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

Abstract

A photosensitive colored resin composition comprising a coloring material, a dispersant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a solvent, wherein the dispersant contains a graft copolymer having a structural unit represented by general formula (I) and / or a block copolymer having block A including a structural unit represented by general formula (I), and the photopolymerizable compound includes a photopolymerizable compound having a caprolactone structure. (The symbols in general formula (I) are as described in the description.)

Description

[Technical Field]

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

[0002] In recent years, the demand for liquid crystal displays (LCDs) has increased with the development of personal computers, particularly portable personal computers. The penetration rate of mobile displays (mobile phones, smartphones, and tablet PCs) is also rising, further expanding the LCD market. Organic light-emitting displays, such as OLEDs, which offer high visibility due to their self-illuminating properties, are also attracting attention as next-generation image display devices. These liquid crystal displays and organic light-emitting displays utilize color filters. For example, in liquid crystal displays, a color image is formed when light passing through a color filter is colored according to the color of each pixel constituting the color filter, and these colored lights are combined to form a color image. As a light source, in addition to conventional cold cathode tubes, white-emitting organic light-emitting elements and white-emitting inorganic light-emitting elements may be used. In organic light-emitting displays, color filters are used for color adjustment and other purposes.

[0003] Here, a color filter generally comprises a substrate, a colored layer formed on the substrate consisting of colored patterns of the three primary colors red, green, and blue, and light-shielding portions formed on the substrate to demarcate each colored pattern. One method for forming the colored layer in a color filter involves, for example, adding an alkali-soluble resin, a photopolymerizable compound, and a photoinitiator to a colorant dispersion liquid, which is made by dispersing colorants with a dispersant, to a colored resin composition. This composition is applied to a glass substrate, dried, exposed using a photomask, and developed to form a colored pattern. The pattern is then fixed by heating to form the colored layer. These steps are repeated for each color to form the color filter.

[0004] In recent years, there has been a growing demand for even higher resolution and image quality in display devices. Consequently, the colored layer of color filters is required to have a high-resolution pattern. Achieving high-resolution colored layers requires increasingly stringent developability. Poor developability can lead to problems such as residue formation when creating colored layer patterns. For example, Patent Document 1 proposes using a polymer containing amino groups, in which a salt is formed between at least a portion of the amino groups and a halogenated hydrocarbon having one or more functional groups selected from the group consisting of acidic groups and their ester groups, and which may also have heteroatoms, as a dispersant to form a colored layer with less developing residue. However, this method is currently insufficient for forming high-resolution patterns.

[0005] On the other hand, Patent Document 2 discloses a pigment dispersion obtained by dispersing a pigment using an AB block copolymer, in which the monomer units constituting the polymer are substantially composed of (meth)acrylate monomers, for the purpose of preventing pigment aggregation and obtaining an extremely fine pigment dispersion in good condition, wherein the polymer block of the A chain constituting the copolymer contains (meth)acrylate monomer units having a carboxyl group and has an acid value of 50 to 250 mgKOH / g, and the polymer block of the B chain constituting the copolymer contains acetoacetoxyethyl (meth)acrylate as a monomer unit.

[0006] Furthermore, Patent Document 3 describes a colored radiation-sensitive composition that aims to provide a colored radiation-sensitive composition capable of forming pixels with a forward taper shape and excellent solvent resistance even at low exposure levels, comprising (A) a colorant, (C) an alkali-soluble resin, (D) a polyfunctional monomer, and (E) a photopolymerization initiator, wherein (D) the polyfunctional monomer contains a polyfunctional monomer having a caprolactone structure and a polyfunctional monomer not having a caprolactone structure, and (E) the photopolymerization initiator contains 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one, and further contains at least one selected from the group consisting of thioxanthone compounds and O-acyloxime compounds. [Prior art documents] [Patent Documents]

[0007] [Patent Document 1] Japanese Patent Publication No. 2015-189950 [Patent Document 2] Japanese Patent Publication No. 2011-241259 [Patent Document 3] Patent No. 5663878 [Overview of the project] [Problems that the invention aims to solve]

[0008] To form a highly detailed colored layer, the challenge lies in achieving both substrate adhesion and developability. To form a fine pattern, the photocurability is weakened, but this results in a smaller contact area between the fine pattern and the substrate, making it prone to peeling. To slow down development and make peeling less likely, the development time increases, leading to a higher rate of development residue. To suppress development residue, development needs to be accelerated, making it difficult to achieve both reduced development time, suppression of development residue, and substrate adhesion of the fine pattern.

[0009] The present invention has been made in view of the above circumstances, and aims to provide a photosensitive colored resin composition that can form a colored layer with a fine pattern that has good adhesion to the substrate, while shortening the development time and suppressing the generation of development residue. The present invention also aims to provide a color filter and a display device formed using the photosensitive colored resin composition. [Means for solving the problem]

[0010] The photosensitive colored resin composition according to the present invention contains a colorant, a dispersant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a solvent. The dispersant contains at least one graft copolymer having a structural unit represented by the following general formula (I), and a block copolymer having an A block containing a structural unit represented by the following general formula (I). The aforementioned photopolymerizable compound contains a photopolymerizable compound having a caprolactone structure.

[0011] [ka] (In general formula (I), R 1 (where represents a hydrogen atom or a methyl group, L represents a direct bond or a divalent linking group, and Q represents an acidic group.)

[0012] The color filter according to the present invention comprises at least a substrate and a colored layer provided on the substrate, wherein at least one of the colored layers is a cured product of the photosensitive colored resin composition according to the present invention. Furthermore, the present invention provides a display device having the color filter according to the present invention. [Effects of the Invention]

[0013] According to the present invention, it is possible to provide a photosensitive colored resin composition that can form a colored layer with a fine pattern that has good adhesion to the substrate, while shortening the development time and suppressing the generation of development residue. Furthermore, according to the present invention, it is possible to provide a color filter and a display device formed using the photosensitive colored resin composition. [Brief explanation of the drawing]

[0014] [Figure 1] Figure 1 is a schematic diagram showing an example of the color filter of the present invention. [Figure 2] Figure 2 is a schematic diagram showing an example of the liquid crystal display device of the present invention. [Figure 3] Figure 3 is a schematic diagram showing an example of the organic light-emitting display device of the present invention. [Modes for carrying out the invention]

[0015] The photosensitive colored resin composition, cured product, color filter, and display device according to the present invention will be described in detail below. In this invention, light includes electromagnetic waves with wavelengths in the visible and invisible regions, as well as radiation, and radiation includes, for example, microwaves and electron beams. Specifically, it refers to electromagnetic waves with wavelengths of 5 μm or less, and electron beams. In this invention, (meth)acryloyl refers to acryloyl and methacryloyl respectively, (meth)acrylic refers to acrylic and methacrylic respectively, and (meth)acrylate refers to acrylate and methacrylate respectively. Furthermore, in this specification, the "~" symbol indicating a numerical range is used to mean that the numbers before and after it are included as the lower and upper limits, respectively. In this specification, "having a caprolactone structure" means "containing a structure in which ε-caprolactone has been opened up."

[0016] I. Photosensitive colored resin composition The photosensitive colored resin composition according to the present invention contains a colorant, a dispersant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a solvent. The dispersant contains at least one graft copolymer having a structural unit represented by the following general formula (I), and a block copolymer having an A block containing a structural unit represented by the following general formula (I). The aforementioned photopolymerizable compound contains a photopolymerizable compound having a caprolactone structure.

[0017] [ka] (In general formula (I), R 1 (where represents a hydrogen atom or a methyl group, L represents a direct bond or a divalent linking group, and Q represents an acidic group.)

[0018] The photosensitive colored resin composition according to the present invention, by using a combination of a specific acidic dispersant consisting of a block copolymer or graft copolymer having an acidic group and a specific photopolymerizable compound containing a photopolymerizable compound having a caprolactone structure, makes it possible to form a colored layer with a fine pattern that has good adhesion to the substrate while shortening the development time and suppressing the generation of development residue. Photopolymerizable compounds having a caprolactone structure have a larger molecular weight per mole of photopolymerizable groups compared to conventional photopolymerizable compounds, making it easier to form fine patterns, while maintaining comparable developability. Certain acidic dispersants consisting of block copolymers or graft copolymers having acidic groups exhibit good dispersibility of colorants, excellent developability, a higher oxygen atom content compared to basic dispersants, and superior substrate adhesion. It is presumed that the synergistic effect of these combinations enables the formation of a colored layer with fine patterns that adheres well to the substrate, while shortening the development time and suppressing the generation of development residue.

[0019] The photosensitive colored resin composition according to the present invention contains a colorant, a dispersant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a solvent, and may further contain other components as long as they do not impair the effects of the present invention. The components of the colored resin composition of the present invention will be described in detail below.

[0020] [Colorants] In the present invention, the colorant is not particularly limited as long as it is capable of producing the desired color when the colored layer of the color filter is formed, and various organic pigments, inorganic pigments, dispersible dyes, dye salt compounds, etc., can be used individually or in mixtures of two or more. Among these, organic pigments are preferred because they have high color development and high heat resistance. Examples of organic pigments include compounds classified as pigments in the Color Index (CI; published by The Society of Dyers and Colourists), specifically those with the following Color Index (CI) numbers.

[0021] 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 Pigment Orange 1, 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 61, 63, 64, 71, 73; CI Pigment 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, 10 4, 105, 106, 108, 112, 113, 114, 122, 123, 144, 146, 149, 150, 151, 166, 168, 170, 171, 172, 174, 175, 176, 177, 178, 179, 180, 185, 187, 188, 190, 193, 194, 202, 206, 207, 208, 209, 215, 216, 220, 224, 226, 242, 243, 245, 254, 255, 264, 265, 269, 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.

[0022] Furthermore, specific examples of the inorganic pigments include titanium dioxide, barium sulfate, calcium carbonate, zinc oxide, lead sulfate, lead yellow, zinc yellow, red iron(III) oxide, cadmium red, ultramarine, Prussian blue, chromium oxide green, cobalt green, amber, titanium black, synthetic iron black, and carbon black.

[0023] For example, when forming a light-shielding layer pattern on a substrate of a color filter using the colorant dispersion liquid according to the present invention as a photosensitive colored resin composition described later, a highly light-shielding black pigment is incorporated into the ink. As the highly light-shielding black pigment, inorganic pigments such as carbon black or iron(II,III) oxide, or organic pigments such as cyanine black can be used.

[0024] Examples of the dispersible dyes mentioned above include dyes that have been made dispersible by adding various substituents to them or by using them in combination with solvents with low solubility. Salt-forming compounds of dyes refer to compounds in which a dye forms a salt with a counterion. Examples include salt-forming compounds of basic dyes and acids, and salt-forming compounds of acidic dyes and bases. The term also includes lake pigments, which are solvent-insoluble dyes obtained by using known lake-forming (chlorination) methods. In the present invention, the dispersibility and dispersion stability of a colorant can be improved by using a colorant containing at least one selected from dyes and dye salt-forming compounds in combination with the dispersant of the present invention.

[0025] The aforementioned dye can be appropriately selected from conventionally known dyes. Examples of such dyes include azo dyes, metal complex azo dyes, anthraquinone dyes, triphenylmethane dyes, xanthene dyes, cyanine dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, and phthalocyanine dyes. As a guideline, if the amount of dye that dissolves in 10g of solvent (or mixed solvent) is 10mg or less, it can be determined that the dye is dispersible in that solvent (or mixed solvent).

[0026] In particular, when the colorant contains at least one selected from the group consisting of diketopyrrolopyrrole pigments, quinophthalone pigments, copper phthalocyanine pigments, zinc phthalocyanine pigments, quinophthalone dyes, coumarin dyes, cyanine dyes, and salt-forming compounds of these dyes, it is preferable that the dispersant has a high effect in suppressing the sublimation or precipitation of the colorant and that a high-luminosity colored layer can be formed. Furthermore, it is preferable that the colorant contains at least one selected from the group consisting of diketopyrrolopyrrole pigments, quinophthalone pigments, copper phthalocyanine pigments, zinc phthalocyanine pigments, and quinophthalone dyes.

[0027] Examples of diketopyrrolopyrrole pigments include CI Pigment Red 254, 255, 264, 272, 291, and diketopyrrolopyrrole pigments represented by the following general formula (i), among which CI Pigment Red 254, 272, 291, and the following general formula (i) have R p1 and R p2 Preferably, at least one is selected from diketopyrrolopyrrole pigments, each of which is a 4-bromophenyl group.

[0028] [ka] (In general formula (i), R p1 and R p2 These are, independently, a 4-chlorophenyl group or a 4-bromophenyl group.

[0029] 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 and 59. Examples of quinophthalone dyes include CI Disperse Yellow 54, 64, 67, 134, 149, 160, and CI Solvent Yellow 114, 157, among which CI Disperse Yellow 54 is preferred.

[0030] The average primary particle size of the colorant used in the present invention is not particularly limited and varies depending on the type of colorant used, as long as it enables the desired color development when used as the colored layer of a color filter. However, it is preferably in the range of 10 to 100 nm, and more preferably in the range of 15 to 60 nm. By having the average primary particle size of the colorant within the above range, a display device equipped with a color filter manufactured using the photosensitive colored resin composition according to the present invention can be made high-contrast and of high quality.

[0031] Furthermore, the average dispersed particle size of the colorant in the photosensitive colored resin composition varies depending on the type of colorant used, but is preferably in the range of 10 to 100 nm, and more preferably in the range of 15 to 60 nm. The average dispersed particle size of the colorant in a photosensitive colored resin composition is the dispersed particle size of the colorant particles dispersed in a dispersion medium containing at least a solvent, and is measured by a laser light scattering particle size analyzer. For particle size measurement using a laser light scattering particle size analyzer, the photosensitive colored resin composition is appropriately diluted with the solvent used in the photosensitive colored resin composition to a concentration measurable by the laser light scattering particle size analyzer (e.g., 1000 times), and measured at 23°C using the dynamic light scattering method with a laser light scattering particle size analyzer (e.g., the NanoTrac particle size analyzer UPA-EX150 manufactured by Nikkiso Co., Ltd.). The average dispersed particle size here is the volume average particle size.

[0032] The colorants used in this invention can be manufactured by known methods such as recrystallization or solvent-salt milling. Alternatively, commercially available colorants may be used after being micronized.

[0033] In the photosensitive colored resin composition according to the present invention, the content of the colorant is not particularly limited. The total content of the colorant is preferably in the range of 3% to 65% by mass, more preferably 4% to 60% by mass, relative to the total solid content of the photosensitive colored resin composition, from the viewpoint of dispersibility and dispersion stability. If it is above the lower limit, the colored layer when the photosensitive colored resin composition is applied to a predetermined film thickness (usually 1.0 μm to 5.0 μm) is likely to have sufficient color density. If it is below the upper limit, it is easy to obtain a colored layer that has excellent storage stability, sufficient hardness, and adhesion to the substrate. In particular, when forming a colored layer with a high colorant density, the total content of the colorant is preferably in the range of 15% to 65% by mass, more preferably 25% to 60% by mass, relative to the total solid content of the photosensitive colored resin composition. In this invention, the solid content refers to everything other than the solvent described later, and includes monomers and the like dissolved in the solvent.

[0034] [Dispersant] In the present invention, at least one of a graft copolymer having a structural unit represented by the general formula (I) and a block copolymer having an A block containing the structural unit represented by the general formula (I) is used as a dispersant.

[0035] <Graft copolymer> The graft copolymer used in the present invention is a copolymer having a main chain which is a structural unit represented by the general formula (I) and which functions as an adsorption site for a colorant, and a side chain which is a graft polymer chain that functions as a solvent affinity site.

[0036] (Constituent units represented by general formula (I)) In general formula (I), R 1 'L' represents a hydrogen atom or a methyl group, 'L' represents a direct bond or a divalent linking group, and 'Q' represents an acidic group. Here, "direct bond" means that the acidic group is directly bonded to a carbon atom in the main chain skeleton without the need for a linking group. In L, examples of divalent linking groups include linear, branched, or cyclic saturated or unsaturated aliphatic hydrocarbon groups, linear, branched, or cyclic saturated or unsaturated aliphatic hydrocarbon groups having a hydroxyl group, aromatic hydrocarbon groups, -CONH- groups, -COO- groups, -NHCOO- groups, ether groups (-O- groups), thioether groups (-S- groups), and combinations thereof. In this invention, the orientation of the divalent linking group bond is arbitrary. That is, if the divalent linking group includes -CONH-, -CO may be on the carbon atom side of the main chain and -NH on the nitrogen atom side of the side chain, or conversely, -NH may be on the carbon atom side of the main chain and -CO on the nitrogen atom side of the side chain.

[0037] Examples of the aliphatic hydrocarbon group include linear alkylene groups such as methylene, dimethylene (ethylene), trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene, and decamethylene; branched alkylene groups such as methylmethylene, methylethylene, 1-methylpentylene, and 1,4-dimethylbutylene; and cyclic alkylene groups such as cyclopentylene and cyclohexylene. The aliphatic hydrocarbon group can have 1 to 20 carbon atoms, with 1 to 16 being preferred, 1 to 12 more preferred, and 2 to 8 even more preferred, from the viewpoint of dispersion stability. Examples of the aforementioned aromatic hydrocarbon groups include, for example, a phenylene group and a naphthylene group.

[0038] In particular, from the viewpoint of dispersibility, L in general formula (I) is preferably a divalent linking group containing at least one of a -CONH- group and a -COO- group, and more preferably a divalent linking group containing at least one of a -CONH- group and a -COO- group and an aliphatic hydrocarbon group having 1 to 12 carbon atoms which may contain an oxygen atom.

[0039] Examples of acidic groups represented by Q include carboxyl groups (-COOH), sulfonic acid groups (SO3H), phosphate groups (-OP(=O)(OH)2), phosphonic acid groups (-P(=O)(OH)2), and acidic phosphorus compound groups (-P(=O)(-R, as described later).4 )(OH)) and its salts (-P(=O)(-R 4 )(O - X + )) etc. may be mentioned. As the acidic group represented by Q, among others, from the viewpoint of dispersion stability, a carboxy group (-COOH), and an acidic phosphorus compound group (the -P(=O)(-R 4 )(OH)) and its salts (-P(=O)(-R 4 )(O<00D0014>X + )) selected from the group consisting of is preferably at least one kind.

[0040] Examples of the sulfonic acid group-containing ethylenically unsaturated monomer include (meth)acryloyloxyethyl sulfonic acid, 2-(meth)acrylamido-2-methylpropanesulfonic acid, etc. Examples of the phosphoric acid group-containing ethylenically unsaturated monomer include, for example, 2-(meth)acryloyloxyethyl acid phosphate, acid phosphoxypolyoxyethylene glycol mono(meth)acrylate, etc.

[0041] As the acidic group represented by Q, among others, from the viewpoints of dispersibility and dispersion stability, a carboxy group is preferable, and it is preferable that the structural unit represented by the general formula (I) contains the structural unit represented by the following general formula (I-0).

[0042]

Chemical formula

[0043] R 1 and L in the general formula (I-0) may be the same as those in the general formula (I). <00004L96>Examples of the structural unit represented by the general formula (I-0) include, for example, a structural unit derived from (meth)acrylic acid, a structural unit derived from vinylbenzoic acid, a structural unit derived from (meth)acrylic acid ester, etc. As for the general formula (I-0), from the viewpoint of variability and variability stability, at least one selected from the group consisting of the constituent units represented by the following general formula (I-1) and the constituent units represented by the following general formula (I-2) is preferred.

