Photosensitive Coloring Resin Composition for Color Filter, Cured Product, Color Filter, and Display Device

Abstract

The present invention relates to a photosensitive colored resin composition for a color filter, which contains a coloring material, a binder resin, a monomer, a photoinitiator, and a solvent, and the coloring material contains at least one selected from dyes and lake colorants. The binder resin contains the following copolymer, which has a polymer structure containing a structural unit derived from a (meth)acrylic acid hydroxyalkyl ester represented by the following general formula (A) in an amount of 5 to 25% by mass, and has a weight average molecular weight of 11,000 or more and an acid value of 60 to 130 mgKOH / g. General formula (A) In the general formula (A), R<supgt;A< / supgt; represents a methyl group or a hydrogen atom, and R<supgt;B< / supgt> represents an alkylene group having 1 to 4 carbon atoms.

Description

Technical Field

[0001] 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. Background Art

[0002] In recent years, with the development of personal computers, especially portable personal computers, the demand for liquid crystal displays has been increasing. The penetration rate of mobile displays (mobile phones, smart phones, tablet PCs (personal computers)) has also been continuously increasing, and the market for liquid crystal displays is in a growing state. In addition, recently, organic light-emitting display devices such as organic EL (Electroluminescence) displays with high visibility due to self-luminescence have also attracted attention as next-generation image display devices. For the performance of these image display devices, there is a strong expectation for further high image quality such as an improvement in contrast and color reproducibility, and a reduction in power consumption.

[0003] Color filters are used in these liquid crystal display devices and organic light-emitting display devices. For example, regarding the formation of a color image of a liquid crystal display device, light passing through the color filter is directly colored into the colors of the respective pixels constituting the color filter, and these colored lights are synthesized to form a color image. As the light source at this time, in addition to the conventional cold cathode tube, an organic light-emitting element that emits white light or an inorganic light-emitting element that emits white light may sometimes be used. In addition, in an organic light-emitting display device, a color filter is used for color adjustment and the like.

[0004] Under such circumstances, there are also demands for high brightness, high contrast, and improvement in color reproducibility for color filters as well.

[0005] Here, a color filter generally has: a transparent substrate; a colored layer formed on the transparent substrate and including colored patterns of the three primary colors of red, green, and blue; and a light-shielding portion formed on the substrate so as to divide the respective colored patterns.

[0006] As a method for forming pixels in a color filter, for example, a binder resin, a photopolymerizable compound, and a photoinitiator are added to a color material dispersion liquid in which a color material is dispersed by a dispersant or the like. After the formed photosensitive colored resin composition is coated on a glass substrate and dried, it is exposed using a photomask, developed to form a colored pattern, and heated to fix the pattern, thereby forming a colored layer. These processes are repeated for each color to form a color filter.

[0007] For a photosensitive colored resin composition for forming a color filter, excellent developability capable of accurately forming a colored layer is required.

[0008] Patent Document 1 discloses a colored photosensitive resin composition for a color filter, which contains a pigment, a binder resin, a polyfunctional monomer, a photoinitiator, a dispersant, and a solvent. The binder resin contains a copolymer having the following main chain structure, which is formed by copolymerizing at least an alkyl cyclohexyl (meth)acrylate having an alkyl cyclohexyl group and a monomer having an acid group, and the hydroxyl value of the copolymer is in the range of 15 mgKOH / g to 200 mgKOH / g.

[0009] Patent Document 1 describes that the developed residue of the unexposed part of the colored photosensitive resin composition is less, and the remaining film rate of the exposed part is higher.

[0010] In addition, for a photosensitive colored resin composition for forming a color filter, it is required to be able to form a colored layer with high brightness. Therefore, research is being conducted on using micronized pigments as color materials, or using dyes or lake color materials as color materials with higher transmittance.

[0011] Prior Art Documents

[0012] Patent Documents

[0013] Patent Document 1: Japanese Patent Application Laid-Open No. 2009-276674 Summary of the Invention

[0014] Problems to be Solved by the Invention

[0015] In order to improve the brightness of the color filter, the inventors have tried to use dyes or lake color materials as the color materials of the photosensitive colored resin composition. However, when using a photosensitive colored resin composition containing a dye or a lake color material to form a colored layer pattern in which two or more colored layers such as red, green, and blue are arranged in a specified pattern, it has been found that the film thickness distribution within the pixel becomes uneven and the flatness of the pixel is impaired.

[0016] The present invention has been completed in view of the above circumstances, and its object is to provide a photosensitive colored resin composition for a color filter, which can form a colored layer with high brightness, excellent flatness, and suppressed generation of developed residue by containing at least one color material selected from dyes and lake color materials. In addition, an object of the present invention is to provide a cured product of the photosensitive colored resin composition, a color filter formed by using the photosensitive colored resin composition, and a display device.

[0017] Means for Solving the Problems

[0018] The photosensitive colored resin composition for a color filter of the present invention contains a color material, a binder resin, a monomer, a photoinitiator, and a solvent.

[0019] The color material contains at least one selected from dyes and lake color materials.

[0020] The above-mentioned binder resin contains the following copolymer, which has a polymer structure containing a structural unit derived from a (meth)acrylic acid hydroxyalkyl ester represented by the following general formula (A) in an amount of 5 to 25% by mass, a weight average molecular weight of 11,000 or more, and an acid value of 60 to 130 mgKOH / g.

[0021] [Chemical formula 1]

[0022] General formula (A)

[0023]

[0024] (In the general formula (A), R A represents a methyl group or a hydrogen atom, and R B represents an alkylene group having 1 to 4 carbon atoms.)

[0025] The present invention provides a cured product, which is a cured product of the photosensitive colored resin composition for a color filter of the present invention described above.

[0026] The present invention provides a color filter, which at least includes a substrate and a colored layer provided on the substrate, and at least one of the colored layers is a cured product of the photosensitive colored resin composition for a color filter of the present invention described above.

[0027] The present invention provides a display device having the color filter of the present invention described above.

[0028] Effects of the invention

[0029] According to the present invention, a photosensitive colored resin composition for a color filter can be provided, which can form a colored layer with high brightness, excellent flatness, and suppressed generation of development residues by containing at least one colorant selected from dyes and lake colorants. In addition, according to the present invention, a cured product of the photosensitive colored resin composition, a color filter formed using the photosensitive colored resin composition, and a display device can be provided. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] Figure 1 is a schematic diagram showing an example of the color filter of the present invention.

[0031] Figure 2 is a schematic diagram showing an example of the liquid crystal display device of the present invention.

[0032] Figure 3 is a schematic diagram showing an example of the organic light-emitting display device of the present invention.

[0033] Figure 4 is a schematic diagram 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.

[0034] Figure 5 This is a schematic diagram showing an example of a conventional method for forming a colored layer of a color filter using a photosensitive colored resin composition containing a dye or a lake pigment. Detailed Description

[0035] Hereinafter, the photosensitive colored resin composition for a color filter of the present invention, a method for producing the same, a cured product of the photosensitive colored resin composition for a color filter of the present invention, a color filter formed using the photosensitive colored resin composition for a color filter of the present invention, and a display device will be described in detail in sequence.

[0036] It should be noted that in the present invention, light includes electromagnetic waves and radiation having wavelengths in the visible and invisible regions, and the radiation includes, for example, microwaves and electron beams. Specifically, it refers to electromagnetic waves having a wavelength of 5 μm or less and electron beams.

[0037] In the present invention, (meth)acryloyl represents acryloyl and / or methacryloyl, (meth)acrylic acid represents acrylic acid and / or methacrylic acid, and (meth)acrylate represents acrylate and / or methacrylate.

[0038] In addition, in this specification, "~" indicating a numerical range is used in the meaning of including the numerical values described before and after as a lower limit value and an upper limit value.

[0039] In the present invention, the solid content refers to all components contained in the photosensitive colored resin composition except for the solvent, and also includes liquid components such as monomers.

[0040] I. Photosensitive Colored Resin Composition for Color Filter

[0041] The photosensitive colored resin composition for a color filter of the present invention (hereinafter, sometimes referred to as "photosensitive colored resin composition") contains a coloring material, a binder resin, a monomer, a photoinitiator, and a solvent.

[0042] The above coloring material includes at least one selected from dyes and lake pigments.

[0043] The above binder resin includes the following copolymer, which has a polymer structure containing a structural unit derived from (meth)acrylic acid hydroxyalkyl ester of 5 to 25% by mass, a weight average molecular weight of 11,000 or more, and an acid value of 60 to 130 mgKOH / g.

[0044] The photosensitive colored resin composition of the present invention contains at least one selected from dyes and lake pigments as a coloring material. Compared with pigments, dyes and lake pigments have higher transmittance. Therefore, by using at least one selected from dyes and lake pigments as the coloring material of the photosensitive colored resin composition, a highly bright colored layer can be formed.

[0045] However, when a photosensitive colored resin composition is coated on a substrate, exposed in a specified pattern, and developed to form a colored layer, and a series of processes of changing the color of the colorant are sequentially performed on one substrate, a colored layer pattern formed by arranging two or more colored layers such as red, green, and blue in a specified pattern is formed. In the above method for forming the colored layer pattern, it has been found that when a photosensitive colored resin composition containing a dye or a lake colorant is used, the film thickness distribution of the colored layers formed after the second layer becomes uneven, and the flatness of the pixels is impaired.

[0046] The uniformity of the film thickness distribution within a pixel is related to the chromaticity uniformity within the pixel and is an important factor for improving the image quality. In particular, if the pixel density increases with the high resolution of the display device, the influence of the uniformity of the film thickness distribution within the pixel on the image quality becomes greater.

[0047] The problem of impaired flatness of the pixels is particularly obvious when a dye or a lake colorant is used as the colorant of the photosensitive colored resin composition.

[0048] Figure 4 A schematic diagram showing an example of a conventional method for forming a colored layer of a color filter using a photosensitive colored resin composition containing a pigment. Figure 4 A process of forming a blue colored layer 3B after sequentially forming a red colored layer 3R and a green colored layer 3G on a substrate is shown. Figure 4 4(a) shows a state in which a blue photosensitive colored resin composition is used to form a blue coating film 3B' on a substrate provided with a light-shielding portion 2 serving as a boundary between the colored layers, a red colored layer 3R, and a green colored layer 3G. Since the blue coating film 3B' follows the uneven shape of the coating surface, the height of the coating film surface becomes relatively low in the region where the blue colored layer is formed and relatively high in the region where the red colored layer 3R and the green colored layer 3G are provided. The thickness of the blue coating film 3B' is fixed only within the region where the blue colored layer is formed, and its surface follows the surface shape of the substrate and becomes flat. Then, the blue coating film 3B' is heated and dried. The blue coating film 3B' after heating and drying is as Figure 4 shown in 4(b), maintaining the same shape as before heating and drying. After heating and drying, the blue coating film 3B' is exposed in a specified pattern, and the region where the blue colored layer is formed is selectively cured and then developed, whereby as Figure 4 shown in 4(c), a flat-shaped blue colored layer 3B is formed.

[0049] On the other hand, Figure 5 A schematic diagram showing an example of a conventional method for forming a colored layer of a color filter using a photosensitive colored resin composition containing a dye or a lake colorant. Figure 5This represents the process of forming the blue colorant layer 3B after sequentially forming the red colorant layer 3R and the green colorant layer 3G on the substrate. Figure 5 Figure 5(a) shows a state where a blue coating film 3B' is formed on a substrate provided with a light-shielding portion 2 serving as a boundary between the colorant layers, a red colorant layer 3R, and a green colorant layer 3G, using a blue photosensitive colorant resin composition. At this stage, the blue coating film 3B' containing a dye or a lake colorant, similar to Figure 4 the blue coating film 3B' containing a pigment in Figure 4(a), has a relatively lower height on the coating film surface in the region where the blue colorant layer is formed and a relatively higher height in the regions where the red colorant layer 3R and the green colorant layer 3G are provided. The thickness of the blue coating film 3B' is fixed only within the region where the blue colorant layer is formed, and its surface follows the surface shape of the substrate and becomes flat. It should be noted that Figure 5 the green colorant layer 3G shown in Figure 5(a) is the second colorant layer formed on the substrate, and is different from Figure 4 the green colorant layer 3G containing a pigment in Figure 4(a), and has a shape with poor flatness. This point will be described below.

[0050] Next, when the blue coating film 3B' is heated and dried, the blue coating film flows due to heating. Therefore, as Figure 5 shown in Figure 5(b), in the blue coating film 3B', the portions with a relatively higher height on the coating film surface existing in the regions where the red colorant layer 3R and the green colorant layer 3G are provided flow across the boundaries between the region where the red colorant layer 3R is provided and the region where the blue colorant layer is formed, and the boundaries between the region where the green colorant layer 3G is provided and the region where the blue colorant layer is formed, into the portions with a relatively lower height on the coating film surface existing in the region where the blue colorant layer is formed. Therefore, the blue coating film 3B' after heating and drying loses its followability to the surface shape of the substrate, and the coating film surface becomes relatively higher near the boundaries between the region where the red colorant layer 3R is provided and the region where the blue colorant layer is formed, and near the boundaries between the region where the green colorant layer 3G is provided and the region where the blue colorant layer is formed, and becomes relatively lower at the central portion of the coating film surface, and overall becomes a surface shape with a central depression. After heating and drying, the blue coating film is exposed in a specified pattern, and the region where the blue colorant layer is formed is selectively cured and then developed, whereby Figure 5 as shown in Figure 5(c), a blue colorant layer 3B with a central depression shape is formed.

[0051] When forming a second and subsequent colored layer on a substrate using a photosensitive colored resin composition containing a dye or a lake pigment, the coating film of the photosensitive colored resin composition softens and flows during the heat drying process as described above, and loses its followability to the surface shape of the substrate. Therefore, it is easy to form a colored layer having the following shape, in which the coating film surface near the boundary adjacent to the colored layer previously formed on the substrate is relatively high.

[0052] For example, when forming a red colored layer, a green colored layer, and a blue colored layer on a substrate in this order using a photosensitive colored resin composition containing a dye or a lake pigment, the green colored layer is likely to be formed in the shape shown in Figure 5 5(a) below, in which the coating film height at the boundary portion adjacent to the red colored layer is relatively high, and the coating film heights at the central portion and the portion away from the red colored layer are relatively low.

[0053] The fluidity of the coating film of the photosensitive colored resin composition during heat drying varies depending on the pigment used. It is presumed that the reason is as follows: when using a pigment as the pigment, the fine particles of the pigment are dispersed in the photosensitive colored resin composition. Therefore, during heat drying, even if the coating film softens, the viscosity does not become too low. In contrast, when using a dye or a lake pigment as the pigment, the dye or the lake pigment is dissolved in the photosensitive colored resin composition or is dispersed in the photosensitive colored resin composition in a more finely divided state than the pigment particles. Therefore, during heat drying, if the coating film softens, the viscosity decreases and the fluidity increases.

[0054] In the present invention, the above-mentioned problems peculiar to using a dye or a lake pigment as the pigment of the photosensitive colored resin composition are solved by using an adhesive resin containing the following copolymer. The copolymer has a polymer structure containing a structural unit derived from a (meth)acrylic acid hydroxyalkyl ester represented by the following general formula (A) in an amount of 5 to 25% by mass, and has a weight average molecular weight of 11,000 or more and an acid value of 60 to 130 mgKOH / g (hereinafter, this copolymer may sometimes be referred to as "copolymer containing (meth)acrylic acid hydroxyalkyl ester unit").

[0055] When using an adhesive resin containing a copolymer containing a (meth)acrylic acid hydroxyalkyl ester unit in a photosensitive colored resin composition containing a dye or a lake pigment, the increase in fluidity is suppressed when the coating film of the photosensitive colored resin composition formed on the substrate is heat dried. Therefore, when the photosensitive colored resin composition is coated on the substrate, the flatness of the coating film is also likely to remain unchanged after heat drying, and a colored layer having an excellent flatness shape is formed.

[0056] The reason for forming a colored layer with excellent flatness when using the adhesive resin containing the copolymer having a (meth)acrylic acid hydroxyalkyl ester unit is presumed as follows.

[0057] It is considered that when the coating film of the photosensitive colored resin composition is heated and dried, the amount of solvent in the coating film decreases, resulting in a smaller intermolecular distance between the adhesive resin molecules and an increased influence of hydrogen bonds on the bonding force between the adhesive resin molecules. Since the content of the structural unit derived from (meth)acrylic acid hydroxyalkyl ester in the copolymer having a (meth)acrylic acid hydroxyalkyl ester unit has been adjusted to an appropriate range, when the coating film of the photosensitive colored resin composition is heated and dried, the viscosity of the softened coating film increases due to the effect of the hydroxyl groups of the copolymer having a (meth)acrylic acid hydroxyalkyl ester unit promoting hydrogen bonds between the adhesive resin molecules, thereby suppressing the fluidization of the coating film.

[0058] In addition, since the weight average molecular weight of the copolymer having a (meth)acrylic acid hydroxyalkyl ester unit has been adjusted to an appropriate range, it is considered that when the coating film of the photosensitive colored resin composition is heated and dried, the viscosity of the softened coating film increases due to the molecular weight effect, thereby suppressing the fluidization of the coating film.

[0059] As other methods for suppressing the softening of the coating film of the photosensitive colored resin composition, a method of using another resin having a higher melt viscosity as the adhesive resin or a method of using a resin having another functional group that promotes hydrogen bonds in the adhesive resin are also considered. However, the copolymer having a (meth)acrylic acid hydroxyalkyl ester unit is excellent in that it can effectively flatten the shape of the colored layer with a relatively small amount and does not have an adverse effect on the hue of the colored layer.

[0060] Furthermore, when using the adhesive resin containing the copolymer having a (meth)acrylic acid hydroxyalkyl ester unit, the acid value of the copolymer having a (meth)acrylic acid hydroxyalkyl ester unit has been adjusted to an appropriate range, so that the development residue can be reduced.

[0061] Generally, the larger the acid value of the adhesive resin, the easier it is to form hydrogen bonds within the adhesive resin. Therefore, based on the above description, the larger the acid value of the copolymer having a (meth)acrylic acid hydroxyalkyl ester unit, the more effective the flattening effect of the shape of the colored layer can be improved. However, if the acid value of the adhesive resin is too large, it will lead to an increase in the development residue on the substrate.

[0062] In the present invention, by adjusting the weight-average molecular weight of the copolymer containing a (meth)acrylic acid hydroxyalkyl ester unit and the content of the structural unit derived from the (meth)acrylic acid hydroxyalkyl ester to an appropriate range, the shape of the colored layer can be effectively flattened. Therefore, from the viewpoint of reducing development residues, the acid value of the copolymer containing a (meth)acrylic acid hydroxyalkyl ester unit can be set within an appropriate range without making the acid value of the copolymer containing a (meth)acrylic acid hydroxyalkyl ester unit extremely large from the viewpoint of flattening the colored layer.

[0063] Hereinafter, each component contained in the photosensitive colored resin composition for a color filter of the present invention will be described.

[0064] [Colorant]

[0065] [Dyes and lake colorants]

[0066] In the present invention, at least one selected from dyes and lake colorants is used as the colorant.

[0067] In the present invention, a dye refers to a colorant that can dissolve an effective amount capable of exhibiting a coloring function in a solvent. A lake colorant refers to a colorant obtained by lake-forming a dye with a lake-forming agent.

[0068] The dyes and lake colorants are dissolved in a matrix such as a binder resin or dispersed therein in an extremely fine particle state, without impairing the transparency of the composition. Therefore, by using at least one selected from dyes and lake colorants as the colorant, the brightness of the color filter can be increased.

[0069] The dyes and lake colorants used in the present invention are not particularly limited.

[0070] Examples of the dyes include azo dyes, metal complex azo dyes, anthraquinone dyes, triarylmethane dyes, xanthene dyes, cyanine dyes, naphthoquinone dyes, quinoneimine dyes, methylene dyes, phthalocyanine dyes, and the like.

[0071] As the lake colorant, for example, a colorant obtained by lake-forming a dye as described above with a lake-forming agent can be mentioned. The lake-forming agent can be appropriately selected and used according to the dye. For anionic dyes (acid dyes), a compound that generates the counter cation of the dye can be used as the lake-forming agent; for cationic dyes (basic dyes), a compound that generates the counter anion of the dye can be used as the lake-forming agent. As such a lake-forming agent, known lake-forming agents can be used and there is no particular limitation. As the lake-forming agent for cationic dyes (basic dyes), for example, alkali metal salts, alkaline earth metal salts of organic anions, and alkali salts, alkali metal salts of inorganic anions can be mentioned. As the lake-forming agent for anionic dyes (acid dyes), for example, amine compounds that generate ammonium cations, and metal salts having the required metal ions can be mentioned.

[0072] In addition, as the lake colorant used in the present invention, for example, a lake colorant obtained by forming a salt of a monovalent or divalent or higher cationic dye (basic dye) and a divalent or higher polyanion, and a lake colorant obtained by forming a salt of a monovalent or divalent or higher anionic dye (acid dye) and a divalent or higher polycation can be preferably used.

[0073] Specifically, as the dye and lake colorant used in the present invention, for example, dyes described in JP-A-2015-96947, blue dyes described in JP-A-2016-27149, compound (Aa) described in JP-A-2017-16099 as a lake colorant, and dye (Ab) can be mentioned.

[0074] Among them, when the photosensitive coloring resin composition of the present invention contains a lake colorant, even if the acid value of the copolymer containing a (meth)acrylic acid hydroxyalkyl ester unit is relatively large, generation of development residues is easily suppressed, and in this regard it is preferable. Since the lake colorant has a salt structure of an acid and a base, it has a high affinity for hydroxyl groups. Therefore, the lake colorant has better compatibility with the copolymer containing a (meth)acrylic acid hydroxyalkyl ester unit than dyes and pigments. Therefore, when the photosensitive coloring resin composition of the present invention contains a lake colorant and a copolymer containing a (meth)acrylic acid hydroxyalkyl ester unit in combination, the solubility in the developer is made uniform, and thereby generation of development residues can be suppressed. Among them, when the hydroxyl value of the copolymer containing a (meth)acrylic acid hydroxyalkyl ester unit is within the following preferable range, the compatibility with the lake colorant is further improved, and thus the effect of suppressing development residues is particularly excellent.

[0075] In addition, among the lake pigments, triarylmethane-based or xanthene-based lake pigments are likely to improve the brightness and heat resistance of the colored layer, and are preferred in this regard. From the viewpoints of achieving high brightness during blue color adjustment and being more likely to further improve heat resistance, a lake pigment containing a triarylmethane-based dye is particularly preferred.

[0076] The triarylmethane-based dyes and xanthene-based dyes used for lake pigments can be appropriately selected from known dyes and are not particularly limited. Examples of triarylmethane-based dyes include C.I. Basic Blue 7, 8, 11, 26, etc. Examples of xanthene-based dyes include xanthene-based acid dyes such as C.I. Acid Red 50, 51, 52, 87, 92, 94, 289, 388, C.I. Acid Violet 9, 30, 102, sulfonylrhodamine G, sulfonylrhodamine B, sulfonylrhodamine 101, sulfonylrhodamine 640, etc., and xanthene-based basic dyes such as C.I. Basic Violet 11, etc.

[0077] In addition, the lake pigment used in the present invention may be a lake pigment having only 1 color-developing site. However, if it is a lake pigment having 2 or more color-developing sites, a colored layer with higher brightness and excellent heat resistance can be obtained, and it is preferred in this regard. Here, a lake pigment having 2 or more color-developing sites refers to a lake pigment formed by ionic bonding of a plurality of dye molecules each having 1 color-developing site with a lake-forming agent, or a lake pigment formed by ionic bonding of 1 dye molecule having a plurality of color-developing sites with a lake-forming agent, or a lake pigment formed by ionic bonding of a plurality of dye molecules each having a plurality of color-developing sites with a lake-forming agent.

[0078] Among them, from the perspective of obtaining a colored layer with high brightness and excellent heat resistance, the colorant used in the present invention preferably contains a lake colorant represented by the following general formula (1) or general formula (2), and more preferably contains a lake colorant represented by the following general formula (1). The lake colorant represented by the following general formula (1) is a lake colorant obtained by forming a salt of a cationic dye (basic dye) with a valence of two or more and a polyacid anion with a valence of two or more. The lake colorant represented by the following general formula (2) is a lake colorant obtained by forming a salt of two or more monovalent cationic dyes and a polyacid anion with a valence of two or more. Any of the lake colorants may generate dye molecules that do not form salts with polyacid anions. Especially when the number of cations and anions in the lake colorant represented by the following general formula (1) is different, it is easy to generate dye molecules that do not form salts with polyacid anions. The dye molecules that do not form salts with polyacid anions can form salts with acidic groups in the copolymer containing (meth)acrylic acid hydroxyalkyl ester units. The lake colorants represented by the following general formula (1) or general formula (2) not only have a high affinity between the salt structure of acid and base and the (meth)acrylic acid hydroxyalkyl ester units in the above copolymer, but also the dye molecules that do not form salts with polyacid anions can form salts with the structural units having acidic groups in the above copolymer. Therefore, the photosensitive colored resin composition of the present invention containing the lake colorant represented by the following general formula (1) or general formula (2) can form a complex formed by the association of the lake colorant and the above copolymer, so that the effect of hindering thermal motion becomes larger, and thus it is presumed that the heat resistance is improved.

[0079] In addition, the lake colorants represented by the following general formula (1) or general formula (2) also have good compatibility with the copolymer containing (meth)acrylic acid hydroxyalkyl ester units due to having a salt structure of acid and base. Therefore, even if the acid value of the copolymer containing (meth)acrylic acid hydroxyalkyl ester units is relatively large, the generation of development residues can be suppressed.

[0080] Among them, when the hydroxyl value of the copolymer containing (meth)acrylic acid hydroxyalkyl ester units is within the following preferred range, the compatibility with the lake colorant represented by the following general formula (1) or general formula (2) is further improved, and thus the effect of suppressing development residues is particularly excellent. When the acid value and hydroxyl value of the copolymer containing (meth)acrylic acid hydroxyalkyl ester units are within the following preferred range, it is easy to form a complex formed by the association of the lake colorant represented by the following general formula (1) or general formula (2), and thus the effect of improving heat resistance is particularly excellent.

[0081] (Lake colorant represented by general formula (1))

[0082] Hereinafter, the lake colorant represented by the general formula (1) preferably used in the present invention will be described in detail.

[0083] [Chemical formula 2]

[0084] Generalist (1)

[0085]

[0086] (In general formula (1), A is an a-valent organic group in which the carbon atom directly bonded to N does not have a π bond, and this organic group represents an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at least at the end directly bonded to N, or an aromatic group having this aliphatic hydrocarbon group, and a heteroatom may be included in the carbon chain. B c- represents a c-valent polyacid anion. R i ~R v each independently represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent, and R ii and R iii , R iv and R v may bond to form a ring structure. R vi and R vii each independently represents an alkyl group which may have a substituent, an alkoxy group which may have a substituent, a halogen atom, or a cyano group. Ar 1 represents a divalent aromatic group which may have a substituent. When there are a plurality of R i ~R vii and Ar 1 may be the same or different from each other.

[0087] a and c represent integers of 2 or more, b and d represent integers of 1 or more. e is 0 or 1, and when e is 0, the bond does not exist. f and g represent integers of 0 or more and 4 or less, and f + e and g + e are integers of 0 or more and 4 or less. When there are a plurality of e, f, and g, they may be the same or different from each other.)

[0088] Since the colorant represented by the above general formula (1) contains an anion of divalent or more and a cation of divalent or more, in the aggregate of this colorant, a molecular aggregate in which a plurality of molecules are associated via ionic bonds can be formed, rather than the anion and the cation forming an ionic bond in a 1:1 molecular form. Therefore, the apparent molecular weight is significantly increased compared to that of conventional lake colorants. It is presumed that by forming such a molecular aggregate, the cohesive force in the solid state is further increased, the thermal motion is reduced, the dissociation of ion pairs or the decomposition of the cationic part can be suppressed, and it is less likely to fade compared to conventional lake colorants.

[0089] In the general formula (1) above, A is an a-valent organic group in which the carbon atom directly bonded to N (nitrogen atom) does not have a π bond. This organic group represents an aliphatic hydrocarbon group having at least a saturated aliphatic hydrocarbon group at the terminal directly bonded to N, or an aromatic group having such an aliphatic hydrocarbon group. Heteroatoms such as O (oxygen atom), S (sulfur atom), and N (nitrogen atom) may be included in the carbon chain. That is, this organic group represents an aliphatic hydrocarbon group having at least a saturated aliphatic hydrocarbon group at the terminal directly bonded to N and heteroatoms such as O, S, and N may be included in the carbon chain, or an aromatic group having an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at the terminal directly bonded to N and heteroatoms such as O, S, and N may be included in the carbon chain. Since the carbon atom directly bonded to N does not have a π bond, color characteristics such as the hue and transmittance of the cationic coloring site can be maintained the same as those of the monomer without being affected by the linking group A and other coloring sites.

