Photosensitive colored resin composition, cured product, color filter, display device, and method for producing laminate of organic light emitting element and external light antireflection film

Abstract

The photosensitive coloring resin composition of the present invention contains a colorant, an alkali-soluble resin, a non-reactive resin, a photopolymerizable compound, a photoinitiator, and a solvent. The alkali-soluble resin has an acid value exceeding 50 mgKOH / g, the non-reactive resin has an acid value of 7 mgKOH / g to 50 mgKOH / g, the content of structural units derived from methyl methacrylate is 50% to 99% by mass of all structural units, and the weight average molecular weight is 5000 to 50000.

Description

[Technical Field]

[0001] This invention relates to a photosensitive coloring resin composition, a cured material, a color filter, a display device, and a method for manufacturing a laminate of an organic light-emitting element and an external light reflection prevention film using the photosensitive coloring resin composition. [Previous Technology]

[0002] In recent years, with the development of personal computers, especially portable personal computers, the demand for liquid crystal displays (LCDs) has been increasing. The penetration rate of mobile displays (mobile phones, smartphones, tablet PCs) is also constantly improving, and the LCD market is expanding rapidly. Organic light-emitting display devices, such as organic EL (Electroluminescence) displays which utilize self-emissive light and have high visibility, are also attracting industry attention as next-generation image display devices. Color filters are used in these LCD or organic light-emitting display devices. For example, the formation of a color image in an LCD device involves directly coloring the light passing through the color filter into the colors of each pixel constituting the color filter, and then synthesizing these colored lights to form a color image. As the light source, in addition to the previously used cold cathode tube, sometimes white-emitting organic light-emitting elements or white-emitting inorganic light-emitting elements are also used. In organic light-emitting display devices, color filters are used to achieve color adjustment, etc.

[0003] Here, a color filter typically includes: a substrate, a color layer formed on the substrate and comprising a color pattern of the three primary colors of red, green, and blue, and a light-shielding portion formed on the substrate to divide each color pattern. As a method for forming the color layer in a color filter, for example, a coloring resin composition is obtained by adding a binder resin, a photopolymerizable compound, and a photoinitiator to a colorant dispersion prepared by dispersing colorants using a dispersant or the like; the obtained coloring resin composition is coated onto a substrate and dried; then exposed using a photomask and developed to form a color pattern; the pattern is fixed by heating to form a color layer. Alternatively, the coloring resin composition is coated onto a substrate in a pattern using an inkjet printing method, dried, and then hardened to form a color pattern; the pattern is fixed by heating to form a color layer. These forming steps are repeated for each color to form a color filter.

[0004] In recent years, with the surge in demands for higher brightness in color filters, the pigment concentration in the color layer of color filters has increased compared to the past. Consequently, the amount of hardening components other than pigments has decreased, making it increasingly difficult to achieve patterning. For example, when forming a colored pattern, the coloring resin composition is exposed from above the layer. Therefore, the exposure amount increases towards the top of the layer and decreases towards the bottom. Consequently, during development after exposure, the lower part of the layer is easily cut off, resulting in a poor pattern shape. That is, the cross-sectional shape of the obtained pattern tends to be the shape with the widest upper surface and the narrowest lower surface, i.e., an undercut shape (also known as an inverted cone shape). If it becomes an undercut shape, various problems arise, such as easy peeling or defects in the pattern, gaps at the pixel ends, or uneven coating when applying it in the next step.

[0005] As a method to solve the problem of errors in the process of forming a pattern shape in the form of an inverted cone before post-baking, Patent Document 1 discloses a coloring photosensitive resin composition, characterized by comprising a non-reactive alkali-soluble resin and a photopolymerization initiator (A), wherein the photopolymerization initiator (A) contains a photopolymerization initiator (a1) having two oxime groups within one molecule, and the glass transition temperature (Tg) of the non-reactive alkali-soluble resin is below 0°C. The coloring photosensitive resin composition of Patent Document 1 employs the following technique: by comprising a resin with a low glass transition temperature, in the color filter manufacturing process, the coloring layer can be melted and flowed after baking at a high heat treatment such as 220°C, forming a pattern shape in the form of an inverted cone after the post-baking step. Previous Art Documents Patent Documents

[0006] Patent Document 1: Japanese Patent No. 6763990 [Summary of the Invention]

[0007] [The problem the invention aims to solve]

[0008] Previously, color filters were formed on glass substrates, but in recent years the industry has demanded that color filters be formed directly on the element substrate. Since organic light-emitting elements and other components have low heat resistance, it is considered that the heat treatment in the manufacturing process of directly forming color filters on the element substrate should preferably be performed at, for example, below 130°C, and further below 100°C. In the usual color filter manufacturing process, the color layer is hardened by heat treatment on the glass substrate at around 230°C. In contrast, heat treatment at temperatures below 130°C or 100°C results in the absence of thermal melting and flow, and the resulting undercut shape is easily formed. On the other hand, when using components without acid value to suppress undercut, there is a problem of easily generating development residue. Therefore, it is difficult to simultaneously achieve the suppression of development residue and the formation of a good pattern shape.

[0009] This invention was made in view of the above-mentioned actual situation, and its object is to provide a photosensitive coloring resin composition that can suppress the generation of developing residue and form a colored layer with a good pattern shape even during low-temperature heat treatment. Furthermore, this invention aims to provide a color filter and display device formed using the photosensitive coloring resin composition, and a method for manufacturing a laminate of an organic light-emitting element and an anti-reflective film using the photosensitive coloring resin composition. [Technical Means for Solving the Problem]

[0010] The photosensitive coloring resin composition of the present invention contains a colorant, an alkali-soluble resin, a non-reactive resin, a photopolymerizable compound, a photoinitiator, and a solvent, wherein the acid value of the alkali-soluble resin exceeds 50 mgKOH / g, the acid value of the non-reactive resin is 7 mgKOH / g to 50 mgKOH / g, the content of structural units derived from methyl methacrylate is 50% to 99% by mass of all structural units, and the weight average molecular weight is 5000 to 50000.

[0011] The cured product of the present invention is the cured product of the photosensitive coloring resin composition of the present invention described above.

[0012] The color filter of the present invention comprises at least a substrate and a coloring layer disposed on the substrate, and at least one of the coloring layers is a hardened form of the photosensitive coloring resin composition of the present invention.

[0013] The display device of the present invention includes the color filter of the present invention described above. Furthermore, the display device of the present invention has a hardened film of the photosensitive coloring resin composition of the present invention on an organic light-emitting element.

[0014] The method for manufacturing the laminate of the organic light-emitting element and the external light reflection anti-reflection film of the present invention comprises the following steps: forming a hardened film of the photosensitive coloring resin composition of the present invention on the organic light-emitting element by coating the organic light-emitting element with the photosensitive coloring resin composition of the present invention to form a coating film; irradiating the coating film with light; heating and baking the film after irradiation; and developing the film after irradiation. [Effects of the Invention]

[0015] According to the present invention, a photosensitive coloring resin composition can be provided that can suppress the generation of developing residues and form a colored layer with a good pattern shape even during low-temperature heat treatment. Furthermore, according to the present invention, a method for manufacturing a color filter and display device formed using the photosensitive coloring resin composition, and a laminate of an organic light-emitting element and an anti-reflective film using the photosensitive coloring resin composition can be provided.

Implementation Method

[0017] Hereinafter, embodiments and examples of the present invention will be described with reference to drawings, etc. However, the present invention can be implemented in many different ways and is not limited to the description of the embodiments and examples shown below. Furthermore, to make the explanation clearer, the drawings sometimes show the width, thickness, shape, etc. of each part in a patterned manner compared to the actual form, but these are merely examples and do not limit the interpretation of the present invention. Also, in this specification and the drawings, the same symbols are sometimes used for elements that are the same as those described above with respect to the proposed figures, and detailed descriptions are appropriately omitted. Furthermore, for ease of explanation, terms such as "above" or "below" are sometimes used, but the up and down directions can also be reversed. In this specification, when a component or region is located "above (or below)" other components or regions, this includes not only being located directly above (or below) other components, but also being located above (or below) other components, that is, including situations where other constituent elements are included between the top (or bottom) of other components, unless otherwise specified. Furthermore, in this invention, light includes electromagnetic waves of wavelengths in both visible and invisible regions, and further includes radiation, such as microwaves and electron beams. Specifically, it refers to electromagnetic waves and electron beams with wavelengths of 5 μm or less. In this invention, (meth)acrylic acid represents both acrylonitrile and methacrylic acid, (meth)acrylic acid represents both acrylic acid and methacrylic acid, and (meth)acrylate represents both acrylate and methacrylate. Also, in this invention, the "~" indicating a numerical range is used to encompass the values ​​described before and after it as a lower and upper limit value. The following describes in detail the manufacturing method of the photosensitive coloring resin composition, the cured material, the color filter, the display device, and the laminate of the organic light-emitting element and the external light reflection anti-reflection film of the present invention.

[0018] I. Photosensitive coloring resin composition The photosensitive coloring resin composition of the present invention contains a pigment, an alkali-soluble resin, a non-reactive resin, a photopolymerizable compound, a photoinitiator, and a solvent, wherein the acid value of the alkali-soluble resin exceeds 50 mgKOH / g, the acid value of the non-reactive resin is 7 mgKOH / g to 50 mgKOH / g, the content of structural units derived from methyl methacrylate is 50% to 99% by mass of all structural units, and the weight average molecular weight is 5000 to 50000.

[0019] Regarding the photosensitive coloring resin composition of the present invention, an alkali-soluble resin with an acid value exceeding 50 mgKOH / g contains a non-reactive resin with an acid value of 7 mgKOH / g to 50 mgKOH / g. In the aforementioned non-reactive resin, the content of structural units derived from methyl methacrylate is 50% to 99% by mass of all structural units, and the weight average molecular weight is 5000 to 50000. Therefore, even during low-temperature heat treatment, the generation of developing residue can be suppressed, and a colored layer with a good pattern shape can be formed. By combining the aforementioned non-reactive resin with a specific acid value, structural units, and weight average molecular weight into an alkali-soluble resin with an acid value above a certain value, the developability of the unexposed portion can be ensured through the combined effect, and the lower part of the resin composition layer in the exposed portion is less likely to flow due to development, suppressing undercutting of the cross-section after development. Depending on the type of non-reactive resin used, developing residues can easily be generated. However, the specific non-reactive resins used in this invention are selected in a manner that has the aforementioned specific acid value, structural units, and weight-average molecular weight. Therefore, when combined with an alkali-soluble resin with an acid value above a certain value, developing residues can be suppressed.

[0020] Furthermore, the photosensitive coloring resin composition of the present invention can suppress the generation of developing residues even during low-temperature heat treatment and form a colored layer with a good pattern shape, thus it can be suitably used for hardening films formed on organic light-emitting elements. That is, the photosensitive coloring resin composition of the present invention can be suitably used for hardening films formed directly on a substrate having an organic light-emitting element. When the photosensitive coloring resin composition of the present invention is used to form a hardening film adjacent to or separated from an organic light-emitting element, compared with a display device formed by bonding an external color filter formed on a substrate such as a glass substrate to an organic light-emitting element, a display device with improved thinness or flexibility can be manufactured. When the photosensitive coloring resin composition of the present invention is used to form a hardening film adjacent to or separated from an organic light-emitting element, a color filter that acts as a substitute for a polarizing plate to suppress external light reflection can also be used.

[0021] The photosensitive coloring resin composition of the present invention contains at least a colorant, an alkali-soluble resin, a non-reactive resin, a photopolymerizable compound, a photoinitiator, and a solvent, and may further contain other components within the scope that does not impair the effects of the present invention. Hereinafter, each component of the photosensitive coloring resin composition of the present invention will be described in detail in sequence.

[0022] <Colorant> In this invention, the colorant is any substance that displays the desired color when forming the color layer of the color filter, and there is no particular limitation. Various organic pigments, inorganic pigments, disperse dyes, and salt compounds of dyes can be used alone or in combination of two or more. Among them, organic pigments are preferred because they have higher color rendering and higher heat resistance. Examples of organic pigments include compounds classified as pigments in the Dyestuff Index (CI; published by The Society of Dyers and Colourists). Specifically, examples include those marked with Dyestuff Index (CI) numbers as follows.

[0023] CI Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 55, 60, 61, 65, 71, 73, 74, 81, 83, 93, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 116, 117, 119, 120, 126, 127, 128, 129, 138, 139, 150, 151, 152, 153, 154, 155, 156, 166, 168, 175, 185, and derivative pigments of CI Pigment Yellow 150; CI pigments: Orange 1, 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 61, 63, 64, 71, 73; CI pigments: Violet 1, 19, 23, 29, 32, 36, 38; CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48:1, 48:2, 48:3, 48:4, 49:1, 49:2, 50:1, 52:1, 53:1, 57, 57:1, 57:2, 58:2, 58:4, 60:1, 63:1, 63:2, 64:1, 81:1, 83, 88, 90:1, 97, 101, 102, 104, 1 05, 106, 108, 112, 113, 114, 122, 123, 144, 146, 149, 150, 151, 166, 168, 170, 171, 172, 174, 175, 176, 177, 178, 179, 180, 185, 187, 188, 190, 193, 194, 202, 206, 207, 208, 209, 215, 216, 220, 224, 226, 242, 243, 245, 254, 255, 264, 265, 269, 272, 291; CI Pigment Blue 15, 15:3, 15:4, 15:6, 60; CI Pigment Green 7, 36, 58, 59, 62, 63; CI Pigment Brown 23, 25; CI Pigment Black 1, 7.

[0024] Furthermore, specific examples of the above-mentioned inorganic pigments include: titanium dioxide, barium sulfate, calcium carbonate, zinc white, lead sulfate, litharge, zinc yellow, iron oxide red (iron oxide red (III)), cadmium red, ultramarine, iron blue, chromium oxide green, cobalt green, brown clay, titanium black, synthetic iron black, carbon black, etc.

[0025] For example, when the pigment dispersion of the present invention is used as the following photosensitive coloring resin composition to form a pattern of a light-shielding layer on a substrate of a color filter, a black pigment with high light-shielding properties is formulated into the ink. As a black pigment with high light-shielding properties, inorganic pigments such as carbon black or iron oxide, or organic pigments such as phthalocyanine black, can be used.

[0026] Examples of the aforementioned dispersible dyes include dyes that can be dispersed by imparting various substituents to the dye or by combining it with a solvent of low solubility. A salt-forming compound of a dye refers to a compound in which the dye forms a salt with a relative ion. Examples include salt-forming compounds of basic dyes and acids, and salt-forming compounds of acidic dyes and bases. Lake pigments are also included, which are obtained by using a known lake formation (salting) method to render a soluble dye insoluble in the solvent insoluble in the solvent. In this invention, by combining a pigment containing at least one selected from dyes and salt-forming compounds of dyes with the dispersant of this invention described above, the dispersibility or dispersion stability of the pigment can be improved.

[0027] The dyes described above can be appropriately selected from previously known dyes. Examples of such dyes include: azo dyes, metal zirconium salt azo dyes, anthraquinone dyes, triphenylmethane dyes, α-dyes, cyanine dyes, naphthoquinone dyes, quinone imine dyes, methylene dyes, phthalocyanine dyes, etc. Furthermore, regarding standards, if the amount of dye dissolved relative to 10 g of solvent (or mixed solvent) is 10 mg or less, it can be determined that the dye can be dispersed in the solvent (or mixed solvent).

[0028] Wherein, when the pigment contains at least one of the group consisting of pyrrolopyrrole dione pigment, quinophthalone pigment, copper phthalocyanine pigment, zinc phthalocyanine pigment, quinophthalone dye, coumarin dye, cyanine dye, and salt compounds of such dyes, it is preferable to form a high-brightness colored layer because it has a higher effect in suppressing the sublimation or precipitation of the pigment caused by the use of the above-mentioned dispersant. Furthermore, as the above-mentioned pigment, it is particularly preferable to contain at least one of the group consisting of pyrrolopyrrole dione pigment, quinophthalone pigment, copper phthalocyanine pigment, zinc phthalocyanine pigment, and quinophthalone dye.

[0029] Examples of pyrrolopyrrole dione pigments include CI Pigment Red 254, 255, 264, 272, 291 and pyrrolopyrrole dione pigments represented by the following general formula (i), wherein preferably at least one is selected from CI Pigment Red 254, 272, 291 and pyrrolopyrrole dione pigments in which R21 and R22 are 4-bromophenyl.

[0030] [Chemical 1] (In general formula (i), R51 and R52 are independently 4-chlorophenyl or 4-bromophenyl)

[0031] Examples of quinophthalone pigments include CI Pigment Yellow 138. Examples of copper phthalocyanine pigments include CI Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:5, 15:6, CI Pigment Green 7, 36, etc., with CI Pigment Blue 15:6 being preferred. Examples of zinc phthalocyanine pigments include CI Pigment Green 58, 59, etc. Examples of quinophthalone dyes include CI Disperse Yellow 54, 64, 67, 134, 149, 160, CI Solvent Yellow 114, 157, etc., with CI Disperse Yellow 54 being preferred.

[0032] The average primary particle size of the pigment used in this invention is not particularly limited, as long as it can suppress external light reflection during the fabrication of the hardened film and allow the required light from the light-emitting element to pass through, thereby suppressing the reduction of brightness in the display device. It also varies depending on the type of pigment used, but is preferably in the range of 10 nm to 100 nm, and more preferably 15 nm to 60 nm. By making the average primary particle size of the pigment within the above range, a display device equipped with a hardened film made using the photosensitive coloring resin composition of this invention can be made to suppress external light reflection, have high contrast, and high quality.

[0033] Furthermore, the average dispersed particle size of the pigment in the photosensitive coloring resin composition varies depending on the type of pigment used, preferably in the range of 10 nm to 100 nm, and more preferably in the range of 15 nm to 60 nm. The average dispersed particle size of the pigment in the photosensitive coloring resin composition is the dispersed particle size of the pigment particles dispersed in a dispersion medium containing at least a solvent, and is measured using a laser light scattering particle size analyzer. As a particle size measurement performed using a laser light scattering particle size analyzer, the photosensitive coloring resin composition can be appropriately diluted to a concentration that can be measured by a laser light scattering particle size analyzer (e.g., 1000 times, etc.) using the solvent used in the photosensitive coloring resin composition, and measured at 23°C using a laser light scattering particle size analyzer (e.g., the Nanotrac particle size distribution measuring device UPA-EX150 manufactured by Nikkiso Corporation) by dynamic light scattering method. Here, the average dispersed particle size is the volume average particle size.

[0034] The pigments used in this invention can be manufactured using known methods such as recrystallization and solvent salt milling. Alternatively, commercially available pigments can be micronized before use.

[0035] In the photosensitive coloring resin composition of the present invention, the content of the pigment is not particularly limited. Based on dispersibility and dispersion stability, the pigment content relative to the total solid content of the photosensitive coloring resin composition is preferably in the range of 3% to 65% by mass, and more preferably 4% to 60% by mass. When the content is above the lower limit, the hardened film obtained by coating the photosensitive coloring resin composition to a specific film thickness (typically 1.0 μm to 5.0 μm, for example 3.0 μm) easily has sufficient color concentration. Furthermore, when the content is below the upper limit, excellent storage stability is achieved, and a hardened film with sufficient hardness and adhesion to the substrate can be obtained. In the case of low-temperature heat treatment, the pigment content (pigment concentration) relative to the total solid content of the photosensitive coloring resin composition is preferably in the range of 3% to 50% by mass, and more preferably 4% to 40% by mass. Furthermore, in this invention, the solid component is all components other than the solvent described below, and also includes monomers dissolved in the solvent.

[0036] <Alkali-soluble resin> The alkali-soluble resin used in this invention is a resin with an acid value exceeding 50 mgKOH / g and having acidic groups, which can function as an adhesive resin, and is appropriately selected from those soluble in the alkaline developing solution used when forming patterns.

[0037] Regarding the preferred alkali-soluble resin of the present invention, examples include: (meth)acrylic copolymers having carboxyl groups and styrene-(meth)acrylic copolymers having carboxyl groups, as well as epoxy (meth)acrylic ester resins having carboxyl groups. Among these, reactive alkali-soluble resins having carboxyl groups on the side chains and further having reactive groups on the side chains are particularly preferred. This is because the strength of the hardened film formed by containing reactive groups is improved. As reactive groups, at least one can be selected from the group consisting of groups containing vinyl unsaturated bonds, epoxy groups, oxocyclobutyl groups, and terminal isocyanate groups.

[0038] Methacrylic resins, such as (meth)acrylic copolymers containing carboxyl groups and styrene-(meth)acrylic copolymers containing carboxyl groups, are (co)polymers obtained by (co)polymerizing carboxyl-containing vinyl unsaturated monomers and other monomers that can be copolymerized as needed using known methods. Examples of carboxyl-containing vinyl unsaturated monomers include: (meth)acrylic acid, vinylbenzoic acid, maleic acid, monoalkyl maleic acid esters, fumaric acid, itconic acid, butenoic acid, cinnamic acid, acrylic acid dimers, etc. Furthermore, addition reactions of monomers with hydroxyl groups, such as 2-hydroxyethyl (meth)acrylic acid, with cyclic anhydrides such as maleic anhydride or phthalic anhydride, cyclohexanedicarboxylic anhydride, ω-carboxyl-polycaprolactone mono(meth)acrylate, etc., can also be used. Furthermore, as a carboxyl precursor, monomers containing anhydrides such as maleic anhydride, itaconic anhydride, and citraconic anhydride can be used. Among these, (meth)acrylic acid is particularly preferred due to its copolymerization properties, cost, solubility, and glass transition temperature.

[0039] Based on the excellent adhesion of the coloring layer, the alkali-soluble resin preferably further contains a hydrocarbon ring. It is known that by making the alkali-soluble resin contain a hydrocarbon ring as a large-volume group, the solvent resistance of the obtained coloring layer, especially the swelling of the coloring layer, is suppressed. Although the effect has not yet been clarified, it is speculated that by containing a large-volume hydrocarbon ring in the coloring layer, the movement of molecules within the coloring layer is suppressed, resulting in increased coating strength and suppression of swelling caused by solvent. Examples of such hydrocarbon rings include: cyclic aliphatic hydrocarbon rings that may have substituents, aromatic rings that may have substituents, and combinations thereof. The hydrocarbon ring may have substituents such as carbonyl, carboxyl, oxycarbonyl, and amide groups. In the case of containing an aliphatic ring, the heat resistance or adhesion of the coloring layer is improved, and the brightness of the obtained coloring layer is increased. Specific examples of hydrocarbon rings include: aliphatic hydrocarbon rings such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, nordecane, tricyclo[5.2.1.0(2,6)]decane (dicyclopentane), and adamantane; aromatic rings such as benzene, naphthalene, anthracene, phenanthrene, and fumonisin; chain polycyclic rings such as biphenyl, biphenylene, diphenylmethane, triphenylmethane, and succinate; or the Cardo structure represented by the following chemical formula (ii).

