Colored resin composition, color filter, and image display device

Abstract

The present invention provides a colored resin composition capable of forming pixels with high brightness. The colored resin composition of the present invention comprises (A) a colorant, (B) a solvent, (C) an alkali-soluble resin, and (D) a photopolymerization initiator, wherein the colorant (A) contains a zinc phthalocyanine dye (a1) that has a maximum peak at a diffraction angle (2θ) within a range of 2 to 5° in a thin-film X-ray diffraction spectrum using CuKα radiation after heating at 230°C.

Description

[Technical field]

[0001] The present invention relates to a colored resin composition, a color filter, and an image display device. The entire contents of the specification, claims, drawings and abstract of Japanese Patent Application No. 2019-029160, filed with the Japan Patent Office on February 21, 2019, the entire contents of the specification, claims, drawings and abstract of Japanese Patent Application No. 2019-124095, filed with the Japan Patent Office on July 3, 2019, and the contents disclosed in the documents cited in this specification, in whole or in part, are hereby incorporated by reference into this specification as the disclosure contents. [Background technology]

[0002] Conventionally, pigment dispersion method, dyeing method, electrodeposition method, and printing method are known as methods for producing color filters used in liquid crystal displays, etc. Among them, the pigment dispersion method is most widely adopted because it has excellent characteristics on average in terms of spectral characteristics, durability, pattern shape, accuracy, etc.

[0003] In recent years, there has been a demand for higher brightness, higher contrast, and a wider color gamut for color filters. Pigments are generally used as colorants that determine the color of color filters from the viewpoints of heat resistance, light resistance, etc., but pigments are no longer able to meet market demands, particularly for high brightness, and active research is being conducted into the use of dyes as colorants instead of pigments. Research is being conducted into the use of specific phthalocyanine dyes as dyes for green pixels (see, for example, Patent Documents 1 to 5). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 2009-051896 [Patent Document 2] Japanese Patent Application Publication No. 2013-213208 [Patent Document 3] Japanese Patent Application Publication No. 2014-043556 [Patent Document 4] Japanese Patent Application Publication No. 2014-125460 [Patent Document 5] Japanese Patent Application Publication No. 2014-153554 Summary of the Invention [Problem to be solved by the invention]

[0005] As a result of investigations, the present inventors have found that the colored resin compositions described in Patent Documents 1 to 5 do not provide sufficient brightness for pixels of the resulting color filter for practical use. Therefore, an object of the present invention is to provide a colored resin composition capable of forming pixels with high brightness. [Means for solving the problem]

[0006] As a result of extensive investigations, the present inventors have found that the above problems can be solved by using a specific phthalocyanine dye as a colorant, and have arrived at the present invention. That is, the present invention has the following configuration.

[0007] [1] A colored resin composition comprising: (A) a colorant; (B) a solvent; (C) an alkali-soluble resin; and (D) a photopolymerization initiator, The colored resin composition, characterized in that the (A) colorant contains a zinc phthalocyanine dye (a1) having a maximum peak in a diffraction angle (2θ) range of 2 to 5° in a thin-film X-ray diffraction spectrum using CuKα radiation after heating at 230°C. [2] The colored resin composition according to [1], wherein the zinc phthalocyanine dye (a1) has a diffraction angle at the peak top of the maximum peak of 3.9° or less. [3] The colored resin composition according to [1] or [2], wherein the zinc phthalocyanine dye (a1) has a diffraction angle at the peak top of the maximum peak of 3.5° or more.

[0008] [4] The colored resin composition according to any one of [1] to [3], wherein the zinc phthalocyanine dye (a1) is a zinc phthalocyanine dye represented by the following general formula (1):

[0009] [ka]

[0010] (In formula (1), A 1 ~A 16 each independently represents a hydrogen atom, a chlorine atom, a fluorine atom, or a group represented by the following general formula (2):

[0011] [ka]

[0012] (In formula (2), X represents a divalent linking group. The benzene ring in formula (2) may have any substituent. * represents a bond.)

[0013] [5] The colored resin composition according to any one of [1] to [4], wherein the (A) colorant further contains a yellow pigment and / or a yellow dye. [6] The colored resin composition according to any one of [1] to [5], wherein the content of the zinc phthalocyanine dye (a1) is 5 mass % or more based on the total solid content. [7] The colored resin composition according to any one of [1] to [6], further comprising a photopolymerizable monomer. [8] The colored resin composition according to any one of [1] to [7], which is used for forming pixels of a color filter.

[0014] [9] A color filter having pixels formed using the colored resin composition according to any one of [1] to [8].

[10] An image display device having the color filter according to [9]. Effect of the Invention

[0015] According to the present invention, it is possible to provide a colored resin composition capable of forming pixels with high brightness. [Brief description of the drawings]

[0016] [Figure 1] FIG. 1 is a schematic cross-sectional view showing an example of an organic EL display device having a color filter of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0017] The constituent elements of the present invention will be described in detail below, however, these are merely examples of embodiments of the present invention and the present invention is not limited to these contents. In the present invention, "(meth)acrylic", "(meth)acrylate", etc. mean "acrylic and / or methacrylic", "acrylate and / or methacrylate", etc., for example, "(meth)acrylic acid" means "acrylic acid and / or methacrylic acid". In the present invention, the term "total solid content" means all components contained in the pigment dispersion or colored resin composition other than the solvent component. In the present invention, a numerical range expressed using "to" means a range including the numerical values ​​written before and after "to".

[0018] In the present invention, the "weight average molecular weight" refers to the weight average molecular weight (Mw) calculated in terms of polystyrene by GPC (gel permeation chromatography). In the present invention, the term "amine value" means the amine value calculated based on the effective solid content, unless otherwise specified, and is a value expressed as the mass of KOH equivalent to the amount of base per gram of solid content of the dispersant. In the present invention, "CI" means color index.

[0019] [1] Components of the colored resin composition Each of the components of the colored resin composition of the present invention will be described below. The colored resin composition of the present invention contains (A) a colorant, (B) a solvent, (C) an alkali-soluble resin, and (D) a photopolymerization initiator as essential components, and may further contain other additives other than the above components as necessary. Each component will be described below.

[0020] [1-1] (A) Colorant The colorant (A) contained in the colored resin composition of the present invention contains a zinc phthalocyanine dye (a1) (hereinafter, sometimes referred to as "zinc phthalocyanine dye (a1)") having a maximum peak in a diffraction angle (2θ) range of 2 to 5° in a thin film X-ray diffraction spectrum using CuKα radiation after heating at 230°C.

[0021] The zinc phthalocyanine dye (a1) is a zinc phthalocyanine dye having a maximum peak in the diffraction angle (2θ) range of 2 to 5° in a thin film X-ray diffraction spectrum using CuKα radiation after heating at 230°C, but it is considered that the zinc phthalocyanine dye molecules are associated with each other and regularly arranged (crystallized) during heating (230°C) in the baking process when manufacturing the pixels of the color filter, resulting in the maximum peak at the diffraction angle within the range. Zinc phthalocyanine dyes tend to crystallize easily, but especially when the phthalocyanine rings form H-aggregates in which the faces face each other in parallel and are regularly arranged, the maximum absorption wavelength shifts to the short wavelength side (for example, wavelength 640 to 660 nm), and the tail of the short wave absorption side of the absorption peak is reduced and shows a steep rise. As a result, it is considered that a cured film with high color purity, low absorption in unnecessary parts as a color filter, and high transmittance can be formed, resulting in high brightness. In particular, the zinc phthalocyanine dye (a1) has a higher absorbance and a steeper absorption peak due to the central metal being zinc, and is therefore considered to have a higher brightness than those having a central metal of copper.

[0022] The procedure and method for measuring the thin-film X-ray diffraction spectrum of the zinc phthalocyanine dye (a1) contained in the colored resin composition using CuKα radiation after heating at 230° C. are not particularly limited, but the colored cured film obtained by applying the colored resin composition, drying under reduced pressure, exposing it to a high-pressure mercury lamp, and baking it for 30 minutes at 230° C. is used as the measurement subject, and it can be measured by thin-film X-ray diffraction using CuKα radiation. It is preferable to adopt the conditions for preparing the colored cured film as described in the Examples below.

[0023] The conditions for measuring the thin film X-ray diffraction spectrum using CuKα radiation are not particularly limited, but it is preferable to use an automatic X-ray diffractometer RINT2000 manufactured by Rigaku Corporation, and to use an out-of-plane method with an X-ray output of 50 kV, 250 mA, a fixed incidence angle (θ) of 0.20°, a scanning range (2θ) of 2 to 40°, and a scanning speed of 3.0° / min. It is preferable to adopt the measurement conditions described in the examples below.

[0024] In the thin film X-ray diffraction spectrum thus obtained, it is sufficient to confirm whether or not there is a maximum peak within the diffraction angle (2θ) range of 2 to 5°. The maximum peak refers to a peak that exists within the measurement range (2 to 5°), that is, a peak whose peak top is within the measurement range and whose intensity at the peak top is the maximum value within the measurement range. For example, even if a peak exists within the measurement range, if the intensity at the peak top is not the maximum value within the measurement range, it is not a maximum peak.

[0025] In the thin film X-ray diffraction spectrum of zinc phthalocyanine dye (a1) using CuKα radiation after heating at 230°C, the diffraction angle of the peak top of the maximum peak (hereinafter sometimes referred to as "maximum peak A") existing within the range of 2 to 5° of diffraction angle (2θ) is not particularly limited, but is preferably 2.0° or more, more preferably 2.5° or more, even more preferably 3.0° or more, even more preferably 3.2° or more, particularly preferably 3.4° or more, most preferably 3.5° or more, and is preferably 5.0° or less, more preferably 4.5° or less, even more preferably 4.0° or less, even more preferably 3.9° or less, and particularly preferably 3.8° or less. By setting it to the lower limit or more, the regularity of the arrangement of the aggregate tends to be high, and by setting it to the upper limit or less, the decrease in contrast due to aggregation tends to be suppressed. For example, the peak top diffraction angle of the maximum peak A is preferably 2.0° to 5.0°, more preferably 2.5° to 5.0°, even more preferably 3.0° to 5.0°, even more preferably 3.2° to 4.5°, particularly preferably 3.4° to 4.0°, particularly preferably 3.5° to 3.9°, and most preferably 3.5° to 3.8°.

[0026] The full width at half maximum of the maximum peak A of the zinc phthalocyanine dye (a1) is not particularly limited, but is preferably 2.0° or less, more preferably 1.6° or less, even more preferably 1.2° or less, particularly preferably 1.0° or less, and usually 0.4° or more. By making it below the upper limit, the formation of aggregates is promoted, and the brightness tends to increase by showing a steep absorption spectrum. For example, the full width at half maximum of the maximum peak A is preferably 0.4° to 2.0°, more preferably 0.4° to 1.6°, even more preferably 0.4° to 1.2°, and particularly preferably 0.4° to 1.0°.

[0027] In addition, in the thin film X-ray diffraction spectrum of the zinc phthalocyanine dye (a1) using CuKα radiation after heating at 230°C, a halo may be observed within the diffraction angle (2θ) range of 15 to 25°. When a halo is observed within the diffraction angle (2θ) range of 15 to 25°, the ratio (I1 / I2) of the peak top intensity I1 of the maximum peak A to the peak top intensity I2 of the halo is not particularly limited, but is preferably 1 or more, more preferably 1.5 or more, even more preferably 2 or more, even more preferably 3 or more, particularly preferably 5 or more, and usually 10 or less. By making it equal to or greater than the lower limit, the formation of an aggregate is promoted, and the luminance tends to be increased by showing a steep absorption spectrum. For example, I1 / I2 is preferably 1 to 10, more preferably 1.5 to 10, even more preferably 2 to 10, even more preferably 3 to 10, and particularly preferably 5 to 10.

[0028] Among zinc phthalocyanine dyes, those with highly symmetric chemical structures tend to have the maximum peak A.

[0029] The chemical structure of the zinc phthalocyanine dye (a1) is not particularly limited as long as it is a zinc phthalocyanine dye having a maximum peak at a diffraction angle (2θ) within a range of 2 to 5° in a thin-film X-ray diffraction spectrum using CuKα radiation after heating at 230°C. From the viewpoint of accelerating the formation of associations between dye molecules and making the rise of the main absorption peak on the short-wavelength side steeper, the zinc phthalocyanine dye is preferably represented by the following general formula (1).

[0030] [ka]

[0031] (In formula (1), A 1 ~A 16 each independently represents a hydrogen atom, a chlorine atom, a fluorine atom, or a group represented by the following general formula (2):

[0032] [ka]

[0033] (In formula (2), X represents a divalent linking group. The benzene ring in formula (2) may have any substituent. * represents a bond.)

[0034] (A 1 ~A 16 ) In the formula (1), A 1 ~A 16 each independently represents a hydrogen atom, a chlorine atom, a fluorine atom, or a group represented by the following general formula (2).

[0035] [ka]

[0036] In formula (2), X represents a divalent linking group. The benzene ring in formula (2) may have any substituent. * represents a bond.

[0037] (X) X in the general formula (2) represents a divalent linking group. The divalent linking group is not particularly limited, but may be an oxygen atom, a sulfur atom, or -N(R a1 )-group. a1 represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 6 carbon atoms. Among these, from the viewpoint of reducing the tail on the short wavelength side of the main absorption maximum and showing a steep rise, an oxygen atom or a sulfur atom is preferred, and an oxygen atom is more preferred.

[0038] (Substituents that the benzene ring may have) The benzene ring in formula (2) may have any substituent. The substituent is not particularly limited, but may be a halogen atom, an alkyl group (-R A Group (where R A represents an alkyl group, an alkoxy group (-OR A Group (where R A represents an alkyl group. A Group (where R Arepresents an alkyl group; B Group (where R B represents an aryl group; B Group (where R B represents an aryl group. B Group (where R B represents an aryl group.)), a cyano group, etc., and the alkyl group (-R A group) and aryl groups (-R B The alkyl group (-R A group) and aryl groups (-R B The alkyl group) may be substituted with a halogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group, an aryl group, an aryloxy group, an aryloxycarbonyl group, or a cyano group. The alkyl group may be interrupted by an oxygen atom, a sulfur atom, a nitrogen atom, or the like, or may not be interrupted. Among these, from the viewpoint of selective light transmission and solubility in a solvent, an alkoxycarbonyl group or an alkyl group substituted with an alkoxycarbonyl group is preferred, and an alkoxycarbonyl group is more preferred.

[0039] The alkyl group contained in these groups may be linear, branched, or cyclic, or a combination thereof. However, linear or branched groups are preferred, and linear groups are preferred from the viewpoints of ease of synthesis and solubility in alkali-soluble resins and solvents. The number of carbon atoms in the alkyl group is not particularly limited, but is usually at least 1, preferably at least 2, and preferably at most 6, more preferably at most 5, even more preferably at most 4, and particularly preferably at most 3. By making the number equal to or greater than the lower limit, the solubility in the solvent tends to be improved, and by making the number equal to or less than the upper limit, hydrophobic interaction with the hydrophobic portion in the alkali-soluble resin tends to occur, suppressing intermolecular aggregation during the heating step. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, an isobutyl group, a pentyl group, and a hexyl group. From the viewpoints of maintaining solubility in a solvent and efficiently exerting hydrophobic interaction with the hydrophobic portion in the alkali-soluble resin, an ethyl group, a propyl group, an isobutyl group, or a butyl group is preferred, an ethyl group or a propyl group is more preferred, and an ethyl group is even more preferred.

[0040] The aryl group contained in these groups may be an aromatic hydrocarbon ring group or an aromatic heterocyclic group. The number of carbon atoms in the aryl group is not particularly limited, but is usually 4 or more, preferably 6 or more, and preferably 12 or less, more preferably 10 or less, and even more preferably 8 or less. By making the number equal to or more than the lower limit, the availability of raw materials tends to be facilitated, and by making the number equal to or less than the upper limit, the solubility in a solvent tends to be improved.

[0041] The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a single ring or a condensed ring. Examples of the aromatic hydrocarbon ring group include a benzene ring, a naphthalene ring, a pentalene ring, an indene ring, an azulene ring, a heptalene ring, and the like, each having one free valence. The aromatic heterocycle in the aromatic heterocyclic group may be a single ring or a condensed ring. Examples of the aromatic heterocyclic group include a furan ring, a thiophene ring, a pyrrole ring, a 2H-pyran ring, a 4H-thiopyran ring, a pyridine ring, a 1,3-oxazole ring, an isoxazole ring, a 1,3-thiazole ring, an isothiazole ring, an imidazole ring, a pyrazole ring, a furazan ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, a 1,3,5-triazine ring, a benzofuran ring, a 2-benzofuran ring, a benzo[b]pyridine ... Examples of such rings include a zothiophene ring, a 2-benzothiophene ring, a 1H-pyrrolidine ring, an indole ring, an isoindole ring, an indolizine ring, a 2H-1-benzopyran ring, a 1H-2-benzopyran ring, a quinoline ring, an isoquinoline ring, a 4H-quinolizine ring, a benzimidazole ring, a 1H-indazole ring, a quinoxaline ring, a quinazoline ring, a cinnoline ring, a phthalazine ring, a 1,8-naphthyridine ring, a purine ring, and a pteridine ring.

