Photosensitive colored resin composition, color filter and display device

Abstract

The photosensitive coloring resin composition of the present invention comprises a colorant, at least one of a block copolymer having an acidic group and a graft copolymer having an acidic group, an alkali-soluble resin of a random copolymer having an acidic group, a photopolymerizable compound, a photoinitiator, and a solvent, wherein the colorant comprises a specific phthalocyanine compound.

Description

Technical Field

[0001] This invention relates to a photosensitive coloring resin composition, a color filter, and a display device. Prior Technology

[0002] In recent years, with the development of personal computers, especially portable personal computers, the demand for LCD monitors has increased. The penetration rate of mobile displays (mobile phones, smartphones, and tablet PCs) has also increased, leading to a gradual expansion of the LCD monitor market. Organic light-emitting display devices, such as organic EL (Electroluminescence) displays, which offer higher visibility due to their self-emissive nature, are also attracting attention as next-generation image display devices. These liquid crystal display devices or organic light-emitting display devices use color filters. For example, the formation of a color image in a liquid crystal display device involves directly coloring the light through a color filter into the colors of each pixel constituting the color filter, and then combining the light of these colors to form a color image. As the light source, in addition to the previously mentioned cold cathode tube, sometimes white-emitting organic light-emitting elements or white-emitting inorganic light-emitting elements are also used. In organic light-emitting display devices, color filters are used to adjust colors, etc.

[0003] Here, a color filter typically has a substrate, a color layer formed on the substrate and containing color patterns of the three primary colors of red, green and blue, and a light-shielding portion formed on the substrate in a manner that divides each color 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 pigment dispersion (formed by dispersing pigments with a dispersant, etc.) to a glass substrate, coating it with the mixture, drying it, exposing it with a photomask, and developing it to form a colored pattern. Heating is then applied to fix the pattern and form the colored layer. These steps are repeated for each color to form a color filter.

[0004] As colorants, pigments are typically used from the perspective of heat resistance and lightfastness. However, pigments are increasingly unable to meet market demands, especially for high brightness. Therefore, dyes are being extensively researched. Dyes excel in improving the hue or brightness of displayed images due to their inherent color purity or the vividness of their hue. On the other hand, dyes generally suffer from poor heat resistance or solvent resistance, and their low solubility in solvents makes them difficult to apply practically. Research is underway on using specific phthalocyanine dyes as dyes for green coloring layers (see, for example, Patent Documents 1-3). Previous technical documents Patent documents

[0005] Patent Document 1: Japanese Patent Application Publication No. 2009-051896 Patent Document 2: Japanese Patent Application Publication No. 2014-125460 Patent Document 3: Japanese Patent No. 2020-42263 Summary of the Invention

[0006] [The problem the invention aims to solve]

[0007] However, it has been found that when the concentration of phthalocyanine dye in the coloring resin compositions described in Patent Documents 1-3 is high, foreign matter precipitates in the obtained colored layer. Patent Document 3 describes a coloring resin composition that aims to form a pattern with sufficient brightness for practical use and suppresses the generation of foreign matter. However, as shown in the comparative examples below, this coloring resin composition has the problem that foreign matter is easily precipitated after the post-baking step, resulting in poor contrast.

[0008] The present invention was made in view of the above-mentioned actual situation, and its object is to provide a photosensitive coloring resin composition that can form a coloring layer that inhibits the precipitation of foreign matter and improves contrast. Furthermore, the present invention aims to provide a color filter and a display device formed using this photosensitive coloring resin composition. [Technical means to solve the problem]

[0009] The photosensitive coloring resin composition of the present invention comprises at least one of a colorant, a block copolymer having acidic groups and a graft copolymer having acidic groups, an alkali-soluble resin of a random copolymer having acidic groups, a photopolymerizable compound, a photoinitiator, and a solvent, and The above-mentioned colorant contains phthalocyanine compounds represented by the following general formula (1).

[0010] [Chemistry 1] (In general formula (1), X1 to X16 independently represent hydrogen atoms, halogen atoms, or -YRD, -Y- represents -O-, -S-, or -NH-, and RD represents a monovalent organic group. Among them, one or more of X1 to X16 represent -YRD.)

[0011] The color filter of the present invention comprises at least a substrate and a coloring layer disposed on the substrate, wherein at least one of the coloring layers is a hardened form of the photosensitive coloring resin composition of the present invention. Furthermore, the present invention provides a display device having the color filter of the present invention described above. [Effects of the Invention]

[0012] According to the present invention, a photosensitive coloring resin composition is provided that can form a coloring layer that inhibits the precipitation of foreign matter and improves contrast. Furthermore, according to the present invention, a color filter and a display device formed using the photosensitive coloring resin composition are provided. Simple Explanation of the Diagram

[0013] Figure 1 is a schematic diagram showing one example of the color filter of the present invention. Figure 2 is a schematic diagram showing an example of the liquid crystal display device of the present invention. Figure 3 is a schematic diagram showing an example of the organic light-emitting display device of the present invention. Implementation

[0014] The photosensitive coloring resin composition, the cured material, the color filter, and the display device of the present invention will be described in detail below. Furthermore, in this invention, light includes electromagnetic waves of wavelengths in both visible and invisible regions, and further includes radiation, such as microwaves and electron beams. Specifically, it refers to electromagnetic waves with wavelengths below 5 μm and electron beams. In this invention, (meth)acrylic acid group represents either acrylonitrile or methacrylic acid group, (meth)acrylic acid group represents either acrylic acid or methacrylic acid group, and (meth)acrylate group represents either acrylate or methacrylate group. Furthermore, the "~" used in this specification to indicate a numerical range is used to include the numerical values ​​before and after it as the lower and upper limits.

[0015] I. Photosensitive coloring resin composition The photosensitive coloring resin composition of the present invention comprises at least one of a colorant, a block copolymer having acidic groups and a graft copolymer having acidic groups, an alkali-soluble resin of a random copolymer having acidic groups, a photopolymerizable compound, a photoinitiator, and a solvent, and The above-mentioned colorant contains phthalocyanine compounds represented by the following general formula (1).

[0016] [Chemistry 2] (In general formula (1), X1 to X16 independently represent hydrogen atoms, halogen atoms, or -YRD, -Y- represents -O-, -S-, or -NH-, and RD represents a monovalent organic group. Among them, one or more of X1 to X16 represent -YRD.)

[0017] The photosensitive coloring resin composition of the present invention can form a coloring layer that inhibits the precipitation of foreign matter and improves contrast by using at least one of a block copolymer having an acidic group and a graft copolymer having an acidic group in combination with the above-mentioned specific phthalocyanine compound. It is presumed that the aforementioned specific phthalocyanine compounds, due to the wider π-electron conjugation and higher planarity of the phthalocyanine ring, are prone to agglomeration through π-π interactions. This agglomeration is easily generated during the baking step after forming a color filter, and the agglomerates readily precipitate on the coating surface, becoming foreign matter. Foreign matter is particularly prone to precipitate in the obtained colored layer when the concentration of the aforementioned specific phthalocyanine compounds is high. At least one acidic dispersant in the block copolymer with an acidic group and the graft copolymer with an acidic group has hydrophobic and hydrophilic (acidic) groups respectively positioned, possessing hydrophobic and hydrophilic portions. Therefore, the hydrophobic to hydrophilic portions of the aforementioned specific acidic dispersant interact strongly with each other relative to the hydrophobic to hydrophilic portions of the substituent -YR D of the aforementioned specific phthalocyanine compound. Furthermore, the acidic dispersant also exhibits good affinity with alkali-soluble resins, thus improving the overall affinity of the resin composition. It is presumed that through these synergistic effects, even when the concentration of the aforementioned specific phthalocyanine compounds is high, the solubility and solubility stability of the aforementioned specific phthalocyanine compounds are also improved, and after the post-baking step, the aggregation of the aforementioned specific phthalocyanine compounds in the coating film is also suppressed, thereby improving the contrast.

[0018] Furthermore, it has been found that the photosensitive coloring resin composition of the present invention, by combining at least one of a block copolymer having an acidic group and a graft copolymer having an acidic group with the aforementioned specific phthalocyanine compound, exhibits improved alkaline developability, i.e., developing speed, and consequently, improved solvent resolvability of the coating film. It is presumed that due to the strong interaction between the aforementioned specific phthalocyanine compound and at least one of the aforementioned block copolymer having an acidic group and a graft copolymer having an acidic group, the aforementioned specific phthalocyanine compound is easily washed away by the developing solution during development, and is also easily dissolved after forming the coating film.

[0019] The photosensitive coloring resin composition of the present invention contains at least one of a colorant, a block copolymer having an acidic group and a graft copolymer having an acidic group, an alkali-soluble resin of a random copolymer having an acidic group, a photopolymerizable compound, a photoinitiator, and a solvent, and may further contain other components within the scope of not impairing the effects of the present invention. The components of the coloring resin composition of this invention will be described in detail below.

[0020] [Colorant] In this invention, the colorant comprises a phthalocyanine compound represented by the above general formula (1). In the phthalocyanine compounds represented by the above general formula (1), X1 to X16 independently represent hydrogen atoms, halogen atoms, or -YRD, -Y- represents -O-, -S-, or -NH-, and RD represents a monovalent organic group. Among them, one or more of X1 to X16 represent -YRD.

[0021] Among X1 to X16, halogen atoms can be exemplified by, for example, fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc. Furthermore, when there are two or more halogen atoms in the above formula (1), these plurality of halogen atoms may be identical or distinct. In terms of hue, the halogen atoms in X1 to X16 preferably include at least fluorine atoms, and more preferably are all fluorine atoms.

[0022] Regarding high brightness, the number of halogen atoms in X1 to X16 is preferably 4 or more, more preferably 6 or more, and even more preferably 7 or more. Furthermore, the number of halogen atoms in X1 to X16 is preferably 12 or less, more preferably 10 or less, and even more preferably 9 or less. The number of halogen atoms in X1 to X16 can be 8. In terms of hue and the region of maximum absorption wavelength, it is preferable that 6 to 10, and further 7 to 9, of X 1 to X 16 are fluorine atoms.

[0023] X1 to X16 can also be hydrogen atoms. The number of hydrogen atoms in X1 to X16 can be selected appropriately according to the hue adjustment, and can be 0 to 8, 0 to 4, or 0 to 2.

[0024] In -YR D, -Y- represents -O-, -S-, or -NH-. For obtaining the desired transmission spectrum, -O- or -S- is preferred, and -O- is even more preferred. Furthermore, when there are two or more -YRDs in the above formula (1), the multiple -YRDs can be the same or different from each other.

[0025] In -YR D, RD stands for monovalent organic group. Here, organic group refers to a group containing a carbon atom. RD can be exemplified by hydrocarbon groups or heterocyclic groups that can have substituents. As hydrocarbon groups, examples include straight-chain, branched, or cyclic aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and combinations thereof. As straight-chain or branched aliphatic hydrocarbon groups, they can be straight-chain or branched aliphatic hydrocarbon groups with 1 to 10 carbon atoms; as cyclic aliphatic hydrocarbon groups, they can be alicyclic hydrocarbon groups with 3 to 20 carbon atoms; as aromatic hydrocarbon groups, they can be aromatic hydrocarbon groups with 6 to 20 carbon atoms; as heterocyclic groups, examples include nitrogen-containing heterocycles, sulfur-containing heterocycles, oxygen-containing heterocycles, etc., and can also be any of aromatic or non-aromatic rings.

[0026] Examples of aliphatic hydrocarbon groups that are straight-chain or branched include methyl, ethyl, propyl, butyl, pentyl, and hexyl; examples of alicyclic hydrocarbon groups include cyclopentyl and cyclohexyl. Furthermore, as aromatic hydrocarbon groups, examples include phenyl, naphthyl, biphenyl, etc. Furthermore, examples of heterocyclic groups include furan rings, thiophene rings, pyrrole rings, 2H-pyran rings, 4H-thiopyran rings, pyridine rings, 1,3-oxazolium rings, isooxazolium rings, 1,3-thiazole rings, isothiazole rings, imidazole rings, pyrazole rings, furazolium rings, pyridine rings, pyrazine rings, and pyrazine rings, etc., which have one free atomic valence.

[0027] When the hydrocarbon group or heterocyclic group of RD has a substituent, examples of such substituents include halogen atoms, -OR d1, -COR d1, -COOR d1 (here, R d1 is a hydrocarbon group or heterocyclic group), and more specifically, examples include alkoxy, aryloxy, acetyl, alkoxycarbonyl, aryloxycarbonyl, etc.

[0028] In terms of controlling crystallinity (inhibiting the precipitation of foreign matter) and imparting solubility during coating hardening (baking), the RD in -YR D is preferably an aromatic hydrocarbon group that can have substituents, preferably a monovalent group represented by the following formula (2).

[0029] [Chemistry 3] In formula (2), -W- represents a single bond or -O-, Rd1 represents an aliphatic hydrocarbon group with 1 to 10 carbon atoms that may have a substituent, an alicyclic hydrocarbon group with 3 to 12 carbon atoms that may have a substituent, or an aromatic hydrocarbon group with 6 to 20 carbon atoms that may have a substituent. Rd2 represents a halogen atom, an alkyl group with 1 to 4 carbon atoms, or an alkoxy group with 1 to 4 carbon atoms. p is an integer from 1 to 3, and q is an integer from 0 to 2. When p is 2 or 3, the plurality of W and Rd1 can be the same or different, and when q is 2, the plurality of Rd2 can be the same or different. -Y- indicates -O-, -S-, or -NH-, and * indicates the bond position with the phthalocyanine skeleton in formula (1).

[0030] In formula (2) above, examples of substituents for the aforementioned aliphatic hydrocarbon group, alicyclic hydrocarbon group, and aromatic hydrocarbon group include alkoxy groups with 1 to 5 carbon atoms and hydroxyl groups. Rd1 is preferably an aliphatic hydrocarbon group with 1 to 10 carbon atoms that can have a substituent, and more preferably an alkyl group with 1 to 10 carbon atoms that can have a substituent. The alkyl group is preferably an alkyl group with 1 to 5 carbon atoms, and more preferably a straight-chain alkyl group with 1 to 5 carbon atoms. When Rd1 is a substituted alkyl group, the substituent is preferably an alkoxy group with 1 to 5 carbon atoms. p is preferably 1 or 2, more preferably 1. When p=1, it is preferable that -CO-WR d1 is bonded to the -O- at bit 3 or bit 4, more preferably bit 4. When p=2, it is preferable that two -CO-WR d1 are bonded to the -O- at bits 3 and 5 or bits 2 and 4, more preferably bits 3 and 5. q is preferably 0 or 1, and even better is 0. In terms of solubility, the above formula (2) can be expressed as the following formula (2').

[0031] [Chemistry 4] (In equation (2'), Y, W, and R d1 are the same as in equation (2).)

[0032] As a preferred specific example of the basis represented by the above formula (2), the bases represented by the following formulas (2-1) to (2-10) can be cited, but are not limited to these.

[0033] [Chemistry 5] (In equations (2-1) to (2-10), -Y- represents -O-, -S-, or -NH-, and * represents the bonding position with the phthalocyanine skeleton in equation (1).)

[0034] Regarding obtaining the desired transmission spectrum (high brightness) and controlling the crystallinity specific to phthalocyanine compounds during coating curing (baking) (inhibition of foreign matter precipitation), the number of -YRD in X1 to X16 is preferably 4 or more, more preferably 6 or more, and even more preferably 7 or more. Furthermore, the number of -YRD in X1 to X16 is preferably 12 or less, more preferably 10 or less, and even more preferably 9 or less. The number of -YRD in X1 to X16 can be 8. In terms of obtaining the desired transmission spectrum (high brightness), it is preferable that at least four of X1 to X16, X2, X3, X6, X7, X10, X11, X14 and X15 are -YRD, and more preferably all of X2, X3, X6, X7, X10, X11, X14 and X15 are radical -YRD, and the remainder (X1, X4, X5, X8, X9, X12, X13 and X16) are halogen atoms.

[0035] As preferred specific examples of phthalocyanine compounds represented by general formula (1), compounds represented by formulas (1-1) to (1-5) below can be cited, but are not limited to these.

[0036] [Chemistry 6]

[0037] [Chemistry 7]

[0038] [Chemistry 8]

[0039] As a method for manufacturing phthalocyanine halide pigments, previously known methods can be appropriately selected. For example, a method that involves cyclizing a phthalonitrile compound with a metal salt in a molten state or in an organic solvent can be preferred, as described in Japanese Patent Application Publication No. 2014-43556 or Japanese Patent Application Publication No. 2020-42263. Regarding the phthalonitrile compound used as the starting material, previously known methods can be appropriately selected for synthesis, or commercially available products can be used.

[0040] In this invention, the colorant may include other colorants in addition to the phthalocyanine compound represented by the above general formula (1). Other pigments are not particularly limited as long as they can achieve the desired color. Various organic pigments, inorganic pigments, dyes, and dye salts can be used alone or in mixtures of two or more. Among them, organic pigments are preferred due to their higher color rendering and 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 a Color Index (CI) number can be listed below.

