Colored resin composition, color filter, and image display device

Abstract

The present invention provides a colored resin composition capable of forming high-brightness pixels. 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, wherein the colorant (A) contains a zinc phthalocyanine dye (a1), and in a thin film X-ray diffraction spectrum of the zinc phthalocyanine dye (a1) using CuKα rays after heating at 230°C, the zinc phthalocyanine dye (a1) has a maximum peak in the range of a diffraction angle (2θ) of 2 to 5°.

Description

Technical Field

[0001] The present invention relates to a colored resin composition, a color filter, and an image display device.

[0002] 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 a part or all of the contents disclosed in the documents cited in this specification are incorporated herein as the disclosed contents of this specification. Background Art

[0003] Currently, as methods for manufacturing color filters used in liquid crystal display devices, the pigment dispersion method, dyeing method, electrodeposition method, and printing method are known. Among them, the pigment dispersion method, which has excellent properties in a balanced manner, is the most widely used from the viewpoints of spectral characteristics, durability, pattern shape, and precision.

[0004] In recent years, color filters have been required to have higher brightness, higher contrast, and higher color gamut. As a colorant that determines the color of a color filter, pigments are generally used from the perspectives of heat resistance, light resistance, etc. However, pigments cannot meet market requirements, especially in terms of high brightness, and extensive research has been conducted to try to use dyes instead of pigments as colorants. For green pixels, research has been conducted on the use of specific phthalocyanine compounds as dyes (for example, refer to Patent Documents 1 to 5).

[0005] Prior art literature

[0006] Patent Literature

[0007] Patent Document 1: Japanese Patent Application Publication No. 2009-051896

[0008] Patent Document 2: Japanese Patent Application Publication No. 2013-213208

[0009] Patent Document 3: Japanese Patent Application Publication No. 2014-043556

[0010] Patent Document 4: Japanese Patent Application Publication No. 2014-125460

[0011] Patent Document 5: Japanese Patent Application Publication No. 2014-153554 Summary of the invention

[0012] Problems to be solved by the invention

[0013] As a result of the investigations conducted by the present inventors, it was found that the brightness of pixels of the color filters obtained by using the colored resin compositions described in Patent Documents 1 to 5 was not practically sufficient.

[0014] Therefore, an object of the present invention is to provide a colored resin composition capable of forming a pixel with high brightness.

[0015] Solutions to the problem

[0016] The present inventors have conducted intensive studies and, as a result, have found that the above-mentioned problems can be solved by using a specific phthalocyanine dye as a colorant, thereby completing the present invention.

[0017] That is, the present invention has the following configurations.

[0018] [1] A colored resin composition comprising: (A) a colorant, (B) a solvent, (C) an alkali-soluble resin, and (D) a photopolymerization initiator, wherein:

[0019] The colorant (A) contains a zinc phthalocyanine dye (a1), and in a thin film X-ray diffraction spectrum of the zinc phthalocyanine dye (a1) using CuKα rays after heating at 230°C, the zinc phthalocyanine dye (a1) has a maximum peak within a diffraction angle (2θ) range of 2 to 5°.

[0020] [2] The colored resin composition according to [1] above, wherein the diffraction angle of the peak top of the maximum peak of the zinc phthalocyanine dye (a1) is 3.9° or less.

[0021] [3] The colored resin composition according to [1] or [2], wherein the diffraction angle of the peak top of the maximum peak of the zinc phthalocyanine dye (a1) is 3.5° or more.

[0022] [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):

[0023] [Chemical formula 1]

[0024]

[0025] (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).

[0026] [Chemical formula 2]

[0027]

[0028] (In formula (2), X represents a divalent linking group, the benzene ring in formula (2) may have any substituent, and * represents a bonding position.)

[0029] [5] The colored resin composition according to any one of [1] to [4] above, wherein the (A) colorant further contains a yellow pigment and / or a yellow dye.

[0030] [6] The colored resin composition according to any one of [1] to [5] above, wherein the content of the zinc phthalocyanine dye (a1) in the total solid content is 5% by mass or more.

[0031] [7] The colored resin composition according to any one of [1] to [6], further comprising a photopolymerizable monomer.

[0032] [8] The colored resin composition according to any one of [1] to [7], which is used for forming pixels of a color filter.

[0033] [9] A color filter having pixels formed using the colored resin composition according to any one of [1] to [8] above.

[0034]

[10] An image display device comprising the color filter described in [9] above.

[0035] Effects of the Invention

[0036] According to the present invention, a colored resin composition capable of forming a pixel with high brightness can be provided. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] Figure 1 This is a schematic cross-sectional view showing an example of an organic EL display element including the color filter of the present invention.

[0038] Explanation of symbols

[0039] 10 Transparent support substrate

[0040] 20 pixels

[0041] 30 Organic protective layer

[0042] 40 Inorganic oxide film

[0043] 50 Transparent Anode

[0044] 51 Hole injection layer

[0045] 52 Hole transport layer

[0046] 53 Luminous layer

[0047] 54 Electron injection layer

[0048] 55 cathode

[0049] 100 Organic EL components

[0050] 500 Organic light emitting body DETAILED DESCRIPTION

[0051] Hereinafter, constituent elements and the like of the present invention will be described in detail. However, the following description is merely an example of the embodiment of the present invention, and the present invention is not limited to these contents.

[0052] It should be noted that in the present invention, "(meth)acryl", "(meth)acrylate" and the like mean "acryl and / or methacryl", "acrylate and / or methacrylate", etc. For example, "(meth)acrylic acid" means "acrylic acid and / or methacrylic acid".

[0053] In the present invention, the "total solid content" refers to all components other than the solvent component contained in the pigment dispersion or the colored resin composition.

[0054] In addition, in the present invention, a numerical range expressed using "to" means a range including the numerical values ​​described before and after "to".

[0055] In the present invention, the "weight average molecular weight" refers to a weight average molecular weight (Mw) measured by GPC (gel permeation chromatography) and converted into polystyrene.

[0056] In the present invention, unless otherwise specified, the "amine value" refers to the amine value converted to the effective solid content, and is a value expressed by the mass of KOH corresponding to the amount of alkali per 1g of the solid content of the dispersant.

[0057] In addition, in the present invention, "CI" means a color index.

[0058] [1] Constituent components of the colored resin composition

[0059] The following describes the components of the colored resin composition of the present invention. The colored resin composition of the present invention includes (A) a colorant, (B) a solvent, (C) an alkali-soluble resin, and (D) a photopolymerization initiator as essential components, and other additives other than the above components may be added as needed.

[0060] Hereinafter, each constituent component will be described.

[0061] [1-1] (A) Colorant

[0062] The coloring agent (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)"), and in a thin film X-ray diffraction spectrum using CuKα rays after heating the zinc phthalocyanine dye (a1) at 230°C, the zinc phthalocyanine dye (a1) has a maximum peak in the range of a diffraction angle (2θ) of 2 to 5°.

[0063] 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 rays after heating at 230°C. It is believed that during the heating (230°C) of the firing process when manufacturing the pixels of the color filter, the zinc phthalocyanine dye molecules are associated with each other and arranged regularly (crystallized), so that the diffraction angle has a maximum peak in the above range. Although the zinc phthalocyanine dye has a tendency to be easily crystallized, especially when the phthalocyanine ring forms an H association body facing each other in parallel with each other and arranged regularly, the maximum absorption wavelength moves to the short wavelength side (for example, wavelength 640 to 660nm), and the tailing of the short-wave absorption side of the absorption peak is reduced, thereby showing a sharp rise. As a result, it is believed that a cured film with high color purity, less absorption as an unnecessary part of the color filter, and high transmittance can be formed, thereby achieving high brightness.

[0064] In particular, the zinc phthalocyanine dye (a1) is considered to have a higher absorbance and a more steeply rising absorption peak due to zinc as the central metal, and therefore has higher brightness than the phthalocyanine dye whose central metal is copper.

[0065] The order and method of measuring the thin film X-ray diffraction spectrum of the zinc phthalocyanine dye (a1) contained in the colored resin composition after heating at 230°C using CuKα rays are not particularly limited, and the measurement object can be measured by thin film X-ray diffraction using CuKα rays, wherein the measurement object is obtained by applying the colored resin composition and drying under reduced pressure, exposing it with a high-pressure mercury lamp, and baking it at 230°C for 30 minutes, and the obtained colored cured film is used as the measurement object. As the conditions for producing the colored cured film, the conditions described in the examples described later are preferably used.

[0066] In addition, the measurement conditions of the thin film X-ray diffraction spectrum using CuKα rays are not particularly limited, but preferably based on the out-of-plane method using an automatic X-ray diffraction apparatus RINT2000 manufactured by Rigaku Co., Ltd., an X-ray output power of 50 kV, 250 mA, a fixed incident angle (θ) of 0.20°, a scanning range (2θ) of 2 to 40°, and a scanning speed of 3.0° / min. As the measurement conditions, the measurement conditions described in the examples described later are preferably adopted.

[0067] In the thin film X-ray diffraction spectrum thus obtained, it is sufficient to confirm whether there is a maximum peak within the diffraction angle (2θ) range of 2 to 5°. It should be noted that the so-called 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 the intensity of the peak top is the maximum value within the measurement range. For example, even if it is a peak that exists within the measurement range, a peak whose peak top intensity is not the maximum value within the measurement range is not a maximum peak.

[0068] In the thin film X-ray diffraction spectrum of the zinc phthalocyanine dye (a1) using CuKα rays after heating at 230°C, the diffraction angle of the peak top of the maximum peak (hereinafter sometimes referred to as "maximum peak A") having a diffraction angle (2θ) in the range of 2 to 5° is not particularly limited, but is preferably 2.0° or more, more preferably 2.5° or more, further preferably 3.0° or more, further preferably 3.2° or more, particularly preferably 3.4° or more, and most preferably 3.5° or more, and is preferably 5.0° or less, more preferably 4.5° or less, further preferably 4.0° or less, further preferably 3.9° or less, and particularly preferably 3.8° or less. By setting the value to be equal to or greater than the lower limit, the arrangement regularity of the aggregate tends to be higher, and by setting the value to be equal to or less than the upper limit, the contrast reduction 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°, further preferably 3.0° to 5.0°, further preferably 3.2° to 4.5°, further preferably 3.4° to 4.0°, particularly preferably 3.5° to 3.9°, and most preferably 3.5° to 3.8°.

[0069] 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, further preferably 1.2° or less, particularly preferably 1.0° or less, and is usually 0.4° or more. By setting it below the above upper limit, there is a tendency to promote the formation of an aggregate and improve the brightness by showing a sharply rising 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°, further preferably 0.4° to 1.2°, and particularly preferably 0.4° to 1.0°.

[0070] In addition, in the thin film X-ray diffraction spectrum of the zinc phthalocyanine dye (a1) using CuKα rays after heating at 230°C, a halo is sometimes observed in the range of diffraction angle (2θ) of 15 to 25°. When the halo is observed in the range of diffraction angle (2θ) of 15 to 25°, the ratio (I1 / I2) of the intensity I1 of the peak top of the maximum peak A to the intensity I2 of the peak top of the halo is not particularly limited, but is preferably 1 or more, more preferably 1.5 or more, further preferably 2 or more, further preferably 3 or more, particularly preferably 5 or more, and usually 10 or less. By setting it to be above the above lower limit, there is a tendency to promote the formation of an aggregate and improve the brightness by showing a sharply rising absorption spectrum. For example, I1 / I2 is preferably 1 to 10, more preferably 1.5 to 10, further preferably 2 to 10, further preferably 3 to 10, and particularly preferably 5 to 10.

[0071] Among zinc phthalocyanine dyes, those having a highly symmetrical chemical structure tend to have the largest peak A.

[0072] The chemical structure of the zinc phthalocyanine dye (a1) is not particularly limited as long as it has a maximum peak within the diffraction angle (2θ) range of 2 to 5° in a thin film X-ray diffraction spectrum using CuKα rays after heating at 230°C. From the viewpoint that the association formation between dye molecules is promoted and the rise of the short-wavelength side of the main absorption peak is sharpened, the zinc phthalocyanine dye represented by the following general formula (1) is preferred.

[0073] [Chemical formula 3]

[0074]

[0075] (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).

[0076] [Chemical formula 4]

[0077]

[0078] (In formula (2), X represents a divalent linking group, the benzene ring in formula (2) may have any substituent, and * represents a bonding position.)

[0079] (A 1 ~A 16 )

[0080] In the above formula (1), A 1 ~A 16Each independently represents a hydrogen atom, a chlorine atom, a fluorine atom, or a group represented by the following general formula (2).

[0081] [Chemical formula 5]

[0082]

[0083] In the formula (2), X represents a divalent linking group, the benzene ring in the formula (2) may have an arbitrary substituent, and * represents a bonding position.

[0084] (X)

[0085] In the general formula (2), X represents a divalent linking group. The divalent linking group is not particularly limited, and examples thereof include an oxygen atom, a sulfur atom, or -N(R a1 )-base. a1 represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 6 carbon atoms. Among these, an oxygen atom or a sulfur atom is preferred, and an oxygen atom is more preferred, from the viewpoint of reducing tailing on the short-wave side of the maximum absorption of the main absorption and obtaining a peak showing a steep rise.

[0086] (Substituents optionally possessed by benzene ring)

[0087] The benzene ring in formula (2) may have any substituent. The substituent is not particularly limited, and examples thereof include a halogen atom, an alkyl group (-R A Base (where R A represents an alkyl group)), an alkoxy group (-OR A Base (where R A represents an alkyl group)), an alkoxycarbonyl group (-COOR A Base (where R A represents an alkyl group)), an aryl group (-R B Base (where R B represents an aryl group)), an aryloxy group (-OR B Base (where R B represents an aryl group)), an aryloxycarbonyl group (-COOR B Base (where R B represents an aryl group)), a cyano group, etc., and the alkyl groups (-R A yl), aryl (-R B The alkyl (-R A yl), aryl (-R BThe 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. In addition, 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 light selective transmittance and solubility in solvents, an alkyl group substituted with an alkoxycarbonyl group or an alkoxycarbonyl group is preferred, and an alkoxycarbonyl group is more preferred.

[0088] It should be noted that the alkyl groups contained in these groups may be linear, branched, cyclic, or a combination thereof, but are preferably linear or branched. From the viewpoint of ease of synthesis and solubility in alkali-soluble resins and solvents, linear groups are preferred.

[0089] The number of carbon atoms in the alkyl group is not particularly limited, but is usually 1 or more, preferably 2 or more, preferably 6 or less, more preferably 5 or less, further preferably 4 or less, and particularly preferably 3 or less. When the number is equal to or more than the lower limit, the solubility in the solvent tends to be improved, and when the number is equal to or less than the upper limit, the hydrophobic interaction with the hydrophobic part in the alkali-soluble resin tends to suppress the aggregation between molecules in the heating step.

[0090] Specific examples of the alkyl group include methyl, ethyl, propyl, butyl, isobutyl, pentyl, hexyl, etc. From the viewpoint of maintaining solubility in the solvent and effectively exerting the hydrophobic interaction with the hydrophobic part in the alkali-soluble resin, an ethyl, propyl, isobutyl, or butyl group is preferred, an ethyl or propyl group is more preferred, and an ethyl group is further preferred.

[0091] In addition, the aryl group contained in these groups may be an aromatic hydrocarbon ring group or an aromatic heterocyclic group.

[0092] 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 further preferably 8 or less. When the number is equal to or more than the above lower limit, the raw material tends to be easily available, and when the number is equal to or less than the above upper limit, the solubility in the solvent tends to be improved.

[0093] The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a monocyclic ring or a condensed ring. Examples of the aromatic hydrocarbon ring group include groups having one free valence, such as a benzene ring, a naphthalene ring, a pentylene ring, an indene ring, an azulene ring, and a heptalene ring.

