Colorant-containing liquid, colored resin composition, color filter, image display device, and method for producing colored resin composition

Abstract

Provided is a colored resin composition which has little decrease in exposure sensitivity even in storage over time after preparation of the composition. The colored resin composition contains (A) a colorant, (B) a solvent, (C) an alkali-soluble resin, (D) a photopolymerization initiator, and contains a compound having a specific structure and / or a benzoquinone compound, wherein the colorant (A) contains a phthalocyanine compound having a specific structure.

Description

Technical Field

[0001] The present invention relates to a colorant-containing liquid, a colored resin composition, a color filter, an image display device, and a method for producing the colored resin composition.

[0002] This application claims priority based on Japanese Patent Application No. 2022-161334 filed in Japan on October 6, 2022, and Japanese Patent Application No. 2022-161335 filed in Japan on October 6, 2022, the contents of which are incorporated herein by reference. Background Art

[0003] Conventionally, pigment dispersion, dyeing, electrodeposition, and printing methods are known as methods for manufacturing color filters for liquid crystal display devices, etc. Among them, the pigment dispersion method is the most widely used because it has excellent average properties 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 coloring material that determines the color of a color filter, pigments are generally used from the perspectives of heat resistance and light resistance, but pigments, especially high brightness, are gradually failing to meet market demand, and research is being actively conducted on using dyes as coloring materials instead of pigments.

[0005] For example, research has been conducted on the use of phthalocyanine dyes for green pixel applications (see, for example, Patent Document 1), and research has been conducted on the use of xanthene dyes for blue pixel applications (see, for example, Patent Document 2).

[0006] On the other hand, Patent Document 3 describes that a curable composition containing a specific photopolymerization initiator can achieve satisfactory compatibility between sensitivity and the transparency and brightness of a cured product.

[0007] Prior art literature

[0008] Patent Literature

[0009] Patent Document 1: Japanese Patent Application Publication No. 2019-113732

[0010] Patent Document 2: International Publication No. 2018 / 052022

[0011] Patent Document 3: Japanese Patent Application Publication No. 2017-179211 Summary of the invention

[0012] Problem that the invention aims to solve

[0013] The present inventors have conducted research and found that, for the colored resin composition containing a dye as described in Patent Documents 1 and 2, the exposure sensitivity of the colored resin composition is greatly reduced due to storage over time after the preparation of the colored resin composition, and pattern formation becomes difficult. As a result, it is clear that there is a problem that a high-definition color filter that can cope with 4K and 8K resolutions and requires precise line width adjustment cannot be stably manufactured.

[0014] Therefore, an object of the present invention is to provide a colorant-containing liquid that can suppress a decrease in exposure sensitivity of a colored resin composition even during storage over time after preparation of the colored resin composition, and a colored resin composition in which a decrease in exposure sensitivity is small even during storage over time after preparation of the composition.

[0015] Solutions for solving problems

[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 polymerization inhibitor in a coloring resin composition containing a specific dye, thereby completing the present invention.

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

[0018] [1] A colorant-containing liquid comprising (A) a colorant, (B) a solvent, and a compound represented by the following general formula (3) and / or a benzoquinone compound,

[0019] The colorant (A) contains a phthalocyanine compound having a chemical structure represented by the following general formula (1):

[0020] The total content of the compound represented by the following general formula (3) and the benzoquinone-based compound is 0.05 parts by mass or more and 10 parts by mass or less relative to 100 parts by mass of the phthalocyanine compound.

[0021]

[0022] (In formula (1), A 1 ~A 16 Each independently represents a hydrogen atom, a halogen atom, or a group represented by the following general formula (2). 1 ~A 16 One or more of them represent a fluorine atom or a group represented by the following general formula (2).

[0023]

[0024] (In formula (2), X represents a divalent linking group. The benzene ring in formula (2) may have any substituent. * represents a linking bond.)

[0025]

[0026] (In formula (3), R a , R b , R c , R d and R f Each independently represents a hydrogen atom, an unsubstituted alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, and R e represents a hydrogen atom or an unsubstituted alkyl group having 1 to 6 carbon atoms.

[0027] [2] The colorant-containing liquid according to [1], wherein the content of the phthalocyanine compound is 50% by mass or more and 99.5% by mass or less relative to the total solid content of the colorant-containing liquid.

[0028] [3] The colorant-containing liquid according to [1], further comprising (E) a dispersant.

[0029] [4] The colorant-containing liquid according to [3], wherein the content ratio of the (A) colorant to the (E) dispersant ((A) colorant / (E) dispersant) based on mass is 10 or more.

[0030] [5] A colored resin composition comprising: the colorant-containing liquid described in [1], (C) an alkali-soluble resin, and (D) a photopolymerization initiator.

[0031] [6] The colored resin composition according to [5], wherein the total content of the compound represented by the formula (3) and the benzoquinone compound is 30 parts by mass or less relative to 100 parts by mass of the (D) photopolymerization initiator.

[0032] [7] The colored resin composition according to [5], wherein the colorant (A) further contains another colorant in addition to the phthalocyanine compound.

[0033] [8] A color filter having pixels produced using the colored resin composition described in [5].

[0034] [9] An image display device comprising the color filter described in [8].

[0035]

[10] A colored resin composition comprising (A) a colorant, (B) a solvent, (C) an alkali-soluble resin, and (D) a photopolymerization initiator, and comprising a compound represented by the following general formula (3) and / or a benzoquinone compound,

[0036] The colorant (A) contains a phthalocyanine compound having a chemical structure represented by the following general formula (1).

[0037]

[0038] (In formula (1), A 1 ~A 16 Each independently represents a hydrogen atom, a halogen atom, or a group represented by the following general formula (2). 1 ~A 16 At least one of A represents a fluorine atom, and A 1 ~A 16 One or more of them represent a group represented by the following general formula (2).

[0039]

[0040] (In formula (2), X represents a divalent linking group. The benzene ring in formula (2) may have any substituent. * represents a linking bond.)

[0041]

[0042] (In formula (3), R a , R b , R c , R d and R f Each independently represents a hydrogen atom, an unsubstituted alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, and R e represents a hydrogen atom or an unsubstituted alkyl group having 1 to 6 carbon atoms.

[0043]

[11] The colored resin composition according to

[10] , wherein the total content of the compound represented by the formula (3) and the benzoquinone-based compound is 0.001% by mass or more in the total solid content of the colored resin composition.

[0044]

[12] The colored resin composition according to

[10] , wherein the total content of the compound represented by the formula (3) and the benzoquinone-based compound is 0.02% by mass or more in the total solid content of the colored resin composition.

[0045]

[13] The colored resin composition according to

[10] , wherein the total content of the compound represented by the formula (3) and the benzoquinone-based compound is 0.80% by mass or less in the total solid content of the colored resin composition.

[0046]

[14] The colored resin composition according to

[10] , wherein the content of the phthalocyanine compound is 5% by mass or more and 80% by mass or less in the total solid content of the colored resin composition.

[0047]

[15] The colored resin composition according to

[10] , wherein the total content of the compound represented by the formula (3) and the benzoquinone-based compound is 20 parts by mass or less per 100 parts by mass of the (D) photopolymerization initiator.

[0048]

[16] The colored resin composition according to

[10] , wherein the colorant (A) further contains another colorant in addition to the phthalocyanine compound.

[0049]

[17] A color filter having pixels produced using the colored resin composition according to any one of

[10] to

[16] .

[0050]

[18] An image display device comprising the color filter described in

[17] .

[0051]

[19] A method for producing a colored resin composition, the colored resin composition comprising (A) a colorant, (B) a solvent, (C) an alkali-soluble resin, and (D) a photopolymerization initiator, and comprising a compound represented by the following general formula (3) and / or a benzoquinone-based compound,

[0052] In the production method, a phthalocyanine compound having a chemical structure represented by the following general formula (1) is blended as the colorant (A).

[0053] In the production of the colored resin composition, the phthalocyanine compound is mixed with a compound represented by the following general formula (3) and / or a benzoquinone compound before the phthalocyanine compound is mixed with the (D) photopolymerization initiator.

[0054]

[0055] (In formula (1), A 1 ~A 16 Each independently represents a hydrogen atom, a halogen atom, or a group represented by the following general formula (2). 1 ~A 16 At least one of A represents a fluorine atom, and A 1 ~A 16 One or more of them represent a group represented by the following general formula (2).

[0056]

[0057] (In formula (2), X represents a divalent linking group. The benzene ring in formula (2) may have any substituent. * represents a linking bond.)

[0058]

[0059] (In formula (3), R a , R b , Rc , R d and R f Each independently represents a hydrogen atom, an unsubstituted alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, and R e represents a hydrogen atom or an unsubstituted alkyl group having 1 to 6 carbon atoms.

[0060]

[20] The method for producing a colored resin composition according to

[19] , wherein the total amount of the compound represented by the formula (3) and the benzoquinone compound is 0.001% by mass or more in the total solid content of the colored resin composition.

[0061]

[21] The method for producing a colored resin composition according to

[19] , wherein the total amount of the compound represented by the formula (3) and the benzoquinone-based compound is 0.02% by mass or more in the total solid content of the colored resin composition.

[0062]

[22] The method for producing a colored resin composition according to

[19] , wherein the total amount of the compound represented by the formula (3) and the benzoquinone-based compound is 0.80% by mass or less in the total solid content of the colored resin composition.

[0063] Effects of the Invention

[0064] According to the present invention, it is possible to provide a colorant-containing liquid capable of suppressing a decrease in the exposure sensitivity of a colored resin composition even during storage over time after the colored resin composition is prepared.

[0065] According to the present invention, it is possible to provide a colored resin composition in which a decrease in exposure sensitivity is small even during storage over time after preparation of the composition. BRIEF DESCRIPTION OF THE DRAWINGS

[0066] Figure 1 It is a schematic cross-sectional view showing an example of an organic EL display element having the color filter of the present invention. DETAILED DESCRIPTION

[0067] In the present invention, the "weight average molecular weight" refers to a polystyrene-equivalent weight average molecular weight (Mw) based on GPC (gel permeation chromatography).

[0068] In the present invention, the "total solid content" refers to all components other than the solvent in the liquid containing the colorant or the colored resin composition. Even if the components other than the solvent are liquid at room temperature, the components are not included in the solvent but are included in the total solid content.

[0069] In the present invention, the "amine value" means the amine value converted to the effective solid content unless otherwise specified, and is a value represented by the mass of KOH equivalent to the amount of alkali per 1 g of the solid content.

[0070] In the present invention, the acid value refers to the acid value converted into effective solid content unless otherwise specified, and is calculated by neutralization titration.

[0071] In the present invention, "CI" means Color Index.

[0072] In the present invention, “(meth)acrylic acid” means “either or both of acrylic acid and methacrylic acid”.

[0073] In the present invention, a numerical range expressed using "to" means a range including the numerical values ​​described before and after "to" as the lower limit and the upper limit.

[0074] [1] Liquid containing colorant

[0075] The colorant-containing liquid of the present invention contains (A) a colorant, (B) a solvent, and a compound represented by formula (3) and / or a benzoquinone compound as essential components, and may further contain other additives other than the above components, if necessary.

[0076] [1-1] (A) Colorant

[0077] The colorant-containing liquid of the present invention contains (A) a colorant. The (A) colorant is a component that colors the colorant-containing liquid. By containing the (A) colorant, desired light absorption can be obtained.

[0078] The colorant (A) in the colorant-containing liquid of the present invention includes a phthalocyanine compound having a chemical structure represented by the following general formula (1) (hereinafter sometimes referred to as "phthalocyanine compound (1)"). By including the phthalocyanine compound (1), the transmittance is improved, and a colored resin composition with high brightness can be obtained.

[0079]

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

[0081]

[0082] In formula (2), X represents a divalent linking group. The benzene ring in formula (2) may have any substituent. * represents a linking bond.

[0083] (A 1 ~A 16)

[0084] In formula (1), A 1 ~A 16 Each independently represents a hydrogen atom, a halogen atom, or a group represented by the following general formula (2). 1 ~A 16 One or more of represents a fluorine atom or a group represented by the following general formula (2). From the viewpoint of heat resistance and solubility, A is preferably 1 ~A 16 One or more of A represents a fluorine atom, and A 1 ~A 16 One or more of represents a group represented by the following general formula (2).

[0085]

[0086] In formula (2), X represents a divalent linking group. The benzene ring in formula (2) may have any substituent. * represents a linking bond.

[0087] As A 1 ~A 16 Examples of the halogen atom in the photosensitive resin include a fluorine atom, a chlorine atom, and a bromine atom. From the viewpoint of increasing brightness, a fluorine atom is preferred.

[0088] Preferred A 1 ~A 16 At least one fluorine atom is more preferably 6 or more, further preferably 7 or more, and particularly preferably 8 or more. Also, it is preferably 15 or less, more preferably 12 or less, and further preferably 10 or less. When it is equal to or more than the above lower limit, the stability of the phthalocyanine compound (1) tends to be improved, and when it is equal to or less than the above upper limit, the affinity with the dispersant and the solvent in the colored resin composition tends to be improved.

[0089] The above upper and lower limits can be combined arbitrarily. 1 ~A 16 The number of the substituents representing fluorine atoms in is 1-15, preferably 6-12, more preferably 7-10.

[0090] (X)

[0091] X in formula (2) 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 (R a1 represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 6 carbon atoms). From the viewpoint of the stability of the phthalocyanine compound (1) during calcination, an oxygen atom or a sulfur atom is preferred, and an oxygen atom is more preferred.

[0092] (Substituents optionally possessed by benzene ring)

[0093] 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 alkyl), alkoxy (-OR A Base (where R A represents an alkyl group. )), alkoxycarbonyl (-COOR A Base (where R A represents an alkyl group. )), an aryl group (-R B yl), aryloxy (-OR B Base (where R B Represents an aryl group. )), aryloxycarbonyl (-COOR B Base (where R B represents an aryl group.)) From the viewpoint of development solubility and brightness, an alkoxycarbonyl group is preferred.

[0094] The alkyl groups contained in these groups may be linear, branched or cyclic, but are preferably linear in view of affinity with organic solvents.

[0095] The carbon number of the alkyl group is not particularly limited, and is usually 1 or more, preferably 2 or more, and preferably 6 or less, more preferably 5 or less, and further preferably 4 or less. By setting the above lower limit or more, there is a tendency to suppress aggregation and foreign matter. In addition, by setting the above upper limit or less, there is a tendency to improve solvent affinity and improve stability over time.

[0096] The above upper and lower limits may be arbitrarily combined. For example, the number of carbon atoms in the alkyl group is preferably 1 to 6, more preferably 1 to 5, and even more preferably 2 to 4.

[0097] Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group. From the viewpoint of suppressing aggregation, a methyl group or an ethyl group is preferred, and an ethyl group is more preferred.

[0098] The aryl group contained in these groups may be an aromatic hydrocarbon ring group or an aromatic heterocyclic group.

[0099] The carbon number of the aryl group is not particularly limited, and 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. By setting it to above the aforementioned lower limit, there is a tendency to suppress aggregation caused by steric repulsion. In addition, by setting it to below the aforementioned upper limit, there is a tendency to improve solvent affinity and improve stability over time.

[0100] The above upper and lower limits may be arbitrarily combined. For example, the number of carbon atoms in the aryl group is preferably 4 to 12, more preferably 4 to 10, and even more preferably 6 to 8.

[0101] 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 a benzene ring, a naphthalene ring, a pentalene ring, an indene ring, an azulene ring, and a heptalene ring having one free valence.

[0102] 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-oxazole ring, an isoxazole ring, a 1,3-thiazole ring, an isothiazole ring, an imidazole ring, a pyrazole ring, a furazan ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, a 1,3,5-triazine ring, a benzofuran ring, a 2-benzofuran ring, a benzothiophene ring, a 2-benzothiophene ring, a 1H-pyrrolidine ring, an indole ring, an isoindole ring, an indolizine ring, a 2H-benzopyran ring, a 1H-2-benzopyran ring, a quinoline ring, an isoquinoline ring, a 4H-quinolizine ring, a benzimidazole ring, a 1H-indazole ring, a quinoxaline ring, a quinazoline ring, a cinnoline ring, a phthalazine ring, a 1,8-naphthyridine ring, a purine ring, and a pteridine ring.

[0103] When the benzene ring in formula (2) has any substituent, the number of substitution is not particularly limited. From the viewpoint of improving heat resistance by π-π stacking between dye molecules and suppressing brightness reduction caused by decomposition of the dye, the number of substitution is preferably 1 per benzene ring.

[0104] When the benzene ring in formula (2) has any substituent, the substitution position may be the ortho position, the meta position or the para position. From the viewpoint of promoting π-π stacking between molecules of the phthalocyanine compound (1), improving heat resistance and suppressing the reduction in brightness caused by the decomposition of the phthalocyanine compound (1), the para position is preferred.

[0105] From the viewpoint of solubility in organic solvents and brightness, it is preferred that: in formula (1), A 1 ~A 16 At least one of them is A 1 ~A 4 One or more of A is a group represented by formula (2), 5 ~A 8 One or more of A is a group represented by formula (2), 9 ~A 12 At least one of A is a group represented by formula (2), and 13 ~A 16 More preferably, one or more of A is a group represented by formula (2); 1 ~A 4 Two or more of them are groups represented by formula (2), A 5 ~A 8Two or more of them are groups represented by formula (2), A 9 ~A 12 Two or more of them are groups represented by formula (2), and A 13 ~A 16 Two or more of them are groups represented by formula (2).

[0106] From the viewpoint of the stability of the phthalocyanine compound, it is preferred that: in the above formula (1), A 1 ~A 4 At least one of A is a fluorine atom. 5 ~A 8 At least one of A is a fluorine atom. 9 ~A 12 At least one of A is a fluorine atom, and 13 ~A 16 More preferably, one or more of A is a fluorine atom. 1 ~A 4 Two or more of them are fluorine atoms, A 5 ~A 8 Two or more of them are fluorine atoms, A 9 ~A 12 Two or more of A are fluorine atoms, and 13 ~A 16 Two or more of them are fluorine atoms.

[0107] In view of the maximum transmission wavelength of the phthalocyanine compound (1), transmittance, affinity with the dispersant and solvent in the liquid containing the colorant, uniformity of crystallization of the phthalocyanine compound during firing of the color filter, and color tone required in the color filter, A is particularly preferred. 2 , A 3 , A 6 , A 7 , A 10 , A 11 , A 14 and A 15 is a group represented by formula (2), and A 1 , A 4 , A 5 , A 8 , A 9 , A 12 , A 13 and A 16 A fluorine atom.

[0108] Specific examples of the phthalocyanine compound (1) include the following compounds.

[0109]

[0110] It should be noted that, in the above formula, Et represents an ethyl group.

[0111]

[0112]

[0113]

[0114]

[0115] As a method for producing the phthalocyanine compound (1), a known method can be adopted, for example, the method described in Japanese Patent Application Laid-Open No. 05-345861 can be adopted.

[0116] (A) The colorant may include other colorants in addition to the phthalocyanine compound (1). As other colorants, dyes and pigments other than the phthalocyanine compound (1) may be listed. Among these, when used for green pixel applications, green pigments, yellow pigments, etc. are preferably used. In addition, when used for blue pixel applications, blue pigments, purple pigments, etc. are preferably used.

[0117] 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.

[0118] 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 5, 81, 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 、151、153、154、155、157、158、159、160、161、162、163、164、165、166、167、168、169、170、172、173、174、175、176、180、181、182、183、184、185、188、189、190、191、191:1 , 192, 193, 194, 195, 196, 197, 198, 199, 200, 202, 203, 204, 205, 206, 207, 208, and compounds formed by inserting other compounds into a 1:1 complex of azobarbituric acid and nickel represented by the following formula (i), or its tautomer (hereinafter sometimes referred to as "nickel azo complex represented by formula (i)").

[0119]

[0120] Examples of the other compound include compounds represented by the following formula (ii).

[0121]

[0122] Among these, CI Pigment Yellow 83, 117, 129, 138, 139, 154, 155, 180, 185 and the nickel azo complex represented by formula (i) are preferred from the viewpoint of high brightness and high color gamut, and CI Pigment Yellow 83, 138, 139, 180, 185 and the nickel azo complex represented by formula (i) are more preferred.

[0123] On the other hand, examples of blue pigments include CI Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56:1, 60, 61, 61:1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, and 79.

[0124] Among these, phthalocyanine pigments having a central metal are preferred from the viewpoint of heat resistance and structural stability, and blue copper phthalocyanine pigments are particularly preferred. Preferred examples of the copper phthalocyanine pigment include CI Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, and 15:6, and CI Pigment Blue 15:6 is more preferred.

[0125] Examples of the violet pigment include CI Pigment Violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, and 50.

[0126] Among these, from the viewpoint of heat resistance, a violet dioxazine pigment is preferred. As the dioxazine pigment, for example, CI Pigment Violet 19 and 23 are preferably mentioned, and CI Pigment Violet 23 is more preferred.

[0127] The average primary particle size of the pigment is preferably 0.2 μm or less, more preferably 0.1 μm or less, and even more preferably 0.04 μm or less. When the pigment is finely divided, a method such as the above-mentioned solvent salt grinding can be suitably used.

[0128] The content ratio of the phthalocyanine compound (1) in the colorant-containing liquid of the present invention is preferably 50% by mass or more, more preferably 80% by mass or more, relative to the total solid content of the colorant-containing liquid. In addition, it is preferably 99.5% by mass or less, more preferably 99% by mass or less. By setting it below the above upper limit, there is a tendency for the stability of the colorant-containing liquid to be improved. By setting it above the above lower limit, there is a tendency for the tinting power to be improved. The above upper and lower limits may be combined arbitrarily.

[0129] For example, the content ratio of the phthalocyanine compound (1) in the total solid content of the liquid containing the colorant is preferably 50 to 99.5% by mass, more preferably 80 to 99% by mass.

[0130] The content ratio of the colorant (A) in the total solid content of the colorant-containing liquid is preferably 40% by mass or more, more preferably 50% by mass or more, and even more preferably 60% by mass or more, and is preferably 99.9% by mass or less, more preferably 99.5% by mass or less, and even more preferably 99% by mass or less. If the content ratio of the colorant (A) is at least the lower limit, the coloring power tends to be improved, and if it is at most the upper limit, the stability of the colorant-containing liquid tends to be improved.

[0131] The above upper and lower limits may be arbitrarily combined, and are, for example, preferably 40 to 99.9% by mass, more preferably 50 to 99.5% by mass, and even more preferably 60 to 99% by mass.

[0132] [1-2] (B) Solvent

[0133] The (B) solvent has the function of dissolving or dispersing the (A) colorant, the compound represented by the above formula (3) and / or the benzoquinone compound, and other components in the colorant-containing liquid of the present invention and adjusting the viscosity.

[0134] The (B) solvent may be any solvent as long as it can dissolve or disperse the components.

[0135] Examples of such solvents include glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, propylene glycol-tert-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethylpentanol, propylene glycol monoethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, and tripropylene glycol methyl ether;

[0136] Glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, and dipropylene glycol dimethyl ether;

[0137] Glycol alkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, methoxybutyl acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, and 3-methyl-3-methoxybutyl acetate;

[0138] Glycol diacetates such as ethylene glycol diacetate, 1,3-butanediol diacetate, and 1,6-hexanol diacetate;

[0139] Alkyl acetates such as cyclohexanol acetate;

[0140] Ethers such as amyl ether, propyl ether, diethyl ether, dipropyl ether, diisopropyl ether, butyl ether, diamyl ether, ethyl isobutyl ether, and dihexyl ether;

[0141] Ketones such as acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone, and methoxymethyl amyl ketone;

[0142] Monohydric or polyhydric alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethylpentanol, glycerol, and benzyl alcohol;

[0143] Aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, and dodecane;

[0144] Alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, and bicyclohexane;

[0145] Aromatic hydrocarbons such as benzene, toluene, xylene, and cumene;

[0146] Chain or cyclic esters such as amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl octanoate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, and γ-butyrolactone;

[0147] Alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid;

[0148] Halogenated hydrocarbons such as butyl chloride and amyl chloride;

[0149] Ether ketones such as methoxymethylpentyl ketone;

[0150] Nitriles such as acetonitrile and benzonitrile.

[0151] Examples of commercially available solvents that meet the above requirements include mineral spirits, VALSOL#2, APCO#18solvent, Apco thinner, Socal solvent No.1 and No.2, SOLVESSO#150, SHELL TS28solvent, carbitol, ethyl carbitol, butyl carbitol, methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, methyl cellosolve acetate, and diethylene glycol dimethyl ether (all trade names). These solvents may be used alone or in combination of two or more.

[0152] When forming color filter pixels by photolithography, it is preferred to select a solvent having a boiling point in the range of 100 to 200°C (under a pressure of 1013.25 [hPa]. Hereinafter, the same shall apply to boiling points.) More preferably, a solvent having a boiling point of 120 to 170°C is selected.

[0153] 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 liquid containing the colorant.

[0154] 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, propylene glycol monomethyl ether is preferred, especially from the aspect of the solubility of the constituent components in the liquid containing the colorant. It should be noted that glycol monoalkyl ethers have high polarity. If the amount added is too much, there is a tendency that the pigment is easy to aggregate, the viscosity of the colored resin composition obtained thereafter increases, and the storage stability tends to decrease. Therefore, the proportion of glycol monoalkyl ethers in the (B) solvent is preferably 5% to 30% by mass, and more preferably 5% to 20% by mass.

[0155] As another embodiment, a solvent having a boiling point of 150° C. or higher may be used in combination.

[0156] By using a solvent having a boiling point of 150°C or more in combination, the colored resin composition becomes difficult to dry, but there is an effect that the mutual relationship of the constituent components in the liquid containing the colorant is not easily destroyed due to rapid drying. When a solvent having a boiling point of 150°C or more is used in combination, the content ratio of the solvent having a boiling point of 150°C or more in the solvent (B) is preferably 3% by mass to 50% by mass, more preferably 5% by mass to 40% by mass, and particularly preferably 5% by mass to 30% by mass. By setting it to be above the lower limit, there is a tendency to avoid, for example, the precipitation / solidification of the coloring material component at the front end of the slit nozzle to cause foreign matter defects. In addition, by setting it to be below the upper limit, there is a tendency to easily avoid the drying speed of the colored resin composition being slowed down, causing problems such as poor rhythm of the reduced pressure drying process and pin marks of pre-baking.

[0157] The solvent having a boiling point of 150° C. or higher may be a glycol alkyl ether acetate or a glycol alkyl ether. In this case, it is not necessary to separately contain a solvent having a boiling point of 150° C. or higher.

[0158] Preferred examples of the solvent having a boiling point of 150° C. or higher include diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1,3-butanediol diacetate, 1,6-hexanol diacetate, and glycerol triacetate.

[0159] When forming pixels of a color filter by an inkjet method, a solvent having a boiling point of generally 130° C. to 300° C., preferably 150° C. to 280° C. is suitable. When the boiling point is set to be equal to or higher than the lower limit, the uniformity of the obtained coating film tends to be improved, and when the boiling point is set to be equal to or lower than the upper limit, the residual solvent during firing tends to be easily reduced.

[0160] From the viewpoint of uniformity of the obtained coating film, a solvent having a vapor pressure of usually 10 mmHg or less, preferably 5 mmHg or less, and more preferably 1 mmHg or less can be used.

[0161] In the manufacture of color filters based on the inkjet method, the liquid (ink) containing the colorant ejected from the nozzle is several pL to tens of pL, which is very fine, so there is a tendency for the solvent to evaporate and the ink to concentrate / dry before landing on the periphery of the nozzle or in the pixel storage body. In order to avoid this, the (B) solvent preferably contains a solvent with a high boiling point, specifically, preferably contains a solvent with a boiling point of 180°C or more. It is more preferred to contain a solvent with a boiling point of 200°C or more, and it is particularly preferred to contain a solvent with a boiling point of 220°C or more. When a solvent with a boiling point of 180°C or more is used in combination, the content ratio of the solvent with a boiling point of 180°C or more in the (B) solvent is preferably 50% by mass or more, more preferably 70% by mass or more, and most preferably 90% by mass or more. By setting it to above the aforementioned lower limit, there is a tendency to easily exert the effect of preventing the solvent from evaporating from the droplets.

[0162] Examples of the solvent having a boiling point of 180° C. or higher include diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1,3-butanediol diacetate, 1,6-hexanol diacetate, and glycerol triacetate among the various solvents described above.

[0163] In order to adjust the viscosity of the colorant-containing liquid or the colored resin composition and the solubility of the solid component, it is also effective to contain a part of a solvent having a boiling point lower than 180°C. Such a solvent is preferably a solvent having low viscosity, high solubility, and low surface tension, such as ethers, esters, and ketones. Among them, cyclohexanone, dipropylene glycol dimethyl ether, and cyclohexanol acetate are preferred.

[0164] On the other hand, if the solvent contains alcohols, the discharge stability in the inkjet method may be deteriorated. When alcohols are used in combination, the content of alcohols in the (B) solvent is preferably 20% by mass or less, more preferably 10% by mass or less, and particularly preferably 5% by mass or less.