[0041] Examples of yellow pigments include: 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, 1 Yellow pigments such as 26, 127, 128, 129, 138, 139, 150, 151, 152, 153, 154, 155, 156, 166, 168, 175, 185, 231, and their derivatives, coumarin dyes, cyanine dyes, terpineine dyes, azo dyes, methylene dyes, methylene azo dyes, quinoline dyes, etc.

[0042] Among yellow pigments, quinoline-based pigments are preferred in terms of good heat and light resistance and high transmittance. Furthermore, quinoline-based pigments are also superior in terms of having hues suitable for color filter applications. Quinoline pigments refer to pigments synthesized by condensation of quinoline derivatives such as quinazonidine with phthalic anhydride derivatives or naphthalic anhydride derivatives. They can be any of pigments, dyes, or salt compounds of dyes. Examples of quinoline pigments include CI Pigment Yellow 138. Examples of quinoline dyes include CI Disperse Yellow 54, 64, 67, 134, 149, 160, CI Solvent Yellow 114, 157, etc.

[0043] Other examples of green pigments include: CI Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55, 58, 59, 62, 63, etc., as well as green dyes such as squartz, triarylmethane, anthraquinone, coumarin, anthocyanin, or azo dyes. In terms of ease of color adjustment, phthalocyanine green pigment is preferred as an alternative green pigment to the aforementioned halogenated phthalocyanine compounds. Examples of phthalocyanine green pigments include CI pigment green 7, 36, 58, 59, 62, and 63. In terms of ease of brightness adjustment, CI pigment green 7, 58, 59, 62, or 63 are preferred, CI pigment green 58, 59, 62, or 63 are even more preferred, and CI pigment green 59 is the most desirable.

[0044] Furthermore, examples of orange pigments include: CI Pigment Orange 1, 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 61, 63, 64, 71, and 73; Examples of blue pigments include: CI Pigment Blue 15, 15:3, 15:4, 15:6, and 60. Examples of purple pigments include: CI pigment purple 1, 19, 23, 29, 32, 36, 38, etc.

[0045] Phthalocyanine compounds represented by the above general formula (1) are usually green. Therefore, as other colorants, one or more selected from the group consisting of yellow colorants and other green colorants can be used more preferably.

[0046] In the photosensitive coloring resin composition of the present invention, the content ratio of the phthalocyanine compound represented by the above general formula (1) relative to the total colorant can be adjusted appropriately according to the desired color, and is not particularly limited. It can also be 100% by mass relative to the total colorant containing the phthalocyanine compound represented by the above general formula (1). When the photosensitive coloring resin composition of the present invention contains other colorants, in terms of the desired color adjustment, relative to the total colorant containing the phthalocyanine compound represented by the above general formula (1), it can contain 30% to 95% by mass of the phthalocyanine compound represented by the above general formula (1), or 40% to 85% by mass of the phthalocyanine compound represented by the above general formula (1), or 50% to 80% by mass of the phthalocyanine compound represented by the above general formula (1). Furthermore, in the photosensitive coloring resin composition of the present invention, the content ratio of the phthalocyanine compound represented by the above general formula (1) can be increased by combining it with at least one of the following: a block copolymer having an acidic group and a graft copolymer having an acidic group. The ratio of the phthalocyanine compound (D) represented by the above general formula (1) to the solid component (V) other than the colorant can be (D: phthalocyanine compound represented by the above general formula (1)) / V (solid component other than the colorant) = 0.1 or more, or it can be 0.3 or more, and the upper limit is usually 0.6 or less.

[0047] When the photosensitive coloring resin composition of the present invention contains a yellow pigment, the yellow pigment may be appropriately selected, and one type may be used alone or two or more types may be used in combination. In the photosensitive coloring resin composition of the present invention, the ratio of yellow pigment to the halide phthalocyanine pigment of the present invention can be adjusted appropriately according to the desired color intensity, and there is no particular limitation. In terms of adjusting the desired color intensity, relative to 100 parts by mass of the phthalocyanine compound represented by the above general formula (1), the composition may contain 5 to 233 parts by mass of yellow pigment, 18 to 150 parts by mass, or 25 to 100 parts by mass.

[0048] When the photosensitive coloring resin composition of the present invention contains a green pigment that is different from the phthalocyanine compound represented by the above general formula (1), a green pigment that is different from the phthalocyanine compound represented by the above general formula (1) may be appropriately selected, and one type may be used alone or two or more types may be used in combination. In the photosensitive coloring resin composition of the present invention, the content ratio of a green pigment different from the phthalocyanine compound represented by the above general formula (1) relative to the phthalocyanine compound represented by the above general formula (1) can be appropriately adjusted to the desired chroma, and there is no particular limitation. In terms of the desired chroma adjustment and brightness adjustment, relative to 100 parts by mass of the phthalocyanine compound represented by the above general formula (1), it may contain 5 to 233 parts by mass of a green pigment different from the phthalocyanine compound represented by the above general formula (1), or it may contain 18 to 150 parts by mass, or it may contain 25 to 100 parts by mass.

[0049] Furthermore, when the photosensitive coloring resin composition of the present invention contains a green pigment other than the phthalocyanine compound represented by the above general formula (1), the content ratio of the green pigment containing the phthalocyanine compound represented by the above general formula (1) to the total pigment content can be adjusted appropriately according to the desired chromaticity, and is not particularly limited. In terms of the desired chromaticity adjustment and brightness adjustment, it is preferable to contain 30% to 95% by mass of the green pigment containing the phthalocyanine compound represented by the above general formula (1) relative to the total pigment content, more preferably 50% to 80% by mass. Furthermore, the ratio of the yellow pigment to the green pigment containing the halogenated phthalocyanine pigment of the present invention can be adjusted appropriately according to the desired chromaticity, and there is no particular limitation. In terms of the desired chromaticity and brightness adjustment, it is preferable to contain 5 to 70 parts by mass of yellow pigment, and more preferably 20 to 50 parts by mass, relative to 100 parts by mass of green pigment containing the phthalocyanine compound represented by the above general formula (1).

[0050] Furthermore, in the photosensitive coloring resin composition of the present invention, other colorants besides green and yellow colorants may be included in the colorant without impairing the effect of the present invention. The total content of green and yellow colorants containing phthalocyanine compounds represented by the above general formula (1) relative to the total colorant may be 70% to 100% by mass, and may be 80% to 100% by mass.

[0051] In the photosensitive coloring resin composition of the present invention, the content of pigment is not particularly limited. Regarding dispersibility and dispersion stability, the total content of pigment relative to the total solid content of the photosensitive coloring resin composition is preferably in the range of 3% to 65% by mass, more preferably 4% to 60% by mass. If it is above the lower limit, the colored layer when the photosensitive coloring resin composition is coated to a specific film thickness (typically 1.0 μm to 5.0 μm) has sufficient color concentration. Furthermore, if it is below the upper limit, a colored layer with excellent storage stability and sufficient hardness or adhesion to the substrate can be obtained. Especially when forming a colored layer with a high pigment concentration, the total content of pigment relative to the total solid content of the photosensitive coloring resin composition is preferably in the range of 15% to 65% by mass, more preferably 25% to 60% by mass. Furthermore, in this invention, the solid components are all except the solvent described below, and also include monomers dissolved in the solvent.

[0052] [At least one of a block copolymer having an acidic group and a graft copolymer having an acidic group] In this invention, in order to improve the solubility and solubility stability of the phthalocyanine compound represented by the above general formula (1), at least one of a block copolymer having an acidic group and a graft copolymer having an acidic group is used. Hereinafter, "the solubility and solubility stability of the phthalocyanine compound represented by the above general formula (1)" is sometimes simply referred to as "solubility and solubility stability". As at least one of a block copolymer having an acidic group and a graft copolymer having an acidic group, it may be a block copolymer having an A block comprising a structural unit represented by the following general formula (I) and a graft copolymer having a structural unit represented by the following general formula (I).

[0053] [Chemistry 9] (In general formula (I), R1 represents a hydrogen atom or a methyl group, L represents a direct bond or a divalent bond, and Q is an acidic group.)

[0054] {block copolymer} The block copolymer used in this invention has an A block that typically functions as an adsorption site for pigments, comprising the structural unit represented by the above general formula (I). The block copolymer used in this invention may further have a B block that typically functions as a solvent-affinity site. In this invention, in the block copolymer used, the A block comprising the structural unit represented by the above general formula (I) is relatively hydrophilic, and the B block, which functions as a solvent-affinity site, is relatively hydrophobic.

[0055] (A segment) (Structural unit represented by general formula (I)) In general formula (I), R1 represents a hydrogen atom or a methyl group, L represents a direct bond or a divalent linkage, and Q is an acidic group. Here, L stands for direct bond, meaning that the acidic group is directly bonded to the carbon atom of the main chain backbone without the aid of a linker. In L, examples of divalent linking groups include straight-chain, branched, or cyclic saturated or unsaturated aliphatic hydrocarbon groups, straight-chain, branched, or cyclic saturated or unsaturated aliphatic hydrocarbon groups with hydroxyl groups, aromatic hydrocarbon groups, -CONH- groups, -COO- groups, -NHCOO- groups, ether groups (-O- groups), thioether groups (-S- groups), and combinations thereof. Furthermore, in this invention, the bonding direction of the divalent linking group is arbitrary. That is, when the divalent linking group contains -CONH-, -CO can be on the carbon atom side of the main chain and -NH on the nitrogen atom side of the side chain; conversely, -NH can be on the carbon atom side of the main chain and -CO on the nitrogen atom side of the side chain.

[0056] Specifically, examples of the aforementioned aliphatic hydrocarbon groups include: straight-chain alkyl groups such as methylene, dimethylene (ethyl), trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene, and decamethylene; branched alkyl groups such as methylmethylene, methylethyl, 1-methylpentyl, and 1,4-dimethylbutyl; and cyclic alkyl groups such as cyclopentyl and cyclohexyl. Examples of the number of carbon atoms in the aforementioned aliphatic hydrocarbon groups range from 1 to 20. In terms of solubility stability, 1 to 16 is preferred, 1 to 12 is more preferred, and 2 to 8 is even more preferred. Specifically, examples of the aforementioned aromatic hydrocarbon groups include, for instance, pentylene and pentylenaphthalene.

[0057] In terms of solubility, L in general formula (I) is preferably a divalent linker containing at least one of -CONH- and -COO- groups, and more preferably a divalent linker containing at least one of -CONH- and -COO- groups and an aliphatic hydrocarbon group having 1 to 12 carbon atoms containing an oxygen atom.

[0058] Examples of acidic groups represented by Q include carboxyl groups (-COOH), sulfonic acid groups (SO3H), and phosphorus-containing acidic groups. Examples of phosphorus-containing acidic groups include phosphate groups (-OP(=O)(OH)2), phosphonic acid groups (-P(=O)(OH)2), acidic phosphorus compound groups (hereinafter -P(=O)(-R4)(OH)) and their salts (-P(=O)(-R4)(O-X+)). As for the acidic group represented by Q, in terms of solubility stability, it is preferably at least one of a carboxyl group (-COOH) and a phosphorus-containing acidic group, and more preferably at least one of the group consisting of a carboxyl group (-COOH) and an acidic phosphorus compound group (hereinafter -P(=O)(-R 4)(OH)) and its salt (-P(=O)(-R 4)(O -X +)).

[0059] Examples of vinyl unsaturated monomers containing sulfonic acid groups include (meth)acryloxyethylsulfonic acid and 2-(meth)acrylamide-2-methylpropanesulfonic acid. Examples of ethylene-unsaturated monomers containing phosphate groups include 2-(meth)propenyloxyethyl acid phosphate and acid phosphate-oxyethylene glycol mono(meth)acrylate.

[0060] As the acidic group represented by Q, in terms of solubility and solubility stability, it is preferably a carboxyl group, and the structural unit represented by the above general formula (I) includes the structural unit represented by the following general formula (I-O).

[0061] [Chemistry 10] (In the general formula (I-0), R1 represents a hydrogen atom or a methyl group, and L represents a direct bond or a divalent linkage.)

[0062] In the above general formula (I-0), R1 and L can be the same as in the above general formula (I). Examples of structural units represented by the above general formula (I-0) include structural units derived from (meth)acrylic acid, structural units derived from vinylbenzoic acid, and structural units derived from (meth)acrylates. As for the above general formula (I-0), in terms of solubility and solubility stability, it is preferred to select at least one from the group consisting of structural units represented by general formula (I-1) and structural units represented by general formula (I-2).

[0063] [Chemistry 11] (In general formula (I-1), R1 represents a hydrogen atom or a methyl group, In general formula (I-2), R1 represents a hydrogen atom or a methyl group, R2 represents an aliphatic hydrocarbon group that may contain an oxygen atom, and R3 represents a hydrocarbon group.

[0064] The structural unit represented by general formula (I-1) is derived from the structural unit of (meth)acrylic acid. In the structural unit represented by general formula (I-2), R2 represents an aliphatic hydrocarbon group that may contain oxygen atoms. As an aliphatic hydrocarbon group in R2, it can be the same as described above. The aliphatic hydrocarbon group containing an oxygen atom in R2 has a structure in which the carbon atom in the aforementioned aliphatic hydrocarbon group is replaced by an oxygen atom, or a structure in which the hydrogen atom in the aforementioned aliphatic hydrocarbon group is replaced by a substituent containing an oxygen atom. Examples of aliphatic hydrocarbon groups that may contain oxygen atoms include structures in which the carbon chain of the hydrocarbon group contains linkers such as -O-, -COO-, and -OCO-. Specifically, examples of aliphatic hydrocarbon groups containing oxygen atoms include -R20-(OR21)s- (where R20 and R21 independently represent aliphatic hydrocarbon groups, and s represents a number from 1 to 80) and -R22-(OCO-R23)t- (where R22 and R23 independently represent aliphatic hydrocarbon groups, and t represents a number from 1 to 40). The aliphatic hydrocarbon groups of R20, R21, R22, and R23 may be the same as the aforementioned aliphatic hydrocarbon groups. Regarding solubility stability, R20 is preferably an alkyl group having 1 to 20 carbon atoms, R21 is preferably an alkyl group having 1 to 20 carbon atoms, and s is preferably 1 to 40, more preferably 2 to 25, and even more preferably 2 to 10. Furthermore, regarding solubility stability, R22 is preferably an alkyl group having 1 to 20 carbon atoms, R23 is preferably an alkyl group having 1 to 20 carbon atoms, and t is preferably 1 to 30, more preferably 1 to 20, and even more preferably 1 to 10. R 20 and R 22 are each preferably an alkyl group having 1 to 12 carbon atoms, and more preferably an alkyl group having 2 to 8 carbon atoms. R 21 is preferably an alkyl group having 2 to 8 carbon atoms, and more preferably an ethyl or propyl group. R 23 is preferably an alkyl group having 2 to 8 carbon atoms, and more preferably an alkyl group having 3 to 7 carbon atoms. Furthermore, examples of substituents containing oxygen atoms include hydroxyl or alkoxy groups. In the structural unit represented by general formula (I-2), R2 can be an aliphatic hydrocarbon group, which can be an aliphatic hydrocarbon group with 1 to 20 carbon atoms, in terms of solvent resolubility.

[0065] In the structural unit represented by general formula (I-2), R3 represents a hydrocarbon group. Examples of hydrocarbon groups in R3 include aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and combinations thereof. Aliphatic hydrocarbon groups can be the same as those described above. Examples of aromatic hydrocarbon groups include phenyl, naphthyl, and biphenyl groups. Examples of the number of carbon atoms in the hydrocarbon group of R3 can be 1 to 20, and in terms of solubility stability, 1 to 16 is preferred, 2 to 12 is more preferred, and 2 to 6 is even more preferred. As for the R 3 hydrocarbon group, an aliphatic hydrocarbon group is preferred in terms of solubility stability.

[0066] The structural unit represented by general formula (I-2) can be derived, for example, from monomers that are addition reactants of (meth)acrylates with hydroxyl groups and dicarboxylic acids or dicarboxylic anhydrides. Examples of (meth)acrylates containing hydroxyl groups include: 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and ε-caprolactone modified with unsaturated fatty acid hydroxyalkyl esters. Furthermore, examples of aliphatic dicarboxylic acids or aliphatic dicarboxylic anhydrides include: malonic acid, succinic acid, glutaric acid, adipic acid, 1,6-hexamethylene dicarboxylic acid, hexahydrophthalic acid, succinic anhydride, adipic anhydride, hexahydrophthalic anhydride, maleic anhydride, etc. Examples of aromatic dicarboxylic acids or aromatic dicarboxylic anhydrides include: terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, diphenyl dicarboxylic acid, phthalic anhydride, naphthalenedicarboxylic anhydride, etc.

[0067] As for the structural unit represented by the above general formula (I), in terms of substrate adhesion of fine patterns, suppression of development residue, solubility and dissolution stability, it is preferred to have the structural unit represented by the above general formula (I-1) and the structural unit represented by the above general formula (I-2).

[0068] Furthermore, as the acidic group represented by Q, in terms of the inhibition of the occurrence of developing residue, solubility and solubility stability, it is preferably an acidic phosphorus compound group, and preferably the structural unit represented by the above general formula (I) includes the structural unit represented by the following general formula (I-3).