[0090] In A, regarding the aliphatic hydrocarbon group having at least a saturated aliphatic hydrocarbon group at the terminal directly bonded to N, as long as the carbon atom at the terminal directly bonded to N does not have a π bond, it can be any of linear, branched, or cyclic. The carbon atoms other than the terminal may have an unsaturated bond or a substituent, and O, S, and N may be included in the carbon chain. For example, a carbonyl group, a carboxyl group, an oxycarbonyl group, an amide group, etc. may be included, and a hydrogen atom may be further substituted with a halogen atom or the like.

[0091] In addition, in A, regarding the aromatic group having the above aliphatic hydrocarbon group, a monocyclic or polycyclic aromatic group having an aliphatic hydrocarbon group having at least a saturated aliphatic hydrocarbon group at the terminal directly bonded to N can be cited. It may have a substituent and may be a heterocycle containing O, S, and N.

[0092] Among them, from the viewpoint of the firmness of the skeleton, A preferably includes a cyclic aliphatic hydrocarbon group or an aromatic group.

[0093] As the cyclic aliphatic hydrocarbon group, groups containing cyclohexane, cyclopentane, norbornane, bicyclo[2.2.2]octane, tricyclo[5.2.1.0 2，6 decane, adamantane, etc. can be cited. In addition, as the aromatic group, groups containing a benzene ring, a naphthalene ring, etc. can be cited, for example. 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 obtained by substituting two alkylene groups having 1 to 20 carbon atoms such as benzenedimethylene can be cited.

[0094] In the present invention, from the viewpoints of achieving both firmness and freedom of molecular movement and improving heat resistance, A is preferably an aliphatic hydrocarbon group having two or more cyclic aliphatic hydrocarbon groups, having a saturated aliphatic hydrocarbon group at the terminal directly bonded to N, and capable of containing O, S, or N in the carbon chain. A is more preferably an aliphatic hydrocarbon group having two or more cycloalkylene groups, having a saturated aliphatic hydrocarbon group at the terminal directly bonded to N, and capable of containing O, S, or N in the carbon chain, and among them, it is further preferably a structure in which two or more cyclic aliphatic hydrocarbon groups are connected by a linear or branched aliphatic hydrocarbon group.

[0095] The two or more cyclic aliphatic hydrocarbon groups may be the same or different, and examples thereof include hydrocarbon groups the same as the above-mentioned cyclic aliphatic hydrocarbon groups, and among them, cyclohexane and cyclopentane are preferred.

[0096] In the present invention, from the viewpoint of heat resistance, among them, the above-mentioned A is preferably a substituent represented by the following general formula (1a).

[0097] [Chemical formula 3]

[0098] General formula (1a)

[0099]

[0100] (In general formula (1a), R xi represents an alkylene group having 1 to 3 carbon atoms which may have an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms as a substituent, R xii and R xiii each independently represent an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, p represents an integer of 1 to 3, q and r each independently represent an integer of 0 to 4; when there are a plurality of R xi , R xii , R xiii and r, the plurality of R xi , R xii , R xiii and r may be the same as or different from each other.)

[0101] From the viewpoints of excellent balance between firmness and thermal movement of the coloring part and improved heat resistance, as the alkylene group having 1 to 3 carbon atoms in R xi , examples include methylene, ethylene, propylene, etc., and among them, methylene or ethylene is preferred, and methylene is more preferred.

[0102] As the alkyl group having 1 to 4 carbon atoms, examples include methyl, ethyl, propyl, and butyl, which may be linear or branched.

[0103] In addition, examples of the alkoxy group having 1 to 4 carbon atoms include methoxy, ethoxy, propoxy, and butoxy, which may be linear or branched.

[0104] Regarding R xii and R xiii For the alkyl group having 1 to 4 carbon atoms and the alkoxy group having 1 to 4 carbon atoms in xi the same substituents as those that R

[0105] In the general formula (1a), from the viewpoint of heat resistance, it is preferable that the number of cyclohexane (cyclohexylene) is 2 or more and 4 or less, that is, p is 1 or more and 3 or less, and more preferably p is 1 or more and 2 or less.

[0106] In addition, the substituents R xii and R xiii of cyclohexylene are not particularly limited, but from the viewpoint of heat resistance, it is preferably 1 or more and 3 or less, and more preferably 1 or more and 2 or less. That is, it is preferable that q and r are integers of 1 or more and 3 or less, and it is preferable that q and r are integers of 1 or more and 2 or less.

[0107] Preferred specific examples of such a linking group A include the following groups, but are not limited thereto.

[0108] [Chemical formula 4]

[0109]

[0110] R i to R v The alkyl group in is not particularly limited. Examples include linear, branched, or cyclic alkyl groups having 1 to 20 carbon atoms, etc., and among them, linear or branched alkyl groups having 1 to 8 carbon atoms can be cited. From the viewpoints of brightness and heat resistance, linear or branched alkyl groups having 1 to 5 carbon atoms can be cited. The alkyl group in R i to R v can be ethyl or methyl. The substituents that the alkyl group can have are not particularly limited, and examples include aryl groups, halogen atoms, hydroxyl groups, alkoxy groups, etc. As the substituted alkyl group, aralkyl groups such as benzyl can be cited.

[0111] R i to R v The aryl group in is not particularly limited. Examples include phenyl, naphthyl, etc. The substituents that the aryl group can have include, for example, alkyl groups, halogen atoms, alkoxy groups, hydroxyl groups, etc.

[0112] Among them, from the viewpoint of chemical stability, as R i to R v, are each independently preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group, or R ii and R iii , R iv and R v are bonded to form a pyrrolidine ring, a piperidine ring, or a morpholine ring.

[0113] 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. It is considered that due to at least one of R ii to R v having a cycloalkyl group or an aryl group, steric hindrance reduces intermolecular interaction, so the influence of heat on the color-developing site can be suppressed, and thus the heat resistance is excellent.

[0114] 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).

[0115] [Chemical formula 5]

[0116] General formula (1b)

[0117]

[0118] (In general formula (1b), R xiv , R XV , and R XVi each independently represent a hydrogen atom, an alkyl group having 1 or more and 4 or less carbon atoms which may have a substituent, or an alkoxy group having 1 or more and 4 or less carbon atoms which may have a substituent.)

[0119] [Chemical formula 6]

[0120] General formula (1c)

[0121]

[0122] (In general formula (1c), R XVii , R XViii , and R xiX each independently represent a hydrogen atom, an alkyl group having 1 or more and 4 or less carbon atoms which may have a substituent, or an alkoxy group having 1 or more and 4 or less carbon atoms which may have a substituent.)

[0123] As R xiv , R xv , R xvi , R xvii , R xviii , and R xixThe alkyl group having 1 to 4 carbon atoms may include methyl, ethyl, propyl, and butyl, which may be linear or branched. In addition, as the alkoxy group having 1 to 4 carbon atoms, methoxy, ethoxy, propoxy, and butoxy may be mentioned, which may be linear or branched.

[0124] Examples of the substituents that the above alkyl group and alkoxy group may have include a halogen atom, a hydroxyl group, etc.

[0125] In the case of having the substituent represented by the above general formula (1b), from the viewpoint of heat resistance, it is preferable that at least one of R xiV , R xv , and R xvi is an alkyl group having 1 to 4 carbon atoms that may have a substituent, or an alkoxy group having 1 to 4 carbon atoms that may have a substituent. More preferably, at least one of R xiv and R xv is an alkyl group having 1 to 4 carbon atoms that may have a substituent, or an alkoxy group having 1 to 4 carbon atoms that may have a substituent.

[0126] In addition, in the case of having the substituent represented by the above general formula (1c), from the viewpoint of heat resistance, it is preferable that at least one of R xvii , R xviii , and R xix is an alkyl group having 1 to 4 carbon atoms that may have a substituent, or an alkoxy group having 1 to 4 carbon atoms that may have a substituent. More preferably, at least one of R xvii and R xviii is an alkyl group having 1 to 4 carbon atoms that may have a substituent, or an alkoxy group having 1 to 4 carbon atoms that may have a substituent.

[0127] Preferred specific examples of the substituent represented by the general formula (1b) and the substituent represented by the general formula (1c) may include the following substituents, but are not limited to these.

[0128] [Chemical formula 7]

[0129]

[0130] R vi and R vii each independently represent an alkyl group that may have a substituent, an alkoxy group that may have a substituent, a halogen atom, or a cyano group. As R vi and R viiThe alkyl group therein is not particularly limited, and is preferably a linear or branched alkyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms include methyl, ethyl, propyl, and butyl, which may be linear or branched. The substituents that the alkyl group may have are not particularly limited, and examples thereof include an aryl group, a halogen atom, a hydroxyl group, an alkoxy group, and the like.

[0131] In addition, as for R vi and R viii the alkoxy group therein is not particularly limited, and is preferably a linear or branched alkoxy group having 1 to 8 carbon atoms, more preferably an alkoxy group having 1 to 4 carbon atoms. Examples of the alkoxy group having 1 to 4 carbon atoms include methoxy, ethoxy, propoxy, and butoxy, which may be linear or branched. The substituents that the alkoxy group may have are not particularly limited, and examples thereof include an aryl group, a halogen atom, a hydroxyl group, an alkoxy group, and the like.

[0132] As for R vi and R vii the halogen atoms therein include, for example: fluorine atom, chlorine atom, bromine atom, iodine atom.

[0133] R vi and R vii The substitution numbers of R

[0134] i.e., f and g, each independently represent an integer of 0 or more and 4 or less, wherein preferably 0 or more and 2 or less, more preferably 0 or more and 1 or less. Multiple f's and g's may be the same or different. vi and R vii can be substituted at any position of the aromatic ring having a resonance structure in the triarylmethane skeleton or the xanthene skeleton, wherein preferably substituted at the meta position based on the substitution position of the amino group represented by -NR ii R iii or -NR iv R v

[0135]

[0135] The divalent aromatic group in Ar 1 is not particularly limited. Ar 1The aromatic group in can be a heterocyclic group in addition to the aromatic hydrocarbon group composed of a carbon ring. As the aromatic hydrocarbon in the aromatic hydrocarbon group, in addition to the benzene ring, the following can be cited: condensed polycyclic aromatic hydrocarbons such as naphthalene ring, tetrahydronaphthalene ring, indene ring, fluorene ring, anthracene ring, and phenanthrene ring; chain polycyclic hydrocarbons such as biphenyl, terphenyl, diphenylmethane, triphenylmethane, and stilbene. Regarding this chain polycyclic hydrocarbon, it may have O, S, N in the chain skeleton like diphenyl ether. On the other hand, as the heterocycle in the heterocyclic group, the following can be cited: 5-membered heterocycles such as furan, thiophene, pyrrole, oxazole, thiazole, imidazole, and pyrazole; 6-membered heterocycles such as pyran, pyrone, pyridine, pyridone, pyridazine, pyrimidine, and pyrazine; condensed polycyclic heterocycles such as benzofuran, benzothiophene, indole, carbazole, coumarin, benzopyrone, quinoline, isoquinoline, acridine, phthalazine, quinazoline, and quinoxaline. These aromatic groups may further have substituents such as an alkyl group, an alkoxy group, a hydroxyl group, a halogen atom, and a phenyl group that can be substituted by them.

[0136] There are multiple Rs in one molecule i ~R vii and Ar 1 may be the same or different. Through R i ~R vii and Ar 1 The combination of can be adjusted to the desired color.

[0137] The valence number a in A is the number of the color-developing cationic moiety constituting the cation, and a is an integer of 2 or more. In this lake colorant, since the valence number of the cation is 2 or more, the heat resistance is excellent. The upper limit of a is not particularly limited, but from the viewpoint of ease of production, a is preferably 4 or less, more preferably 3 or less.

[0138] In the colorant represented by the general formula (1), from the viewpoint of excellent heat resistance and easy suppression of color change during heating, the cation moiety preferably has a molecular weight of 1200 or more, preferably 1300 or more.

[0139] In the colorant represented by the general formula (1), from the viewpoint of high brightness and excellent heat resistance, the anion moiety (B c- ) is a c-valent polyacid anion and is an anion of divalent or more.

[0140] As the polyacid anion formed by condensation of multiple oxoacids, it may be a homopolyacid anion (M m O n ) c- , or it may be a heteropolyacid anion (X 1 M m O n ) c-In the above formula, M represents a polyatom, X represents a heteroatom, m represents the composition ratio of the polyatom, n represents the composition ratio of oxygen atoms, and l represents the composition ratio of heteroatoms. Examples of the polyatom M include Mo, W, V, Ti, Nb, etc. In addition, examples of the heteroatom X include Si, P, As, S, Fe, Co, etc. Further, a part thereof may contain Na + , H + and other counter cations.

[0141] Among them, from the viewpoint of excellent heat resistance, a polyoxoacid having one or more elements selected from tungsten (W) and molybdenum (Mo) is preferred.

[0142] Examples of such polyoxoacids include: tungstate ions [W 10 O 32 4- , molybdate ions [Mo 6 O 19 2- , or phosphotungstate ions [PW 12 O 40 3- , [P 2 W 18 O 62 6- , silicotungstate ions [SiW 12 O 40 4- , phosphomolybdate ions [PMo 12 O 40 3- , silicomolybdate ions [SiMo 12 O 40 4- , phosphotungstomolybdate ions [PW 12-s Mo s O 40 3- (s is an integer of 1 or more and 11 or less), [P 2 W 18 - t Mo t O 62 6- (t is an integer of 1 or more and 17 or less), silicotungstomolybdate ions [SiW 12-u Mo u O 40 4- (u is an integer of 1 or more and 11 or less), etc. Among the above, as a polyoxoacid containing at least one of tungsten (W) and molybdenum (Mo), from the viewpoints of heat resistance and ease of obtaining raw materials, a heteropolyacid is preferred, and a heteropolyacid containing phosphorus (P) is more preferred.​​​​​​​​​​

[0143] Furthermore, in terms of heat resistance, it is further preferably phosphotungstomolybdate ion [PW 10 Mo 2 O 40 3- 、[PW 11 Mo 1 O 40 3- 、phosphotungstate ion [PW 12 O 40 3- or any one of them.

[0144] In the general formula (1), b represents the number of cations, d represents the number of anions in the molecular aggregate, and b and d represent integers of 1 or more. When b is 2 or more, the multiple cations present in the molecular aggregate can be a single type or a combination of two or more types. In addition, when d is 2 or more, the multiple anions present in the molecular aggregate can be a single type or a combination of two or more types.

[0145] From the viewpoint of easily improving heat resistance by combining with a copolymer containing a (meth)acrylic acid hydroxyalkyl ester unit, b and d in the general formula (1) are preferably different integers from each other. When b and d in the general formula (1) are different integers from each other, it is presumed that the dye molecule as a cation easily interacts with the copolymer containing a (meth)acrylic acid hydroxyalkyl ester unit, and easily forms a complex formed by the association of the colorant and the copolymer. Therefore, the effect of hindering thermal motion becomes larger and the heat resistance is improved.

[0146] e in the general formula (1) is an integer of 0 or 1. When e is 0, the bond does not exist. e = 0 represents a triarylmethane skeleton, and e = 1 represents a xanthene skeleton. Multiple e's can be the same or different. Regarding the lake colorant represented by the general formula (1) used in the present invention, a lake colorant containing at least a triarylmethane skeleton can be preferably used.

[0147] It should be noted that, as the lake colorant represented by the general formula (1), for example, it can be prepared with reference to the specifications of International Publication No. 2012 / 144520 and International Publication No. 2018 / 003706.

[0148] The lake colorant represented by the general formula (1) can be used alone or in combination of two or more.

[0149] (Lake colorant represented by the general formula (2))

[0150] Next, the lake colorant represented by the general formula (2) preferably used in the present invention will be described in detail. ​​​

[0151] [Chemical Formula 8]

[0152] General formula (2)

[0153]

[0154] (In general formula (2), R I ~R VI each independently represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent. R I and R II , R III and R IV , R V and R VI may be bonded to form a ring structure; R VII and R VIII each independently represents an alkyl group which may have a substituent, an alkoxy group which may have a substituent, a halogen atom, or a cyano group; Ar 2 represents a divalent aromatic heterocyclic group which may have a substituent. When there are a plurality of R I ~R VIII and Ar 2 , they may be the same or different; E m- represents an m-valent polyacid anion;

[0155] m represents an integer of 2 or more; j is 0 or 1. When j is 0, the bond does not exist; k and l represent integers of 0 or more and 4 or less, and k + j and l + j are integers of 0 or more and 4 or less. When there are a plurality of j, k, and l, they may be the same or different.)

[0156] In general formula (2), R I ~R VI each independently represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent, and R I and R II , R III and R IV , R V and R VI may be bonded to form a ring structure. R I ~R VI may be the same as R i ~R v in the above general formula (1).

[0157] In general formula (2), R VII and R VIII each independently represents an alkyl group which may have a substituent, an alkoxy group which may have a substituent, a halogen atom, or a cyano group, and they may also be the same as R vi and R vii in the above general formula (1).

[0158] In general formula (2), Ar 2 represents a divalent aromatic heterocyclic group which may have a substituent, and this Ar 2 may be the same as the aromatic heterocyclic group in the above general formula (1). 1

[0159] In addition, in general formula (2), E m- represents an m-valent polyacid anion, and this m-valent polyacid anion may be the same as the c-valent polyacid anion in the above general formula (1).

[0160] In general formula (2), m represents the number of cations and anions, and represents an integer of 2 or more. The plurality of cations present in general formula (2) may be a single kind or a combination of two or more kinds. In addition, the anions may also be a single kind or a combination of two or more kinds.

[0161] In general formula (2), j is 0 or 1, and when j is 0, the bond does not exist. j in general formula (2) may be the same as e in the above general formula (1). In addition, k and l in general formula (2) may be the same as f and g in the above general formula (1).

[0162] It should be noted that, as the lake colorant represented by general formula (2), for example, it can be prepared with reference to Japanese Patent Laid-Open No. 2017-16099.

[0163] The lake colorant represented by general formula (2) may be used alone or in combination of two or more kinds.

[0164] The colorant used in the present invention may also contain a plurality of colorants in order to adjust the hue.

[0165] When the colorant used in the present invention contains the lake colorant represented by the above general formula (1) or general formula (2), and further contains other colorants in order to adjust the hue, as this other colorant, from the viewpoint of obtaining a high-luminance colored layer, it is preferably selected from at least one of xanthene dyes, lake colorants of xanthene dyes different from the lake colorant represented by the above general formula (1) or general formula (2), and C.I. Pigment Blue 15:6.

[0166] (Xanthene dyes)

[0167] As the xanthene dye used in combination with the lake colorant represented by the above general formula (1) or general formula (2), as long as it is a dye having a xanthene skeleton in the molecule, known xanthene dyes can be used, and there is no particular limitation. Among them, from the viewpoint of obtaining a high-luminance colored layer, the xanthene dyes represented by the following general formula (3) or general formula (4) are preferred.

[0168] ​In the photosensitive coloring resin composition of the present invention, by using the xanthene dye represented by the following general formula (3), the brightness and light resistance of the colored layer can be improved.

[0169] [Chemical formula 9]

[0170] General formula (3)

[0171]

[0172] (In general formula (3), R 1 and R 2 are each independently an alkyl group or an aryl group, and R 3 and R 4 are each independently an aryl group or a heteroaryl group.)

[0173] The xanthene dye represented by the above general formula (3) is characterized in that: in addition to having xanthene as a basic skeleton, it has only 1 functional group containing SO 2 , and any one of R 1 to R 4 bonded to the nitrogen atom is not a hydrogen atom, and R 3 and R 4 are aryl groups or heteroaryl groups, so that only a saturated hydrocarbon group is not bonded to the nitrogen atom and no alkali metal ion is present. By using the xanthene dye represented by the above general formula (3) having such characteristics, although the mechanism by which the brightness and light resistance of the colored layer are improved is unclear, it is considered as follows. The xanthene dye represented by the above general formula (3) has a cationic xanthene skeleton and 1 anionic -SO 3 - group, so it is electrically stable. Therefore, it is presumed that even when it is dispersed in a solvent, it will not dissociate and has excellent stability. In addition, it is presumed that the nitrogen atom has an aromatic substituent such as an aryl group or a heteroaryl group, so the lone pair of electrons of the nitrogen atom resonates not only with the xanthene skeleton but also with the aryl group or heteroaryl group, making the molecule more stable. Furthermore, since the nitrogen atom is not directly bonded to a hydrogen atom, there is no situation where the hydrogen atom detaches from the nitrogen atom and causes the color material to be unstable. Based on the above, the xanthene dye represented by the above general formula (3) is stable even under light irradiation and has excellent light resistance. By using this color material, a colored layer with excellent light resistance can be formed. In addition, the fading of the color material is suppressed, and as a result, the brightness of the colored layer can be improved.

[0174] In addition, regarding the xanthene dye represented by the above general formula (3), R 3 and R 4 can be made different from each other, so the scope of molecular design is wide, and thus the scope of adjustment of spectral characteristics and the like is also wide. Therefore, it is easy to make the color material approach the target chromaticity, and furthermore, it is easy to improve the brightness.

[0175] In addition, the xanthene-based dye represented by the above general formula (3) has a cationic xanthene skeleton and only one anionic -SO 3 - group, and has only an intramolecular salt, so it does not have alkali metal ions. Therefore, when the xanthene-based dye represented by the above general formula (3) is used to form a colored layer, the elution of alkali metal ions from the colored layer into the liquid crystal layer can be suppressed when manufacturing a liquid crystal panel, and thus a colored layer with excellent electrical reliability can be obtained.

[0176] In addition, the xanthene-based dye represented by the above general formula (3) has only one functional group containing SO 2 Therefore, its affinity with low-polarity solvents such as PGMEA (Propylene Glycol Monomethyl Ether Acetate) becomes higher. In addition, when dissolving the xanthene-based dye represented by the above general formula (3) in a solvent, a solvent with relatively low polarity can be used, so the stability of the photosensitive colored resin composition can be improved.

[0177] In the above general formula (3), the alkyl groups in R 1 and R 2 are not particularly limited, and examples thereof include linear or branched alkyl groups having 1 to 20 carbon atoms which may have substituents. Among them, linear or branched alkyl groups having 1 to 8 carbon atoms are preferred, and linear or branched alkyl groups having 1 to 5 carbon atoms are more preferred. The substituents that the alkyl group may have are not particularly limited, and examples thereof include: halogen atoms, aryl groups, carbamoyl groups, monovalent groups represented by -CO-O-R a , monovalent groups represented by -O-CO-R a′ , monovalent groups represented by -SO 2 -R a″ , monovalent groups represented by -R b -CO-O-R c , monovalent groups represented by -R b′ -O-CO-R c′ , and monovalent groups represented by -R b″ -SO 2 -R c″ etc.

[0178] R 1 ~R 4 The aryl groups in are not particularly limited, and examples thereof include aryl groups having 6 to 20 carbon atoms which may have substituents. Among them, groups having a phenyl group, a naphthyl group, etc. are preferred.

[0179] R 3 and R 4The heteroaryl group therein is not particularly limited, and examples thereof include heteroaryl groups having 5 to 20 carbon atoms which may have substituents, and preferably include, for example, nitrogen atoms, oxygen atoms, and sulfur atoms as heteroatoms. In addition, specific examples of the heteroaryl group include, for example, furan, thiophene, pyrrole, pyridine, and the like.

[0180] The substituents that the aryl group or heteroaryl group may have are not particularly limited, and examples thereof include: alkyl groups, halogen atoms, alkoxy groups, hydroxyl groups, carbamoyl groups, a monovalent group represented by -CO-O-R a a monovalent group represented by -O-CO-R a′ a monovalent group represented by -SO 2 -R a″ a monovalent group represented by -R b -CO-O-R c a monovalent group represented by -R b′ -O-CO-R c′ a monovalent group represented by -R b″ -SO 2 -R c″ a monovalent group represented by and the like.

[0181] The above R a 、R a′ 、R a″ 、R c 、R c′ and R c″ represent alkyl groups, and the above R b 、R b′ and R b″ represent alkylene groups. These substituents do not have an adverse effect on heat resistance and the like, and in this regard, they can be preferably used. By adjusting the electron-withdrawing property and electron-donating property based on these substituents, the spectral characteristics can be adjusted.

[0182] It should be noted that the alkyl group in R 1 ~R 4 is preferably unsubstituted or has an aryl group as a substituent, and the substituent of the aryl group or heteroaryl group is preferably an alkyl group. This is because, in this case, the polarity of the xanthene-based dye represented by the above general formula (3) is reduced, and thus the affinity with a low-polarity solvent such as PGMEA is improved. In addition, when dissolving the xanthene-based dye represented by the above general formula (3) in a solvent, a lower-polarity solvent can also be used, and by using a low-polarity solvent, the stability of the photosensitive coloring resin composition is improved.

[0183] In addition, R 1 ~R 4 can be the same or different from each other, and R 1 ~R 4 in the xanthene-based dye represented by the above general formula (3) can be symmetric or asymmetric with respect to the xanthene ring. Among them, when making R3 and R 4 When they are different from each other, the scope of molecular design of the xanthene-based dye represented by the above general formula (3) is wide, and the scope of adjustment of spectral characteristics also becomes wide. Therefore, it is easy to make the colorant approach the target chromaticity and it is easy to further improve the brightness. In this regard, it is preferable.

[0184] In addition, in the above general formula (3), regarding the substitution position of the -SO 3 - group on the benzene ring bonded to the xanthene skeleton, there is no particular limitation, and it is preferably ortho or para to the xanthene skeleton. From the viewpoints of heat resistance and light resistance, it is preferably that the -SO 3 - group is substituted at the ortho position with respect to the xanthene skeleton. Although its mechanism of action is not clear, it is presumed as follows: If the -SO 3 - group is in the ortho position, it can resonate with the carbon atom of the xanthene skeleton bonded to the benzene ring to form a ring structure, and thus the heat resistance and light resistance are improved.

[0185] In addition, the xanthene-based dye represented by the above general formula (3) can be used by converting the -SO 3 - group into a -SO 3 H group. The method of converting the -SO 3 - group into a -SO 3 H group is not particularly limited. Examples include: an acid treatment method using a weak acid dissociation reaction, a method using a cation exchange resin, etc.

[0186] As the acid treatment method, for example, the following method can be cited: dissolving the above colorant in a good solvent such as methanol and a solvent that can dissolve an acid, and adding an acid to convert the -SO 3 - group into a -SO 3 H group. The acid used in this acid treatment method is not particularly limited as long as it is an acid with higher acidity than the acid for converting the -SO 3 - group into a -SO 3 H group. As an acid with relatively high versatility, for example, hydrochloric acid, sulfuric acid, nitric acid, p-toluenesulfonic acid (PTS), trifluoromethanesulfonic acid, etc. can be cited.

[0187] On the other hand, as the ion exchange resin used in the method using a cation exchange resin, a cation exchange resin with a sulfonic acid end such as Diaion PK-216H (manufactured by Mitsubishi Chemical Corporation, trade name) can be cited.

[0188] It should be noted that for the -SO 3- Group conversion to -SO 3 The sulfonation treatment of the H group is carried out after dissolving the coloring material in a good solvent, and without taking out the coloring material having a sulfo group (-SO 3 H) as a solid, it can be carried out by adding PGMEA or a dispersant, etc. when preparing the photosensitive colored resin composition. Alternatively, after sulfonating the coloring material, the coloring material having a sulfo group as a solid can be taken out by a reprecipitation method or a recrystallization method, and then the photosensitive colored resin composition can be prepared. Among them, from the viewpoint of the recovery rate of the coloring material, the former method is preferred.

[0189] The manufacturing method of the xanthene-based dye represented by the above general formula (3) is not particularly limited. Specifically, the following methods can be exemplified.

[0190] Reflux the amine compound corresponding to the sulfofluorescent xanthene compound in a solvent, filter the reaction solution at 60 °C to remove insoluble components, then remove a part of the solvent, and pour it into 6% hydrochloric acid. Next, add a large amount of water, stir at room temperature for 30 minutes, and then filter to take out the wet filter cake. After washing the wet filter cake with water or hot water and drying it, the coloring material of the above general formula (3) is obtained. In addition, when manufacturing the coloring material of the general formula (3) in which R 1 and R 3 are different from a part of the structure of R 2 and R 4 and is asymmetric with respect to the xanthene ring, half of the corresponding amine compound is added dropwise little by little to a sufficiently diluted methanol solution of the sulfofluorescent xanthene compound, and the remaining half of the amine compound is added dropwise after the reaction, or a 1:1 solution of each amine compound is slowly added dropwise to the methanol solution of the sulfofluorescent xanthene compound, whereby an asymmetric coloring material of the general formula (3) can be obtained in a high yield.