[0094] In addition, the aromatic heterocyclic ring in the aromatic heterocyclic group may be a monocyclic 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- Azole ring, iso azole ring, 1,3-thiazole ring, isothiazole ring, imidazole ring, pyrazole ring, furazan ring, pyrazine ring, pyrimidine ring, pyridazine ring, 1,3,5-triazine ring, benzofuran ring, 2-benzofuran ring, benzothiophene ring, 2-benzothiophene ring, 1H-pyrrolidine ring, indole ring, isoindole ring, indolizine ring, 2H-1-benzopyran ring, 1H-2-benzopyran ring, quinoline ring, isoquinoline ring, 4H-quinolizine ring, benzimidazole ring, 1H-indazole ring, quinoxaline ring, quinazoline ring, cinnoline ring, phthalazine ring, 1,8-naphthyridine ring, purine ring, pteridine ring and the like.

[0095] When the benzene ring in formula (2) has any substituent, the number of substitutions is not particularly limited, but is preferably 4 or less, more preferably 3 or less, further preferably 2 or less, and particularly preferably 1. By setting the number below the upper limit, the association formation of phthalocyanine is promoted and the absorption on the short wavelength side of the main absorption tends to be sharpened.

[0096] When the benzene ring in formula (2) has any substituent, the substitution position is not particularly limited, and may be the 2-position, 3-position, or 4-position. From the viewpoint of the ease of association formation of phthalocyanine, the 4-position is preferred.

[0097] In addition, in a plurality of groups represented by the formula (2) contained in one molecule, any substituent that may be possessed by the benzene ring may be the same or different.

[0098] In the zinc phthalocyanine dye represented by the general formula (1), A 1 ~A 16 Each independently represents a hydrogen atom, a chlorine atom, a fluorine atom, or a group represented by the above general formula (2), preferably A 1 ~A 16 In the formula (2), at least one of the groups is preferably a group represented by the general formula (2), at least two of the groups are more preferably a group represented by the general formula (2), at least four of the groups are more preferably a group represented by the general formula (2), at least six of the groups are particularly preferably a group represented by the general formula (2), and at most 15 of the groups are preferably a group represented by the general formula (2), at most 14 of the groups are more preferably a group represented by the general formula (2), at most 12 of the groups are more preferably a group represented by the general formula (2), at most 10 of the groups are particularly preferably a group represented by the general formula (2). By setting the value to be above the lower limit, there is a tendency for the solubility in organic solvents to be improved, and by setting the value to be below the upper limit, there is a tendency for the solubility in organic solvents to be maintained and for the hydrophobic interaction with the hydrophobic part in the alkali-soluble resin to be effectively exerted. For example, A 1 ~A 16The number of groups represented by the general formula (2) is preferably 1 to 15, more preferably 2 to 14, further preferably 4 to 12, particularly preferably 6 to 10.

[0099] In the zinc phthalocyanine dye represented by the general formula (1), A 1 ~A 16 Each independently represents a hydrogen atom, a chlorine atom, a fluorine atom, or a group represented by the general formula (2), preferably A 1 ~A 16 1 or more of them are chlorine atoms or fluorine atoms, more preferably 2 or more of them are chlorine atoms or fluorine atoms, further preferably 4 or more of them are chlorine atoms or fluorine atoms, and particularly preferably 6 or more of them are chlorine atoms or fluorine atoms. In addition, preferably 15 or less of them are chlorine atoms or fluorine atoms, more preferably 14 or less of them are chlorine atoms or fluorine atoms, further preferably 12 or less of them are chlorine atoms or fluorine atoms, and particularly preferably 10 or less of them are chlorine atoms or fluorine atoms. By setting it to be above the aforementioned lower limit, there is a tendency to maintain solubility in organic solvents and effectively exert hydrophobic interaction with the hydrophobic part in the alkali-soluble resin. In addition, by setting it to be below the aforementioned upper limit, there is a tendency to improve solubility in organic solvents. For example, A 1 ~A 16 The number of chlorine atoms or fluorine atoms is preferably 1 to 15, more preferably 2 to 14, further preferably 4 to 12, particularly preferably 6 to 10.

[0100] 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 of promoting the association formation between dye molecules and showing a sharp rise on the short wavelength side of the main absorption.

[0101] [Chemical formula 6]

[0102]

[0103] In formula (3), A 20 Each independently represents a hydrogen atom, a chlorine atom or a fluorine atom, X represents a divalent linking group, and the benzene ring in the formula (3) may have any substituent.

[0104] (A 20 )

[0105] In the above 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 preferred, and a fluorine atom is more preferred. 20The groups may be the same or different, but are preferably the same from the viewpoint of the ease of association formation of phthalocyanine. For example, the eight A groups contained in the above formula (3) may be 20 In the embodiment where all of them are fluorine atoms, the eight A atoms contained in the above formula (3) 20 All of them are chlorine atoms.

[0106] (X)

[0107] In the above formula (3), X represents a divalent linking group, and as this X, the divalent linking groups exemplified as X in the above formula (2) can be used.

[0108] (Substituents optionally possessed by benzene ring)

[0109] The benzene rings in formula (3) (eight benzene rings bonded to the phthalocyanine ring via X) may have any substituents, and the substituents may be those listed as the substituents that the benzene rings in formula (2) may have.

[0110] The number of the substituents possessed by one benzene ring is not particularly limited, but is preferably 4 or less, more preferably 3 or less, further preferably 2 or less, and particularly preferably 1. By setting it below the above upper limit, there is a tendency that the association formation of phthalocyanine can be promoted and the absorption on the short wavelength side of the main absorption is sharpened.

[0111] When the benzene ring has a substituent, the substitution position is not particularly limited, and examples thereof include the 2-position, 3-position, and 4-position. From the viewpoint of easiness of association formation of phthalocyanine, the 4-position is preferred.

[0112] Specific examples of the zinc phthalocyanine dye (a1) include the following.

[0113] [Chemical formula 7]

[0114]

[0115] Me in the formula represents a methyl group.

[0116] [Chemical formula 8]

[0117]

[0118] In the formula, Et represents an ethyl group.

[0119] [Chemical formula 9]

[0120]

[0121] In the formula, n-Pr represents n-propyl.

[0122] [Chemical formula 10]

[0123]

[0124] i-Bu in the formula represents an isobutyl group.

[0125] [Chemical formula 11]

[0126]

[0127] [Chemical formula 12]

[0128]

[0129] [Chemical formula 13]

[0130]

[0131] [Chemical formula 14]

[0132]

[0133] [Chemical formula 15]

[0134]

[0135] [Chemical formula 16]

[0136]

[0137] iBu in the formula represents an isobutyl group.

[0138] [Chemical formula 17]

[0139]

[0140] As a method for producing the zinc phthalocyanine dye (a1), a known method can be adopted, for example, the method described in JP-A-5-345861, JP-A-2014-153554, and JP-A-2015-152861 can be adopted.

[0141] (A) The colorant may include other colorants in addition to the zinc phthalocyanine dye (a1). As other colorants, pigments and dyes can be listed. Among these, when the colored resin composition of the present invention is used for green pixel applications, green pigments, green dyes, yellow pigments, yellow dyes, etc. are preferably used, and yellow pigments and / or yellow dyes are more preferably used.

[0142] Examples of the green pigment include CI Pigment Green 7, 36, 58, 59, 62, and 63. CI Pigment Green 58 is preferred from the viewpoint of brightness.

[0143] As green dyes, among green dyes classified as dyes in the color index, CI solvent dyes include CI Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, and 35, and CI acid dyes include CI Acid Green 1, 3, 5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106, and 109. As CI mordant dyes, CI Mordant Green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43, and 53 are mentioned. Among these, CI Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, and 35 are preferred from the viewpoint of suppressing decomposition of the dye during thermal calcination.

[0144] Examples of 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, 8 1, 83, 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, 15 1, 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, 197, 198, 199, 200, 202, 203, 204, 205, 206, 207, 208, and compounds formed by inserting other compounds into a 1:1 coordination compound of azobarbituric acid and nickel represented by the following formula (i) or its tautomer (hereinafter sometimes referred to as "nickel azo coordination compound represented by formula (i)"), etc.

[0145] [Chemical formula 18]

[0146]

[0147] In addition, examples of other compounds to be inserted into the 1:1 coordination compound of azobarbituric acid and nickel represented by the above formula (i) or its tautomer include compounds represented by the following formula (ii).

[0148] [Chemical formula 19]

[0149]

[0150] Among them, from the viewpoint of high brightness and high 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.

[0151] Examples of the yellow dye include barbituric acid azo dyes, pyridone azo dyes, pyrazolone azo dyes, quinophthalone dyes, and cyanamide dyes, etc. Specific examples thereof include specific compounds described in Japanese Patent Application Laid-Open No. 2010-168531.

[0152] Among the yellow dyes classified as dyes 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, 163, etc.; 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, 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, CI mordant dyes include dyes such as CI Mordant Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65, and the like; CI Solvent Yellow 4, 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 162, 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, 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.

[0153] Among these, from the viewpoint of suppressing decomposition of the dye during thermal calcination, at least one selected from CI Solvent Yellow 4, 14, 15, 23, 24, 38, 62, 63, 68, 79, 82, 94, 98, 99, 162 and 163 is preferred.

[0154] 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. When the pigment is micronized, a method such as solvent salt milling is preferably used.

[0155] The content ratio of the coloring agent (A) in the colored resin composition of the present invention is not particularly limited, and is preferably 5% by mass or more, more preferably 10% by mass or more, more preferably 20% by mass or more, more preferably 30% by mass or more, and particularly preferably 35% by mass or more in the total solid content of the colored resin composition. In addition, it is preferably 70% by mass or less, more preferably 60% by mass or less, more preferably 50% by mass or less, more preferably 45% by mass or less, and particularly preferably 40% by mass or less. By setting it to more than the above lower limit, there is a tendency for the color characteristics to be improved, and by setting it to less than the above upper limit, there is a tendency for the pattern forming property to become good. For example, the content ratio of the coloring agent (A) is preferably 5 to 70% by mass, more preferably 10 to 60% by mass, more preferably 20 to 50% by mass, more preferably 30 to 45% by mass, and particularly preferably 35 to 40% by mass.

[0156] The content ratio of the zinc phthalocyanine dye (a1) in the colored resin composition of the present invention is not particularly limited, and is preferably 5% by mass or more, more preferably 8% by mass or more, more preferably 10% by mass or more, and particularly preferably 15% by mass or more in the total solid content of the colored resin composition, and preferably 45% by mass or less, more preferably 40% by mass, more preferably 35% by mass or less, further preferably 30% by mass or less, and particularly preferably 25% by mass or less. By setting it to the above lower limit or more, there is a tendency for color characteristics such as brightness to be improved, and by setting it to the above upper limit or less, there is a tendency for pattern formation to become good. For example, the content ratio of the zinc phthalocyanine dye (a1) is preferably 5 to 45% by mass, more preferably 5 to 40% by mass, further preferably 8 to 35% by mass, further preferably 10 to 30% by mass, and particularly preferably 15 to 25% by mass.

[0157] When other colorants are included, the content ratio is not particularly limited, and is preferably 1% by mass or more, more preferably 5% by mass or more, more preferably 8% by mass or more, more preferably 10% by mass or more, and particularly preferably 15% by mass or more in the total solid content of the colored resin composition, and is preferably 40% by mass or less, more preferably 35% by mass or less, more preferably 30% by mass or less, and particularly preferably 25% by mass or less. By setting it to be above the above lower limit, there is a tendency that thermal decomposition during thermal firing when making a color filter is suppressed, and by setting it to be below the above upper limit, there is a tendency that pattern formation becomes 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, more preferably 10 to 30% by mass, and particularly preferably 15 to 25% by mass.

[0158] [1-2] (B) Solvent

[0159] (B) The solvent has a function 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 to adjust the viscosity.

[0160] The (B) solvent may be any solvent as long as it can dissolve or disperse the components.

[0161] Examples of the solvent include glycol monoalkyl ethers such as propylene glycol monomethyl ether (PGME); and glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate (PGMEA).

[0162] In addition, glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether and ethylene glycol monobutyl ether can be mentioned;

[0163] Glycol dialkyl ethers such as ethylene glycol dimethyl ether and ethylene glycol diethyl ether;

[0164] Glycol alkyl ether acetates such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate, and ethers such as dimethyl ether, diethyl ether, dipropyl ether and diisopropyl ether;

[0165] Ketones such as methyl ethyl ketone and diisopropyl ketone;

[0166] Alcohols such as ethanol, propanol, and butanol;

[0167] Aliphatic hydrocarbons such as n-pentane, n-octane, and n-hexane;

[0168] Alicyclic hydrocarbons such as cyclohexane and methylcyclohexane;

[0169] Aromatic hydrocarbons such as benzene and toluene;

[0170] Esters such as ethyl acetate and butyl acetate, etc.

[0171] These solvents may be used alone or in combination of two or more.

[0172] When forming color filter pixels by photolithography, it is preferred 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 boiling points hereinafter), and more preferably a solvent having a boiling point of 120 to 150°C.

[0173] Among the above solvents, glycol alkyl ether acetates are preferred because they have a good balance between coating properties and surface tension and have high solubility of components in the composition. Examples thereof include propylene glycol monomethyl ether acetate.

[0174] In addition, glycol alkyl ether acetates can be used alone or in combination with other solvents. As a solvent used in combination, glycol monoalkyl ethers are particularly preferred. Among them, in particular, from the viewpoint of the solubility of the constituent components in the composition, propylene glycol monomethyl ether is preferred. It should be noted that glycol monoalkyl ethers have high polarity. If the amount added is too much, the pigment is easy to aggregate, and there is a tendency for the storage stability of the colored resin composition obtained thereafter to increase, such as an increase in viscosity. Therefore, the proportion of glycol monoalkyl ethers in the solvent is preferably 5% to 30% by mass, and more preferably 5% to 20% by mass.

[0175] The content ratio of the solvent in the colored resin composition of the present invention is not particularly limited, and its upper limit is usually 99% by mass or less, preferably 90% by mass or less, and more preferably 85% by mass or less. By setting it below the above upper limit, there is a tendency to easily form a coating film. On the other hand, considering the viscosity suitable for coating, the lower limit of the solvent content ratio is usually 70% by mass or more, preferably 75% by mass or more, and more preferably 78% by mass or more. For example, the content ratio of the solvent is preferably 70 to 99% by mass, more preferably 75 to 90% by mass, and further preferably 78 to 85% by mass.

[0176] [1-3] (C) Alkali-soluble resin

[0177] In the colored resin composition of the present invention, the alkali-soluble resin (C) is not limited as long as it is soluble in the aforementioned solvent, can form a cured film with a sufficient degree of curing, and can be alkali-developed to form a pattern. For example, the 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 listed.

[0178] (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 other radical polymerizable monomers, 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 of the polybasic acid anhydride (hereinafter sometimes referred to as "resin (C-1)")

[0179] (C-2) Carboxyl group-containing linear alkali-soluble resin (hereinafter, sometimes referred to as "resin (C-2)")

[0180] (C-3) A resin obtained by adding an epoxy group-containing unsaturated compound to the carboxyl group portion of the above-mentioned resin (C-2) (hereinafter, sometimes referred to as "resin (C-3)")

[0181] (C-4) (meth)acrylic resin (hereinafter, sometimes referred to as "resin (C-4)")

[0182] (C-5) Epoxy (meth)acrylate resin having a carboxyl group (hereinafter, sometimes referred to as "resin (C-5)")

[0183] Among them, resin (C-1) is particularly preferred and will be described in detail below.