[0165] (B) The proportion of the solvent in the colorant-containing liquid of the present invention is not particularly limited, and its upper limit is preferably 99% by mass or less, more preferably 95% by mass or less, and further preferably 90% by mass or less. By setting it below the above-mentioned 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 is preferably 60% by mass or more, more preferably 70% by mass or more, and further preferably 75% by mass or more. The above upper and lower limits can be combined arbitrarily. For example, the proportion of the solvent in the colored resin composition is preferably 60 to 99% by mass, more preferably 70 to 95% by mass, and further preferably 75 to 90% by mass.

[0166] [1-3] Compound represented by formula (3), benzoquinone compound

[0167] The colorant-containing liquid of the present invention contains a compound represented by the following general formula (3) and / or a benzoquinone-based compound, and preferably contains a compound represented by the following general formula (3).

[0168]

[0169] (In formula (3), R a , R b , R c , R d and R f Each independently represents a hydrogen atom, an unsubstituted alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, and R e represents a hydrogen atom or an unsubstituted alkyl group having 1 to 6 carbon atoms.

[0170] Since the phthalocyanine compound (1) has a fluorine atom with a very large electronegativity or a group represented by the formula (2) as an electron-donating group, it is considered that the polarity of the molecule is large and the affinity with the compound represented by the formula (3) and the benzoquinone compound is high. In addition, the phthalocyanine compound molecule is generally highly planar. Among them, since the phthalocyanine compound (1) has a fluorine atom with a very small atomic radius or a group represented by the formula (2) with high planarity, it is considered that the steric hindrance of the molecule is small and the affinity with the compound represented by the formula (3) and the benzoquinone compound is high. Therefore, it is considered that the colorant-containing liquid of the present invention contains the compound represented by the formula (3) and / or the benzoquinone compound, so that the phthalocyanine compound (1) and the compound represented by the formula (3) and the benzoquinone compound are present in close proximity in the colorant-containing liquid. Therefore, even when a colorant-containing liquid and a (D) photopolymerization initiator are mixed in order to prepare a colored resin composition, the phthalocyanine compound (1) and the (D) photopolymerization initiator are brought into proximity and interact with each other, thereby being able to suppress a decrease in the polymerization ability and film curing ability of the (D) photopolymerization initiator.

[0171] Examples of the compound represented by formula (3) include hydroquinones such as methylhydroquinone (MHQ), phenols such as 4-methoxyphenol (MEHQ) and butylhydroxytoluene (BHT), and hindered phenols such as pentaerythritol tetrakis[3-[3,5-di(tert-butyl)-4-hydroxyphenyl]propionate].

[0172] As a benzoquinone type compound, 1, 4-benzoquinone is mentioned, for example.

[0173] Among the compounds represented by formula (3) and benzoquinone compounds, from the viewpoint of affinity with the phthalocyanine compound (1), specifically, the polarity of the molecule, and the steric hindrance of the molecule, methylhydroquinone (MHQ), 4-methoxyphenol (MEHQ), butylated hydroxytoluene (BHT), and pentaerythritol tetrakis[3-[3,5-di(tert-butyl)-4-hydroxyphenyl]propionate] are preferred, and methylhydroquinone (MHQ) and 4-methoxyphenol (MEHQ) are particularly preferred.

[0174] The compound represented by formula (3) and the benzoquinone-based compound may be used alone or in combination of two or more.

[0175] The total content of the compound represented by formula (3) and the benzoquinone-based compound is preferably 0.80% by mass or less, more preferably 0.50% by mass or less, further preferably 0.30% by mass or less, and particularly preferably 0.10% by mass or less relative to the total solid content of the liquid containing the colorant. In addition, it is preferably 0.001% by mass or more, more preferably 0.005% by mass or more, further preferably 0.008% by mass or more, and particularly preferably 0.01% by mass or more. By setting it to be above the aforementioned lower limit, there is a tendency to suppress the interaction between the phthalocyanine compound (1) and the photopolymerization initiator. In addition, by setting it to be below the aforementioned upper limit, there is a tendency to have high curability and to be able to form a pattern with good linearity. The above upper and lower limits can be combined arbitrarily. For example, the total content of the compound represented by formula (3) and the benzoquinone compound is preferably 0.001 to 0.80 mass %, more preferably 0.005 to 0.50 mass %, further preferably 0.008 to 0.10 mass %, particularly preferably 0.01 to 0.10 mass % based on the total solid content of the colorant-containing liquid.

[0176] The total content of the compound represented by formula (3) and the benzoquinone-based compound is 0.05 parts by mass or more and 10 parts by mass or less relative to 100 parts by mass of the phthalocyanine compound (1). By setting it to be above the aforementioned lower limit, there is a tendency to suppress the interaction between the phthalocyanine compound (1) and the photopolymerization initiator. In addition, by setting it to be below the aforementioned upper limit, there is a tendency to have high curability and to be able to form a pattern with good linearity.

[0177] The total content of the compound represented by formula (3) and the benzoquinone-based compound is preferably 0.08 parts by mass or more, and more preferably 0.1 parts by mass or more, relative to 100 parts by mass of the phthalocyanine compound (1). In addition, it is preferably 5 parts by mass or less, more preferably 3 parts by mass or less, and further preferably 1 part by mass or less. The above upper and lower limits can be combined arbitrarily. For example, the total content of the compound represented by formula (3) and the benzoquinone-based compound is preferably 0.05 to 5 parts by mass, more preferably 0.08 to 3 parts by mass, and further preferably 0.1 to 1 parts by mass, relative to 100 parts by mass of the phthalocyanine compound (1).

[0178] Here, "the total content of the compound represented by formula (3) and the benzoquinone-based compound" does not presuppose that both the compound represented by formula (3) and the benzoquinone-based compound are contained, and includes a form in which only one of the compound represented by formula (3) or the benzoquinone-based compound is contained.

[0179] [1-4] (E) Dispersant

[0180] The colorant-containing liquid of the present invention may contain (E) a dispersant. When a pigment is contained as the (A) colorant, it is preferred to contain (E) a dispersant in the colorant-containing liquid for the purpose of stably dispersing the pigment. Among dispersants, it is preferred to use a polymer dispersant because it has excellent dispersion stability over time.

[0181] Examples of polymer dispersants include urethane dispersants, polyethyleneimine dispersants, polyoxyethylene alkyl ether dispersants, polyoxyethylene glycol diester dispersants, sorbitan aliphatic ester dispersants, and aliphatic modified polyester dispersants. Examples of polymer dispersants include 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 Lubrizol Corporation), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), POLYFLOW (manufactured by Kyoeisha Chemical Co., Ltd.), and polymer dispersants described in Japanese Patent Application Publication No. 2013-119568.

[0182] Among the polymer dispersants, from the viewpoint of dispersibility and storage stability, a block copolymer having a functional group containing a nitrogen atom is preferred, and an acrylic block copolymer is more preferred.

[0183] The block copolymer having a functional group containing a nitrogen atom is preferably an AB block copolymer and / or a BAB block copolymer including 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.

[0184] Examples of the functional group containing a nitrogen atom include primary and tertiary amino groups and quaternary ammonium salt groups. From the viewpoint of dispersibility and storage stability, it is preferred to have a primary and tertiary amino group, and it is more preferred to have a tertiary amino group.

[0185] 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 (11) from the viewpoint of dispersibility and storage stability.

[0186]

[0187] In formula (11), R 11 and R 12 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 11 and R 12 Optionally, they are bonded to each other to form a ring structure. 13is a hydrogen atom or a methyl group. X is a divalent linking group.

[0188] The carbon number of the alkyl group optionally having a substituent in formula (11) is not particularly limited, and is generally 1 or more, and preferably 10 or less, more preferably 6 or less, and further preferably 4 or less. As the alkyl group, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl can be listed, preferably methyl, ethyl, propyl, butyl, pentyl, and hexyl, and more preferably methyl, ethyl, propyl, and butyl. It can be any one of a straight chain and a branched chain. In addition, it can contain a cyclic structure such as a cyclohexyl group and a cyclohexylmethyl group.

[0189] The carbon number of the aryl group which may have a substituent in formula (11) 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. Examples of the aryl group include phenyl, methylphenyl, ethylphenyl, dimethylphenyl, diethylphenyl, naphthyl, and anthracenyl, preferably phenyl, methylphenyl, ethylphenyl, dimethylphenyl, and diethylphenyl, and more preferably phenyl, methylphenyl, and ethylphenyl.

[0190] The carbon number of the aralkyl group which may have a substituent in formula (11) 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. Examples of the aralkyl group include phenylmethylene, phenylethylene, phenylpropylene, phenylbutylene, and phenylisopropylene, preferably phenylmethylene, phenylethylene, phenylpropylene, and phenylbutylene, and more preferably phenylmethylene and phenylethylene.

[0191] From the perspective of dispersibility, storage stability, electrical reliability, and developability, R 11 and R 12 Preferably, each independently is an alkyl group which may have a substituent, and more preferably a methyl group or an ethyl group.

[0192] Examples of the substituent that the alkyl group, aralkyl group or aryl group in formula (11) may have include a halogen atom, an alkoxy group, a benzoyl group and a hydroxyl group. From the viewpoint of ease of synthesis, the substituent is preferably unsubstituted.

[0193] In formula (11), as R 11 and R 12 The cyclic structure formed by bonding to each other 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 a saturated ring is more preferred. For example, the nitrogen-containing heterocyclic ring (VII) below can be mentioned.

[0194]

[0195] These cyclic structures may further have a substituent.

[0196] In the formula (11), 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 23 -base, -COOR 24 -base〔where R 23 and R 24 is a single bond, an alkylene group having 1 to 10 carbon atoms, or an ether group having 2 to 10 carbon atoms (alkyloxyalkyl group), preferably -COO-R 24 -base.

[0197] The repeating unit shown in formula (11) 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%, most preferably more than 25 mol%, and preferably less than 90 mol%, more preferably less than 70 mol%, more preferably less than 50 mol%, particularly preferably less than 40 mol%. The above upper and lower limits can be combined arbitrarily. For example, it can be 1 to 90 mol%, 5 to 90 mol%, 10 to 70 mol%, 15 to 70 mol%, 20 to 50%, or 25 to 40 mol%. In the case of the aforementioned range, there is a tendency to be able to take into account both dispersion stability and high brightness.

[0198] From the viewpoint of improving the compatibility of the dispersant with the binder component such as the solvent and improving the dispersion stability, the block copolymer preferably has a repeating unit represented by the following general formula (12).

[0199]

[0200] In formula (12), R 110 is ethylene or propylene, R 111 is an alkyl group optionally having a substituent, R 112 is a hydrogen atom or a methyl group. n is an integer of 1 to 20.

[0201] R in formula (12) 111The carbon number 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 the alkyl group, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl can be listed, preferably methyl, ethyl, propyl, butyl, pentyl, hexyl, more preferably methyl, ethyl, propyl, butyl. It can be any one of straight chain and branched. In addition, it can contain cyclic structures such as cyclohexyl and cyclohexylmethyl. As the substituent, for example, a halogen atom, an alkoxy group, a benzoyl group, a hydroxyl group can be listed, and from the viewpoint of ease of synthesis, it is preferably unsubstituted.

[0202] From the viewpoint of compatibility and dispersibility with binder components such as solvents, n in formula (12) is preferably 1 or more, more preferably 2 or more, and preferably 10 or less, more preferably 5 or less. The above upper and lower limits may be arbitrarily combined. For example, it may be 1 to 10, or 2 to 5.

[0203] The ratio of the repeating unit shown in formula (12) in all the repeating units of the block copolymer is preferably 1 mol% or more, more preferably 2 mol% or more, and further preferably 4 mol% or more. In addition, it is preferably 30 mol% or less, more preferably 20 mol% or less, and further preferably 10 mol% or less. The above upper and lower limits can be combined arbitrarily. For example, it can be 1 to 30 mol%, 2 to 20 mol%, or 4 to 10 mol%. In the case of the aforementioned range, there is a tendency to be able to take into account the compatibility and dispersion stability of binder components such as solvents.

[0204] From the viewpoint of improving the compatibility of the dispersant with the binder component such as the solvent and improving the dispersion stability, the block copolymer preferably has a repeating unit represented by the following general formula (13).

[0205]

[0206] In formula (13), 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.

[0207] R in formula (13) 8The carbon number of the alkyl group optionally having a substituent is not particularly limited, and is usually 1 or more, preferably 1 or more, and preferably 10 or less, and more preferably 6 or less. As the alkyl group, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl can be listed, preferably methyl, ethyl, propyl, butyl, pentyl, and hexyl, and more preferably methyl, ethyl, propyl, and butyl. It can be any one of a straight chain and a branched chain. In addition, it can contain cyclic structures such as cyclohexyl and cyclohexylmethyl.

[0208] R in formula (13) 8 The carbon number 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. Examples of the aryl group include phenyl, methylphenyl, ethylphenyl, dimethylphenyl, diethylphenyl, naphthyl, and anthracenyl, preferably phenyl, methylphenyl, ethylphenyl, dimethylphenyl, and diethylphenyl, and more preferably phenyl, methylphenyl, and ethylphenyl.

[0209] R in formula (13) 8 The carbon number 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. Examples of the aralkyl group include phenylmethylene, phenylethylene, phenylpropylene, phenylbutylene, and phenylisopropylidene, preferably phenylmethylene, phenylethylene, phenylpropylene, and phenylbutylene, and more preferably phenylmethylene and phenylethylene.

[0210] From the viewpoint of solvent compatibility and dispersion stability, 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.

[0211] As R 8 Examples of the substituents that the alkyl group in the formula (R) may have include halogen atoms and alkoxy groups. Examples of the substituents that the aryl group or aralkyl group may have include chain alkyl groups, halogen atoms, and alkoxy groups. 8 The chain alkyl group shown includes both linear and branched ones.

[0212] The ratio of the repeating unit shown in formula (13) in all the repeating units of the block copolymer is preferably 30 mol% or more, more preferably 40 mol% or more, further preferably 50 mol% or more, and preferably 80 mol% or less, more preferably 70 mol% or less. The above upper and lower limits can be combined arbitrarily. For example, it can be 30 to 80 mol%, 40 to 80 mol%, or 50 to 70 mol%. In the case of the aforementioned range, there is a tendency to be able to take into account both dispersion stability and high brightness.

[0213] The block copolymer may also have repeating units other than the repeating units represented by formula (11), the repeating units represented by formula (12), and the repeating units represented by formula (13). Examples of such repeating units include: repeating units derived from styrene monomers such as styrene and α-methylstyrene; (meth)acrylate monomers such as (meth)acryloyl chloride; (meth)acrylamide monomers such as (meth)acrylamide and N-hydroxymethylacrylamide; and repeating units derived from monomers such as vinyl acetate, acrylonitrile, allyl glycidyl ether, crotonic acid glycidyl ether, and N-methacryloylmorpholine.

[0214] From the viewpoint of further improving dispersibility, it is preferred that the block copolymer comprises an A block having a repeating unit represented by formula (11) and a B block not having a repeating unit represented by formula (11). The block copolymer is preferably an AB block copolymer or a BAB block copolymer. In addition, the B block more preferably comprises a repeating unit represented by formula (12) and a repeating unit represented by formula (13).

[0215] The A block may also contain repeating units other than the repeating unit represented by formula (11), and examples of such repeating units include repeating units derived from the aforementioned (meth)acrylate monomers. The content of repeating units other than the repeating units represented by formula (11) in the A block is preferably 0 to 50 mol%, more preferably 0 to 20 mol%, and it is particularly preferred that the A block does not contain such repeating units.

[0216] The B block may also contain repeating units other than the repeating units represented by formula (12) and the repeating units represented by formula (13). Examples of such repeating units include repeating units derived from styrene monomers such as styrene and α-methylstyrene; (meth)acrylate monomers such as (meth)acryloyl chloride; (meth)acrylamide monomers such as N-methylolacrylamide; vinyl acetate; acrylonitrile; allyl glycidyl ether, crotonic acid glycidyl ether; and N-methacryloylmorpholine. The content of repeating units other than the repeating units represented by formula (12) and the repeating units represented by formula (13) in the B block is preferably 0 to 50 mol%, more preferably 0 to 20 mol%, and it is particularly preferred that the B block does not contain such repeating units.

[0217] From the viewpoint of dispersibility, the acid value of the block copolymer is preferably low, and particularly preferably 0 mgKOH / g. Here, the acid value refers to the number of mg of KOH required to neutralize 1 g of the solid content of the dispersant.

[0218] 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, most preferably 105 mgKOH / g or more, and preferably 150 mgKOH / g or less, more preferably 130 mgKOH / g or less. The above upper and lower limits can be combined arbitrarily. For example, it can be 30 to 150 mgKOH / g, 50 to 150 mgKOH / g, 70 to 150 mgKOH / g, 90 to 130 mgKOH / g, 100 to 130 mgKOH / g, or 105 to 130 mgKOH / g. Here, the amine value represents the amine value converted to the effective solid content, which is a value represented by the mass of KOH equivalent to the alkali amount per 1 g solid content of the dispersant.

[0219] The molecular weight of the block copolymer is preferably in the range of 1000 to 30000 in terms of polystyrene-equivalent weight average molecular weight (hereinafter sometimes referred to as "Mw"). Within the above range, dispersion stability becomes good and dried foreign matter tends to be less likely to be generated during coating by a slit nozzle method.

[0220] The block copolymer can be produced by a known method, for example, by living polymerizing a monomer into which each of the above-mentioned repeating units is introduced.

[0221] As living polymerization methods, Japanese Patent Application Laid-Open No. 9-62002, Japanese Patent Application Laid-Open No. 2002-31713, P. Lutz, P. Masson et al., Polym. Bull. 12, 79 (1984), BC Anderson, GD Andrews et al., Macromolecules, 14, 1601 (1981), K. Hatada, K. Ute, et al., Polym. J. 17, 977 (1985 ... Bull. 12, 79 (1984), BC Anderson, GD Andrews et al., Macromolecules, 14, 1601 (1981), K. Hatada, K. Ute, et al., Polym. J. 17, 977 (1985), K. Hatada, K. Ute, et al., Polym. al, Polym.J.18, 1037 (1986), Yuhei Koichi, Hata Koichi, 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).

[0222] When the colorant-containing liquid of the present invention contains (E) dispersant, the content ratio of (E) dispersant is not particularly limited, and is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, further preferably 0.1% by mass or more, particularly preferably 1% by mass or more, relative to the total solid content of the colorant-containing liquid, and preferably 20% by mass or less, more preferably 15% by mass or less, further preferably 10% by mass or less, particularly preferably 5% by mass or less. By setting it to above the aforementioned lower limit, there is a tendency for dispersibility and storage stability to be improved, and by setting it to below the aforementioned upper limit, there is a tendency for electrical reliability and developability to be improved. The above upper and lower limits can be combined arbitrarily. For example, it can be 0.001 to 20% by mass, it can be 0.01 to 15% by mass, it can be 0.1 to 10% by mass, and it can be 1 to 5% by mass or more.

[0223] When the colorant-containing liquid of the present invention contains (E) dispersant, the mass-based content ratio of (A) colorant to (E) dispersant ((A) colorant / (E) dispersant) is preferably 10 or more, more preferably 25 or more, and further preferably 50 or more. In addition, it is preferably 200 or less, more preferably 150 or less, and further preferably 100 or less. By setting it below the aforementioned upper limit, there is a tendency for the storage stability of the colorant-containing liquid to be improved, and by setting it above the aforementioned lower limit, there is a tendency for electrical reliability and developability to be improved. The above-mentioned upper and lower limits may be arbitrarily combined. For example, it may be 10 to 200 to 100, it may be 25 to 150, or it may be 50 to 100.

[0224] When the colorant-containing liquid of the present invention contains a pigment and a (E) dispersant, the content ratio of the (E) 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, particularly preferably 20 parts by mass or more, relative to 100 parts by mass of the pigment, and preferably 70 parts by mass or less, more preferably 50 parts by mass or less, further preferably 40 parts by mass or less, particularly preferably 30 parts by mass or less. The above upper and lower limits can be combined arbitrarily. For example, it can be 0.5 to 70 parts by mass, 5 to 70 parts by mass, 10 to 50 parts by mass, 15 to 40 parts by mass, or 20 to 30 parts by mass. By setting it within the above range, there is a tendency to obtain a coloring resin composition with excellent dispersion stability and high brightness.

[0225] When the colorant-containing liquid of the present invention contains a pigment, in order to improve the dispersibility of the pigment and improve the dispersion stability, a pigment derivative or the like may also be included as a dispersing aid. As pigment derivatives, for example, derivatives of azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, isoindolinone, isoindolinone, dioxazine, anthraquinone, indanthrene, perylene, perinone, diketopyrrolopyrrole, and dioxazine pigments can be listed. As substituents of pigment derivatives, groups directly or by means of alkyl, aryl, heterocyclic groups, such as sulfonic acid groups, sulfonamide groups, and quaternary salts thereof, phthalimidomethyl, dialkylaminoalkyl, hydroxyl, carboxyl, and amide groups bonded to the pigment skeleton can be listed, and preferably sulfonamide groups and quaternary salts thereof, sulfonic acid groups, and more preferably sulfonic acid groups can be listed. These substituents can be substituted with multiple groups in one pigment skeleton, or a mixture of compounds with different substitution numbers. Examples of the pigment derivatives include sulfonic acid derivatives of azo pigments, sulfonic acid derivatives of phthalocyanine pigments, sulfonic acid derivatives of quinophthalone pigments, sulfonic acid derivatives of isoindoline pigments, sulfonic acid derivatives of anthraquinone pigments, sulfonic acid derivatives of quinacridone pigments, sulfonic acid derivatives of diketopyrrolopyrrole pigments, and sulfonic acid derivatives of dioxazine pigments.

[0226] The colorant-containing liquid of the present invention may contain (A) a colorant, (B) a solvent, a compound represented by formula (3), a benzoquinone compound, and other components as necessary. Examples of other components include other components in the coloring resin composition described below.

[0227] The content of other components is preferably 5% by mass or less, more preferably 1% by mass or less, and may be 0% by mass, relative to the total solid content of the colorant-containing liquid.

[0228] [1-5] Method for producing liquid containing colorant

[0229] The colorant-containing liquid of the present invention is produced, for example, by mixing (A) a colorant, (B) a solvent, a compound represented by formula (3), a benzoquinone compound, and optionally, (E) a dispersant and other optional components, and subjecting the resulting mixed liquid to a dispersion treatment.

[0230] The dispersion treatment can be carried out using a known dispersion treatment device such as a paint conditioner, sand mill, ball mill, roll mill, stone mill, jet mill, homogenizer, etc. When the dispersion treatment is carried out using a sand mill, glass beads or zirconia beads having a diameter of about 0.1 to 8 mm are preferably used.

[0231] The dispersion treatment conditions are not particularly limited, and the temperature is, for example, in the range of 0° C. to 100° C., preferably in the range of room temperature to 60° C. The dispersion time is appropriately adjusted because the appropriate time varies depending on the composition of the liquid and the size of the dispersion treatment apparatus.

[0232] After the dispersion treatment, the obtained dispersion treatment product may be subjected to filtration treatment using a filter or the like, if necessary, for example, to separate the beads used in the dispersion treatment from the liquid containing the colorant.

[0233] When the dispersion treatment is not performed, the colorant-containing liquid of the present invention is produced by mixing (A) the colorant, (B) the solvent, the compound represented by the above formula (3), the benzoquinone compound, and optional components as required.

[0234] [2] Colored resin composition (first embodiment)

[0235] One embodiment of the colored resin composition of the present invention contains the colorant-containing liquid of the present invention, (C) an alkali-soluble resin, and (D) a photopolymerization initiator.

[0236] [2-1] (C) Alkali-soluble resin

[0237] The colored resin composition of the present invention contains (C) an alkali-soluble resin. By containing (C) an alkali-soluble resin, it is possible to achieve both film curability by photopolymerization and solubility in a developer.

[0238] As the alkali-soluble resin (C), known polymer compounds described in, for example, JP-A-7-207211, JP-A-8-259876, JP-A-10-300922, JP-A-11-140144, JP-A-11-174224, JP-A-2000-56118, and JP-A-2003-233179 can be used, and preferably the following resins (C-1) to (C-5) (hereinafter sometimes referred to as resins (C-1) to (C-5), respectively) can be listed.

[0239] (C-1): A resin obtained by adding an unsaturated monobasic acid to at least a portion of the epoxy groups in a copolymer of an epoxy (meth)acrylate and other free radical polymerizable monomers; or an alkali-soluble resin obtained by adding a polyacid anhydride to at least a portion of the hydroxyl groups generated by the addition reaction (hereinafter sometimes referred to as "resin (C-1)").

[0240] (C-2) A linear alkali-soluble resin having a carboxyl group in its main chain (hereinafter sometimes referred to as "resin (C-2)").

[0241] (C-3) A resin obtained by adding an epoxy group-containing unsaturated compound to the carboxyl portion of the above-mentioned resin (C-2) (hereinafter, sometimes referred to as "resin (C-3)").

[0242] (C-4) (Meth)acrylic resin (hereinafter sometimes referred to as "resin (C-4)").

[0243] (C-5) Epoxy (meth)acrylate resin having a carboxyl group (hereinafter sometimes referred to as "resin (C-5)").

[0244] Particularly preferably, resin (C-1) is used.

[0245] Resins (C-2) to (C-5) may be any resin as long as they are soluble in an alkaline developer and can be subjected to a desired development process. Resins described in Japanese Patent Application Laid-Open No. 2009-025813 may be used.

[0246] (C-1) A resin obtained by adding an unsaturated monobasic acid to at least a portion of the epoxy groups of a copolymer of an epoxy (meth)acrylate and other free radical polymerizable monomers; or an alkali-soluble resin obtained by adding a polybasic acid anhydride to at least a portion of the hydroxyl groups generated by the addition reaction.

[0247] As one of the preferred forms of resin (C-1), there can be listed "a resin obtained by adding an unsaturated monobasic acid to 10 to 100 mol % of the epoxy groups in a copolymer containing 5 to 90 mol % of epoxy (meth)acrylate and 10 to 95 mol % of other free radical polymerizable monomers; or an alkali-soluble resin obtained by adding a polyacid anhydride to 10 to 100 mol % of the hydroxyl groups generated by the addition reaction."

[0248] Examples of epoxy group-containing (meth)acrylates include glycidyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, (3,4-epoxycyclohexyl)methyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate glycidyl ether. Among them, glycidyl (meth)acrylate is preferred. These epoxy group-containing (meth)acrylates may be used alone or in combination of two or more.

[0249] As another radical polymerizable monomer to be copolymerized with the epoxy group-containing (meth)acrylate, a mono(meth)acrylate having a structure represented by the following general formula (V) is preferred.

[0250]

[0251] In formula (V), R 91 ~R 98Each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. 96 With R 98 , or R 95 With R 97 They are optionally linked to each other to form a ring.

[0252] In formula (V), R 96 With R 98 , or R 95 With R 97 The ring formed by connecting is preferably an aliphatic ring, and may be saturated or unsaturated, and preferably has 5 to 6 carbon atoms.

[0253] The structure represented by formula (V) is preferably a structure represented by the following formula (Va), (Vb), or (Vc).

[0254] By introducing these structures into the alkali-soluble resin, when the colored resin composition of the present invention is used for forming a color filter, the heat resistance of the colored resin composition tends to be improved, and the intensity of pixels formed using the colored resin composition tends to be increased.

[0255] The mono(meth)acrylate having a structure represented by formula (V) may be used alone or in combination of two or more.

[0256]

[0257] As the mono(meth)acrylate having a structure represented by formula (V), various known substances can be used as long as they have the structure, and the mono(meth)acrylate represented by formula (VI) is particularly preferred.

[0258]

[0259] In formula (VI), R 89 represents a hydrogen atom or a methyl group, R 90 It represents the structure represented by formula (V).

[0260] When the copolymer of epoxy group-containing (meth)acrylate and other radical polymerizable monomers contains repeating units derived from the mono(meth)acrylate represented by formula (VI), the content ratio of the repeating units derived from the mono(meth)acrylate represented by formula (VI) in the repeating units derived from the other radical polymerizable monomers is preferably 5 to 90 mol%, more preferably 10 to 70 mol%, and particularly preferably 15 to 50 mol%.