[0191] It should be noted that the xanthene-based dye represented by the above general formula (3) can be used alone or in combination of two or more.

[0192] In the photosensitive colored resin composition of the present invention, by using the xanthene-based dye represented by the following general formula (4), the generation of foreign substances can be suppressed, and a colored layer with improved brightness can be formed.

[0193] [Chemical formula 10]

[0194] General formula (4)

[0195]

[0196] (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, R 7 and R8 Each independently represents an aromatic hydrocarbon group or an aromatic heterocyclic group which may have a substituent, R 7 and R 8 At least one of the aromatic hydrocarbon group or the aromatic heterocyclic group of is substituted with an aliphatic hydrocarbon group, R 7 and R 8 Are different from each other. L 1 and L 2 Each independently represents a direct bond, -SO 2 -, or -CO-, R 9 Is a halogenated aliphatic hydrocarbon group.)

[0197] The xanthene-based dye represented by the above general formula (4) is characterized in that: in addition to having xanthene as a basic skeleton, it also has only one specific -L 1 -N - -L 2 -R 9 Such a functional group containing an anion moiety, and R bonded to the nitrogen atom 5 ~R 8 None of them is a hydrogen atom, R 7 and R 8 Are an aromatic hydrocarbon group or an aromatic heterocyclic group, R 7 and R 8 At least one of the aromatic hydrocarbon group or the aromatic heterocyclic group of is substituted with an aliphatic hydrocarbon group, R 7 and R 8 Are different from each other. By using the xanthene-based dye represented by the above general formula (4) having such characteristics, the generation of foreign substances is suppressed and a colored layer with improved brightness can be formed. Although the mechanism is unclear, it is considered as follows. The xanthene-based dye represented by the above general formula (4) has a monovalent cationic xanthene skeleton and one anionic -L 1 -N - -L 2 -R 9 group, and has only an inner salt, so it is electrically stable within one molecule. On the other hand, it is presumed that in the anionic -L 1 -N - -L 2 -R 9 group, a halogen with a relatively high electronegativity is bonded to R 9 , so the electrons in the anion part are easily attracted to R 9 , and the anionic property becomes weak, thus weakening the intermolecular ionic bond. In addition, it is presumed that in the xanthene-based dye represented by the above general formula (4), none of R 5 ~R 8 bonded to the nitrogen atom is a hydrogen atom, R 7 and R 8is an aromatic hydrocarbon group or an aromatic heterocyclic group, R 7 and R 8 at least one of which is substituted with an aliphatic hydrocarbon group, R 7 and R 8 are different from each other and have an asymmetric structure with respect to the xanthene skeleton. Therefore, they have a lower crystallinity, are not easily aggregated, and have a higher solvent affinity. From their synergistic effects, it can be presumed that the solvent solubility of the xanthene-based dye represented by the above general formula (4) is improved, and when a colored resin composition containing the xanthene-based dye represented by the above general formula (4) is used to form a colored layer, the generation of foreign matters is suppressed.

[0198] In addition, in the xanthene-based dye represented by the above general formula (4), since the nitrogen atom bonded to the xanthene skeleton is not directly bonded to a hydrogen atom, there is no case where the hydrogen atom detaches from the nitrogen atom and causes the color material to be unstable. Since the nitrogen atom has an aromatic substituent such as an aromatic hydrocarbon group or an aromatic heterocyclic group, the lone pair of electrons possessed by the nitrogen atom resonates not only with the xanthene skeleton but also with the aromatic hydrocarbon group or the aromatic heterocyclic group. Therefore, the xanthene-based dye represented by the above general formula (4) has a molecular structure with higher stability. Since the xanthene-based dye represented by the above general formula (4) has a molecular structure with higher stability as described above, it has good heat resistance.

[0199] Furthermore, in the xanthene-based dye represented by the above general formula (4), since the aromatic hydrocarbon group or the aromatic heterocyclic group of at least one of R 7 and R 8 is substituted with an aliphatic hydrocarbon group, and R 7 and R 8 are different from each other, the dyes are not easily aggregated with each other, and have a higher solvent solubility. Therefore, foreign matters are not easily generated either, and thus the light transmittance of the colored layer is not attenuated.

[0200] In addition, in the xanthene-based dye represented by the above general formula (4), R 7 and R 8 are different from each other, and the range of molecular design is wide. Therefore, the range of adjustment of spectral characteristics and the like is also wide. Therefore, it is easy to make the color material approach the target chromaticity, and it is further easy to improve the brightness.

[0201] As described above, when the xanthene-based dye represented by the above general formula (4) is used, since it has good heat resistance, the decrease in brightness after baking in the color filter manufacturing process is suppressed. In the color filter manufacturing process, the aggregation of dyes and the generation of foreign matters are suppressed, and the structure can be designed according to the required chromaticity to adjust spectral characteristics and the like. It is presumed that the brightness of the colored layer can also be improved thereby.

[0202] In the above general formula (4), R 5 and R 6The aliphatic hydrocarbon group therein may be any of linear, branched, or cyclic forms, without particular limitation. Examples include linear or branched aliphatic hydrocarbon groups having 1 or more and 20 or fewer carbon atoms, or cyclic aliphatic hydrocarbon groups (alicyclic hydrocarbon groups) having 5 or more and 8 or fewer carbon atoms. From the perspective of heat resistance, those having 10 or fewer carbon atoms are preferred. As the aliphatic hydrocarbon group, linear, branched, or cyclic alkyl groups that are saturated aliphatic hydrocarbon groups are preferred.

[0203] As substituents that the aliphatic hydrocarbon group may have, there is no particular limitation, and examples include: halogen atoms, aromatic hydrocarbon groups, carbamoyl groups, monovalent groups represented by -CO-O-R d monovalent groups represented by -O-CO-R d′ monovalent groups represented by -SO 2 -R d″ monovalent groups represented by -R e monovalent groups represented by -CO-O-R f monovalent groups represented by -R e′ monovalent groups represented by -O-CO-R f′ monovalent groups represented by -R, and -R e″ -SO 2 -R f" monovalent groups represented by etc.

[0204] R 5 ~R 8 The aromatic hydrocarbon group in R~R has no particular limitation, and examples include aromatic hydrocarbon groups having 6 or more and 20 or fewer carbon atoms that may have substituents. Among them, groups having a phenyl group, a naphthyl group, etc. are preferred.

[0205] R 7 and R 8 The aromatic heterocyclic group in R and R has no particular limitation, and examples include aromatic heterocyclic groups having 5 or more and 20 or fewer carbon atoms that may have substituents, and aromatic heterocyclic groups preferably containing, for example, nitrogen atoms, oxygen atoms, or sulfur atoms as heteroatoms. Additionally, as the aromatic heterocyclic group, specifically, examples include furan, thiophene, pyrrole, pyridine, etc.

[0206] As substituents that the aromatic hydrocarbon group or aromatic heterocyclic group may have, there is no particular limitation, and examples include: aliphatic hydrocarbon groups, halogen atoms, alkoxy groups, hydroxyl groups, carbamoyl groups, monovalent groups represented by -CO-O-R d monovalent groups represented by -O-CO-R d′ monovalent groups represented by -SO 2 -R d″ monovalent groups represented by -R e monovalent groups represented by -CO-O-R f monovalent groups represented by -R e′ monovalent groups represented by -O-CO-R f′The monovalent group represented, -R e″ -SO 2 -R f″ The monovalent group represented, etc. The above R e 、R e′ 、R e″ 、R d 、R d′ 、R d″ 、R f 、R f′ and R f″ represent aliphatic hydrocarbon groups. These substituents do not have an adverse effect on heat resistance, etc., and can be preferably used in this regard. By adjusting the electron-withdrawing and electron-donating properties brought about by these substituents, the spectral characteristics can be adjusted. In addition, the aliphatic hydrocarbon group here can be the same as the aliphatic hydrocarbon group in R 5 and R 6 .

[0207] From the viewpoint that the generation of foreign matters is suppressed and a colored layer with improved brightness is easily formed, at least one of R 5 and R 6 is preferably an aliphatic hydrocarbon group, and it is preferable that R 5 and R 6 are aliphatic hydrocarbon groups, and a straight-chain aliphatic hydrocarbon group is particularly preferable. As this aliphatic hydrocarbon group, a straight-chain alkyl group having 1 or more and 10 or less carbon atoms is preferable, and a straight-chain alkyl group having 1 or more and 6 or less carbon atoms is more preferable.

[0208] From the viewpoint that the generation of foreign matters is suppressed and a colored layer with improved brightness is easily formed, at least one of R 7 and R 8 is preferably an aromatic hydrocarbon group, and it is preferable that R 7 and R 8 are aromatic hydrocarbon groups. As this aromatic hydrocarbon group, an aromatic hydrocarbon group having 6 or more and 10 or less carbon atoms is preferable, and a phenyl group is more preferable.

[0209] In addition, at least one of R 7 and R 8 , which is an aromatic hydrocarbon group or an aromatic heterocyclic group that may have a substituent, is substituted with an aliphatic hydrocarbon group, and R 7 and R 8 are different from each other.

[0210] As the aliphatic hydrocarbon group that substitutes the hydrogen atom of this aromatic hydrocarbon group or aromatic heterocyclic group, a straight-chain aliphatic hydrocarbon group is preferable. As this aliphatic hydrocarbon group, a straight-chain alkyl group having 1 or more and 10 or less carbon atoms is preferable, and a straight-chain alkyl group having 1 or more and 6 or less carbon atoms is more preferable. In addition, it is preferable that both R 7 and R 8 are substituted with the aliphatic hydrocarbon group as described above.

[0211] Further, from the viewpoint that the generation of foreign matter is suppressed and a colored layer with increased brightness is easily formed, R is preferred. 7 and R 8 in at least one of the aromatic hydrocarbon group or aromatic heterocyclic group, each aromatic hydrocarbon group or aromatic heterocyclic group is substituted with two or more aliphatic hydrocarbon groups.

[0212] Further, in the case where any 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 further 3 or more carbon atoms, there is a tendency to easily adjust the electron density in the molecule.

[0213] In the case where at least one of R 5 and R 6 is substituted with a linear aliphatic hydrocarbon group, and at least one of the aromatic hydrocarbon group or aromatic heterocyclic group of R 7 and R 8 is substituted with a linear alkyl group having 2 or more carbon atoms, there is a tendency to easily suppress the generation of foreign matter and easily form a colored layer with increased brightness.

[0214] Further, in R 5 ~R 8 , the aliphatic hydrocarbon group is preferably unsubstituted, or when it is a branched or linear alkyl group, the substituent is preferably an aromatic hydrocarbon group, and the substituent of the aromatic hydrocarbon group or aromatic heterocyclic group is preferably an aliphatic hydrocarbon group. This is because, in this case, the polarity of the xanthene-based dye represented by the above general formula (4) is reduced, and thus the affinity with a low-polarity solvent such as PGMEA is increased. In addition, when dissolving the above colorant in a solvent, a lower-polarity solvent can also be used. By using a low-polarity solvent, the stability of the photosensitive colored resin composition of the present invention is improved. Among them, from the viewpoint of increasing the affinity with a low-polarity solvent, as the substituent of the aromatic hydrocarbon group or aromatic heterocyclic group, it is preferable to have only an aliphatic hydrocarbon group.

[0215] In the -L 1 -N - -L 2 -R 9 group, L 1 and L 2 are each independently a direct bond, -SO 2 -, or -CO-, among which, -SO 2 - or -CO- is preferred. In addition, from the viewpoint that the generation of foreign matter is suppressed and a colored layer with excellent heat resistance and increased brightness is easily formed, -SO 2 - is preferred.

[0216] -L 1 -N - -L 2 -R 9 R in the group 9 is a halogenated aliphatic hydrocarbon group. As the halogen, fluorine atom, chlorine atom, iodine atom, etc. can be cited, and among them, fluorine atom is preferred. As the halogenated aliphatic hydrocarbon group of R 9 is preferably a linear or branched halogenated aliphatic hydrocarbon group having 1 or more and 8 or less carbon atoms, more preferably a linear or branched halogenated aliphatic hydrocarbon group having 1 or more and 5 or less carbon atoms, and still more preferably a linear or branched halogenated aliphatic hydrocarbon group having 1 or more and 3 or less carbon atoms. Among them, the substitution rate of halogen atoms in the aliphatic hydrocarbon group (number of halogen atoms / total number of hydrogen atoms in the aliphatic hydrocarbon group) is preferably 50% or more, more preferably 70% or more, and particularly preferably 100%.

[0217] As R 9 , preferably, it is a linear or branched perfluoroalkyl group having 1 or more and 5 or less carbon atoms.

[0218] In addition, in the above general formula (4), regarding the -L 1 -N - -L 2 -R 9 group bonded to the benzene ring of the xanthene skeleton, there is no particular limitation on the substitution position, and it is preferably ortho or para to the xanthene skeleton. From the viewpoint of various resistances of the xanthene-based dye represented by the above general formula (4), it is preferred that -L 1 -N - -L 2 -R 9 group is substituted at the ortho position with respect to the xanthene skeleton. Although its action mechanism is not clear, it is presumed as follows: If the -L 1 -N - -L 2 -R 9 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 the stability of the molecule becomes higher, so various resistances of the colorant are improved.

[0219] Regarding the production method of the xanthene-based dye represented by the above general formula (4), there is no particular limitation, and specifically, the following methods can be cited.

[0220] Reacting a sulfonated fluorane compound with R 7 and R 8The corresponding amine compound is refluxed in a solvent at 60 °C. After filtering the reaction solution at 60 °C to remove insoluble components, a part of the solvent is removed, and it is poured into 6% hydrochloric acid. Then, a large amount of water is added, and after stirring at room temperature for 30 minutes, the wet filter cake is taken out by filtration. After washing the wet filter cake with water or hot water and drying it, the intermediate of the pigment represented by the above general formula (4) can be obtained. It should be noted that in the present invention, in order to manufacture the pigment of the general formula (4) in which a part of the structures of R 7 and R 8 are different and asymmetric with respect to the xanthene ring, half of the corresponding amine compound is gradually added dropwise in small amounts to a methanol solution of a sulfo-fluoran compound diluted sufficiently. After the reaction, the remaining half of the amine compound is added dropwise, or a 1:1 solution of each amine compound is slowly added dropwise to a methanol solution of the sulfo-fluoran compound, whereby the intermediate of the pigment represented by the asymmetric general formula (4) can be obtained in a high yield.

[0221] Then, in a polar solvent such as 1-methyl-2-pyrrolidone, in the presence of a base such as potassium carbonate, the pigment intermediate represented by the general formula (4), and the halide corresponding to R 5 and R 6 are stirred at 80 °C for 2 hours to react. After the reaction is completed, the reaction solution is cooled 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 taken out by filtration, and the residue is dried at 60 °C for 24 hours, whereby the precursor of the pigment represented by the general formula (4) is obtained.

[0222] Then, the precursor of the colorant of the asymmetric general formula (4) and trifluoromethylsulfonamide are dissolved in chloroform, and triethylamine is added dropwise to react. Then, the obtained reaction solution is washed with water, and then the organic layer is separated. The organic layer is dried with sodium sulfate, purified by column chromatography, and concentrated under reduced pressure, whereby the xanthene-based dye represented by the above general formula (4) can be obtained.

[0223] In addition, when L 1 is represented by -CO-, a fluoran compound can be used instead of the sulfo-fluoran compound, and the same procedure is carried out otherwise to obtain the xanthene-based dye represented by the above general formula (4).

[0224] The xanthene dyes represented by the above general formula (4) have high solvent solubility even for low-polarity solvents. Therefore, even without using a solvent having an alcohol hydroxyl group, they have solvent solubility at a concentration required for the use in a coloring layer. The xanthene dyes represented by the above general formula (4) preferably have a solubility of 2.0 (g / 100 g of solvent) or more, more preferably 2.5 (g / 100 g of solvent) or more, 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.

[0225] It should be noted that the xanthene dyes represented by the above general formula (4) may be used alone or in combination of two or more.

[0226] (Lake pigment of xanthene dye)

[0227] As the lake pigment of the xanthene dye used in combination with the lake pigment represented by the above general formula (1) or general formula (2), there is no particular limitation, and a known lake pigment of a xanthene dye different from the lake pigment represented by the above general formula (1) or general formula (2) can be used, for example. Among them, from the viewpoints of excellent heat resistance and dispersibility of the pigment and a high-luminance coloring layer can be obtained, a metal lake pigment of a xanthene dye obtained by lake-coloring a xanthene dye with a lake-coloring agent containing a metal atom can be preferably used. It should be noted that a metal lake pigment is a lake pigment to which a metal as a lake-coloring agent is added.

[0228] As the lake pigment of the xanthene dye different from the lake pigment represented by the above general formula (1) or general formula (2), a lake pigment of a xanthene dye having a phenyl group at the 9-position of the xanthene skeleton is preferably used. Specifically, a lake pigment obtained by lake-coloring a xanthene dye represented by the following general formula (5) with a lake-coloring agent can be preferably used, and a metal lake pigment obtained by lake-coloring a xanthene dye represented by the following general formula (5) with a lake-coloring agent containing a metal atom can be particularly preferably used.

[0229] [Chemical formula 11]

[0230] General formula (5)

[0231]

[0232] (In general formula (5), R 1′ 、R 2′ 、R 3′ and R 4′ each independently represent a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group, and R 1′ and R 3′ 、R 2′ and R 4′are each capable of bonding to form a ring structure, R 1′ is bonded to the 5-position carbon atom of the xanthene ring, R 3′ is bonded to the 7-position carbon atom of the xanthene ring, R 2′ is bonded to the 4-position carbon atom of the xanthene ring, or R 4′ is bonded to the 2-position carbon atom of the xanthene ring to form a ring structure respectively. The hydrogen atoms of the above-mentioned aryl or heteroaryl group may be substituted by an acidic group or its salt or a halogen atom; R 5′ represents an acidic group or its salt, and x is an integer of 0 to 5. Among them, the general formula (5) has at least 2 acidic groups or their salts, and one of them forms an intramolecular salt.)

[0233] Regarding R 1′ ~R 4′ in the alkyl group, preferably, it is a linear or branched alkyl group having 1 to 20 carbon atoms which may have substituents, more preferably a linear or branched alkyl group having 1 to 8 carbon atoms, and still more preferably a linear or branched alkyl group having 1 to 5 carbon atoms. As the substituents that the alkyl group may have, there is no particular limitation, and examples thereof include an aryl group, a halogen atom, etc., and the aryl group may further have a halogen atom, or an acidic group or its salt as a substituent.)

[0234] Regarding R 1′ ~R 4′ in the aryl group, preferably, it is an aryl group having substituents with 6 to 20 carbon atoms, and more preferably a group having a phenyl group, a naphthyl group, etc.)

[0235] In addition, regarding R 1′ ~R 4′ in the heteroaryl group, preferably, it is a heteroaryl group having 5 to 20 carbon atoms which may have substituents, and preferably contains nitrogen atoms, oxygen atoms, sulfur atoms as heteroatoms.)

[0236] As the substituents that the aryl or heteroaryl group may have, examples thereof include: an alkyl group having 1 to 5 carbon atoms, a halogen atom, an acidic group or its salt, a hydroxyl group, an alkoxy group, a nitrile group, a carbamoyl group, a carboxylic acid ester group, etc.)

[0237] The so-called R 1′ and R 3′ , R 2′ and R 4′ bonded to form a ring structure respectively means that R 1′ and R 3′ , R 2′ and R 4′ form a ring structure via nitrogen atoms respectively. The ring structure is not particularly limited, and examples thereof include a 5- to 7-membered nitrogen-containing heterocycle, and specifically, a pyrrolidine ring, a piperidine ring, a morpholine ring, etc. can be cited.)

[0238] In addition, the so-called R 1′with the 5-position carbon atom of the xanthene ring, R 3′ with the 7-position carbon atom of the xanthene ring, R 2′ with the 4-position carbon atom of the xanthene ring, or R 4′ bonded to the 2-position carbon atom of the xanthene ring to form a ring structure, means R 1′ ~R 4′ The above combinations of the carbon atoms at the specified positions of the xanthene ring respectively form a ring structure via a nitrogen atom and a part of the xanthene skeleton. The ring structure is not particularly limited, and examples thereof include 5- to 7-membered nitrogen-containing heterocycles.

[0239] As specific examples of the acidic group or its salt, carboxyl group (-COOH), carboxylate group (-COO-), carboxylate salt group (-COOM, where M represents a metal atom), sulfonate group (-SO 3 -), sulfo group (-SO 3 H), sulfonate salt group (-SO 3 M, where M represents a metal atom), etc. can be cited. Among them, those having a sulfonate group (-SO 3 -), sulfo group (-SO 3 H), or sulfonate salt group (-SO 3 M) are preferred. It should be noted that as the metal atom M, sodium atom, potassium atom, etc. can be cited.

[0240] As specific examples of the xanthene-based dye represented by the above general formula (5), Acid Red 50, Acid Red 52, Acid Red 289, Acid Violet 9, Acid Violet 30, Acid Blue 19, etc. can be cited.

[0241] <Lake former>

[0242] The lake former used in the lake formation of the metal lake pigment of the xanthene-based dye only needs to be a lake former containing a metal atom. As the lake former containing a metal atom, a lake former containing a metal atom that becomes a metal cation of divalent or higher is preferred. Specifically, barium chloride, calcium chloride, calcium carbonate, aluminum chloride, aluminum sulfate, aluminum acetate, lead acetate, magnesium sulfate, zirconium chloride, zirconium sulfate, zirconium carbonate, polyaluminum chloride, polyaluminum sulfate, etc. can be cited. Among them, a lake former containing a metal atom that becomes a metal cation of trivalent or higher is more preferred. In addition, from the viewpoints of easy synthesis of the lake pigment and excellent dispersibility of the lake pigment, a lake former containing aluminum is preferred. That is, as the metal lake pigment of the xanthene-based dye, an aluminum lake pigment of the xanthene-based dye is preferred, and an aluminum lake pigment of the xanthene-based dye represented by the above general formula (5) is particularly preferred.

[0243] It is presumed that by using a lake-forming agent containing aluminum which becomes a trivalent cation, compared with a lake-forming agent containing a metal atom which becomes a divalent metal cation, its cohesive force as a lake-forming agent is stronger. Therefore, the solubility of the lake-formed xanthene-based dye in a solvent is greatly reduced, and it becomes a property closer to that of a pigment. Therefore, it also has the following advantages: excellent dispersibility and heat resistance of the color material, and it is easy to recover (filter and separate) the lake color material when manufacturing the color material.

[0244] As the lake-forming agent containing aluminum, from the viewpoints of excellent heat resistance of the color material and easy suppression of sublimation of the color material, polyaluminum chloride represented by the following general formula (6) is preferred.

[0245] [Chemical formula 12]

[0246] General formula (6)

[0247] Al n (OH) m Cl (3n-m)

[0248] (In the general formula (6), n is an integer from 2 to 20, and m is an integer from (n / 2) to (3n - 1).)

[0249] 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 relatively small polyaluminum chloride with 2 to 20 aluminum atoms as the lake-forming agent, the dispersed particle size of the color material will not become too large, and the dispersibility of the color material can be made good. In the present invention, preferably, n is an integer from 2 to 10.

[0250] In addition, in the polyaluminum chloride represented by the above general formula (6), m represents the number of hydroxyl groups (OH groups), which is an integer from (n / 2) to (3n - 1). It should be noted that when n is an odd number, the lower limit of m is {(n + 1) / 2} which becomes the smallest integer within the above range.

[0251] Aluminum in polyaluminum chloride has trivalent cationicity, and hydroxyl has monovalent anionicity. Therefore, the whole polyaluminum chloride has (3n - m)-valent cationicity. In the present invention, from the viewpoints of stronger cohesive force, easy recovery of the color material, or excellent dispersibility of the color material, preferably, it has a higher alkalinity, and preferably m is an integer from 2n to (3n - 1).

[0252] Among them, from the viewpoints of improving the dispersibility of the color material and the contrast of the coating film, in the polyaluminum chloride represented by the above general formula (6), preferably, n is an integer from 2 to 10, and m is an integer from 2n to (3n - 1).

[0253] In addition, from the viewpoints of further improving the heat resistance of the colorant, easily suppressing the sublimation of the colorant, and easily making the dispersibility of the colorant good, the basicity of the polyaluminum chloride represented by the general formula (6), defined by (m / 3n×100(%)), is preferably 15 to 99%, more preferably 60 to 97%, and still more preferably 70 to 95%.

[0254] (C.I. Pigment Blue 15:6)

[0255] C.I. Pigment Blue 15:6 preferably used in the present invention is a copper phthalocyanine pigment having an ε-type crystal structure and is preferred from the viewpoint of excellent dispersion stability.

[0256] C.I. Pigment Blue 15:6 used in the present invention can be subjected to alkaline treatment or acidic treatment. From the viewpoints of excellent dispersibility and storage stability, when the dispersant used in combination is acidic, alkaline treatment is preferably performed, and when the dispersant used in combination is alkaline, acidic treatment is preferably performed. Among them, C.I. Pigment Blue 15:6 used in the present invention is preferably subjected to alkaline treatment, and the alkaline-treated C.I. Pigment Blue 15:6 is preferably used in combination with an acidic dispersant.

[0257] In the present invention, a colorant derivative having a basic site or a derivative of a colorless compound having a basic site is preferably used during the alkaline treatment. In addition, in the present invention, examples of having a basic site include a mode having a basic group as a substituent, a mode in which an acidic group and a basic compound form a salt at the substituent, and the like.

[0258] Examples of the basic site of the colorant derivative or the derivative of the colorless compound in the present invention include, for example: an amino group, an ammonium sulfonate, a sulfonamide group having an amino group, an amide group having an amino group, a basic heterocyclic group, and the like.

[0259] Regarding the colorant used in the colorant derivative having a basic site, a known colorant can be appropriately selected and used. It is preferably a structure that is easily adsorbed to C.I. Pigment Blue 15:6, preferably has the same or a similar pigment skeleton, or has a structure that easily undergoes interaction. In addition, a colorant that does not damage the hue of C.I. Pigment Blue 15:6 used during the alkaline treatment is preferred.

[0260] As a colorant derivative having a basic site, preferably a blue colorant derivative. As the blue colorant used in the colorant derivative having a basic site, phthalocyanine-based colorants, triarylmethane-based colorants, anthraquinone-based colorants, naphthol-based colorants, benzimidazolone-based colorants, etc. can be used, but from the viewpoints of hue and heat resistance, phthalocyanine-based colorants are preferably used. Among them, from the viewpoints of improving dispersibility and brightness, as the colorant used in the colorant derivative having a basic site, a phthalocyanine-based colorant having the same skeleton as C.I. Pigment Blue 15:6 used in the alkaline treatment is preferably used. In addition, among them, from the viewpoints of improving dispersibility and brightness, as the blue colorant used in the colorant derivative having a basic site, copper phthalocyanine is preferably used.

[0261] Regarding the colorless compound used in the derivative of the colorless compound having a basic site, the following compound can be used as a standard. Even if the derivative of the colorless compound is used to perform alkaline treatment on C.I. Pigment Blue 15:6, the color of C.I. Pigment Blue 15:6 does not change before and after the alkaline treatment. As such a colorless compound, for example, condensed ring compounds such as naphthalene-based and triazine-based compounds or aromatic polycyclic compounds having a plurality of aromatic rings bonded thereto can be used. As the triazine-based aromatic polycyclic compound, for example, a structure in which 3 phenylamino groups or the like having an aromatic hydrocarbon group as a substituent are substituted on the triazine ring can be cited. Among them, from the viewpoints of improving dispersibility and brightness, triazine-based aromatic polycyclic compounds are preferably used.

[0262] Regarding, for example, a method for preparing C.I. Pigment Blue 15:6 containing a colorant derivative having a basic site as C.I. Pigment Blue 15:6 having a structure derived from a basic compound, the following method can be cited: After dry-crushing a colorant derivative having a basic site and C.I. Pigment Blue 15:6, the colorant derivative having a basic site is further mixed. In this case, as the dry-crusher, a ball mill, a vibration mill, a grinder, etc. can be used, and the crushing temperature can be freely set within 20 to 130°C.

[0263] In addition, as a method for preparing C.I. Pigment Blue 15:6 containing a colorant derivative having a basic site, the following methods can be cited: A colorant derivative having a basic site, C.I. Pigment Blue 15:6, and 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 kneading is performed by a kneader-type grinder by the solvent salt grinding method.