[0184] It should be noted that resins (C-2) to (C-5) are not limited as long as they are soluble in an alkaline developer and have a solubility sufficient to perform the target development process, and those described as the same item in Japanese Patent Application Publication No. 2009-025813 can be preferably used.

[0185] (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 other radical polymerizable monomers, 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 of the polybasic acid anhydride.

[0186] One preferred embodiment of the resin (C-1) includes a copolymer of 5 to 90 mol % of epoxy (meth)acrylate and 10 to 95 mol % of other radical polymerizable monomers, wherein an unsaturated monobasic acid is added to 10 to 100 mol % of the epoxy groups possessed by the copolymer, or an alkali-soluble resin is added to 10 to 100 mol % of the hydroxyl groups generated by the addition reaction of a polyacid anhydride.

[0187] Examples of epoxy-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 them, glycidyl (meth)acrylate is preferred. These epoxy-containing (meth)acrylates may be used alone or in combination of two or more.

[0188] As other free radical polymerizable monomers copolymerized with the epoxy group-containing (meth)acrylate, there is no particular limitation as long as the effects of the present invention are not impaired, and examples thereof include: vinyl aromatics, dienes, (meth)acrylates, (meth)acrylamides, vinyl compounds, unsaturated carboxylic acid diesters, monomaleimides, etc. Among them, mono(meth)acrylate having a structure represented by the following formula (III) is preferred.

[0189] The content ratio of the repeating units derived from the mono(meth)acrylate having the structure represented by the following formula (III) in the repeating units derived from "other radical polymerizable monomers" is preferably 5 to 90 mol %, more preferably 10 to 70 mol %, and even more preferably 15 to 50 mol %.

[0190] [Chemical formula 20]

[0191]

[0192] In the above formula (III), R 89 represents a hydrogen atom or a methyl group, R 90 It shows the structure represented by the following formula (IV).

[0193] [Chemical formula 21]

[0194]

[0195] In the above formula (IV), R 91 ~R 98 Each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. It should be noted that R 96 With R 98 They can be connected to each other to form a ring.

[0196] R 96 With R 98 The ring formed by the mutual connection is preferably an aliphatic ring, which may be saturated or unsaturated. 96 With R 98 The number of carbon atoms in the ring formed by linking each other is preferably 5 to 6.

[0197] Among them, as the structure represented by formula (IV), the structure represented by the following structural formula (IVa), (IVb) or (IVc) is particularly preferred.

[0198] [Chemical formula 22]

[0199]

[0200] The mono(meth)acrylate having a structure represented by the above formula (IV) may be used alone or in combination of two or more.

[0201] As the “other radical polymerizable monomer” other than the mono(meth)acrylate having the structure represented by formula (IV), from the viewpoint of being able to improve the excellent heat resistance and strength of the colored resin composition, 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, N-cyclohexylmaleimide, etc. can be mentioned.

[0202] In the repeating units derived from "other radical polymerizable monomers", the content ratio of the repeating units derived from at least one selected from the above monomer group is preferably 1 to 70 mol %, more preferably 3 to 50 mol %.

[0203] In addition, the copolymerization reaction of the said epoxy group-containing (meth)acrylate and the said other radical polymerizable monomer can apply a well-known solution polymerization method.

[0204] In the present invention, the copolymer of the epoxy-containing (meth)acrylate and the other radical polymerizable monomer preferably contains 5 to 90 mol% of repeating units derived from the epoxy-containing (meth)acrylate and 10 to 95 mol% of repeating units derived from the other radical polymerizable monomer, more preferably contains 20 to 80 mol% of the former and 80 to 20 mol% of the latter, and further preferably contains 30 to 70 mol% of the former and 70 to 30 mol% of the latter.

[0205] When the content is within the above range, the addition amount of the polymerizable component and the alkali-soluble component described below is sufficient, and the heat resistance and the strength of the film are also sufficient, which is preferred.

[0206] An unsaturated monobasic acid (polymerizable component) and a polybasic acid anhydride (alkali-soluble component) are reacted with the epoxy group portion of the epoxy group-containing copolymer synthesized as described above.

[0207] As the unsaturated monobasic acid to be added to the epoxy group, known ones can be used, and examples thereof include unsaturated carboxylic acids having an ethylenically unsaturated double bond.

[0208] Specific examples include: (meth)acrylic acid; crotonic acid; o-, m-, p-vinylbenzoic acid; monocarboxylic acids such as (meth)acrylic acid substituted at the α-position by a haloalkyl group, an alkoxy group, a halogen atom, a nitro group, or a cyano group, etc. Among them, (meth)acrylic acid is preferred. These may be used alone or in combination of two or more.

[0209] By adding such a component, polymerizability can be imparted to the alkali-soluble resin used in the present invention.

[0210] These unsaturated monobasic acids are usually added to 10 to 100 mol % of the epoxy groups of the copolymer, preferably 30 to 100 mol %, and more preferably 50 to 100 mol %. When it is within the above range, the stability of the colored resin composition over time is excellent, so it is preferred. It should be noted that as a method for adding an unsaturated monobasic acid to the epoxy group of the copolymer, a known method can be used.

[0211] 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, a known polybasic acid anhydride can be used.

[0212] Examples include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, hexachloronadic anhydride and other dibasic anhydrides; and anhydrides of tribasic or higher acids such as trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, and biphenyl tetracarboxylic anhydride. Among them, succinic anhydride and tetrahydrophthalic anhydride are preferred. These polybasic anhydrides may be used alone or in combination of two or more.

[0213] By adding such a component, alkali solubility can be imparted to the alkali-soluble resin used in the present invention.

[0214] These polybasic acid anhydrides are usually added to 10 to 100 mol %, more preferably 20 to 90 mol %, and even more preferably 30 to 80 mol % of the hydroxyl groups generated when the unsaturated monobasic acid and the epoxy groups of the copolymer are added.

[0215] When the content is within the above range, the residual film rate and solubility during development are sufficient, which is preferred.

[0216] In addition, as a method for adding a polybasic acid anhydride to a hydroxyl group, a known method can be adopted.

[0217] In addition, in order to improve the photosensitivity, after the addition of the polyacid anhydride, 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 in, for example, Japanese Patent Publication No. 8-297366 and Japanese Patent Publication No. 2001-89533.

[0218] (C) The weight average molecular weight (Mw) of the alkali-soluble resin measured by GPC (gel permeation chromatography) in terms of polystyrene is preferably 3,000 or more, more preferably 5,000 or more, and further preferably 7,000 or more. It is preferably 100,000 or less, more preferably 50,000 or less, further preferably 30,000 or less, further preferably 15,000 or less, and particularly preferably 13,000 or less. When the weight average molecular weight (Mw) is within the above range, it is preferred from the perspective 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 3,000 to 100,000, more preferably 3,000 to 50,000, further preferably 5,000 to 30,000, further preferably 5,000 to 15,000, and particularly preferably 7,000 to 13,000.

[0219] In addition, as a standard of molecular weight distribution, the ratio of weight average molecular weight (Mw) / number average molecular weight (Mn) is preferably 2.0 to 5.0.

[0220] It should be noted that the acid value of the (C) alkali-soluble resin is usually 10 mgKOH / g or more, preferably 15 mgKOH / g or more, more preferably 25 mgKOH / g or more, and further preferably 50 mgKOH / g or more. In addition, it 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 be above the aforementioned lower limit, there is a tendency for the solubility in the developer to become good. In addition, by setting it to be below the aforementioned upper limit, there is a tendency to suppress the generation of film roughness. For example, the acid value of the alkali-soluble resin is preferably 10 to 200 mgKOH / g, more preferably 15 to 200 mgKOH / g, further preferably 25 to 150 mgKOH / g, and particularly preferably 50 to 100 mgKOH / g.

[0221] In the colored resin composition of the present invention, the content ratio of the alkali-soluble resin (C) is not particularly limited, and is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 15% by mass or more, and particularly preferably 20% by mass or more in the total solid content of the colored resin composition. In addition, it is preferably 50% by mass or less, more preferably 40% by mass or less, further preferably 35% by mass or less, further preferably 30% by mass or less, and particularly preferably 25% by mass or less. By setting it to be above the aforementioned lower limit, there is a tendency that a pattern can be formed well, and by setting it to be below the aforementioned upper limit, there is a tendency that the resolution and residual film rate are improved. For example, the content ratio of the alkali-soluble resin (C) is preferably 5 to 50% by mass, more preferably 5 to 40% by mass, further preferably 10 to 35% by mass, further preferably 15 to 30% by mass, and particularly preferably 20 to 25% by mass.

[0222] [1-4] (D) Photopolymerization initiator

[0223] The colored resin composition of the present invention contains (D) a photopolymerization initiator. By containing the (D) photopolymerization initiator, film curability by photopolymerization can be obtained.

[0224] (D) The photopolymerization initiator may also be used in the form of a mixture with an accelerator (chain transfer agent) and additives such as a sensitizing dye added as needed (photopolymerization initiation system). The photopolymerization initiation system is a component that has the function of directly absorbing light or causing a decomposition reaction or a hydrogen abstraction reaction by being photosensitized to generate polymerization active free radicals.

[0225] As the photopolymerization initiator, for example, there can be mentioned: the metallocene compounds containing ditiocene compounds described in Japanese Patent Publication No. 59-152396 and Japanese Patent Publication No. 61-151197, the hexaarylbiimidazole derivatives described in Japanese Patent Publication No. 10-39503, halomethyl-s-triazine derivatives, N-aryl-α-amino acids such as N-phenylglycine, N-aryl-α-amino acid salts, free radical activators such as N-aryl-α-amino acid esters, α-aminoalkylphenol compounds, and oxime ester initiators described in Japanese Patent Publication No. 2000-80068.

[0226] Specific examples of the photopolymerization initiator that can be used in the present invention are listed below.

[0227] 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, 2-(4-ethoxycarbonylnaphthyl)-4,6-bis(trichloromethyl)-s-triazine and the like halomethyl-s-triazine derivatives;

[0228] 2-Trichloromethyl-5-(2'-benzofuranyl)-1,3,4- oxadiazole, 2-trichloromethyl-5-[β-(2'-benzofuranyl)vinyl]-1,3,4- oxadiazole, 2-trichloromethyl-5-[β-(2'-(6"-benzofuranyl)vinyl)]-1,3,4- Oxadiazole, 2-trichloromethyl-5-furanyl-1,3,4- Halogenation of oxadiazoles Oxadiazole derivatives;

[0229] 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;

[0230] Benzoin alkyl ethers such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether and benzoin isopropyl ether;

[0231] Anthraquinone derivatives such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, and 1-chloroanthraquinone;

[0232] Benzophenone derivatives such as benzophenone, Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, and 2-carboxybenzophenone;

[0233] Acetophenone derivatives such as 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexylphenyl ketone, α-hydroxy-2-methylphenylacetone, 1-hydroxy-1-methylethyl-(p-isopropylphenyl) ketone, 1-hydroxy-1-(p-dodecylphenyl) ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one, and 1,1,1-trichloromethyl (p-butylphenyl) ketone;

[0234] Thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone and other thioxanthone derivatives;

[0235] Benzoate derivatives such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate;

[0236] Acridine derivatives such as 9-phenylacridine and 9-(p-methoxyphenyl)acridine;

[0237] Phenazine derivatives such as 9,10-dimethylbenzphenazine;

[0238] Anthraquinone derivatives such as benzanthrone;

[0239] Titanocene derivatives such as bis(cyclopentadienyl)titanium dichloride, bis(cyclopentadienyl)diphenyltitanium, bis(cyclopentadienyl)di(2,3,4,5,6-pentafluorophenyl)titanium, bis(cyclopentadienyl)di(2,3,5,6-tetrafluorophenyl)titanium, bis(cyclopentadienyl)di(2,4,6-trifluorophenyl)titanium, bis(cyclopentadienyl)-2,6-difluorophenyltitanium, bis(cyclopentadienyl)-2,4-difluorophenyltitanium, bis(methylcyclopentadienyl)di(2,3,4,5,6-pentafluorophenyl)titanium, bis(methylcyclopentadienyl)di(2,6-difluorophenyl)titanium, and bis(cyclopentadienyl)-2,6-difluoro-3-(pyrrol-1-yl)phenyltitanium;

[0240] α-aminoalkylphenone compounds such as 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butane-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butane-1-one, 4-dimethylaminobenzoic acid ethyl ester, 4-dimethylaminobenzoic acid isopentyl ester, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, 1,4-dimethylaminobenzoic acid 2-ethylhexyl ester, 2,5-bis(4-diethylaminobenzylidene)cyclohexanone, 7-diethylamino-3-(4-diethylaminobenzoyl)coumarin, and 4-(diethylamino)chalcone;

[0241] Oxime ester compounds such as 1-[4-(phenylthio)phenyl]-1,2-octanedione 2-(O-benzoyl oxime), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethanone 1-(O-acetyl oxime).

[0242] Among these, oxime ester compounds (oxime ester photopolymerization initiators) are preferred from the viewpoint of sensitivity and surface properties.

[0243] Oxime ester compounds have structures that absorb ultraviolet rays, transmit light energy, and generate free radicals, so they have high sensitivity even in small amounts, are stable to thermal reactions, and can design highly sensitive photosensitive resin compositions with small amounts. In particular, oxime ester compounds containing a carbazole ring that may have a substituent are preferred from the viewpoint of light absorption for i-rays (365 nm) of an exposure light source.

[0244] Examples of the oxime ester compounds include compounds represented by the following general formula (I-1).

[0245] [Chemical formula 23]

[0246]

[0247] In the above formula (I-1), R 21a represents a hydrogen atom, an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent.

[0248] R 21b It represents an arbitrary substituent containing an aromatic ring or a heteroaromatic ring.

[0249] R 22a It represents an alkanoyl group which may have a substituent, or an aroyl group which may have a substituent.

[0250] R 21a The number of carbon atoms in the alkyl group is not particularly limited, but is usually 1 or more, preferably 2 or more, and is usually 20 or less, preferably 15 or less, more preferably 10 or less, and further preferably 5 or less, from the viewpoint of solubility in solvents and sensitivity to exposure. Specific examples of the alkyl group include methyl, ethyl, propyl, and cyclopentylethyl.

[0251] Examples of the substituent which the alkyl group may have include an aromatic ring group, a hydroxyl group, a carboxyl group, a halogen atom, an amino group, an amide group, 4-(2-methoxy-1-methyl)ethoxy-2-methylphenyl, and N-acetyl-N-acetoxyamino. From the viewpoint of ease of synthesis, the alkyl group is preferably unsubstituted.

[0252] As R 21a The aromatic ring group in the formula (A) may be an aromatic hydrocarbon ring group or 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, further preferably 12 or less, and particularly preferably 8 or less.

[0253] Specific examples of the aromatic ring group include a phenyl group, a naphthyl group, a pyridyl group, a furyl group, a fluorenyl group, and the like. 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.

[0254] 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, and an alkyl group. From the viewpoint of developability, a hydroxyl group and a carboxyl group are preferred, and a carboxyl group is more preferred. In addition, 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.

[0255] Among these, R 21a It is an alkyl group which may have a substituent, more preferably an unsubstituted alkyl group, and still more preferably a methyl group.

[0256] R 21b It is an arbitrary substituent containing an aromatic ring or a heteroaromatic ring. From the viewpoint of solubility in a solvent and sensitivity to exposure, preferably, a carbazolyl group optionally having a substituent, a thioxanthone group optionally having a substituent, a diphenyl sulfide group optionally having a substituent or a fluorenyl group optionally having a substituent, or a group formed by linking these groups to a carbonyl group are mentioned. Among these, from the viewpoint of light absorption to i-rays (365 nm) of an exposure light source, a carbazolyl group optionally having a substituent or a group formed by linking a carbazolyl group optionally having a substituent and a carbonyl group is preferred.