[0261] The free radical polymerizable monomers other than the mono(meth)acrylate represented by formula (VI) are not particularly limited, and specific examples thereof include: vinyl aromatics such as styrene, α-, o-, m-, p-alkyl, nitro, cyano, amide, and ester derivatives of styrene; dienes such as butadiene, 2,3-dimethylbutadiene, isoprene, and chloroprene; methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate, neopentyl (meth)acrylate, isopentyl (meth)acrylate, and (meth)acrylate. 2-Methylhexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, dodecyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, dicyclohexyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, anthracenyl (meth)acrylate, piperidinyl (meth)acrylate, salicyl (meth)acrylate, furanyl (meth)acrylate, furfuryl (meth)acrylate, tetrahydrofuranyl (meth)acrylate, pyranyl (meth)acrylate , benzyl (meth)acrylate, phenylethyl (meth)acrylate, toluene (meth)acrylate, 1,1,1-trifluoroethyl (meth)acrylate, perfluoroethyl (meth)acrylate, perfluoro-n-propyl (meth)acrylate, perfluoroisopropyl (meth)acrylate, triphenylmethyl (meth)acrylate, isopropyl (meth)acrylate, 3-(N,N-dimethylamino)propyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, etc. (meth)acrylates; (meth)acrylamide, N,N-dimethyl (meth)acrylate, N,N-diethyl (meth)acrylate, N,N-diethyl (meth)acrylate, N,N-(meth)acrylate (Meth)acrylamides such as (meth)acrylic acid aniline, (meth)acryloyl nitrile, acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinyl pyrrolidone, vinyl pyridine, vinyl acetate, etc.; unsaturated dicarboxylic acid diesters such as diethyl citrate, diethyl maleate, diethyl fumarate, diethyl itaconate, etc.; monomaleimides such as N-phenylmaleimide, N-cyclohexylmaleimide, N-laurylmaleimide, N-(4-hydroxyphenyl)maleimide, etc.; N-(meth)acryloylphthalimide.

[0262] Among these other radical polymerizable monomers, styrene, benzyl (meth)acrylate, and monomaleimide are preferred from the viewpoint of imparting excellent heat resistance and strength to the colored resin composition.

[0263] When the copolymer of epoxy group-containing (meth)acrylate and other radical polymerizable monomers contains any repeating unit derived from styrene, benzyl (meth)acrylate or monomaleimide, the total content of the repeating unit derived from styrene, the repeating unit derived from benzyl (meth)acrylate and the repeating unit derived from monomaleimide in the repeating units derived from other radical polymerizable monomers is preferably 1 to 70 mol%, more preferably 3 to 50 mol%.

[0264] The copolymerization reaction of the epoxy group-containing (meth)acrylate and other radical polymerizable monomers can be carried out by a known solution polymerization method. The solvent used is not particularly limited as long as it is inactive to radical polymerization, and a commonly used organic solvent can be used.

[0265] Examples of the solvent used in the solution polymerization method include ethylene glycol monoalkyl ether acetates such as ethyl acetate, isopropyl acetate, cellosolve acetate, and butyl cellosolve acetate; diethylene glycol monoalkyl ether acetates such as diethylene glycol monomethyl ether acetate, carbitol acetate, and butyl carbitol acetate; propylene glycol monoalkyl ether acetates; acetates such as dipropylene glycol monoalkyl ether acetates; ethylene glycol dialkyl ethers; methyl carbitol, ethyl carbitol, and butyl carbitol; Diethylene glycol dialkyl ethers; triethylene glycol dialkyl ethers; propylene glycol dialkyl ethers; dipropylene glycol dialkyl ethers; ethers such as 1,4-dioxane and tetrahydrofuran; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; hydrocarbons such as benzene, toluene, xylene, octane, and decane; petroleum solvents such as petroleum ether, naphtha, hydrogenated naphtha, and solvent naphtha; lactic acid esters such as methyl lactate, ethyl lactate, and butyl lactate; dimethylformamide and N-methylpyrrolidone. These solvents may be used alone or in combination of two or more.

[0266] The amount of the solvent used in the solution polymerization method is usually 30 to 1000 parts by mass, preferably 50 to 800 parts by mass based on 100 parts by mass of the obtained copolymer. When the amount of the solvent used is within the above range, the molecular weight of the copolymer tends to be easily controlled.

[0267] The radical polymerization initiator used in the copolymerization reaction is not particularly limited as long as it can initiate radical polymerization, and commonly used organic peroxide catalysts and azo compound catalysts can be used. As the organic peroxide catalyst, known substances classified as ketone peroxides, peroxyketals, hydroperoxides, diallyl peroxides, diacyl peroxides, peroxyesters, and peroxydicarbonates can be cited.

[0268] Examples of the radical polymerization initiator used in the copolymerization reaction include benzoyl peroxide, dicumyl peroxide, diisopropyl peroxide, di-tert-butyl peroxide, tert-butyl peroxybenzoate, tert-hexyl peroxybenzoate, tert-butyl peroxy-2-ethylhexanoate, tert-hexyl peroxy-2-ethylhexanoate, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, 3,3-isopropyl hydroperoxide, tert-butyl hydroperoxide, diisopropyl peroxide, diisopropyl hydroperoxide, acetyl peroxide, bis(4-tert-butylcyclohexyl)peroxydicarbonate, diisopropyl peroxydicarbonate, isobutyl peroxide, 3,3,5-trimethylhexanoyl peroxide, lauryl peroxide, 1,1-bis(tert-butylperoxide)3,3,5-trimethylcyclohexane, 1,1-bis(tert-hexylperoxide)3,3,5-trimethylcyclohexane.

[0269] Examples of the azo compound catalyst include azobisisobutyronitrile and azobiscarbonamide.

[0270] Among these, one or more radical polymerization initiators having an appropriate half-life may be used depending on the polymerization temperature.

[0271] The amount of the radical polymerization initiator used is usually 0.5 to 20 parts by mass, preferably 1 to 10 parts by mass, based on 100 parts by mass of the total of the monomers used in the copolymerization reaction.

[0272] The copolymerization reaction can be carried out by dissolving the monomers and the radical polymerization initiator used in the copolymerization reaction in a solvent and heating the mixture while stirring, or by dropping the monomers to which the radical polymerization initiator is added into the heated and stirred solvent, or by adding the radical polymerization initiator to the solvent and dropping the monomers while heating the mixture. The reaction conditions can be set according to the target molecular weight.

[0273] In the present invention, as a copolymer of epoxy-containing (meth)acrylate and other free radical polymerizable monomers, it is preferred that the copolymer contains 5 to 90 mol% of repeating units derived from epoxy-containing (meth)acrylate and 10 to 95 mol% of repeating units derived from other free radical polymerizable monomers in all repeating units of the copolymer; it is further preferred that the copolymer contains 20 to 80 mol% of repeating units derived from epoxy-containing (meth)acrylate and 80 to 20 mol% of repeating units derived from other free radical polymerizable monomers; it is particularly preferred that the copolymer contains 30 to 70 mol% of repeating units derived from epoxy-containing (meth)acrylate and 70 to 30 mol% of repeating units derived from other free radical polymerizable monomers.

[0274] By setting the content ratio of the repeating unit derived from the epoxy group-containing (meth)acrylate to be equal to or more than the above lower limit, there is a tendency that the addition amount of the unsaturated monobasic acid or polybasic acid anhydride described later becomes sufficient.

[0275] When the content ratio of repeating units derived from other radical polymerizable monomers is equal to or greater than the above lower limit, heat resistance and strength tend to be sufficient.

[0276] Regarding the resin (C-1), the epoxy group of a copolymer of epoxy group-containing (meth)acrylate and other radical polymerizable monomers is reacted with an unsaturated monobasic acid (polymerizable component) and a polybasic acid anhydride (alkali-soluble component).

[0277] Examples of unsaturated monobasic acids to which epoxy groups are added include: (meth)acrylic acid; crotonic acid; o-, m-, and p-vinylbenzoic acid; and monocarboxylic acids such as (meth)acrylic acid in which the α-position is substituted with a haloalkyl group, an alkoxy group, a halogen atom, a nitro group, or a cyano group. Among them, (meth)acrylic acid is preferred. These unsaturated monobasic acids may be used alone or in combination of two or more.

[0278] By adding an unsaturated monobasic acid to an epoxy group, polymerizability can be imparted to the resin (C-1).

[0279] The unsaturated monobasic acid is usually added in an amount of 10 to 100 mol %, preferably 30 to 100 mol %, more preferably 50 to 100 mol %, based on 100 mol % of all epoxy groups in the copolymer of epoxy-containing (meth)acrylate and other radical polymerizable monomers.

[0280] By setting it to more than the said lower limit, there exists a tendency for the temporal stability of a colored resin composition to become favorable.

[0281] As a method for adding an unsaturated monobasic acid to the epoxy group of the copolymer, a known method can be adopted.

[0282] Furthermore, as the polybasic acid anhydride to be added to the hydroxyl group generated when the unsaturated monobasic acid is added to the epoxy group of the copolymer, a known polybasic acid anhydride can be used.

[0283] Examples of the polyacid anhydride include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, chlorendic anhydride and other dibasic acid anhydrides; and anhydrides of tribasic or higher acids such as trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, and biphenyl tetracarboxylic anhydride. Among them, tetrahydrophthalic anhydride and succinic anhydride are preferred. These polyacid anhydrides may be used alone or in combination of two or more.

[0284] Alkali solubility can be imparted to the resin (C-1) by adding a polybasic acid anhydride to a hydroxyl group generated when an unsaturated monobasic acid is added to an epoxy group of a copolymer.

[0285] When all hydroxyl groups generated by addition of the epoxy groups possessed by the copolymer and the unsaturated monobasic acid are set to 100 mol%, the polyacid anhydride is usually added at 10 to 100 mol%, preferably 20 to 90 mol%, and more preferably 30 to 80 mol%. By setting it below the upper limit, there is a tendency that the residual film rate during development becomes good, and by setting it above the lower limit, there is a tendency that the solubility becomes sufficient.

[0286] As a method for adding a polybasic acid anhydride to a hydroxyl group generated by adding an unsaturated monobasic acid to an epoxy group possessed by the copolymer, a known method can be adopted.

[0287] In order to improve photosensitivity, after adding the polybasic acid anhydride, a part of the generated carboxyl groups may be added with glycidyl (meth)acrylate or a glycidyl ether compound having a polymerizable unsaturated group.

[0288] In order to improve the developability, a part of the generated carboxyl groups may be added with a glycidyl ether compound having no polymerizable unsaturated group.

[0289] These may be added alone or in combination of two or more.

[0290] Examples of the glycidyl ether compound having no polymerizable unsaturated group include glycidyl ether compounds having a phenyl group or an alkyl group.

[0291] Examples of commercially available products include "Denacol EX-111", "Denacol EX-121", "Denacol EX-141", "Denacol EX-145", "Denacol EX-146", "Denacol EX-171" and "Denacol EX-192" manufactured by Nagase ChemteX Corporation.

[0292] The structure of the resin (C-1) is described in, for example, Japanese Patent Application Laid-Open No. 8-297366 and Japanese Patent Application Laid-Open No. 2001-89533.

[0293] The weight average molecular weight (Mw) of the resin (C-1) measured by GPC in terms of polystyrene is not particularly limited, but is preferably 3,000 or more, particularly preferably 5,000 or more. It is preferably 100,000 or less, particularly preferably 50,000 or less. The above upper and lower limits may be arbitrarily combined. For example, it may be 3,000 to 100,000, or 5,000 to 50,000. By setting it to above the aforementioned lower limit, there is a tendency for heat resistance and film strength to become good, and by setting it to below the aforementioned upper limit, there is a tendency for solubility in a developer to become good.

[0294] As a standard of molecular weight distribution, the ratio of the weight average molecular weight to the number average molecular weight of the resin (C-1) (Mw / Mn) is preferably 2.0 to 5.0.

[0295] From the viewpoint of coating film curability upon ultraviolet exposure, among the resins (C-4), (c1) acrylic copolymer resins having an ethylenically unsaturated group in a side chain (hereinafter sometimes referred to as (c1) acrylic copolymer resins) are preferred.

[0296] The partial structure of the acrylic copolymer resin (c1) containing a side chain having an ethylenically unsaturated group is not particularly limited, but preferably has a partial structure represented by the following general formula (I) from the viewpoint of achieving both film curability during ultraviolet exposure and alkali solubility during alkali development.

[0297]

[0298] In formula (I), R 1 and R 2 Each independently represents a hydrogen atom or a methyl group. * represents a connecting bond.

[0299] Among the partial structures represented by the formula (I), the partial structures represented by the following general formula (I′) are preferred from the viewpoints of sensitivity and alkali developability.

[0300]

[0301] In formula (I'), R 1 and R 2 Each independently represents a hydrogen atom or a methyl group. X represents a hydrogen atom or a polyacid residue.

[0302] The polyacid residue refers to a monovalent or divalent group obtained by removing one or two OH groups from a polyacid. Examples of the polyacid include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid.

[0303] Among these, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are preferred from the viewpoint of patterning properties, and tetrahydrophthalic acid and biphenyltetracarboxylic acid are more preferred.

[0304] In the case where the (c1) acrylic copolymer resin contains a partial structure represented by formula (I), the content ratio of the partial structure represented by formula (I) contained in the (c1) acrylic copolymer resin is not particularly limited, and is preferably 10 mol% or more, more preferably 20 mol% or more, further preferably 30 mol% or more, further preferably 40 mol% or more, particularly preferably 50 mol% or more, and most preferably 65 mol% or more. In addition, it is preferably 95 mol% or less, more preferably 90 mol% or less, further preferably 85 mol% or less, further preferably 80 mol% or less, particularly preferably 75 mol% or less, and most preferably 70 mol% or less. By setting it to above the aforementioned lower limit, there is a tendency for the curability of the coating film to be improved during ultraviolet exposure, and by setting it to below the aforementioned upper limit, there is a tendency for the alkali solubility to be improved during alkali development. The above upper and lower limits can be combined arbitrarily. For example, the content of the partial structure represented by formula (I) contained in the (c1) acrylic copolymer resin is preferably 10 to 95 mol%, more preferably 20 to 90 mol%, further preferably 30 to 85 mol%, further preferably 40 to 80 mol%, particularly preferably 50 to 75 mol%, and most preferably 65 to 70 mol%.

[0305] In the case where the (c1) acrylic copolymer resin contains a partial structure represented by formula (I'), the content ratio of the partial structure represented by formula (I') contained in the (c1) acrylic copolymer resin is not particularly limited, and is preferably 10 mol% or more, more preferably 20 mol% or more, further preferably 30 mol% or more, further preferably 40 mol% or more, particularly preferably 50 mol% or more, and most preferably 65 mol% or more. In addition, it is preferably 95 mol% or less, more preferably 90 mol% or less, further preferably 85 mol% or less, further preferably 80 mol% or less, particularly preferably 75 mol% or less, and most preferably 70 mol% or less. By setting it to above the aforementioned lower limit, there is a tendency for the curability of the coating film to be improved during ultraviolet exposure, and by setting it to below the aforementioned upper limit, there is a tendency for the alkali solubility to be improved during alkali development. The above upper and lower limits can be combined arbitrarily. For example, the content of the partial structure represented by formula (I') contained in the acrylic copolymer resin (c1) is preferably 10 to 95 mol%, more preferably 20 to 90 mol%, further preferably 30 to 85 mol%, further preferably 40 to 80 mol%, particularly preferably 50 to 75 mol%, and most preferably 65 to 70 mol%.

[0306] When the (c1) acrylic copolymer resin contains a partial structure represented by formula (I), other partial structures that may be contained are not particularly limited, but from the viewpoint of alkali solubility during alkali development, for example, it preferably has a partial structure represented by the following general formula (II).

[0307]

[0308] In formula (II), R 3 represents a hydrogen atom or a methyl group, R 4 It represents an alkyl group which may have a substituent, an aromatic ring group which may have a substituent, or an alkenyl group which may have a substituent.

[0309] (R 4 )

[0310] In formula (II), R 4 It represents an alkyl group which may have a substituent, an aromatic ring group which may have a substituent, or an alkenyl group which may have a substituent.

[0311] As R 4The alkyl group in can be a linear, branched or cyclic alkyl group. The carbon number is preferably 1 or more, more preferably 3 or more, further preferably 5 or more, particularly preferably 8 or more, and preferably 20 or less, more preferably 18 or less, further preferably 16 or less, further preferably 14 or less, and particularly preferably 12 or less. By setting it to be above the aforementioned lower limit, there is a tendency for the lipophilicity to be improved and the solubility in the solvent to be improved. In addition, by setting it to be below the aforementioned upper limit, there is a tendency for the hydrophilicity to be improved and the alkali solubility to be improved. The above upper and lower limits can be combined arbitrarily. For example, the carbon number of the alkyl group is preferably 1 to 20, more preferably 1 to 18, further preferably 3 to 16, further preferably 5 to 14, and particularly preferably 8 to 12.

[0312] Examples of the alkyl group include a methyl group, an ethyl group, a cyclohexyl group, a dicyclopentyl group, and a dodecyl group. From the viewpoint of developability, a dicyclopentyl group and a dodecyl group are preferred, and a dicyclopentyl group is more preferred.

[0313] Examples of the substituent which the alkyl group may have include a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxyl group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, a carboxyl group, an acryloyl group, and a methacryloyl group. From the viewpoint of developability, a hydroxyl group and an oligoethylene glycol group are preferred.

[0314] As R 4 The aromatic ring group in the formula (a) may include a monovalent aromatic hydrocarbon ring group and a monovalent aromatic heterocyclic group. The carbon number is preferably 6 or more, and preferably 24 or less, more preferably 22 or less, further preferably 20 or less, and particularly preferably 18 or less. By setting it to be above the aforementioned lower limit, there is a tendency for the lipophilicity to be improved and the solubility in the solvent to be improved. In addition, by setting it to be below the aforementioned upper limit, there is a tendency for the hydrophilicity to be improved and the alkali solubility to be improved. The above upper and lower limits may be combined arbitrarily. For example, the carbon number of the aromatic ring group is preferably 6 to 24, more preferably 6 to 22, further preferably 6 to 20, and particularly preferably 6 to 18.

[0315] The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a single ring or a condensed ring, and examples thereof include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzopyrene ring, Ring, triphenylene ring, acenaphthene ring, fluoranthene ring, fluorene ring.

[0316] In addition, the aromatic heterocyclic ring in the aromatic heterocyclic group may be a monocyclic ring or a condensed ring, and examples thereof include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, an indole ring, a carbazole ring, a pyrroloimidazole ring, a pyrrolopyrazole ring, a pyrrolopyrrole ring, a thienopyrrole ring, a thienothiophene ring, a furopyrrole ring, a furofuran ring, a thienofuran ring, a benzisoxazole ring, a benzisothiazole ring, a benzimidazole ring, a pyridine ring, a pyrazine ring, a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a cinnoline ring, a quinoxaline ring, a phenanthridine ring, a phenanthridine ring, a quinazoline ring, a quinazolinone ring, and an azulene ring. From the viewpoint of developability, a benzene ring group and a naphthyl ring group are preferred, and a benzene ring group is more preferred.

[0317] Examples of the substituent that the aromatic ring group may have include a methyl group, an ethyl group, a propyl group, a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxyl group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, and a carboxyl group. From the viewpoint of developability, a hydroxyl group and an oligoethylene glycol group are preferred.

[0318] As R 4 The alkenyl group in the group may be a linear, branched or cyclic alkenyl group. The carbon number is preferably 2 or more, and preferably 22 or less, more preferably 20 or less, further preferably 18 or less, further preferably 16 or less, and particularly preferably 14 or less. By setting it to be above the aforementioned lower limit, there is a tendency for the lipophilicity to be improved and the solubility in the solvent to be improved. In addition, by setting it to be below the aforementioned upper limit, there is a tendency for the hydrophilicity to be improved and the alkali solubility to be improved. The above upper and lower limits may be combined arbitrarily. For example, the carbon number of the alkenyl group is preferably 2 to 22, more preferably 2 to 20, further preferably 2 to 18, further preferably 2 to 16, and particularly preferably 2 to 14.

[0319] Examples of the alkenyl group include vinyl, allyl, 2-propylene-2-yl, 2-butene-1-yl, 3-butene-1-yl, 2-pentene-1-yl, 3-pentene-2-yl, hexenyl, cyclobutenyl, cyclopentenyl, and cyclohexenyl. From the viewpoint of developability, vinyl and allyl groups are preferred, and vinyl groups are more preferred.

[0320] Examples of the substituent that the alkenyl group may have include a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxyl group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, and a carboxyl group. From the viewpoint of developability, a hydroxyl group and an oligoethylene glycol group are preferred.

[0321] R 4 It represents an alkyl group which may have a substituent, an aromatic ring group which may have a substituent, or an alkenyl group which may have a substituent, and from the viewpoint of developability and film strength, an alkyl group or an alkenyl group is preferred, and an alkyl group is more preferred.

[0322] When the (c1) acrylic copolymer resin contains a partial structure represented by formula (II), the content ratio of the partial structure represented by formula (II) in the (c1) acrylic copolymer resin is not particularly limited, and is preferably 1 mol% or more, more preferably 5 mol% or more, further preferably 10 mol% or more, and particularly preferably 20 mol% or more. In addition, it is preferably 70 mol% or less, more preferably 60 mol% or less, further preferably 50 mol% or less, and particularly preferably 40 mol% or less. By setting it to be above the aforementioned lower limit, there is a tendency for the alkali solubility to be improved, and by setting it to be below the aforementioned upper limit, there is a tendency for the storage stability of the colored resin composition to be improved. For example, the content ratio of the partial structure represented by formula (II) in the (c1) acrylic copolymer resin is preferably 1 to 70 mol%, more preferably 5 to 60 mol%, further preferably 10 to 50 mol%, and particularly preferably 20 to 40 mol%.

[0323] When the (c1) acrylic copolymer resin contains the partial structure represented by formula (I), it preferably contains a partial structure represented by the following general formula (III) as another partial structure that may be contained from the viewpoint of suppressing a decrease in brightness by improving heat resistance.

[0324]

[0325] In formula (III), R 5 represents a hydrogen atom or a methyl group, R 6 It represents an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, a hydroxyl group, a carboxyl group, a halogen atom, an alkoxy group which may have a substituent, a thiol group or an alkylthioether group which may have a substituent.

[0326] t represents an integer from 0 to 5.

[0327] (R 6 )

[0328] In formula (III), R 6 It represents an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, a hydroxyl group, a carboxyl group, a halogen atom, an alkoxy group which may have a substituent, a thiol group or an alkylthioether group which may have a substituent.

[0329] As R 6The alkyl group in can be a linear, branched or cyclic alkyl group. The carbon number is preferably 1 or more, more preferably 3 or more, and further preferably 5 or more. In addition, it is preferably 20 or less, more preferably 18 or less, further preferably 16 or less, further preferably 14 or less, and particularly preferably 12 or less. By setting it to be above the aforementioned lower limit, there is a tendency for the lipophilicity to be improved and the solubility in the solvent to be improved. In addition, by setting it to be below the aforementioned upper limit, there is a tendency for the hydrophilicity to be improved and the alkali solubility to be improved. The above upper and lower limits can be combined arbitrarily. For example, the carbon number of the alkyl group is preferably 1 to 20, more preferably 1 to 18, further preferably 3 to 16, further preferably 3 to 14, and particularly preferably 5 to 12.

[0330] Examples of the alkyl group include a methyl group, an ethyl group, a cyclohexyl group, a dicyclopentyl group, and a dodecyl group. Among these, from the viewpoint of heat resistance, a dicyclopentyl group and a dodecyl group are preferred, and a dicyclopentyl group is more preferred.

[0331] Examples of the substituent which the alkyl group may have include a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxyl group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, a carboxyl group, an acryloyl group, and a methacryloyl group. From the viewpoint of developability, a hydroxyl group and an oligoethylene glycol group are preferred.

[0332] As R 6 The alkenyl group in the group may be a linear, branched or cyclic alkenyl group. The carbon number is preferably 2 or more, and preferably 22 or less, more preferably 20 or less, further preferably 18 or less, further preferably 16 or less, and particularly preferably 14 or less. By setting it to be above the aforementioned lower limit, there is a tendency for the lipophilicity to be improved and the solubility in the solvent to be improved. In addition, by setting it to be below the aforementioned upper limit, there is a tendency for the hydrophilicity to be improved and the alkali solubility to be improved. The above upper and lower limits may be combined arbitrarily. For example, the carbon number of the alkenyl group is preferably 2 to 22, more preferably 2 to 20, further preferably 2 to 18, further preferably 2 to 16, and particularly preferably 2 to 14.

[0333] Examples of the alkenyl group include vinyl, allyl, 2-propylene-2-yl, 2-butene-1-yl, 3-butene-1-yl, 2-pentene-1-yl, 3-pentene-2-yl, hexenyl, cyclobutenyl, cyclopentenyl, and cyclohexenyl. Among these, vinyl and allyl are preferred, and vinyl is more preferred from the viewpoint of exposure sensitivity during ultraviolet exposure.

[0334] Examples of the substituent that the alkenyl group may have include a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxyl group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, and a carboxyl group. From the viewpoint of developability, a hydroxyl group and an oligoethylene glycol group are preferred.

[0335] As R 6 The alkynyl in may be a linear, branched or cyclic alkynyl. The carbon number is preferably 2 or more, preferably 22 or less, more preferably 20 or less, further preferably 18 or less, further preferably 16 or less, and particularly preferably 14 or less. By setting it to be above the aforementioned lower limit, there is a tendency for the lipophilicity to be improved and the solubility in the solvent to be improved. In addition, by setting it to be below the aforementioned upper limit, there is a tendency for the hydrophilicity to be improved and the alkali solubility to be improved. The above upper and lower limits may be combined arbitrarily. For example, the carbon number of the alkynyl is preferably 2 to 22, more preferably 2 to 20, further preferably 2 to 18, further preferably 2 to 16, and particularly preferably 2 to 14.

[0336] Examples of the alkynyl group include 1-propyn-3-yl, 1-butyn-4-yl, 1-pentyn-5-yl, 2-methyl-3-butyn-2-yl, 1,4-pentadiyn-3-yl, 1,3-pentadiyn-5-yl, and 1-hexyn-6-yl.

[0337] Examples of the substituent that the alkynyl group may have include a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxyl group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, and a carboxyl group. From the viewpoint of developability, a hydroxyl group and an oligoethylene glycol group are preferred.

[0338] As R 6 Examples of the halogen atom in include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. From the viewpoint of the storage stability of the acrylic copolymer resin (c1), a fluorine atom is preferred.

[0339] As R 6 The alkoxy group in the group may be a linear, branched or cyclic alkoxy group. The number of carbon atoms is preferably 1 or more, and preferably 20 or less, more preferably 18 or less, further preferably 16 or less, further preferably 14 or less, and particularly preferably 12 or less. By setting the value above the lower limit, there is a tendency for the lipophilicity to be improved and the solubility in the solvent to be improved. By setting the value below the upper limit, there is a tendency for the hydrophilicity to be improved and the alkali solubility to be improved. The upper and lower limits mentioned above may be combined arbitrarily. For example, the number of carbon atoms in the alkoxy group is preferably 1 to 20, more preferably 1 to 18, further preferably 1 to 16, further preferably 1 to 14, and particularly preferably 1 to 12.

[0340] Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, and an isobutoxy group.

[0341] Examples of the substituent that the alkoxy group may have include a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxyl group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, a carboxyl group, an acryloyl group, and a methacryloyl group. From the viewpoint of developability, a hydroxyl group and an oligoethylene glycol group are preferred.

[0342] As R 6 The alkyl thioether group in the alkyl thioether group may be a linear, branched or cyclic alkyl thioether group. The carbon number is preferably 1 or more, and preferably 20 or less, more preferably 18 or less, further preferably 16 or less, further preferably 14 or less, and particularly preferably 12 or less. By setting it to be above the aforementioned lower limit, there is a tendency for the lipophilicity to be improved and the solubility in the solvent to be improved. In addition, by setting it to be below the aforementioned upper limit, there is a tendency for the hydrophilicity to be improved and the alkali solubility to be improved. The above upper and lower limits may be combined arbitrarily. For example, the carbon number of the alkyl thioether group is preferably 1 to 20, more preferably 1 to 18, further preferably 1 to 16, further preferably 1 to 14, and particularly preferably 1 to 12.

[0343] Examples of the alkyl sulfide group include a methyl sulfide group, an ethyl sulfide group, a propyl sulfide group, and a butyl sulfide group. From the viewpoint of developability, a methyl sulfide group and an ethyl sulfide group are preferred.

[0344] Examples of the substituent that the alkyl group in the alkyl thioether group may have include a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxyl group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, a carboxyl group, an acryloyl group, and a methacryloyl group. From the viewpoint of developability, a hydroxyl group and an oligoethylene glycol group are preferred.

[0345] R 6 It represents an alkyl group optionally having a substituent, an alkenyl group optionally having a substituent, an alkynyl group optionally having a substituent, a hydroxyl group, a carboxyl group, a halogen atom, an alkoxy group, a hydroxyalkyl group, a thiol group or an alkyl thioether group optionally having a substituent, and among these, a hydroxyl group or a carboxyl group is preferred, and a carboxyl group is more preferred, from the viewpoint of developability.

[0346] In formula (III), t represents an integer of 0 to 5, and t is preferably 0 from the viewpoint of ease of production.

