Azo dye, colored curable resin composition, color filter, display device, solid-state imaging element, and method for producing azo dye

Abstract

The present invention addresses the problem of providing an azo dye and a colored curable resin composition capable of forming a color filter having improved heat resistance and light resistance, and also providing a method for producing an azo dye capable of forming a color filter having improved heat resistance and light resistance. An azo dye represented by formula (I) having a prescribed crystal structure as determined by powder X-ray diffraction of CuK [alpha] rays using a mixture of 50 parts of an azo dye and 50 parts of aluminum oxide. [In formula (I), L1 represents a group represented by formula (ph1-1), formula (ph1-2), formula (ph11-1), or formula (ph11-2), A represents a group represented by formula (ia), and in formula (ph1-1), formula (ph1-2), formula (ph11-1), and formula (ph11-2), * represents a bonding site with A, and * * represents a bonding site with a group represented by formula (ib). ] # imgabs0 #

Description

Technical Field

[0001] The present invention relates to an azo dye, a colored curable resin composition containing the azo dye, a color filter formed from the colored curable resin composition, a display device and a solid-state imaging element including the color filter, and a method for producing the azo dye. Background Art

[0002] As an azo colorant, for example, a disazo pigment described in Patent Document 1 which is used in an ink composition is known.

[0003] Prior art literature

[0004] Patent Literature

[0005] Patent Document 1: Japanese Patent Application Publication No. 2018-123321 Summary of the invention

[0006] When an azo dye is used as a colorant contained in a coloring curable resin composition that can form a color filter used in a display device such as a liquid crystal display device, an electroluminescent display device, and a plasma display, and a solid-state imaging element such as a CCD and a CMOS sensor, if a previously known azo dye such as a disazo pigment described in Patent Document 1 is used, the heat resistance and light resistance of the formed color filter are sometimes not fully satisfactory. Therefore, one of the problems of the present invention is to provide an azo dye and a coloring curable resin composition that can form a color filter with improved heat resistance and light resistance. In addition, the problem of the present invention is to provide a method for producing an azo dye that can form a color filter with improved heat resistance and light resistance.

[0007] The gist of the present invention is as follows.

[0008] [1] An azo dye represented by the following formula (I):

[0009] The azo dye has a diffraction pattern of powder X-ray diffraction using CuKα rays of a mixture of 50 parts of the azo dye and 50 parts of aluminum oxide.

[0010] There is a peak in the range of diffraction angle (2θ±0.2°) = 5° to 25°.

[0011] The maximum peak among 5° to 25° exists at 9.8° to 16.0°.

[0012] There is one or more peaks at 11.0° to 11.8°.

[0013] The maximum peak intensity (I1) at 9.8° to 16.0° and the maximum peak intensity (I2) at 11.0° to 11.8° satisfy I2 / I1 ≥ 0.05, and

[0014] Between the peak intensity (I3) at the diffraction angle (2θ±0.2°)=35.1° from aluminum oxide and the above-mentioned I1, I1 / I3≥0.35 is satisfied.

[0015] AL 1 (I)

[0016] [In formula (I),

[0017] L 1 represents a group represented by formula (ph1-1), formula (ph1-2), formula (ph11-1) or formula (ph11-2),

[0018] A represents a group represented by formula (ia).

[0019]

[0020] [In formula (ph1-1), formula (ph1-2), formula (ph11-1) and formula (ph11-2),

[0021] X 1a , X 1b , X 10 , X 11a , X 11b Each independently represents a substituent or a hydrocarbon group which may have a substituent.

[0022] n1 represents an integer of 0 to 5, and n2 represents an integer of 0 to 4. When n1 represents an integer greater than 2, a plurality of X 1a may be the same or different. When n2 represents an integer greater than 2, multiple X 1b may be the same or different. n1 represents an integer greater than 2 and X 1a When bonded to an adjacent carbon atom, X bonded to the adjacent carbon atom 1a may be bonded to each other to form a ring, n2 represents an integer greater than 2 and X 1b When bonded to an adjacent carbon atom, X bonded to the adjacent carbon atom 1b They may be bonded to each other to form a ring.

[0023] p represents an integer of 0 to 4. When p represents an integer of 2 or more, a plurality of X 10 may be the same or different. p represents an integer greater than 2 and X 10 When bonded to an adjacent carbon atom, X bonded to the adjacent carbon atom 10 They may be bonded to each other to form a ring.

[0024] q1 represents an integer of 0 to 5, and q2 represents an integer of 0 to 4. When q1 represents an integer greater than 2, a plurality of X 11a may be the same or different. When q2 represents an integer greater than 2, multiple X11b may be the same or different. q1 represents an integer greater than 2 and X 11a When bonded to an adjacent carbon atom, X bonded to the adjacent carbon atom 11a may be bonded to each other to form a ring, q2 represents an integer greater than 2 and X 11b When bonded to an adjacent carbon atom, X bonded to the adjacent carbon atom 11b They may be bonded to each other to form a ring.

[0025] Y represents -O-, -CO-, -SO2- or -C(CF3)2-.

[0026] * indicates the bonding site with A.

[0027] ** represents the bonding site to the group represented by formula (ib).]

[0028]

[0029] [In formula (ia) and formula (ib),

[0030] X 6 ~X 9 Each independently represents a hydrocarbon group which may have a substituent, wherein -CH2- contained in the hydrocarbon group may replace -O-, -CO- or -NH-, -CH= contained in the hydrocarbon group may be replaced by -N=, and -C< contained in the hydrocarbon group may be replaced by -N<.

[0031] X 6 With X 7 Can bond to each other to form a ring, X 8 With X 9 They may be bonded to each other to form a ring.

[0032] *Indicates the same as L 1 The bonding site of .

[0033] [2] The azo dye according to [1], wherein the group represented by the formula (ph1-2) is a group represented by the formula (ph2-2),

[0034] The group represented by the above formula (ph11-1) is a group represented by the formula (ph12-1),

[0035] The group represented by the above formula (ph11-2) is a group represented by the formula (ph12-2).

[0036]

[0037] [In formula (ph2-2), formula (ph12-1) and formula (ph12-2),

[0038] X2b ~X 5b , X 12a ~X 15a , X 21a ~X 25a , X 12b ~X 15b , X 22b ~X 25b Each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an amino group, an amide group, a carboxamide group, a carboxyl group, an alkoxy group having 1 to 4 carbon atoms, an alkylthio group having 1 to 4 carbon atoms, a cyano group, or a halogen atom.

[0039] X 2b With X 3b , X 4b With X 5b , X 12a With X 13a , X 14a With X 15a , X 22a With X 23a , X 21a With X 23a , X 21a With X 25a , X 24a With X 25a , X 12b With X 13b , X 14b With X 15b , X 22b With X 23b , X 24b With X 25b They may be bonded to each other to form a ring.

[0040] Y has the same meaning as above.

[0041] * indicates the bonding site with A.

[0042] ** represents the bonding site to the group represented by formula (ib).]

[0043] [3] The azo dye according to [1] or [2], wherein the groups represented by formula (ia) and formula (ib) are each independently any one of the groups represented by formula (t1) to formula (t5).

[0044]

[0045] [In formula (t1) to formula (t5),

[0046] R 1 ~R 16 Each independently represents a hydrogen atom, a hydrocarbon group which may have a substituent, a heterocyclic group, a cyano group or a halogen atom.

[0047] *Indicates the same as L 1 The bonding site of .]

[0048] [4] A colored curable resin composition comprising the azo dye according to any one of [1] to [3], a resin, a polymerizable compound, a polymerization initiator, and a solvent.

[0049] [5] A color filter formed from the colored curable resin composition according to [4].

[0050] [6] A display device comprising the color filter described in [5].

[0051] [7] A solid-state imaging element comprising the color filter described in [5].

[0052] [8] A method for producing an azo dye, comprising: a contact step of bringing an azo dye (A) into contact with a solvent (Z) in a slurry state at a temperature of 80 to 200° C., and a separation step of removing the azo dye (A) in contact with the solvent (Z) by solid-liquid separation, wherein the solvent (Z) comprises at least one selected from an ester solvent, an ether solvent, an ether ester solvent, a ketone solvent, a nitrile solvent, an alcohol solvent, an amide solvent, an aromatic hydrocarbon solvent, a sulfoxide solvent, a sulfone solvent, a halogen solvent and an amine solvent, and the amount of the solvent (Z) in the contact step is 0.1 to 120.0 times by mass relative to the azo dye (A).

[0053] According to the present invention, an azo dye and a colored curable resin composition capable of forming a color filter having improved heat resistance and light resistance can be provided. In addition, according to the present invention, a new method for producing an azo dye capable of forming a color filter having improved heat resistance and light resistance is provided. BRIEF DESCRIPTION OF THE DRAWINGS

[0054] Figure 1 This is the X-ray diffraction spectrum of the azo dye (1) obtained in Example 1. It should be noted that the peaks at diffraction angles (2θ±0.2°) = 25.5, 35.1, 37.8, 43.3, and 43.4° are peaks derived from aluminum oxide as an internal standard ( Figures 2 to 14 The same is true in ).

[0055] Figure 2 This is the X-ray diffraction pattern of the azo dye (1-1) obtained in Synthesis Example 1.

[0056] Figure 3 This is the X-ray diffraction pattern of the azo dye (2) obtained in Example 2.

[0057] Figure 4 This is the X-ray diffraction pattern of the azo dye (2-1) obtained in Synthesis Example 2.

[0058] Figure 5 This is the X-ray diffraction pattern of the azo dye (3) obtained in Example 3.

[0059] Figure 6 This is the X-ray diffraction pattern of the azo dye (3-1) obtained in Synthesis Example 3.

[0060] Figure 7 This is the X-ray diffraction pattern of the azo dye (4) obtained in Example 4.

[0061] Figure 8 This is the X-ray diffraction pattern of the azo dye (4-1) obtained in Synthesis Example 4.

[0062] Fig. 9 This is the X-ray diffraction pattern of the azo dye (5a) obtained in Example 5.

[0063] Fig.10 This is the X-ray diffraction pattern of the azo dye (5b) obtained in Example 6.

[0064] Fig.11 This is the X-ray diffraction pattern of the azo dye (5c) obtained in Example 7.

[0065] Fig.12 This is the X-ray diffraction pattern of the azo dye (5d) obtained in Example 8.

[0066] Fig.13 This is the X-ray diffraction pattern of the azo dye (5e) obtained in Example 9.

[0067] Fig.14 This is the X-ray diffraction pattern of the azo dye (5f) obtained in Example 10.

[0068] Fig.15 This is the X-ray diffraction pattern of the azo dye (5 g) obtained in Example 11.

[0069] Fig.16 This is the X-ray diffraction pattern of the azo dye (5h) obtained in Example 12.

[0070] Fig.17 This is the X-ray diffraction pattern of the azo dye (5i) obtained in Example 13.

[0071] Fig.18 This is the X-ray diffraction pattern of the azo dye (5j) obtained in Example 14.

[0072] Fig.19 This is the X-ray diffraction pattern of the azo dye (5k) obtained in Example 15.

[0073] Fig. 20 This is the X-ray diffraction pattern of the azo dye (51) obtained in Example 16.

[0074] Fig.21 This is the X-ray diffraction pattern of the azo dye (5-1) obtained in Synthesis Example 5.

[0075] Fig. 22 It is the X-ray diffraction pattern of the glass sample plate. DETAILED DESCRIPTION

[0076] <Azo Colorants>

[0077] The azo pigment of the present invention has a predetermined crystal structure. The crystal structure is determined by powder X-ray diffraction. Specifically, the azo pigment of the present invention has the following crystal structure:

[0078] In the diffraction pattern of powder X-ray diffraction using CuKα rays of a mixture of 50 parts of the azo dye and 50 parts of aluminum oxide,

[0079] There is a peak in the range of diffraction angle (2θ±0.2°) = 5° to 25°.

[0080] The maximum peak among 5° to 25° exists at 9.8° to 16.0°.

[0081] There is one or more peaks at 11.0° to 11.8°.

[0082] Between the maximum peak intensity (I1) at 9.8° to 16.0° and the maximum peak intensity (I2) at 11.0° to 11.8°, I2 / I1≥0.05, and

[0083] Between the peak intensity (I3) at the diffraction angle (2θ±0.2°)=35.1° from aluminum oxide and the above-mentioned I1, I1 / I3≥0.35 is satisfied.

[0084] The azo dye having such a crystal structure can form a color filter having excellent heat resistance and light resistance. In the present invention, the excellent heat resistance or light resistance of the color filter means that the color difference (ΔE*ab) before and after heating or light irradiation is small.

[0085] In the diffraction pattern of the above X-ray diffraction, the maximum peak existing in the range of 5° to 25° within the range of diffraction angle (2θ±0.2°)=9.8° to 16.0° may exist at 11.0° to 11.8°, but preferably exists outside the range of 11.0° to 11.8°.

[0086] The above-mentioned I2 / I1 is preferably 0.07 or more, more preferably 0.09 or more, and is preferably 0.6 or less, more preferably 0.5 or less, further preferably 0.45 or less, further preferably 0.40 or less, and even more preferably 0.38 or less.

[0087] The above-mentioned I1 / I3 is preferably greater than 0.37, more preferably greater than 0.39, further preferably greater than 0.41, further preferably greater than 0.43, and is preferably less than 1.0, more preferably less than 0.95, further preferably less than 0.90, further preferably less than 0.85, even more preferably less than 0.80, and can be less than 0.70.

[0088] In the X-ray diffraction analysis of the present invention, CuKα radiation from the cathode is used. As an X-ray source. In the X-ray diffraction analysis of the present invention, alumina is used as an internal standard.

[0089] As a specific method of X-ray diffraction analysis, 50 parts by mass of aluminum oxide is added as an internal standard to 50 parts by mass of azo dye as a sample, and the mixture is crushed while passing through a 150-mesh metal mesh. The crushed sample is then filled into a depression (inner dimensions 20 mm×20 mm×0.5 mm) of a glass sample plate manufactured by Rigaku Corporation, and the surface is flattened for measurement. It should be noted that there are peaks from the glass sample plate (halo: Koji Ohara, "Halo in X-ray Diffraction", NEW GLASS, 2016, Vol. 31, No. 118, pp. 24-26), which need to be distinguished from the peaks from the colorant. Therefore, in the present invention, the X-ray diffraction spectrum of the azo dye is calculated based on the X-ray diffraction spectrum containing the colorant and the difference spectrum of the X-ray diffraction spectrum in the case of only the glass sample plate. In addition, since the thickness of the sample depends on the intensity of the X-ray diffraction spectrum, an X-ray diffraction spectrum in which the peak intensity I3 of aluminum oxide as an internal standard was standardized to 100,000 was used.

[0090] The azo dye of the present invention preferably has two or more peaks having a relative intensity of 10% or more and less than 100% when the maximum peak intensity I1 is set to 100% in the range of the diffraction angle (2θ±0.2°)=5° to 25° of the above-mentioned X-ray diffraction, more preferably three or more, further preferably 15 or less, more preferably 10 or less, and further preferably 7 or less.

[0091] Examples of the azo dye of the present invention include those having a peak at the following diffraction angles (2θ±0.2°) in the above X-ray diffraction pattern.