[0069] [Chemistry 12] In general formula (I-3), L1 represents a direct bond or a divalent linkage, R1 represents a hydrogen atom or a methyl group, R4 represents a hydroxyl group, a hydrocarbon group, -[CH(R5)-CH(R6)-O]x1-R7, -[(CH2)y1-O]z1-R7, or a monovalent group represented by -OR8, and R8 represents a hydrocarbon group, -[CH(R5)-CH(R6)-O]x1-R7, -[(CH2)y1-O]z1-R7, -C(R9)(R10)-C(R11)(R12)-OH, or a monovalent group represented by -CH2-C(R13)(R14)-CH2-OH. R5 and R6 are each independently a hydrogen atom or a methyl group. R7 is a hydrogen atom, a hydrocarbon group, or a valence group represented by -CHO, -CH2CHO, -CO-CH=CH2, -CO-C(CH3)=CH2, or -CH2COOR15. R15 is a hydrogen atom or an alkyl group with 1 to 5 carbon atoms. R9, R10, R11, R12, R13, and R14 are each independently a hydrogen atom, a hydrocarbon group, or a hydrocarbon group selected from ether bonds and ester bonds. R9 and R11 can be bonded to each other to form a ring structure. In the case of forming the above-mentioned ring structure, the ring structure may further have a substituent R16, which is a hydrocarbon group or a hydrocarbon group selected from ether bonds and ester bonds. The above-mentioned hydrocarbon group may also have substituents. X represents a hydrogen atom or an organic cation. x1 represents an integer from 1 to 18, y1 represents an integer from 1 to 5, and z1 represents an integer from 1 to 18.

[0070] In general formula (I-3), L1 can be the same as L above. As preferred specific examples of L1 in general formula (I-3), examples include -COO-CH 2CH(OH)CH 2-O-, -COO-CH 2CH 2-O-CH 2CH(OH)CH 2-O-, -COO-CH 2C(CH 2CH 3)(CH 2OH)CH 2-O-, etc., but are not limited to these.

[0071] Examples of hydrocarbon groups in R4 include alkyl groups with 1 to 18 carbon atoms, alkenyl groups with 2 to 18 carbon atoms, aralkyl groups, and aryl groups. The alkyl groups having 1 to 18 carbon atoms can be linear, branched, or cyclic. Examples include: methyl, ethyl, n-propyl, isopropyl, n-butyl, cyclopentyl, cyclohexyl, alkyl, isoalkyl, dicyclopentyl, adamantyl, and adamantyl substituted with lower alkyl groups. The alkenyl groups with 2 to 18 carbon atoms can be linear, branched, or cyclic. Examples of such alkenyl groups include vinyl, allyl, and propenyl. The position of the double bond in the alkenyl group is not limited, but it is preferable for the obtained polymer to have a double bond at the end of the alkenyl group in terms of reactivity. Examples of aryl groups include phenyl, biphenyl, naphthyl, tolyl, and xylyl, and they may also have substituents. The number of carbon atoms in the aryl group is preferably 6 to 24, and more preferably 6 to 12. Furthermore, examples of aralkyl groups include benzyl, phenethyl, naphthylmethyl, and biphenylmethyl, and they may also have substituents. The number of carbon atoms in the aralkyl group is preferably 7 to 20, and more preferably 7 to 14. The aforementioned alkyl or alkenyl groups may also have substituents, such as halogen atoms like F, Cl, and Br, and nitro groups. Furthermore, as substituents for the aforementioned aryl or aralkyl rings, in addition to straight-chain or branched alkyl groups having 1 to 4 carbon atoms, alkenyl, nitro, halogen atoms, etc., can also be cited. Furthermore, the preferred carbon number mentioned above does not include the carbon number of substituents. In R 4 above, x1 is an integer from 1 to 18, preferably an integer from 1 to 4, and more preferably an integer from 1 to 2; y1 is an integer from 1 to 5, preferably an integer from 1 to 4, and more preferably 2 or 3; z1 is an integer from 1 to 18, preferably an integer from 1 to 4, and more preferably an integer from 1 to 2. For example, the hydrocarbon groups in R7 to R14 can be the same as those in R4 mentioned above.

[0072] R9, R10, R11, R12, R13, and R14 are groups having one or more hydrocarbon groups selected from ether and ester bonds, namely -R'-O-R'', -R'-(C=O)-O-R'', or -R'-O-(C=O)-R'' (where R' and R'' are hydrocarbon groups or groups with at least one hydrocarbon group bonded by an ether or ester bond). A single group may also have two or more ether and ester bonds. When the hydrocarbon group is monovalent, examples include alkyl, alkenyl, aralkyl, and aryl groups; when the hydrocarbon group is divalent, examples include alkylene, alkenyl, aryl, and combinations thereof.

[0073] When a ring structure is formed by the bonding of R9 and R11, the number of carbons in the ring structure is preferably 5 to 8, more preferably 6, i.e., a 6-membered ring, and preferably a cyclohexane ring. The hydrocarbon group in substituent R16, or the hydrocarbon group having one or more selected from ether bonds and ester bonds, may be the same as the groups in R9, R10, R11, R12, R13 and R14 mentioned above.

[0074] In terms of excellent solubility and solubility stability, it is preferable that R4 is a hydroxyl, hydrocarbon, -[CH(R5)-CH(R6)-O]x1-R7, -[(CH2)y1-O]z1-R7, or -OR8 valence group, more preferably that R4 is a hydroxyl, methyl, ethyl, vinyl, aryl or aralkyl group with substituents, vinyl, allyl, -[CH(R5)-CH(R6)-O]x1-R7, -[(CH2)y1-O]z1-R7, or -OR8 valence group, R5 and R6 are each independently hydrogen atoms or methyl, and R7 is -CO-CH=CH2 or -CO-C(CH3)=CH2, wherein R4 is more preferably an aryl, vinyl, methyl, or hydroxyl group with substituents.

[0075] Furthermore, regarding improving alkali resistance, R4 is preferably a hydrocarbon group, or a valence group represented by -[CH(R5)-CH(R6)-O]x1-R7, or -[(CH2)y1-O]z1-R7. It is speculated that in the case of a structure where carbon atoms are directly bonded to phosphorus atoms, the resin layer with excellent alkali resistance can be formed because it is not easily hydrolyzed. In terms of excellent alkali resistance, solubility, and solubility stability, R4 is preferably a methyl, ethyl, aryl or aralkyl group with substituents, vinyl, allyl, -[CH(R5)-CH(R6)-O]x1-R7, or -[(CH2)y1-O]z1-R7 group, where R5 and R6 are independently hydrogen atoms or methyl groups, and R7 is -CO-CH=CH2 or -CO-C(CH3)=CH2. In terms of solubility, R4 is more preferably an aryl group with substituents.

[0076] Furthermore, in general formula (I-3), X represents a hydrogen atom or an organic cation. An organic cation refers to one whose cation portion contains a carbon atom. Examples of organic cations include: imidazolium cations, pyridinium cations, ammonium cations, piperidinium cations, pyrrolidinium cations, tetraalkylammonium cations, and trialkylammonium cations, as well as strontium cations such as trialkylstrontium cations and phosphonium cations such as tetraalkylphosphonium cations. Among these, protonated nitrogen-containing organic cations are preferred in terms of solubility and alkaline reproducibility. In particular, when the organic cation has an ethylene-unsaturated bond, it can impart hardening properties, which is better in this respect.

[0077] The copolymer may also contain both structural units represented by general formula (I-3) where X is a hydrogen atom and structural units where X is an organic cation. When both structural units are included, there are no particular limitations as long as good solubility and solubility stability are achieved. Preferably, the ratio of the number of structural units where X is an organic cation to the total number of structural units represented by general formula (I-3) is 0 mol% to 50 mol.

[0078] The structural unit represented by general formula (I-3) is the product of the reaction between a structural unit having at least one of an epoxy group and a cyclic ether group in the side chain and an acidic phosphorus compound, preferably a structural unit in which at least a portion of the acidic phosphorus compound group can form a salt.

[0079] In segment A, the structural unit represented by general formula (I) may include one type or more types of structural units. As for the structural unit represented by the above general formula (I), in terms of compatibility with alkali-soluble resins, solubility in developer, and suppression of developing residue, the structural unit represented by the above general formula (I-1) is preferred. Furthermore, in the structural unit represented by the above general formula (I), the acidic group represented by Q is preferably an acidic phosphorus compound group in terms of compatibility with alkali-soluble resins, solubility in developer, and suppression of developing residue. The structural unit represented by the above general formula (I) is preferably a structural unit including the structural unit represented by the above general formula (I-3).

[0080] Within block A, in addition to the structural units represented by the general formula (I) above, other structural units may be further included without compromising the effects of the present invention. As other structural units, vinyl unsaturated monomers that can be copolymerized with vinyl unsaturated monomers that derive structural units from the general formula (I) above may be appropriately selected, thereby introducing other structural units. Other structural units included in block A without impairing the effects of the present invention may include, for example, the structural unit represented by the following general formula (III) or a structural unit containing an acidic group that is different from the structural unit represented by the above general formula (I).

[0081] Monomers containing acidic groups that are derived from structural units different from those represented by the general formula (I) above can be exemplified by maleic acid, monoalkyl maleic acid esters, trans-butenedioic acid, icosinic acid, butenoic acid, cinnamic acid, etc.

[0082] The total percentage of other structural units contained in block A is not particularly limited, as long as it is within the range that does not impair the effect of the present invention. In terms of solubility and solubility stability, it is preferably 40% by mass or less, more preferably 20% by mass or less, and can be 0% by mass relative to the total structural units of block A.

[0083] That is, in terms of solubility and solubility stability, the proportion of the structural unit represented by general formula (I) contained in block A relative to the total structural units of block A is preferably 60% by mass or more, more preferably 80% by mass or more, and can be 100% by mass.

[0084] (B-segment) In the block copolymers used in this invention, the B-block functions as a solvent-affinity site. The aforementioned B-block is selected appropriately from vinyl unsaturated monomers that can be copolymerized with vinyl unsaturated monomers that derive structural units from the above general formula (I), in a manner that ensures solvent affinity. Preferably, the B-block is introduced as a standard such that the solubility of the block copolymer at 23°C is 20 (g / 100 g solvent) or higher for the solvents used in combination.

[0085] In the block copolymers used in this invention, the B block that functions as the solvent affinity site is preferably composed of at least one structural unit represented by the following general formula (III) in terms of improving solvent affinity, solubility and solubility stability.

[0086] [Chemistry 13] (In general formula (III), R 1'' is a hydrogen atom or a methyl group, L'' is a divalent linkage group, and R 30 is a hydrocarbon group that may have substituents or contain heteroatoms.)

[0087] In general formula (III), L'' is a divalent linker. For example, the same divalent linker as the one in L can be cited as a divalent linker in L. In terms of solubility and solubility stability, L'' in general formula (III) is preferably a divalent linker containing -CONH- or -COO- groups, and more preferably -CONH- or -COO- groups.

[0088] R 30 may include, for example, combinations of alkyl groups having 1 to 18 carbon atoms, alkenyl groups having 2 to 18 carbon atoms, aryl groups, and aralkyl or alkyl-substituted aryl groups. The alkyl groups having 1 to 18 carbon atoms can be linear, branched, or cyclic, and examples include: methyl, ethyl, n-propyl, isopropyl, n-butyl, n-nonyl, n-lauryl, n-stearyl, cyclopentyl, cyclohexyl, alkyl, isoalkyl, dicyclopentyl, adamantyl, and adamantyl substituted with lower alkyl groups. The alkyl group preferably has 1 to 12 carbon atoms, and more preferably 1 to 6 carbon atoms. The alkenyl group with 2 to 18 carbon atoms can be linear, branched, or cyclic. Examples of such alkenyl groups include vinyl, allyl, and propenyl. The position of the double bond in the alkenyl group is not limited, but it is preferable for the obtained polymer to have a double bond at the end of the alkenyl group, in terms of reactivity. The alkenyl group preferably has 2 to 12 carbon atoms, and more preferably 2 to 8 carbon atoms. Examples of aryl groups include phenyl, biphenyl, naphthyl, tolyl, and xylyl. The number of carbon atoms in an aryl group is preferably 6 to 24, and more preferably 6 to 12. Furthermore, examples of aralkyl groups include benzyl, phenethyl, naphthylmethyl, and biphenylmethyl, and they may also have substituents. The number of carbon atoms in the aralkyl group is preferably 7 to 20, and more preferably 7 to 14. Alternatively, straight-chain or branched alkyl groups with 1 to 30 carbon atoms can be bonded to the aforementioned aryl or aralkyl rings as substituents.

[0089] As for the hydrocarbon group in R 30, in terms of solubility and solubility stability, it is preferably selected from one or more of the group consisting of alkyl groups having 1 to 18 carbons, aryl groups having 6 to 12 carbons that can be substituted by alkyl groups, and aralkyl groups having 7 to 14 carbons that can be substituted by alkyl groups. It is more preferably selected from one or more of the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, n-nonyl, n-lauryl, n-stearyl, phenyl groups that can be substituted by alkyl groups, and benzyl groups.

[0090] R 30 contains a hydrocarbon group that includes a heteroatom, having a structure in which the carbon atom in the hydrocarbon group is replaced by a heteroatom or in which the hydrogen atom in the hydrocarbon group is replaced by a substituent containing a heteroatom. Examples of heteroatoms that may be included in the hydrocarbon group include oxygen, nitrogen, sulfur, and silicon atoms. Examples of hydrocarbon groups that may contain heteroatoms include structures in which the carbon chain of the hydrocarbon group contains linkages 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-, and -O-NH-. Furthermore, the hydrocarbon group may also have substituents within a range that does not impair the solubility and other properties of the graft copolymer. Examples of substituents include: halogen atoms, hydroxyl groups, carboxyl groups, alkoxy groups, nitro groups, cyano groups, epoxy groups, isocyanate groups, thiol groups, etc.

[0091] Furthermore, the hydrocarbon group in R 30 that can contain heteroatoms can also be a structure in which a polymerizable group such as an alkenyl group is added to the end of the hydrocarbon group via a link containing heteroatoms. For example, the structural unit represented by general formula (III) can also be a structure obtained by reacting glycidyl methacrylate with a structural unit derived from (meth)acrylic acid. That is, the structure of -L''-R 30 in general formula (III) can also be a structure represented by -COO-CH 2CH(OH)CH 2-OCO-CR=CH 2 (here, R is a hydrogen atom or a methyl group). Furthermore, the structural unit represented by general formula (III) can also be a structure obtained by reacting 2-isocyanoalkyl ester of (meth)acrylic acid with a structural unit derived from hydroxyalkyl ester of (meth)acrylic acid. That is, R 30 in general formula (III) can also be represented by the structure -R'-OCONH-R''OCO-CR=CH 2 (here, R' and R'' are independently alkyl groups, and R is a hydrogen atom or a methyl group).

[0092] Monomers representing structural units of the derived general formula (III) are preferably derived from methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tributyl methacrylate, 2-ethylhexyl methacrylate, 2-ethoxyethyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, phenyl methacrylate, isobutyl methacrylate, dicyclopentyl methacrylate, and propylene methacrylate. The structural units of adamantyl acrylate, (meth)acrylic acid, 2-methacryloxyethyl succinate, 2-hydroxyethyl (meth)acrylic acid, 2-hydroxypropyl (meth)acrylic acid, 2-hydroxybutyl (meth)acrylic acid, 4-hydroxybutyl (meth)acrylic acid, 2-hydroxy-3-phenoxypropyl (meth)acrylic acid, phenoxyethyl (meth)acrylic acid, methoxy polyethylene glycol (meth)acrylic acid, polyethylene glycol (meth)acrylic acid, phenoxyethylene glycol (meth)acrylic acid, and unsaturated fatty acid hydroxyalkyl ester modified ε-caprolactone, etc. However, it is not limited to these.

[0093] In this invention, R 30 is preferably an organic solvent with excellent solubility, and can be appropriately selected according to the organic solvent used in the pigment solution. Specifically, when the organic solvent used is a commonly used organic solvent such as ether alcohol acetate, ether, ester, or alcohol, it is preferably methyl, ethyl, isobutyl, n-butyl, 2-ethylhexyl, benzyl, cyclohexyl, dicyclopentyl, hydroxyethyl, phenoxyethyl, adamantyl, methoxy polyethylene glycol, methoxy polypropylene glycol, or polyethylene glycol.

[0094] In the above B block, the structural unit represented by the above general formula (III) can be a single type or a mixture of two or more types. Regarding solubility and solubility stability, in the aforementioned B block, the total ratio of the structural units represented by the aforementioned general formula (III) relative to the total structural units of the B block may also be 100% by mass. Regarding solubility and solubility stability, in the aforementioned B block, the total ratio of the structural units represented by the aforementioned general formula (III) relative to the total structural units of the B block is preferably 40% by mass or more, more preferably 70% by mass or more, and may also be 90% by mass or more.