[0264] Preparing or preparing the alkaline-treated C.I. Pigment Blue 15:6 in advance before the colorant is dispersed to disperse the colorant, whereby the colorant dispersibility can be improved.

[0265] In C.I. Pigment Blue 15:6 containing a colorant derivative having a basic site or a derivative of a colorless compound, from the viewpoints of dispersibility and storage stability, the content of the colorant derivative having a basic site or the derivative of the colorless compound is preferably 0.5 parts by mass or more, more preferably 3 parts by mass or more, still more preferably 5 parts by mass or more, and even more preferably 8 parts by mass or more with respect to 100 parts by mass of C.I. Pigment Blue 15:6. On the other hand, from the viewpoint of excellent brightness, the content of the colorant derivative having a basic site or the derivative of the colorless compound is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, and still more preferably 30 parts by mass or less with respect to 100 parts by mass of C.I. Pigment Blue 15:6.

[0266] It should be noted that regarding whether C.I. Pigment Blue 15:6 is subjected to alkaline treatment or acidic treatment, it can be appropriately analyzed using, for example, mass spectrometry, elemental analysis, surface analysis, potentiometric titration, and combinations thereof.

[0267] In addition, as the acidic dispersant used in combination with the alkali-treated C.I. Pigment Blue 15:6, the same acidic dispersants as those that can be used in the following colorant dispersion can be cited.

[0268] In the present invention, from the viewpoint of easily improving the brightness of the colored layer, the total content of the dye and the lake colorant is preferably 5 parts by mass or more and 100 parts by mass or less, more preferably 10 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 colorants.

[0269] Among them, from the viewpoints of obtaining a colored layer with high brightness and improving the compatibility between the colorant and the copolymer containing a (meth)acrylic acid hydroxyalkyl ester unit to enhance the effect of suppressing development residues, the content of the lake colorant is preferably 20 parts by mass or more and 100 parts by mass or less, more preferably 30 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 colorants.

[0270] Furthermore, from the viewpoint of obtaining a colored layer with high brightness, the total content of the lake colorants represented by the above general formula (1) or general formula (2) is preferably 20 parts by mass or more and 100 parts by mass or less, more preferably 30 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 colorants. If the total content of the lake colorants represented by the above general formula (1) or general formula (2) is at least the above lower limit value, it is also preferable from the viewpoints of improving the compatibility between the colorant and the copolymer containing a (meth)acrylic acid hydroxyalkyl ester unit to enhance the effect of suppressing development residues and improving heat resistance.

[0271] When the colorant contains a combination of a lake colorant represented by the above general formula (1) or general formula (2) and a colorant different from the lake colorant, the color adjustment is carried out in such a way as to obtain a desired hue. Although there is no particular limitation, from the viewpoints of obtaining a highly bright colored layer, improving the compatibility between the colorant and the copolymer containing a (meth)acrylic acid hydroxyalkyl ester unit to enhance the effect of suppressing development residues, and improving heat resistance, the total content of the lake colorants represented by the above general formula (1) or general formula (2) is preferably 20 parts by mass or more and 98 parts by mass or less, and may also be 30 parts by mass or more and 95 parts by mass or less, relative to 100 parts by mass of the total amount of the colorants.

[0272] When the colorant contains a lake colorant represented by the above general formula (1) or general formula (2) and at least one selected from xanthene dyes and lake colorants of xanthene dyes different from the lake colorant represented by the above general formula (1) or general formula (2), from the viewpoint of obtaining a desired hue, the total content of the xanthene dye and the lake colorant of the xanthene dye may be 2 parts by mass or more, and may also be 5 parts by mass or more, relative to 100 parts by mass of the total amount of the colorants. On the other hand, from the viewpoint of suppressing a decrease in heat resistance, it is preferably 30 parts by mass or less, and may also be 25 parts by mass or less.

[0273] In addition, when the colorant contains a lake colorant represented by the above general formula (1) or general formula (2) and C.I. Pigment Blue 15:6, from the viewpoint of obtaining a desired hue, the content of C.I. Pigment Blue 15:6 may be 20 parts by mass or more, and may also be 30 parts by mass or more, relative to 100 parts by mass of the total amount of the colorants. On the other hand, from the viewpoints of suppressing a decrease in the brightness of the colored layer, suppressing the generation of development residues, and suppressing a decrease in the heat resistance of the colorant, it is preferably 80 parts by mass or less, and may also be 70 parts by mass or less.

[0274] In addition, relative to the total solid content of the photosensitive colored resin composition of the present invention, the content of the dye and the lake colorant is usually 0.5% by mass or more and 35% by mass or less, preferably 1% by mass or more and 30% by mass or less, and more preferably 2% by mass or more and 25% by mass or less.

[0275] <Other pigments>

[0276] The photosensitive colored resin composition of the present invention may further contain other pigments different from the above C.I. Pigment Blue 15:6 within a range not impairing the effects of the present invention to adjust the hue. As the other pigments, various organic pigments and inorganic pigments conventionally used as colorants for color filters can be used, and there is no particular limitation, but from the viewpoints of excellent color rendering properties and heat resistance, organic pigments are preferred.

[0277] In the case of blue use, as the above-mentioned other pigments, from the viewpoint of excellent dispersion stability, blue pigments such as copper phthalocyanine pigments having an ε-type or β-type crystal structure, and purple pigments such as C.I. Pigment Violet 23 can be preferably used. As the copper phthalocyanine pigment having an ε-type or β-type crystal structure, at least one selected from C.I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, and 15:5 can be preferably used.

[0278] It should be noted that the above-mentioned other pigments can be acid-treated or alkali-treated in the same manner as C.I. Pigment Blue 15:6 to improve dispersion stability. Regarding the above-mentioned other pigments, similarly, when the dispersant used in combination is acidic, alkali treatment is preferred, and when the dispersant used in combination is alkaline, acid treatment is preferred.

[0279] 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, it is preferable that the content of the above-mentioned other pigments is 25% by mass or less based on the total solid content of the photosensitive coloring resin composition, or the content of the above-mentioned other pigments is 80 parts by mass or less based on 100 parts by mass of the total amount of dyes and lake colorants. Furthermore, the smaller of the above two upper limit amounts is used as a more preferable upper limit amount.

[0280] [Binder resin]

[0281] <Copolymer containing (meth)acrylic acid hydroxyalkyl ester unit>

[0282] The binder resin contained in the photosensitive coloring resin composition of the present invention includes the following copolymer (copolymer containing (meth)acrylic acid hydroxyalkyl ester unit), which has a polymer structure containing a structural unit derived from (meth)acrylic acid hydroxyalkyl ester represented by the following general formula (A) in an amount of 5 to 25% by mass, and has a weight average molecular weight of 11,000 or more and an acid value of 60 to 130 mgKOH / g.

[0283] The above-mentioned copolymer containing (meth)acrylic acid hydroxyalkyl ester unit is an alkali-soluble copolymer containing a structural unit derived from (meth)acrylic acid hydroxyalkyl ester in the chain structure of the polymer skeleton.

[0284] The polymer structure of the copolymer containing (meth)acrylic acid hydroxyalkyl ester unit may be a structure having only a main chain or a structure having a main chain and side chains. The main chain of the copolymer containing (meth)acrylic acid hydroxyalkyl ester unit typically has a chain structure formed by connecting structural units generated by addition polymerization of monomers having an ethylenically unsaturated bond, and may further contain structural units generated by addition polymerization or condensation polymerization of monomers having a functional group other than an ethylenically unsaturated bond.

[0285] The side chains of the copolymer containing (meth)acrylic acid hydroxyalkyl ester units are typically bonded to the main chain via a linking group formed by the reaction of a functional group on the main chain with a functional group of the monomer for forming the side chain, and can also branch out from the main chain via a carbon-carbon bond.

[0286] As an example of forming a side chain by the reaction of a functional group on the main chain with a functional group of the monomer for forming the side chain, for example, when a carboxyl group is present on the main chain, an ester linking group is formed by reacting a monomer having a glycidyl group with the carboxyl group, and a side chain containing a structural unit derived from the monomer having a glycidyl group can be introduced. Additionally, as another example, when a hydroxyl group is present on the main chain, a urethane linking group is formed by reacting a monomer having an isocyanate group with the hydroxyl group, and a side chain containing a structural unit derived from the monomer having an isocyanate group can be introduced.

[0287] The side chain can be a pendant structure having a structural unit of one monomer, or can have a polymer structure formed by connecting two or more structural units. Additionally, when the side chain has a polymer structure, it can be composed only of structural units derived from monomers having an ethylenically unsaturated bond, or can contain structural units generated by addition polymerization or condensation polymerization of monomers having functional groups other than ethylenically unsaturated bonds.

[0288] In addition to the hydroxyl group derived from (meth)acrylic acid hydroxyalkyl ester, the copolymer containing (meth)acrylic acid hydroxyalkyl ester units optionally has other functional groups such as acidic groups that impart alkali solubility, groups containing ethylenically unsaturated bonds, and groups such as bulky groups that regulate the molecular structure, and these atomic groups can be present anywhere on the main chain or side chain.

[0289] As a preferred example of the copolymer containing (meth)acrylic acid hydroxyalkyl ester units, a copolymer can be cited in which the following side chain is bonded to the following main chain, the side chain contains a structural unit having a photopolymerizable functional group such as an ethylenically unsaturated bond, and the main chain contains a structural unit derived from (meth)acrylic acid hydroxyalkyl ester, a structural unit having an acidic group, a structural unit having a bulky group, and other structural units as required.

[0290] The copolymer containing a (meth)acrylic acid hydroxyalkyl ester unit is rendered alkali-soluble by the acidic groups on the main chain and is rendered crosslinkable by the photopolymerizable functional groups on the side chain. When the copolymer containing a (meth)acrylic acid hydroxyalkyl ester unit has a photopolymerizable functional group, in the curing step of the resin composition in the manufacture of a color filter, the binder resins can form crosslinks with each other or the binder resin can form crosslinks with monomers such as photopolymerizable compounds. As a result, the film strength of the cured film is further improved, thereby improving the developability resistance. In addition, the thermal shrinkage of the cured film is suppressed, and the adhesion to the substrate becomes excellent.

[0291] As the above-mentioned preferred copolymer containing a (meth)acrylic acid hydroxyalkyl ester unit, for example, a copolymer containing a (meth)acrylic acid hydroxyalkyl ester unit having a side chain with a photopolymerizable functional group can be produced in the following manner: copolymerize a (meth)acrylic acid hydroxyalkyl ester having an alkylene group with 1 to 4 carbon atoms, an ethylenically unsaturated monomer having an acidic group, an ethylenically unsaturated monomer having a bulky group, and other ethylenically unsaturated monomers as required to synthesize the main chain portion, and then react a monomer containing a photopolymerizable functional group having a functional group that reacts with the functional group on the main chain to generate a bond with it.

[0292] Hereinafter, the structural units constituting the main chain and side chain of the copolymer containing a (meth)acrylic acid hydroxyalkyl ester unit, and the monomers that can be used to form the structural units will be described.

[0293] (Structural unit derived from (meth)acrylic acid hydroxyalkyl ester represented by general formula (A))

[0294] The structural unit derived from (meth)acrylic acid hydroxyalkyl ester represented by the following general formula (A) (hereinafter, sometimes referred to as “(meth)acrylic acid hydroxyalkyl ester unit”) has the following chemical structure: the ethylenic double bond of the (meth)acrylic acid hydroxyalkyl ester having an alkylene group with 1 to 4 carbon atoms is broken by an addition reaction, generating two single bonds.

[0295] [Chemical formula 13]

[0296] General formula (A)

[0297]

[0298] (In general formula (A), R A represents a methyl group or a hydrogen atom, and R B represents an alkylene group with 1 to 4 carbon atoms.)

[0299] As the structural unit derived from (meth)acrylic acid hydroxyalkyl ester represented by the above general formula (A), among them, it is preferred that R in the above general formula (A) AA structural unit derived from a hydroxyalkyl (meth)acrylate and being methyl.

[0300] As specific examples of the hydroxyalkyl (meth)acrylate unit represented by the above general formula (A), structural units derived from hydroxyalkyl (meth)acrylates such as hydroxyethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxy-1-methylethyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-hydroxyisobutyl (meth)acrylate, etc. can be mentioned. Among them, 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 preferred, and a structural unit derived from 2-hydroxyethyl (meth)acrylate is particularly preferred.

[0301] In the present invention, with respect to 100% by mass of the total amount of the structural units constituting the copolymer, the amount of the hydroxyalkyl (meth)acrylate unit contained in the copolymer containing the hydroxyalkyl (meth)acrylate unit is set to 5% by mass or more and 25% by mass or less. By making the amount of the hydroxyalkyl (meth)acrylate unit within the above range, a colored layer with excellent flatness and suppressed development residues can be obtained.

[0302] When the amount of the hydroxyalkyl (meth)acrylate unit is less than 5% by mass, the fluidization of the coating film of the photosensitive colored resin composition cannot be sufficiently suppressed during heat drying, and thus the flatness of the obtained colored layer deteriorates. On the other hand, when the amount of the hydroxyalkyl (meth)acrylate unit exceeds 25% by mass, the viscosity of the photosensitive colored resin composition increases, resulting in poor coatability or a decrease in the solvent re-dissolubility of the photosensitive colored resin composition, and thus foreign matters or unevenness are likely to occur in the obtained colored layer.

[0303] The amount of the hydroxyalkyl (meth)acrylate unit contained in the copolymer containing the hydroxyalkyl (meth)acrylate unit is particularly preferably 5% by mass or more and 20% by mass or less.

[0304] (Structural unit having an acidic group)

[0305] In the structural unit having an acidic group, examples of the acidic group include a carboxyl group, a phosphoric acid group, a sulfo group, etc. Among them, from the viewpoint of being easily introduced with a side chain having a photopolymerizable functional group, a carboxyl group is preferred. As the structural unit having an acidic group, for example, a structural unit derived from an ethylenically unsaturated monomer having a carboxyl group can be preferably used. The structural unit derived from an ethylenically unsaturated monomer having a carboxyl group has the following chemical structure: in this chemical structure, the ethylenically unsaturated bond of the ethylenically unsaturated monomer having a carboxyl group is broken by an addition reaction, generating two single bonds.

[0306] It should be noted that in the present invention, the structural unit derived from an ethylenically unsaturated monomer refers to the structural unit in which the carbon-carbon double bond capable of free-radical polymerization of the ethylenically unsaturated monomer has become a carbon-carbon single bond.

[0307] Examples of the ethylenically unsaturated monomer having a carboxyl group include (meth)acrylic acid, vinylbenzoic acid, maleic acid, monoalkyl maleate, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, acrylic acid dimer, etc. In addition, an addition reaction product of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate or 4-hydroxybutyl (meth)acrylate and a cyclic anhydride such as maleic anhydride, succinic anhydride, phthalic anhydride, cyclohexanedicarboxylic anhydride, etc., ω-carboxy-polycaprolactone mono(meth)acrylate, etc. can also be used. In addition, acid anhydride monomers such as maleic anhydride, itaconic anhydride, citraconic anhydride, etc. can also be used as precursors of the carboxyl group. Among them, (meth)acrylic acid is particularly preferred from the viewpoints of copolymerizability, cost, solubility, glass transition temperature, etc.

[0308] Relative to 100% by mass of the total amount of the structural units constituting the copolymer, the amount of the structural unit having an acidic group contained in the copolymer containing a hydroxyalkyl (meth)acrylate unit is preferably 8% by mass or more and 30% by mass or less. By making 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 a decrease in solvent solubility can be suppressed.

[0309] When the amount of the structural unit having an acidic group is less than 8% by mass, the acid value is too low, and sufficient alkali solubility may not be obtained. 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 a solvent.

[0310] 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.

[0311] (Structural unit having a bulky group)

[0312] 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 an ethylenically unsaturated monomer having a bulky group has the following chemical structure: in this chemical structure, the ethylenically unsaturated bond of the ethylenically unsaturated monomer having a bulky group is broken by an addition reaction, generating two single bonds.

[0313] When the copolymer containing (meth)acrylic acid hydroxyalkyl ester units has bulky groups, the shrinkage during curing of the binder resin is suppressed, the peeling between the substrate is alleviated, and the adhesion to the substrate is improved. It should be noted that the bulky groups can be included in the form of monovalent groups or divalent or higher groups.

[0314] Examples of such bulky groups include: aliphatic hydrocarbon rings which may have substituents, aromatic hydrocarbon rings which may have substituents, and hydrocarbon rings such as combinations thereof. The hydrocarbon ring may have substituents such as alkyl, cycloalkyl, alkylcycloalkyl, carbonyl, carboxyl, oxycarbonyl, amide, hydroxyl, nitro, amino, and halogen atoms.

[0315] Specific examples of the hydrocarbon ring include: aliphatic hydrocarbon rings such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, norbornane, isobornane, tricyclo[5.2.1.0(2,6)]decane (dicyclopentane), adamantane; aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, phenanthrene, fluorene; chain polycycles or Cardo structures (9,9-diarylfluorene) such as biphenyl, terphenyl, diphenylmethane, triphenylmethane, stilbene; groups obtained by substituting a part of these groups with substituents, and the like.

[0316] In the case where an aliphatic hydrocarbon ring is included as the hydrocarbon ring, the heat resistance and adhesion of the colored layer are improved, and the brightness of the obtained colored layer is improved, and in this regard, it is preferable.

[0317] In addition, when the structural unit contains the above Cardo structure, the curability of the colored layer is improved, the fading of the colorant is suppressed, and the solvent resistance (suppressing NMP (N-Methyl pyrrolidone) swelling) is improved, and in this regard, it is particularly preferable.

[0318] Examples of the ethylenically unsaturated monomer having a hydrocarbon ring include: cyclohexyl (meth)acrylate, dicyclopentyl (meth)acrylate, adamantyl (meth)acrylate, isobornyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, styrene, etc. From the viewpoint of a large effect of maintaining the cross-sectional shape of the developed colored layer during heat treatment, it is preferable to use at least one selected from cyclohexyl (meth)acrylate, dicyclopentyl (meth)acrylate, adamantyl (meth)acrylate, benzyl (meth)acrylate, and styrene.

[0319] Regarding the amount of the structural unit having a bulky group contained in the copolymer containing (meth)acrylic acid hydroxyalkyl ester units, relative to the total amount of the structural units constituting the copolymer of 100% by mass, it is preferably 20% by mass or more and 70% by mass or less. By making the amount of the structural unit having a bulky group within this range, the adhesion of the coating film to the substrate can be made excellent.

[0320] 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 become insufficient. On the other hand, when the amount of the structural unit having a bulky group exceeds 70% by mass, it may be impossible to sufficiently introduce a (meth)acrylic hydroxyalkyl ester unit, an acidic group, or a photopolymerizable functional group, and the developability or film-forming property of the photosensitive colored resin composition, or the flatness of the obtained colored layer becomes insufficient.

[0321] 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.

[0322] (Other structural units constituting the main chain)

[0323] By including a structural unit having neither a functional group nor a bulky group in the main chain of the copolymer containing a (meth)acrylic hydroxyalkyl ester unit, physical properties such as the inhibition of alkali solubility, the improvement of solvent solubility, and the improvement of solvent redissolvability can be adjusted.

[0324] As the ethylenically unsaturated monomer that derives other structural units constituting the main chain of the copolymer containing a (meth)acrylic hydroxyalkyl ester unit, for example, (meth)acrylic esters having no functional group and having a low molecular ester residue such as methyl (meth)acrylate and ethyl (meth)acrylate can be used.

[0325] (Structural units constituting the side chain having a photopolymerizable functional group)

[0326] The side chain having a photopolymerizable functional group may be a side group structure composed of only 1 structural unit having a photopolymerizable functional group, or may have a polymer structure formed by connecting 2 or more structural units. When the side chain is a side group structure having 1 monomer structural unit, it has the following chemical structure: in this chemical structure, the functional group of the monomer containing a photopolymerizable functional group that reacts with the functional group on the main chain to generate a bond generates a linking group that bonds to the main chain.

[0327] As the monomer containing a photopolymerizable functional group having a photopolymerizable functional group and a functional group that reacts with the functional group on the main chain to generate a bond, for example, compounds such as glycidyl (meth)acrylate having an ethylenically unsaturated bond as a photopolymerizable functional group and having an epoxy group as a functional group that reacts with the functional group on the main chain to generate a bond; and compounds having an ethylenically unsaturated bond as a photopolymerizable functional group and having an isocyanate group as a functional group that reacts with the functional group on the main chain to generate a bond, etc. can be cited.

[0328] 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 carboxyl group on the main chain. In this case, while introducing a photopolymerizable functional group into a copolymer containing a hydroxyalkyl (meth)acrylate unit, the carboxyl group on the main chain is consumed by the reaction with the epoxy group, thereby reducing the acid value, and thus the photocurability and developability of the copolymer containing the hydroxyalkyl (meth)acrylate unit change in conjunction. Therefore, the balance between the photocurability and developability of the copolymer containing the hydroxyalkyl (meth)acrylate unit must be considered to adjust the amount of the monomer having a carboxyl group or the structural unit derived from the monomer, and the amount of the monomer having a photopolymerizable functional group and an epoxy group or the structural unit derived from the monomer.

[0329] 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.

[0330] Among these monomers containing photopolymerizable functional groups, monomers having photopolymerizable functional groups and epoxy groups are preferably used. In the present invention, from the viewpoint of improving the flatness of the colored layer, the amount of the hydroxyalkyl (meth)acrylate unit in the copolymer containing the hydroxyalkyl (meth)acrylate unit is important, but the monomer having a photopolymerizable functional group and an epoxy group has a high reactivity with a carboxyl group and hardly consumes the hydroxyl group in the copolymer containing the hydroxyalkyl (meth)acrylate unit, so it is easy to adjust the amount of the hydroxyalkyl (meth)acrylate unit.

[0331] In the case where the copolymer containing the (meth) hydroxyalkyl acrylate unit has an ethylenically unsaturated group in the side chain, the ethylenically unsaturated bond equivalent is preferably in the range of 100 to 2000, and particularly preferably in the range of 140 to 1500, from the viewpoint of obtaining the effects of improved film strength of the cured film, improved development resistance, excellent adhesion to the substrate, etc. If the ethylenically unsaturated bond equivalent is 100 or more, the development resistance and adhesion are excellent. In addition, if it is 2000 or less, the ratio of other structural units such as the structural unit having the acidic group and the structural unit having a bulky group can be relatively increased, so that the developability and heat resistance are excellent.

[0332] Here, the ethylenically unsaturated bond equivalent refers to the weight average molecular weight per 1 mol of the ethylenically unsaturated bonds in the copolymer containing the hydroxyalkyl (meth)acrylate unit, and is represented by the following mathematical formula (1).

[0333] Mathematical formula (1)

[0334] Ethylenically unsaturated bond equivalent (g / mol) = W (g) / M (mol)

[0335] (In the formula (1), W represents the mass (g) of the copolymer containing a hydroxyalkyl (meth)acrylate unit, and M represents the number of moles (mol) of the ethylenic double bonds contained in the copolymer containing a hydroxyalkyl (meth)acrylate unit.)

[0336] The above-mentioned ethylenically unsaturated bond equivalent can be calculated, for example, by measuring the number of ethylenic double bonds contained in 1 g of the copolymer containing a hydroxyalkyl (meth)acrylate unit according to the test method for iodine value described in JIS K 0070:1992.)

[0337] With respect to 100% by mass of the total amount of the structural units constituting the copolymer, the amount of the structural unit having a photopolymerizable functional group contained in the copolymer containing a hydroxyalkyl (meth)acrylate unit is preferably 2.5% by mass or more and 35% by mass or less. By making the amount of the structural unit having a photopolymerizable functional group within the above range, the photocurability of the copolymer containing a hydroxyalkyl (meth)acrylate unit can be improved.)

[0338] When the amount of the structural unit having a photopolymerizable functional group is less than 2.5% by mass, the photocurability of the copolymer containing a hydroxyalkyl (meth)acrylate unit 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 groups in the main chain may be excessively consumed, and sufficient alkali solubility may not be obtained.)

[0339] 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.)

[0340] In the present invention, the weight average molecular weight (Mw) of the copolymer containing a hydroxyalkyl (meth)acrylate unit is set to 11,000 or more. By setting the weight average molecular weight of the copolymer containing a hydroxyalkyl (meth)acrylate unit to 11,000 or more, when the coating film of the photosensitive colored resin is heated and dried, the viscosity of the softened coating film can be increased by the molecular weight effect of the copolymer containing a hydroxyalkyl (meth)acrylate unit, thereby suppressing the fluidization of the coating film. When the weight average molecular weight of the copolymer containing a hydroxyalkyl (meth)acrylate unit is less than 11,000, the fluidization of the coating film cannot be sufficiently suppressed during heating and drying.)

[0341] The weight average molecular weight of the copolymer containing a hydroxyalkyl (meth)acrylate unit is not particularly limited, and is preferably set to 25,000 or less. When the weight average molecular weight (Mw) of the copolymer containing a hydroxyalkyl (meth)acrylate unit exceeds 25,000, the viscosity of the photosensitive resin composition becomes too high, and the viscosity suitable for coating may be deviated.)

[0342] The weight-average molecular weight of the copolymer containing a (meth)acrylic acid hydroxyalkyl ester unit is more preferably 11,000 or more and 20,000 or less, and further preferably 11,000 or more and 19,000 or less.

[0343] It should be noted that in the present invention, the weight-average molecular weight (Mw) is a value measured by GPC (gel permeation chromatography). The measurement is carried out as follows: Using HLC-8220GPC manufactured by Tosoh Corporation, N-methylpyrrolidone added with 0.01 mol / L lithium bromide is used as the elution solvent, and Mw: 8×10 5 (F-80), Mw: 4×10 5 (F-40), Mw: 2×10 5 (F-20), Mw: 1×10 5 (F-10), Mw: 4×10 4 (F-4), Mw: 2×10 4 (F-2), Mw: 5×10 3 (A-5000), Mw: 2.5×10 3 (A-2500), Mw: 1×10 3 (A-1000), Mw: 5×10 2 (A-500) (all of the above are manufactured by Tosoh Corporation) are used as polystyrene standards for the calibration curve, and two TSK-GEL ALPHA-M (manufactured by Tosoh Corporation) are used as the measurement columns.

[0344] In the present invention, the acid value of the copolymer containing a (meth)acrylic acid hydroxyalkyl ester unit is set to 60 mgKOH / g or more and 130 mgKOH / g or less. By setting the acid value of the copolymer containing a (meth)acrylic acid hydroxyalkyl ester unit to 60 mgKOH / g or more, sufficient alkali solubility can be imparted to the coating film of the photosensitive colored resin, and the effect of flattening the shape of the colored layer is excellent. On the other hand, by setting the acid value of the copolymer containing a (meth)acrylic acid hydroxyalkyl ester unit to 130 mgKOH / g or less, the development residue on the substrate can be reduced when developing the coating film.

[0345] The acid value of the copolymer containing a (meth)acrylic acid hydroxyalkyl ester unit 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 even more preferably 70 mgKOH / g or more and 100 mgKOH / g or less.

[0346] When the photosensitive colored resin composition of the present invention contains a lake pigment as a coloring material, the effect of suppressing the generation of development residues is relatively high. Therefore, the acid value of the copolymer containing a (meth)acrylic acid hydroxyalkyl ester unit can be 100 mgKOH / g or more, can be 110 mgKOH / g or more, or can be 120 mgKOH / g or more. The higher the acid value of the copolymer containing a (meth)acrylic acid hydroxyalkyl ester unit, the easier it is to planarize the colored layer.

[0347] The hydroxyl value of the copolymer containing a (meth)acrylic acid hydroxyalkyl ester unit is preferably 50 mgKOH / g or more and 200 mgKOH / g or less. When the hydroxyl value of the copolymer containing a (meth)acrylic acid hydroxyalkyl ester unit is less than 50 mgKOH / g, the hydrophobicity of the coating film of the photosensitive colored resin composition becomes too high, which may lead to poor developability. On the other hand, when the hydroxyl value of the copolymer containing a (meth)acrylic acid hydroxyalkyl ester unit exceeds 200 mgKOH / g, the solvent re-dissolubility of the photosensitive colored resin composition deteriorates, and there is a risk of impaired coatability.

[0348] The hydroxyl value of the copolymer containing a (meth)acrylic acid hydroxyalkyl ester unit 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.

[0349] The copolymer containing a (meth)acrylic acid hydroxyalkyl ester unit is usually added to the photosensitive colored resin composition for a color filter of the present invention in the form of a varnish obtained by dissolving it in a solvent. Although not particularly limited, from the viewpoint of easily obtaining a colored layer with excellent flatness, the viscosity of the copolymer containing a (meth)acrylic acid hydroxyalkyl ester unit in the state of a varnish obtained by dissolving it in a solvent so that the solid content concentration becomes 60% by mass 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 above viscosity can be 10,000 mPa·s or less, or can be 9,000 mPa·s or less. If the above viscosity is below the above upper limit value, the photosensitive colored resin composition is easily dried, so the productivity of the color filter can be improved.