[0040] [Chemical 2]

[0041] Furthermore, the alkali-soluble resin is preferably a cis-butene diamide structure represented by the following general formula (iii).

[0042] [Chemical 3] (In general formula (iii), RM is a substituted hydrocarbon ring)

[0043] When the alkali-soluble resin has the maleic diamide structure represented by the above general formula (iii), since the hydrocarbon ring has a nitrogen atom, it has excellent compatibility with the dispersant of the present invention, and the effect of suppressing development residue is improved. As a specific example of the substituted hydrocarbon ring in the RM of the above general formula (iii), examples of the same hydrocarbon ring as the above-described specific examples can be given.

[0044] When an aliphatic ring is contained as a hydrocarbon ring, it is preferable in terms of improving the heat resistance or adhesion of the colored layer and increasing the brightness of the obtained colored layer. Furthermore, when the colored layer contains the Cardo structure represented by the above chemical formula (ii), it is particularly preferable in terms of improving the hardening properties of the colored layer and improving solvent resistance (NMP (N-Methylpyrrolidone) swelling inhibition).

[0045] In the alkali-soluble resin used in this invention, based on the aspect that it is easy to adjust the amount of each structural unit and increase the amount of structural units having the above-mentioned hydrocarbon rings to easily improve the function of the structural units, it is preferable to use a (meth)acrylic copolymer that contains structural units having the above-mentioned hydrocarbon rings in addition to structural units having carboxyl groups. The (meth)acrylic copolymer containing structural units having carboxyl groups and the above-mentioned hydrocarbon rings can be prepared by using an vinyl unsaturated monomer having a hydrocarbon ring as the above-mentioned "other monomers that can be copolymerized". Examples of the aforementioned vinyl unsaturated monomers with hydrocarbon rings include: cyclohexyl methacrylate, dicyclopentyl methacrylate, adamantyl methacrylate, isobutyl methacrylate, benzyl methacrylate, phenoxyethyl methacrylate, and styrene. Based on the advantage that the cross-sectional shape of the colored layer after development is better maintained even during heat treatment, cyclohexyl methacrylate, dicyclopentyl methacrylate, adamantyl methacrylate, benzyl methacrylate, phenoxyethyl methacrylate, and styrene are preferred.

[0046] Furthermore, the alkali-soluble resin used in this invention is preferably a reactive alkali-soluble resin with a side chain containing an ethylene-unsaturated bond. When the side chain contains an ethylene-unsaturated bond, during the curing step of the resin composition, the alkali-soluble resin can form cross-links with each other, or with a photopolymerizable compound, etc. Therefore, if a reactive alkali-soluble resin with a side chain containing an ethylene-unsaturated bond is used, the film strength of the cured film is further improved through a synergistic effect. Therefore, even during low-temperature heat treatment, the solvent resistance of the coloring layer can be further improved, thereby enhancing the developability. Furthermore, the thermal shrinkage of the cured film is suppressed, and the adhesion to the substrate becomes superior. The method for introducing the ethylene-unsaturated bond group into the alkali-soluble resin can be appropriately selected from previously known methods. For example, the following methods can be cited: adding the carboxyl group of the alkali-soluble resin to a compound that has both epoxy groups and vinyl unsaturated bonds in the molecule, such as glycidyl (meth)acrylate, to introduce vinyl unsaturated bonds into the side chain; or introducing structural units with hydroxyl groups into the copolymer in advance, so that they can add to a compound that has isocyanate groups and vinyl unsaturated bonds in the molecule, thereby introducing vinyl unsaturated bonds into the side chain, etc.

[0047] The alkali-soluble resin used in this invention may further contain other structural units such as methyl methacrylate and ethyl methacrylate, which have ester groups. The structural units with ester groups not only function as components that inhibit the alkali solubility of the photosensitive coloring resin composition, but also function as components that improve solubility in solvents and thus improve solvent redissolution.

[0048] The alkali-soluble resin used in this invention is preferably a (meth)acrylic copolymer or a styrene-(meth)acrylic copolymer containing structural units having carboxyl groups and structural units having hydrocarbon rings, and more preferably a (meth)acrylic copolymer or a styrene-(meth)acrylic copolymer containing structural units having carboxyl groups, structural units having hydrocarbon rings, and structural units having vinyl unsaturated bonds.

[0049] By appropriately adjusting the amount of each structural unit added to the alkali-soluble resin, an alkali-soluble resin with the desired properties can be prepared.

[0050] Regarding obtaining a good pattern, the amount of carboxyl-containing vinyl unsaturated monomer added is preferably 5% by mass or more, and more preferably 10% by mass or more, relative to the total amount of monomer. On the other hand, regarding suppressing film roughness on the pattern surface after development, the amount of carboxyl-containing vinyl unsaturated monomer added is preferably 50% by mass or less, and more preferably 40% by mass or less, relative to the total amount of monomer. If the ratio of carboxyl-containing vinyl unsaturated monomer is at or above the aforementioned lower limit, the obtained coating tends to have sufficient solubility in alkaline developer. Furthermore, if the ratio of carboxyl-containing vinyl unsaturated monomer is at or below the aforementioned upper limit, the formed pattern is less likely to peel off from the substrate or the pattern surface film tends to be rough when developing with alkaline developer.

[0051] Furthermore, in (meth)acrylic resins such as (meth)acrylic copolymers and styrene-(meth)acrylic copolymers containing structural units with ethylene unsaturated bonds in the side chains, which can be more preferably used as alkali-soluble resins, the amount of the compound having both epoxy groups and ethylene unsaturated bonds added relative to the carboxyl-containing ethylene unsaturated monomer is preferably 10% to 95% by mass, and more preferably 15% to 90% by mass.

[0052] Regarding the adhesive function after curing, the weight average molecular weight (Mw) of the alkali-soluble resin, such as the carboxyl-containing copolymer, is preferably 3,000 or more, more preferably 5,000 or more, and regarding the pattern-forming properties during development with an alkaline developer, it is preferably 30,000 or less, more preferably 20,000 or less. Furthermore, the weight average molecular weight (Mw) of the present invention can be measured using polystyrene as a standard, THF as the elution solution, and a Shodex GPC System-21H.

[0053] There is no particular limitation on the epoxy (meth)acrylate resin having a carboxyl group, but it is preferable to be an epoxy (meth)acrylate compound obtained by reacting an epoxy compound and a reactant containing an unsaturated monocarboxylic acid with an acid anhydride. The epoxy compound, the unsaturated monocarboxylic acid, and the acid anhydride can be appropriately selected from those known. For example, the description in paragraphs 0226 to 0240 of Japanese Patent No. 6911365 can be used appropriately. As an epoxy (meth)acrylate resin having a carboxyl group, for example, it can be an alkali-soluble resin, which is obtained by adding at least a portion of the epoxy groups of a polymer of epoxy-containing (meth)acrylate such as glycidyl methacrylate or a copolymer of epoxy-containing (meth)acrylate with other vinyl unsaturated monomers to an unsaturated monocarboxylic acid, and then adding at least a portion of the hydroxyl groups generated by the addition reaction to an acid anhydride. Epoxy (meth)acrylate resins having carboxyl groups can be used alone or in combination of two or more.

[0054] Based on the developerability (solubility) in the alkaline aqueous solution used in the developer, the alkali-soluble resin is selected with an acid value exceeding 50 mgKOH / g. Based on the developerability in the alkaline aqueous solution used in the developer and the adhesion to the substrate, the alkali-soluble resin preferably has an acid value of 60 mgKOH / g or higher and 300 mgKOH / g or lower, particularly 70 mgKOH / g or higher and 200 mgKOH / g or lower. The upper limit of the acid value can be 150 mgKOH / g or lower, 120 mgKOH / g or lower, or 100 mgKOH / g or lower. Furthermore, the acid value of the present invention can be determined according to JIS K 0070:1992.

[0055] In order to obtain the effects of improving the strength of the hardened film, improving solvent resistance or developability, and excellent adhesion to the substrate, the ethylene unsaturated bond equivalent of the side chain of the alkali-soluble resin is preferably in the range of 100 to 2000, especially in the range of 140 to 1500. When the ethylene unsaturated bond equivalent is less than 2000, the solvent resistance, developability, or adhesion is excellent. Furthermore, when it is 100 or more, the ratio of other structural units such as the structural units with carboxyl groups or the structural units with hydrocarbon rings can be relatively increased, so the developability or heat resistance is excellent. Here, the ethylene unsaturated bond equivalent refers to the weight average molecular weight corresponding to 1 mole of the ethylene unsaturated bond of the alkali-soluble resin, and is expressed by the following formula (1).

[0056] Equation (1) Equivalent amount of ethylene unsaturated bonds (g / mol) = W(g) / M(mol) (In equation (1), W represents the mass (g) of alkali-soluble resin, and M represents the number of moles (mol) of ethylene unsaturated bonds contained in alkali-soluble resin W(g))

[0057] The equivalent of the above-mentioned vinyl unsaturated bonds can be calculated, for example, by determining the number of vinyl unsaturated bonds contained in 1 g of alkali-soluble resin by means of the iodine value test method described in JIS K 0070:1992.

[0058] The alkali-soluble resin used in the photosensitive coloring resin composition may be used alone or in combination of two or more. There is no particular limitation on the content of the alkali-soluble resin, but relative to the total solid content of the photosensitive coloring resin composition, it is preferably in the range of 5% to 60% by mass, and more preferably 10% to 40% by mass. If the content of the alkali-soluble resin is above the lower limit mentioned above, sufficient alkaline developability can be obtained; and if the content of the alkali-soluble resin is below the upper limit mentioned above, film roughness or pattern defects can be suppressed during development.

[0059] <Non-reactive resin> The non-reactive resin used in this invention has an acid value of 7 mgKOH / g to 50 mgKOH / g, a content of methyl methacrylate structural units of 50% to 99% by mass in all structural units, and a weight average molecular weight of 5000 to 50000. The non-reactive resin used in this invention is a resin that is substantially free of at least one reactive group selected from the group consisting of groups containing vinyl unsaturated bonds, epoxy groups, oxobutyl groups, and terminal isocyanate groups.

[0060] Regarding the suppression of developing residue, the acid value of the non-reactive resin used in this invention is 7 mgKOH / g or more, preferably 20 mgKOH / g or more, and even more preferably 30 mgKOH / g or more. On the other hand, regarding the improvement of undercut shape, the acid value of the non-reactive resin used in this invention is 50 mgKOH / g or less, preferably 47 mgKOH / g or less, preferably 45 mgKOH / g or less, and even more preferably 40 mgKOH / g or less.

[0061] The non-reactive resin used in this invention may be a copolymer containing structural units derived from methyl methacrylate. In the non-reactive resin used in this invention, based on improving the undercut shape, the content of structural units derived from methyl methacrylate in all structural units is 50% by mass or more, preferably 90% by mass or more, and more preferably 92% by mass or more. On the other hand, based on suppressing developing residue, the content of structural units derived from methyl methacrylate in all structural units is 99% by mass or less, preferably 98% by mass or less, and more preferably 97% by mass or less.

[0062] The non-reactive resin used in this invention may be a (meth)acrylic copolymer containing structural units derived from methyl methacrylate and structural units derived from vinyl unsaturated monomers capable of copolymerizing therewith; it may be a (meth)acrylic copolymer containing structural units derived from methyl methacrylate and structural units having acidic groups; or it may be a (meth)acrylic copolymer containing structural units derived from methyl methacrylate and structural units having carboxyl groups. Examples of carboxyl-containing structural units include structural units derived from carboxyl-containing vinyl unsaturated monomers. The carboxyl-containing vinyl unsaturated monomer may be the same as the carboxyl-containing vinyl unsaturated monomers exemplified in the above-mentioned alkali-soluble resins, wherein (meth)acrylic acid is particularly preferred based on copolymerization, cost, solubility, and other factors. The content of structural units with carboxyl groups can be adjusted appropriately according to the acid value. It can be selected from 1% to 10% by mass of all structural units, preferably 2% or more, more preferably 3% or more, and preferably 9% or less, more preferably 8% or less.

[0063] The non-reactive resin used in this invention may, to the extent that it does not impair the effects of this invention, contain structural units derived from methyl methacrylate and structural units having acidic groups, as well as other structural units derived from vinyl unsaturated monomers capable of copolymerizing with structural units derived from methyl methacrylate. These other vinyl unsaturated monomers capable of copolymerization may be the same as those exemplified in the above-described alkali-soluble resins. These other vinyl unsaturated monomers capable of copolymerization may, based on the aspect of suppressing undercut shape, be those without alkali-soluble substituents. Other vinyl unsaturated monomers that can be copolymerized include, for example: ethyl methacrylate, butyl methacrylate, benzyl methacrylate, phenoxyethyl methacrylate, cyclohexyl methacrylate, dicyclopentyl methacrylate, isobutyl methacrylate, tetrahydrofurfuryl methacrylate, 2-methoxyethyl methacrylate, 2-ethoxyethyl methacrylate, dimethylaminomethyl methacrylate, diethylaminoethyl methacrylate, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, etc. Two or more of these other structural units can be mixed. Preferably, these other structural units are 49% by mass or less, more preferably 9% by mass or less, may be 5% by mass or less, and may even be 0% by mass.

[0064] Regarding the non-reactive resin used in this invention, the total content of structural units derived from methyl methacrylate and structural units having acidic groups in all structural units may be 100% by mass, and the total content of structural units derived from methyl methacrylate and structural units having carboxyl groups in all structural units may be 100% by mass.

[0065] Regarding improving the undercut shape, the non-reactive resin used in this invention has a weight-average molecular weight (Mw) of 5000 or more, preferably 7000 or more, and more preferably 9000 or more. On the other hand, regarding suppressing development residue, the weight-average molecular weight (Mw) is 50000 or less, preferably 30000 or less, and more preferably 20000 or less. The non-reactive resin used in this invention can be prepared in the same manner as the aforementioned alkali-soluble resin.

[0066] The glass transition temperature (Tg) of the non-reactive resin used in this invention can exceed 0°C, be 20°C or higher, or be 50°C or higher. Furthermore, the glass transition temperature (Tg) of the alkali-soluble resin can be measured using a differential scanning calorimeter (DSC) (e.g., an EXSTAR DSC 7020 manufactured by SII Nano Technologies) based on the method described in JIS K 7121. When two or more peaks representing the glass transition temperature are observed, the peak with the largest peak area (i.e., the area of ​​the portion protruding from the baseline of the obtained graph) is taken as the representative value of the glass transition temperature. Also, the glass transition temperature (Tg) of the copolymer can be calculated using the following formula, and the obtained value is used as a standard: 1 / Tg=Σ(Xi / Tgi) Here, it is assumed that the copolymer is composed of n monomer components i=1 to n. Xi is the weight fraction of the i-th monomer (ΣXi=1), and Tgi is the glass transition temperature (absolute temperature) of the homopolymer of the i-th monomer. Here, Σ is the sum of i=1 to n. Furthermore, the glass transition temperature (Tgi) of the homopolymer of each monomer can be obtained from the Polymer Handbook (3rd Edition) (J. Brandrup, E. Himmergut, Wiley-Interscience, 1989).

[0067] The non-reactive resin used in the photosensitive coloring resin composition may be used alone or in combination with two or more other resins. The content of the non-reactive resin can be appropriately selected; for improving the undercut shape, it is preferably 1% by mass or more, more preferably 2% by mass or more, and even more preferably 4% by mass or more, relative to the total solid content of the photosensitive coloring resin composition. On the other hand, for suppressing developing residue, the content of the non-reactive resin is preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 12% by mass or less, relative to the total solid content of the photosensitive coloring resin composition.

[0068] Furthermore, regarding the content of non-reactive resin used in the photosensitive coloring resin composition, for the purpose of improving the undercut shape, the content of non-reactive resin relative to the total content of the aforementioned reactive alkali-soluble resin and the aforementioned non-reactive resin is preferably 1% by mass or more, more preferably 5% by mass or more, and even more preferably 10% by mass or more. On the other hand, for the purpose of suppressing developing residue, the content of non-reactive resin relative to the total content of the aforementioned reactive alkali-soluble resin and the aforementioned non-reactive resin is preferably 80% by mass or less, more preferably 70% by mass or less, and even more preferably 60% by mass or less.

[0069] <Photopolymerizable Compound> Examples of photopolymerizable compounds used in photosensitive coloring resin compositions include compounds having photopolymerizable groups in their molecules. The photopolymerizable group is not particularly limited as long as it can be polymerized by a photoinitiator; examples include groups containing vinyl unsaturated bonds, such as vinyl, allyl, acrylonitrile, or methacrylonitrile. Among these, acrylonitrile or methacrylonitrile are suitable for UV curing. For curing purposes, the photopolymerizable compound is preferably a compound containing two or more photopolymerizable groups per molecule, and more preferably a compound containing three or more photopolymerizable groups per molecule.

[0070] As a photopolymerizable compound, it is suitable to use a compound having two or more vinyl unsaturated bonds, and more preferably a polyfunctional (meth)acrylate having two or more acrylonitrile or methacrylonitrile groups. Such a polyfunctional (meth)acrylate can be appropriately selected from those previously known. Specific examples include those described in Japanese Patent Application Publication No. 2013-029832.

[0071] These multifunctional (meth)acrylates can be used alone or in combination of two or more. Furthermore, when the photosensitive coloring resin composition of the present invention is required to have excellent photocurability (high sensitivity), the multifunctional (meth)acrylate is preferably one having three or more polymerizable vinyl unsaturated bonds, preferably a poly(meth)acrylate of a polyol with three or more nucleotides or a dicarboxylic acid modified thereof. Specifically, it is preferably trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, a succinic acid modified version of pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, a succinic acid modified version of dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc.

[0072] There is no particular limitation on the content of the aforementioned photopolymerizable compound used in the photosensitive coloring resin composition. For example, it is preferably 5% to 60% by mass, and more preferably 10% to 40% by mass, relative to the total solid content of the photosensitive coloring resin composition. If the content of the photopolymerizable compound is above or below the aforementioned lower limit, sufficient photocuring can be achieved, suppressing the dissolution of the exposed portion during development. Furthermore, if the content of the photopolymerizable compound is below the aforementioned upper limit, sufficient alkaline developability is achieved.

[0073] <Photoinitiator> As the photoinitiator used in the photosensitive coloring resin composition of the present invention, one or more photoinitiators can be used from various previously known photoinitiators. Examples of photoinitiators include: aromatic ketones, benzoin ethers, halomethyl diazole compounds, α-amino ketones, biimidazoles, N,N-dimethylaminobenzophenone, halomethyl-symmetric triterpenoids, 9-oxosulfuron, oxime esters, etc. Such photoinitiators can be previously known photoinitiators, such as those described in International Publication No. 2018 / 062105.

[0074] Furthermore, as the oxime ester-based photoinitiator used in this invention, examples include 1,2-octanedione-1-[4-(phenylthio)phenyl]-,2-(o-benzoyl oxime), acetone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-,1-(o-acetylgoxime), Japanese Patent Application Publication No. 2000-80068, and Japanese Patent Application Publication No. 2000-80068. Appropriately select from the oxime ester-based photoinitiators described in Japanese Patent Publication No. 2001-233842, Japanese Patent Publication No. 2010-527339, Japanese Patent Publication No. 2010-527338, Japanese Patent Publication No. 2013-041153, International Publication No. 2015 / 152153, and Japanese Patent Publication No. 2010-256891.

[0075] In view of the fact that a hardened film with good solvent resistance and substrate adhesion can be easily formed even when heated at low temperature, the above-mentioned oxime ester photoinitiator is preferably one of the compounds represented by the following general formula (A) and the compounds represented by the following general formula (B).

[0076] [Chemical 4] (wherein, R1 and R2 independently represent R11, OR11, COR11, SR11, CONR12R13 or CN, respectively; R11, R12 and R13 independently represent hydrogen atoms, alkyl groups with 1 to 20 carbon atoms, aryl groups with 6 to 30 carbon atoms, aralkyl groups with 7 to 30 carbon atoms, or heterocyclic groups with 2 to 20 carbon atoms, respectively; the hydrogen atoms of the groups represented by R11, R12 and R13 can be further substituted with R21, OR21, COR21, SR21, NR22R23, CONR22R23, -NR22-OR23, -NCOR22-OCOR23, NR22COR21, OCOR21, COOR21, SCOR21, OCSR21, COSR21, CSOR21, hydroxyl, nitro, CN, or halogen atoms, R21, R22, and R23 independently represent a hydrogen atom, an alkyl group with 1 to 20 carbon atoms, an aryl group with 6 to 30 carbon atoms, an aralkyl group with 7 to 30 carbon atoms, or a heterocyclic group with 2 to 20 carbon atoms, respectively. The hydrogen atom of the group represented by R21, R22, and R23 can be further substituted with a hydroxyl group, a nitro group, a CN group, a halogen atom, or a carboxyl group. The alkyl portion of the group represented by R11, R12, R13, R21, R22, and R23 can contain 1 to 5 -O-, -S-, -COO-, -OCO-, -NR24-, -NR24CO-, -NR24COO-, -OCONR24-, -SCO-, -COS-, -OCS-, or -CSO-, provided that the oxygen atom is not adjacent to it. R24 represents a hydrogen atom, an alkyl group with 1 to 20 carbon atoms, an aryl group with 6 to 30 carbon atoms, an aralkyl group with 7 to 30 carbon atoms, or a heterocyclic group with 2 to 20 carbon atoms. The alkyl portion of the groups represented by R11, R12, R13, R21, R22, R23, and R24 may have branched side chains or be cyclic alkyl groups. R3 represents a hydrogen atom, an alkyl group with 1 to 20 carbon atoms, an aryl group with 6 to 30 carbon atoms, an aralkyl group with 7 to 30 carbon atoms, or a heterocyclic group with 2 to 20 carbon atoms. The alkyl portion of the group represented by R3 may have branched side chains or be cyclic alkyl groups. Furthermore, R3 and R7, and R3 and R8, can each form a ring together. The hydrogen atom in the radical represented by R3 can be further substituted with R21, OR21, COR21, SR21, NR22R23, CONR22R23, -NR22-OR23, -NCOR22-OCOR23, NR22COR21, OCOR21, COOR21, SCOR21, OCSR21, COSR21, CSOR21, hydroxyl, nitro, CN, or a halogen atom. R4, R5, R6, and R7 independently represent R11, OR11, SR11, COR14, CONR15R16, NR12COR11, OCOR11, COOR14, SCOR11, OCSR11, COSR14, CSOR11, hydroxyl, CN, or a halogen atom, respectively.R4 and R5, R5 and R6, and R6 and R7 can each form a ring together. R14, R15, and R16 represent hydrogen atoms or alkyl groups with 1 to 20 carbon atoms. The alkyl portion of the groups represented by R14, R15, and R16 can have branched side chains or be cyclic alkyl groups. R8 represents R11, OR11, SR11, COR11, CONR12R13, NR12COR11, OCOR11, COOR11, SCOR11, OCSR11, COSR11, CSOR11, hydroxyl, CN, or halogen atoms. k represents 0 or 1.