[0095] In the above B block, in addition to the structural unit represented by the above general formula (III), other structural units may also be included. Other structural units can be exemplified by structural units derived from vinyl unsaturated monomers that can be copolymerized with vinyl unsaturated monomers that can derive the structural units represented by the above general formula (III). As monomers for deriving other structural units, examples include: styrene, α-methylstyrene and other styrene derivatives, phenyl vinyl ethers and other vinyl ether derivatives.

[0096] In the above-mentioned B block, in terms of the effect of the present invention, the total ratio of other structural units relative to the total structural units of the B block is preferably 30% by mass or less, and more preferably 10% by mass or less.

[0097] In terms of solubility and solubility stability, the mass average molecular weight Mw of the above-mentioned B block is preferably 2000 or more, more preferably 3000 or more, even more preferably 4000 or more, even more preferably 15000 or less, and even more preferably 12000 or less. By using the above-mentioned range, sufficient stereorepulsion effect as a surfactant can be maintained, and the specific surface area of ​​the solvent-affinity portion of the block copolymer can be increased, thereby achieving good solubility stability. The mass-average molecular weight Mw of the B-block alone can be determined for polymers consisting solely of B-blocks in the same manner as the copolymers described below.

[0098] Furthermore, regarding the solubility stability of the aforementioned B block, the acid value is preferably below 10 mgKOH / g, and more preferably 0 mgKOH / g. Here, the acid value can be determined for polymers consisting solely of the B block in the same manner as the acid value of the copolymers described below. As long as the effects of the present invention are not impaired, the above-mentioned B block may also contain at least one structural unit selected from the group of structural units represented by the above-mentioned general formula (I) containing acidic groups. In terms of solubility stability, the total ratio of structural units containing acidic groups relative to the total structural units of the above-mentioned B block is preferably 5% by mass or less, and more preferably 0% by mass.

[0099] Furthermore, regarding the solubility stability of the aforementioned B-block, the amine value is preferably below 10 mgKOH / g, and more preferably 0 mgKOH / g. Here, the amine value of the B-block can be determined for polymers consisting solely of B-blocks in the same manner as the amine value of the aforementioned polymer chains. As long as the effects of the present invention are not impaired, the above-mentioned B block may also contain nitrogen-containing structural units. In terms of solubility stability, the total ratio of nitrogen-containing structural units relative to the total structural units of the above-mentioned B block is preferably less than 5% by mass, and more preferably 0% by mass.

[0100] Furthermore, the aforementioned B-block can be selected as long as it functions as a solvent affinity site, and the structural unit can include one type or a mixture of two or more types. When the aforementioned B-block includes two or more structural units, the two or more structural units within the B-block can also be randomly copolymerized.

[0101] The bonding sequence of the block copolymers can be as long as it allows the phthalocyanine compound represented by the general formula (1) to dissolve stably, and there is no particular limitation. In terms of excellent interaction with pigments and effective suppression of the aggregation of block copolymers, it is preferable that the A block is bonded to one end of the block copolymer, preferably an AB type block copolymer, an ABA type block copolymer, or a BAB type block copolymer, wherein the AB type block copolymer or the BAB type block copolymer is preferred.

[0102] In the aforementioned block copolymer, the total content of A blocks relative to the total structural units of the main chain of the block copolymer is preferably 3% to 60% by mass, more preferably 6% to 45% by mass, and even more preferably 9% to 35% by mass. If the total content of A blocks in the block copolymer is within the above range, the ratio of the portion of the block copolymer that is compatible with the pigment is appropriate, and the reduction in solubility with organic solvents can be suppressed. Therefore, the adsorption of pigments is improved, thereby obtaining excellent solubility, dissolution stability, and substrate adhesion. In the block copolymer described above, the content ratio of the structural unit represented by the general formula (I) relative to the total structural units of the main chain of the block copolymer is preferably 3% to 60% by mass, more preferably 6% to 45% by mass, and even more preferably 9% to 40% by mass, and even more preferably 9% to 35% by mass. If the content ratio of the structural unit represented by the general formula (I) in the block copolymer is within the above range, the ratio of the part of the block copolymer that is compatible with the pigment is appropriate, and the reduction in solubility with organic solvents can be suppressed. Therefore, the adsorption of pigments becomes better, thereby obtaining excellent solubility, dissolution stability and substrate adhesion.

[0103] On the other hand, in the above-mentioned block copolymer, the total content ratio of B blocks relative to the total structural units of the main chain of the block copolymer is preferably 40% to 97% by mass, more preferably 55% to 94% by mass, further preferably 60% to 91% by mass, and even more preferably 65% ​​to 91% by mass. If the total content ratio of B blocks in the block copolymer is within the above range, the ratio of solvent-affinity portions in the block copolymer is appropriate, which can maintain sufficient stereorepulsion effect as a surfactant, and can increase the specific surface area of ​​the solvent-affinity portions of the block copolymer, thereby achieving good solubility stability. Furthermore, the content ratio of the above-mentioned structural units can be calculated based on the amount of monomers added during the synthesis of the block copolymer, including the structural units represented by the above-mentioned general formula (I) and the structural units represented by the above-mentioned general formula (III).

[0104] (Method for manufacturing block copolymers) There are no particular limitations on the manufacturing method of the aforementioned block copolymers. Block copolymers can be manufactured by known methods, with living polymerization being preferred. This is because chain transfer or deactivation is less likely to occur, copolymers with consistent molecular weights can be produced, and solubility can be improved. Examples of living polymerization methods include living radical polymerization, group transfer polymerization, and other living anionic and cationic polymerization methods. By sequentially polymerizing monomers using these methods, copolymers can be manufactured. For example, block A can be manufactured first, and then the structural units constituting block B can be polymerized with block A to produce a block copolymer. Furthermore, in the above manufacturing method, the polymerization order of block A and block B can be reversed. Alternatively, block A and block B can be manufactured separately, and then block A and block B can be coupled together.

[0105] Furthermore, copolymers having at least one of the structural units selected from those represented by the above general formula (I-3) can be synthesized, for example, with reference to Japanese Patent Application Publication No. 2017-2191.

[0106] {graft copolymer} The graft copolymer used in this invention is a copolymer in which the main chain has the structural unit represented by the above general formula (I) that usually functions as an adsorption site for pigments, and the side chain has a graft polymer chain that usually functions as a solvent affinity site. As a graft copolymer used in this invention, the main chain portion containing the structural unit represented by the above general formula (I) is relatively hydrophilic, and the side chain portion that functions as a solvent-affinity portion is relatively hydrophobic.

[0107] (Structural unit represented by general formula (I)) In graft copolymers, the structural unit represented by the above general formula (I) may be the same as that described above, so the description here is omitted. In graft copolymers, the structural unit represented by general formula (I) may include one type or more types of structural units.

[0108] (Structural units with grafted polymer chains) The above-mentioned graft copolymer has graft polymer chains in the side chains that function as solvent affinity sites. The preferred standard for the above polymer chain is a solubility of 20 (g / 100 g solvent) or higher at 23°C for use in combination with organic solvents. The solubility of the polymer chain can be measured by the solubility of the raw material used to introduce the polymer chain during the preparation of the graft copolymer. For example, when introducing the polymer chain into the graft copolymer using a polymeric oligomer (macromonomer) containing a polymer chain and a group having an ethylene unsaturated bond at its end, it is sufficient that the polymeric oligomer has the aforementioned solubility. Furthermore, when a copolymer is formed using a monomer containing an ethylene unsaturated bond, and 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 that the polymer chain containing the reactive group has the aforementioned solubility.

[0109] The graft copolymer used in this invention preferably has a main chain having a structural unit represented by the above general formula (I) that functions as an adsorption site for pigments, and a side chain having a polymer chain that functions as a solvent affinity site, i.e., has a structural unit represented by the following general formula (II).

[0110] [Chemistry 14] (In general formula (II), R 1' represents a hydrogen atom or a methyl group, L' represents a direct bond or a divalent linker, and Polymer represents a polymer chain).

[0111] In the above general formula (II), L' is a direct bond or a divalent linker. There are no particular restrictions on the divalent linker in L', as long as a carbon atom derived from an ethylene unsaturated bond can be linked to the polymer chain. As a divalent linker, it can be the same as L in general formula (I). In terms of solubility and solubility stability, L' in general formula (II) is preferably a divalent linker containing a -CONH- group or a -COO- group, and more preferably a divalent linker containing a -CONH- group or a -COO- group and an aliphatic hydrocarbon group with 1 to 12 carbon atoms that may contain an oxygen atom.

[0112] In terms of solubility and solubility stability, it is preferable that the polymer chain contains at least one structural unit represented by the above general formula (III). The structural unit represented by the above general formula (III) contained in the above polymer chain may be the same as that described in the block copolymer, so the description here is omitted.

[0113] In the polymer chain described above, the structural unit represented by the general formula (III) may be a single type or a mixture of two or more types. Regarding solubility and solubility stability, in the aforementioned polymer chain, the total ratio of the structural units represented by the aforementioned general formula (III) relative to the total structural units (100% by mass) of the polymer chain may also be 100% by mass. Regarding solubility and solubility stability, in the aforementioned polymer chain, the total ratio of the structural units represented by the aforementioned general formula (III) relative to the total structural units of the polymer chain is preferably 40% by mass or more, and more preferably 70% by mass or more.

[0114] In addition to the structural units represented by the general formula (II) above, other structural units may also be included in the polymer chain structural units of the above graft copolymer. Other structural units can be exemplified by structural units derived from vinyl unsaturated monomers that can be copolymerized with the structural units represented by the above general formula (III). As monomers for deriving other structural units, examples include: styrene, α-methylstyrene and other styrene derivatives, phenyl vinyl ethers and other vinyl ether derivatives.

[0115] In terms of the effects of the present invention, the total percentage of other structural units in the polymer chain of the structural unit represented by the above general formula (II) of the above graft copolymer is preferably 30% by mass or less, and more preferably 10% by mass or less, relative to the total structural units of the polymer chain.

[0116] Furthermore, in terms of solubility and solubility stability, the mass average molecular weight Mw of the aforementioned polymer chains is preferably 2000 or more, more preferably 3000 or more, even more preferably 4000 or more, even more preferably 15000 or less, and even more preferably 12000 or less. By using the above-mentioned range, sufficient stereorepulsion effect as a surfactant can be maintained, and the effects described above due to the increased specific surface area of ​​the solvent-affinity portion of the graft copolymer can be effectively achieved. The mass average molecular weight Mw of the polymer chains described above can be determined in the same manner as that of the polymeric oligomers or polymer chains containing the reactive groups described above, for the polymeric oligomers described above.

[0117] Furthermore, regarding the solubility stability of the aforementioned polymer chains, the acid value is preferably below 10 mgKOH / g, and more preferably 0 mgKOH / g. Here, the acid value can be determined for the aforementioned polymeric oligomers or the aforementioned polymer chains containing reactive groups in the same manner as the acid value of the copolymers described below. As long as the effect of the present invention is not compromised, the polymer chain may also contain the structural unit represented by the general formula (I) above. However, in terms of solubility stability, the total ratio of structural units containing acidic groups relative to the total structural units of the polymer chain is preferably 5% by mass or less, and more preferably 0% by mass.

[0118] Furthermore, regarding the solubility and solubility stability of the aforementioned polymer chain, the amine value is preferably below 10 mgKOH / g, and more preferably 0 mgKOH / g. 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 component of the aforementioned polymeric oligomer or the aforementioned polymer chain containing reactive groups, and is determined by the method described in JIS K 7237:1995. As long as the effect of the present invention is not compromised, the above-mentioned polymer chain may also contain nitrogen-containing structural units. However, in terms of solubility stability, the total ratio of nitrogen-containing structural units relative to the total structural units of the above-mentioned polymer chain is preferably less than 5% by mass, and more preferably 0% by mass.

[0119] In the above-mentioned graft copolymer, the content ratio of the structural unit represented by the above-mentioned general formula (I) relative to the total structural units of the main chain of the graft copolymer is preferably 3% to 60% by mass, more preferably 6% to 45% by mass, and even more preferably 9% to 35% by mass. If the content ratio of the structural unit represented by the above-mentioned general formula (I) in the graft copolymer is within the above-mentioned range, the ratio of the part of the graft copolymer that is compatible with the pigment is appropriate, and the reduction of solubility in organic solvents can be suppressed. Therefore, the adsorption of pigments becomes better, thereby obtaining excellent solubility, dissolution stability, and substrate adhesion. On the other hand, in the above-mentioned graft copolymer, the total content ratio of structural units containing graft polymer chains or structural units represented by the above-mentioned general formula (II) relative to the total structural units of the main chain of the graft copolymer is preferably 40% to 97% by mass, more preferably 55% to 94% by mass, and even more preferably 65% ​​to 91% by mass. If the total content ratio of structural units containing graft polymer chains or structural units represented by the above-mentioned general formula (II) in the graft copolymer is within the above range, the ratio of solvent-affinity portions in the graft copolymer is appropriate, which can maintain sufficient stereorepulsion effect as a surfactant, and can increase the specific surface area of ​​the solvent-affinity portions of the graft copolymer, thereby achieving good solubility stability. In the above-mentioned graft copolymer, when the total structural units of the main chain containing the structural units represented by the above-mentioned general formula (I) are set to 100% by mass, the ratio of the structural units represented by the above-mentioned general formula (I) and the structural units represented by the above-mentioned general formula (II) is preferably 70% by mass or more, more preferably 90% by mass or more, and may also be 100% by mass.

[0120] The graft copolymer used in this invention can have other structural units besides those represented by general formula (I) and general formula (II) without compromising the effects of this invention. As other structural units, vinyl unsaturated monomers that can be copolymerized with vinyl unsaturated monomers that derive structural units from general formula (I) can be appropriately selected to introduce other structural units. Other structural units that copolymerize with the structural units represented by the above general formula (I) in the main chain include, for example, the structural units represented by the above general formula (III) or structural units containing acidic groups that are different from the structural units represented by the above general formula (I). In the above-mentioned graft copolymer, the total percentage of other structural units copolymerized in the main chain relative to the total number of structural units in the main chain of the graft copolymer is preferably 40% by mass or less, more preferably 20% by mass or less, and may be 0% by mass. Furthermore, the content ratio of the above-mentioned structural units is calculated based on the amount of monomers added during the synthesis of the graft copolymer, including the structural units represented by the above-mentioned general formula (I) and the structural units represented by the above-mentioned general formula (II).

[0121] (Method for manufacturing graft copolymers) In this invention, the method for manufacturing the graft copolymer is not particularly limited, as long as it is a method capable of manufacturing a graft copolymer having the structural unit represented by the general formula (I) above. When manufacturing a graft copolymer having the structural unit represented by the general formula (I) above, for example, a method can be used to copolymerize a monomer represented by the following general formula (Ia) and a polymeric oligomer (macromonomer) containing the above polymer chain and a group having an ethylene unsaturated bond at its end as a copolymer component to manufacture the graft copolymer. Other monomers may also be used as needed, and graft copolymers may be manufactured using known polymerization methods.

[0122] [Chemistry 15] (In general formula (Ia), R1, L, and Q are the same as in general formula (I).)

[0123] Furthermore, when manufacturing graft copolymers having structural units represented by the above general formula (I), after forming a copolymer by addition polymerization of the monomer represented by the above general formula (Ia) with other vinyl unsaturated monomers, a polymer chain containing reactive groups that can react with the reactive groups contained in the copolymer can be used to introduce the polymer chain. Specifically, for example, after synthesizing a copolymer having substituents such as alkoxy, hydroxyl, carboxyl, amino, epoxy, isocyanate, and hydrogen-bonding groups, it can be reacted with a polymer chain containing functional groups that react with the substituents to introduce the polymer chain. For example, a polymer chain with a carboxyl group at the end can be reacted with a copolymer with a glycidyl group on the side chain, or a polymer chain with a hydroxyl group at the end can be reacted with a copolymer with an isocyanate group on the side chain to introduce the polymer chain. Furthermore, additives commonly used in polymerization, such as polymerization initiators, dispersion stabilizers, and chain transfer agents, can also be used in the above polymerization process.

[0124] {Characteristics of block copolymers or graft copolymers with acidic groups} Regarding solubility and solubility stability, the mass average molecular weight Mw of the graft copolymer or block copolymer having the structural unit represented by the above general formula (I) is preferably 4000 or more, more preferably 5000 or more, and even more preferably 6000 or more. On the other hand, regarding solvent resolubility, it is preferably 50000 or less, and more preferably 30000 or less. Furthermore, regarding solubility stability, the ratio (Mw / Mn) of the above-mentioned graft copolymer's mass average molecular weight Mw to its number average molecular weight Mn is preferably 4.0 or less, more preferably 3.5 or less, and even more preferably 3.0 or less. Furthermore, regarding solubility stability, the ratio of the mass average molecular weight Mw to the number average molecular weight Mn of the block copolymer (Mw / Mn) is preferably 1.8 or less, more preferably 1.6 or less, and even more preferably 1.4 or less. Furthermore, 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 determination was performed using a Tosoh-manufactured HLC-8120GPC, with the dissolution solvent being N-methylpyrrolidone containing 0.01 moles / L of lithium bromide. The calibration curves were performed using polystyrene standards Mw377400, 210500, 96000, 50400, 20650, 10850, 5460, 2930, 1300, and 580 (all of which are Polymer Laboratories Easi PS-2 series) and Mw1090000 (manufactured by Tosoh). The measurement column was set to TSK-GEL ALPHA-M×2 (manufactured by Tosoh).