[0257] R 22a The number of carbon atoms of the alkanoyl group in is not particularly limited, but is usually 2 or more, preferably 3 or more, and is usually 20 or less, preferably 15 or less, more preferably 10 or less, and further preferably 5 or less, from the viewpoint of solubility and sensitivity to solvents. Specific examples of the alkanoyl group include acetyl, propionyl, butyryl, and the like.

[0258] Examples of the substituent that the alkanoyl group may have include an aromatic ring group, a hydroxyl group, a carboxyl group, a halogen atom, an amino group, an amide group, and the like. From the viewpoint of ease of synthesis, the alkanoyl group is preferably unsubstituted.

[0259] In addition, R 22a The number of carbon atoms of the aromatic acyl group in is not particularly limited, but is usually 7 or more, preferably 8 or more, and is usually 20 or less, preferably 15 or less, and more preferably 10 or less, from the viewpoint of solubility and sensitivity to solvents. Specific examples of the aromatic acyl group include benzoyl and naphthoyl.

[0260] Examples of the substituent that the aroyl group may have include a hydroxyl group, a carboxyl group, a halogen atom, an amino group, an amide group, and an alkyl group. From the viewpoint of ease of synthesis, the aroyl group is preferably unsubstituted.

[0261] Among the compounds represented by the general formula (I-1), from the viewpoint of light absorption of i-rays (365 nm) of an exposure light source, compounds represented by the following general formula (I-2) or (I-3) can be mentioned.

[0262] [Chemical formula 24]

[0263]

[0264] [Chemical formula 25]

[0265]

[0266] In the above formula (I-2) or (I-3), R 21a and R 22a The same meaning as the aforementioned general formula (I-1).

[0267] R 23a It represents an alkyl group which may have a substituent.

[0268] R 24a It represents an alkyl group which may have a substituent, an aroyl group which may have a substituent, a heteroaroyl group which may have a substituent, or a nitro group.

[0269] The benzene ring constituting the carbazole ring may be further fused with an aromatic ring to form a fused aromatic ring.

[0270] R 23a and R 24a The number of carbon atoms in the alkyl group is not particularly limited, but is usually 1 or more, preferably 2 or more, and is usually 20 or less, preferably 15 or less, more preferably 10 or less, and further preferably 5 or less from the viewpoint of solubility in a solvent. Specific examples of the alkyl group include methyl, ethyl, propyl, butyl, and cyclohexyl.

[0271] Examples of the substituent that the alkyl group may have include a carboxyl group, a hydroxyl group, a phenyl group, a benzyl group, a cyclohexyl group, and a nitro group. From the viewpoint of ease of synthesis, the alkyl group is preferably unsubstituted.

[0272] Among these, as R 23a From the viewpoint of solubility in solvents and ease of synthesis, an ethyl group is more preferred.

[0273] R 24a The number of carbon atoms of the aromatic acyl group in is not particularly limited, but is usually 7 or more, preferably 8 or more, more preferably 9 or more, from the viewpoint of solubility in a solvent, and is usually 20 or less, preferably 15 or less, more preferably 10 or less, and further preferably 9 or less. Specific examples of the aromatic acyl group include benzoyl and naphthoyl.

[0274] Examples of the substituent which the aroyl group may have include a carboxyl group, a hydroxyl group, a phenyl group, a benzyl group, a cyclohexyl group, and a nitro group. From the viewpoint of ease of synthesis, an ethyl group is preferred.

[0275] R 24aThe number of carbon atoms of the heteroaroyl group in is not particularly limited, but is usually 7 or more, preferably 8 or more, more preferably 9 or more, from the viewpoint of solubility in a solvent, and is usually 20 or less, preferably 15 or less, more preferably 10 or less, and further preferably 9 or less. Specific examples of the heteroaroyl group include furancarbonyl, thiophenecarbonyl, pyrrolecarbonyl, pyridinecarbonyl, and the like.

[0276] Examples of the substituent that the heteroaroyl group may have include a carboxyl group, a hydroxyl group, a phenyl group, a benzyl group, a cyclohexyl group, and a nitro group. From the viewpoint of ease of synthesis, the heteroaroyl group is preferably unsubstituted.

[0277] The benzene ring constituting the carbazole ring may be further fused with an aromatic ring to form a fused aromatic ring.

[0278] 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 Qiangli Electronics Co., Ltd., and N-1919, NCI-930 and NCI-831 manufactured by ADEKA.

[0279] Specific examples of the oxime ester compound include the compounds exemplified below, but the oxime ester compound is not limited to these compounds.

[0280] [Chemical formula 26]

[0281]

[0282] [Chemical formula 27]

[0283]

[0284] [Chemical formula 28]

[0285]

[0286] These photopolymerization initiators may be used alone or in combination of two or more.

[0287] In addition to the (D) photopolymerization initiator, a chain transfer agent may be used. The chain transfer agent is a compound having a function of accepting generated radicals and transferring the accepted radicals to other compounds.

[0288] As the chain transfer agent, any compound having the above functions may be used, and various compounds having the above functions may be used, for example, mercapto-containing compounds, carbon tetrachloride, etc., and compounds having mercapto groups are more preferably used because of the tendency of high chain transfer effect. It is believed that this is because mercapto-containing compounds are prone to bond cleavage, hydrogen abstraction reaction, and chain transfer reaction due to low SH bond energy, and are effective for increasing sensitivity and surface curing.

[0289] Examples of the mercapto group-containing compound include 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzo azole, 3-mercapto-1,2,4-triazole, 2-mercapto-4(3H)-quinazoline, β-mercaptonaphthalene, 1,4-dimethylmercaptobenzene and other thiol-containing compounds with aromatic rings; hexanediol, decanedithiol, butanediol bis(3-mercaptopropionate), butanediol dimercaptoacetate, ethylene glycol bis(3-mercaptopropionate), ethylene glycol dimercaptoacetate, trimethylolpropane tris(3-mercaptopropionate), trimethylolpropane trimercaptoacetate, trihydroxyethyl trimercaptopropionate, pentaerythritol tetrakis(3-mercaptopropionate), quaternary Aliphatic mercapto group-containing compounds such as 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-mercaptobutoxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione are preferred, and compounds having multiple mercapto groups are particularly preferred from the viewpoint of surface smoothness.

[0290] Among them, 2-mercaptobenzothiazole and 2-mercaptobenzimidazole are preferred among the mercapto-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-mercaptobutoxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione are preferred among the mercapto-containing compounds of aliphatic type.

[0291] In addition, from the viewpoint of sensitivity, aliphatic mercapto-containing compounds are preferred, and 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-mercaptobutoxyethyl)-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.

[0292] These may be used alone or in combination of two or more.

[0293] In the colored resin composition of the present invention, the content ratio of the (D) photopolymerization initiator is not particularly limited, and is preferably 1% by mass or more, more preferably 2% by mass or more, further preferably 3% by mass or more, further preferably 4% by mass or more, particularly preferably 6% by mass or more, and most preferably 7% by mass or more in the total solid content of the colored resin composition. In addition, it is preferably 20% by mass or less, more preferably 15% by mass or less, further preferably 12% by mass or less, and particularly preferably 10% by mass or less. By setting it to be above the above lower limit, there is a tendency to ensure the patterning characteristics after development, and by setting it to be below the above upper limit, there is a tendency to suppress the decrease in transmittance caused by excessive addition of the photopolymerization initiator. For example, the content ratio of the (D) photopolymerization initiator is preferably 1 to 20% by mass, more preferably 2 to 20% by mass, further preferably 3 to 15% by mass, further preferably 4 to 15% by mass, particularly preferably 6 to 12% by mass, and most preferably 7 to 10% by mass.

[0294] When the colored resin composition of the present invention contains a chain transfer agent, the content ratio is not particularly limited, and 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, and particularly preferably 1.5% by mass or more, and ia, 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 to ensure storage stability and pattern forming ability during alkali development. When a chain transfer agent is included, for example, its content ratio is preferably 0.01-5% by mass, more preferably 0.1-5% by mass, more preferably 0.2-3% by mass, more preferably 0.5-3% by mass, more preferably 1-2% by mass, and particularly preferably 1.5-2% by mass.

[0295] [1-5] Other solid ingredients

[0296] The colored resin composition of the present invention may further contain solid components other than the above components as necessary. Examples of such components include photopolymerizable monomers, dispersants, dispersing aids, and surfactants.

[0297] [1-5-1] Photopolymerizable monomer

[0298] The photopolymerizable monomer is not particularly limited as long as it is a low molecular compound that can be polymerized, and preferably a compound that can be addition polymerized and has at least one olefinic double bond (hereinafter referred to as an "olefinic compound"). The olefinic compound is a compound having an olefinic double bond that is addition polymerized and cured by the action of a photopolymerization initiator when the colored resin composition of the present invention is irradiated with active light. It should be noted that the monomer in the present invention refers to a concept relative to the so-called high molecular substance, and refers to the concept of including dimers, trimers, and oligomers in addition to monomers in a narrow sense.

[0299] In the present invention, it is particularly desirable to use a multifunctional olefinic monomer having two or more olefinic double bonds in one molecule. The number of olefinic double bonds possessed by the multifunctional olefinic monomer is not particularly limited, and is generally 2 or more, preferably 4 or more, more preferably 5 or more, and preferably 8 or less, more preferably 7 or less. By setting it to above the aforementioned lower limit, there is a tendency to become highly sensitive, and by setting it to below the aforementioned upper limit, there is a tendency to improve solubility in solvents.

[0300] Examples of the olefinic 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 of unsaturated carboxylic acids and polyhydroxy compounds such as aliphatic polyhydroxy compounds and aromatic polyhydroxy compounds, and olefinic compounds having a carbamate skeleton obtained by reacting a polyisocyanate compound with a hydroxy compound containing a (meth)acryloyl group.

[0301] Examples of esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids include acrylates 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 include methacrylates obtained by replacing the acrylic acid moiety of these acrylic esters with a methacrylic acid moiety, itaconates obtained by replacing the acrylic acid moiety with an itaconic acid moiety, crotonic acid moieties obtained by replacing the acrylic acid moieties with crotonic acid moieties, or maleates obtained by replacing the acrylic acid moieties with maleic acid moieties.

[0302] Examples of the esters of the aromatic polyhydroxy compound and the unsaturated carboxylic acid include hydroquinone diacrylate, hydroquinone dimethacrylate, resorcinol diacrylate, resorcinol dimethacrylate, and 1,2,3-pyrogallol triacrylate.

[0303] The ester obtained by the esterification reaction of unsaturated carboxylic acid and polycarboxylic acid with polyhydroxy compound does not need to be a single substance, but may be a mixture. Representative examples include: condensation products of acrylic acid, phthalic acid and ethylene glycol; condensation products of acrylic acid, maleic acid and diethylene glycol; condensation products of methacrylic acid, terephthalic acid and pentaerythritol; condensation products of acrylic acid, adipic acid, butanediol and glycerol, etc.

[0304] Examples of the olefinic compound having a carbamate skeleton obtained by reacting a polyisocyanate compound with a hydroxy compound containing a (meth)acryloyl group include: aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate; alicyclic diisocyanates such as cyclohexane diisocyanate and isophorone diisocyanate; and reaction products of aromatic diisocyanates such as benzal diisocyanate and diphenylmethane diisocyanate with hydroxy compounds containing a (meth)acryloyl group such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxy(1,1,1-triacryloyloxymethyl)propane and 3-hydroxy(1,1,1-trimethacryloyloxymethyl)propane.

[0305] In addition, as the olefinic compound used in the present invention, for example, acrylamides such as ethylenebisacrylamide; allyl esters such as diallyl phthalate; vinyl group-containing compounds such as divinyl phthalate, etc. are also useful.

[0306] In addition, the olefinic compound may be a monomer having an acid value. The monomer having an acid value is an ester formed by an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, preferably a polyfunctional monomer having an acid group by reacting a non-aromatic carboxylic acid anhydride with an unreacted hydroxyl group of the aliphatic polyhydroxy compound, and particularly preferably, in the ester, the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol.

[0307] These monomers can be used alone as one, but owing to being difficult to use a single compound when preparing, therefore can also be mixed with more than two kinds and use.In addition, can also be used in combination with the polyfunctional monomer with acid group as monomer without acid group as required.

[0308] 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 be above the aforementioned lower limit, there is a tendency to improve the developing dissolution characteristics, and by setting it to be below the aforementioned upper limit, there is a tendency to improve the manufacturing and handling, and the curing properties such as photopolymerization performance and surface smoothness of pixels tend to be improved. Therefore, in the case of combining two or more polyfunctional monomers with different acid groups, or in the case of combining polyfunctional monomers without an acid group, it is preferred to adjust so that the acid groups of all polyfunctional monomers fall within the above range.

[0309] In the present invention, a more preferred polyfunctional monomer having an acid group is a monomer commercially available as TO1382 manufactured by Toagosei Co., Ltd., which is a mixture of dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and succinate of dipentaerythritol pentaacrylate as main components. Polyfunctional monomers other than this polyfunctional monomer may also be used in combination. In addition, polyfunctional monomers described in paragraphs

[0056] and

[0057] of Japanese Patent Publication No. 2013-140346 may also be used.

[0310] In the present invention, from the viewpoint of improving the chemical resistance of pixels and the linearity of pixel edges, the polymerizable monomers described in Japanese Patent Application Laid-Open No. 2013-195971 are preferred. From the viewpoint of achieving both the sensitivity of the coating film and the shortening of the development time, the polymerizable monomers described in Japanese Patent Application Laid-Open No. 2013-195974 are preferred.

[0311] When the colored resin composition of the present invention contains a photopolymerizable monomer, the content ratio of the photopolymerizable monomer is usually 0% by mass or more, preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 15% by mass or more, further preferably 20% by mass or more, and particularly preferably 22% by mass or more in the total solid content of the colored resin composition, and is usually 80% by mass or less, preferably 70% by mass or less, more preferably 50% by mass or less, further preferably 40% by mass or less, and particularly preferably 30% by mass or less. For example, the content ratio of the photopolymerizable monomer is preferably 0 to 80% by mass, more preferably 5 to 80% by mass, further preferably 10 to 70% by mass, further 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.

[0312] In addition, the ratio relative to 100 parts by mass of the colorant (A) is usually 0 parts by mass or more, preferably 5 parts by mass or more, more preferably 10 parts by mass or more, further preferably 20 parts by mass or more, further preferably 40 parts by mass or more, and particularly preferably 60 parts by mass or more, and is usually 200 parts by mass or less, preferably 100 parts by mass or less, and more preferably 80 parts by mass or less. By setting it to be above the aforementioned lower limit, there is a tendency for the curability to be higher, and by setting it to be below the aforementioned upper limit, there is a tendency to suppress the decrease in developability. For example, the content ratio of the photopolymerizable monomer relative to 100 parts by mass of the colorant (A) is preferably 0 to 200 parts by mass, more preferably 5 to 200 parts by mass, further preferably 10 to 100 parts by mass, further preferably 20 to 100 parts by mass, particularly preferably 40 to 80 parts by mass, and most preferably 60 to 80 parts by mass.

[0313] [1-5-2] Dispersants and dispersing aids

[0314] When the colored resin composition of the present invention contains a pigment as the (A) colorant, it is preferred to contain a dispersant for the purpose of stably dispersing the pigment. Among dispersants, a polymer dispersant is preferred because it is excellent in dispersion stability over time.

