkali resistance and excellent dispersibility and dispersion stability of the dispersed particles. Among them, R ¹² is more preferably an aryl group which may have a substituent from the viewpoint of dispersibility.

Further, in the general formula (I), X represents a hydrogen atom or an organic cation. The organic cation means a cation containing a carbon atom. Examples of the organic cation include ammonium cations such as imidazolium cations, pyridinium cations, aminidium cations, piperidinium cations, pyrrolidinium cations, tetraalkylammonium cations and trialkylammonium cations, and sulfonium cations such as trialkylsulfonium cations. , A phosphonium cation such as a tetraalkylphosphonium cation, and the like. Above all, a protonated nitrogen-containing organic cation is preferable from the viewpoint of dispersibility and alkali developability.
Above all, when the organic cation has an ethylenically unsaturated double bond, it is preferable because it can impart curability.

The structural unit represented by the general formula (I) may be contained alone in the polymer, or may be contained in two or more types.

In the polymer, among the structural units represented by the general formula (I), X may contain both a structural unit of a hydrogen atom and X may contain both a structural unit of an organic cation. When both of the constituent units are included, it is sufficient as long as good dispersibility and dispersion stability are exhibited, and there is no particular limitation, but the ratio of the number of constituent units in which X is an organic cation is the general formula (I). It is preferably 0 mol% or more and 50 mol% or less with respect to the total number of constituent units represented by.

The method for synthesizing the polymer having the structural unit represented by the general formula (I) is not particularly limited, but for example, with reference to JP-A-2017-2191, the structural unit represented by the general formula (I) can be used. The polymer can be synthesized. The polymer having a structural unit represented by the general formula (I) is a reaction product of a polymer having at least one of an epoxy group and a cyclic ether group in the side chain and an acidic phosphorus compound, and is an acidic phosphorus compound. It is preferably a polymer in which at least a part of the group may form a salt.

In the embodiment of the present invention, the polymer having the structural unit represented by the general formula (I) preferably has a solvent-affinity moiety further from the viewpoint of dispersibility. Such a polymer is, among others, a graft copolymer having a structural unit represented by the general formula (I) and a structural unit represented by the following general formula (II), or the above-mentioned polymer. A block copolymer having a structural unit represented by the general formula (I) and a structural unit represented by the following general formula (III) is excellent in dispersibility and storage stability, and after long-term storage. However, it is preferable because a high-contrast coating film can be formed.

(In the general formula (II), L ²¹ is a direct bond or a divalent linking group, R ²⁵ is a hydrogen atom or a methyl group, and Polymer is a polymer chain having a structural unit represented by the following general formula (IV). Represents.
In the general formula (III), R ²⁶ is a hydrogen atom or a methyl group, R ²⁷ is a hydrocarbon group,-[CH (R ²⁸ ) -CH (R ²⁹ ) -O] _x2 -R ³⁰ ,-[(CH). ₂ ) _y2 -O] _z2 -R ³⁰ ,-[CO- (CH ₂ ) _y2 -O] _z2 -R ³⁰ , -CO-OR ^30'or -O-CO-R ^{30 "} , R ²⁸ and R ²⁹ are independent hydrogen atoms or methyl groups, respectively, and R ³⁰ is a hydrogen atom, a hydrocarbon group, a monovalent group represented by -CHO, -CH ₂ CHO or -CH ₂ COOR ³¹ . R ^30'is a hydrocarbon group,-[CH (R ²⁸ ) -CH (R ²⁹ ) -O] _x2' -R ³⁰ ,-[(CH ₂ ) _y2' -O] _z2' -R ³⁰ . ,-[CO- (CH ₂ ) _y2' -O] _z2' -R ³⁰ is a monovalent group, R ^{30 "} is an alkyl group having 1 or more and 18 or less carbon atoms, and R ³¹ is hydrogen. It is an alkyl group having 1 or more and 5 or less atoms or carbon atoms. The hydrocarbon group may have a substituent.
x2 and x2'indicate an integer of 1 or more and 18 or less, y2 and y2' indicate an integer of 1 or more and 5 or less, and z2 and z2'indicate an integer of 1 or more and 18 or less. )

(In general formula (IV), R ³² is a hydrogen atom or a methyl group, R ³³ is a hydrocarbon group,-[CH (R ³⁴ ) -CH (R ³⁵ ) -O] _x3 -R ³⁶ ,-[((IV). CH ₂ ) _y3 -O] _z3 -R ³⁶ ,-[CO- (CH ₂ ) _y3 -O] _z3 -R ³⁶ , -CO-O-R ³⁷ or -O-CO-R ³⁸ The groups, R ³⁴ and R ³⁵ , are independent hydrogen atoms or methyl groups, respectively, and R ³⁶ is a hydrogen atom, a hydrocarbon group, a monovalent group represented by -CHO, -CH ₂ CHO or -CH ₂ COOR ³⁹ , respectively. R ³⁷ is a hydrocarbon group,-[CH (R ³⁴ ) -CH (R ³⁵ ) -O] _x4 -R ³⁶ ,-[(CH ₂ ) _y4 -O] _z4 -R ³⁶ ,-[CO- (CH). ₂ ) _y4 -O] A monovalent group represented by _z4 -R ³⁶ , R ³⁸ is an alkyl group having 1 or more and 18 or less carbon atoms, and R ³⁹ is a hydrogen atom or 1 or more and 5 or less carbon atoms. It is an alkyl group, and the hydrocarbon group may have a substituent.
n represents an integer of 5 or more and 200 or less. x3 and x4 are integers of 1 or more and 18 or less, y3 and y4 are integers of 1 or more and 5 or less, and z3 and z4 are integers of 1 or more and 18 or less. )

(Graft copolymer)
Examples of the graft copolymer preferable as the acidic dispersant include a graft copolymer having a structural unit represented by the general formula (I) and a structural unit represented by the general formula (II). Can be done.
In the general formula (II), L ²¹ is a direct coupling or a divalent linking group. The divalent linking group in L ²¹ is not particularly limited as long as the carbon atom derived from the ethylenically unsaturated double bond and the polymer chain can be linked. Examples of the divalent linking group in L ²¹ include the same as the divalent linking group in L ¹¹ .

In the general formula (II), Polymer represents a polymer chain having a structural unit represented by the general formula (IV).
In the general formula (IV), the hydrocarbon group in R ³³ is an alkyl group having 1 or more and 18 or less carbon atoms, an alkenyl group having 2 or more and 18 or less carbon atoms, an aralkyl group, or an aryl group. Is preferable. These include, for example, the same as the above-mentioned ^R12 .

R ³⁶ is preferably a hydrogen atom or a monovalent group represented by an alkyl group having 1 or more and 18 or less carbon atoms, an aralkyl group, an aryl group, -CHO, -CH ₂ CHO or -CH ₂ COOR ³⁹ . R ³⁷ has an alkyl group having 1 or more and 18 or less carbon atoms, an aralkyl group, an aryl group,-[CH (R ³⁴ ) -CH (R ³⁵ ) -O] _x4 -R ³⁶ ,-[(CH ₂ ). _y4 -O] _z4 -R ³⁶ ,-[CO- (CH ₂ ) _y4 -O] The monovalent group represented by _z4 -R ³⁶ is preferable. R ³⁸ is an alkyl group having 1 or more and 18 or less carbon atoms, and R ³⁹ is a hydrogen atom or an alkyl group having 1 or more and 5 or less carbon atoms.
Examples of the alkyl group, aralkyl group, and aryl group having 1 or more and 18 or less carbon atoms among R ³⁶ and R ³⁷ are the same as those of R ¹² .
Examples of the alkyl group among the R ³⁸ and R ³⁹ are the same as those of the R ¹² described above.
When the R ³⁶ , R ³⁷ and R ³⁹ are groups having an aromatic ring, the aromatic ring may further have a substituent. Examples of the substituent include linear, branched and cyclic alkyl groups having 1 or more and 5 or less carbon atoms, as well as halogen atoms such as alkenyl groups, nitro groups, F, Cl and Br. ..
The preferable carbon number does not include the carbon number of the substituent.
In R ³³ and R ³⁷ , x3 and x4 are the same as the x, y3 and y4 are the same as the y, and z3 and z4 are the same as the z.

Further, the R ³³ , R ³⁶ , R ³⁷ , R ³⁸ and R ³⁹ further include an alkoxy group, a hydroxyl group, a carboxy group, an amino group and an epoxy group as long as they do not interfere with the dispersion performance of the graft copolymer. It may be substituted with a substituent such as an isocyanate group or a hydrogen bond forming group. Further, after synthesizing a graft copolymer having these substituents, a compound having a functional group and a polymerizable group that reacts with the substituent may be reacted to add a polymerizable group. For example, a polymerizable group may be added by reacting a graft copolymer having a carboxy group with glycidyl (meth) acrylate, or by reacting a graft copolymer having an isocyanate group with hydroxyethyl (meth) acrylate. Can be done.

The polymer chain having a structural unit represented by the general formula (IV) includes methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl among the above-mentioned structural units. (Meta) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, isobornyl ( Those having a structural unit derived from meth) acrylate, dicyclopentanyl (meth) acrylate, adamantyl (meth) acrylate, styrene, α-methylstyrene, vinylcyclohexane and the like are preferable. However, it is not limited to these.

In the embodiment of the present invention, the R ³³ and R ³⁷ are preferably those having excellent solubility in an organic solvent, and are appropriately selected according to the organic solvent used in the colorant dispersion. It's fine. Specifically, for example, when an organic solvent such as ether alcohol acetate-based, ether-based, or ester-based, which is generally used as an organic solvent for a colorant dispersion, is used as an organic solvent, a methyl group or an ethyl group is used. , Isobutyl group, n-butyl group, 2-ethylhexyl group, 2-ethoxyethyl group, cyclohexyl group, benzyl group and the like are preferable.
Here, the reason for setting the R ³³ and R ³⁷ in this way is that the structural unit containing the R ³³ and R ³⁷ has solubility in the organic solvent, and the acidic phosphorus compound group of the monomer and the acidic phosphorus compound group of the monomer are used. This is because the salt portion has a high adsorptivity to particles such as a coloring material, so that the dispersibility and stability of the particles such as the coloring material can be made particularly excellent.