[0125] Regarding solubility stability, the graft copolymer or block copolymer having the structural unit represented by the above general formula (I) preferably has an acid value of 20 mgKOH / g or more, more preferably 30 mgKOH / g or more, further preferably 40 mgKOH / g or more, and further preferably 60 mgKOH / g or more. On the other hand, in terms of solvent resolubility, the acid value of at least one of the above-mentioned graft copolymer and block copolymer is preferably 250 mgKOH / g or less, more preferably 180 mgKOH / g or less, even more preferably 160 mgKOH / g or less, and even more preferably 140 mgKOH / g or less. In this invention, the acid value of the copolymer represents the mass (mg) of potassium hydroxide required to neutralize the acidic components contained in 1 g of the solid component of the copolymer, and is a value measured by the method described in JIS K 0070:1992.

[0126] In this invention, the content ratio or structure of each structural unit of at least one of the block copolymers with acidic groups and the graft copolymers with acidic groups, or other dispersants described below, can be determined using various mass analysis methods, NMR (Nuclear Magnetic Resonance), etc. Furthermore, if necessary, at least one of the block copolymers with acidic groups and the graft copolymers with acidic groups, or other dispersants described below, can be decomposed by thermal decomposition or the like. The obtained decomposition products are then determined using high-performance liquid chromatography, gas chromatography-mass spectrometry, NMR, elemental analysis, XPS / ESCA (X-ray photoelectron spectroscopy / Electron Spectroscopy for Chemical Analysis), and TOF-SIMS (Time-of-Flight Secondary Ion Mass Spectrometry).

[0127] In the photosensitive coloring resin composition of the present invention, the content of at least one of the block copolymers having acidic groups and the graft copolymers having acidic groups is not particularly limited, as long as it is selected in a manner that provides excellent solubility and solubility stability of the phthalocyanine compound represented by the above general formula (1). The content is preferably in the range of 2% to 30% by mass, more preferably 3% to 25% by mass, relative to the total solid content of the photosensitive coloring resin composition. If the content is above the lower limit, the solubility and solubility stability are excellent, and the storage stability of the photosensitive coloring resin composition is even better. Furthermore, if the content is below the upper limit, the developability is good. Especially in the case of forming a coloring layer with a high pigment concentration, the content of at least one of the block copolymers having acidic groups and the graft copolymers having acidic groups is preferably in the range of 2% to 25% by mass, more preferably 3% to 20% by mass, relative to the total solid content of the photosensitive coloring resin composition.

[0128] [Other dispersants] In this invention, at least one other dispersant different from both the block copolymer with acidic groups and the graft copolymer with acidic groups may be included, which can function as a dispersant for the pigment. This other dispersant may also be used to dissolve the pigment rather than to disperse it. As other dispersants mentioned above, appropriate selections can be made from previously known dispersants. Examples of such other dispersants include cationic, anionic, nonionic, amphoteric, polysiloxane, and fluorinated surfactants. Among surfactants, polymeric dispersants are preferred in terms of their ability to disperse uniformly and finely.

[0129] Examples of polymeric dispersants among the aforementioned dispersants include: (co)polymers of unsaturated carboxylic acid esters such as polyacrylates; (partial) amine salts, (partial) ammonium salts, or (partial) alkylamine salts of (co)polymers of unsaturated carboxylic acid esters such as polyacrylic acid; (co)polymers of hydroxyl-containing unsaturated carboxylic acid esters such as hydroxyl-containing polyacrylates, or their modifications; polyurethane esters; unsaturated polyamides; polysiloxanes; long-chain polyamide phosphates; amides or their bases obtained by reacting polyethyleneimine derivatives (poly(lower alkylimine) with polyesters containing free carboxyl groups); polyallylamine derivatives (reaction products obtained by reacting polyallylamine with one or more compounds selected from three compounds: polyesters having free carboxyl groups, polyamides, or cocondensates of esters and amides (polyesteramides)). When the polymeric dispersant is a copolymer, it can be any of a block copolymer, graft copolymer, or random copolymer, but from the point of view of dispersibility, block copolymers and graft copolymers are preferred.

[0130] As a polymeric dispersant among the other dispersants mentioned above, it can also contain an alkaline dispersant to better disperse the pigments and thus achieve good dispersion stability. As an alkaline dispersant, it can be a polymeric dispersant whose main chain or side chain contains nitrogen atoms and has an amine value. It can be a polymeric dispersant comprising a polymer containing at least one structural unit of a tertiary amine, a salt of a tertiary amine, or a quaternary ammonium salt (hereinafter referred to as tertiary amine, etc.). Examples of polymeric main chain structures include (meth)acrylic resins and styrene resins. Among these, (meth)acrylic resins are preferred for ease of synthesis of block copolymers or graft copolymers. The structural units containing tertiary amines are sites that have an affinity for the aforementioned pigments. Polymer dispersants, including those containing structural units with basic groups such as tertiary amines, typically contain structural units that serve as solvent-affinity sites. Examples of polymers containing structural units with basic groups such as tertiary amines include block copolymers or graft copolymers containing structural units with basic groups such as tertiary amines. The solvent-affinity site may be the same as at least one of a block copolymer having an A block comprising the structural unit represented by the above general formula (I) and a graft copolymer having the structural unit represented by the above general formula (I). As other dispersants mentioned above, those that improve solvent resolubility may further include block copolymers containing basic groups such as tertiary amines.

[0131] Regarding the dispersibility, the amine value of an alkaline dispersant can be, for example, 50 mgKOH / g or more, or 80 mgKOH / g or more. On the other hand, it can be less than 200 mgKOH / g or more than 150 mgKOH / g. As a polymeric dispersant including polymers containing structural units such as tertiary amines, commercially available products can also be used, such as LPN-6919 manufactured by BYK-Chemie. LPN-6919 manufactured by BYK-Chemie can also be used, and those in which the tertiary amine portion is formed into a salt or a tertiary ammonium salt can also be used.

[0132] In the photosensitive coloring resin composition of the present invention, the content of other dispersants is not particularly limited, as long as they are selected in a manner that provides excellent solubility or dispersibility and solubility or dispersibility stability of the pigment. The total content of other dispersants and at least one of the above-mentioned block copolymers with acidic groups and graft copolymers with acidic groups, relative to the total solid content in the photosensitive coloring resin composition, is preferably in the range of 2% to 30% by mass, more preferably 3% to 25% by mass. If the content is above or below the lower limit of the above-mentioned value, the solubility or dispersibility and solubility or dispersibility stability of the pigment are excellent, and the storage stability of the photosensitive coloring resin composition is even better. Furthermore, if the content is below the upper limit of the above-mentioned value, the developability becomes better. Especially when forming a colored layer with a high pigment concentration, the total content of other dispersants and at least one of the above-mentioned block copolymers with acidic groups and graft copolymers with acidic groups is, for example, preferably in the range of 2% to 25% by mass, and more preferably in the range of 3% to 20% by mass, relative to the total solid content of the photosensitive coloring resin composition.

[0133] When at least one of the block copolymers with acidic groups and the graft copolymers with acidic groups is used in combination with other dispersants, the content ratio of other dispersants relative to the total content (total solids content) of the block copolymers with acidic groups and the graft copolymers with acidic groups and other dispersants may be 5% by mass or more, 20% by mass or more, or 30% by mass or more; on the other hand, it may be 60% by mass or less, 50% by mass or less, or 40% by mass or less. When at least one of a block copolymer with an acidic group and a graft copolymer with an acidic group is used in combination with an alkaline dispersant, the content ratio of the alkaline dispersant relative to the total content (total solids content) of the block copolymer with an acidic group and the graft copolymer with an acidic group and the alkaline dispersant may be 5% by mass or more, 20% by mass or more, or 30% by mass or more; on the other hand, it may be 60% by mass or less, 50% by mass or less, or 40% by mass or less.

[0134] [Alkali-soluble resin] The alkali-soluble resin used in this invention has acidic groups and can function as an adhesive resin. It can be appropriately selected from alkali-soluble resins that are soluble in the alkaline developing solution used in pattern formation. In this invention, the term "alkali-soluble resin" can be defined as having an acid value of 40 mgKOH / g or higher. The alkali-soluble resin used in this invention is different from at least one of the block copolymers and graft copolymers with acidic groups mentioned above, and is a random copolymer with acidic groups.

[0135] As an alkali-soluble resin, a previously known alkali-soluble resin may be appropriately selected, such as the alkali-soluble resin described in International Publication No. 2016 / 104493. The preferred alkali-soluble resin of this invention is a resin having an acidic group and a carboxyl group. Specifically, examples include (meth)acrylic copolymers having carboxyl groups and styrene-(meth)acrylic copolymers having carboxyl groups, as well as (meth)acrylic epoxy ester resins having carboxyl groups. (Meth)acrylic copolymers having carboxyl groups and styrene-(meth)acrylic copolymers having carboxyl groups are preferred. Among these, those having carboxyl groups on the side chains, and further having photopolymerizable functional groups such as vinyl unsaturated groups on the side chains, are particularly preferred. This is because the film strength of the hardened film formed by containing photopolymerizable functional groups is improved. Furthermore, two or more of these (meth)acrylic copolymers and styrene-(meth)acrylic copolymers, as well as (meth)acrylic epoxy ester resins, can also be used in combination.

[0136] The alkali-soluble resin used in the photosensitive coloring resin composition may be used alone or in combination of two or more. There is no particular limitation on the content of the alkali-soluble resin, but 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 coloring resin composition. If the content of the alkali-soluble resin is above or below the aforementioned lower limit, sufficient alkaline developability is obtained; conversely, if the content of the alkali-soluble resin is below the aforementioned upper limit, uneven film formation or pattern defects can be suppressed during development.

[0137] [Photopolymerizable compounds] The photopolymerizable compound used in the photosensitive coloring resin composition of the present invention refers to a compound having a photopolymerizable group in its molecule. There is no particular limitation on the photopolymerizable group; it can be polymerizable by a photoinitiator. Examples include vinyl unsaturated bonds, such as vinyl, allyl, acrylonitrile, or methacrylonitrile. Regarding UV curability, acrylonitrile or methacrylonitrile are preferred as photopolymerizable groups. In terms of curing properties, a photopolymerizable compound is preferably a compound having two or more photopolymerizable groups per molecule, and more preferably a compound having three or more photopolymerizable groups per molecule.

[0138] There are no particular limitations on photopolymerizable compounds, as long as they can be polymerized by the following photoinitiators. Compounds with two or more vinyl unsaturated bonds are generally used, and polyfunctional (meth)acrylates with two or more acrylonitrile or methacrylonitrile groups are preferred. As for such multifunctional (meth)acrylates, any appropriate selection from previously known sources may be used. For specific examples, such as those described in Japanese Patent Application Publication No. 2013-029832, etc.

[0139] These photopolymerizable compounds can be used alone or in combination of two or more. Furthermore, when excellent photocurability (high sensitivity) is required for the color-curing composition of the present invention, the photopolymerizable compound is preferably one having three or more polymerizable vinyl unsaturated bonds (trifunctional), preferably a poly(meth)acrylate of a ternary or higher polyol or a dicarboxylic acid modified thereof. Specifically, it is preferably trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, a succinic acid modified version of pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, a succinic acid modified version of dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc.

[0140] There is no particular limitation on the content of the aforementioned photopolymerizable compound used in the photosensitive coloring resin composition. For example, it is preferably 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 coloring resin composition. If the content of the photopolymerizable compound is above or below the aforementioned lower limit, photocuring is sufficiently achieved, and the dissolution of the exposed portion during development can be suppressed. Furthermore, if the content of the photopolymerizable compound is below the aforementioned upper limit, alkaline developability is sufficient.

[0141] [Photoinitiator] As a photoinitiator used in the photosensitive coloring resin composition of the present invention, one or more photoinitiators can be used from a variety of previously known photoinitiators. Examples of photoinitiators include: aromatic ketones, benzoin ethers, halomethyl diazole compounds, α-amino ketones, biimidazoles, N,N-dimethylaminobenzophenone, halomethyl-symmetric triterpenoids, and 9-oxosulfuron. Oxime esters and thiol sensitizers, etc., can be used as such photoinitiators. Previously known photoinitiators can be used, such as those described in International Publication No. 2018 / 062105.

[0142] As a photoinitiator used in the photosensitive coloring resin composition of the present invention, in terms of curability, it is preferred to be an oxime ester-based photoinitiator. As oxime ester-based photoinitiators used in this invention, examples include 1,2-octanedione-1-[4-(phenylthio)phenyl]-,2-(o-benzoyl oxime), acetone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-,1-(o-acetylated oxime), Japanese Patent Application Publication No. 2000-80068, and Japanese Patent Application Publication No. 2001. Appropriately select from the oxime ester photoinitiators described in Japanese Patent Publication No. 233842, Japanese Patent Publication No. 2010-527339, Japanese Patent Publication No. 2010-527338, Japanese Patent Application Publication No. 2013-041153, International Publication No. 2015 / 152153, and Japanese Patent Application Publication No. 2010-256891.

[0143] Furthermore, as an oxime ester photoinitiator, it is preferable to contain at least one oxime ester compound represented by the following general formula (A) in terms of having less color change related to a decrease in brightness.

[0144] [Chemistry 16] General formula (A) (In general formula (A), Z1, Z3, Z4 and Z5 independently represent a hydrogen atom, a straight-chain or branched alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or a phenyl group. The aforementioned alkyl, cycloalkyl, and phenyl groups may also be substituted with substituents selected from the group consisting of halogen atoms, alkoxy groups having 1 to 6 carbon atoms, and phenyl groups. Z2 represents an alkyl group having 1 to 20 carbon atoms substituted with a cycloalkyl group.)

[0145] In the above general formula (A), the straight-chain or branched alkyl groups having 1 to 12 carbon atoms in Z1, Z3, Z4 and Z5 can be exemplified by: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, dibutyl, tributyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, etc. Examples of cycloalkyl groups with 3 to 20 carbon atoms in Z1, Z3, Z4 and Z5 include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclooctadecyl, etc. The cycloalkyl group in Z2 can be the same as the cycloalkyl group with 3 to 20 carbon atoms, and is preferably cyclopentyl or cyclohexyl. As for the alkyl groups with 1 to 20 carbon atoms in Z 2, in addition to the straight-chain or branched alkyl groups with 1 to 12 carbon atoms, examples include tetradecyl, hexadecyl, and octadecyl.

[0146] Furthermore, among Z1, Z3, Z4, and Z5, examples of halogen atoms that can be substituted in the aforementioned alkyl, cycloalkyl, and phenyl groups include fluorine atoms, chlorine atoms, and bromine atoms. Among Z1, Z3, Z4 and Z5, the alkoxy group having 1 to 6 carbon atoms that can be substituted in the above-mentioned alkyl, cycloalkyl and phenyl groups can be exemplified by methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tributoxy and the like.

[0147] In general formula (A), Z1 is preferably an alkyl or phenyl group having 1 to 6 carbon atoms, more preferably methyl, ethyl, or phenyl, and even more preferably methyl. Furthermore, in general formula (A), Z3, Z4 and Z5 are preferably hydrogen atoms, methyl, ethyl, n-propyl or isopropyl in terms of brightness.

[0148] In general formula (A), Z2, in terms of compatibility, is preferably an alkyl group of 1 to 14 carbons substituted with a cycloalkyl group of 5 to 6 carbons, and more preferably an alkyl group of 1 to 10 carbons substituted with a cycloalkyl group of 5 to 6 carbons, and even more preferably cyclohexylmethyl or cyclopentylmethyl, and especially preferably cyclohexylmethyl.

[0149] As a photoinitiator represented by the above general formula (A), the oxime ester compound represented by the following chemical formula (A-1) is preferred in terms of suppressing brightness reduction. Examples of commercially available products include TR-PBG-3057 (manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.).

[0150] [Chem. 17] Chemical formula (A-1)

[0151] The photoinitiator represented by the above general formula (A) can be synthesized, for example, by using diphenyl sulfide or its derivatives, with appropriate selection of solvent, reaction temperature, reaction time, purification method, etc., depending on the materials used, according to Japanese Patent Publication No. 2012-526185. Alternatively, commercially available products can also be used.

[0152] Furthermore, α-aminoketone photoinitiators can also be used in this invention. As an α-aminoketone photoinitiator, in terms of inhibiting sublimation, an α-aminoketone photoinitiator containing a genus structure is preferred, and a compound represented by the following general formula (B) is preferred.

[0153] [Chemistry 18] General formula (B) (In general formula (B), Ra and Rb are each independently an alkyl group having 2 or more carbon atoms and 8 or fewer carbon atoms.)