[0044] [ka] (In general formula (I-1), R 1 represents a hydrogen atom or a methyl group, In general formula (I-2), R 1 R represents a hydrogen atom or a methyl group. 2 R represents an aliphatic hydrocarbon group which may contain an oxygen atom. 3 (This represents a hydrocarbon group.)

[0045] The constituent unit represented by general formula (I-1) is a constituent unit derived from (meth)acrylic acid. In the constituent unit represented by the general formula (I-2), R 2 This represents an aliphatic hydrocarbon group that may contain an oxygen atom, and encompasses both aliphatic hydrocarbon groups and aliphatic hydrocarbon groups containing an oxygen atom. R 2 The aliphatic hydrocarbon group in this may be the same as described above. R 2 An aliphatic hydrocarbon group containing an oxygen atom in the above-mentioned aliphatic hydrocarbon group has a structure in which a carbon atom in the aliphatic hydrocarbon group is replaced by an oxygen atom, or a hydrogen atom in the aliphatic hydrocarbon group has a structure in which a substituent containing an oxygen atom is replaced. An example of an aliphatic hydrocarbon group that may contain an oxygen atom is a structure in which a linking group such as -O-, -COO-, or -OCO- is included in the carbon chain of the hydrocarbon group. Specifically, an example of an aliphatic hydrocarbon group containing an oxygen atom is -R 20 -(OR 21 )s-(Here, R 20 and R 21 Each of these is independently an aliphatic hydrocarbon group, (s represents a number from 1 to 80), -R 22 -(OCO-R 23 )t-(Here, R 22 and R 23Each of these independently represents an aliphatic hydrocarbon group, and t represents a number from 1 to 40. 20 , R 21 , R 22 and R 23 The aliphatic hydrocarbon group may be the same as the aliphatic hydrocarbon group. From the viewpoint of dispersion stability, the R 20 It is preferably an alkylene group having 1 to 20 carbon atoms, and the R 21 It is preferable that is an alkylene group having 1 to 20 carbon atoms, and s is preferably a number of 1 to 40, more preferably 2 to 25, and even more preferably 2 to 10. Also, from the viewpoint of dispersion stability, the R 22 It is preferably an alkylene group having 1 to 20 carbon atoms, and the R 23 It is preferably an alkylene group having 1 to 20 carbon atoms, and t is preferably a number of 1 to 30, more preferably 1 to 20, and even more preferably 1 to 10. The aforementioned R 20 and R 22 Each of these groups is preferably an alkylene group having 1 to 12 carbon atoms, and more preferably an alkylene group having 2 to 8 carbon atoms. The aforementioned R 21 It is preferably an alkylene group having 2 to 8 carbon atoms, and more preferably an ethylene group or a propylene group. The aforementioned R 23 It is preferably an alkylene group having 2 to 8 carbon atoms, and more preferably an alkylene group having 3 to 7 carbon atoms. Examples of substituents containing an oxygen atom include hydroxyl groups and alkoxy groups. In the constituent unit represented by the general formula (I-2), R 2 In particular, from the viewpoint of solvent resolubility, it may be an aliphatic hydrocarbon group, and may be an aliphatic hydrocarbon group having 1 to 20 carbon atoms.

[0046] In the constituent unit represented by the general formula (I-2), R 3 R represents a hydrocarbon group. 3Examples of hydrocarbon groups in this context include aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and combinations thereof. The aliphatic hydrocarbon group may be the same as described above. Examples of aromatic hydrocarbon groups include phenylene groups, naphthylene groups, biphenylene groups, and the like. R 3 The number of carbon atoms in the hydrocarbon group can range from 1 to 20, with 1 to 16 being preferred, 2 to 12 being more preferred, and 2 to 6 being even more preferred, from the viewpoint of dispersion stability. R 3 From the viewpoint of dispersion stability, an aliphatic hydrocarbon group is more preferable as the hydrocarbon group.

[0047] The constituent units represented by general formula (I-2) can be derived, for example, from monomers that are addition products of a (meth)acrylate having a hydroxyl group and a dicarboxylic acid or dicarboxylic acid anhydride. Examples of (meth)acrylates having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, (poly)ethylene glycol mono(meth)acrylate, (poly)propylene glycol mono(meth)acrylate, and unsaturated fatty acid hydroxyalkyl ester-modified ε-caprolactone. Examples of aliphatic dicarboxylic acids or aliphatic dicarboxylic acid anhydrides include malonic acid, succinic acid, glutaric acid, adipic acid, 1,6-hexanedicarboxylic acid, hexahydrophthalic acid, succinic anhydride, adipic anhydride, hexahydrophthalic anhydride, and maleic anhydride. Examples of aromatic dicarboxylic acids or aromatic dicarboxylic acid anhydrides include terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, diphenyldicarboxylic acid, phthalic anhydride, and naphthalic anhydride.

[0048] As for the constituent units represented by the general formula (I), it is preferable to have a constituent unit represented by the general formula (I-1) and a constituent unit represented by the general formula (I-2) in terms of substrate adhesion of the fine pattern, suppression of development residue generation, dispersibility, and dispersion stability.

[0049] Furthermore, among the acidic groups represented by Q, an acidic phosphorus compound group is preferred from the viewpoint of suppressing the generation of developing residue, dispersibility, and dispersion stability, and it is preferable that the constituent unit represented by the general formula (I) includes the constituent unit represented by the following general formula (I-3).

[0050] [ka] (In general formula (I-3), L 1 R is a direct bond or a divalent linking group. 1 is a hydrogen atom or a methyl group, R 4 is a hydroxyl group, a hydrocarbon group, -[CH(R 5 )-CH(R 6 )-O] x1 -R 7 ,-[(CH2) y1 -O] z1 -R 7 , or -OR 8 It is a monovalent group represented by R 8 The hydrocarbon group is -[CH(R 5 )-CH(R 6 )-O] x1 -R 7 ,-[(CH2) y1 -O] z1 -R 7 , -C(R 9 )(R 10 )-C(R 11 )(R 12 )-OH, or -CH2-C(R 13 )(R 14 It is a monovalent group represented by )-CH2-OH. R 5 and R 6 Each is independently a hydrogen atom or a methyl group, and R 7is a monovalent group represented by a hydrogen atom, a hydrocarbon group, -CHO, -CH2CHO, -CO-CH=CH2, -CO-C(CH3)=CH2 or -CH2COOR 15 where R 15 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. R 9 , R 10 , R 11 , R 12 , R 13 and R 14 are each independently a hydrogen atom, a hydrocarbon group, or a hydrocarbon group having one or more selected from an ether bond and an ester bond, and R 9 and R 11 may be bonded to each other to form a ring structure. When the above ring structure is formed, the ring structure may further have a substituent R 16 , and R 16 is a hydrocarbon group or a hydrocarbon group having one or more selected from an ether bond and an ester bond. The hydrocarbon group may have a substituent. X represents a hydrogen atom or an organic cation. x1 represents an integer of 1 to 18, y1 represents an integer of 1 to 5, and z1 represents an integer of 1 to 18.)

[0051] In the general formula (I-3), L 1 may be the same as the above L. Preferred specific examples of L 1 in the general formula (I-3) include, for example, -COO-CH2CH(OH)CH2-O-, -COO-CH2CH2-O-CH2CH(OH)CH2-O-, -COO-CH2C(CH2CH3)(CH2OH)CH2-O-, etc., but are not limited thereto.

[0052] Examples of the hydrocarbon group in R 4 include, for example, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, and an aryl group. The alkyl group having 1 to 18 carbon atoms may be linear, branched, or cyclic. Examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, cyclopentyl group, cyclohexyl group, bornyl group, isobornyl group, dicyclopentanyl group, adamantyl group, and lower alkyl group-substituted adamantyl group. The aforementioned alkenyl group having 2 to 18 carbon atoms may be linear, branched, or cyclic. Examples of such alkenyl groups include vinyl groups, allyl groups, and propenyl groups. There are no limitations on the position of the double bond of the alkenyl group, but from the viewpoint of the reactivity of the resulting polymer, it is preferable that the double bond be at the end of the alkenyl group. Examples of aryl groups include phenyl, biphenyl, naphthyl, tolyl, and xylyl groups, and may further have substituents. The number of carbon atoms in the aryl group is preferably 6 to 24, and more preferably 6 to 12. Examples of aralkyl groups include benzyl groups, phenethyl groups, naphthylmethyl groups, and biphenylmethyl groups, and may further have substituents. The number of carbon atoms in the aralkyl group is preferably 7 to 20, and more preferably 7 to 14. The alkyl or alkenyl group may have substituents, and examples of such substituents include halogen atoms such as F, Cl, and Br, and nitro groups. Furthermore, examples of substituents on aromatic rings such as aryl groups and aralkyl groups include linear and branched alkyl groups having 1 to 4 carbon atoms, as well as alkenyl groups, nitro groups, and halogen atoms. Note that the preferred number of carbon atoms mentioned above does not include the number of carbon atoms of substituents. The aforementioned R 4 In this equation, x1 is an integer between 1 and 18, preferably between 1 and 4, more preferably between 1 and 2, and y1 is an integer between 1 and 5, preferably between 1 and 4, more preferably between 2 or 3. z1 is an integer between 1 and 18, preferably between 1 and 4, more preferably between 1 and 2. R 7 ~R 14Examples of the hydrocarbon group in include the same ones as the hydrocarbon group in the above R 4 as described above.

[0053] R 9 、R 10 、R 11 、R 12 、R 13 and R 14 The hydrocarbon group having at least one selected from an ether bond and an ester bond in is a group represented by -R'-O-R", -R'-(C=O)-O-R", or -R'-O-(C=O)-R" (R' and R" are a hydrocarbon group or a group in which hydrocarbon groups are bonded by at least one of an ether bond and an ester bond). Two or more ether bonds and ester bonds may be present in one group. When the hydrocarbon group is monovalent, examples include an alkyl group, an alkenyl group, an aralkyl group, and an aryl group. When the hydrocarbon group is divalent, examples include an alkylene group, an alkenylene group, an arylene group, and a group combining these.

[0054] R 9 and R 11 When they are bonded to form a ring structure, the number of carbon atoms forming the ring structure is preferably 5 to 8, more preferably 6, that is, a 6-membered ring, and preferably forms a cyclohexane ring. The hydrocarbon group or the hydrocarbon group having at least one selected from an ether bond and an ester bond in the substituent R 16 can be the same as those in the above R 9 、R 10 、R 11 、R 12 、R 13 and R 14 .

[0055] From the viewpoint of excellent dispersibility and dispersion stability of the dispersed particles, the above R 4 is a hydroxyl group, a hydrocarbon group, -[CH(R 5 )-CH(R 6 )-O] x1 -R 7 、-[(CH2)y1 -O] z1 -R 7 , or -OR 8 It is preferably a monovalent group represented by -[CH(R 5 )-CH(R 6 )-O] x1 -R 7 ,-[(CH2) y1 -O] z1 -R 7 , or -OR 8 The monovalent group shown is R 5 and R 6 Each of these is independently a hydrogen atom or a methyl group, and R 7 It is more preferable that -CO-CH=CH2 or -CO-C(CH3)=CH2, and among them, R 4 However, aryl groups, vinyl groups, methyl groups, and hydroxyl groups, which may have substituents, are more preferred.

[0056] Furthermore, R is improved in terms of alkali resistance. 4 The hydrocarbon group is -[CH(R 5 )-CH(R 6 )-O] x1 -R 7 , or -[(CH2) y1 -O] z1 -R 7 It is preferable that the group is a monovalent group represented by . If it has a structure in which a carbon atom is directly bonded to a phosphorus atom, it is presumed that it is possible to form a resin layer with excellent alkali resistance because it is less susceptible to hydrolysis. In particular, R 4 This includes a methyl group, an ethyl group, an optionally substituted aryl or aralkyl group, a vinyl group, an allyl group, and -[CH(R 5 )-CH(R 6 )-O] x1 -R 7 , or -[(CH2) y1 -O] z1 -R 7 The monovalent group shown is R 5 and R 6 Each of these is independently a hydrogen atom or a methyl group, and R7 Those in which are -CO-CH=CH2 or -CO-C(CH3)=CH2 are preferred because they have excellent alkali resistance and excellent dispersibility and dispersion stability of the dispersed particles. Among them, R 4 From the viewpoint of dispersibility, an aryl group which may have substituents is more preferable.

[0057] Furthermore, in general formula (I-3), X represents a hydrogen atom or an organic cation. An organic cation is one in which a carbon atom is contained in the cation portion. Examples of organic cations include imidazolium cation, pyridinium cation, aminidium cation, piperidinium cation, pyrrolidinium cation, ammonium cations such as tetraalkylammonium cation and trialkylammonium cation, sulfonium cations such as trialkylsulfonium cation, and phosphonium cations such as tetraalkylphosphonium cation. Among these, protonated nitrogen-containing organic cations are preferred from the viewpoint of dispersibility and alkali developability. In particular, when the organic cation has an ethylenically unsaturated double bond, it is preferable because it can impart curability.

[0058] In copolymers, the constituent units represented by general formula (I-3) may include both constituent units where X is a hydrogen atom and constituent units where X is an organic cation. When both constituent units are included, there are no particular restrictions as long as good dispersibility and dispersion stability are exhibited, however, the proportion of constituent units where X is an organic cation is preferably 0 mol% to 50 mol% of the total number of constituent units represented by general formula (I-3).

[0059] The structural unit represented by general formula (I-3) is preferably a structural unit that is a reaction product of a structural unit having at least one of an epoxy group and a cyclic ether group in its side chain and an acidic phosphorus compound, wherein at least a portion of the acidic phosphorus compound group may form a salt.

[0060] In copolymers, the constituent units represented by general formula (I) may consist of only one type, or they may contain two or more types of constituent units.

[0061] (Constituent units having graft polymer chains) The graft copolymer has graft polymer chains in its side chains that function as solvent affinity sites. The polymer chain preferably has a solubility of 20 g / 100 g of solvent or more at 23°C in the organic solvent used in combination with it. The solubility of the polymer chain can be determined by whether the raw material into which the polymer chain is introduced during the preparation of the graft copolymer has the aforementioned solubility. For example, when a polymerizable oligomer (macromonomer) containing a polymer chain and a group having an ethylenically unsaturated double bond at its end is used to introduce a polymer chain into a graft copolymer, it is sufficient if the polymerizable oligomer has the aforementioned solubility. Alternatively, when a copolymer is formed using a monomer containing a group having an ethylenically unsaturated double bond, and then a polymer chain containing a reactive group that can react with the reactive group contained in the copolymer is used to introduce the polymer chain, it is sufficient if the polymer chain containing the reactive group has the aforementioned solubility.

[0062] The graft copolymer used in the present invention preferably has a main chain comprising a structural unit represented by the general formula (I) above, which functions as an adsorption site for colorants, and a side chain comprising a polymer chain that functions as a solvent affinity site, which is a structural unit represented by the general formula (II) below.

[0063] [ka] (In general formula (II), R 1’ is a hydrogen atom or a methyl group, L ’ (where '' represents a direct bond or a divalent linking group, and '' represents a polymer chain.)

[0064] In the above general formula (II), L ’ L is a direct bond or a divalent linking group.’ The divalent linking group in this formula is not particularly limited as long as it can link the carbon atom derived from the ethylenically unsaturated double bond to the polymer chain. The divalent linking group may be the same as L in general formula (I). In particular, from the standpoint of dispersion and dispersion stability, L in general formula (II) ’ It is preferably a divalent linking group containing a -CONH- group or a -COO- group, and more preferably a divalent linking group containing a -CONH- group or a -COO- group and an aliphatic hydrocarbon group having 1 to 12 carbon atoms, which may contain an oxygen atom.

[0065] The polymer chain preferably contains at least one structural unit represented by the following general formula (III) from the viewpoint of the dispersibility and dispersion stability of the colorant.

[0066] [ka] (In general formula (III), R 1” is a hydrogen atom or a methyl group, L ” R is a divalent linking group. 30 This is a hydrocarbon group that may have substituents and may contain heteroatoms.

[0067] In general formula (III), L ” L is a divalent linking group. ” Examples of divalent linking groups in this context include those similar to the divalent linking groups in L. In particular, from the standpoint of the dispersibility and dispersion stability of the colorant, L in general formula (III) ” It is preferably a divalent linking group containing a -CONH- group or a -COO- group, and more preferably a -CONH- group or a -COO- group.

[0068] R 30 Examples of hydrocarbon groups in which heteroatoms may be included include C1-C18 alkyl groups, C2-C18 alkenyl groups, aryl groups, and combinations thereof such as aralkyl groups and alkyl-substituted aryl groups. The C1-C18 alkyl group may be linear, branched, or cyclic. Examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, n-nonyl, n-lauryl, n-stearyl, cyclopentyl, cyclohexyl, bornyl, isobornyl, dicyclopentanyl, adamantyl, and lower alkyl-substituted adamantyl groups. The number of carbon atoms in the alkyl group is preferably 1-12, and more preferably 1-6. The C2-C18 alkenyl group may be linear, branched, or cyclic. Examples of such alkenyl groups include vinyl, allyl, and propenyl groups. There are no limitations on the position of the double bond in the alkenyl group, but from the viewpoint of the reactivity of the resulting polymer, it is preferable that the double bond be at the end of the alkenyl group. The number of carbon atoms in the alkenyl group is preferably 2-12, and more preferably 2-8. Examples of aryl groups include phenyl, biphenyl, naphthyl, tolyl, and xylyl groups. The number of carbon atoms in the aryl group is preferably 6 to 24, and more preferably 6 to 12. Examples of aralkyl groups include benzyl groups, phenethyl groups, naphthylmethyl groups, and biphenylmethyl groups, and may further have substituents. The number of carbon atoms in the aralkyl group is preferably 7 to 20, and more preferably 7 to 14. Furthermore, the aromatic rings such as the aryl group and aralkyl group may have linear or branched alkyl groups having 1 to 30 carbon atoms bonded to them as substituents.

[0069] R 30In particular, the hydrocarbon group in is preferably one or more selected from the group consisting of C1-C18 alkyl groups, C6-C12 aryl groups which may be alkyl groups substituted with alkyl groups, and C7-C14 aralkyl groups which may be alkyl groups substituted with alkyl groups, from the viewpoint of dispersibility and dispersion stability. It is also preferably one or more selected from the group consisting of methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, n-nonyl group, n-lauryl group, n-stearyl group, phenyl group which may be alkyl groups substituted with alkyl groups, and benzyl group.

[0070] R 30 A hydrocarbon group containing a heteroatom in the above-mentioned hydrocarbon group has a structure in which a carbon atom in the hydrocarbon group is replaced by a heteroatom, or a hydrogen atom in the hydrocarbon group is replaced by a substituent containing a heteroatom. Examples of heteroatoms that the hydrocarbon group may contain include oxygen atoms, nitrogen atoms, sulfur atoms, silicon atoms, etc. Examples of hydrocarbon groups that may contain a heteroatom include structures in which the carbon chain of the hydrocarbon group contains linking groups such as -CO-, -COO-, -OCO-, -O-, -S-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -OCO-NH-, -NH-COO-, -NH-CO-NH-, -NH-O-, -O-NH-. Furthermore, the hydrocarbon group may have substituents to the extent that they do not impede the dispersion performance of the graft copolymer, and examples of substituents include halogen atoms, hydroxyl groups, carboxyl groups, alkoxy groups, nitro groups, cyano groups, epoxy groups, isocyanate groups, thiol groups, and the like.