[0092] Example (i): 10.0, 11.2, 13.1, 15.3, 15.6, 15.8, 18.5, 18.9, 19.0, 22.1, 22.5, 23.3, 25.6, 26.1, 26.4, 26.9, 28.6, 29.1°

[0093] Example (ii): 7.1, 13.0, 13.3, 14.2, 17.5, 19.1, 19.4, 20.2, 21.3, 21.7, 24.1, 24.3, 27, 2, 28.3, 29.4°

[0094] Example (iii): 5.7, 10.6, 11.4, 14.6, 17.2, 20.3, 21.4, 24.8, 26.1, 26.5, 26.8, 28.4°

[0095] Example (iv): 7.5, 11.0, 11.6, 15.0, 15.3, 19.8, 20.5, 22.2, 23.7, 24.6, 26.4, 27.7, 28.5, 30.1, 32.3°

[0096] Example (v): 6.0, 10.2, 11.9, 15.6, 16.0, 18.0, 18.6, 20.1, 20.7, 22.5, 23.1, 23.5, 24.6, 25.2, 27.4, 30.3°

[0097] The azo dye having the above-mentioned crystal structure can be obtained, for example, by the following production method.

[0098] The method for producing an azo dye of the present invention comprises: a contact step of bringing an azo dye (hereinafter, also referred to as an azo dye (A)) into contact with a solvent (Z) in a slurry state at a temperature of 80 to 200° C., and a separation step of taking out the azo dye (A) after contact with the solvent (Z) by solid-liquid separation, wherein the solvent (Z) comprises at least one selected from an ester solvent, an ether solvent, an ether ester solvent, a ketone solvent, a nitrile solvent, an alcohol solvent, an amide solvent, an aromatic hydrocarbon solvent, a sulfoxide solvent, a sulfone solvent, a halogen solvent, and an amine solvent, and the amount of the solvent (Z) in the contact step is 0.1 to 120.0 times by mass relative to the azo dye (A). Here, the temperature is not the temperature of the container but refers to the internal temperature of the reaction system.

[0099] That is, the production method of the present invention relates to a method for producing a purified azo dye (A), which includes: a contact step of contacting the azo dye (A) with a prescribed solvent (Z) in a slurry state at a prescribed temperature, and a separation step of obtaining the purified azo dye (A) by solid-liquid separation such as filtration. Hereinafter, the azo dye having a prescribed crystal structure obtained by the production method of the present invention is also referred to as an azo dye (Aa).

[0100] According to the azo dye (Aa) obtained by this production method, a color filter having excellent heat resistance and light resistance can be formed.

[0101] The azo dye (A) may be a single dye consisting of one azo dye or a mixed dye containing two or more azo dyes. In addition, the azo dye (A) preferably contains the azo dye (I) described below.

[0102] <Precipitation process>

[0103] The manufacturing method of the present invention may be included in a precipitation process for recrystallizing the azo dye (A) before the contact process. As the precipitation process for recrystallizing the azo dye (A), a poor solvent addition method, etc. can be cited, specifically, a method for adding an azo dye (A) dissolved in a high solubility liquid (good solvent, etc.) to a low solubility liquid (poor solvent, etc.) and a method for adding a low solubility liquid to an azo dye dissolved in a high solubility liquid. It should be noted that as the azo dye (A) supplied to the precipitation process, an azo dye manufactured by the manufacturing method of the azo dye (I) described later, etc. can be used.

[0104] When the crystal structure of the azo dye (A) fluctuates, the crystal structure can be made consistent by recrystallization. Therefore, by having a precipitation step before the contacting step, an azo dye (Aa) having a desired crystal structure (i.e., having a desired diffraction pattern) can be obtained with a higher yield and higher selectivity.

[0105] In the precipitation step, the azo dye (A) is not brought into contact with the solvent in a slurry state at a temperature (internal temperature) of 80° C. or higher. Therefore, the azo dye (A) obtained in the precipitation step does not have a desired crystal structure (desired diffraction pattern).

[0106] Examples of the high-solubility liquid and / or low-solubility liquid used in the precipitation step include basic compounds, basic solutions, acidic compounds, acidic solutions, and the like.

[0107] Examples of the alkaline compound and alkaline solution include amines such as propylamine, butylamine, hexylamine, benzylamine, dimethylamine, diethylamine, dipropylamine, dihexylamine, trimethylamine, diisopropylethylamine, pyridine, and pyrrole; aqueous ammonia; solutions (preferably aqueous solutions) of quaternary ammonium salts such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and benzyltrimethylammonium hydroxide; alcohol solutions of alkali metal alkoxides such as a methanol solution of sodium methoxide, an ethanol solution of sodium ethoxide, and a tert-butanol solution of potassium tert-butoxide; and solutions (preferably aqueous solutions) of alkaline metal hydroxides such as sodium hydroxide and potassium hydroxide.

[0108] Examples of the acidic compound and the acidic solution include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, boric acid, hexafluorophosphoric acid, and sulfamic acid; organic acids such as formic acid, acetic acid, trifluoroacetic acid, propionic acid, citric acid, benzenesulfonic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, and salicylic acid; and solutions thereof (preferably aqueous solutions).

[0109] The above-mentioned alkaline compound, alkaline solution, acidic compound and acidic solution may be used alone or in combination of two or more.

[0110] The highly soluble liquid may be appropriately selected depending on the azo dye (A) to be used, and a basic compound or a basic solution is preferred.

[0111] As the high solubility liquid, an organic solvent can be further contained in the above-mentioned alkaline compound, alkaline solution, acidic compound, and acidic solution. As the above-mentioned organic solvent, for example, alcohol solvents, ester solvents, ether solvents, ether ester solvents, ketone solvents, aromatic hydrocarbon solvents, nitrile solvents, etc. can be enumerated, and these organic solvents can be used alone or in combination of two or more. As the above-mentioned organic solvent, alcohol solvents such as methanol, ethanol, and isopropanol, nitrile solvents such as acetonitrile, and more preferably alcohol solvents.

[0112] As the usage amount of high solubility liquid, as long as it is the required amount of dissolving azo dye (A), it can be appropriately determined according to the type, concentration, etc. of high solubility liquid. For example, using the solution of quaternary ammonium salt as the situation of high solubility liquid, relative to azo dye (A) (1 mole), quaternary ammonium salt is preferably 0.1~20 molar equivalents, more preferably more than 0.5 molar equivalents, more preferably more than 1 molar equivalents, in addition, more preferably below 15 molar equivalents, more preferably below 10 molar equivalents. In addition, for example, using inorganic acid or organic acid or their solution as the situation of high solubility liquid, relative to azo dye (A) (1 mole), inorganic acid or organic acid is preferably 10~500 molar equivalents, more preferably more than 20 molar equivalents, more preferably more than 30 molar equivalents, in addition more preferably below 450 molar equivalents, more preferably below 400 molar equivalents.

[0113] The mixing time, mixing temperature, stirring conditions, etc. of the azo dye (A) and the high-solubility liquid can be any conditions required for dissolving the azo dye (A). Among them, the high-solubility liquid is a liquid that easily dissolves the azo dye (A), and it is not necessary to be high temperature in order to dissolve the azo dye (A). Therefore, the mixing temperature (internal temperature) is less than 80°C, preferably below 60°C, more preferably below 40°C, and preferably above 5°C.

[0114] The low-solubility liquid may be appropriately selected depending on the types of the azo dye (A) and the high-solubility liquid used. For example, when a basic compound or a basic solution is used as the high-solubility liquid, an acidic compound or an acidic solution is preferred.

[0115] As low-solubility liquid, organic solvent can be further contained in the above-mentioned alkaline compound, alkaline solution, acidic compound, acidic solution. As the above-mentioned organic solvent, for example, alcohol solvent, ester solvent, ether solvent, ether ester solvent, ketone solvent, aromatic hydrocarbon solvent, nitrile solvent etc. can be enumerated, and these organic solvents can be used alone, and also can be used in combination of 2 or more. As the above-mentioned organic solvent, alcohol solvents such as methanol, ethanol, isopropanol, nitrile solvents such as acetonitrile are preferred, and alcohol solvent is more preferred.

[0116] In addition, for example, when an acidic compound or an acidic solution is used as the high-solubility liquid, it is preferred to use an organic solvent such as an alcohol solvent, an ester solvent, an ether solvent, an ether-ester solvent, a ketone solvent, an aromatic hydrocarbon solvent, or a nitrile solvent as the low-solubility liquid, and more preferably an alcohol solvent such as methanol, ethanol, or isopropanol, or a nitrile solvent such as acetonitrile. These may be used alone or in combination of two or more.

[0117] The amount of the low-solubility liquid used may be an amount required for precipitating the azo dye (A), and may be appropriately determined depending on the types and concentrations of the high-solubility liquid and the low-solubility liquid.

[0118] The mixing time, mixing temperature, stirring conditions, etc. of the mixed solution of the azo dye (A) and the high-solubility liquid and the low-solubility liquid can be any conditions required for precipitating the azo dye (A). As the mixing temperature, from the aspect of effective precipitation, it is preferably 60° C. or less, more preferably 40° C. or less, and further preferably 20° C. or less, and it can also be carried out under ice cooling.

[0119] As a method of adding a low-solubility liquid to a mixed solution of an azo dye (A) and a high-solubility liquid, or adding a mixed solution of an azo dye (A) and a high-solubility liquid to a low-solubility liquid, it can be added all at once, but it is preferably added in multiple times, or added dropwise continuously. In the case of multiple times, it is also preferred to dropwise add the input components continuously when adding.

[0120] The azo dye (A) precipitated in the precipitation step can be taken out using known solid-liquid separation methods such as filtration and centrifugation, and can be supplied to the contacting step after washing with water or a solvent as required. As the solvent used in the washing, for example, the solvent described as the solvent (Z) described later can be cited. In addition, the washed azo dye (A) can be dried by vacuum drying, warm air drying, etc. as required.

[0121] <Contact process>

[0122] The contact between the azo dye (A) and the solvent (Z) is carried out in a slurry state at a temperature (internal temperature) of 80 to 200° C. The slurry state means a state in which a solid azo dye (A) that is insoluble in the solvent (Z) exists in the mixture of the azo dye (A) and the solvent (Z), and a part of the azo dye (A) can be dissolved in the solvent (Z).

[0123] By bringing the azo dye (A) and the solvent (Z) into contact at 80 to 200° C. in a slurry state, an azo dye (Aa) having a desired crystal structure (that is, having a desired diffraction pattern) can be obtained.

[0124] <Solvent (Z)>

[0125] The solvent (Z) used in the contacting step is at least one selected from an ester solvent (a solvent containing -COO- and not containing -O- in the molecule), an ether solvent (a solvent containing -O- and not containing -COO- in the molecule), an ether ester solvent (a solvent containing -COO- and -O- in the molecule), a ketone solvent (a solvent containing -CO- and not containing -COO- in the molecule), an alcohol solvent (a solvent containing -OH and not containing -O-, -CO- and -COO- in the molecule), an aromatic hydrocarbon solvent (a solvent containing an aromatic hydrocarbon group and not containing -O-, -OH and a halogen atom in the molecule), an amide solvent, a sulfoxide solvent, a sulfone solvent, a halogen solvent (a solvent containing a halogen atom and not containing -OH in the molecule), an amine solvent (a solvent containing -N< and not containing -OH in the molecule), and a nitrile solvent. The solvent (Z) may be a single solvent consisting of one solvent or a solvent mixture containing two or more solvents.

[0126] Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, and γ-butyrolactone.

[0127] Examples of the ether solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dihydrofu ... Alkane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenethyl ether and methyl anisole, etc.

[0128] Examples of the ether ester solvent include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, and diethylene glycol monobutyl ether acetate.

[0129] Examples of the ketone solvent include 4-hydroxy-4-methyl-2-pentanone (diacetone alcohol), acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone, and isophorone.

[0130] The ketone solvent is preferably cyclopentanone or cyclohexanone, and more preferably cyclohexanone.

[0131] Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, 2-aminoethanol, benzyl alcohol, 1-phenyl-1-propanol, 2-chlorophenol, 1-amino-2-propanol, 3-amino-1-propanol, ethylene glycol, propylene glycol, and glycerin.

[0132] The alcohol solvent is preferably methanol or 2-aminoethanol, and more preferably 2-aminoethanol.

[0133] Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, mesitylene, nitrobenzene, and anisole.

[0134] As the aromatic hydrocarbon solvent, toluene and xylene are preferred, and xylene is more preferred.

[0135] Examples of the amide solvent include formamide, N-methylformamide, N,N-dimethylformamide, acetamide, N,N-dimethylacetamide, N,N-dimethylisobutyramide, N,N-diethylformamide, N,N-diethylacetamide, N,N-dimethylacetoacetamide, N-methylpyrrolidone, N-methyl-ε-caprolactam, 1,3-dimethyl-2-imidazolidinone, and 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone.

[0136] As the amide solvent, N,N-dimethylacetamide, N-methylpyrrolidone, N,N-dimethylacetoacetamide, and 1,3-dimethyl-2-imidazolidinone are preferred, and N,N-dimethylacetamide and N-methylpyrrolidone are more preferred.

[0137] Examples of the sulfoxide solvent include dimethyl sulfoxide, diethyl sulfoxide, dipropyl sulfoxide and tetramethylene sulfoxide.

[0138] As the sulfoxide solvent, dimethyl sulfoxide and diethyl sulfoxide are preferred, and dimethyl sulfoxide is more preferred.

[0139] Examples of the sulfone solvent include dimethyl sulfone, diethyl sulfone, dipropyl sulfone, isopropyl methyl sulfone and sulfolane.

[0140] The sulfone solvent is preferably dimethyl sulfone, diethyl sulfone, or sulfolane, and more preferably sulfolane.

[0141] Examples of the halogen solvent include chlorobenzene, dichlorobenzene, chloroform, dichloromethane, and carbon tetrachloride.

[0142] Examples of the amine solvent include propylamine, butylamine, hexylamine, benzylamine, dimethylamine, diethylamine, dipropylamine, dihexylamine, trimethylamine, diisopropylethylamine, 1-methylimidazole, pyridine, and pyrrole.

[0143] Examples of the nitrile solvent include acetonitrile, propionitrile, and methacrylonitrile.

[0144] As the nitrile solvent, acetonitrile is preferred.

[0145] The solvent (Z) preferably contains at least one selected from the group consisting of ester solvents, ketone solvents, alcohol solvents, amide solvents, aromatic hydrocarbon solvents, sulfoxide solvents, sulfone solvents, halogen solvents, and amine solvents, more preferably contains at least one selected from the group consisting of ester solvents, ketone solvents, alcohol solvents, amide solvents, aromatic hydrocarbon solvents, sulfoxide solvents, sulfone solvents, and amine solvents, further preferably contains at least one selected from the group consisting of alcohol solvents, amide solvents, aromatic hydrocarbon solvents, sulfoxide solvents, sulfone solvents, and amine solvents, further preferably contains at least one selected from the group consisting of alcohol solvents, amide solvents, aromatic hydrocarbon solvents, sulfoxide solvents, and amine solvents, further preferably contains at least one selected from the group consisting of alcohol solvents, amide solvents, aromatic hydrocarbon solvents, and amine solvents, further preferably contains at least one selected from the group consisting of alcohol solvents, amide solvents, aromatic hydrocarbon solvents, and amine solvents. The total volume ratio of the alcohol solvents, amide solvents, aromatic hydrocarbon solvents, sulfoxide solvents, sulfone solvents, and amine solvents is preferably 40% or more, more preferably 50% or more, and further preferably 60% or more. The total volume ratio of the alcohol solvent, the amide solvent and the aromatic hydrocarbon solvent in 100% of the solvent (Z) is preferably 40% or more, more preferably 50% or more, and even more preferably 60% or more.

[0146] As a method for bringing the azo dye (A) and the solvent (Z) into contact at a temperature of 80 to 200° C., a method of mixing the azo dye (A) and the solvent (Z) in a container is preferred. During the mixing, the mixture containing the azo dye (A) and the solvent (Z) may be stirred using a stirrer or the like, or may be stirred using ultrasonic vibration.

[0147] The contact time (preferably stirring time) in the contact step is preferably 1 minute or more, more preferably 10 minutes or more, further preferably 1 hour or more, and preferably 24 hours or less, more preferably 12 hours or less, further preferably 5 hours or less.