The weight average molecular weight of the polymer chain in Polymer is preferably in the range of 500 or more and 15,000 or less, and more preferably in the range of 1000 or more and 8000 or less. Within the above range, a sufficient steric repulsion effect as a dispersant can be maintained, and an increase in time required for dispersion of particles such as a coloring material due to the steric effect can be suppressed.

Further, as a guide, the polymer chain in Polymer preferably has a solubility of 50 (g / 100 g solvent) or more at 23 ° C. with respect to the organic solvent used in combination.

The polymer chain may be a homopolymer or a copolymer. Further, the polymer chain contained in the structural unit represented by the general formula (II) may be used alone or in combination of two or more in the graft copolymer.

It is preferable that the total of the structural units represented by the general formula (I) is contained in a proportion of 3% by mass or more and 80% by mass or less with respect to all the structural units of the graft copolymer. It is more preferably 20% by mass or more and 70% by mass or less, and further preferably 20% by mass or more and 60% by mass or less. When the total content of the structural units represented by the general formula (I) in the graft copolymer is within the above range, the ratio of the affinity sites with the particles in the graft copolymer is appropriate, and the organic solvent is used. Since the decrease in solubility of the colorant can be suppressed, the adsorptivity to particles such as a coloring material is improved, and excellent dispersibility and dispersion stability can be obtained. Further, since the acidic phosphorus compound group of the graft copolymer can be stably localized around the coloring material, a color filter having excellent heat resistance and contrast can be obtained.
On the other hand, the structural unit represented by the general formula (II) is preferably contained in a proportion of 20% by mass or more and 97% by mass or less, preferably 25% by mass, with respect to all the structural units of the graft copolymer. % Or more and 95% by mass or less are more preferable, and 40% by mass or more and 90% by mass or less are further preferable.
In the present invention, the content ratio of each structural unit in the copolymer is calculated from the amount charged when synthesizing the copolymer.

The weight average molecular weight of the graft copolymer is preferably in the range of 1,000 or more and 500,000 or less, more preferably in the range of 3,000 or more and 400,000 or less, and in the range of 5,000 or more and 300,000 or less. Is even more preferable. Within the above range, particles such as coloring materials can be uniformly dispersed.

The graft copolymer used in the embodiment of the present invention has a structural unit represented by the general formula (I) and a structural unit represented by the general formula (II), as well as other structural units. You may be doing it. For example, an ethylenically unsaturated monomer copolymerizable with an ethylenically unsaturated monomer or the like that induces a structural unit represented by the general formula (I) is appropriately selected and copolymerized, and another structural unit is introduced. be able to.

(Block copolymer)
As the block copolymer preferable as the acidic dispersant, for example, a block portion containing the structural unit represented by the general formula (I) and a block portion containing the structural unit represented by the general formula (III) may be used. Examples thereof include block copolymers having.
In the block copolymer, it is preferable that the block portion containing the structural unit represented by the general formula (I) contains three or more structural units represented by the general formula (I) in total. .. Among them, from the viewpoint of improving dispersibility and improving heat resistance, it is preferable to include 3 or more and 200 or less, more preferably 3 or more and 50 or less, and further include 3 or more and 30 or less. Is more preferable.
The structural unit represented by the general formula (I) may function as a color material affinity site, may be composed of one type, or may include two or more types of structural units. When two or more types of structural units are included, two or more types of structural units may be randomly arranged in the block portion including the structural units represented by the general formula (I).

In the block copolymer, the total content ratio of the structural units represented by the general formula (I) is 5% by mass or more and 80% by mass or less with respect to all the structural units of the block copolymer. It is more preferable that it is 10% by mass or more and 70% by mass or less, and further preferably 20% by mass or more and 60% by mass or less.
If it is within the above range, the ratio of the affinity site with the particles in the block copolymer becomes appropriate, and the decrease in the solubility in the organic solvent can be suppressed, so that the adsorptivity to the particles such as the coloring material becomes good. Excellent dispersibility and dispersion stability can be obtained. Further, since the acidic phosphorus compound group of the block copolymer can be stably localized around the coloring material, a color filter having excellent heat resistance and contrast can be obtained.

By having the block portion containing the structural unit represented by the general formula (III), the block copolymer has good solvent affinity, good dispersibility and dispersion stability of the coloring material, and heat resistance. The properties are also good, and the resistance to N-methylpyrrolidone (NMP) (NMP resistance) is also excellent.

In the general formula (III), R ²⁷ is a hydrocarbon group,-[CH (R ²⁸ ) -CH (R ²⁹ ) -O] _x2 -R ³⁰ ,-[(CH ₂ ) _y2 -O] _z2 -R ³⁰ . ,-[CO- (CH ₂ ) _y2 -O] _z2 -R ³⁰ , -CO-O-R ^30'or -O-CO-R ^{30 "} , which is a monovalent group.
The hydrocarbon group in R ²⁷ can be the same as that shown in R ¹² .

Further, R ³⁰ is a monovalent group represented by a hydrogen atom, a hydrocarbon group, -CHO, -CH ₂ CHO or -CH ₂ COOR ³¹ , and R ^30'is a hydrocarbon group,-[CH ( R ²⁸ ) -CH (R ²⁹ ) -O] _x2' -R ³⁰ ,-[(CH ₂ ) _y2' -O] _z2' -R ³⁰ ,-[CO- (CH ₂ ) _y2' -O] _z2' -R ³⁰ is a monovalent group, R ^{30 "} is an alkyl group having 1 or more and 18 or less carbon atoms, and R ³¹ is a hydrogen atom or an alkyl group having 1 or more and 5 or less carbon atoms. , The hydrocarbon group may have a substituent.
The hydrocarbon group in R ³⁰ can be the same as that shown in R ¹² .
In the R ²⁷ and R ^30' , x2 and x2'are the same as the x, y2 and y2'are the same as the y, and z2 and z2'are the same as the z.
Further, the R ^27s in the structural unit represented by the general formula (III) may be the same as each other or may be different from each other.

As the R ²⁷ and R ^30' , it is preferable to use those having excellent solubility in an organic solvent, and examples thereof include the same as those of R ³³ and R ³⁷ .
Further, R ²⁷ , R ³⁰ , R ^30' , R ^{30 "} and R ³¹ in the general formula (IV) have an alkoxy group, a hydroxyl group, a carboxy group, and the like, as long as they do not interfere with the dispersion performance of the block copolymer. It may be substituted with a substituent such as an amino group, an epoxy group, an isocyanate group or a hydrogen bond forming group, or after the synthesis of the block copolymer, it may be reacted with a compound having the substituent to carry out the substitution. A group may be added. Further, after synthesizing a block copolymer having these substituents, a compound having a functional group and a polymerizable group that reacts with the substituent is reacted to form a polymerizable group. It may be added. For example, a block copolymer having a glycidyl group may be reacted with (meth) acrylic acid, or a block copolymer having an isocyanate group may be reacted with hydroxyethyl (meth) acrylate. A polymerizable group can be added.

The number of the constituent units constituting the block portion including the constituent unit represented by the general formula (III) is not particularly limited, but the solvent-affinity portion and the color material-affinity portion act effectively, and the color material dispersion liquid From the viewpoint of improving dispersibility, it is preferably 10 or more and 200 or less, more preferably 20 or more and 100 or less, and further preferably 30 or more and 80 or less.

The content ratio of the structural unit represented by the general formula (III) in the block copolymer is preferably 30% by mass or more and 95% by mass or less with respect to all the structural units of the block copolymer. It is more preferably 40% by mass or more and 90% by mass or less.

The block portion containing the structural unit represented by the general formula (III) may be selected so as to function as a solvent-affinity site, and the structural unit represented by the general formula (III) is composed of one kind. It may be present, or it may contain two or more kinds of structural units. In the embodiment of the present invention, when the structural unit represented by the general formula (III) includes two or more types of structural units, there are two types in the block portion including the structural units represented by the general formula (III). The above structural units may be randomly arranged.

In a block copolymer used as a dispersant, the number of units m of the structural unit of the block unit including the structural unit represented by the general formula (I) and the block unit containing the structural unit represented by the general formula (III). The ratio m / n of the number of units n of the constituent units is preferably in the range of 0.01 or more and 1 or less, and is preferably in the range of 0.1 or more and 0.7 or less for the dispersion of the coloring material. It is more preferable from the viewpoint of property and dispersion stability.

The block copolymer has a block portion containing the structural unit represented by the general formula (I) and a block portion including the structural unit represented by the general formula (III) as the binding order of the block copolymer, and the coloring material is used. Anything that can be stably dispersed is not particularly limited, but the block portion containing the structural unit represented by the general formula (I) is bonded only to one end of the block copolymer. However, it is preferable because it has excellent interaction with the coloring material and can effectively suppress the aggregation of the dispersants.

The weight average molecular weight of the block copolymer is not particularly limited, but is preferably 2500 or more and 500,000 or less, and more preferably 3000 or more and 400,000 or less, from the viewpoint of good dispersibility and excellent heat resistance. It is preferable, and more preferably 6000 or more and 300,000 or less.

The acid value of the polymer having the structural unit represented by the general formula (I) is preferably 20 mgKOH / g or more, preferably 30 mgKOH / g or more, from the viewpoint of the dispersibility and storage stability of the coloring material. It is more preferably present, and more preferably 40 mgKOH / g or more. On the other hand, from the viewpoint of excellent developability, the acid value of the polymer having the structural unit represented by the general formula (I) is preferably 150 mgKOH / g or less, and more preferably 120 mgKOH / g or less. , 100 mgKOH / g or less is more preferable.
In the present invention, the acid value refers to the number of mg of potassium hydroxide required to neutralize the acid component contained in 1 g of the sample, and can be measured according to JIS K 0070: 1992.

<Other acid dispersants>
The color material dispersion liquid of the present invention may further contain other acidic dispersants different from the polymer having the structural unit represented by the general formula (I).
Examples of other acidic dispersants include dispersants having an acidic group. Here, examples of the acidic group include a carboxy group, a sulfo group, a phosphoric acid group, and the like, and the acidic group contained in the dispersant of other acidic dispersants is dispersed, among which, the carboxy group. It is preferable because it has excellent properties.

The acid value of the other acidic dispersants is preferably in the range of 30 mgKOH / g or more and 250 mgKOH / g or less, and more preferably 40 mgKOH / g or more, and 50 mgKOH / g or more, from the viewpoint of excellent dispersibility. Is more preferable, and 70 mgKOH / g or more is further preferable. On the other hand, from the viewpoint of suppressing the development residue, the acid value of the other acidic dispersants is preferably 200 mgKOH / g or less, more preferably 190 mgKOH / g or less, and even more preferably 180 mgKOH / g or less. ..