[0350] It should be noted that the solvent used to dissolve the copolymer containing a (meth)acrylic acid hydroxyalkyl ester unit is not particularly limited, and for example, the same solvent as the solvent contained in the photosensitive resin composition for a color filter of the present invention can be used.

[0351] <Other binder resins>

[0352] The photosensitive colored resin composition of the present invention may contain other binder resins in combination with a copolymer containing a (meth)acrylic acid hydroxyalkyl ester unit. As the other binder resins, the following can be used: acrylic resins having a structure obtained by removing the (meth)acrylic acid hydroxyalkyl ester unit from the structure of the copolymer containing the (meth)acrylic acid hydroxyalkyl ester unit, acrylic resins containing other structural units and side chains, styrene-acrylic resins, polyolefin resins, etc., which are photosensitive or non-photosensitive polymers obtained by polymerizing monomers containing an ethylenically unsaturated bond. In addition, as the other binder resins, polymers that have always been used as binder resins for forming the colored layer of a color filter, such as photosensitive or non-photosensitive resins such as epoxy resins, urethane resins, polyester resins, polyimide resins, and phenolic resins, can also be used.

[0353] In the photosensitive colored 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, preferably 5% by mass or more and 22% by mass or less, and more preferably 5% by mass or more and 20% by mass or less, based on the total solid content of the photosensitive colored resin composition.

[0354] In addition, in the photosensitive colored resin composition of the present invention, the content of the copolymer containing a (meth)acrylic acid hydroxyalkyl ester unit is usually 50 parts by mass or more and 95 parts by mass or less, preferably 60 parts by mass or more and 92 parts by mass or less, and more preferably 65 parts by mass or more and 90 parts by mass or less, based on 100 parts by mass of the total amount of the binder resin.

[0355] [Monomer (Photopolymerizable Compound)]

[0356] The monomer used as the photopolymerizable compound in the photosensitive colored resin composition of the present invention is not particularly limited as long as it can be polymerized using a photoinitiator, and a polyfunctional monomer having two or more polymerizable double bonds is preferred. As the polyfunctional monomer, a polyfunctional monomer having two or more ethylenically unsaturated double bonds is preferred, and a polyfunctional (meth)acrylate having two or more acryloyl or methacryloyl groups is particularly preferred.

[0357] As the polyfunctional (meth)acrylate, it can be appropriately selected from conventionally known polyfunctional (meth)acrylates. As specific examples, polyfunctional (meth)acrylates described in, for example, Japanese Patent Application Laid-Open No. 2013-029832 can be cited.

[0358] In addition, when excellent photocurability (high sensitivity) is required for the photosensitive colored resin composition of the present invention, as the polyfunctional monomer, a polyfunctional monomer having three or more (trifunctional) polymerizable double bonds is preferred. For example, poly(meth)acrylates of polyhydric alcohols having a valence of three or more or their dicarboxylic acid modified products can be preferably used. Specifically, preferred are: trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, succinic acid modified product of pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, succinic acid modified product of dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tris(2-(meth)acryloyloxyethyl) phosphate, etc.

[0359] When a phosphorus atom-containing polyfunctional (meth)acrylate such as tris(2-(meth)acryloyloxyethyl) phosphate is used, it is easy to suppress the fading of the lake pigment and easy to improve the brightness after post-baking, and it is preferred in this regard.

[0360] These polyfunctional (meth)acrylates can be used alone or in combination of two or more.

[0361] In the photosensitive colored resin composition of the present invention, from the viewpoint of easily making the viscosity of the coating film of the photosensitive colored resin composition appropriate and improving the flatness of the obtained colored layer, the content of the polyfunctional monomer is preferably 90 parts by mass or more, more preferably 95 parts by mass or more, and particularly preferably 100 parts by mass, based on 100 parts by mass of the total amount of the monomers.

[0362] In the photosensitive colored resin composition of the present invention, the content of the monomer is not particularly limited, and is preferably 5% by mass or more and 60% by mass or less, more preferably 10% by mass or more and 50% by mass or less, based on the total solid content of the photosensitive colored resin composition. If the content of the monomer is above the above lower limit value, the photocuring reaction is likely to proceed, whereby the dissolution of the exposed portion during development can be suppressed. In addition, if the content of the monomer is below the above upper limit value, the alkaline developability can be improved.

[0363] [Photoinitiator]

[0364] 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 can be used from various conventionally known initiators.

[0365] Examples of the photoinitiator include aromatic ketones such as benzophenone, N,N-dimethylaminobenzophenone, 4,4′-bis(diethylamino)benzophenone (e.g., Hicure ABP, manufactured by Kawaguchi Pharmaceutical Co., Ltd.), 4-methoxy-4′-dimethylaminobenzophenone; benzoin ethers such as benzoin methyl ether; benzoins such as ethyl benzoin; biimidazoles such as 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer; halomethyl oxadiazole compounds such as 2-(trichloromethyl)-5-(p-methoxystyryl)-1,3,4-oxadiazole; halomethyl-S-triazines such as 2-(4-butoxynaphthalen-1-yl)-4,6-bis-trichloromethyl-S-triazine; oxime esters such as oxime ester-based photoinitiators described in JP-A-2000-80068, JP-A-2001-233842, JP-T-2010-527339, JP-T-2010-527338, JP-A-2013-041153, etc.; α-amino ketones such as 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (e.g., Irgacure 907, manufactured by BASF), 2-benzyl-2-(dimethylamino)-1-(4-morpholinophenyl)-1-butanone (e.g., Irgacure 369, manufactured by BASF), 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone (Irgacure 379EG, manufactured by BASF); thioxanthones such as diethylthioxanthone.

[0366] Among them, from the viewpoint of excellent sensitivity, the photoinitiator used in the present invention preferably contains at least one selected from oxime esters and α-amino ketones, and from the viewpoints of adjustment of line width and developability resistance during pattern formation, α-amino ketones are preferred. α-Amino ketones having a tertiary amine structure have a tertiary amine structure as an oxygen quencher in the molecule, so the radicals generated by the initiator are not easily inactivated by oxygen, and the sensitivity can be improved. In this regard, they are preferred.

[0367] In addition, from the viewpoints of suppressing water marks and improving sensitivity, it is also preferable to use an oxime ester and an α - amino ketone in combination as a photoinitiator. It should be noted that the so - called water marks refer to the traces like water infiltration that occur after alkaline development and rinsing with pure water when using components that increase alkaline developability. These water marks will disappear after post - baking, so there is no problem with the product, but there will be a problem that they are detected in the form of uneven abnormalities in the appearance inspection of the patterned surface after development, making it impossible to distinguish normal products from abnormal products. Therefore, if the inspection sensitivity of the inspection device is reduced in the appearance inspection, the result will be a reduction in the yield of the final color filter product, which becomes a problem.

[0368] In addition, from the viewpoints of adjusting sensitivity, suppressing water marks, and improving developability resistance, it is preferable to use at least one selected from oxime esters and α - amino ketones in combination with thioxanthones as a photoinitiator.

[0369] The total content of the photoinitiator used in the photosensitive coloring resin composition of the present invention is not particularly limited as long as the effects of the present invention are not impaired, and is preferably in the range of 0.1% by mass or more and 12.0% by mass or less, more preferably 1.0% by mass or more and 8.0% by mass or less, relative to the total solid content of the photosensitive coloring resin composition. If the content is at least the above - mentioned lower limit value, photocuring proceeds sufficiently, and dissolution of the exposed part during development is suppressed. On the other hand, if it is at most the above - mentioned upper limit value, yellowing of the obtained colored layer is suppressed, thereby suppressing a decrease in brightness.

[0370] [Antioxidant]

[0371] From the viewpoints of improving heat resistance, suppressing fading of color materials, and increasing brightness, the photosensitive coloring resin composition of the present invention preferably further contains an antioxidant. By containing an antioxidant in the photosensitive coloring resin composition of the present invention, an excessive radical chain reaction in the micropores can be controlled without impairing the curability when forming micropores in the cured film, so that micropores of a desired shape can be more easily formed. In addition, from the viewpoint of easily obtaining the above - mentioned effects, the antioxidant is preferably used in combination with an oxime - based photoinitiator.

[0372] The antioxidant used in the present invention is not particularly limited, and can be appropriately selected from conventionally known antioxidants. Specific examples of the antioxidant include, for example, hindered phenol - based antioxidants, amine - based antioxidants, phosphorus - based antioxidants, sulfur - based antioxidants, hydrazine - based antioxidants, etc. From the viewpoints of heat resistance and making the shape of the micropores good, it is preferable to use hindered phenol - based antioxidants. It can also be a latent antioxidant as described in International Publication No. 2014 / 021023.

[0373] Examples of the hindered phenol-based antioxidants include pentaerythritol tetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (trade name: IRGANOX 1010, manufactured by BASF), 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate (trade name: Irganox 3114, manufactured by BASF), 2,4,6-tris(4-hydroxy-3,5-di-tert-butylbenzyl) mesitylene (trade name: Irganox 1330, manufactured by BASF), 2,2'-methylenebis(6-tert-butyl-4-methylphenol) (trade name: Sumilizer MDP-S, manufactured by Sumitomo Chemical), 6,6'-thiobis(2-tert-butyl-4-methylphenol) (trade name: Irganox 1081, manufactured by BASF), diethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate (trade name: Irgamod 195, manufactured by BASF), etc.

[0374] Among them, from the viewpoints of heat resistance and light resistance, pentaerythritol tetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (trade name: IRGANOX 1010, manufactured by BASF) is preferred.

[0375] As the content of the antioxidant, relative to the total amount of the solid components in the photosensitive coloring resin composition, the antioxidant is preferably 0.1% by mass or more and 10.0% by mass or less, more preferably 0.5% by mass or more and 5.0% by mass or less. If it is above the above lower limit value, the heat resistance and light resistance are excellent. On the other hand, if it is below the above upper limit value, the photosensitive resin composition can be made highly sensitive.

[0376] When the antioxidant is used in combination with the above oxime ester-based photoinitiator, as the content of the antioxidant, relative to 100 parts by mass of the total amount of the above oxime ester-based photoinitiator, the antioxidant is preferably 1 part by mass or more and 250 parts by mass or less, more preferably 3 parts by mass or more and 80 parts by mass or less, and still more 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.

[0377] [Optional additive]

[0378] The photosensitive coloring resin composition of the present invention may contain various additives as needed. Examples of the additives include mercapto compounds, polymerization terminators, chain transfer agents, leveling agents, plasticizers, surfactants, defoaming agents, silane coupling agents, ultraviolet absorbers, adhesion promoters, etc.

[0379] As specific examples of the surfactant and the plasticizer, surfactants and plasticizers described in, for example, Japanese Patent Application Laid-Open No. 2013-029832 can be cited.

[0380] [Solvent]

[0381] As the solvent used in the present invention, any organic solvent that does not react with the components of the photosensitive coloring resin composition and can dissolve or disperse them can be used, and there is no particular limitation. The solvent can be used alone or in combination of two or more.

[0382] Specific examples of the solvent include, for example: alcohol solvents such as methanol, ethanol, N-propanol, isopropanol, methoxy alcohol, and ethoxy alcohol; carbitol solvents such as methoxyethoxyethanol and ethoxyethoxyethanol; ester solvents such as ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl methoxypropionate, ethyl ethoxypropionate, ethyl lactate, methyl hydroxypropionate, ethyl hydroxypropionate, n-butyl acetate, isobutyl acetate, isobutyl butyrate, n-butyl butyrate, ethyl lactate, cyclohexyl acetate; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and 2-heptanone; glycol ether acetate solvents such as methoxyethyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy-3-methylbutyl 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-butanediol diacetate; glycol ether solvents such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, and dipropylene glycol dimethyl ether; aprotic amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; lactone solvents such as γ-butyrolactone; cyclic ether solvents such as tetrahydrofuran; unsaturated hydrocarbon solvents such as benzene, toluene, xylene, and naphthalene; saturated hydrocarbon solvents such as n-heptane, n-hexane, and n-octane; and aromatic hydrocarbons such as toluene and xylene. Among these solvents, from the viewpoint of the solubility of other components, glycol ether acetate solvents, carbitol acetate solvents, glycol ether solvents, and ester solvents are preferably used.

[0383] Among them, as the solvent used in the present invention, from the viewpoints of the solubility of other components and coating adaptability, one or more selected from propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, butyl carbitol acetate (BCA), carbitol acetate, 3-methoxy-3-methylbutyl acetate, ethyl ethoxypropionate, ethyl lactate, and 3-methoxybutyl acetate are preferred.

[0384] The content of the solvent is not particularly limited, and is preferably 75% by mass or more and 95% by mass or less, more preferably 80% by mass or more and 90% by mass or less, relative to the total amount of the photosensitive colored resin composition. By making the content of the solvent in the photosensitive colored resin composition be above the above lower limit value, the solubility and coating adaptability of other components can be improved. On the other hand, by making the above content be below the above upper limit value, the amount of the photosensitive colored resin composition used in the formation of the color filter can be reduced.

[0385] II. Method for manufacturing photosensitive colored resin composition for color filter

[0386] The method for manufacturing the photosensitive colored resin composition of the present invention is not particularly limited. For example, each component such as the above colorant, binder resin, monomer, photoinitiator, etc. can be mixed into a solvent and dissolved or dispersed therein, thereby manufacturing the photosensitive colored resin composition. It is preferred to manufacture the photosensitive colored resin composition in the following manner: A colorant dispersion liquid obtained by dispersing a colorant in a solvent using a dispersant in advance, or a colorant solution obtained by dissolving a colorant in a solvent, is prepared in advance, and the colorant dispersion liquid or colorant solution, and components of the photosensitive colored resin composition other than the colorant such as a binder resin, monomer, photoinitiator, etc. are mixed into a solvent and dissolved or dispersed using a known dispersion method.

[0387] In addition, in the case of using two or more colorants, the photosensitive colored resin composition can be manufactured in the following manner: After preparing a colorant dispersion liquid or colorant solution for each color of the colorant, the colorant dispersion liquid or colorant solution for each color, and components of the photosensitive colored resin composition other than the colorant such as a binder resin, photoinitiator, etc. are mixed into a solvent and dissolved or dispersed.

[0388] The colorant dispersion liquid and the colorant solution are used as pre-preparations for preparing the colored resin composition. That is, the colorant dispersion liquid and the colorant solution are pre-prepared at the preparation stage of preparing the colored resin composition, and the P / V ratio, that is, the ratio of (the mass of the colorant component in the composition) / (the mass of the solid components other than the colorant component in the composition) is high. Specifically, the P / V ratio of the colorant dispersion liquid and the colorant solution is usually 1.0 or more.

[0389] The photosensitive colored resin composition of the present invention manufactured using the colorant dispersion liquid contains a dispersant. The photosensitive colored resin composition containing a lake colorant or a pigment is preferably manufactured using a colorant dispersion liquid in which the lake colorant or the pigment is dispersed, and thus preferably contains a dispersant.

[0390] Hereinafter, the colorant dispersion liquid used in the manufacture of the photosensitive colored resin composition of the present invention will be described in detail.

[0391] The colorant dispersion used in the present invention contains a solvent, a dispersant, and the above colorant dispersed in the solvent by the dispersant, and may further contain other components such as a dispersion aid as needed.

[0392] [Dispersant]

[0393] As the dispersant, it can be appropriately selected and used from those conventionally used as dispersants. As the dispersant, for example, surfactants such as cationic, anionic, nonionic, amphoteric, silicone-based, and fluorine-based can be used. Among the surfactants, from the viewpoint of being able to disperse uniformly and finely, polymer surfactants (polymer dispersants) are preferred.

[0394] Examples of the polymer dispersant include: (co)polymers of unsaturated carboxylic acid esters such as polyacrylate; (partial) amine salts, (partial) ammonium salts, or (partial) alkylamine salts of (co)polymers of unsaturated carboxylic acids such as polyacrylic acid; (co)polymers of hydroxyl-containing unsaturated carboxylic acid esters such as hydroxyl-containing polyacrylate or modified products thereof; polyurethanes; unsaturated polyamides; polysiloxanes; long-chain polyaminoamide phosphates; polyethyleneimine derivatives (amides obtained by the reaction of poly(lower alkyleneimine) with a polyester containing a free carboxyl group or their bases); polyallylamine derivatives (reaction products obtained by reacting polyallylamine with one or more compounds selected from three compounds of a polyester containing a free carboxyl group, a polyamide, or a co-condensate of an ester and an amide (polyester amide)), etc.

[0395] The dispersant can be appropriately selected to have good dispersibility according to the type of the colorant, and there is no particular limitation. However, in the case of dispersing the lake colorant represented by the above general formula (1) or (2), or the metal lake colorant of the xanthene-based dye represented by the above general formula (5), and in the case of co-dispersing these lake colorants with dyes such as xanthene-based dyes or pigments such as C.I. Pigment Blue 15:6, as the dispersant, an acidic dispersant as an acidic polymer dispersant is preferably used. It should be noted that in the present invention, the dye can be used dissolved in the solvent.

[0396] In the case of dispersing the pigment, it is preferred to use at least one selected from acidic or basic polymer dispersants and urethane-based dispersants according to the type of the pigment, and more preferably an acidic or basic polymer dispersant. In the case of dispersing the pigment treated with a base, an acidic dispersant as an acidic polymer dispersant is preferably used, and in the case of dispersing the pigment treated with an acid, a basic dispersant as a basic polymer dispersant is preferably used.

[0397] As an acidic dispersant for the dispersion of lake pigments, it is possible to preferably use, for example, at least one selected from polymers having a structural unit represented by the following general formula (I) and the following carboxyl group-containing block copolymer. As an acidic dispersant for the dispersion of pigments, it is possible to preferably use, for example, a carboxyl group-containing block copolymer.

[0398] As a basic dispersant, it is possible to preferably use, for example, at least one selected from the following polymers: a polymer containing a repeating unit having a tertiary amine, and a salt-type polymer obtained by forming a salt of at least a part of the amino group in the polymer containing a repeating unit having a tertiary amine with an organic acid compound.

[0399] A urethane-based dispersant is a compound having one or more urethane bonds (-NH-COO-) in one molecule. As a urethane-based dispersant, it is possible to preferably use, for example, a reaction product of a polyisocyanate having two or more isocyanate groups in one molecule and a polyester having a hydroxyl group at one terminal or both terminals.

[0400] <Polymer having a structural unit represented by general formula (I)>

[0401] The polymer having a structural unit represented by the following general formula (I) can be preferably used as a dispersant for lake pigments, and in particular, can be preferably used as a dispersant for the lake pigments represented by the above general formula (1) or general formula (2). If the polymer having a structural unit represented by the following general formula (I) is used as an acidic dispersant, the dispersibility and heat resistance of the lake pigment can be improved, and the chromaticity change of the lake pigment after heating can be suppressed. In addition, when a lake pigment and a pigment are used together as a coloring material, by using the polymer having a structural unit represented by the following general formula (I) as a dispersant, the dispersibility and storage stability of the pigment can be improved, and a colored layer with improved substrate adhesion and coating film uniformity can be formed.

[0402] The polymer having a structural unit represented by the following general formula (I) is a polymer of an ethylenically unsaturated monomer, and thus it is presumed that: compared with a polyether-based or polyester-based polymer, the heat resistance of the skeleton is higher, and in this polymer, there are a plurality of acidic phosphorus compound groups (-P(=O)(-R 12 )(OH)) and its salt (-P(=O)(-R 12 )(O - X + )) have a strong adsorption force on the surface of the micronized coloring material. In addition, it is presumed that if the surface of the coloring material is in a state of being coated with at least one of the acidic phosphorus compound group and its salt, the attack (hydrogen abstraction or substitution reaction, etc.) of active oxygen such as peroxyl radicals on the pigment skeleton of the lake pigment is suppressed, and the deterioration (oxidative deterioration) of the lake pigment is suppressed.

[0403] [Chemical formula 14]

[0404]

[0405] (In 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, a hydrocarbon group, -[CH(R 13 )-CH(R 14 )-O] x1 -R 15 、-[(CH 2 ) y1 -O] z1 -R 巧 、or -O-R 16 -represented monovalent group, 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(R 19 )(R 20 )-OH、or -CH 2 -C(R 21 )(R 22 )-CH 2 -OH-represented monovalent group.

[0406] R 13 and R 14 are each independently a hydrogen atom or a methyl group, 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 -represented monovalent group, 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, R 17 and R19 They can be bonded to each other to form a ring structure. In the case of forming the above-mentioned cyclic structure, the cyclic structure may further have a substituent R 24 , R 24 is a hydrocarbon group, or a hydrocarbon group having one or more selected from an ether bond and an ester bond. The above-mentioned hydrocarbon group may have a substituent. X represents a hydrogen atom or an organic cation. x1 represents an integer of 1 or more and 18 or less, y1 represents an integer of 1 or more and 5 or less, and z1 represents an integer of 1 or more and 18 or less.)

[0407] In the general formula (I), L 11 is a direct bond or a divalent linking group. Here, the so-called L 11 being a direct bond means that the phosphorus atom is directly bonded to the carbon atom of the main chain skeleton without passing through a linking group.

[0408] As the divalent linking group in L 11 , as long as it can connect the carbon atom of the main chain skeleton and the phosphorus atom, there is no particular limitation. As the divalent linking group in L 11 , examples include: linear, branched or cyclic alkylene groups, linear, branched or cyclic alkylene groups having a hydroxyl group, arylene groups, -CONH- groups, -COO- groups, -NHCOO- groups, ether groups (-O- groups), thioether groups (-S- groups), and combinations thereof, etc. It should be noted that in the present invention, the orientation of the bond of the divalent linking group is arbitrary. That is, in the case where the divalent linking group contains -CONH-, it can be -CO on the carbon atom side of the main chain and -NH on the phosphorus atom side of the side chain, and conversely, it can also be -NH on the carbon atom side of the main chain and -CO on the phosphorus atom side of the side chain.

[0409] Among them, from the viewpoint of dispersibility, L 11 in the general formula (I) preferably contains a divalent linking group containing a -CONH- group or a -COO- group.

[0410] For example, in the case where L 11 is a divalent linking group containing a -COO- group, L 11 is preferably a -COO-L 11′ - group (here, L 11′ is an alkylene group having 1 or more and 8 or less carbon atoms which may have a hydroxyl group, -[CH(R L11 )-CH(R L12 )-O] x -, or -[(CH 2 ) y -O] z -(CH 2 ) y -O-, -[CH(R L13 )] w-O-, R L11 , R L12 and R L13 are each independently a hydrogen atom, a methyl group, or a hydroxyl group; x represents an integer of 1 or more and 18 or less, y represents an integer of 1 or more and 5 or less, z represents an integer of 1 or more and 18 or less, and w represents an integer of 1 or more and 18 or less).

[0411] L 11′ The alkylene group having 1 to 8 carbon atoms in 11′ can be any of linear, branched, or cyclic, and examples thereof include methylene, ethylene, trimethylene, propylene, various butylene groups, various pentylene groups, various hexylene groups, various octylene groups, etc., and a part of the hydrogen may be substituted with a hydroxyl group.

[0412] 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, 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 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, 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.

[0413] As the L in the general formula (I) 11 preferred specific examples 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- etc., but are not limited to these.

[0414] As the hydrocarbon group in R 12 examples include: an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, and an aryl group, etc.

[0415] The above-mentioned alkyl group having 1 to 18 carbon atoms can be any of linear, branched, or cyclic, and examples thereof include: methyl, ethyl, n-propyl, isopropyl, n-butyl, cyclopentyl, cyclohexyl, borneol, isoborneol, dicyclopentyl, adamantyl, a lower alkyl-substituted adamantyl, etc.

[0416] The alkenyl group having 2 or more and 18 or less carbon atoms may be linear, branched or cyclic. Examples of such alkenyl groups include vinyl, allyl, propenyl, etc. 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 a double bond is present at the end of the alkenyl group.

[0417] Examples of the aryl group include phenyl, biphenyl, naphthyl, tolyl, xylyl, etc., and it may further have a substituent. The aryl group preferably has 6 or more and 24 or less carbon atoms, more preferably 6 or more and 12 or less carbon atoms.

[0418] In addition, examples of the aralkyl group include benzyl, phenethyl, naphthylmethyl, biphenylmethyl, etc., and it may further have a substituent. The aralkyl group preferably has 7 or more and 20 or less carbon atoms, more preferably 7 or more and 14 or less carbon atoms.

[0419] The above alkyl and alkenyl groups may have a substituent, and examples of the substituent include halogen atoms such as F, Cl, Br, and nitro groups.

[0420] In addition, as the substituent of the aromatic ring such as the above aryl and aralkyl groups, in addition to linear or branched alkyl groups having 1 or more and 4 or less carbon atoms, alkenyl groups, nitro groups, halogen atoms, etc. may also be mentioned.

[0421] It should be noted that the preferred number of carbon atoms above does not include the number of carbon atoms of the substituent.

[0422] In the above R 12 , x1 is the same as x above, y1 is the same as y above, and z1 is the same as z above.

[0423] Examples of the hydrocarbon group in R 15 ~R 22 include, for example, the same hydrocarbon groups as those in the above R 12 .

[0424] R 17 , R 18 , R 19 , R 20 , R 21 and R 22 The hydrocarbon group having one or more selected from ether bonds and ester bonds is a group represented by -R'-O-R'', -R'-(C=O)-O-R'', or -R'-O-(C=O)-R'' (R' and R'' are hydrocarbon groups, or groups in which hydrocarbon groups are bonded by at least one of ether bonds and ester bonds). Two or more ether bonds and ester bonds may be present in one group. Examples of the monovalent hydrocarbon group include alkyl, alkenyl, aralkyl, and aryl, and examples of the divalent hydrocarbon group include alkylene, alkenylene, arylene, and combined groups thereof.

[0425] In the case of forming a ring structure by bonding with R 17 bonded to R 19 to form a ring structure, the number of carbon atoms constituting the ring structure is preferably 5 or more and 8 or less, more preferably 6, that is, a 6-membered ring, and a cyclohexane ring is preferably formed.

[0426] Regarding the substituent R 24 in the hydrocarbon group, or the hydrocarbon group having one or more selected from an ether bond and an ester bond, it can be set to be the same as the hydrocarbon group in the above R 17 , R 18 , R 19 , R 20 , R 21 and R 22 in the hydrocarbon group, or the hydrocarbon group having one or more selected from an ether bond and an ester bond.

[0427] From the viewpoint of excellent dispersibility and dispersion stability of the dispersed particles, the above R 12 is preferably a hydroxyl group, a hydrocarbon group, -[CH(R 13 )-CH(R 14 )-O] x1 -R 15 , -[(CH 2 ) y1 -O] z1 -R 巧 , or a monovalent group represented by -O-R 16 , more preferably a hydroxyl group, a methyl group, an ethyl group, a vinyl group, an aryl group or an aralkyl group which may have a substituent, a vinyl group, an allyl group, -[CH(R 13 )-CH(R 14 )-O] x1 -R 15 , -[(CH 2 ) y1 -O] z1 -R 15 , or a monovalent group represented by -O-R 16 , R 13 and R 14 are each independently a hydrogen atom or a methyl group, and R 巧 is -CO-CH=CH 2 or -CO-C(CH 3 )=CH 2 , wherein, R 12 is more preferably an aryl group which may have a substituent, a vinyl group, a methyl group and a hydroxyl group.

[0428] In addition, from the viewpoint of improving the alkali resistance, R 12 is preferably a hydrocarbon group, -[CH(R 13 )-CH(R 14 )-O]x1 -R 15 、 or -[(CH 2 )y 1 -O] z1 -R 15 A monovalent group represented thereby. It is presumed that in the case of having a structure in which a carbon atom is directly bonded to a phosphorus atom, it is not easily hydrolyzed, and thus a resin layer excellent in alkali resistance can be formed. Among them, from the viewpoints of excellent alkali resistance and excellent dispersibility and dispersion stability of the dispersed particles, R 12 is preferably methyl, ethyl, an aryl or aralkyl group which may have a substituent, vinyl, allyl, -[CH(R 13 )-CH(R 14 )-O] x1 -R 15 、 or -[(CH 2 ) y1 -O] z1 -R 15 A monovalent group represented thereby, R 13 and R 14 are each independently a hydrogen atom or a methyl group, and R 巧 is -CO-CH=CH 2 or -CO-C(CH 3 )=CH 2 。 Among them, from the viewpoint of dispersibility, R 12 is more preferably an aryl group which may have a substituent.