[0154] <Compounds represented by general formula (B)> In the above general formula (B), Ra and Rb are each independently an alkyl group having 2 or more and 8 or fewer carbon atoms. This alkyl group can be any of a straight-chain, branched, cyclic, or combination thereof alkyl group. As this alkyl group, it can be the same as the alkyl group in the above general formula (A), wherein, from the viewpoint of suppressing the formation of sublimation and precipitates during drying, a straight-chain or branched alkyl group is preferred, and a straight-chain alkyl group is more preferred. Furthermore, the alkyl group preferably has 2 or more and 6 or fewer carbon atoms, and more preferably 3 or more and 5 or fewer carbon atoms. In the above general formula (B), Ra and Rb can be the same or different. If Ra and Rb are the same, they are easy to synthesize and have excellent productivity, which is better in this respect.

[0155] As a preferred specific example of a compound represented by the above general formula (B), the following chemical formula (B-1) can be cited, but is not limited thereto.

[0156] [Chemistry 19] Chemical formula (B-1)

[0157] The compound represented by the above general formula (B) can be synthesized, for example, by a method having the following steps: Step 1: React fumaryl with isobutyl chloride in the presence of aluminum trichloride to obtain 2-methyl-1-fumaryl-2-chloro-1-propanone; Step 2: Under a nitrogen atmosphere, using sodium methoxide as a catalyst, the 2-methyl-1-tandem-2-chloro-1-propanone obtained in Step 1 is epoxidized, and then reacted with sulfophylline to obtain 2-methyl-1-tandem-2-sulfophylline-1-propanone; and Step 3: The 2-methyl-1-furoyl-2-olinyl-1-propanone obtained in Step 2 is reacted with a chlorinated alkane having 2 or more carbon atoms and less in the presence of tetrabutylammonium bromide (TBAB) to obtain the compound represented by the above general formula (B). Furthermore, in step 3 above, by using two or more chloroalkanes, compounds in general formula (B) whose Ra and Rb are different can be obtained.

[0158] [Chemistry 20] Step 1 Step 2 Step 3

[0159] Regarding adjusting the pattern linewidth of the coloring layer, the above-mentioned oxime ester photoinitiator can also be used in combination with the α-aminoketone photoinitiator. In terms of improving contrast and suppressing sublimation, it is preferable to use the above-mentioned oxime ester photoinitiator in combination with the α-aminoketone photoinitiator containing a fusiform structure. Preferably, at least one of the oxime ester compounds represented by the above general formula (A) is used in combination with the compound represented by the above general formula (B).

[0160] Furthermore, in this invention, the photoinitiator is preferably a combination of the above-mentioned photoinitiator and a thiol sensitizer, wherein, in terms of improving hardening properties and contrast, it is preferably a combination of an oxime ester initiator and a thiol sensitizer. Furthermore, in this invention, in terms of adjusting sensitivity, the photoinitiator may also include oxime ester-based initiators, α-aminoketone-based photoinitiators, and thiol-based sensitizers.

[0161] Examples of thiol sensitizers include monofunctional thiol compounds with one thiol group and polyfunctional thiol compounds with two or more thiol groups. Examples of monofunctional thiols include: 2-mercaptobenzothiazole, 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercapto-5-methoxybenzothiazole, 2-mercapto-5-methoxybenzimidazole, 3-mercaptopropionic acid, methyl 3-mercaptopropionic acid, ethyl 3-mercaptopropionic acid, octyl 3-mercaptopropionic acid, etc. Examples of polyfunctional thiols include 1,4-bis(3-mercaptobutoxy)butane, 1,3,5-tris(3-mercaptobutoxyethyl)-1,3,5-tris(2,4,6(1H,3H,5H)-trione, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetra(3-mercaptobutyrate), pentaerythritol tetra(3-mercaptopropionate), dipentaerythritol hexa(3-mercaptopropionate), and tetraethylene glycol bis(3-mercaptopropionate).

[0162] There is no particular limitation on the total content of photoinitiator used in the photosensitive coloring resin composition of the present invention, as long as it does not impair the effect of the present invention. The content 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 coloring resin composition. If the content is above the lower limit, photocuring proceeds sufficiently, and the dissolution of the exposed portion during development can be suppressed. On the other hand, if it is below the upper limit, the reduction in brightness of the obtained colored layer due to yellowing can be suppressed. Furthermore, the solid components include all components except the solvent, and also include liquid multifunctional monomers, etc.

[0163] When the aforementioned photoinitiator contains an oxime ester-based photoinitiator, in terms of curability, the lower limit of the total content of the oxime ester-based photoinitiator in 100% by mass can be 40% or more by mass, 50% or more by mass, or 60% or more by mass, and the upper limit can be 100% by mass, and can be 90% or less by mass or 80% or less by mass.

[0164] When the above-mentioned photoinitiator contains a thiol-based sensitizer, the lower limit of the thiol-based sensitizer in the total amount of 100% by mass of the photoinitiator can be more than 1% by mass, more than 2% by mass, and the upper limit can be less than 20% by mass, less than 15% by mass, or less than 10% by mass. When the aforementioned photoinitiator includes oxime ester initiators and thiol sensitizers, in terms of curability, the total content of oxime ester initiators and thiol sensitizers in 100% by mass can be at least 5% by mass, at most 50% by mass, and at most 100% by mass, and can be at least 90% by mass or at least 80% by mass.

[0165] When the above-mentioned photoinitiator contains an α-aminoketone photoinitiator, the lower limit of the total content of α-aminoketone photoinitiators in 100% by mass of the total photoinitiator can be 5% by mass or more, 20% by mass or more, or 50% by mass or more, and the upper limit can be 95% by mass or less, and 80% by mass or less. When the aforementioned photoinitiator includes oxime ester initiators and α-aminoketone photoinitiators, in terms of adjusting sensitivity, the lower limit of the total content of α-aminoketone photoinitiators may be 5 parts by mass or more, 10 parts by mass or more, or 30% by mass or more, and the upper limit may be 80 parts by mass or less, or 50 parts by mass or less, relative to the total content of 100 parts by mass of oxime ester initiators.

[0166] [solvent] The solvent used in this invention is not particularly limited, as long as it is an organic solvent that does not react with the components in the photosensitive coloring resin composition and can dissolve or disperse them. The solvent can be used alone or in combination of two or more. Specific examples of solvents include: alcohol solvents such as methanol, ethanol, N-propanol, isopropanol, methoxy alcohol, and ethoxy alcohol; carbitol solvents such as methoxyethoxyethanol and ethoxyethoxyethanol; ester solvents such as ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl methoxypropionate, ethyl ethoxypropionate, ethyl lactate, methyl hydroxypropionate, ethyl hydroxypropionate, n-butyl acetate, isobutyl acetate, isobutyl butyrate, n-butyl butyrate, ethyl lactate, and cyclohexanol acetate; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and 2-heptanone; and glycol ether acetate solvents such as methoxyethyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy-3-methyl-1-butyl acetate, 3-methoxybutyl acetate, and ethoxyethyl acetate. Carbitol acetate solvents such as methoxyethoxyethyl ester, ethoxyethoxyethyl acetate, and butyl carbitol acetate (BCA); diacetates such as propylene glycol diacetate and 1,3-butanediol diacetate; glycol ether solvents such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, and dipropylene glycol dimethyl ether; aprotic amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; lactone solvents such as γ-butyrolactone; cyclic ether solvents such as tetrahydrofuran; unsaturated hydrocarbon solvents such as benzene, toluene, xylene, and naphthalene; saturated hydrocarbon solvents such as N-heptane, N-hexane, and N-octane; and aromatic hydrocarbons such as toluene and xylene. Among these solvents, in terms of the solubility of other components, glycol ether acetate-based solvents, carbitol acetate-based solvents, glycol ether-based solvents, and ester-based solvents are preferred. Specifically, the solvent used in this invention, in terms of the solubility of other components or suitability for coating, is preferably selected from one or more of the group consisting of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, butyl carbitol acetate (BCA), 3-methoxy-3-methyl-1-butyl acetate, ethyl ethoxypropionate, ethyl lactate, and 3-methoxybutyl acetate.

[0167] Furthermore, when using alkaline dispersants as other dispersants, it is preferable to use solvents containing alcoholic hydroxyl groups as solvents used in this invention in order to improve the overall solubility of the composition, suppress the precipitation of foreign matter in the coating film, and improve contrast. As a solvent containing an alcoholic hydroxyl group, an alkyl glycol monoalkyl ether is preferred, for example, one or more selected from the group consisting of ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether and propylene glycol monomethyl ether, with propylene glycol monomethyl ether being more preferred. When a solvent containing an alcoholic hydroxyl group is used as the solvent, the amount relative to the total amount of solvent may be 5% by mass or more, 10% by mass or more, with an upper limit of 100% by mass, and may be 50% by mass or less, or 30% by mass or less.

[0168] In the photosensitive coloring resin composition of the present invention, the solvent content only needs to be appropriately set within a range that allows for the precise formation of the colored layer. The solvent content relative to the total amount of the photosensitive coloring resin composition containing the solvent is typically preferably in the range of 55% to 95% by mass, more preferably 65% ​​to 88% by mass. By keeping the solvent content within the above range, excellent coatability can be achieved.

[0169] [Add any ingredients] Various additives may also be included in the photosensitive coloring resin composition as needed. Examples of additives include: antioxidants, polymerization stoppers, chain transfer agents, leveling agents, plasticizers, surfactants, defoamers, silane coupling agents, ultraviolet absorbers, and adhesion promoters. Specific examples of surfactants and plasticizers include those described in Japanese Patent Application Publication No. 2013-029832.

[0170] <Method for manufacturing photosensitive coloring resin composition> The method for manufacturing the photosensitive coloring resin composition of the present invention, in terms of improving contrast, preferably comprises a colorant, at least one of the above-mentioned block copolymers having acidic groups and graft copolymers having acidic groups, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, a solvent, and various additives as needed. The colorant can be prepared by uniformly dissolving or dispersing at least one of the above-mentioned block copolymers having acidic groups and graft copolymers having acidic groups in a solvent, and can be prepared by mixing using a known mixing method. As a method for preparing the resin composition, examples include: (1) firstly, adding a colorant and at least one of the above-mentioned block copolymers with acidic groups and graft copolymers with acidic groups to a solvent to prepare a colorant solution or colorant dispersion, and mixing an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and various additives as needed into the colorant solution or colorant dispersion; (2) simultaneously adding a colorant, at least one of the above-mentioned block copolymers with acidic groups and graft copolymers with acidic groups, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and various additives as needed to a solvent. (2) A method of adding components and mixing; (3) A method of adding at least one of the above-mentioned block copolymers with acidic groups and graft copolymers with acidic groups, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and various additives as needed to a solvent and mixing them, and then adding a colorant and dissolving or dispersing it; (4) A method of adding a colorant, a dispersant, and an alkali-soluble resin to a solvent to prepare a colorant solution or a colorant dispersion, and then adding an alkali-soluble resin, a solvent, a photopolymerizable compound, a photoinitiator, and various additives as needed to the colorant solution or colorant dispersion and mixing them. Of these methods, the methods described in (1) and (4) above are preferred in terms of effectively preventing pigment aggregation so as to allow it to be evenly dispersed.

[0171] Examples of dispersers used for dispersion processing include: two-roll mills, three-roll mills, ball mills, vibratory ball mills, paint conditioners, continuous disc bead mills, and continuous ring bead mills. For optimal dispersion conditions in bead mills, the particle diameter used is preferably 0.03 mm or more and 2.00 mm or less, more preferably 0.10 mm or more and 1.0 mm or less.

[0172] II. Color Filters The color filter of the present invention comprises at least a substrate and a coloring layer disposed on the substrate, wherein at least one of the coloring layers is a hardened form of the photosensitive coloring resin composition of the present invention.

[0173] The color filter of 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 coloring layer 3.

[0174] (Coloring layer) At least one of the color layers used in the color filter of the present invention is a cured product of the photosensitive coloring resin composition of the present invention. The coloring layer is usually formed in the opening of the light-shielding part on the substrate below, and usually contains a coloring pattern of three or more colors. Furthermore, there are no particular limitations on the arrangement of the color layers; for example, they can be set to common arrangements such as stripes, mosaics, triangles, or 4-pixel configurations. Also, the width and area of ​​the color layers can be set arbitrarily. The thickness of the coloring layer is appropriately controlled by adjusting the coating method, the concentration or viscosity of the solid components in the photosensitive coloring resin composition, etc., and is usually preferably in the range of 1 μm to 5 μm.

[0175] The aforementioned coloring layer can be formed, for example, by the following method. First, the photosensitive coloring resin composition of the present invention is coated onto the substrate using coating methods such as spraying, dip coating, rod coating, roller coating, spin coating, and die coating to form a wet coating film. Spin coating and die coating are preferred methods. Subsequently, the wet coating is heated and dried using a heating plate or oven. It is then exposed to light through a mask with a specific pattern, causing the alkali-soluble resin and photopolymerizable compounds to undergo a photopolymerization reaction, thus forming a hardened coating. Examples of light sources used for exposure include low-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, ultraviolet light, and electron beams. The exposure amount is adjusted appropriately based on the light source used and the thickness of the coating. Furthermore, after exposure, heat treatment can be performed to promote the polymerization reaction. The heating conditions are appropriately selected based on the mixing ratio of the components in the photosensitive coloring resin composition used or the thickness of the coating film.

[0176] Next, a developing solution is used to develop the film, dissolving and removing the unexposed areas to form the desired pattern. The developing solution is typically a solution made by dissolving an alkali in water or a water-soluble solvent. An appropriate amount of surfactant may also be added to this alkaline solution. Furthermore, the developing method can be a conventional method. After development, the coating is typically washed with the developer and dried to form a hardened film of the photosensitive coloring resin composition. Alternatively, after development, heat treatment can be performed to fully harden the coating. There are no particular limitations on the heating conditions; they can be selected appropriately based on the intended use of the coating. The coloring layer can be a coloring layer for fine patterns with a line width of less than 40 μm, or it can be a coloring layer for fine patterns with a line width of less than 20 μm.

[0177] (shading part) The light-shielding portion in the color filter of the present invention is formed in a pattern on the substrate described below, and can be configured to be the same as that used as the light-shielding portion in a conventional color filter. The shape of the pattern for the aforementioned light-shielding portion is not particularly limited; for example, striped or matrix-like shapes can be used. The light-shielding portion can also be a thin film of metal such as chromium formed by sputtering or vacuum evaporation. Alternatively, the light-shielding portion can be a resin layer containing light-shielding particles such as carbon microparticles, metal oxides, inorganic pigments, or organic pigments in the resin binder. In the case of a resin layer containing light-shielding particles, methods include using a photosensitive resist and patterning by development, using inkjet ink containing light-shielding particles for patterning, and heat transfer printing of the photosensitive resist.

[0178] The thickness of the light-shielding part is set to about 0.2 μm to 0.4 μm when it is a metal thin film, and to about 0.5 μm to 2 μm when it is formed by dispersing or dissolving black pigment in adhesive resin.

[0179] (Substrate) The substrate can be a transparent substrate, a silicon substrate, or a substrate on which aluminum, silver, or silver / copper / palladium alloy thin films are formed. Other color filter layers, resin layers, TFTs (Thin-Film Transistors), circuits, etc., can also be formed on such substrates.

[0180] The transparent substrate used in the color filter of this invention is not particularly limited, as long as it is a substrate that is transparent to visible light, and the transparent substrate used in ordinary color filters can be used. Specifically, examples include: transparent rigid materials that do not have flexibility, such as quartz glass, alkali-free glass, and synthetic quartz plates, or transparent flexible materials that have flexibility, such as transparent resin films, optical resin plates, and flexible glass. The thickness of the transparent substrate is not particularly limited, and can be, for example, around 100 μm to 1 mm, for use in the color filter of the present invention. Furthermore, in addition to the aforementioned substrate, light-shielding portion, and coloring layer, the color filter of the present invention may also have, for example, an outer coating layer or a transparent electrode layer, and further an alignment film or alignment protrusion, columnar spacers, etc.

[0181] III. Display Device The display device of the present invention is characterized by having the color filter described above. In the present invention, the configuration of the display device is not particularly limited, and can be appropriately selected from previously known display devices, such as liquid crystal displays or organic light-emitting displays.

[0182] Liquid crystal display device The liquid crystal display device of the present invention includes the color filter, the opposing substrate, and the liquid crystal layer formed between the color filter and the opposing substrate as described above. The liquid crystal display device of the present invention will be described with reference to the reference figures. FIG2 is a schematic diagram showing an example of the liquid crystal display device of the present invention. As illustrated in FIG2, the liquid crystal display device 40 of the present invention includes a color filter 10, a counter substrate 20 having a TFT array substrate, etc., and a liquid crystal layer 30 formed between the color filter 10 and the counter substrate 20. Furthermore, the liquid crystal display device of the present invention is not limited to the configuration shown in FIG2, and can be configured in a configuration commonly known as a liquid crystal display device using a color filter.

[0183] The driving method for the liquid crystal display device of the present invention is not particularly limited, and a driving method commonly used in liquid crystal display devices can be adopted. Examples of such driving methods include TN (Twisted Nematic), IPS (In-Plane Switching), OCB (optically compensated bend), and MVA (Multi-Domain Vertical Alignment). In the present invention, any of these methods may preferably be used. Furthermore, as a counter substrate, it can be appropriately selected and used according to the driving method of the liquid crystal display device of the present invention. Furthermore, as the liquid crystal constituting the liquid crystal layer, various liquid crystals with different dielectric anisotropy and mixtures thereof can be used in the driving method of the liquid crystal display device according to the present invention.