In the present invention, the other acidic dispersant has a carboxy group from the viewpoint of improving the suppressibility of the development residue when used in combination with the polymer having the structural unit represented by the general formula (I). It is preferably a polymer dispersant, and above all, when it is used in combination with a polymer having a structural unit represented by the general formula (I), the suppressibility of development residue is improved and the coating film is uniform. From the viewpoint of better properties, a block copolymer containing an A block containing a structural unit derived from a carboxy group-containing ethylenically unsaturated monomer and a B block containing a structural unit derived from a (meth) acrylic acid alkyl ester. It is preferable to include.
Hereinafter, a block copolymer containing an A block containing a structural unit derived from a carboxy group-containing ethylenically unsaturated monomer and a B block containing a structural unit derived from a (meth) acrylic acid alkyl ester is simply referred to as "carboxy group-containing." Sometimes referred to as "block copolymer". The carboxy group-containing block copolymer is suitably used, for example, as a dispersant for metal lake coloring materials and pigments of xanthene dyes.

(Ccarboxy group-containing block copolymer)
{A block}
In the carboxy group-containing block copolymer, the A block is a polymer block containing a structural unit derived from a carboxy group-containing ethylenically unsaturated monomer.
Examples of the carboxy group-containing ethylenically unsaturated monomer used in the A block include the same as the ethylenically unsaturated monomer having a carboxy group used in the hydroxyalkyl (meth) acrylate unit-containing copolymer. ..
When two or more kinds of structural units are contained in the A block, each structural unit in the A block may be contained in any mode such as random copolymerization and block copolymerization, and is randomly co-polymerized from the viewpoint of uniformity. It is preferably contained in the form of polymerization.
In the A block, the structural unit derived from the carboxy group-containing ethylenically unsaturated monomer is preferably 40% by mass or more, more preferably 70% by mass or more, and more preferably the carboxy group, based on all the structural units of the A block. It is even more preferable that the polymer block is composed of only the structural units derived from the ethylenically unsaturated monomer contained.

The A block may be composed of only a structural unit derived from a carboxy group-containing ethylenically unsaturated monomer, or may be a carboxy group-containing ethylenically unsaturated monomer in a range in which the acidity of the A block is stronger than that of the B block. May contain building blocks derived from different ethylenically unsaturated monomers. When the A block contains a structural unit derived from an ethylenically unsaturated monomer different from the carboxy group-containing ethylenically unsaturated monomer, it is preferably 60% by mass or less with respect to all the structural units of the A block. It is more preferable to make it by mass% or less. Examples of the ethylenically unsaturated monomer different from the carboxy group-containing ethylenically unsaturated monomer include structural units used in the B block described later.

From the viewpoint of dispersibility and dispersion stability, the content of A block is preferably 5% by mass or more, more preferably 10% by mass or more, and more preferably 10% by mass or more, based on all the constituent units of the block copolymer. It is preferably 95% by mass or less, and more preferably 40% by mass or less.

{B block}
In the carboxy group-containing block copolymer, the B block is a polymer block containing a structural unit derived from a (meth) acrylic acid alkyl ester.
The (meth) acrylic acid alkyl ester monomer used in the B block may be the same as the (meth) acrylic acid alkyl ester monomer used in the polymer chain having the structural unit represented by the general formula (IV). It is used by one kind or a mixture of two or more kinds.
The B block may contain a structural unit derived from another ethylenically unsaturated monomer in addition to the structural unit derived from the (meth) acrylic acid alkyl ester. Examples of the structural unit derived from the other ethylenically unsaturated monomer include a structural unit represented by the general formula (III), which is different from the structural unit derived from the (meth) acrylic acid alkyl ester.

When two or more kinds of structural units are included in the B block, each structural unit in the B block may be contained in any mode such as random copolymerization, block copolymerization, etc., and is a random copolymer from the viewpoint of uniformity. It is preferably contained in the form of polymerization.

In the B block, the structural unit derived from the ethylenically unsaturated monomer having an acidic group is preferably 10% by mass or less, more preferably 5% by mass or less, based on the total structural unit of the B block. It is more preferably mass% or less. In the present invention, the B block is more preferably a polymer block containing no structural unit derived from an ethylenically unsaturated monomer having an acidic group.

The carboxy 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 content ratio of the two B blocks to each other is preferably adjusted in the range of 50:50 to 70:30 in terms of mass ratio from the viewpoint of dispersibility. ..

The acid value of the carboxy group-containing block copolymer is preferably in the range of 30 mgKOH / g or more and 250 mgKOH / g or less from the viewpoint of dispersibility, so that the acid value of the block copolymer is in this range. , A block preferably contains a structural unit derived from a carboxy group-containing ethylenically unsaturated monomer. The acid value is preferably 50 mgKOH / g or more, and more preferably 70 mgKOH / g or more. The acid value is preferably 200 mgKOH / g or less, and more preferably 150 mgKOH / g or less.

The weight average molecular weight of the carboxy 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 carboxy group-containing block copolymer is more preferably 8,000 or more, further preferably 10,000 or more, and more preferably 80,000 or less, 70. It is more preferably 000 or less.

The molecular weight distribution of the carboxy group-containing block copolymer is preferably less than 2, more preferably less than 1.5, and even more preferably less than 1.3. In the present invention, the molecular weight distribution is determined by "weight average molecular weight (Mw)) / (number average molecular weight (Mn)". The larger the molecular weight distribution, the larger the molecular weight as compared with the molecular weight of the designed polymer. It is preferable that the molecular weight distribution is small because those having a small molecular weight and those having a large molecular weight are included and tend to deteriorate the dispersibility of the coloring material.

As the method for producing the carboxy group-containing block copolymer, a conventionally known method for producing a block copolymer can be appropriately selected and used. Since it is easy to produce a polymer having a uniform composition, it is preferable to use a living polymerization method, and as the living polymerization method, a method using an organic acid catalyst and a silyl-based initiator (GTP method) and a method using a transition metal catalyst ( ATRP method), a method using a sulfur-based reversible chain transfer agent (RAFT method), a method using an organic tellurium compound (TERP method), and the like can be mentioned.

The content of the dispersant in the color material dispersion may be appropriately adjusted, but from the viewpoint of dispersibility and storage stability, the content may be 5 parts by mass or more and 80 parts by mass or less with respect to 100 parts by mass of the color material. It is more preferably 20 parts by mass or more and 70 parts by mass or less.

[Other ingredients]
The colorant dispersion may further contain a dispersion auxiliary resin and other components, if necessary, as long as the effects of the present invention are not impaired.
Examples of the dispersion auxiliary resin include an alkali-soluble resin. Since the steric hindrance of the alkali-soluble resin makes it difficult for the coloring material particles to come into contact with each other, the dispersion of the coloring material may be stabilized, or the amount of the dispersant may be reduced due to the dispersion stabilizing effect.
In addition, examples of other components include a surfactant for improving wettability, a silane coupling agent for improving adhesion, a defoaming agent, an anti-repellent agent, an anti-aggregation agent, an ultraviolet absorber, and the like. ..

[solvent]
As the solvent contained in the color material dispersion liquid, the same solvent as that contained in the above-mentioned photosensitive coloring resin composition of the present invention can be used.
The amount of the solvent is usually preferably in the range of 55% by mass or more and 95% by mass or less, and particularly preferably in the range of 65% by mass or more and 90% by mass or less with respect to the total amount of the colorant dispersion liquid. , 70% by mass or more and 88% by mass or less is more preferable. If the amount of solvent is too small, the viscosity increases and the dispersibility tends to decrease. Further, if the amount of the solvent is too large, the concentration of the coloring material decreases, and it may be difficult to achieve the target chromaticity coordinates.

[Manufacturing method of color material dispersion]
The method for producing the color material dispersion liquid is not particularly limited as long as it is a method for obtaining a color material dispersion liquid in which the color material is dispersed in a solvent by a dispersant. For example, a manufacturing method having a step of preparing a coloring material, a step of preparing a dispersant, and a step of dispersing the coloring material in a solvent in the presence of the dispersant can be applied. Two or more kinds of coloring materials may be co-dispersed in a solvent in the presence of a dispersant, or one or more kinds of coloring materials may be dispersed or co-dispersed, and then two or more kinds of coloring material dispersions are mixed. May be.
The colorant can be dispersed using a conventionally known disperser. Specific examples of the disperser include a roll mill such as a two-roll and three-roll mill, a ball mill such as a ball mill and a vibrating ball mill, a paint conditioner, a continuous disc type bead mill, and a bead mill such as a continuous annular type bead mill. As a preferable dispersion condition of the bead mill, the bead diameter used is preferably 0.03 mm or more and 3.0 mm or less, and more preferably 0.05 mm or more and 2.0 mm or less.

III. Cured product of photosensitive colored resin composition Since the photosensitive colored resin composition of the present invention contains a monomer which is a photopolymerizable compound as a photocurable component, the photosensitive colored resin composition of the present invention is subjected to a photopolymerization reaction. By doing so, the cured product of the present invention can be obtained. For example, the 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 the coating film, and developing the coating film as necessary. As a method for forming, exposing, and developing a coating film, for example, the same method as that used for forming a colored layer included in the color filter according to the present invention described later can be used.
In a preferred embodiment, the photosensitive colored resin composition of the present invention also has a polymerizable functional group in a binder resin such as a hydroxyalkyl (meth) acrylate unit-containing copolymer. The cured product of the photosensitive colored resin composition of the present invention in such a preferred embodiment is a dye in a matrix produced by a photopolymerization reaction of a binder resin containing a hydroxyalkyl (meth) acrylate unit-containing copolymer and a monomer. And a cured product in which a coloring material containing at least one selected from the group consisting of a rake coloring material is dissolved or dispersed.
In the cured product according to the present invention, a coloring material containing at least one selected from the group consisting of dyes and rake coloring materials is dissolved or dissolved in a matrix containing a binder resin containing a hydroxyalkyl (meth) acrylate unit-containing copolymer. Since it is dispersed, it has high brightness, excellent flatness, and suppresses the generation of development residue when developed, and is suitably used as a colored layer of a color filter.