[0077] [Chemical 5](In formula (B), X1, X3 and X6 independently represent R41, OR41, COR41, SR41, CONR42R43 or CN, respectively; X2 represents an alkyl group with 1 to 20 carbon atoms, an aryl group with 6 to 30 carbon atoms, an aralkyl group with 7 to 30 carbon atoms, or a heterocyclic group with 2 to 20 carbon atoms, respectively; X4 and X5 independently represent R41, OR41, SR41, COR41, CONR42R43, NR42COR41, OCOR41, COOR41, SCOR41, COSR41, COSR41, CSOR41, CN, a halogen atom or a hydroxyl group, respectively; R41, R42 and R43 independently represent a hydrogen atom, an alkyl group with 1 to 20 carbon atoms, an aryl group with 6 to 30 carbon atoms, an aralkyl group with 7 to 30 carbon atoms, or a heterocyclic group with 2 to 20 carbon atoms, respectively.) The hydrogen atoms of the groups represented by R41, R42, and R43, and X2, can be further substituted with R51, OR51, COR51, SR51, NR52R53, CONR52R53, -NR52-OR53, -NCOR52-OCOR53, NR52COR51, OCOR51, COOR51, SCOR51, OCSR51, COSR51, CSOR51, hydroxyl, nitro, CN, or halogen atoms. R51, R52, and R53 independently represent hydrogen atoms, alkyl groups with 1 to 20 carbon atoms, aryl groups with 6 to 30 carbon atoms, aralkyl groups with 7 to 30 carbon atoms, or heterocyclic groups with 2 to 20 carbon atoms. The hydrogen atoms of the groups represented by R51, R52, and R53 can be further substituted with hydroxyl, nitro, CN, halogen atoms, or carboxyl groups. The alkyl moiety of the groups represented by R41, R42, R43, X2, R51, R52, and R53 may contain 1 to 5 -O-, -S-, -COO-, -OCO-, -NR54-, -NR54CO-, -NR54COO-, -OCONR54-, -SCO-, -COS-, -OCS-, or -CSO-, provided that the oxygen atom is not adjacent. R54 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms. The alkyl moiety of the groups represented by R41, R42, R43, R51, R52, R53, and R54 may have branched side chains or may be cyclic alkyl groups; (a and b are each an independent integer from 0 to 3).

[0078] (Compounds represented by general formula (A)) The oxime ester compounds represented by the above general formula (A) exist as geometric isomers depending on the double bond of the oxime, but such is not distinguished. That is, in the present invention, the compounds represented by the above general formula (A), and the compounds represented by the following general formula (A') as preferred forms of the compounds described below, and their exemplary compounds represent mixtures of the two or any one of them, and are not limited to showing the structures of the isomers.

[0079] The alkyl groups represented by R3, R11, R12, R13, R14, R15, R16, R21, R22, R23 and R24 in the above general formula (A) having 1 to 20 carbon atoms can be exemplified by: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, dibutyl, tributyl, pentyl, isopentyl, tripentyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, trioctyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, cyclopentyl, cyclopentylmethyl, cyclopentylethyl, cyclohexyl, cyclohexylmethyl, cyclohexylethyl, etc.

[0080] The aryl groups represented by R3, R11, R12, R13, R21, R22, R23 and R24 in the above general formula (A) having 6 to 30 carbon atoms can be exemplified by: phenyl, tolyl, xylyl, ethylphenyl, naphthyl, anthracene, phenanthryl, phenyl, biphenyl, naphthyl, anthracene, etc., which are substituted with one or more of the above alkyl groups.

[0081] The aralkyl group represented by R3, R11, R12, R13, R21, R22, R23 and R24 in the above general formula (A) having 7 to 30 carbon atoms can be exemplified by, for example: benzyl, α-methylbenzyl, α,α-dimethylbenzyl, phenylethyl, etc.

[0082] The heterocyclic groups with 2 to 20 carbon atoms represented by R3, R11, R12, R13, R21, R22, R23, and R24 in the above general formula (A) can be exemplified by, for example, pyridinyl, pyrimidinyl, furanyl, thiopheneyl, tetrahydrofuranyl, dioxolanecycloyl, benzo[a]azol-2-yl, tetrahydropyranyl, pyrrolidinyl, imidazodimethyl, pyrazolylalkyl, thiazodimethyl, isothiazolyl, acezodimethyl, isoacezodimethyl, piperidinyl, piperidine, morpholinyl, and other 5 to 7-membered heterocycles. As for the rings that can be formed together in the above general formula (A), such as R4 and R5, R5 and R6, R6 and R7, and R3 and R7 and R3 and R8, examples of 5 to 7 member rings include: cyclopentane ring, cyclohexane ring, cyclopentene ring, benzene ring, piperidine ring, morpholine ring, lactone ring, lactamine ring, etc.

[0083] Furthermore, examples of halogen atoms represented by R4, R5, R6, R7 and R8 in the above general formula (A), and halogen atoms in the above general formula (A) that can substitute for R3, R11, R12, R13, R21, R22 and R23, include fluorine, chlorine, bromine and iodine.

[0084] The alkyl portion of the groups represented by R11, R12, R13, R21, R22 and R23 in the above general formula (A) may contain 1 to 5 -O-, -S-, -COO-, -OCO-, -NR24-, -NR24CO-, -NR24COO-, -OCONR24-, -SCO-, -COS-, -OCS- or -CSO-, provided that the oxygen atoms are not adjacent. In this case, the divalent group contained may be one or more groups, and when it is a group that can be continuously contained, it may contain 2 or more groups continuously.

[0085] Furthermore, the alkyl (extrinyl) moiety represented by R11, R12, R13, R21, R22, R23, and R24 in the above general formula (A) may have branched side chains or may be cyclic alkyl groups. Among the compounds represented by the above general formula (A), R3 being a condensable aromatic ring, or the compounds represented by the following general formula (A'), are preferred because they have higher sensitivity and are easier to manufacture.

[0086] [Chemical 6] (In the formula, R1, R2, R4, R5, R6, R7, R8 and k are the same as in the above general formula (A), R31, R32, R33, R34 and R35 independently represent R11, OR11, SR11, COR11, CONR15, R16, NR12, COR11, OCOR11, COOR14, SCOR11, OCSR11, COSR14, CSOR11, hydroxyl, nitro, CN or halogen atom, respectively, and R31 and R32, R32 and R33, R33 and R34 and R34 and R35 can form a ring together)

[0087] As an example of a ring formed by R31 and R32, R32 and R33, R33 and R34 and R34 and R35, the same rings as those exemplified above as rings formed by R4 and R5, R5 and R6 and R6 and R7, and R3 and R7 and R3 and R8 can be given.

[0088] In the above general formulas (A) and (A'), R1 being an alkyl group with 1 to 12 carbon atoms or an aralkyl group with 7 to 15 carbon atoms, R11 being an aryl group with 6 to 12 carbon atoms, or an alkyl group with 1 to 8 carbon atoms are preferred due to their higher solvent solubility; R2 being a methyl, ethyl, or phenyl group is preferred due to its higher reactivity; R4 to R7 being hydrogen atoms or cyano groups, especially hydrogen atoms, are preferred due to their ease of synthesis; R8 being a hydrogen atom is preferred due to its ease of synthesis; k is... The sensitivity is higher at step 1, which is therefore preferred. In the above general formula (A'), at least one of R31 to R35 is nitro, CN, halogen atom, or COR11, and R11 is an aryl group with 6 to 12 carbon atoms or an alkyl group with 1 to 8 carbon atoms. Therefore, the sensitivity is higher, which is therefore preferred. More preferably, at least one of R31 to R35 is nitro, CN, halogen atom, or COPh (here, Ph is phenyl). Especially preferred is R33 being nitro, CN, halogen atom, or COPh.

[0089] As a preferred specific example of a compound represented by the above general formula (A), the following compounds may be cited. Also, compounds No. 1 to No. 212 described in International Publication No. 2015 / 152153 may be cited.

[0090] [Chemical 7]

[0091] The compound represented by the above general formula (A) can be synthesized, for example, by referring to International Publication No. 2015 / 152153, by appropriately selecting the solvent, reaction temperature, reaction time, purification method, etc., according to the materials used. Alternatively, commercially available products can be purchased for use.

[0092] (Compounds represented by general formula (B)) The oxime ester compounds represented by the above general formula (B) also have geometric isomers depending on the double bond of the oxime, but these are not distinguished. That is, in the present invention, the compounds represented by the above general formula (B) and the exemplary compounds represent mixtures of the two or either one, and are not limited to showing the structure of the isomers.

[0093] Examples of alkyl groups with 1 to 20 carbon atoms represented by X2, R41, R42, R43, R51, R52, R53, and R54 in general formula (B) above are the same as those in general formula (A) above. Examples of aryl groups with 6 to 30 carbon atoms represented by X2, R41, R42, R43, R51, R52, R53, and R54 in general formula (B) above are the same as those in general formula (A) above. Examples of aralkyl groups with 7 to 30 carbon atoms represented by X2, R41, R42, R43, R51, R52, R53, and R54 in general formula (B) above are the same as those in general formula (A) above. As for the heterocyclic groups with 2 to 20 carbon atoms represented by X2, R41, R42, R43, R51, R52, R53, and R54 in the above general formula (B), examples can be given that are the same as the heterocyclic groups with 2 to 20 carbon atoms in the above general formula (A). Furthermore, as for the halogen atoms in the above general formula (B), examples can be given that are the same as the halogen atoms in the above general formula (A).

[0094] The alkyl portion of the groups represented by R41, R42, R43, X2, R51, R52 and R53 in the above general formula (B) may contain 1 to 5 -O-, -S-, -COO-, -OCO-, -NR54-, -NR54CO-, -NR54COO-, -OCONR54-, -SCO-, -COS-, -OCS- or -CSO-, provided that the oxygen atoms are not adjacent. In this case, the divalent group may be one or more groups, and when it is a group that can be continuously included, it may contain 2 or more groups continuously.

[0095] In terms of sensitivity, solubility, and compatibility, X1 in the above general formula (B) is preferably an alkyl group having 1 to 10 carbons, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tributyl, n-pentyl, isopentyl, tripentyl, n-hexyl, and 2-ethylhexyl; a cyclic alkyl group having 5 to 10 carbons and possibly having a side chain, such as cyclopentyl and cyclohexyl; or an alkyl group having 2 to 10 carbons, such as methoxymethyl, ethoxymethyl, ethoxyethyl, 2-(1-methoxypropyl) and 2-(1-ethoxypropyl) and having one ether bond in a methylene chain; and more preferably an alkyl group having 1 to 10 carbons, such as methyl, ethyl, and 2-ethylhexyl.

[0096] In terms of sensitivity, solubility, and compatibility, X2, X3, and X6 in the above general formula (B) are preferably, independently, alkyl groups having 1 to 6 carbons, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tributyl, n-pentyl, isopentyl, tripentyl, and n-hexyl; cyclic alkyl groups having 5 to 6 carbons, such as cyclopentyl and cyclohexyl; or alkyl groups having one ether bond in a methylene chain having 2 to 6 carbons, such as methoxymethyl, ethoxymethyl, ethoxyethyl, 2-(1-methoxypropyl) and 2-(1-ethoxypropyl); and more preferably, alkyl groups having 1 to 6 carbons, or alkyl groups having one ether bond in a methylene chain having 2 to 6 carbons. In terms of sensitivity, solubility, and compatibility, X3 and X6 are preferably, independently, alkyl groups having 1 to 6 carbons. Based on sensitivity, solubility, and compatibility, X2 is preferably an alkyl group having one ether bond in a methylene chain having 2 to 6 carbons.

[0097] In terms of sensitivity, solubility, and compatibility, X4 and X5 in the above general formula (B) are preferably, independently, hydrogen, or alkyl groups having 1 to 6 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tributyl, n-pentyl, isopentyl, tripentyl, and n-hexyl. a and b are independently, independently, integers from 0 to 3, integers from 0 to 1, and may also be 0.

[0098] As a preferred specific example of a compound represented by the above general formula (B), the following compounds may be cited as examples.

[0099] [Chemical 8]

[0100] [Chemistry 9]

[0101] The compound represented by the above general formula (B) can be synthesized, for example, by referring to Japanese Patent Application Publication No. 2010-256891, by appropriately selecting the solvent, reaction temperature, reaction time, purification method, etc., according to the materials used. Alternatively, commercially available products can be purchased and used.

[0102] The total content of photoinitiator used in the photosensitive coloring resin composition of the present invention is not particularly limited as long as it does not impair the effect of the present invention. It is preferably in the range of 0.1% to 15.0% by mass relative to the total solid content of the photosensitive coloring resin composition, and more preferably in the range of 1.0% to 10.0% by mass. When this content is above the lower limit, photocuring is easily and sufficiently achieved, and solvent resistance or substrate adhesion becomes good. On the other hand, when it is below the upper limit, linewidth shift is suppressed, and high-precision patterns are easily formed.

[0103] Regarding the total content of at least one of the compounds represented by the above general formula (A) and the compounds represented by the above general formula (B), based on the fact that a hardened film with good substrate adhesion and solvent resistance can be formed even during low-temperature heating treatment, the total amount of photoinitiator is preferably 30.0% by mass or more, more preferably 50.0% by mass or more, and even more preferably 70.0% by mass or more, and can be 100% by mass.

[0104] <Solvent> The solvent used in this invention is any organic solvent that can dissolve or disperse the components in the photosensitive coloring resin composition without reacting with them, and is not particularly limited thereto. The solvent may be used alone or in combination of two or more. Specific examples of solvents include: alcohol solvents such as methanol, ethanol, n-propanol, isopropanol, methoxy alcohol, and ethoxy alcohol; carbitol solvents such as methoxyethoxyethanol and ethoxyethoxyethanol; ester solvents such as ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl methoxypropionate, ethyl ethoxypropionate, ethyl lactate, methyl hydroxypropionate, ethyl hydroxypropionate, n-butyl acetate, isobutyl acetate, isobutyl butyrate, n-butyl butyrate, ethyl lactate, and cyclohexanol acetate; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and 2-heptanone; and glycol ether acetate solvents such as methoxyethyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy-3-methyl-1-butyl acetate, 3-methoxybutyl acetate, and ethoxyethyl acetate. Carbitol acetate solvents such as carbitol acetate (BCA), methoxyethoxyethyl acetate, ethoxyethoxyethyl acetate, and butyl carbitol acetate; diacetates such as propylene glycol diacetate and 1,3-butanediol diacetate; glycol ether solvents such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, and dipropylene glycol dimethyl ether; aprotic amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; lactone solvents such as γ-butyrolactone; cyclic ether solvents such as tetrahydrofuran; unsaturated hydrocarbon solvents such as benzene, toluene, xylene, and naphthalene; saturated hydrocarbon solvents such as n-heptane, n-hexane, and n-octane; and aromatic hydrocarbons such as toluene and xylene. Among these solvents, based on the solubility of other components, glycol ether acetate-based solvents, carbitol acetate-based solvents, glycol ether-based solvents, and ester-based solvents are suitable. Of these, the solvent used in this invention, based on the solubility of other components or coating adaptability, is preferably selected from one or more of the group consisting of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, butyl carbitol acetate (BCA), 3-methoxy-3-methyl-1-butyl acetate, ethyl ethoxypropionate, ethyl lactate, and 3-methoxybutyl acetate.

[0105] In the photosensitive coloring resin composition of the present invention, the solvent content can be appropriately set within a range that allows for the precise and good formation of the colored layer. The solvent content relative to the total amount of the photosensitive coloring resin composition including the solvent is generally preferably in the range of 55% to 95% by mass, and more preferably in the range of 65% to 88% by mass. By keeping the solvent content within the above range, excellent coatability can be achieved.

[0106] <Dispersant> In the photosensitive coloring resin composition of the present invention, when dispersing the pigment, a dispersant may be included to improve the dispersibility and stability of the pigment dispersion. In the present invention, the dispersant may be appropriately selected from previously known dispersants. Examples of dispersants include cationic, anionic, nonionic, amphoteric, silicone, and fluorinated surfactants. Among surfactants, polymeric dispersants are preferred because they can be uniformly and finely dispersed.

[0107] Examples of polymeric dispersants include: (meth)acrylate copolymer dispersants; polyurethane esters; unsaturated polyamides; polysiloxanes; long-chain polyamide phosphates; amides or bases thereof obtained by reacting poly(lower alkylimide) with polyesters containing free carboxyl groups; polyallylamine derivatives (reaction products obtained by reacting polyallylamine with one or more of the following three compounds: polyesters, polyamides, or cocondensates of esters and amides (polyesteramides) containing free carboxyl groups).

[0108] In this invention, the use of a (meth)acrylate copolymer-based dispersant is preferred because it readily improves solvent resistance even during low-temperature heat treatment. It is speculated that since the (meth)acrylate copolymer-based dispersant exhibits good compatibility with the aforementioned alkali-soluble resin, the aforementioned non-reactive resin, the aforementioned photopolymerizable compound, and the photoinitiator, the initiator readily and uniformly exists within the coloring layer, resulting in uniform hardening of the coloring layer. This reduces unreacted components and decreases internal stress within the coloring layer, thus minimizing changes in the coloring layer upon immersion in the solvent.

[0109] In this invention, a (meth)acrylate copolymer dispersant refers to a dispersant that contains at least structural units derived from (meth)acrylate and is a copolymer. Preferably, the (meth)acrylate copolymer dispersant is a copolymer containing structural units that function as pigment adsorption sites and structural units that function as solvent affinity sites, and more preferably, the structural units functioning as solvent affinity sites contain at least structural units derived from (meth)acrylate.

[0110] Regarding the structural unit that functions as a pigment adsorption site, examples can be given of structural units derived from vinyl unsaturated monomers capable of copolymerizing with structural units derived from (meth)acrylates. The pigment adsorption site can be a structural unit derived from a vinyl unsaturated monomer containing an acidic group or a structural unit derived from a vinyl unsaturated monomer containing a basic group. As a structural unit derived from a vinyl unsaturated monomer containing a basic group, the structural unit represented by the following general formula (I) is preferred due to its excellent dispersibility.

[0111] [Chemical 10] (In general formula (I), R71 represents a hydrogen atom or a methyl group, A1 represents a divalent linkage group, R72 and R73 represent hydrogen atoms or hydrocarbon groups that may contain heteroatoms, and R72 and R73 may also bond together to form a ring structure)

[0112] In general formula (I), A1 is a divalent linker. Examples of divalent linkers include: straight-chain, branched or cyclic alkyl groups, straight-chain, branched or cyclic alkyl groups having hydroxyl groups, aryl groups, -CONH- groups, -COO- groups, -NHCOO- groups, ether groups (-O- groups), thioether groups (-S- groups), and combinations thereof. Furthermore, in this invention, the orientation of the bonds in the divalent linker is arbitrary. That is, when the divalent linker contains -CONH-, -CO can be on the carbon atom side of the main chain and -NH can be on the nitrogen atom side of the side chain; conversely, -NH can be on the carbon atom side of the main chain and -CO can be on the nitrogen atom side of the side chain. In terms of dispersibility, A1 in general formula (I) is preferably a divalent linkage containing a -CONH- group or a -COO- group, and more preferably a divalent linkage containing a -CONH- group or a -COO- group and an alkyl group having 1 to 10 carbon atoms.

[0113] Examples of hydrocarbon groups containing heteroatoms in R72 and R73 include alkyl, aralkyl, and aryl groups. Examples of alkyl groups include methyl, ethyl, propyl, butyl, isopropyl, tributyl, 2-ethylhexyl, cyclopentyl, and cyclohexyl, with the alkyl group preferably having 1 to 18 carbon atoms, more preferably methyl or ethyl. Examples of aralkyl groups include benzyl, phenethyl, naphthylmethyl, and biphenylmethyl, with the aralkyl group preferably having 7 to 20 carbon atoms, and more preferably 7 to 14. Examples of aryl groups include phenyl, biphenyl, naphthyl, tolyl, and xylyl, with the aryl group preferably having 6 to 24 carbon atoms, and more preferably 6 to 12. Furthermore, the preferred carbon numbers mentioned above do not include the carbon numbers of substituents. The hydrocarbon group containing heteroatoms has a structure in which the carbon atom in the aforementioned hydrocarbon group is replaced by a heteroatom, or a structure in which the hydrogen atom in the aforementioned hydrocarbon group is replaced by a substituent containing a heteroatom. Examples of heteroatoms that may be included in the hydrocarbon group include oxygen atoms, nitrogen atoms, sulfur atoms, silicon atoms, etc. Furthermore, the hydrogen atom in the hydrocarbon group may be replaced by a halogen atom such as a fluorine atom, chlorine atom, or bromine atom.

[0114] The ring structure formed by the mutual bonding of R72 and R73 refers to the ring structure formed by R72 and R73 through nitrogen atoms. The ring structure formed by R72 and R73 may contain heteroatoms. There are no particular limitations on the ring structure; examples include pyrrolidine rings, piperidine rings, and morpholine rings.

[0115] In this invention, it is preferred that R72 and R73 are independently hydrogen atoms, alkyl groups having 1 to 5 carbon atoms, or phenyl groups, or that R72 and R73 are bonded together to form a pyrrolidine ring, a piperidine ring, or a morpholine ring.