[0071] Also, R 30 The hydrocarbon group that may contain a heteroatom may have a structure in which a polymerizable group such as an alkenyl group is attached to the terminal via a linking group containing a heteroatom in the hydrocarbon group. For example, the constituent unit represented by general formula (III) may be a structure obtained by reacting a constituent unit derived from (meth)acrylic acid with glycidyl (meth)acrylate. That is, the -L in general formula (III) ” -R30 The structure may also be represented by -COO-CH2CH(OH)CH2-OCO-CR=CH2 (where R is a hydrogen atom or a methyl group). Alternatively, the constituent unit represented by general formula (III) may be a structure obtained by reacting a hydroxyalkyl (meth)acrylate-derived constituent unit with a 2-isocyanatoalkyl (meth)acrylate. That is, R in general formula (III) 30 However, the structure may also be represented by -R'-OCONH-R”-OCO-CR=CH2 (where R' and R” are independently alkylene groups, and R is a hydrogen atom or a methyl group).

[0072] Examples of monomers that derive the constituent unit represented by general formula (III) include methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, adamantyl (meth)acrylate, and (meth)acrylic. Preferably, the material has constituent units derived from acids, 2-methacryloyloxyethyl succinate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, phenoxyethyl (meth)acrylate, methoxypolyethylene glycol (meth)acrylate and polyethylene glycol (meth)acrylate, phenoxyethylene glycol (meth)acrylate, unsaturated fatty acid hydroxyalkyl ester-modified ε-caprolactone, etc. However, it is not limited to these.

[0073] In the present invention, the R 30In particular, it is preferable to use one that has excellent solubility with the organic solvent described later, and it should be appropriately selected according to the organic solvent used in the colorant dispersion. Specifically, for example, when the organic solvent used is an organic solvent such as ether alcohol acetate, ether, ester, or alcohol, which is commonly used as an organic solvent for colorant dispersions, methyl group, ethyl group, isobutyl group, n-butyl group, 2-ethylhexyl group, benzyl group, cyclohexyl group, dicyclopentanyl group, hydroxyethyl group, phenoxyethyl group, adamantyl group, methoxypolyethylene glycol group, methoxypolypropylene glycol group, polyethylene glycol group, etc. are preferred.

[0074] In the polymer chain, the constituent unit represented by the general formula (III) may be a single unit or a mixture of two or more units. From the viewpoint of the dispersibility and dispersion stability of the colorant, the total proportion of the constituent units represented by the general formula (III) in the polymer chain may be 100% by mass relative to the total constituent units (100% by mass) of the polymer chain. From the viewpoint of the dispersibility and dispersion stability of the colorant, the total proportion of the constituent units represented by the general formula (III) in the polymer chain is preferably 40% by mass or more, and more preferably 70% by mass or more, relative to the total constituent units of the polymer chain.

[0075] The polymer chain components in the graft copolymer represented by the general formula (II) may include other components in addition to the components represented by the general formula (III). Other constituent units include constituent units derived from ethylenically unsaturated monomers that can be copolymerized with ethylenically unsaturated monomers that derive the constituent unit represented by the general formula (III) mentioned above. Examples of monomers that can be used to derive other constituent units include styrenes such as styrene and α-methylstyrene, and vinyl ethers such as phenyl vinyl ether.

[0076] In the polymer chain of the graft copolymer represented by the general formula (II), the total proportion of other constituent units is preferably 30% by mass or less, and more preferably 10% by mass or less, relative to the total constituent units of the polymer chain, from the viewpoint of the effects of the present invention.

[0077] Furthermore, the mass-average molecular weight Mw of the polymer chain is preferably 2000 or more, more preferably 3000 or more, even more preferably 4000 or more, more preferably 15000 or less, and even more preferably 12000 or less, from the viewpoint of the dispersibility and dispersion stability of the colorant. By staying within the aforementioned range, sufficient steric repulsion as a dispersant can be maintained, and the above-mentioned effects can be improved by increasing the specific surface area of ​​the solvent affinity portion of the dispersant. The mass-average molecular weight Mw of the polymer chain can be measured for the polymerizable oligomer or the polymer chain containing the reactive group in the same manner as the mass-average molecular weight Mw of the dispersant described later.

[0078] Furthermore, from the viewpoint of dispersion stability, it is preferable that the polymer chain has an acid value of 10 mg KOH / g or less, and more preferably 0 mg KOH / g or less. Here, the acid value can be measured for the polymerizable oligomer or the polymer chain containing the reactive group in the same way as the acid value of the dispersant described later. The polymer chain may contain the constituent units represented by the general formula (I) as long as the effects of the present invention are not impaired. However, from the viewpoint of dispersion stability, it is preferable that the total proportion of constituent units containing acidic groups to all constituent units of the polymer chain be 5% by mass or less, and more preferably 0% by mass.

[0079] Furthermore, it is preferable that the polymer chain has an amine value of 10 mg KOH / g or less, and more preferably 0 mg KOH / g or less, from the viewpoint of dispersibility and dispersion stability. Here, the amine value of the polymer chain represents the mass (mg) of potassium hydroxide equivalent to the amount of hydrochloric acid required to neutralize 1 g of the solid content of the polymerizable oligomer or the polymer chain containing the reactive group, and is a value measured by the method described in JIS K 7237:1995. The polymer chain may contain nitrogen atom-containing structural units as long as the effects of the present invention are not impaired. However, from the viewpoint of dispersion stability, it is preferable that the total proportion of nitrogen atom-containing structural units to the total structural units of the polymer chain be 5% by mass or less, and more preferably 0% by mass.

[0080] In the graft copolymer, the content of the constituent unit represented by the general formula (I) is preferably 3% to 60% by mass, more preferably 6% to 45% by mass, and even more preferably 9% to 35% by mass, relative to the total constituent units of the main chain of the graft copolymer. If the content of the constituent unit represented by the general formula (I) in the graft copolymer is within the above range, the proportion of the affinity portion with the colorant in the graft copolymer becomes appropriate, and the decrease in solubility in organic solvents can be suppressed, resulting in good adsorption to the colorant, and making it easier to obtain excellent dispersibility, dispersion stability, and substrate adhesion. On the other hand, in the graft copolymer, the total content of constituent units including graft polymer chains and constituent units represented by the general formula (II) is preferably 40% to 97% by mass, more preferably 55% to 94% by mass, and even more preferably 65% ​​to 91% by mass, relative to the total content of constituent units of the main chain of the graft copolymer. If the total content of constituent units including graft polymer chains and constituent units represented by the general formula (II) in the graft copolymer is within the above range, the proportion of solvent affinity portion in the graft copolymer becomes appropriate, allowing for sufficient steric repulsion as a dispersant, and increasing the specific surface area of ​​the solvent affinity portion of the dispersant, which makes it easier to improve dispersion stability. The content ratio of the aforementioned constituent units is calculated from the amount of monomers used to produce the constituent units represented by general formula (I) and the constituent units represented by general formula (II) when synthesizing the graft copolymer.

[0081] The graft copolymer used in the present invention may have other constituent units in addition to the constituent units represented by general formula (I) and general formula (II), as long as the effects of the present invention are not impaired. As other constituent units, ethylenically unsaturated monomers that can be copolymerized with ethylenically unsaturated monomers that induce the constituent units represented by general formula (I), etc., can be appropriately selected and copolymerized to introduce other constituent units. Other structural units copolymerized in the main chain with the structural unit represented by the general formula (I) include, for example, the structural unit represented by the general formula (III), and structural units containing acidic groups different from those of the structural unit represented by the general formula (I). Examples of monomers that derive constituent units containing acidic groups different from the constituent units represented by the general formula (I) above include maleic acid, monoalkyl maleic acid, fumaric acid, itaconic acid, crotonic acid, and cinnamic acid. In the graft copolymer, the total content of other constituent units copolymerized to the main chain is preferably 40% by mass or less, more preferably 20% by mass or less, and may be 0% by mass, relative to the total constituent units of the main chain of the graft copolymer.

[0082] (Method for manufacturing graft copolymers) In the present invention, the method for producing the graft copolymer is not particularly limited, as long as it is a method capable of producing a graft copolymer having the constituent units represented by the general formula (I). When producing a graft copolymer having the constituent units represented by the general formula (I), for example, a method can be used in which a monomer represented by the following general formula (Ia) and a polymerizable oligomer (macromonomer) consisting of the polymer chain and a group having an ethylenically unsaturated double bond at its end are copolymerized as copolymerization components to produce a graft copolymer. If necessary, other monomers can also be used, and graft copolymers can be produced using known polymerization methods.

[0083] [ka] (In general formula (Ia), R 1 L and Q are the same as in general formula (I).

[0084] Furthermore, when producing a graft copolymer having a structural unit represented by the general formula (I), a copolymer may be formed by addition polymerization of a monomer represented by the general formula (Ia) with other ethylenically unsaturated monomers, and then a polymer chain may be introduced using a polymer chain containing a reactive group that can react with the reactive group contained in the copolymer. Specifically, for example, a copolymer having substituents such as alkoxy groups, hydroxyl groups, carboxyl groups, amino groups, epoxy groups, isocyanate groups, and hydrogen bond-forming groups may be synthesized, and then a polymer chain containing a functional group that reacts with the substituent may be reacted to introduce the polymer chain. For example, polymer chains can be introduced by reacting a polymer chain having a carboxyl group at its terminus with a copolymer having a glycidyl group in its side chain, or by reacting a polymer chain having a hydroxyl group at its terminus with a copolymer having an isocyanate group in its side chain. In addition, additives commonly used in polymerization, such as polymerization initiators, dispersion stabilizers, and chain transfer agents, may be used in the polymerization process.

[0085] Furthermore, a copolymer having at least one selected from the constituent units represented by the general formula (I-3) can be synthesized, for example, by referring to Japanese Patent Application Publication No. 2017-2191.

[0086] {block copolymer} The block copolymer used in the present invention has a block A containing a constituent unit represented by the general formula (I) that functions as an adsorption site for the colorant. The block copolymer used in the present invention preferably further has a B block that functions as a solvent affinity site.

[0087] (Block A) In Block A, the constituent units represented by the general formula (I) may be the same as described above, so their explanation is omitted here. In block A, the constituent unit represented by general formula (I) may consist of one type, or it may contain two or more types of constituent units. As for the constituent units represented by the general formula (I), it is preferable to have a constituent unit represented by the general formula (I-1) and a constituent unit represented by the general formula (I-2) in terms of substrate adhesion of the fine pattern, suppression of development residue generation, dispersibility, and dispersion stability. Furthermore, in the constituent unit represented by the general formula (I), the acidic group represented by Q is preferably an acidic phosphorus compound group from the viewpoint of suppressing the generation of developing residue, dispersibility, and dispersion stability, and it is preferable that the constituent unit represented by the general formula (I) includes the constituent unit represented by the general formula (I-3).

[0088] In block A, other structural units may be present in addition to the structural unit represented by the general formula (I), as long as the effects of the present invention are not impaired. As other structural units, ethylenically unsaturated monomers that can be copolymerized with ethylenically unsaturated monomers that induce the structural unit represented by the general formula (I) can be appropriately selected and copolymerized to introduce other structural units. Other constituent units that can be included in Block A without impairing the effects of the present invention include, for example, the constituent unit represented by the general formula (III) and the constituent unit containing an acidic group different from the constituent unit represented by the general formula (I). The constituent units represented by the aforementioned general formula (III) and the constituent units containing acidic groups different from those represented by the aforementioned general formula (I) may be the same as those described in the graft copolymer, so their explanation is omitted here. The total percentage of other constituent units contained in Block A is not particularly limited as long as the effects of the present invention are not impaired, but from the viewpoint of dispersibility and dispersion stability, it is preferably 40% by mass or less, more preferably 20% by mass or less, and may be 0% by mass relative to the total constituent units of Block A.

[0089] In other words, the content of the constituent units represented by general formula (I) in block A is preferably 60% by mass or more, more preferably 80% by mass or more, and may be 100% by mass, relative to the total constituent units of block A, from the viewpoint of dispersibility and dispersion stability.

[0090] (Block B) In the block copolymer used in the present invention, block B is a block that functions as a solvent affinity site. Preferably, block B is appropriately selected from among ethylenically unsaturated monomers that can copolymerize with the ethylenically unsaturated monomer that derives the constituent unit represented by the general formula (I), so as to have solvent affinity, depending on the solvent. As a guideline, it is preferable to introduce block B in such a way that the solubility of the block copolymer at 23°C is 20 (g / 100g solvent) or more in relation to the solvent used in combination.

[0091] In the block copolymer used in the present invention, the B block, which functions as a solvent affinity site, preferably contains at least one constituent unit represented by the general formula (III) above, in order to improve solvent affinity and improve the dispersibility and dispersion stability of the colorant. The constituent units represented by the general formula (III) included in block B may be the same as those described for graft copolymers, so their explanation is omitted here.

[0092] In block B, the constituent unit represented by the general formula (III) may be a single unit or a mixture of two or more units. From the viewpoint of the dispersibility and dispersion stability of the colorant, the total proportion of the constituent units represented by the general formula (III) in block B may be 100% by mass relative to the total constituent units of block B. From the viewpoint of the dispersibility and dispersion stability of the colorant, the total proportion of the constituent units represented by the general formula (III) in block B is preferably 40% by mass or more, and more preferably 70% by mass or more, relative to the total constituent units of block B.

[0093] Block B may include other constituent units in addition to the constituent unit represented by the general formula (III). Other constituent units include constituent units derived from ethylenically unsaturated monomers that can be copolymerized with ethylenically unsaturated monomers that derive the constituent unit represented by the general formula (III) mentioned above. Examples of monomers that can be used to derive other constituent units include styrenes such as styrene and α-methylstyrene, and vinyl ethers such as phenyl vinyl ether.

[0094] In the aforementioned Block B, the total proportion of other constituent units is preferably 30% by mass or less, and more preferably 10% by mass or less, relative to all constituent units of Block B, from the viewpoint of the effects of the present invention.

[0095] The mass-average molecular weight Mw of block B is preferably 2000 or more, more preferably 3000 or more, even more preferably 4000 or more, more preferably 15000 or less, and even more preferably 12000 or less, from the viewpoint of the dispersibility and dispersion stability of the colorant. By staying within the aforementioned range, sufficient steric repulsion as a dispersant can be maintained, and the specific surface area of ​​the solvent affinity portion of the dispersant can be increased, thereby improving dispersion stability. The mass-average molecular weight Mw of block B alone can be measured for polymers consisting only of block B, in the same manner as the dispersant described later.

[0096] Furthermore, from the viewpoint of dispersion stability, it is preferable that the acid value of block B is 10 mg KOH / g or less, and more preferably 0 mg KOH / g. Here, the acid value of the polymer consisting only of block B can be measured in the same way as the acid value of the dispersant described later. Block B may contain at least one component containing an acidic group, such as a component selected from the group consisting of components represented by the general formula (I), as long as the effects of the present invention are not impaired. However, from the viewpoint of dispersion stability, it is preferable that the total proportion of component units containing an acidic group to all component units of Block B be 5% by mass or less, and more preferably 0% by mass.

[0097] Furthermore, from the viewpoint of dispersion stability, it is preferable that the amine value of block B is 10 mg KOH / g or less, and more preferably 0 mg KOH / g. Here, the amine value of block B can be measured for a polymer consisting only of block B in the same way as the amine value of the polymer chain described above. The aforementioned Block B may contain nitrogen atom-containing structural units as long as the effects of the present invention are not impaired. However, from the viewpoint of dispersion stability, it is preferable that the total proportion of nitrogen atom-containing structural units to all structural units of Block B be 5% by mass or less, and more preferably 0% by mass.

[0098] Furthermore, the B block only needs to be selected to function as a solvent affinity site, and the constituent units may consist of one type, or they may be a mixture of two or more types. If the B block contains two or more constituent units, the two or more constituent units may be randomly copolymerized within the B block.

[0099] The bonding order of the block copolymer is not particularly limited, as long as it allows for stable dispersion of the colorant. However, it is preferable that the A block is bonded to one end of the block copolymer, as this provides excellent interaction with the colorant and effectively suppresses aggregation of the dispersants. Therefore, it is preferable that the block copolymer is of type AB, type ABA, or type BAB, and among these, type AB or type BAB is preferable.

[0100] In the block copolymer, the total content of block A is preferably 3% to 60% by mass, more preferably 6% to 45% by mass, and even more preferably 9% to 35% by mass, relative to the total structural units of the main chain of the block copolymer. If the total content of block A in the block copolymer is within the above range, the proportion of affinity portion with colorants in the block copolymer becomes appropriate, and the decrease in solubility in organic solvents can be suppressed, resulting in good adsorption to colorants, and making it easier to obtain excellent dispersibility, dispersion stability, and substrate adhesion. In the block copolymer, the content of the constituent unit represented by the general formula (I) is preferably 3% to 60% by mass, more preferably 6% to 45% by mass, and even more preferably 9% to 35% by mass, relative to the total constituent units of the main chain of the block copolymer. If the content of the constituent unit represented by the general formula (I) in the block copolymer is within the above range, the proportion of the affinity portion with the colorant in the block copolymer becomes appropriate, and the decrease in solubility in organic solvents can be suppressed, resulting in good adsorption to the colorant, and making it easier to obtain excellent dispersibility, dispersion stability, and substrate adhesion.

[0101] On the other hand, in the block copolymer, the total content of B blocks is preferably 40% to 97% by mass, more preferably 55% to 94% by mass, and even more preferably 65% ​​to 91% by mass, relative to the total constituent units of the main chain of the block copolymer. If the total content of B blocks in the block copolymer is within the above range, the proportion of the solvent affinity portion in the block copolymer becomes appropriate, allowing for sufficient steric repulsion as a dispersant, and the specific surface area of ​​the solvent affinity portion of the dispersant becomes larger, making it easier to improve dispersion stability. The content ratio of the aforementioned constituent units is calculated from the amount of monomers used to produce the constituent units represented by general formula (I) and the constituent units represented by general formula (III) when synthesizing the block copolymer.

[0102] (Method of manufacturing block copolymers) The method for producing the block copolymer is not particularly limited. Block copolymers can be produced by known methods, but production by living polymerization is preferred. This is because chain transfer and deactivation are less likely to occur, copolymers with uniform molecular weights can be produced, and dispersibility can be improved. Examples of living polymerization methods include living radical polymerization, living anionic polymerization methods such as group transfer polymerization, and living cationic polymerization. Copolymers can be produced by sequentially polymerizing monomers using these methods. For example, a block copolymer can be produced by first producing block A and then polymerizing the constituent units of block B onto block A. In the above production method, the order of polymerization of block A and block B can also be reversed. Furthermore, block A and block B can be produced separately and then coupled together.