IV. Color filter The color filter according to the present invention includes at least a transparent substrate and a colored layer provided on the transparent substrate, and at least one of the colored layers is a cured product of the photosensitive colored resin composition according to the present invention. A color filter.
In the color filter according to the present invention, at least one of the colored layers is selected from the group consisting of a dye and a lake colorant in a matrix containing a binder resin containing a hydroxyalkyl (meth) acrylate unit-containing copolymer. Since it is formed of a cured product in which a coloring material containing seeds is dissolved or dispersed, it has a colored layer having high brightness, excellent flatness, and suppressed generation of development residue.

FIG. 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 FIG. 1 has a transparent substrate 1, a light-shielding portion 2, and a red colored layer 3R, a green colored layer 3G, and a blue colored layer 3B as the colored layer 3.
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 three or more colored patterns. In the example of FIG. 3, the red colored layer 3R, the green colored layer 3G, and the blue colored layer 3B are formed and arranged in a predetermined order. The colored layer of each color is formed in the order of the red colored layer 3R, the green colored layer 3G, and the blue colored layer 3B.
The arrangement method of the colored layer is not particularly limited, and may be, for example, a general arrangement such as a stripe type, a mosaic type, a triangle type, and a 4-pixel arrangement type. Further, the width, area and the like of the colored layer can be arbitrarily set.
The thickness of the colored layer is appropriately controlled by adjusting the coating method, the solid content concentration, the viscosity, and the like of the colored resin composition, but it is usually preferably in the range of 1 μm or more and 5 μm or less.

Colored layers of individual colors can be formed by the following procedure. First, the photosensitive colored resin composition is applied onto a transparent substrate on which a light-shielding portion is previously formed by using a coating means such as a spray coating method, a dip coating method, a bar coating method, a roll coating method, and a spin coating method. Apply to form a wet coating.
Next, the wet coating film is dried using a hot plate, an oven, or the like, and then exposed to the wet coating film through a mask having a predetermined pattern, and the binder resin, the monomer, or the like is subjected to a photopolymerization reaction to make the wet coating film photosensitive. Use as a coating. Examples of the light source used for exposure include ultraviolet rays such as low-pressure mercury lamps, high-pressure mercury lamps, and metal halide lamps, electron beams, and the like. The exposure amount is appropriately adjusted depending on the light source used, the thickness of the coating film, and the like.
In addition, heat treatment may be performed in order to accelerate the polymerization reaction after exposure. The heating conditions are appropriately selected depending on the mixing ratio of each component in the colored resin composition to be used, the thickness of the coating film, and the like.

Next, a coating film is formed in a desired pattern by developing with a developing solution to dissolve and remove the unexposed portion. As the developing solution, a solution obtained by dissolving an alkali in water or a water-soluble solvent is usually used. An appropriate amount of a surfactant or the like may be added to this alkaline solution. Further, a general method can be adopted as the developing method.
After the development treatment, the developer is usually washed and the cured coating film of the colored resin composition is dried to form a colored layer. After the development treatment, a heat treatment may be performed in order to sufficiently cure the coating film. The heating conditions are not particularly limited and may be appropriately selected depending on the intended use of the coating film.

[Shading 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 the light-shielding portion in a general color filter.
The pattern shape of the light-shielding portion is not particularly limited, and examples thereof include a stripe shape and a matrix shape. The light-shielding portion may be a metal thin film such as chromium obtained by a sputtering method, a vacuum vapor deposition method, or the like. Alternatively, the light-shielding portion may be a resin layer in which light-shielding particles such as carbon fine particles, metal oxides, inorganic pigments, and organic pigments are contained in the resin binder. In the case of a resin layer containing light-shielding particles, a method of patterning by development using a photosensitive resist, a method of patterning using an inkjet ink containing light-shielding particles, a method of thermally transferring a photosensitive resist, etc. be.
The film thickness of the light-shielding portion is set to about 0.2 μm or more and 0.4 μm or less in the case of a metal thin film, and about 0.5 μm or more and 2 μm or less in the case of a black pigment dispersed or dissolved in a binder resin. Set in.

[Transparent board]
The transparent substrate may be a substrate that is transparent to visible light, and is not particularly limited, and a transparent substrate used for a general color filter can be used. Specifically, it has flexibility and flexibility such as inflexible transparent rigid material such as quartz glass, non-alkali glass, and synthetic quartz plate, or transparent resin film, optical resin plate, flexible glass, and the like. A transparent flexible material can be mentioned. The transparent substrate used for such a color filter usually has a polar group on the surface.
From the viewpoint of improving the substrate adhesion of the photosensitive colored resin composition of the present invention, the transparent substrate is preferably a substrate containing silicon dioxide such as quartz glass, non-alkali glass, and synthetic quartz plate.
The thickness of the transparent substrate is not particularly limited, but for example, one having a thickness of 50 μm or more and 1 mm or less can be used depending on the use of the color filter.
In addition to the transparent substrate, light-shielding portion, and colored layer, the color filter of the present invention forms, for example, an overcoat layer, a transparent electrode layer, an alignment film for orienting a liquid crystal material, a columnar spacer, and the like. It may be the one that has been done. The color filter of the present invention is not limited to the above-exemplified configuration, and a known configuration generally used for a color filter can be appropriately selected and used.

V. Display device The display device according to the present invention is characterized by having the color filter according to the present invention. In the present invention, the configuration of the display device is not particularly limited and can be appropriately selected from conventionally known display devices, and examples thereof include a liquid crystal display device and an organic light emitting display device.

[Liquid crystal display device]
The liquid crystal display device of the present invention is characterized by having the above-mentioned color filter according to the present invention, a facing substrate, and a liquid crystal layer formed between the color filter and the facing substrate.
FIG. 2 is a schematic view showing an example of a liquid crystal display device belonging to the display device of the present invention. As illustrated in FIG. 2, the liquid crystal display device 40 of the present invention has a liquid crystal layer formed between a color filter 10, a facing substrate 20 having a TFT array substrate and the like, and the color filter 10 and the facing substrate 20. It has 30 and.
The liquid crystal display device of the present invention is not limited to the configuration shown in FIG. 2, and can be generally known as a liquid crystal display device using a color filter.

The drive method of the liquid crystal display device of the present invention is not particularly limited, and a drive method generally used for the liquid crystal display device can be adopted. Examples of such a drive system include a TN system, an IPS system, an OCB system, an MVA system, and the like. In the present invention, any of these methods can be suitably used.
Further, as the facing substrate, it can be appropriately selected and used according to the drive method and the like of the liquid crystal display device of the present invention.
As a method for forming the liquid crystal layer, a method generally used as a method for producing a liquid crystal cell can be used, and examples thereof include a vacuum injection method and a liquid crystal dropping method.

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

As a method of laminating the organic light emitting body 80, for example, 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 are sequentially formed on the upper surface of a color filter. Examples thereof include a method and a method in which an organic light emitter 80 formed on another substrate is bonded onto an inorganic oxide film 60. As the transparent anode 71, the hole injection layer 72, the hole transport layer 73, the light emitting layer 74, the electron injection layer 75, the cathode 76, and other configurations of the organic light emitter 80, known ones can be appropriately used. The organic light emitting display device 100 produced in this way can be applied to, for example, both a passive drive type organic EL display and an active drive type organic EL display.
The organic light emitting display device of the present invention is not limited to the configuration shown in FIG. 3, and can be generally known as an organic light emitting display device using a color filter.

Hereinafter, the present invention will be specifically described with reference to examples. These descriptions do not 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 above-mentioned measuring method of the present invention.
The acid value and the hydroxyl value were determined by a method according to JIS K 0070: 1992.
The viscosity of the binder resin produced in each production example is such that the obtained binder resin solution (solid content 40% by mass) is dried under reduced pressure under the conditions of a pressure of 20 to 30 hPa and a temperature of 80 ° C., and the solid content concentration is 60% by mass. After concentrating until it became, the mixture was circulated and heated in a hot water bath at 90 ° C., and determined using a B-type viscometer.

(Synthesis example 1: Synthesis of rake coloring material 1)
(1) Synthesis of Intermediate 1 Refer to the methods for producing Intermediate A-2, Intermediate B-1 and Compound 1-3 described in JP-A-2018-3013, which are represented by the following chemical formula (a). Intermediate 1 was obtained (yield 87%).
It was confirmed from the following analysis results that the obtained compound was the target compound.
-MS (ESI) (m / z): 677 (+), divalent / elemental analysis value: CHN measured value (81.81%, 7.31%, 5.85%); theoretical value (81.77%) , 7.36%, 5.90%)

(2) Synthesis of rake colorant 1 2.59 g (0.76 mmol) of 12 tongue steric acid / n hydrate manufactured by Kanto Chemical Co., Inc. was dissolved by heating in a mixed solution of 40 mL of methanol and 40 mL of water, and the intermediate 1 1.6 g. (1.19 mmol) was added, and the mixture was stirred for 1 hour. The precipitate was collected by filtration and washed with water. The obtained precipitate was dried under reduced pressure to obtain a rake coloring material 1 represented by the following chemical formula (b) (yield 95%).
It was confirmed from the following analysis results that the obtained compound was the target compound.
31P NMR (d-dmso, ppm) δ-15.15
-MS (MALDI) (m / z): 1355 (M ⁺ ), 2879 ( _MH2- ⁾
-Elemental analysis value: CHN measured value (35.55%, 3.24%, 2.61%); theoretical value (35.61%, 3.20%, 2.57%)
-Fluorescent X-ray analysis: MoW actual measurement ratio (0%, 100%); theoretical value (0%, 100%)

(Synthesis Example 2: Synthesis of Xanthene Dye 1)
In a 500 ml four-necked flask, 40.2 parts by mass of the 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 N-methyl-o-toluidine. 6.0 parts by mass was charged and refluxed for 30 hours. After filtering this reaction solution at 60 ° C. to remove insoluble matter, the solvent was removed under reduced pressure until the reaction solution became about 70 ml, and the mixture was poured into 200 parts by mass of 6% hydrochloric acid. Then, 600 parts by mass of water was added, and the mixture was stirred at room temperature for 30 minutes, and then the wet cake was collected by filtration. This wet cake is suspended in 100 parts by mass of water, stirred at 60 ° C. for 2 hours, collected again, washed with hot water at 60 ° C., and dried to obtain a xanthene dye represented by the following chemical formula. 1 was obtained in an amount of 27.4 parts by mass.