[0429] In addition, in the general formula (I), X represents a hydrogen atom or an organic cation. An organic cation refers to a cation in which the cationic part contains a carbon atom. Examples of the organic cation include: ammonium cations such as imidazolium cation, pyridinium cation, amidinium cation, piperidinium cation, pyrrolidinium cation, tetraalkylammonium cation and trialkylammonium cation, sulfonium cations such as trialkylsulfonium cation, and phosphonium cations such as tetraalkylphosphonium cation. Among them, from the viewpoints of dispersibility and alkali developability, a protonated nitrogen-containing organic cation is preferred.

[0430] Among them, in the case where the organic cation has an ethylenically unsaturated double bond, curability can be imparted, and in this regard it is preferred.

[0431] The structural unit represented by the general formula (I) may be contained alone or in two or more kinds in the polymer.

[0432] In the polymer, there may be included two types of structural units: a structural unit in which X is a hydrogen atom and a structural unit in which X is an organic cation in the structural unit represented by the general formula (I). When these two types of structural units are included, as long as good dispersibility and dispersion stability are exhibited, there are no particular limitations. The proportion of the number of structural units in which X is an organic cation is preferably 0 mol% or more and 50 mol% or less relative to the total number of structural units represented by the general formula (I).

[0433] The method for synthesizing the polymer having the structural unit represented by the general formula (I) is not particularly limited. For example, the polymer having the structural unit represented by the general formula (I) can be synthesized with reference to Japanese Unexamined Patent Application Publication No. 2017-2191. The polymer having the structural unit represented by the general formula (I) is preferably the following polymer: 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 at least a part of the acidic phosphorus compound group can form a salt.

[0434] In an embodiment of the present invention, from the viewpoint of dispersibility, the polymer having the structural unit represented by the general formula (I) preferably further has a solvent affinity site. As such a polymer, from the viewpoints of excellent dispersibility and storage stability and being able to form a high-contrast coating film even after long-term storage, among them, a graft copolymer having the structural unit represented by the above general formula (I) and the structural unit represented by the following general formula (II), or a block copolymer having the structural unit represented by the above general formula (I) and the structural unit represented by the following general formula (III) is preferred.

[0435] [Chemical formula 15]

[0436]

[0437] (In the general formula (II), L 21 represents a direct bond or a divalent linking group, R 25 represents a hydrogen atom or a methyl group, and Polymer represents a polymer chain having the structural unit represented by the following general formula (IV).

[0438] 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-O-R 30′ or -O-CO-R 30″ represents a monovalent group, R 28 and R 29 are each independently a hydrogen atom or a methyl group, and R 30 is a hydrogen atom, a hydrocarbon group, -CHO, -CH 2 CHO or -CH 2 COOR 31 represents a monovalent group, 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 represents 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 above hydrocarbon group may have a substituent.

[0439] x2 and x2' represent integers of 1 or more and 18 or less, y2 and y2' represent integers of 1 or more and 5 or less, and z2 and z2' represent integers of 1 or more and 18 or less.)

[0440] [Chemical Formula 16]

[0441]

[0442] (In General Formula (IV), R 32 is a hydrogen atom or a methyl group, and R 33 is a hydrocarbon group, -[CH(R 34 )-CH(R 35 )-O] x3 -R 36 ,-[(CH 2 ) y3 -O] z3 -R 36 ,-[CO-(CH 2 ) y3 -O] z3 -R 36 ,-CO-O-R 37 or -O-CO-R 38The monovalent group represented, R 34 and R 33 are each independently a hydrogen atom or a methyl group, and R 36 is a hydrogen atom, a hydrocarbon group, -CHO, -CH 2 CHO or -CH 2 COOR 39 The monovalent group represented, 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] z4 -R 36 The monovalent group represented, 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, and the above hydrocarbon group may have a substituent.

[0443] n represents an integer of 5 or more and 200 or less; x3 and x4 represent an integer of 1 or more and 18 or less, y3 and y4 represent an integer of 1 or more and 5 or less, and z3 and z4 represent an integer of 1 or more and 18 or less.)

[0444] (Graft copolymer)

[0445] Regarding the graft copolymer preferably used as an acidic dispersant, for example, a graft copolymer having a structural unit represented by the above general formula (I) and a structural unit represented by the above general formula (II) can be mentioned.

[0446] In the above general formula (II), L 21 is a direct bond or a divalent linking group. As the divalent linking group in L 21 , there is no particular limitation as long as it can connect the carbon atom derived from the ethylenically unsaturated double bond to the polymer chain. As the divalent linking group in L 21 , for example, a linking group the same as the divalent linking group in the above L 11 can be mentioned.

[0447] In the above general formula (II), Polymer represents a polymer chain having a structural unit represented by the above general formula (IV).

[0448] In the general formula (IV), as R 33The hydrocarbon group therein is preferably 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. Examples of them include those 12 same as the above R.

[0449] R 36 is preferably a hydrogen atom, or 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 represents a monovalent group, and R 37 is preferably 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] z4 -R 36 represents a monovalent group. R 38 is an alkyl group having 1 or more and 18 or less carbon atoms, and R 39 represents a hydrogen atom or an alkyl group having 1 or more and 5 or less carbon atoms.

[0450] Regarding the above R 36 and R 37 for the alkyl group, aralkyl group, and aryl group having 1 or more and 18 or less carbon atoms, examples include those 12 same as the above R.

[0451] Regarding the above R 38 and R 39 for the alkyl group, examples include those 12 same as the above R.

[0452] In the case where the above 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, in addition to linear, branched, and cyclic alkyl groups having 1 or more and 5 or less carbon atoms, alkenyl groups, nitro groups, halogen atoms such as F, Cl, and Br, etc.

[0453] It should be noted that the preferred number of carbon atoms does not include the number of carbon atoms of the substituent.

[0454] The above R 33and R 37 Among them, x3 and x4 are the same as the above-mentioned x, y3 and y4 are the same as the above-mentioned y, and z3 and z4 are the same as the above-mentioned z.

[0455] In addition, the above-mentioned R 33 、R 36 、R 37 、R 38 and R 39 can be further substituted by substituents such as alkoxy groups, hydroxyl groups, carboxyl groups, amino groups, epoxy groups, isocyanate groups, and hydrogen bond-forming groups within the range that does not hinder the dispersion performance of the above graft copolymer, etc. In addition, after synthesizing a graft copolymer having these substituents, a compound having a functional group and a polymerizable group that reacts with the substituent can be made to react to add a polymerizable group. For example, glycidyl (meth)acrylate can be reacted with a graft copolymer having a carboxyl group, or 2-hydroxyethyl (meth)acrylate can be reacted with a graft copolymer having an isocyanate group to add a polymerizable group.

[0456] The polymer chain having the structural unit represented by the general formula (IV) preferably has the structural units derived from methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentyl (meth)acrylate, adamantyl (meth)acrylate, styrene, α-methylstyrene, vinylcyclohexane, etc. in the above structural units. However, it is not limited to these.

[0457] In an embodiment of the present invention, as the above-mentioned R 33 and R 37 , preferably those having excellent solubility in organic solvents are used, and they can be appropriately selected according to the organic solvents used in the colorant dispersion liquid. Specifically, for example, when using organic solvents such as ether alcohol acetate-based, ether-based, and ester-based organic solvents commonly used as organic solvents in the colorant dispersion liquid, methyl, ethyl, isobutyl, n-butyl, 2-ethylhexyl, 2-ethoxyethyl, cyclohexyl, benzyl, etc. are preferred.

[0458] Here, the reason for setting the above-mentioned R 33 and R 37 is that the above-mentioned R 33 and R 37The structural unit is soluble in the above-mentioned organic solvent, and the acidic phosphorus compound group of the above monomer and the part of its salt have a high adsorption property with respect to particles such as coloring materials. Thus, the dispersibility and stability of particles such as coloring materials can be made particularly excellent.

[0459] The weight-average molecular weight of the polymer chain in the Polymer is preferably in the range of 500 or more and 15000 or less, more preferably in the range of 1000 or more and 8000 or less. By being in the above range, a sufficient steric repulsion effect as a dispersant can be maintained, and the time required for dispersing particles such as coloring materials due to the steric effect can also be suppressed.

[0460] In addition, regarding the polymer chain in the Polymer, its standard is preferably: the solubility at 23 °C is 50 (g / 100 g solvent) or more with respect to the organic solvent used in combination.

[0461] The above polymer chain can be a homopolymer or a copolymer. In addition, the polymer chains contained in the structural unit represented by the general formula (II) can be a single type or a mixture of two or more in the graft copolymer.

[0462] With respect to all the structural units of the above graft copolymer, it is preferably contained in a proportion of 3% by mass or more and 80% by mass or less in total, more preferably 10% by mass or more and 70% by mass or less, and still more preferably 20% by mass or more and 60% by mass or less. If the total content of the structural unit represented by the general formula (I) in the graft copolymer is within the above range, the proportion of the affinity part with the particles in the graft copolymer becomes appropriate, and the decrease in solubility in the organic solvent can be suppressed. Therefore, the adsorption property with respect to particles such as coloring materials becomes good, and excellent dispersibility and dispersion stability can be obtained. In addition, the acidic phosphorus compound group of the above graft copolymer can stably exist locally around the coloring material, so a color filter with excellent heat resistance and contrast can be obtained.

[0463] On the other hand, with respect to all the structural units of the above graft copolymer, it is preferably contained in a proportion of 20% by mass or more and 97% by mass or less, more preferably 25% by mass or more and 95% by mass or less, and still more preferably 40% by mass or more and 90% by mass or less.

[0464] It should be noted that in the present invention, the content ratio of each structural unit in the copolymer can be calculated from the addition amount during the synthesis of the copolymer.

[0465] In addition, the weight-average molecular weight of the above 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 still more preferably in the range of 5,000 or more and 300,000 or less. By being in the above range, particles such as color materials can be uniformly dispersed.

[0466] The above graft copolymer used in the embodiments of the present invention may further have other structural units in addition to the structural units represented by the above general formula (I) and the structural units represented by the above general formula (II). For example, an ethylenically unsaturated monomer capable of copolymerizing with an ethylenically unsaturated monomer such as the one that gives rise to the structural unit represented by the above general formula (I) can be appropriately selected for copolymerization to introduce other structural units.

[0467] (Block copolymer)

[0468] Regarding the block copolymer preferably used as an acidic dispersant, for example, a block copolymer having a block portion containing the structural unit represented by the above general formula (I) and a block portion containing the structural unit represented by the above general formula (III) can be cited.

[0469] In this block copolymer, in the block portion containing the structural unit represented by the above general formula (I), it is preferred that a total of 3 or more of the structural units represented by the above general formula (I) are contained. Among them, from the viewpoint of improving dispersibility and heat resistance, it is preferably 3 or more and 200 or less, more preferably 3 or more and 50 or less, and still more preferably 3 or more and 30 or less.

[0470] The structural unit represented by the above general formula (I) only needs to function as a color material affinity site, and may contain one structural unit or two or more structural units. In the case of containing two or more structural units, in the block portion containing the structural unit represented by the above general formula (I), the two or more structural units may be randomly arranged.

[0471] In the above block copolymer, the total content ratio of the structural units represented by the above general formula (I) is preferably 5% by mass or more and 80% by mass or less, more preferably 10% by mass or more and 70% by mass or less, and still more preferably 20% by mass or more and 60% by mass or less, based on all the structural units of the above block copolymer.

[0472] If it is within the above range, the proportion of the affinity sites for the particles in the block copolymer becomes appropriate, and a decrease in solubility in the organic solvent can be suppressed. Therefore, the adsorptivity for particles such as coloring materials becomes good, and excellent dispersibility and dispersion stability can be obtained. In addition, the acidic phosphorus compound groups of the above block copolymer can stably exist locally around the coloring material, so a color filter with excellent heat resistance and contrast can be obtained.

[0473] The above block copolymer has a block portion containing a structural unit represented by the above general formula (III), whereby the solvent affinity becomes good, the dispersibility and dispersion stability of the coloring material are good, and the heat resistance is also good. Furthermore, the resistance to N-methylpyrrolidone (NMP) (NMP resistance) is excellent.

[0474] 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″ represents a monovalent group.

[0475] As the hydrocarbon group in R 27 , those the same as the hydrocarbon groups shown in the above R 12 can be selected.

[0476] In addition, the above R 30 is a hydrogen atom, a hydrocarbon group, -CHO, -CH 2 CHO or -CH 2 COOR 31 represents a monovalent group, R 30′ is a hydrocarbon group, -[CH(R 28 )-CH(R 29 )-O] x2′ - R30 , -[(CH 2 ) y2′ -O] z2′ -R 30 , -[CO-(CH 2 ) y2′ -O] z2′ -R 30 represents a monovalent group, R30″ is an alkyl group having 1 or more and 18 or less carbon atoms, R 31 is a hydrogen atom or an alkyl group having 1 or more and 5 or less carbon atoms, and the above hydrocarbon group may have a substituent.

[0477] The above R 30 The hydrocarbon group in can be selected from those same as the hydrocarbon group shown in the above R 12 above.

[0478] In the above R 27 and R 30′ above, x2 and x2′ are the same as the above x, y2 and y2′ are the same as the above y, and z2 and z2′ are the same as the above z.

[0479] In addition, the Rs in the structural unit represented by the above general formula (III) 27 may be the same as or different from each other.

[0480] As the above R 27 and R 30′ above, those having excellent solubility in an organic solvent are preferably used, and examples thereof include those same as the above R 33 and R 37 above.

[0481] In addition, the Rs in the above general formula (IV) 27 , R 30 , R 30′ , R 30″ and R 31 above may be substituted with substituents such as an alkoxy group, a hydroxyl group, a carboxyl group, an amino group, an epoxy group, an isocyanate group, a hydrogen bond-forming group, etc. within a range that does not hinder the dispersion performance, etc. of the above block copolymer. In addition, after synthesizing the above block copolymer, it may be reacted with a compound having the above substituent to add the above substituent. Alternatively, after synthesizing a block copolymer having these substituents, a compound having a functional group reactive with the substituent and a polymerizable group may be reacted to add a polymerizable group. For example, (meth)acrylic acid may be reacted with a block copolymer having a glycidyl group, or 2-hydroxyethyl (meth)acrylate may be reacted with a block copolymer having an isocyanate group to add a polymerizable group.

[0482] The number of structural units constituting the block portion containing the structural unit represented by the general formula (III) is not particularly limited, but from the viewpoint of effectively functioning the solvent affinity portion and the colorant affinity portion and improving the dispersibility of the colorant dispersion liquid, the number of the above structural units is preferably 10 or more and 200 or less, more preferably 20 or more and 100 or less, and still more preferably 30 or more and 80 or less.

[0483] In the above block copolymer, the content ratio of the structural unit represented by the general formula (III) is preferably 30% by mass or more and 95% by mass or less, more preferably 40% by mass or more and 90% by mass or less, relative to all the structural units of the above block copolymer.

[0484] The block portion containing the structural unit represented by the general formula (III) may be selected as long as it functions as a solvent affinity site. The structural unit represented by the general formula (III) may include one structural unit or two or more structural units. In an embodiment of the present invention, when the structural unit represented by the general formula (III) includes two or more structural units, the two or more structural units may be randomly arranged within the block portion containing the structural unit represented by the general formula (III).

[0485] In the block copolymer used as a dispersant, the ratio m / n of the number of units m of the structural unit of the block portion containing the structural unit represented by the general formula (I) to the number of units n of the structural unit of the block portion containing the structural unit represented by the general formula (III) is preferably in the range of 0.01 or more and 1 or less, and more preferably in the range of 0.1 or more and 0.7 or less, from the viewpoints of the dispersibility and dispersion stability of the colorant.

[0486] As the bonding order of the above block copolymer, as long as it has 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) and can stably disperse the colorant, there is no particular limitation. However, from the viewpoint of excellent interaction with the colorant and effective suppression of the aggregation of the dispersants, it is preferred that the block portion containing the structural unit represented by the general formula (I) is bonded only to one end of the above block copolymer.

[0487] The weight average molecular weight of the above block copolymer is not particularly limited, but from the viewpoints of good dispersibility and excellent heat resistance, it is preferably 2500 or more and 500000 or less, more preferably 3000 or more and 400000 or less, and still more preferably 6000 or more and 300000 or less.

[0488] Regarding the acid value of the polymer having the structural unit represented by the general formula (I), from the viewpoints of the dispersibility and storage stability of the above colorant, it is preferably 20 mgKOH / g or more, more preferably 30 mgKOH / g or more, and still 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, more preferably 120 mgKOH / g or less, and still more preferably 100 mgKOH / g or less.

[0489] It should be noted that in the present invention, the acid value refers to the number of milligrams of potassium hydroxide required to neutralize the acid components contained in 1 g of the sample, and can be measured in accordance with JIS K 0070:1992.

[0490] <Other acidic dispersants>

[0491] In the colorant dispersion of the present invention, other acidic dispersants different from the polymer having the structural unit represented by the above general formula (I) may be further contained.

[0492] As the other acidic dispersants, dispersants having acidic groups can be cited. Here, as the acidic groups, for example, carboxyl group, sulfo group, or phosphoric acid group, etc. can be cited. However, among the acidic groups contained in the dispersants as the other acidic dispersants, from the viewpoint of excellent dispersibility, the carboxyl group is preferred.

[0493] From the viewpoint of excellent dispersibility, the acid value of the other acidic dispersant is preferably in the range of 30 mgKOH / g or more and 250 mgKOH / g or less, among which, it is preferably 40 mgKOH / g or more, more preferably 50 mgKOH / g or more, and further preferably 70 mgKOH / g or more. On the other hand, from the viewpoint of suppressing development residues, the acid value of the other acidic dispersant is preferably 200 mgKOH / g or less, more preferably 190 mgKOH / g or less, and further preferably 180 mgKOH / g or less.

[0494] In the present invention, as the other acidic dispersant, from the viewpoint of improving the suppression of development residues by using it in combination with the polymer having the structural unit represented by the above general formula (I), a polymer dispersant having a carboxyl group is preferred; among which, from the viewpoint of improving the suppression of development residues by using it in combination with the polymer having the structural unit represented by the above general formula (I) and making the uniformity of the coating film better, a block copolymer containing the following A block and the following B block is preferred: The A block contains a structural unit derived from an ethylenically unsaturated monomer containing a carboxyl group, and the B block contains a structural unit derived from an alkyl (meth)acrylate.

[0495] Hereinafter, the block copolymer containing the following A block and the following B block may sometimes be simply referred to as "carboxyl group-containing block copolymer": The A block contains a structural unit derived from an ethylenically unsaturated monomer containing a carboxyl group, and the B block contains a structural unit derived from an alkyl (meth)acrylate. This carboxyl group-containing block copolymer is, for example, suitably used as a dispersant for metal lake colorants and pigments of xanthene dyes.

[0496] (Carboxyl group-containing block copolymer)

[0497] {A block}

[0498] In the carboxyl group-containing block copolymer, the A block is a polymer block containing a structural unit derived from a carboxyl group-containing ethylenically unsaturated monomer.

[0499] Examples of the carboxyl group-containing ethylenically unsaturated monomer used in the A block include those the same as the carboxyl group-containing ethylenically unsaturated monomers used in the copolymer containing a (meth)acrylic acid hydroxyalkyl ester unit.

[0500] When two or more structural units are included in the A block, each structural unit in the A block can be included in any manner such as random copolymerization or block copolymerization. From the viewpoint of uniformity, it is preferable to include each structural unit in the A block by random copolymerization.

[0501] In the A block, the structural unit derived from the carboxyl group-containing ethylenically unsaturated monomer is preferably 40% by mass or more, more preferably 70% by mass or more, and still more preferably a polymer block composed only of the structural unit derived from the carboxyl group-containing ethylenically unsaturated monomer, relative to all the structural units of the A block.

[0502] The A block may be composed only of the structural unit derived from the carboxyl group-containing ethylenically unsaturated monomer, or may include a structural unit derived from an ethylenically unsaturated monomer different from the carboxyl group-containing ethylenically unsaturated monomer within the range where the acidity of the A block is stronger than that of the B block. When the A block includes a structural unit derived from an ethylenically unsaturated monomer different from the carboxyl group-containing ethylenically unsaturated monomer, it is preferably 60% by mass or less, more preferably 30% by mass or less, relative to all the structural units of the A block. Examples of the ethylenically unsaturated monomer different from the above carboxyl group-containing ethylenically unsaturated monomer include the structural units used in the following B block.

[0503] From the viewpoints of dispersibility and dispersion stability, the content of the A block is preferably 5% by mass or more, more preferably 10% by mass or more, and on the other hand, preferably 95% by mass or less, more preferably 40% by mass or less, relative to all the structural units of the block copolymer.

[0504] {B block}

[0505] In the carboxyl group-containing block copolymer, the B block is a polymer block containing a structural unit derived from an alkyl (meth)acrylate.

[0506] As the alkyl (meth)acrylate monomer used in the B block, it may be the same as the alkyl (meth)acrylate monomer used in the polymer chain having the structural unit represented by the above general formula (IV), and one kind or a mixture of two or more kinds may be used.

[0507] In the B block, in addition to the structural units derived from (meth)acrylic acid alkyl esters, structural units derived from other ethylenically unsaturated monomers may also be included. As the structural units derived from other ethylenically unsaturated monomers, structural units different from the structural units derived from (meth)acrylic acid alkyl esters in the structural units represented by the above general formula (III) can be cited.

[0508] When two or more types of structural units are included in the B block, each structural unit within the B block can be contained in any manner such as random copolymerization or block copolymerization. From the viewpoint of uniformity, it is preferably contained in the B block in a random copolymerization manner.

[0509] Relative to all the structural units of the B block, the structural units of the B block derived from ethylenically unsaturated monomers having an acidic group are preferably 10% by mass or less, more preferably 5% by mass or less, and still more preferably 2% by mass or less. In the present invention, the B block is still more preferably a polymer block that does not contain structural units derived from ethylenically unsaturated monomers having an acidic group.

[0510] The above carboxyl-containing block copolymer can be an AB block copolymer or a BAB block copolymer. Regarding the content ratio of the two B blocks when the block copolymer is a BAB block copolymer, from the viewpoint of dispersibility, it is preferably adjusted within the range of 50:50 to 70:30 by mass ratio.

[0511] From the viewpoint of dispersibility, the acid value of the above carboxyl-containing block copolymer is preferably in the range of 30 mgKOH / g or more and 250 mgKOH / g or less. It is preferable to include structural units derived from carboxyl-containing ethylenically unsaturated monomers in the A block so that the acid value of the block copolymer falls within this range. The acid value is preferably 50 mgKOH / g or more, more preferably 70 mgKOH / g or more. The acid value is preferably 200 mgKOH / g or less, more preferably 150 mgKOH / g or less.

[0512] From the viewpoint of dispersibility, the weight average molecular weight of the above carboxyl-containing block copolymer is preferably 5,000 or more and 100,000 or less. The weight average molecular weight of the above carboxyl-containing block copolymer is more preferably 8,000 or more, still more preferably 10,000 or more. On the other hand, it is more preferably 80,000 or less, still more preferably 70,000 or less.

[0513] The molecular weight distribution of the above carboxyl group-containing block copolymer is preferably less than 2, more preferably less than 1.5, and further preferably less than 1.3. It should be noted that in the present invention, the molecular weight distribution refers to the value obtained according to "(weight average molecular weight (Mw)) / (number average molecular weight (Mn))". The larger the molecular weight distribution, the more polymers with molecular weights smaller and larger than the designed polymer molecular weight will be included, resulting in a tendency to deteriorate the dispersibility of the colorant. Therefore, a smaller molecular weight distribution is preferred.

[0514] As a method for producing the above carboxyl group-containing block copolymer, a conventionally well-known method for producing a block copolymer can be appropriately selected and used. From the viewpoint of easily producing a polymer with a uniform composition, a living polymerization method is preferably used. Examples of the living polymerization method include: a method using an organic acid catalyst and a silyl-based initiator (GTP method), 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.

[0515] In the colorant dispersion, the content of the dispersant can be appropriately adjusted. However, from the viewpoints of dispersibility and storage stability, it is preferably 5 parts by mass or more and 80 parts by mass or less, more preferably 20 parts by mass or more and 70 parts by mass or less, based on 100 parts by mass of the colorant.

[0516] [Other components]

[0517] In the colorant dispersion, as long as the effects of the present invention are not impaired, a dispersion auxiliary resin and other components can be further formulated as needed.

[0518] Examples of the dispersion auxiliary resin include an alkali-soluble resin. Since the colorant particles are less likely to come into contact with each other due to the steric hindrance of the alkali-soluble resin, it is sometimes possible to obtain the effect of stabilizing the dispersion of the colorant or reducing the amount of the dispersant through this dispersion stabilizing effect.

[0519] In addition, examples of other components include: a surfactant for improving wettability, a silane coupling agent for improving adhesion, an antifoaming agent, an anti-cratering agent, an anticoagulant, an ultraviolet absorber, and the like.

[0520] [Solvent]

[0521] As the solvent contained in the colorant dispersion, the same solvent as that contained in the above photosensitive coloring resin composition of the present invention can be used.

[0522] The amount of the solvent is generally preferably in the range of 55% by mass or more and 95% by mass or less, more preferably in the range of 65% by mass or more and 90% by mass or less, and still more preferably in the range of 70% by mass or more and 88% by mass or less, relative to the total amount of the colorant dispersion. If the amount of the solvent is too small, the viscosity increases and the dispersibility is likely to decrease. In addition, if the amount of the solvent is too large, the colorant concentration decreases and it may be difficult to achieve the target chromaticity coordinates.

[0523] [Method for producing colorant dispersion]

[0524] The method for producing the colorant dispersion is not particularly limited as long as it can obtain a colorant dispersion obtained by dispersing a colorant in a solvent using a dispersant. For example, the following production method can be applied, which includes: a step of preparing a colorant; a step of preparing a dispersant; and a step of dispersing the colorant in the solvent in the presence of the dispersant. In the solvent, in the presence of a dispersant, two or more colorants can be co-dispersed, or one or more colorants can be dispersed or co-dispersed and then two or more colorant dispersions can be mixed.

[0525] When dispersing the colorant, a conventionally well-known disperser can be used. Specific examples of the disperser include: roll mills such as two-roll grinders and three-roll grinders, ball mills such as ball mills and vibration ball mills, paint conditioners, bead mills such as continuous disk bead mills and continuous annular bead mills. As the preferred dispersion conditions of the bead mill, the diameter of the beads used is preferably 0.03 mm or more and 3.0 mm or less, more preferably 0.05 mm or more and 2.0 mm or less.

[0526] III. Cured product of photosensitive colored resin composition

[0527] The photosensitive colored resin composition of the present invention contains a monomer as a photopolymerizable compound as a photocurable component. Therefore, by subjecting the photosensitive colored resin composition of the present invention to a photopolymerization reaction, the cured product of the present invention can be obtained. For example, a coating film of the photosensitive colored resin composition of the present invention is formed, dried, exposed, and developed as needed, whereby the cured product of the present invention can be obtained. As the methods for forming the coating film, exposure, and development, for example, the same methods as those used for forming the colored layer provided in the following color filter of the present invention can be adopted.

[0528] In a preferred embodiment of the photosensitive colored resin composition of the present invention, a binder resin such as a copolymer containing a (meth)acrylic acid hydroxyalkyl ester unit also has a polymerizable functional group. The cured product of the photosensitive colored resin composition of the present invention in such a preferred embodiment is a cured product obtained by dissolving or dispersing a coloring material containing at least one selected from dyes and lake pigments in the following matrix, and the matrix is formed by a photopolymerization reaction of a binder resin containing a copolymer containing a (meth)acrylic acid hydroxyalkyl ester unit and a monomer.

[0529] The cured product of the present invention is obtained by dissolving or dispersing a coloring material containing at least one selected from dyes and lake pigments in a matrix containing the following binder resin, and the binder resin contains a copolymer containing a (meth)acrylic acid hydroxyalkyl ester unit. Therefore, the cured product of the present invention has high brightness, excellent flatness, and the generation of development residues is suppressed in the case of development, and is suitably used as a colored layer of a color filter.

[0530] IV. Color Filter

[0531] The color filter of 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 of the present invention.

[0532] At least one of the above-mentioned colored layers of the color filter of the present invention is formed of a cured product obtained by dissolving or dispersing a coloring material containing at least one selected from dyes and lake pigments in a matrix containing the following binder resin, and the binder resin contains a copolymer containing a (meth)acrylic acid hydroxyalkyl ester unit. Therefore, the color filter of the present invention has a colored layer with high brightness, excellent flatness, and suppression of the generation of development residues.

[0533] Figure 1 Schematic cross-sectional view showing an example of the color filter of the present invention. Figure 1 The color filter 10 of the present invention shown 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.