[0042] When the benzene ring in formula (2) has any substituent, the number of the substituents is not particularly limited, but is preferably 4 or less, more preferably 3 or less, even more preferably 2 or less, and particularly preferably 1. By making the number equal to or less than the upper limit, the formation of associations of the phthalocyanine is promoted, and the absorption on the short wavelength side of the main absorption tends to be sharpened. In addition, when the benzene ring in formula (2) has an arbitrary substituent, the substitution position is not particularly limited, and examples thereof include the 2-position, the 3-position, and the 4-position, from the viewpoint of ease of forming an association of phthalocyanine.

[0043] In addition, in multiple groups represented by formula (2) contained in one molecule, optional substituents that the benzene rings may have may be the same or different.

[0044] In the zinc phthalocyanine dye represented by the general formula (1), 1 ~A 16 each independently represents a hydrogen atom, a chlorine atom, a fluorine atom, or a group represented by the general formula (2), 1 ~A 16Among them, it is preferable that one or more are groups represented by the general formula (2), it is more preferable that two or more are groups represented by the general formula (2), it is even more preferable that four or more are groups represented by the general formula (2), it is particularly preferable that six or more are groups represented by the general formula (2), it is preferable that 15 or less are groups represented by the general formula (2), it is more preferable that 14 or less are groups represented by the general formula (2), it is even more preferable that 12 or less are groups represented by the general formula (2), it is particularly preferable that 10 or less are groups represented by the general formula (2). By making it equal to or more than the lower limit, solubility in organic solvents tends to be improved, and by making it equal to or less than the upper limit, solubility in organic solvents tends to be maintained while efficiently acting as a hydrophobic interaction with the hydrophobic portion in the alkali-soluble resin. For example, A 1 ~A 16 Among these, the group represented by the general formula (2) is preferably 1 to 15, more preferably 2 to 14, further preferably 4 to 12, and particularly preferably 6 to 10.

[0045] In the zinc phthalocyanine dye represented by the general formula (1), 1 ~A 16 each independently represents a hydrogen atom, a chlorine atom, a fluorine atom, or a group represented by the general formula (2), 1 ~A 16 Among them, it is preferable that 1 or more are chlorine atoms or fluorine atoms, more preferably 2 or more are chlorine atoms or fluorine atoms, even more preferably 4 or more are chlorine atoms or fluorine atoms, and particularly preferably 6 or more are chlorine atoms or fluorine atoms, and it is preferable that 15 or less are chlorine atoms or fluorine atoms, more preferably 14 or less are chlorine atoms or fluorine atoms, even more preferably 12 or less are chlorine atoms or fluorine atoms, and particularly preferably 10 or less are chlorine atoms or fluorine atoms. By making it equal to or more than the lower limit, there is a tendency that the solubility in organic solvents is maintained and hydrophobic interaction with the hydrophobic portion in the alkali-soluble resin works efficiently, and by making it equal to or less than the upper limit, there is a tendency that the solubility in organic solvents is improved. For example, A 1 ~A 16Among these, the number of chlorine or fluorine atoms is preferably 1 to 15, more preferably 2 to 14, further preferably 4 to 12, and particularly preferably 6 to 10.

[0046] Among the zinc phthalocyanine dyes represented by the general formula (1), the zinc phthalocyanine dyes represented by the following general formula (3) are preferred, from the viewpoint that the formation of associations between dye molecules is promoted and the short-wavelength side of the main absorption exhibits a steep rise.

[0047] [ka]

[0048] In formula (3), A 20 each independently represents a hydrogen atom, a chlorine atom, or a fluorine atom. X represents a divalent linking group. The benzene ring in formula (3) may have any substituent.

[0049] (A 20 ) In the formula (3), A 20 Each independently represents a hydrogen atom, a chlorine atom, or a fluorine atom. From the viewpoint of solubility in a solvent, a chlorine atom or a fluorine atom is preferable, and a fluorine atom is more preferable. 20 may be the same or different, but from the viewpoint of ease of forming an association of phthalocyanine, it is preferable that they are the same. For example, the eight A 20 are all fluorine atoms; 20 are all chlorine atoms.

[0050] (X) In the formula (3), X represents a divalent linking group. As this X, the divalent linking groups exemplified as X in the formula (2) can be adopted.

[0051] (Substituents that the benzene ring may have) The benzene rings in formula (3) (the eight benzene rings bonded to the phthalocyanine ring via X) may have any substituent, and as the substituent, those exemplified as the substituents that the benzene ring in formula (2) may have can be used.

[0052] The number of the substituents on one benzene ring is not particularly limited, and is preferably 4 or less, more preferably 3 or less, even more preferably 2 or less, and particularly preferably 1. By making the number equal to or less than the upper limit, the formation of associations of the phthalocyanine is promoted, and the absorption on the short wavelength side of the main absorption tends to be sharpened.

[0053] When the benzene ring has a substituent, the substitution position is not particularly limited, but examples include the 2-position, 3-position and 4-position, and from the viewpoint of ease of forming an association of phthalocyanine, the 4-position is preferred.

[0054] Specific examples of the zinc phthalocyanine dye (a1) include the following:

[0055] [ka]

[0056] In the formula, Me represents methyl.

[0057] [ka]

[0058] In the formula, Et represents ethyl.

[0059] [ka]

[0060] In the formula, n-Pr represents n-propyl.

[0061] [ka]

[0062] In the formula, i-Bu represents isobutyl.

[0063] [ka]

[0064] [ka]

[0065] [ka]

[0066] [ka]

[0067] [ka]

[0068] [ka]

[0069] In the formula, iBu represents isobutyl.

[0070] [ka]

[0071] The zinc phthalocyanine dye (a1) can be produced by a known method, such as the methods described in JP-A-5-345861, JP-A-2014-153554, and JP-A-2015-152861.

[0072] The (A) colorant may contain other colorants in addition to the zinc phthalocyanine dye (a1). Examples of other colorants include pigments and dyes. Among these, when the colored resin composition of the present invention is used for green pixel applications, it is preferable to use a green pigment, a green dye, a yellow pigment, a yellow dye, etc., and it is more preferable to use a yellow pigment and / or a yellow dye. Examples of green pigments include CI Pigment Green 7, 36, 58, 59, 62, and 63, and from the viewpoint of brightness, CI Pigment Green 58 is preferred. As green dyes, among those classified as dyes in the Color Index, CI Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35 can be mentioned as CI Solvent Dyes, CI Acid Green 1, 3, 5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106, 109 can be mentioned as CI Acid Dyes, and CI Mordant Green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43, 53 can be mentioned as CI Mordant Dyes. Among these, CI Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35 are preferred from the viewpoint of suppressing dye decomposition during thermal baking.

[0073] Yellow pigments include CI Pigment Yellow 1, 1:1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 20, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62:1, 63, 65, 73, 74, 75, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, 105, 106, 107, 108, 109, 110, 111, 112, 113, 114, 115, 116, 117, 118, 119, 120, 121, 122, 123, 124, 125, 126, 127, 128, 129, 130, 131, 132, 133, 134, 135, 136, 137, 138, 139, 140, 141, 142, 143, 144, 145, 146, 147, 148, 149, 150, 151, 15 3, 86, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 125, 126, 127, 127:1, 128, 129, 133, 134, 136, 137, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 173, 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191:1, 192, 193, 194, 195, 196, Examples of the compound include 197, 198, 199, 200, 202, 203, 204, 205, 206, 207, 208, and a compound in which another compound is inserted into a 1:1 complex of azobarbituric acid and nickel represented by the following formula (i) or a tautomer thereof (hereinafter, sometimes referred to as "nickel azo complex represented by formula (i)").

[0074] [ka]

[0075] Further, examples of other compounds that may be inserted into the 1:1 complex of azobarbituric acid and nickel represented by the above formula (i) or its tautomer include compounds represented by the following formula (ii).

[0076] [ka]

[0077] Among these, from the viewpoint of high luminance and wide color gamut, CI Pigment Yellow 83, 117, 129, 138, 139, 154, 155, 180, 185, and the nickel azo complex represented by formula (i) are preferred, and CI Pigment Yellow 83, 138, 139, 180, 185, and the nickel azo complex represented by formula (i) are more preferred.

[0078] Examples of the yellow dye include barbituric acid azo dyes, pyridone azo dyes, pyrazolone azo dyes, quinophthalone dyes, cyanine dyes, etc. Specific examples thereof include the specific compounds described in JP-A-2010-168531. Among the dyes classified in the Color Index, CI Solvent Dyes include CI Solvent Yellow 4, 14, 15, 23, 24, 38, 62, 63, 68, 79, 82, 94, 98, 99, 162, and 163, and CI Acid Dyes include CI Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, and 155. , 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251 and their derivatives. CI direct dyes include CI Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 136, 138, 141, etc.Further, examples of CI Mordant dyes include CI Mordant Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, and 65, and preferably CI Solvent Yellow 4, 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, and 162, and CI Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, and 119. , 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251, 23, 25, 29, 34, 40, 42, 72, 76, 99, 111, 112, 114, 116, 163, 243 and their derivatives. Among these, at least one selected from the group consisting of CI Solvent Yellow 4, 14, 15, 23, 24, 38, 62, 63, 68, 79, 82, 94, 98, 99, 162 and 163 is preferred from the viewpoint of suppressing dye decomposition during thermal baking.

[0079] The average primary particle size of the pigment is usually 0.2 μm or less, preferably 0.1 μm or less, and more preferably 0.04 μm or less. For the fine particle size of the pigment, a method such as solvent salt milling is preferably used.

[0080] The content of the (A) colorant in the colored resin composition of the present invention is not particularly limited, but is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 20% by mass or more, even more preferably 30% by mass or more, particularly preferably 35% by mass or more, and also preferably 70% by mass or less, more preferably 60% by mass or less, even more preferably 50% by mass or less, even more preferably 45% by mass or less, and particularly preferably 40% by mass or less. By making it equal to or more than the lower limit, the color characteristics tend to be improved, and by making it equal to or less than the upper limit, the pattern formability tends to be good. For example, the content of the (A) colorant is preferably 5 to 70% by mass, more preferably 10 to 60% by mass, more preferably 20 to 50% by mass, even more preferably 30 to 45% by mass, and particularly preferably 35 to 40% by mass.

[0081] The content of the zinc phthalocyanine dye (a1) in the colored resin composition of the present invention is not particularly limited, but is preferably 5% by mass or more, more preferably 8% by mass or more, even more preferably 10% by mass or more, particularly preferably 15% by mass or more, preferably 45% by mass or less, more preferably 40% by mass or less, even more preferably 35% by mass or less, even more preferably 30% by mass or less, and particularly preferably 25% by mass or less in the total solid content of the colored resin composition. By making it equal to or more than the lower limit, color characteristics such as brightness tend to be improved, and by making it equal to or less than the upper limit, pattern formability tends to be good. For example, the content of the zinc phthalocyanine dye (a1) is preferably 5 to 45% by mass, more preferably 5 to 40% by mass, more preferably 8 to 35% by mass, even more preferably 10 to 30% by mass, and particularly preferably 15 to 25% by mass.

[0082] When other colorants are included, the content ratio is not particularly limited, but is preferably 1% by mass or more, more preferably 5% by mass or more, even more preferably 8% by mass or more, even more preferably 10% by mass or more, particularly preferably 15% by mass or more, preferably 40% by mass or less, more preferably 35% by mass or less, even more preferably 30% by mass or less, and particularly preferably 25% by mass or less in the total solid content of the colored resin composition. By making it equal to or more than the lower limit, thermal decomposition during thermal baking during the production of a color filter tends to be suppressed, and by making it equal to or less than the upper limit, pattern formability tends to be good. When other colorants are included, for example, the content ratio is more preferably 5 to 40% by mass, more preferably 8 to 35% by mass, even more preferably 10 to 30% by mass, and particularly preferably 15 to 25% by mass.

[0083] [1-2] (B) Solvent The solvent (B) has the functions of dissolving or dispersing the colorant, the alkali-soluble resin, the photopolymerization initiator, and other components in the colored resin composition of the present invention, and adjusting the viscosity. The solvent (B) may be any solvent capable of dissolving or dispersing each component.

[0084] Examples of the solvent include glycol monoalkyl ethers such as propylene glycol monomethyl ether (PGME); glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate (PGMEA); and the like.

[0085] Others include glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; Glycol dialkyl ethers such as ethylene glycol dimethyl ether and ethylene glycol diethyl ether; glycol alkyl ether acetates such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate, ethers such as dimethyl ether, diethyl ether, dipropyl ether and diisopropyl ether; Ketones such as methyl ethyl ketone, diisopropyl ketone; Alcohols such as ethanol, propanol, butanol; Aliphatic hydrocarbons such as n-pentane, n-octane, and n-hexane; Alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; Aromatic hydrocarbons such as benzene and toluene; Examples of the esters include ethyl acetate and butyl acetate. These solvents may be used alone or in combination of two or more.

[0086] When forming pixels of a color filter by photolithography, it is preferable to select a solvent having a boiling point in the range of 100 to 155°C (under a pressure of 1013.25 [hPa]. The same applies to all boiling points below.) More preferably, it is a solvent having a boiling point of 120 to 150°C. Glycol alkyl ether acetates are preferred because they have a good balance of application properties, surface tension, etc., and the solubility of the components in the composition is relatively high in the above-mentioned solvents. For example, propylene glycol monomethyl ether acetate can be mentioned.

[0087] The glycol alkyl ether acetates may be used alone or in combination with other solvents. As the solvent to be used in combination, glycol monoalkyl ethers are particularly preferred. Among them, propylene glycol monomethyl ether is particularly preferred from the viewpoint of the solubility of the components in the composition. Note that glycol monoalkyl ethers have high polarity, and if the amount added is too large, the pigment is likely to aggregate, and the viscosity of the colored resin composition obtained later tends to increase, resulting in a decrease in storage stability. Therefore, the ratio of glycol monoalkyl ethers in the solvent is preferably 5% by mass to 30% by mass, more preferably 5% by mass to 20% by mass.

[0088] The content of the solvent in the colored resin composition of the present invention is not particularly limited, but the upper limit is usually 99% by mass or less, preferably 90% by mass or less, and more preferably 85% by mass or less. By making it equal to or less than the upper limit, it tends to be easier to form a coating film. On the other hand, the lower limit of the solvent content is usually 70% by mass or more, preferably 75% by mass or more, and more preferably 78% by mass or more, taking into consideration the viscosity suitable for coating, etc. For example, the content of the solvent is preferably 70 to 99% by mass, more preferably 75 to 90% by mass, and even more preferably 78 to 85% by mass.

[0089] [1-3] (C) Alkali-soluble resin In the colored resin composition of the present invention, the (C) alkali-soluble resin is not limited as long as it is soluble in the above-mentioned solvent, can form a cured film with sufficient curing degree, and can be developed in alkali to form a pattern. For example, polymer compounds described in Japanese Patent Application Laid-Open No. 7-207211, Japanese Patent Application Laid-Open No. 8-259876, Japanese Patent Application Laid-Open No. 10-300922, Japanese Patent Application Laid-Open No. 11-140144, Japanese Patent Application Laid-Open No. 11-174224, Japanese Patent Application Laid-Open No. 2000-56118, Japanese Patent Application Laid-Open No. 2003-233179, etc. can be used, and among them, the following resins (C-1) to (C-5) are preferably mentioned.

[0090] (C-1): A resin obtained by adding an unsaturated monobasic acid to at least a part of the epoxy groups of a copolymer of an epoxy group-containing (meth)acrylate and another radically polymerizable monomer, or an alkali-soluble resin obtained by adding a polybasic acid anhydride to at least a part of the hydroxyl groups generated by the addition reaction (hereinafter sometimes referred to as "resin (C-1)"). (C-2): Carboxyl group-containing linear alkali-soluble resin (hereinafter sometimes referred to as "resin (C-2)") (C-3): A resin in which an epoxy-containing unsaturated compound is added to the carboxyl group portion of the resin (C-2) (hereinafter, sometimes referred to as "resin (C-3)") (C-4): (meth)acrylic resin (hereinafter sometimes referred to as “resin (C-4)”) (C-5): Epoxy acrylate resin having a carboxyl group (hereinafter sometimes referred to as "resin (C-5)") Of these, resin (C-1) is particularly preferred, which will be described in detail below.