[0116] Examples of monomers that derive the structural unit represented by the above general formula (I) include: dimethylaminoethyl methacrylate, dimethylaminopropyl methacrylate, diethylaminoethyl methacrylate, diethylaminopropyl methacrylate, and other (meth)acrylates containing alkyl-substituted amino groups; dimethylaminoethyl (meth)acrylamide, dimethylaminopropyl (meth)acrylamide, and other (meth)acrylamides containing alkyl-substituted amino groups. Among these, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, and dimethylaminopropyl (meth)acrylamide are preferred for their improved dispersibility and dispersion stability. In the polymer, the structural unit represented by general formula (I) may consist of one type or may contain two or more structural units.

[0117] Furthermore, regarding the structural unit that functions as the pigment adsorption site, at least a portion of the nitrogen site of the structural unit represented by the above general formula (I) can form a salt with at least one of the group consisting of organic acid compounds and halogenated hydrocarbons (hereinafter, such copolymers are sometimes referred to as salt-type copolymers). Among the above-mentioned organic acid compounds, the compounds represented by the following general formula (1) and the following general formula (3) are preferred, and among the above-mentioned halogenated hydrocarbons, the compounds represented by the following general formula (2) are preferred. That is, as at least one of the group consisting of the above-mentioned organic acid compounds and halogenated hydrocarbons, one or more compounds selected from the group consisting of the following general formulas (1) to (3) are preferably used.

[0118] [Chemical 11](In general formula (1), Ra represents a straight-chain, branched or cyclic alkyl, vinyl, phenyl or benzyl with substituents, or -O-Re, Re represents a straight-chain, branched or cyclic alkyl, vinyl, phenyl or benzyl with substituents, or (meth)acrylonitrile with alkyl groups of 1 to 4 carbons interposed; In general formula (2), Rb, Rb', and Rb'' independently represent a hydrogen atom, an acidic group or its ester group, a straight-chain, branched or cyclic alkyl with 1 to 20 carbons, a vinyl with substituents, a phenyl or benzyl with substituents, or -O-Rf, Rf represents a substituted group. The group consists of a straight-chain, branched, or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group having substituents, a phenyl or benzyl group having substituents, or a (meth)acrylyl group with 1 to 4 carbon atoms interposed, where X represents a chlorine atom, a bromine atom, or an iodine atom; in general formula (3), Rc and Rd independently represent a hydrogen atom, a hydroxyl group, a straight-chain, branched, or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, a phenyl or benzyl group having substituents, or -O-Re, where Re represents a straight-chain, branched, or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, a phenyl or benzyl group having substituents, or a (meth)acrylyl group with 1 to 4 carbon atoms interposed; wherein at least one of Rc and Rd contains a carbon atom)

[0119] The symbols in the above general formulas (1) to (3) may be the same as those described in International Publication No. 2016 / 104493. Based on the excellent dispersibility and dispersion stability of the pigment, the above-mentioned organic acid compound is preferably an acidic organophosphorus compound such as phenylphosphonic acid or phenylphosphine. Specific examples of the organic acid compound used as such a dispersant include, for example, the organic acid compounds described in Japanese Patent Application Publication No. 2012-236882. Furthermore, based on the excellent dispersibility and dispersion stability of the pigment, the above-mentioned halogenated hydrocarbon is preferably at least one of allyl bromide, benzyl chloride, or halogenated aryl group.

[0120] Regarding the content of at least one of the organic acid compounds and halogenated hydrocarbons selected from the group consisting of salt-type copolymers, since salts are formed with the nitrogen sites at the ends of the structural units represented by general formula (I), it is preferable that the total content of at least one of the organic acid compounds and halogenated hydrocarbons selected from the group consisting of the organic acid compounds and halogenated hydrocarbons relative to the nitrogen sites at the ends of the structural units represented by general formula (I) is 0.01 mol or more, more preferably 0.05 mol or more, further preferably 0.1 mol or more, and even more preferably 0.2 mol or more. When the content is at or above the lower limit, it is easy to obtain the effect of improving pigment dispersibility due to salt formation. Similarly, it is preferable to set it to 1 mol or less, more preferably 0.8 mol or less, further preferably 0.7 mol or less, and even more preferably 0.6 mol or less. When the content is at or below the upper limit, it is possible to achieve excellent development adhesion or solvent resolvability. Furthermore, at least one of the compounds selected from the group consisting of organic acid compounds and halogenated hydrocarbons may be used alone or in combination with two or more compounds. When two or more compounds are combined, their total content is preferably within the range mentioned above.

[0121] Examples of methods for preparing salt-type copolymers include: adding at least one of the above-mentioned organic acid compounds and halogenated hydrocarbons to a solvent in which the copolymer before salt formation is dissolved or dispersed, stirring, and then heating as needed. Furthermore, the formation of a salt by the terminal nitrogen site of the structural unit represented by the general formula (I) of the copolymer with at least one of the above-mentioned organic acid compounds and halogenated hydrocarbons, and the ratio thereof, can be confirmed, for example, by known methods such as NMR (Nuclear Magnetic Resonance).

[0122] In terms of dispersibility and dispersion stability, the copolymer having the structural unit represented by the above general formula (I) is preferably a graft copolymer having the structural unit represented by the above general formula (I) and having a structural unit derived from (meth)acrylate in the graft polymer chain, and a block copolymer comprising an A block containing a structural unit represented by the above general formula (I) and a B block containing a structural unit derived from (meth)acrylate. Among the above graft copolymers, the graft polymer chain having a structural unit derived from (meth)acrylate can be appropriately selected from previously known structures. For example, at least one of the graft copolymers and salt-type graft copolymers described in International Publication No. 2021 / 006077 can also be used. Furthermore, among the above block copolymers, the B block containing a structural unit derived from (meth)acrylate can be appropriately selected from previously known structures. For example, at least one of the block copolymers and salt-type block copolymers described in International Publication No. 2016 / 104493 may also be used.

[0123] Among the block copolymers used as dispersants, based on the aspects that the substrate adhesion and solvent resistance of the hardened film become good even during low-temperature heating treatment, and the aspects that suppress the generation of developing residues, it is preferable to contain at least one of the following block copolymers and salt-type block copolymers, wherein the block copolymers include an A block containing a structural unit represented by the above general formula (I), and a B block containing a structural unit derived from a carboxyl-containing monomer and a structural unit derived from (meth)acrylate, wherein the salt-type block copolymer is obtained by forming a salt with at least a portion of the nitrogen site of the structural unit represented by the above general formula (I) of the block copolymer and at least one of the group consisting of organic acid compounds and halogenated hydrocarbons, wherein the acid value of the above block copolymers and at least one of the salt-type block copolymers is 1 mgKOH / g to 18 mgKOH / g, and the glass transfer temperature is 30°C or higher. Furthermore, for the purpose of further improving solvent resistance, this particular dispersant is preferably combined with a photoinitiator containing a compound represented by the above general formula (A). In this case, the B block contains a structural unit derived from (meth)acrylate as an essential component, and may also be the same as the B block in International Publication No. 2016 / 104493.

[0124] Based on the advantages of good dispersibility, preventing the precipitation of foreign matter during film formation and thus improving brightness and contrast, the (meth)acrylate copolymer containing the structural unit represented by the above general formula (I) preferably has an amine value of 40 mgKOH / g to 120 mgKOH / g. By keeping the amine value within the above range, the viscosity exhibits excellent stability over time or heat resistance, and also excellent alkaline developability and solvent resolubility. In this invention, regarding the amine value of the (meth)acrylate copolymer containing the structural unit represented by the above general formula (I), the amine value is preferably 80 mgKOH / g or more, and more preferably 90 mgKOH / g or more. On the other hand, regarding solvent resolubility, the amine value of the (meth)acrylate copolymer containing the structural unit represented by the above general formula (I) is preferably 110 mgKOH / g or less, and more preferably 105 mgKOH / g or less. The amine value refers to the number of milligrams (mg) of perchloric acid and equivalent potassium hydroxide required to neutralize the amine content in 1 g of a sample, and can be determined according to the method defined in JIS-K7237. When this method is used, even if an amine group forms a salt with an organic acid compound in the dispersant, the amine value of the block copolymer used as a dispersant can still be determined because the organic acid compound usually dissociates.

[0125] The content ratio (moles%) of each structural unit in the copolymer of the dispersant can be determined based on the amount of raw materials added during manufacturing, and can also be measured using analytical instruments such as NMR. Furthermore, the structure of the dispersant can be determined using NMR, various mass spectrometry analyses, etc. Additionally, if necessary, the dispersant can be decomposed by thermal decomposition, etc., and the obtained decomposition products can be determined using high-performance liquid chromatography, gas chromatography-mass spectrometry, NMR, elemental analysis, XPS / ESCA (X-ray photoelectron spectroscopy / Electron Spectroscopy for Chemical Analysis), and TOF-SIMS (time of flight secondary ion mass spectrometer).

[0126] In the photosensitive coloring resin composition of the present invention, the content of the dispersant is selected only to achieve excellent dispersibility and dispersion stability of the pigment, and is not particularly limited. Relative to the total solid content in the photosensitive coloring resin composition, it is preferably in the range of 2% to 30% by mass, more preferably 3% to 25% by mass. When the content is above the lower limit, the dispersibility and dispersion stability of the pigment are excellent, and the storage stability of the photosensitive coloring resin composition is even better. Furthermore, when the content is below the upper limit, the developability is good. Especially in the case of forming a hardened film with a high pigment concentration, the content of the dispersant relative to the total solid content of the photosensitive coloring resin composition is preferably in the range of 2% to 25% by mass, more preferably 3% to 20% by mass.

[0127] <At least one of a polyfunctional epoxy compound and a polyfunctional terminal isocyanate compound> For the purpose of improving solvent resistance after low-temperature heat treatment, the photosensitive coloring resin composition of the present invention preferably contains at least one of a polyfunctional epoxy compound and a polyfunctional terminal isocyanate compound. A polyfunctional epoxy compound is a compound having two or more epoxy groups in one molecule. An epoxy group refers to a group containing a cyclic ether structure with a three-membered ring, and also includes alicyclic epoxy groups. Examples of epoxy groups include ethylene oxide, 3,4-epoxycyclohexyl, etc. These epoxy groups may also be those in which one or all of the hydrogen atoms are substituted by substituents such as alkyl groups.

[0128] Examples of polyglycidyl ethers of bisphenols include: bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol AD ​​diglycidyl ether, etc.; 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether. Polyglycidyl ethers of polyols such as ethers and polypropylene glycol diglycidyl ether; aliphatic polyglycidyl ethers of polyether polyols obtained by adding one or more epoxides to aliphatic polyols such as ethylene glycol, propylene glycol, and glycerol; (3,4-epoxy)cyclohexylcarboxylic acid-3,4-epoxycyclohexyl methyl ester, 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-m-dimethyl ester, bis(3,4-epoxycyclohexylmethyl) adipic acid, bis(3,4-epoxycyclohexylmethyl) adipic acid, bis(3,4-epoxycyclohexylmethyl) adipic acid. 4-Epoxy-6-methylcyclohexylmethyl ester, 3',4'-epoxy-6'-methylcyclohexylcarboxylic acid-3,4-epoxy-6-methylcyclohexyl ester, methylene bis(3,4-epoxycyclohexane), dicyclopentadiene diepoxide, ethylene glycol di(3,4-epoxycyclohexylmethyl) ether, ethyl bis(3,4-epoxycyclohexylcarboxylic acid ester), lactone-modified 3',4'-epoxycyclohexylcarboxylic acid-3,4-epoxycyclohexylmethyl ester, etc., have two or more intramolecular groups. Compounds of 3,4-epoxycyclohexyl; phenolic varnish-type epoxy resins such as bisphenol A phenolic varnish-type epoxy resin; cresol phenolic varnish-type epoxy resin; polyphenolic epoxy resins; cyclic aliphatic epoxy resins; diglycidyl esters of aliphatic long-chain dicarboxylic acids; glycidyl esters of higher fatty acids; epoxidized soybean oil, epoxidized linseed oil, and 1,2-epoxy-4-(2-epoxyethylene)cyclohexane adducts of 2,2-bis(hydroxymethyl)-1-butanol, etc.

[0129] The multifunctional epoxy compound can be used alone or in combination of two or more. Among them, the 1,2-epoxy-4-(2-epoxyethylene)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol is preferred because it can easily improve the solvent resistance after low-temperature heat treatment.

[0130] On the other hand, a polyfunctional isocyanate compound is a compound having two or more isocyanate groups in one molecule. The isocyanate group is formed by capping the isocyanate group with a capping agent. A polyfunctional isocyanate compound is stable near room temperature and can be obtained by heat treatment to dissociate the capping agent and regenerate an active isocyanate group. It can be obtained by reacting a polyfunctional isocyanate compound having two or more isocyanate groups in one molecule with a capping agent.

[0131] Examples of polyfunctional isocyanate compounds include: aromatic diisocyanates such as 2,4- and / or 2,6-toluene diisocyanate, diphenylmethane-4,4'-diisocyanate, terephthalic diisocyanate, phenyl dimethyl diisocyanate, 1,5-naphthalene diisocyanate, and 3,3'-dimethyldiphenyl-4,4'-diisocyanate; alicyclic diisocyanates such as isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, trans-1,4-cyclohexyl diisocyanate, and norethane diisocyanate; and diethyl ether diisocyanate. 1,6-Hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, 1,3-bis(isocyanomethyl)cyclohexane, 3-(2'-isocyanocyclohexyl)propyl isocyanate, isopropylidene bis(cyclohexyl)isocyanate, 2,2'-bis(4-isocyanophenyl)propane, 2,6-bis(isocyanomethyl)tetrahydrodicyclopentadiene, bis(isocyanomethyl)dicyclopentadiene, bis( Aliphatic diisocyanates such as (methyl isocyanate)adamantane and 2,5-diisocyanatemethylnorphine; heterocyclic diisocyanates such as bis(methyl isocyanate)tetrahydrothiophene and bis(methyl isocyanate)thiophene; and, for example, modified diisocyanates obtained by modifying such diisocyanate compounds with carbodiimide, isocyanurate, or biuret; isocyanurate trimers, biuret trimers, and trimethylolpropane adducts of the diisocyanates mentioned above; triphenylmethane triisocyanate, 1-methylbenzene-2,4,6-triisocyanate, etc. Isocyanates include esters, dimethyltriphenylmethane tetraisocyanate, N,N',N''-tris(1-isocyanohexyl) ester, lysine triisocyanate, tri(phenylisocyanate) ester of thiophosphate, 4,4',4''-triisocyano-2,5-dimethoxyphenylamine, 1,3,5-triisocyanocyclohexane, and 1,3,5-tris(isocyanomethyl)cyclohexane. Examples of other isocyanate compounds include modified compounds obtained by modifying these isocyanate compounds with carbodiimide, isocyanurate, or biuret. One or more of these compounds may be used. Among these isocyanate compounds, alicyclic diisocyanates and aliphatic diisocyanates are preferred for their transparency. On the other hand, as a capping agent, a known capping agent can be appropriately selected for use. Among them, carboxylic acid esters such as dimethyl malonate, diethyl malonate, dibenzyl malonate, and diethyl methyl malonate are suitable; active methylene compounds such as malonic acid, acetone, acetoacetate (methyl acetoacetate, ethyl acetate, etc.), and 3,5-dimethylpyrazole are also suitable.

[0132] The content of at least one of the polyfunctional epoxy compound and the polyfunctional end-capped isocyanate compound is typically 3% to 30% by mass, and preferably 5% to 20% by mass, relative to the total solid content of the photosensitive coloring resin composition. When the content is above the lower limit, the solvent resistance and substrate adhesion after low-temperature heat treatment are easily improved. On the other hand, when the content is below the upper limit, the developability of the photosensitive coloring resin composition of the present invention is easily improved.

[0133] <Thiol Compound> To improve solvent resistance and substrate adhesion after low-temperature heat treatment, the photosensitive coloring resin composition of the present invention preferably contains a thiol compound. Examples of thiol compounds include monofunctional thiol compounds having one thiol group per molecule and polyfunctional thiol compounds having two or more thiol groups per molecule. To suppress linewidth shift and improve substrate adhesion, monofunctional thiol compounds containing one thiol group are more preferably used. Examples of monofunctional thiol compounds include: 2-mercaptobenzothiazole, 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercapto-5-methoxybenzothiazole, 2-mercapto-5-methoxybenzimidazole, 3-mercaptopropionic acid, methyl 3-mercaptopropionate, ethyl 3-mercaptopropionate, octyl 3-mercaptopropionate, etc. Examples of multifunctional thiols include 1,4-bis(3-mercaptobutoxy)butane, 1,3,5-tris(3-mercaptobutoxyethyl)-1,3,5-tris(2,4,6(1H,3H,5H)-trione), trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetra(3-mercaptobutyrate), pentaerythritol tetra(3-mercaptopropionate), dipentaerythritol hexa(3-mercaptopropionate), and tetraethylene glycol bis(3-mercaptopropionate). Thiol compounds can be used alone or in combination of two or more. 2-Mercaptobenzothiazole or 2-mercaptobenzothiazole are preferred for improving solvent resistance and substrate adhesion after low-temperature heat treatment. Regarding the content of thiol compounds, relative to the total solid content of the photosensitive coloring resin composition, it is typically in the range of 0.5% to 10% by mass, preferably in the range of 1% to 5% by mass. When the content is above the lower limit, the solvent resistance and substrate adhesion after low-temperature heat treatment are excellent. On the other hand, when the content is below the upper limit, the photosensitive coloring resin composition of the present invention is more likely to have good developability and suppressed linewidth shift.

[0134] <Other Components> The photosensitive coloring resin composition of the present invention may also contain various additives as needed. Examples of additives include antioxidants, polymerization terminators, chain transfer agents, leveling agents, plasticizers, surfactants, defoamers, silane coupling agents, ultraviolet absorbers, and adhesion promoters. Specific examples of surfactants and plasticizers include those described in Japanese Patent Application Publication No. 2013-029832.

[0135] Based on the aspect of suppressing the linewidth offset of the hardened film, the photosensitive coloring resin composition of the present invention preferably further contains an antioxidant. The photosensitive coloring resin composition of the present invention contains an antioxidant, for example, by combining it with a compound represented by the above general formula (A). This allows for the control of excessive free radical chain reactions during the formation of the hardened film without compromising curability. Therefore, when forming fine line patterns, the straightness is further improved, or the ability to form fine line patterns according to the mask linewidth design is enhanced. Furthermore, heat resistance can be improved, and the reduction in brightness after exposure and post-baking can be suppressed, thus increasing brightness. The antioxidant used in the present invention is not particularly limited, and can be appropriately selected from those previously known. Specific examples of antioxidants include hindered phenolic antioxidants, amine antioxidants, phosphorus antioxidants, sulfur antioxidants, and hydrazine antioxidants. Due to the improved ability to form fine line patterns based on linewidth masking linewidth design and the better heat resistance, hindered phenolic antioxidants are preferred. Potential antioxidants such as those described in International Publication No. 2014 / 021023 may also be used.

[0136] As hindered phenolic antioxidants, examples 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)trimethylbenzyl (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. Among them, pentaerythritol tetratetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (trade name: IRGANOX 1010, manufactured by BASF) is preferred in terms of heat resistance and light resistance.

[0137] Regarding the content of the antioxidant, it is generally in the range of 0.1% to 10.0% by mass relative to the total solid content of the photosensitive coloring resin composition, preferably in the range of 0.5% to 5.0% by mass. When it is above the lower limit, it is excellent in terms of improving the ability to form fine line patterns according to the mask line width design, and it also has excellent heat resistance. On the other hand, when it is below the upper limit, it is easy to make the photosensitive coloring resin composition of the present invention a high-sensitivity photosensitive coloring resin composition.

[0138] Furthermore, examples of silane coupling agents include: KBM-502, KBM-503, KBE-502, KBE-503, KBM-5103, KBM-903, KBE-903, KBM573, KBM-403, KBE-402, KBE-403, KBM-303, KBM-802, KBM-803, KBE-9007, and X-12-967C (manufactured by Shin-Etsu Silicones). Among these, KBM-502, KBM-503, KBE-502, KBE-503, and KBM-5103, which have methacrylate or acrylic groups, are preferred for their adhesion to the SiN substrate.

[0139] Regarding the content of the silane coupling agent, relative to the total amount of solid components in the photosensitive coloring resin composition, it is typically in the range of 0.05% by mass to 10.0% by mass, preferably in the range of 0.1% by mass to 5.0% by mass. When it is above the lower limit and below the upper limit, the substrate adhesion improvement effect tends to become good.

[0140] <Method for Manufacturing Photosensitive Coloring Resin Composition> The method for manufacturing the photosensitive coloring resin composition of the present invention can be prepared by mixing pigments, alkali-soluble resins, non-reactive resins, photopolymerizable compounds, photoinitiators, solvents, and various additives as needed using a known mixing method. When the photosensitive coloring resin composition of the present invention contains, for example, pigments, alkali-soluble resins, non-reactive resins, photopolymerizable compounds, photoinitiators, dispersants, solvents, and various additives as needed, the preparation method of the resin composition can be exemplified as follows: (1) First, pigments and dispersants are added to a solvent to prepare a pigment dispersion, and alkali-soluble resins, non-reactive resins, photopolymerizable compounds, photoinitiators, and various additives as needed are mixed into the dispersion; (2) Pigments, dispersants, alkali-soluble resins, non-reactive resins are simultaneously added to a solvent. The methods include: (1) mixing a pigment, a photopolymerizable compound, a photoinitiator, and various additives as needed; (3) mixing a dispersant, an alkali-soluble resin, a non-reactive resin, a photopolymerizable compound, a photoinitiator, and various additives as needed into a solvent, and then adding a pigment for dispersion; and (4) preparing a pigment dispersion by adding a pigment, a dispersant, and an alkali-soluble resin into a solvent, and then adding an alkali-soluble resin, a non-reactive resin, a solvent, a photopolymerizable compound, a photoinitiator, and various additives as needed into the dispersion and mixing them. Among these methods, methods (1) and (4) are preferred because they can effectively prevent pigment aggregation and achieve uniform dispersion. In the case where no dispersant is used, it is sufficient to prepare the pigment using methods (2), (3), or (4) above without adding a dispersant.