[0534] In the color filter of the present invention, the colored layer is usually formed in the opening portion of the light-shielding portion on the following transparent substrate and includes three or more colored patterns. In Figure 3 In the example, a red colored layer 3R, a green colored layer 3G, and a blue colored layer 3B are formed and arranged in a predetermined order. The colored layers of each color are formed in the order of the red colored layer 3R, the green colored layer 3G, and the blue colored layer 3B.

[0535] The arrangement of the coloring layer is not particularly limited. For example, it can be set to a general arrangement such as a stripe type, a mosaic type, a triangle type, a 4-pixel configuration type, etc. In addition, the width, area, etc. of the coloring layer can be arbitrarily set.

[0536] The thickness of the coloring layer is appropriately controlled by adjusting the coating method, the solid content concentration and viscosity of the coloring resin composition, etc., and is usually preferably in the range of 1 μm or more and 5 μm or less.

[0537] The coloring layers of each color can be formed in the order described below. First, using a coating method such as a spraying method, a dipping coating method, a bar coating method, a roll coating method, a spin coating method, etc., a photosensitive coloring resin composition is coated on a transparent substrate on which a light-shielding portion has been previously formed to form a wet film.

[0538] Next, after drying the wet film using a hot plate or an oven, etc., it is exposed through a photomask having a specified pattern, and a photopolymerization reaction occurs in the binder resin and monomers, etc. to form a photosensitive film. As the light source used during exposure, for example, ultraviolet rays such as a low-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, etc., an electron beam, etc. can be cited. The exposure amount can be appropriately adjusted according to the light source used or the thickness of the film, etc.

[0539] In addition, a heat treatment can also be performed after exposure to promote the polymerization reaction. The heating conditions can be appropriately selected according to the blending ratio of each component in the coloring resin composition used, the thickness of the film, etc.

[0540] Next, a development treatment is performed using a developer to dissolve and remove the unexposed portion, thereby forming a film in a desired pattern. As the developer, a solution obtained by dissolving an alkali in water or a water-soluble solvent is usually used. In this alkaline solution, a surfactant, etc. can be added in an appropriate amount. In addition, the development method can adopt a general method.

[0541] After the development treatment, the developer is usually washed and the cured film of the coloring resin composition is dried to form a coloring layer. It should be noted that a heat treatment can also be performed after the development treatment to fully cure the film. As the heating conditions, there is no particular limitation and can be appropriately selected according to the use of the film.

[0542] [Light-shielding portion]

[0543] The light-shielding portion in the color filter of the present invention is formed in a pattern shape on the substrate and can be the same as those used as the light-shielding portion in a general color filter.

[0544] The pattern shape of the light-shielding portion is not particularly limited, and examples thereof include stripe shapes, matrix shapes, etc. The light-shielding portion may be a metal thin film such as chromium formed by sputtering, vacuum evaporation, or the like. Alternatively, the light-shielding portion may also be a resin layer containing light-shielding particles such as carbon fine particles, metal oxides, inorganic pigments, and organic pigments in a resin binder. If the resin layer contains light-shielding particles, there are the following methods: a method of patterning using a photosensitive resist by development, a method of patterning using an inkjet ink containing light-shielding particles, a method of thermal transfer of a photosensitive resist, etc.

[0545] Regarding the film thickness of the light-shielding portion, in the case of a metal thin film, it can be set to about 0.2 μm or more and 0.4 μm or less, and in the case of dispersing or dissolving a black pigment in a binder resin, it can be set to about 0.5 μm or more and 2 μm or less.

[0546] [Transparent substrate]

[0547] As the transparent substrate, any substrate that is transparent to visible light can be used, and there is no particular limitation. Transparent substrates used in general color filters can be used. Specifically, examples include transparent rigid materials without flexibility such as quartz glass, alkali-free glass, and synthetic quartz plates, or transparent flexible materials with flexibility or flexibility such as transparent resin films, optical resin plates, and flexible glass. Such transparent substrates for color filters usually have polar groups on their surfaces.

[0548] From the viewpoint of improving the substrate adhesion of the photosensitive colored resin composition of the present invention, as the transparent substrate, substrates containing silica such as quartz glass, alkali-free glass, and synthetic quartz plates are preferred.

[0549] The thickness of the transparent substrate is not particularly limited, and a transparent substrate of, for example, 50 μm or more and 1 mm or less can be used according to the use of the color filter.

[0550] It should be noted that the color filter of the present invention may also be formed with, for example, an overcoat layer or a transparent electrode layer, an alignment film for aligning liquid crystal materials, or columnar spacers in addition to the above-mentioned transparent substrate, light-shielding portion, and colored layer. The color filter of the present invention is not limited to the above-described configuration, and a known configuration generally used for color filters can be appropriately selected and used.

[0551] V. Display device

[0552] The display device of the present invention is characterized by having the color filter of the present invention. In the present invention, the configuration of the display device is not particularly limited, and it can be appropriately selected from conventionally known display devices. Examples include liquid crystal display devices, organic light-emitting display devices, etc.

[0553] [Liquid crystal display device]

[0554] The liquid crystal display device of the present invention is characterized by having the color filter of the present invention described above, a counter substrate, and a liquid crystal layer formed between the color filter and the counter substrate.

[0555] Figure 2 A schematic diagram showing an example of the liquid crystal display device to which the display device of the present invention belongs. As Figure 2 shown, the liquid crystal display device 40 of the present invention has a color filter 10, a counter substrate 20 having a TFT (thin-film transistor) array substrate, etc., and a liquid crystal layer 30 formed between the color filter 10 and the counter substrate 20.

[0556] It should be noted that the liquid crystal display device of the present invention is not limited to the Figure 2 configuration shown, and can be set to a known configuration of a liquid crystal display device generally using a color filter.

[0557] As the driving method of the liquid crystal display device of the present invention, there is no particular limitation, and a driving method generally used for liquid crystal display devices can be adopted. As such a driving method, for example, TN (Twisted Nematic) method, IPS (In Plane Switching) method, OCB (Optically Compensated Bend) method, and MVA (Multi-domain Vertal Alignment) method, etc. can be cited. In the present invention, any of these methods can be preferably used.

[0558] In addition, as the counter substrate, it can be appropriately selected and used according to the driving method, etc. of the liquid crystal display device of the present invention.

[0559] As a method for forming the liquid crystal layer, a method generally used as a method for manufacturing a liquid crystal cell can be used, and for example, a vacuum injection method, a liquid crystal dropping method, etc. can be cited.

[0560] [Organic light-emitting display device]

[0561] The organic light-emitting display device of the present invention is characterized by having the color filter of the present invention described above and an organic light-emitting body.

[0562] Figure 3 A schematic diagram showing an example of the organic light-emitting display device to which the display device of the present invention belongs. As Figure 3As shown, 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 and an inorganic oxide film 60 may be provided between the color filter 10 and the organic light-emitting body 80.

[0563] As a method of laminating the organic light-emitting body 80, for example, the following methods can be cited: a method of sequentially forming a transparent anode 71, a hole injection layer 72, a hole transport layer 73, a light-emitting layer 74, an electron injection layer 75, and a cathode 76 on the upper surface of the color filter, a method of attaching the organic light-emitting body 80 formed on another substrate to the inorganic oxide film 60, etc. For the transparent anode 71, hole injection layer 72, hole transport layer 73, light-emitting layer 74, electron injection layer 75, cathode 76, and other components in the organic light-emitting body 80, those well-known ones can be appropriately used. The thus-prepared organic light-emitting display device 100 can be applied, for example, to both a passive driving type organic EL display and an active driving type organic EL display.

[0564] It should be noted that the organic light-emitting display device of the present invention is not limited to the Figure 3 shown configuration, and can be set to a well-known configuration of an organic light-emitting display device generally using a color filter.

[0565] Examples

[0566] Hereinafter, examples are shown to specifically describe the present invention. The present invention is not limited by these descriptions.

[0567] The weight-average molecular weight (Mw) is determined by the above-described measurement method of the present invention in the form of a standard polystyrene conversion value by GPC (gel permeation chromatography).

[0568] The acid value and hydroxyl value are determined by the method based on JIS K 0070:1992.

[0569] The viscosity of the adhesive resin produced in each production example is determined as follows: The obtained adhesive 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 until the solid content concentration reaches 60% by mass, and then heated in a hot water bath at 90°C in a circulating manner, and the above viscosity is determined using a B-type viscometer.

[0570] (Synthesis Example 1: Synthesis of Lake Colorant 1)

[0571] (1) Synthesis of Intermediate 1

[0572] Referring to the production methods of Intermediate A-2, Intermediate B-1, and Compound 1-3 described in Japanese Patent Application Laid-Open No. 2018-3013, Intermediate 1 represented by the following chemical formula (a) was obtained (yield: 87%).

[0573] Based on the following analysis results, it was confirmed that the obtained compound is the target compound.

[0574] · MS(ESI)(m / z): 677(+), divalent

[0575] · Elemental analysis values: CHN measured values (81.81%, 7.31%, 5.85%); theoretical values (81.77%, 7.36%, 5.90%)

[0576] [Chemical formula 17]

[0577] Chemical formula (a)

[0578]

[0579] (2) Synthesis of Lake Colorant 1

[0580] 2.59 g (0.76 mmol) of dodecatungstophosphoric acid - n - hydrate manufactured by Kanto Chemical Co., Inc. was heated and dissolved in a mixed solution of 40 mL of methanol and 40 mL of water, 1.6 g (1.19 mmol) of the above Intermediate 1 was added, and the mixture was stirred for 1 hour. The precipitate was filtered out and washed with water. The obtained precipitate was dried under reduced pressure to obtain Lake Colorant 1 represented by the following chemical formula (b) (yield 95%).

[0581] Based on the following analysis results, it was confirmed that the obtained compound is the target compound.

[0582] · 31P NMR (d - dmso, ppm) δ - 15.15

[0583] · MS(MALDI)(m / z): 1355(M + )、2879(MH 2 - )

[0584] · Elemental analysis values: CHN measured values (35.55%, 3.24%, 2.61%); theoretical values (35.61%, 3.20%, 2.57%)

[0585] · Fluorescent X - ray analysis: MoW actual measurement ratio (0%, 100%); theoretical value (0%, 100%)

[0586] [Chemical formula 18]

[0587] Chemical formula (b)

[0588]

[0589] (Synthesis Example 2: Synthesis of Xanthene - based Dye 1)

[0590] Add 40.2 parts by mass of the sulfonated fluorane compound represented by the following chemical formula (c), 312 parts by mass of methanol, 6.8 parts by mass of 2,6-dimethylaniline, and 6.0 parts by mass of N-methyl-o-toluidine to a 500 ml four-necked flask, and reflux for 30 hours. After filtering the reaction solution at 60 °C to remove insoluble components, remove the solvent under reduced pressure until the reaction solution becomes about 70 ml, and pour it into 200 parts by mass of 6% hydrochloric acid. Then, add 600 parts by mass of water and stir at room temperature for 30 minutes, and then filter to obtain a wet filter cake. Suspend the wet filter cake in 100 parts by mass of water, stir at 60 °C for 2 hours, filter again, wash with hot water at 60 °C, and then dry it to obtain 27.4 parts by mass of the xanthene dye 1 represented by the following chemical formula.

[0591] [Chemical formula 19]

[0592] Chemical formula (c)

[0593]

[0594] [Chemical formula 20]

[0595] Xanthene dye 1

[0596]

[0597] (Synthesis example 3: Synthesis of xanthene dye 2)

[0598] Add 18.0 parts by mass of the sulfonated fluorane compound represented by the above chemical formula (c), 312 parts by mass of methanol, 5.4 parts by mass of 2,6-dimethylaniline, and 4.8 parts by mass of o-toluidine to a 500 ml four-necked flask, and reflux for 30 hours. After filtering the reaction solution at 60 °C to remove insoluble components, remove the solvent under reduced pressure until the reaction solution becomes about 70 ml, and pour it into 200 parts by mass of 6% hydrochloric acid. Then, add 600 parts by mass of water and stir at room temperature for 30 minutes, and then filter to obtain a wet filter cake. Suspend the wet filter cake in 100 parts by mass of water, stir at 60 °C for 2 hours, filter again, wash with hot water at 60 °C, and then dry it to obtain 21.9 parts by mass of the intermediate I-1 represented by the following chemical formula.

[0599] [Chemical formula 21]

[0600] Intermediate I-1

[0601]

[0602] Next, a mixture of 120 parts by mass of the above intermediate I-120, 135.3 parts by mass of 1-methyl-2-pyrrolidone, 7.8 parts by mass of potassium carbonate, and 16.2 parts by mass of methyl iodide was stirred at 80 °C for 2 hours. After the reaction was completed, the reaction solution was cooled 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 filtered out, and the residue was dried at 60 °C for 24 hours to obtain 20.4 parts by mass of crystals.

[0603] 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 cooled to room temperature, and the reaction solution was added dropwise to 1500 parts by mass of ice water and stirred for 30 minutes. The obtained crystals were separated by filtration, washed with 200 parts by mass of water, and dried for 10 hours. 7 parts by mass of the crystals 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 for washing, and then the organic layer was separated. The organic layer was dried with sodium sulfate for purification, and concentrated under reduced pressure to obtain 6.8 parts by mass of the xanthene-based dye 2 represented by the following chemical formula (yield 80%).

[0604] [Chemical formula 22]

[0605] Xanthene-based dye 2

[0606]

[0607] (Synthesis Example 4: Synthesis of xanthene-based metal lake pigment 3)

[0608] 5.0 parts by mass of Acid Red 289 was added to 500 ml of water and dissolved at 80 °C to prepare a dye solution. Poly aluminum chloride (“trade name: Takibaine #1500”, manufactured by Taki Chemical Co., Ltd., Al 2 (OH) 5 Cl, alkalinity 83.5% by mass, 23.5% by mass based on the amount of alumina) 3.85 parts by mass was added to 200 ml of water and stirred at 80 °C to prepare an aqueous poly aluminum chloride solution. The prepared aqueous poly aluminum chloride solution was added dropwise to the above dye solution over 15 minutes at 80 °C, and further stirred at 80 °C for 1 hour. The formed precipitate was filtered out and washed with water. The obtained filter cake was dried to obtain 6.30 parts by mass of xanthene-based metal lake pigment 3 as a xanthene-based dye (yield 96.2%).

[0609] (Synthesis Example 5: Synthesis of Basic Treatment PB15:6)

[0610] Add 300 parts by mass of chlorosulfonic acid and 30 parts by mass of copper phthalocyanine to a reaction vessel. After complete dissolution, add 24 parts by mass of thionyl chloride, slowly raise the temperature, and react at 101 °C for 3 hours. Inject the reaction solution into 9000 parts by mass of ice water, stir, filter, and wash with water. After making a slurry of the obtained filter cake with 300 parts by mass of water, add 13 parts by mass of 1,1 - diethyl - 1,5 - diazapentane, stir at 65 °C for 4 hours, then filter, wash with water, and dry to obtain a blue colorant derivative 1 with a basic site for surface treatment. Regarding the obtained blue colorant derivative 1 with a basic site, it was confirmed to have the structure of the following chemical formula (d).

[0611] ·TOF - MS: 768.35

[0612] [Chemical formula 23]

[0613] Chemical formula (d)

[0614]

[0615] Dry - grind 100 parts by mass of commercially available C.I. Pigment Blue 15:6 (ε - type copper phthalocyanine pigment, manufactured by DIC Corporation, FASTOGENBLUE A510) and 5 parts by mass of the above - mentioned blue colorant derivative 1 with a basic site at 60 °C for 1.5 hours. Further mix 5 parts by mass of the above - mentioned blue colorant derivative 1 with a basic site with the ground product to obtain C.I. Pigment Blue 15:6 after alkaline treatment, i.e., alkaline - treated PB15:6.

[0616] (Synthesis Example 6: Synthesis of Acidic Dispersant A1 (Polymer Having a Structural Unit Represented by the Above - Mentioned General Formula (I)))

[0617] (1) Synthesis of Macromonomer MM - 1

[0618] 80.0 parts by mass of propylene glycol monomethyl ether acetate (hereinafter referred to as PGMEA) was added to a reactor equipped with a condenser, a dropping funnel, a nitrogen inlet, a mechanical stirrer, and a digital thermometer, and the mixture was heated to 90 °C while stirring under a nitrogen stream. A mixed solution of 50.0 parts by mass of methyl methacrylate, 30.0 parts by mass of n-butyl methacrylate, 20.0 parts by mass of benzyl methacrylate, 4.0 parts by mass of 2-mercaptoethanol, 30 parts by mass of PGMEA, and 1.0 part by mass of α,α'-azobisisobutyronitrile (hereinafter referred to as AIBN) was added dropwise over 1.5 hours, and the reaction was further continued for 3 hours. Then, the nitrogen stream was stopped, the reaction solution was cooled to 80 °C, 8.74 parts by mass of Karenz MOI (manufactured by Showa Denko K.K.), 0.125 part by mass of dibutyltin dilaurate, 0.125 part by mass of p-methoxyphenol, and 10 parts by mass of PGMEA were added, and the mixture was stirred for 3 hours to obtain a 49.5% by mass solution of the macromonomer MM-1. The results of GPC measurement of the obtained macromonomer MM-1 were a weight-average molecular weight (Mw) of 4010, a number-average molecular weight (Mn) of 1910, and a molecular weight distribution (Mw / Mn) of 2.10.

[0619] (2) Synthesis of graft copolymer A1

[0620] 85.0 parts by mass of PGMEA was added to a reactor equipped with a condenser, a dropping funnel, a nitrogen inlet, a mechanical stirrer, and a digital thermometer, and the mixture was heated to 90 °C while stirring under a nitrogen stream. A mixed solution of 67.34 parts by mass (33.33 parts by mass of solid content) of the above macromonomer MM-1 solution, 16.67 parts by mass of glycidyl methacrylate (hereinafter referred to as GMA), 1.24 parts by mass of n-dodecyl mercaptan, 25.0 parts by mass of PGMEA, and 0.5 part by mass of AIBN was added dropwise over 1.5 hours. After heating and stirring for 3 hours, 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, and the mixture was further aged at the same temperature for 1 hour to obtain a 25.0% by mass solution of the graft copolymer A1. The results of GPC measurement of the obtained graft copolymer A1 were a weight-average molecular weight (Mw) of 10570, a number-average molecular weight (Mn) of 4370, and a molecular weight distribution (Mw / Mn) of 2.42.

[0621] (3) Production of a polymer (acidic dispersant A1) having a structural unit represented by the above general formula (I)

[0622] Into a reactor equipped with a condenser, an addition funnel, a nitrogen inlet, a mechanical stirrer, and a digital thermometer, 27.80 parts by mass of PGMEA and 9.27 parts by mass of phenylphosphonic acid (product name "PPA", manufactured by Nissan Chemical Industries, Ltd.) were added, and the mixture was heated to 90 °C while stirring under a nitrogen stream. 100.0 parts by mass of the above graft copolymer A1 was added dropwise over 30 minutes, and the mixture was heated and stirred for 2 hours to obtain a solution (solid content: 25.0 mass%) of a polymer (acidic dispersant A1) having a structural unit represented by the above general formula (I). The progress of the esterification reaction between GMA and PPA of the obtained acidic dispersant A1 was confirmed by acid value measurement and 1 1H-NMR measurement (the disappearance of the peak derived from the epoxy group was confirmed). The acid value of the obtained acidic dispersant A1 was 98 mgKOH / g.

[0623] (Synthesis Example 7: Synthesis of acidic dispersant B1 (block copolymer containing A block having a structural unit derived from a carboxyl group-containing ethylenically unsaturated monomer and B block having a structural unit derived from an alkyl (meth)acrylate))

[0624] The following triblock copolymer having a block of 20 parts by mass of methyl methacrylate (MMA) and 40 parts by mass of n-butyl methacrylate (BMA), a block of 20 parts by mass of methacrylic acid (MAA) and 20 parts by mass of BMA, and a block of 20 parts by mass of MMA and 40 parts by mass of BMA was synthesized with reference to Example 1 described in International Publication No. 2016 / 132863. The weight-average molecular weight (Mw) of the obtained block copolymer was 11,000, the molecular weight distribution (Mw / Mn) was 1.50, and the acid value was 130 mgKOH / g.

[0625] (Synthesis Example 8: Synthesis of alkali-soluble resin A)

[0626] 150 parts by mass of PGMEA was added to a polymerization tank, and after heating to 100 °C under a nitrogen atmosphere, 22 parts by mass of methacrylic acid (MAA), 64 parts by mass of cyclohexyl methacrylate (CHMA), 6 parts by mass of PERBUTYL O (manufactured by NOF Corporation) as a photoinitiator, and 2 parts by mass of a chain transfer agent (n-dodecyl mercaptan) were continuously added dropwise over 1.5 hours. Then, the temperature was maintained at 100 °C and the reaction was continued. After 2 hours from the end of the dropwise addition of the main-chain-forming mixture, 0.1 part by mass of p-methoxyphenol was added as a polymerization inhibitor to terminate the polymerization.

[0627] Next, while blowing air, 14 parts by mass of glycidyl methacrylate (GMA) was added as an epoxy group-containing compound. After heating to 110 °C, 0.8 parts by mass of triethylamine was added, and an addition reaction was carried out at 110 °C for 15 hours to obtain an alkali-soluble resin A solution (weight-average molecular weight (Mw) 9,000, acid value 90 mgKOH / g, solid content 40 mass%).

[0628] (Synthesis Example 9: Synthesis of Lake Colorant 4)

[0629] (1) Preparation of K 6 (P 2 MoW 17 o 62 )

[0630] Dissolve 44.0 g of NaWo 4 ·2H 2 o (manufactured by Wako Pure Chemical Industries, Ltd.) and 1.90 g of Na 2 MoO 4 ·2H 2 O (manufactured by Kanto Chemical Co., Inc.) in 230 g of purified water. While stirring, 64.9 g of 85% phosphoric acid was added dropwise to this solution using a dropping funnel. The obtained solution was heated under reflux for 8 hours. The reaction solution was cooled to room temperature, 1 drop of bromine water was added, and 45 g of potassium chloride was added while stirring. After further stirring for 1 hour, the precipitate was separated by filtration. The obtained solid was dried at 90 °C to obtain 29.4 g of K 6 (P 2 MoW 17 O 62 ).

[0631] (2) Synthesis of Lake Colorant 4

[0632] Put 5.30 g of C.I. Basic Blue 7 (BB7) (manufactured by Tokyo Chemical Industry Co., Ltd.) into 350 ml of purified water, and stir at 40 °C to dissolve it to prepare a BB7 solution. Separately, dissolve 10.0 g of K 6 (P 2 MoW 17 O 62 ) prepared in the above (1) in 40 ml of purified water. Add K 6 (P 2 MoW 17 O 62) The solution was directly stirred at 40 °C for 1 hour. Then, the internal temperature was raised to 80 °C and further stirred for 1 hour for lake formation. After cooling, filtration was carried out, and it was washed 3 times with 300 ml of purified water. The obtained solid was dried at 90 °C to obtain 10.4 g of a lake colorant 4 which was a blue-black solid and had an average primary particle size of 40 nm as a lake colorant of a triarylmethane-based dye and a polyacid anion.

[0633] (Production Example 1: Production of Adhesive Resin 1)

[0634] 150 parts by mass of PGMEA was added to a polymerization tank. After heating to 100 °C under a nitrogen atmosphere, 26.9 parts by mass of methacrylic acid (MAA), 38.9 parts by mass of benzyl methacrylate (BzMA), 5 parts by mass of 2-hydroxyethyl methacrylate (HEMA), 1.4 parts by mass of PERBUTYL O (manufactured by NOF Corporation) as a photoinitiator, and 2.5 parts by mass of a chain transfer agent (n-dodecyl mercaptan) were continuously added dropwise over 1.5 hours. Then, the temperature was maintained at 100 °C and the reaction was continued. After 2 hours from the end of the dropwise addition of the main-chain-forming mixture, 0.1 part by mass of p-methoxyphenol was added as a polymerization inhibitor to stop the polymerization.

[0635] Next, while blowing air, 29.2 parts by mass of glycidyl methacrylate (GMA) as an epoxy group-containing compound was added, and after heating to 110 °C, 0.8 part by mass of triethylamine was added, and an addition reaction was carried out at 110 °C for 15 hours to obtain an adhesive resin 1 solution (weight-average molecular weight (Mw) 14,900, acid value 67 mgKOH / g, hydroxyl value 129 mgKOH / g, solid content 40 mass%).

[0636] (Production Examples 2 to 9, Comparative Production Examples 1 to 9: Production of Adhesive Resins 2 to 9, Comparative Adhesive Resins C1 to C9)

[0637] In Production Example 1, the addition amounts of the monomers, photoinitiator, and chain transfer agent were changed according to Table 1. Other than that, adhesive resin 2 to 9 solutions of Production Examples 2 to 9 and comparative adhesive resin C1 to C9 solutions of Comparative Production Examples 1 to 9 were obtained in the same manner as in Production Example 1 (each adhesive resin solution had a solid content of 40 mass%).

[0638] (Comparative Production Example 10: Production of Comparative Adhesive Resin C10)

[0639] Add 150 parts by mass of PGMEA to the polymerization tank. After heating to 110°C under a nitrogen atmosphere, 81.5 parts by mass of t-butylcyclohexyl methacrylate (t-BuCHMA), 15.0 parts by mass of methacrylic acid (MAA), 3.5 parts by mass of 2-hydroxyethyl methacrylate (HEMA), and 3.0 parts by mass of AIBN as a photoinitiator were continuously added dropwise over 1.5 hours, respectively. Then, it was maintained at 110°C and stirred for 2 hours to obtain a comparative adhesive resin C10 solution (solid content: 40 mass%).

[0640] [Table 1]

[0641]

[0642] (Preparation Example 1: Preparation of Lake Colorant 1 Dispersion)

[0643] Mix 10 parts by mass of the lake colorant 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), 7.5 parts by mass of the alkali-soluble resin A solution of Synthesis Example 8 (effective solid content: 3.0 parts by mass), and 62.5 parts by mass of PGMEA. Pre-disperse for 1 hour with 2 mm zirconia beads in a paint shaker (manufactured by Asada Iron Works Co., Ltd.), and further perform formal dispersion for 4 hours with 0.1 mm zirconia beads to obtain a lake colorant 1 dispersion.

[0644] (Preparation Example 2: Preparation of Xanthene-based Metal Lake Colorant 3 Dispersion)

[0645] Mix 10 parts by mass of the xanthene-based metal lake colorant 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), 7.5 parts by mass of the alkali-soluble resin A solution of Synthesis Example 8 (effective solid content: 3.0 parts by mass), and 65.8 parts by mass of PGMEA. Pre-disperse for 1 hour with 2 mm zirconia beads in a paint shaker (manufactured by Asada Iron Works Co., Ltd.), and further perform formal dispersion for 4 hours with 0.1 mm zirconia beads to obtain a xanthene-based metal lake colorant 3 dispersion.

[0646] (Preparation Example 3: Preparation of Xanthene-based Dye 1 Solution)

[0647] Dissolve 5.0 parts by mass of the xanthene-based dye 1 of Synthesis Example 2 in 45 parts by mass of diacetone alcohol to obtain a xanthene-based dye 1 solution.

[0648] (Preparation Example 4: Preparation of Xanthene-based Dye 2 Solution)

[0649] Dissolve 5.0 parts by mass of the xanthene-based dye 2 of Synthesis Example 3 in 45 parts by mass of diacetone alcohol to obtain a xanthene-based dye 2 solution.

[0650] (Preparation Example 5: Preparation of PB15:6 Dispersion Liquid)

[0651] 10 parts by mass of the basic-treated PB15:6 of Synthesis Example 5, 16.7 parts by mass (effective solid content: 5.0 parts by mass) of the acidic dispersant B1 solution of Synthesis Example 7, 7.5 parts by mass (effective solid content: 3.0 parts by mass) of the alkali-soluble resin A solution of Synthesis Example 8, and 65.8 parts by mass of PGMEA were mixed, and pre-dispersed for 1 hour using 2 mm zirconia beads in a paint shaker (manufactured by Asada Iron Works Co., Ltd.), and then further subjected to formal dispersion for 6 hours using 0.1 mm zirconia beads to obtain a PB15:6 dispersion liquid.

[0652] (Preparation Example 6: Preparation of PV23 Dispersion Liquid)

[0653] 10 parts by weight of commercially available C.I. Pigment Violet 23 (PV23), 16.7 parts by mass (effective solid content: 5.0 parts by mass) of the acidic dispersant B1 solution of Synthesis Example 7, 7.5 parts by mass (effective solid content: 3.0 parts by mass) of the alkali-soluble resin A solution of Synthesis Example 8, 65.8 parts by weight of PGMEA, and 30 parts by weight of zirconia beads with a diameter of 2 mm were placed in a 30 ml mayonnaise bottle, and pre-crushed for 1 hour in a paint shaker (manufactured by Asada Steel Co., Ltd.). Then, the mixed liquid was transferred to another 30 ml mayonnaise bottle, 30 parts by weight of zirconia beads with a diameter of 0.1 mm were added, and the mixture was shaken in the paint shaker for 5 hours to obtain a PV23 dispersion liquid.