[0091] The resins (C-2) to (C-5) are not limited as long as they are dissolved in an alkaline developer and have a solubility to such an extent that the intended development process can be carried out, and are the same as those described in the same section of JP-A-2009-025813. The preferred embodiments are also the same. (C-1): A resin obtained by adding an unsaturated monobasic acid to at least a portion of the epoxy groups of a copolymer of an epoxy group-containing (meth)acrylate and another radically polymerizable monomer, or an alkali-soluble resin obtained by adding a polybasic acid anhydride to at least a portion of the hydroxyl groups generated by the addition reaction. One particularly preferred resin for the resin (C-1) is a resin obtained by adding an unsaturated monobasic acid to 10 to 100 mol % of the epoxy groups in a copolymer of 5 to 90 mol % of an epoxy group-containing (meth)acrylate and 10 to 95 mol % of other radically polymerizable monomers, or an alkali-soluble resin obtained by adding a polybasic acid anhydride to 10 to 100 mol % of the hydroxyl groups generated by the addition reaction.

[0092] Examples of epoxy group-containing (meth)acrylates include glycidyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, (3,4-epoxycyclohexyl)methyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate glycidyl ether. Among these, glycidyl (meth)acrylate is preferred. These epoxy group-containing (meth)acrylates may be used alone or in combination of two or more.

[0093] The other radical polymerizable monomer to be copolymerized with the epoxy group-containing (meth)acrylate is not particularly limited as long as it does not impair the effects of the present invention, and examples thereof include vinyl aromatics, dienes, (meth)acrylic acid esters, (meth)acrylic acid amides, vinyl compounds, unsaturated dicarboxylic acid diesters, monomaleimides, etc. Among them, a mono(meth)acrylate having a structure represented by the following formula (III) is preferred.

[0094] The content of the repeating unit derived from the mono(meth)acrylate having the structure represented by the following formula (III) is preferably 5 to 90 mol %, more preferably 10 to 70 mol %, and even more preferably 15 to 50 mol %, of the repeating units derived from the "other radically polymerizable monomers".

[0095] [ka]

[0096] In the above formula (III), R 89 represents a hydrogen atom or a methyl group, R 90 represents a structure represented by the following formula (IV).

[0097] [ka]

[0098] In the above formula (IV), R 91 ~R 98Each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. 96 and R 98 may be linked to each other to form a ring. R 96 and R 98 The ring formed by linking R is preferably an aliphatic ring, and may be either saturated or unsaturated. 96 and R 98 The ring formed by linking the groups preferably has 5 to 6 carbon atoms. Among them, the structure represented by formula (IV) is particularly preferably one represented by the following structural formula (IVa), (IVb), or (IVc).

[0099] [ka]

[0100] The mono(meth)acrylate having the structure represented by the formula (IV) may be used alone or in combination of two or more kinds. Examples of the "other radically polymerizable monomer" other than the mono(meth)acrylate having the structure represented by the formula (IV) include styrene, n-butyl (meth)acrylate, tert-butyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, benzyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, N-phenylmaleimide, and N-cyclohexylmaleimide, which can provide the colored resin composition with excellent heat resistance and strength.

[0101] The content of the repeating unit derived from at least one selected from the above monomer group is preferably 1 to 70 mol %, and more preferably 3 to 50 mol %, of the repeating units derived from the "other radically polymerizable monomers". The copolymerization reaction between the epoxy group-containing (meth)acrylate and the other radically polymerizable monomer is carried out by a known solution polymerization method. In the present invention, the copolymer of the epoxy group-containing (meth)acrylate and the other radical polymerizable monomer is preferably one consisting of 5 to 90 mol % of repeating units derived from the epoxy group-containing (meth)acrylate and 10 to 95 mol % of repeating units derived from the other radical polymerizable monomer, more preferably one consisting of 20 to 80 mol % of the former and 80 to 20 mol % of the latter, and particularly preferably one consisting of 30 to 70 mol % of the former and 70 to 30 mol % of the latter.

[0102] Within the above range, the amounts of the polymerizable component and alkali-soluble component described below are sufficient, and the heat resistance and film strength are also sufficient, which is preferable. The epoxy group portion of the epoxy group-containing copolymer synthesized as described above is reacted with an unsaturated monobasic acid (polymerizable component) and a polybasic acid anhydride (alkali-soluble component). Here, as the unsaturated monobasic acid to be added to the epoxy group, known acids can be used, and examples thereof include unsaturated carboxylic acids having an ethylenically unsaturated double bond.

[0103] Specific examples include monocarboxylic acids such as (meth)acrylic acid, crotonic acid, o-, m- or p-vinylbenzoic acid, and (meth)acrylic acid substituted at the α-position with a haloalkyl group, an alkoxyl group, a halogen atom, a nitro group or a cyano group. Among these, (meth)acrylic acid is preferred. These may be used alone or in combination of two or more.

[0104] By adding such a component, it is possible to impart polymerizability to the alkali-soluble resin used in the present invention. These unsaturated monobasic acids are usually added to 10 to 100 mol % of the epoxy groups of the copolymer, preferably 30 to 100 mol %, more preferably 50 to 100 mol %. Within the above range, the colored resin composition has excellent stability over time, which is preferable. As a method for adding an unsaturated monobasic acid to the epoxy groups of the copolymer, a known method can be adopted.

[0105] Furthermore, as the polybasic acid anhydride to be added to the hydroxyl group generated when the unsaturated monobasic acid is added to the epoxy group of the copolymer, known polybasic acid anhydrides can be used. For example, dibasic acid anhydrides such as maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and chlorendic anhydride; and tribasic or higher acid anhydrides such as trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, and biphenyltetracarboxylic anhydride. Among them, succinic anhydride and tetrahydrophthalic anhydride are preferred. These polybasic acid anhydrides may be used alone or in combination of two or more.

[0106] By adding such a component, it is possible to impart alkali solubility to the alkali-soluble resin used in the present invention. These polybasic acid anhydrides are usually added to 10 to 100 mol %, preferably 20 to 90 mol %, more preferably 30 to 80 mol % of the hydroxyl groups generated by adding an unsaturated monobasic acid to the epoxy groups of the copolymer.

[0107] Within the above range, the remaining film rate and solubility during development are sufficient, which is preferable. As a method for adding a polybasic acid anhydride to a hydroxyl group, a known method can be adopted. Furthermore, in order to improve photosensitivity, after the above-mentioned polybasic acid anhydride is added, glycidyl (meth)acrylate or a glycidyl ether compound having a polymerizable unsaturated group may be added to a part of the generated carboxyl groups. The structure of such a resin is described, for example, in JP-A-8-297366 and JP-A-2001-89533.

[0108] The weight average molecular weight (Mw) of the alkali-soluble resin (C) measured by GPC (gel permeation chromatography) in terms of polystyrene is preferably 3000 or more, more preferably 5000 or more, and even more preferably 7000 or more, and is preferably 100000 or less, more preferably 50000 or less, more preferably 30000 or less, even more preferably 15000 or less, and particularly preferably 13000 or less. If the weight average molecular weight (Mw) is within the above range, it is preferable in terms of good heat resistance, film strength, and solubility in a developer. For example, the weight average molecular weight of the alkali-soluble resin is preferably 3000 to 100000, more preferably 3000 to 50000, more preferably 5000 to 30000, even more preferably 5000 to 15000, and particularly preferably 7000 to 13000. As a guide for the molecular weight distribution, the ratio of weight average molecular weight (Mw) / number average molecular weight (Mn) is preferably 2.0 to 5.0.

[0109] The acid value of the alkali-soluble resin (C) is usually 10 mgKOH / g or more, preferably 15 mgKOH / g or more, more preferably 25 mgKOH / g or more, and even more preferably 50 mgKOH / g or more, and is usually 200 mgKOH / g or less, preferably 150 mgKOH / g or less, and more preferably 100 mgKOH / g or less. By setting it to the lower limit or more, the solubility in the developer tends to be good, and by setting it to the upper limit or less, the occurrence of film roughness tends to be suppressed. For example, the acid value of the alkali-soluble resin is preferably 10 to 200 mgKOH / g, more preferably 15 to 200 mgKOH / g, even more preferably 25 to 150 mgKOH / g, and particularly preferably 50 to 100 mgKOH / g.

[0110] In the colored resin composition of the present invention, the content of the (C) alkali-soluble resin is not particularly limited, but is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 15% by mass or more, particularly preferably 20% by mass or more, and is preferably 50% by mass or less, more preferably 40% by mass or less, even more preferably 35% by mass or less, even more preferably 30% by mass or less, and particularly preferably 25% by mass or less. By making it equal to or more than the lower limit, a pattern tends to be formed well, and by making it equal to or less than the upper limit, the resolution and the residual film rate tend to be improved. For example, the content of the (C) alkali-soluble resin is preferably 5 to 50% by mass, more preferably 5 to 40% by mass, more preferably 10 to 35% by mass, even more preferably 15 to 30% by mass, and particularly preferably 20 to 25% by mass.

[0111] [1-4] (D) Photopolymerization initiator The colored resin composition of the present invention contains a photopolymerization initiator (D). By containing the photopolymerization initiator (D), film curing properties can be obtained by photopolymerization. (D) Photopolymerization initiator can also be used as a mixture (photopolymerization initiation system) with an accelerator (chain transfer agent) and an additive such as a sensitizing dye, which is added as needed. The photopolymerization initiation system is a component that has the function of absorbing light directly or being photosensitized to cause a decomposition reaction or a hydrogen abstraction reaction, thereby generating polymerization active radicals.

[0112] Examples of the photopolymerization initiator include metallocene compounds including titanocene compounds described in JP-A-59-152396 and JP-A-61-151197, hexaarylbiimidazole derivatives described in JP-A-10-39503, halomethyl-s-triazine derivatives, N-aryl-α-amino acids such as N-phenylglycine, N-aryl-α-amino acid salts, N-aryl-α-amino acid esters and other radical activators, α-aminoalkylphenone compounds, and oxime ester initiators described in JP-A-2000-80068.

[0113] Specific examples of the photopolymerization initiator that can be used in the present invention are listed below. halomethylated triazine derivatives such as 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, and 2-(4-ethoxycarbonylnaphthyl)-4,6-bis(trichloromethyl)-s-triazine;

[0114] halomethylated oxadiazole derivatives such as 2-trichloromethyl-5-(2'-benzofuryl)-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2'-benzofuryl)vinyl]-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2'-(6''-benzofuryl)vinyl)]-1,3,4-oxadiazole, and 2-trichloromethyl-5-furyl-1,3,4-oxadiazole; imidazole derivatives such as 2-(2'-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(2'-chlorophenyl)-4,5-bis(3'-methoxyphenyl)imidazole dimer, 2-(2'-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(2'-methoxyphenyl)-4,5-diphenylimidazole dimer, and (4'-methoxyphenyl)-4,5-diphenylimidazole dimer; benzoin alkyl ethers such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether, and benzoin isopropyl ether; Anthraquinone derivatives such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, and 1-chloroanthraquinone;

[0115] Benzophenone, Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone and other benzophenone derivatives; acetophenone derivatives such as 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, α-hydroxy-2-methylphenylpropanone, 1-hydroxy-1-methylethyl-(p-isopropylphenyl)ketone, 1-hydroxy-1-(p-dodecylphenyl)ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, and 1,1,1-trichloromethyl-(p-butylphenyl)ketone; Thioxanthone, thioxanthone derivatives such as 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, and 2,4-diisopropylthioxanthone;

[0116] Benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate; Acridine derivatives such as 9-phenylacridine and 9-(p-methoxyphenyl)acridine; Phenazine derivatives such as 9,10-dimethylbenzphenazine; Anthrone derivatives such as benzanthrone; Titanocene derivatives such as dicyclopentadienyl-Ti-dichloride, dicyclopentadienyl-Ti-bis-phenyl, dicyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophenylyl, dicyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophenylyl, dicyclopentadienyl-Ti-bis-2,4,6-trifluorophenyl, dicyclopentadienyl-Ti-2,6-difluorophenyl, dicyclopentadienyl-Ti-2,4-difluorophenyl, dimethylcyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophenyl, dimethylcyclopentadienyl-Ti-bis-2,6-difluorophenyl, and dicyclopentadienyl-Ti-2,6-difluoro-3-(pyrrol-1-yl)-phenylyl;

[0117] α-aminoalkylphenone compounds such as 2-methyl-1[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 4-dimethylaminoethyl benzoate, 4-dimethylaminoisoamyl benzoate, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis(4-diethylaminobenzal)cyclohexanone, 7-diethylamino-3-(4-diethylaminobenzoyl)coumarin, and 4-(diethylamino)chalcone; Oxime ester compounds such as 1,2-octanedione-1-[4-(phenylthio)phenyl]-2-(O-benzoyloxime)ethanone and 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime).

[0118] Among these, oxime ester compounds are preferred from the viewpoints of sensitivity and surface properties. Oxime ester compounds have a structure that absorbs ultraviolet light, a structure that transmits light energy, and a structure that generates radicals, and therefore have high sensitivity even in small amounts and are stable against thermal reactions, making it possible to design a colored resin composition that has high sensitivity even in small amounts. In particular, from the viewpoint of light absorption for the i-line (365 nm) of the exposure light source, oxime ester compounds having a carbazole ring that may have a substituent are preferred.

[0119] Examples of the oxime ester compounds include compounds represented by the following general formula (I-1).

[0120] [ka]

[0121] In the above formula (I-1), R 21arepresents a hydrogen atom, an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent. R 21b represents an optional substituent containing an aromatic ring or a heteroaromatic ring. R 22a represents an alkanoyl group which may have a substituent, or an aryloyl group which may have a substituent.

[0122] R 21a In the formula, the number of carbon atoms in the alkyl group is not particularly limited, but from the viewpoint of solubility in a solvent and sensitivity to exposure, it is usually 1 or more, preferably 2 or more, and usually 20 or less, preferably 15 or less, more preferably 10 or less, and further preferably 5 or less. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a cyclopentylethyl group. Examples of the substituent that the alkyl group may have include an aromatic ring group, a hydroxyl group, a carboxy group, a halogen atom, an amino group, an amide group, a 4-(2-methoxy-1-methyl)ethoxy-2-methylphenyl group, an N-acetyl-N-acetoxyamino group, and the like. From the viewpoint of ease of synthesis, it is preferable that the alkyl group is unsubstituted.

[0123] R 21a The aromatic ring group in the above formula includes an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The number of carbon atoms in the aromatic ring group is not particularly limited, but is preferably 5 or more from the viewpoint of solubility in the colored resin composition. In addition, from the viewpoint of developability, it is preferably 30 or less, more preferably 20 or less, even more preferably 12 or less, and particularly preferably 8 or less.

[0124] Specific examples of the aromatic ring group include a phenyl group, a naphthyl group, a pyridyl group, a furyl group, and a fluorenyl group. Among these, from the viewpoint of developability, a phenyl group, a naphthyl group, or a fluorenyl group is preferred, and a phenyl group or a fluorenyl group is more preferred. Examples of the substituent that the aromatic ring group may have include a hydroxyl group, an alkyl group that may have a substituent, an alkoxy group that may have a substituent, a carboxyl group, a halogen atom, an amino group, an amide group, an alkyl group, etc., and from the viewpoint of developability, a hydroxyl group and a carboxyl group are preferred, and a carboxyl group is more preferred.Furthermore, examples of the substituent in the alkyl group that may have a substituent and the alkoxy group that may have a substituent include a hydroxyl group, an alkoxy group, a halogen atom, and a nitro group. Among these, from the viewpoint of developability, R 21a is preferably an alkyl group which may have a substituent, more preferably an unsubstituted alkyl group, and further preferably a methyl group.

[0125] R 21b is any substituent containing an aromatic ring or a heteroaromatic ring, and from the viewpoint of solubility in a solvent and sensitivity to exposure, preferred examples include a carbazolyl group which may have a substituent, a thioxanthonyl group which may have a substituent, a diphenylsulfide group which may have a substituent, or a fluorenyl group which may have a substituent, and a group in which these groups are linked to a carbonyl group. Among these, from the viewpoint of light absorption to the i-line (365 nm) of the exposure light source, a carbazolyl group which may have a substituent, or a group in which a carbazolyl group which may have a substituent and a carbonyl group are linked are preferred.