(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. The parts were charged and refluxed for 30 hours. After filtering this reaction solution at 60 ° C. to remove insoluble matter, the solvent was removed under reduced pressure until the reaction solution became about 70 ml, and the mixture was poured into 200 parts by mass of 6% hydrochloric acid. Then, 600 parts by mass of water was added, and the mixture was stirred at room temperature for 30 minutes, and then the wet cake was collected by filtration. This wet cake is suspended in 100 parts by mass of water, stirred at 60 ° C. for 2 hours, collected again, washed with hot water at 60 ° C., and dried to obtain an intermediate I represented by the following chemical formula. -1 was obtained in an amount of 21.9 parts by mass.

Next, a mixture of 20 parts by mass of the 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 added at 80 ° C. for 2 hours. , Stirred. After completion of the reaction, 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 to 10 ° C. and stirred for 1 hour. Then, the precipitate was collected by filtration 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 obtained reaction solution was allowed to cool to room temperature, the reaction solution was added dropwise to 1500 parts by mass of ice water, and the mixture was stirred for 30 minutes. The obtained crystals were separated by filtration, washed with 200 parts by mass of water, and dried for 10 hours. 7 parts by mass of the crystal and 1.8 parts by mass of trifluoromethylsulfonamide were dissolved in 40 parts by mass of chloroform, 1.55 parts by mass of triethylamine was added dropwise, and the mixture was stirred at room temperature for 1 hour. Then, 100 parts by mass of water was added to the obtained reaction solution and washed with water, and then the organic layer was separated. The organic layer was dried over sodium sulfate, purified, and concentrated under reduced pressure to obtain 6.8 parts by mass of the xanthene dye 2 represented by the following chemical formula (yield 80%).

(Synthesis Example 4: Synthesis of Xanthene Metal Lake Coloring Material 3)
Acid Red 289 5.0 parts by mass was added to 500 ml of water and dissolved at 80 ° C. to prepare a dye solution. Polyaluminum chloride (“Takibine # 1500” manufactured by Taki Chemical Co., Ltd., Al ₂ (OH) ₅ Cl, basicity 83.5% by mass, alumina content 23.5% by mass) 3.85 parts by mass of water The mixture was placed in 200 ml and stirred at 80 ° C. to prepare a polyaluminum chloride aqueous solution. The prepared aqueous solution of polyaluminum chloride was added dropwise to the dye solution at 80 ° C. over 15 minutes, and the mixture was further stirred at 80 ° C. for 1 hour. The resulting precipitate was collected by filtration and washed with water. The obtained cake was dried to obtain 6.30 parts by mass (yield 96.2%) of a xanthene-based metal lake coloring material 3 which is a metal lake coloring material of a xanthene dye.

(Synthesis Example 5: Synthesis of basic treatment PB15: 6)
In the reaction vessel, 300 parts by mass of chlorosulfonic acid and 30 parts by mass of copper phthalocyanine were added, and after complete dissolution, 24 parts by mass of thionyl chloride was added, the temperature was gradually raised, and the reaction was carried out 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 obtained press cake was made into a slurry with 300 parts by mass of water, 13 parts by mass of 1,1-diethyl-1,5-diazapentane was added, and the mixture was stirred at 65 ° C. for 4 hours, filtered, washed with water, dried and surfaced. A blue color material derivative 1 having a basic moiety used for the treatment was obtained. It was confirmed that the obtained blue color material derivative 1 having a basic moiety had the structure of the following chemical formula (d).
-TOF-MS: 768.35

Commercially available C.I. I. Pigment Blue 15: 6 (ε-type copper phthalocyanine pigment, DIC FASTOGEN BLUE A510) 100 parts by mass and 5 parts by mass of the blue color material derivative 1 having the basic moiety are 1.5 by mass at 60 ° C. with an attritor. Time-dried crushed. C.I. I. Pigment Blue 15: 6, basic treatment PB 15: 6 was obtained.

(Synthesis Example 6: Synthesis of Acid Dispersant A1 (Polymer having a Structural Unit Represented by the General Formula (I)))
(1) Synthesis of macromonomer MM-1 80.0 parts by mass of propylene glycol monomethyl ether acetate (abbreviated as PGMEA) was added to a reactor equipped with a cooling tube, an addition funnel, an inlet for nitrogen, a mechanical stirrer, and a digital thermometer. The mixture was charged and heated to a temperature of 90 ° C. while stirring under a nitrogen stream. Methyl methacrylate 50.0 parts by mass, methacrylic acid-n-butyl 30.0 parts by mass, benzyl methacrylate 20.0 parts by mass, 2-mercaptoethanol 4.0 parts by mass, PGMEA 30 parts by mass, α, α'-azo A mixed solution of 1.0 part by mass of bisisobutyronitrile (abbreviated as AIBN) was added dropwise over 1.5 hours, and the reaction was further carried out for 3 hours. Next, the nitrogen stream was stopped and the reaction solution was cooled to 80 ° C., and the reaction solution was cooled to 8.74 parts by mass of Karenz MOI (Showa Denko), 0.125 parts by mass of dibutyltin dilaurate, and 0.125 parts by mass of p-methoxyphenol. A 49.5% by mass solution of macromonomer MM-1 was obtained by adding 10 parts by mass and 10 parts by mass of PGMEA and stirring for 3 hours. As a result of GPC measurement, the obtained macromonomer MM-1 had a weight average molecular weight (Mw) 4010, a number average molecular weight (Mn) 1910, and a molecular weight distribution (Mw / Mn) 2.10.

(2) Synthesis of graft copolymer A1 A reactor equipped with a cooling tube, a funnel for addition, an inlet for nitrogen, a mechanical stirrer, and a digital thermometer was charged with 85.0 parts by mass of PGMEA, and the mixture was stirred under a nitrogen stream. It was heated to a temperature of 90 ° C. 67.34 parts by mass (solid content 33.33 parts by mass), 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. , A mixed solution of 0.5 part by mass of AIBN was added dropwise over 1.5 hours, heated and stirred for 3 hours, and then a mixed solution of 0.10 part by mass of AIBN and 10.0 parts by mass of PGMEA was added dropwise over 10 minutes. By aging at warm temperature for 1 hour, a 25.0% by mass solution of the graft copolymer A1 was obtained. As a result of GPC measurement, the obtained graft copolymer A1 had a weight average molecular weight (Mw) 10570, a number average molecular weight (Mn) 4370, and a molecular weight distribution (Mw / Mn) 2.42.

(3) Production of a polymer (acid dispersant A1) having a structural unit represented by the general formula (I) A reactor equipped with a cooling tube, a funnel for addition, an inlet for nitrogen, a mechanical stirrer, and a digital thermometer. 2.80 parts by mass of PGMEA and 9.27 parts by mass of phenylphosphonic acid (product name "PPA" manufactured by Nissan Chemical Industries, Ltd.) were charged and heated to a temperature of 90 ° C. while stirring under a nitrogen stream. A polymer having a structural unit represented by the general formula (I) (acidic dispersant A1) is obtained by dropping 100.0 parts by mass of the graft copolymer A1 over 30 minutes and heating and stirring for 2 hours. A solution (solid content 25.0% by mass) was obtained. The progress of the esterification reaction between GMA and PPA of the obtained acidic dispersant A1 was confirmed by acid value measurement and ¹ H-NMR measurement (it was confirmed that the epoxy-derived peak had disappeared). The acid value of the obtained acid dispersant A1 was 98 mgKOH / g.

(Synthesis Example 7: Block copolymer containing an acidic dispersant B1 (A block containing a structural unit derived from a carboxy group-containing ethylenically unsaturated monomer) and a B block containing a structural unit derived from a (meth) acrylic acid alkyl ester). Synthesis)
With reference to Example 1 described in WO 2016/132863, a block of 20 parts by mass of methyl methacrylate (MMA), 40 parts by mass of n-butyl methacrylate (BMA), and 20 parts by mass of methacrylic acid (MAA). , A triblock copolymer having 20 parts by mass of BMA and 20 parts by mass of MMA and 40 parts by mass of BMA was synthesized. 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.

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

(Synthesis Example 9: Synthesis of Rake Color Material 4)
(1) Preparation of K ₆ (P ₂ MoW ₁₇ O ₆₂ ) NaWO 4.2H ₂ O (manufactured by Wako Pure Chemical Industries, Ltd.) 44.0 g, Na ₂ MoO _4.2H ₂ O (manufactured by Kanto Chemical Co., Inc.) ₁ .90 g was dissolved in 230 g of purified water. 64.9 g of 85% phosphoric acid was added to this solution with stirring using a dropping funnel. The resulting solution was heated to 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 with stirring. After further stirring for 1 hour, the precipitate was filtered off. The obtained solid was dried at 90 ° C. to obtain 29.4 g of _K6 ₍ P2 MoW ₁₇ O ₆₂ ).
(2) Synthesis of rake coloring material 4 C. I. 5.30 g of Basic Blue 7 (BB7) (manufactured by Tokyo Kasei Co., Ltd.) was added to 350 ml of purified water, and the mixture was stirred and dissolved at 40 ° C. to prepare a BB7 solution. Separately, 10.0 g of K6 ₍ P2 MoW ₁₇ O ₆₂ ) prepared in ( ₁ ) above was dissolved in 40 ml of purified water. _The K6 (P2 MoW ₁₇ O ₆₂ ) solution was added to the _BB7 solution, and the mixture was stirred as it was at 40 ° C. for 1 hour. Then, the internal temperature was raised to 80 ° C., and the mixture was further stirred for 1 hour for rake formation. After cooling, it was filtered and washed 3 times with 300 ml of purified water. By drying the obtained solid at 90 ° C., 10.4 g of a lake color material 4 which is a black-blue solid and has an average primary particle size of 40 nm and is a lake color material of a triarylmethane dye and a polyacid anion is obtained. rice field.

(Manufacturing Example 1: Production of Binder Resin 1)
150 parts by mass of PGMEA was charged in the polymerization tank, the temperature was raised to 100 ° C. under a nitrogen atmosphere, and then 26.9 parts by mass of methacrylic acid (MAA), 38.9 parts by mass of benzyl methacrylate (BzMA), and 2-hydroxyethyl. 5 parts by mass of methacrylate (HEMA), 1.4 parts by mass of perbutyl O (manufactured by Nichiyu Co., Ltd.) as a photoinitiator, and 2.5 parts by mass of chain transfer agent (n-dodecyl mercaptan) continuously over 1.5 hours. Dropped. Then, the reaction was continued at 100 ° C., and 0.1 part by mass of p-methoxyphenol was added as a polymerization inhibitor 2 hours after the completion of dropping of the main chain forming mixture to terminate the polymerization.
Next, while blowing air, 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 at 110 ° C. The addition reaction was carried out for 15 hours to obtain one solution of the binder resin (weight average molecular weight (Mw) 14,900, acid value 67 mgKOH / g, hydroxyl value 129 mgKOH / g, solid content 40% by mass).