[0347] When the (c1) acrylic copolymer resin contains a partial structure represented by formula (III), the content ratio of the partial structure represented by formula (III) in the (c1) acrylic copolymer resin is not particularly limited, and is preferably 1 mol% or more, more preferably 2 mol% or more, further preferably 5 mol% or more, and particularly preferably 8 mol% or more. In addition, it is preferably 50 mol% or less, more preferably 40 mol% or less, further preferably 30 mol% or less, and particularly preferably 20 mol% or less. By setting it to be above the aforementioned lower limit, there is a tendency to improve heat resistance and suppress brightness reduction. In addition, by setting it to be below the aforementioned upper limit, there is a tendency to increase the content ratio of other partial structures and improve alkali solubility. The above upper and lower limits can be combined arbitrarily. For example, the content ratio of the partial structure represented by formula (III) in the (c1) acrylic copolymer resin is preferably 1 to 50 mol%, more preferably 2 to 40 mol%, further preferably 5 to 30 mol%, and particularly preferably 8 to 20 mol%.

[0348] When the (c1) acrylic copolymer resin includes the partial structure represented by the formula (I), it preferably includes a partial structure represented by the following general formula (IV) as another partial structure that may be included from the viewpoint of developability.

[0349]

[0350] In formula (IV), R 7 represents a hydrogen atom or a methyl group.

[0351] When the (c1) acrylic copolymer resin contains a partial structure represented by formula (IV), the content ratio of the partial structure represented by formula (IV) in the (c1) acrylic copolymer resin is not particularly limited, and is preferably 5 mol% or more, more preferably 10 mol% or more, and further preferably 20 mol% or more. In addition, it is preferably 80 mol% or less, more preferably 70 mol% or less, and further preferably 60 mol% or less. By setting it to be above the aforementioned lower limit, there is a tendency for the alkali solubility to be improved. In addition, by setting it to be below the aforementioned upper limit, there is a tendency for the storage stability of the colored resin composition to be improved. The above upper and lower limits can be combined arbitrarily. For example, the content ratio of the partial structure represented by formula (IV) in the (c1) acrylic copolymer resin is preferably 5 to 80 mol%, more preferably 10 to 70 mol%, and further preferably 20 to 60% mol%.

[0352] (C) The acid value of the alkali-soluble resin is not particularly limited, but is preferably 10 mgKOH / g or more, more preferably 30 mgKOH / g or more, further preferably 40 mgKOH / g or more, further preferably 50 mgKOH / g or more, and particularly preferably 60 mgKOH / g or more, and is preferably 300 mgKOH / g or less, more preferably 250 mgKOH / g or less, further preferably 200 mgKOH / g or less, and further preferably 150 mgKOH / g or less. By setting it to the above lower limit or more, there is a tendency for alkali solubility to be improved, and by setting it to the above upper limit or less, there is a tendency for the storage stability of the colored resin composition to be improved.

[0353] For example, the acid value of the alkali-soluble resin (C) is preferably 10 to 300 mgKOH / g, more preferably 30 to 300 mgKOH / g, further preferably 40 to 250 mgKOH / g, further preferably 50 to 200 mgKOH / g, and particularly preferably 60 to 150 mgKOH / g.

[0354] The weight average molecular weight (Mw) of the alkali-soluble resin (C) is not particularly limited, and is generally 1000 or more, preferably 2000 or more, more preferably 4000 or more, further preferably 6000 or more, further preferably 7000 or more, and particularly preferably 8000 or more. In addition, it is generally 30000 or less, preferably 20000 or less, more preferably 15000 or less, and further preferably 10000 or less. By setting it to be above the aforementioned lower limit, there is a tendency for heat resistance and coating curability to be improved. In addition, by setting it to be below the aforementioned upper limit, there is a tendency for alkali solubility to be improved. The above upper and lower limits can be combined arbitrarily. For example, the weight average molecular weight of the alkali-soluble resin (C) is preferably 1000 to 30000, more preferably 2000 to 30000, further preferably 4000 to 20000, further preferably 6000 to 20000, further preferably 7000 to 15000, and particularly preferably 8000 to 10000.

[0355] The content ratio of the (C) alkali-soluble resin 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, further preferably 20% by mass or more, particularly preferably 30% by mass or more, and preferably 80% by mass or less, more preferably 70% by mass or less, further preferably 60% by mass or less, and particularly preferably 50% by mass or less. By setting it to above the aforementioned lower limit, there is a tendency for the curability of the coating film to be improved during ultraviolet exposure, and by setting it to below the aforementioned upper limit, there is a tendency for the solubility in the developer to be improved and the residue to be suppressed. The above upper and lower limits can be combined arbitrarily. For example, the content ratio of the (C) alkali-soluble resin in the colored resin composition is preferably 5 to 80% by mass, more preferably 10 to 70% by mass, further preferably 20 to 60% by mass, and further preferably 30 to 50% by mass, relative to the total solid content of the colored resin composition.

[0356] [2-2] (D) Photopolymerization initiator

[0357] 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.

[0358] (D) The photopolymerization initiator can also be used as 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 undergoing a decomposition reaction or a hydrogen abstraction reaction by being photosensitized, thereby generating polymerization-active free radicals.

[0359] (D) Photopolymerization initiator, for example, metallocene compounds including titanocene compounds described in Japanese Patent Application Laid-Open No. 59-152396 and Japanese Patent Application Laid-Open No. 61-151197; hexaarylbiimidazole derivatives described in Japanese Patent Application Laid-Open No. 10-39503; halogenated methyl-s-triazine derivatives, N-aryl-α-amino acids such as N-phenylglycine, N-aryl-α-amino acid salts, N-aryl-α-amino acid esters and other free radical activators, α-aminoalkylphenone derivatives; oxime ester initiators described in Japanese Patent Application Laid-Open No. 2000-80068.

[0360] Specific examples of the photopolymerization initiator that can be used in the present invention are listed below.

[0361] Halogenated methylated s-triazine derivatives such as 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, and 2-(4-ethoxycarbonylnaphthyl)-4,6-bis(trichloromethyl)-s-triazine;

[0362] Halogenated methylated oxadiazole derivatives such as 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 and 2-trichloromethyl-5-furanyl-1,3,4-oxadiazole;

[0363] 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;

[0364] Benzoin alkyl ethers such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether and benzoin isopropyl ether;

[0365] Anthraquinone derivatives such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, and 1-chloroanthraquinone;

[0366] Benzophenone derivatives such as benzophenone, Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, and 2-carboxybenzophenone;

[0367] Acetophenone derivatives such as 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, α-hydroxy-2-methylphenyl acetone, 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;

[0368] Thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone and other thioxanthone derivatives;

[0369] Benzoate derivatives such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate;

[0370] Acridine derivatives such as 9-phenylacridine and 9-(p-methoxyphenyl)acridine;

[0371] Phenazine derivatives such as 9,10-dimethylbenzophenazine;

[0372] Anthraquinone derivatives such as benzanthrone;

[0373] Titanocene derivatives such as dicyclopentadienyl dichloride Ti, dicyclopentadienyl bisphenyl Ti, dicyclopentadienyl bis(2,3,4,5,6-pentafluorophenyl) Ti, dicyclopentadienyl bis(2,3,5,6-tetrafluorophenyl) Ti, dicyclopentadienyl bis(2,4,6-trifluorophenyl) Ti, dicyclopentadienyl(2,6-difluorophenyl) Ti, dicyclopentadienyl(2,4-difluorophenyl) Ti, dimethylcyclopentadienylbis(2,3,4,5,6-pentafluorophenyl-1-yl) Ti, dimethylcyclopentadienylbis(2,6-difluorophenyl) Ti, dicyclopentadienyl(2,6-difluoro-3-(pyrrol-1-yl)phenyl Ti;

[0374] α-Aminoalkylphenone compounds such as 2-methyl-1〔4-(methylthio)phenyl〕-2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 4-dimethylaminoethylbenzoate, 4-dimethylaminoisoamylbenzoate, 4-dimethylaminoacetophenone, 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;

[0375] Oxime ester compounds such as 1,2-octanedione, 1-[4-(phenylthio)phenyl]-2-(O-benzoyloxime)ethanone and 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-(O-acetoxime).

[0376] From the viewpoint of sensitivity and surface properties, oxime ester compounds (oxime ester photopolymerization initiators) are preferred.

[0377] Since the oxime ester compound has a structure that absorbs ultraviolet rays, a structure that transmits light energy, and a structure that generates free radicals in its structure, it has high sensitivity even in a small amount, and is stable to thermal reaction, and a highly sensitive colored resin composition can be designed with a small amount. In particular, from the viewpoint of light absorption of i-rays (365 nm) of the exposure light source, an oxime ester compound containing a carbazole ring that may have a substituent is preferred.

[0378] Examples of the oxime ester compound include compounds represented by the following general formula (I-1).

[0379]

[0380] In 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.

[0381] R 21b It represents an arbitrary substituent containing an aromatic ring or a heteroaromatic ring.

[0382] R 22a It represents an alkanoyl group which may have a substituent or an aroyl group which may have a substituent.

[0383] 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 a solvent and sensitivity to exposure. The above upper and lower limits may be combined arbitrarily. For example, the number of carbon atoms in the alkyl group is preferably 1 to 20, more preferably 1 to 15, further preferably 1 to 10, further preferably 1 to 5, and particularly preferably 2 to 5.

[0384] Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a cyclopentylethyl group, and a propyl group.

[0385] Examples of the substituent that 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.

[0386] As R 21a The aromatic ring group in the composition may include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The number of carbon atoms in the aromatic ring group is not particularly limited, but is preferably 5 or more from the viewpoint of solubility in the colored resin composition. In addition, from the viewpoint of developability, it is preferably 30 or less, more preferably 20 or less, further preferably 12 or less, and particularly preferably 8 or less. The above upper and lower limits may be combined arbitrarily. For example, the number of carbon atoms in the aromatic ring group is preferably 5 to 30, more preferably 5 to 20, further preferably 5 to 12, and particularly preferably 5 to 8.

[0387] Examples of the aromatic ring group include a phenyl group, a naphthyl group, a pyridyl group, a furyl group, and a fluorenyl group. From the viewpoint of developability, a phenyl group, a naphthyl group, and a fluorenyl group are preferred, and a phenyl group and a fluorenyl group are more preferred.

[0388] 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. 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. From the viewpoint of developability, R 21a , preferably an alkyl group which may have a substituent, more preferably an unsubstituted alkyl group, and further preferably a methyl group.

[0389] 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, a fluorenyl group optionally having a substituent, or a group formed by connecting these groups to a carbonyl group. From the viewpoint of light absorption to i-rays (365 nm) of an exposure light source, preferably, a carbazolyl group optionally having a substituent, or a group formed by connecting a carbazolyl group optionally having a substituent and a carbonyl group.

[0390] Examples of the substituent that the carbazolyl group may optionally have include: an alkyl group having 1 to 10 carbon atoms, such as a methyl group and an ethyl group; an alkoxy group having 1 to 10 carbon atoms, such as a methoxy group and an ethoxy group; a halogen atom, such as F, Cl, Br, or I; an acyl group having 1 to 10 carbon atoms; an alkyl ester group having 1 to 10 carbon atoms; an alkoxycarbonyl group having 1 to 10 carbon atoms; a haloalkyl group having 1 to 10 carbon atoms; an aromatic ring group having 4 to 10 carbon atoms; an amino group; an aminoalkyl group having 1 to 10 carbon atoms; a hydroxyl group; a nitro group; a CN group; an aromatic acyl group optionally having a substituent; a heteroaroyl group optionally having a substituent; and a thenoyl group optionally having a substituent.

[0391] R 22a The carbon number 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 in a solvent and sensitivity. The above upper and lower limits may be combined arbitrarily. For example, the carbon number of the alkanoyl group is preferably 2 to 20, more preferably 2 to 15, further preferably 2 to 10, further preferably 2 to 5, and particularly preferably 3 to 5.

[0392] Examples of the alkanoyl group include acetyl, ethyloyl, propionyl, and butyryl.

[0393] 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, and an amide group. From the viewpoint of ease of synthesis, the alkanoyl group is preferably unsubstituted.

[0394] R 22a The carbon number 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 in a solvent and sensitivity. The above upper and lower limits may be combined arbitrarily. For example, the carbon number of the aromatic acyl group is preferably 7 to 20, more preferably 7 to 15, further preferably 7 to 10, and particularly preferably 8 to 10.

[0395] Examples of the aroyl group include a benzoyl group and a naphthoyl group.

[0396] 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, and the aroyl group is preferably unsubstituted from the viewpoint of ease of synthesis.

[0397] From the viewpoint of light absorption of i-rays (365 nm) of an exposure light source, examples of the compound represented by formula (I-1) include compounds represented by the following general formula (I-2) or (I-3).

[0398]

[0399] In formula (I-2) and formula (I-3), R 21a and R 22a It has the same meaning as formula (I-1).

[0400] R 23a It represents an alkyl group which may have a substituent.

[0401] 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.

[0402] The benzene ring constituting the carbazole ring may be further fused with an aromatic ring to form a polycyclic aromatic ring.

[0403] R 23a The number of carbon atoms in the alkyl group is not particularly limited, but is generally 1 or more, preferably 2 or more, and generally 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. The above upper and lower limits may be combined arbitrarily. For example, the number of carbon atoms in the alkyl group is preferably 1 to 20, more preferably 1 to 15, further preferably 1 to 10, further preferably 1 to 5, and particularly preferably 2 to 5.

[0404] Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, and a cyclohexyl group.

[0405] Examples of the substituent which the alkyl group may have include a carbonyl group, a carboxyl group, a hydroxyl group, a phenyl group, a benzyl group, a cyclohexyl group, and a nitro group.

[0406] From the viewpoint of ease of synthesis, unsubstituted is preferred.

[0407] As R 23a , and from the viewpoint of solubility in a solvent and ease of synthesis, an ethyl group is more preferred.

[0408] R 24a The number of carbon atoms in the alkyl group is not particularly limited, but is generally 1 or more, preferably 2 or more, and generally 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. The above upper and lower limits may be combined arbitrarily. For example, the number of carbon atoms in the alkyl group is preferably 1 to 20, more preferably 1 to 15, further preferably 1 to 10, further preferably 1 to 5, and particularly preferably 2 to 5.

[0409] Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, and a cyclohexyl group.

[0410] Examples of the substituent which the alkyl group may have include a carbonyl group, a carboxyl group, a hydroxyl group, a phenyl group, a benzyl group, a cyclohexyl group, and a nitro group.

[0411] From the viewpoint of ease of synthesis, unsubstituted is preferred.

[0412] R 24a The carbon number 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, and is usually 20 or less, preferably 15 or less, more preferably 10 or less, and further preferably 9 or less, from the viewpoint of solubility in a solvent. The above upper and lower limits may be combined arbitrarily. For example, the carbon number of the aromatic acyl group is preferably 7 to 20, more preferably 8 to 15, further preferably 9 to 10, and particularly preferably 9.

[0413] Examples of the aroyl group include a benzoyl group and a naphthoyl group.

[0414] Examples of the substituent that the aroyl group may have include a carbonyl group, 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.

[0415] R 24aThe carbon number 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. The above upper and lower limits may be combined arbitrarily. For example, the carbon number of the heteroaroyl group is preferably 7 to 20, more preferably 8 to 15, further preferably 9 to 10, and particularly preferably 9.

[0416] Examples of the heteroaryl group include a fluorobenzoyl group, a chlorobenzoyl group, a bromobenzoyl group, a fluoronaphthoyl group, a chloronaphthoyl group, and a bromonaphthoyl group.

[0417] Examples of the substituent that the heteroaroyl group may have include a carbonyl group, 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, it is preferably unsubstituted.

[0418] As R 24a From the viewpoint of sensitivity, an aroyl group which may have a substituent is preferred, and a benzoyl group is more preferred.

[0419] The benzene ring constituting the carbazole ring may be further fused with an aromatic ring to form a polycyclic aromatic ring.

[0420] Examples of commercially available products of oxime ester compounds include OXE-02 and OXE-03 manufactured by BASF, TR-PBG-304 and TR-PBG-314 manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd., and N-1919, NCI-930, and NCI-831 manufactured by ADEKA.

[0421] Specific examples of the oxime ester compound include the following compounds.

[0422]

[0423]

[0424]

[0425] These photopolymerization initiators may be used alone or in combination of two or more.

[0426] In the colored resin composition of the present invention, the content ratio of the (D) photopolymerization initiator is not particularly limited, and is preferably 0.5% by mass or more, more preferably 0.8% by mass or more, further preferably 1.0% by mass or more, particularly preferably 1.2% by mass or more, relative to the total solid content of the colored resin composition, and preferably 10% by mass or less, more preferably 9% by mass or less, further preferably 8% by mass or less, and particularly preferably 7% by mass or less. By setting it to be above the aforementioned lower limit, there is a tendency for the curability of the coating film to be improved, and by setting it to be below the aforementioned upper limit, there is a tendency to increase the brightness by reducing visible light absorption. The above upper and lower limits can be combined arbitrarily. For example, in the colored resin composition, the content ratio of the (D) photopolymerization initiator is preferably 0.5-10% by mass, more preferably 0.8-9% by mass, further preferably 1.0-8% by mass, and particularly preferably 1.2-7% by mass, relative to the total solid content of the colored resin composition.

[0427] In the colored resin composition of the present invention, the total content of the compound represented by formula (3) and the benzoquinone compound is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, further preferably 10 parts by mass or less, and particularly preferably 5 parts by mass or less, relative to 100 parts by mass of the photopolymerization initiator (D). In addition, it is preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, further preferably 0.2 parts by mass or more, and particularly preferably 0.2 parts by mass or more. By setting it below the above upper limit, there is a tendency for the curability of the coating film to be improved and the patterning to be improved. In addition, by setting it above the above lower limit, there is a tendency for the time-dependent change of sensitivity to be suppressed. The above upper and lower limits can be combined arbitrarily. For example, relative to 100 parts by mass of the photopolymerization initiator (D), the total content of the compound represented by formula (3) and the benzoquinone compound is preferably 0.05 to 30 parts by mass, more preferably 0.1 to 20 parts by mass, further preferably 0.2 to 10 parts by mass, and particularly preferably 0.5 to 5 parts by mass.

[0428] When the colored resin composition of the present invention contains a chain transfer agent, the content ratio thereof is not particularly limited, but is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, further preferably 0.3% by mass or more, particularly preferably 0.4% by mass or more, and preferably 5% by mass or less, more preferably 3% by mass or less, further preferably 2% by mass or less, particularly preferably 1% by mass or less, relative to the total solid content of the colored resin composition. By setting it to the above lower limit or more, there is a tendency for solvent resistance to improve, and by setting it to the above upper limit or less, there is a tendency for storage stability to improve.

[0429] The above upper and lower limits may be combined arbitrarily. For example, when the colored resin composition contains a chain transfer agent, the content ratio thereof is preferably 0.1 to 5% by mass, more preferably 0.2 to 3% by mass, further preferably 0.3 to 2% by mass, and particularly preferably 0.4 to 1% by mass relative to the total solid content of the colored resin composition.

[0430] [2-3] Other solid ingredients

[0431] The colored resin composition of the present invention may further contain solid components other than the above components as needed.

[0432] Examples of such components include photopolymerizable monomers and surfactants.

[0433] [2-3-1] Photopolymerizable monomer

[0434] The photopolymerizable monomer is not particularly limited as long as it is a polymerizable low molecular compound, and is preferably an addition-polymerizable compound having at least one olefinic double bond (hereinafter referred to as an "olefinic compound"). An olefinic compound refers to a compound having an olefinic double bond that undergoes addition polymerization and curing 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 opposite to the so-called high molecular substance, and refers to the concept of dimers, trimers, and oligomers in addition to monomers in a narrow sense.

[0435] 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 more than 2, preferably more than 4, more preferably more than 5, and preferably less than 8, more preferably less than 7. The above upper and lower limits may be combined arbitrarily. For example, it may be 2 to 8, 4 to 8, or 5 to 7. 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 a solvent.

[0436] Examples of the olefinic compound include unsaturated carboxylic acids, esters thereof with monohydroxy compounds, esters of aliphatic polyhydroxy compounds with unsaturated carboxylic acids, esters of aromatic polyhydroxy compounds with unsaturated carboxylic acids, esters obtained by esterification reaction of unsaturated carboxylic acids and polyhydroxy compounds such as the aliphatic polyhydroxy compounds and aromatic polyhydroxy compounds, and olefinic compounds having a carbamate skeleton obtained by reacting a polyisocyanate compound with a (meth)acryloyl group-containing hydroxy compound.

[0437] Examples of the 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, crotonates obtained by replacing the acrylic acid moiety with a crotonic acid moiety, or maleates obtained by replacing the acrylic acid moiety with a maleic acid moiety.

[0438] Examples of the esters of an aromatic polyhydroxy compound and an unsaturated carboxylic acid include hydroquinone diacrylate, hydroquinone dimethacrylate, resorcinol diacrylate, resorcinol dimethacrylate, and pyrogallol triacrylate.

[0439] The ester obtained by the esterification reaction of unsaturated carboxylic acid and polycarboxylic acid with polyhydroxy compound is not necessarily a single substance, but may be a mixture. Examples thereof include condensates of acrylic acid, phthalic acid and ethylene glycol; condensates of acrylic acid, maleic acid and diethylene glycol; condensates of methacrylic acid, terephthalic acid and pentaerythritol; and condensates of acrylic acid, adipic acid, butanediol and glycerol.

[0440] Examples of the olefinic compound having a carbamate skeleton obtained by reacting a polyisocyanate compound with a (meth)acryloyl group-containing hydroxy compound include aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate; alicyclic diisocyanates such as cyclohexane diisocyanate and isophorone diisocyanate; reaction products of aromatic diisocyanates such as toluene diisocyanate and diphenylmethane diisocyanate with (meth)acryloyl group-containing hydroxy compounds such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxy(1,1,1-triacryloyloxymethyl)propane and 3-hydroxy(1,1,1-trimethacryloyloxymethyl)propane.

[0441] Examples of the olefinic compound used in the present invention include acrylamides such as ethylenebisacrylamide; allyl esters such as diallyl phthalate; and vinyl-containing compounds such as divinyl phthalate.

[0442] The olefinic compound may also be a monomer having an acid value. The monomer having an acid value is an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, preferably a polyfunctional monomer having an acid group by reacting the unreacted hydroxyl group of the aliphatic polyhydroxy compound with a non-aromatic carboxylic anhydride, and particularly preferably the aliphatic polyhydroxy compound in the ester is pentaerythritol and / or dipentaerythritol.

[0443] These monomers can be used alone, but since it is difficult to use a single compound in the manufacture, two or more kinds can also be used in combination. In addition, as required, a polyfunctional monomer without an acid group and a polyfunctional monomer with an acid group can also be used in combination as a monomer.

[0444] 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 to improve the curing properties such as the photopolymerization performance and the surface smoothness of the pixel. Therefore, when two or more polyfunctional monomers having different acid groups are used in combination, or when a polyfunctional monomer having no acid group is used in combination, it is preferred to adjust the acid groups of the overall polyfunctional monomers so that they fall within the above range.

[0445] In the present invention, a more preferred polyfunctional monomer having an acid group is a mixture of dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentaacrylate succinate, which is commercially available as TO1382 manufactured by Toagosei Co., Ltd. and is mainly composed of dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentaacrylate. This polyfunctional monomer may also be used in combination with other polyfunctional monomers. In addition, the compounds described in paragraphs 0056 and 0057 of Japanese Patent Publication No. 2013-140346 may also be used.

[0446] From the viewpoint of improving the chemical resistance of the pixel and the linearity of the edge of the pixel, the polymerizable monomer described in Japanese Patent Application Laid-Open No. 2013-195971 is preferably used. From the viewpoint of achieving both the sensitivity of the coating film and the shortening of the development time, the polymerizable monomer described in Japanese Patent Application Laid-Open No. 2013-195974 is preferably used.

[0447] When the colored resin composition of the present invention contains a photopolymerizable monomer, the content ratio of the photopolymerizable monomer is not particularly limited, and is preferably 5% by mass or more, more preferably 8% by mass or more, further preferably 10% by mass or more, particularly preferably 12% by mass or more, relative to the total solid content of the colored resin composition, and preferably 60% by mass or less, more preferably 50% by mass or less, further preferably 45% by mass or less, and particularly preferably 40% by mass or less. By setting it to above the aforementioned lower limit, there is a tendency for the curability of the coating film to be improved, and by setting it to below the aforementioned upper limit, there is a tendency to ensure the flatness of the coating film surface. The above upper and lower limits can be combined arbitrarily. For example, it can be 5 to 60% by mass, 8 to 50% by mass, 10 to 45% by mass, or 12 to 40% by mass.

[0448] [2-3-2] Surfactants

[0449] As the surfactant, various surfactants such as anionic, cationic, nonionic, and amphoteric surfactants can be used. However, nonionic surfactants are preferably used because they are less likely to adversely affect various properties.

[0450] When the colored resin composition of the present invention contains a surfactant, the content ratio of the surfactant is not particularly limited, and is generally 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 relative to the total solid content of the colored resin composition. It is generally used in the range of 10% by mass or less, preferably 1% by mass or less, more preferably 0.5% by mass or less, and particularly preferably 0.3% by mass or less. The above upper and lower limits can be combined arbitrarily. For example, it can be 0.001 to 10% by mass, it can be 0.01 to 1% by mass, it can be 0.05 to 0.5% by mass, or it can be 0.1 to 0.3% by mass.

[0451] [2-4] Preparation of colored resin composition

[0452] The method for preparing the colored resin composition (hereinafter sometimes referred to as a resist) of the present invention will be described.

[0453] The prepared colorant-containing liquid may be further mixed with (B) a solvent, (C) an alkali-soluble resin, (D) a photopolymerization initiator, and, if necessary, components other than those described above to prepare a uniform solution to obtain a colored resin composition.

[0454] The compound represented by formula (3) and the benzoquinone compound in the present invention are preferably mixed at the time of preparing the colorant-containing liquid.

[0455] Specifically, it is preferred that the compound represented by formula (3) and / or the benzoquinone compound be added in the step of preparing the liquid containing the colorant.

[0456] [3] Colored resin composition (second aspect)

[0457] Another embodiment of the colored resin composition of the present invention contains (A) a colorant, (B) a solvent, (C) an alkali-soluble resin, (D) a photopolymerization initiator, and a compound represented by formula (3) and / or a benzoquinone-based compound as essential components, and further, other additives other than the above components may be blended as necessary.

[0458] [3-1] (A) Colorants

[0459] The colored resin composition of the present invention contains (A) a colorant. The colorant is a component that colors the colored resin composition. By containing the (A) colorant, desired light absorption can be obtained.

[0460] The colorant (A) in the colored resin composition of the present invention includes a phthalocyanine compound having a chemical structure represented by the following general formula (1) (hereinafter sometimes referred to as "phthalocyanine compound (1)"). By including the phthalocyanine compound (1), the transmittance is improved, and a colored resin composition with high brightness can be obtained.

[0461]

[0462] In formula (1), A 1 ~A 16 Each independently represents a hydrogen atom, a halogen atom, or a group represented by the following general formula (2). 1 ~A 16 At least one of A represents a fluorine atom, and A 1 ~A 16 One or more of represents a group represented by the following general formula (2).

[0463]

[0464] In formula (2), X represents a divalent linking group. The benzene ring in formula (2) may have any substituent. * represents a linking bond.

[0465] (A 1 ~A 16 )

[0466] In formula (1), A 1 ~A 16 Each independently represents a hydrogen atom, a halogen atom, or a group represented by the following general formula (2). 1 ~A 16 At least one of A represents a fluorine atom, and A 1 ~A 16 One or more of represents a group represented by the following general formula (2).

[0467]

[0468] In formula (2), X represents a divalent linking group. The benzene ring in formula (2) may have any substituent. * represents a linking bond.

[0469] As A 1 ~A 16 Examples of the halogen atom in the photosensitive resin include a fluorine atom, a chlorine atom, and a bromine atom. From the viewpoint of increasing brightness, a fluorine atom is preferred.

[0470] Preferred A1 ~A 16 6 or more of the fluorine atoms are more preferably 7 or more, and even more preferably 8 or more. Also, it is preferably 15 or less, more preferably 12 or less, and even more preferably 10 or less. When it is equal to or more than the above lower limit, the stability of the phthalocyanine compound (1) tends to be improved, and when it is equal to or less than the above upper limit, the affinity with the dispersant and the solvent in the colored resin composition tends to be improved.

[0471] The above upper and lower limits can be combined arbitrarily. 1 ~A 16 The number of the substituents representing fluorine atoms in is 1-15, preferably 6-12, more preferably 7-10.

[0472] (X)

[0473] X in formula (2) 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 (R a1 represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 6 carbon atoms). From the viewpoint of the stability of the phthalocyanine compound (1) during calcination, an oxygen atom or a sulfur atom is preferred, and an oxygen atom is more preferred.