[0315] As the polymer dispersant, for example, carbamate dispersants, polyethyleneimine dispersants, polyoxyethylene alkyl ether dispersants, polyoxyethylene glycol diester dispersants, sorbitan aliphatic ester dispersants, aliphatic modified polyester dispersants, etc. Specific examples of these dispersants include trade names EFKA (registered trademark, manufactured by BASF), DisperBYK (registered trademark, manufactured by BYK-Chemie), Disparlon (registered trademark, manufactured by Kusumoto Chemicals Co., Ltd.), SOLSPERSE (registered trademark, manufactured by Zeneca), KP (registered trademark, manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (registered trademark, manufactured by Kyoeisha Chemical Co., Ltd.), and dispersants described in Japanese Patent Application Publication No. 2013-119568.

[0316] Among the polymer dispersants, block copolymers having a functional group containing a nitrogen atom are preferred from the viewpoint of dispersibility and storage stability, and acrylic block copolymers are more preferred.

[0317] The block copolymer having a functional group containing a nitrogen atom is preferably an AB block copolymer and / or a BAB block copolymer composed of an A block having a quaternary ammonium salt group and / or an amino group in a side chain and a B block having no quaternary ammonium salt group and / or an amino group.

[0318] Examples of the functional group containing a nitrogen atom include a primary amino group, a secondary amino group, a tertiary amino group, and a quaternary ammonium salt group. From the viewpoint of dispersibility and storage stability, it is preferred to have a primary amino group, a secondary amino group, or a tertiary amino group, and it is more preferred to have a tertiary amino group.

[0319] The structure of the repeating unit having a tertiary amino group in the block copolymer is not particularly limited, but is preferably a repeating unit represented by the following general formula (1) from the viewpoint of dispersibility and storage stability.

[0320] [Chemical formula 29]

[0321]

[0322] In the above formula (1), R 1 and R 2 are each independently a hydrogen atom, an alkyl group optionally having a substituent, an aryl group optionally having a substituent, or an aralkyl group optionally having a substituent, and R 1 and R 2 Optionally bonded to each other to form a ring structure, R 3 is a hydrogen atom or a methyl group, and X is a divalent linking group.

[0323] In the above formula (1), the carbon number of the alkyl group optionally having a substituent is not particularly limited, and is generally 1 or more, and is preferably 10 or less, more preferably 6 or less, and further preferably 4 or less. As specific examples of the alkyl group, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, etc. can be cited, among which methyl, ethyl, propyl, butyl, pentyl or hexyl is preferred, and methyl, ethyl, propyl or butyl is more preferred. In addition, it can be any one of straight chain and branched. In addition, cyclic structures such as cyclohexyl and cyclohexylmethyl can also be included.

[0324] In the above formula (1), the number of carbon atoms of the aryl group which may have a substituent is not particularly limited, but is usually 6 or more, preferably 16 or less, more preferably 12 or less, and further preferably 8 or less. Specific examples of the aryl group include phenyl, methylphenyl, ethylphenyl, dimethylphenyl, diethylphenyl, naphthyl, anthracenyl, etc. Among these, phenyl, methylphenyl, ethylphenyl, dimethylphenyl or diethylphenyl is preferred, and phenyl, methylphenyl or ethylphenyl is more preferred.

[0325] In the above formula (1), the number of carbon atoms of the aralkyl group which may have a substituent is not particularly limited, but is usually 7 or more, preferably 16 or less, more preferably 12 or less, and further preferably 9 or less. Specific examples of the aralkyl group include phenylmethylene, phenylethylene, phenylpropylene, phenylbutylene, and phenylisopropylidene. Among these, phenylmethylene, phenylethylene, phenylpropylene, or phenylbutylene is preferred, and phenylmethylene or phenylethylene is more preferred.

[0326] Among these, R 1 and R 2 Each independently represents an alkyl group which may have a substituent, and is more preferably a methyl group or an ethyl group.

[0327] Examples of the substituent 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 and the like. From the viewpoint of ease of synthesis, an unsubstituted group is preferred.

[0328] In the above formula (1), R 1 and R 2 The cyclic structure formed by mutual bonding includes, for example, a 5- to 7-membered nitrogen-containing heterocyclic monocyclic ring or a condensed ring formed by condensing two of them. The nitrogen-containing heterocyclic ring is preferably non-aromatic, and is more preferably a saturated ring. Specifically, for example, the following cyclic structure (IV) can be mentioned.

[0329] [Chemical formula 30]

[0330]

[0331] These cyclic structures may further have a substituent.

[0332] 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 -base, -COOR 14 -base〔where R 13 and R 14 is a single bond, an alkylene group having 1 to 10 carbon atoms, or an ether group (alkoxyalkyl group) having 2 to 10 carbon atoms, etc., preferably -COOR 14 -base.

[0333] In addition, the repeating unit shown in the aforementioned formula (1) preferably contains more than 1 mol%, more preferably more than 5 mol%, more preferably more than 10 mol%, more preferably more than 15 mol%, particularly preferably more than 20 mol%, most preferably more than 25 mol%, and preferably less than 90 mol%, more preferably less than 70 mol%, more preferably less than 50 mol%, and particularly preferably less than 40 mol%. In the case of the aforementioned range, there is a tendency to have both dispersion stability and high brightness. For example, the repeating unit shown in the aforementioned formula (1) preferably contains 1 to 90 mol%, more preferably 5 to 90 mol%, more preferably 10 to 70 mol%, more preferably 15 to 70 mol%, particularly preferably 20 to 50 mol%, and most preferably 25 to 40 mol%.

[0334] Furthermore, from the viewpoint of improving the compatibility of the dispersant with the binder component such as the solvent and thus improving the dispersion stability, the block copolymer preferably has a repeating unit represented by the following formula (2).

[0335] [Chemical formula 31]

[0336]

[0337] In the above formula (2), R 10 is ethylene or propylene, R 11 is an alkyl group optionally having a substituent, R 12 is a hydrogen atom or a methyl group, and n is an integer of 1 to 20.

[0338] R in the above formula (2) 11In the alkyl group, the number of carbon atoms of the alkyl group optionally having a substituent is not particularly limited, and is generally 1 or more, preferably 2 or more, and preferably 10 or less, more preferably 6 or less, and further preferably 4 or less. As specific examples of alkyl groups, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, etc. can be cited, among which methyl, ethyl, propyl, butyl, pentyl or hexyl is preferred, and methyl, ethyl, propyl or butyl is more preferred. In addition, it can be any one of straight chain and branched. In addition, cyclic structures such as cyclohexyl and cyclohexylmethyl can also be included. As substituents optionally having, halogen atoms, alkoxy groups, benzoyl groups, hydroxyl groups, etc. can be cited, and from the viewpoint of the ease of synthesis, it is preferably unsubstituted.

[0339] In view of compatibility and dispersibility with a binder component such as a solvent, n in the formula (2) is preferably 1 or more, more preferably 2 or more, and is preferably 10 or less, more preferably 5 or less.

[0340] In addition, the repeating unit shown in the aforementioned formula (2) preferably contains more than 1 mol%, more preferably more than 2 mol%, more preferably more than 4 mol%, and preferably less than 30 mol%, more preferably less than 20 mol%, more preferably less than 10 mol%. In the case of the aforementioned range, there is a tendency to have both compatibility and dispersion stability with respect to adhesive components such as solvents. For example, the repeating unit shown in the aforementioned formula (2) preferably contains 1 to 30 mol%, more preferably 2 to 20 mol%, and more preferably 4 to 10 mol%.

[0341] Furthermore, from the viewpoint of improving the compatibility of the dispersant with the binder component such as the solvent and thus improving the dispersion stability, the block copolymer preferably has a repeating unit represented by the following formula (3).

[0342] [Chemical formula 32]

[0343]

[0344] In the above formula (3), R 8 R is an alkyl group which may have a substituent, an aryl group which may have a substituent, or an aralkyl group which may have a substituent. 9 A hydrogen atom or a methyl group.

[0345] R in the above formula (3) 8In the above, the carbon number of the alkyl group optionally having a substituent is not particularly limited, and is generally 1 or more, preferably 1 or more, and preferably 10 or less, and more preferably 6 or less. As specific examples of the alkyl group, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, etc. can be cited, among which methyl, ethyl, propyl, butyl, pentyl or hexyl is preferred, and methyl, ethyl, propyl or butyl is more preferred. In addition, it can be any one of straight chain and branched. In addition, cyclic structures such as cyclohexyl and cyclohexylmethyl can also be included.

[0346] R in the above formula (3) 8 In the above, the number of carbon atoms of the aryl group which may have a substituent is not particularly limited, but is usually 6 or more, preferably 16 or less, and more preferably 12 or less. Specific examples of the aryl group include phenyl, methylphenyl, ethylphenyl, dimethylphenyl, diethylphenyl, naphthyl, anthracenyl, etc. Among them, phenyl, methylphenyl, ethylphenyl, dimethylphenyl or diethylphenyl is preferred, and phenyl, methylphenyl or ethylphenyl is more preferred.

[0347] R in the above formula (3) 8 In the above, the number of carbon atoms of the aralkyl group which may have a substituent is not particularly limited, but is usually 7 or more, preferably 16 or less, and more preferably 12 or less. Specific examples of the aralkyl group include phenylmethylene, phenylethylene, phenylpropylene, phenylbutylene, and phenylisopropylidene. Among these, phenylmethylene, phenylethylene, phenylpropylene, or phenylbutylene is preferred, and phenylmethylene or phenylethylene is more preferred.

[0348] Among these, R 8 It is preferably an alkyl group or an aralkyl group, and more preferably a methyl group, an ethyl group or a phenylmethylene group.

[0349] As R 8 The substituents that the alkyl group in the above may have include halogen atoms, alkoxy groups, etc. In addition, the substituents that the aryl group or aralkyl group may have include chain alkyl groups, halogen atoms, alkoxy groups, etc. In addition, R 8 The chain alkyl group shown includes both straight-chain and branched ones.

[0350] In addition, the repeating unit shown in the aforementioned formula (3) preferably contains a ratio of 30 mol% or more, more preferably 40 mol% or more, more preferably 50 mol% or more, and preferably 80 mol% or less, more preferably 70 mol% or less. In the case of the aforementioned range, there is a tendency to have both dispersion stability and high brightness. For example, the repeating unit shown in the aforementioned formula (3) preferably contains a ratio of 30 to 80 mol%, more preferably 40 to 80 mol%, and more preferably 50 to 70 mol%.

[0351] The block copolymer may further have repeating units other than the repeating units represented by the general formula (1), the repeating units represented by the general formula (2), and the repeating units represented by the general formula (3). Examples of such repeating units include repeating units derived from the following monomers: styrene monomers such as styrene and α-methylstyrene; (meth)acrylate monomers such as (meth)acryloyl chloride; (meth)acrylamide monomers such as N-hydroxymethylacrylamide; vinyl acetate; acrylonitrile; allyl glycidyl ether, crotonic acid glycidyl ether; N-methacryloylmorpholine, etc.

[0352] From the viewpoint of further improving dispersibility, it is preferred to have a block copolymer having an A block and a B block, wherein the A block has a repeating unit represented by the aforementioned general formula (1), and the B block does not have a repeating unit represented by the aforementioned general formula (1). The block copolymer is preferably an AB block copolymer or a BAB block copolymer. In addition, it is more preferred that the B block has a repeating unit represented by the aforementioned general formula (2) and a repeating unit represented by the aforementioned general formula (3).

[0353] In addition, repeating units other than the repeating units represented by the general formula (1) may be contained in the A block, and examples of such repeating units include repeating units derived from the aforementioned (meth)acrylate monomers, etc. The content of repeating units other than the repeating units represented by the general formula (1) in the A block is preferably 0 to 50 mol%, more preferably 0 to 20 mol%, but it is most preferred that such repeating units are not contained in the A block.

[0354] 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. Examples of such repeating units include repeating units derived from the following monomers: styrene-based monomers such as styrene and α-methylstyrene; (meth)acrylic acid salt monomers such as (meth)acryl chloride; (meth)acrylamide and N-methylol acrylamide; 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%, but it is most preferred that such repeating units are not contained in the B block.

[0355] In view of dispersibility, the block copolymer preferably has a low acid value, and particularly preferably 0 mgKOH / g. The acid value here refers to the number of mg of KOH required to neutralize 1 g of the solid content of the dispersant.

[0356] In addition, 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, further preferably 70 mgKOH / g or more, further preferably 90 mgKOH / g or more, particularly preferably 100 mgKOH / g or more, and most preferably 110 mgKOH / g or more, and is preferably 150 mgKOH / g or less, and more preferably 130 mgKOH / g or less. The amine value referred to here means the amine value converted to the effective solid content, which is equivalent to the amount of alkali in the solid content per 1 g of the dispersant and is expressed by the mass of KOH.

[0357] For example, the amine value of the block copolymer is preferably 30 to 150 mgKOH / g, more preferably 50 to 150 mgKOH / g, further preferably 70 to 150 mgKOH / g, further preferably 90 to 130 mgKOH / g, particularly preferably 100 to 130 mgKOH / g, and most preferably 110 to 130 mgKOH / g.

[0358] The molecular weight of the block copolymer is preferably in the range of 1000 to 30000 in terms of weight average molecular weight (hereinafter sometimes referred to as "Mw") converted to polystyrene. Within the above range, dispersion stability is good and dried foreign matter tends to be less likely to be generated during coating using a slit nozzle method.

[0359] The block copolymer can be produced by a known method, for example, by living polymerization of the monomers to be introduced into the above-mentioned repeating units. As living polymerization methods, Japanese Patent Publication No. 9-62002, Japanese Patent Publication No. 2002-31713, and P. Lutz, P. Masson et al, Polym. Bull. 12, 79 (1984); BC Anderson, GD Andrews et al. al, Macromolecules, 14, 1601 (1981); K. Hatada, K. Ute, et al, Polym. J., 17, 977 (1985), 18, 1037 (1986); Koichi Yusuke, Koichi Hatada, Polymer Processing, 36, 366 (1987); Toshinobu Higashimura, Mitsuo Sawamoto, Collected Papers on Polymers, 46, 189 (1989); M. Kuroki, T. Aida, J. Am. Chem. Soc, 109, 4737 (1987); Takuzo Aida, Shohei Inoue, Synthetic Organic Chemistry, 43, 300 (1985); DY Sogoh, WR Hertler et al, Macromolecules, 20, 1473 (1987), etc.

[0360] 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, more preferably 4% by mass or more, and particularly preferably 5% by mass or more in the total solid content of the colored resin composition, and preferably 20% by mass or less, more preferably 15% by mass or less, more preferably 10% by mass or less, and particularly preferably 8% by mass or less. By setting it within the above range, there is a tendency to obtain a colored resin composition with excellent dispersion stability and high brightness.

[0361] When the colored resin composition of the present invention includes a pigment and a dispersant, the content ratio of the dispersant is not particularly limited, and is preferably 0.5 parts by mass or more, more preferably 5 parts by mass or more, further preferably 10 parts by mass or more, further preferably 15 parts by mass or more, and particularly preferably 20 parts by mass or more relative to 100 parts by mass of the pigment. In addition, it is preferably 70 parts by mass or less, more preferably 50 parts by mass or less, further preferably 40 parts by mass or less, and particularly preferably 30 parts by mass or less. By setting it within the above range, there is a tendency to obtain a colored resin composition with excellent dispersion stability and high brightness. For example, when a pigment and a dispersant are included, the content ratio of the dispersant is preferably 0.5 to 70 parts by mass, more preferably 5 to 70 parts by mass, further preferably 10 to 50 parts by mass, further 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.