[0126] R 22a The number of carbon atoms in the alkanoyl group is not particularly limited, but from the viewpoint of solubility in a solvent and sensitivity, it is usually 2 or more, preferably 3 or more, and usually 20 or less, preferably 15 or less, more preferably 10 or less, and further preferably 5 or less. Specific examples of the alkanoyl group include an acetyl group, a propanoyl group, and a butanoyl group. Examples of the substituent that the alkanoyl group may have include an aromatic ring group, a hydroxyl group, a carboxy group, a halogen atom, an amino group, an amide group, and the like. From the viewpoint of ease of synthesis, it is preferable that the alkanoyl group is unsubstituted.

[0127] R 22aThe number of carbon atoms in the aryloyl group is not particularly limited, but from the viewpoint of solubility in a solvent and sensitivity, it is usually 7 or more, preferably 8 or more, and usually 20 or less, preferably 15 or less, more preferably 10 or less. Specific examples of the aryloyl group include a benzoyl group and a naphthoyl group. Examples of the substituent that the aryloyl group may have include a hydroxyl group, a carboxy group, a halogen atom, an amino group, an amide group, an alkyl group, and the like. From the viewpoint of ease of synthesis, it is preferable that the aryloyl group is unsubstituted.

[0128] Among the compounds represented by the general formula (I-1), from the viewpoint of light absorption to the i-line (365 nm) of the exposure light source, compounds represented by the following general formulas (I-2) or (I-3) can be mentioned.

[0129] [ka]

[0130] [ka]

[0131] In the above formula (I-2) or (I-3), R 21a and R 22a has the same meaning as in general formula (I-1). R 23a represents an alkyl group which may have a substituent. R 24a represents an optionally substituted alkyl group, an optionally substituted aryloyl group, an optionally substituted heteroaryloyl group, or a nitro group. The benzene ring constituting the carbazole ring may be further condensed with an aromatic ring to form a polycyclic aromatic ring.

[0132] R 23a Or R 24aIn the formula, the number of carbon atoms of the alkyl group is not particularly limited, but from the viewpoint of solubility in a solvent, it is usually 1 or more, preferably 2 or more, and usually 20 or less, preferably 15 or less, more preferably 10 or less, and further preferably 5 or less. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, and a cyclohexyl group. Examples of the substituent that the alkyl group may have include a carboxy group, a hydroxy group, a phenyl group, a benzyl group, a cyclohexyl group, a nitro group, and the like. From the viewpoint of ease of synthesis, it is preferable that the alkyl group is unsubstituted. Among these, R 23a As the alkyl group, from the viewpoints of solubility in a solvent and ease of synthesis, an alkyl group is preferable, and an ethyl group is more preferable.

[0133] R 24a The number of carbon atoms in the aryloyl group is not particularly limited, but from the viewpoint of solubility in a solvent, it is usually 7 or more, preferably 8 or more, more preferably 9 or more, and usually 20 or less, preferably 15 or less, more preferably 10 or less, and even more preferably 9 or less. Specific examples of the aryloyl group include a benzoyl group, a naphthoyl group, and the like. Examples of the substituent that the aryloyl group may have include a carboxy group, a hydroxy group, a phenyl group, a benzyl group, a cyclohexyl group, a nitro group, and the like, and from the viewpoint of ease of synthesis, an ethyl group is preferred.

[0134] R 24a The number of carbon atoms in the heteroaryloyl group in is not particularly limited, but from the viewpoint of solubility in a solvent, it is usually 7 or more, preferably 8 or more, more preferably 9 or more, and usually 20 or less, preferably 15 or less, more preferably 10 or less, and even more preferably 9 or less. Specific examples of the heteroaryloyl group include a furancarbonyl group, a thiophenecarbonyl group, a pyrrolylcarbonyl group, and a pyridinecarbonyl group. Examples of the substituent that the heteroaryloyl group may have include a carboxy group, a hydroxy group, a phenyl group, a benzyl group, a cyclohexyl group, a nitro group, and the like. From the viewpoint of ease of synthesis, it is preferable that the heteroaryloyl group is unsubstituted.

[0135] The benzene ring constituting the carbazole ring may be further condensed with an aromatic ring to form a polycyclic aromatic ring.

[0136] Commercially available products of such oxime ester compounds include OXE-02 and OXE-03 manufactured by BASF, TR-PBG-304 and TR-PBG-314 manufactured by Changzhou Strong Electronics Co., Ltd., and N-1919, NCI-930, and NCI-831 manufactured by ADEKA.

[0137] Specific examples of the oxime ester compound include the compounds exemplified below, but are not limited to these compounds.

[0138] [ka]

[0139] [ka]

[0140] [ka]

[0141] These photopolymerization initiators may be used alone or in combination of two or more.

[0142] In addition to the photopolymerization initiator (D), a chain transfer agent may be used. The chain transfer agent is a compound that has the function of receiving the generated radicals and transferring the received radicals to another compound. As the chain transfer agent, various compounds having the above functions can be used, for example, mercapto group-containing compounds and carbon tetrachloride, etc. are listed, and it is more preferable to use a compound having a mercapto group because it tends to have a high chain transfer effect. It is considered that this is because the SH bond energy is small, so bond cleavage is likely to occur, and hydrogen abstraction reaction and chain transfer reaction are likely to occur. It is effective in improving sensitivity and surface hardening.

[0143] Examples of the mercapto group-containing compound include mercapto group-containing compounds having an aromatic ring such as 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 3-mercapto-1,2,4-triazole, 2-mercapto-4(3H)-quinazoline, β-mercaptonaphthalene, and 1,4-dimethylmercaptobenzene; hexanedithiol, decanedithiol, butanediol bis(3-mercaptopropionate), butanediol bisthioglycolate, ethylene glycol bis(3-mercaptopropionate), ethylene glycol bisthioglycolate, trimethylolpropane tris(3-mercaptopropionate), trimethylolpropane tristhioglycolate, and trishydroxythio ... Examples of the mercapto group-containing aliphatic compounds include ethyl tristhiopropionate, pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tris(3-mercaptopropionate), butanediol bis(3-mercaptobutyrate), ethylene glycol bis(3-mercaptobutyrate), trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakis(3-mercaptobutyrate), pentaerythritol tris(3-mercaptobutyrate), and 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione. From the viewpoint of surface smoothness, a compound having a plurality of mercapto groups is particularly preferred.

[0144] Of these, 2-mercaptobenzothiazole and 2-mercaptobenzimidazole are preferred among the mercapto group-containing compounds having an aromatic ring, and trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tris(3-mercaptopropionate), trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakis(3-mercaptobutyrate), pentaerythritol tris(3-mercaptobutyrate), and 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione are preferred among the aliphatic mercapto group-containing compounds.

[0145] From the viewpoint of sensitivity, aliphatic mercapto group-containing compounds are preferred, specifically, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tris(3-mercaptopropionate), trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakis(3-mercaptobutyrate), pentaerythritol tris(3-mercaptobutyrate), 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione are preferred, and pentaerythritol tetrakis(3-mercaptopropionate) and pentaerythritol tetrakis(3-mercaptobutyrate) are more preferred. These may be used alone or in combination of two or more.

[0146] In the colored resin composition of the present invention, the content ratio of the (D) photopolymerization initiator is not particularly limited, but is preferably 1% by mass or more, more preferably 2% by mass or more, even more preferably 3% by mass or more, even more preferably 4% by mass or more, particularly preferably 6% by mass or more, and most preferably 7% by mass or more, and is preferably 20% by mass or less, more preferably 15% by mass or less, even more preferably 12% by mass or less, and particularly preferably 10% by mass or less. By making it equal to or more than the lower limit, there is a tendency that the patterning characteristics after development can be secured, and by making it equal to or less than the upper limit, there is a tendency that the decrease in transmittance due to the excessive addition of the photopolymerization initiator is suppressed. For example, the content ratio of the (D) photopolymerization initiator is preferably 1 to 20% by mass, more preferably 2 to 20% by mass, more preferably 3 to 15% by mass, even more preferably 4 to 15% by mass, particularly preferably 6 to 12% by mass, and most preferably 7 to 10% by mass.

[0147] When the colored resin composition of the present invention contains a chain transfer agent, the content ratio is not particularly limited, but is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, more preferably 0.2% by mass or more, more preferably 0.5% by mass or more, more preferably 1% by mass or more, particularly preferably 1.5% by mass or more, and also preferably 5% by mass or less, more preferably 3% by mass or less, and more preferably 2% by mass or less. By setting it within the above range, there is a tendency that storage stability and patterning formability during alkali development can be ensured. When a chain transfer agent is contained, for example, the content ratio thereof is preferably 0.01 to 5% by mass, more preferably 0.1 to 5% by mass, more preferably 0.2 to 3% by mass, more preferably 0.5 to 3% by mass, more preferably 1 to 2% by mass, and particularly preferably 1.5 to 2% by mass.

[0148] [1-5] Other solids The colored resin composition of the present invention may further contain solid components other than the above-mentioned components, if necessary. Such components include photopolymerizable monomers, dispersants, dispersing aids, surfactants, etc.

[0149] [1-5-1] Photopolymerizable monomer The photopolymerizable monomer is not particularly limited as long as it is a polymerizable low molecular compound, but is preferably an addition-polymerizable compound having at least one ethylenic double bond (hereinafter referred to as "ethylenic compound"). The ethylenic compound is a compound having an ethylenic double bond that undergoes addition polymerization and hardening under the action of a photopolymerization initiator when the colored resin composition of the present invention is irradiated with actinic rays. The monomer in the present invention means a concept opposite to the so-called polymeric substance, and means a concept including dimers, trimers, and oligomers in addition to monomers in the narrow sense. In the present invention, it is particularly desirable to use a polyfunctional ethylenic monomer having two or more ethylenic double bonds in one molecule. The number of ethylenic double bonds that the polyfunctional ethylenic monomer has is not particularly limited, but is usually two or more, preferably four or more, more preferably five or more, and preferably eight or less, more preferably seven or less. By making it equal to or more than the lower limit, there is a tendency for high sensitivity to be obtained, and by making it equal to or less than the upper limit, there is a tendency for solubility in a solvent to be improved.

[0150] Examples of the ethylenic compound include unsaturated carboxylic acids, esters of unsaturated carboxylic acids and monohydroxy compounds, esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids, esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids, esters obtained by esterification reactions of unsaturated carboxylic acids with polyvalent carboxylic acids and polyvalent hydroxy compounds such as aliphatic polyhydroxy compounds and aromatic polyhydroxy compounds, and ethylenic compounds having a urethane skeleton obtained by reacting a polyisocyanate compound with a (meth)acryloyl-containing hydroxy compound.

[0151] Examples of esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids include acrylic acid esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and glycerol acrylate. In addition, examples of the acrylic acid moiety of these acrylates include methacrylic acid esters in which the acrylic acid moiety is replaced with a methacrylic acid moiety, itaconic acid esters in which the itaconic acid moiety is replaced with a crotonic acid moiety, and maleic acid esters in which the maleic acid moiety is replaced with a maleic acid moiety.

[0152] Examples of the esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids include hydroquinone diacrylate, hydroquinone dimethacrylate, resorcinol diacrylate, resorcinol dimethacrylate, and pyrogallol triacrylate. The ester obtained by the esterification reaction of an unsaturated carboxylic acid with a polycarboxylic acid and a polyhydroxy compound is not necessarily a single substance, but may be a mixture.Typical examples include a condensation product of acrylic acid, phthalic acid, and ethylene glycol, a condensation product of acrylic acid, maleic acid, and diethylene glycol, a condensation product of methacrylic acid, terephthalic acid, and pentaerythritol, and a condensation product of acrylic acid, adipic acid, butanediol, and glycerin.

[0153] Examples of ethylenic compounds having a urethane skeleton obtained by reacting a polyisocyanate compound with a (meth)acryloyl group-containing hydroxy compound include reaction products of aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate; alicyclic diisocyanates such as cyclohexane diisocyanate and isophorone diisocyanate; aromatic diisocyanates such as tolylene diisocyanate and diphenylmethane diisocyanate, and the like, with (meth)acryloyl group-containing hydroxy compounds such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxy(1,1,1-triacryloyloxymethyl)propane, 3-hydroxy(1,1,1-trimethacryloyloxymethyl)propane, etc.

[0154] Other useful ethylenic compounds for use in the present invention include acrylamides such as ethylenebisacrylamide; allyl esters such as diallyl phthalate; and vinyl group-containing compounds such as divinyl phthalate. The ethylenic compound may be a monomer having an acid value. The monomer having an acid value is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and is preferably a polyfunctional monomer having an acid group provided by reacting an unreacted hydroxy group of an aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride, and more preferably an ester in which the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol.

[0155] Although one of these monomers may be used alone, two or more of them may be used in combination because it is difficult to use a single compound in the production. In addition, a polyfunctional monomer having no acid group and a polyfunctional monomer having an acid group may be used in combination as a monomer, if necessary. The preferred acid value of the polyfunctional monomer having an acid group is 0.1 to 40 mgKOH / g, and particularly preferably 5 to 30 mgKOH / g. By setting it to the lower limit or more, there is a tendency that the development dissolution characteristics can be improved, and by setting it to the upper limit or less, there is a tendency that the production and handling are improved and the curing properties such as photopolymerization performance and pixel surface smoothness are easily improved. Therefore, when two or more polyfunctional monomers having different acid groups are used in combination, or when a polyfunctional monomer having no acid group is used in combination, it is preferable to adjust the acid group of the entire polyfunctional monomer to be within the above range.

[0156] In the present invention, a more preferred polyfunctional monomer having an acid group is a mixture mainly composed of dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and succinic acid ester of dipentaerythritol pentaacrylate, which is commercially available as TO1382 manufactured by Toagosei Co., Ltd. This polyfunctional monomer can also be used in combination with other polyfunctional monomers. Also, those described in paragraphs

[0056] and

[0057] of JP 2013-140346 A can be used.

[0157] In the present invention, from the viewpoint of improving the chemical resistance of pixels and the linearity of pixel edges, it is preferable to use the polymerizable monomer described in JP 2013-195971 A. From the viewpoint of achieving both the sensitivity of the coating film and a shortened development time, it is preferable to use the polymerizable monomer described in JP 2013-195974 A.

[0158] When the colored resin composition of the present invention contains a photopolymerizable monomer, the content of the photopolymerizable monomer is usually 0% by mass or more, preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 15% by mass or more, even more preferably 20% by mass or more, particularly preferably 22% by mass or more, and usually 80% by mass or less, preferably 70% by mass or less, more preferably 50% by mass or less, even more preferably 40% by mass or less, particularly preferably 30% by mass or less. For example, the content of the photopolymerizable monomer is preferably 0 to 80% by mass, more preferably 5 to 80% by mass, more preferably 10 to 70% by mass, even more preferably 15 to 50% by mass, particularly preferably 20 to 40% by mass, and most preferably 22 to 30% by mass, in the total solid content of the colored resin composition. The ratio relative to 100 parts by mass of the (A) colorant is usually 0 parts by mass or more, preferably 5 parts by mass or more, more preferably 10 parts by mass or more, even more preferably 20 parts by mass or more, even more preferably 40 parts by mass or more, particularly preferably 60 parts by mass or more, and usually 200 parts by mass or less, preferably 100 parts by mass or less, and even more preferably 80 parts by mass or less. By making it equal to or more than the lower limit, the curability tends to be high, and by making it equal to or less than the upper limit, the deterioration of the developability tends to be suppressed. For example, the content ratio of the photopolymerizable monomer is preferably 0 to 200 parts by mass, more preferably 5 to 200 parts by mass, more preferably 10 to 100 parts by mass, even more preferably 20 to 100 parts by mass, even more preferably 40 to 80 parts by mass, and most preferably 60 to 80 parts by mass, relative to 100 parts by mass of the (A) colorant.

[0159] [1-5-2] Dispersants, dispersion aids When the colored resin composition of the present invention contains a pigment as the colorant (A), a dispersant can be contained for the purpose of stably dispersing the pigment. Among them, it is preferable to use a polymer dispersant because it has excellent dispersion stability over time. Examples of polymer dispersants include urethane-based dispersants, polyethyleneimine-based dispersants, polyoxyethylene alkyl ether-based dispersants, polyoxyethylene glycol diester-based dispersants, sorbitan aliphatic ester-based dispersants, and aliphatic modified polyester-based dispersants.Specific examples of these dispersants include, by trade name, EFKA (registered trademark, manufactured by BASF), DisperBYK (registered trademark, manufactured by BYK), Disparlon (registered trademark, manufactured by Kusumoto Chemical Industries, Ltd.), SOLSPERSE (registered trademark, manufactured by Lubrizol Corporation), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), and those described in JP 2013-119568 A.