[0474] (Substituents optionally possessed by benzene ring)

[0475] 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 alkyl), alkoxy (-OR A Base (where R A represents an alkyl group. )), alkoxycarbonyl (-COOR A Base (where R A represents an alkyl group. )), an aryl group (-R B yl), aryloxy (-OR B Base (where R B Represents an aryl group. )), aryloxycarbonyl (-COOR B Base (where R B represents an aryl group.)) From the viewpoint of development solubility and brightness, an alkoxycarbonyl group is preferred.

[0476] The alkyl groups contained in these groups may be linear, branched or cyclic, but are preferably linear in view of affinity with organic solvents.

[0477] The carbon number of the alkyl group is not particularly limited, and is usually 1 or more, preferably 2 or more, and preferably 6 or less, more preferably 5 or less, and further preferably 4 or less. By setting the above lower limit or more, there is a tendency to suppress aggregation and foreign matter. In addition, by setting the above upper limit or less, there is a tendency to improve solvent affinity and improve stability over time.

[0478] The above upper and lower limits may be arbitrarily combined. For example, the number of carbon atoms in the alkyl group is preferably 1 to 6, more preferably 1 to 5, and even more preferably 2 to 4.

[0479] Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group. From the viewpoint of suppressing aggregation, the alkyl group is preferably a methyl group and an ethyl group, and more preferably an ethyl group.

[0480] The aryl group contained in these groups may be an aromatic hydrocarbon ring group or an aromatic heterocyclic group.

[0481] The carbon number of the aryl group is not particularly limited, and 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. By setting it to above the aforementioned lower limit, there is a tendency to suppress aggregation caused by steric repulsion. In addition, by setting it to below the aforementioned upper limit, there is a tendency to improve solvent affinity and improve stability over time.

[0482] The above upper and lower limits may be arbitrarily combined. For example, the number of carbon atoms in the aryl group is preferably 4 to 12, more preferably 4 to 10, and even more preferably 6 to 8.

[0483] 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 a benzene ring, a naphthalene ring, a pentalene ring, an indene ring, an azulene ring, and a heptalene ring having one free valence.

[0484] 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-oxazole ring, an isoxazole ring, a 1,3-thiazole ring, an isothiazole ring, an imidazole ring, a pyrazole ring, a furazan ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, a 1,3,5-triazine ring, a benzofuran ring, a 2-benzofuran ring, a benzothiophene ring, a 2-benzothiophene ring, a 1H-pyrrolidine ring, an indole ring, an isoindole ring, an indolizine ring, a 2H-benzopyran ring, a 1H-2-benzopyran ring, a quinoline ring, an isoquinoline ring, a 4H-quinolizine ring, a benzimidazole ring, a 1H-indazole ring, a quinoxaline ring, a quinazoline ring, a cinnoline ring, a phthalazine ring, a 1,8-naphthyridine ring, a purine ring, and a pteridine ring.

[0485] When the benzene ring in formula (2) has any substituent, the number of substitutions is not particularly limited. From the viewpoint of improving heat resistance by π-π stacking between dye molecules and suppressing the reduction in brightness caused by decomposition of the dye, the number of substitutions is preferably 1 relative to one benzene ring.

[0486] When the benzene ring in formula (2) has any substituent, the substitution position may be the ortho position, the meta position or the para position. From the viewpoint of promoting π-π stacking between molecules of the phthalocyanine compound (1), improving heat resistance and suppressing the reduction in brightness caused by the decomposition of the phthalocyanine compound (1), the para position is preferred.

[0487] In formula (1), A 1 ~A 16 In the formula (2), at least one of the above is a group. From the viewpoint of solubility in organic solvents and brightness, preferably: A 1 ~A 4 One or more of A is a group represented by formula (2), 5 ~A 8 One or more of A is a group represented by formula (2), 9 ~A 12 At least one of A is a group represented by formula (2), and 13 ~A 16 More preferably, one or more of A is a group represented by formula (2); 1 ~A 4 Two or more of them are groups represented by formula (2), A 5 ~A 8 Two or more of them are groups represented by formula (2), A 9 ~A 12 Two or more of them are groups represented by formula (2), and A 13 ~A 16 Two or more of them are groups represented by formula (2).

[0488] In the above formula (1), A 1 ~A 16 In the embodiment, at least one of the phthalocyanine atoms represents a fluorine atom. However, from the viewpoint of the stability of the phthalocyanine compound, it is preferred that: A 1 ~A 4 At least one of A is a fluorine atom. 5 ~A 8 At least one of A is a fluorine atom. 9 ~A 12 At least one of A is a fluorine atom, and 13 ~A 16 More preferably, one or more of A is a fluorine atom. 1 ~A 4 Two or more of them are fluorine atoms, A5 ~A 8 Two or more of them are fluorine atoms, A 9 ~A 12 Two or more of A are fluorine atoms, and 13 ~A 16 Two or more of them are fluorine atoms.

[0489] In view of the maximum transmission wavelength and transmittance of the phthalocyanine compound (1), affinity with the dispersant and solvent in the coloring resin composition, uniformity of crystallization of the phthalocyanine compound during firing of the color filter, and color tone required in the color filter, A is particularly preferred. 2 , A 3 , A 6 , A 7 , A 10 , A 11 , A 14 and A 15 is a group represented by formula (2), and A 1 , A 4 , A 5 , A 8 , A 9 , A 12 , A 13 and A 16 A fluorine atom.

[0490] Specific examples of the phthalocyanine compound (1) include the following compounds.

[0491]

[0492] It should be noted that, in the above formula, Et represents an ethyl group.

[0493]

[0494]

[0495]

[0496]

[0497] As a method for producing the phthalocyanine compound (1), a known method can be adopted, for example, the method described in Japanese Patent Application Laid-Open No. 05-345861 can be adopted.

[0498] (A) The colorant may include other colorants in addition to the phthalocyanine compound (1). As other colorants, dyes and pigments other than the phthalocyanine compound (1) may be listed. Among these, when used for green pixel applications, green pigments, yellow pigments, etc. are preferably used. In addition, when used for blue pixel applications, blue pigments, purple pigments, etc. are preferably used.

[0499] 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.

[0500] 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 5, 81, 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 、151、153、154、155、157、158、159、160、161、162、163、164、165、166、167、168、169、170、172、173、174、175、176、180、181、182、183、184、185、188、189、190、191、191:1 , 192, 193, 194, 195, 196, 197, 198, 199, 200, 202, 203, 204, 205, 206, 207, 208, and compounds formed by inserting other compounds into a 1:1 complex of azobarbituric acid and nickel represented by the following formula (i), or its tautomer (hereinafter sometimes referred to as "nickel azo complex represented by formula (i)").

[0501]

[0502] Examples of the other compound include compounds represented by the following formula (ii).

[0503]

[0504] Among these, CI Pigment Yellow 83, 117, 129, 138, 139, 154, 155, 180, 185 and the nickel azo complex represented by formula (i) are preferred from the viewpoint of high brightness and high color gamut, and CI Pigment Yellow 83, 138, 139, 180, 185 and the nickel azo complex represented by formula (i) are more preferred.

[0505] On the other hand, examples of blue pigments include CI Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56:1, 60, 61, 61:1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, and 79.

[0506] Among these, phthalocyanine pigments having a central metal are preferred from the viewpoint of heat resistance and structural stability, and blue copper phthalocyanine pigments are particularly preferred. Preferred examples of the copper phthalocyanine pigment include CI Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, and 15:6, and CI Pigment Blue 15:6 is more preferred.

[0507] Examples of the violet pigment include CI Pigment Violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, and 50.

[0508] Among these, from the viewpoint of heat resistance, a violet dioxazine pigment is preferred. As the dioxazine pigment, for example, CI Pigment Violet 19 and 23 are preferably mentioned, and CI Pigment Violet 23 is more preferred.

[0509] The average primary particle size of the pigment is preferably 0.2 μm or less, more preferably 0.1 μm or less, and even more preferably 0.04 μm or less. When the pigment is finely divided, a method such as the above-mentioned solvent salt grinding can be suitably used.

[0510] The content ratio of the coloring agent (A) in the colored resin composition of the present invention is not particularly limited. In the total solid content of the colored resin composition, it is preferably 1% by mass or more, more preferably 5% by mass or more, further preferably 10% by mass or more, and particularly preferably 15% by mass or more. In addition, it is preferably 80% by mass or less, more preferably 70% by mass or less, further preferably 60% by mass or less, and particularly preferably 50% by mass or less. By setting it to above the aforementioned lower limit, there is a tendency to reproduce a wide hue, and by setting it to below the aforementioned upper limit, there is a tendency to ensure patterning characteristics and stability over time. The above upper and lower limits can be combined arbitrarily. For example, the content ratio of the coloring agent (A) in the colored resin composition is preferably 1 to 80% by mass, more preferably 5 to 70% by mass, further preferably 10 to 60% by mass, and further preferably 15 to 50% by mass in the total solid content of the colored resin composition.

[0511] The content ratio of the phthalocyanine compound (1) in the colored resin composition of the present invention is not particularly limited, and is preferably 1% by mass or more, more preferably 3% by mass or more, further preferably 5% by mass or more, further preferably 10% by mass or more, particularly preferably 15% by mass or more, and preferably 90% by mass or less, more preferably 80% by mass or less, further preferably 70% by mass or less, and particularly preferably 60% by mass or less. By setting it to be above the above lower limit, there is a tendency to improve the brightness, and by setting it to be below the above upper limit, there is a tendency to ensure patterning characteristics and stability over time. The above upper and lower limits can be combined arbitrarily. For example, the content ratio of the phthalocyanine compound (1) in the colored resin composition is preferably 1 to 90% by mass, more preferably 3 to 80% by mass, further preferably 5 to 80% by mass, further preferably 10 to 70% by mass, and further preferably 15 to 60% by mass in the total solid content of the colored resin composition.

[0512] When the colored resin composition of the present invention contains other colorants, the content ratio is not particularly limited, but is preferably 1% by mass or more, more preferably 3% by mass or more, more preferably 5% by mass or more, more preferably 7% by mass or more, and particularly preferably 10% by mass or more, and preferably 30% by mass or less, more preferably 25% by mass or less, more preferably 20% by mass or less, and particularly preferably 15% by mass or less, in the total solid content of the colored resin composition. By setting it to the above lower limit or more, there is a tendency to be able to reproduce a wide hue, and by setting it to the above upper limit or less, there is a tendency to be able to ensure stability over time.

[0513] The above upper and lower limits may be combined arbitrarily. For example, the content ratio of other colorants in the colored resin composition is preferably 1 to 30% by mass, more preferably 3 to 30% by mass, further preferably 5 to 25% by mass, further preferably 7 to 20% by mass, and particularly preferably 10 to 15% by mass in the total solid content of the colored resin composition.

[0514] [3-2] (B) Solvent

[0515] The (B) solvent has the function of dissolving or dispersing the (A) colorant, (C) alkali-soluble resin, (D) photopolymerization initiator, (E) polymerization inhibitor, and other components in the colored resin composition of the present invention and adjusting the viscosity.

[0516] The (B) solvent may be any solvent as long as it can dissolve or disperse the components.

[0517] Examples of such solvents include glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, propylene glycol-tert-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethylpentanol, propylene glycol monoethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, and tripropylene glycol methyl ether;

[0518] Glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, and dipropylene glycol dimethyl ether;

[0519] Glycol alkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, methoxybutyl acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, and 3-methyl-3-methoxybutyl acetate;

[0520] Glycol diacetates such as ethylene glycol diacetate, 1,3-butanediol diacetate, and 1,6-hexanol diacetate;

[0521] Alkyl acetates such as cyclohexanol acetate; ethers such as amyl ether, propyl ether, diethyl ether, dipropyl ether, diisopropyl ether, butyl ether, diamyl ether, ethyl isobutyl ether, and dihexyl ether;

[0522] Ketones such as acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone, and methoxymethyl amyl ketone;

[0523] Monohydric or polyhydric alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethylpentanol, glycerol, and benzyl alcohol;

[0524] Aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, and dodecane;

[0525] Alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, and bicyclohexane;

[0526] Aromatic hydrocarbons such as benzene, toluene, xylene, and cumene;

[0527] Chain or cyclic esters such as amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl octanoate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, and γ-butyrolactone;

[0528] Alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid;

[0529] Halogenated hydrocarbons such as butyl chloride and amyl chloride;

[0530] Ether ketones such as methoxymethylpentyl ketone;

[0531] Nitriles such as acetonitrile and benzonitrile.

[0532] Examples of commercially available solvents that meet the above requirements include mineral spirits, VALSOL#2, APCO#18solvent, Apco thinner, Socal solvent No.1 and No.2, SOLVESSO#150, SHELL TS28solvent, carbitol, ethyl carbitol, butyl carbitol, methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, methyl cellosolve acetate, and diethylene glycol dimethyl ether (all trade names). These solvents may be used alone or in combination of two or more.

[0533] When forming color filter pixels by photolithography, it is preferred to select a solvent having a boiling point in the range of 100 to 200°C (under a pressure of 1013.25 [hPa]. Hereinafter, the same shall apply to boiling points.) More preferably, a solvent having a boiling point of 120 to 170°C is selected.

[0534] 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 the components in the composition.

[0535] 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, propylene glycol monomethyl ether is preferred, especially from the viewpoint of the solubility of the constituent components in the composition. It should be noted that glycol monoalkyl ethers have high polarity. If the amount added is too much, there is a tendency that the pigment is easy to aggregate, the viscosity of the colored resin composition obtained thereafter increases, and the storage stability tends to decrease. Therefore, the proportion of glycol monoalkyl ethers in the (B) solvent is preferably 5% to 30% by mass, and more preferably 5% to 20% by mass.

[0536] As another embodiment, a solvent having a boiling point of 150° C. or higher may be used in combination.

[0537] By using a solvent having a boiling point of 150°C or more in combination, the colored resin composition becomes difficult to dry, but there is an effect that the mutual relationship of the constituent components in the liquid containing the colorant is not easily destroyed due to rapid drying. When a solvent having a boiling point of 150°C or more is used in combination, the content ratio of the solvent having a boiling point of 150°C or more in the solvent (B) is preferably 3% to 50% by mass, more preferably 5% to 40% by mass, and particularly preferably 5% to 30% by mass. By setting it to be above the aforementioned lower limit, there is a tendency to avoid, for example, the precipitation / solidification of the coloring material component at the front end of the slit nozzle to cause foreign matter defects. In addition, by setting it to be below the aforementioned upper limit, there is a tendency to easily avoid the drying speed of the composition being slowed down, causing problems such as poor rhythm of the reduced pressure drying process and pin marks of pre-baking.

[0538] The solvent having a boiling point of 150° C. or higher may be a glycol alkyl ether acetate or a glycol alkyl ether. In this case, it is not necessary to separately contain a solvent having a boiling point of 150° C. or higher.

[0539] Preferred examples of the solvent having a boiling point of 150° C. or higher include diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1,3-butanediol diacetate, 1,6-hexanol diacetate, and glycerol triacetate.

[0540] When forming pixels of a color filter by an inkjet method, a solvent having a boiling point of generally 130° C. to 300° C., preferably 150° C. to 280° C. is suitable. When the boiling point is set to be equal to or higher than the lower limit, the uniformity of the obtained coating film tends to be improved, and when the boiling point is set to be equal to or lower than the upper limit, the residual solvent during firing tends to be easily reduced.

[0541] From the viewpoint of uniformity of the obtained coating film, a solvent having a vapor pressure of usually 10 mmHg or less, preferably 5 mmHg or less, and more preferably 1 mmHg or less can be used.

[0542] In the manufacture of color filters based on the inkjet method, the ink ejected from the nozzle is several pL to tens of pL, which is very fine, so there is a tendency for the solvent to evaporate and the ink to concentrate / dry before landing on the periphery of the nozzle or in the pixel storage body. In order to avoid this, the (B) solvent preferably contains a solvent with a high boiling point, specifically, preferably contains a solvent with a boiling point of 180°C or more. It is more preferred to contain a solvent with a boiling point of 200°C or more, and it is particularly preferred to contain a solvent with a boiling point of 220°C or more. When a solvent with a boiling point of 180°C or more is used in combination, the content ratio of the solvent with a boiling point of 180°C or more in the (B) solvent is preferably 50% by mass or more, more preferably 70% by mass or more, and most preferably 90% by mass or more. By setting it to above the aforementioned lower limit, there is a tendency to easily exert the effect of preventing the solvent from evaporating from the droplets.

[0543] Examples of the solvent having a boiling point of 180° C. or higher include diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1,3-butanediol diacetate, 1,6-hexanol diacetate, and glycerol triacetate among the various solvents described above.

[0544] In order to adjust the viscosity of the colored resin composition and the solubility of the solid content, it is also effective to contain a portion of a solvent having a boiling point lower than 180°C. Such a solvent is preferably a solvent having low viscosity, high solubility, and low surface tension, such as ethers, esters, and ketones. Among them, cyclohexanone, dipropylene glycol dimethyl ether, and cyclohexanol acetate are preferred.

[0545] On the other hand, if the solvent contains alcohols, the discharge stability in the inkjet method may be deteriorated. When alcohols are used in combination, the content of alcohols in the (B) solvent is preferably 20% by mass or less, more preferably 10% by mass or less, and particularly preferably 5% by mass or less.

[0546] The proportion 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-mentioned 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 is usually 70% by mass or more, preferably 75% by mass or more, and more preferably 78% by mass or more. The above upper and lower limits can be combined arbitrarily. For example, the proportion of the solvent in the colored resin composition is preferably 70 to 99% by mass, more preferably 75 to 90% by mass, and further preferably 78 to 85% by mass.

[0547] [3-3] (C) Alkali-soluble resin

[0548] The colored resin composition of the present invention contains (C) an alkali-soluble resin. By containing (C) an alkali-soluble resin, it is possible to achieve both film curability by photopolymerization and solubility in a developer.

[0549] As the alkali-soluble resin (C), known polymer compounds described in, for example, JP-A-7-207211, JP-A-8-259876, JP-A-10-300922, JP-A-11-140144, JP-A-11-174224, JP-A-2000-56118, and JP-A-2003-233179 can be used, and preferably the following resins (C-1) to (C-5) (hereinafter sometimes referred to as resins (C-1) to (C-5), respectively) can be listed.

[0550] (C-1): A resin obtained by adding an unsaturated monobasic acid to at least a portion of the epoxy groups in a copolymer of an epoxy (meth)acrylate and other free radical polymerizable monomers; or an alkali-soluble resin obtained by adding a polyacid anhydride to at least a portion of the hydroxyl groups generated by the addition reaction (hereinafter sometimes referred to as "resin (C-1)").

[0551] (C-2) A linear alkali-soluble resin having a carboxyl group in its main chain (hereinafter sometimes referred to as "resin (C-2)").

[0552] (C-3) A resin obtained by adding an epoxy group-containing unsaturated compound to the carboxyl portion of the above-mentioned resin (C-2) (hereinafter, sometimes referred to as "resin (C-3)").

[0553] (C-4) (Meth)acrylic resin (hereinafter sometimes referred to as "resin (C-4)").

[0554] (C-5) Epoxy (meth)acrylate resin having a carboxyl group (hereinafter sometimes referred to as "resin (C-5)").

[0555] Particularly preferably, resin (C-1) is used.

[0556] Resins (C-2) to (C-5) may be any resin as long as they are soluble in an alkaline developer and can be subjected to a desired development process. Resins described in Japanese Patent Application Laid-Open No. 2009-025813 may be used.

[0557] (C-1) A resin obtained by adding an unsaturated monobasic acid to at least a portion of the epoxy groups of a copolymer of an epoxy (meth)acrylate and other free radical polymerizable monomers; or an alkali-soluble resin obtained by adding a polybasic acid anhydride to at least a portion of the hydroxyl groups generated by the addition reaction.

[0558] As one of the preferred forms of resin (C-1), there can be listed "a resin obtained by adding an unsaturated monobasic acid to 10 to 100 mol % of the epoxy groups in a copolymer containing 5 to 90 mol % of epoxy (meth)acrylate and 10 to 95 mol % of other free radical polymerizable monomers; or an alkali-soluble resin obtained by adding a polyacid anhydride to 10 to 100 mol % of the hydroxyl groups generated by the addition reaction."

[0559] Examples of epoxy group-containing (meth)acrylates include glycidyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, (3,4-epoxycyclohexyl)methyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate glycidyl ether. Among them, glycidyl (meth)acrylate is preferred. These epoxy group-containing (meth)acrylates may be used alone or in combination of two or more.

[0560] As another radical polymerizable monomer to be copolymerized with the epoxy group-containing (meth)acrylate, a mono(meth)acrylate having a structure represented by the following general formula (V) is preferred.

[0561]

[0562] In formula (V), R 91 ~R 98 Each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. 96 With R 98 , or R 95 With R 97 They are optionally linked to each other to form a ring.

[0563] In formula (V), R 96 With R 98 , or R 95 With R 97The ring formed by connecting is preferably an aliphatic ring, and may be saturated or unsaturated, and preferably has 5 to 6 carbon atoms.

[0564] The structure represented by formula (V) is preferably a structure represented by the following formula (Va), (Vb), or (Vc).

[0565] By introducing these structures into the alkali-soluble resin, when the colored resin composition of the present invention is used for forming a color filter, the heat resistance of the colored resin composition tends to be improved, and the intensity of pixels formed using the colored resin composition tends to be increased.

[0566] The mono(meth)acrylate having a structure represented by formula (V) may be used alone or in combination of two or more.

[0567]

[0568] As the mono(meth)acrylate having a structure represented by formula (V), various known substances can be used as long as they have the structure, and the mono(meth)acrylate represented by formula (VI) is particularly preferred.

[0569]

[0570] In formula (VI), R 89 represents a hydrogen atom or a methyl group, R 90 It represents the structure represented by formula (V).

[0571] When the copolymer of epoxy group-containing (meth)acrylate and other radical polymerizable monomers contains repeating units derived from the mono(meth)acrylate represented by formula (VI), the content ratio of the repeating units derived from the mono(meth)acrylate represented by formula (VI) in the repeating units derived from the other radical polymerizable monomers is preferably 5 to 90 mol%, more preferably 10 to 70 mol%, and particularly preferably 15 to 50 mol%.

[0572] The free radical polymerizable monomers other than the mono(meth)acrylate represented by formula (VI) are not particularly limited, and specific examples thereof include: vinyl aromatics such as styrene, α-, o-, m-, p-alkyl, nitro, cyano, amide, and ester derivatives of styrene; dienes such as butadiene, 2,3-dimethylbutadiene, isoprene, and chloroprene; methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate, neopentyl (meth)acrylate, isopentyl (meth)acrylate, and (meth)acrylate. 2-Methylhexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, dodecyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, dicyclohexyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, anthracenyl (meth)acrylate, piperidinyl (meth)acrylate, salicyl (meth)acrylate, furanyl (meth)acrylate, furfuryl (meth)acrylate, tetrahydrofuranyl (meth)acrylate, pyranyl (meth)acrylate , benzyl (meth)acrylate, phenylethyl (meth)acrylate, toluene (meth)acrylate, 1,1,1-trifluoroethyl (meth)acrylate, perfluoroethyl (meth)acrylate, perfluoro-n-propyl (meth)acrylate, perfluoroisopropyl (meth)acrylate, triphenylmethyl (meth)acrylate, isopropyl (meth)acrylate, 3-(N,N-dimethylamino)propyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, etc. (meth)acrylates; (meth)acrylamide, N,N-dimethyl (meth)acrylate, N,N-diethyl (meth)acrylate, N,N-diethyl (meth)acrylate, N,N-(meth)acrylate (Meth)acrylamides such as (meth)acrylic acid aniline, (meth)acryloyl nitrile, acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinyl pyrrolidone, vinyl pyridine, vinyl acetate, etc.; unsaturated dicarboxylic acid diesters such as diethyl citrate, diethyl maleate, diethyl fumarate, diethyl itaconate, etc.; monomaleimides such as N-phenylmaleimide, N-cyclohexylmaleimide, N-laurylmaleimide, N-(4-hydroxyphenyl)maleimide, etc.; N-(meth)acryloylphthalimide.

[0573] Among these other radical polymerizable monomers, styrene, benzyl (meth)acrylate, and monomaleimide are preferred from the viewpoint of imparting excellent heat resistance and strength to the colored resin composition.

[0574] When the copolymer of epoxy group-containing (meth)acrylate and other radical polymerizable monomers contains any repeating unit derived from styrene, benzyl (meth)acrylate or monomaleimide, the total content of the repeating unit derived from styrene, the repeating unit derived from benzyl (meth)acrylate and the repeating unit derived from monomaleimide in the repeating units derived from other radical polymerizable monomers is preferably 1 to 70 mol%, more preferably 3 to 50 mol%.

[0575] The copolymerization reaction of the epoxy group-containing (meth)acrylate and other radical polymerizable monomers can be carried out by a known solution polymerization method. The solvent used is not particularly limited as long as it is inactive to radical polymerization, and a commonly used organic solvent can be used.

[0576] Examples of the solvent used in the solution polymerization method include ethylene glycol monoalkyl ether acetates such as ethyl acetate, isopropyl acetate, cellosolve acetate, and butyl cellosolve acetate; diethylene glycol monoalkyl ether acetates such as diethylene glycol monomethyl ether acetate, carbitol acetate, and butyl carbitol acetate; propylene glycol monoalkyl ether acetates; acetates such as dipropylene glycol monoalkyl ether acetates; ethylene glycol dialkyl ethers; methyl carbitol, ethyl carbitol, and butyl carbitol; Diethylene glycol dialkyl ethers; triethylene glycol dialkyl ethers; propylene glycol dialkyl ethers; dipropylene glycol dialkyl ethers; ethers such as 1,4-dioxane and tetrahydrofuran; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; hydrocarbons such as benzene, toluene, xylene, octane, and decane; petroleum solvents such as petroleum ether, naphtha, hydrogenated naphtha, and solvent naphtha; lactic acid esters such as methyl lactate, ethyl lactate, and butyl lactate; dimethylformamide and N-methylpyrrolidone. These solvents may be used alone or in combination of two or more.

[0577] The amount of the solvent used in the solution polymerization method is usually 30 to 1000 parts by mass, preferably 50 to 800 parts by mass based on 100 parts by mass of the obtained copolymer. When the amount of the solvent used is within the above range, the molecular weight of the copolymer tends to be easily controlled.

[0578] The radical polymerization initiator used in the copolymerization reaction is not particularly limited as long as it can initiate radical polymerization, and commonly used organic peroxide catalysts and azo compound catalysts can be used. As the organic peroxide catalyst, known substances classified as ketone peroxides, peroxyketals, hydroperoxides, diallyl peroxides, diacyl peroxides, peroxyesters, and peroxydicarbonates can be cited.

[0579] Examples of the radical polymerization initiator used in the copolymerization reaction include benzoyl peroxide, dicumyl peroxide, diisopropyl peroxide, di-tert-butyl peroxide, tert-butyl peroxybenzoate, tert-hexyl peroxybenzoate, tert-butyl peroxy-2-ethylhexanoate, tert-hexyl peroxy-2-ethylhexanoate, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, 3,3-isopropyl hydroperoxide, tert-butyl hydroperoxide, diisopropyl peroxide, diisopropyl hydroperoxide, acetyl peroxide, bis(4-tert-butylcyclohexyl)peroxydicarbonate, diisopropyl peroxydicarbonate, isobutyl peroxide, 3,3,5-trimethylhexanoyl peroxide, lauryl peroxide, 1,1-bis(tert-butylperoxide)3,3,5-trimethylcyclohexane, 1,1-bis(tert-hexylperoxide)3,3,5-trimethylcyclohexane.

[0580] Examples of the azo compound catalyst include azobisisobutyronitrile and azobiscarbonamide.

[0581] Among these, one or more radical polymerization initiators having an appropriate half-life may be used depending on the polymerization temperature.

[0582] The amount of the radical polymerization initiator used is usually 0.5 to 20 parts by mass, preferably 1 to 10 parts by mass, based on 100 parts by mass of the total of the monomers used in the copolymerization reaction.

[0583] The copolymerization reaction can be carried out by dissolving the monomers and the radical polymerization initiator used in the copolymerization reaction in a solvent and heating the mixture while stirring, or by dropping the monomers to which the radical polymerization initiator is added into the heated and stirred solvent, or by adding the radical polymerization initiator to the solvent and dropping the monomers while heating the mixture. The reaction conditions can be set according to the target molecular weight.

[0584] In the present invention, as a copolymer of epoxy-containing (meth)acrylate and other free radical polymerizable monomers, it is preferred that the copolymer contains 5 to 90 mol% of repeating units derived from epoxy-containing (meth)acrylate and 10 to 95 mol% of repeating units derived from other free radical polymerizable monomers in all repeating units of the copolymer; it is further preferred that the copolymer contains 20 to 80 mol% of repeating units derived from epoxy-containing (meth)acrylate and 80 to 20 mol% of repeating units derived from other free radical polymerizable monomers; it is particularly preferred that the copolymer contains 30 to 70 mol% of repeating units derived from epoxy-containing (meth)acrylate and 70 to 30 mol% of repeating units derived from other free radical polymerizable monomers.