(Production Examples 2 to 9, Comparative Production Examples 1 to 9: Binder Resins 2 to 9, Production of Comparative Binder Resins C1 to C9)
In Production Example 1, the binder resin 2-9 solutions of Production Examples 2 to 9 and comparative production were carried out in the same manner as in Production Example 1 except that the addition amounts of the monomer, the photoinitiator and the chain transfer agent were changed according to Table 1. Comparative binder resin C1 to C9 solutions of Examples 1 to 9 (each binder resin solution had a solid content of 40% by mass) were obtained.

(Comparative Production Example 10: Production of Comparative Binder Resin C10)
After charging 150 parts by mass of PGMEA in the polymerization tank and raising the temperature to 110 ° C. under a nitrogen atmosphere, 81.5 parts by mass of t-butylcyclohexylmethacrylate (t-BuCHMA), 15.0 parts by mass of methacrylic acid (MAA), 2- 3.5 parts by mass of hydroxyethyl methacrylate (HEMA) and 3.0 parts by mass of AIBN as a photoinitiator were continuously added dropwise over 1.5 hours. Then, the mixture was kept at 110 ° C. and stirred for 2 hours to obtain a comparative binder resin C10 solution (solid content 40% by mass).

(Preparation Example 1: Preparation of rake coloring material 1 dispersion)
10 parts by mass of the rake coloring material 1 of Synthesis Example 1, 20 parts by mass of the acidic dispersant A1 solution of Synthesis Example 6 (effective solid content 5.0 parts by mass), and 7.5 parts by mass of the alkali-soluble resin A solution of Synthesis Example 8. A portion (3.0 parts by mass of effective solid content) and 62.5 parts by mass of PGMEA are mixed, and 2 mm zirconia beads are used as a pre-dispersion in a paint shaker (manufactured by Asada Iron Works) for 1 hour, and 0.1 mm zirconia as a main dispersion. The mixture was dispersed with beads for 4 hours to obtain a rake coloring material 1 dispersion.

(Preparation Example 2: Preparation of xanthene-based metal rake coloring material 3 dispersion)
10 parts by mass of the xanthene-based metal lake coloring material 3 of Synthesis Example 4, 16.7 parts by mass of the acidic dispersant B1 solution of Synthesis Example 7 (effective solid content 5.0 parts by mass), and the alkali-soluble resin A of Synthesis Example 8. 7.5 parts by mass of the solution (3.0 parts by mass of effective solid content) and 65.8 parts by mass of PGMEA are mixed, and a paint shaker (manufactured by Asada Iron Works) is used as a pre-dispersion with 2 mm zirconia beads for 1 hour. The mixture was dispersed with 0.1 mm zirconia beads for 4 hours to obtain a xanthene-based metal lake coloring material 3 dispersion.

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

(Preparation Example 4: Preparation of xanthene dye 2 solution)
5.0 parts by mass of the xanthene dye 2 of Synthesis Example 3 was dissolved in 45 parts by mass of diacetone alcohol to obtain a xanthene dye 2 solution.

(Preparation Example 5: Preparation of PB15: 6 dispersion)
Basic treatment PB15: 6 10 parts by mass of Synthesis Example 5, 16.7 parts by mass (effective solid content 5.0 parts by mass) of acid dispersant B1 solution of Synthesis Example 7, and alkali-soluble resin A solution of Synthesis Example 8. Mix 7.5 parts by mass (effective solid content 3.0 parts by mass) and 65.8 parts by mass of PGMEA, and use a paint shaker (manufactured by Asada Iron Works) as a pre-dispersion for 1 hour with 2 mm zirconia beads, and then as a main dispersion. The mixture was dispersed with 0.1 mm zirconia beads for 6 hours to obtain a PB15: 6 dispersion.

(Preparation Example 6: Preparation of PV23 dispersion)
Commercially available C.I. in a 30 ml mayonnaise bottle. I. 10 parts by weight of Pigment Violet 23 (PV23), 16.7 parts by mass of the acidic dispersant B1 solution of Synthesis Example 7 (5.0 parts by mass of effective solid content), 7.5 parts by mass of the alkali-soluble resin A solution of Synthesis Example 8 ( Effective solid content (3.0 parts by mass), PGMEA 65.8 parts by weight, and 30 parts by weight of zirconia beads having a diameter of 2 mm were added, and the mixture was pre-crushed with a paint shaker (manufactured by Asada Steel) for 1 hour, and then the mixed solution was separated. The mixture was transferred to a 30 ml mayonnaise bottle, 30 parts by weight of zirconia beads having a diameter of 0.1 mm was added, and the mixture was shaken with a paint shaker for 5 hours to obtain a PV23 dispersion.

(Preparation Example 7: Preparation of Rake Color Material 4 Dispersion Liquid)
In Preparation Example 1, the rake color is the same as in Preparation Example 1 except that 10 parts by mass of the rake color material 4 of Synthesis Example 6 is used instead of 10 parts by mass of the rake color material 1 of Synthesis Example 1. A dispersion liquid of the material 4 was prepared.

(Preparation Example I: Preparation of Photosensitive Binder Component 1)
Dipentaerythritol hexaacrylate (DPHA) (Aronix M402 (manufactured by Toa Synthetic)) 24.7 mass as a photopolymerizable compound with respect to 26.5 parts by mass of the binder resin 1 solution (solid content 40% by mass) of Production Example 1. Irgacure 907 (BASF, α-aminoketone-based photoinitiator) 3.53 parts by mass, KayaCure DETX-S (Nippon Kayaku, thioxanthone-based photoinitiator, 2,4-diethylthioxanthone) 0 A photosensitive binder component 1 was obtained by adding .39 parts by mass, 0.78 parts by mass of IRGANOX1010 (manufactured by BASF) and 44.1 parts by mass of PGMEA as an antioxidant.

(Preparation Examples II to IX, Comparative Preparation Examples I to X: Preparation of Photosensitive Binder Components 2 to 9 and Comparative Photosensitive Binder Components 1 to 10)
In the preparation of the photosensitive binder component 1 of Preparation Example I, instead of the binder resin 1 solution of Production Example 1, in Preparation Examples II to IX, the binder resin 2 to 9 solutions of Production Examples 2 to 9 were used, and Comparative Preparation Examples I to In Preparation Examples II to IX, photosensitive binder components 2 to 9 were obtained in the same manner as in Preparation Example I except that the comparative binder resins C1 to C10 solutions of Comparative Production Examples C1 to C10 were used in X, and Comparative Preparation Examples were obtained. In I to X, comparative photosensitive binder components C1 to C10 were obtained.

(Example 1)
23.2 parts by mass of 1 dispersion of rake colorant of Preparation Example 1, 32.1 parts by mass of photosensitive binder component 1 of Preparation Example I, 0.03 parts by mass of surfactant Megafuck R08MH (manufactured by DIC), 44.7 parts by mass of PGMEA The parts by mass were mixed to obtain the photosensitive colored resin composition of Example 1.

(Examples 2 to 9, Comparative Examples 1 to 10)
In the preparation of the photosensitive colored resin composition of Example 1, instead of the photosensitive binder component 1, the photosensitive binder components 2 to 9 are used in Examples 2 to 9, and the comparative photosensitive binder component C1 is used in Comparative Examples 1 to 10. 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 except that C10 was used.

(Comparative Examples 11 to 12)
In the preparation of the photosensitive coloring resin composition of Example 1, the mass ratio of the basic treatment PB15: 6 to PV23 (basic treatment PB15: 6: PV23) was replaced with 23.2 parts by mass of the rake coloring material 1 dispersion. ) Is 86.4: 13.6 by mass of 25.5 parts by mass of PB15: 6 dispersion and 4.0 parts by mass of PV23 dispersion, and further to 32.1 parts by mass of the photosensitive binder component. Instead, in Comparative Example 11, 29.2 parts by mass of the photosensitive binder component was used, and in Comparative Example 12, 29.2 parts by mass of the comparative photosensitive binder component C5 was used, and the amount of PGMEA added was 44.7 parts by mass to 41. The photosensitive colored resin compositions of Comparative Examples 11 to 12 were obtained in the same manner as in Example 1 except that the composition was changed to 3 parts by mass.

(Example 10, Comparative Examples 13 to 15)
In the preparation of the photosensitive coloring resin composition of Example 1, the mass ratio of the rake coloring material 1 and the xanthene-based metal rake coloring material 3 (lake coloring material 1) was replaced with 23.2 parts by mass of the rake coloring material 1 dispersion. : 17.6 parts by mass of the lake color material 1 dispersion and 1.32 parts by mass of the xanthene metal lake color material 3 dispersion so that the xanthene-based metal lake color material 3) is 93.0: 7.0. Further, instead of the photosensitive binder component 1 32.1 parts by mass, the photosensitive binder component 2 34.0 parts by mass was used in Example 10, and the comparative photosensitive binder component C1 34.0 parts by mass was used in Comparative Example 13. In Comparative Example 14, 34.0 parts by mass of the comparative photosensitive binder component C4 was used, and in Comparative Example 15, 34.0 parts by mass of the comparative photosensitive binder component C6 was used, and the amount of PGMEA added was 47.1 to 47.1 parts by mass. The photosensitive colored resin compositions of Example 10 and Comparative Examples 13 to 15 were obtained in the same manner as in Example 1 except that the parts were changed to parts by mass.