[0160] Among the polymer dispersants, from the viewpoints of dispersibility and storage stability, a block copolymer having a functional group containing a nitrogen atom is preferred, and an acrylic block copolymer is more preferred. As the block copolymer having a functional group containing a nitrogen atom, an AB block copolymer and / or a BAB block copolymer consisting of an A block having a quaternary ammonium base and / or an amino group in the side chain and a B block not having a quaternary ammonium base and / or an amino group is preferable.

[0161] Examples of the functional group containing a nitrogen atom include primary to tertiary amino groups and quaternary ammonium salt groups. From the viewpoints of dispersibility and storage stability, it is preferable for the functional group to have a primary to tertiary amino group, and it is more preferable for the functional group to have a tertiary amino group. The structure of the repeating unit having a tertiary amino group in the block copolymer is not particularly limited, but from the viewpoints of dispersibility and storage stability, it is preferable that the repeating unit be represented by the following general formula (1).

[0162] [ka]

[0163] In the above formula (1), R 1 and R 2each independently represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted aralkyl group; R 1 and R 2 may be bonded to each other to form a ring structure. 3 is a hydrogen atom or a methyl group. X is a divalent linking group.

[0164] The number of carbon atoms of the alkyl group which may have a substituent in the above formula (1) is not particularly limited, but is usually 1 or more, preferably 10 or less, more preferably 6 or less, and even more preferably 4 or less. Specific examples of the alkyl group include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, etc., among which, methyl group, ethyl group, propyl group, butyl group, pentyl group, or hexyl group is preferable, and methyl group, ethyl group, propyl group, or butyl group is more preferable. In addition, it may be either linear or branched. In addition, it may include a cyclic structure such as a cyclohexyl group or a cyclohexylmethyl group.

[0165] The number of carbon atoms in the aryl group which may have a substituent in the above formula (1) is not particularly limited, but is usually 6 or more, and preferably 16 or less, more preferably 12 or less, and even more preferably 8 or less. Specific examples of the aryl group include a phenyl group, a methylphenyl group, an ethylphenyl group, a dimethylphenyl group, a diethylphenyl group, a naphthyl group, an anthracenyl group, and the like. Among these, a phenyl group, a methylphenyl group, an ethylphenyl group, a dimethylphenyl group, or a diethylphenyl group is preferred, and a phenyl group, a methylphenyl group, or an ethylphenyl group is more preferred.

[0166] The number of carbon atoms in the aralkyl group which may have a substituent in the above formula (1) is not particularly limited, but is usually 7 or more, and is preferably 16 or less, more preferably 12 or less, and even more preferably 9 or less. Specific examples of the aralkyl group include a phenylmethylene group, a phenylethylene group, a phenylpropylene group, a phenylbutylene group, a phenylisopropylene group, and the like. Among these, a phenylmethylene group, a phenylethylene group, a phenylpropylene group, or a phenylbutylene group is preferred, and a phenylmethylene group or a phenylethylene group is more preferred.

[0167] Among these, R 1 and R 2 are each independently preferably an alkyl group which may have a substituent, and more preferably a methyl group or an ethyl group.

[0168] Substituents that the alkyl group, aralkyl group, or aryl group in the above formula (1) may have include a halogen atom, an alkoxy group, a benzoyl group, a hydroxyl group, etc., and from the viewpoint of ease of synthesis, it is preferable that they are unsubstituted.

[0169] In addition, in the above formula (1), R 1 and R 2 Examples of the cyclic structure formed by bonding with each other include a 5- to 7-membered nitrogen-containing heterocyclic monocycle and a condensed ring formed by condensing two of these. The nitrogen-containing heterocycle is preferably one that does not have aromaticity, and more preferably a saturated ring. Specific examples include the following (IV).

[0170] [ka]

[0171] These cyclic structures may further have a substituent.

[0172] In the above formula (1), examples of the divalent linking group X include an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 12 carbon atoms, -CONH-R 13 -GROUP, -COOR 14 - group [wherein R 13 and R 14 is a single bond, an alkylene group having 1 to 10 carbon atoms, or an ether group (alkyloxyalkyl group) having 2 to 10 carbon atoms, and preferably -COO-R 14 -based.

[0173] The content ratio of the repeating unit represented by the formula (1) in the total repeating units of the block copolymer is preferably 1 mol% or more, more preferably 5 mol% or more, even more preferably 10 mol% or more, even more preferably 15 mol% or more, particularly preferably 20% or more, and most preferably 25 mol% or more, and is preferably 90 mol% or less, more preferably 70 mol% or less, even more preferably 50 mol% or less, and particularly preferably 40 mol% or less. Within the above range, there is a tendency that both dispersion stability and high brightness can be achieved. For example, the content ratio of the repeating unit represented by the formula (1) in the total repeating units of the block copolymer is preferably 1 to 90 mol%, more preferably 5 to 90 mol%, even more preferably 10 to 70 mol%, even more preferably 15 to 70 mol%, particularly preferably 20 to 50%, and most preferably 25 to 40 mol%.

[0174] The block copolymer preferably has a repeating unit represented by the following formula (2) from the viewpoint of increasing the compatibility of the dispersant with binder components such as a solvent and improving dispersion stability.

[0175] [ka]

[0176] In the above formula (2), R 10 is an ethylene group or a propylene group, R 11 is an alkyl group which may have a substituent, and R 12is a hydrogen atom or a methyl group. n is an integer from 1 to 20.

[0177] R in the above formula (2) 11 The number of carbon atoms of the alkyl group which may have a substituent in is not particularly limited, but is usually 1 or more, preferably 2 or more, and preferably 10 or less, more preferably 6 or less, and even more preferably 4 or less. Specific examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl groups, among which methyl, ethyl, propyl, butyl, pentyl, or hexyl groups are preferred, and methyl, ethyl, propyl, or butyl groups are more preferred. The alkyl group may be either linear or branched. It may also include a cyclic structure such as a cyclohexyl group or a cyclohexylmethyl group. Examples of the substituent which may have a substituent include a halogen atom, an alkoxy group, a benzoyl group, and a hydroxyl group, and it is preferable that the alkyl group is unsubstituted from the viewpoint of ease of synthesis.

[0178] From the viewpoint of compatibility and dispersibility in binder components such as solvents, n in the above formula (2) is preferably 1 or more, more preferably 2 or more, and is preferably 10 or less, more preferably 5 or less.

[0179] The content of the repeating unit represented by the formula (2) in the total repeating units of the block copolymer is preferably 1 mol% or more, more preferably 2 mol% or more, and even more preferably 4 mol% or more, and is preferably 30 mol% or less, more preferably 20 mol% or less, and even more preferably 10 mol% or less. Within the above range, compatibility with binder components such as solvents and dispersion stability tend to be compatible. For example, the content of the repeating unit represented by the formula (2) in the total repeating units of the block copolymer is preferably 1 to 30 mol%, more preferably 2 to 20 mol%, and even more preferably 4 to 10 mol%.

[0180] In addition, from the viewpoint of increasing the compatibility of the dispersant with binder components such as a solvent and improving dispersion stability, the block copolymer preferably has a repeating unit represented by the following formula (3).

[0181] [ka]

[0182] In the above formula (3), R 8 R is an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted aralkyl group. 9 is a hydrogen atom or a methyl group.

[0183] R in the above formula (3) 8 The number of carbon atoms of the alkyl group which may have a substituent in the above is not particularly limited, but is usually 1 or more, preferably 1 or more, and more preferably 10 or less, and more preferably 6 or less. Specific examples of the alkyl group include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, etc., among which, methyl group, ethyl group, propyl group, butyl group, pentyl group, or hexyl group is preferred, and methyl group, ethyl group, propyl group, or butyl group is more preferred. In addition, it may be either linear or branched. In addition, it may include a cyclic structure such as a cyclohexyl group or a cyclohexylmethyl group.

[0184] R in the above formula (3) 8 The number of carbon atoms of the aryl group which may have a substituent in the formula (I) is not particularly limited, but is usually 6 or more, and preferably 16 or less, and more preferably 12 or less. Specific examples of the aryl group include a phenyl group, a methylphenyl group, an ethylphenyl group, a dimethylphenyl group, a diethylphenyl group, a naphthyl group, an anthracenyl group, and the like. Among these, a phenyl group, a methylphenyl group, an ethylphenyl group, a dimethylphenyl group, or a diethylphenyl group is preferred, and a phenyl group, a methylphenyl group, or an ethylphenyl group is more preferred.

[0185] R in the above formula (3) 8 The number of carbon atoms in the aralkyl group which may have a substituent in the formula (I) is not particularly limited, but is usually 7 or more, and preferably 16 or less, and more preferably 12 or less. Specific examples of the aralkyl group include a phenylmethylene group, a phenylethylene group, a phenylpropylene group, a phenylbutylene group, a phenylisopropylene group, and the like. Among these, a phenylmethylene group, a phenylethylene group, a phenylpropylene group, or a phenylbutylene group is preferred, and a phenylmethylene group or a phenylethylene group is more preferred.

[0186] Among these, R 8 is preferably an alkyl group or an aralkyl group, and more preferably a methyl group, an ethyl group, or a phenylmethylene group. R 8 In the above, examples of the substituent that the alkyl group may have include a halogen atom and an alkoxy group. Examples of the substituent that the aryl group or aralkyl group may have include a chain-like alkyl group, a halogen atom, and an alkoxy group. 8 The chain alkyl group represented by the formula (I) includes both straight chain and branched chain alkyl groups.

[0187] The content ratio of the repeating unit represented by the formula (3) in all repeating units of the block copolymer is preferably 30 mol% or more, more preferably 40 mol% or more, even more preferably 50 mol% or more, and is preferably 80 mol% or less, more preferably 70 mol% or less. Within the above range, there is a tendency that both dispersion stability and high brightness can be achieved. For example, the content ratio of the repeating unit represented by the formula (3) in all repeating units of the block copolymer is preferably 30 to 80 mol%, more preferably 40 to 80 mol%, even more preferably 50 to 70 mol%.

[0188] The block copolymer may have a repeating unit other than the repeating unit represented by the general formula (1), the repeating unit represented by the general formula (2), and the repeating unit represented by the general formula (3). Examples of such repeating units include repeating units derived from monomers such as styrene-based monomers, such as styrene and α-methylstyrene, (meth)acrylate-based monomers, such as (meth)acrylic acid chloride, (meth)acrylamide-based monomers, such as (meth)acrylamide and N-methylolacrylamide, vinyl acetate, acrylonitrile, allyl glycidyl ether, crotonic acid glycidyl ether, and N-methacryloylmorpholine.

[0189] From the viewpoint of further improving dispersibility, it is preferable that the block copolymer has an A block having a repeating unit represented by the general formula (1) and a B block having no repeating unit represented by the general formula (1). The block copolymer is preferably an AB block copolymer or a BAB block copolymer. It is more preferable that the B block has a repeating unit represented by the general formula (2) and a repeating unit represented by the general formula (3).

[0190] Furthermore, a repeating unit other than the repeating unit represented by the general formula (1) may be contained in the A block, and examples of such a repeating unit include the repeating unit derived from the (meth)acrylic acid ester monomer described above. The content of the repeating unit other than the repeating unit represented by the general formula (1) in the A block is preferably 0 to 50 mol %, more preferably 0 to 20 mol %, and it is most preferable that such a repeating unit is not contained in the A block.

[0191] Repeating units other than the repeating units represented by the general formula (2) and the repeating units represented by the general formula (3) may be contained in the B block, and examples of such repeating units include repeating units derived from styrene-based monomers such as styrene and α-methylstyrene, (meth)acrylate-based monomers such as (meth)acrylic acid chloride, (meth)acrylamide-based monomers such as (meth)acrylamide and N-methylolacrylamide, vinyl acetate, acrylonitrile, allyl glycidyl ether, crotonic acid glycidyl ether, N-methacryloylmorpholine, etc. The content of repeating units other than the repeating units represented by the general formula (2) and the repeating units represented by the general formula (3) in the B block is preferably 0 to 50 mol%, more preferably 0 to 20 mol%, and most preferably, such repeating units are not contained in the B block.

[0192] From the viewpoint of dispersibility, the acid value of the block copolymer is preferably low, and is particularly preferably 0 mg KOH / g, where the acid value represents the number of mg of KOH required to neutralize 1 g of the dispersant solid content.

[0193] From the viewpoint of dispersibility and developability, the amine value of the block copolymer is preferably 30 mgKOH / g or more, more preferably 50 mgKOH / g or more, even more preferably 70 mgKOH / g or more, even more preferably 90 mgKOH / g or more, particularly preferably 100 mgKOH / g or more, most preferably 110 mgKOH / g or more, and is preferably 150 mgKOH / g or less, more preferably 130 mgKOH / g or less. Here, the amine value represents the amine value in terms of effective solid content, and is a value represented by the mass of KOH equivalent to the amount of base per gram of solid content of the dispersant. For example, the amine value of the block copolymer is preferably 30 to 150 mgKOH / g, more preferably 50 to 150 mgKOH / g, even more preferably 70 to 150 mgKOH / g, even more preferably 90 to 130 mgKOH / g, particularly preferably 100 to 130 mgKOH / g, and most preferably 110 to 130 mgKOH / g.

[0194] The molecular weight of the block copolymer is preferably in the range of 1000 to 30000 in terms of polystyrene equivalent weight average molecular weight (hereinafter sometimes referred to as "Mw"). When it is within the above range, the dispersion stability becomes good, and there is a tendency that the generation of dried foreign matter during application by the slit nozzle method becomes more unlikely.

[0195] The block copolymer can be produced by a known method, for example, by living polymerization of monomers that introduce the above-mentioned repeating units. Examples of living polymerization methods include those described in Japanese Patent Application Laid-Open No. 9-62002 and Japanese Patent Application Laid-Open No. 2002-31713, and those described in P. Lutz, P. Masson et al., Polym. Bull. 12, 79 (1984), BC Anderson, GD Andrews et al., Macromolecules, 14, 1601 (1981), K. Hatada, K. Ute, et al. al, Polym. J. 17, 977 (1985), 18, 1037 (1986); Koichi Migite, Koichi Hatada, Polymer Processing, 36, 366 (1987); Toshinobu Higashimura, Mitsuo Sawamoto, Polymer Research Papers, 46, 189 (1989); M. Kuroki, T. Aida, J. Am. Chem. Soc, 109, 4737 (1987); Takuzo Aida, Shohei Inoue, Organic Synthesis Chemistry, 43, 300 (1985); DY Sogoh, WRHertler et al, Macromolecules, 20, 1473 (1987), and other known methods can be used.

[0196] When the colored resin composition of the present invention contains a dispersant, the content ratio of the dispersant is not particularly limited, but is preferably 1% by mass or more, more preferably 2% by mass or more, even more preferably 4% by mass or more, particularly preferably 5% by mass or more, and is preferably 20% by mass or less, more preferably 15% by mass or less, even more preferably 10% by mass or less, and particularly preferably 8% by mass or less, based on the total solid content of the colored resin composition. By keeping the content within the above range, it is possible to obtain a colored resin composition having excellent dispersion stability and high brightness.

[0197] When the colored resin composition of the present invention contains a pigment and a dispersant, the content ratio of the dispersant is not particularly limited, but is preferably 0.5 parts by mass or more, more preferably 5 parts by mass or more, even more preferably 10 parts by mass or more, even more preferably 15 parts by mass or more, particularly preferably 20 parts by mass or more, and is also preferably 70 parts by mass or less, more preferably 50 parts by mass or less, even more preferably 40 parts by mass or less, and particularly preferably 30 parts by mass or less, relative to 100 parts by mass of the pigment. By setting it within the above range, there is a tendency that a colored resin composition having excellent dispersion stability and high brightness can be obtained. For example, when the colored resin composition contains a pigment and a dispersant, the content ratio of the dispersant is preferably 0.5 to 70 parts by mass, more preferably 5 to 70 parts by mass, more preferably 10 to 50 parts by mass, even more preferably 15 to 40 parts by mass, and particularly preferably 20 to 30 parts by mass, relative to 100 parts by mass of the pigment.