[0184] As a method for forming the liquid crystal layer, methods commonly used for fabricating liquid crystal cells can be used, such as vacuum injection or liquid crystal droplet application. After forming the liquid crystal layer by the above methods, the liquid crystal cell is slowly cooled to room temperature, thereby allowing the encapsulated liquid crystal to align.

[0185] Organic light-emitting display device The organic light-emitting display device of the present invention includes the color filter and organic light-emitting body described above. The organic light-emitting display device of the present invention will be described with reference to the reference 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 includes a color filter 10 and an organic light-emitting element 80. An organic protective layer 50 or an inorganic oxide film 60 may also be provided between the color filter 10 and the organic light-emitting element 80.

[0186] As a method for stacking the organic light-emitting diode 80, examples include forming a transparent anode 71, a hole injection layer 72, a hole transport layer 73, a light-emitting layer 74, an electron injection layer 75, and a cathode 76 sequentially on the upper surface of a color filter, or bonding the organic light-emitting diode 80 formed on another 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, and cathode 76, and other components of the organic light-emitting diode 80, can be appropriately made using known methods. The organic light-emitting display device 100 manufactured in the above manner can be applied, for example, to a passively driven organic EL display or an actively driven organic EL display. Furthermore, the organic light-emitting display device of the present invention is not limited to the configuration shown in FIG3, but can be configured in a configuration commonly known as an organic light-emitting display device using a color filter. [Example]

[0187] Hereinafter, specific embodiments of the present invention will be described. However, these descriptions are not intended to limit the scope of the invention. The acid value was determined according to the measurement method described in the specification of this invention. Furthermore, the mass average molecular weight (Mw) and Mw / Mn were determined according to the determination method described in the above-mentioned specification of the present invention, and by using GPC (gel permeation chromatography) as a standard polystyrene conversion value.

[0188] (Manufacturing Example 1: Synthesis of Phthalocyanine Compound 1) Add 5.0 g (25.0 mmol) of tetrachlorophthalonitrile and 25 ml of acetone to a 100 ml flask, and stir at 40 °C until dissolved. Then add 8.31 g (50.0 mmol) of ethyl 4-hydroxybenzoate, and stir at 40 °C until dissolved. Next, add 5.18 g (37.5 mmol) of potassium carbonate, and react at 0 °C for 3 hours. After the reaction is complete, remove the potassium carbonate by filtration. For the obtained reaction solution, remove the solvent by evaporation using an evaporator, dissolve the obtained solid in chloroform, and separate the liquid using pure water. The organic layer after separation was recrystallized in acetone to obtain intermediate 1. Intermediate 1 was analyzed using LC-MS (liquid chromatography-mass spectrometer) (manufactured by Agilent Technologies, quadrupole LC / MS, Agilent 1260 Infinity). The representative chemical structure of intermediate 1 is shown below.

[0189] [Chemistry 21] Intermediate 1

[0190] 13.94 g (8.00 mmol) of intermediate and 19.7 g of benzonitrile were added to a 50 ml flask, followed by 0.64 g (2.00 mmol) of zinc iodide. The mixture was stirred at 150 °C for 16 hours while reacting. After cooling the reaction solution to room temperature, 20 ml of a mixture of water and methanol (3:7) was added. The precipitate was collected using filter paper and washed repeatedly with isopropanol in a beaker by stirring and filtration. The obtained product was dried to obtain phthalocyanine halide compound 1. The phthalocyanine halide compound 1 was analyzed using MALDI-TOF-MS (Matrix Assisted Laser Desorption Ionization Time of Flight Mass Spectrometer) (manufactured by Shimadzu Corporation, MALDI-8020). The representative chemical structure of halophthalocyanine compound 1 is shown below.

[0191] [Chemistry 22]

[0192] (Preparation Example 1: Synthesis of an acid-containing block copolymer 1 (a block copolymer containing A blocks comprising structural units derived from carboxyl-containing vinyl unsaturated monomers and B blocks comprising structural units derived from (meth)acrylate alkyl esters)) 150.0 parts by weight of propylene glycol monomethyl ether acetate (PGMEA), 2.0 parts by weight of iodine (manufactured by Fujifilm and Koichi Chemical Co., Ltd.), 8.0 parts by weight of 2,2'-azobis(4-methoxy-2,4-dimethylpentanonitrile) (manufactured by Fujifilm and Koichi Chemical Co., Ltd., "V-70"), 50.0 parts by weight of methyl methacrylate (manufactured by Mitsubishi Chemical Co., Ltd., abbreviated as MMA), 30.0 parts by weight of butyl methacrylate (manufactured by Mitsubishi Chemical Co., Ltd., abbreviated as BMA), and 0.04 parts by weight of succinimide (manufactured by Fujifilm and Koichi Chemical Co., Ltd.) were added to a four-necked flask equipped with a stirrer and a nitrogen inlet tube. The mixture was stirred at 40°C for 5 hours under nitrogen atmosphere to produce a B-block copolymer. Next, 20.0 parts by weight of methacrylic acid (manufactured by Mitsubishi Chemical Corporation, MAA) were added, and the mixture was stirred at 40°C for 5 hours. The solids composition was determined and converted based on the non-volatile components, resulting in a polymerization conversion rate of 99%. The reaction solution was purified using n-hexane, and PGMEA was added at a solids content of 30% to obtain a block copolymer 1 solution containing acidic groups. The obtained block copolymer 1 containing acidic groups had a mass-average molecular weight (Mw) of 13,000, a molecular weight distribution (mass-average molecular weight / number-average molecular weight, hereinafter referred to as "Mw / Mn") of 1.3, and an acid value of 130 mgKOH / g.

[0193] (Preparation Example 2: Synthesis of Graft Copolymer 2 Containing Acid Groups) (1) Synthesis of giant monomer m1 Add 80.0 parts by weight of PGMEA to a four-necked flask equipped with a stirrer and a nitrogen inlet tube, and heat to 90°C under nitrogen atmosphere. Over 1.5 hours, add dropwise a mixed solution of 62.5 parts by weight of MMA, 37.5 parts by weight of BMA, 4.0 parts by weight of 2-mercaptoethanol (manufactured by Fujifilm and Kogyo Pharmaceutical Co., Ltd.), 30 parts by weight of PGMEA, and 1.0 part by weight of 2,2'-azobisisobutyronitrile (manufactured by Fujifilm and Kogyo Pure Chemicals Co., Ltd., AIBN), and then heat and stir for 3 hours. The nitrogen flow was then stopped, and the reaction solution was cooled to 80°C. 8.74 parts by weight of Karenz MOI (manufactured by Showa Denko, Ltd.), 0.125 parts by weight of dibutyltin dilaurate (manufactured by Fujifilm and Kogyo Pure Chemical Industries, Ltd.), 0.125 parts by weight of p-methoxyphenol (manufactured by Fujifilm and Kogyo Pure Chemical Industries, Ltd.), and 10 parts by weight of PGMEA were added, and the mixture was stirred for 3 hours to obtain a 49.5% by weight solution of the macromonomer m1. GPC analysis of the obtained macromonomer m1 showed a mass-average molecular weight (Mw) of 4400 and a molecular weight distribution (Mw / Mn) of 1.7.

[0194] (2) Synthesis of graft copolymer 2 containing acidic groups 100.0 parts by weight of PGMEA was added to a four-necked flask equipped with a stirrer and a nitrogen inlet tube, and the mixture was heated to 85°C under nitrogen atmosphere. Over 1.5 hours, a mixed solution of the above-mentioned macromonomer m1 solution (79.9 parts by weight of solids), 20.1 parts by weight of MAA, 2.7 parts by weight of n-dodecyl mercaptan (manufactured by Nippon Oil Co., Ltd.), 40.0 parts by weight of PGMEA, and 1.0 parts by weight of AIBN was added dropwise, and the mixture was heated and stirred for 3 hours. Then, over 10 minutes, a mixture of 0.10 parts by weight of AIBN and 10.0 parts by weight of PGMEA was added dropwise, and the mixture was heated and stirred at the same temperature for 1 hour, thereby obtaining a 30.0% by weight solution of the acidic graft copolymer 2. The obtained acidic graft copolymer 2 had a mass-average molecular weight (Mw) of 13300, a molecular weight distribution (Mw / Mn) of 2.1, and an acid value of 128 mgKOH / g.

[0195] (Preparation Example 3: Manufacturing of an acid-containing block copolymer 3 (a block copolymer having at least one of the structural units selected from those represented by the above general formula (I-3))) (1) Synthesis of block copolymer A Referring to Synthesis Example 6 described in Japanese Patent No. 5895925, a 40% PGMEA solution of a diblock copolymer comprising 50.0 parts by weight of MMA, 30.0 parts by weight of BMA, 20.0 parts by weight of benzyl methacrylate (manufactured by Mitsubishi Chemical Co., Ltd., abbreviated as BzMA), and 25 parts by weight of glycidyl methacrylate (manufactured by Mitsubishi Chemical Co., Ltd., abbreviated as GMA) was obtained. The obtained block copolymer A had a mass-average molecular weight (Mw) of 9500 and a molecular weight distribution (Mw / Mn) of 1.2. (2) Manufacturing of a polymer (block copolymer 3 containing an acidic group) having at least one of the structural units selected from those represented by the above general formula (I-3). Block copolymer A100.0 parts by weight, PGMEA86.70 parts by weight, and phenylphosphonic acid (Nikssan Chemical Manufacturing Co., Ltd., PPA)8.90 parts by weight were added to a reactor, and the mixture was stirred at 90°C for 2 hours to obtain a polymer solution (25% by weight of solids) containing at least one structural unit selected from the structural units represented by the above general formula (I-3). The acid value of the obtained block copolymer 3 containing acid groups was 65 mgKOH / g.

[0196] (Comparative Preparation Example 1: Preparation of random copolymer C1 containing acid groups) 150.0 parts by weight of PGMEA were added to a four-necked flask equipped with a stirrer and a nitrogen inlet tube. The flask was heated to 100°C under nitrogen atmosphere, and then a mixture of 50.0 parts by weight of MMA, 30.0 parts by weight of BMA, 20.0 parts by weight of MAA, and 3.0 parts by weight of AIBN was added dropwise over 1.5 hours. The mixture was then heated at 100°C for 3 hours, followed by the addition of 83.3 parts by weight of PGMEA to obtain a 30% by weight solution. The obtained random copolymer containing acidic groups had a mass-average molecular weight (Mw) of 12700, a molecular weight distribution (Mw / Mn) of 1.8, and an acid value of 128 mgKOH / g.

[0197] (Preparation Example 4: Preparation of Alkali-Soluble Resin 1 Solution) 150.0 parts by weight of PGMEA were added to a four-necked flask equipped with a stirrer and a nitrogen inlet tube. The flask was heated to 100°C under nitrogen atmosphere, and a mixture of 40 parts by weight of BzMA, 15.0 parts by weight of MMA, 25.0 parts by weight of MAA, and 3.0 parts by weight of AIBN was continuously added dropwise over 3 hours. After the addition was completed, the flask was heated at 100°C for 3 hours to obtain a polymer solution. The mass average molecular weight (Mw) of this polymer solution was 7000. Subsequently, 20 parts by weight of GMA, 0.2 parts by weight of triethylamine, and 0.05 parts by weight of p-methoxyphenol were added to the obtained polymer solution, and the mixture was heated at 110°C for 10 hours to obtain alkali-soluble resin solution 1. The obtained resin had an acid value of 74 mgKOH / g and a mass average molecular weight (Mw) of 12000. The solid content of alkali-soluble resin solution 1 was 40% by weight.

[0198] (Preparation Example 5: Manufacturing of Compound A) (1) Synthesis of intermediate A1 Add 0.2 mol of diphenyl sulfide, 0.22 mol of pulverized AlCl3, and 150 ml of dichloroethane to a 500 ml four-necked flask and stir. Introduce argon gas and cool in an ice bath until the temperature drops to 0°C. Then, begin dropwise addition of a solution containing 0.22 mol of cyclohexylpropionic acid chloride and 42 g of dichloroethane, while maintaining the temperature below 10°C for approximately 1.5 hours. Raise the temperature to 15°C and stir for 2 hours, then drain the reaction mixture. The reaction mixture was slowly added to a solution of 400 g ice and 65 ml concentrated hydrochloric acid under stirring. The lower layer was separated using a separatory funnel, and the upper layer was extracted with 50 ml of dichloroethane. The extract was then combined with the lower layer. The mixture was then washed with a NaHCO3 solution containing 10 g NaHCO3 and 200 g water, followed by three washes with 200 ml of water until the pH was neutral. The mixture was dried over 60 g anhydrous MgSO4 to remove moisture, and the dichloroethane was evaporated by rotary evaporation. The remaining solid powder in the rotary evaporator was added to 200 ml of petroleum ether, filtered by suction, and then added to 150 ml of anhydrous ethanol and heated under reflux. The mixture was then cooled to room temperature and then cooled on ice for 2 hours. After filtration by suction, the mixture was dried in an oven at 50°C for 2 hours to obtain intermediate A1.

[0199] [Chemistry 23] Intermediate A1

[0200] (2) Synthesis of intermediate A2 Add 42 g of the above intermediate A1, 400 g of tetrahydrofuran, 200 g of concentrated hydrochloric acid, and 24.2 g of isoamyl nitrite to a 500 ml four-necked flask. Stir at room temperature for 5 hours, then drain the reaction solution. The reaction solution was placed in a large beaker, 1000 ml of water was added, and the mixture was stirred and allowed to stand overnight, allowing for layering to obtain a yellow, viscous liquid. The viscous liquid was extracted with dichloroethane, and then dried with 50 g of anhydrous MgSO₄. The mixture was then filtered under suction, and the solvent was removed by rotary evaporation of the filtrate, yielding an oily, viscous substance. This substance was then placed in 150 ml of petroleum ether, stirred, precipitated, and filtered under suction to obtain a white powdery solid. This powder was then dried at 60°C for 5 hours to obtain intermediate A2.

[0201] [Chemistry 24] Intermediate A2

[0202] (3) Synthesis of compound A Add 34 g of the above intermediate A2, 350 ml of dichloroethane, and 12.7 g of triethylamine to a 1000 ml four-necked flask and stir. Cool in an ice bath until the temperature reaches 0°C. Then, begin adding a solution containing 15.7 g of acetyl chloride and 15 g of dichloroethane dropwise over approximately 1.5 hours. After stirring for 1 hour, add 500 ml of cold water dropwise and separate the layers using a separatory funnel. Wash once with 200 ml of 5% NaHCO3 solution, then twice with 200 ml of water until the pH is neutral. Next, wash once with a dilute hydrochloric acid solution of 20 g concentrated hydrochloric acid and 400 ml of water, then three times with 200 ml of water. Finally, dry with 100 g of anhydrous MgSO4 to remove the solvent by rotary evaporation, obtaining a viscous liquid. The white solid precipitated by adding an appropriate amount of methanol to the viscous liquid was filtered and dried to obtain compound IA. Furthermore, the molecular weight of compound A is 395.51.

[0203] [Chemistry 25] Compound A

[0204] (Preparation Example 6: Manufacturing of Compound B) 35.5 g of fumonisin, 120 g of dichloromethane, and 30.1 g of isobutyl chloride were mixed and cooled to a temperature above -5°C and below 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 injected into a mixture of 50 g of hydrochloric acid and 150 g of ice, followed by the addition of 150 g of dichloromethane and stirring for 3 hours. The resulting organic phase was then concentrated by separation, and 150 g of methanol was added to produce a solid phase. This solid phase was then cooled to crystallize, filtered, and dried to obtain 2-methyl-1-fumonisin-2-chloro-1-propanone. 27 g of the obtained 2-methyl-1-tandem-2-chloro-1-propanone was added to a 250 mL three-necked flask, followed by the addition of 1.76 g of calcium oxide and 7.0 g of sodium methoxide. The mixture was reacted at 68 °C for 6 hours to carry out epoxidation. Subsequently, after cooling to 50 °C, 68 g of ferroline was added and the reaction was carried out for 14 hours. The mixture was then decolorized with activated carbon and filtered, followed by reflux using a mixed solvent of toluene and methanol to obtain 2-methyl-1-tandem-2-ferroline-1-propanone. 20 g of the obtained 2-methyl-1-enyl-2-oline-1-propanone, 0.6 g of butylammonium 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. Subsequently, the temperature was lowered, and 50 g of water and 58 g of toluene were added, followed by stirring for 0.5 hours. The obtained organic phase was decolorized with activated carbon, filtered, and then crystallized using a mixed solvent of toluene and methanol. The precipitate was filtered and dried to obtain compound B. Furthermore, the molecular weight of compound B is 433.63.