[0654] (Preparation Example 7: Preparation of Lake Colorant 4 Dispersion Liquid)

[0655] In Preparation Example 1, 10 parts by mass of the lake colorant 4 of Synthesis Example 6 was used instead of 10 parts by mass of the lake colorant 1 of Synthesis Example 1 as the colorant, and except for this, the dispersion liquid of the lake colorant 4 was prepared in the same manner as in Preparation Example 1.

[0656] (Preparation Example I: Preparation of Photosensitive Adhesive Component 1)

[0657] With respect to 26.5 parts by mass of the binder resin 1 solution (solid content: 40% by mass) of Production Example 1, 24.7 parts by mass of dipentaerythritol hexaacrylate (DPHA) (ARONIX M402, manufactured by Toagosei Co., Ltd.), which is a photopolymerizable compound, 3.53 parts by mass of Irgacure 907 (manufactured by BASF, an α - aminoketone - based photoinitiator), 0.39 parts by mass of kayacure DETX - S (manufactured by Nippon Kayaku Co., Ltd., a thioxanthone - based photoinitiator, 2,4 - diethylthioxanthone), 0.78 parts by mass of IRGANOX1010 (manufactured by BASF), which is an antioxidant, and 44.1 parts by mass of PGMEA were added to obtain the photosensitive binder component 1.

[0658] (Preparation Examples II - IX, Comparative Preparation Examples I - X: Preparation of Photosensitive Binder Components 2 - 9, Comparative Photosensitive Binder Components 1 - 10)

[0659] In the preparation of the photosensitive binder component 1 of Preparation Example I, for Preparation Examples II - IX, the binder resin 2 - 9 solutions of Production Examples 2 - 9 were used instead of the binder resin 1 solution of Production Example 1, and for Comparative Preparation Examples I - X, the comparative binder resin C1 - C10 solutions of Comparative Production Examples C1 - C10 were used instead of the binder resin 1 solution of Production Example 1. Otherwise, in the same manner as in Preparation Example I, photosensitive binder components 2 - 9 were obtained in Preparation Examples II - IX, and comparative photosensitive binder components C1 - C10 were obtained in Comparative Preparation Examples I - X.

[0660] (Example 1)

[0661] 23.2 parts by mass of the lake pigment 1 dispersion of Preparation Example 1, 32.1 parts by mass of the photosensitive binder component 1 of Preparation Example I, 0.03 parts by mass of the surfactant MEGAFAC R08MH (manufactured by DIC Corporation), and 44.7 parts by mass of PGMEA were mixed to obtain the photosensitive colored resin composition of Example 1.

[0662] (Examples 2 - 9, Comparative Examples 1 - 10)

[0663] In the preparation of the photosensitive colored resin composition of Example 1, for Examples 2 - 9, photosensitive binder components 2 - 9 were used instead of the photosensitive binder component 1, and for Comparative Examples 1 - 10, comparative photosensitive binder components C1 - C10 were used instead of the photosensitive binder component 1. Otherwise, in the same manner as in Example 1, photosensitive colored resin compositions of Examples 2 - 9 and Comparative Examples 1 - 10 were obtained.

[0664] (Comparative Examples 11 - 12)

[0665] In the preparation of the photosensitive colored resin composition of Example 1, 25.5 parts by mass of the PB15:6 dispersion and 4.0 parts by mass of the PV23 dispersion were used in such a way that the mass ratio of the alkali-treated PB15:6 to PV23 (alkali-treated PB15:6:PV23) became 86.4:13.6 to replace 23.2 parts by mass of the lake pigment 1 dispersion. Further, in Comparative Example 11, 29.2 parts by mass of the photosensitive binder component 2 was used to replace 32.1 parts by mass of the photosensitive binder component 1. In Comparative Example 12, 29.2 parts by mass of the comparative photosensitive binder component C5 was used to replace 32.1 parts by mass of the photosensitive binder component 1, and the addition amount of PGMEA was changed from 44.7 parts by mass to 41.3 parts by mass. Except for this, the photosensitive colored resin compositions of Comparative Examples 11 to 12 were obtained in the same manner as in Example 1.

[0666] (Example 10, Comparative Examples 13 to 15)

[0667] In the preparation of the photosensitive colored resin composition of Example 1, 17.6 parts by mass of the lake pigment 1 dispersion and 1.32 parts by mass of the xanthene-based metal lake pigment 3 dispersion were used in such a way that the mass ratio of the lake pigment 1 to the xanthene-based metal lake pigment 3 (lake pigment 1:xanthene-based metal lake pigment 3) became 93.0:7.0 to replace 23.2 parts by mass of the lake pigment 1 dispersion. Further, in Example 10, 34.0 parts by mass of the photosensitive binder component 2 was used to replace 32.1 parts by mass of the photosensitive binder component 1. In Comparative Example 13, 34.0 parts by mass of the comparative photosensitive binder component C1 was used to replace 32.1 parts by mass of the photosensitive binder component 1. In Comparative Example 14, 34.0 parts by mass of the comparative photosensitive binder component C4 was used to replace 32.1 parts by mass of the photosensitive binder component 1. In Comparative Example 15, 34.0 parts by mass of the comparative photosensitive binder component C6 was used to replace 32.1 parts by mass of the photosensitive binder component 1, and the addition amount of PGMEA was changed from 44.7 parts by mass to 47.1 parts by mass. Except for this, the photosensitive colored resin compositions of Example 10 and Comparative Examples 13 to 15 were obtained in the same manner as in Example 1.

[0668] (Example 11, Comparative Examples 16 to 18)

[0669] In the preparation of the photosensitive colored resin composition of Example 1, 17.3 parts by mass of the lake pigment 1 dispersion liquid and 1.06 parts by mass of the xanthene dye 1 solution were used in such a manner that the mass ratio of the lake pigment 1 to the xanthene dye 1 (lake pigment 1:xanthene dye 1) became 94.2:5.8 to replace 23.2 parts by mass of the lake pigment 1 dispersion liquid. Further, in Example 11, 34.4 parts by mass of the photosensitive binder component 2 was used to replace 32.1 parts by mass of the photosensitive binder component 1. In Comparative Example 16, 34.4 parts by mass of the comparative photosensitive binder component C1 was used to replace 32.1 parts by mass of the photosensitive binder component 1. In Comparative Example 17, 34.4 parts by mass of the comparative photosensitive binder component C4 was used to replace 32.1 parts by mass of the photosensitive binder component 1. In Comparative Example 18, 34.4 parts by mass of the comparative photosensitive binder component C6 was used to replace 32.1 parts by mass of the photosensitive binder component 1, and the addition amount of PGMEA was changed from 44.7 parts by mass to 47.2 parts by mass. Except for this, the photosensitive colored resin compositions of Example 11 and Comparative Examples 16 to 18 were obtained in the same manner as in Example 1.

[0670] (Example 12, Comparative Examples 19 to 21)

[0671] In the preparation of the photosensitive colored resin composition of Example 1, 17.3 parts by mass of the lake pigment 1 dispersion liquid and 1.06 parts by mass of the xanthene dye 2 solution were used in such a manner that the mass ratio of the lake pigment 1 to the xanthene dye 2 (lake pigment 1:xanthene dye 2) became 94.2:5.8 to replace 23.2 parts by mass of the lake pigment 1 dispersion liquid. Further, in Example 12, 34.4 parts by mass of the photosensitive binder component 2 was used to replace 32.1 parts by mass of the photosensitive binder component 1. In Comparative Example 19, 34.4 parts by mass of the comparative photosensitive binder component C1 was used to replace 32.1 parts by mass of the photosensitive binder component 1. In Comparative Example 20, 34.4 parts by mass of the comparative photosensitive binder component C4 was used to replace 32.1 parts by mass of the photosensitive binder component 1. In Comparative Example 21, 34.4 parts by mass of the comparative photosensitive binder component C6 was used to replace 32.1 parts by mass of the photosensitive binder component 1, and the addition amount of PGMEA was changed from 44.7 parts by mass to 47.2 parts by mass. Except for this, the photosensitive colored resin compositions of Example 12 and Comparative Examples 19 to 21 were obtained in the same manner as in Example 1.

[0672] (Comparative Examples 22 to 23)

[0673] In the preparation of the photosensitive colored resin composition of Example 1, 17.4 parts by mass of the PB15:6 dispersion and 5.35 parts by mass of the PV23 dispersion were used in such a way that the mass ratio of the alkali-treated PB15:6 to PV23 (alkali-treated PB15:6:PV23) became 76.5:23.5 to replace 23.2 parts by mass of the lake pigment 1 dispersion. Further, in Comparative Example 22, 32.2 parts by mass of the photosensitive binder component 2 was used instead of 32.1 parts by mass of the photosensitive binder component 1. In Comparative Example 23, 32.2 parts by mass of the comparative photosensitive binder component C5 was used instead of 32.1 parts by mass of the photosensitive binder component 1, and the addition amount of PGMEA was changed from 44.7 parts by mass to 44.9 parts by mass. Except for this, the photosensitive colored resin compositions of Comparative Examples 22 to 23 were obtained in the same manner as in Example 1.

[0674] (Examples 13, Comparative Examples 24 to 26)

[0675] In the preparation of the photosensitive colored resin composition of Example 1, 18.3 parts by mass of the lake pigment 1 dispersion and 12.4 parts by mass of the PB15:6 dispersion were used in such a way that the mass ratio of the lake pigment 1 to the alkali-treated PB15:6 (lake pigment 1:alkali-treated PB15:6) became 59.6:40.4 to replace 23.2 parts by mass of the lake pigment 1 dispersion. Further, in Example 13, 28.7 parts by mass of the photosensitive binder component 2 was used instead of 32.1 parts by mass of the photosensitive binder component 1. In Comparative Example 24, 28.7 parts by mass of the comparative photosensitive binder component C1 was used instead of 32.1 parts by mass of the photosensitive binder component 1. In Comparative Example 25, 28.7 parts by mass of the comparative photosensitive binder component C4 was used instead of 32.1 parts by mass of the photosensitive binder component 1. In Comparative Example 26, 28.7 parts by mass of the comparative photosensitive binder component C6 was used instead of 32.1 parts by mass of the photosensitive binder component 1, and the addition amount of PGMEA was changed from 44.7 parts by mass to 40.6 parts by mass. Except for this, the photosensitive colored resin compositions of Example 13 and Comparative Examples 24 to 26 were obtained in the same manner as in Example 1.

[0676] (Comparative Examples 27 to 28)

[0677] In the preparation of the photosensitive colored resin composition of Example 1, 34.8 parts by mass of the PB15:6 dispersion liquid and 2.82 parts by mass of the PV23 dispersion liquid were used to replace 23.2 parts by mass of the lake pigment 1 dispersion liquid so that the mass ratio of the alkali-treated PB15:6 to PV23 (alkali-treated PB15:6:PV23) became 92.5:7.5. Further, in Comparative Example 27, 25.6 parts by mass of the photosensitive binder component 2 was used to replace 32.1 parts by mass of the photosensitive binder component 1. In Comparative Example 28, 25.6 parts by mass of the comparative photosensitive binder component C5 was used to replace 32.1 parts by mass of the photosensitive binder component 1, and the addition amount of PGMEA was changed from 44.7 parts by mass to 36.8 parts by mass. Except for this, the photosensitive colored resin compositions of Comparative Examples 27 to 28 were obtained in the same manner as in Example 1.

[0678] (Examples 1-2 to 9-2, Comparative Examples 1-2 to 10-2)

[0679] In the preparation of the photosensitive colored resin compositions of Examples 1 to 9 and Comparative Examples 1 to 10, the lake pigment 4 dispersion liquid of Preparation Example 7 was used to replace the lake pigment 1 dispersion liquid of Preparation Example 1. Except for this, the photosensitive colored resin compositions of Examples 1-2 to 9-2 and Comparative Examples 1-2 to 10-2 were obtained in the same manner as in Examples 1 to 9 and Comparative Examples 1 to 10.

[0680] [Evaluation method]

[0681] [Coloring layer shape]

[0682] The photosensitive colored resin composition of Example 1 was applied onto a glass substrate (manufactured by NH TECHNO GLASS Co., Ltd., "NA35") with a thickness of 0.7 mm by a spin coater so that the film thickness after post-baking became 2.5 μm, and then heated and dried at 80 °C for 3 minutes using a hot plate. Then, through a photomask for forming lines and spaces (line&space) of 60 μm, ultraviolet rays of 60 mJ / cm 2 were irradiated using an ultra-high pressure mercury lamp. Next, a 0.05 mass% aqueous potassium hydroxide solution was used as an alkaline developer for spray development for 60 seconds. Then, post-baking was performed in a clean oven at 230 °C for 30 minutes, thereby producing a pattern-formed substrate having a colored layer formed on the glass substrate in a pattern of lines and spaces of 60 μm.

[0683] Using a spin coater, the photosensitive colored resin compositions of each example and each comparative example were coated on the pattern-forming substrate produced as described above such that the film thickness after post-baking was 2.5 μm, and then heated and dried at 90 °C for 3 minutes using a hot plate. Then, ultraviolet rays of 60 mJ / cm 2 were irradiated using an ultra-high pressure mercury lamp without using a photomask, and then post-baked in a clean oven at 230 °C for 30 minutes, whereby a colored layer as a cured film of the photosensitive colored resin composition of each example or each comparative example was formed between patterns of 60 μm. After forming the colored layer, the pattern profile was measured using a film thickness gauge of a stylus profiler "P-17" manufactured by KLA-Tencor Corporation. Taking the center of the base pattern as a reference, the film thickness difference between the portion 15 μm away from the center and the center portion was determined, and evaluation was performed according to the following evaluation criteria.

[0684] (Evaluation criteria for colored layer shape)

[0685] A: The film thickness difference is less than 0.05 μm

[0686] B: The film thickness difference is 0.05 μm or more and less than 0.1 μm

[0687] C: The film thickness difference is 0.1 μm or more

[0688] (Development residue evaluation)

[0689] After the photosensitive colored resin compositions of the examples and comparative examples were respectively coated on a glass substrate (manufactured by NH TECHNO GLASS Co., Ltd., "NA35") with a thickness of 0.7 mm using a spin coater and dried at 60 °C for 3 minutes using a hot plate, a colored layer with a thickness of 2.5 μm was formed. For the above glass plate with a colored layer formed thereon, 0.05 mass% aqueous potassium hydroxide solution was used as an alkaline developer, and spray development was performed for 60 seconds. After visually observing the formation portion of the colored layer after development, it was wiped thoroughly with a lens cleaning cloth containing ethanol (manufactured by TORAY Industries, Inc., trade name Toraysee MK Clean Cloth), and the coloring degree of the lens cleaning cloth was visually observed, and evaluation was performed according to the following evaluation criteria.

[0690] (Evaluation criteria for development residue)

[0691] A: No development residue was visually confirmed, and the lens cleaning cloth was not colored at all.

[0692] B: No development residue was visually confirmed, and slight coloring of the lens cleaning cloth was confirmed.

[0693] C: A small amount of development residue was visually observed, and coloring of the lens cleaning cloth was confirmed.

[0694] D: Visual observation of development residues and confirmation of the coloring of the lens cleaning cloth.

[0695] <Brightness>

[0696] The photosensitive coloring resin compositions of the examples and comparative examples were each spin-coated on a glass substrate (manufactured by NH TECHNO GLASS Co., Ltd., "NA35") with a thickness of 0.7 mm such that the chromaticity after post-baking became y = 0.099. Then, they were heated and dried on a hot plate at 80°C for 3 minutes and irradiated with ultraviolet rays of 60 mJ / cm 2 using an ultra-high pressure mercury lamp without a photomask. Subsequently, they were post-baked in a clean oven at 230°C for 30 minutes to obtain cured films (colored films). The brightness (Y) of the obtained colored substrates was measured using the "Microscopic Spectrophotometer OSP-SP200" manufactured by Olympus Corporation and evaluated according to the following evaluation criteria.

[0697] (Brightness evaluation)

[0698] A: The brightness (Y) is 13.0 or more

[0699] B: The brightness (Y) is 12.0 or more and less than 13.0

[0700] C: The brightness (Y) is less than 12.0

[0701] <Heat resistance>

[0702] After obtaining the cured film (colored film) by the same method as the evaluation of the above brightness, the obtained colored film was further post-baked in a clean oven at 240°C for 25 minutes, and the chromaticity (L 0 , a 0 , b 0 ) of the colored film was measured. Then, it was further post-baked in a clean oven at 240°C for 50 minutes, and the chromaticity (L 1 , a 1 , b 1 ) of the obtained colored film was measured again.

[0703] The chromaticity change of the colored film during the period from 25 minutes to 75 minutes at 240°C was evaluated by the following formula.

[0704] ΔEab = {(L 1 - L 0 ) 2 + (a 1 - a 0 ) 2 + (b 1 - b 0 ) 2} 1 / 2

[0705] The smaller the value of ΔEab, the better the heat resistance is evaluated. If ΔEab is less than 3.0, it is judged that there is no problem in practical use.

[0706] (Heat resistance evaluation criteria)

[0707] A: ΔEab is less than 2.0

[0708] B: ΔEab is 2.0 or more and less than 3.0

[0709] C: ΔEab is 3.0 or more

[0710] In Tables 2 to 5 below, the metal lake colorant 3 refers to the xanthene-based metal lake colorant 3 obtained in Synthesis Example 4, PB15:6 refers to the alkali-treated PB15:6 obtained in Synthesis Example 5, and PV23 refers to the commercially available C.I. Pigment Violet 23. In addition, A1 of the dispersant refers to the acidic dispersant A1 obtained in Synthesis Example 6, and B1 of the dispersant refers to the acidic dispersant B1 obtained in Synthesis Example 7.

[0711] [Table 2]

[0712]

[0713] [Table 3]

[0714]

[0715] [Table 4]

[0716]

[0717] [Table 5]

[0718]

[0719] [Result summary]

[0720] The results in Tables 2 to 5 show that the colored layers formed using the photosensitive colored resin compositions of Examples 1 to 13 and Examples 1-2 to 9-2 have high brightness, excellent flatness, and suppression of the generation of development residues. The photosensitive colored resin compositions of Examples 1 to 13 and Examples 1-2 to 9-2 contain in combination: a colorant containing at least one selected from dyes and lake colorants, and an adhesive resin containing the following copolymer (a copolymer containing a (meth)acrylic acid hydroxyalkyl ester unit), the copolymer having a polymer structure containing a structural unit derived from (meth)acrylic acid hydroxyalkyl ester represented by the general formula (A) in an amount of 5 to 25% by mass, a weight average molecular weight of 11,000 or more, and an acid value of 60 to 130 mgKOH / g.

[0721] In addition, the comparison between Examples 1 to 9 and Comparative Examples 1 to 10 shown in Table 2, and the comparison between Examples 1-2 to 9-2 and Comparative Examples 1-2 to 10-2 shown in Table 5 indicate that in a photosensitive coloring resin composition containing the lake colorant represented by the above general formula (1), i.e., lake colorant 1, or the lake colorant represented by the above general formula (2), i.e., lake colorant 4, when a copolymer containing a (meth)acrylic acid hydroxyalkyl ester unit is used as the binder resin, the heat resistance is improved.

[0722] 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, any one of Comparative Binder Resins C1 to C4 that do not contain a (meth)acrylic acid hydroxyalkyl ester unit was used, so the effect of suppressing development residues was poor. Among them, in Comparative Examples 4, 14, 17, 20, 25, and 4-2 using Comparative Binder Resin C4 that does not contain a (meth)acrylic acid hydroxyalkyl ester unit, has a weight average molecular weight of less than 11,000, and an acid value exceeding 130 mgKOH / g, the effect of suppressing development residues is particularly poor.

[0723] It should be noted that in Comparative Examples 1 to 4, 13 to 14, 16 to 17, 19 to 20, 24 to 25, and 1-2 to 4-2, although the copolymer used as the binder resin does not contain a hydroxyalkyl (meth)acrylate unit, the flatness of the colored layer is also excellent. It is considered that the reason is that the acid value of the copolymer is relatively high, being 108 to 147 mgKOH / g. On the other hand, in the photosensitive colored resin composition of the present invention, the copolymer containing a hydroxyalkyl (meth)acrylate unit used as the binder resin contains the hydroxyalkyl (meth)acrylate unit in the above-mentioned specific amount. Thus, if the acid value is within the range of 60 to 130 mgKOH / g, even if the acid value is relatively high, the generation of development residues is suppressed. For example, in Examples 8 and 9, although the acid values of the binder resins 8 and 9 used are as high as those in Comparative Examples 1 to 3, the generation of development residues is suppressed. In the photosensitive colored resin composition of the present invention, the copolymer containing a hydroxyalkyl (meth)acrylate unit used as the binder resin contains the hydroxyalkyl (meth)acrylate unit in the above-mentioned specific amount. As a result, components with lower developability other than the binder resin in the resin composition interact with the hydroxyalkyl (meth)acrylate unit and are developed together with the components with lower developability. Therefore, it is considered that the generation of residues is suppressed. It is considered that in the case where the binder resin does not sufficiently contain the hydroxyalkyl (meth)acrylate unit and has a high acid value, the developability of the binder resin alone becomes too high, so that components with lower developability are discarded, and thus residues are easily generated. It is considered that in the comparative examples using Comparative Binder Resins C1 to C3, since they do not contain a hydroxyalkyl (meth)acrylate unit, the generation of development residues is easily affected by the acid value, and development residues are generated when the acid value is 108 mgKOH / g or more.

[0724] In Comparative Examples 5 and 5-2, Comparative Binder Resin C5 which does not contain a hydroxyalkyl (meth)acrylate unit and has a weight average molecular weight of less than 11,000 was used. In Comparative Examples 6 to 10, 15, 18, 21, 26, and 6-2 to 10-2, Comparative Binder Resins C6 to C10 with a weight average molecular weight of less than 11,000 were used. Therefore, the flatness of the colored layer was poor in each case.

[0725] In Comparative Examples 11 to 12, 22 to 23, and 27 to 28, only a pigment was used as the color material. Therefore, the brightness of the colored layer was poor. It should be noted that in Comparative Examples 12, 23, and 28, although the same Comparative Binder Resin C5 as in Comparative Example 5 was used, the flatness of the colored layer was excellent. From this, it is clear that when a pigment is used as the color material, the problem of impaired flatness of the colored layer is not likely to occur.

[0726] Explanation of Reference Numerals

[0727] 1: Substrate

[0728] 2: Light-shielding part

[0729] 3: Coloring layer

[0730] 3R: Red coloring layer

[0731] 3G: Green coloring layer

[0732] 3B: Blue coloring layer

[0733] 3B′: Blue coating film

[0734] 10: Color filter

[0735] 20: Opposite substrate

[0736] 30: Liquid crystal layer

[0737] 40: Liquid crystal display device

[0738] 50: Organic protective layer

[0739] 60: Inorganic oxide film

[0740] 71: Transparent anode

[0741] 72: Hole injection layer

[0742] 73: Hole transport layer

[0743] 74: Light-emitting layer

[0744] 75: Electron injection layer

[0745] 76: Cathode

[0746] 80: Organic light-emitting body

[0747] 100: Organic light-emitting display device

Claims

1. A photosensitive colored resin composition for a color filter, which contains a coloring material, a binder resin, a monomer, a photoinitiator, and a solvent. The coloring material contains at least one selected from dyes and lake color materials. The binder resin contains the following copolymer, which has the following polymer structure, and the weight average molecular weight is 11,000 or more and 20,000 or less, the acid value is 60 mgKOH / g to 130 mgKOH / g, and the hydroxyl value is 50 mgKOH / g or more and 200 mgKOH / g or less. The polymer structure contains 5 to 25% by mass of a structural unit derived from a (meth)acrylic acid hydroxyalkyl ester represented by the following general formula (A) and contains 2.5 to 35% by mass of a structural unit having a photopolymerizable functional group. General formula (A) In general formula (A), R A represents a methyl group or a hydrogen atom, and R B represents an alkylene group having 1 to 4 carbon atoms.

2. The photosensitive colored resin composition for a color filter according to claim 1. Wherein, The coloring material contains a lake color material.

3. The photosensitive colored resin composition for a color filter according to claim 1 or 2. Wherein, The coloring material contains a lake color material represented by the following general formula (1) or general formula (2). General formula (1) In general formula (1), A represents an a-valent organic group in which the carbon atom directly bonded to N does not have a π bond, and this organic group represents an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at least at the terminal directly bonded to N, or an aromatic group having this aliphatic hydrocarbon group, and a heteroatom may be optionally included in the carbon chain; B c- represents a c-valent polyacid anion; R i ~R v each independently represents a hydrogen atom, an alkyl group optionally having a substituent, or an aryl group optionally having a substituent, and R ii and R iii , R iv and R v may optionally bond to form a ring structure; R vi and R vii each independently represents an alkyl group optionally having a substituent, an alkoxy group optionally having a substituent, a halogen atom, or a cyano group; Ar 1 represents a divalent aromatic group optionally having a substituent; when there are a plurality of R i ~R vii and Ar 1 they may be the same or different respectively, a and c represent integers of 2 or more, b and d represent integers of 1 or more; e is 0 or 1, and when e is 0, the bond does not exist; f and g represent integers of 0 or more and 4 or less, and f + e and g + e are 0 or more and 4 or less; when there are multiple e, f, and g, they can be the same or different respectively. General formula (2) In general formula (2), R I ~R VI each independently represents a hydrogen atom, an alkyl group optionally having a substituent, or an aryl group optionally having a substituent, and R I and R II , R III and R IV , R V and R VI optionally bond to form a ring structure; R VII and R VIII each independently represents an alkyl group optionally having a substituent, an alkoxy group optionally having a substituent, a halogen atom, or a cyano group; Ar 2 represents a divalent aromatic heterocyclic group optionally having a substituent, and when there are a plurality of R I ~R VIII and Ar 2 may be the same or different from each other; E m- represents an m-valent polyacid anion; m represents an integer of 2 or more; j is 0 or 1, and when j is 0, the bond does not exist; 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; when there are multiple j, k, and l, they can be the same or different respectively.

4. The photosensitive colored resin composition for a color filter according to claim 3. Wherein, The coloring material further contains at least one selected from xanthene dyes, lake color materials of xanthene dyes different from the lake color materials represented by the general formula (1) or general formula (2), and C.I. Pigment Blue 15:

6.

5. The photosensitive colored resin composition for a color filter according to claim 4. Wherein, The xanthene dye is a xanthene dye represented by the following general formula (3) or general formula (4). The lake color material of a xanthene dye different from the lake color materials represented by the general formula (1) or general formula (2) is a metal lake color material of a xanthene dye represented by the following general formula (5). General formula (3) In general formula (3), R 1 and R 2 are each independently an alkyl group or an aryl group, R 3 and R 4 are each independently an aryl group or a heteroaryl group, General formula (4) In general formula (4), R 5 and R 6 are each independently an optionally substituted aliphatic hydrocarbon group or aromatic hydrocarbon group, R 7 and R 8 are each independently an optionally substituted aromatic hydrocarbon group or aromatic heterocyclic group, and the aromatic hydrocarbon group or aromatic heterocyclic group of at least one of R 7 and R 8 is substituted by an aliphatic hydrocarbon group, R 7 and R 8 are different from each other; L 1 and L 2 are each independently a direct bond, -SO 2 -, or -CO-, and R 9 is a halogenated aliphatic hydrocarbon group. General formula (5) In general formula (5), R 1' , R 2' , R 3' and R 4' each independently represent a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group, and R 1' and R 3' , R 2' and R 4' optionally bond 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, 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 optionally bond to each other to form a ring structure; the hydrogen atom(s) of the aryl group or heteroaryl group is / are optionally substituted with an acidic group or its salt, or a halogen atom; R 5' represents an acidic group or its salt, and x is an integer from 0 to 5; wherein, general formula (5) has at least 2 acidic groups or their salts, and one of them forms an inner salt.

6. The photosensitive colored resin composition for a color filter according to claim 1 or 2, which further contains a dispersant.

7. A cured product, which is a cured product of the photosensitive colored resin composition for a color filter according to any one of claims 1 to 6.

8. A color filter, which at least includes a substrate and a colored layer provided on the substrate, and at least one of the colored layers is a cured product of the photosensitive colored resin composition for a color filter according to any one of claims 1 to 6.

9. A display device, which has the color filter of claim 8.

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