[0198] In addition, when the colored resin composition of the present invention contains a pigment, it may contain a pigment derivative or the like as a dispersing aid to improve the dispersibility and dispersion stability of the pigment. Examples of the pigment derivative include azo-based, phthalocyanine-based, quinacridone-based, benzimidazolone-based, quinophthalone-based, isoindolinone-based, isoindoline-based, dioxazine-based, anthraquinone-based, indanthrene-based, perylene-based, perinone-based, diketopyrrolopyrrole-based, and dioxazine-based pigment derivatives. Examples of the substituent of the pigment derivative include sulfonic acid groups, sulfonamide groups and quaternary salts thereof, phthalimidomethyl groups, dialkylaminoalkyl groups, hydroxyl groups, carboxy groups, and amide groups that are bonded to the pigment skeleton directly or via alkyl groups, aryl groups, and heterocyclic groups, and preferably sulfonamide groups and quaternary salts thereof, and sulfonic acid groups, and more preferably sulfonic acid groups. In addition, these substituents may be substituted in a plurality on one pigment skeleton, or a mixture of compounds with different numbers of substitutions may be used. Specific examples of pigment derivatives include sulfonic acid derivatives of azo pigments, sulfonic acid derivatives of phthalocyanine pigments, sulfonic acid derivatives of quinophthalone pigments, sulfonic acid derivatives of isoindoline pigments, sulfonic acid derivatives of anthraquinone pigments, sulfonic acid derivatives of quinacridone pigments, sulfonic acid derivatives of diketopyrrolopyrrole pigments, and sulfonic acid derivatives of dioxazine pigments.

[0199] [1-5-3] Surfactants As the surfactant, various surfactants such as anionic, cationic, nonionic, and amphoteric surfactants can be used, but it is preferable to use a nonionic surfactant because it is less likely to adversely affect various properties. The content ratio of the surfactant is not particularly limited, but is usually 0.001 mass% or more, preferably 0.01 mass% or more, more preferably 0.05 mass% or more, and even more preferably 0.1 mass% or more in the total solid content of the colored resin composition, and is usually used in the range of 10 mass% or less, preferably 1 mass% or less, more preferably 0.5 mass% or less, and most preferably 0.3 mass% or less. For example, when a surfactant is included, the content ratio of the surfactant is preferably 0.001 to 10 mass%, more preferably 0.01 to 1 mass%, more preferably 0.05 to 0.5 mass%, and even more preferably 0.1 to 0.3 mass% relative to the total solid content of the colored resin composition.

[0200] [2] Preparation of colored resin composition Next, a method for preparing the colored resin composition (hereinafter, sometimes referred to as a resist) according to the present invention will be described.

[0201] When preparing a colorant containing a pigment, first, the pigment, solvent, and dispersant are weighed in predetermined amounts, and the pigment is dispersed in a dispersion process to prepare a pigment dispersion. In this dispersion process, a paint conditioner, a sand grinder, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer, or the like can be used. By carrying out this dispersion process, the pigment is microparticulated, improving the coating properties of the colored resin composition and improving the transmittance of pixels in the product color filter substrate.

[0202] When dispersing the pigment, it is preferable to use a dispersing aid or a dispersing resin in combination as described above. When the dispersion treatment is carried out using a sand grinder, it is preferable to use glass beads or zirconia beads having a diameter of 0.1 to several mm. The temperature during the dispersion treatment is usually set to 0° C. or higher, preferably room temperature or higher, and usually 100° C. or lower, preferably 80° C. or lower. The optimum dispersion time varies depending on the composition of the pigment dispersion and the size of the sand grinder device, and may be adjusted as appropriate.

[0203] The pigment dispersion obtained by the above dispersion treatment is mixed with a solvent, an alkali-soluble resin, a photopolymerization initiator, and in some cases, other components than the above, to obtain a uniform dispersion solution. Since fine dust particles may be mixed in during the dispersion treatment process and each mixing process, it is preferable to filter the obtained pigment dispersion using a filter or the like.

[0204] In the case where the colorant does not contain a pigment, a homogeneous solution can be obtained by mixing the colorant, the solvent, the alkali-soluble resin, the photopolymerization initiator, and, in some cases, other components than those mentioned above. It is preferable to filter the obtained solution using a filter or the like.

[0205] [3] Manufacturing of color filter substrates Next, the color filter according to the present invention will be described. The color filter according to the present invention has pixels formed using the colored resin composition of the present invention. The colored resin composition of the present invention is preferably a colored resin composition for forming pixels of a color filter.

[0206] [3-1]Transparent substrate (support) The transparent substrate of the color filter is not particularly limited in material as long as it is transparent and has a suitable strength. Examples of the material include polyester resins such as polyethylene terephthalate, polyolefin resins such as polypropylene and polyethylene, thermoplastic resin sheets such as polycarbonate, polymethyl methacrylate, and polysulfone, thermosetting resin sheets such as epoxy resin, unsaturated polyester resin, and poly(meth)acrylic resin, and various glasses. Among these, glass or heat-resistant resins are preferred from the viewpoint of heat resistance.

[0207] The transparent substrate and the black matrix-formed substrate may be subjected to corona discharge treatment, ozone treatment, thin film formation treatment with a silane coupling agent, or various resins such as urethane resins, as necessary, in order to improve surface properties such as adhesion. The thickness of the transparent substrate is usually 0.05 mm or more, preferably 0.1 mm or more, and usually 10 mm or less, preferably 7 mm or less. When a thin film formation treatment with various resins is performed, the film thickness is usually 0.01 μm or more, preferably 0.05 μm or more, and usually 10 μm or less, preferably 5 μm or less.

[0208] [3-2] Black matrix A color filter according to the present invention can be manufactured by providing a black matrix on the above-mentioned transparent substrate and then forming pixel images, usually red, green, and blue. The above-mentioned colored resin composition is preferably used as a coating liquid for forming a green pixel (resist pattern) among the red, green, and blue pixels (hereinafter, sometimes abbreviated as "green resist"). Using the green resist, a pixel image is formed by carrying out each process of coating, heating and drying, image exposure, development, and heat curing on a resin black matrix formed on a transparent substrate or a metal black matrix formed using a chromium compound or other light-shielding metal material.

[0209] The black matrix is ​​formed on a transparent substrate by using a light-shielding metal thin film or a colored resin composition for a black matrix. As the light-shielding metal material, metal chromium, chromium compounds such as chromium oxide and chromium nitride, nickel-tungsten alloys, etc. are used, and these may be laminated in a multi-layer structure. These metal light-shielding films are generally formed by a sputtering method. After forming a desired pattern in a film shape using positive photoresist, the film is etched using an etching solution of a mixture of ceric ammonium nitrate and perchloric acid and / or nitric acid for chromium, or an etching solution appropriate for the material for other materials. Finally, the positive photoresist is stripped off with a dedicated stripper to form a black matrix.

[0210] In this case, first, a thin film of the metal or metal / metal oxide is formed on a transparent substrate by vapor deposition or sputtering, etc. Next, a coating film of a colored resin composition is formed on the thin film, and then the coating film is exposed and developed using a photomask having a repeating pattern such as stripes, mosaics, triangles, etc. to form a resist image. Then, the coating film is etched to form a black matrix.

[0211] When using a photosensitive colored resin composition for black matrix, a black matrix is ​​formed using a colored resin composition containing a black colorant. For example, a colored resin composition containing a single or multiple black colorants such as carbon black, graphite, iron black, aniline black, cyanine black, titanium black, or a black colorant consisting of a mixture of red, green, blue, etc. appropriately selected from inorganic or organic pigments and dyes can be used to form a black matrix in the same manner as in the method for forming red, green, and blue pixel images described below.

[0212] [3-3] Pixel formation A method for forming pixels will be described. A colored resin composition of one of red, green, and blue colors is applied onto a transparent substrate provided with a black matrix, and then dried. A photomask is placed on the applied film, and a pixel image is formed by image exposure through the photomask, development, and, if necessary, heat curing or photocuring. This operation is performed for each of the three colored resin compositions of red, green, and blue, to form a color filter image.

[0213] The colored resin composition for color filters can be applied by a spinner method, a wire bar method, a flow coating method, a die coating method, a roll coating method, a spray coating method, etc. Among them, the die coating method is preferable from an overall viewpoint, since the amount of coating solution used can be significantly reduced, there is no influence of mist or the like that adheres when using the spin coating method, and furthermore, the generation of foreign matter can be suppressed.

[0214] If the thickness of the coating film is too large, it may be difficult to develop the pattern and to adjust the gap in the liquid crystal cell formation process, while if the thickness is too small, it may be difficult to increase the pigment concentration, making it impossible to express the desired color. The thickness of the coating film after drying is usually 0.2 μm or more, preferably 0.5 μm or more, more preferably 0.8 μm or more, and usually 20 μm or less, preferably 10 μm or less, more preferably 5 μm or less.

[0215] [3-4] Drying of the coating film The coating film after the colored resin composition is applied to the substrate is preferably dried by a drying method using a hot plate, an IR oven, or a convection oven. Usually, after pre-drying, the coating film is heated again to dry. The pre-drying conditions can be appropriately selected according to the type of the solvent component, the performance of the dryer used, etc. The drying temperature and drying time are selected according to the type of the solvent component, the performance of the dryer used, etc. Specifically, the drying temperature is usually 40° C. or higher, preferably 50° C. or higher, and usually 80° C. or lower, preferably 70° C. or lower, and the drying time is usually 15 seconds or higher, preferably 30 seconds or higher, and usually 5 minutes or less, preferably 3 minutes or less.

[0216] The temperature condition of the reheating and drying is preferably higher than the preliminary drying temperature, specifically, usually 50°C or higher, preferably 70°C or higher, usually 200°C or lower, preferably 160°C or lower, particularly preferably 130°C or lower. The drying time depends on the heating temperature, but is usually 10 seconds or higher, preferably 15 seconds or higher, and usually 10 minutes or lower, preferably 5 minutes. The higher the drying temperature, the better the adhesion to the transparent substrate, but if the temperature is too high, the alkali-soluble resin may decompose, inducing thermal polymerization and causing development defects. The drying process of this coating film may be performed in a vacuum chamber without increasing the temperature, using a vacuum drying method.

[0217] [3-5] Exposure process Image exposure is performed by superposing a negative matrix pattern on the coating film of the colored resin composition, and irradiating the film with a light source of ultraviolet or visible light through this mask pattern. At this time, if necessary, in order to prevent a decrease in the sensitivity of the photopolymerizable layer due to oxygen, an oxygen barrier layer such as a polyvinyl alcohol layer may be formed on the photopolymerizable layer before exposure. The light source used for the image exposure is not particularly limited. Examples of light sources include lamp light sources such as xenon lamps, halogen lamps, tungsten lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, medium-pressure mercury lamps, low-pressure mercury lamps, carbon arcs, and fluorescent lamps, and laser light sources such as argon ion lasers, YAG lasers, excimer lasers, nitrogen lasers, helium cadmium lasers, and semiconductor lasers. When using light of a specific wavelength, an optical filter can also be used.

[0218] [3-6]Developing process The color filter according to the present invention can be produced by forming an image on a substrate by imagewise exposing a coating film using the colored resin composition according to the present invention to the above-mentioned light source, and then developing the film using an organic solvent or an aqueous solution containing a surfactant and an alkaline compound. The aqueous solution can further contain an organic solvent, a buffer, a complexing agent, a dye or a pigment.

[0219] Examples of the alkaline compound include inorganic alkaline compounds such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, potassium phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, and ammonium hydroxide, and organic alkaline compounds such as mono-, di-, or triethanolamine, mono-, di-, or trimethylamine, mono-, di-, or triethylamine, mono- or diisopropylamine, n-butylamine, mono-, di-, or triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH), and choline. These alkaline compounds may be a mixture of two or more kinds.

[0220] Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, and monoglyceride alkyl esters; anionic surfactants such as alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfonates, and sulfosuccinate salts; and amphoteric surfactants such as alkyl betaines and amino acids.

[0221] Examples of the organic solvent include isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone alcohol, etc. The organic solvent may be used alone or in combination with an aqueous solution. The conditions for the development process are not particularly limited, but the development temperature is usually 10° C. or higher, preferably 15° C. or higher, and more preferably 20° C. or higher, and usually 50° C. or lower, preferably 45° C. or lower, and more preferably 40° C. or lower. The development method may be any of immersion development, spray development, brush development, ultrasonic development, and the like.

[0222] [3-7] Heat curing treatment The color filter after development is subjected to a heat curing treatment. The heat curing conditions are selected such that the temperature is usually 100° C. or higher, preferably 150° C. or higher, and usually 280° C. or lower, preferably 250° C. or lower, and the time is selected in the range of 5 minutes or more and 60 minutes or less. Through this series of steps, the formation of a patterned image of one color is completed. This process is repeated in sequence to pattern black, red, green, and blue, forming a color filter. The order of patterning the four colors is not limited to the above order.

[0223] [3-8] Formation of transparent electrodes The color filter according to the present invention is used as it is as a part of a component of a color display, a liquid crystal display device, etc., by forming a transparent electrode such as ITO on the image, but in order to improve the surface smoothness and durability, a top coat layer of polyamide, polyimide, etc. can be provided on the image as necessary. In some applications such as a planar alignment type driving system (IPS mode), a transparent electrode may not be formed.

[0224] [4] Image display device (panel) Next, the image display device of the present invention will be described. The image display device of the present invention has the above-mentioned color filter. Hereinafter, as the image display device, a liquid crystal display device and an organic EL display device will be described in detail.

[0225] [4-1]Liquid crystal display device A method for manufacturing a liquid crystal display device according to the present invention will be described. A liquid crystal display device according to the present invention is usually manufactured by forming an alignment film on the color filter according to the present invention, dispersing spacers on the alignment film, and then bonding it to an opposing substrate to form a liquid crystal cell. Liquid crystal is injected into the formed liquid crystal cell, and the liquid crystal cell is connected to the opposing electrode to complete the device. A resin film such as polyimide is suitable for the alignment film. A gravure printing method and / or a flexographic printing method is usually used to form the alignment film, and the thickness of the alignment film is set to several tens of nm. After hardening the alignment film by thermal baking, the surface is treated by irradiation with ultraviolet light or treatment with a rubbing cloth to make the surface state capable of adjusting the tilt of the liquid crystal.

[0226] The size of the spacer used depends on the gap (gap) with the opposing substrate, and typically 2 to 8 μm is suitable. A photospacer (PS) made of a transparent resin film can be formed on the color filter substrate by photolithography, and used instead of the spacer. An array substrate is typically used as the opposing substrate, and a TFT (thin film transistor) substrate is particularly suitable.

[0227] The gap between the opposing substrate and the substrate varies depending on the application of the liquid crystal display device, but is usually selected to be in the range of 2 μm or more and 8 μm or less. After bonding with the opposing substrate, the area other than the liquid crystal injection port is sealed with a sealant such as epoxy resin. The sealant is hardened by UV irradiation and / or heating, sealing the periphery of the liquid crystal cell. The liquid crystal cell with the sealed periphery is cut into panel units, and then the pressure is reduced in a vacuum chamber. The liquid crystal injection port is immersed in the liquid crystal, and the liquid crystal is injected into the liquid crystal cell by leaking the chamber. The degree of pressure reduction in the liquid crystal cell is usually 1×10 -2 Pa or more, preferably 1×10 -3 Above, and usually 1×10 -7 Pa or less, preferably 1×10 -6 The pressure is preferably in the range of not more than Pa. It is also preferable to heat the liquid crystal cell during the reduced pressure, and the heating temperature is usually 30° C. or higher, preferably 50° C. or higher, and usually 100° C. or lower, preferably 90° C. or lower.

[0228] The heating and holding time during reduced pressure is usually within the range of 10 minutes to 60 minutes, after which the cell is immersed in liquid crystal. The liquid crystal cell into which the liquid crystal has been injected is sealed by curing the liquid crystal injection port with UV curable resin to complete the liquid crystal display device (panel). The type of liquid crystal is not particularly limited, and may be any of conventionally known liquid crystals such as aromatic, aliphatic, polycyclic compounds, lyotropic liquid crystals, thermotropic liquid crystals, etc. Known thermotropic liquid crystals include nematic liquid crystals, smectic liquid crystals, and cholesteric liquid crystals, and any of these may be used.

[0229] [4-2] Organic EL display device When producing an organic EL display device having the color filter of the present invention, for example, as shown in FIG. 1, a multi-color organic EL element is produced by laminating an organic light-emitting body 500 on a blue color filter having pixels 20 formed thereon using the colored resin composition of the present invention on a transparent supporting substrate 10 via an organic protective layer 30 and an inorganic oxide film 40.