[0362] In addition, when the colored resin composition of the present invention contains a pigment, it may contain a pigment derivative as a dispersing aid in order to improve the dispersibility of the pigment and improve the dispersion stability. Examples of the pigment derivative include azo derivatives, phthalocyanine derivatives, quinacridone derivatives, benzimidazolone derivatives, quinophthalone derivatives, isoindolinone derivatives, isoindolinone derivatives, diisocyanate derivatives, and the like. Oxadiazoles, anthraquinones, indanthrenes, perylenes, pyrenes, diketopyrrolopyrroles, Derivatives of oxazine and the like. As substituents of the pigment derivatives, there can be mentioned: sulfonic acid group, sulfonamide group and its quaternary salt, phthalimide methyl, dialkylaminoalkyl, hydroxyl group, carboxyl group, amide group and the like, which can be bonded to the pigment skeleton directly or through an alkyl group, an aryl group, a heterocyclic group and the like, preferably sulfonamide group and its quaternary salt, sulfonic acid group, more preferably sulfonic acid group. In addition, these substituents can be substituted multiple times on one pigment skeleton, or can be a mixture of compounds with different numbers of substitutions. 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, dioxazolidinone pigments, sulfonic acid derivatives of dioxazolidinone pigments, ... Sulfonic acid derivatives of oxazine pigments, etc.

[0363] [1-5-3] Surfactants

[0364] As a surfactant, various surfactants such as anionic, cationic, nonionic, and amphoteric surfactants can be used. From the perspective of the low possibility of adverse effects on various properties, nonionic surfactants are preferably used. The content ratio of the surfactant is not particularly limited, and is usually 0.001% by mass or more, preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and further preferably 0.1% by mass or more in the total solid content of the colored resin composition, and is usually used in the range of 10% by mass or less, preferably 1% by mass or less, further preferably 0.5% by mass or less, and particularly preferably 0.3% by mass or less. For example, when a surfactant is included, for example, the content ratio of the surfactant is preferably 0.001 to 10% by mass, more preferably 0.01 to 1% by mass, further preferably 0.05 to 0.5% by mass, and further preferably 0.1 to 0.3% by mass relative to the total solid content of the colored resin composition.

[0365] [2] Preparation of colored resin composition

[0366] Next, a method for preparing the colored resin composition (hereinafter, sometimes referred to as a resist) of the present invention will be described.

[0367] In the case of preparing a colored resin composition containing a pigment as a colorant, first, a given amount of pigment, solvent and dispersant are weighed respectively, and in a dispersion treatment process, the pigment is dispersed to prepare a pigment dispersion. In this dispersion treatment process, a paint oscillator, a sand mill, a ball mill, a roller mill, a stone mill, an air flow mill, a homogenizer, etc. can be used. By performing this dispersion treatment, the pigment is micronized, and therefore, the coating characteristics of the colored resin composition are improved, and the transmittance of the pixels in the color filter substrate of the product is improved.

[0368] When the pigment is dispersed, it is preferable to appropriately use a dispersing aid, a dispersing resin, or the like in combination as described above.

[0369] When a sand mill is used for dispersion treatment, glass beads or zirconium oxide beads with a particle size of 0.1 to several mm are preferably used. The temperature during the dispersion treatment is usually set to a range of 0°C or higher, preferably above room temperature, and usually below 100°C, preferably below 80°C. It should be noted that the appropriate dispersion time varies depending on the composition of the pigment dispersion and the size of the sand mill, so it is necessary to make appropriate adjustments.

[0370] In the pigment dispersion obtained by the above dispersion treatment, a solvent, an alkali-soluble resin, a photopolymerization initiator, and components other than the above components as needed are mixed to prepare a uniform dispersion solution. It should be noted that fine dust may be mixed in the dispersion treatment process and each mixing process, so it is preferred to filter the obtained pigment dispersion using a filter or the like.

[0371] When the colorant does not contain a pigment, a uniform solution can be obtained by mixing a colorant, a solvent, an alkali-soluble resin, a photopolymerization initiator, and components other than the above as needed. The obtained solution is preferably filtered using a filter or the like.

[0372] [3] Manufacturing of color filter substrates

[0373] Next, the color filter of the present invention will be described.

[0374] The color filter of 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.

[0375] [3-1] Transparent substrate (support)

[0376] As the transparent substrate of the color filter, as long as it is transparent and has appropriate strength, its material is not particularly limited. As its material, for example, 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 resins, unsaturated polyester resins, and poly (meth) acrylic resins, or various glasses can be cited. Among them, from the viewpoint of heat resistance, glass or heat-resistant resins are preferred.

[0377] In order to improve the surface properties such as adhesion, as required, the transparent substrate and the black matrix forming substrate can be subjected to corona discharge treatment, ozone treatment, thin film formation treatment of various resins such as silane coupling agent or urethane resin, etc. The thickness of the transparent substrate is usually set at more than 0.05mm, preferably more than 0.1mm, and usually below 10mm, preferably within the range of less than 7mm. In addition, when the thin film formation treatment of various resins is carried out, the film thickness is usually more than 0.01μm, preferably more than 0.05μm, and usually below 10μm, preferably within the range of less than 5μm.

[0378] [3-2] Black Matrix

[0379] By arranging a black matrix on the above-mentioned transparent substrate, and generally further forming a red, green, blue pixel image, the color filter of the present invention can be manufactured. In red, green, blue pixels, it is preferred that the above-mentioned colored resin composition is used as a coating liquid (hereinafter, sometimes referred to as "green resist") for forming a green pixel (resist pattern). Using a green resist, a pixel image is formed by coating, heating and drying, image exposure, developing and heat curing on a resin black matrix forming surface formed on a transparent substrate or on a metal black matrix forming surface formed using other light-shielding metal materials such as chromium compounds.

[0380] The black matrix is ​​formed on the transparent substrate using a light-shielding metal film or a colored resin composition for a black matrix. As the light-shielding metal material, chromium compounds such as metal chromium, chromium oxide, and chromium nitride, nickel and tungsten alloys, etc. can be used, and these can be stacked in multiple layers.

[0381] These metal shading films are usually formed by sputtering. After forming the desired pattern in a film form using a positive photoresist, chromium is etched using an etching solution mixed with ammonium cerium nitrate and perchloric acid and / or nitric acid; other materials are etched using an etching solution corresponding to the material. Finally, the positive photoresist is stripped off with a special stripper, thereby forming a black matrix.

[0382] In this case, first, a thin film of these metals or metal / metal oxides is formed on a transparent substrate by evaporation or sputtering. Then, after forming a coating film of a colored resin composition on the thin film, the coating film is exposed and developed using a photomask having a repeated pattern such as stripes, mosaics, triangles, etc. to form a resist image. Then, the coating film can be etched to form a black matrix.

[0383] When a photosensitive colored resin composition for a black matrix is ​​used, a colored resin composition containing a black colorant is used to form a black matrix. For example, a colored resin composition containing one or more black colorants such as carbon black, graphite, iron black, aniline black, cyanine black, titanium black, or a black colorant obtained by mixing red, green, blue, etc. appropriately selected from inorganic or organic pigments and dyes is used, and the method for forming red, green, and blue pixels described later is the same as the operation to form a black matrix.

[0384] [3-3] Pixel formation

[0385] A method of forming a pixel will be described.

[0386] A colored resin composition of one color among red, green and blue is applied to a transparent substrate provided with a black matrix, and after drying, a photomask is overlapped on the coating film, and image exposure and development are performed through the photomask, and thermal curing or photocuring is performed as required to form a pixel image. This operation is performed for the colored resin compositions of the three colors of red, green and blue, respectively, thereby forming a color filter image.

[0387] The color filter colored resin composition can be applied by spin coating, wire bar, flow coating, die coating, roll coating, spray coating, etc. Among them, die coating can significantly reduce the amount of coating liquid used, and there is no effect of fogging attached during coating by spin coating, and the generation of foreign matter can be suppressed, which is preferred from a comprehensive point of view.

[0388] When the thickness of the coating film is too thick, pattern development becomes difficult, and it is sometimes difficult to adjust the gap in the liquid crystal unitization process. On the other hand, when the thickness of the coating film is too thin, it is difficult to increase the pigment concentration, and sometimes the desired color cannot be presented. The thickness of the coating film is generally 0.2 μm or more, preferably 0.5 μm or more, more preferably 0.8 μm or more, and is generally 20 μm or less, preferably 10 μm or less, and more preferably 5 μm or less, based on the film thickness after drying.

[0389] [3-4] Drying of coating film

[0390] The drying of the coating film after applying the colored resin composition on the substrate is preferably carried out 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 above-mentioned solvent component, the performance of the dryer used, etc. The drying temperature and the 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 above 40°C, preferably above 50°C, and usually below 80°C, preferably below 70°C, and the drying time is usually above 15 seconds, preferably above 30 seconds, and usually above 5 minutes, preferably below 3 minutes.

[0391] Regarding the temperature conditions for reheat drying, the temperature is preferably higher than the pre-drying temperature, specifically, it is usually above 50°C, preferably above 70°C, and usually below 200°C, preferably below 160°C, and particularly preferably below 130°C. In addition, the drying time is related to the heating temperature, but is usually above 10 seconds, preferably above 15 seconds, and usually below 10 minutes, preferably below 5 minutes. The higher the drying temperature, the higher the adhesion to the transparent substrate, but when it is too high, the alkali-soluble resin decomposes and causes thermal polymerization, sometimes resulting in poor development. It should be noted that as the drying process of the coating, a reduced pressure drying method in which the temperature is not increased but the drying is carried out in a reduced pressure box can also be used.

[0392] [3-5] Exposure process

[0393] Image exposure is performed as follows: a negative matrix pattern is superimposed on the coating film of the colored resin composition, and a light source of ultraviolet or visible light is irradiated through the matrix pattern. At this time, in order to prevent the sensitivity of the photopolymer layer from decreasing due to oxygen, an oxygen blocking layer such as a polyvinyl alcohol layer may be formed on the photopolymer layer as needed before exposure. The light source used in the above image exposure is not particularly limited. As the light source, for example, a xenon lamp, a halogen lamp, a tungsten lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, a medium-pressure mercury lamp, a low-pressure mercury lamp, a carbon arc, a fluorescent lamp, or a laser light source such as an argon ion laser, a YAG laser, an excimer laser, a nitrogen laser, a helium-cadmium laser, a semiconductor laser, etc. When irradiating with light of a specific wavelength, an optical filter can also be used.

[0394] [3-6] Development process

[0395] After the coating film using the colored resin composition of the present invention is image-exposed using the above-mentioned light source, it is developed using an organic solvent or an aqueous solution containing a surfactant and an alkaline compound, thereby forming an image on the substrate, thereby manufacturing the color filter of the present invention. The aqueous solution may further contain an organic solvent, a buffer, a complexing agent, a dye or a pigment.

[0396] As the alkaline compound, there can be listed inorganic alkaline compounds such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, potassium phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide; organic alkaline compounds such as monoethanolamine, diethanolamine or triethanolamine, monomethylamine, dimethylamine or trimethylamine, monoethylamine, diethylamine or triethylamine, monoisopropylamine or diisopropylamine, n-butylamine, monoisopropanolamine, diisopropanolamine or triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH), choline, etc. These alkaline compounds can also be a mixture of two or more.

[0397] Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, and monoglycerol alkyl esters; anionic surfactants such as alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfonates, and sulfosuccinates; and amphoteric surfactants such as alkyl betaines and amino acids.

[0398] 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 in combination with an aqueous solution.

[0399] The conditions for the development treatment are not particularly limited, but the development temperature is preferably in the following range: usually 10° C. or higher, preferably 15° C. or higher, more preferably 20° C. or higher, and usually 50° C. or lower, preferably 45° C. or lower, more preferably 40° C. or lower. The development method may be any of immersion development, spray development, brush development, ultrasonic development, and the like.

[0400] [3-7] Thermal curing treatment

[0401] The developed color filter is subjected to a heat curing treatment. As the heat curing treatment conditions at this time, the temperature is selected in the following range: usually above 100°C, preferably above 150°C, and usually below 280°C, preferably below 250°C; the time is selected in the range of 5 minutes to 60 minutes. After this series of steps, the image formation of a pattern of one color is completed. Repeat this process in sequence to pattern black, red, green, and blue to form a color filter. It should be noted that the order of pattern formation of these four colors is not limited to the above order.

[0402] [3-8] Formation of transparent electrodes

[0403] The color filter of the present invention can directly form a transparent electrode such as ITO on the image in such a state, and be used as a part of a component of a color display, a liquid crystal display device, etc., but in order to improve the surface smoothness and durability, a surface coating of polyamide, polyimide, etc. can also be provided on the image as needed. In addition, in some uses such as a planar alignment drive mode (IPS mode), a transparent electrode is sometimes not formed.

[0404] [4] Image display device (panel)

[0405] Next, the image display device of the present invention is described. The image display device of the present invention has the above-mentioned color filter. Hereinafter, a liquid crystal display device and an organic EL display device as image display devices are described in detail.

[0406] [4-1] Liquid crystal display device

[0407] The manufacturing method of the liquid crystal display device of the present invention is described. The liquid crystal display device of the present invention is usually completed by the following operation, that is, an orientation film is formed on the color filter of the present invention, and after distributing spacers on the orientation film, it is bonded to the opposing substrate to form a liquid crystal box, and liquid crystal is injected into the formed liquid crystal box and connected to the opposing electrode. The orientation film is preferably a resin film of polyimide or the like. When the orientation film is formed, the thickness of the orientation film is set to several 10nm by gravure printing and / or flexographic printing. After the orientation film is cured by thermal sintering, it is surface treated by ultraviolet irradiation or rubbing cloth treatment to be processed into a surface state that can adjust the tilt of the liquid crystal.

[0408] The spacer can be a spacer of a size corresponding to the gap of the opposing substrate, and 2 to 8 μm is usually preferred. A photosensitive spacer (PS) of a transparent resin film is formed on the color filter substrate by photolithography, and is used instead of the spacer. As the opposing substrate, an array substrate is usually used, and a TFT (thin film transistor) substrate is particularly preferred.

[0409] The gap between the sheet and the opposing substrate varies depending on the purpose of the liquid crystal display device, but is usually selected within a range of 2 μm to 8 μm. After being bonded to the opposing substrate, the portion other than the liquid crystal injection port is sealed with a sealing material such as epoxy resin. The sheet is cured by UV irradiation and / or heating, and the periphery of the liquid crystal cell is sealed.

[0410] After the sealed liquid crystal box is disconnected from the panel unit, the vacuum container is depressurized, the liquid crystal injection port is immersed in liquid crystal, and then leaks into the container, thereby injecting liquid crystal into the liquid crystal box. The degree of decompression in the liquid crystal box is usually 1×10 -2 Pa or more, preferably 1×10 -3 Pa or more, and usually 1×10 -7 Pa or less, preferably 1×10 - 6 The liquid crystal cell is preferably heated under 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.

[0411] The heating and holding during the decompression is usually set in the range of 10 minutes to 60 minutes, and then immersed in liquid crystal. The liquid crystal cell into which the liquid crystal is injected is cured by curing the UV curable resin to seal the liquid crystal injection port, thereby completing the liquid crystal display device (panel).

[0412] The type of liquid crystal is not particularly limited, and it can be currently known liquid crystals such as aromatic, aliphatic, and polycyclic compounds, or any of 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 them can be used.

[0413] [4-2] Organic EL display device

[0414] When an organic EL display having a color filter of the present invention is produced, for example, Figure 1 As shown, the colored resin composition of the present invention is used to form pixels 20 on a transparent supporting substrate 10, and an organic light emitting body 500 is stacked on the blue color filter having the pixels 20 via an organic protective layer 30 and an inorganic oxide film 40, thereby manufacturing a multi-color organic EL element.

[0415] As a lamination method of the organic light emitting body 500, there can be cited: 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; a method of laminating an organic light emitting body 500 formed on another substrate on an inorganic oxide film 40, etc. The organic EL element 100 manufactured in this way can be applied to an organic EL display device of a passive driving mode, and can also be applied to an organic EL display device of an active driving mode.