[0205] [Chemistry 26] Compound B

[0206] (Examples 1-9, Comparative Examples 1-3: Manufacturing of photosensitive coloring resin compositions 1-9 and comparative photosensitive coloring resin compositions C1-C3) Phthalocyanine compound 1, used as a pigment in Example 1, a copolymer solution, and a solvent were mixed in the amounts shown in Table 1 by mass to dissolve the pigment and obtain a pigment solution. In this solution, an alkali-soluble resin 1 solution, a photopolymerizable compound (DPHA, dipentaerythritol hexaacrylate, trade name ARONIXM403, manufactured by Toa Synthetic Co., Ltd.), compound A (oxime ester photoinitiator) obtained in Example 5 as a photoinitiator, a thiol sensitizer (trade name Karenz MT PE1, manufactured by Showa Denko), a fluorinated surfactant (trade name MEGAFAC F-559, manufactured by DIC), and a silane coupling agent (trade name KBM503, manufactured by Shin-Etsu Silicones) were mixed in the manner shown in Table 1 to obtain photosensitive coloring resin compositions 1-9 and comparative photosensitive coloring resin compositions C1-C3.

[0207] (Comparative Example 4: Comparative manufacture of photosensitive coloring resin composition C4) Without using a copolymer solution, phthalocyanine compound 1 (used in Example 1 of pigment manufacturing) and a solvent were mixed in the amounts shown in Table 1 by mass to obtain a pigment solution. Then, an alkali-soluble resin 1 solution, a photopolymerizable compound, a photoinitiator, a fluorinated surfactant, and a silane coupling agent were mixed into this solution in such a manner as shown in Table 1 to obtain a comparative photosensitive coloring resin composition C4.

[0208] [Evaluation Method] (1) Evaluation of the solubility of the photosensitive coloring resin composition After the photosensitive coloring resin composition is prepared, and after it is left to stand at 25°C and 45% humidity for 2 weeks, visually observe whether there are any insoluble substances. (Evaluation Criteria) 〇: No insoluble matter exists ×: Insoluble matter is present.

[0209] (2) Evaluation of the hardened film of the photosensitive coloring resin composition The photosensitive coloring resin compositions were coated to a thickness of 0.7 mm onto a 100 mm × 100 mm glass substrate (manufactured by NH TECHNO GLASS, Inc., "NA35") using a spin coater. The substrate was then dried at 80°C for 3 minutes using a heating plate, irradiated with 60 mJ / cm² ultraviolet light using an ultra-high pressure mercury lamp, and then baked in a cleanroom oven at 230°C for 30 minutes. The film thickness was adjusted to achieve a chromaticity of y=0.425 under C light source, thus forming a colored layer.

[0210] <Extraction of Foreign Matter> The colored layer was observed under 200x reflected light using an optical microscope and evaluated according to the following evaluation criteria. (Evaluation criteria for foreign matter precipitation) A: No precipitates were observed under 200x reflected light using an optical microscope. B: Under 200x reflected light observation with an optical microscope, less than 10 tiny precipitates less than 1 μm were observed in each 1 mm square area. C: Under 200x reflected light observation with an optical microscope, more than 10 tiny precipitates less than 1 μm were observed in each 1 mm square area. D: Under 200x reflected light observation with an optical microscope, more than 10 precipitates larger than 1 μm were observed in each 1 mm square area.

[0211] Contrast The contrast ratio of each colored layer obtained in the examples and comparative examples was measured using a contrast measurement device CT-1B manufactured by Tsubosaka Electric and a fiber spectrophotometer OSP-SP200 manufactured by Olympus.

[0212] (3) Evaluation of the plate-making properties of photosensitive coloring resin compositions <Development Time Evaluation> The photosensitive coloring resin compositions obtained in the examples and comparative examples were coated onto glass substrates (manufactured by NH TECHNO GLASS, Inc., "NA35") using a spin coater. After baking, the resulting colored layers were formed on the glass substrates at 80°C for 3 minutes, thereby forming the colored layers. The colored layers were then irradiated with 60 mJ / cm² ultraviolet light through a photomask using an ultra-high pressure mercury lamp. Subsequently, the glass substrates with the colored layers were developed using a 0.05% (w / w) potassium hydroxide aqueous solution as an alkaline developer for 60 seconds. The development time was measured as the time until the colored layers completely dissolved and the glass surface at the location where the colored layers were formed appeared. (Evaluation Criteria) A: The time until the glass surface appeared was less than 30 seconds. B: The time from when the glass surface appears to be more than 30 seconds but less than 40 seconds. C: The time until the glass surface appears is more than 40 seconds. If the above evaluation criteria are A or B, it can be used in actual applications; if the evaluation result is A, the effect is even better.

[0213] <Line width offset> The photosensitive coloring resin compositions obtained in the examples and comparative examples were coated onto glass substrates (manufactured by NH TECHNO GLASS, Inc., "NA35") using a spin coater. After baking, the resulting colored layers were formed on the glass substrates at 80°C for 3 minutes, thereby forming the colored layers. The colored layers were then irradiated with 60 mJ / cm² ultraviolet light through a 90 μm aperture using an ultra-high pressure mercury lamp. Subsequently, the glass substrates with the colored layers were showered and developed for 60 seconds using a 0.05% by mass potassium hydroxide aqueous solution as an alkaline developer, and then baked in a cleanroom oven at 230°C for 30 minutes to produce colored substrates with individual fine line patterns. The width of the fine line patterns of the formed colored layers was measured at five locations using an optical microscope, and the line width offset was evaluated by the difference between the average line width and the aperture of the mask.

[0214] <Solvent Resolvability Evaluation> A glass substrate, 0.5 cm wide and 10 cm long, was immersed at its front end in the photosensitive coloring resin composition for color filters obtained in the examples and comparative examples, coating a 1 cm length portion of the glass substrate. The glass substrate was then lifted and placed horizontally in a constant temperature and humidity chamber for drying at 23°C and 70% RH for 30 minutes. Subsequently, the glass substrate with the dried coating was immersed in PGMEA for 15 seconds. The redissolution status of the dried coating was then visually assessed and evaluated. (Solvent redissolvability evaluation criteria) A: The dried coating has completely dissolved. B: Insoluble residues from the release flaking of the dried coating film produced in the solvent. C: The release liner of the dried coating did not dissolve in the solvent. D: The dried coating has not peeled off or dissolved. If the above evaluation criteria are A or B, it can be used in actual applications; if the evaluation result is A, the effect is even better.

[0215] [Table 1] Table 1 Material Solid content Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Pigment Compound 1 100.0% 6.64 6.64 6.64 6.64 6.64 6.64 6.64 6.64 6.64 6.64 6.64 6.64 6.64 copolymer solution Solution of block copolymer containing acid groups 30.0% 5.06 2.53 2.53 5.06 5.06 5.06 5.06 Solution of graft copolymer containing acid groups 30.0% 5.06 Solution of block copolymer containing acidic groups 25.0% 6.07 Block copolymer solution containing basic groups 60.0% 1.26 1.26 2.53 2.53 C1 solution of random copolymer containing acidic groups 30.0% 5.06 solvent PGMEA - 73.83 73.83 72.82 62.58 75.10 61.31 73.83 73.83 73.83 73.83 63.84 76.36 75.09 PGME - 12.52 12.52 12.52 Photopolymers DPHA 100.0% 7.08 7.08 7.08 7.08 7.08 7.08 7.08 7.08 7.08 7.08 7.08 7.08 7.08 Photoinitiator Starting agent 1 100.0% 2.53 2.53 2.53 2.53 2.53 2.53 1.77 1.77 3.16 2.53 2.53 2.53 2.53 Initiator 2 100.0% 0.63 0.63 0.63 0.63 0.63 0.63 0.63 0.63 0.63 0.63 0.63 0.63 Initiator 3 100.0% 0.76 Initiator 4 100.0% 0.76 Alkali-soluble resins Resin 1 solution 40.0% 3.79 3.79 3.79 3.79 3.79 3.79 3.79 3.79 3.79 3.79 3.79 3.79 7.59 Surface and Interface Adjuster Additive 1 100.0% 0.04 0.04 0.04 0.04 0.04 0.04 0.04 0.04 0.04 0.04 0.04 0.04 0.04 Additive 2 100.0% 0.40 0.40 0.40 0.40 0.40 0.40 0.40 0.40 0.40 0.40 0.40 0.40 0.40 total 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 resin Solubility (initial) 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 × × 〇 Composition Solubility (over time) 〇 〇 〇 〇 〇 〇 〇 〇 〇 × 〇 〇 × Hardened film Foreign matter precipitation A A A A B A A B A D D D D Contrast 19910 18539 19652 21174 15689 18161 17632 14831 17756 11148 7891 3617 575 plate making radioactivity A A A B B A A A A B C C A Line width offset (μm) - 90 μm opening mask +2 μm +2 μm +2 μm +2 μm +2 μm +2 μm -1 μm -1 μm -3 μm +2 μm +2 μm +2 μm +2 μm Resolubility B B B A A B B B B C A A D

[0216] Furthermore, the abbreviations in the table are as follows. Solution of block copolymer 1 containing acidic groups: Preparation Example 1 (solid content 30.0%) Solution of graft copolymer 2 containing acidic groups: Preparation Example 2 (solid content 30.0%) Solution of block copolymer 3 containing acidic groups: Preparation Example 3 (solid content 25.0%) Block copolymer solution containing basic groups: Trade name LP-N6919, manufactured by BYK-Chemie Japan Co., Ltd., solids content 60% by mass. Random copolymer C1 solution containing acidic groups: Comparative preparation example 1 (solid content 30.0%) PGMEA: Propylene Glycol Monomethyl Ether Acetate PGME: Propylene Glycol Monomethyl Ether DPHA: Dipentaerythritol hexaacrylate (trade name ARONIX M403, manufactured by Toa Sangyo Co., Ltd.) Initiator 1: Compound A (oxime ester-based photoinitiator) obtained in Preparation Example 5. Initiator 2: Thiol-based sensitizer (trade name Karenz MT PE1, manufactured by Showa Denko) Initiator 3: Compound B obtained in Preparation Example 6 (an α-aminophenolic photoinitiator containing a genus structure). Initiator 4: α-Aminophenol-based photoinitiator (trade name Lunacure 907, manufactured by DKSH) Resin 1 solution: The alkali-soluble resin 1 solution (40% solids) obtained in Preparation Example 4 Additive 1: Fluorinated surfactant (trade name MEGAFAC F-559, manufactured by DIC Corporation) Additive 2: Silane coupling agent (trade name KBM503, manufactured by Shin-Etsu Silicones)

[0217] <Summary of Results> It was clarified that the photosensitive coloring resin compositions of Examples 1-9, which combine at least one of a block copolymer with acidic groups and a graft copolymer with acidic groups with a specific phthalocyanine compound, exhibit good solubility and storage stability even with a high dye concentration composition (D(dye:phthalocyanine compound) / V(solids other than pigment) = 0.5), and can form a colored layer that inhibits the precipitation of foreign matter in the hardened film after baking and improves contrast. The photosensitive coloring resin compositions of Examples 1-9 were also found to have good developability and solvent resolubility. Although Examples 4 and 5 combined block copolymers with basic and acidic groups, both showed improved solvent resolubility. Furthermore, it was clarified that when combining block copolymers with basic and acidic groups, using a solvent with alcoholic hydroxyl groups in combination with PGMEA as the solvent resulted in improved contrast compared to using only the block copolymers with acidic groups. It is speculated that combining block copolymers with acidic and basic groups, and using a solvent with alcoholic hydroxyl groups in combination with PGMEA as the solvent, would improve compatibility with other materials and thus enhance contrast. Furthermore, a comparison of Example 1 with Example 7 or Example 8 shows that when an α-aminophenol photoinitiator is used in combination with an oxime ester photoinitiator and a thiol sensitizer, the linewidth offset is reduced. It is shown that when an α-aminophenol photoinitiator containing a fusiform structure is used in combination, the contrast also becomes better. Furthermore, a comparison between Example 1 and Example 9 clearly shows that if a thiol-based sensitizer is used, the contrast is further improved.

[0218] In contrast, in Comparative Example 1, which used a random copolymer C1 containing acidic groups that had the same composition as block copolymer 1 but was a random copolymer instead of the block copolymer 1 containing acidic groups used in Example 1, the resin composition initially exhibited good solubility, but its solubility deteriorated after standing for 2 weeks, resulting in a colored layer with poor contrast due to the precipitation of foreign matter in the hardened film after post-baking. Comparative Example 1 also showed poorer solvent resolubility compared to Example 1. Furthermore, in Comparative Examples 2 and 3, which used only basic block copolymers instead of acidic block copolymers or acidic graft copolymers, even when a solvent with alcoholic hydroxyl groups was used in combination with PGMEA as the solvent, the solubility of the resin composition immediately after preparation was poor, resulting in a colored layer with poor contrast due to the precipitation of foreign matter in the hardened film after baking. Also, the developability of Comparative Examples 2 and 3 was poor. In Comparative Example 4, which uses only an alkali-soluble resin without using a block copolymer with an acidic group or a graft copolymer with an acidic group, the initial solubility of the resin composition was good, but the solubility deteriorated after standing for 2 weeks, resulting in a colored layer with extremely poor contrast due to the precipitation of foreign matter in the hardened film after baking.

[0219] 1:Substrate 2:Light shielding part 3: Coloring layer 10: Color Filter 20: Opposing substrate 30: Liquid Crystal Layer 40: Liquid crystal display device 50: Organic protective layer 60: Inorganic oxide film 71: Transparent Anode 72: Hole Injection Layer 73: Hole Transport Layer 74: Emissive Layer 75: Electron Injection Layer 76: Cathode 80: Organic light-emitting body 100: Organic light-emitting display device

Claims

1. A photosensitive coloring resin composition comprising a colorant, at least one of a block copolymer having an acidic group and a graft copolymer having an acidic group, an alkali-soluble resin of a random copolymer having an acidic group, a photopolymerizable compound, a photoinitiator, and a solvent, wherein the colorant comprises a phthalocyanine compound represented by the following general formula (1), and the at least one of the block copolymer having an acidic group and a graft copolymer having an A block having a structural unit represented by the following general formula (I) and a B block having a structural unit represented by the following general formula (III), wherein the amine value of the B block is less than 10 mgKOH / g, and the at least one of the graft copolymer having a structural unit represented by the following general formula (I) and a structural unit represented by the following general formula (II), wherein, (in general formula (1), X1 to X16 independently represent a hydrogen atom, a halogen atom, or -Y-RD, and -Y-RD represents a valence group represented by the following formula (2); wherein, One or more of X1 to X16 represent -Y-RD) (In formula (2), -W- is a single bond or -O-, Rd1 is an aliphatic hydrocarbon group with 1 to 10 carbon atoms that may have substituents, an alicyclic hydrocarbon group with 3 to 12 carbon atoms that may have substituents, or an aromatic hydrocarbon group with 6 to 20 carbon atoms that may have substituents; Rd2 is a halogen atom, an alkyl group with 1 to 4 carbon atoms, or an alkoxy group with 1 to 4 carbon atoms; p is an integer from 1 to 3, and q is an integer from 0 to 2; wherein, when p is 2 or 3, the plurality of W and Rd1 may be the same or different, and when q is 2, the plurality of Rd2 may be the same or different; -Y- represents -O-, -S-, or -NH-, and * represents the bond position with the phthalocyanine skeleton in formula (1)) (In general formula (I), R1 represents a hydrogen atom or a methyl group, L represents a direct bond or a divalent linkage, and Q is an acidic group.) (In general formula (III), R1'' is a hydrogen atom or a methyl group, L'' is a divalent linkage, and R30 is a hydrocarbon group that may have substituents or contain heteroatoms.) (In general formula (II), R1' represents a hydrogen atom or a methyl group, L' represents a direct bond or a divalent linkage, and Polymer represents a polymer chain.) 2. The photosensitive coloring resin composition of claim 1, wherein the block copolymer having an acidic group comprises at least one of a block copolymer having a carboxyl group and a block copolymer having a phosphorus-containing acidic group.

3. The photosensitive coloring resin composition of claim 1 or 2, further comprising a block copolymer having a basic group.

4. The photosensitive coloring resin composition of claim 1 or 2, wherein the solvent comprises an alcoholic hydroxyl group.

5. The photosensitive coloring resin composition of claim 1 or 2, wherein the solvent comprises an alkyl diol monoalkyl ether.

6. The photosensitive coloring resin composition of claim 1 or 2, wherein the initiator comprises an oxime ester photoinitiator and a thiol sensitizer.

7. The photosensitive coloring resin composition of claim 6, wherein the initiator further comprises an α-aminoketone initiator.

8. The photosensitive coloring resin composition of claim 7, wherein the α-aminoketone initiator comprises a fusiform structure.

9. The photosensitive coloring resin composition of claim 1 or 2, wherein in at least one of the following: a block copolymer having an A block comprising a structural unit represented by general formula (I) and a B block comprising a structural unit represented by general formula (III) and the amine value of the B block being 10 mgKOH / g or less; and a graft copolymer having a structural unit represented by general formula (I) and a structural unit represented by general formula (II), wherein the structural unit represented by general formula (I) comprises one type.

10. A color filter comprising at least a substrate and a coloring layer disposed on the substrate, wherein at least one layer of the coloring layer is a cured form of a photosensitive coloring resin composition as claimed in any one of claims 1 to 9.

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

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