[0148] The contact temperature in the contact step is 80 to 200°C, and the upper limit of the temperature is preferably not more than the boiling point of the solvent (Z) at 1 atm. The contact temperature is preferably 80 to 190°C, more preferably 85 to 170°C, and even more preferably 85 to 150°C.

[0149] The amount of the solvent (Z) in the contact process can be appropriately determined in a slurry-like manner according to the type of the azo dye (A) and the solvent (Z) used. From the aspect of yield, relative to the azo dye (A), it is 0.1 times by mass or more, preferably 0.5 times by mass or more, more preferably 2 times by mass or more, and in addition, it is 120.0 times by mass or less, preferably 100.0 times by mass or less, more preferably 80.0 times by mass or less, and further preferably 60.0 times by mass or less. The azo dye (A) provided for the contact process is preferably not only dried, but also preferably a residue containing azo dye (A) separated from solid and liquid in the reaction mixture. In the case of the latter, the residue sometimes contains a solvent used in the reaction and a solvent used in the cleaning. As the amount of the solvent (Z) in the contact process, the reaction contained in the residue and the solvent used in the cleaning are also calculated. In addition, when the solid-liquid separation is performed without drying after the above-mentioned precipitation step, the precipitate may contain the solvent used for precipitation and the solvent used for washing. The amount of the solvent (Z) used in the contacting step is calculated including the solvent used for precipitation and washing contained in the precipitate.

[0150] In the contacting step, the contacting of the azo dye (A) and the solvent (Z) is preferably carried out in the following manner: the ratio (I1 / I3) of the maximum peak intensity (I1) from the azo dye (A) in the range of diffraction angle (2θ±0.2°)=5° to 25° to the peak intensity (I3) from the α-alumina at a diffraction angle (2θ±0.2°)=35.1° in the diffraction pattern of the mixture of the azo dye (A) and 50 parts of α-alumina by powder X-ray diffraction using CuKα rays is 0.1%, where I1 / I3 before contacting with the solvent (Z) is set to I1 / I3.R1 , let I1 / I3 after contact with the above solvent (Z) be I R2 When R1 with I R2 Between, satisfy I R2 / I R1 ≥1.4.

[0151] As a specific method of X-ray diffraction analysis, the same method as the above-mentioned X-ray diffraction analysis method can be used.

[0152] Above I R2 / I R1 It is preferably 1.45 or more, more preferably 1.5 or more, further preferably 1.55 or more, further preferably 1.6 or more, and is preferably 20 or less, more preferably 18 or less, further preferably 15 or less, further preferably 12 or less.

[0153] After the azo dye (A) and the solvent (Z) are brought into contact in a slurry state at a temperature of 80 to 200° C., a step of further adding a mixed solvent (Z2) to the mixture at a temperature of less than 80° C. may be included. By adding the mixed solvent (Z2) to the mixture obtained in the contact step at a temperature of less than 80° C., an azo dye (Aa) having a desired crystal structure (i.e., having a desired diffraction pattern) can be obtained at a higher yield.

[0154] As the solvent (Z2), the solvents exemplified as the solvent (Z) used in the contacting step can be cited. As the solvent (Z2), at least one selected from a nitrile solvent and an alcohol solvent is preferred, and at least one selected from a nitrile solvent and an alcohol solvent not having an amine structure is more preferred. As the nitrile solvent, acetonitrile is preferred, and as the alcohol solvent, primary alcohols such as methanol, ethanol, propanol, butanol, hexanol, and cyclohexanol are preferred.

[0155] As a method for adding a solvent (Z2) to a mixture of an azo dye (A) and a solvent (Z), the solvent (Z2) can be added all at once, but preferably divided into multiple additions, or continuously added dropwise. In the case of multiple additions, it is also preferred to continuously dropwise add the input components when adding. Preferably, the solvent (Z2) is stirred during and / or after the addition by a stirrer, ultrasonic vibration, etc.

[0156] The total stirring time during and after the addition of the solvent (Z2) is preferably 1 minute or more, more preferably 5 minutes or more, further preferably 10 minutes or more, and is preferably 20 hours or less, more preferably 10 hours or less, further preferably 3 hours or less.

[0157] The temperature (internal temperature) during addition and stirring of the solvent (Z2) is less than 80° C., preferably 75° C. or less, more preferably 70° C. or less, further preferably 65° C. or less, further preferably 60° C. or less, and preferably 0° C. or more, more preferably 5° C. or more. When the solvent (Z2) is added in multiple times, the temperature during each addition may be different.

[0158] The amount of the solvent (Z2) used may be appropriately determined depending on the type and amount of the azo dye (A), the solvent (Z), and the type of the solvent (Z2) used. From the viewpoint of yield, the amount is preferably 0.1 times by mass or more, more preferably 0.5 times by mass or more, and even more preferably 2 times by mass or more, and is preferably 80.0 times by mass or less, more preferably 60.0 times by mass or less, even more preferably 50.0 times by mass or less, and even more preferably 40.0 times by mass or less, relative to the azo dye (A).

[0159] <Separation process>

[0160] The azo dye (A) in contact with the solvent (Z) is separated from the solvent (Z) (when the solvent (Z2) is added, the solvent (Z) and the solvent (Z2)) by solid-liquid separation and taken out in the form of a solid. That is, the purified azo dye (A) can be taken out by solid-liquid separation. The purified azo dye (A) preferably has the above-defined crystal structure.

[0161] The solid-liquid separation is preferably carried out by natural filtration, reduced pressure filtration, pressure filtration, centrifugal filtration, centrifugal separation, etc. The azo dye (A) after the solid-liquid separation to remove the solvent (Z) may be further subjected to treatments such as washing, recrystallization, and drying.

[0162] As the azo dye (Aa) showing the above-mentioned predetermined crystal structure, it is particularly preferred to select a compound showing the predetermined crystal structure from the compounds represented by the following formula (I) (hereinafter, also referred to as azo dye (I)). According to the azo dye (I) (hereinafter, also referred to as azo dye (Ia)) showing the predetermined crystal structure and having a predetermined chemical structure, a color filter having further improved heat resistance and light resistance can be formed.

[0163] AL 1 (I)

[0164] [In formula (I),

[0165] L 1 represents a group represented by formula (ph1-1), formula (ph1-2), formula (ph11-1) or formula (ph11-2),

[0166] A represents a group represented by formula (ia).]

[0167]

[0168] [In formula (ph1-1), formula (ph1-2), formula (ph11-1) and formula (ph11-2), X 1a , X 1b , X 10 , X 11a , X 11b Each independently represents a substituent or a hydrocarbon group which may have a substituent.

[0169] n1 represents an integer of 0 to 5, and n2 represents an integer of 0 to 4. When n1 represents an integer greater than 2, a plurality of X 1a may be the same or different. When n2 represents an integer greater than 2, multiple X 1b may be the same or different. n1 represents an integer greater than 2, and X 1a When bonded to an adjacent carbon atom, X bonded to the adjacent carbon atom 1a may be bonded to each other to form a ring, n2 represents an integer greater than 2, and X 1b When bonded to an adjacent carbon atom, X bonded to the adjacent carbon atom 1b They may be bonded to each other to form a ring.

[0170] p represents an integer of 0 to 4. When p represents an integer of 2 or more, a plurality of X 10 may be the same or different. p represents an integer greater than 2, and X 10 When bonded to an adjacent carbon atom, X bonded to the adjacent carbon atom 10 They may be bonded to each other to form a ring.

[0171] q1 represents an integer of 0 to 5, and q2 represents an integer of 0 to 4. When q1 represents an integer greater than 2, a plurality of X 11a may be the same or different. When q2 represents an integer greater than 2, multiple X 11b may be the same or different. q1 represents an integer greater than 2, and X 11a When bonded to an adjacent carbon atom, X bonded to the adjacent carbon atom 11a may be bonded to each other to form a ring, q2 represents an integer greater than 2, and X 11b When bonded to an adjacent carbon atom, X bonded to the adjacent carbon atom 11b They may be bonded to each other to form a ring.

[0172] Y represents -O-, -CO-, -SO2- or -C(CF3)2-.

[0173] * indicates the bonding site with A.

[0174] ** represents the bonding site to the group represented by formula (ib).]

[0175]

[0176] [In formula (ia) and formula (ib),

[0177] X 6 ~X 9 Each independently represents a hydrocarbon group which may have a substituent, wherein -CH2- contained in the hydrocarbon group may replace -O-, -CO- or -NH-, -CH= contained in the hydrocarbon group may be replaced by -N=, and -C< contained in the hydrocarbon group may be replaced by -N<.

[0178] X 6 With X 7 Can bond to each other to form a ring, X 8 With X 9 They may be bonded to each other to form a ring.

[0179] *Indicates the same as L 1 The bonding site of .]

[0180] Hereinafter, azo dye (I) is described in detail, and azo dye (I) also includes stereoisomers such as the resonance structure of formula (I), the tautomer of formula (I), and the geometrical isomer of formula (I). The tautomer of formula (I) can be exemplified by compounds in which A in formula (I) is a group represented by formula (iia); when formula (I) has a group represented by formula (ib) (hereinafter, also referred to as group (ib)), the group (ib) in formula (I) is a compound in which the group represented by formula (iib); and when formula (I) has a group (ib), A in formula (I) is a group represented by formula (iia), and the group (ib) in formula (I) is a compound in which the group represented by formula (iib) is etc.

[0181]

[0182] [In formula (iia) and formula (iib),

[0183] X 6 ~X 9 Same as above, * indicates the same as L 1 The bonding site of .]

[0184] As X in formula (ph1-1), formula (ph1-2), formula (ph11-1) and formula (ph11-2) 1a , X 1b , X 10 , X 11a , X 11b The substituent represented by (hereinafter also referred to as substituent A) includes an amino group, an amide group, a carboxamide group, a carboxyl group, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, a cyano group, a halogen atom and the like.

[0185] As X 1a , X 1b , X 10 , X 11a , X 11b The hydrocarbon group represented by may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The aliphatic hydrocarbon group may be saturated or unsaturated, and may be chain-shaped or cyclic (alicyclic hydrocarbon group). In addition, the alicyclic hydrocarbon group may be monocyclic or polycyclic.

[0186] Examples of the saturated chain hydrocarbon group (hereinafter also referred to as an alkyl group) include straight-chain alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl and decyl; and branched-chain alkyl groups such as isopropyl, isobutyl, sec-butyl, tert-butyl, 1,3-dimethylbutyl, 2-ethylbutyl and 2-ethylhexyl.

[0187] Examples of the unsaturated chain hydrocarbon group include alkenyl groups such as ethenyl, propenyl (e.g., 1-propenyl, 2-propenyl) and butenyl (e.g., 1-butenyl, 3-butenyl); and alkynyl groups such as ethynyl, propynyl (e.g., 1-propynyl, 2-propynyl) and butynyl (e.g., 1-butynyl, 3-butynyl).

[0188] The saturated or unsaturated chain hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 4 carbon atoms.

[0189] Examples of the saturated alicyclic hydrocarbon group include cycloalkyl groups such as cyclopropyl, 1-methylcyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and 2-methylcyclohexyl.

[0190] Examples of the unsaturated alicyclic hydrocarbon group include cyclohexenyl groups (e.g., cyclohex-1-en-1-yl, cyclohex-2-en-1-yl, cyclohex-3-en-1-yl), cycloheptenyl groups, and cyclooctenyl groups.

[0191] Examples of the alicyclic hydrocarbon group include polycyclic saturated alicyclic hydrocarbon groups such as norbornyl, adamantyl, and bicyclo[2.2.2]octyl; and polycyclic unsaturated alicyclic hydrocarbon groups such as norbornenyl.

[0192] The alicyclic hydrocarbon group has preferably 3 to 12 carbon atoms, more preferably 3 to 10 carbon atoms, and further preferably 3 to 8 carbon atoms.

[0193] Examples of the aromatic hydrocarbon group include phenyl, o-tolyl, m-tolyl, p-tolyl, 2,4-dimethylphenyl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2,4-diisopropylphenyl, 2,6-diisopropylphenyl, 4-vinylphenyl, o-tert-butylphenyl, m-tert-butylphenyl, p-tert-butylphenyl, 3,5-di(tert-butyl)phenyl, 1-naphthyl, 2-naphthyl, and a group obtained by removing one hydrogen atom from tetralin.

[0194] The number of carbon atoms in the aromatic hydrocarbon group is preferably 6-18, more preferably 6-12, and even more preferably 6-10.

[0195] X 1a , X 1b , X 10 , X 11a , X 11b The hydrocarbon group represented may be a group formed by combining the above-mentioned hydrocarbon groups, for example, an aralkyl group, an alkyl group bonded with an alicyclic hydrocarbon group; an aromatic hydrocarbon group condensed with a cycloalkyl group; an alkyl group bonded with an aromatic hydrocarbon group condensed with a cycloalkyl group, and the like.

[0196] Examples of the aralkyl group include benzyl, (4-methylphenyl)methyl, and phenethyl. The aralkyl group preferably has 7 to 18 carbon atoms, more preferably 7 to 12 carbon atoms, and even more preferably 7 to 10 carbon atoms.

[0197] Examples of the alkyl group bonded with an alicyclic hydrocarbon group include cyclopropylmethyl, cyclopropylethyl, cyclobutylmethyl, cyclohexylmethyl, cyclohexylethyl, and adamantylmethyl. The alkyl group bonded with an alicyclic hydrocarbon group preferably has 4 to 20 carbon atoms, more preferably 4 to 15, and even more preferably 4 to 10 carbon atoms.

[0198] Examples of the aromatic hydrocarbon group in which a cycloalkyl group is condensed include a group obtained by removing one hydrogen atom from an indane benzene ring, a group obtained by removing one hydrogen atom from a 1-methyl-indane benzene ring, and a group obtained by removing one hydrogen atom from a 2-methyl-indane.

[0199] Examples of the alkyl group to which a cycloalkyl group is condensed include a group in which an alkyl group having 1 to 4 carbon atoms is bonded to an indane benzene ring, a group in which an alkyl group having 1 to 4 carbon atoms is bonded to a 1-methyl-indane benzene ring, and a group in which an alkyl group having 1 to 4 carbon atoms is bonded to a 2-methyl-indane benzene ring.

[0200] As X 1a , X 1b , X 10 , X 11a , X 11bThe substituents (hereinafter also referred to as substituents B) which the hydrocarbon group represented may have include amino, amide, carboxamide, carboxyl, alkoxy having 1 to 10 carbon atoms, alkylthio having 1 to 10 carbon atoms, cyano, halogen atoms, hydroxyl and the like.

[0201] The amino group as the substituent A and the substituent B may be an unsubstituted amino group or a substituted amino group. Preferably, the substituted amino group is an amino group having 1 or 2 hydrocarbon groups. Examples of the hydrocarbon group include the above-mentioned X 1a , X 1b , X 10 , X 11a , X 11b The same group as the hydrocarbon group represented by is preferably an alkyl group. The number of carbon atoms of the hydrocarbon group is preferably 1 to 10, more preferably 1 to 4. Examples of the substituted amino group include N-methylamino, N,N-dimethylamino, N-ethylamino, N,N-diethylamino, N-propylamino, N,N-dipropylamino, N-isopropylamino, N,N-diisopropylamino, N-phenylamino, N,N-diphenylamino, and N,N-ethylmethylamino.