[0141] The method for preparing a pigment dispersion can be appropriately selected from previously known dispersion methods. For example, the following methods can be used: (1) mixing the dispersant in a solvent and stirring to prepare a dispersant solution, and then mixing an organic acid compound as needed to form a salt of the amine group of the dispersant and the organic acid compound; mixing it with the pigment and other components as needed, and dispersing it using a known mixer or disperser; (2) mixing the dispersant in a solvent and stirring to prepare a dispersant solution, and then mixing the pigment, organic acid compound as needed, and other components as needed, and dispersing it using a known mixer or disperser; (3) mixing the dispersant in a solvent and stirring to adjust the dispersant solution, and then mixing the pigment and other components as needed, preparing a dispersion using a known mixer or disperser, and then adding an organic acid compound as needed, etc.

[0142] Examples of dispersers used for dispersion processing include: roller mills such as two-roll mills and three-roll mills, ball mills such as vibrating ball mills, paint conditioners, continuous disc bead mills, and continuous annular bead mills. For preferred dispersion conditions in bead mills, the diameter of the beads used is preferably 0.03 mm to 2.00 mm, more preferably 0.10 mm to 1.0 mm.

[0143] <Applications> The photosensitive coloring resin composition of the present invention can suppress the generation of developing residues and form a colored layer with a good pattern shape even during low-temperature heat treatment. Therefore, it is suitable for use in color filter applications, and is particularly suitable for use in low-temperature heat treatment applications at 130°C or below, and further at 100°C or below, or 90°C or below, on substrates on which elements with low heat resistance, such as organic light-emitting elements, are formed directly. Furthermore, it is suitable for use in hardening films formed on organic light-emitting elements. Since the photosensitive coloring resin composition of the present invention can be used in hardening films formed on organic light-emitting elements, it is suitable for forming colored hardening films that have an external light reflection suppression effect as a substitute for a circular polarizer. When a hardening film of the photosensitive coloring resin composition of the present invention is used instead of a circular polarizer, a display device without a polarizer can be manufactured. Therefore, the photosensitive coloring resin composition of the present invention is suitable for use in display devices without polarizers. Furthermore, since the photosensitive coloring resin composition of the present invention is a photosensitive coloring resin composition for forming a hardened film on an organic light-emitting element, it is suitable for use in display devices that do not have an external color filter substrate, and for use in organic light-emitting display devices with thin films and improved flexibility.

[0144] II. Cured Product The cured product of the present invention is the cured product of the photosensitive coloring resin composition of the present invention described above. The cured product of the present invention can be obtained, for example, by forming a coating film of the photosensitive coloring resin composition of the present invention, drying the coating film, and then exposing it to light, and developing and heating it as needed. The methods for forming, exposing, developing, and heating the coating film can be, for example, the same methods used for forming the color layer of the color filter of the present invention described below. The cured product of the present invention exhibits good solvent resistance and good pattern shape even when heated at low temperatures of 130°C or below, further 100°C or below, or 90°C. The cured product of the present invention exhibits good solvent resistance and good pattern shape even when heated at low temperatures, making it suitable for use as a color layer of a color filter and suitable for use as a cured film formed on an organic light-emitting element.

[0145] III. Color Filter The color filter of the present invention comprises at least a substrate and a coloring layer disposed on the substrate, wherein at least one of the coloring layers is a cured form of the photosensitive coloring resin composition of the present invention.

[0146] Referring to the figures, the color filter of the present invention will be described. Figure 1 is a schematic cross-sectional view showing an example of the color filter of the present invention. According to Figure 1, the color filter 10 of the present invention has a substrate 1, a light-shielding portion 2, and a coloring layer 3.

[0147] <Coloring Layer> At least one of the coloring layers used in the color filter of the present invention is a cured form of the photosensitive coloring resin composition of the present invention described above. The coloring layer is generally formed on the opening of the light-shielding portion of the substrate described below, and is generally composed of a coloring pattern of three or more colors. Furthermore, the arrangement of the coloring layer is not particularly limited, and can be arranged in general patterns such as stripes, mosaics, triangles, or four-pixel configurations. Furthermore, the width and area of ​​the coloring layer can be arbitrarily set. The thickness of the coloring layer is appropriately controlled by adjusting the coating method, the concentration or viscosity of the solid component of the photosensitive coloring resin composition, etc., and is generally preferably in the range of 1 to 5 μm.

[0148] This coloring layer can be formed, for example, by the following method. First, the photosensitive coloring resin composition of the present invention described above is coated onto the substrate using a coating method such as spraying, dip coating, rod coating, roller coating, spin coating, or die coating to form a wet coating film. Spin coating or die coating is preferred. Then, the wet coating film is dried using a heating plate or oven, and then exposed through a mask with a specific pattern to allow the alkali-soluble resin and polyfunctional monomers to undergo a photopolymerization reaction, forming a hardened coating film. Examples of light sources for exposure include ultraviolet light from low-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, and electron beams. The exposure amount is adjusted appropriately according to the light source used or the thickness of the coating film. Furthermore, to promote the polymerization reaction, a heat treatment can be performed after exposure. The heating conditions are appropriately selected according to the mixing ratio of each component in the photosensitive coloring resin composition used or the thickness of the coating film.

[0149] Next, a developing solution is used to perform a developing process, dissolving and removing the unexposed portions, thereby forming a coating with the desired pattern. The developing solution is typically a solution containing an alkali dissolved in water or a water-soluble solvent. An appropriate amount of surfactant may also be added to the alkali solution. Furthermore, a general developing method can be used. After the developing process, the developing solution is usually washed off, and the hardened coating of the photosensitive coloring resin composition is dried to form a colored layer. Furthermore, after the developing process, a heat treatment may also be performed to fully harden the coating. The heating conditions are not particularly limited and are appropriately selected according to the intended use of the coating. In the manufacturing step of directly forming the colored layer on the component substrate, the heat treatment is preferably performed at 30°C to 100°C, more preferably at 35°C to 95°C, and even more preferably at 40°C to 90°C.

[0150] When the photosensitive coloring resin composition of the present invention does not have alkaline developability, the coloring layer is formed into a coating with the desired pattern by a previously known patterned coating forming method, such as inkjet printing, and then exposed to allow the photopolymerizable compound to undergo a photopolymerization reaction to form a hardened coating. Similarly, in order to promote the polymerization reaction, a heat treatment may also be performed after exposure.

[0151] <Light-shielding portion> The light-shielding portion of the color filter of the present invention is formed in a pattern on the substrate described below, and can be the same as that used as a light-shielding portion in a conventional color filter. The pattern shape of the light-shielding portion is not particularly limited, and for example, striped, matrix, or other shapes can be used. The light-shielding portion can also be a thin film of metal such as chromium formed by sputtering, vacuum evaporation, or the like. Alternatively, the light-shielding portion can also be a resin layer containing light-shielding particles such as carbon microparticles, metal oxides, inorganic pigments, and organic pigments in a resin binder. In the case of a resin layer containing light-shielding particles, there are methods such as patterning by developing a photosensitive resist, patterning by using inkjet ink containing light-shielding particles, and heat transfer of a photosensitive resist.

[0152] Regarding the film thickness of the light-shielding part, it is set to about 0.2 to 0.4 μm when it is a metal film, and to about 0.5 to 2 μm when it is a black pigment dispersed or dissolved in an adhesive resin.

[0153] <Substrate> As the substrate, the following transparent substrates, silicon substrates, and transparent substrates or silicon substrates on which aluminum, silver, silver / copper / palladium alloy thin films are formed can be used. Other color filter layers, resin layers, TFT (Thin-Film Transistor) transistors, circuits, etc., can also be formed on these substrates. The substrate can also be a component substrate such as an organic light-emitting element. As the transparent substrate in the color filter of the present invention, it is not particularly limited as long as it is a substrate transparent to visible light, and the transparent substrate commonly used in color filters can be used. Specifically, examples include: transparent rigid materials that do not have flexibility, such as quartz glass, alkali-free glass, and synthetic quartz plates, or transparent flexible materials that have flexibility, such as transparent resin films, optical resin plates, and flexible glass. Examples of transparent resin films and optical resin plates include polyethylene terephthalate (PET) films, polyimide films, and polycarbonate films. Among these, PET films and polyimide films containing heteroatoms such as oxygen and nitrogen atoms are particularly suitable. The thickness of the transparent substrate is not particularly limited; for example, a thickness of about 100 μm to 1 mm can be used for the application of the color filter according to the present invention. Furthermore, in addition to the aforementioned substrate, light-shielding portion, and coloring layer, the color filter of the present invention may also have an outer coating layer or a transparent electrode layer, and further form an alignment film or columnar spacers. Moreover, the color filter of the present invention can also be used as a substitute for a circular polarizer to prevent external light reflection.

[0154] IV. Display Device The display device of the present invention is characterized by having the color filter described above. In the present invention, the configuration of the display device is not particularly limited, and can be appropriately selected from previously known display devices, such as liquid crystal display devices and organic light-emitting display devices.

[0155] [Liquid Crystal Display Device] As a liquid crystal display device of the present invention, an example can be a liquid crystal display device having the color filter, the opposing substrate, and the liquid crystal layer formed between the color filter and the opposing substrate described above. Referring to the figures, such a liquid crystal display device of the present invention will be described. FIG2 shows a schematic diagram of an example of a liquid crystal display device of the present invention. As illustrated in FIG2, the liquid crystal display device 40 of the present invention includes a color filter 10, an opposing substrate 20 having a TFT array substrate, etc., and a liquid crystal layer 30 formed between the color filter 10 and the opposing substrate 20. Furthermore, the liquid crystal display device of the present invention is not limited to the configuration shown in FIG2, and can be configured as a liquid crystal display device commonly using a color filter.

[0156] The driving method of the liquid crystal display device of the present invention is not particularly limited, and a driving method commonly used in liquid crystal display devices can be adopted. Examples of such driving methods include TN (Twisted Nematic), IPS (in-plane switching), OCB (Optically Compensated Bend), and MVA (Multi-Domain Vertical Alignment). In the present invention, any of these methods can be suitably used. Furthermore, as the opposing substrate, it can be appropriately selected and used according to the driving method of the liquid crystal display device of the present invention. Moreover, as the liquid crystal constituting the liquid crystal layer, various liquid crystals with different dielectric anisotropy and mixtures thereof can be used according to the driving method of the liquid crystal display device of the present invention.

[0157] As a method for forming the liquid crystal layer, a method commonly used for fabricating liquid crystal cells can be used, such as vacuum injection or liquid crystal droplet method. After forming the liquid crystal layer using the above method, the liquid crystal cell is slowly cooled to room temperature, thereby aligning the sealed liquid crystal.

[0158] [Organic Light Emitting Display Device] As an organic light emitting display device of the present invention, an example can be an organic light emitting display device having the color filter and organic light emitting element of the present invention described above. Referring to the figures, such an organic light emitting display device of the present invention will be described. FIG3 is a schematic diagram showing an example of an organic light emitting display device of the present invention. As illustrated in FIG3, the organic light emitting display device 100 of the present invention has an organic light emitting element 80 and a sealing layer 90 formed on a substrate 50, and a color filter 10 formed thereon. The substrate 50 can be a flexible substrate on which a TFT is formed. In the organic light emitting display device of FIG3, the color filter 10 can be a color filter that replaces a circular polarizer.

[0159] As a method for stacking the organic light-emitting element 80, examples include 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 sequentially on a substrate 50. The transparent anode 71, hole injection layer 72, hole transport layer 73, light-emitting layer 74, electron injection layer 75, and cathode 76, and other components of the organic light-emitting element 80, can be appropriately made using known methods. Furthermore, the sealing layer 90 can be appropriately made using known methods. The organic light-emitting display device 100 manufactured in this way can be used, for example, in both passively driven organic EL displays and actively driven organic EL displays. Moreover, the organic light-emitting display device of the present invention is not limited to the configuration shown in FIG3, and can be configured as a known configuration for organic light-emitting display devices that typically use color filters.

[0160] Furthermore, the display device of the present invention may be one in which a hardened film of the photosensitive coloring resin composition of the present invention is formed on an organic light-emitting element. Regarding this type of display device, since the hardened film of the photosensitive coloring resin composition of the present invention is formed on the organic light-emitting element, there is no need for an external circular polarizer or an external color filter substrate; it may be without such components. Since this type of display device uses the photosensitive coloring resin composition of the present invention to form a hardened film on the organic light-emitting element, there is no substrate between the organic light-emitting element and the hardened film as is used in external color filter substrates, thus improving thin-film design and flexibility.

[0161] Referring to the figures, an organic light-emitting display device incorporating the organic light-emitting element of the present invention will be described. FIG4 is a schematic cross-sectional view showing another example of a display device incorporating the organic light-emitting element of the present invention. As illustrated in FIG4, the display device 200 of the present invention includes: an element substrate 130 having an organic light-emitting element, an anti-reflection film 120 including color-curing films (109R, 109G, 109B) located on the element substrate 130, and a sealing film 111 thereon. The aforementioned element substrate 130 with organic light-emitting elements has thin-film transistors (TFTs) 102 arranged on a substrate 101 in a manner corresponding to each sub-pixel. A sealing film 103 is provided on the TFT, and further, electrodes 104 (anodes) corresponding to each sub-pixel and spacers 105 dividing each sub-pixel are provided on the sealing film 103. Organic light-emitting elements (106R, 106G, 106B) constituting R, G, and B color sub-pixels are arranged within these spacers, and electrodes 107 (cathodes) are provided on each organic light-emitting element (106R, 106G, 106B). The aforementioned element substrate 130 with organic light-emitting elements further includes a sealing layer 108 covering the organic light-emitting elements from above. An anti-reflection film 120 is provided on the sealing layer 108 of the organic EL elements (106R, 106G, 106B) in the element substrate 130, and a sealing film 111 is provided thereon. The anti-reflection film 120 includes three colored curing films (109R, 109G, 109B) corresponding to each organic EL element, formed using a photocurable coloring resin composition, and a light-shielding portion 110. Regarding the display device 200 of the present invention in FIG4, a cover material 113 is further provided on the sealing film 111 via a transparent adhesive layer 112. Although not shown, the display device 200 of the present invention may, for example, provide a touch sensing layer including an insulating film and a transparent electrode layer on the sealing film 111, and further, appropriately provide a hard coating layer or other known configurations on the touch sensing layer. As described above, the colored curing film (109R, 109G, 109B) and the light-shielding layer 110 disposed on the element substrate 130 having the organic light-emitting element can be used as an external light reflection prevention film 120. Therefore, the external light reflection prevention film used in this invention may not contain other substrates such as external circular polarizers or external color filter substrates, which can improve thin film and flexibility.

[0162] In the display device of the present invention, it is preferable to adjust the color of the sub-pixels (106R, 106G, 106B) of the organic light-emitting element to the same color as that of at least one colored curing film (109R, 109G, 109B) disposed directly above, such as through a sealing layer 108. By using the colored curing film disposed on the organic light-emitting element, external light is blocked except for the color of the light originally emitted by the organic light-emitting element, and the light emitted by the organic light-emitting element is not blocked. Therefore, external light reflection can be suppressed without reducing light utilization efficiency. The curing film of the photosensitive coloring resin composition of the present invention can be any one of the three colored curing films (109R, 109G, 109B) mentioned above, or all three.

[0163] The substrate 101, the thin-film transistor (TFT) 102 serving as a driving element, the sealing film 103, the electrode 104 (anode), the spacer 105 dividing each sub-pixel, the organic light-emitting elements (106R, 106G, 106B) constituting the sub-pixels, and the electrode 107 (cathode) used in the display device of the present invention can be appropriately selected from known configurations. In addition to the light-emitting layer, the organic light-emitting elements may also have known configurations such as a hole injection layer, a hole transport layer, and an electron injection layer.

[0164] The sealing layer 108 on the organic EL element used in the display device of the present invention includes an inorganic film, an organic film, or a multilayer film having such layers. Multilayer films are preferred for their superior ability to inhibit moisture or oxygen penetration. Specifically, examples include multilayer films obtained by laminating inorganic films such as metal films, metal oxide films, SiOx, SiON, and SiNx with organic films.

[0165] At least one of the color-curing films used in the display device of the present invention is a curing film of the photosensitive coloring resin composition of the present invention described above. The color-curing film is generally formed on the opening of the light-shielding portion of the sealing layer 108 on the organic light-emitting element, and is generally composed of a coloring pattern of three or more colors. These can be the same coloring pattern as the sub-pixels (106R, 106G, 106B) of the organic light-emitting element. As for the arrangement of the color-curing films (109R, 109G, 109B), for example, a general arrangement such as a striped type, a mosaic type, a triangular type, or a four-pixel configuration type can be adopted. Furthermore, the width, area, etc. of the coloring layer can be appropriately set in a manner that matches the sub-pixels (106R, 106G, 106B) of the organic light-emitting element. The thickness of the color-curing film is appropriately controlled by adjusting the coating method, the concentration or viscosity of the solid component of the photosensitive coloring resin composition, etc., and is generally in the range of 1 μm to 5 μm.

[0166] The light-shielding portion 110 used in the display device of the present invention is typically formed in a pattern on the sealing layer 108 of the organic light-emitting element, and can be the same as that used in a conventional color filter. The pattern shape of the light-shielding portion can be appropriately selected according to the shape of the color-curing film, for example, a striped pattern, a matrix pattern, etc. The light-shielding portion can also be a thin film of metal such as chromium formed by sputtering, vacuum evaporation, etc. Alternatively, the light-shielding portion can also be a resin layer containing light-shielding particles such as carbon microparticles, metal oxides, inorganic pigments, and organic pigments in the resin binder. In the case of a resin layer containing light-shielding particles, there are methods such as patterning by developing a photosensitive resist, patterning by using inkjet ink containing light-shielding particles, and heat transfer of photosensitive resist.

[0167] Regarding the film thickness of the light-shielding part, it is set to about 0.2 μm to 0.4 μm when it is a metal film, and to about 0.5 μm to 2 μm when it is an adhesive resin in which black pigment is dispersed or dissolved.

[0168] The sealing film 111 provided on the colored curing film (109R, 109G, 109B) and the light-shielding portion 110 can be made of known materials. Furthermore, the transparent adhesive layer 112 or the cover material 113 provided on the sealing film 111 can also be made of known materials. In this invention, since the green curing film has good weather resistance even when glass is used as the cover material, and to suppress the reduction of transmittance, glass can be used as the cover material.

[0169] Furthermore, the display device of the present invention is not limited to the configuration shown in FIG4 above, and may also include the configuration of a known display device having an organic light-emitting element.

[0170] V. Method for Manufacturing a Laminate of Organic Light-Emitting Element and Anti-Reflection Film The method for manufacturing a laminate of organic light-emitting element and anti-reflection film according to the present invention comprises the following steps: forming a hardened film of the photosensitive coloring resin composition of the present invention on an organic light-emitting element by coating the organic light-emitting element with the photosensitive coloring resin composition of the present invention to form a coating film; irradiating the coating film with light; heating and baking the film after irradiation; and developing the film after irradiation. Each step will be described below.

[0171] In the step of coating the photosensitive coloring resin composition of the present invention onto the organic light-emitting element, the coating can be performed without being adjacent to the organic light-emitting element, and at least one layer can be in between. As shown in FIG4, on the element substrate 130 having the organic light-emitting element, electrodes 107 or sealing layers 108 for inhibiting the penetration of moisture or oxygen are generally provided on the sub-pixels (106R, 106G, 106B) of the organic light-emitting element. Therefore, the coating can be performed on the organic light-emitting element with respect to these electrodes and sealing layers.

[0172] For example, by means of the known method illustrated above, a light-shielding part 110 can be pre-provided on the sealing layer 108, and a colored hardening film (109R, 109G, 109B) can be formed at the opening of the light-shielding part 110.

[0173] The photosensitive coloring resin composition of the present invention is applied to the organic light-emitting element by coating methods such as spraying, dip coating, rod coating, roller coating, spin coating, and die coating. Spin coating and die coating are particularly preferred as coating methods. The wet coating is then dried using a heating plate or oven to form a coating film.

[0174] The obtained coating is exposed to light through a mask with a specific pattern, causing the photopolymerizable compound and, if necessary, the alkali-soluble resin to undergo a photopolymerization reaction. Examples of light sources used for exposure include ultraviolet light from low-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, and electron beams. The exposure amount is adjusted appropriately according to the light source used or the thickness of the coating.

[0175] Subsequently, in order to promote the polymerization reaction, a post-baking step can be performed on the light-irradiated film after exposure by heating. The heating conditions can be appropriately selected according to the mixing ratio of each component in the photosensitive coloring resin composition used or the thickness of the coating film. The post-baking step can be performed on the light-irradiated film before the development step, after the development step, or simultaneously with the development step.

[0176] In this invention, a colored curing film is directly formed on a substrate containing an organic light-emitting element. Therefore, the heating temperature in the post-baking step is preferably 130°C or lower. More preferably, the heating temperature is 100°C or lower, and even more preferably 90°C or lower. Furthermore, the heating temperature can be 30°C or higher, 35°C or higher, or 40°C or higher.

[0177] Next, the film irradiated by the light is developed. The film irradiated by the light to be developed can also be a film after baking. In the development step, a developing solution is used to develop the film, dissolving and removing the unexposed parts, thereby forming a coating film with the desired pattern. As the developing solution, a solution containing an alkali dissolved in water or a water-soluble solvent is usually used. An appropriate amount of surfactant may also be added to the alkali solution. Furthermore, a general method can be used for development. After the development treatment, the developing solution is usually washed off and the hardened film of the photosensitive coloring resin composition is dried to form a colored hardened film. Furthermore, after the development treatment, a heat treatment may also be performed to fully harden the coating film.

[0178] In this invention, since the colored curing film is directly formed on the element substrate having the organic light-emitting element, the heating temperature in the subsequent baking step is preferably below 130°C, more preferably below 100°C, and even more preferably below 90°C. Furthermore, the heating temperature can be above 30°C, above 35°C, or above 40°C.

[0179] Furthermore, in order to further harden the film after development or baking, additional light irradiation (exposure) may be performed. Example

[0180] Hereinafter, embodiments will be shown to specifically illustrate the present invention. The present invention is not limited to these descriptions.