(Example 11, Comparative Examples 16 to 18)
In the preparation of the photosensitive coloring resin composition of Example 1, the mass ratio of the lake coloring material 1 to the xanthene dye 1 (lake coloring material 1: xanthene based) instead of 23.2 parts by mass of the lake coloring material 1 dispersion. In order to make the dye 1) 94.2: 5.8, 17.3 parts by mass of the lake coloring material 1 dispersion and 1.06 parts by mass of the xanthene dye 1 solution were used, and further, the photosensitive binder component 1 32 .1 Instead of 1 part by mass, in Example 11, the photosensitive binder component 2 34.4 parts by mass, in Comparative Example 16, the comparative photosensitive binder component C1 34.4 parts by mass, and in Comparative Example 17, the comparative photosensitive binder component. Examples were used except that 34.4 parts by mass of C4 was used and 34.4 parts by mass of the comparative photosensitive binder component C6 was used in Comparative Example 18 and the amount of PGMEA added was changed from 44.7 parts by mass to 47.2 parts by mass. In the same manner as in No. 1, photosensitive colored resin compositions of Examples 11 and Comparative Examples 16 to 18 were obtained.

(Example 12, Comparative Examples 19 to 21)
In the preparation of the photosensitive coloring resin composition of Example 1, the mass ratio of the lake coloring material 1 and the xanthene dye 2 (lake coloring material 1: xanthene based) instead of 23.2 parts by mass of the lake coloring material 1 dispersion. To make the dye 2) 94.2: 5.8, use 17.3 parts by mass of the rake coloring material 1 dispersion and 1.06 parts by mass of the xanthene dye 2 solution, and further, the photosensitive binder component 1 32. .1 Instead of 1 part by mass, in Example 12, the photosensitive binder component 2 34.4 parts by mass, in Comparative Example 19, the comparative photosensitive binder component C1 34.4 parts by mass, and in Comparative Example 20, the comparative photosensitive binder component. Example 21 except that 34.4 parts by mass of C4 was used and 34.4 parts by mass of the comparative photosensitive binder component C6 was used in Comparative Example 21 and the amount of PGMEA added was changed from 44.7 parts by mass to 47.2 parts by mass. In the same manner as in No. 1, photosensitive colored resin compositions of Example 12 and Comparative Examples 19 to 21 were obtained.

(Comparative Examples 22 to 23)
In the preparation of the photosensitive coloring resin composition of Example 1, the mass ratio of the basic treatment PB15: 6 to PV23 (basic treatment PB15: 6: PV23) was replaced with 23.2 parts by mass of the rake coloring material 1 dispersion. ) Was 76.5: 23.5 by mass of 17.4 parts by mass of PB15: 6 dispersion and 5.35 parts by mass of PV23 dispersion, and further to 32.1 parts by mass of the photosensitive binder component. Instead, in Comparative Example 22, the photosensitive binder component 2 32.2 parts by mass was used, and in Comparative Example 23, the comparative photosensitive binder component C5 32.2 parts by mass was used, and the amount of PGMEA added was 44.7 parts by mass to 44. The photosensitive colored resin compositions of Comparative Examples 22 to 23 were obtained in the same manner as in Example 1 except that the content was changed to 9 parts by mass.

(Example 13, Comparative Examples 24-26)
In the preparation of the photosensitive coloring resin composition of Example 1, the mass ratio of the rake coloring material 1 to the basic treatment PB 15: 6 was replaced with 23.2 parts by mass of the rake coloring material 1 dispersion (lake coloring material 1: 18.3 parts by mass of rake coloring material 1 dispersion and 12.4 parts by mass of PB15: 6 dispersion were used so that the basic treatment PB15: 6) was 59.6: 40.4, and further photosensitive. Binder component 1 Instead of 32.1 parts by mass, in Example 13, the photosensitive binder component 2 28.7 parts by mass was compared, in Comparative Example 24, the comparative photosensitive binder component C1 28.7 parts by mass was compared, and in Comparative Example 25, the comparison was made. 28.7 parts by mass of the photosensitive binder component C4 was used, and 28.7 parts by mass of the comparative photosensitive binder component C6 was used in Comparative Example 26, except that the amount of PGMEA added was changed from 44.7 parts by mass to 40.6 parts by mass. Obtained the photosensitive colored resin compositions of Example 13 and Comparative Examples 24 to 26 in the same manner as in Example 1.

(Comparative Examples 27 to 28)
In the preparation of the photosensitive coloring resin composition of Example 1, the mass ratio of the basic treatment PB15: 6 to PV23 (basic treatment PB15: 6: PV23) was replaced with 23.2 parts by mass of the rake coloring material 1 dispersion. ) Was 92.5: 7.5 by mass of 34.8 parts by mass of PB15: 6 dispersion and 2.82 parts by mass of PV23 dispersion, and further to 32.1 parts by mass of the photosensitive binder component. Instead, in Comparative Example 27, 25.6 parts by mass of the photosensitive binder component was used, and in Comparative Example 28, 25.6 parts by mass of the comparative photosensitive binder component C5 was used, and the amount of PGMEA added was 44.7 parts by mass to 36. The photosensitive colored resin compositions of Comparative Examples 27 to 28 were obtained in the same manner as in Example 1 except that the composition was changed to 8 parts by mass.

(Examples 1-2 to 9-2, Comparative Examples 1-2 to 10-2)
In the preparation of the photosensitive colored resin compositions of Examples 1 to 9 and Comparative Examples 1 to 10, the rake colorant 4 dispersion of Preparation Example 7 was used instead of the rake colorant 1 dispersion of Preparation Example 1. Obtained photosensitive colored resin compositions of Examples 1-2 to 9-2 and Comparative Examples 1-2 to 10-2 in the same manner as in Examples 1 to 9 and Comparative Examples 1 to 10.

[Evaluation methods]
<Colored layer shape>
The photosensitive colored resin composition of Example 1 was placed on a glass substrate (manufactured by NH Techno Glass Co., Ltd., “NA35”) having a thickness of 0.7 mm so that the film thickness after post-baking was 2.5 μm. After applying using a spin coater, the mixture was heated and dried at 80 ° C. for 3 minutes using a hot plate. Then, through a photomask forming a line & space of 60 μm, ultraviolet rays of 60 mJ / cm ² are irradiated using an ultrahigh pressure mercury lamp, and then 60 by 0.05 mass% potassium hydroxide aqueous solution is used as an alkaline developer. Shower developed for seconds. Then, by post-baking in a clean oven at 230 ° C. for 30 minutes, a pattern-forming substrate in which a colored layer was formed with a pattern of 60 μm line and space was produced on the glass substrate.
The photosensitive colored resin compositions of each Example and each Comparative Example were applied onto the pattern-forming substrate thus produced using a spin coater so that the film thickness after post-baking was 2.5 μm, and then a hot plate was applied. Was heated and dried at 90 ° C. for 3 minutes. Then, after irradiating 60 mJ / cm ² of ultraviolet rays with an ultra-high pressure mercury lamp without using a photomask, post-baking in a clean oven at 230 ° C. for 30 minutes allows each example or each to be between 60 μm patterns. A colored layer, which is a cured film of the photosensitive colored resin composition of the comparative example, was formed. After forming the colored layer, the pattern profile was measured with a film thickness meter of a stylus type profiler "P-17" manufactured by KLA-Tencor. Using the center of the base pattern as a reference, the film thickness difference between the portion 15 μm away from the center and the central portion was determined and evaluated according to the following evaluation criteria.
(Colored layer shape evaluation criteria)
A: Film thickness difference is less than 0.05 μm B: Film thickness difference is 0.05 μm or more and less than 0.1 μm C: Film thickness difference is 0.1 μm or more

<Evaluation of development residue>
The photosensitive colored resin compositions of Examples and Comparative Examples were each applied on a glass substrate (manufactured by NH Techno Glass Co., Ltd., “NA35”) having a thickness of 0.7 mm using a spin coater, and then a hot plate was applied. By drying at 60 ° C. for 3 minutes using the above, a colored layer having a thickness of 2.5 μm was formed. The glass plate on which the colored layer was formed was subjected to shower development for 60 seconds using a 0.05 mass% potassium hydroxide aqueous solution as an alkaline developer. After visually observing the formed portion of the colored layer after development, wipe it off sufficiently with a lens cleaner (manufactured by Toray Industries, Inc., trade name: Toraysee MK Clean Cloth) soaked in ethanol, and visually observe the degree of coloring of the lens cleaner. Then, it was evaluated according to the following evaluation criteria.
(Development residue evaluation criteria)
A: No development residue was visually confirmed and the lens cleaner was not colored at all. B: No development residue was visually confirmed and the lens cleaner was slightly colored. C: Development residue was slightly confirmed by visual inspection. D: The development residue was visually confirmed and the coloring of the lens cleaner was confirmed.

<Brightness>
The photosensitive colored resin compositions of Examples and Comparative Examples were placed on a glass substrate (manufactured by NH Techno Glass Co., Ltd., “NA35”) having a thickness of 0.7 mm, respectively, and the chromaticity after post-baking was y = 0.099. It was applied using a spin coater so as to become. After that, it is heated and dried on a hot plate at 80 ° C. for 3 minutes, irradiated with ultraviolet rays of 60 mJ / cm ² using an ultra-high pressure mercury lamp without a photomask, and then post-baked in a clean oven at 230 ° C. for 30 minutes. As a result, a cured film (colored film) was obtained. The brightness (Y) of the obtained colored substrate was measured using a "microspectroscopy measuring device OSP-SP200" manufactured by Olympus Corporation, and evaluated according to the following evaluation criteria.
(Brightness evaluation)
A: Brightness (Y) is 13.0 or more B: Brightness (Y) is 12.0 or more and less than 13.0 C: Brightness (Y) is less than 12.0

<Heat resistance>
After obtaining a cured film (colored film) by the same method as the above-mentioned evaluation of luminance, the obtained colored film is further post-baked in a clean oven at 240 ° C. for 25 minutes, and the chromaticity (L ₀ ) of this colored film is obtained. , A ₀ , b ₀ ) were measured, and then post-baked in a clean oven at 240 ° C. for 50 minutes, and the chromaticity (L ₁ , ₁ , b ₁ ) of the obtained colored film was measured again.
The change in chromaticity of the colored film from 25 minutes to 75 minutes at 240 ° C. was evaluated by the following formula.
ΔEab = {(L ₁ − L ₀ ) ² + (a ₁ − a ₀ ) ² + (b ₁ − b ₀ ) ² } ^1/2
It is evaluated that the smaller the value of ΔEab, the better the heat resistance. If ΔEab is less than 3.0, it is judged that there is no practical problem.
(Heat resistance evaluation standard)
A: ΔEab is less than 2.0 B: ΔEab is 2.0 or more and less than 3.0 C: ΔEab is 3.0 or more

In Tables 2 to 5 below, the metal lake coloring material 3 means the xanthene-based metal lake coloring material 3 obtained in Synthesis Example 4, and PB15: 6 means the basic treatment obtained in Synthesis Example 5. It means PB15: 6, and PV23 is a commercially available C.I. I. Means Pigment Violet 23. Further, the dispersant A1 means the acidic dispersant A1 obtained in Synthesis Example 6, and the dispersant B1 means the acidic dispersant B1 obtained in Synthesis Example 7.