[0202] Examples of the amide group as the substituent A and the substituent B include *-CONR X1 R X2 (R X1 , R X2 Each independently represents a hydrogen atom or a hydrocarbon group which may have a substituent, and * represents a bonding site). X1 , R X2 The hydrocarbon group represented by X may be exemplified by the above 1a , X 1b , X 10 , X 11a , X 11b The same group as the hydrocarbon group represented by , preferably includes an aromatic hydrocarbon group. The number of carbon atoms in the hydrocarbon group is preferably 6 to 15, more preferably 6 to 12. X1 , R X2 The substituents that the hydrocarbon group represented by may have include the same substituents as those for the substituent B. X1 , R X2 , preferably one of them is a hydrocarbon group having 6 to 15 carbon atoms, and the other is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, more preferably one of them is an aromatic hydrocarbon group or aralkyl group having 6 to 15 carbon atoms, and the other is a hydrogen atom or a saturated chain hydrocarbon group having 1 to 4 carbon atoms. Examples of the amide group include amide groups represented by the following formulas (am1) to (am9).

[0203]

[0204] The carboxamide group as the substituent A and the substituent B refers to a group obtained by removing one hydrogen atom bonded to a nitrogen atom from an amide, and examples thereof include formamide, acetamide, propylamide, butylamide, benzamide, trifluoroacetamide, pentafluorobenzamide, etc. The number of carbon atoms in the amide group is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 6.

[0205] Examples of the alkoxy group as the substituent A and the substituent B include methoxy, ethoxy, propoxy, n-butoxy, tert-butoxy, etc. The number of carbon atoms in the alkoxy group is preferably 1 to 8, more preferably 1 to 5, further preferably 1 to 4, and further preferably 1 or 2.

[0206] Examples of the alkylthio group as the substituent A and the substituent B include methylthio, ethylthio, propylthio, and n-butylthio. The number of carbon atoms in the alkylthio group is preferably 1 to 8, more preferably 1 to 5, further preferably 1 to 4, and further preferably 1 or 2.

[0207] Examples of the halogen atom as the substituent A and the substituent B include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Among them, a fluorine atom, a chlorine atom or a bromine atom is preferred, and a chlorine atom is more preferred.

[0208] As X 1a , X 11a , each independently preferably is a hydrocarbon group having 1 to 20 carbon atoms, an amino group, an amide group, a carboxamide group, a carboxyl group, an alkoxy group having 1 to 10 carbon atoms, a cyano group, a halogen atom or a hydroxyl group, more preferably a hydrocarbon group containing an alkyl group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, an amino group, an amide group, a carboxamide group, an alkoxy group having 1 to 8 carbon atoms, a cyano group, a halogen atom or a hydroxyl group, further preferably an alkyl group having 1 to 4 carbon atoms, an aromatic hydrocarbon group or an aralkyl group having 6 to 12 carbon atoms, an amide group, a carboxamide group, an alkoxy group having 1 to 4 carbon atoms, a halogen atom or a hydroxyl group, further preferably an alkyl group having 1 to 4 carbon atoms, an aralkyl group having 6 to 12 carbon atoms, the above *-CONR X1 R X2 , a carboxamide group having 2 to 20 carbon atoms, an alkoxy group having 1 to 4 carbon atoms or a halogen atom, more preferably an alkyl group having 1 to 4 carbon atoms, an amide group represented by the above formulas (am1) to (am9), an alkoxy group having 1 to 4 carbon atoms or a halogen atom.

[0209] As X 1b , X 10 , X 11b, each independently, is preferably an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group or a halogen atom, more preferably an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group or a halogen atom, further preferably an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms or a halogen atom, further preferably an alkyl group having 1 to 4 carbon atoms or a halogen atom.

[0210] It is preferable that n1, n2, p, q1, and q2 are each independently an integer of 0 to 2.

[0211] In formula (ph1-1), when n1 is an integer greater than 2, a plurality of X 1a may be the same or different. In formula (ph1-2), when n2 is an integer greater than 2, multiple X 1b In formula (ph11-1) and formula (ph11-2), when p is an integer greater than or equal to 2, a plurality of X 10 may be the same or different. In formula (ph11-1), when q1 is an integer greater than 2, multiple X 11a may be the same or different. In formula (ph11-2), when q2 is an integer greater than 2, multiple X 11b Can be the same or different.

[0212] n1 represents an integer greater than 2, and X 1a When bonded to an adjacent carbon atom, X bonded to the adjacent carbon atom 1a may be bonded to each other to form a ring, n2 represents an integer greater than 2, and X 1b When bonded to an adjacent carbon atom, X bonded to the adjacent carbon atom 1b may be bonded to each other to form a ring. In addition, p represents an integer greater than 2, and X 10 When bonded to an adjacent carbon atom, X bonded to the adjacent carbon atom 10 may be bonded to each other to form a ring. In addition, q1 represents an integer greater than 2, and X 11a When bonded to an adjacent carbon atom, X bonded to the adjacent carbon atom 11a may be bonded to each other to form a ring, q2 represents an integer greater than 2, and X 11b When bonded to an adjacent carbon atom, X bonded to the adjacent carbon atom 11b They may be bonded to each other to form a ring.

[0213] Examples of the ring formed by the above bonding include the following structures. In the structural formula, * represents 1 The bonding sites of adjacent carbon atoms in .

[0214]

[0215] Y is -O-, -CO-, -SO2- or -C(CF3)2-, preferably -O- or -CO-, and more preferably -CO-.

[0216] The bonding positions with A and group (ib) in formula (ph1-2) and formula (ph11-2), and the bonding position with A in formula (ph11-1) are not particularly limited. From the perspective of ease of obtaining raw materials, formula (ph1-2) is preferably a group represented by the following formula (ph2-2), formula (ph11-1) is preferably a group represented by the following formula (ph12-1), and formula (ph11-2) is preferably a group represented by the following formula (ph12-2).

[0217]

[0218] [In formula (ph2-2), formula (ph12-1) and formula (ph12-2),

[0219] X 2b ~X 5b , X 12a ~X 15a , X 21a ~X 25a , X 12b ~X 15b , X 22b ~X 25b Each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an amino group, an amide group, a carboxamide group, a carboxyl group, an alkoxy group having 1 to 4 carbon atoms, an alkylthio group having 1 to 4 carbon atoms, a cyano group or a halogen atom.

[0220] X 2b With X 3b , X 4b With X 5b , X 12a With X 13a , X 14a With X 15a , X 22a With X 23a , X 21a With X 23a , X 21a With X 25a , X 24a With X 25a , X 12b With X 13b , X 14b With X 15b , X 22b With X 23b , X 24b With X 25b They may be bonded to each other to form a ring.

[0221] Y has the same meaning as above.

[0222] * indicates the bonding site with A.

[0223] ** indicates the bonding site to group (ib).]

[0224] As X 2b ~X 5b , X 12a ~X 15a , X 21a ~X 25a , X 12b ~X 15b , X 22b ~X 25b Examples of the alkyl group having 1 to 4 carbon atoms represented by include methyl, ethyl, propyl, n-butyl, isobutyl, tert-butyl, etc. Among them, methyl or ethyl is preferred.

[0225] As X 2b ~X 5b , X 12a ~X 15a , X 21a ~X 25a , X 12b ~X 15b , X 22b ~X 25b The amino group represented by may include the groups explained as the amino group in the substituent A and the substituent B, and the preferred range thereof is the same.

[0226] As X 2b ~X 5b , X 12a ~X 15a , X 21a ~X 25a , X 12b ~X 15b , X 22b ~X 25b The amide group represented by includes the groups explained as the amide group in the substituent A and the substituent B, and the preferred range thereof is the same.

[0227] As X 2b ~X 5b , X 12a ~X 15a , X 21a ~X 25a , X 12b ~X 15b , X 22b ~X 25b The carboxamide group represented by may include the groups explained as the carboxamide group in the substituent A and the substituent B, and the preferred range thereof is the same.

[0228] As X 2b ~X 5b , X 12a ~X 15a , X 21a ~X 25a , X 12b ~X 15b , X 22b ~X 25b The alkoxy group represented by ' may include the groups explained as the alkoxy group in the substituent A and the substituent B, and the preferred range thereof is the same.

[0229] As X 2b ~X 5b , X 12a ~X 15a , X 21a ~X 25a , X 12b ~X 15b , X 22b ~X 25b The alkylthio group represented by may include the groups explained as the alkylthio group in the substituent A and the substituent B, and the preferred range thereof is the same.

[0230] As X 2b ~X 5b , X 12a ~X 15a , X 21a ~X 25a , X 12b ~X 15b , X 22b ~X 25b The halogen atom represented by includes the halogen atoms explained as the halogen atom in the substituent A and the substituent B, and the preferred range thereof is the same.

[0231] As X 2b With X 3b , X 4b With X 5b , X 12a With X 13a , X 14a With X 15a , X 22a With X 23a , X 21a With X 23a , X 21a With X 25a , X 24a With X 25a , X 12b With X 13b , X 14b With X 15b , X 22b With X23b or X 24b With X 25b The ring formed by bonding to each other includes the above-mentioned X 1a , X 1b , X 10 , X 11a or X 11b The ring described is a ring formed by two or more groups bonded to each other.

[0232] As the group represented by the formula (ph1-1), n1 is preferably an integer of 0 to 2, more preferably 1 or 2, and further preferably 2. n1 is 2 and has two X 1a When the 2 X 1a The compound may be bonded at any of the ortho, meta, and para positions, but is preferably bonded at the meta or para position, and more preferably at the para position.

[0233] As the group represented by formula (ph1-1), X is preferably 1a It is a hydrocarbon group having a substituent B, or a substituent A, more preferably a chain hydrocarbon group having 1 to 10 carbon atoms or a substituent A having a substituent B, further preferably a saturated chain hydrocarbon group having 1 to 4 carbon atoms or a substituent A having a substituent B, further preferably a saturated chain hydrocarbon group having 1 to 4 carbon atoms, an amino group, an amide group, a carboxamide group, an alkoxy group having 1 to 10 carbon atoms, or a halogen atom having a substituent B (preferably an amino group, an amide group, a carboxamide group, an alkoxy group having 1 to 10 carbon atoms, and / or a halogen atom), further preferably an amino group, an amide group, a carboxamide group, an alkoxy group having 1 to 10 carbon atoms, or a halogen atom, further preferably an amide group, a carboxamide group, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom, and particularly preferably an amide group or an alkoxy group having 1 to 4 carbon atoms.

[0234] As the group represented by formula (ph1-1), for example, preferably there are groups represented by the following formulas (ph1-12-1) to (ph1-12-8), and more preferably there are groups represented by formulas (ph1-12-3) to (ph1-12-5).

[0235]

[0236] As a group represented by formula (ph2-2), X 2b ~X 5b Each independently is preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group or a halogen atom, more preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms or a chlorine atom, and still more preferably a hydrogen atom or a chlorine atom.

[0237] As the group represented by formula (ph2-2), for example, preferably, groups represented by the following formulas (ph2-22-1) to (ph2-22-8) are mentioned, and groups represented by formulas (ph2-22-1) to (ph2-22-7) are more preferred. In the formula, * represents a bonding site to A, and ** represents a bonding site to group (ib).

[0238]

[0239] As a group represented by formula (ph12-1), X 12a ~X 15a Each independently is preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group or a halogen atom, more preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms or a chlorine atom, and still more preferably a hydrogen atom or a chlorine atom.

[0240] As a group represented by formula (ph12-1), X 21a ~X 25a Each is independently preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an amino group, an amide group, a carboxamide group, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom, more preferably a hydrogen atom, an amino group, an amide group, a carboxamide group, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom, further preferably a hydrogen atom, an amide group, a carboxamide group, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom, and still more preferably a hydrogen atom, an amide group, or an alkoxy group having 1 to 4 carbon atoms.

[0241] As the group represented by formula (ph12-1), for example, preferably there are groups represented by the following formulas (ph12-12-1) to (ph12-12-8), and more preferably groups represented by formulas (ph12-12-3) to (ph12-12-5).

[0242]

[0243] As a group represented by formula (ph12-2), X 12b ~X 15b , X 22b ~X 25b Each independently is preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group or a halogen atom, more preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms or a chlorine atom, and still more preferably a hydrogen atom or a chlorine atom.

[0244] As the group represented by formula (ph12-2), for example, preferably, there are groups represented by the following formulas (ph12-22-1) to (ph12-22-8), and more preferably, there are groups represented by formulas (ph12-22-1) to (ph12-22-5). In the formula, Y has the same meaning as above, * represents a bonding site with A, and ** represents a bonding site with group (ib).

[0245]

[0246] As X in formula (ia) and formula (ib) 6 ~X 9 The hydrocarbon group represented by X may be exemplified as the above-mentioned 1a , X 1b , X 10 , X 11a , X 11b It should be noted that X 6 ~X 9 The -CH2- in the hydrocarbon group represented by X may replace -O-, -CO- or -NH-. 6 ~X 9 The -CH= contained in the hydrocarbon group represented by may be substituted with -N=, X 6 ~X 9 -C< contained in the hydrocarbon group represented by may be substituted with -N<.

[0247] In addition, X 6 With X 7 Can bond to each other to form a ring, X 8 With X 9 They may be bonded to each other to form a ring. 6 With X 7 The ring formed by bonding to each other, and X 8 With X 9 The -CH2- contained in the ring formed by mutual bonding is substituted with -O-, -CO- or -NH-; X 6 With X 7 The ring formed by bonding to each other, and X 8 With X 9 The -CH= contained in the ring formed by mutual bonding is substituted with -N=; X 6 With X 7 The ring formed by bonding to each other, and X 8 With X 9 The embodiment in which -C< included in the ring formed by mutual bonding is substituted with -N< is also included in the present invention.

[0248] As X in formula (ia) 6 With X 7The groups bonded to each other to form a ring, and X in formula (ib) 8 With X 9 The groups that are bonded to each other to form a ring include, for example, the following groups. 1 It should be noted that at least one of the hydrogen atoms possessed by the group represented by the following formula may be substituted with a substituent C described below.

[0249]

[0250] As X 6 ~X 9 The substituents (hereinafter also referred to as substituent C) that the hydrocarbon group represented may have include hydroxyl, alkoxy having 1 to 4 carbon atoms, alkylthio having 1 to 4 carbon atoms, carboxyl, amino, amide, carboxamide, cyano, halogen atoms, -SO3H, -SO3M, -SO3T 0.5 ,-SO2N(R 17 )2, etc. M represents an alkali metal atom, T represents an alkaline earth metal atom, R 17 represents a hydrogen atom or a hydrocarbon group.

[0251] Examples of the alkoxy group as the substituent C include the groups described as the alkoxy group in the substituent A and the substituent B, and the preferred range thereof is the same.

[0252] Examples of the alkylthio group as the substituent C include the groups explained as the alkylthio group in the substituent A and the substituent B, and the preferred range thereof is the same.

[0253] As the amino group as the substituent C, the groups explained as the amino group in the substituent A and the substituent B can be mentioned, and the preferred range thereof is the same.

[0254] Examples of the amide group as the substituent C include the groups described as the amide group in the substituent A and the substituent B, and the preferred range thereof is the same.

[0255] Examples of the carboxamide group as the substituent C include the groups described as the carboxamide group in the substituent A and the substituent B, and the preferred range thereof is the same.

[0256] Examples of the halogen atom as the substituent C include the halogen atoms described as the halogen atom in the substituent A and the substituent B, and a chlorine atom, a bromine atom or a fluorine atom is preferred.

[0257] Examples of the alkali metal atom represented by M include sodium and potassium.

[0258] Examples of the alkaline earth metal atom represented by T include magnesium, calcium, and barium, and magnesium and calcium are preferred. 6 ~X 9Any one of them has 1 -SO3T 0.5 When the azo dye (I) is a hydrocarbon group, the azo dye (I) has the following structure.

[0259]

[0260] [Wherein, L 1 , A and T have the same meanings as above. -SO3 - Replaces X 6 ~X 9 Any of the hydrogen atoms possessed by the hydrocarbon group represented by .]