[0416] Example

[0417] Next, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the present invention is not limited to the following Examples unless the scope of the invention exceeds the scope of the invention.

[0418] In addition, as the medium pressure liquid chromatography described in the synthesis examples, a medium pressure preparative chromatography apparatus W-Prep (flow rate 20 mL / min, silica gel 30 μm column) manufactured by Yamazen Co., Ltd. was used.

[0419] <Synthesis Example 1: Synthesis of Dye A>

[0420] After mixing 4.00 g (20 mmol) of tetrafluorophthalonitrile, 2.90 g (5.0 mmol) of potassium fluoride and 10 mL of acetone and cooling with ice, a solution of 6.65 g (40 mmol) of ethyl p-hydroxybenzoate in acetone (30 mL) was added, and the mixture was stirred for 5 hours. After the reaction was completed, the reaction solution was filtered and concentrated, 60 mL of ethanol was added, and the precipitate was separated by filtration and dried to obtain 6.20 g (yield 63%, purity 97.6%) of intermediate A. It should be noted that the purity is the value of area % calculated from the results of high performance liquid chromatography analysis.

[0421] [Chemical formula 33]

[0422]

[0423] In the formula, Et represents an ethyl group.

[0424] 1 H-NMR (CDCl3)

[0425] δ: 1.38(t,6H), 4.36(m,4H), 6.81(d,4H), 7.98(d,4H)

[0426] 6.20 g (12.6 mmol) of intermediate A, 1.21 g (3.78 mmol) of zinc iodide and 12 mL of benzonitrile were mixed and reacted at 160° C. for 10 hours. After the reaction was completed, the reaction solution was cooled and put into 20 mL of ethanol. The generated solid component was washed with ethanol and dried under reduced pressure at 50° C., thereby obtaining 5.66 g (yield 88%) of dye A.

[0427] [Chemical formula 34]

[0428]

[0429] In the formula, Et represents an ethyl group.

[0430] 1 H-NMR (DMSO-d6)

[0431] δ: 1.30(t,24H), 4.27(m,16H), 7.26(d,16H), 7.79(d,16H)

[0432] 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 (U-4100 manufactured by Hitachi High-Technology Co., Ltd.) and a 1 cm square quartz cell. The results showed that the maximum absorption wavelength was 665.5 nm and the molar absorption coefficient (ε) was 1.195×105 .

[0433] <Synthesis Example 2: Synthesis of Dye B>

[0434] 3.02 g (15.0 mmol) of tetrafluorophthalonitrile, 4.14 g (30.0 mmol) of potassium carbonate and 50 mL of acetone were mixed and ice-cooled. A solution of 5.40 g (30.0 mmol) of n-propyl p-hydroxybenzoate in acetone (30 mL) was added at 2-4°C and stirred for 5 hours. After the reaction was completed, the reaction solution was filtered, dried with anhydrous magnesium sulfate, and the desiccant was separated by filtration. The solvent was concentrated, and the precipitated solid was filtered to obtain 4.0 g (yield 51%, purity 95.9%) of intermediate B. It should be noted that the purity is the value of area % calculated from the results of high performance liquid chromatography analysis.

[0435] [Chemical formula 35]

[0436]

[0437] In the formula, n-Pr represents n-propyl.

[0438] 1 H-NMR (CDCl3)

[0439] δ: 1.03(t,6H), 1.78(m,4H), 4.29(t,4H), 6.82(d,4H), 7.98(d,4H)

[0440] 1.00 g (2.15 mmol) of intermediate B, 0.21 g (0.65 mmol) of zinc iodide and 2.4 mL of benzonitrile were mixed and reacted at 170°C for 13 hours. After the reaction was completed, the reaction solution was cooled and put into 20 mL of methanol. The generated solid component was filtered, washed with methanol and water, and dried under reduced pressure at 50°C to obtain 0.33 g (yield 29%) of dye B.

[0441] [Chemical formula 36]

[0442]

[0443] In the formula, n-Pr represents n-propyl.

[0444] 1 H-NMR (DMSO-d6)

[0445] δ: 0.94(t,24H), 1.88(m,16H), 4.16(t,16H), 7.25(d,16H), 7.78(d,16H)

[0446] 1 mg of dye B was dissolved in 100 mL of DMSO, and the visible absorption spectrum was measured using a UV-visible spectrophotometer (U-4100 manufactured by Hitachi High-Technology Co., Ltd.) and a 1 cm square quartz cell. The results showed that the maximum absorption wavelength was 665.0 nm and the molar absorption coefficient (ε) was 1.202×10 5 .

[0447] <Synthesis Example 3: Synthesis of Dye C>

[0448] After 2.00 g (10 mmol) of tetrafluorophthalonitrile, 1.45 g (2.5 mmol) of potassium fluoride and 5 mL of acetone were mixed and ice-cooled, a solution of 3.89 g (20 mmol) of isobutyl p-hydroxybenzoate in acetone (5 mL) was added, and the mixture was stirred for 5 hours. After the reaction was completed, the reaction solution was filtered and concentrated, and the residue was purified by medium pressure liquid chromatography (developing solvent was a mixed solvent of hexane and acetic acid, gradient of 94:6 to 73:27 (volume ratio)), thereby obtaining 2.50 g (yield 46%, purity 97.8%) of intermediate C. It should be noted that the purity is the value of area % calculated from the results of high performance liquid chromatography analysis.

[0449] [Chemical formula 37]

[0450]

[0451] i-Bu in the formula represents an isobutyl group.

[0452] 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, the reaction solution was cooled and purified by medium pressure liquid chromatography (developing solvent: a mixed solvent of chloroform and methanol, 100:0 to 85:15 (volume ratio) gradient) to obtain 1.06 g (yield 41%) of dye C.

[0453] [Chemical formula 38]

[0454]

[0455] i-Bu in the formula represents an isobutyl group.

[0456] 1 H-NMR (DMSO-d6)

[0457] δ: 0.94(d,48H), 1.98(m,8H), 4.00(d,16H), 7.27(d,16H), 7.80(d,16H)

[0458] 1 mg of dye C was dissolved in 100 mL of DMSO, and the visible absorption spectrum was measured using a UV-visible spectrophotometer (U-4100 manufactured by Hitachi High-Technology Co., Ltd.) and a 1 cm square quartz cell. The results showed that the maximum absorption wavelength was 665.0 nm and the molar absorption coefficient (ε) was 1.156 × 10 5 .

[0459] <Synthesis Example 4: Synthesis of Dye D>

[0460] After 2.00 g (10 mmol) of tetrafluorophthalonitrile, 1.45 g (2.5 mmol) of potassium fluoride and 5 mL of acetone were mixed and ice-cooled, a solution of 3.78 g (21 mmol) of methyl 3-(4-hydroxyphenyl)propionate in acetone (5 mL) was added, and the mixture was 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 liquid chromatography (developing solvent was a mixed solvent of hexane and ethyl acetate, with a gradient of 94:6 to 73:27 (volume ratio)), thereby obtaining 3.00 g (yield 58%, purity 97.8%) of intermediate D. It should be noted that the purity is the value of area % calculated from the results of high performance liquid chromatography analysis.

[0461] [Chemical formula 39]

[0462]

[0463] 1 H-NMR (CDCl3)

[0464] δ: 2.58(t,2H), 2.90(t,2H), 3.67(s,3H), 6.70(d,2H), 7.09(d,2H)

[0465] 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, the reaction solution was cooled and purified by medium pressure liquid chromatography (developing solvent: a mixed solvent of chloroform and methanol, 100:0 to 93:7 (volume ratio) gradient), thereby obtaining 0.75 g (yield 70%) of dye D.

[0466] [Chemical formula 40]

[0467]

[0468] 1 mg of dye D was dissolved in 100 mL of DMSO, and the visible absorption spectrum was measured using a UV-visible spectrophotometer (U-4100 manufactured by Hitachi High-Technology Co., Ltd.) and a 1 cm square quartz cell. The results showed that the maximum absorption wavelength was 700.0 nm and the molar absorption coefficient (ε) was 2.278×10 5 .

[0469] <Synthesis Example 5: Synthesis of Dye E>

[0470] 5.00 g (18.8 mmol) of tetrachlorophthalonitrile, 7.30 g (37.6 mmol) of isobutyl p-hydroxybenzoate, 3.89 g (28.2 mmol) of potassium carbonate and 50 mL of acetonitrile were mixed, heated to 50 ° C, and stirred for 2 hours. After the reaction was completed, it was cooled to room temperature, and the reaction solution was filtered and concentrated. The obtained residue was purified by medium pressure liquid chromatography (the developing solvent was a mixed solvent of hexane and ethyl acetate, with a gradient of 100:0 to 86:14 (volume ratio)), thereby obtaining 0.49 g (yield 4.4%, purity 77.9%) of intermediate E. It should be noted that the purity is the value of area % calculated from the results of high performance liquid chromatography analysis.

[0471] [Chemical formula 41]

[0472]

[0473] i-Bu in the formula represents an isobutyl group.

[0474] 1 H-NMR (CDCl3)

[0475] δ: 1.03(d,6H), 2.09(m,1H), 4.11(d,2H), 6.70(d,2H), 7.99(d,2H)

[0476] 0.45 g (0.77 mmol) of intermediate E, 0.074 g (0.23 mmol) of zinc iodide and 1.0 g of benzonitrile were mixed and reacted at 170°C for 5 hours. After the reaction was completed, the reaction solution was cooled and put into 20 mL of methanol. The generated solid component was filtered, washed with methanol and water, and dried under reduced pressure at 50°C to obtain 0.32 g (yield 73%) of dye E.

[0477] [Chemical formula 42]

[0478]

[0479] iBu in the formula represents an isobutyl group.

[0480] 1 H-NMR (DMSO-d6)

[0481] δ: 1.00(d,6H), 2.01(m,1H), 4.03(d,2H), 6.95(d,2H), 7.87(d,2H)

[0482] 1 mg of dye E was dissolved in 100 mL of DMSO, and the visible absorption spectrum was measured using a UV-visible spectrophotometer (U-4100 manufactured by Hitachi High-Technology Co., Ltd.) and a 1 cm square quartz cell. The results showed that the maximum absorption wavelength was 697.0 nm and the molar absorption coefficient (ε) was 1.391×10 5 .

[0483] <Synthesis Example 6: Synthesis of Dye F>

[0484] 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 the mixture was reacted at 160° C. for 8 hours. After the reaction, the reaction solution was cooled and poured into 10 mL of ethanol. The generated solid component was washed with ethanol and dried under reduced pressure at 50° C., thereby obtaining 0.30 g (yield 48%) of dye F.

[0485] [Chemical formula 43]

[0486]

[0487] In the formula, Et represents an ethyl group.

[0488] 1 mg of dye F was dissolved in 100 mL of DMSO, and the visible absorption spectrum was measured using a UV-visible spectrophotometer (U-4100 manufactured by Hitachi High-Technology Co., Ltd.) and a 1 cm square quartz cell. The results showed that the maximum absorption wavelength was 698.0 nm and the molar absorption coefficient (ε) was 3.759 × 10 4 .

[0489] <Synthesis Example 7: Synthesis of Dye G>

[0490] 3.00 g (15.0 mmol) of tetrafluorophthalonitrile, 1.03 g (7.50 mmol) of potassium carbonate and 50 mL of acetonitrile were mixed and ice-cooled. A solution of 3.21 g (15.0 mmol) of phenyl p-hydroxybenzoate in acetonitrile (20 mL) was added at 2°C and stirred for 5 hours. After the reaction was completed, the reaction solution was filtered and concentrated. The obtained residue was purified by medium pressure liquid chromatography (developing solvent was a mixed solvent of hexane and ethyl acetate, with a gradient of 97:3 to 77:23 (volume ratio)), thereby obtaining 1.43 g (yield 24%, purity 94.8%) of intermediate G. It should be noted that the purity is the value of area % calculated from the results of high performance liquid chromatography analysis.

[0491] [Chemical formula 44]

[0492]

[0493] 1 H-NMR (CDCl3)

[0494] δ: 7.10(d,2H), 7.20(d,2H), 7.28(t,1H), 7.42(d,2H), 8.24(d,2H)

[0495] 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 put into 30 mL of methanol. The generated solid component 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.

[0496] [Chemical formula 45]

[0497]

[0498] Ph in the formula represents a phenyl group.

[0499] 1 mg of dye G was dissolved in 100 mL of DMSO, and the visible absorption spectrum was measured using a UV-visible spectrophotometer (U-4100 manufactured by Hitachi High-Technology Co., Ltd.) and a 1 cm square quartz cell. The results showed that the maximum absorption wavelength was 650.0 nm and the molar absorption coefficient (ε) was 8.826×10 4 .

[0500] <Synthesis Example 8: Synthesis of Dye H>

[0501] 2.55 g (12.7 mmol) of tetrafluorophthalonitrile, 1.76 g (12.7 mmol) of potassium carbonate and 30 mL of acetonitrile were mixed, and a solution of 5.35 g (25.5 mmol) of dimethyl 4-hydroxyisophthalate in acetonitrile (20 mL) 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 obtained residue was purified by medium pressure liquid chromatography (developing solvent was a mixed solvent of hexane and ethyl acetate, with a gradient of 78:22 to 50:50 (volume ratio)), thereby obtaining 0.30 g (yield 4.1%, purity 86.3%) of intermediate H. It should be noted that the purity is the value of area % calculated from the results of high performance liquid chromatography analysis.

[0502] [Chemical formula 46]

[0503]

[0504] Me in the formula represents a methyl group.

[0505] 1 H-NMR (CDCl3)

[0506] δ: 3.78(s,6H), 3.93(s,3H), 6.92(d,2H), 8.07(d,2H), 8.49(s,2H)

[0507] 1.00 g (1.72 mmol) of intermediate H, 0.165 g (0.52 mmol) of zinc iodide and 2.4 g of benzonitrile were mixed and reacted at 160°C for 7 hours. After the reaction, the reaction solution was cooled and concentrated. The obtained residue was purified by medium pressure liquid chromatography (the developing solvent was a mixed solvent of chloroform and methanol, with a gradient of 99:1 to 50:50 (volume ratio)), thereby obtaining 0.19 g (yield 16%) of dye H.

[0508] [Chemical formula 47]

[0509]

[0510] Me in the formula represents a methyl group.

[0511] 1 H-NMR (DMSO-d6)

[0512] δ: 3.56(s,24H), 3.86(s,24H), 7.17(d,8H), 8.01(d,8H), 8.25(s,8H)

[0513] 1 mg of dye H was dissolved in 100 mL of DMSO, and the visible absorption spectrum was measured using a UV-visible spectrophotometer (U-4100 manufactured by Hitachi High-Technology Co., Ltd.) and a 1 cm square quartz cell. The results showed that the maximum absorption wavelength was 668.0 nm and the molar absorption coefficient (ε) was 6.103×10 4 .

[0514] <Synthesis Example 9: Binder Resin A>

[0515] While nitrogen replacement was performed on 148.0 parts by mass of propylene glycol monomethyl ether acetate, the mixture was stirred 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 monoacrylate having a tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.) were added dropwise, and stirring was continued at 120°C for 2 hours. Next, the reaction vessel was changed to air replacement, 0.7 parts by mass of tris(dimethylaminomethyl)phenol 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 mixture was reacted at 120°C for 3.5 hours. The weight average molecular weight Mw of the binder resin A thus obtained, which was measured by GPC and converted to polystyrene, was 5700, and the acid value was 88 mgKOH / g. Propylene glycol monomethyl ether acetate was added to the resin so as to have a solid content of 58.7% by mass.