[0103] {Properties of graft copolymers or block copolymers having constituent units represented by general formula (I)} The mass-average molecular weight Mw of the graft copolymer or block copolymer having the constituent units represented by the general formula (I) is preferably 4000 or more, more preferably 5000 or more, and even more preferably 6000 or more, from the viewpoint of dispersibility and dispersion stability. On the other hand, from the viewpoint of solvent resolubility, it is preferably 50000 or less, and more preferably 30000 or less. Furthermore, the ratio of the mass-average molecular weight Mw to the number-average molecular weight Mn (Mw / Mn) of the dispersant, which is the graft copolymer, is preferably 4.0 or less, more preferably 3.5 or less, and even more preferably 3.0 or less, from the viewpoint of dispersion stability. Furthermore, the ratio of the mass-average molecular weight Mw to the number-average molecular weight Mn (Mw / Mn) of the dispersant, which is the block copolymer, is preferably 1.8 or less, more preferably 1.6 or less, and even more preferably 1.4 or less, from the viewpoint of dispersion stability. In this invention, the mass-average molecular weight Mw and the number-average molecular weight Mn are values ​​measured by GPC (gel permeation chromatography). The measurements were performed using a Tosoh HLC-8120GPC, with N-methylpyrrolidone mixed with 0.01 mol / liter lithium bromide as the eluent, and the polystyrene standards for the calibration curve were Mw377400, 210500, 96000, 50400, 20650, 10850, 5460, 2930, 1300, and 580 (all from Polymer Laboratories' Easi PS-2 series) and Mw1090000 (Tosoh). The measurement column was two TSK-GEL ALPHA-M tubes (Tosoh).

[0104] The acid value of the graft copolymer or block copolymer having the constituent unit represented by the general formula (I) is preferably 20 mg KOH / g or more, more preferably 30 mg KOH / g or more, even more preferably 40 mg KOH / g or more, and even more preferably 60 mg KOH / g or more, from the viewpoint of dispersion stability. On the other hand, the acid value of at least one of the graft copolymer and the block copolymer is preferably 250 mg KOH / g or less, more preferably 180 mg KOH / g or less, even more preferably 160 mg KOH / g or less, and even more preferably 120 mg KOH / g or less, from the viewpoint of solvent resolubility. The acid value of the dispersant represents the mass (mg) of potassium hydroxide required to neutralize the acidic components contained in 1 g of the copolymer's solid content, and is a value measured by the method described in JIS K 0070:1992.

[0105] In the present invention, the dispersant may further contain other dispersants other than at least one of the graft copolymer having the constituent units represented by the general formula (I) and the block copolymer having A blocks containing the constituent units represented by the general formula (I). The aforementioned other dispersants can be appropriately selected from conventionally known dispersants. Examples of such other dispersants include cationic, anionic, nonionic, amphoteric, silicone, and fluorine-based surfactants. Among surfactants, polymeric dispersants are preferred because they can disperse uniformly and finely.

[0106] Examples of polymeric dispersants in the aforementioned other dispersants include (co)polymers of unsaturated carboxylic acid esters such as polyacrylic acid esters; (partial)amine salts, (partial) ammonium salts, and (partial) alkylamine salts of (co)polymers of unsaturated carboxylic acid esters such as polyacrylic acid; (co)polymers of hydroxyl group-containing unsaturated carboxylic acid esters such as hydroxyl group-containing polyacrylic acid esters and their modified products; polyurethanes; unsaturated polyamides; polysiloxanes; long-chain polyaminoamide phosphates; polyethyleneimine derivatives (amides obtained by the reaction of poly(lower alkyleneimine) with free carboxyl group-containing polyesters and their bases); polyallylamine derivatives (reaction products obtained by reacting polyallylamine with one or more compounds selected from three types of compounds: polyesters having free carboxyl groups, polyamides, or ester-amide cocondensates (polyesteramides)). When the polymer dispersant is a copolymer, it may be a block copolymer, a graft copolymer, or a random copolymer, but block copolymers and graft copolymers are preferred from the viewpoint of dispersibility.

[0107] The polymeric dispersant in the aforementioned other dispersants may further contain a basic dispersant, as it can suitably disperse the colorant and has good dispersion stability. The basic dispersant may be a polymeric dispersant containing nitrogen atoms in its main chain or side chain and having an amine value, and may be a polymeric dispersant comprising a polymer containing a structural unit having at least one of a tertiary amine, a salt of a tertiary amine, and a quaternary ammonium salt (hereinafter abbreviated as tertiary amine, etc.). Examples of the main chain structure of the polymer include (meth)acrylic resins and styrene resins. Among these, (meth)acrylic resins are preferred because they are easy to synthesize as block copolymers and graft copolymers. The constituent units having tertiary amines, etc., are the parts that have affinity for the colorant. Polymer dispersants made of polymers containing constituent units having tertiary amines usually contain constituent units that are solvent-affinity parts. Examples of polymers containing constituent units having tertiary amines include graft copolymers having constituent units having tertiary amines and block copolymers having constituent units having tertiary amines. The solvent-affinity parts may be the same as those of at least one of the graft copolymer having constituent units represented by the general formula (I) and the block copolymer having A blocks containing constituent units represented by the general formula (I). The amine value of the basic dispersant may be, for example, 50 mg KOH / g or more, 80 mg KOH / g or more, while it may be 200 mg KOH / g or less, or 150 mg KOH / g or more, from the viewpoint of dispersibility. As a polymer dispersant comprising a polymer containing a constituent unit having a tertiary amine, for example, commercially available products may be used, such as DISPERBYK-2000 and LPN-6919 manufactured by BIC-Chemie. In addition, LPN-6919 manufactured by BIC-Chemie may be used in the form of a salt or quaternary ammonium salt in which the tertiary amine portion is obtained.

[0108] In the dispersant, the content ratio of at least one of the graft copolymer having a structural unit represented by the general formula (I) and the block copolymer having an A block containing the structural unit represented by the general formula (I) may be 40% by mass or more with respect to the total amount of solids in the dispersant, but from the viewpoint of easily obtaining the effects of the present invention, it is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 90% by mass or more, and may be 100% by mass.

[0109] In this invention, the content ratio and structure of each constituent unit of the dispersant can be determined using various mass spectrometers, NMR, etc. Furthermore, the dispersant can be decomposed by thermal decomposition or other methods as needed, and the decomposition products obtained can be determined using high-performance liquid chromatography, gas chromatography-mass spectrometry, NMR, elemental analysis, XPS / ESCA, TOF-SIMS, etc.

[0110] In the photosensitive colored resin composition according to the present invention, the content of the dispersant is not particularly limited, but should be selected to provide excellent dispersibility and dispersion stability of the colorant. For example, it is preferably in the range of 2% to 30% by mass, more preferably 3% to 25% by mass, based on the total amount of solids in the photosensitive colored resin composition. If it is above the lower limit, the dispersibility and dispersion stability of the colorant will be excellent, and the storage stability of the photosensitive colored resin composition will be excellent. If it is below the upper limit, the developability will be good. In particular, when forming a colored layer with a high colorant concentration, the content of the dispersant is preferably in the range of 2% to 25% by mass, more preferably 3% to 20% by mass, based on the total amount of solids in the photosensitive colored resin composition.

[0111] [Alkali-soluble resin] The alkali-soluble resin used in the present invention is one that has an acidic group, acts as a binder resin, and is soluble in the alkaline developer used when forming patterns. These can be appropriately selected and used from among such resins. In this invention, an alkali-soluble resin can be defined as one with an acid value of 40 mgKOH / g or higher. The alkali-soluble resin used in the present invention is different from the dispersant, and if it is an acrylic copolymer, it is a random copolymer.

[0112] As the alkali-soluble resin, conventionally known alkali-soluble resins can be appropriately selected and used. For example, alkali-soluble resins described in International Publication No. 2016 / 104493 can be appropriately selected and used. The preferred alkali-soluble resins in the present invention are resins having acidic groups, usually carboxyl groups. Specifically, these include acrylic resins such as acrylic copolymers having carboxyl groups and styrene-acrylic copolymers having carboxyl groups, and epoxy (meth)acrylate resins having carboxyl groups. Acrylic resins such as acrylic copolymers having carboxyl groups and styrene-acrylic copolymers having carboxyl groups are preferably used. Among these, those having carboxyl groups in the side chain and further having photopolymerizable functional groups such as ethylenically unsaturated groups in the side chain are particularly preferred. This is because the film strength of the cured film formed by including photopolymerizable functional groups is improved. Furthermore, two or more of these acrylic resins such as acrylic copolymers and styrene-acrylic copolymers, as well as epoxy acrylate resins, may be used in mixture form. For alkali-soluble resins, it is preferable to select and use those with an acid value of 50 mg KOH / g or higher, from the viewpoint of developability (solubility) in alkaline aqueous solutions used in the developing solution. From the viewpoint of developability (solubility) in alkaline aqueous solutions used in the developing solution and adhesion to the substrate, the acid value of the alkali-soluble resin may be 60 mg KOH / g or more and 300 mg KOH / g or less, and 70 mg KOH / g or more and 200 mg KOH / g or less, and the upper limit may be 120 mg KOH / g or less.

[0113] The alkali-soluble resin used in the photosensitive colored resin composition may be used alone or in combination of two or more types. There are no particular restrictions on the content of the alkali-soluble resin, but it is preferably in the range of 5% to 60% by mass, and more preferably 10% to 40% by mass, relative to the total solid content of the photosensitive colored resin composition. If the content of the alkali-soluble resin is above the lower limit, sufficient alkali developability can be obtained, and if the content of the alkali-soluble resin is below the upper limit, film roughness and pattern defects can be suppressed during development.

[0114] [Photopolymerizable compound] The photopolymerizable compound used in the photosensitive colored resin composition of the present invention contains a photopolymerizable compound having a caprolactone structure.

[0115] A photopolymerizable compound is a compound that has a photopolymerizable group in its molecule. The photopolymerizable group can be any group that can be polymerized by a photoinitiator and is not particularly limited, but examples include ethylenically unsaturated double bonds, such as vinyl groups, allyl groups, acryloyl groups, or methacryloyl groups. Among the photopolymerizable groups, acryloyl groups or methacryloyl groups are preferably used from the viewpoint of ultraviolet curability. As for the photopolymerizable compound, from the viewpoint of curability, it is preferable to contain a compound having two or more photopolymerizable groups in one molecule, and more preferable to contain a compound having three or more photopolymerizable groups in one molecule.

[0116] A photopolymerizable compound having a caprolactone structure is one in which the caprolactone structure is contained within the molecule of the photopolymerizable compound. Having a caprolactone structure means that it contains a ring-opened ε-caprolactone structure, and it may also contain a ring-opened ε-caprolactone structure as a repeating unit. Photopolymerizable compounds having a caprolactone structure can be obtained, for example, by esterifying an alcohol with (meth)acrylic acid and ε-caprolactone. Among these, compounds obtained by esterifying a polyhydric alcohol with (meth)acrylic acid and ε-caprolactone are preferably used. Examples of photopolymerizable compounds having a preferred caprolactone structure from the viewpoint of curability include compounds represented by the following general formula (1).

[0117] [ka] (In general formula (1), A is an n-valent alcohol residue, and R i Each of these is independently a hydrogen atom, a group represented by the following general formula (2), or a group represented by the following general formula (3), and R iAt least one of the bases is represented by the following general formula (2), where n is an integer greater than or equal to 2.

[0118] [ka] (In general formulas (2) and (3), R ii Each of the symbols independently represents a hydrogen atom or a methyl group, m represents the number 1 or 2, and * represents a bond.

[0119] The photopolymerizable compound having a caprolactone structure may have a hydroxyl value, which may be, for example, 300 mgKOH / g or less, or 260 mgKOH / g or less, from the viewpoint of curability. Here, hydroxyl value refers to the number of milligrams of potassium hydroxide equivalent to the hydroxyl groups in 1 g of sample, and can be measured by the method defined in JIS K0070.

[0120] Examples of polyhydric alcohols that induce the n-valent alcohol residue A in general formula (1) include dipropylene glycol, glycerin, trimethylolethane, trimethylolpropane, triethylolpropane, 1,2,6-hexanetriol, diglycerol, pentaerythritol, dipentaerythritol, tripentaerythritol, sorbitol, and trimethylolmelamine. Among these, polyhydric alcohols that induce the n-valent alcohol residue A are preferably trivalent or higher.

[0121] The photopolymerizable compound having a caprolactone structure preferably has two or more caprolactone structures in one molecule, and the upper limit of the caprolactone structure may be the same as the valency of the polyhydric alcohol. n is not particularly limited, but may be 10 or less, or 8 or less.

[0122] In particular, from the viewpoint of curability, it is preferable to contain a photopolymerizable compound having a caprolactone structure represented by the following general formula (1-1).

[0123] [ka] (In general formula (1-1), R i Each of these is independently a group represented by the general formula (2) or a group represented by the general formula (3), and R i At least one of them is a base represented by the general formula (2) above. (j represents an integer from 1 to 3.)

[0124] In a compound represented by general formula (1-1), R i It is preferable that two or more of the groups are represented by the general formula (2). i All (2 × j + 2) of these may be groups represented by the general formula (2), and when j = 2, R i Six or fewer of these may be groups represented by the general formula (2). Because it allows for a short development time, suppresses the generation of development residue, and facilitates the formation of a finely patterned colored layer with good substrate adhesion, j may be an integer between 2 and 3, and in particular may be 2.

[0125] As the photopolymerizable compound having a caprolactone structure, commercially available products may be used as appropriate. For example, commercially available products are sold by Nippon Kayaku Co., Ltd. as the KAYARAD DPCA series. In photopolymerizable compounds, a single photopolymerizable compound having a caprolactone structure may be used alone, or two or more may be used in combination.

[0126] From the standpoint of easily forming fine patterns, the ratio of the total mass of the alkali-soluble resin to the total mass of the photopolymerizable compound having a caprolactone structure (alkali-soluble resin / photopolymerizable compound having a caprolactone structure) is preferably 5% to 67%, more preferably 5% to 53%, and even more preferably 10% to 43%.

[0127] The weight-average molecular weight per mole of photopolymerizable group of a photopolymerizable compound having a caprolactone structure, for example, the ethylenically unsaturated double bond equivalent, is preferably 100 or more, more preferably 110 or more, even more preferably 130 or more, while preferably 400 or less, more preferably 350 or less, and even more preferably 330 or less, in order to shorten the development time, suppress the generation of development residue, and facilitate the formation of a finely patterned colored layer with good substrate adhesion. Here, the ethylenically unsaturated double bond equivalent refers to the weight-average molecular weight per mole of ethylenically unsaturated double bonds in a photopolymerizable compound, and is expressed by the following formula (1). Formula (1) Ethylene-unsaturated double bond equivalent (g / mol) = W(g) / M(mol) (In formula (1), W represents the mass (g) of the photopolymerizable compound, and M represents the number of moles (mol) of ethylenically unsaturated double bonds contained in W (g) of the photopolymerizable compound.)

[0128] Furthermore, in order to enable the formation of a colored layer with a fine pattern that has good adhesion to the substrate while shortening the development time and suppressing the generation of development residue, the content of the photopolymerizable compound having a caprolactone structure is preferably 30% by mass or more, more preferably 50% by mass or more, even more preferably 60% by mass or more, even more preferably 70% by mass or more, and may be 100% by mass, in the total amount of photopolymerizable compounds.

[0129] The photopolymerizable compound used in the photosensitive colored resin composition of the present invention may include a photopolymerizable compound different from the photopolymerizable compound having a caprolactone structure, that is, a photopolymerizable compound that does not have a caprolactone structure. As photopolymerizable compounds other than the aforementioned caprolactone structure, polyfunctional (meth)acrylates having three or more ethylenically unsaturated double bonds (trifunctional) are preferred from the viewpoint of excellent photocurability, and poly(meth)acrylates of trivalent or higher polyhydric alcohols and their dicarboxylic acid modified products are preferred, specifically trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, succinic acid modified product of pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, succinic acid modified product of dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc. are preferred. These polyfunctional (meth)acrylates may be used individually or in combination of two or more types. The content of photopolymerizable compounds other than the photopolymerizable compound having the caprolactone structure may be 70% by mass or less, 50% by mass or less, 40% by mass or less, 30% by mass or less, or 0% by mass in the total amount of photopolymerizable compounds.

[0130] In the photosensitive colored resin composition of the present invention, the weight-average molecular weight per mole of photopolymerizable groups of the entire photopolymerizable compound, for example, the ethylenically unsaturated double bond equivalent, is preferably 100 or more, more preferably 110 or more, even more preferably 130 or more, while preferably 400 or less, more preferably 350 or less, and even more preferably 330 or less, in order to shorten the development time, suppress the generation of development residue, and facilitate the formation of a fine patterned colored layer with good substrate adhesion.

[0131] The content of the above photopolymerizable compound used in the photosensitive colored resin composition is not particularly limited, but is, for example, preferably in the range of 5% by mass to 60% by mass, more preferably 10% by mass to 40% by mass, based on the total solid content of the photosensitive colored resin composition. When the content of the photopolymerizable compound is at least the above lower limit value, sufficient photocuring proceeds and elution during development of the exposed portion is easily suppressed. Also, when the content of the photopolymerizable compound is at most the above upper limit value, alkali developability is likely to be sufficient.

[0132] [Photoinitiator] The initiator used in the photosensitive colored resin composition of the present invention is not particularly limited, and one or more kinds can be used in combination from various conventionally known initiators. Examples of the initiator include polymerization initiators such as thermal polymerization initiators and photopolymerization initiators. Specifically, for example, those described in JP-A-2013-029832 can be mentioned.

[0133] Examples of the photoinitiator include aromatic ketones, benzoin ethers, halomethyloxadiazole compounds, α-aminoketones, biimidazoles, N,N-dimethylaminobenzophenone, halomethyl-S-triazine-based compounds, thioxanthone, oxime esters, and the like.

[0134] Biimidazole-based photoinitiators are preferable because they have the property of curing the deep part of the coating film and tend to improve the adhesion of the substrate after development. Examples of biimidazole-based photoinitiators include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(4-ethoxycarbonylphenyl)-1,2'-biimidazole, 2,2'-bis(2-bromophenyl)-4,4',5,5'-tetrakis(4-ethoxycarbonylphenyl)-1,2'-biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4,6-trichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, and 2,2'-bis(2,4,6-trichlorophenyl). Examples include tetraphenyl-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2-bromophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4-dibromophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4,6-tribromophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, and 2,2',4-tri(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4',5'-diphenyl-1,1'-biimidazole. Biimidazole-based photoinitiators may be used alone or in combination of two or more, and among them, 2,2',4-tri(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4',5'-diphenyl-1,1'-biimidazole is preferred because it improves curability.

[0135] Furthermore, since the present invention contains a photopolymerizable compound having the caprolactone structure, it is possible to use a highly sensitive oxime ester-based photoinitiator because it is easy to form a narrow pattern line width. Among the oxime ester-based photoinitiators, it is preferable to include at least one of the oxime ester compound represented by the following general formula (A) and the oxime ester compound represented by the following general formula (B), as this makes it less likely for the pattern line width to become thick when combined with the photopolymerizable compound having the caprolactone structure. In particular, using a combination of the biimidazole-based photoinitiator and at least one oxime ester compound represented by the following general formula (A) and oxime ester compound represented by the following general formula (B) is preferable because it improves the adhesion of fine patterns, makes the film tougher, and tends to have good chipping resistance and solvent resistance.