[0585] By setting the content ratio of the repeating unit derived from the epoxy group-containing (meth)acrylate to be equal to or more than the above lower limit, there is a tendency that the addition amount of the unsaturated monobasic acid or polybasic acid anhydride described later becomes sufficient.

[0586] When the content ratio of repeating units derived from other radical polymerizable monomers is equal to or greater than the above lower limit, heat resistance and strength tend to be sufficient.

[0587] Regarding the resin (C-1), the epoxy group of a copolymer of a (meth)acrylate containing an epoxy resin and other radical polymerizable monomers is reacted with an unsaturated monobasic acid (polymerizable component) and a polybasic acid anhydride (alkali-soluble component).

[0588] Examples of unsaturated monobasic acids added to epoxy groups include (meth)acrylic acid; crotonic acid; o-, m-, and p-vinylbenzoic acid; and monocarboxylic acids such as (meth)acrylic acid in which the α-position is substituted with a haloalkyl group, an alkoxy group, a halogen atom, a nitro group, or a cyano group. Among them, (meth)acrylic acid is preferred. These unsaturated monobasic acids may be used alone or in combination of two or more.

[0589] By adding an unsaturated monobasic acid to an epoxy group, polymerizability can be imparted to the resin (C-1).

[0590] When all epoxy groups contained in the copolymer of epoxy resin (meth)acrylate and other radical polymerizable monomers are taken as 100 mol%, the unsaturated monobasic acid is usually added at 10 to 100 mol%, preferably 30 to 100 mol%, and more preferably 50 to 100 mol%. By setting it to the above lower limit or more, the temporal stability of the colored resin composition tends to be good.

[0591] As a method for adding an unsaturated monobasic acid to the epoxy group of the copolymer, a known method can be adopted.

[0592] Furthermore, as the polybasic acid anhydride to be added to the hydroxyl group generated when the unsaturated monobasic acid is added to the epoxy group of the copolymer, a known polybasic acid anhydride can be used.

[0593] Examples of the polyacid anhydride include dibasic acid anhydrides such as maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and chlorendic anhydride; and anhydrides of tribasic or higher acids such as trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, and biphenyl tetracarboxylic anhydride. Among them, tetrahydrophthalic anhydride and succinic anhydride are preferred. These polyacid anhydrides may be used alone or in combination of two or more.

[0594] Alkali solubility can be imparted to the resin (C-1) by adding a polybasic acid anhydride to a hydroxyl group generated when an unsaturated monobasic acid is added to an epoxy group of a copolymer.

[0595] When all hydroxyl groups generated by addition of the epoxy groups possessed by the copolymer and the unsaturated monobasic acid are set to 100 mol%, the polyacid anhydride is usually added at 10 to 100 mol%, preferably 20 to 90 mol%, and more preferably 30 to 80 mol%. By setting it below the upper limit, there is a tendency that the residual film rate during development becomes good, and by setting it above the lower limit, there is a tendency that the solubility becomes sufficient.

[0596] As a method for adding a polybasic acid anhydride to a hydroxyl group generated by adding an unsaturated monobasic acid to an epoxy group possessed by the copolymer, a known method can be adopted.

[0597] In order to improve photosensitivity, after adding the polybasic acid anhydride, a part of the generated carboxyl groups may be added with glycidyl (meth)acrylate or a glycidyl ether compound having a polymerizable unsaturated group.

[0598] In order to improve the developability, a part of the generated carboxyl groups may be added with a glycidyl ether compound having no polymerizable unsaturated group.

[0599] These may be added alone or in combination of two or more.

[0600] Examples of the glycidyl ether compound having no polymerizable unsaturated group include glycidyl ether compounds having a phenyl group or an alkyl group.

[0601] Examples of commercially available products include "Denacol EX-111", "Denacol EX-121", "Denacol EX-141", "Denacol EX-145", "Denacol EX-146", "Denacol EX-171" and "Denacol EX-192" manufactured by Nagase ChemteX Corporation.

[0602] The structure of the resin (C-1) is described in, for example, Japanese Patent Application Laid-Open No. 8-297366 and Japanese Patent Application Laid-Open No. 2001-89533.

[0603] The weight average molecular weight (Mw) of the resin (C-1) measured by GPC in terms of polystyrene is not particularly limited, but is preferably 3,000 or more, particularly preferably 5,000 or more. It is preferably 100,000 or less, particularly preferably 50,000 or less. The above upper and lower limits may be arbitrarily combined. For example, it may be 3,000 to 100,000, or 5,000 to 50,000. By setting it to above the aforementioned lower limit, there is a tendency for heat resistance and film strength to become good, and by setting it to below the aforementioned upper limit, there is a tendency for solubility in a developer to become good.

[0604] As a standard of molecular weight distribution, the ratio of the weight average molecular weight to the number average molecular weight of the resin (C-1) (Mw / Mn) is preferably 2.0 to 5.0.

[0605] From the viewpoint of coating film curability upon ultraviolet exposure, among the resins (C-4), (c1) acrylic copolymer resins having an ethylenically unsaturated group in a side chain (hereinafter sometimes referred to as (c1) acrylic copolymer resins) are preferred.

[0606] The partial structure of the acrylic copolymer resin (c1) containing a side chain having an ethylenically unsaturated group is not particularly limited, but preferably has a partial structure represented by the following general formula (I) from the viewpoint of achieving both film curability during ultraviolet exposure and alkali solubility during alkali development.

[0607]

[0608] In formula (I), R 1 and R 2 Each independently represents a hydrogen atom or a methyl group. * represents a connecting bond.

[0609] Among the partial structures represented by the formula (I), the partial structures represented by the following general formula (I′) are preferred from the viewpoints of sensitivity and alkali developability.

[0610]

[0611] In formula (I'), R 1 and R 2 Each independently represents a hydrogen atom or a methyl group. X represents a hydrogen atom or a polyacid residue.

[0612] The polyacid residue refers to a monovalent or divalent group obtained by removing one or two OH groups from a polyacid. Examples of the polyacid include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid.

[0613] Among these, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are preferred from the viewpoint of patterning properties, and tetrahydrophthalic acid and biphenyltetracarboxylic acid are more preferred.

[0614] In the case where the (c1) acrylic copolymer resin contains a partial structure represented by formula (I), the content ratio of the partial structure represented by formula (I) contained in the (c1) acrylic copolymer resin is not particularly limited, and is preferably 10 mol% or more, more preferably 20 mol% or more, further preferably 30 mol% or more, further preferably 40 mol% or more, particularly preferably 50 mol% or more, and most preferably 65 mol% or more. In addition, it is preferably 95 mol% or less, more preferably 90 mol% or less, further preferably 85 mol% or less, further preferably 80 mol% or less, particularly preferably 75 mol% or less, and most preferably 70 mol% or less. By setting it to above the aforementioned lower limit, there is a tendency for the curability of the coating film to be improved during ultraviolet exposure, and by setting it to below the aforementioned upper limit, there is a tendency for the alkali solubility to be improved during alkali development. The above upper and lower limits can be combined arbitrarily. For example, the content of the partial structure represented by formula (I) contained in the (c1) acrylic copolymer resin is preferably 10 to 95 mol%, more preferably 20 to 90 mol%, further preferably 30 to 85 mol%, further preferably 40 to 80 mol%, particularly preferably 50 to 75 mol%, and most preferably 65 to 70 mol%.

[0615] In the case where the (c1) acrylic copolymer resin contains a partial structure represented by formula (I'), the content ratio of the partial structure represented by formula (I') contained in the (c1) acrylic copolymer resin is not particularly limited, and is preferably 10 mol% or more, more preferably 20 mol% or more, further preferably 30 mol% or more, further preferably 40 mol% or more, particularly preferably 50 mol% or more, and most preferably 65 mol% or more. In addition, it is preferably 95 mol% or less, more preferably 90 mol% or less, further preferably 85 mol% or less, further preferably 80 mol% or less, particularly preferably 75 mol% or less, and most preferably 70 mol% or less. By setting it to above the aforementioned lower limit, there is a tendency for the curability of the coating film to be improved during ultraviolet exposure, and by setting it to below the aforementioned upper limit, there is a tendency for the alkali solubility to be improved during alkali development. The above upper and lower limits can be combined arbitrarily. For example, the content of the partial structure represented by formula (I') contained in the acrylic copolymer resin (c1) is preferably 10 to 95 mol%, more preferably 20 to 90 mol%, further preferably 30 to 85 mol%, further preferably 40 to 80 mol%, particularly preferably 50 to 75 mol%, and most preferably 65 to 70 mol%.

[0616] When the (c1) acrylic copolymer resin contains a partial structure represented by formula (I), other partial structures that may be contained are not particularly limited, but from the viewpoint of alkali solubility during alkali development, for example, it preferably has a partial structure represented by the following general formula (II).

[0617]

[0618] In formula (II), R 3 represents a hydrogen atom or a methyl group, R 4 It represents an alkyl group which may have a substituent, an aromatic ring group which may have a substituent, or an alkenyl group which may have a substituent.

[0619] (R 4 )

[0620] In formula (II), R 4 It represents an alkyl group which may have a substituent, an aromatic ring group which may have a substituent, or an alkenyl group which may have a substituent.

[0621] As R 4The alkyl group in can be a linear, branched or cyclic alkyl group. The carbon number is preferably 1 or more, more preferably 3 or more, further preferably 5 or more, particularly preferably 8 or more, and preferably 20 or less, more preferably 18 or less, further preferably 16 or less, further preferably 14 or less, and particularly preferably 12 or less. By setting it to be above the aforementioned lower limit, there is a tendency for the lipophilicity to be improved and the solubility in the solvent to be improved. In addition, by setting it to be below the aforementioned upper limit, there is a tendency for the hydrophilicity to be improved and the alkali solubility to be improved. The above upper and lower limits can be combined arbitrarily. For example, the carbon number of the alkyl group is preferably 1 to 20, more preferably 1 to 18, further preferably 3 to 16, further preferably 5 to 14, and particularly preferably 8 to 12.

[0622] Examples of the alkyl group include a methyl group, an ethyl group, a cyclohexyl group, a dicyclopentyl group, and a dodecyl group. From the viewpoint of developability, a dicyclopentyl group and a dodecyl group are preferred, and a dicyclopentyl group is more preferred.

[0623] Examples of the substituent which the alkyl group may have include a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxyl group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, a carboxyl group, an acryloyl group, and a methacryloyl group. From the viewpoint of developability, a hydroxyl group and an oligoethylene glycol group are preferred.

[0624] As R 4 The aromatic ring group in the formula (a) may include a monovalent aromatic hydrocarbon ring group and a monovalent aromatic heterocyclic group. The carbon number is preferably 6 or more, and preferably 24 or less, more preferably 22 or less, further preferably 20 or less, and particularly preferably 18 or less. By setting it to be above the aforementioned lower limit, there is a tendency for the lipophilicity to be improved and the solubility in the solvent to be improved. In addition, by setting it to be below the aforementioned upper limit, there is a tendency for the hydrophilicity to be improved and the alkali solubility to be improved. The above upper and lower limits may be combined arbitrarily. For example, the carbon number of the aromatic ring group is preferably 6 to 24, more preferably 6 to 22, further preferably 6 to 20, and particularly preferably 6 to 18.

[0625] The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a single ring or a condensed ring, and examples thereof include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzopyrene ring, Ring, triphenylene ring, acenaphthene ring, fluoranthene ring, fluorene ring.

[0626] In addition, the aromatic heterocyclic ring in the aromatic heterocyclic group may be a monocyclic ring or a condensed ring, and examples thereof include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, an indole ring, a carbazole ring, a pyrroloimidazole ring, a pyrrolopyrazole ring, a pyrrolopyrrole ring, a thienopyrrole ring, a thienothiophene ring, a furopyrrole ring, a furofuran ring, a thienofuran ring, a benzisoxazole ring, a benzisothiazole ring, a benzimidazole ring, a pyridine ring, a pyrazine ring, a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a cinnoline ring, a quinoxaline ring, a phenanthridine ring, a phenanthridine ring, a quinazoline ring, a quinazolinone ring, and an azulene ring. From the viewpoint of developability, a benzene ring group and a naphthyl ring group are preferred, and a benzene ring group is more preferred.

[0627] Examples of the substituent that the aromatic ring group may have include a methyl group, an ethyl group, a propyl group, a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxyl group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, and a carboxyl group. From the viewpoint of developability, a hydroxyl group and an oligoethylene glycol group are preferred.

[0628] As R 4 The alkenyl group in the group may be a linear, branched or cyclic alkenyl group. The carbon number is preferably 2 or more, and preferably 22 or less, more preferably 20 or less, further preferably 18 or less, further preferably 16 or less, and particularly preferably 14 or less. By setting it to be above the aforementioned lower limit, there is a tendency for the lipophilicity to be improved and the solubility in the solvent to be improved. In addition, by setting it to be below the aforementioned upper limit, there is a tendency for the hydrophilicity to be improved and the alkali solubility to be improved. The above upper and lower limits may be combined arbitrarily. For example, the carbon number of the alkenyl group is preferably 2 to 22, more preferably 2 to 20, further preferably 2 to 18, further preferably 2 to 16, and particularly preferably 2 to 14.

[0629] Examples of the alkenyl group include vinyl, allyl, 2-propylene-2-yl, 2-butene-1-yl, 3-butene-1-yl, 2-pentene-1-yl, 3-pentene-2-yl, hexenyl, cyclobutenyl, cyclopentenyl, and cyclohexenyl. From the viewpoint of developability, vinyl and allyl groups are preferred, and vinyl groups are more preferred.

[0630] Examples of the substituent that the alkenyl group may have include a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxyl group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, and a carboxyl group. From the viewpoint of developability, a hydroxyl group and an oligoethylene glycol group are preferred.

[0631] R 4 It represents an alkyl group which may have a substituent, an aromatic ring group which may have a substituent, or an alkenyl group which may have a substituent, and from the viewpoint of developability and film strength, an alkyl group or an alkenyl group is preferred, and an alkyl group is more preferred.

[0632] When the (c1) acrylic copolymer resin contains a partial structure represented by formula (II), the content ratio of the partial structure represented by formula (II) in the (c1) acrylic copolymer resin is not particularly limited, and is preferably 1 mol% or more, more preferably 5 mol% or more, further preferably 10 mol% or more, and particularly preferably 20 mol% or more. In addition, it is preferably 70 mol% or less, more preferably 60 mol% or less, further preferably 50 mol% or less, and particularly preferably 40 mol% or less. By setting it to be above the aforementioned lower limit, there is a tendency for the alkali solubility to be improved, and by setting it to be below the aforementioned upper limit, there is a tendency for the storage stability of the colored resin composition to be improved. For example, the content ratio of the partial structure represented by formula (II) in the (c1) acrylic copolymer resin is preferably 1 to 70 mol%, more preferably 5 to 60 mol%, further preferably 10 to 50 mol%, and particularly preferably 20 to 40 mol%.

[0633] When the (c1) acrylic copolymer resin contains the partial structure represented by formula (I), it preferably contains a partial structure represented by the following general formula (III) as another partial structure that may be contained from the viewpoint of suppressing a decrease in brightness by improving heat resistance.

[0634]

[0635] In formula (III), R 5 represents a hydrogen atom or a methyl group, R 6 It represents an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, a hydroxyl group, a carboxyl group, a halogen atom, an alkoxy group which may have a substituent, a thiol group or an alkylthioether group which may have a substituent.

[0636] t represents an integer from 0 to 5.

[0637] (R 6 )

[0638] In formula (III), R 6 It represents an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, a hydroxyl group, a carboxyl group, a halogen atom, an alkoxy group which may have a substituent, a thiol group or an alkylthioether group which may have a substituent.

[0639] As R 6The alkyl group in can be a linear, branched or cyclic alkyl group. The carbon number is preferably 1 or more, more preferably 3 or more, and further preferably 5 or more. In addition, it is preferably 20 or less, more preferably 18 or less, further preferably 16 or less, further preferably 14 or less, and particularly preferably 12 or less. By setting it to be above the aforementioned lower limit, there is a tendency for the lipophilicity to be improved and the solubility in the solvent to be improved. In addition, by setting it to be below the aforementioned upper limit, there is a tendency for the hydrophilicity to be improved and the alkali solubility to be improved. The above upper and lower limits can be combined arbitrarily. For example, the carbon number of the alkyl group is preferably 1 to 20, more preferably 1 to 18, further preferably 3 to 16, further preferably 3 to 14, and particularly preferably 5 to 12.

[0640] Examples of the alkyl group include a methyl group, an ethyl group, a cyclohexyl group, a dicyclopentyl group, and a dodecyl group. Among these, from the viewpoint of heat resistance, a dicyclopentyl group and a dodecyl group are preferred, and a dicyclopentyl group is more preferred.

[0641] Examples of the substituent which the alkyl group may have include a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxyl group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, a carboxyl group, an acryloyl group, and a methacryloyl group. From the viewpoint of developability, a hydroxyl group and an oligoethylene glycol group are preferred.

[0642] As R 6 The alkenyl group in the group may be a linear, branched or cyclic alkenyl group. The carbon number is preferably 2 or more, and preferably 22 or less, more preferably 20 or less, further preferably 18 or less, further preferably 16 or less, and particularly preferably 14 or less. By setting it to be above the aforementioned lower limit, there is a tendency for the lipophilicity to be improved and the solubility in the solvent to be improved. In addition, by setting it to be below the aforementioned upper limit, there is a tendency for the hydrophilicity to be improved and the alkali solubility to be improved. The above upper and lower limits may be combined arbitrarily. For example, the carbon number of the alkenyl group is preferably 2 to 22, more preferably 2 to 20, further preferably 2 to 18, further preferably 2 to 16, and particularly preferably 2 to 14.

[0643] Examples of the alkenyl group include vinyl, allyl, 2-propylene-2-yl, 2-butene-1-yl, 3-butene-1-yl, 2-pentene-1-yl, 3-pentene-2-yl, hexenyl, cyclobutenyl, cyclopentenyl, and cyclohexenyl. Among these, vinyl and allyl are preferred, and vinyl is more preferred from the viewpoint of exposure sensitivity during ultraviolet exposure.

[0644] Examples of the substituent that the alkenyl group may have include a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxyl group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, and a carboxyl group. From the viewpoint of developability, a hydroxyl group and an oligoethylene glycol group are preferred.

[0645] As R 6 The alkynyl in may be a linear, branched or cyclic alkynyl. The carbon number is preferably 2 or more, preferably 22 or less, more preferably 20 or less, further preferably 18 or less, further preferably 16 or less, and particularly preferably 14 or less. By setting it to be above the aforementioned lower limit, there is a tendency for the lipophilicity to be improved and the solubility in the solvent to be improved. In addition, by setting it to be below the aforementioned upper limit, there is a tendency for the hydrophilicity to be improved and the alkali solubility to be improved. The above upper and lower limits may be combined arbitrarily. For example, the carbon number of the alkynyl is preferably 2 to 22, more preferably 2 to 20, further preferably 2 to 18, further preferably 2 to 16, and particularly preferably 2 to 14.

[0646] Examples of the alkynyl group include 1-propyn-3-yl, 1-butyn-4-yl, 1-pentyn-5-yl, 2-methyl-3-butyn-2-yl, 1,4-pentadiyn-3-yl, 1,3-pentadiyn-5-yl, and 1-hexyn-6-yl.

[0647] Examples of the substituent that the alkynyl group may have include a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxyl group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, and a carboxyl group. From the viewpoint of developability, a hydroxyl group and an oligoethylene glycol group are preferred.

[0648] As R 6 Examples of the halogen atom in include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. From the viewpoint of the storage stability of the acrylic copolymer resin (c1), a fluorine atom is preferred.

[0649] As R 6 The alkoxy group in the group may be a linear, branched or cyclic alkoxy group. The number of carbon atoms is preferably 1 or more, and preferably 20 or less, more preferably 18 or less, further preferably 16 or less, further preferably 14 or less, and particularly preferably 12 or less. By setting the value above the lower limit, there is a tendency for the lipophilicity to be improved and the solubility in the solvent to be improved. By setting the value below the upper limit, there is a tendency for the hydrophilicity to be improved and the alkali solubility to be improved. The upper and lower limits mentioned above may be combined arbitrarily. For example, the number of carbon atoms in the alkoxy group is preferably 1 to 20, more preferably 1 to 18, further preferably 1 to 16, further preferably 1 to 14, and particularly preferably 1 to 12.

[0650] Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, and an isobutoxy group.

[0651] Examples of the substituent that the alkoxy group may have include a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxyl group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, a carboxyl group, an acryloyl group, and a methacryloyl group. From the viewpoint of developability, a hydroxyl group and an oligoethylene glycol group are preferred.

[0652] As R 6 The alkyl thioether group in the alkyl thioether group may be a linear, branched or cyclic alkyl thioether group. The carbon number is preferably 1 or more, and preferably 20 or less, more preferably 18 or less, further preferably 16 or less, further preferably 14 or less, and particularly preferably 12 or less. By setting it to be above the aforementioned lower limit, there is a tendency for the lipophilicity to be improved and the solubility in the solvent to be improved. In addition, by setting it to be below the aforementioned upper limit, there is a tendency for the hydrophilicity to be improved and the alkali solubility to be improved. The above upper and lower limits may be combined arbitrarily. For example, the carbon number of the alkyl thioether group is preferably 1 to 20, more preferably 1 to 18, further preferably 1 to 16, further preferably 1 to 14, and particularly preferably 1 to 12.

[0653] Examples of the alkyl sulfide group include a methyl sulfide group, an ethyl sulfide group, a propyl sulfide group, and a butyl sulfide group. From the viewpoint of developability, a methyl sulfide group and an ethyl sulfide group are preferred.

[0654] Examples of the substituent that the alkyl group in the alkyl thioether group may have include a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxyl group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, a carboxyl group, an acryloyl group, and a methacryloyl group. From the viewpoint of developability, a hydroxyl group and an oligoethylene glycol group are preferred.

[0655] R 6 It represents an alkyl group optionally having a substituent, an alkenyl group optionally having a substituent, an alkynyl group optionally having a substituent, a hydroxyl group, a carboxyl group, a halogen atom, an alkoxy group, a hydroxyalkyl group, a thiol group or an alkyl thioether group optionally having a substituent, and among these, a hydroxyl group or a carboxyl group is preferred, and a carboxyl group is more preferred, from the viewpoint of developability.

[0656] In formula (III), t represents an integer of 0 to 5, and t is preferably 0 from the viewpoint of ease of production.

[0657] When the (c1) acrylic copolymer resin contains a partial structure represented by formula (III), the content ratio of the partial structure represented by formula (III) in the (c1) acrylic copolymer resin is not particularly limited, and is preferably 1 mol% or more, more preferably 2 mol% or more, further preferably 5 mol% or more, and particularly preferably 8 mol% or more. In addition, it is preferably 50 mol% or less, more preferably 40 mol% or less, further preferably 30 mol% or less, and particularly preferably 20 mol% or less. By setting it to be above the aforementioned lower limit, there is a tendency to improve heat resistance and suppress brightness reduction. In addition, by setting it to be below the aforementioned upper limit, there is a tendency to increase the content ratio of other partial structures and improve alkali solubility. The above upper and lower limits can be combined arbitrarily. For example, the content ratio of the partial structure represented by formula (III) in the (c1) acrylic copolymer resin is preferably 1 to 50 mol%, more preferably 2 to 40 mol%, further preferably 5 to 30 mol%, and particularly preferably 8 to 20 mol%.

[0658] When the (c1) acrylic copolymer resin includes the partial structure represented by the formula (I), it preferably includes a partial structure represented by the following general formula (IV) as another partial structure that may be included from the viewpoint of developability.

[0659]

[0660] In formula (IV), R 7 represents a hydrogen atom or a methyl group.

[0661] When the (c1) acrylic copolymer resin contains a partial structure represented by formula (IV), the content ratio of the partial structure represented by formula (IV) in the (c1) acrylic copolymer resin is not particularly limited, and is preferably 5 mol% or more, more preferably 10 mol% or more, and further preferably 20 mol% or more. In addition, it is preferably 80 mol% or less, more preferably 70 mol% or less, and further preferably 60 mol% or less. By setting it to be above the aforementioned lower limit, there is a tendency for the alkali solubility to be improved. In addition, by setting it to be below the aforementioned upper limit, there is a tendency for the storage stability of the colored resin composition to be improved. The above upper and lower limits can be combined arbitrarily. For example, the content ratio of the partial structure represented by formula (IV) in the (c1) acrylic copolymer resin is preferably 5 to 80 mol%, more preferably 10 to 70 mol%, and further preferably 20 to 60% mol%.

[0662] (C) The acid value of the alkali-soluble resin is not particularly limited, but is preferably 10 mgKOH / g or more, more preferably 30 mgKOH / g or more, further preferably 40 mgKOH / g or more, further preferably 50 mgKOH / g or more, and particularly preferably 60 mgKOH / g or more, and is preferably 300 mgKOH / g or less, more preferably 250 mgKOH / g or less, further preferably 200 mgKOH / g or less, and further preferably 150 mgKOH / g or less. By setting it to the above lower limit or more, there is a tendency for alkali solubility to be improved, and by setting it to the above upper limit or less, there is a tendency for the storage stability of the colored resin composition to be improved.

[0663] For example, the acid value of the alkali-soluble resin (C) is preferably 10 to 300 mgKOH / g, more preferably 30 to 300 mgKOH / g, further preferably 40 to 250 mgKOH / g, further preferably 50 to 200 mgKOH / g, and particularly preferably 60 to 150 mgKOH / g.

[0664] The weight average molecular weight (Mw) of the alkali-soluble resin (C) is not particularly limited, and is generally 1000 or more, preferably 2000 or more, more preferably 4000 or more, further preferably 6000 or more, further preferably 7000 or more, and particularly preferably 8000 or more. In addition, it is generally 30000 or less, preferably 20000 or less, more preferably 15000 or less, and further preferably 10000 or less. By setting it to be above the aforementioned lower limit, there is a tendency for heat resistance and coating curability to be improved. In addition, by setting it to be below the aforementioned upper limit, there is a tendency for alkali solubility to be improved. The above upper and lower limits can be combined arbitrarily. For example, the weight average molecular weight of the alkali-soluble resin (C) is preferably 1000 to 30000, more preferably 2000 to 30000, further preferably 4000 to 20000, further preferably 6000 to 20000, further preferably 7000 to 15000, and particularly preferably 8000 to 10000.

[0665] The content ratio of the (C) alkali-soluble resin in the colored resin composition of the present invention is not particularly limited. In the total solid content of the colored resin composition, it is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 20% by mass or more, and particularly preferably 30% by mass or more. In addition, it is preferably 80% by mass or less, more preferably 70% by mass or less, further preferably 60% by mass or less, and particularly preferably 50% by mass or less. By setting it to above the aforementioned lower limit, there is a tendency for the curability of the coating film to be improved during ultraviolet exposure, and by setting it to below the aforementioned upper limit, there is a tendency for the solubility of the developer to be improved and the residue to be suppressed. The above upper and lower limits can be combined arbitrarily.

[0666] For example, the content of the (C) alkali-soluble resin in the colored resin composition is preferably 5 to 80% by mass, more preferably 10 to 70% by mass, further preferably 20 to 60% by mass, and further preferably 30 to 50% by mass in the total solid content of the colored resin composition.

[0667] [3-4] (D) Photopolymerization initiator

[0668] 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.

[0669] (D) The photopolymerization initiator can also be used as 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 undergoing a decomposition reaction or a hydrogen abstraction reaction by being photosensitized, thereby generating polymerization-active free radicals.

[0670] The (D) photopolymerization initiator in the colored resin composition of the present invention preferably contains a photopolymerization initiator (d1) represented by the following general formula (DI) (hereinafter sometimes referred to as "photopolymerization initiator (d1)"). It is believed that the photopolymerization initiator (d1) has a slow decomposition / reaction rate and can intermittently continue to generate free radicals by making the group bonded to the (keto)oxime ester group an indole ring with low reactivity, and can suppress the deactivation of free radicals caused by the dye and maintain high curability. Therefore, even if the residual solvent increases and the sensitivity decreases due to the pre-baking temperature being in the low temperature range, the penetration of the developer into the coating film can be suppressed, and the influence of the pre-baking temperature change on the sensitivity can be reduced.

[0671]

[0672] (In formula (DI), R d1 It represents an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent.

[0673] R d2 It represents an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent.

[0674] p represents 0 or 1.

[0675] R d3 represents an aromatic ring group which may have a substituent. )

[0676] (R d1 )

[0677] In formula (DI), R d1It represents an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent.

[0678] R d1 The alkyl group in the group may be straight chain, branched chain, cyclic, or a structure formed by bonding them. The carbon number of the alkyl group is not particularly limited, but is preferably 10 or less, more preferably 7 or less, further preferably 5 or less, particularly preferably 3 or less, most preferably 2 or less, and usually 1 or more. By setting the carbon number of the alkyl group to be below the aforementioned upper limit, there is a tendency to ensure solubility in a solvent and ease of synthesis.