[0261] R 17 represents a hydrogen atom or a hydrocarbon group. 17 They may be the same or different, and preferably one is a hydrogen atom and the other is a hydrocarbon group. 17 The hydrocarbon group represented by X may be exemplified as the above-mentioned 1a , X 1b , X 10 , X 11a , X 11b The group described as a hydrocarbon group represented by is preferably an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a polycyclic saturated alicyclic hydrocarbon group having 3 to 12 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 carbon atoms.

[0262] When the azo dye (I) has a group represented by formula (ib), the group represented by formula (ia) is preferably the same as the group represented by formula (ib). 6 and X 8 represents the same group, X 7 and X 9 When the group represented by the formula (ia) and the group represented by the formula (ib) are the same, the color density of the color filter is further improved.

[0263] The group represented by formula (ia) and the group represented by formula (ib) are each independently more preferably any one of the groups represented by formulas (t1) to (t5), further preferably any one of the groups represented by formulas (t1) to (t4), further preferably any one of the groups represented by formulas (t1) to (t3), and even more preferably any one of the groups represented by formulas (t1) and (t3).

[0264]

[0265] [In formula (t1) to formula (t5), R 1 ~R 16 Each independently represents a hydrogen atom, a hydrocarbon group which may have a substituent, a heterocyclic group, a cyano group or a halogen atom. * represents the same 1The bonding site of .]

[0266] As R 1 ~R 16 The hydrocarbon group represented by X may be exemplified as the above-mentioned 1a , X 1b , X 10 , X 11a , X 11b The group described is a hydrocarbon group represented by . Among them, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, and an aromatic hydrocarbon group having 6 to 12 carbon atoms are preferred, an alkyl group having 1 to 6 carbon atoms, an aromatic hydrocarbon group having 6 to 12 carbon atoms are more preferred, and an alkyl group having 1 to 6 carbon atoms and a phenyl group are further preferred.

[0267] As R 1 ~R 16 The substituent that the hydrocarbon group represented may have includes the groups explained as the above-mentioned substituent C, and the preferred range thereof is the same.

[0268] As R 1 ~R 16 The heterocyclic group represented by ' includes thienyl, benzo[b]thienyl, thianthrenyl, furanyl, pyranyl, isobenzofuranyl, chromenyl, xanthenyl, pyrrolyl, imidazolyl, pyrazolyl, pyridinyl, pyrazinyl, pyrimidinyl, pyridazinyl, indolizinyl, indolyl, 1H-indazolyl, isoquinolyl, quinolyl, phthalazinyl, carbazolyl, acridinyl, chromanyl, pyrrolidinyl, piperidinyl, piperazinyl, indolinyl, isoindolinyl and benzimidazolyl. Among them, preferred are heterocyclic groups having a benzene ring, such as benzo[b]thienyl, thianthrenyl, isobenzofuranyl, chromenyl, xanthenyl, indolyl, 1H-indazolyl, isoquinolyl, quinolyl, phthalazinyl, carbazolyl, acridinyl, chromanyl, indolinyl, isoindolinyl, and benzimidazolyl; more preferred are indolyl, 1H-indazolyl, isoquinolyl, quinolyl, phthalazinyl, carbazolyl, acridinyl, indolinyl, isoindolinyl, and benzimidazolyl.

[0269] As R 1 ~R 16 The halogen atom represented by includes the halogen atoms explained as the halogen atom in the substituent A and the substituent B, and among them, a chlorine atom and a fluorine atom are preferred.

[0270] R 1 It is preferably an aromatic hydrocarbon group which may have a substituent, more preferably an aromatic hydrocarbon group having 6 to 12 carbon atoms which may have a substituent, further preferably an aromatic hydrocarbon group having 6 to 12 carbon atoms, further preferably an aromatic hydrocarbon group having 6 to 10 carbon atoms, and still more preferably a phenyl group.

[0271] R 2 It is preferably a chain hydrocarbon group which may have a substituent, more preferably a chain hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, further preferably a saturated chain hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, further preferably an alkyl group having 1 to 6 carbon atoms, and even more preferably an alkyl group having 1 to 4 carbon atoms.

[0272] R 3 and R 4 Each R is independently preferably a hydrogen atom, an alkyl group, a cycloalkyl group or an aromatic hydrocarbon group, and more preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms or a phenyl group. 3 and R 4 Preferably they are the same.

[0273] R 5 It is preferably a chain hydrocarbon group which may have a substituent or a hydrogen atom, more preferably a chain hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, further preferably a saturated chain hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, further preferably an alkyl group having 1 to 8 carbon atoms, and even more preferably an alkyl group having 1 to 6 carbon atoms.

[0274] R 6 An alkyl group or a cyano group which may have a substituent is preferred, an alkyl group or a cyano group which may have a halogen atom is more preferred, an alkyl group or a cyano group which may have a halogen atom is further preferred, and an alkyl group or a cyano group which may have 1 to 4 carbon atoms and may have a halogen atom is further preferred, and a cyano group is further preferred.

[0275] R 7 It is preferably a chain hydrocarbon group which may have a substituent, more preferably a chain hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, further preferably a saturated chain hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, further preferably an alkyl group having 1 to 8 carbon atoms, and even more preferably an alkyl group having 1 to 6 carbon atoms.

[0276] R 8 An alkyl group which may have a substituent is preferred, and an alkyl group having 1 to 4 carbon atoms is more preferred.

[0277] R 9 An alkyl group which may have a substituent or a hydrogen atom is preferred, and an alkyl group having 1 to 4 carbon atoms or a hydrogen atom is more preferred.

[0278] R 10 An aromatic hydrocarbon group or a heterocyclic group which may have a substituent is preferred, a phenyl group which may have a substituent or a heterocyclic group having a benzene ring is more preferred, and a phenyl group or a benzimidazolyl group which may have a halogen atom is further preferred.

[0279] R 11 ~R 16Each independently is preferably an alkyl group or a hydrogen atom which may have a substituent, more preferably an alkyl group or a hydrogen atom which may have a halogen atom, and still more preferably an alkyl group having 1 to 4 carbon atoms or a hydrogen atom which may have a halogen atom.

[0280] More specifically, as the azo dye (I), for example, there may be mentioned azo dyes (AI-1) to (AI-378) shown in Tables 1 to 5. In Tables 1 to 5, ib represents a group (ib), ph1-12-3 to ph1-12-5, ph2-22-1 to ph2-22-3, ph2-22-7, ph12-12-3 to ph12-12-5, ph12-22-1 to ph12-22-5 represent the groups represented by the above-mentioned formulas (ph1-12-3) to (ph1-12-5), (ph2-22-1) to (ph2-22-3), (ph2-22-7), (ph12-12-3) to (ph12-12-5), and (ph12-22-1) to (ph12-22-5), respectively, and t6 to t11 represent groups represented by the following formulas (t6) to (t11).

[0281] [Table 1]

[0282] Azo pigments <![CDATA[L 1 ]]> A ib Azo pigments <![CDATA[L 1 ]]> A ib (AI-1) ph1-12-3 t6 - (AI-34) ph2-22-1 t8 t9 (AI-2) ph1-12-3 t7 - (AI-35) ph2-22-1 t8 t10 (AI-3) ph1-12-3 t8 - (AI-36) ph2-22-1 t8 t11 (AI-4) ph1-12-3 t9 - (AI-37) ph2-22-1 t9 t10 (AI-5) ph1-12-3 t10 - (AI-38) ph2-22-1 t9 t11 (AI-6) ph1-12-3 t11 - (Al-39) ph2-22-1 t10 t11 (AI-7) ph1-12-4 t6 - (AI-40) ph2-22-2 t6 t6 (AI-8) ph1-12-4 t7 - (AI-41) ph2-22-2 t7 t7 (AI-9) ph1-12-4 t8 - (AI-42) ph2-22-2 t8 t8 (AI-10) ph1-12-4 t9 - (Al-43) ph2-22-2 t9 t9 (AI-11) ph1-12-4 t10 - (AI-44) ph2-22-2 t10 t10 (AI-12) ph1-12-4 t11 - (AI-45) ph2-22-2 t11 t11 (AI-13) ph1-12-5 t6 - (AI-46) ph2-22-2 t6 t7 (AI-14) ph1-12-5 t7 - (AI-47) ph2-22-2 t6 t8 (AI-15) ph1-12-5 t8 - (AI-48) ph2-22-2 t6 t9 (AI-16) ph1-12-5 t9 - (AI-49) ph2-22-2 t6 t10 (AI-17) ph1-12-5 t10 - (AI-50) ph2-22-2 t6 t11 (AI-18) ph1-12-5 t11 - (AI-51) ph2-22-2 t7 t6 (AI-19) ph2-22-1 t6 t6 (AI-52) ph2-22-2 t7 t8 (AI-20) ph2-22-1 t7 t7 (AI-53) ph2-22-2 t7 t9 (AI-21) ph2-22-1 t8 t8 (AI-54) ph2-22-2 t7 t10 (AI-22) ph2-22-1 t9 t9 (AI-55) ph2-22-2 t7 t11 (AI-23) ph2-22-1 t10 t10 (AI-56) ph2-22-2 t8 t6 (AI-24) ph2-22-1 t11 t11 (AI-57) ph2-22-2 t8 t7 (AI-25) ph2-22-1 t6 t7 (AI-58) ph2-22-2 t8 t9 (AI-26) ph2-22-1 t6 t8 (AI-59) ph2-22-2 t8 t10 (AI-27) ph2-22-1 t6 t9 (AI-60) ph2-22-2 t8 t11 (AI-28) ph2-22-1 t6 t10 (AI-61) ph2-22-2 t9 t6 (AI-29) ph2-22-1 t6 t11 (AI-62) ph2-22-2 t9 t7 (AI-30) ph2-22-1 t7 t8 (AI-63) ph2-22-2 t9 t8 (AI-31) ph2-22-1 t7 t9 (AI-64) ph2-22-2 t9 t10 (AI-32) ph2-22-1 t7 t10 (AI-65) ph2-22-2 t9 t11 (AI-33) ph2-22-1 t7 t11 (AI-66) ph2-22-2 t10 t6

[0283] [Table 2]

[0284] Azo dye <![CDATA[L 1 ]]> A ib Azo dye <![CDATA[L 1 ]]> A ib (AI-67) ph2-22-2 t10 t7 (AI-100) ph2-22-3 t9 t10 (AI-68) ph2-22-2 t10 t8 (AI-101) ph2-22-3 t9 t11 (AI-69) ph2-22-2 t10 t9 (AI-102) ph2-22-3 t10 t6 (AI-70) ph2-22-2 t10 t11 (AI-103) ph2-22-3 t10 t7 (AI-71) ph2-22-2 t11 t6 (AI-104) ph2-22-3 t10 t8 (AI-72) ph2-22-2 t11 t7 (AI-105) ph2-22-3 t10 t9 (AI-73) ph2-22-2 t11 t8 (AI-106) ph2-22-3 t10 t11 (AI-74) ph2-22-2 t11 t9 (AI-107) ph2-22-3 t11 t6 (AI-75) ph2-22-2 t11 t10 (AI-108) ph2-22-3 t11 t7 (AI-76) ph2-22-3 t6 t6 (AI-109) ph2-22-3 t11 t8 (AI-77) ph2-22-3 t7 t7 (AI-110) ph2-22-3 t11 t9 (AI-78) ph2-22-3 t8 t8 (AI-111) ph2-22-3 t11 t10 (AI-79) ph2-22-3 t9 t9 (AI-112) ph2-22-7 t6 t6 (AI-80) ph2-22-3 t10 t10 (AI-113) ph2-22-7 t7 t7 (AI-81) ph2-22-3 t11 t11 (AI-114) ph2-22-7 t8 t8 (AI-82) ph2-22-3 t6 t7 (AI-115) ph2-22-7 t9 t9 (AI-83) ph2-22-3 t6 t8 (AI-116) ph2-22-7 t10 t10 (AI-84) ph2-22-3 t6 t9 (AI-117) ph2-22-7 t11 t11 (AI-85) ph2-22-3 t6 t10 (AI-118) ph2-22-7 t6 t7 (AI-86) ph2-22-3 t6 t11 (AI-119) ph2-22-7 t6 t8 (AI-87) ph2-22-3 t7 t6 (AI-120) ph2-22-7 t6 t9 (AI-88) ph2-22-3 t7 t8 (AI-121) ph2-22-7 t6 t10 (AI-89) ph2-22-3 t7 t9 (AI-122) ph2-22-7 t6 t11 (AI-90) ph2-22-3 t7 t10 (AI-123) ph2-22-7 t7 t8 (AI-91) ph2-22-3 t7 t11 (AI-124) ph2-22-7 t7 t9 (AI-92) ph2-22-3 t8 t6 (AI-125) ph2-22-7 t7 t10 (AI-93) ph2-22-3 t8 t7 (AI-126) ph2-22-7 t7 t11 (AI-94) ph2-22-3 t8 t9 (AI-127) ph2-22-7 t8 t9 (AI-95) ph2-22-3 t8 t10 (AI-128) ph2-22-7 t8 t10 (AI-96) ph2-22-3 t8 t11 (AI-129) ph2-22-7 t8 t11 (AI-97) ph2-22-3 t9 t6 (AI-130) ph2-22-7 t9 t10 (AI-98) ph2-22-3 t9 t7 (AI-131) ph2-22-7 t9 t11 (AI-99) ph2-22-3 t9 t8 (AI-132) ph2-22-7 t10 t11

[0285] [Table 3]

[0286] Azo dye <![CDATA[L 1 ]]> A ib Y Azo dye <![CDATA[L 1 ]]> A ib Y (AI-133) ph12-12-3 t6 - -0- (AI-174) ph12-22-1 t11 t11 -0- (AI-134) ph12-12-3 t7 - -0- (AI-175) ph12-22-1 t6 t7 -0- (AI-135) ph12-12-3 t8 - -0- (AI-176) ph12-22-1 t6 t8 -0- (AI-136) ph12-12-3 t9 - -0- (AI-177) ph12-22-1 t6 t9 -0- (AI-137) ph12-12-3 t10 - -0- (AI-178) ph12-22-1 t6 t10 -0- (AI-138) ph12-12-3 t11 - -0- (AI-179) ph12-22-1 t6 t11 -0- (AI-139) ph12-12-4 t6 - -0- (AI-180) ph12-22-1 t7 t8 -0- (AI-140) ph12-12-4 t7 - -0- (AI-181) h12-22-1 t7 t9 -0- (AI-141) ph12-12-4 t8 - -0- (AI-182) ph12-22-1 t7 t10 -0- (AI-142) ph12-12-4 t9 - -0- (AI-183) ph12-22-1 t7 t11 -0- (AI-143) ph12-12-4 t10 -0- (AI-184) ph12-22-1 t8 t9 -0- (AI-144) ph12-12-4 t11 - -0- (AI-185) ph12-22-1 t8 t10 -0- (AI-145) ph12-12-5 t6 - -0- (AI-186) ph12-22-1 t8 t11 -0- (AI-146) ph12-12-5 t7 - -0- (AI-187) ph12-22-1 t9 t10 -0- (AI-147) ph12-12-5 t8 - -0- (AI-188) ph12-22-1 t9 t11 -0- (AI-148) ph12-12-5 t9 - -0- (AI-189) ph12-22-1 t10 t11 -0- (AI-149) ph12-12-5 t10 - -0- (AI-190) ph12-22-2 t6 t6 -0- (AI-150) ph12-12-5 t11 - -0- (AI-191) ph12-22-2 t7 t7 -0- (AI-151) h12-12-3 t6 - -C0- (AI-192) h12-22-2 t8 t8 -0- (AI-152) h12-12-3 t7 - -C0- (AI-193) ph12-22-2 t9 t9 -0- (AI-153) ph12-12-3 t8 - -C0- (AI-194) ph12-22-2 t10 t10 -0- (AI-154) ph12-12-3 t9 - -C0- (AI-195) ph12-22-2 t11 t11 -0- (AI-155) ph12-12-3 t10 - -C0- (AI-196) ph12-22-2 t6 t7 -0- (AI-156) ph12-12-3 t11 - -C0- (AI-197) ph12-22-2 t6 t8 -0- (AI-157) ph12-12-4 t6 - -C0- (AI-198) ph12-22-2 t6 t9 -0- (AI-158) ph12-12-4 t7 - -C0- (AI-199) ph12-22-2 t6 t10 -0- (AI-159) ph12-12-4 t8 - -C0- (AI-200) ph12-22-2 t6 t11 -0- (AI-160) ph12-12-4 t9 - -C0- (AI-201) ph12-22-2 t7 t8 -0- (AI-161) ph12-12-4 t10 - -C0- (AI-202) ph12-22-2 t7 t9 -0- (AI-162) ph12-12-4 t11 - -C0- (AI-203) ph12-22-2 t7 t10 -0- (AI-163) ph12-12-5 t6 - -C0- (AI-204) ph12-22-2 t7 t11 -0- (AI-164) ph12-12-5 t7 - -C0- (AI-205) ph12-22-2 t8 t9 -0- (AI-165) ph12-12-5 t8 - -C0- (AI-206) ph12-22-2 t8 t10 -0- (AI-166) ph12-12-5 t9 - -C0- (AI-207) ph12-22-2 t8 t11 -0- (AI-167) ph12-12-5 t10 - -C0- (AI-208) ph12-22-2 t9 t10 -0- (AI-168) ph12-12-5 t11 - -C0- (AI-209) ph12-22-2 t9 t11 -0- (AI-169) ph12-22-1 t6 t6 -0- (AI-210) ph12-22-2 t10 t11 -0- (AI-170) ph12-22-1 t7 t7 -0- (AI-211) ph12-22-3 t6 t6 -0- (AI-171) ph12-22-1 t8 t8 -0- (AI-212) ph12-22-3 t7 t7 -0- (AI-172) ph12-22-1 t9 t9 -0- (AI-213) ph12-22-3 t8 t8 -0- (AI-173) ph12-22-1 t10 t10 -0- (AI-214) ph12-22-3 t9 t9 -0-