[0136] [ka] (In general formula (A), Z 1 , Z 3 , Z 4 and Z 5 Each of these independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or a phenyl group, and the alkyl group, cycloalkyl group, and phenyl group may each be substituted with a substituent selected from the group consisting of a halogen atom, an alkoxy group having 1 to 6 carbon atoms, and a phenyl group. 2 (This represents an alkyl group with 1 to 20 carbon atoms that is substituted with a cycloalkyl group.)

[0137] [ka] (In general formula (B), R a and R b Each is independently a hydrogen atom or an alkyl group, and R c is a hydrocarbon group which may contain at least one divalent linking group selected from a thioether bond (-S-), an ether bond (-O-), and a carbonyl bond (-CO-), and Z is a hydrogen atom or -(C=O)R d And R d R is a hydrocarbon group which may contain at least one atom selected from oxygen and sulfur atoms, or a heterocyclic group which does not contain a nitrogen atom but contains at least one atom selected from oxygen and sulfur atoms, e (This refers to a hydrocarbon group having 1 to 10 carbon atoms.)

[0138] <Compounds represented by general formula (A)> In the above general formula (A), Z 1 , Z 3 , Z 4 and Z 5 Examples of linear or branched alkyl groups having 1 to 12 carbon atoms include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, and n-dodecyl group. Z 1 , Z 3 , Z 4 and Z 5 Examples of the cycloalkyl group having 3 to 20 carbon atoms in the above are cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclooctadecyl group, and the like. Z 2 The cycloalkyl group in may be the same as the cycloalkyl group having 3 to 20 carbon atoms, and a cyclopentyl group or a cyclohexyl group is preferred. Z 2 Examples of the C1-C20 alkyl group in this context include, in addition to the C1-C12 linear or branched alkyl group, n-tetradecyl, n-hexadecyl, n-octadecyl groups, and the like.

[0139] Also, Z 1 , Z 3 , Z 4 and Z 5 Examples of halogen atoms that may be substituted with alkyl groups, cycloalkyl groups, and phenyl groups include fluorine atoms, chlorine atoms, bromine atoms, and the like. Z 1 , Z 3 , Z 4 and Z 5In this context, examples of the C1-C6 alkoxy group that may be substituted with an alkyl group, a cycloalkyl group, or a phenyl group include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, a t-butoxy group, and the like.

[0140] In general formula (A), Z 1 As such, from the standpoint of improving sensitivity, an alkyl group or phenyl group having 1 to 6 carbon atoms is preferred, a methyl group, an ethyl group, or a phenyl group is more preferred, and a methyl group is even more preferred. Furthermore, in general formula (A), Z 3 , Z 4 and Z 5 From the viewpoint of brightness, hydrogen atoms, methyl groups, ethyl groups, n-propyl groups, or i-propyl groups are preferred.

[0141] In general formula (A), Z 2 From the viewpoint of compatibility, alkyl groups having 1 to 14 carbon atoms substituted with cycloalkyl groups having 5 to 6 carbon atoms are preferred, alkyl groups having 1 to 10 carbon atoms substituted with cycloalkyl groups having 5 to 6 carbon atoms are more preferred, cyclohexylmethyl groups or cyclopentylmethyl groups are even more preferred, and cyclohexylmethyl groups are particularly preferred.

[0142] Among the photoinitiators represented by the general formula (A), oxime ester compounds represented by the following chemical formula (A-1) are preferred from the viewpoint of suppressing brightness reduction. Examples of commercially available products include TR-PBG-3057 (manufactured by Changzhou Strong Electronic New Materials Co., Ltd.).

[0143] [ka]

[0144] The photoinitiator represented by the general formula (A) can be synthesized, for example, by using diphenyl sulfide or its derivatives, and by appropriately selecting the solvent, reaction temperature, reaction time, purification method, etc., depending on the materials used, as described in Japanese Patent Publication No. 2012-526185. Alternatively, commercially available products may be obtained and used as appropriate.

[0145] <Compounds represented by general formula (B)> In the above general formula (B), R a and R b Each of these is preferably an alkyl group. The alkyl group may be linear, branched, cyclic, or a combination thereof, and in the general formula (A), Z 1 , Z 3 , Z 4 and Z 5 The alkyl group may be the same as a linear or branched alkyl group having 1 to 12 carbon atoms, or a cycloalkyl group, but is more preferably an alkyl group having 2 to 4 carbon atoms, and even more preferably a linear alkyl group having 2 to 4 carbon atoms.

[0146] In the above general formula (B), R c This is a hydrocarbon group which may contain at least one divalent linking group selected from a thioether bond (-S-), an ether bond (-O-), and a carbonyl bond (-CO-). The aforementioned R c Examples of hydrocarbon groups in include alkyl groups, alkenyl groups, aryl groups, and aralkyl groups. The alkyl group may be linear, branched, or cyclic, or a combination of linear and cyclic. The alkyl group is the one in the general formula (A) above, Z 1 , Z 3 , Z 4 and Z 5 The linear or branched alkyl group having 1 to 12 carbon atoms in Z may be the same as a cycloalkyl group, 2It may be the same as an alkyl group having 1 to 20 carbon atoms substituted with a cycloalkyl group. The alkenyl group may be linear, branched, or cyclic, and examples thereof include a vinyl group, an allyl group, and a propenyl group. Examples of the aryl group include a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, and a xylyl group. Examples of the aralkyl group include a benzyl group, a phenethyl group, a naphthylmethyl group, and a naphthylethyl group. R c Among the hydrocarbon groups in c , a hydrocarbon group having 1 to 14 carbon atoms is preferable, an alkyl group having 1 to 10 carbon atoms, an aralkyl group having 7 to 8 carbon atoms, and an aryl group having 6 to 10 carbon atoms are more preferable, and an alkyl group having 1 to 10 carbon atoms is even more preferable. Also, R c The hydrocarbon group in c is preferably a structure including cyclic and linear alkyl groups such as a cyclopentylmethyl group and a cyclohexylmethyl group from the viewpoints of solvent solubility and compatibility. Also, in the case of the above-mentioned R c In <0, the solvent solubility and compatibility can be improved by the hydrocarbon group containing the divalent linking group. Among the divalent linking groups, from the viewpoint of improving solvent solubility, a thioether bond (-S-) or an ether bond (-O-) is preferable. In the case of the above-mentioned R c When the hydrocarbon group contains the divalent linking group in c , the hydrocarbon group may be bonded to the carbon atom of the oxime ester group via the divalent linking group, or the carbon atom of the hydrocarbon group may be directly bonded to the carbon atom of the oxime ester group.

[0147] In the general formula (B), Z is a hydrogen atom or -(C=O)R d where R d is a hydrocarbon group that may contain at least one selected from an oxygen atom and a sulfur atom, or a heterocyclic group that does not contain a nitrogen atom and contains at least one selected from an oxygen atom and a sulfur atom. Examples of the hydrocarbon group that may contain at least one selected from an oxygen atom and a sulfur atom in the above-mentioned R d are, for example, the above-mentioned Rc The hydrocarbon group described above, R c The hydrocarbon group described above may include a group further comprising at least one linking group selected from linking groups containing an oxygen atom, such as an ether bond (-O-) or a carbonyl bond (-CO-), and linking groups containing a sulfur atom, such as a thioether bond (-S-). Among these, a hydrocarbon group having 1 to 14 carbon atoms is preferred, an alkyl group having 1 to 10 carbon atoms, an aralkyl group having 7 to 8 carbon atoms, and an aryl group having 6 to 10 carbon atoms are more preferred, and an aryl group having 6 to 10 carbon atoms is even more preferred. Furthermore, examples of heterocyclic groups that do not contain a nitrogen atom and contain at least one atom selected from oxygen and sulfur atoms include furan rings, benzofuran rings, thiophene rings, benzothiophene rings, thienothiophene rings, frofuran rings, and thienofuran rings. d The hydrocarbon group or heterocyclic group in the above is preferably having 1 to 10 carbon atoms from the viewpoint of developability. In particular, Z is preferably a hydrogen atom from the viewpoint of developability and brightness. On the other hand, if Z is -(C=O)R d This allows for improved solvent solubility and compatibility. Furthermore, in the general formula (1) above, R e In the above general formula (A), Z 2 It can be the same as that.

[0148] Examples of oxime ester compounds represented by the general formula (B) include R a and R b Both are alkyl groups having 1 to 4 carbon atoms, and R c A is an alkyl group having 1 to 4 carbon atoms, Z is a hydrogen atom, and R e A compound in which C1 to C4 is an alkyl group; R a and R b Both are alkyl groups having 1 to 6 carbon atoms, and R c A is an alkyl group having 4 to 10 carbon atoms, which is a combination of a linear alkyl group and a cyclic alkyl group, Z is a hydrogen atom, and R e A compound in which C1 to C4 is an alkyl group; R a and Rb Both are hydrogen atoms or alkyl groups having 1 to 4 carbon atoms, R c Z is an alkyl group with 1 to 4 carbon atoms, and Z is -(C=O)R d And R d R is an aryl group having 6 to 10 carbon atoms. e Compounds in which the parent molecule is an alkyl group having 1 to 4 carbon atoms; and so on are preferred examples, but the invention is not limited to these.

[0149] As the oxime ester compound represented by the general formula (B), at least one selected from the following compounds (B-1) to (B-4) is more preferred.

[0150] [ka]

[0151] The oxime ester compound represented by the general formula (B) can be synthesized, for example, by referring to Japanese Patent Publication No. 2012-526185, using fluorene or its derivatives instead of diphenyl sulfide or its derivatives, and appropriately selecting the solvent, reaction temperature, reaction time, purification method, etc., depending on the materials used.

[0152] Furthermore, since the present invention contains a photopolymerizable compound having the caprolactone structure, it is possible to relatively increase the initiator content, and therefore an α-aminoketone-based photoinitiator may be used. Among the α-aminoketone-based photoinitiators, it is preferable to include a compound represented by the following general formula (C) because it suppresses sublimation and improves chipping resistance.

[0153] [ka] (In general formula (C), R f and R g Each of these is an alkyl group having 2 to 8 carbon atoms.

[0154] <Compounds represented by general formula (C)> In the above general formula (C), R f and R g Each of these is an alkyl group having 2 to 8 carbon atoms. The alkyl group may be linear, branched, cyclic, or a combination thereof. The alkyl group may be the same as the alkyl group of general formula (A) above, and among these, linear or branched alkyl groups are preferred from the viewpoint of suppressing the generation of sublimation and precipitates during drying, and linear alkyl groups are more preferred. Furthermore, the number of carbon atoms in the alkyl group is preferably 2 to 6, and more preferably 3 to 5. In the above general formula (C), R f and R g They may be the same or different from each other, but R f and R g It is preferable that the components are identical to each other, as this facilitates synthesis and improves productivity.

[0155] A suitable specific example of the compound represented by the general formula (C) is, for example, the following chemical formula (C-1), but is not limited thereto.

[0156] [ka]

[0157] The compound represented by the general formula (C) is, for example, Step 1 involves reacting fluorene with isobutyryl chlorochloride in the presence of aluminum trichloride to obtain 2-methyl-1-fluorenyl-2-chloro-1-propanone, Step 2 involves epoxidizing the 2-methyl-1-fluorenyl-2-chloro-1-propanone obtained in Step 1 using sodium methoxide under a nitrogen atmosphere via the catalytic action of calcium oxide, and then reacting it with morpholine to obtain 2-methyl-1-fluorenyl-2-morpholino-1-propanone. The compound can be synthesized by a method comprising step 3, in which 2-methyl-1-fluorenyl-2-morpholino-1-propanone obtained in step 2 is reacted with an alkyl chloride having 2 to 8 carbon atoms in the presence of tetrabutylammonium bromide (TBAB) to obtain the compound represented by the general formula (C). Furthermore, by using two or more alkyl chlorides in step 3, the R in the general formula (C) can be reduced. f and R g This allows us to obtain compounds that are different from each other.

[0158] [ka]

[0159] In particular, using a combination of the biimidazole-based photoinitiator and the compound represented by the general formula (C) is preferable because it tends to improve the resistance to chipping of fine patterns. In particular, using a combination of the biimidazole-based photoinitiator, an oxime ester compound represented by general formula (A), at least one of the oxime ester compounds represented by general formula (B), and the compound represented by general formula (C) is preferable because it improves the adhesion of the fine patterns while maintaining excellent fine pattern formation, and the film tends to become tougher, with good chipping resistance and solvent resistance.

[0160] The total content of the photoinitiator used in the photosensitive colored resin composition of the present invention is not particularly limited as long as the effects of the present invention are not impaired, but is preferably in the range of 0.1% to 12.0% by mass, and more preferably 1.0% to 8.0% by mass, relative to the total solid content of the photosensitive colored resin composition. If this content is above the lower limit, sufficient photocuring will proceed and the elution of the exposed portion during development will be suppressed, while if it is below the upper limit, the decrease in brightness due to yellowing of the resulting colored layer can be suppressed. The term "solids" refers to everything except the solvent, and includes liquid polyfunctional monomers, etc.

[0161] If the photoinitiator contains a biimidazole-based photoinitiator, the total content of the biimidazole-based photoinitiator in 100% by mass of the total amount of photoinitiators may be 40% by mass or more, 50% by mass or more, or 60% by mass or more, with an upper limit of 100% by mass, but may also be 90% by mass or less, or 80% by mass or less, from the viewpoint of curability and substrate adhesion after development. If the photoinitiator contains one or more compounds selected from the group consisting of the compound represented by general formula (A) and the compound represented by general formula (B), the total content of one or more compounds selected from the group consisting of the compound represented by general formula (A) and the compound represented by general formula (B) in 100% by mass of the total amount of the photoinitiator may be, from the viewpoint of solvent resistance, at a lower limit of 10% by mass or more, at a lower limit of 20% by mass or more, at a lower limit of 30% by mass or more, and at an upper limit of 70% by mass or less, at a lower limit of 60% by mass or less, or at a lower limit of 50% by mass or less. If the photoinitiator contains a compound represented by the general formula (C), the total content of the compound represented by the general formula (C) in 100% by mass of the total amount of the photoinitiator may be, from the viewpoint of chipping resistance, at a lower limit of 10% by mass or more, 20% by mass or more, 30% by mass or more, and at an upper limit of 70% by mass or less, 60% by mass or less, or 50% by mass or less.

[0162] [solvent] The solvent used in the present invention is not particularly limited and can be any organic solvent that does not react with the components in the photosensitive colored resin composition but is capable of dissolving or dispersing them. The solvent can be used alone or in combination of two or more types. Specific examples of solvents include, for example, alcohol-based solvents such as methyl alcohol, ethyl alcohol, N-propyl alcohol, i-propyl alcohol, methoxy alcohol, and ethoxy alcohol; carbitol-based solvents such as methoxyethoxyethanol and ethoxyethoxyethanol; ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl methoxypropionate, ethyl ethoxypropionate, ethyl lactate, methyl hydroxypropionate, ethyl hydroxypropionate, n-butyl acetate, isobutyl Ester solvents such as ammonium 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; glycol ether acetate solvents such as methoxyethyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy-3-methyl-1-butyl acetate, 3-methoxybutyl acetate, and ethoxyethyl acetate; methoxyethoxyethyl acetate Examples of solvents include carbitol acetate solvents such as ethoxyethoxyethyl acetate and butyl carbitol acetate (BCA); diacetates such as propylene glycol diacetate and 1,3-butylene glycol diacetate; glycol ether solvents such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, and dipropylene glycol dimethyl ether; aprotic amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; lactone solvents such as γ-butyrolactone; cyclic ether solvents such as tetrahydrofuran; unsaturated hydrocarbon solvents such as benzene, toluene, xylene, and naphthalene; saturated hydrocarbon solvents such as N-heptane, N-hexane, and N-octane; and organic hydrocarbons such as toluene and xylene.Among these solvents, glycol ether acetate solvents, carbitol acetate solvents, glycol ether solvents, and ester solvents are preferably used in terms of their solubility with other components. In particular, the solvent used in the present invention is preferably one or more selected from the group consisting of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, butyl carbitol acetate (BCA), 3-methoxy-3-methyl-1-butyl acetate, ethyl ethoxypropionate, ethyl lactate, and 3-methoxybutyl acetate, in terms of solubility with other components and suitability for application.

[0163] In the photosensitive colored resin composition according to the present invention, the solvent content can be appropriately set within a range that allows for accurate formation of a colored layer. The solvent content is usually preferably in the range of 55% to 95% by mass, and more preferably 65% ​​to 88% by mass, based on the total amount of the photosensitive colored resin composition containing the solvent. By having the solvent content within the above range, excellent coatability can be achieved.

[0164] [Optional addition ingredients] The photosensitive colored resin composition may contain various additives as needed. Examples of additives include antioxidants, polymerization inhibitors, chain transfer agents, leveling agents, plasticizers, surfactants, defoamers, silane coupling agents, ultraviolet absorbers, adhesion promoters, and the like. Specific examples of surfactants and plasticizers include, for example, those described in Japanese Patent Publication No. 2013-029832.

[0165] The photosensitive colored resin composition of the present invention is preferably further enriched with an antioxidant, from the viewpoint of suppressing line width shift. By including an antioxidant in combination with the specific photoinitiator, the photosensitive colored resin composition of the present invention can control excessive radical chain reactions without impairing curability when forming a cured film. This improves linearity when forming fine line patterns and enhances the ability to form fine line patterns according to the mask line width design. Furthermore, it can improve heat resistance and suppress brightness reduction after exposure and post-baking, thereby improving brightness. The antioxidant used in the present invention is not particularly limited and may be appropriately selected from those conventionally known. Specific examples of antioxidants include, for example, hindered phenol antioxidants, amine antioxidants, phosphorus antioxidants, sulfur antioxidants, and hydrazine antioxidants. Hindered phenol antioxidants are preferred because they improve the ability to form fine line patterns according to the line width mask design and because they offer good heat resistance. Latent antioxidants, such as those described in International Publication No. 2014 / 021023, may also be used.

[0166] Examples of hindered phenol antioxidants include pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (trade name: IRGANOX1010, manufactured by BASF), 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate (trade name: Irganox 3114, manufactured by BASF), and 2,4,6-tris(4-hydroxy-3,5-di-tert-butyl Examples include 2,2'-methylenebis(6-tert-butyl-4-methylphenol) (product name: Sumirizer MDP-S, manufactured by Sumitomo Chemical), 6,6'-thiobis(2-tert-butyl-4-methylphenol) (product name: Irganox 1081, manufactured by BASF), and 3,5-di-tert-butyl-4-hydroxybenzylphosphonate diethyl (product name: Irgamod 195, manufactured by BASF). Among these, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (product name: IRGANOX 1010, manufactured by BASF) is preferred in terms of heat resistance and light resistance.

[0167] The antioxidant content is preferably in the range of 0.1% to 10.0% by mass, more preferably 0.5% to 5.0% by mass, relative to the total solid content of the photosensitive colored resin composition. If the content is above the lower limit, the ability to form fine line patterns according to the mask line width design is improved, and heat resistance is excellent. On the other hand, if the content is below the upper limit, the photosensitive colored resin composition of the present invention can be made into a highly sensitive photosensitive resin composition.