[0679] As the alkyl group, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, isopentyl, cyclopentyl, hexyl, and cyclohexyl can be listed. From the viewpoint of ease of synthesis, methyl, ethyl, propyl, and butyl are preferred, methyl and ethyl are more preferred, and methyl is further preferred.

[0680] Examples of the substituent that the alkyl group may have include an aromatic ring group having 6 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, a halogen atom such as F, Cl, Br, I, and a hydroxyl group. From the viewpoint of solvent solubility, an alkoxy group having 1 to 3 carbon atoms is preferred. From the viewpoint of sensitivity, unsubstituted is preferred.

[0681] As R d1 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 usually 4 or more, preferably 6 or more, and preferably 12 or less, more preferably 10 or less, and further preferably 8 or less. By setting the number of carbon atoms in the aromatic ring group to be greater than the aforementioned lower limit, the molecule tends to be stable, and by setting it to be less than the aforementioned upper limit, the solvent solubility tends to be good.

[0682] 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 a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzopyrene ring, Ring, triphenylene ring, acenaphthene ring, fluoranthene ring, fluorene ring.

[0683] 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 benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, an indole ring, a carbazole ring, a pyrroloimidazole ring, a pyrrolopyrazole ring, a pyrrolopyrrole ring, a thienopyrrole ring, a thienothiophene ring, a furanopyrrole ring, a furanofuran ring, a thienofuran ring, a benzisoxazole ring, a benzisothiazole ring, a benzimidazole ring, a pyridine ring, a pyrazine ring, a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a cinnoline ring, a quinoxaline ring, a phenanthridine ring, a phenanthridine ring, a quinazoline ring, a quinazolinone ring, and an azulene ring.

[0684] From the viewpoint of solvent solubility, the aromatic heterocyclic group is preferably a benzene ring or a naphthalene ring having one free valence, and more preferably a benzene ring having one free valence.

[0685] Examples of the substituent that the aromatic ring group may have include an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, a halogen atom such as F, Cl, Br, or I, a hydroxyl group, and a nitro group. From the viewpoint of solvent solubility, an alkoxy group having 1 to 3 carbon atoms and a hydroxyl group are preferred.

[0686] From the viewpoint of solubility in solvents and ease of synthesis, R d1 An alkyl group which may have a substituent is preferred, an unsubstituted alkyl group is more preferred, a methyl group or an ethyl group is further preferred, and a methyl group is particularly preferred.

[0687] (R d2 )

[0688] In formula (DI), R d2 It represents an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent.

[0689] R d2 The alkyl group in the group may be straight chain, branched chain, cyclic, or a structure formed by bonding these. From the viewpoint of solvent solubility, the straight chain or branched chain is preferred, and the straight chain is more preferred. On the other hand, from the viewpoint of sensitivity, an unsubstituted straight chain alkyl group is preferred.

[0690] The number of carbon atoms in the alkyl group is not particularly limited, and is generally 1 or more, preferably 2 or more, more preferably 3 or more, further preferably 4 or more, further preferably 5 or more, and particularly preferably 6 or more. In addition, it is preferably 12 or less, more preferably 10 or less, further preferably 9 or less, and particularly preferably 8 or less. By setting the number of carbon atoms in the alkyl group to be above the aforementioned lower limit, there is a tendency for the sensitivity to be improved, and by setting it to be below the aforementioned upper limit, there is a tendency for the solvent affinity to be improved. The above upper and lower limits may be combined arbitrarily. For example, it may be 1 to 12, 2 to 12, 3 to 10, 4 to 10, 5 to 9, or 6 to 8.

[0691] As the substituent which the alkyl group may have, for example, an aromatic ring group having 6 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an alkoxycarbonyl group having 1 to 10 carbon atoms, a halogen atom such as F, Cl, Br, I, and a hydroxyl group can be cited. From the viewpoint of solvent solubility, an alkoxy group having 1 to 3 carbon atoms is preferred. From the viewpoint of ease of synthesis, unsubstituted is preferred.

[0692] Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, isopentyl, cyclopentyl, hexyl, cyclohexyl, cyclopentylmethyl, cyclopentylethyl, cyclohexylmethyl, and cyclohexylethyl. Among these, from the viewpoint of sensitivity and solvent affinity, propyl, butyl, pentyl, and hexyl are preferred, pentyl and hexyl are more preferred, and hexyl is still more preferred.

[0693] As R d2 The aromatic ring group in the formula (a) may include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The number of carbon atoms in the aromatic ring group 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. By setting the number of carbon atoms in the aromatic ring group to be above the aforementioned lower limit, there is a tendency for the molecule to become stable, and by setting it to be below the aforementioned upper limit, there is a tendency for the solvent solubility to become good. The above upper and lower limits may be combined arbitrarily. For example, it may be 4 to 12, 4 to 10, or 6 to 8.

[0694] 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 a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzopyrene ring, Ring, triphenylene ring, acenaphthene ring, fluoranthene ring, fluorene ring.

[0695] 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 benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, an indole ring, a carbazole ring, a pyrroloimidazole ring, a pyrrolopyrazole ring, a pyrrolopyrrole ring, a thienopyrrole ring, a thienothiophene ring, a furanopyrrole ring, a furanofuran ring, a thienofuran ring, a benzisoxazole ring, a benzisothiazole ring, a benzimidazole ring, a pyridine ring, a pyrazine ring, a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a cinnoline ring, a quinoxaline ring, a phenanthridine ring, a phenanthridine ring, a quinazoline ring, a quinazolinone ring, and an azulene ring.

[0696] From the viewpoint of solvent solubility, a benzene ring or a naphthalene ring having one free valence is preferred, and a benzene ring having one free valence is more preferred.

[0697] As the substituent that the aromatic ring group may have, for example, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, a halogen atom such as F, Cl, Br, I, a hydroxyl group, and a nitro group can be listed. From the viewpoint of solvent solubility, an alkoxy group having 1 to 5 carbon atoms and a hydroxyl group are preferred. The alkyl chain part of the substituent may be linear or branched, and further, it may have a substituent such as an alkoxy group having 1 to 3 carbon atoms, an alkylthio group having 1 to 3 carbon atoms, a halogen atom, a hydroxyl group, a nitro group, and the like.

[0698] From the viewpoint of solvent affinity and sensitivity, R d2 An alkyl group which may have a substituent is preferred, an unsubstituted alkyl group is more preferred, a butyl group, a pentyl group, and a hexyl group is further preferred, and a hexyl group is particularly preferred.

[0699] (R d3 )

[0700] In formula (DI), R d3 It represents an aromatic ring group which may have a substituent.

[0701] As R d3 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 usually 4 or more, preferably 6 or more, preferably 12 or less, more preferably 10 or less, and further preferably 8 or less. By setting the number of carbon atoms in the aromatic ring group to be above the aforementioned lower limit, there is a tendency for the sensitivity during exposure to be improved, and by setting it to be below the aforementioned upper limit, there is a tendency for the solvent affinity to be improved. The above upper and lower limits may be combined arbitrarily. For example, it may be 4 to 12, 4 to 10, or 6 to 8.

[0702] 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 a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzopyrene ring, Ring, triphenylene ring, acenaphthene ring, fluoranthene ring, fluorene ring.

[0703] 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 benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, an indole ring, a carbazole ring, a pyrroloimidazole ring, a pyrrolopyrazole ring, a pyrrolopyrrole ring, a thienopyrrole ring, a thienothiophene ring, a furanopyrrole ring, a furanofuran ring, a thienofuran ring, a benzisoxazole ring, a benzisothiazole ring, a benzimidazole ring, a pyridine ring, a pyrazine ring, a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a cinnoline ring, a quinoxaline ring, a phenanthridine ring, a phenanthridine ring, a quinazoline ring, a quinazolinone ring, and an azulene ring.

[0704] From the viewpoint of solvent affinity, a benzene ring or a naphthalene ring having one free valence is preferred, and a benzene ring having one free valence is more preferred.

[0705] Examples of the substituent that the aromatic ring group may have include an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an aroyl group having 6 to 10 carbon atoms, a halogen atom such as F, Cl, Br, and I, a hydroxyl group, and a nitro group. From the viewpoint of sensitivity during exposure, an aryl group having 6 to 10 carbon atoms and an aroyl group having 6 to 10 carbon atoms are preferred.

[0706] From the viewpoint of solvent affinity and sensitivity during exposure, R d3 It is preferably an aromatic hydrocarbon group having one free valence and optionally having a substituent, and more preferably a benzene ring group having one free valence and optionally having a substituent.

[0707] (p)

[0708] In the formula (DI), p represents 0 or 1. From the viewpoint of sensitivity, p is preferably 0, while from the viewpoint of suppressing residues by improving solvent affinity, p is preferably 1.

[0709] Among the photopolymerization initiators (d1), a photopolymerization initiator represented by the following general formula (DII) is preferred from the viewpoint of solvent affinity and sensitivity during exposure.

[0710]

[0711] (In formula (DII), R d1 , R d2 and p have the same meanings as in the aforementioned formula (DI).

[0712] R d4 represents an arbitrary monovalent substituent. q represents an integer of 0 to 3. )

[0713] (R d4 )

[0714] In formula (DII), R d4 represents an arbitrary monovalent substituent.

[0715] As arbitrary monovalent substituents, for example, alkyl groups having 1 to 10 carbon atoms, such as methyl and ethyl groups; alkoxy groups having 1 to 10 carbon atoms, such as methoxy and ethoxy groups; halogen atoms, such as F, Cl, Br, and I; acyl groups having 1 to 10 carbon atoms; alkyl ester groups having 1 to 10 carbon atoms; alkoxycarbonyl groups having 1 to 10 carbon atoms; halogenated alkyl groups having 1 to 10 carbon atoms; aromatic ring groups having 4 to 10 carbon atoms; amino groups; aminoalkyl groups having 1 to 10 carbon atoms; hydroxyl groups; nitro groups; CN groups; benzoyl groups optionally having substituents; and thenoyl groups optionally having substituents. As substituents optionally possessed by benzoyl and thenoyl groups, alkyl groups having 1 to 3 carbon atoms and alkoxy groups having 1 to 3 carbon atoms can be cited, and the number of substituents can be 0 to 3. From the viewpoint of sensitivity, nitro groups, CN groups, benzoyl groups optionally having substituents, and thenoyl groups optionally having substituents are preferred, and benzoyl groups are more preferred.

[0716] R d4 When q is greater than 2, multiple R d4 They are optionally bonded to each other to form a ring. The ring may be an aliphatic ring or an aromatic ring.

[0717] R d4 The substitution position of is not particularly limited and may be any of the ortho, meta, and para positions. From the viewpoint of solvent affinity and sensitivity, the para position is preferred.

[0718] (q)

[0719] In formula (DII), q represents an integer of 0 to 3. From the viewpoint of suppressing residues by improving solubility in a solvent and improving sensitivity during exposure, 0 or 1 is preferred, and 1 is more preferred.

[0720] The method for producing the photopolymerization initiator (d1) is not particularly limited, and it can be produced, for example, by the method described in JP-A-2017-179211.

[0721] As a specific example of a photoinitiator (d1), the following are mentioned, for example.

[0722]

[0723] (D) The photopolymerization initiator may further contain another photopolymerization initiator (d2) in addition to the photopolymerization initiator (d1).

[0724] As other photopolymerization initiators (d2), for example, titanocene derivatives containing titanocene compounds described in Japanese Patent Publication No. 59-152396 and Japanese Patent Publication No. 61-151197; hexaarylbiimidazole derivatives described in Japanese Patent Publication No. 2000-56118; halogenated methylated oxadiazole derivatives, halogenated methyl-s-triazine derivatives, N-aryl-α-amino acids such as N-phenylglycine, N-aryl-α-amino acid salts, N-aryl-α-amino acid esters and other free radical activators, α-aminoalkylphenone derivatives recorded in Japanese Patent Publication No. 10-39503; oxime ester derivatives described in Japanese Patent Publication No. 2000-80068 and Japanese Patent Publication No. 2006-36750.

[0725] Examples of the titanocene derivatives include dicyclopentadienyl titanium dichloride, dicyclopentadienyl bisphenyl titanium, dicyclopentadienyl bis(2,3,4,5,6-pentafluorophenyl)titanium, dicyclopentadienyl bis(2,3,5,6-tetrafluorophenyl)titanium, dicyclopentadienyl bis(2,4,6-trifluorophenyl)titanium, dicyclopentadienyl bis(2,6-difluorophenyl)titanium, dicyclopentadienyl bis(2,4-difluorophenyl)titanium, bis(methylcyclopentadienyl)bis(2,3,4,5,6-pentafluorophenyl)titanium, bis(methylcyclopentadienyl)bis(2,6-difluorophenyl)titanium, and dicyclopentadienyl [2,6-difluoro-3-(pyrrol-1-yl)-phenyl]titanium.

[0726] Examples of biimidazole derivatives include 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.

[0727] Examples of the halogenated methylated oxadiazole derivatives include 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, and 2-trichloromethyl-5-furanyl-1,3,4-oxadiazole.

[0728] Examples of the halomethyl-s-triazine derivatives include 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, and 2-(4-ethoxycarbonylnaphthyl)-4,6-bis(trichloromethyl)-s-triazine.

[0729] Examples of the α-aminoalkylphenone derivatives include 2-methyl-1〔4-(methylthio)phenyl〕-2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 4-dimethylaminoethyl benzoate, 4-dimethylaminoisoamyl benzoate, 4-dimethylaminoacetophenone, 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.

[0730] Examples of the oxime ester derivatives include oxime ester compounds described in JP-A No. 2004-534797, JP-A No. 2000-80068, JP-A No. 2006-36750, JP-A No. 2008-179611, JP-A No. 2012-526185, and JP-A No. 2012-519191. From the viewpoint of sensitivity, preferred substances include 4-acetoxyimino-5-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-5-oxopentanoic acid methyl ester, and product names OXE-01, OXE-02, OXE-03, OXE-04 (manufactured by BASF), TR-PBG-304, TR-PBG-305, TR-PBG314 (manufactured by Changzhou Qiangli Company), NCI-831, and NCI-930 (manufactured by ADEKA).

[0731] The above-mentioned other photopolymerization initiators (d2) may be used alone or in combination of two or more.

[0732] These (D) photopolymerization initiators may be used alone or in combination of two or more.

[0733] In addition to the (D) photopolymerization initiator, a chain transfer agent may be further used. The chain transfer agent is a compound having a function of receiving a generated radical and transferring it to another compound.

[0734] As chain transfer agent, as long as it is a compound with the above-mentioned function, various compounds can be used, for example, mercapto-containing compounds and carbon tetrachloride can be listed. Since there is a tendency that the chain transfer effect is high, mercapto-containing compounds are more preferably used. It is believed that this is because the SH bond energy is small and bond cleavage is easy to occur, and hydrogen abstraction reaction and chain transfer reaction are easy to occur. It is effective for improving sensitivity and surface curing.

[0735] Examples of the mercapto group-containing compound include: mercapto group-containing compounds having an aromatic ring, such as 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 3-mercapto-1,2,4-triazole, 2-mercapto-4(3H)-quinazoline, β-mercaptonaphthalene, and 1,4-dimethylmercaptobenzene; hexanedithiol, decanedithiol, butanediol bis(3-mercaptopropionate), butanediol bisthioglycolate, ethylene glycol bis(3-mercaptopropionate), ethylene glycol bisthioglycolate, trimethylolpropane tris(3-mercaptopropionate), trimethylolpropane tris(3-mercaptopropionate), and trimethylolpropane tris(3-mercaptopropionate). Aliphatic mercapto group-containing compounds such as trimercaptoacetate, trishydroxyethyl trithiopropionate, pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tris(3-mercaptopropionate), butanediol bis(3-mercaptobutyrate), ethylene glycol bis(3-mercaptobutyrate), trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakis(3-mercaptobutyrate), pentaerythritol tris(3-mercaptobutyrate), and 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione. From the viewpoint of surface smoothness, compounds having a plurality of mercapto groups are preferred.

[0736] As the mercapto-containing compound having an aromatic ring, 2-mercaptobenzothiazole and 2-mercaptobenzimidazole are preferred, and as the aliphatic mercapto-containing compound, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tris(3-mercaptopropionate), trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakis(3-mercaptobutyrate), pentaerythritol tris(3-mercaptobutyrate), and 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione are preferred.

[0737] From the viewpoint of sensitivity, aliphatic mercapto-containing compounds are preferred, 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), 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione is more preferred, and pentaerythritol tetrakis(3-mercaptopropionate) and pentaerythritol tetrakis(3-mercaptobutyrate) are more preferred.

[0738] These various substances may be used alone or in combination of two or more.

[0739] In the colored resin composition of the present invention, the content ratio of the photopolymerization initiator (D) is not particularly limited, and is preferably 0.5% by mass or more, more preferably 0.8% by mass or more, further preferably 1.0% by mass or more, particularly preferably 1.2% by mass or more, and preferably 10% by mass or less, more preferably 9% by mass or less, further preferably 8% by mass or less, and particularly preferably 7% by mass or less. By setting it to be above the aforementioned lower limit, there is a tendency for the curability of the coating film to be improved, and by setting it to be below the aforementioned upper limit, there is a tendency to increase the brightness by reducing visible light absorption. The above upper and lower limits can be combined arbitrarily. For example, in the colored resin composition, the content ratio of the photopolymerization initiator (D) is preferably 0.5-10% by mass, more preferably 0.8-9% by mass, further preferably 1.0-8% by mass, and particularly preferably 1.2-7% by mass in the total solid content of the colored resin composition.

[0740] When the colored resin composition of the present invention contains a photopolymerization initiator (d1), the content ratio of the photopolymerization initiator (d1) in the colored resin composition is not particularly limited, and is preferably 0.5% by mass or more, more preferably 0.8% by mass or more, further preferably 1.0% by mass or more, particularly preferably 1.2% by mass or more, and preferably 7% by mass or less, more preferably 5% by mass or less, further preferably 4% by mass or less, and particularly preferably 3% by mass or less. By setting it to the above lower limit or more, there is a tendency for the curability of the coating film to be improved during low-temperature prebaking, and by setting it to the above upper limit or less, there is a tendency to increase the brightness by reducing visible light absorption. The above upper and lower limits can be combined arbitrarily. For example, in the colored resin composition, the content ratio of the photopolymerization initiator (d1) is preferably 0.5-7% by mass, more preferably 0.8-5% by mass, further preferably 1.0-4% by mass, and particularly preferably 1.2-3% by mass in the total solid content of the colored resin composition.

[0741] When the colored resin composition of the present invention contains a chain transfer agent, the content ratio is not particularly limited, and is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, further preferably 0.3% by mass or more, particularly preferably 0.4% by mass or more, and preferably 5% by mass or less, more preferably 3% by mass or less, further preferably 2% by mass or less, and particularly preferably 1% by mass or less. By setting it to be above the aforementioned lower limit, there is a tendency for solvent resistance to improve, and by setting it to be below the aforementioned upper limit, there is a tendency for storage stability to improve. The above upper and lower limits can be combined arbitrarily. For example, when the colored resin composition contains a chain transfer agent, its content ratio is preferably 0.1 to 5% by mass, more preferably 0.2 to 3% by mass, further preferably 0.3 to 2% by mass, and particularly preferably 0.4 to 1% by mass in the total solid content of the colored resin composition.

[0742] [3-5] Compound represented by formula (3), benzoquinone compound

[0743] The colored resin composition of the present invention contains a compound represented by the following general formula (3) and / or a benzoquinone-based compound.

[0744]

[0745] (In formula (3), R a , R b , R c , R d and R f Each independently represents a hydrogen atom, an unsubstituted alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, and R e represents a hydrogen atom or an unsubstituted alkyl group having 1 to 6 carbon atoms.

[0746] Since the phthalocyanine compound (1) has a fluorine atom with a very large electronegativity, it is considered that the polarity of the molecule is large and the affinity with the compound represented by formula (3) and the benzoquinone compound is high. In addition, the phthalocyanine compound molecule is generally highly planar, and in particular, the phthalocyanine compound (1) has a fluorine atom with a very small atomic radius, so the steric hindrance of the molecule is small and the affinity with the compound represented by formula (3) and the benzoquinone compound is high. Therefore, it is considered that the colored resin composition of the present invention contains the compound represented by formula (3) and / or the benzoquinone compound, so that the phthalocyanine compound (1) and the compound represented by formula (3) and the benzoquinone compound are close to each other in the colored resin composition, and it is possible to suppress the decrease in the polymerization ability and film curing ability of the (D) photopolymerization initiator due to the proximity of the phthalocyanine compound (1) and the (D) photopolymerization initiator and the interaction between the phthalocyanine compound (1) and the (D) photopolymerization initiator.

[0747] Examples of the compound represented by formula (3) include hydroquinones such as methylhydroquinone (MHQ), phenols such as 4-methoxyphenol (MEHQ) and butylhydroxytoluene (BHT), and hindered phenols such as pentaerythritol tetrakis[3-[3,5-di(tert-butyl)-4-hydroxyphenyl]propionate].

[0748] As a benzoquinone type compound, 1, 4-benzoquinone is mentioned, for example.

[0749] Among the compounds represented by formula (3) and benzoquinone compounds, from the viewpoint of affinity with the phthalocyanine compound (1), specifically, the polarity of the molecule, and the steric hindrance of the molecule, methylhydroquinone (MHQ), 4-methoxyphenol (MEHQ), butylated hydroxytoluene (BHT), and pentaerythritol tetrakis[3-[3,5-di(tert-butyl)-4-hydroxyphenyl]propionate] are preferred, and methylhydroquinone (MHQ) and 4-methoxyphenol (MEHQ) are particularly preferred.

[0750] The compound represented by formula (3) and the benzoquinone-based compound may be used alone or in combination of two or more.

[0751] The total content of the compound represented by formula (3) and the benzoquinone-based compound is preferably 0.80% by mass or less, more preferably 0.50% by mass or less, further preferably 0.30% by mass or less, and particularly preferably 0.10% by mass or less in the total solid content of the colored resin composition. In addition, it is preferably 0.001% by mass or more, more preferably 0.02% by mass or more, further preferably 0.03% by mass or more, and particularly preferably 0.05% by mass or more. By setting it to be above the above lower limit, there is a tendency for the inhibitory effect on the interaction between the phthalocyanine compound (1) and the photopolymerization initiator to be improved. In addition, by setting it to be below the above upper limit, there is a tendency for the curability to be high and a pattern with good linearity to be formed. The above upper and lower limits can be combined arbitrarily. For example, the total content of the compound represented by formula (3) and the benzoquinone-based compound is preferably 0.001 to 0.80 mass %, more preferably 0.02 to 0.50 mass %, further preferably 0.03 to 0.10 mass %, particularly preferably 0.05 to 0.10 mass % in the total solid content of the colored resin composition.

[0752] In the colored resin composition of the present invention, the total content of the compound represented by formula (3) and the benzoquinone compound is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, further preferably 10 parts by mass or less, and particularly preferably 5 parts by mass or less, relative to 100 parts by mass of the photopolymerization initiator (D). In addition, it is preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, further preferably 0.2 parts by mass or more, and particularly preferably 0.2 parts by mass or more. By setting it below the above upper limit, there is a tendency for the curability of the coating film to be improved and the patterning to be improved. In addition, by setting it above the above lower limit, there is a tendency for the time-dependent change of sensitivity to be suppressed. The above upper and lower limits can be combined arbitrarily. For example, relative to 100 parts by mass of the photopolymerization initiator (D), the total content of the compound represented by formula (3) and the benzoquinone compound is preferably 0.05 to 30 parts by mass, more preferably 0.1 to 20 parts by mass, further preferably 0.2 to 10 parts by mass, and particularly preferably 0.5 to 5 parts by mass.

[0753] Here, "the total content of the compound represented by formula (3) and the benzoquinone compound" does not presuppose that both the compound represented by formula (3) and the benzoquinone compound are contained, but includes a form containing only one of the compound represented by formula (3) or the benzoquinone compound.

[0754] [3-6] Other solid ingredients

[0755] The colored resin composition of the present invention may further contain solid components other than the above components as needed.

[0756] Examples of such components include photopolymerizable monomers, dispersants, dispersing aids, and surfactants.

[0757] [3-6-1] Photopolymerizable monomer

[0758] The photopolymerizable monomer is not particularly limited as long as it is a polymerizable low molecular compound, and is preferably an addition-polymerizable compound having at least one olefinic double bond (hereinafter referred to as an "olefinic compound"). An olefinic compound refers to a compound having an olefinic double bond that undergoes addition polymerization and curing 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 opposite to the so-called high molecular substance, and refers to the concept of dimers, trimers, and oligomers in addition to monomers in a narrow sense.

[0759] 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 more than 2, preferably more than 4, more preferably more than 5, and preferably less than 8, more preferably less than 7. The above upper and lower limits may be combined arbitrarily. For example, it may be 2 to 8, 4 to 8, or 5 to 7. 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 a solvent.

[0760] Examples of the olefinic compound include unsaturated carboxylic acids, esters thereof with monohydroxy compounds, esters of aliphatic polyhydroxy compounds with unsaturated carboxylic acids, esters of aromatic polyhydroxy compounds with unsaturated carboxylic acids, esters obtained by esterification reaction of unsaturated carboxylic acids and polyhydroxy compounds such as the aliphatic polyhydroxy compounds and aromatic polyhydroxy compounds, and olefinic compounds having a carbamate skeleton obtained by reacting a polyisocyanate compound with a (meth)acryloyl group-containing hydroxy compound.

[0761] Examples of the 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, crotonates obtained by replacing the acrylic acid moiety with a crotonic acid moiety, or maleates obtained by replacing the acrylic acid moiety with a maleic acid moiety.

[0762] Examples of the esters of an aromatic polyhydroxy compound and an unsaturated carboxylic acid include hydroquinone diacrylate, hydroquinone dimethacrylate, resorcinol diacrylate, resorcinol dimethacrylate, and pyrogallol triacrylate.

[0763] The ester obtained by the esterification reaction of unsaturated carboxylic acid and polycarboxylic acid with polyhydroxy compound is not necessarily a single substance, but may be a mixture. Examples thereof include condensates of acrylic acid, phthalic acid and ethylene glycol; condensates of acrylic acid, maleic acid and diethylene glycol; condensates of methacrylic acid, terephthalic acid and pentaerythritol; and condensates of acrylic acid, adipic acid, butanediol and glycerol.

[0764] Examples of the olefinic compound having a carbamate skeleton obtained by reacting a polyisocyanate compound with a (meth)acryloyl group-containing hydroxy compound include aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate; alicyclic diisocyanates such as cyclohexane diisocyanate and isophorone diisocyanate; aromatic diisocyanates such as toluene diisocyanate and diphenylmethane diisocyanate, and the like, and reaction products of (meth)acryloyl group-containing hydroxy compounds such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxy(1,1,1-triacryloyloxymethyl)propane and 3-hydroxy(1,1,1-trimethacryloyloxymethyl)propane.

[0765] Examples of the olefinic compound used in the present invention include acrylamides such as ethylenebisacrylamide; allyl esters such as diallyl phthalate; and vinyl-containing compounds such as divinyl phthalate.

[0766] The olefinic compound may also be a monomer having an acid value. The monomer having an acid value is an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, preferably a polyfunctional monomer having an acid group by reacting the unreacted hydroxyl group of the aliphatic polyhydroxy compound with a non-aromatic carboxylic anhydride, and particularly preferably the aliphatic polyhydroxy compound in the ester is pentaerythritol and / or dipentaerythritol.

[0767] These monomers can be used alone, but since it is difficult to use a single compound in the manufacture, two or more kinds can also be used in combination. In addition, as required, a polyfunctional monomer without an acid group and a polyfunctional monomer with an acid group can also be used in combination as a monomer.

[0768] 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 to improve the curing properties such as the photopolymerization performance and the surface smoothness of the pixel. Therefore, when two or more polyfunctional monomers having different acid groups are used in combination, or when a polyfunctional monomer having no acid group is used in combination, it is preferred to adjust the acid groups of the overall polyfunctional monomers so that they fall within the above range.

[0769] In the present invention, a more preferred polyfunctional monomer having an acid group is a mixture of dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentaacrylate succinate, which is commercially available as TO1382 manufactured by Toagosei Co., Ltd. and is mainly composed of dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentaacrylate. Other polyfunctional monomers of the polyfunctional monomer may also be used in combination. In addition, the compounds described in paragraphs 0056 and 0057 of Japanese Patent Publication No. 2013-140346 may also be used.

[0770] From the viewpoint of improving the chemical resistance of the pixel and the linearity of the edge of the pixel, the polymerizable monomer described in Japanese Patent Application Laid-Open No. 2013-195971 is preferably used. From the viewpoint of achieving both the sensitivity of the coating film and the shortening of the development time, the polymerizable monomer described in Japanese Patent Application Laid-Open No. 2013-195974 is preferably used.