[0287] [Table 4]

[0288] Azo pigment <![CDATA[L 1 ]]> A ib Y Azo pigment <![CDATA[L 1 ]]> A ib Y (AI-215) ph12-22-3 t10 t10 -0- (AI-256) ph12-22-5 t9 t9 -0- (AI-216) ph12-22-3 t11 t11 -0- (AI-257) ph12-22-5 t10 t10 -0- (AI-217) ph12-22-3 t6 t7 -0- (AI-258) ph12-22-5 t11 t11 -0- (AI-218) h12-22-3 t6 t8 -0- (AI-259) ph12-22-5 t6 t7 -0- (AI-219) ph12-22-3 t6 t9 -0- (AI-260) ph12-22-5 t6 t8 -0- (AI-220) h12-22-3 t6 t10 -0- (AI-261) ph12-22-5 t6 t9 -0- (AI-221) ph12-22-3 t6 t11 -0- (AI-262) ph12-22-5 t6 t10 -0- (AI-222) ph12-22-3 t7 t8 -0- (AI-263) ph12-22-5 t6 t11 -0- (AI-223) ph12-22-3 t7 t9 -0- (AI-264) ph12-22-5 t7 t8 -0- (AI-224) ph12-22-3 t7 t10 -0- (AI-265) ph12-22-5 t7 t9 -0- (AI-225) ph12-22-3 t7 t11 -0- (AI-266) ph12-22-5 t7 t10 -0- (AI-226) ph12-22-3 t8 t9 -0- (AI-267) ph12-22-5 t7 t11 -0- (AI-227) ph12-22-3 t8 t10 -0- (AI-268) ph12-22-5 t8 t9 -0- (AI-228) h12-22-3 t8 t11 -0- (AI-269) ph12-22-5 t8 t10 -0- (AI-229) ph12-22-3 t9 t10 -0- (AI-270) ph12-22-5 t8 t11 -0- (AI-230) ph12-22-3 t9 t11 -0- (AI-271) ph12-22-5 t9 t10 -0- (AI-231) ph12-22-3 t10 t11 -0- (AI-272) ph12-22-5 t9 t11 -0- (AI-232) h12-22-4 t6 t6 -0- (AI-273) ph12-22-5 t10 t11 -0- (AI-233) ph12-22-4 t7 t7 -0- (AI-274) ph12-22-1 t6 t6 -C0- (AI-234) ph12-22-4 t8 t8 -0- (AI-275) ph12-22-1 t7 t7 -C0- (AI-235) ph12-22-4 t9 t9 -0- (AI-276) ph12-22-1 t8 t8 -C0- (AI-236) ph12-22-4 t10 t10 -0- (AI-277) ph12-22-1 t9 t9 -C0- (AI-237) ph12-22-4 t11 t11 -0- (AI-278) ph12-22-1 t10 t10 -C0- (AI-238) ph12-22-4 t6 t7 -0- (AI-279) ph12-22-1 t11 t11 -C0- (AI-239) ph12-22-4 t6 t8 -0- (AI-280) ph12-22-1 t6 t7 -C0- (AI-240) ph12-22-4 t6 t9 -0- (AI-281) ph12-22-1 t6 t8 -C0- (AI-241) ph12-22-4 t6 t10 -0- (AI-282) ph12-22-1 t6 t9 -C0- (AI-242) ph12-22-4 t6 t11 -0- (AI-283) ph12-22-1 t6 t10 -C0- (AI-243) ph12-22-4 t7 t8 -0- (AI-284) ph12-22-1 t6 t11 -C0- (AI-244) ph12-22-4 t7 t9 -0- (AI-285) h12-22-1 t7 t8 -C0- (AI-245) ph12-22-4 t7 t10 -0- (AI-286) ph12-22-1 t7 t9 -C0- (AI-246) ph12-22-4 t7 t11 -0- (AI-287) ph12-22-1 t7 t10 -C0- (AI-247) h12-22-4 t8 t9 -0- (AI-288) ph12-22-1 t7 t11 -C0- (AI-248) ph12-22-4 t8 t10 -0- (AI-289) ph12-22-1 t8 t9 -C0- (AI-249) ph12-22-4 t8 t11 -0- (AI-290) ph12-22-1 t8 t10 -C0- (AI-250) ph12-22-4 t9 t10 -0- (AI-291) ph12-22-1 t8 t11 -C0- (AI-251) ph12-22-4 t9 t11 -0- (AI-292) ph12-22-1 t9 t10 -C0- (AI-252) ph12-22-4 t10 t11 -0- (AI-293) ph12-22-1 t9 t11 -C0- (AI-253) ph12-22-5 t6 t6 -0- (AI-294) ph12-22-1 t10 t11 -C0- (AI-254) ph12-22-5 t7 t7 -0- (AI-295) ph12-22-2 t6 t6 -C0- (AI-255) ph12-22-5 t8 t8 -0- (AI-296) ph12-22-2 t7 t7 -C0-

[0289] [Table 5]

[0290] Azo dye <![CDATA[L 1 ]]> A ib Y Azo dye <![CDATA[L 1 ]]> A ib Y (AI-297) ph12-22-2 t8 t8 -C0- (AI-338) ph12-22-4 t7 t7 -C0- (AI-298) ph12-22-2 t9 t9 -C0- (AI-339) ph12-22-4 t8 t8 -C0- (AI-299) ph12-22-2 t10 t10 -C0- (AI-340) ph12-22-4 t9 t9 -C0- (AI-300) ph12-22-2 t11 t11 -C0- (AI-341) ph12-22-4 t10 t10 -C0- (AI-301) ph12-22-2 t6 t7 -C0- (AI-342) ph12-22-4 t11 t11 -C0- (AI-302) ph12-22-2 t6 t8 -C0- (AI-343) ph12-22-4 t6 t7 -C0- (AI-303) ph12-22-2 t6 t9 -C0- (AI-344) ph12-22-4 t6 t8 -C0- (AI-304) ph12-22-2 t6 t10 -C0- (AI-345) ph12-22-4 t6 t9 -C0- (AI-305) ph12-22-2 t6 t11 -C0- (AI-346) ph12-22-4 t6 t10 -C0- (AI-306) ph12-22-2 t7 t8 -C0- (AI-347) ph12-22-4 t6 t11 -C0- (AI-307) ph12-22-2 t7 t9 -C0- (AI-348) ph12-22-4 t7 t8 -C0- (AI-308) ph12-22-2 t7 t10 -C0- (AI-349) ph12-22-4 t7 t9 -C0- (AI-309) ph12-22-2 t7 t11 -C0- (AI-350) ph12-22-4 t7 t10 -C0- (AI-310) ph12-22-2 t8 t9 -C0- (AI-351) ph12-22-4 t7 t11 -C0- (AI-311) ph12-22-2 t8 t10 -C0- (AI-352) ph12-22-4 t8 t9 -C0- (AI-312) ph12-22-2 t8 t11 -C0- (AI-353) ph12-22-4 t8 t10 -C0- (AI-313) ph12-22-2 t9 t10 -C0- (AI-354) ph12-22-4 t8 t11 -C0- (AI-314) ph12-22-2 t9 t11 -C0- (AI-355) ph12-22-4 t9 t10 -C0- (AI-315) ph12-22-2 t10 t11 -C0- (AI-356) ph12-22-4 t9 t11 -C0- (AI-316) ph12-22-3 t6 t6 -C0- (AI-357) ph12-22-4 t10 t11 -C0- (AI-317) ph12-22-3 t7 t7 -C0- (AI-358) ph12-22-5 t6 t6 -C0- (AI-318) ph12-22-3 t8 t8 -C0- (AI-359) ph12-22-5 t7 t7 -C0- (AI-319) ph12-22-3 t9 t9 -C0- (AI-360) ph12-22-5 t8 t8 -C0- (AI-320) ph12-22-3 t10 t10 -C0- (AI-361) ph12-22-5 t9 t9 -C0- (AI-321) ph12-22-3 t11 t11 -C0- (AI-362) ph12-22-5 t10 t10 -C0- (AI-322) ph12-22-3 t6 t7 -C0- (AI-363) ph12-22-5 t11 t11 -C0- (AI-323) ph12-22-3 t6 t8 -C0- (AI-364) ph12-22-5 t6 t7 -C0- (AI-324) ph12-22-3 t6 t9 -C0- (AI-365) ph12-22-5 t6 t8 -C0- (AI-325) ph12-22-3 t6 t10 -C0- (AI-366) ph12-22-5 t6 t9 -C0- (AI-326) ph12-22-3 t6 t11 -C0- (AI-367) ph12-22-5 t6 t10 -C0- (AI-327) ph12-22-3 t7 t8 -C0- (AI-368) ph12-22-5 t6 t11 -C0- (AI-328) ph12-22-3 t7 t9 -C0- (AI-369) ph12-22-5 t7 t8 -C0- (AI-329) ph12-22-3 t7 t10 -C0- (AI-370) ph12-22-5 t7 t9 -C0- (AI-330) ph12-22-3 t7 t11 -C0- (AI-371) ph12-22-5 t7 t10 -C0- (AI-331) ph12-22-3 t8 t9 -C0- (AI-372) ph12-22-5 t7 t11 -C0- (AI-332) ph12-22-3 t8 t10 -C0- (AI-373) ph12-22-5 t8 t9 -C0- (AI-333) ph12-22-3 t8 t11 -C0- (AI-374) ph12-22-5 t8 t10 -C0- (AI-334) ph12-22-3 t9 t10 -C0- (AI-375) ph12-22-5 t8 t11 -C0- (AI-335) ph12-22-3 t9 t11 -C0- (AI-376) ph12-22-5 t9 t10 -C0- (AI-336) ph12-22-3 t10 t11 -C0- (AI-377) ph12-22-5 t9 t11 -C0- (AI-337) ph12-22-4 t6 t6 -C0- (AI-378) ph12-22-5 t10 t11 -C0-

[0291]

[0292] [In formula (t6) to formula (t11), * represents 1 The bonding site of .]

[0293] As the azo dye (I),

[0294] Preferred are azo dyes (AI-1) to (AI-24), azo dyes (AI-40) to (AI-45), azo dyes (AI-76) to (AI-81), azo dyes (AI-112) to (AI-117), azo dyes (AI-151) to (AI-174), and azo dyes (AI-274) to (AI-378),

[0295] More preferred are azo dyes (AI-1) to (AI-6), azo dyes (AI-19) to (AI-24), azo dyes (AI-112) to (AI-117), azo dyes (AI-151) to (AI-156), azo dyes (AI-169) to (AI-174), azo dyes (AI-274) to (AI-279), azo dyes (AI-295) to (AI-300), azo dyes (AI-316) to (AI-321), azo dyes (AI-337) to (AI-342), azo dyes (AI-358) to (AI-363),

[0296] More preferred are azo dyes (AI-1) to (AI-6), azo dyes (AI-19) to (AI-24), azo dyes (AI-151) to (AI-156), azo dyes (AI-169) to (AI-174), and azo dyes (AI-274) to (AI-279).

[0297] More preferably, azo dyes (AI-1) to (AI-6), azo dyes (AI-19) to (AI-24), azo dyes (AI-169), azo dyes (AI-172), azo dyes (AI-274) to (AI-279) are used.

[0298] More preferred are azo dye (AI-1), azo dye (AI-4), azo dye (AI-19), azo dye (AI-22), azo dye (AI-274), and azo dye (AI-277).

[0299] The azo dye (I) can be produced, for example, by the following method.

[0300] When the azo dye (I) is a compound represented by the following formula (I1) (hereinafter also referred to as compound (I1)), first, the amine represented by the formula (pt1-1) is diazotized to produce a diazonium salt represented by the formula (q1-1). The compound represented by the formula (pt2) is reacted with the obtained diazonium salt represented by the formula (q1-1) to produce the compound represented by the formula (I1).

[0301]

[0302] [In formula (pt1-1), formula (pt2), formula (q1-1) and formula (I1),

[0303] X 1a , X 6 , X 7 and n1 represent the same meanings as above.

[0304] Q 1 represents an inorganic anion or an organic anion.]

[0305] When the azo dye (I) is a compound represented by the following formula (I2) (hereinafter, also referred to as compound (I2)), first, the amine represented by formula (pt1-2) is diazotized to produce a diazonium salt represented by formula (q1-2). The compound represented by formula (pt2) is reacted with the obtained diazonium salt represented by formula (q1-2) to produce a compound represented by formula (q2). Next, the compound represented by formula (q2) is reduced to produce an amine represented by formula (q3). Furthermore, the obtained amine is diazotized to produce a diazonium salt represented by formula (q4), and then reacted with a compound represented by formula (pt3), thereby producing a compound represented by formula (I2).

[0306]

[0307] [In formula (pt1-2), formula (pt2), formula (pt3), formula (q1-2), formula (q2) to formula (q4) and formula (I2),

[0308] X 1b , X 6 ~X 9 and n2 represent the same meanings as above.

[0309] Q 1 and Q 2 Each independently represents an inorganic anion or an organic anion.]

[0310] In addition, when the azo dye (I) is a compound (I2), it can also be produced by the following method. First, one of the amino groups in the diamine represented by formula (pt1-2A) is diazotized to produce a diazonium salt represented by formula (q1-2A). The compound represented by formula (pt2) is reacted with the obtained diazonium salt represented by formula (q1-2A) to produce an amine represented by formula (q3). Furthermore, the amine represented by formula (q3) is diazotized to produce a diazonium salt represented by formula (q4), which is then reacted with the compound represented by formula (pt3) to produce a compound represented by formula (I2).