[0168] <Method for producing a photosensitive colored resin composition> The present invention relates to a method for producing a photosensitive colored resin composition that contains a colorant, a dispersant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, a solvent, and various optional additives. The method is preferable in that the colorant is uniformly dispersed in the solvent by the dispersant, as this improves contrast. The composition can be prepared by mixing using known mixing methods. Examples of methods for preparing the resin composition include: (1) first adding a colorant and a dispersant to a solvent to prepare a colorant dispersion, and then mixing an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and various optional additives into the dispersion; (2) simultaneously adding and mixing a colorant, a dispersant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and various optional additives into a solvent; (3) adding and mixing a dispersant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and various optional additives into a solvent, and then adding and dispersing the colorant; (4) preparing a colorant dispersion by adding a colorant, a dispersant, and an alkali-soluble resin to a solvent, and then further adding and mixing an alkali-soluble resin, a solvent, a photopolymerizable compound, a photoinitiator, and various optional additives into the dispersion; and so on. Among these methods, methods (1) and (4) above are preferred because they effectively prevent aggregation of the colorant and allow for uniform dispersion.

[0169] Examples of dispersers for dispersion processing include roll mills such as 2-roll and 3-roll mills, ball mills such as ball mills and vibrating ball mills, paint conditioners, continuous disc-type bead mills, and continuous annular-type bead mills. Preferred dispersion conditions for bead mills are that the bead diameter used is preferably 0.03 mm to 2.00 mm, and more preferably 0.10 mm to 1.0 mm.

[0170] II. Cured product The cured product according to the present invention is a cured product of the photosensitive colored resin composition according to the present invention. The cured product according to the present invention can be obtained, for example, by forming a coating film of the photosensitive colored resin composition according to the present invention, drying the coating film, exposing it to light, and developing it as necessary. The method for forming the coating film, exposure to light, and development can be, for example, the same as the method used for forming the colored layer of the color filter according to the present invention, which will be described later. The cured product according to the present invention has a short development time, suppresses the generation of development residue, and forms a fine pattern with good adhesion to the substrate, making it suitable for use as a colored layer for color filters. The cured product according to the present invention may have a fine pattern with a line width of 40 μm or less, or a fine pattern with a line width of 20 μm or less.

[0171] PRO Color Filters The color filter according to the present invention comprises at least a substrate and a colored layer provided on the substrate, wherein at least one of the colored layers is a cured product of the photosensitive colored resin composition according to the present invention.

[0172] The color filter according to the present invention will be described with reference to the figures. 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 colored layer 3.

[0173] (colored layer) At least one of the colored layers used in the color filter of the present invention is a cured product of the photosensitive colored resin composition according to the present invention. The colored layer is typically formed in the openings of the light-shielding portion on the substrate, as described later, and usually consists of a colored pattern of three or more colors. Furthermore, the arrangement of the colored layer is not particularly limited and can be a general arrangement such as a stripe pattern, mosaic pattern, triangle pattern, or 4-pixel arrangement. The width and area of ​​the colored layer can also be set arbitrarily. The thickness of the colored layer can be appropriately controlled by adjusting the coating method, the solid content concentration and viscosity of the photosensitive colored resin composition, etc., but it is generally preferable to have a thickness in the range of 1 μm to 5 μm.

[0174] The colored layer can be formed, for example, by the following method. First, the photosensitive colored resin composition of the present invention described above is applied to a substrate, described later, using coating methods such as spray coating, dip coating, bar coating, roll coating, spin coating, and die coating to form a wet coating film. Among these, spin coating and die coating are preferably used. Next, the wet coating is heated and dried using a hot plate or oven, and then exposed to light through a mask with a predetermined pattern to cause a photopolymerization reaction of alkali-soluble resin and photopolymerizable compounds to form a cured coating. Examples of light sources used for exposure include ultraviolet light from low-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, and electron beams. The amount of exposure is adjusted as appropriate depending on the light source used and the thickness of the coating. Furthermore, heat treatment may be performed after exposure to promote the polymerization reaction. The heating conditions are appropriately selected depending on the mixing ratio of each component in the photosensitive colored resin composition used, the thickness of the coating film, etc.

[0175] Next, the coating is developed using a developing solution to dissolve and remove the unexposed areas, thereby forming a coating with the desired pattern. Typically, a solution of alkali dissolved in water or a water-soluble solvent is used as the developing solution. A suitable amount of surfactant or other additives may be added to this alkaline solution. Furthermore, a standard development method can be used. After the developing process, the developing solution is usually washed off and the cured coating film of the photosensitive colored resin composition is dried to form the colored layer. Alternatively, heat treatment may be performed after the developing process to sufficiently cure the coating film. There are no particular limitations on the heating conditions, and they can be appropriately selected depending on the application of the coating film. The colored layer may be a colored layer with a fine pattern having a line width of 40 μm or less, or a colored layer with a fine pattern having a line width of 20 μm or less.

[0176] (Light-blocking part) The light-shielding portion in the color filter of the present invention is formed in a pattern on a substrate, as described later, and can be the same as that used as a light-shielding portion in a general color filter. The pattern shape of the light-shielding portion is not particularly limited, and examples include stripe-like and matrix-like shapes. The light-shielding portion may be a thin metal film such as chromium produced by sputtering or vacuum deposition. Alternatively, the light-shielding portion may be a resin layer containing light-shielding particles such as carbon nanoparticles, metal oxides, inorganic pigments, or organic pigments in a resin binder. In the case of a resin layer containing light-shielding particles, methods include patterning by developing with a photosensitive resist, patterning with an inkjet ink containing light-shielding particles, or thermal transfer of a photosensitive resist.

[0177] The film thickness of the light-shielding portion is set to approximately 0.2 μm to 0.4 μm for thin metal films, and approximately 0.5 μm to 2 μm for films in which black pigment is dispersed or dissolved in a binder resin.

[0178] (substrate) As substrates, transparent substrates, silicon substrates, and substrates on which aluminum, silver, silver / copper / palladium alloy thin films are formed are used, as described later. Other color filter layers, resin layers, transistors such as TFTs, circuits, etc. may be formed on these substrates.

[0179] The transparent substrate in the color filter of the present invention is not particularly limited and can be any substrate that is transparent to visible light; a transparent substrate commonly used in color filters can be used. Specifically, examples include rigid transparent materials that do not allow flexibility, such as quartz glass, alkali-free glass, or synthetic quartz plates, or flexible transparent materials that allow flexibility, such as transparent resin films, optical resin plates, or flexible glass. The thickness of the transparent substrate is not particularly limited, but depending on the application of the color filter of the present invention, for example, a thickness of about 100 μm to 1 mm can be used. Furthermore, the color filter of the present invention may have, in addition to the substrate, light-shielding portion, and colored layer described above, other components such as an overcoat layer, a transparent electrode layer, an alignment film, alignment protrusions, or columnar spacers formed on it.

[0180] IV.Display device The display device according to the present invention is characterized by having the color filter according to the present invention. The configuration of the display device in the present invention is not particularly limited and can be appropriately selected from conventionally known display devices, such as liquid crystal display devices and organic light-emitting display devices.

[0181] [Liquid crystal display device] The liquid crystal display device according to the present invention comprises the color filter according to the present invention described above, a counter substrate, and a liquid crystal layer formed between the color filter and the counter substrate. The liquid crystal display device of the present invention will be described with reference to the figures. Figure 2 is a schematic diagram showing an example of the liquid crystal display device of the present invention. As illustrated in Figure 2, the liquid crystal display device 40 of the present invention has a color filter 10, a counter substrate 20 having a TFT array substrate or the like, and a liquid crystal layer 30 formed between the color filter 10 and the counter substrate 20. It should be noted that the liquid crystal display device of the present invention is not limited to the configuration shown in Figure 2, and can be configured in a way that is generally known as a liquid crystal display device using a color filter.

[0182] The driving method for the liquid crystal display device of the present invention is not particularly limited, and any driving method commonly used in liquid crystal display devices can be employed. Examples of such driving methods include the TN method, IPS method, OCB method, and MVA method. Any of these methods can be suitably used in the present invention. Furthermore, the opposing substrate can be appropriately selected and used depending on the driving method of the liquid crystal display device of the present invention. Furthermore, as the liquid crystals constituting the liquid crystal layer, various liquid crystals with different dielectric anisotropy, and mixtures thereof, can be used depending on the driving method of the liquid crystal display device of the present invention.

[0183] As for the method of forming the liquid crystal layer, methods generally used for manufacturing liquid crystal cells can be used, such as the vacuum injection method or the liquid crystal drop method. After forming the liquid crystal layer by the above method, the sealed liquid crystal can be aligned by slowly cooling the liquid crystal cell to room temperature.

[0184] [Organic light-emitting display device] The organic light-emitting display device according to the present invention comprises the color filter according to the present invention described above and an organic light-emitting element. The organic light-emitting display device of the present invention will be described with reference to the figures. Figure 3 is a schematic diagram showing an example of the organic light-emitting display device of the present invention. As illustrated in Figure 3, the organic light-emitting display device 100 of the present invention has a color filter 10 and an organic light-emitting element 80. An organic protective layer 50 or an inorganic oxide film 60 may be provided between the color filter 10 and the organic light-emitting element 80.

[0185] Examples of methods for laminating the organic light-emitting element 80 include sequentially forming a transparent anode 71, a hole injection layer 72, a hole transport layer 73, a light-emitting layer 74, an electron injection layer 75, and a cathode 76 on the upper surface of a color filter, or laminating an organic light-emitting element 80 formed on a separate substrate onto an inorganic oxide film 60. The transparent anode 71, hole injection layer 72, hole transport layer 73, light-emitting layer 74, electron injection layer 75, cathode 76, and other components of the organic light-emitting element 80 can be those of known origin or design. The organic light-emitting display device 100 thus fabricated can be applied to both passively driven organic EL displays and actively driven organic EL displays, for example. It should be noted that the organic light-emitting display device of the present invention is not limited to the configuration shown in Figure 3, and can be configured in a way that is generally known as an organic light-emitting display device using a color filter. [Examples]

[0186] The present invention will be described in detail below with reference to examples. These descriptions are not intended to limit the present invention. The acid values ​​of the graft copolymer and block copolymer were determined according to the measurement method described in the specification of the present invention. The weight-average molecular weight (Mw) and Mw / Mn of the graft copolymer and block copolymer were determined as standard polystyrene equivalent values ​​by GPC (gel permeation chromatography) according to the measurement method described in the specification of the present invention. The following examples 20 and 21 are referred to as Reference Examples 20 and 21, respectively.

[0187] (Synthesis Example 1: Preparation of Acidic Dispersant 1) In a reactor equipped with a condenser, an additive funnel, a nitrogen inlet, a mechanical stirrer, and a digital thermometer, 150.0 parts by mass of PGMEA, 3.0 parts of iodine, 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile) (trade name: V-70, manufactured by Wako Pure Chemical Industries, Ltd.), 50.2 parts by mass of methyl methacrylate (MMA), 8.4 parts by mass of n-butyl methacrylate (BMA), 25.1 parts by mass of benzyl methacrylate (BzMA), and 0.04 parts by mass of succinimide were charged. The mixture was stirred at 40°C for 5 hours under a nitrogen stream to produce the copolymer of block B. Next, 16.3 parts by mass of methacrylic acid (MAA) was added and the mixture was stirred at 40°C for 5 hours. The solid content was measured, and the polymerization conversion rate was calculated from the non-volatile content to be 99%. This reaction solution was reprecipitated with 3000 parts by mass of hexane to obtain 99.0 parts by mass of AB block copolymer. The acidic dispersant 1 thus obtained had a weight-average molecular weight (Mw) of 8300, an Mw / Mn ratio of 1.2, and an acid value of 80 mgKOH / g.

[0188] (Synthesis Example 2: Preparation of Acidic Dispersant 2) The preparation was carried out in the same manner as in Synthesis Example 1, except that instead of 16.3 parts by mass of MAA, the constituent monomer of block A in Synthesis Example 1, 9.9 parts by mass of MAA and 6.4 parts by mass of 2-methacryloyloxyethyl succinic acid (2-MOES) were used. The resulting acidic dispersant 2 had a weight-average molecular weight (Mw) of 8300, an Mw / Mn ratio of 1.2, and an acid value of 80 mgKOH / g.

[0189] (Synthesis Example 3: Preparation of Acidic Dispersant 3) (1) Production of macromonomer m1 In a reactor equipped with a condenser, an additive funnel, a nitrogen inlet, a mechanical stirrer, and a digital thermometer, 30.0 parts by mass of propylene glycol methyl ether acetate (PGMEA) was charged and heated to 90°C while stirring under a nitrogen stream. A mixed solution of 60.0 parts by mass of methyl methacrylate (MMA), 10.0 parts by mass of butyl methacrylate (BMA), 30.0 parts by mass of benzyl methacrylate (BzMA), 7.0 parts by mass of mercaptopropionic acid, and 1.0 part by mass of α,α'-azobisisobutyronitrile (AIBN) was added dropwise over 1.5 hours, and the reaction was continued for a further 3 hours. After cooling, the reaction solution was diluted with 200 parts by mass of tetrahydrofuran (THF) and reprecipitation with 3000 parts by mass of hexane to obtain 106.0 parts by mass of a white powder. Next, 50.0 parts by mass of this white powder were added to 50.0 parts by mass of PGMEA, 3.7 parts by mass of glycidyl methacrylate (GMA), 0.15 parts by mass of N,N-dimethyldodecylamine, and 0.1 parts by mass of p-methoxyphenol. The mixture was stirred at 110°C for 24 hours while bubbling air. After cooling, the reaction solution was reprecipitated with 3000 parts by mass of hexane to obtain 52.0 parts by mass of macromonomer m1. The obtained macromonomer m1 was examined by GPC (gel permeation chromatography) under the conditions of N-methylpyrrolidone, 0.01 mol / L lithium bromide addition, and polystyrene standard. The weight-average molecular weight (Mw) was 4800 and the molecular weight distribution (Mw / Mn) was 1.6.

[0190] (2) Production of acidic dispersant 3 In a reactor equipped with a condenser, an additive funnel, a nitrogen inlet, a mechanical stirrer, and a digital thermometer, 100.0 parts by mass of PGMEA were charged, and the mixture was heated to 85°C while stirring under a nitrogen stream. A mixed solution of 83.7 parts by mass of the macromonomer m1, 9.9 parts by mass of methacrylic acid (MAA), 6.4 parts by mass of 2-methacryloyloxyethyl succinic acid (2-MOES), 1.3 parts by mass of n-dodecyl mercaptan, 50.0 parts by mass of PGMEA, and 1.0 part by mass of AIBN was added dropwise over 1.5 hours, and the mixture was heated and stirred for 3 hours. Then, a mixed solution of 0.10 parts by mass of AIBN and 6.0 parts by mass of PGMEA was added dropwise over 10 minutes, and the mixture was further aged at the same temperature for 1 hour. After cooling, the reaction solution was reprecipitated with 3000 parts by mass of hexane to obtain 399.0 parts by mass of an acidic dispersant. The obtained acidic dispersant 3 had a weight-average molecular weight (Mw) of 14300, an Mw / Mn ratio of 2.5, and an acid value of 80 mgKOH / g.

[0191] (Synthesis Example 4: Preparation of Acidic Dispersant 4) (1) Production of block copolymer D4 Referring to Synthesis Example 6 described in Japanese Patent No. 5895925, a 40% PGMEA solution of a diblock copolymer was obtained, comprising a block containing 50 parts by mass of methyl methacrylate (MMA), 30 parts by mass of n-butyl methacrylate (BMA), and 20 parts by mass of benzyl methacrylate (BzMA), and a block containing 25 parts by mass of glycidyl methacrylate (GMA). The obtained block copolymer D4 had a mass-average molecular weight (Mw) of 9470, a number-average molecular weight (Mn) of 7880, and a molecular weight distribution (Mw / Mn) of 1.20. (2) Production of acidic dispersant 4 In a reactor, 100.0 parts by mass of block copolymer D4, 86.70 parts by mass of PGMEA, and 8.90 parts by mass of phenylphosphonic acid (PPA) were charged and stirred at 90°C for 2 hours to obtain acidic dispersant 4. The progress of the esterification reaction between GMA and PPA in block copolymer D4 was determined by acid value measurement and 1 This was confirmed by 1H-NMR measurement. The acid value of the obtained acidic dispersant 4 was 65 mgKOH / g.

[0192] (Synthesis Example 5: Preparation of Alkali-Soluble Resin Solution) In a reactor equipped with a condenser, an additive funnel, a nitrogen inlet, a mechanical stirrer, and a digital thermometer, 300 parts by mass of PGMEA were charged. The temperature was raised to 100°C under a nitrogen atmosphere, and then 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 NOF Corporation), and 2 parts by mass of a chain transfer agent (n-dodecyl mercaptan) were continuously added dropwise over 1.5 hours. The reaction was then continued while maintaining the temperature at 100°C, and 2 hours after the completion of the dropwise addition of the main chain forming mixture, 0.1 parts by mass of p-methoxyphenol was added as a polymerization inhibitor to stop the polymerization. Next, while blowing air in, 20 parts by mass of glycidyl methacrylate (GMA) as an epoxy group-containing compound was added, the temperature was raised to 110°C, and then 0.8 parts by mass of triethylamine was added and the addition reaction was carried out at 110°C for 15 hours to obtain an alkali-soluble resin solution (weight-average molecular weight (Mw) 8500, acid value 75 mg KOH / g, solid content 40% by mass).

[0193] (Synthesis Example 6: Preparation of Compound IA) (1) Synthesis of intermediate IA1 In a 500 ml four-necked flask, 0.2 mol of diphenylthioether, 30.22 mol of pulverized AlCl, and 150 ml of dichloroethane were added and stirred. Argon gas was then passed through the mixture and cooled in an ice bath until the temperature dropped to 0°C. At this point, a solution consisting of 0.22 mol of cyclohexylpropionyl chloride and 42 g of dichloroethane was added dropwise, gradually increasing the temperature to below 10°C over approximately 1.5 hours. The temperature was then raised to 15°C and stirred for another 2 hours before the reaction mixture was drained. The reaction mixture was gradually added to a dilute hydrochloric acid solution containing 400g of ice and 65ml of concentrated hydrochloric acid under stirring. The lower layer was separated using a separatory funnel, and the upper layer was extracted with 50ml of dichloroethane. The extract and the lower layer were then combined. The mixture was then washed with a NaHCO3 solution containing 100g of NaHCO3 and 200g of water, and further washed three times with 200ml of water until the pH was neutral. After drying with 60g of anhydrous MgSO4 to remove moisture, the dichloroethane was evaporated by rotary evaporation. The solid powder remaining in the rotary evaporator was placed in 200ml of petroleum ether, filtered by suction, and then added to 150ml of anhydrous ethanol, heated, and refluxed. After cooling to room temperature, it was further cooled with ice for 2 hours, filtered by suction, and dried in a 50°C oven for 2 hours to obtain the intermediate IA1 described below.

[0194] [ka]

[0195] (2) Synthesis of intermediate IA2 42 g of the intermediate IA1, 400 g of tetrahydrofuran, 200 g of concentrated hydrochloric acid, and 24.2 g of isoamyl nitrite were added to a 500 ml four-necked flask, and the mixture was stirred at room temperature for 5 hours before the reaction solution was drained. The reaction mixture was placed in a large beaker, 1000 ml of water was added and stirred, then allowed to stand overnight to separate into layers, yielding a yellow, viscous liquid. The viscous liquid was extracted with dichloroethane, 50 g of anhydrous MgSO4 was added and dried, then suction filtration was performed, and the filtrate was rotated and evaporated to remove the solvent, yielding an oily viscosity. Subsequently, this viscosity was placed in 150 ml of petroleum ether, stirred, precipitated, and suction filtration was performed to obtain a white powdery solid. After that, it was dried at 60°C for 5 hours to obtain the intermediate IA2 described below.