[0181] (Synthesis Example 1: Synthesis of Non-Reactive Resin 1) 300 parts by mass of PGMEA (Propylene glycol monomethyl ether acetate) were added to a polymerization tank. The mixture was heated to 100°C under a nitrogen atmosphere. Then, over a period of 1.5 hours, 190 parts by mass of methyl methacrylate (MMA) (95% by mass of all monomers), 10 parts by mass of methacrylic acid (MAA) (5% by mass of all monomers), 3 parts by mass of Perbutyl O (manufactured by Nippon Oil Co., Ltd.), and 2 parts by mass of chain transfer agent (n-dodecyl mercaptan) were continuously added dropwise. The reaction was then continued at 100°C. Two hours after the addition of the above main chain forming mixture was completed, 0.1 parts by mass of p-methoxyphenol, as a polymerization inhibitor, was added to terminate the polymerization, yielding a solution of non-reactive resin 1 (40% by mass of solids). The weight-average molecular weight and acid value of the obtained non-reactive resin 1 are shown in Table 2.

[0182] (Synthesis Example 2: Synthesis of Non-Reactive Resin 2) In Synthesis Example 1, the percentage of methyl methacrylate was changed from 95% by mass to 93% by mass of all monomers, and the percentage of methacrylic acid was changed from 5% by mass to 7% by mass of all monomers. Otherwise, non-reactive resin 2 was synthesized in the same manner as in Synthesis Example 1. The weight average molecular weight and acid value of the obtained non-reactive resin 2 are shown in Table 2.

[0183] (Synthesis Example 3: Synthesis of Non-Reactive Resin 3) In Synthesis Example 1, the percentage of methyl methacrylate was changed from 95% by mass to 99% by mass of all monomers, and the percentage of methacrylic acid was changed from 5% by mass to 1% by mass of all monomers. Otherwise, non-reactive resin 3 was synthesized in the same manner as in Synthesis Example 1. The weight average molecular weight and acid value of the obtained non-reactive resin 3 are shown in Table 2.

[0184] (Synthesis Example 4: Synthesis of Non-Reactive Resin 4) In Synthesis Example 3, the amount of chain transfer agent (n-dodecyl mercaptan) added was changed to 0.5 parts by mass. Otherwise, non-reactive resin 4 was synthesized in the same manner as in Synthesis Example 3. The weight average molecular weight and acid value of the obtained non-reactive resin 4 are shown in Table 2.

[0185] (Synthesis Example 5: Synthesis of Non-Reactive Resin 5) In Synthesis Example 1, the amount of chain transfer agent (n-dodecyl mercaptan) added was changed to 0.5 parts by mass. Otherwise, non-reactive resin 5 was synthesized in the same manner as in Synthesis Example 1. The weight average molecular weight and acid value of the obtained non-reactive resin 5 are shown in Table 2.

[0186] (Synthesis Example 6: Synthesis of Non-Reactive Resin 6) In Synthesis Example 1, the amount of chain transfer agent (n-dodecyl mercaptan) added was changed to 6 parts by mass. Otherwise, non-reactive resin 6 was synthesized in the same manner as in Synthesis Example 1. The weight average molecular weight and acid value of the obtained non-reactive resin 6 are shown in Table 2.

[0187] (Synthesis Example 7: Synthesis of Non-Reactive Resin 7) In Synthesis Example 2, the amount of chain transfer agent (n-dodecyl mercaptan) added was changed to 6 parts by mass. Otherwise, non-reactive resin 7 was synthesized in the same manner as in Synthesis Example 2. The weight average molecular weight and acid value of the obtained non-reactive resin 7 are shown in Table 2.

[0188] (Synthesis Example 8: Synthesis of Non-Reactive Resin 8) In Synthesis Example 1, the methacrylic acid content in all monomers was changed to 5% by mass, and the acrylic acid content in all monomers was changed to 5% by mass. Otherwise, the non-reactive resin 8 was synthesized in the same manner as in Synthesis Example 1. The weight average molecular weight and acid value of the obtained non-reactive resin 8 are shown in Table 2.

[0189] (Synthesis Example 9: Synthesis of Non-Reactive Resin 9) In Synthesis Example 1, the content of methyl methacrylate in all monomers was changed from 95% by mass to 90% by mass and ethyl methacrylate to 5% by mass. Otherwise, non-reactive resin 9 was synthesized in the same manner as in Synthesis Example 1. The weight average molecular weight and acid value of the obtained non-reactive resin 9 are shown in Table 2.

[0190] (Synthesis Example 10: Synthesis of Non-Reactive Resin 10) In Synthesis Example 1, the content of methyl methacrylate in all monomers was changed from 95% by mass to 70% by mass and ethyl methacrylate to 25% by mass. Otherwise, non-reactive resin 10 was synthesized in the same manner as in Synthesis Example 1. The weight average molecular weight and acid value of the obtained non-reactive resin 10 are shown in Table 2.

[0191] (Synthesis Example 11: Synthesis of Non-Reactive Resin 11) In Synthesis Example 1, the content of methyl methacrylate in all monomers was changed from 95% by mass to 50% by mass and ethyl methacrylate to 45% by mass. Otherwise, non-reactive resin 11 was synthesized in the same manner as in Synthesis Example 1. The weight average molecular weight and acid value of the obtained non-reactive resin 11 are shown in Table 2.

[0192] (Comparative Synthesis Example 1: Synthesis of Comparative Non-Reactive Resin C1) In Synthesis Example 1, 95% by mass of methyl methacrylate monomer was replaced with 95% by mass of butyl methacrylate monomer. Otherwise, comparative non-reactive resin C1 was synthesized in the same manner as in Synthesis Example 1. The weight average molecular weight and acid value of the obtained comparative non-reactive resin C1 are shown in Table 5.

[0193] (Comparative Synthesis Example 2: Synthesis of Comparative Non-Reactive Resin C2) In Synthesis Example 1, the amount of chain transfer agent (n-dodecyl mercaptan) added was changed to 0 parts by mass. Otherwise, comparative non-reactive resin C2 was synthesized in the same manner as in Synthesis Example 1. The weight average molecular weight and acid value of the obtained comparative non-reactive resin C2 are shown in Table 5.

[0194] (Comparative Synthesis Example 3: Synthesis of Comparative Non-Reactive Resin C3) In Synthesis Example 1, the amount of chain transfer agent (n-dodecyl mercaptan) added was changed to 10 parts by mass. Otherwise, comparative non-reactive resin C3 was synthesized in the same manner as in Synthesis Example 1. The weight average molecular weight and acid value of the obtained comparative non-reactive resin C3 are shown in Table 5.

[0195] (Comparative Synthesis Example 4: Synthesis of Comparative Non-Reactive Resin C4) In Synthesis Example 1, the methyl methacrylate monomer was changed from 95% by mass to 100% by mass. Otherwise, the comparative non-reactive resin C4 was synthesized in the same manner as in Synthesis Example 1. The weight average molecular weight and acid value of the obtained comparative non-reactive resin C4 are shown in Table 5.

[0196] (Comparative Synthesis Example 5: Synthesis of Comparative Non-Reactive Resin C5) In Synthesis Example 1, the methyl methacrylate monomer was changed from 95% by mass to 90% by mass, and the methacrylic acid monomer was changed from 5% by mass to 10% by mass. Otherwise, the comparative non-reactive resin C5 was synthesized in the same manner as in Synthesis Example 1. The weight average molecular weight and acid value of the obtained comparative non-reactive resin C5 are shown in Table 5.

[0197] (Preparation Example 1: Preparation of Alkali-Soluble Resin A) 300 parts by mass of PGMEA were added to a polymerization tank. After heating to 100°C under a nitrogen atmosphere, 90 parts by mass of 2-phenoxyethyl methacrylate (PhEMA), 54 parts by mass of MMA, 36 parts by mass of methacrylic acid (MAA), 6 parts by mass of Perbutyl O (manufactured by Nippon Oil Co., Ltd.), and 2 parts by mass of chain transfer agent (n-dodecyl mercaptan) were continuously added dropwise over 1.5 hours. The reaction was then continued at 100°C. Two hours after the addition of the above-mentioned main chain forming mixture was completed, 0.1 parts by mass of p-methoxyphenol, as a polymerization inhibitor, was added to terminate the polymerization. Next, while blowing air, 20 parts by mass of glycidyl methacrylate (GMA), an epoxy-containing compound, were added. The mixture was heated to 110°C, and then 0.8 parts by mass of triethylamine were added. The addition reaction was carried out at 110°C for 15 hours to obtain an alkali-soluble resin A solution (solid content 40% by mass). The weight-average molecular weight and acid value of the obtained alkali-soluble resin A are shown in Table 1. Furthermore, the weight-average molecular weight was determined using polystyrene as a standard, THF as the precipitate, and a Shodex GPC System-21H. The acid value was determined based on JIS K 0070.

[0198] (Preparation Example 2: Preparation of Alkali-Soluble Resin B) 300 parts by mass of PGMEA were added to a polymerization tank. After heating to 100°C under a nitrogen atmosphere, 90 parts by mass of 2-phenoxyethyl methacrylate (PhEMA), 48 parts by mass of MMA, 42 parts by mass of methacrylic acid (MAA), 6 parts by mass of Perbutyl O (manufactured by Nippon Oil Co., Ltd.), and 2 parts by mass of chain transfer agent (n-dodecyl mercaptan) were continuously added dropwise over 1.5 hours. The reaction was then continued at 100°C. Two hours after the addition of the above-mentioned main chain forming mixture was completed, 0.1 parts by mass of p-methoxyphenol, as a polymerization inhibitor, was added to terminate the polymerization. Next, while blowing air, 20 parts by mass of glycidyl methacrylate (GMA), an epoxy-containing compound, were added. After heating to 110°C, 0.8 parts by mass of triethylamine were added, and the addition reaction was carried out at 110°C for 15 hours to obtain an alkali-soluble resin B solution (solid content 40% by mass). The weight average molecular weight and acid value of the obtained alkali-soluble resin B are shown in Table 1.

[0199] (Preparation Example 3: Preparation of Alkali-Soluble Resin C) 300 parts by mass of PGMEA were added to a polymerization tank. After heating to 100°C under a nitrogen atmosphere, 90 parts by mass of 2-phenoxyethyl methacrylate (PhEMA), 60 parts by mass of MMA, 30 parts by mass of methacrylic acid (MAA), 6 parts by mass of Perbutyl O (manufactured by Nippon Oil Co., Ltd.), and 2 parts by mass of chain transfer agent (n-dodecyl mercaptan) were continuously added dropwise over 1.5 hours. The reaction was then continued at 100°C. Two hours after the addition of the above-mentioned main chain forming mixture was completed, 0.1 parts by mass of p-methoxyphenol, as a polymerization inhibitor, was added to terminate the polymerization. Next, while blowing air, 20 parts by mass of glycidyl methacrylate (GMA), an epoxy-containing compound, were added. After heating to 110°C, 0.8 parts by mass of triethylamine were added, and the addition reaction was carried out at 110°C for 15 hours to obtain an alkali-soluble resin C solution (solid content 40% by mass). The weight average molecular weight and acid value of the obtained alkali-soluble resin C are shown in Table 1.

[0200] (Preparation Example 4: Preparation of Alkali-Soluble Resin D) 300 parts by mass of PGMEA were added to a polymerization tank. After heating to 100°C under a nitrogen atmosphere, 90 parts by mass of 2-phenoxyethyl methacrylate (PhEMA), 32 parts by mass of MMA, 58 parts by mass of methacrylic acid (MAA), 6 parts by mass of Perbutyl O (manufactured by Nippon Oil Co., Ltd.), and 2 parts by mass of chain transfer agent (n-dodecyl mercaptan) were continuously added dropwise over 1.5 hours. The reaction was then continued at 100°C. Two hours after the addition of the above-mentioned main chain forming mixture was completed, 0.1 parts by mass of p-methoxyphenol, as a polymerization inhibitor, was added to terminate the polymerization. Next, while blowing air, 20 parts by mass of glycidyl methacrylate (GMA), an epoxy-containing compound, were added. After heating to 110°C, 0.8 parts by mass of triethylamine were added, and the addition reaction was carried out at 110°C for 15 hours to obtain an alkali-soluble resin D solution (solid content 40% by mass). The weight average molecular weight and acid value of the obtained alkali-soluble resin D are shown in Table 1.

[0201] (Preparation Example 5: Preparation of Alkali-Soluble Resin E) 300 parts by mass of PGMEA were added to a polymerization tank. After heating to 100°C under a nitrogen atmosphere, 90 parts by mass of 2-phenoxyethyl methacrylate (PhEMA), 54 parts by mass of MMA, 36 parts by mass of methacrylic acid (MAA), 6 parts by mass of Perbutyl O (manufactured by Nippon Oil Co., Ltd.), and 6 parts by mass of chain transfer agent (n-dodecyl mercaptan) were continuously added dropwise over 1.5 hours. The reaction was then continued at 100°C. Two hours after the addition of the above-mentioned main chain forming mixture was completed, 0.1 parts by mass of p-methoxyphenol, as a polymerization inhibitor, was added to terminate the polymerization. Next, while blowing air, 20 parts by mass of glycidyl methacrylate (GMA), an epoxy-containing compound, were added. After heating to 110°C, 0.8 parts by mass of triethylamine were added, and the addition reaction was carried out at 110°C for 15 hours to obtain an alkali-soluble resin E solution (solid content 40% by mass). The weight average molecular weight and acid value of the obtained alkali-soluble resin E are shown in Table 1.

[0202] (Preparation Example 6: Preparation of Alkali-Soluble Resin F) 300 parts by mass of PGMEA were added to a polymerization tank. After heating to 100°C under a nitrogen atmosphere, 90 parts by mass of 2-phenoxyethyl methacrylate (PhEMA), 54 parts by mass of MMA, 36 parts by mass of methacrylic acid (MAA), 6 parts by mass of Perbutyl O (manufactured by Nippon Oil Co., Ltd.), and 4 parts by mass of chain transfer agent (n-dodecyl mercaptan) were continuously added dropwise over 1.5 hours. The reaction was then continued at 100°C. Two hours after the addition of the above-mentioned main chain forming mixture was completed, 0.1 parts by mass of p-methoxyphenol, as a polymerization inhibitor, was added to terminate the polymerization. Next, while blowing air, 20 parts by mass of glycidyl methacrylate (GMA), an epoxy-containing compound, were added. After heating to 110°C, 0.8 parts by mass of triethylamine were added, and the addition reaction was carried out at 110°C for 15 hours to obtain an alkali-soluble resin F solution (solid content 40% by mass). The weight average molecular weight and acid value of the obtained alkali-soluble resin F are shown in Table 1.

[0203] (Preparation Example 7: Preparation of Alkali-Soluble Resin G) 300 parts by mass of PGMEA were added to a polymerization tank. After heating to 100°C under a nitrogen atmosphere, 90 parts by mass of 2-phenoxyethyl methacrylate (PhEMA), 54 parts by mass of MMA, 36 parts by mass of methacrylic acid (MAA), 6 parts by mass of Perbutyl O (manufactured by Nippon Oil Co., Ltd.), and 1.5 parts by mass of chain transfer agent (n-dodecyl mercaptan) were continuously added dropwise over 1.5 hours. The reaction was then continued at 100°C. Two hours after the addition of the above-mentioned main chain forming mixture was completed, 0.1 parts by mass of p-methoxyphenol, as a polymerization inhibitor, was added to terminate the polymerization. Next, while blowing air, 20 parts by mass of glycidyl methacrylate (GMA), an epoxy-containing compound, were added. After heating to 110°C, 0.8 parts by mass of triethylamine were added, and the addition reaction was carried out at 110°C for 15 hours to obtain an alkali-soluble resin G solution (solid content 40% by mass). The weight average molecular weight and acid value of the obtained alkali-soluble resin G are shown in Table 1.

[0204] (Preparation Example 8: Preparation of Alkali-Soluble Resin H) 300 parts by mass of PGMEA were added to a polymerization tank. After heating to 100°C under a nitrogen atmosphere, 90 parts by mass of 2-phenoxyethyl methacrylate (PhEMA), 54 parts by mass of MMA, 36 parts by mass of methacrylic acid (MAA), 6 parts by mass of Perbutyl O (manufactured by Nippon Oil Co., Ltd.), and 0.5 parts by mass of chain transfer agent (n-dodecyl mercaptan) were continuously added dropwise over 1.5 hours. The reaction was then continued at 100°C. Two hours after the addition of the above-mentioned main chain forming mixture was completed, 0.1 parts by mass of p-methoxyphenol, as a polymerization inhibitor, was added to terminate the polymerization. Next, while blowing air, 20 parts by mass of glycidyl methacrylate (GMA), an epoxy-containing compound, were added. After heating to 110°C, 0.8 parts by mass of triethylamine were added, and the addition reaction was carried out at 110°C for 15 hours to obtain an alkali-soluble resin H solution (solid content 40% by mass). The weight average molecular weight and acid value of the obtained alkali-soluble resin H are shown in Table 1.

[0205] (Preparation Example 9: Synthesis of Alkali-Soluble Resin I) In Preparation Example 1, 2-phenoxyethyl methacrylate (PhEMA) was replaced with benzyl methacrylate (BzMA). Otherwise, alkali-soluble resin I was synthesized in the same manner as in Preparation Example 1. The weight average molecular weight and acid value of the obtained alkali-soluble resin I (solid content 40% by mass) are shown in Table 1.

[0206] (Preparation Example 10: Synthesis of Alkali-Soluble Resin J) In Preparation Example 1, 2-phenoxyethyl methacrylate (PhEMA) was replaced with cyclohexyl methacrylate (CHMA). Otherwise, alkali-soluble resin J was synthesized in the same manner as in Preparation Example 1. The weight average molecular weight and acid value of the obtained alkali-soluble resin J (solid content 40% by mass) are shown in Table 1.

[0207] (Preparation Example 11: Preparation of Alkali-Soluble Resin K) 300 parts by mass of PGMEA were added to a polymerization tank. Under a nitrogen atmosphere, the temperature was raised to 100°C. Then, over a period of 1.5 hours, 116 parts by mass of glycidyl methacrylate (GMA), 6 parts by mass of Perbutyl O (manufactured by Nippon Oil Co., Ltd.), and 2 parts by mass of chain transfer agent (n-dodecyl mercaptan) were continuously added dropwise. The reaction was then continued at 100°C. Two hours after the addition of the above-mentioned main chain forming mixture was completed, 0.1 parts by mass of p-methoxyphenol, as a polymerization inhibitor, was added to terminate the polymerization. Next, while blowing air, 56 parts by mass of acrylic acid (AA) were added. The temperature was raised to 110°C, and then 0.8 parts by mass of triethylamine were added. An addition reaction was carried out at 110°C for 8 hours. Then, 28 parts by mass of succinic anhydride were added, and an addition reaction was carried out at 110°C for 8 hours. An alkali-soluble resin K solution (solid content 40% by mass) was obtained. The weight-average molecular weight and acid value of the obtained alkali-soluble resin K are shown in Table 1.

[0208] [Table 1] Table 1. Alkali-soluble resins No. Monomer composition Weight average molecular weight acid value (mgKOH / g) A PhEMA / MMA / MAA / GMA=45 / 27 / 18 / 10 8500 75 B PhEMA / MMA / MAA / GMA=45 / 24 / 21 / 10 8500 95 C PhEMA / MMA / MAA / GMA=45 / 30 / 15 / 10 8500 55 D PhEMA / MMA / MAA / GMA=45 / 16 / 29 / 10 8500 145 E PhEMA / MMA / MAA / GMA=45 / 27 / 18 / 10 3000 75 F PhEMA / MMA / MAA / GMA=45 / 27 / 18 / 10 5000 75 G PhEMA / MMA / MAA / GMA = 45 / 27 / 18 / 10 15000 75 H PhEMA / MMA / MAA / GMA = 45 / 27 / 18 / 10 30000 75 I BzMA / MMA / MAA / GMA = 45 / 27 / 18 / 10 8500 75 J CHMA / MMA / MAA / GMA = 45 / 27 / 18 / 10 8500 75 K GMA / AA / Succinic anhydride = 58 / 28 / 14 8500 75

[0209] (Preparation Example 12: Synthesis of Block Copolymer 1) 250 parts by weight of THF and 0.6 parts by weight of lithium chloride were added to a 500 mL round-bottom four-necked separable flask equipped with a condenser, a funnel for adding, a nitrogen inlet, a mechanical stirrer, and a digital thermometer, and the mixture was thoroughly purged with nitrogen. After cooling the reaction flask to -60°C, 4.9 parts by weight of butyllithium (15% hexane solution), 1.1 parts by weight of diisopropylamine, and 1.0 parts by weight of methyl isobutyrate were injected using a syringe. Using an additive funnel, 2.2 parts by mass of 1-ethoxyethyl methacrylate (EEMA), 29.1 parts by mass of 2-(trimethylsiloxy)ethyl methacrylate (TMSMA), 12.8 parts by mass of 2-ethylhexyl methacrylate (EHMA), 13.7 parts by mass of n-butyl methacrylate (BMA), 9.5 parts by mass of benzyl methacrylate (BzMA), and 17.5 parts by mass of methyl methacrylate (MMA), the monomers for block B, were added dropwise over a period of 60 minutes. After 30 minutes, 26.7 parts by mass of dimethylaminoethyl methacrylate (DMMA), the monomer for block A, was added dropwise over a period of 20 minutes. After reacting for 30 minutes, 1.5 parts by mass of methanol was added to stop the reaction. The obtained precursor block copolymer THF solution was reprecipitated in hexane, purified by filtration and vacuum drying, and diluted with PGMEA to prepare a 30% by mass solution of solids. Add 32.5 parts by mass of water, heat to 100°C and react for 7 hours. This process deprotects the EEMA-derived structural units to form methacrylic acid (MAA)-derived structural units, and deprotects the TMSMA-derived structural units to form 2-hydroxyethyl methacrylate (HEMA)-derived structural units. The resulting block copolymer PGMEA solution is then redeprecipitated in hexane, purified by filtration and vacuum drying to obtain block copolymer 1 (amine value 95 mgKOH / g, acid value 8 mgKOH / g, Tg 38°C) containing the structural units represented by the above general formula (I). The weight average molecular weight (Mw) is 7730.

[0210] (Preparation Example 13: Synthesis of Oxime Ester Photoinitiator Represented by Formula (A-2)) The oxime ester photoinitiator represented by the above formula (A-2) was synthesized in the same manner as the preparation of compound No. 73 in paragraphs 0114 to 0117 of International Publication No. 2015 / 152153.