[0311]

[0312] [In formula (pt1-2A), formula (pt2), formula (pt3), formula (q1-2A), formula (q3), formula (q4) and formula (I2),

[0313] X 1b , X 6 ~X 9 and n2 represent the same meanings as above.

[0314] Q 1 and Q 2 Each independently represents an inorganic anion or an organic anion.]

[0315] When the azo dye (I) is a compound represented by the following formula (I3) (hereinafter also referred to as compound (I3)), first, the amine represented by the formula (pt11-1) is diazotized to produce a diazonium salt represented by the formula (q11-1). The compound represented by the formula (pt2) is reacted with the obtained diazonium salt represented by the formula (q11-1) to produce the compound represented by the formula (I3).

[0316]

[0317] [In formula (pt11-1), formula (pt2), formula (q11-1) and formula (I3),

[0318] X 10 , X 11a , X 6 , X 7 , Y, p and q1 represent the same meanings as above.

[0319] Q 1 represents an inorganic anion or an organic anion.]

[0320] When the azo dye (I) is a compound represented by the following formula (I4) (hereinafter also referred to as compound (I4)), first, the amine represented by the formula (pt11-2) is diazotized to produce the diazonium salt represented by the formula (q11-2). The compound represented by the formula (pt2) is reacted with the obtained diazonium salt represented by the formula (q11-2) to produce the compound represented by the formula (q2-1). Next, the compound represented by the formula (q2-1) is reduced to produce the amine represented by the formula (q3-1). Furthermore, the obtained amine is diazotized to produce the diazonium salt represented by the formula (q4-1), and then reacted with the compound represented by the formula (pt3) to produce the compound represented by the formula (I4).

[0321]

[0322] [In formula (pt11-2), formula (pt2), formula (pt3), formula (q11-2), formula (q2-1) to formula (q4-1) and formula (I4),

[0323] X 10 , X 11b , X 6 ~X 9 , Y, p and q2 represent the same meanings as above.

[0324] Q 1 and Q 2 Each independently represents an inorganic anion or an organic anion.]

[0325] In addition, the azo dye (I) is a compound (I4), wherein X 6 and X 8 Same, and X 7 and X 9 In the same manner, first, the diamine represented by the following formula (pt11-2A) is diazotized to produce the diazonium salt represented by the formula (q11-2A). The compound represented by the formula (pt2) and the formula (pt3) is reacted with the obtained diazonium salt represented by the formula (q11-2A) to produce the compound represented by the formula (I4).

[0326]

[0327] [In formula (pt11-2A), formula (pt2), formula (pt3), formula (q11-2A) and formula (I4),

[0328] X 10 , X 11b , X 6 ~X 9 , Y, p and q2 have the same meanings as above,

[0329] X6 and X 8 Same, X 7 and X 9 same.

[0330] Q 1 and Q 2 Each independently represents an inorganic anion or an organic anion.]

[0331] The diazonium salts represented by Formula (q1-1), Formula (q1-2), Formula (q1-2A), Formula (q11-1), Formula (q11-2), and Formula (q11-2A) can be obtained by diazotizing an amine represented by Formula (pt1-1), Formula (pt1-2), Formula (pt1-2A), Formula (pt11-1), Formula (pt11-2), or Formula (pt11-2A) with nitrous acid, a nitrite, or a nitrite ester. The diazotization can be carried out by any known method.

[0332] Examples of the inorganic anions include fluoride ions, chloride ions, bromide ions, iodide ions, perchlorate ions, hypochlorite ions, and the like. Examples of the organic anions include CH3COO - 、C6H5COO - As Q 1 and Q 2 , preferably chloride ion, bromide ion, CH3COO - .

[0333] When the diazotization reaction is performed, an acidic catalyst may be used to facilitate the reaction. Examples of the acidic catalyst include inorganic acids such as sulfuric acid and hydrochloric acid.

[0334] Compound (I1) can be produced by diazo coupling a diazonium salt represented by formula (q1-1) with a compound represented by formula (pt2). Compound (q2) can be produced by diazo coupling a diazonium salt represented by formula (q1-2) with a compound represented by formula (pt2). Compound (q3) can be produced by diazo coupling a diazonium salt represented by formula (q1-2A) with a compound represented by formula (pt2). Compound (I3) can be produced by diazo coupling a diazonium salt represented by formula (q11-1) with a compound represented by formula (pt2). Compound (q2-1) can be produced by diazo coupling a diazonium salt represented by formula (q11-2) with a compound represented by formula (pt2). In addition, compound (I4) can be produced by diazo coupling a diazonium salt represented by formula (q11-2A) with compounds represented by formula (pt2) and formula (pt3) (in this case, formula (pt2) and formula (pt3) are the same). These diazo couplings can be carried out by any known method. Preferably, the diazo coupling reaction is carried out in the presence of an aqueous solvent. As aqueous solvents, water-soluble organic solvents such as methanol, ethanol, propanol, 2-propanol, water, or a mixed solvent of water and the above-mentioned water-soluble organic solvents can be mentioned, preferably water, or a mixed solvent of water and a water-soluble organic solvent.

[0335] The compound represented by formula (q3) can be produced by reducing the compound represented by formula (q2). In addition, the compound represented by formula (q3-1) can be produced by reducing the compound represented by formula (q2-1). These reduction methods are not particularly limited and can be implemented by any known method. For example, reduction based on a reducing agent such as a sulfide can be utilized. The above-mentioned sulfide is not particularly limited, and examples thereof include hydrosulfides such as sodium hydrosulfide, potassium hydrosulfide, and ammonium hydrosulfide, and sulfides such as sodium sulfide, potassium sulfide, and ammonium sulfide. They can be anhydrous or contain water of crystallization. The reduction reaction is preferably carried out in the presence of an aqueous solvent. As the aqueous solvent, the same solvents as the above-mentioned aqueous solvents can be mentioned, preferably water, or a mixed solvent of water and a water-soluble organic solvent.

[0336] The diazonium salt represented by formula (q4) can be obtained by diazotizing the amine represented by formula (q3). In addition, the diazonium salt represented by formula (q4-1) can be obtained by diazotizing the amine represented by formula (q3-1). As the method for these diazotizations, the same method as the diazotization of the compounds represented by the above-mentioned formula (pt1-1), formula (pt1-2), formula (pt1-2A), formula (pt11-1), formula (pt11-2), and formula (pt11-2A) can be adopted.

[0337] Compound (I2) can be produced by diazo coupling a diazonium salt represented by formula (q4) with a compound represented by formula (pt3). Compound (I4) can be produced by diazo coupling a diazonium salt represented by formula (q4-1) with a compound represented by formula (pt3-1). As the method for these diazo couplings, the same method as the diazo coupling of the diazonium salt represented by formula (q1-1), formula (q1-2), formula (q11-1) or formula (q11-2) with the compound represented by formula (pt2) can be used.

[0338] In addition, manufacturing with -SO3M or -SO3T 0.5 When the azo dye (I) as a substituent, it can be made by reacting the sulfonic acid group of an alkali metal salt or an alkaline earth metal salt with the sulfonic acid group of the azo dye after manufacturing the azo dye with a sulfonic acid group as a substituent by the above-mentioned method. As the above-mentioned alkali metal compound or alkaline earth metal compound, salts with chloride ions, salts with iodide ions, salts with bromide ions, salts with acetate ions, salts with formate ions, salts with benzoic acid ions, etc. can be enumerated, preferably salts with acetate ions.

[0339] The above reaction with the alkali metal compound or alkaline earth metal compound is preferably carried out in the presence of a mixed solvent of an organic solvent and an aqueous solvent. As the aqueous solvent, the same solvent as the above aqueous solvent can be cited, preferably water. As the organic solvent, ester solvents such as ethyl lactate, butyl lactate, n-butyl acetate, ethyl butyrate, methyl acetoacetate, etc.; ether solvents such as ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, etc.; ketone solvents such as diacetone alcohol; amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, etc.; halogenated solvents such as chloroform and dichloromethane, etc., preferably amide solvents.

[0340] In addition, manufacturing with -SO2N(R 17 )2 as a substituent, the azo dye (I) can be prepared by the above method having a sulfonic acid group as a substituent, reacting the sulfonic acid group of the azo dye with a halogenating agent, and adding a base and NH (R 17 ) 2 is reacted to produce. Examples of the halogenating agent include thionyl chloride, oxalyl chloride, phosphorus trichloride, phosphorus pentachloride and the like.

[0341] Preferably the above-mentioned halogenating agent and base and NH (R 17 The reaction of )2 is carried out in the presence of an organic solvent. Examples of the organic solvent include the same solvents as those mentioned above, and amide solvents and halogen solvents are preferred.

[0342] Examples of the base include organic bases such as triethylamine, 4-(N,N-dimethylamino)pyridine, pyridine, and piperidine; metal alkoxides such as sodium methoxide, sodium ethoxide, sodium tert-butoxide, and potassium tert-butoxide; organic metal compounds such as butyl lithium, tert-butyl lithium, and phenyl lithium; and inorganic bases such as lithium hydroxide, sodium hydroxide, and potassium hydroxide. Among them, organic bases are preferred.

[0343] The method for obtaining the azo dye (I) (for example, azo dye (I1)~(I4)) as the target compound from the reaction mixture is not particularly limited, and known various methods can be used. For example, acid (for example, acetic acid, etc.) can be added to the reaction mixture as required, and the crystal separated out can be filtered out. Alternatively, the solvent of the reaction mixture can be distilled off after the reaction is completed, a small amount of methanol is added to stir, acid (for example, acetic acid, etc.) and water are added to the resulting solution, and the crystal separated out can be filtered out. The crystal separated out can be cleaned with solvents such as water and methanol, or can be further dried. In addition, known methods such as recrystallization can be utilized as required for further purification.

[0344] When the obtained crystal structure of the azo dye (I) does not show the above-mentioned predetermined X-ray diffraction pattern, the obtained crystal is treated by the method comprising the above-mentioned contacting step and separating step to obtain a crystal structure showing the predetermined X-ray diffraction pattern.

[0345] <Colored curable resin composition>

[0346] The azo dye (Aa) (preferably the above-mentioned azo dye (Ia)) having a predetermined crystal structure may be contained in the following colored curable resin composition.

[0347] The colored curable resin composition of the present invention comprises the above-mentioned azo dye (Aa) (preferably the above-mentioned azo dye (Ia)), a resin (hereinafter referred to as resin (B)), a polymerizable compound (hereinafter referred to as polymerizable compound (C)), a polymerization initiator (hereinafter referred to as polymerization initiator (D)) and a solvent (hereinafter referred to as solvent (E)). The above-mentioned azo dye (Aa) can be used as a colorant (hereinafter referred to as colorant (A1)).

[0348] The colored curable resin composition of the present invention may further contain a leveling agent (hereinafter, also referred to as a leveling agent (F)).

[0349] In addition, in this specification, the compound illustrated as each component can be used individually or in combination of 2 or more types unless otherwise specified.

[0350] <Colorant (A1)>

[0351] The colorant (A1) contains an azo dye (Aa) having a predetermined crystal structure. When the colorant (A) contains the azo dye (Aa), a color filter having improved heat resistance and light resistance can be formed from a colored curable resin composition containing the colorant.

[0352] <Azo dyes (Aa)>

[0353] As described above, the preferred embodiment of the azo dye (Aa) is also the same.

[0354] The content of the azo dye (Aa) is preferably 30% by mass or more, more preferably 40% by mass or more, further preferably 50% by mass or more, further preferably 60% by mass or more, further preferably 70% by mass or more, further preferably 80% by mass or more, and may be 100% by mass or less, or 95% by mass or less, based on the total amount of the colorant (A1).

[0355] <Colorant (A1)>

[0356] The colorant (A1) may include a colorant different from the azo colorant (Aa) in addition to the azo colorant (Aa). The colorant different from the azo colorant (Aa) may be any one of a dye (hereinafter, also referred to as a dye (A1-1)) and a pigment (hereinafter, also referred to as a pigment (A1-2)), and the colorant different from the azo colorant (Aa) may include one or both of these dyes (A1-1) and pigments (A1-2).

[0357] As long as the dye (A1-1) does not contain an azo dye (Aa), known dyes can be used without particular limitation, and examples thereof include solvent dyes, acid dyes, direct dyes, mordant dyes, and the like. Examples of dyes include compounds classified as substances having a hue other than pigments in the Color Index (published by The Society of Dyers and Colourists), and known dyes described in the Dyeing Guide (published by Dyeing Co., Ltd.). Based on the chemical structure, examples of dyes (A1-1) include cyanine dyes, triphenylmethane dyes, xanthene dyes, phthalocyanine dyes, anthraquinone dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, azomethine dyes, and squaric acid dyes. Dyes, acridine dyes, styryl dyes, coumarin dyes, quinoline dyes, nitro dyes, etc. In addition, the azo dye as the dye (A1-1) may include azo dyes other than the azo dye (Aa) according to the crystal structure. Among them, the dye (A1-1) is preferably an organic solvent-soluble dye.

[0358] Specific examples of the dye (A1-1) include CI Solvent Yellow 4 (hereinafter, CI Solvent Yellow is omitted and only the number is described), 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 117, 162, 163, 167, and 189;

[0359] CI Solvent Red 45, 49, 111, 125, 130, 143, 145, 146, 150, 151, 155, 168, 169, 172, 175, 181, 207, 218, 222, 227, 230, 245, 247;

[0360] CI Solvent Orange 2, 7, 11, 15, 26, 56, 77, 86;

[0361] CI Solvent Violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60;

[0362] CI Solvent Blue 4, 5, 14, 18, 35, 36, 37, 45, 58, 59, 59:1, 63, 67, 68, 69, 70, 78, 79, 83, 90, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139;

[0363] CI solvent dyes such as CI solvent green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35, etc.

[0364] CI Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 156 7, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251;

[0365] CI Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 33, 34, 35, 37, 40, 42, 44, 50, 51, 52, 57, 66, 73, 76, 80, 87, 88, 91, 92, 94, 95, 97, 98, 103, 106, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 155, 158, 160, 172, 176, 182 , 183, 195, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 289, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, ​​383, 388, 394, 401, 412, 417, 418, 422, 426;

[0366] CI Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173;

[0367] CI Acid Violet 6B, 7, 9, 15, 16, 17, 19, 21, 23, 24, 25, 30, 34, 38, 49, 72, 102;

[0368] CI Acid Blue 1, 3, 5, 7, 9, 11, 13, 15, 17, 18, 22, 23, 24, 25, 26, 27, 29, 34, 38, 40, 41, 42, 43, 45, 48, 51, 54, 59, 60, 62, 70, 72, 74, 75, 78, 80, 82, 83, 86, 87, 88, 90, 90:1, 91, 92, 93, 93:1, 96, 99, 100, 102, 103, 104, 108, 109, 110, 112, 113, 117, 119, 120, 123 , 126, 127, 129, 130, 131, 138, 140, 142, 143, 147, 150, 151, 154, 158, 161, 166, 167, 168, 170, 171, 175, 182, 183, 184, 187, 192, 199, 203, 204, 205, 210, 213, 229, 234, 236, 242, 243, 256, 259, 267, 269, 278, 280, 285, 290, 296, 315, 324:1, 335, 340;

[0369] CI acid green 1, 3, 5, 6, 7, 8, 9, 11, 13, 14, 15, 16, 22, 25, 27, 28, 41, 50, 50:1, 58, 63, 65, 80, 104, 105, 106, 109 and other CI acid dyes,

[0370] CI Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 136, 138, 141;

[0371] CI Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250;

[0372] CI Direct Orange 26, 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;

[0373] CI Direct Violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104;

[0374] CI Direct Blue 1, 2, 3, 6, 8, 15, 22, 25, 28, 29, 40, 41, 42, 47, 52, 55, 57, 71, 76, 77, 78, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 120, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167 7, 168, 170, 171, 172, 173, 188, 189, 190, 192, 193, 194, 195, 196, 198, 199, 200, 201, 202, 203, 207, 209, 210, 212, 213, 214, 222, 225, 226, 228, 229, 236, 237, 238, 242, 243, 244, 245, 246, 247, 248, 249, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293;

[0375] CI direct green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82 and other CI direct dyes,

[0376] CI Disperse Yellow 51, 54, 76;

[0377] CI Disperse Violet 26, 27;

[0378] CI disperse blue 1, 14, 56, 60 and other CI disperse dyes,

[0379] CI Basic Red 1, 10;

[0380] CI basic blue 1, 3, 5, 7, 9, 19, 21, 22, 24, 25, 26, 28, 29, 40, 41, 45, 47, 54, 58, 59, 60, 64, 65, 66, 67, 68, 81, 83, 88, 89;

[0381] CI Basic Violet 2;

[0382] CI Basic Red 9;

[0383] CI basic green 1; etc. CI basic dyes,

[0384] CI Reactive Yellow 2, 76, 116;

[0385] CI Reactive Orange 16;

[0386] CI Reactive Red 36; etc. CI Reactive Dyes,

[0387] CI Medium Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;

[0388] CI Medium Red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 27, 29, 30, 32, 33, 36, 37, 38, 39, 41, 42, 43, 45, 46, 48, 52, 53, 56, 62, 63, 71, 74, 76, 78, 85, 86, 88, 90, 94, 95;

[0389] CI Medium Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48;

[0390] CI medium violet 1, 1:1, 2, 3, 4, 5, 6, 7, 8, 10, 11, 14, 15, 16, 17, 18, 19, 21, 22, 23, 24, 27, 28, 30, 31, 32, 33, 36, 37, 39, 40, 41, 44, 45, 47, 48, 49, 53, 58;

[0391] CI Medium Blue 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43, 44, 48, 49, 53, 61, 74, 77, 83, 84;

[0392] CI mordant green 1, 3, 4, 5, 10, 13, 15, 19, 21, 23, 26, 29, 31, 33, 34, 35, 41, 43, 53 and other CI mordant dyes,

[0393] CI vat dyes such as CI vat green 1, etc.