[0230] Examples of the method for laminating the organic light-emitting body 500 include a method of sequentially forming a transparent anode 50, a hole injection layer 51, a hole transport layer 52, a light-emitting layer 53, an electron injection layer 54, and a cathode 55 on the upper surface of a color filter, and a method of bonding an organic light-emitting body 500 formed on a separate substrate onto an inorganic oxide film 40. The organic EL element 100 thus fabricated can be applied to both passively driven organic EL display devices and actively driven organic EL display devices. EXAMPLES

[0231] Next, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited to the following examples as long as it does not depart from the gist of the present invention. In addition, for the medium pressure preparative liquid chromatography described in the synthesis examples, a medium pressure preparative apparatus manufactured by Yamazen Corporation; W-Prep (flow rate 20 mL / min, silica gel 30 μm column) was used.

[0232] <Synthesis Example 1: Synthesis of Dye A> Tetrafluorophthalonitrile 4.00g (20mmol), potassium fluoride 2.90g (5.0mmol) and acetone 10mL were mixed and cooled on ice, and then a solution of ethyl p-hydroxybenzoate 6.65g (40mmol) in acetone (30mL) was added and stirred for 5 hours. After the reaction was completed, the reaction solution was filtered and concentrated, and ethanol 60mL was added to filter out the precipitate and dry it to obtain 6.20g (yield 63%, purity 97.6%) of intermediate A. The purity is an area % value calculated from the results of high performance liquid chromatography analysis.

[0233] [ka]

[0234] In the formula, Et represents ethyl.

[0235] 1 H-NMR (CDCl3) δ:1.38(t,6H), 4.36(m,4H), 6.81(d,4H), 7.98(d,4H)

[0236] 6.20g (12.6mmol) of intermediate A, 1.21g (3.78mmol) of zinc iodide, and 12mL of benzonitrile were mixed and reacted at 160°C for 10 hours. After the reaction was completed, the reaction solution was cooled and poured into 20mL of ethanol. The resulting solid was washed with ethanol and dried under reduced pressure at 50°C to obtain 5.66g (yield 88%) of dye A.

[0237] [ka]

[0238] In the formula, Et represents ethyl.

[0239] 1 H-NMR(DMSO-d6) δ:1.30(t,24H), 4.27(m,16H), 7.26(d,16H), 7.79(d,16H)

[0240] 1 mg of dye A was dissolved in 100 mL of DMSO (dimethyl sulfoxide), and the visible absorption spectrum was measured using a UV-visible spectrophotometer (Hitachi High-Technologies Corporation U-4100) in a 1 cm square quartz cell. The maximum absorption wavelength was 665.5 nm, and the molar extinction coefficient (ε) was 1.195 × 10 5 It was.

[0241] <Synthesis Example 2: Synthesis of Dye B> 3.02g (15.0mmol) of tetrafluorophthalonitrile, 4.14g (30.0mmol) of potassium carbonate, and 50mL of acetone were mixed and cooled on ice. At 2-4°C, a solution of 5.40g (30.0mmol) of n-propyl p-hydroxybenzoate in acetone (30mL) was added, and the mixture was stirred for 5 hours. After the reaction was completed, the reaction solution was filtered, dried over anhydrous magnesium sulfate, and the desiccant was filtered off. The solvent was concentrated, and the precipitated solid was filtered to obtain 4.0g (yield 51%, purity 95.9%) of intermediate B. The purity is an area % value calculated from the results of high performance liquid chromatography analysis.

[0242] [ka]

[0243] In the formula, n-Pr represents n-propyl.

[0244] 1 H-NMR (CDCl3) δ:1.03(t,6H), 1.78(m,4H), 4.29(t,4H), 6.82(d,4H), 7.98(d,4H)

[0245] 1.00g (2.15mmol) of intermediate B, 0.21g (0.65mmol) of zinc iodide, and 2.4mL of benzonitrile were mixed and reacted at 170°C for 13 hours. After the reaction was completed, the reaction solution was cooled and poured into 20mL of methanol. The solid matter formed was filtered, washed with methanol and water, and dried under reduced pressure at 50°C to obtain 0.33g (yield 29%) of dye B.

[0246] [ka]

[0247] In the formula, n-Pr represents n-propyl.

[0248] 1 H-NMR(DMSO-d6) δ:0.94(t,24H), 1.88(m,16H), 4.16(t,16H), 7.25(d,16H), 7.78(d,16H)

[0249] 1 mg of dye B was dissolved in 100 mL of DMSO, and the visible absorption spectrum was measured using a UV-Vis spectrophotometer (Hitachi High-Technologies Corporation U-4100) in a 1 cm square quartz cell. The maximum absorption wavelength was 665.0 nm, and the molar extinction coefficient (ε) was 1.202 × 10 5 It was.

[0250] <Synthesis Example 3: Synthesis of Dye C> 2.00g (10mmol) of tetrafluorophthalonitrile, 1.45g (2.5mmol) of potassium fluoride and 5mL of acetone were mixed and cooled on ice, and then a solution of 3.89g (20mmol) of isobutyl p-hydroxybenzoate in acetone (5mL) was added and stirred for 5 hours. After the reaction was completed, the reaction solution was filtered and concentrated, and the resulting residue was purified by medium pressure preparative liquid chromatography (developing solvent was a mixed solvent of hexane and acetic acid, 94:6 to 73:27 (volume ratio) gradient) to obtain 2.50g (yield 46%, purity 97.8%) of intermediate C. The purity is the area % value calculated from the results of high performance liquid chromatography analysis.

[0251] [ka]

[0252] In the formula, i-Bu represents isobutyl.

[0253] 2.50 g (4.56 mmol) of intermediate C, 0.44 g (1.37 mmol) of zinc iodide, and 4 mL of benzonitrile were mixed and reacted at 160° C. for 9 hours. After the reaction was completed, the reaction solution was cooled and purified by medium pressure preparative liquid chromatography (developing solvent was a mixed solvent of chloroform and methanol, gradient of 100:0 to 85:15 (volume ratio)) to obtain 1.06 g (yield 41%) of dye C.

[0254] [ka]

[0255] In the formula, i-Bu represents isobutyl.

[0256] 1 H-NMR(DMSO-d6) δ:0.94(d,48H), 1.98(m,8H), 4.00(d,16H), 7.27(d,16H), 7.80(d,16H)

[0257] 1 mg of dye C was dissolved in 100 mL of DMSO, and the visible absorption spectrum was measured using a UV-Vis spectrophotometer (Hitachi High-Technologies Corporation U-4100) in a 1 cm square quartz cell. The maximum absorption wavelength was 665.0 nm, and the molar extinction coefficient (ε) was 1.156 × 10 5 It was.

[0258] <Synthesis Example 4: Synthesis of Dye D> 2.00g (10mmol) of tetrafluorophthalonitrile, 1.45g (2.5mmol) of potassium fluoride and 5mL of acetone were mixed and cooled on ice, and then a solution of 3.78g (21mmol) of methyl 3-(4-hydroxyphenyl)propanoate in acetone (5mL) was added and stirred for 5 hours. After the reaction was completed, the reaction solution was extracted with chloroform-water, and the organic layer was extracted with saturated saline. The concentrated product was purified by medium pressure preparative liquid chromatography (developing solvent was a mixed solvent of hexane and ethyl acetate, 94:6 to 73:27 (volume ratio) gradient) to obtain 3.00g (yield 58%, purity 97.8%) of intermediate D. The purity is the area % value calculated from the results of high performance liquid chromatography analysis.

[0259] [ka]

[0260] 1 H-NMR (CDCl3) δ:2.58(t,2H), 2.90(t,2H), 3.67(s,3H), 6.70(d,2H), 7.09(d,2H)

[0261] 1.04 g (2.00 mmol) of intermediate D, 0.19 g (0.6 mmol) of zinc iodide, and 2 mL of benzonitrile were mixed and reacted at 160° C. for 8 hours. After the reaction was completed, the reaction solution was cooled and purified by medium pressure preparative liquid chromatography (developing solvent was a mixed solvent of chloroform and methanol, gradient of 100:0 to 93:7 (volume ratio)) to obtain 0.75 g (yield 70%) of dye D.

[0262] [ka]

[0263] 1 mg of dye D was dissolved in 100 mL of DMSO, and the visible absorption spectrum was measured using a UV-Vis spectrophotometer (Hitachi High-Technologies Corporation U-4100) in a 1 cm square quartz cell. The maximum absorption wavelength was 700.0 nm, and the molar extinction coefficient (ε) was 2.278 × 10 5 It was.

[0264] <Synthesis Example 5: Synthesis of Dye E> 5.00g (18.8mmol) of tetrachlorophthalonitrile, 7.30g (37.6mmol) of isobutyl p-hydroxybenzoate, 3.89g (28.2mmol) of potassium carbonate, and 50mL of acetonitrile were mixed and heated to 50°C, and stirred for 2 hours. After the reaction was completed, the mixture was cooled to room temperature, and the reaction liquid was filtered and concentrated. The residue was purified by medium pressure preparative liquid chromatography (developing solvent was a mixed solvent of hexane and ethyl acetate, gradient of 100:0 to 86:14 (volume ratio)) to obtain 0.49g (yield 4.4%, purity 77.9%) of intermediate E. The purity is an area % value calculated from the results of high performance liquid chromatography analysis.

[0265] [ka]

[0266] In the formula, i-Bu represents isobutyl.

[0267] 1 H-NMR (CDCl3) δ:1.03(d,6H), 2.09(m,1H), 4.11(d,2H), 6.70(d,2H), 7.99(d,2H)

[0268] 0.45g (0.77mmol) of intermediate E, 0.074g (0.23mmol) of zinc iodide, and 1.0g of benzonitrile were mixed and reacted at 170°C for 5 hours. After the reaction was completed, the reaction solution was cooled and poured into 20mL of methanol. The solid matter formed was filtered, washed with methanol and water, and dried under reduced pressure at 50°C to obtain 0.32g (yield 73%) of dye E.

[0269] [ka]

[0270] In the formula, iBu represents isobutyl.

[0271] 1 H-NMR(DMSO-d6) δ:1.00(d,6H), 2.01(m,1H), 4.03(d,2H), 6.95(d,2H), 7.87(d,2H)

[0272] 1 mg of dye E was dissolved in 100 mL of DMSO, and the visible absorption spectrum was measured using a UV-Vis spectrophotometer (Hitachi High-Technologies Corporation U-4100) in a 1 cm square quartz cell. The maximum absorption wavelength was 697.0 nm, and the molar extinction coefficient (ε) was 1.391 × 10 5 It was.

[0273] <Synthesis Example 6: Synthesis of Dye F> 0.60 g (1.22 mmol) of intermediate A, 0.041 g (0.30 mmol) of copper(II) chloride, and 2 mL of benzonitrile were added and reacted at 160° C. for 8 hours. After the reaction was completed, the reaction solution was cooled and poured into 10 mL of ethanol. The resulting solid was washed with ethanol and dried under reduced pressure at 50° C. to obtain 0.30 g (48% yield) of dye F.

[0274] [ka]

[0275] In the formula, Et represents ethyl.

[0276] 1 mg of dye F was dissolved in 100 mL of DMSO, and the visible absorption spectrum was measured using a UV-Vis spectrophotometer (Hitachi High-Technologies Corporation U-4100) in a 1 cm square quartz cell. The maximum absorption wavelength was 698.0 nm, and the molar extinction coefficient (ε) was 3.759 × 10 4 It was.

[0277] <Synthesis Example 7: Synthesis of Dye G> 3.00g (15.0mmol) of tetrafluorophthalonitrile, 1.03g (7.50mmol) of potassium carbonate, and 50mL of acetonitrile were mixed and cooled on ice. At 2°C, a solution of 3.21g (15.0mmol) of phenyl p-hydroxybenzoate in acetonitrile (20mL) was added, and the mixture was stirred for 5 hours. After the reaction was completed, the reaction solution was filtered and concentrated. The resulting residue was purified by medium pressure preparative liquid chromatography (developing solvent was a mixed solvent of hexane and ethyl acetate, gradient of 97:3 to 77:23 (volume ratio)) to obtain 1.43g (yield 24%, purity 94.8%) of intermediate G. The purity is an area % value calculated from the results of high performance liquid chromatography analysis.

[0278] [ka]

[0279] 1 H-NMR (CDCl3) δ:7.10(d,2H), 7.20(d,2H), 7.28(t,1H), 7.42(d,2H), 8.24(d,2H)

[0280] 1.43 g (3.63 mmol) of intermediate G, 0.29 g (0.91 mmol) of zinc iodide, and 3.4 g of benzonitrile were mixed and reacted at 170° C. for 5 hours. After the reaction was completed, the reaction solution was cooled and poured into 30 mL of methanol. The solid matter formed was filtered, washed with methanol and water, and dried under reduced pressure at 50° C. to obtain 1.00 g (yield 68%) of dye G.

[0281] [ka]

[0282] In the formula, Ph represents phenyl.

[0283] 1 mg of dye G was dissolved in 100 mL of DMSO, and the visible absorption spectrum was measured using a UV-Vis spectrophotometer (Hitachi High-Technologies Corporation U-4100) in a 1 cm square quartz cell. The maximum absorption wavelength was 650.0 nm, and the molar extinction coefficient (ε) was 8.826 × 10 4 It was.

[0284] <Synthesis Example 8: Synthesis of Dye H> 2.55g (12.7mmol) of tetrafluorophthalonitrile, 1.76g (12.7mmol) of potassium carbonate, and 30mL of acetonitrile were mixed, and a solution of 5.35g (25.5mmol) of dimethyl 4-hydroxyisophthalate in acetonitrile (20mL) was added at room temperature, and the mixture was stirred for 9 hours. After the reaction was completed, the reaction solution was filtered and concentrated. The resulting residue was purified by medium pressure preparative liquid chromatography (developing solvent was a mixed solvent of hexane and ethyl acetate, gradient of 78:22 to 50:50 (volume ratio)) to obtain 0.30g (yield 4.1%, purity 86.3%) of intermediate H. The purity is an area % value calculated from the results of high performance liquid chromatography analysis.

[0285] [ka]

[0286] In the formula, Me represents methyl.

[0287] 1 H-NMR (CDCl3) δ:3.78(s,6H), 3.93(s,3H), 6.92(d,2H), 8.07(d,2H), 8.49(s,2H)

[0288] 1.00g (1.72mmol) of intermediate H, 0.165g (0.52mmol) of zinc iodide, and 2.4g of benzonitrile were mixed and reacted at 160°C for 7 hours. After the reaction was completed, the reaction solution was cooled and concentrated. The resulting residue was purified by medium pressure preparative liquid chromatography (developing solvent was a mixed solvent of chloroform and methanol, 99:1 to 50:50 (volume ratio) gradient) to obtain 0.19g (yield 16%) of dye H.

[0289] [ka]

[0290] In the formula, Me represents methyl.

[0291] 1 H-NMR(DMSO-d6) δ:3.56(s,24H), 3.86(s,24H), 7.17(d,8H), 8.01(d,8H), 8.25(s,8H)

[0292] 1 mg of dye H was dissolved in 100 mL of DMSO, and the visible absorption spectrum was measured using a UV-Vis spectrophotometer (Hitachi High-Technologies Corporation U-4100) in a 1 cm square quartz cell. The maximum absorption wavelength was 668.0 nm, and the molar extinction coefficient (ε) was 6.103 × 10 4 It was.

[0293] <Synthesis Example 9: Binder Resin A> 148.0 parts by mass of propylene glycol monomethyl ether acetate was stirred while replacing with nitrogen and heated to 120 ° C. 7.3 parts by mass of styrene, 91.0 parts by mass of glycidyl methacrylate, and 61.7 parts by mass of monomethacrylate having a tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.) were dropped therein, and further stirring was continued at 120 ° C. for 2 hours. Next, the inside of the reaction vessel was changed to air replacement, and 0.7 parts by mass of trisdimethylaminomethylphenol and 0.12 parts by mass of hydroquinone were added to 43.8 parts by mass of acrylic acid, and the reaction was continued at 120 ° C. for 6 hours. Then, 39.0 parts by mass of succinic anhydride and 0.7 parts by mass of triethylamine were added, and the reaction was continued at 120 ° C. for 3.5 hours. The weight average molecular weight Mw in terms of polystyrene measured by GPC of the binder resin A thus obtained was 5700, and the acid value was 88 mg KOH / g. Propylene glycol monomethyl ether acetate was added to this resin so that the solid content was 58.7% by mass.