[0211] (Example 1: Preparation of photosensitive coloring resin composition R-1) (1) Preparation of colorant dispersion R(1) 72.1 parts by weight of PGMEA, 15.0 parts by weight of the alkali-soluble resin A solution (solid content 40% by weight) of Preparation Example 1, and 10.2 parts by weight of the PGMEA solution (solid content 35% by weight) of the block copolymer 1 of Preparation Example 12 were added to a 225 mL mayonnaise bottle and stirred. 0.4 parts by weight of phenylphosphonic acid (trade name: PPA, manufactured by Nissan Chemical Co., Ltd.) were added and stirred at room temperature for 30 minutes. 13.3 parts by weight of CI pigment red 177 (R177) as a red pigment and 100 parts by weight of zirconia beads with a particle size of 2.0 mm were added to the mixture. The mixture was pre-crushed by shaking it for 1 hour using a paint shaker (manufactured by Asada Iron Works). Then, 200 parts of zirconia beads with a particle size of 0.1 mm were added and dispersed using a paint shaker for 4 hours as formal crushing to obtain pigment dispersion R(1). Furthermore, the block copolymer 1 forms a salt by forming a salt with phenylphosphonic acid, thus becoming a salt-type block copolymer 1.

[0212] (2) Manufacturing of photosensitive coloring resin composition R-1: 111 parts by mass of the pigment dispersion R(1) obtained above, 10 parts by mass of the non-reactive resin 1 solution (solid content 40% by mass) obtained in Synthesis Example 1, 17.2 parts by mass of the multifunctional monomer (trade name ARONIX M-305, manufactured by Toa Synthetic Co., Ltd.), 2 parts by mass of the oxime ester photoinitiator represented by the above formula (A-2), 0.1 parts by mass of the fluorine surfactant (trade name MEGAFAC R-08MH, manufactured by DIC Co., Ltd.), and 170.5 parts by mass of PGMEA were added to obtain photosensitive coloring resin composition R-1.

[0213] (Examples 2-11: Manufacturing of photosensitive coloring resin compositions R-2 to R-11) In the manufacturing of photosensitive coloring resin composition R-1 of Example 1, the type and / or mass ratio of non-reactive resin were changed as shown in Table 2. The mass ratio of more functional monomers was changed in the same way as in Example 1 while keeping the ratio of oxime ester photoinitiator represented by the above formula (A-2) the same as in Example 1. Otherwise, photosensitive coloring resin compositions R-2 to R-11 were obtained in the same way as photosensitive coloring resin composition R-1.

[0214] (Examples 12-21: Manufacturing of photosensitive coloring resin compositions R-12-R-21) (1) Manufacturing of pigment dispersions R(2)-(11) In the manufacturing of pigment dispersion R(1) in Example 1, as shown in Table 2, the type of alkali-soluble resin was changed to alkali-soluble resin B, C, D, E, F, G, H, I, J, or K instead of alkali-soluble resin A. Otherwise, pigment dispersions R(2)-(11) were obtained in the same manner as pigment dispersion R(1). (2) The photosensitive coloring resin compositions R-12 to R-21 were prepared in the same manner as in the preparation of the photosensitive coloring resin composition R-1 in Example 1. As shown in Table 2, the pigment dispersion R(1) was replaced with pigment dispersion R(2) to (11) of different types of alkali-soluble resins. The mass ratio of non-reactive resins was changed. The ratio of oxime ester photoinitiator represented by the above formula (A-2) was kept the same as in Example 1, and the mass ratio of more functional monomers was changed in the same way as in Example 1. Otherwise, the photosensitive coloring resin compositions R-12 to R-21 were obtained in the same manner as the photosensitive coloring resin composition R-1.

[0215] (Example 22: Manufacturing of photosensitive coloring resin composition R-22) 111 parts by mass of the pigment dispersion R(1) obtained above, 10 parts by mass of the non-reactive resin 1 obtained in Synthesis Example 1, 7.2 parts by mass of the multifunctional monomer (trade name ARONIX M-305, manufactured by Toa Synthetic Co., Ltd.), 2 parts by mass of the oxime ester photoinitiator represented by the above formula (A-2), 0.1 parts by mass of the fluorine surfactant (trade name MEGAFAC R-08MH, manufactured by DIC Co., Ltd.), 10 parts by mass of the multifunctional epoxy compound (1,2-epoxy-4-(2-epoxyethylene)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol, trade name EHPE3150, manufactured by Daicel Co., Ltd.), and 170.5 parts by mass of PGMEA were added to obtain photosensitive coloring resin composition R-22.

[0216] (Example 23: Manufacturing of photosensitive coloring resin composition R-23) In Example 22, the multifunctional epoxy compound was replaced with a multifunctional end-capped isocyanate compound (trade name Duranate MF-K60B, manufactured by Asahi Kasei Corporation). Otherwise, the photosensitive coloring resin composition R-23 was obtained in the same manner as the photosensitive coloring resin composition R-22.

[0217] (Example 24: Preparation of photosensitive coloring resin composition G-1) (1) Preparation of colorant dispersion G(1) 72.1 parts by weight of PGMEA, 15 parts by weight of the alkali-soluble resin A solution (solid content 40% by weight) of Preparation Example 1, and 10.2 parts by weight of the PGMEA solution (solid content 35% by weight) of the block copolymer 1 of Preparation Example 12 were added to a 225 mL mayonnaise bottle and stirred. 0.4 parts by weight of phenylphosphonic acid (trade name: PPA, manufactured by Nissan Chemical Co., Ltd.) were added and stirred at room temperature for 30 minutes. 8.0 parts by weight of CI pigment green 59 (G59) as a green pigment, 5.3 parts by weight of CI pigment yellow 150 (Y150) as a yellow pigment, and 100 parts by weight of zirconia beads with a particle size of 2.0 mm were added. The mixture was pre-crushed by shaking in a paint shaker (manufactured by Asada Iron Works) for 1 hour. Then, 200 parts by weight of zirconia beads with a particle size of 0.1 mm were added and dispersed in the paint shaker for 4 hours as formal crushing to obtain pigment dispersion G(1). Furthermore, the block copolymer 1 forms a salt by forming a salt with phenylphosphonic acid, thus becoming a salt-type block copolymer 1.

[0218] (2) Preparation of photosensitive coloring resin composition G-1: 111 parts by mass of the pigment dispersion G(1) obtained above, 110 parts by mass of the non-reactive resin obtained in Synthesis Example 1, 17.2 parts by mass of the multifunctional monomer (trade name ARONIX M-305, manufactured by Toa Synthetic Co., Ltd.), 2 parts by mass of the oxime ester photoinitiator represented by the above formula (A-2), 0.1 parts by mass of the fluorine surfactant (trade name MEGAFAC R-08MH, manufactured by DIC Co., Ltd.), and 170.5 parts by mass of PGMEA were added to obtain photosensitive coloring resin composition G-1.

[0219] (Examples 25-34: Manufacturing of photosensitive coloring resin compositions G-2 to G-11) In the manufacturing of photosensitive coloring resin composition G-1 of Example 24, the type and / or mass ratio of the non-reactive resin were changed as shown in Table 3. The mass ratio of more functional monomers was changed in the same way as in Example 24, while keeping the ratio of oxime ester photoinitiator represented by the above formula (A-2) the same as in Example 24. Otherwise, photosensitive coloring resin compositions G-2 to G-11 were obtained in the same way as photosensitive coloring resin composition G-1.

[0220] (Examples 35-44: Manufacturing of photosensitive coloring resin compositions G-12-G-21) (1) Manufacturing of pigment dispersions G(2)-(11) In the manufacturing of pigment dispersion G(1) in Example 24, as shown in Table 3, the type of alkali-soluble resin was changed to alkali-soluble resin B, C, D, E, F, G, H, I, J, or K instead of alkali-soluble resin A. Otherwise, pigment dispersions G(2)-(11) were obtained in the same manner as pigment dispersion G(1). (2) The photosensitive coloring resin compositions G-12 to G-21 were manufactured in the same manner as the photosensitive coloring resin composition G-1 in Example 24. As shown in Table 3, the pigment dispersion G(2) to (11) of different types of alkali-soluble resins were used instead of pigment dispersion G(1). The mass ratio of non-reactive resins was changed. The ratio of oxime ester photoinitiator represented by the above formula (A-2) was kept the same as in Example 24, and the mass ratio of more functional monomers was changed in the same way as in Example 24. Otherwise, the photosensitive coloring resin compositions G-12 to G-21 were obtained in the same manner as the photosensitive coloring resin composition G-1.

[0221] (Example 45: Manufacturing of photosensitive coloring resin composition G-22) 111 parts by mass of the pigment dispersion G(1) obtained above, 10 parts by mass of the non-reactive resin 1 obtained in Synthesis Example 1, 7.2 parts by mass of the multifunctional monomer (trade name ARONIX M-305, manufactured by Toa Synthetic Co., Ltd.), 2 parts by mass of the oxime ester photoinitiator represented by the above formula (A-2), 0.1 parts by mass of the fluorine surfactant (trade name MEGAFAC R-08MH, manufactured by DIC Co., Ltd.), 10 parts by mass of the multifunctional epoxy resin (1,2-epoxy-4-(2-epoxyethylene)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol, trade name EHPE3150, manufactured by Daicel Co., Ltd.), and 170.5 parts by mass of PGMEA were added to obtain photosensitive coloring resin composition G-22.

[0222] (Example 46: Manufacturing of photosensitive coloring resin composition G-23) In Example 45, the multifunctional epoxy compound was replaced with a multifunctional end-capped isocyanate compound (trade name Duranate MF-K60B, manufactured by Asahi Kasei Corporation). Otherwise, the photosensitive coloring resin composition G-23 was obtained in the same manner as the photosensitive coloring resin composition G-22.

[0223] (Example 47: Preparation of photosensitive coloring resin composition B-1) (1) Preparation of colorant dispersion B(1) Add 48.1 parts by weight of PGMEA, 10 parts by weight of the alkali-soluble resin A solution (solid content 40% by weight) of Preparation Example 1, and 6.8 parts by weight of the PGMEA solution (solid content 35% by weight) of the block copolymer 1 of Preparation Example 12 to a 225 mL mayonnaise bottle, and stir. Add 0.3 parts by weight of phenylphosphonic acid (trade name: PPA, manufactured by Nissan Chemical Co., Ltd.) to it, and stir at room temperature for 30 minutes. 7.1 parts by weight of CI pigment blue 15:6 (B15:6) as a blue pigment, 1.8 parts by weight of CI pigment purple 23 (V23) as a purple pigment, and 100 parts by weight of zirconia beads with a particle size of 2.0 mm were added. The mixture was pre-crushed by shaking in a paint shaker (manufactured by Asada Iron Works) for 1 hour. Then, 200 parts by weight of zirconia beads with a particle size of 0.1 mm were added and dispersed in the paint shaker for 4 hours as formal crushing to obtain pigment dispersion B(1). Furthermore, the block copolymer 1 forms a salt by forming a salt with phenylphosphonic acid, thus becoming a salt-type block copolymer 1.

[0224] (2) Preparation of photosensitive coloring resin composition B-1: 74.1 parts by weight of the pigment dispersion B(1) obtained above, 15 parts by weight of the non-reactive resin obtained in Synthesis Example 1, 16 parts by weight of the multifunctional monomer (trade name ARONIX M-305, manufactured by Toa Synthetic Co., Ltd.), 2 parts by weight of the oxime ester photoinitiator represented by the above formula (A-2), 0.1 parts by weight of the fluorine surfactant (trade name MEGAFAC R-08MH, manufactured by DIC Co., Ltd.), and 0.6 parts by weight of PGMEA 14 were added to obtain photosensitive coloring resin composition B-1.

[0225] (Examples 48-57: Manufacturing of photosensitive coloring resin compositions B-2 to B-11) In the manufacturing of photosensitive coloring resin composition B-1 of Example 47, the type and / or mass ratio of the non-reactive resin were changed as shown in Table 4. The mass ratio of more functional monomers was changed in the same way as in Example 47, while keeping the ratio of oxime ester photoinitiator represented by the above formula (A-2) the same as in Example 47. Otherwise, photosensitive coloring resin compositions B-2 to B-11 were obtained in the same way as photosensitive coloring resin composition B-1.

[0226] (Examples 58-67: Manufacturing of photosensitive coloring resin compositions B-12-B-21) (1) Manufacturing of pigment dispersions B(2)-(11) In the manufacturing of pigment dispersion B(1) in Example 47, as shown in Table 4, the type of alkali-soluble resin was changed to alkali-soluble resin B, C, D, E, F, G, H, I, J, or K instead of alkali-soluble resin A. Otherwise, pigment dispersions B(2)-(11) were obtained in the same manner as pigment dispersion B(1). (2) The photosensitive coloring resin compositions B-12 to B-21 were prepared in the same manner as the photosensitive coloring resin composition B-1 in Example 47. As shown in Table 4, the pigment dispersion B(1) was replaced with pigment dispersion B(2) to (11) of different types of alkali-soluble resin. The mass ratio of non-reactive resin was changed. The ratio of oxime ester photoinitiator represented by the above formula (A-2) was kept the same as in Example 47, and the mass ratio of more functional monomers was changed in the same way as in Example 47. Otherwise, the photosensitive coloring resin compositions B-12 to B-21 were obtained in the same manner as the photosensitive coloring resin composition B-1.

[0227] (Example 68: Manufacturing of photosensitive coloring resin composition B-22) 74.1 parts by mass of the pigment dispersion B(1) obtained above, 15 parts by mass of the non-reactive resin obtained in Synthesis Example 1, 6 parts by mass of the multifunctional monomer (trade name ARONIX M-305, manufactured by Toa Synthetic Co., Ltd.), 2 parts by mass of the oxime ester photoinitiator represented by the above formula (A-2), 0.1 parts by mass of the fluorine surfactant (trade name MEGAFAC R-08MH, manufactured by DIC Co., Ltd.), 10 parts by mass of the multifunctional epoxy compound (1,2-epoxy-4-(2-epoxyethylene)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol, trade name EHPE3150, manufactured by Daicel Co., Ltd.), and 140.6 parts by mass of PGMEA were added to obtain photosensitive coloring resin composition B-22.

[0228] (Example 69: Manufacturing of photosensitive coloring resin composition B-23) In Example 68, the above-mentioned polyfunctional epoxy compound was replaced with a polyfunctional end-capped isocyanate compound (trade name Duranate MF-K60B, manufactured by Asahi Kasei Corporation). Otherwise, photosensitive coloring resin composition B-23 was obtained in the same manner as photosensitive coloring resin composition B-22.

[0229] (Comparative Examples 1-6: Manufacturing of Comparative Photosensitive Coloring Resin Compositions CR-1-CR-6) In Example 1, as shown in Table 5, the comparative photosensitive coloring resin compositions CR-1-CR-6 were obtained in the same manner as the photosensitive coloring resin composition R-1, except that a non-reactive resin was not used, or any of the comparative non-reactive resins c1-c5 were used instead of non-reactive resin 1.

[0230] (Comparative Examples 7-12: Manufacturing of Comparative Photosensitive Coloring Resin Compositions CG-1-CG-6) In Example 24, as shown in Table 5, the comparative photosensitive coloring resin compositions CG-1-CG-6 were obtained in the same manner as the photosensitive coloring resin composition G-1, except that a non-reactive resin was not used, or any of the comparative non-reactive resins c1-c5 were used instead of non-reactive resin 1.

[0231] (Comparative Examples 13-18: Manufacturing of Comparative Photosensitive Coloring Resin Compositions CB-1 to CB-6) In Example 47, as shown in Table 5, the comparative photosensitive coloring resin compositions CB-1 to CB-6 were obtained in the same manner as the photosensitive coloring resin composition B-1, except that a non-reactive resin was not used, or any of the comparative non-reactive resins c1 to c5 were used instead of non-reactive resin 1.

[0232] [Evaluation Method] Using a spin coater, the photosensitive coloring resin compositions obtained in each example and comparative example were coated onto a glass substrate (manufactured by NH TECHNO GLASS, Inc., "NA35") to a hardened coating thickness of 3.0 μm. The coatings were then dried at 80°C for 3 minutes using a heated plate to form a coating on the substrate. The coating was then exposed to ultraviolet light at 50 mJ / cm² using a high-pressure mercury lamp through a photomask (chrome mask) with an opening size of 2 μm to 100 μm used to form individual fine lines, thereby forming an exposed coating. Subsequently, spin development was performed using a 0.05 wt% potassium hydroxide aqueous solution as the developer. After contacting the coating with the developer for 60 seconds, it was washed with pure water, and this development process was repeated to obtain a coating with an individual fine line pattern. Afterward, the coating was baked in a cleanroom oven at 90°C for 30 minutes to form a hardened film with an individual fine line pattern. The obtained hardened film was evaluated for its transmittance, cross-sectional shape, and solvent resistance.

[0233] <Evaluation of Developing Residue> Using a spin coater, the photosensitive coloring resin compositions obtained in the Examples and Comparative Examples were coated onto glass substrates (manufactured by NH TECHNO GLASS, Inc., "NA35") to form a colored layer with a thickness of 3.0 μm after coating. The substrates were then dried at 80°C for 3 minutes using a heated plate to form a colored layer. The glass substrates with the colored layer formed were spray-developed for 60 seconds using a 0.05% potassium hydroxide aqueous solution as an alkaline developer, followed by rinsing with pure water. After visually observing the formed portion of the colored layer after development, the substrates were thoroughly wiped with an ethanol-containing lens cloth (manufactured by Toray, Inc., trade name Toraysee MK Clean Cloth), and the degree of coloration on the lens cloth was visually observed. (Developer residue evaluation criteria) ◎: No developer residue was visually detected, and the lens cloth was completely unstained. ○: No developer residue was visually detected, and the lens cloth was slightly stained. ×: Developer residue was visually detected, and the lens cloth was stained. When the evaluation result is ○, it can be used in practice, but when the judgment result is ◎, the effect is better.

[0234] <Evaluation of the Cross-sectional Shape of the Fine Line Patterned Colored Layer> The cross-sectional shape of the obtained independent fine line patterned colored layer in the thickness direction was observed using a scanning electron microscope (manufactured by Shimadzu Corporation, Super Scan Model 220, 10000x magnification). The tilt angle (θ1) of the cross-sectional shape of the colored layer was evaluated according to the following evaluation criteria (see Figure 5). (Evaluation Criteria for the Cross-sectional Shape of the Patterned Colored Layer) ◎: Tilt angle (θ1) is 15 degrees or more but less than 100 degrees ○: Tilt angle (θ1) is 100 degrees or more but less than 110 degrees △: Tilt angle (θ1) is 110 degrees or more but less than 120 degrees ×: Tilt angle (θ1) is 120 degrees or more When the evaluation result is △, it can be used in practice, but when the evaluation result is ○, the cross-sectional shape of the colored layer is good. When the evaluation result is ◎, the cross-sectional shape of the colored layer is excellent.

[0235] <Soluble Resistance (PGME Resistance) Evaluation> After measuring the thickness of the obtained colored layer, it was immersed in propylene glycol monomethyl ether (PGME) for 10 minutes and then air-dried. The film thickness was measured again. Furthermore, the film thickness was measured using a stylus-type profile film thickness gauge "P-15Tencor" (manufactured by Instruments). The film thickness after solvent immersion / film thickness before solvent immersion × 100 was calculated as the residual film rate. (Soluble resistance evaluation criteria) ◎: Residual film rate after solvent immersion is 98% or more ○: Residual film rate after solvent immersion is 96% or more but less than 98% △: Residual film rate after solvent immersion is 94% or more but less than 96% ×: Residual film rate after solvent immersion is less than 94% When the evaluation result is △, it can be used in practice. When the evaluation result is ○, the solvent resistance is good. When the evaluation result is ◎, the solvent resistance is excellent.