[0196] [ka]

[0197] (3) Synthesis of compound IA In a 1000 ml four-necked flask, 34 g of the intermediate IA2, 350 ml of dichloroethane, and 12.7 g of triethylamine were added and stirred. The mixture was cooled in an ice bath, and when the temperature dropped to 0°C, a solution consisting of 15.7 g of acetate chloride and 15 g of dichloroethane was added dropwise, over approximately 1.5 hours. After stirring for another hour, 500 ml of cold water was added dropwise, and the mixture was separated using a separatory funnel. The mixture was washed once with 200 ml of 5% NaHCO3 solution, then twice with 200 ml of water until the pH was neutral, then once with dilute hydrochloric acid (20 g of concentrated hydrochloric acid and 400 ml of water), followed by three washes with 200 ml of water. The mixture was then dried over 100 g of anhydrous MgSO4, and the solvent was removed by rotary evaporation to obtain a viscous liquid. An appropriate amount of methanol was added to the viscous liquid, and the resulting white solid was filtered and dried to obtain compound IA. The molecular weight of compound IA is 395.51.

[0198] [ka]

[0199] (Synthesis Example 7: Preparation of Compound IB) (1) Synthesis of intermediate IB1 0.60 mol of fluorene, 2.4 mol of potassium hydroxide, and 0.06 mol of potassium iodide were dissolved in 500 ml of anhydrous dimethyl sulfoxide under a nitrogen atmosphere and maintained at 15°C. 1.33 mol of bromobutane was gradually added over 2 hours, and the reaction mixture was stirred at 15°C for 1 hour. Then, 2 L of distilled water was added to the reaction mixture and stirred for about 30 minutes. The product was extracted with 2 L of dichloromethane, and the extracted organic layer was washed twice with 2 L of distilled water. Next, the recovered organic layer was dried over anhydrous MgSO4, and the solvent was distilled under reduced pressure. The product obtained was purified by silica gel column chromatography (developing solvent: ethyl acetate:n-hexane = 1:20) to obtain the following intermediate IB1.

[0200] [ka]

[0201] (2) Synthesis of intermediate IB2 The aforementioned intermediate IB1 (0.11 mol) was dissolved in 500 ml of dichloromethane and cooled to -5°C. Then, 30.13 mol of AlCl was gradually added, and a solution consisting of 15 ml of dichloromethane and 0.13 mol of cyclohexylpropionyl chloride was gradually added dropwise over 1 hour to prevent the temperature of the reactants from rising, and the mixture was stirred at -5°C for 1 hour. After that, the reactants were gradually poured into 500 ml of ice water and stirred for 30 minutes, and the organic layer was washed with 200 ml of distilled water. Next, the recovered organic layer was distilled under reduced pressure, and the product obtained was purified by silica gel column chromatography (developing solvent: ethyl acetate:n-hexane=1:4) to obtain the following intermediate IB2.

[0202] [ka]

[0203] (3) Synthesis of intermediate IB3 The aforementioned intermediate IB2 (0.042 mol) was dissolved in 200 ml of tetrahydrofuran (THF), and 25 ml of 4N HCl dissolved in 1,4-dioxane and 0.063 mol of isobutyl nitrite were added in sequence, and the reaction mixture was stirred at 25°C for 6 hours. Then, 200 ml of ethyl acetate was added to the reaction solution and stirred for 30 minutes to separate the organic layer, which was then washed with 200 ml of distilled water. Next, the recovered organic layer was dried over anhydrous MgSO4, and the solvent was distilled under reduced pressure. The product obtained was purified by silica gel column chromatography (developing solvent: ethyl acetate:n-hexane = 1:4) to obtain the following intermediate IB3.

[0204] [ka]

[0205] (4) Synthesis of compound IB The intermediate IB3 (0.056 mol) was dissolved in 200 ml of N-methyl-2-pyrrolidinone (NMP) under a nitrogen atmosphere and maintained at -5°C. 0.068 mol of triethylamine was added, and the reaction solution was stirred for 30 minutes. Then, a solution consisting of 0.068 mol of acetyl chloride and 10 ml of N-methyl-2-pyrrolidinone was gradually added over 30 minutes, and the mixture was stirred for 30 minutes to prevent the reaction mixture from rising in temperature. Subsequently, 200 ml of distilled water was gradually added to the reaction mixture and stirred for 30 minutes to separate the organic layer. The recovered organic layer was then dried over anhydrous MgSO4, and the solvent was distilled under reduced pressure. The resulting product was recrystallized using 1 L of ethanol and then dried to obtain the compound IB described below.

[0206] [ka]

[0207] (Synthesis Example 8: Synthesis of Compound IC) 35.5 g of fluorene, 120 g of dichloromethane, and 30.1 g of isobutyryl chlorochloride were mixed and cooled to a temperature between -5°C and 0°C. Aluminum trichloride was then added in 10 portions, and the mixture was reacted at 10°C for 6 hours. The resulting reaction solution was poured into a mixture of 50 g of hydrochloric acid and 150 g of ice, to which 150 g of dichloromethane was added and the mixture was stirred for 3 hours. After separation, the organic phase was concentrated, and 150 g of methanol was added to form a solid phase. The mixture was then cooled to crystallize, filtered, and dried to obtain 2-methyl-1-fluorenyl-2-chloro-1-propanone. 27 g of the obtained 2-methyl-1-fluorenyl-2-chloro-1-propanone was placed in a 250 mL three-necked flask, and then 1.76 g of calcium oxide and 7.0 g of sodium methoxide were added. The mixture was reacted at 68 °C for 6 hours to carry out epoxidation. After cooling to 50 °C, 68 g of morpholine was added and the mixture was reacted for 14 hours. Subsequently, the mixture was decolorized with activated carbon and filtered, and then refluxed with a mixed solvent of toluene and methanol to obtain 2-methyl-1-fluorenyl-2-morpholino-1-propanone. 20 g of 2-methyl-1-fluorenyl-2-morpholino-1-propanone, 0.6 g of tetrabutylammonium bromide (TBAB), and 34 g of chlorobutane were mixed and heated to 78°C. 72 g of 50% NaOH aqueous solution was added dropwise, and the reaction was maintained at 82°C for 4 hours. The temperature was then lowered, 50 g of water and 58 g of toluene were added, and the mixture was stirred for 0.5 hours. The resulting organic phase was decolorized using activated carbon, filtered, and then crystallized using a mixed solvent of toluene and methanol. The precipitate was filtered and dried to obtain the compound IC described below. The molecular weight of compound IC is 433.63.

[0208] [ka]

[0209] (Manufacturing Example 1: Manufacturing of colorant dispersion GA-1) As an acidic dispersant, 6.5 parts by mass of acidic dispersant 1 from Synthesis Example 1, 3.9 parts by mass of CI Pigment Green 58 (PG58), 9.1 parts by mass of CI Pigment Yellow 150 (PY150), 80.5 parts by mass of PGMEA, and 100 parts by mass of 2.0 mm particle size zirconia beads were placed in a mayonnaise bottle. For preliminary crushing, the mixture was shaken for 1 hour using a paint shaker (manufactured by Asada Iron Works Co., Ltd.). Then, the 2.0 mm particle size zirconia beads were removed, and 200 parts by mass of 0.1 mm particle size zirconia beads were added. The mixture was similarly dispersed using a paint shaker for 4 hours to obtain colorant dispersion GA-1.

[0210] (Manufacturing Examples 2-4: Manufacturing of colorant dispersions GA-2-4) Colorant dispersions GA-2 to GA-4 were obtained in the same manner as in Production Example 1, except that acidic dispersants 2 to 4 from Synthesis Examples 2 to 4 were used instead of acidic dispersant 1.

[0211] (Manufacturing Example 5: Manufacturing of colorant dispersion GB-1) Colorant dispersion GB-1 was obtained in the same manner as in Production Example 1, except that a basic blocking dispersant (product name LP-N6919, manufactured by Big Chemie Japan Co., Ltd., solid content 60% by mass) was used instead of acidic dispersant 1.

[0212] (Manufacturing Example 6: Manufacturing of colorant dispersion GR-1) As a dispersant, 26.0 parts by mass (10.4 parts by mass of effective solids) of the alkali-soluble resin solution (acidic group-containing random copolymer, 40% by mass of solids) from Synthesis Example 5 was used. As colorants, 3.9 parts by mass of CI Pigment Green 58 (PG58), 9.1 parts by mass of CI Pigment Yellow 150 (PY150), 61.0 parts by mass of PGMEA, and 100 parts by mass of 2.0 mm particle size zirconia beads were placed in a mayonnaise bottle. For preliminary crushing, the mixture was shaken for 1 hour using a paint shaker (manufactured by Asada Iron Works Co., Ltd.). Then, the 2.0 mm particle size zirconia beads were removed, and 200 parts by mass of 0.1 mm particle size zirconia beads were added. The mixture was similarly dispersed using a paint shaker for 4 hours to obtain colorant dispersion GR-1.

[0213] (Example 1: Production of photosensitive colored resin composition 1) 38.34 parts by mass of the colorant dispersion GA-1 obtained in Production Example 1, 3.51 parts by mass of the alkali-soluble resin solution obtained in Synthesis Example 5 (effective solids content 1.41 parts by mass), and a photopolymerizable compound having a caprolactone structure (trade name KAYARAD DPCA-60 (a compound represented by general formula (1-1), where j=2, R i The six of these are the groups represented by the general formula (2) above (m=1, R ii 5.62 parts by mass of (all hydrogen atoms), manufactured by Nippon Kayaku Co., Ltd., 0.45 parts by mass of 2,2',4-tri(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4',5'-diphenyl-1,1'-biimidazole (photoinitiator: trade name TR-HABI-102, manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), 0.30 parts by mass of fluorine-based surfactant (trade name Megafac R-08MH, manufactured by DIC Corporation), and 51.48 parts by mass of PGMEA were added to obtain photosensitive colored resin composition 1.

[0214] (Example 2: Production of photosensitive colored resin composition 2) In Example 1, instead of the photopolymerizable compound having a caprolactone structure (trade name KAYARAD DPCA-60), a photopolymerizable compound having a caprolactone structure (trade name KAYARAD DPCA-20 (a compound represented by general formula (1-1), where j=2, R i The two are the group represented by the general formula (2) above (m=1, R ii A photosensitive colored resin composition 2 was obtained in the same manner as in Example 1, except that equal amounts of (all hydrogen atoms) and (manufactured by Nippon Kayaku Co., Ltd.) were used.

[0215] (Example 3: Production of photosensitive colored resin composition 3) 38.34 parts by mass of the colorant dispersion GA-1 obtained in Production Example 1, 0.88 parts by mass (effective solids content 0.35 parts by mass) of the alkali-soluble resin solution obtained in Synthesis Example 5, 6.68 parts by mass of a photopolymerizable compound having a caprolactone structure (trade name KAYARAD DPCA-60, manufactured by Nippon Kayaku Co., Ltd.), 0.45 parts by mass of 2,2',4-tri(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4',5'-diphenyl-1,1'-biimidazole (photoinitiator: trade name TR-HABI-102, manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), 0.30 parts by mass of a fluorine-based surfactant (trade name Megafac R-08MH, manufactured by DIC Corporation), and 53.06 parts by mass of PGMEA were added to obtain photosensitive colored resin composition 3.

[0216] (Example 4: Production of photosensitive colored resin composition 4) 38.34 parts by mass of the colorant dispersion GA-1 obtained in Production Example 1, 7.03 parts by mass (effective solids content 2.81 parts by mass) of the alkali-soluble resin solution obtained in Synthesis Example 5, 4.22 parts by mass of a photopolymerizable compound having a caprolactone structure (trade name KAYARAD DPCA-60, manufactured by Nippon Kayaku Co., Ltd.), 0.45 parts by mass of 2,2',4-tri(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4',5'-diphenyl-1,1'-biimidazole (photoinitiator: trade name TR-HABI-102, manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), 0.30 parts by mass of a fluorine-based surfactant (trade name Megafac R-08MH, manufactured by DIC Corporation), and 49.38 parts by mass of PGMEA were added to obtain photosensitive colored resin composition 4.

[0217] (Example 5: Production of photosensitive colored resin composition 5) 38.34 parts by mass of the colorant dispersion GA-1 obtained in Production Example 1, 3.51 parts by mass (effective solids content 1.41 parts by mass) of the alkali-soluble resin solution obtained in Synthesis Example 5, 5.62 parts by mass of a photopolymerizable compound having a caprolactone structure (trade name KAYARAD DPCA-60, manufactured by Nippon Kayaku Co., Ltd.), 0.31 parts by mass of 2,2',4-tri(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4',5'-diphenyl-1,1'-biimidazole (photoinitiator: trade name TR-HABI-102, manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), 0.13 parts by mass of compound IA obtained in Synthesis Example 6, 0.30 parts by mass of a fluorine-based surfactant (trade name Megafac R-08MH, manufactured by DIC Corporation), and 51.48 parts by mass of PGMEA were added to obtain photosensitive colored resin composition 5.

[0218] (Example 6: Production of photosensitive colored resin composition 6) In Example 5, a photosensitive colored resin composition 6 was obtained in the same manner as in Example 5, except that 0.13 parts by mass of compound IB obtained in Synthesis Example 7 was used instead of 0.13 parts by mass of compound IA obtained in Synthesis Example 6.

[0219] (Example 7: Production of photosensitive colored resin composition 7) In Example 5, a photosensitive colored resin composition 7 was obtained in the same manner as in Example 5, except that the colorant dispersion GA-1 was replaced with the colorant dispersion GA-2 obtained in Production Example 2.

[0220] (Example 8: Production of photosensitive colored resin composition 8) In Example 5, a photosensitive colored resin composition 8 was obtained in the same manner as in Example 5, except that the colorant dispersion GA-1 was replaced with the colorant dispersion GA-3 obtained in Production Example 3.

[0221] (Example 9: Production of photosensitive colored resin composition 9) In Example 5, a photosensitive colored resin composition 9 was obtained in the same manner as in Example 5, except that the colorant dispersion GA-1 was replaced with the colorant dispersion GA-4 obtained in Production Example 4.

[0222] (Example 10: Production of photosensitive colored resin composition 10) 38.34 parts by mass of the colorant dispersion GA-1 obtained in Production Example 1, 3.36 parts by mass (effective solids content 1.35 parts by mass) of the alkali-soluble resin solution obtained in Synthesis Example 5, 5.38 parts by mass of a photopolymerizable compound having a caprolactone structure (trade name KAYARAD DPCA-60, manufactured by Nippon Kayaku Co., Ltd.), 0.52 parts by mass of 2,2',4-tri(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4',5'-diphenyl-1,1'-biimidazole (photoinitiator: trade name TR-HABI-102, manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), 0.22 parts by mass of compound IC obtained in Synthesis Example 8, 0.30 parts by mass of a fluorine-based surfactant (trade name Megafac R-08MH, manufactured by DIC Corporation), and 51.57 parts by mass of PGMEA were added to obtain a photosensitive colored resin composition 10.

[0223] (Example 11: Production of photosensitive colored resin composition 11) In Example 10, a photosensitive colored resin composition 11 was obtained in the same manner as in Example 10, except that the colorant dispersion GA-1 was replaced with the colorant dispersion GA-2 obtained in Production Example 2.

[0224] (Example 12: Production of photosensitive colored resin composition 12) In Example 10, a photosensitive colored resin composition 12 was obtained in the same manner as in Example 10, except that the colorant dispersion GA-1 was replaced with the colorant dispersion GA-3 obtained in Production Example 3.

[0225] (Example 13: Production of photosensitive colored resin composition 13) In Example 10, a photosensitive colored resin composition 13 was obtained in the same manner as in Example 10, except that the colorant dispersion GA-1 was replaced with the colorant dispersion GA-4 obtained in Production Example 4.

[0226] (Example 14: Production of photosensitive colored resin composition 14) 38.34 parts by mass of the colorant dispersion GA-1 obtained in Production Example 1, 3.36 parts by mass of the alkali-soluble resin solution obtained in Synthesis Example 5 (effective solids content 1.35 parts by mass), and a photopolymerizable compound having a caprolactone structure (trade name KAYARAD 5.38 parts by mass of DPCA-60 (manufactured by Nippon Kayaku Co., Ltd.), 0.30 parts by mass of 2,2',4-tri(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4',5'-diphenyl-1,1'-biimidazole (photoinitiator: trade name TR-HABI-102, manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), 0.22 parts by mass of compound IA obtained in Synthesis Example 6, 0.22 parts by mass of compound IC obtained in Synthesis Example 8, 0.30 parts by mass of fluorine-based surfactant (trade name Megafac R-08MH, manufactured by DIC Corporation), and 51.57 parts by mass of PGMEA were added to obtain photosensitive colored resin composition 14.

[0227] (Example 15: Production of photosensitive colored resin composition 15) In Example 14, a photosensitive colored resin composition 15 was obtained in the same manner as in Example 14, except that the colorant dispersion GA-1 was replaced with the colorant dispersion GA-2 obtained in Production Example 2.

[0228] (Example 16: Production of photosensitive colored resin composition 16) In Example 14, a photosensitive colored resin composition 16 was obtained in the same manner as in Example 14, except that the colorant dispersion GA-1 was replaced with the colorant dispersion GA-3 obtained in Production Example 3.

[0229] (Example 17: Production of photosensitive colored resin composition 17) In Example 14, a photosensitive colored resin composition 17 was obtained in the same manner as in Example 14, except that the colorant dispersion GA-1 was replaced with the colorant dispersion GA-4 obtained in Production Example 4.

[0230] (Example 18: Manufacture of photosensitive colored resin composition 18) 38.34 parts by mass of the colorant dispersion GA-1 obtained in Production Example 1, 3.51 parts by mass of the alkali-soluble resin solution obtained in Synthesis Example 5 (effective solids content 1.41 parts by mass), and a photopolymerizable compound having a caprolactone structure (trade name KAYARAD 3.94 parts by mass of DPCA-60 (manufactured by Nippon Kayaku Co., Ltd.), 1.69 parts by mass of a photopolymerizable compound without a caprolactone structure (trade name Aronics M-403, manufactured by Toagosei Co., Ltd.), 0.45 parts by mass of 2,2',4-tri(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4',5'-diphenyl-1,1'-biimidazole (photoinitiator: trade name TR-HABI-102, manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), 0.30 parts by mass of a fluorine-based surfactant (trade name Megafac R-08MH, manufactured by DIC Corporation), and 51.48 parts by mass of PGMEA were added to obtain a photosensitive colored resin composition 18.