[0771] When the colored resin composition of the present invention contains a photopolymerizable monomer, the content ratio of the photopolymerizable monomer is not particularly limited, and is preferably 5% by mass or more, more preferably 8% by mass or more, further preferably 10% by mass or more, and particularly preferably 12% by mass or more in the total solid content of the colored resin composition. In addition, it is preferably 60% by mass or less, more preferably 50% by mass or less, further preferably 45% by mass or less, and particularly preferably 40% by mass or less. By setting it to above the aforementioned lower limit, there is a tendency for the curability of the coating film to be improved, and by setting it to below the aforementioned upper limit, there is a tendency to ensure the flatness of the coating film surface. The above upper and lower limits can be combined arbitrarily. For example, it can be 5 to 60% by mass, it can be 8 to 50% by mass, it can be 10 to 45% by mass, or it can be 12 to 40% by mass.

[0772] [3-6-2] Dispersants and dispersing aids

[0773] 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.

[0774] Examples of polymer dispersants include urethane dispersants, polyethyleneimine dispersants, polyoxyethylene alkyl ether dispersants, polyoxyethylene glycol diester dispersants, sorbitan aliphatic ester dispersants, and aliphatic modified polyester dispersants. Examples of polymer dispersants include, by trade name, 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 Lubrizol Corporation), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), POLYFLOW (manufactured by Kyoeisha Chemical Co., Ltd.), and polymer dispersants described in Japanese Patent Application Publication No. 2013-119568.

[0775] Among the polymer dispersants, from the viewpoint of dispersibility and storage stability, a block copolymer having a functional group containing a nitrogen atom is preferred, and an acrylic block copolymer is more preferred.

[0776] The block copolymer having a functional group containing a nitrogen atom is preferably an AB block copolymer and / or a BAB block copolymer including 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.

[0777] Examples of the functional group containing a nitrogen atom include primary and tertiary amino groups and quaternary ammonium salt groups. From the viewpoint of dispersibility and storage stability, it is preferred to have a primary and tertiary amino group, and it is more preferred to have a tertiary amino group.

[0778] 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 (11) from the viewpoint of dispersibility and storage stability.

[0779]

[0780] In formula (11), R 11 and R 12 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 11 and R 12 Optionally, they are bonded to each other to form a ring structure. 13 is a hydrogen atom or a methyl group. X is a divalent linking group.

[0781] The carbon number of the alkyl group optionally having a substituent in formula (11) is not particularly limited, and is generally 1 or more, and preferably 10 or less, more preferably 6 or less, and further preferably 4 or less. As the alkyl group, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl can be listed, preferably methyl, ethyl, propyl, butyl, pentyl, and hexyl, and more preferably methyl, ethyl, propyl, and butyl. It can be any one of a straight chain and a branched chain. In addition, it can contain a cyclic structure such as a cyclohexyl group and a cyclohexylmethyl group.

[0782] The carbon number of the aryl group which may have a substituent in formula (11) 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. Examples of the aryl group include phenyl, methylphenyl, ethylphenyl, dimethylphenyl, diethylphenyl, naphthyl, and anthracenyl, preferably phenyl, methylphenyl, ethylphenyl, dimethylphenyl, and diethylphenyl, and more preferably phenyl, methylphenyl, and ethylphenyl.

[0783] The carbon number of the aralkyl group which may have a substituent in formula (11) 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. Examples of the aralkyl group include phenylmethylene, phenylethylene, phenylpropylene, phenylbutylene, and phenylisopropylene, preferably phenylmethylene, phenylethylene, phenylpropylene, and phenylbutylene, and more preferably phenylmethylene and phenylethylene.

[0784] From the perspective of dispersibility, storage stability, electrical reliability, and developability, R 11 and R 12 Preferably, each independently is an alkyl group which may have a substituent, and more preferably a methyl group or an ethyl group.

[0785] Examples of the substituent that the alkyl group, aralkyl group or aryl group in formula (11) may have include a halogen atom, an alkoxy group, a benzoyl group and a hydroxyl group. From the viewpoint of ease of synthesis, the substituent is preferably unsubstituted.

[0786] In formula (11), as R 11 and R 12 The cyclic structure formed by bonding to each other 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 a saturated ring is more preferred. For example, the nitrogen-containing heterocyclic ring (VII) below can be mentioned.

[0787]

[0788] These cyclic structures may further have a substituent.

[0789] In the formula (11), 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 23 -base, -COOR 24 -base〔where R 23 and R 24 is a single bond, an alkylene group having 1 to 10 carbon atoms, or an ether group having 2 to 10 carbon atoms (alkyloxyalkyl group), preferably -COO-R 24 -base.

[0790] The repeating unit shown in formula (11) 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%, most preferably more than 25 mol%, and preferably less than 90 mol%, more preferably less than 70 mol%, more preferably less than 50 mol%, particularly preferably less than 40 mol%. The above upper and lower limits can be combined arbitrarily. For example, it can be 1 to 90 mol%, 5 to 90 mol%, 10 to 70 mol%, 15 to 70 mol%, 20 to 50 mol%, or 25 to 40 mol%. In the case of the aforementioned range, there is a tendency to be able to take into account both dispersion stability and high brightness.

[0791] From the viewpoint of improving the compatibility of the dispersant with the binder component such as the solvent and improving the dispersion stability, the block copolymer preferably has a repeating unit represented by the following general formula (12).

[0792]

[0793] In formula (12), R 110 is ethylene or propylene, R 111 is an alkyl group optionally having a substituent, R 112 is a hydrogen atom or a methyl group. n is an integer of 1 to 20.

[0794] R in formula (12) 111 The carbon number 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 the alkyl group, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl can be listed, preferably methyl, ethyl, propyl, butyl, pentyl, hexyl, more preferably methyl, ethyl, propyl, butyl. It can be any one of straight chain and branched. In addition, it can contain cyclic structures such as cyclohexyl and cyclohexylmethyl. As the substituent, for example, a halogen atom, an alkoxy group, a benzoyl group, a hydroxyl group can be listed, and from the viewpoint of ease of synthesis, it is preferably unsubstituted.

[0795] From the viewpoint of compatibility and dispersibility with binder components such as solvents, n in formula (12) is preferably 1 or more, more preferably 2 or more, and preferably 10 or less, more preferably 5 or less. The above upper and lower limits may be arbitrarily combined. For example, it may be 1 to 10, or 2 to 5.

[0796] The ratio of the repeating unit shown in formula (12) in all the repeating units of the block copolymer is preferably 1 mol% or more, more preferably 2 mol% or more, and further preferably 4 mol% or more. In addition, it is preferably 30 mol% or less, more preferably 20 mol% or less, and further preferably 10 mol% or less. The above upper and lower limits can be combined arbitrarily. For example, it can be 1 to 30 mol%, 2 to 20 mol%, or 4 to 10 mol%. In the case of the aforementioned range, there is a tendency to be able to take into account the compatibility and dispersion stability of binder components such as solvents.

[0797] From the viewpoint of improving the compatibility of the dispersant with the binder component such as the solvent and improving the dispersion stability, the block copolymer preferably has a repeating unit represented by the following general formula (13).

[0798]

[0799] In formula (13), 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.

[0800] R in formula (13) 8 The carbon number of the alkyl group optionally having a substituent is not particularly limited, and is usually 1 or more, preferably 1 or more, and preferably 10 or less, and more preferably 6 or less. As the alkyl group, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl can be listed, preferably methyl, ethyl, propyl, butyl, pentyl, and hexyl, and more preferably methyl, ethyl, propyl, and butyl. It can be any one of a straight chain and a branched chain. In addition, it can contain cyclic structures such as cyclohexyl and cyclohexylmethyl.

[0801] R in formula (13) 8 The carbon number 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. Examples of the aryl group include phenyl, methylphenyl, ethylphenyl, dimethylphenyl, diethylphenyl, naphthyl, and anthracenyl, preferably phenyl, methylphenyl, ethylphenyl, dimethylphenyl, and diethylphenyl, and more preferably phenyl, methylphenyl, and ethylphenyl.

[0802] R in formula (13) 8 The carbon number 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. Examples of the aralkyl group include phenylmethylene, phenylethylene, phenylpropylene, phenylbutylene, and phenylisopropylidene, preferably phenylmethylene, phenylethylene, phenylpropylene, and phenylbutylene, and more preferably phenylmethylene and phenylethylene.

[0803] From the viewpoint of solvent compatibility and dispersion stability, 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.

[0804] As R 8 Examples of the substituents that the alkyl group in the formula (R) may have include halogen atoms and alkoxy groups. Examples of the substituents that the aryl group or aralkyl group may have include chain alkyl groups, halogen atoms, and alkoxy groups. 8 The chain alkyl group shown includes both linear and branched ones.

[0805] The ratio of the repeating unit shown in formula (13) in all the repeating units of the block copolymer is preferably 30 mol% or more, more preferably 40 mol% or more, further preferably 50 mol% or more, and preferably 80 mol% or less, more preferably 70 mol% or less. The above upper and lower limits can be combined arbitrarily. For example, it can be 30 to 80 mol%, 40 to 80 mol%, or 50 to 70 mol%. In the case of the aforementioned range, there is a tendency to be able to take into account both dispersion stability and high brightness.

[0806] The block copolymer may also have repeating units other than the repeating units represented by formula (11), the repeating units represented by formula (12), and the repeating units represented by formula (13). Examples of such repeating units include: repeating units derived from styrene monomers such as styrene and α-methylstyrene; (meth)acrylate monomers such as (meth)acryloyl chloride; (meth)acrylamide monomers such as (meth)acrylamide and N-hydroxymethylacrylamide; and repeating units derived from monomers such as vinyl acetate, acrylonitrile, allyl glycidyl ether, crotonic acid glycidyl ether, and N-methacryloylmorpholine.

[0807] From the viewpoint of further improving dispersibility, it is preferred that the block copolymer comprises an A block having a repeating unit represented by formula (11) and a B block not having a repeating unit represented by formula (11). The block copolymer is preferably an AB block copolymer or a BAB block copolymer. In addition, the B block more preferably comprises a repeating unit represented by formula (12) and a repeating unit represented by formula (13).

[0808] The A block may also contain repeating units other than the repeating unit represented by formula (11), and examples of such repeating units include repeating units derived from the aforementioned (meth)acrylate monomers. The content of repeating units other than the repeating units represented by formula (11) in the A block is preferably 0 to 50 mol%, more preferably 0 to 20 mol%, and it is particularly preferred that the A block does not contain such repeating units.

[0809] The B block may also contain repeating units other than the repeating units represented by formula (12) and the repeating units represented by formula (13). Examples of such repeating units include repeating units derived from styrene monomers such as styrene and α-methylstyrene; (meth)acrylate monomers such as (meth)acryloyl chloride; (meth)acrylamide monomers such as N-methylolacrylamide; vinyl acetate; acrylonitrile; allyl glycidyl ether, crotonic acid glycidyl ether; and N-methacryloylmorpholine. The content of repeating units other than the repeating units represented by formula (12) and the repeating units represented by formula (13) in the B block is preferably 0 to 50 mol%, more preferably 0 to 20 mol%, and it is particularly preferred that the B block does not contain such repeating units.

[0810] From the viewpoint of dispersibility, the acid value of the block copolymer is preferably low, and particularly preferably 0 mgKOH / g. Here, the acid value refers to the number of mg of KOH required to neutralize 1 g of the solid content of the dispersant.

[0811] 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, most preferably 105 mgKOH / g or more, and preferably 150 mgKOH / g or less, more preferably 130 mgKOH / g or less. The above upper and lower limits can be combined arbitrarily. For example, it can be 30 to 150 mgKOH / g, 50 to 150 mgKOH / g, 70 to 150 mgKOH / g, 90 to 130 mgKOH / g, 100 to 130 mgKOH / g, or 105 to 130 mgKOH / g. Here, the amine value represents the amine value converted to the effective solid content, which is a value represented by the mass of KOH equivalent to the alkali amount per 1 g solid content of the dispersant.

[0812] The molecular weight of the block copolymer is preferably in the range of 1000 to 30000 in terms of polystyrene-equivalent weight average molecular weight (hereinafter sometimes referred to as "Mw"). Within the above range, dispersion stability is improved and dried foreign matter tends to be less likely to be generated during coating by a slit nozzle method.

[0813] The block copolymer can be produced by a known method, for example, by living polymerizing a monomer into which each of the above-mentioned repeating units is introduced.

[0814] As living polymerization methods, Japanese Patent Application Laid-Open No. 9-62002, Japanese Patent Application Laid-Open No. 2002-31713, P. Lutz, P. Masson et al., Polym. Bull. 12, 79 (1984), BC Anderson, GD Andrews et al., Macromolecules, 14, 1601 (1981), K. Hatada, K. Ute, et al., Polym. J. 17, 977 (1985 ... Bull. 12, 79 (1984), BC Anderson, GD Andrews et al., Macromolecules, 14, 1601 (1981), K. Hatada, K. Ute, et al., Polym. J. 17, 977 (1985), K. Hatada, K. Ute, et al., Polym. al, Polym.J.18, 1037 (1986), Yuichi Hirokazu, Koichi Hata, 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).

[0815] When the colored resin composition of the present invention includes a dispersant, the content ratio of the dispersant is not particularly limited, and is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, further preferably 0.1% by mass or more, particularly preferably 1% by mass or more, and preferably 25% by mass or less, more preferably 20% by mass or less, further preferably 15% by mass or less, and particularly preferably 10% by mass or less. By setting it to above the aforementioned lower limit, there is a tendency for dispersibility and storage stability to be improved. In addition, by setting it to below the aforementioned upper limit, there is a tendency for electrical reliability and developability to be improved. The above upper and lower limits can be combined arbitrarily. For example, it can be 0.001 to 25% by mass, it can be 0.01 to 20% by mass, it can be 0.1 to 15% by mass, or it can be 1 to 10% by mass.

[0816] When the colored resin composition of the present invention contains a pigment and a dispersant, the content ratio of the dispersant is not particularly limited. It 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. The above upper and lower limits can be combined arbitrarily. For example, it can be 0.5 to 70 parts by mass, 5 to 70 parts by mass, 10 to 50 parts by mass, 15 to 40 parts by mass, or 20 to 30 parts by mass. By setting it within the above range, there is a tendency to obtain a colored resin composition with excellent dispersion stability and high brightness.

[0817] When the colored resin composition of the present invention contains a pigment, in order to improve the dispersibility of the pigment and improve the dispersion stability, a pigment derivative or the like may also be contained as a dispersing aid. As pigment derivatives, for example, derivatives of azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, isoindolinone, isoindolinone, dioxazine, anthraquinone, indanthrene, perylene, perinone, diketopyrrolopyrrole, and dioxazine pigments can be cited. As substituents of the pigment derivatives, groups directly or via alkyl, aryl, heterocyclic groups, such as sulfonic acid groups, sulfonamide groups, and quaternary salts thereof, phthalimidomethyl, dialkylaminoalkyl, hydroxyl, carboxyl, and amide groups bonded to the pigment skeleton can be cited, and preferably sulfonamide groups and quaternary salts thereof, sulfonic acid groups, and more preferably sulfonic acid groups can be cited. These substituents may be substituted with multiple groups in one pigment skeleton, or may be a mixture of compounds with different numbers of substitutions. Examples of the pigment derivatives include sulfonic acid derivatives of azo pigments, sulfonic acid derivatives of phthalocyanine pigments, sulfonic acid derivatives of quinophthalone pigments, sulfonic acid derivatives of isoindoline pigments, sulfonic acid derivatives of anthraquinone pigments, sulfonic acid derivatives of quinacridone pigments, sulfonic acid derivatives of diketopyrrolopyrrole pigments, and sulfonic acid derivatives of dioxazine pigments.

[0818] [3-6-3] Surfactants

[0819] As a surfactant, various surfactants such as anionic, cationic, nonionic, and amphoteric surfactants can be used. From the perspective of the low possibility of adversely affecting each characteristic, nonionic surfactants are preferably used. The content ratio of the surfactant is not particularly limited. It is usually 0.001% by mass or more, preferably 0.01% by mass or more, more preferably 0.05% by mass or more, more preferably 0.1% by mass or more, and usually 10% by mass or less, preferably 1% by mass or less, more preferably 0.5% by mass or less, and particularly preferably 0.3% by mass or less in the total solid content of the colored resin composition. The above upper and lower limits can be combined arbitrarily. For example, it can be 0.001 to 10% by mass, it can be 0.01 to 1% by mass, it can be 0.05 to 0.5% by mass, or it can be 0.1 to 0.3% by mass.

[0820] [3-7] Preparation of colored resin composition

[0821] The method for preparing the colored resin composition (hereinafter sometimes referred to as a resist) of the present invention will be described.

[0822] When the colorant is dispersed, the colorant, solvent and dispersant are weighed in predetermined amounts, and the colorant is dispersed in the dispersion process to prepare a liquid containing the colorant. In the dispersion process, a paint conditioner, a sand mill, a ball mill, a roller mill, a stone mill, a jet mill, a homogenizer, etc. can also be used. By performing the dispersion process, the colorant is micronized, so that the coating characteristics of the colored resin composition are improved and the transmittance of the pixels of the color filter substrate of the product is improved.

[0823] When the colorant is dispersed, it is preferable to use a dispersing aid, a dispersing resin, or the like in combination as appropriate, as described above.

[0824] When a sand mill is used for dispersion treatment, glass beads or zirconium oxide beads having a diameter of 0.1 to several mm are preferably used. The temperature during dispersion treatment is usually set to be above 0°C, preferably above room temperature, and usually below 100°C, preferably below 80°C. It should be noted that the dispersion time is different depending on the composition of the liquid containing the colorant and the size of the sand mill, so it can be adjusted appropriately.

[0825] The colorant-containing liquid obtained by the above dispersion treatment may be further mixed with a solvent, an alkali-soluble resin, a photopolymerization initiator, and other components as required to prepare a uniform solution to obtain a colored resin composition. It should be noted that fine dust may be mixed in each of the dispersion treatment steps and mixing steps, so it is preferred that the obtained composition be filtered using a filter or the like.

[0826] When the colorant is not dispersed, the colorant, solvent, alkali-soluble resin, photopolymerization initiator, and other components as required may be mixed to form a uniform solution to obtain a colored resin composition. The obtained composition is preferably filtered using a filter or the like.

[0827] The compound represented by the formula (3) and the benzoquinone compound in the present invention are preferably already mixed with the phthalocyanine compound (1) at the time of mixing the phthalocyanine compound (1) and the photopolymerization initiator.

[0828] Specifically, it is preferred that: the compound represented by the above formula (3) and / or the benzoquinone-based compound is added in the step of preparing a colorant-containing liquid containing the phthalocyanine compound (1) (i.e., before adding the (D) photopolymerization initiator); or that the phthalocyanine compound (1) and the compound represented by the above formula (3) and / or the benzoquinone-based compound are added before mixing the phthalocyanine compound (1) and the photopolymerization initiator in the step of preparing a colored resin composition.

[0829] [4]Manufacturing of color filter substrates

[0830] Next, the color filter of the present invention will be described.

[0831] The color filter of the present invention has pixels formed using the above-mentioned colored resin composition.

[0832] [4-1] Transparent substrate (support)

[0833] As the transparent substrate of the color filter, the material thereof is not particularly limited as long as it is transparent and has appropriate strength. As the material, for example, polyester resins such as polyethylene terephthalate, polyolefin resins such as polypropylene and polyethylene, thermoplastic resin films such as polycarbonate, polymethyl methacrylate, and polysulfone, thermosetting resin films such as epoxy resins, unsaturated polyester resins, and poly(meth)acrylic resins, or various glasses can be cited. Among them, glass or heat-resistant resins are preferred from the viewpoint of heat resistance.

[0834] In order to improve the surface properties such as adhesion, the transparent substrate and the black matrix forming substrate can be subjected to corona discharge treatment, ozone treatment, silane coupling agent, urethane resin and other resin film forming treatments as needed. The thickness of the transparent substrate is usually more than 0.05mm, preferably more than 0.1mm, and is usually set to a range of less than 10mm, preferably less than 7mm. In addition, when the film forming treatment of various resins is carried out, the film thickness is usually more than 0.01μm, preferably more than 0.05μm, and is usually less than 10μm, preferably less than 5μm.

[0835] [4-2] Black Matrix

[0836] By arranging a black matrix on the above-mentioned transparent substrate and then generally forming a red, green, and blue pixel image, the color filter of the present invention can be manufactured. The above-mentioned colored resin composition is preferably made into a green or blue pixel (resist pattern) forming coating liquid in red, green, and blue pixels and used. Using the coating liquid for resist pattern formation, coating, heating and drying, image exposure, development, and heat curing are performed on the resin black matrix forming surface formed on the transparent substrate or on the metal black matrix forming surface formed using a light-shielding metal material such as a chromium compound to form a pixel image.

[0837] The black matrix is ​​formed on a transparent substrate using a light-shielding metal film or a black matrix colored resin composition. 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.

[0838] These metal light-shielding films are usually formed by a sputtering method. After forming the desired pattern in a film form using a positive photoresist, an etching solution prepared by mixing ammonium cerium nitrate with perchloric acid and / or nitric acid is used for chromium. For other materials, etching is performed using an etching solution corresponding to the material. Finally, the positive photoresist is stripped off with a special stripper, thereby forming a black matrix.

[0839] In this case, a thin film of these metals or metal / metal oxides is first formed on a transparent substrate by evaporation or sputtering. Then, a coating film of a colored resin composition is formed on the thin film, and then the coating film is exposed / developed using a photomask having a repeated pattern such as stripes, mosaics, triangles, etc. to form a resist image. Thereafter, the coating film is subjected to an etching treatment to form a black matrix.

[0840] In the case of using a colored resin composition for a black matrix, a colored resin composition containing a black colorant is used to form a black matrix. For example, a colored resin composition containing a black coloring material such as carbon black, graphite, iron black, aniline black, cyanine black, titanium black, etc., or a black coloring material obtained by mixing red, green, blue, etc. appropriately selected from inorganic or organic pigments and dyes can be used to form a black matrix in the same manner as the following method for forming a red, green, and blue pixel image.

[0841] [4-3] Pixel formation

[0842] After a colored resin composition of one color among red, green and blue is applied to a transparent substrate provided with a black matrix and dried, a photomask is superimposed on the coated film, and a pixel image is formed through the photomask by image exposure, development, and thermal curing or photocuring as required. This operation is performed for each of the three colored resin compositions of red, green and blue, thereby forming a color filter image.

[0843] The coloring resin composition for color filters can be applied by spin coating, wire bar coating, flow coating, die coating, roll coating, spray coating, etc. Among them, die coating is preferred from the comprehensive viewpoints that the amount of coating liquid used is greatly reduced, the influence of mist attached in the case of spin coating is completely eliminated, and the generation of foreign matter can be suppressed.

[0844] When the thickness of the coating film is too large, pattern development becomes difficult, and sometimes the gap adjustment in the liquid crystal unitization process becomes difficult. On the other hand, if it is too small, it is difficult to increase the pigment concentration, and sometimes the desired color cannot be expressed. The thickness of the coating film is measured as the film thickness after drying, usually 0.2 μm or more, preferably 0.5 μm or more, more preferably 0.8 μm or more, and usually 20 μm or less, preferably 10 μm or less, more preferably 5 μm or less. ...

Claims

1. A colorant-containing liquid, comprising (A) a colorant, (B) a solvent, and a compound represented by the following general formula (3) and / or a benzoquinone compound, The colorant (A) contains a phthalocyanine compound having a chemical structure represented by the following general formula (1): The total content of the compound represented by the following general formula (3) and the benzoquinone compound is 0.05 parts by mass or more and 10 parts by mass or less relative to 100 parts by mass of the phthalocyanine compound, In formula (1), A 1 ~A 16 Each independently represents a hydrogen atom, a halogen atom, or a group represented by the following general formula (2), wherein: A 1 ~A 16 One or more of represents a fluorine atom or a group represented by the following general formula (2), In formula (2), X represents a divalent linking group, the benzene ring in formula (2) may have any substituent, * represents a linking bond, In formula (3), R a , R b , R c , R d and R f Each independently represents a hydrogen atom, an unsubstituted alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, and R e It represents a hydrogen atom or an unsubstituted alkyl group having 1 to 6 carbon atoms.

2. The colorant-containing liquid according to claim 1, wherein The content of the phthalocyanine compound is 50% by mass or more and 99.5% by mass or less relative to the total solid content of the liquid containing the colorant. 3 . The colorant-containing liquid according to claim 1 , further comprising (E) a dispersant.

4. The colorant-containing liquid according to claim 3, wherein The content ratio of the (A) colorant to the (E) dispersant based on mass, that is, (A) colorant / (E) dispersant, is 10 or more. 5 . A colored resin composition comprising: the colorant-containing liquid according to claim 1 , (C) an alkali-soluble resin, and (D) a photopolymerization initiator.

6. The colored resin composition according to claim 5, wherein The total content of the compound represented by the formula (3) and the benzoquinone-based compound is 30 parts by mass or less relative to 100 parts by mass of the (D) photopolymerization initiator.

7. The colored resin composition according to claim 5, wherein The (A) colorant contains other colorants in addition to the phthalocyanine compound. 8 . A color filter having pixels produced using the colored resin composition according to claim 5 . 9 . An image display device comprising the color filter according to claim 8 .

10. A colored resin composition comprising (A) a colorant, (B) a solvent, (C) an alkali-soluble resin, and (D) a photopolymerization initiator, and comprising a compound represented by the following general formula (3) and / or a benzoquinone compound, The colorant (A) contains a phthalocyanine compound having a chemical structure represented by the following general formula (1): In formula (1), A 1 ~A 16 Each independently represents a hydrogen atom, a halogen atom, or a group represented by the following general formula (2), wherein: A 1 ~A 16 At least one of A represents a fluorine atom, and A 1 ~A 16 One or more of them represent a group represented by the following general formula (2), In formula (2), X represents a divalent linking group, the benzene ring in formula (2) may have any substituent, * represents a linking bond, In formula (3), R a , R b , R c , R d and R f Each independently represents a hydrogen atom, an unsubstituted alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, and R e It represents a hydrogen atom or an unsubstituted alkyl group having 1 to 6 carbon atoms.

11. The colored resin composition according to claim 10, wherein The total content of the compound represented by the formula (3) and the benzoquinone-based compound is 0.001% by mass or more in the total solid content of the colored resin composition.

12. The colored resin composition according to claim 10, wherein The total content of the compound represented by the formula (3) and the benzoquinone-based compound is 0.02% by mass or more in the total solid content of the colored resin composition.

13. The colored resin composition according to claim 10, wherein The total content of the compound represented by the formula (3) and the benzoquinone-based compound is 0.80% by mass or less in the total solid content of the colored resin composition.

14. The colored resin composition according to claim 10, wherein The content of the phthalocyanine compound is 5% by mass or more and 80% by mass or less in the total solid content of the colored resin composition.

15. The colored resin composition according to claim 10, wherein The total content of the compound represented by the formula (3) and the benzoquinone-based compound is 20 parts by mass or less relative to 100 parts by mass of the (D) photopolymerization initiator.

16. The colored resin composition according to claim 10, wherein The (A) colorant contains other colorants in addition to the phthalocyanine compound. 17 . A color filter having pixels produced using the colored resin composition according to claim 10 .

18. An image display device comprising the color filter according to claim 17.

19. A method for producing a colored resin composition, the colored resin composition comprising (A) a colorant, (B) a solvent, (C) an alkali-soluble resin, and (D) a photopolymerization initiator, and comprising a compound represented by the following general formula (3) and / or a benzoquinone-based compound, In the manufacturing method, As the colorant (A), a phthalocyanine compound having a chemical structure represented by the following general formula (1) is blended: In the production of the colored resin composition, the phthalocyanine compound is mixed with a compound represented by the following general formula (3) and / or a benzoquinone compound before the phthalocyanine compound is mixed with the (D) photopolymerization initiator. In formula (1), A 1 ~A 16 Each independently represents a hydrogen atom, a halogen atom, or a group represented by the following general formula (2), wherein: A 1 ~A 16 At least one of A represents a fluorine atom, and A 1 ~A 16 One or more of them represent a group represented by the following general formula (2), In formula (2), X represents a divalent linking group, the benzene ring in formula (2) may have any substituent, * represents a linking bond, In formula (3), R a , R b , R c , R d and R f Each independently represents a hydrogen atom, an unsubstituted alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, and R e It represents a hydrogen atom or an unsubstituted alkyl group having 1 to 6 carbon atoms.

20. The method for producing a colored resin composition according to claim 19, wherein The total amount of the compound represented by the formula (3) and the benzoquinone-based compound is 0.001% by mass or more in the total solid content of the colored resin composition.

21. The method for producing a colored resin composition according to claim 19, wherein The total amount of the compound represented by the formula (3) and the benzoquinone-based compound is 0.02% by mass or more in the total solid content of the colored resin composition.

22. The method for producing a colored resin composition according to claim 19, wherein The total amount of the compound represented by the formula (3) and the benzoquinone-based compound is 0.80% by mass or less in the total solid content of the colored resin composition.

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