[Summary of results]
From the results of Tables 2 to 5, the structural units derived from the color material containing at least one selected from the group consisting of dyes and lake color materials and the hydroxyalkyl (meth) acrylate represented by the general formula (A) are 5 to 5. Binder resin containing a copolymer (hydroxyalkyl (meth) acrylate unit-containing copolymer) having a polymer structure containing 25% by mass, a weight average molecular weight of 11,000 or more, and an acid value of 60 to 130 mgKOH / g. The colored layers formed by using the photosensitive colored resin compositions of Examples 1 to 13 and Examples 1-2 to 9-2, which are contained in combination with the above, have high brightness, excellent flatness, and are developed. It was shown that the generation of the residue was suppressed.
Further, from the comparison between Examples 1 to 9 shown in Table 2 and Comparative Examples 1 to 10, and the comparison between Examples 1-2 to 9-2 and Comparative Examples 1-2 to 10-2 shown in Table 5, In the photosensitive coloring resin composition containing the rake color material 1 which is the rake color material represented by the general formula (1) or the rake color material 4 which is the rake color material represented by the general formula (2). It has been shown that the heat resistance is improved when a hydroxyalkyl (meth) acrylate unit-containing copolymer is used as the binder resin.

On the other hand, in Comparative Examples 1 to 4, 13 to 14, 16 to 17, 19 to 20, 24 to 25 and 1-2 to 4-2, the comparative binder resins C1 to C4 containing no hydroxyalkyl (meth) acrylate unit were used. Since either one was used, the effect of suppressing the development residue was inferior. Among them, Comparative Examples 4, 14, 17, 20, 25 using the comparative binder resin C4 which does not contain hydroxyalkyl (meth) acrylate units, has a weight average molecular weight of less than 11000, and has an acid value of more than 130 mgKOH / g. And 4-2 were particularly inferior in the effect of suppressing the development residue.
In Comparative Examples 1 to 4, 13 to 14, 16 to 17, 19 to 20, 24 to 25, and 1-2 to 4-2, the copolymer used as the binder resin contained a hydroxyalkyl (meth) acrylate unit. It is considered that the reason why the colored layer was excellent in flatness even though it was not contained was that the acid value of the copolymer was relatively high at 108 to 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 the hydroxyalkyl (meth) acrylate unit in the above-mentioned specific amount, so that the acid value is 60. Within the range of ~ 130 mgKOH / g, the generation of development residue is suppressed even if the acid value is relatively high. For example, in Examples 8 and 9, the acid values of the binder resins 8 and 9 used are as high as those of Comparative Examples 1 to 3, but the generation of development residues is suppressed. In the photosensitive colored resin composition of the present invention, the hydroxyalkyl (meth) acrylate unit-containing copolymer used as the binder resin contains the hydroxyalkyl (meth) acrylate unit in the above-mentioned specific amount, whereby the binder in the resin composition is contained. It is considered that the generation of residue is suppressed because the component having low developability other than the resin interacts with the hydroxyalkyl (meth) acrylate unit and the component having low developability is involved in the development. If the binder resin does not contain enough hydroxyalkyl (meth) acrylate units and has a high acid value, the developability of the binder resin alone becomes too high, and the components with low developability are left behind, resulting in a residue. It is thought that it is likely to occur. In the comparative example using the comparative binder resins C1 to C3, since the hydroxyalkyl (meth) acrylate unit is not contained, the generation of the development residue is easily affected by the acid value, and when the acid value is 108 mgKOH / g or more, the development residue is generated. It is probable that it occurred.

In Comparative Examples 5 and 5-2, since the comparative binder resin C5 which does not contain the hydroxyalkyl (meth) acrylate unit and has a weight average molecular weight of less than 11000 was used, Comparative Examples 6 to 10, 15, 18, 21, 26 and In 6-2 to 10-2, the comparative binder resins C6 to C10 having a weight average molecular weight of less than 11000 were used, so that the flatness of the colored layer was inferior.
In Comparative Examples 11 to 12, 22 to 23 and 27 to 28, the brightness of the colored layer was inferior because only the pigment was used as the coloring material. In Comparative Examples 12, 23 and 28, the same comparative binder resin C5 as in Comparative Example 5 was used, but the flatness of the colored layer was excellent. As a result, it was clarified that when a pigment is used as a coloring material, the problem of impairing the flatness of the colored layer is unlikely to occur.

1 Substrate 2 Light-shielding part 3 Colored layer 3R Red colored layer 3G Green colored layer 3B Blue colored layer 3B'Blue coating 10 Color filter 20 Opposing substrate 30 Liquid crystal layer 40 Liquid crystal display device 50 Organic protective layer 60 Inorganic oxide film 71 Transparent anode 72 Hole injection layer 73 Hole transport layer 74 Light emitting layer 75 Electron injection layer 76 Cathode 80 Organic light emitter 100 Organic light emission display device

Claims

A photosensitive coloring resin composition for a color filter containing a coloring material, a binder resin, a monomer, a photoinitiator, and a solvent.
The coloring material contains at least one selected from the group consisting of dyes and lake coloring materials.
The binder resin has a polymer structure containing 5 to 25% by mass of a structural unit derived from hydroxyalkyl (meth) acrylate represented by the following general formula (A), has a weight average molecular weight of 11,000 or more, and has an acid value. A photosensitive coloring resin composition for a color filter, which comprises a copolymer having a molecular weight of 60 to 130 mgKOH / g.

(In the general formula ( A ), RA represents a methyl group or a hydrogen atom, and RB represents an alkylene group having 1 to 4 carbon atoms.)
The photosensitive coloring resin composition for a color filter according to claim 1, wherein the coloring material contains a lake coloring material.
The photosensitive coloring resin composition for a color filter according to claim 1 or 2, wherein the coloring material contains a rake coloring material represented by the following general formula (1) or general formula (2).

(In the 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, and the organic group is at least saturated aliphatic hydrocarbon at the terminal directly bonded to N. It represents an aliphatic hydrocarbon group having a hydrogen group 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. Represented. 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 represents R ii and R ii i , and R iv and R. v may be bonded to form a ring structure. R vi and R vii may independently have an alkyl group which may have a substituent, an alkoxy group which may have a substituent, a halogen atom or a cyano. Representing a group. Ar 1 represents a divalent aromatic group which may have a substituent. A plurality of Ri to R vii and Ar 1 may be the same or different from each other.
a and c represent integers of 2 or more, and b and d represent integers of 1 or more. e is 0 or 1, and when e is 0, there is no bond. f and g represent integers of 0 or more and 4 or less, and f + e and g + e are 0 or more and 4 or less. The plurality of e, f, and g may be the same or different from each other. )

(In the general formula (2), RI to RVI each independently represent a hydrogen atom, an alkyl group which may have a substituent or an aryl group which may have a substituent, and RI and R represent each. II , R III and R IV , R V and R VI may be bonded to form a ring structure. R VII and R VIII may independently have an alkyl group and a substituent which may have a substituent. It represents an alkoxy group, a halogen atom or a cyano group which may have, Ar 2 represents a divalent aromatic heterocyclic group which may have a substituent, and a plurality of RI to R VIII and Ar 2 are represented. They may be the same or different. Em- represents an m-valent polyacid anion.
m represents an integer of 2 or more. j is 0 or 1, and when j is 0, there is no bond. k and l represent integers of 0 or more and 4 or less, and k + j and l + j are 0 or more and 4 or less. The plurality of j, k, and l may be the same or different. )
The color material is further a xanthene dye, a rake color material of a xanthene dye different from the rake color material represented by the general formula (1) or the general formula (2), and C.I. I. The photosensitive coloring resin composition for a color filter according to claim 3, which comprises at least one selected from the group consisting of Pigment Blue 15: 6.
The xanthene dye is a xanthene dye represented by the following general formula (3) or general formula (4).
The photosensitive coloring resin composition for a color filter according to claim 4, wherein the rake coloring material of the xanthene dye is a metal rake coloring material of the xanthene dye represented by the following general formula (5).

(In the general formula (3), R 1 and R 2 are independently alkyl groups or aryl groups, respectively, and R 3 and R 4 are independently aryl groups or hetero aryl groups, respectively.)

(In the general formula (4), R 5 and R 6 are independently aliphatic hydrocarbon groups or aromatic hydrocarbon groups which may have a substituent, and R 7 and R 8 are independent of each other. , An aromatic hydrocarbon group or an aromatic heterocyclic group which may have a substituent, wherein at least one aromatic hydrocarbon group or aromatic heterocyclic group of R 7 and R 8 is an aliphatic hydrocarbon. Substituentally substituted, R 7 and R 8 are different from each other. L 1 and L 2 are independently directly bonded, -SO 2- , or -CO-, and R 9 is a halogenated aliphatic hydrocarbon. Is the basis.)

(In the general formula (5), R 1' , R 2' , R 3'and R 4'independently represent a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group, respectively, and R 1'and R 3' , R 2'and R 4'may be bonded to each other to form a ring structure, and R 1'and the 5-position carbon atom of the xanthene ring, R 3'and the 7-position carbon atom of the xanthene ring, respectively. R 2'and the 4-position carbon atom of the xanthene ring, or R 4'and the 2-position carbon atom of the xanthene ring may be bonded to form a ring structure. The above aryl group or heteroaryl group may form a ring structure. The hydrogen atom to have may be substituted with an acidic group or a salt thereof, or a halogen atom. R 5'represents an acidic group or a salt thereof, and x is an integer of 0 to 5. However, the general formula ( 5) has at least two acidic groups or salts thereof, one of which forms an intramolecular salt.)
The photosensitive coloring resin composition for a color filter according to any one of claims 1 to 5, further containing a dispersant.
A cured product of the photosensitive coloring resin composition for a color filter according to any one of claims 1 to 6.
A color filter including at least a substrate and a coloring layer provided on the substrate, wherein at least one of the coloring layers is the photosensitive coloring resin for a color filter according to any one of claims 1 to 6. A color filter that is a cured product of the composition.
A display device having the color filter according to claim 8.