[0516] <Synthesis Example 10: Binder resin B>

[0517] The mixture was stirred while nitrogen replacement was performed with 145 parts by mass of propylene glycol monomethyl ether acetate, and the temperature was raised to 120°C. A mixed solution of 5.2 parts by mass of styrene, 132 parts by mass of glycidyl methacrylate, 4.4 parts by mass of monoacrylate 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 added dropwise over 3 hours, and stirring was continued at 90°C for 2 hours. Next, the reaction container was replaced with air, and 1.1 parts by mass of tris(dimethylaminomethyl)phenol 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 as measured by GPC and converted to polystyrene was 9000, and the acid value was 25 mgKOH / g. Propylene glycol monomethyl ether acetate was added to the resin so that the solid content was 59.5% by mass, and the resin was used.

[0518] <Synthesis Example 11: Binder Resin C>

[0519] As a reaction tank, a separable flask equipped with a condenser was prepared, 400 parts by mass of propylene glycol monomethyl ether acetate was charged, and after nitrogen substitution, the reaction tank was heated in an oil bath while stirring to raise the temperature of the reaction tank to 90°C.

[0520] On the other hand, 30 parts by mass of dimethyl-2,2'-[oxybis(methylene)]bis-2-propionate, 60 parts by mass of methacrylic acid, 110 parts by mass of cyclohexyl methacrylate, 5.2 parts by mass of tert-butyl peroxy(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 was stabilized at 90° C., the monomer tank and the chain transfer agent tank were started to drip to start polymerization. The temperature was kept at 90° C. while dripping for 135 minutes each. After 60 minutes after the dripping was completed, the temperature of the reaction tank was raised to 110° C.

[0521] After maintaining at 110°C for 3 hours, a gas introduction tube was installed on the separable flask to start bubbling of a mixed gas of oxygen / nitrogen = 5 / 95 (v / v). Next, 39.6 parts by mass of glycidyl methacrylate, 0.4 parts by mass of 2,2'-methylenebis(4-methyl-6-tert-butylphenol), and 0.8 parts by mass of triethylamine were added to the reaction tank, and the reaction was maintained at 110°C for 9 hours.

[0522] The mixture was cooled to room temperature to obtain a binder resin C having a weight average molecular weight Mw of 9000 in terms of polystyrene measured by GPC and an acid value of 101 mgKOH / g. Propylene glycol monomethyl ether acetate was added to the resin so that the solid content was 44.0% by mass.

[0523] <Dispersant A: BYK-LPN6919, manufactured by BYK-Chemie>

[0524] A methacrylic AB block copolymer comprising an A block having a nitrogen atom-containing functional group and a B block having a solvophilic group, having repeating units of the following formulae (2a) and (3a) but not having a repeating unit of the following formula (1a), and having an amine value of 120 mgKOH / g and an acid value of 1 mgKOH / g or less.

[0525] The content ratios of the following formulae (2a) and (3a) in all repeating units were 33.3 mol % and 6.7 mol %, respectively.

[0526] [Chemical formula 48]

[0527]

[0528] <Preparation of yellow pigment dispersion>

[0529] 12.0 parts by mass of CI Pigment Yellow 138, 3.0 parts by mass of dispersant A in terms of solid content, 6.0 parts by mass of binder resin C in terms of solid content, 79.0 parts by mass of propylene glycol monomethyl ether acetate as a solvent (including the amount of solvent from dispersant A and the amount of solvent from binder resin C), and 225 parts by mass of zirconia beads with a diameter of 0.5 mm were filled in a stainless steel container and dispersed for 6 hours using a paint shaker. Then, the beads and the dispersion were separated using a filter to prepare a yellow pigment dispersion.

[0530] <Preparation of green pigment dispersion>

[0531] 13.1 parts by mass of CI Pigment Green 58, 1.8 parts by mass of dispersant A in terms of solid content, 4.0 parts by mass of binder resin C in terms of solid content, 81.1 parts by mass of propylene glycol monomethyl ether acetate as a solvent (including the amount of solvent from dispersant A and the amount of solvent from binder resin C), and 225 parts by mass of zirconia beads with a diameter of 0.5 mm were filled in a stainless steel container and dispersed for 6 hours using a paint shaker. Then, the beads and the dispersion were separated using a filter to prepare a green pigment dispersion.

[0532] <Photopolymerization initiator A>

[0533] As the photopolymerization initiator A, 3-(2-acetoxyimino-1,5-dioxo-5-methoxypentyl)-9-ethyl-6-(o-toluoyl)-9H-carbazole synthesized according to the method described in International Publication No. 2009 / 131189 was used.

[0534] <Preparation of Colored Resin Composition>

[0535] 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 according to the compositions described in Tables 1 to 4 to prepare colored resin compositions.

[0536] In addition, in each component other than the solvent in Tables 1 to 4, the upper numerical value represents the content ratio (mass %) of each component to be added in the colored resin composition, and the lower numerical value represents the content ratio (mass %) of each component (solid content) in the total solid content.

[0537] During mixing, the mixture was stirred for 10 minutes or more until the components were fully mixed, and then ultrasonic treatment was performed for 10 minutes at 23° C. Finally, foreign matter was removed by filtration through a saddle filter with a pore size of 5 μm.

[0538] [Table 1]

[0539]

[0540] [Table 2]

[0541]

[0542] [Table 3]

[0543]

[0544] [Table 4]

[0545]

[0546] The abbreviations and the like in Tables 1 to 4 are as follows, respectively.

[0547] F559: Megafac (registered trademark) F-559 (manufactured by DIC Corporation, perfluoroalkyl group-containing oligomer)

[0548] BYK330: BYK (registered trademark)-330 (manufactured by BYK-Chemie, polyether-modified polydimethylsiloxane)

[0549] PGMEA: Propylene glycol monomethyl ether acetate

[0550] PGME: Propylene glycol monomethyl ether

[0551] <Measurement of thin film X-ray diffraction spectrum>

[0552] On a glass substrate (manufactured by AGC, AN100) cut into 5 cm squares and 0.7 mm thick, each of the colored resin compositions of Examples 1 to 8 and Comparative Examples 1 to 4 described in Tables 1 to 3 was applied by spin coating so that the film thickness after firing was 2 μm, and after drying under reduced pressure, it was pre-baked on a hot plate at 80° C. for 3 minutes. Then, a 2 kW high-pressure mercury lamp was used to heat the glass substrate at 32 mW / cm 2 、60mJ / cm 2 The entire surface was exposed to an exposure amount of , and then baked in a clean oven at 230° C. for 30 minutes to obtain a colored cured film.

[0553] The obtained colored cured film was used to measure the thin film X-ray diffraction spectrum. The measuring device used was an X-ray diffractometer for thin film samples using CuKα rays as the radiation source (manufactured by Rigaku Co., Ltd., automatic X-ray diffractometer RINT2000). As the measuring conditions, an out-of-plane method with an X-ray output power of 50 kV, 250 mA, a fixed incident angle (θ) of 0.20°, a scanning range (2θ) of 2 to 40°, and a scanning speed of 3.0° / min. was adopted.

[0554] The presence or absence of a maximum peak in the diffraction angle (2θ) range of 2 to 5° was confirmed from the obtained X-ray diffraction spectrum. When a maximum peak was present, the diffraction angle of the peak top and the full width at half maximum of the peak were calculated, and the results are shown in Table 5. It should be noted that for dyes F to H of Comparative Examples 1 to 4, no maximum peak was observed within the measurement range (2 to 5°).

[0555] The full width at half maximum was calculated using analysis software "PDXL" manufactured by Rigaku Co., Ltd. The maximum peak refers to a peak whose peak top intensity present within the measurement range (2 to 5°) is the maximum value within the measurement range.

[0556] 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.

[0557] [Table 5]

[0558]

[0559] The colored resin composition of Example 1 was applied by spin coating on a glass substrate (manufactured by AGC Corporation, AN100) cut into 5 cm squares and having a thickness of 0.7 mm, so that the film thickness after firing was 2 μm, and after drying under reduced pressure, it was pre-baked on a hot plate at 80° C. for 3 minutes, and heated with a 2 kW high-pressure mercury lamp at 32 mW / cm 2 、60mJ / cm 2 The entire surface was exposed with an exposure amount of , and the resulting colored coating film (not calcined at 230°C for 30 minutes in a clean oven) was used to measure the thin film X-ray diffraction spectrum in the same order. The results showed that the diffraction angle of 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 I1 / I2 was 1.29.

[0560] <Evaluation of Color Characteristics (Examples 1 to 5 and Comparative Examples 1 to 3)>

[0561] On a glass substrate (manufactured by AGC, AN100) cut into 5 cm squares and 0.7 mm thick, each of the colored resin compositions of Examples 1 to 8 and Comparative Examples 1 to 4 described in Tables 1 to 3 was applied by spin coating so that the film thickness after firing was 2 μm, and after drying under reduced pressure, it was pre-baked on a hot plate at 80° C. for 3 minutes. Then, a 2 kW high-pressure mercury lamp was used to heat the glass substrate at 32 mW / cm 2 、60mJ / cm 2 After the entire surface was exposed to an exposure amount of , the film was baked in a clean oven at 230° C. for 30 minutes. The spectral transmittance of the obtained colored cured film was measured using a spectrophotometer U-3310 (manufactured by Hitachi, Ltd.) to obtain a transmission spectrum.

[0562] Next, a colored cured film was prepared in the same manner except that the colored resin composition of Reference Example 1 described in Table 4 was used so as to adjust the film thickness after firing to 2.32 μm, and the spectral transmittance was measured to obtain a transmission spectrum.

[0563] 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 were adjusted so that the chromaticity (SB2 light source) in the XYZ colorimetric system became sx=0.304 and sy=0.607, and a synthetic spectrum was obtained, and the brightness (SB2 light source) was calculated. The results are shown in Table 6.

[0564] [Table 6]

[0565] dye sx sy brightness Example 1 Dye A 0.304 0.607 64.0 Example 2 Dye B 0.304 0.607 62.5 Example 3 Dye C 0.304 0.607 62.6 Example 4 Dye D 0.304 0.607 62.5 Example 5 Dye E 0.304 0.607 58.9 Comparative Example 1 Dye F 0.304 0.607 27.2 Comparative Example 2 Dye G 0.304 0.607 55.5 Comparative Example 3 Dye H 0.304 0.607 30.9

[0566] <Evaluation of Color Characteristics (Examples 6 to 8 and Comparative Example 4)>

[0567] The colored resin compositions of Examples 6 to 8 and Comparative Example 4 described in Tables 2 and 3 were applied by spin coating on a glass substrate (manufactured by AGC, AN100) cut into 5 cm squares and 0.7 mm thick, and dried under reduced pressure, and then pre-baked on a hot plate at 80° C. for 3 minutes. Then, the colored resin compositions were heated to 32 mW / cm2 using a 2 kW high-pressure mercury lamp. 2 、60mJ / cm 2 After the entire surface was exposed to an exposure amount of , the film was fired in a clean oven at 230°C for 30 minutes. In addition, the spectral transmittance of the obtained colored cured film was measured using a spectrophotometer U-3310 (manufactured by Hitachi, Ltd.) to obtain a transmission spectrum. It should be noted that the film thickness of the colored cured film is as shown in Table 7.

[0568] Next, using this transmission spectrum, the film thickness was adjusted so that the chromaticity (SB2 light source) in the XYZ colorimetric system would be sy=0.607, and the brightness at that time was calculated. The results are shown in Table 7.

[0569] The contrast of the colored cured film was measured using a contrast meter (CT-1: manufactured by Tsubosaka Electric Co., Ltd., colorimeter BM-5AS: manufactured by TOPCON, light source: F-10, polarizing plate: manufactured by Tsubosaka Electric Co., Ltd.) with the blank set to 18000. The results are shown in Table 7.

[0570] [Table 7]

[0571]

[0572] As can be seen from Table 6, the brightness of the colored resin compositions of Examples 1 to 5 containing the dyes A to E is high, whereas the brightness of the colored resin compositions of Comparative Examples 1 to 3 containing the dyes F to H is low.

[0573] As is clear from Table 5, it is believed that the dyes A to E contained in Examples 1 to 5 have a maximum peak in the diffraction angle (2θ) range of 2 to 5° in the thin film X-ray diffraction spectrum using CuKα rays after heating at 230°C, and that zinc phthalocyanine dye molecules are associated with each other and crystallized in the firing process when the colored cured film is obtained. Therefore, it is believed that the electronic state of the dye changes, the maximum absorption wavelength of the main absorption is shortened to around 640 to 660 nm, and the tail on the short wavelength side of the absorption peak is reduced, showing a sharp rise, thereby achieving high brightness.

[0574] On the other hand, since 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 rays after heating at 230°C, crystallization of the zinc phthalocyanine dye did not proceed in the firing step when obtaining the colored cured film, and the electronic state change of the dye and the accompanying absorption spectrum change were small. Therefore, it is believed that the absorption near 620nm is small, similar to before heating, and the content ratio of the dye required for adjustment to a given chromaticity is increased, thereby reducing the brightness.

[0575] Moreover, from the comparison of Examples 6 to 8 and Comparative Example 4 in Table 7, it was confirmed that when a coloring agent other than the zinc phthalocyanine dye (a1) was further included, the brightness was high and the contrast was high.

[0576] While the present invention has been described in detail and with reference to specific embodiments, it will be apparent to one skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the present invention.

Claims

1. A colored resin composition comprising: (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), and in a thin film X-ray diffraction spectrum of the zinc phthalocyanine dye (a1) using CuKα rays after heating at 230° C., the zinc phthalocyanine dye (a1) has a maximum peak in a diffraction angle (2θ) range of 2 to 5°, The zinc phthalocyanine dye (a1) is a zinc phthalocyanine dye represented by the following general formula (1): In formula (1), A 1 ~A 16 Each independently represents a fluorine atom or a group represented by the following general formula (2), and A 1 ~A 16 One or more and 15 or less of them are groups represented by the following general formula (2), In formula (2), X represents a divalent linking group, the benzene ring in formula (2) has a substituent selected from an alkoxycarbonyl group and an alkyl group substituted with an alkoxycarbonyl group, * represents a bonding position, The (C) alkali-soluble resin contains a resin (C-1), wherein the resin (C-1) is a resin obtained by adding an unsaturated monobasic acid to at least a part of the epoxy groups of a copolymer of an epoxy-containing (meth)acrylate and other free radical polymerizable monomers, or a resin obtained by adding a polyacid anhydride to at least a part of the hydroxyl groups generated by the addition reaction of the polyacid anhydride.

2. The colored resin composition according to claim 1, wherein The diffraction angle of the peak top of the maximum peak of the zinc phthalocyanine dye (a1) 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 of the zinc phthalocyanine dye (a1) is 3.5° or more.

4. The colored resin composition according to claim 1 or 2, wherein The (A) colorant further comprises a yellow pigment and / or a yellow dye.

5. The colored resin composition according to claim 1 or 2, wherein The content of the zinc phthalocyanine dye (a1) in the total solid content is 5% by mass or more. The colored resin composition according to claim 1 or 2, further comprising a photopolymerizable monomer. 7 . The colored resin composition according to claim 1 , which is used for forming pixels of a color filter.

8. The colored resin composition according to claim 1 or 2, wherein The content ratio of the (C) alkali-soluble resin is in the range of 5 to 50% by mass in the total solid content of the colored resin composition.

9. The colored resin composition according to claim 1 or 2, wherein The content of the (C) alkali-soluble resin is in the range of 20 to 25% by mass in the total solid content of the colored resin composition. 10 . A color filter having pixels formed using the colored resin composition according to claim 1 .

11. An image display device comprising the color filter according to claim 10.

Images