[0231] (Example 19: Production of photosensitive colored resin composition 19) In Example 18, a photosensitive colored resin composition 19 was obtained in the same manner as in Example 18, except that instead of 3.94 parts by mass of a photopolymerizable compound having a caprolactone structure (trade name KAYARAD DPCA-60, manufactured by Nippon Kayaku Co., Ltd.) and 1.69 parts by mass of a photopolymerizable compound without a caprolactone structure (trade name Aronix M-403, manufactured by Toagosei Co., Ltd.), the composition was changed to 2.25 parts by mass of a photopolymerizable compound having a caprolactone structure (trade name KAYARAD DPCA-60, manufactured by Nippon Kayaku Co., Ltd.) and 3.37 parts by mass of a photopolymerizable compound without a caprolactone structure (trade name Aronix M-403, manufactured by Toagosei Co., Ltd.).

[0232] (Example 20: Production of photosensitive colored resin composition 20) In Example 1, a photosensitive colored resin composition 20 was obtained in the same manner as in Example 1, except that instead of 38.34 parts by mass of the colorant dispersion GA-1 obtained in Production Example 1, 26.83 parts by mass of the colorant dispersion GA-1 obtained in Production Example 1 and 11.50 parts by mass of the colorant dispersion GB-1 obtained in Production Example 5 were used.

[0233] (Example 21: Production of photosensitive colored resin composition 21) In Example 1, a photosensitive colored resin composition 21 was obtained in the same manner as in Example 1, except that instead of 38.34 parts by mass of the colorant dispersion GA-1 obtained in Production Example 1, 15.33 parts by mass of the colorant dispersion GA-1 obtained in Production Example 1 and 23.00 parts by mass of the colorant dispersion GB-1 obtained in Production Example 5 were used.

[0234] (Comparative Example 1: Production of Comparative Photosensitive Colored Resin Composition 1) A comparatively photosensitive colored resin composition 1 was obtained in the same manner as in Example 1, except that in Example 1, 38.34 parts by mass of colorant dispersion GB-1 obtained in Production Example 5 was replaced with 38.34 parts by mass of colorant dispersion GB-1 obtained in Production Example 5 instead of 38.34 parts by mass of colorant dispersion GA-1 obtained in Production Example 1.

[0235] (Comparative Example 2: Production of Comparative Photosensitive Colored Resin Composition 2) A comparatively photosensitive colored resin composition 2 was obtained in the same manner as in Example 1, except that 5.62 parts by mass of a photopolymerizable compound without a caprolactone structure (trade name Aronix M-403, manufactured by Toagosei Co., Ltd.) was replaced with 5.62 parts by mass of a photopolymerizable compound without a caprolactone structure (trade name Aronix M-403, manufactured by Toagosei Co., Ltd.) in the same manner as in Example 1.

[0236] (Comparative Example 3: Production of Comparative Photosensitive Colored Composition 3) 38.34 parts by mass of the colorant dispersion GR-1 obtained in Production Example 6, 0.42 parts by mass of the alkali-soluble resin solution obtained in Synthesis Example 5 (effective solids content 0.17 parts by mass), and a photopolymerizable compound having a caprolactone structure (trade name KAYARAD DPCA-60 (a compound represented by general formula (1-1), where j=2, R i The six of these are the groups represented by the general formula (2) above (m=1, R iiA comparatively photosensitive colored composition 3 was obtained by adding 5.39 parts by mass of (all hydrogen atoms), manufactured by Nippon Kayaku Co., Ltd., 0.42 parts by mass of 2,2',4-tri(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4',5'-diphenyl-1,1'-biimidazole (photoinitiator: trade name TR-HABI-102, manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), 0.30 parts by mass of a fluorine-based surfactant (trade name Megafac R-08MH, manufactured by DIC Corporation), and 54.84 parts by mass of PGMEA.

[0237] [Evaluation Method] <Fine pattern formation> The photosensitive colored resin compositions obtained in the examples and comparative examples were each coated onto a glass substrate ("NA35" manufactured by NH Techno Glass Co., Ltd.) using a spin coater to a thickness that would form a colored layer with a thickness of 2.0 μm after post-baking. The colored layer was then dried on a hot plate at 80°C for 3 minutes to form a colored layer on the glass substrate. A high-pressure mercury lamp at 60 mJ / cm² was used on this colored layer through a photomask with a 20 μm opening. 2 The substrate was irradiated with ultraviolet light. Subsequently, the glass substrate on which the colored layer was formed was shower-developed for 60 seconds using a 0.05% by mass potassium hydroxide aqueous solution as an alkaline developer, and then post-baked in a clean oven at 230°C for 30 minutes to create a colored substrate with an independent fine-line pattern. The width of the fine-line pattern of the formed colored layer was measured at five locations using an optical microscope, and the amount of line width shift was evaluated by the difference between the average line width and the mask aperture. (Evaluation Criteria) 5: The line width shift was less than 1.0 μm. 4: The line width shift was between 1.0 μm and 1.5 μm. 3: The line width shift was between 1.5 μm and 2.0 μm. 2: The line width shift was between 2.0 μm and less than 3.0 μm. 1: The line width shift was 3.0 μm or more.

[0238] <Substrate adhesion> The photosensitive colored resin compositions obtained in the examples and comparative examples were each coated onto a glass substrate ("NA35" manufactured by NH Techno Glass Co., Ltd.) using a spin coater to a film thickness that would form a colored layer with a thickness of 2.0 μm after post-baking. The colored layer was then formed on the glass substrate by drying it at 80°C for 3 minutes using a hot plate. A high-pressure mercury lamp at 60 mJ / cm² was used to form independent fine lines on this colored layer using a photomask with an aperture size of 2 μm to 100 μm. 2 The substrate was irradiated with ultraviolet light. Subsequently, the glass substrate on which the colored layer had formed was shower-developed for 60 seconds using a 0.05% by mass potassium hydroxide aqueous solution as an alkaline developer to form an independent fine-line pattern. The resulting colored layer was then observed with an optical microscope to determine the minimum micrometer size of the mask opening that remained in close contact with the pattern and to confirm the line width of the finest pattern. (Evaluation Criteria) 5: The pattern remains visible even with a mask opening of 4 μm or less (the line width of the thinnest pattern is 3 μm or less). 4: The thinnest pattern line width is 4 μm to 5 μm or less. 3: The thinnest pattern line width is 6 μm to 10 μm or less. 2: The line width of the thinnest pattern is 11 μm to 15 μm or less. 1: The line width of the thinnest pattern is greater than 15 μm.

[0239] <Development Time Evaluation> The photosensitive colored resin compositions obtained in the examples and comparative examples were each coated onto a glass substrate ("NA35" manufactured by NH Techno Glass Co., Ltd.) using a spin coater to a thickness that would form a colored layer with a thickness of 2.0 μm after post-baking. The colored layer was then dried on a hot plate at 80°C for 3 minutes to form a colored layer on the glass substrate. A high-pressure mercury lamp at 60 mJ / cm² was used on this colored layer via a photomask. 2 The glass substrate was irradiated with ultraviolet light. Subsequently, the glass substrate on which the colored layer was formed was shower-developed for 60 seconds using a 0.05% by mass potassium hydroxide aqueous solution as the alkaline developer. The time until the colored layer was completely dissolved and the glass surface in the area where the colored layer was formed was exposed was measured as the development time. (Evaluation Criteria) 5. The time it took for the glass surface to appear was 15 seconds or less. 4. The time it took for the glass surface to appear was 15 seconds or less than 30 seconds. 3: The time it took for the glass surface to appear was more than 30 seconds, but less than or equal to 45 seconds. 2: The time it took for the glass surface to appear was more than 45 seconds, but less than or equal to 60 seconds. 1: The glass surface did not appear.

[0240] <developing residue> The photosensitive colored resin compositions obtained in the examples and comparative examples were each applied to a glass substrate ("NA35" manufactured by NH Techno Glass Co., Ltd.) using a spin coater to a film thickness that would form a colored layer with a thickness of 2.0 μm after post-baking. The colored layer was then formed on the glass substrate by drying it at 100°C for 3 minutes using a hot plate. A high-pressure mercury lamp at 60 mJ / cm² was used on this colored layer through a photomask with a 90 μm opening. 2 The glass substrate was irradiated with ultraviolet light. Subsequently, the glass substrate on which the above-mentioned colored layer was formed was shower-developed for 60 seconds using a 0.05% by mass potassium hydroxide aqueous solution as the alkaline developer to form an independent fine-line pattern, and the presence or absence of development residue on the glass substrate was checked. Development residue was evaluated with 100% defined as the presence of residue in the entire area of ​​the 7cm x 7cm portion of a 10cm x 10cm glass substrate, excluding the 1.5cm wide outer perimeter. (Evaluation Criteria) 5. No development residue is generated on the glass substrate. 4: Less than 10% of the development residue was generated on the glass substrate. 3: Development residue of 10% or more but less than 15% was generated on the glass substrate. 2: Development residue of 15% or more and less than 30% was generated on the glass substrate. 1: More than 30% of the development residue was generated on the glass substrate.

[0241] <Solvent resistance> The photosensitive colored resin compositions obtained in the examples and comparative examples were each applied to a glass substrate ("NA35" manufactured by NH Techno Glass Co., Ltd.) using a spin coater to a film thickness that would form a colored layer with a thickness of 2.0 μm after post-baking. The colored layer was then dried on a hot plate at 80°C for 3 minutes to form a colored layer on the glass substrate. A high-pressure mercury lamp at 60 mJ / cm² was used to test this colored layer. 2 Ultraviolet light was applied. Next, the colored substrate was post-baked in a clean oven at 230°C for 30 minutes to create a colored substrate. The prepared colored substrates were immersed in N-methylpyrrolidone (NMP) at 60°C for 5 minutes, and the color change (ΔEab) before and after immersion was evaluated. (Evaluation Criteria) 5: ΔEab was less than 1. 4: ΔEab was between 1 and 1.5. 3: ΔEab was between 1.5 and 2. 2: ΔEab was greater than or equal to 2 and less than 3. 1: ΔEab was 3 or greater.

[0242] <Chipping resistance> The photosensitive colored resin compositions obtained in the examples and comparative examples were each applied to a glass substrate ("NA35" manufactured by NH Techno Glass Co., Ltd.) using a spin coater to a film thickness that would form a colored layer with a thickness of 2.0 μm after post-baking. The colored layer was then dried on the glass substrate at 80°C for 3 minutes using a hot plate. A high-pressure mercury lamp at 60 mJ / cm² was used to illuminate this colored layer through a photomask with a 90 μm opening. 2 The glass substrate was irradiated with ultraviolet light. Subsequently, the glass substrate on which the above colored layer was formed was shower-developed for 60 seconds using a 0.05% by mass potassium hydroxide aqueous solution as an alkaline developer to form an independent fine-line pattern, and the number of pixel defects with missing parts in the pattern on a 10cm × 10cm piece of glass was counted. (Evaluation Criteria) 5. No pixel defects were found. 4. Fewer than 10 pixel defects were identified. 3. More than 10 but less than 25 pixel defects were identified. 2: More than 25 but less than 50 pixel defects were identified. 1: More than 50 pixel defects were identified.

[0243] [Table 1]

[0244] [Table 2]

[0245] <Summary of Results> In Comparative Example 1, where only a basic dispersant was used as the photopolymerizable compound, the adhesion of the independent nano-line pattern to the substrate was poor. Furthermore, although an acidic dispersant similar to that used in the present invention was used as a dispersant, in Comparative Example 2, which used only photopolymerizable compounds that do not have a caprolactone structure as the photopolymerizable compound, the desired fine pattern could not be formed. Furthermore, although a photopolymerizable compound having a caprolactone structure was used as the photopolymerizable compound, in Comparative Example 3, where an acidic group-containing random copolymer was used as the dispersant, pigment dispersion in the colorant dispersion was difficult unless the amount added was increased. In Comparative Example 3, the adhesion of the independent fine line pattern to the substrate was poor, and the desired fine pattern could not be formed. It is presumed that when an acidic group-containing random copolymer was used as the dispersant, the substrate adhesion was weakened due to the randomly arranged acidic groups. In addition, it is presumed that because the amount of acidic group-containing random copolymer (alkali-soluble resin) added as a dispersant had to be increased, the curable component was relatively reduced, making it impossible to form the desired fine pattern and increasing the likelihood of chipping.

[0246] In contrast, in the embodiment corresponding to the photosensitive colored resin composition of the present invention, which uses a photopolymerizable compound having a caprolactone structure as the photopolymerizable compound and an acidic dispersant as the dispersant, it was possible to form a colored layer with a fine pattern that had good adhesion to the substrate, while shortening the development time and suppressing the generation of development residue. A comparison of Example 1 and Comparative Example 2 revealed that even when using the same acidic dispersant, combining it with a photopolymerizable compound having a caprolactone structure improves development time and development residue. Furthermore, a comparison of Example 1 and Comparative Example 1 revealed that even when using photopolymerizable compounds having the same caprolactone structure, combining them with an acidic dispersant improves development time and development residue. [Explanation of symbols]

[0247] 1 circuit board 2. Light-shielding part 3 Colored layer 10 Color Filters 20 Opposing substrate 30 liquid crystal layers 40 LCD display device 50 Organic protective layer 60 Inorganic oxide film 71 Transparent anode 72 Hole injection layer 73 Hole transport layer 74. Emitting layer 75 Electron injection layer 76 Cathode 80 Organic light-emitting materials 100 Organic Light-Emitting Display Devices

Claims

1. It contains a colorant, a dispersant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a solvent. The dispersant is an acidic dispersant containing only one of the following: a graft copolymer having a structural unit represented by the following general formula (I) and a structural unit represented by the following general formula (II); and a block copolymer having an A block containing the structural unit represented by the following general formula (I). A photosensitive colored resin composition in which the photopolymerizable compound is a photopolymerizable compound having a ring-opened ε-caprolactone structure, and contains a compound represented by the following general formula (1). 【Chemistry 1】 (In general formula (I), R １ (where represents a hydrogen atom or a methyl group, L represents a direct bond or a divalent linking group, and Q represents an acidic group.) 【Chemistry 2】 (In general formula (II), R 1' represents a hydrogen atom or a methyl group, L' represents a direct bond or a divalent linking group, and Polymer represents a polymer chain.) 【Transformation 3】 (In general formula (1), A is an n-valent alcohol residue, and the polyhydric alcohol that induces the n-valent alcohol residue A is dipentaerythritol, R ｉ Each of these is independently a group represented by the following general formula (2) or a group represented by the following general formula (3), R ｉ At least two of these are bases represented by the following general formula (2), where n is an integer of 6. 【Chemistry 4】 (In general formulas (2) and (3), R ｉｉ Each of these independently represents a hydrogen atom or a methyl group, m represents a number of 1 or 2, and * represents a bond.

2. The photosensitive colored resin composition according to claim 1, wherein the dispersant contains only an acidic dispersant containing at least one of the following: a graft copolymer having a structural unit represented by the following general formula (I-1), a structural unit represented by the following general formula (I-2), and a structural unit represented by the following general formula (II); and a block copolymer having an A block containing the structural unit represented by the following general formula (I-1) and a structural unit represented by the following general formula (I-2). 【Transformation 5】 (In general formulas (I-1) and (I-2), R １ Each of these independently represents a hydrogen atom or a methyl group, R ２ R represents an aliphatic hydrocarbon group which may contain an oxygen atom. ３ (This represents an aliphatic hydrocarbon group.)

3. The photosensitive colored resin composition according to claim 1, wherein the dispersant contains only an acidic dispersant containing at least one of a graft copolymer having a structural unit represented by the following general formula (I-3) and a structural unit represented by the general formula (II), and a block copolymer having an A block containing the structural unit represented by the general formula (I-3). 【Transformation 6】 (In general formula (I-3), L １ is a direct bond or a divalent linking group, R １ is a hydrogen atom or a methyl group, R ４ is a hydroxyl group, a hydrocarbon group, -[CH(R ５ )-CH(R ６ )-O] ｘ１ -R ７ , -[(CH ２ ) ｙ１ -O] ｚ１ -R ７ , or a monovalent group represented by -O-R ８ , and R ８ is a hydrocarbon group, -[CH(R ５ )-CH(R ６ )-O] ｘ１ -R ７ , -[(CH ２ ) ｙ１ -O] ｚ１ -R ７ , -C(R ９ )(R １０ )-C(R １１ )(R １２ )-OH, or -CH ２ -C(R １３ )(R １４ )-CH ２ -OH, which is a monovalent group. R ５ and R ６ Each is independently a hydrogen atom or a methyl group, R ７ These are hydrogen atoms, hydrocarbon groups, -CHO, -CH ２ CHO, -CO-CH=CH ２ , -CO-C(CH ３ ) = CH ２ or -CH ２ COOR １５ It is a monovalent group represented by R １５ R is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. ９ , R １０ , R １１ , R １２ , R １３ and R １４ Each is independently a hydrogen atom, a hydrocarbon group, or a hydrocarbon group having one or more selected from ether bonds and ester bonds, R ９ and R １１ These may bond to each other to form a ring structure. When the above ring structure is formed, the ring structure may further have substituent R １６ It may have R １６ (x1 is an integer from 1 to 18, y1 is an integer from 1 to 5, and z1 is an integer from 1 to 18.)

4. The photosensitive colored resin composition according to any one of claims 1 to 3, wherein the ratio of the total mass of the alkali-soluble resin to the total mass of the compound represented by general formula (1) as a photopolymerizable compound having a ring-opened ε-caprolactone (alkali-soluble resin / compound represented by general formula (1) as a photopolymerizable compound having a ring-opened ε-caprolactone) is 5% to 67%.

5. The photosensitive colored resin composition according to any one of claims 1 to 4, wherein the photoinitiator contains at least one oxime ester compound represented by the following general formula (A) and an oxime ester compound represented by the following general formula (B). 【Transformation 7】 (In general formula (A), Z １ Z ３ Z ４ and Z ５ Each of these independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or a phenyl group, and the alkyl group, cycloalkyl group, and phenyl group may each be substituted with a substituent selected from the group consisting of a halogen atom, an alkoxy group having 1 to 6 carbon atoms, and a phenyl group. ２ (This represents an alkyl group having 1 to 20 carbon atoms that is substituted with a cycloalkyl group.) 【Transformation 8】 (In general formula (B), R ａ and R ｂ Each is independently a hydrogen atom or an alkyl group, and R ｃ is a hydrocarbon group which may contain at least one divalent linking group selected from a thioether bond (-S-), an ether bond (-O-), and a carbonyl bond (-CO-), and Z is a hydrogen atom or -(C=O)R ｄ And R ｄ R is a hydrocarbon group which may contain at least one selected from oxygen atoms and sulfur atoms, or a heterocyclic group which does not contain a nitrogen atom and contains at least one selected from oxygen atoms and sulfur atoms, ｅ (This refers to a hydrocarbon group having 1 to 10 carbon atoms.)

6. The photosensitive colored resin composition according to any one of claims 1 to 5, wherein the photoinitiator contains a compound represented by the following general formula (C). 【Chemistry 9】 (In general formula (C), R ｆ and R ｇ Each of these is independently an alkyl group having between 2 and 8 carbon atoms.

7. The photosensitive colored resin composition according to any one of claims 1 to 6, wherein the photopolymerizable compound further contains a photopolymerizable compound different from the photopolymerizable compound having the caprolactone structure.

8. A cured product of a photosensitive colored resin composition according to any one of claims 1 to 7.

9. A color filter comprising at least a substrate and a colored layer provided on the substrate, wherein at least one of the colored layers is a cured product of the photosensitive colored resin composition described in claim 8.

10. A display device having the color filter described in claim 9.

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