[0294] <Synthesis Example 10: Binder Resin B> 145 parts by mass of propylene glycol monomethyl ether acetate was stirred while replacing with nitrogen, and the temperature was raised to 120 ° C. A mixture of 5.2 parts by mass of styrene, 132 parts by mass of glycidyl methacrylate, 4.4 parts by mass of monomethacrylate FA-513M (manufactured by Hitachi Chemical Co., Ltd.) having a tricyclodecane skeleton, and 8.47 parts by mass of 2,2'-azobis-2-methylbutyronitrile was dropped into the mixture over 3 hours, and the mixture was further stirred at 90 ° C. for 2 hours. Next, the atmosphere in the reaction vessel was replaced with air, and 1.1 parts by mass of trisdimethylaminomethylphenol and 0.19 parts by mass of hydroquinone were added to 67.0 parts by mass of acrylic acid, and the reaction was continued at 100 ° C. for 12 hours. Then, 15.2 parts by mass of tetrahydrophthalic anhydride (THPA) and 0.2 parts by mass of triethylamine were added, and the mixture was reacted at 100 ° C. for 3.5 hours. The weight average molecular weight Mw of the binder resin B thus obtained was 9000 and the acid value was 25 mgKOH / g as measured by GPC in terms of polystyrene. Propylene glycol monomethyl ether acetate was added to this resin so that the solid content was 59.5% by mass.

[0295] <Synthesis Example 11: Binder Resin C> A separable flask equipped with a cooling tube was prepared as a reaction vessel, 400 parts by mass of propylene glycol monomethyl ether acetate was added, and the atmosphere was replaced with nitrogen. The temperature of the reaction vessel was then raised to 90°C by heating in an oil bath with stirring.

[0296] Meanwhile, 30 parts by mass of dimethyl-2,2'-[oxybis(methylene)]bis-2-propenoate, 60 parts by mass of methacrylic acid, 110 parts by mass of cyclohexyl methacrylate, 5.2 parts by mass of t-butylperoxy-2-ethylhexanoate, and 40 parts by mass of propylene glycol monomethyl ether acetate were added to the monomer tank, and 5.2 parts by mass of n-dodecyl mercaptan and 27 parts by mass of propylene glycol monomethyl ether acetate were added to the chain transfer agent tank. After the temperature of the reaction tank stabilized at 90 ° C., the monomer tank and the chain transfer agent tank were dropped to start polymerization. The drop was carried out over 135 minutes while maintaining the temperature at 90 ° C., and 60 minutes after the drop was completed, the temperature was raised to 110 ° C.

[0297] After maintaining the temperature at 110°C for 3 hours, a gas inlet tube was attached to the separable flask, and bubbling of a mixed gas of oxygen / nitrogen = 5 / 95 (v / v) was started. Next, 39.6 parts by mass of glycidyl methacrylate, 0.4 parts by mass of 2,2'-methylenebis(4-methyl-6-t-butylphenol), and 0.8 parts by mass of triethylamine were added to the reaction vessel, and the mixture was reacted at 110°C for 9 hours. After cooling to room temperature, a weight average molecular weight Mw of 9000 in terms of polystyrene measured by GPC and an acid value of 101 mgKOH / g were obtained as binder resin C. Propylene glycol monomethyl ether acetate was added to this resin so that the solid content was 44.0% by mass.

[0298] <Dispersant A: BYK-LPN6919, a dispersant manufactured by BYK Chemie> A methacrylic acid-based AB block copolymer consisting of an A block having a nitrogen atom-containing functional group and a B block having a solvent-philic group. It has repeating units of the following formulae (2a) and (3a), but does not have a repeating unit of the following formula (1a). The amine value is 120 mg KOH / g, and the acid value is 1 mg KOH / g or less.

[0299] The contents of the following formulae (2a) and (3a) in all repeating units are 33.3 mol % and 6.7 mol %, respectively.

[0300] [ka]

[0301] <Preparation of Yellow Pigment Dispersion> A stainless steel container was filled with 12.0 parts by mass of CI Pigment Yellow 138, 3.0 parts by mass of dispersant A converted into solid content, 6.0 parts by mass of binder resin C converted into solid content, 79.0 parts by mass of propylene glycol monomethyl ether acetate as a solvent (including the amount of solvent derived from dispersant A and the amount of solvent derived from binder resin C), and 225 parts by mass of zirconia beads with a diameter of 0.5 mm, and the mixture was dispersed for 6 hours using a paint shaker. The zirconia beads and the dispersion were then separated using a filter to prepare a yellow pigment dispersion.

[0302] <Preparation of green pigment dispersion> A stainless steel container was filled with 13.1 parts by mass of CI Pigment Green 58, 1.8 parts by mass of dispersant A converted into solid content, 4.0 parts by mass of binder resin C converted into solid content, 81.1 parts by mass of propylene glycol monomethyl ether acetate as a solvent (including the amount of solvent derived from dispersant A and the amount of solvent derived from binder resin C), and 225 parts by mass of zirconia beads with a diameter of 0.5 mm, and the mixture was dispersed for 6 hours using a paint shaker. The zirconia beads and the dispersion were then separated using a filter to prepare a green pigment dispersion.

[0303] <Photopolymerization initiator A> 3-(2-acetoxyimino-1,5-dioxo-5-methoxypentyl)-9-ethyl-6-(o-toluoyl)-9H-carbazole, synthesized by the method described in WO 2009 / 131189, was used as the photopolymerization initiator A.

[0304] <Preparation of Colored Resin Composition> The dyes A to H synthesized above, the binder resins A and B obtained in Synthesis Examples 9 and 10, the yellow pigment dispersion, the green pigment dispersion, the photopolymerization initiator A, and other components were mixed to obtain the compositions shown in Tables 1 to 4 to prepare colored resin compositions. In addition, for each component other than the solvent in Tables 1 to 4, the numerical value in the upper row represents the content (mass%) of each added component in the colored resin composition, and the numerical value in the lower row represents the content (mass%) of each component (solid content) in the total solid content. When mixing, the components were stirred for 10 minutes or more until they were thoroughly mixed, and then ultrasonically treated for 10 minutes at 23° C. Finally, the mixture was filtered through a 5 μm pore size filter to remove foreign matter.

[0305] [Table 1]

[0306] [Table 2]

[0307] [Table 3]

[0308] [Table 4]

[0309] The abbreviations in Tables 1 to 4 are as follows. F559: Megafac (registered trademark) F-559 (manufactured by DIC, perfluoroalkyl group-containing oligomer) BYK330: BYK (registered trademark)-330 (manufactured by BYK-Chemie, polyether-modified polydimethylsiloxane) PGMEA: Propylene glycol monomethyl ether acetate PGME: Propylene glycol monomethyl ether

[0310] <Measurement of thin film X-ray diffraction spectrum> Each of the colored resin compositions of Examples 1 to 8 and Comparative Examples 1 to 4 shown in Tables 1 to 3 was applied by spin coating onto a 0.7 mm thick glass substrate (AGC, AN100) cut into a 5 cm square so that the film thickness after baking would be 2 μm, and after drying under reduced pressure, the coating was prebaked on a hot plate at 80° C. for 3 minutes. Thereafter, the coating was irradiated with 32 mW / cm 2 of a 2 kW high pressure mercury lamp. 2 , 60mJ / cm 2 After that, the coating was baked in a clean oven at 230° C. for 30 minutes to obtain a colored cured film. The thin film X-ray diffraction spectrum was measured using the obtained colored cured film. The measurement device used was an X-ray diffractometer for thin film samples (Rigaku Corporation, automatic X-ray diffractometer RINT2000) with CuKα radiation as the radiation source. The measurement conditions were an out-of-plane method with an X-ray output of 50 kV, 250 mA, a fixed incidence angle (θ) of 0.20°, a scanning range (2θ) of 2 to 40°, and a scanning speed of 3.0° / min.

[0311] From the obtained X-ray diffraction spectrum, the presence or absence of a maximum peak within the diffraction angle (2θ) range of 2 to 5° was confirmed, and if a maximum peak was present, the diffraction angle at the peak top and the full width at half maximum of the peak were calculated. The results are shown in Table 5. Note that for dyes F to H of Comparative Examples 1 to 4, no maximum peak was observed within the measurement range (2 to 5°). This full width at half maximum was calculated using the analysis software "PDXL" manufactured by Rigaku Corp. The maximum peak refers to a peak that exists within the measurement range (2 to 5°) and whose intensity at the peak top is the maximum value within the measurement range.

[0312] In addition, the ratio (I1 / I2) of the peak top intensity I1 of the maximum peak in the range of 2 to 5° to the peak top intensity I2 of the maximum peak in the range of 15 to 25° was calculated. The results are shown in Table 5.

[0313] [Table 5]

[0314] The colored resin composition of Example 1 was applied by spin coating onto a 0.7 mm thick glass substrate (AN100, manufactured by AGC) cut into 5 cm squares so that the film thickness after baking would be 2 μm, and after drying under reduced pressure, it was pre-baked on a hot plate at 80° C. for 3 minutes and then heated at 32 mW / cm 2 with a 2 kW high-pressure mercury lamp. 2 , 60mJ / cm 2 The thin film X-ray diffraction spectrum was measured in the same manner using a colored coating film (which was not baked in a clean oven at 230°C for 30 minutes) obtained by exposing the entire surface to an exposure amount of 1000 x 1000 x 1000 (exposure amount: 1000 x 1000 x 1000) and the thin film X-ray diffraction spectrum was measured in the same manner using a colored coating film (which was not baked in a clean oven at 230°C for 30 minutes). The diffraction angle at the peak top of the maximum peak in the range of 2 to 5° was 3.99°, the full width at half maximum was 2.43°, and the I1 / I2 was 1.29.

[0315] <Evaluation of Color Characteristics (Examples 1 to 5 and Comparative Examples 1 to 3)> Each of the colored resin compositions of Examples 1 to 5 and Comparative Examples 1 to 3 shown in Table 1 was applied by spin coating onto a 0.7 mm thick glass substrate (AN100, manufactured by AGC) cut into a 5 cm square so that the film thickness after baking would be 2 μm, and after drying under reduced pressure, the coating was prebaked on a hot plate at 80° C. for 3 minutes. Thereafter, the coating was irradiated with 32 mW / cm 2 of a 2 kW high pressure mercury lamp. 2 , 60mJ / cm 2 After the entire surface was exposed to light at an exposure amount of 1000 nm, the coating was baked in a clean oven for 30 minutes at 230° C. The spectral transmittance of the resulting colored cured film was measured using a spectrophotometer U-3310 (manufactured by Hitachi, Ltd.) to obtain a transmission spectrum.

[0316] Next, a colored cured film was prepared in the same manner as above, except that the colored resin composition of Reference Example 1 shown in Table 4 was used to adjust the film thickness after baking to 2.32 μm, and the spectral transmittance was measured to obtain a transmission spectrum.

[0317] Using the transmission spectra of the colored cured films of Examples 1 to 5 and Comparative Examples 1 to 3 and the transmission spectrum of the colored cured film of Reference Example 1, a synthetic spectrum was obtained by adjusting the chromaticity (SB2 light source) in the XYZ color system to sx = 0.304 and sy = 0.607, and the luminance (SB2 light source) was calculated. The results are shown in Table 6.

[0318] [Table 6]

[0319] <Evaluation of Color Characteristics (Examples 6 to 8 and Comparative Example 4)> Each of the colored resin compositions of Examples 6 to 8 and Comparative Example 4 shown in Tables 2 and 3 was applied by spin coating onto a 0.7 mm thick glass substrate (AN100, manufactured by AGC) cut into a 5 cm square, dried under reduced pressure, and then prebaked on a hot plate at 80°C for 3 minutes. Thereafter, the substrate was irradiated with 32 mW / cm 2 of a 2 kW high pressure mercury lamp. 2 , 60mJ / cm 2 After the entire surface was exposed to light at an exposure dose of 1000 nm, the film was baked in a clean oven at 230° C. for 30 minutes. The spectral transmittance of the resulting colored cured film was measured using a spectrophotometer U-3310 (manufactured by Hitachi, Ltd.) to obtain a transmission spectrum. The film thickness of the colored cured film is shown in Table 7.

[0320] Next, using this transmission spectrum, the luminance was calculated when the film thickness was adjusted so that the chromaticity (SB2 light source) in the XYZ color system was sy = 0.607. The results are shown in Table 7.

[0321] In addition, the contrast of this colored cured film was measured using a contrast meter (CT-1: manufactured by Tsubosaka Electric Co., Ltd., color difference meter BM-5AS: manufactured by Topcon Corporation, light source: F-10, polarizing plate: manufactured by Tsubosaka Electric Co., Ltd.) with a blank of 18000. The results are shown in Table 7.

[0322] [Table 7]

[0323] From Table 6, the colored resin compositions of Examples 1 to 5 containing dyes A to E have high luminance, whereas the colored resin compositions of Comparative Examples 1 to 3 containing dyes F to H have low luminance. As is clear from Table 5, the dyes A to E contained in Examples 1 to 5 have maximum peaks in the diffraction angle (2θ) range of 2 to 5° in the thin film X-ray diffraction spectrum using CuKα radiation after heating at 230°C, so it is believed that zinc phthalocyanine dye molecules associate with each other and crystallization progresses during the baking process when obtaining a colored cured film. Therefore, it is believed that the electronic state of the dye changes, the main absorption maximum absorption wavelength is shortened to around 640 to 660 nm, and the tail on the short wavelength side of the absorption peak is reduced to show a steep rise, resulting in high brightness.

[0324] On the other hand, dyes F to H contained in Comparative Examples 1 to 3 do not have a maximum peak in the diffraction angle (2θ) range of 2 to 5° in the thin film X-ray diffraction spectrum using CuKα radiation after heating at 230°C. This suggests that crystallization of the zinc phthalocyanine dye does not proceed during the baking process for obtaining a colored cured film, and there is little change in the electronic state of the dye and the associated change in the absorption spectrum. As a result, absorption at around 620 nm is small, just like before heating, and the content of the dye required to adjust to a specified chromaticity becomes high, resulting in a decrease in brightness.

[0325] Moreover, from a comparison of Examples 6 to 8 and Comparative Example 4 in Table 7, it was confirmed that even when a colorant other than the zinc phthalocyanine dye (a1) was further contained, the brightness and contrast were high.

[0326] Although the present invention has been described in detail with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention. [Explanation of symbols]

[0327] 10 Transparent support substrate 20 pixels 30 Organic protective layer 40 Inorganic oxide film 50 transparent anode 51 Hole injection layer 52 Hole transport layer 53 Light-emitting layer 54 Electron injection layer 55 Cathode 100 Organic EL element 500 Organic Light Emitting Materials

Claims

1. A colored resin composition comprising: (A) a colorant; (B) a solvent; (C) an alkali-soluble resin; and (D) a photopolymerization initiator, The colorant (A) contains a zinc phthalocyanine dye (a1), The zinc phthalocyanine dye (a1) is one or more dyes selected from the following dyes A to E, the (D) photopolymerization initiator contains 3-(2-acetoxyimino-1,5-dioxo-5-methoxypentyl)-9-ethyl-6-(o-toluoyl)-9H-carbazole, A colored resin composition is applied onto a 0.7 mm thick glass substrate cut into 5 cm squares so that the film thickness after baking is 2 μm, dried, pre-baked at 80° C. for 3 minutes, exposed to an exposure of 32 mW / cm 2 and 60 mJ / cm 2 over the entire surface, and then baked at 230° C. for 30 minutes to obtain a colored cured film, which has a maximum peak in the diffraction angle (2θ) range of 2 to 5° in a thin film X-ray diffraction spectrum using CuKα radiation (measurement conditions: X-ray output 50 kV, 250 mA, fixed incident angle (θ) 0.20°, scanning range (2θ) 2 to 40°, scanning speed 3.0° / min. out-of-plane method). 【Chemistry 1】 (In the formula, Et represents ethyl.) 【Chemistry 2】 (In the formula, n-Pr represents n-propyl.) 【Chemistry 3】 (In the formula, i-Bu represents isobutyl.) 【Chemistry 4】 【Chemistry 5】 (In the formula, iBu represents isobutyl.)

2. 2. The colored resin composition according to claim 1, wherein the diffraction angle of the peak top of the maximum peak is 3.9° or less.

3. The colored resin composition according to claim 1 or 2, wherein the diffraction angle of the peak top of the maximum peak is 3.5° or more.

4. The colored resin composition according to any one of claims 1 to 3, wherein the (A) colorant further comprises a yellow pigment and / or a yellow dye.

5. The content of the zinc phthalocyanine dye (a1) is 5 mass% or more in the total solid content, the colored resin composition according to any one of claims 1 to 4.

6. The colored resin composition according to any one of claims 1 to 5, further comprising a photopolymerizable monomer.

7. The colored resin composition according to any one of claims 1 to 6, which is used for forming pixels of a color filter.

8. A color filter having pixels formed using the colored resin composition according to any one of claims 1 to 7.

9. An image display device comprising the color filter according to claim 8 .

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