[0236] [Table 2] Table 2. Non-reactive resin (I) Alkali-soluble resin (II) Mixing ratio Multifunctional epoxy resin Multifunctional terminal isocyanates Pigment residue Cross-sectional shape Solvent resistant No. Monomer composition Weight average molecular weight acid value (mgKOH / g) (parts by weight) No. (parts by weight) I / (I+II) (parts by weight) (parts by weight) Example 1 1 MMA / MAA = 95 / 5 15000 33 10 A 15 40% - - R177 ◎ ◎ 〇 Example 2 2 MMA / MAA = 93 / 7 15000 46 15 A 15 50% - - R177 ◎ 〇 〇 Example 3 3 MMA / MAA = 99 / 1 15000 8 10 A 15 40% - - R177 〇 ◎ 〇 Example 4 4 MMA / MAA = 99 / 1 50000 33 0.2 A 15 1% - - R177 ◎ △ 〇 Example 5 5 MMA / MAA = 95 / 5 50000 33 1 A 15 6% - - R177 ◎ 〇 〇 Example 6 6 MMA / MAA = 95 / 5 5000 33 20 A 15 57% - - R177 〇 ◎ 〇 Example 7 7 MMA / MAA = 93 / 7 5000 46 40 A 15 73% - - R177 △ 〇 〇 Example 8 8 MMA / AA = 95 / 5 15000 39 10 A 15 40% - - R177 ◎ ◎ 〇 Example 9 9 MMA / EMA / MMA = 90 / 5 / 5 15000 33 10 A 15 40% - - R177 ◎ 〇 〇 Example 10 10 MMA / EMA / MMA = 70 / 25 / 5 15000 33 10 A 15 40% - - R177 ◎ △ 〇 Example 11 11 MMA / EMA / MMA = 50 / 45 / 5 15000 33 10 A 15 40% - - R177 ◎ △ △ Example 12 1 MMA / MAA = 95 / 5 15000 33 15 B 15 50% - - R177 ◎ ◎ 〇 Example 13 1 MMA / MAA = 95 / 5 15000 33 5 C 15 25% - - R177 ◎ ◎ 〇 Example 14 1 MMA / MAA = 95 / 5 15000 33 20 D 15 57% - - R177 〇 ◎ 〇 Example 15 1 MMA / MAA = 95 / 5 15000 33 15 E 15 50% - - R177 ◎ ◎ 〇 Example 16 1 MMA / MAA = 95 / 5 15000 33 12 F 15 44% - - R177 ◎ ◎ 〇 Example 17 1 MMA / MAA = 95 / 5 15000 33 8 G 15 35% - - R177 ◎ ◎ 〇 Example 18 1 MMA / MAA = 95 / 5 15000 33 8 H 15 35% - - R177 ◎ ◎ 〇 Example 19 1 MMA / MAA = 95 / 5 15000 33 10 I 15 40% - - R177 ◎ ◎ 〇 Example 20 1 MMA / MAA = 95 / 5 15000 33 10 J 15 40% - - R177 ◎ ◎ 〇 Example 21 1 MMA / MAA = 95 / 5 15000 33 10 K 15 40% - - R177 ◎ ◎ 〇 Example 22 1 MMA / MAA = 95 / 5 15000 33 10 A 15 40% 10 - R177 ◎ ◎ ◎ Example 23 1 MMA / MAA = 95 / 5 15000 33 10 A 15 40% - 10 R177 ◎ ◎ ◎

[0237] [Table 3] Table 3. Non-reactive resin (I) Alkali-soluble resin (II) Mixing ratio Multifunctional epoxy resin Multifunctional terminal isocyanates Pigment residue section shape Solvent resistant No. Monomer composition Weight average molecular weight acid value (mgKOH / g) (parts by weight) No. (parts by weight) I / (I+II) (parts by weight) (parts by weight) Example 24 1 MMA / MAA = 95 / 5 15000 33 10 A 15 40% - - G59 / Y150 ◎ ◎ 〇 Example 25 2 MMA / MAA = 93 / 7 15000 46 15 A 15 50% - - G59 / Y150 ◎ 〇 〇 Example 26 3 MMA / MAA = 99 / 1 15000 8 10 A 15 40% - - G59 / Y150 〇 ◎ 〇 Example 27 4 MMA / MAA = 99 / 1 50000 33 0.2 A 15 1% - - G59 / Y150 ◎ △ 〇 Example 28 5 MMA / MAA = 95 / 5 50000 33 1 A 15 6% - - G59 / Y150 ◎ 〇 〇 Example 29 6 MMA / MAA = 95 / 5 5000 33 20 A 15 57% - - G59 / Y150 〇 ◎ 〇 Example 30 7 MMA / MAA = 93 / 7 5000 46 40 A 15 73% - - G59 / Y150 △ 〇 〇 Example 31 8 MMA / AA = 95 / 5 15000 39 10 A 15 40% - - G59 / Y150 ◎ ◎ 〇 Example 32 9 MMA / EMA / MMA = 90 / 5 / 5 15000 33 10 A 15 40% - - G59 / Y150 ◎ 〇 〇 Example 33 10 MMA / EMA / MMA = 70 / 25 / 5 15000 33 10 A 15 40% - - G59 / Y150 ◎ △ 〇 Example 34 11 MMA / EMA / MMA = 50 / 45 / 5 15000 33 10 A 15 40% - - G59 / Y150 ◎ △ △ Example 35 1 MMA / MAA = 95 / 5 15000 33 15 B 15 50% - - G59 / Y150 ◎ ◎ 〇 Example 36 1 MMA / MAA = 95 / 5 15000 33 5 C 15 25% - - G59 / Y150 ◎ ◎ 〇 Example 37 1 MMA / MAA = 95 / 5 15000 33 20 D 15 57% - - G59 / Y150 〇 ◎ 〇 Example 38 1 MMA / MAA = 95 / 5 15000 33 15 E 15 50% - - G59 / Y150 ◎ ◎ 〇 Example 39 1 MMA / MAA = 95 / 5 15000 33 12 F 15 44% - - G59 / Y150 ◎ ◎ 〇 Example 40 1 MMA / MAA = 95 / 5 15000 33 8 G 15 35% - - G59 / Y150 ◎ ◎ 〇 Example 41 1 MMA / MAA = 95 / 5 15000 33 8 H 15 35% - - G59 / Y150 ◎ ◎ 〇 Example 42 1 MMA / MAA = 95 / 5 15000 33 10 I 15 40% - - G59 / Y150 ◎ ◎ 〇 Example 43 1 MMA / MAA = 95 / 5 15000 33 10 J 15 40% - - G59 / Y150 ◎ ◎ 〇 Example 44 1 MMA / MAA = 95 / 5 15000 33 10 K 15 40% - - G59 / Y150 ◎ ◎ 〇 Example 45 1 MMA / MAA = 95 / 5 15000 33 10 A 15 40% 10 - G59 / Y150 ◎ ◎ ◎ Example 46 1 MMA / MAA = 95 / 5 15000 33 10 A 15 40% - 10 G59 / Y150 ◎ ◎ ◎

[0238] [Table 4] Table 4. Non-reactive resin (I) Alkali-soluble resin (II) Mixing ratio Multifunctional epoxy resin Multifunctional terminal isocyanates Pigment residue Cross-sectional shape Solvent resistant No. Monomer composition Weight average molecular weight acid value (mgKOH / g) (parts by weight) No. (parts by weight) I / (I+II) (parts by weight) (parts by weight) Example 47 1 MMA / MAA = 95 / 5 15000 33 5 A 10 33% - - B15: 6 / V23 ◎ ◎ 〇 Example 48 2 MMA / MAA = 93 / 7 15000 46 10 A 10 50% - - B15: 6 / V23 ◎ 〇 〇 Example 49 3 MMA / MAA = 99 / 1 15000 8 5 A 10 33% - - B15: 6 / V23 〇 〇 Example 50 4 MMA / MAA = 99 / 1 50000 33 0.2 A 10 2% - - B15: 6 / V24 ◎ △ 〇 Example 51 5 MMA / MAA = 95 / 5 50000 33 1 A 10 9% - - B15: 6 / V23 ◎ 〇 〇 Example 52 6 MMA / MAA = 95 / 5 5000 33 20 A 10 67% - - B15: 6 / V23 〇 ◎ 〇 Example 53 7 MMA / MAA = 93 / 7 5000 46 40 A 10 80% - - B15: 6 / V23 △ 〇 〇 Example 54 8 MMA / AA = 95 / 5 15000 39 5 A 10 33% - - B15: 6 / V23 ◎ ◎ 〇 Example 55 9 MMA / EMA / MMA = 90 / 5 / 5 15000 33 10 A 15 40% - - B15: 6 / V23 ◎ 〇 〇 Example 56 10 MMA / EMA / MMA = 70 / 25 / 5 15000 33 10 A 15 40% - - B15: 6 / V23 ◎ △ 〇 Example 57 11 MMA / EMA / MMA = 50 / 45 / 5 15000 33 10 A 15 40% - - B15: 6 / V23 ◎ △ △ Example 58 1 MMA / MAA = 95 / 5 15000 33 15 B 10 80% - - B15: 6 / V23 ◎ ◎ 〇 Example 59 1 MMA / MAA = 95 / 5 15000 33 5 C 10 33% - - B15: 6 / V23 ◎ ◎ 〇 Example 60 1 MMA / MAA = 95 / 5 15000 33 20 D 10 67% - - B15: 6 / V23 〇 ◎ 〇 Example 61 1 MMA / MAA = 95 / 5 15000 33 15 E 10 80% - - B15: 6 / V23 ◎ ◎ 〇 Example 62 1 MMA / MAA = 95 / 5 15000 33 12 F 10 55% - - B15: 6 / V23 ◎ ◎ 〇 Example 63 1 MMA / MAA = 95 / 5 15000 33 8 G 10 44% - - B15: 6 / V23 ◎ ◎ 〇 Example 64 1 MMA / MAA = 95 / 5 15000 33 8 H 10 44% - - B15: 6 / V23 ◎ ◎ 〇 Example 65 1 MMA / MAA = 95 / 5 15000 33 10 I 10 50% - - B15: 6 / V23 ◎ ◎ 〇 Example 66 1 MMA / MAA = 95 / 5 15000 33 10 J 10 50% - - B15: 6 / V23 ◎ ◎ 〇 Example 67 1 MMA / MAA = 95 / 5 15000 33 10 K 10 50% - - B15: 6 / V23 ◎ ◎ 〇 Example 68 1 MMA / MAA = 95 / 5 15000 33 5 A 10 33% 10 - B15: 6 / V23 ◎ ◎ ◎ Example 69 1 MMA / MAA = 95 / 5 15000 33 5 A 10 33% - 10 B15: 6 / V23 ◎ ◎ ◎

[0239] [Table 5] Table 5. Non-reactive resin (I) Alkali-soluble resin (II) Mixing ratio Multifunctional epoxy resin Multifunctional terminal isocyanates Pigment residue section shape Solvent resistant No. Monomer composition Weight average molecular weight acid value (mgKOH / g) (parts by weight) No. (parts by weight) I / (I+II) (parts by weight) (parts by weight) Comparative Example 1 - - - - 0 A 15 0% - - R177 ◎ × 〇 Comparative Example 2 c1 BMA / MAA = 95 / 5 15000 33 10 A 15 67% - - R177 ◎ × △ Comparative Example 3 c2 MMA / MAA = 95 / 5 60000 35 10 A 15 67% - - R177 × ◎ 〇 Comparative Example 4 c3 MMA / MAA = 95 / 5 3000 35 10 A 15 67% - - R177 ◎ × 〇 Comparative Example 5 c4 MMA / MAA = 100 / 0 15000 0 10 A 15 67% - - R177 × ◎ 〇 Comparative Example 6 c5 MMA / MAA = 90 / 10 15000 65 10 A 15 67% - - R177 ◎ × 〇 Comparative Example 7 - - - - 0 A 15 0% - - G59 / Y150 ◎ × 〇 Comparative Example 8 c1 BMA / MAA = 95 / 5 15000 33 10 A 15 67% - - G59 / Y150 ◎ × △ Comparative Example 9 c2 MMA / MAA = 95 / 5 60000 35 10 A 15 67% - - G59 / Y150 × ◎ 〇 Comparative Example 10 c3 MMA / MAA = 95 / 5 3000 35 10 A 15 67% - - G59 / Y150 ◎ × 〇 Comparative Example 11 c4 MMA / MAA = 100 / 0 15000 0 10 A 15 67% - - G59 / Y150 × ◎ 〇 Comparative Example 12 c5 MMA / MAA = 90 / 10 15000 65 10 A 15 67% - - G59 / Y150 ◎ × 〇 Comparative Example 13 - - - - 0 A 10 0% - - B15: 6 / V23 ◎ × 〇 Comparative Example 14 c1 BMA / MAA = 95 / 5 15000 33 5 A 10 50% - - B15: 6 / V23 ◎ × △ Comparative Example 15 c2 MMA / MAA = 95 / 5 60000 35 5 A 10 50% - - B15: 6 / V23 × ◎ 〇 Comparative Example 16 c3 MMA / MAA = 95 / 5 3000 35 5 A 10 50% - - B15: 6 / V23 ◎ × 〇 Comparative Example 17 c4 MMA / MAA = 100 / 0 15000 0 5 A 10 50% - - B15: 6 / V23 × ◎ 〇 Comparative Example 18 c5 MMA / MAA = 90 / 10 15000 65 5 A 10 50% - - B15: 6 / V23 ◎ × 〇

[0240] [Summary of Results] It is shown that in Examples 1 to 69, which are the photosensitive coloring resin compositions of the present invention, the formation of developing residues can be suppressed even during low-temperature heat treatment due to the use of a specific non-reactive resin in the alkali-soluble resin composition, and a colored layer with a good pattern shape can be formed. It is shown that, in particular, if a non-reactive resin in which the content of structural units derived from methyl methacrylate is 90% to 99% by mass of all structural units is used as the aforementioned non-reactive resin, the cross-sectional shape becomes even better. Furthermore, it is shown that, in particular, the solvent resistance is improved when a polyfunctional epoxy resin or a polyfunctional isocyanate compound is added. In contrast, it is shown that the cross-sectional shape of the colored layer of the photosensitive coloring resin compositions of Comparative Examples 1, 7, and 13, which do not use the specific non-reactive resin, becomes an undercut shape. Furthermore, it is shown that the photosensitive coloring resin compositions of Comparative Examples 2, 8, and 14 exhibit an undercut shape in the cross-sectional shape of their colored layers. These photosensitive coloring resin compositions of Comparative Examples 2, 8, and 14 are non-reactive resins that use butyl methacrylate monomer instead of methyl methacrylate monomer, although their acid values ​​and weight-average molecular weights are within the same range as the non-reactive resins of the present invention. Furthermore, it is shown that the photosensitive coloring resin compositions of Comparative Examples 3, 9, and 15 produce developing residue in the formed portion of their colored layers. These photosensitive coloring resin compositions of Comparative Examples 3, 9, and 15 are non-reactive resins that use alkali-soluble resin compositions that, although their structural units and acid values ​​are within the same range as the non-reactive resins of the present invention, exhibit a weight-average molecular weight greater than the specific value of the present invention. Furthermore, it is shown that the photosensitive coloring resin compositions of Comparative Examples 4, 10, and 16 exhibit an undercut shape in the cross-sectional shape of their colored layers. These photosensitive coloring resin compositions of Comparative Examples 4, 10, and 16 are alkali-soluble resin compositions, and although their structural units and acid values ​​are within the same range as the non-reactive resins of the present invention, their weight-average molecular weight is less than the specific value of the present invention. Furthermore, it is shown that the photosensitive coloring resin compositions of Comparative Examples 5, 11, and 17 produce developing residue in the formed portion of their colored layers. These photosensitive coloring resin compositions of Comparative Examples 5, 11, and 17 are alkali-soluble resin compositions, and although their weight-average molecular weight is within the same range as the non-reactive resins of the present invention, their content of structural units derived from methyl methacrylate is 100 mol% of all structural units, and their acid value is 0 mgKOH / g. Furthermore, it is shown that the cross-sectional shape of the colored layer of the photosensitive coloring resin compositions of Comparative Examples 6, 12 and 18 becomes an undercut shape. The photosensitive coloring resin compositions of Comparative Examples 6, 12 and 18 are alkali-soluble resin compositions that, although the structural units and weight average molecular weight are in the same range as the non-reactive resins of the present invention, have an acid value greater than the specific value of the present invention. [Simplified Explanation of the Diagram]

[0016] FIG1 is a schematic cross-sectional view showing an example of the color filter of the present invention. FIG2 is a schematic cross-sectional view showing an example of the liquid crystal display device of the present invention. FIG3 is a schematic cross-sectional view showing an example of the organic light-emitting display device of the present invention. FIG4 is a schematic cross-sectional view showing another example of a display device equipped with the organic light-emitting element of the present invention. FIG5 is a schematic cross-sectional view illustrating the tilt angle (θ1) of the cross-sectional shape of the color layer.

Claims

1. A photosensitive coloring resin composition comprising a colorant, an alkali-soluble resin, a non-reactive resin, a photopolymerizable compound, a photoinitiator, and a solvent, wherein the alkali-soluble resin has an acid value exceeding 50 mgKOH / g, the non-reactive resin is a (meth)acrylic copolymer containing structural units derived from methyl methacrylate and structural units having acidic groups, wherein the total content of structural units derived from methyl methacrylate, structural units derived from ethyl methacrylate, and structural units having acidic groups is 100% by mass of all structural units, the acid value is 7 mgKOH / g to 50 mgKOH / g, the content of structural units derived from methyl methacrylate is 50% by mass to 99% by mass of all structural units, and the weight average molecular weight is 5000 to 50000.

2. The photosensitive coloring resin composition of claim 1, wherein the content of the non-reactive resin is 1% to 20% by mass relative to the total solid content of the photosensitive coloring resin composition.

3. The photosensitive coloring resin composition of claim 1 or 2, wherein the weight average molecular weight of the alkali-soluble resin is 3,000 to 30,000.

4. The photosensitive coloring resin composition of claim 1 or 2, wherein the content of the non-reactive resin is 1% to 80% by mass relative to the total content of the alkali-soluble resin and the non-reactive resin.

5. The photosensitive coloring resin composition of claim 1 or 2, wherein the content of the structural unit derived from methyl methacrylate of the above-mentioned non-reactive resin is 90% to 99% by mass of all structural units.

6. The photosensitive coloring resin composition of claim 1 or 2, wherein the photoinitiator contains at least one of the compounds represented by general formula (A) and general formula (B); [Chemical 1] (wherein, R1 and R2 independently represent R11, OR11, COR11, SR11, CONR12R13 or CN, respectively, and R11, R12 and R13 independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms, respectively. The hydrogen atoms of the groups represented by R11, R12, and R13 can be further substituted with R21, OR21, COR21, SR21, NR22R23, CONR22R23, -NR22-OR23, -NCOR22-OCOR23, NR22COR21, OCOR21, COOR21, SCOR21, OCSR21, COSR21, CSOR21, hydroxyl, nitro, CN, or halogen atoms. R21, R22, and R23 independently represent hydrogen atoms, alkyl groups with 1 to 20 carbon atoms, aryl groups with 6 to 30 carbon atoms, aralkyl groups with 7 to 30 carbon atoms, or heterocyclic groups with 2 to 20 carbon atoms. The hydrogen atoms of the groups represented by R21, R22, and R23 can be further substituted with hydroxyl, nitro, CN, halogen atoms, or carboxyl groups. The alkyl moiety of the groups represented by R11, R12, R13, R21, R22, and R23 may contain 1 to 5 -O-, -S-, -COO-, -OCO-, -NR24-, -NR24CO-, -NR24COO-, -OCONR24-, -SCO-, -COS-, -OCS-, or -CSO-, provided that the oxygen atom is not adjacent. R24 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms. The alkyl moiety of the groups represented by R11, R12, R13, R21, R22, R23, and R24 may have branched side chains or may be cyclic alkyl groups. R3 represents a hydrogen atom, an alkyl group with 1 to 20 carbon atoms, an aryl group with 6 to 30 carbon atoms, an aralkyl group with 7 to 30 carbon atoms, or a heterocyclic group with 2 to 20 carbon atoms. The alkyl portion of the group represented by R3 may have branched side chains or may be a cyclic alkyl group. Furthermore, R3 and R7, and R3 and R8 may form a ring together. The hydrogen atom of the group represented by R3 may be further substituted with R21, OR21, COR21, SR21, NR22R23, CONR22R23, -NR22-OR23, -NCOR22-OCOR23, NR22COR21, OCOR21, COOR21, SCOR21, OCSR21, COSR21, CSOR21, a hydroxyl group, a nitro group, CN, or a halogen atom.R4, R5, R6, and R7 independently represent R11, OR11, SR11, COR14, CONR15, R16, NR12, COR11, OCOR11, COOR14, SCOR11, OCSR11, COSR14, CSOR11, hydroxyl, CN, or halogen atom, respectively. R4 and R5, R5 and R6, and R6 and R7 can form a ring together. R14, R15, and R16 represent hydrogen atoms or alkyl groups with 1 to 20 carbon atoms. The alkyl portion of the groups represented by R14, R15, and R16 can have branched side chains or be cyclic alkyl groups. R8 represents R11, OR11, SR11, COR11, CONR12, R13, NR12, COR11, OCOR11, COOR11, SCOR11, OCSR11, COSR11, CSOR11, hydroxyl, CN, or halogen atom. (k represents 0 or 1) [Chemical 2] (In formula (B), X1, X3, and X6 independently represent R41, OR41, COR41, SR41, CONR42R43, or CN, respectively; X2 represents an alkyl group with 1 to 20 carbon atoms, an aryl group with 6 to 30 carbon atoms, an aralkyl group with 7 to 30 carbon atoms, or a heterocyclic group with 2 to 20 carbon atoms; X4 and X5 independently represent R41, OR41, SR41, COR41, CONR42R43, NR42COR41, OCOR41, COOR41, SCOR41, COSR41, COSR41, CSOR41, CN, a halogen atom, or a hydroxyl group; R41, R42, and R43 independently represent a hydrogen atom, an alkyl group with 1 to 20 carbon atoms, an aryl group with 6 to 30 carbon atoms, an aralkyl group with 7 to 30 carbon atoms, or a heterocyclic group with 2 to 20 carbon atoms, respectively.) The hydrogen atoms of the groups represented by R41, R42, and R43, and X2, can be further substituted with R51, OR51, COR51, SR51, NR52R53, CONR52R53, -NR52-OR53, -NCOR52-OCOR53, NR52COR51, OCOR51, COOR51, SCOR51, OCSR51, COSR51, CSOR51, hydroxyl, nitro, CN, or halogen atoms. R51, R52, and R53 independently represent hydrogen atoms, alkyl groups with 1 to 20 carbon atoms, aryl groups with 6 to 30 carbon atoms, aralkyl groups with 7 to 30 carbon atoms, or heterocyclic groups with 2 to 20 carbon atoms. The hydrogen atoms of the groups represented by R51, R52, and R53 can be further substituted with hydroxyl, nitro, CN, halogen atoms, or carboxyl groups. The alkyl moiety of the groups represented by R41, R42, R43, X2, R51, R52, and R53 may contain 1 to 5 -O-, -S-, -COO-, -OCO-, -NR54-, -NR54CO-, -NR54COO-, -OCONR54-, -SCO-, -COS-, -OCS-, or -CSO-, provided that the oxygen atoms are not adjacent.R54 represents a hydrogen atom, an alkyl group with 1 to 20 carbon atoms, an aryl group with 6 to 30 carbon atoms, an aralkyl group with 7 to 30 carbon atoms, or a heterocyclic group with 2 to 20 carbon atoms. The alkyl portion of the groups represented by R41, R42, R43, R51, R52, R53, and R54 may have branched side chains or be cyclic alkyl groups; a and b are independently integers from 0 to 3.

7. The photosensitive coloring resin composition of claim 1 or 2, further comprising at least one of a multifunctional epoxy compound and a multifunctional capped isocyanate compound in an amount of 5% to 20% by mass relative to the total solid content of the photosensitive coloring resin composition.

8. The photosensitive coloring resin composition of claim 1 or 2, used for forming a hardened film on an organic light-emitting element.

9. A cured product, which is a cured product of the photosensitive coloring resin composition of any one of claims 1 to 8.

10. A color filter comprising at least a substrate and a coloring layer disposed on the substrate, wherein at least one of the coloring layers is a cured form of the photosensitive coloring resin composition as claimed in claim 9.

11. A display device having a color filter as claimed in claim 10.

12. A display device having a hardened film of a photosensitive coloring resin composition as claimed in any one of claims 1 to 7 on an organic light-emitting element.

13. A method for manufacturing a laminate of an organic light-emitting element and an external light reflection anti-reflection film, comprising the following steps to form a hardened film of a photosensitive coloring resin composition as claimed in any one of claims 1 to 7 on an organic light-emitting element: a step of forming a coating film by coating the organic light-emitting element with a photosensitive coloring resin composition as claimed in any one of claims 1 to 7; a step of irradiating the coating film with light; a step of heating and baking the film after irradiation; and a step of developing the film after irradiation.

14. The method for manufacturing the laminate of organic light-emitting element and external light reflection anti-reflection film as claimed in claim 13, wherein the heating temperature in the post-baking step is 130°C or below.

Images