[0394] These dyes may be appropriately selected so as to match the spectral spectrum of a desired color filter.

[0395] When the colorant (A1) contains the dye (A1-1), the content thereof is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, further preferably 1% by mass or more, further preferably 3% by mass or more, and is preferably 15% by mass or less, more preferably 10% by mass or less, based on the total amount of the colorant (A1).

[0396] As the pigment (A1-2), any known pigment may be used without particular limitation as long as it does not contain an azo dye (Aa), and examples thereof include pigments classified as pigments in the Color Index (published by The Society of Dyers and Colourists).

[0397] Examples of the pigment (A1-2) include yellow pigments such as CI Pigment Yellow 1, 3, 10, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 81, 83, 86, 93, 94, 109, 110, 117, 125, 128, 129, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 185, 194, 214, and 231;

[0398] CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 62, 64, 65, 71, 72, 73 and other orange pigments;

[0399] CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 179, 180, 190, 192, 202, 209, 215, 216, 224, 242, 254, 255, 264, 265, 266, 268, 269, 273, 291, 295, 296 and other red pigments;

[0400] CI Pigment Blue 15, 15:3, 15:4, 15:6, 60 and other blue pigments;

[0401] CI Pigment Violet 1, 19, 23, 29, 32, 36, 38 and other purple pigments;

[0402] CI Pigment Green 7, 36, 58, 59, 62, 63 and other green pigments;

[0403] CI Pigment Brown 23, 25 and other brown pigments;

[0404] Black pigments such as CI Pigment Black 1, 7, etc.

[0405] The pigment may be subjected to rosin treatment, surface treatment using a pigment derivative into which an acidic group or a basic group is introduced, grafting treatment on the pigment surface using a polymer compound, micronization treatment using a sulfuric acid micronization method, or a cleaning treatment using an organic solvent, water, or the like for removing impurities, or removal treatment of ionic impurities using an ion exchange method, etc., as required.

[0406] As the colorant (A1) other than the azo dye (Aa), the pigment (A1-2) is preferred, and the pigment surface-treated with the above-mentioned pigment derivative is more preferred. By using the pigment surface-treated with the pigment derivative, the dispersibility of the azo dye (Aa) in the colored curable resin composition is improved.

[0407] Preferred examples of the pigment surface-treated with a pigment derivative include compounds (A1-21) having a pigment (preferably an organic pigment) as a base material and a sulfonic acid group or a salt thereof, or a sulfonamide group bonded to the base material (hereinafter also referred to as compound (A1-21)).

[0408] As the compound (A1-21), at least one of sulfonic acid and sulfonic acid amine salt is preferably bonded.

[0409] The organic pigment as the matrix of the compound (A1-21) is preferably a quinophthalone pigment such as CI Pigment Yellow 138, CI Pigment Yellow 231, or CI Pigment Yellow 233, and more preferably CI Pigment Yellow 138.

[0410] Compound (A1-21) can be produced according to the contents described in, for example, JP-A-2002-179979.

[0411] The pigment preferably has a uniform particle size. By performing a dispersion treatment containing a dispersant, a pigment dispersion in which the pigment is uniformly dispersed in a solution can be obtained.

[0412] As the above-mentioned dispersant, for example, surfactants such as cationic, anionic, nonionic, amphoteric, polyester, polyamine, acrylic acid, etc. can be enumerated. These dispersants can be used alone or in combination of two or more. As dispersant, represented by trade name, KP (Shin-Etsu Chemical Industry (Strain) system), FLOWLEN (Kyoeisha Chemical (Strain) system), Solsperse (Zeneca (Strain) system), EFKA (BASF company system), AJISPER (Ajinomoto Fine Chemicals (Strain) system), Disperbyk (BYK-Chemie company system) etc. can be enumerated.

[0413] When a dispersant is used, its usage amount is preferably 1 to 100% by mass, more preferably 5 to 50% by mass, relative to the total amount of the pigment. When the usage amount of the dispersant is within the above range, a uniformly dispersed pigment dispersion tends to be obtained.

[0414] When the colorant (A1) contains the pigment (A1-2), the content thereof is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, further preferably 0.5% by mass or more, further preferably 0.8% by mass or more, and is preferably 15% by mass or less, more preferably 10% by mass or less, based on the total amount of the colorant (A1).

[0415] The content of the colorant (A1) is preferably 0.1% to 70% by mass, more preferably 0.5% to 60% by mass, and further preferably 1% to 50% by mass relative to the total amount of the solid component. If the content of the colorant (A1) is within the above range, the color concentration when the color filter is prepared is sufficient, and the composition contains the required amounts of the resin (B) and the polymerizable compound (C), so that a colored coating film (colored pattern) with sufficient mechanical strength can be formed.

[0416] Here, the "total amount of solid content" in this specification refers to the amount obtained by removing the content of the solvent from the total amount of the colored curable resin composition. The total amount of solid content and the content of each component relative to the total amount can be measured by known analytical means such as liquid chromatography or gas chromatography.

[0417] <Resin (B)>

[0418] The resin (B) is not particularly limited, but is preferably an alkali-soluble resin. Examples of the resin (B) include the following resins [K1] to [K6], and at least one selected from the resins [K1] to [K6] is preferred.

[0419] Resin [K1]: A copolymer having a structural unit derived from at least one monomer (a) selected from unsaturated carboxylic acids and unsaturated carboxylic anhydrides (hereinafter, also referred to as “(a)”), and a structural unit derived from a monomer (b) having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond (hereinafter, also referred to as “(b)”);

[0420] Resin [K2]: a copolymer having a structural unit derived from the above-mentioned (a), a structural unit derived from the above-mentioned (b), and a structural unit derived from a monomer (c) copolymerizable with (a) (which is different from (a) and (b)) (hereinafter also referred to as "(c)");

[0421] Resin [K3]: a copolymer having a structural unit derived from the above (a) and a structural unit derived from the above (c);

[0422] Resin [K4]: a copolymer having a structural unit derived from the structural unit derived from the above-mentioned (a) to which the above-mentioned (b) is added and a structural unit derived from the above-mentioned (c), and a copolymer containing a structural unit derived from (a) to which (b) is not added;

[0423] Resin [K4′]: a copolymer having a structural unit derived from the structural unit of the above-mentioned (a) to which the above-mentioned (b) is added and a structural unit derived from the above-mentioned (c), and is a copolymer not containing a structural unit derived from (a) to which (b) is not added;

[0424] Resin [K5]: a copolymer having a structural unit derived from the structural unit derived from the above-mentioned (b) to which the above-mentioned (a) is added and a structural unit derived from the above-mentioned (c) (it may contain a structural unit derived from (b) to which (a) is not added, but preferably does not contain);

[0425] Resin [K6]: A copolymer having a structural unit derived from the structural unit derived from the above-mentioned (b) to which the above-mentioned (a) and further to which a carboxylic acid anhydride are added, and a structural unit derived from (c).

[0426] Specific examples of (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, and o-, m-, and p-vinylbenzoic acid;

[0427] Unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid, 1,4-cyclohexenedicarboxylic acid, etc.;

[0428] Bicyclic unsaturated compounds containing a carboxyl group, such as methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene, 5-carboxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo[2.2.1]hept-2-ene, and 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene;

[0429] Unsaturated dicarboxylic anhydrides such as maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride;

[0430] Unsaturated mono(meth)acryloyloxyalkyl) esters of polycarboxylic acids having a valence of 2 or more, such as mono(2-(meth)acryloyloxyethyl)succinate and mono(2-(meth)acryloyloxyethyl)phthalate;

[0431] Unsaturated acrylic acid esters containing a hydroxyl group and a carboxyl group in the same molecule, such as α-(hydroxymethyl) acrylate.

[0432] Among them, acrylic acid, methacrylic acid, maleic anhydride and the like are preferred from the viewpoint of copolymerization reactivity and solubility of the obtained resin in a developer (particularly an aqueous alkaline solution).

[0433] In addition, in this specification, "(meth)acrylic acid" means at least one selected from acrylic acid and methacrylic acid. Expressions such as "(meth)acryloyl" and "(meth)acrylate" have the same meaning.

[0434] (b) refers to, for example, a polymerizable compound having a cyclic ether structure having 2 to 4 carbon atoms (e.g., at least one selected from an oxirane ring, an oxetane ring, and a tetrahydrofuran ring) and an ethylenically unsaturated bond. (b) is preferably a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth)acryloyloxy group.

[0435] As (b), for example, there can be mentioned a monomer (b1) having an oxetane group and an ethylenically unsaturated bond (hereinafter also referred to as "(b1)"), a monomer (b2) having an oxetane group and an ethylenically unsaturated bond (hereinafter also referred to as "(b2)"), a monomer (b3) having a tetrahydrofuran group and an ethylenically unsaturated bond (hereinafter also referred to as "(b3)"), and the like.

[0436] Examples of (b1) include a monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized (hereinafter also referred to as “(b1-1)”) and a monomer (b1-2) having a structure in which an alicyclic unsaturated hydrocarbon is epoxidized (hereinafter also referred to as “(b1-2)”).

[0437] Examples of (b1-1) include glycidyl (meth)acrylate, β-methyl glycidyl (meth)acrylate, β-ethyl glycidyl (meth)acrylate, glycidyl vinyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, α-methyl-o-vinyl benzyl glycidyl ether, α-methyl-m-vinyl benzyl glycidyl ether, α-methyl-p-vinyl benzyl glycidyl ether, 2,3-bis(glycidyl)acrylate, 2,4-bis(glycidyloxymethyl)styrene, 2,5-bis(glycidyloxymethyl)styrene, 2,6-bis(glycidyloxymethyl)styrene, 2,3,4-tris(glycidyloxymethyl)styrene, 2,3,5-tris(glycidyloxymethyl)styrene, 2,3,6-tris(glycidyloxymethyl)styrene, 3,4,5-tris(glycidyloxymethyl)styrene, 2,4,6-tris(glycidyloxymethyl)styrene, etc.

[0438] Examples of (b1-2) include vinylcyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane (e.g., Celloxide 2000; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth)acrylate (e.g., Cyclomer A400; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth)acrylate (e.g., Cyclomer M100; manufactured by Daicel Corporation), compounds represented by formula (R1), and compounds represented by formula (R2).

[0439]

[0440] [In formula (R1) and formula (R2), R ra and R rb It represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted by a hydroxyl group.

[0441] X ra and X rb Indicates a single bond, *-R rc -, * - R rc -O-, *-R rc -S-, or *-R rc -NH-.

[0442] R rc It represents an alkanediyl group having 1 to 6 carbon atoms.

[0443] * indicates the bonding site with O. ]

[0444] Examples of the alkyl group having 1 to 4 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group and tert-butyl group.

[0445] Examples of the alkyl group in which a hydrogen atom is substituted with a hydroxy group include hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, 1-hydroxy-1-methylethyl, 2-hydroxy-1-methylethyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl and 4-hydroxybutyl.

[0446] As R ra and R rb , preferably, a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group, and a 2-hydroxyethyl group are mentioned, and more preferably, a hydrogen atom and a methyl group are mentioned.

[0447] Examples of the alkanediyl group include a methylene group, an ethylene group, a propane-1,2-diyl group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, and a hexane-1,6-diyl group.

[0448] As X ra and X rb , preferably, a single bond, a methylene group, an ethylene group, *-CH2-O-, and *-CH2CH2-O-, and more preferably, a single bond and *-CH2CH2-O- (* represents a bonding site with O).

[0449] Examples of the compound represented by formula (R1) include compounds represented by any one of formula (R1-1) to formula (R1-15). Among them, preferred are compounds represented by formula (R1-1), formula (R1-3), formula (R1-5), formula (R1-7), formula (R1-9) or formula (R1-11) to formula (R1-15), and more preferred are compounds represented by formula (R1-1), formula (R1-7), formula (R1-9) or formula (R1-15).

[0450]

[0451]

[0452] Examples of the compound represented by formula (R2) include compounds represented by any one of formula (R2-1) to formula (R2-15). Among them, preferred are compounds represented by formula (R2-1), formula (R2-3), formula (R2-5), formula (R2-7), formula (R2-9) or formula (R2-11) to formula (R2-15), and more preferred are compounds represented by formula (R2-1), formula (R2-7), formula (R2-9) or formula (R2-15).

[0453]

[0454]

[0455] The compound represented by formula (R1) and the compound represented by formula (R2) may be used alone or in combination of two or more thereof. When the compound represented by formula (R1) and the compound represented by formula (R2) are used in combination, the ratio of their content [compound represented by formula (R1): compound represented by formula (R2)] is preferably 5:95 to 95:5, more preferably 20:80 to 80:20 on a molar basis.

[0456] As (b2), a monomer having an oxetane group and a (meth)acryloyloxy group is more preferred. Examples of (b2) include 3-methyl-3-methacryloyloxymethyloxetane, 3-methyl-3-acryloyloxymethyloxetane, 3-ethyl-3-methacryloyloxymethyloxetane, 3-ethyl-3-acryloyloxymethyloxetane, 3-methyl-3-methacryloyloxyethyloxetane, 3-methyl-3-acryloyloxyethyloxetane, 3-ethyl-3-methacryloyloxyethyloxetane, and 3-ethyl-3-acryloyloxyethyloxetane.

[0457] As (b3), a monomer having a tetrahydrofuranyl group and a (meth)acryloyloxy group is more preferred. Specific examples of (b3) include tetrahydrofurfuryl acrylate (for example, Viscoat V#150, manufactured by Osaka Organic Chemical Industry Co., Ltd.) and tetrahydrofurfuryl methacrylate.

[0458] (b) is preferably (b1) from the viewpoint of being able to improve the reliability of the obtained color filter in terms of heat resistance, chemical resistance, etc. Furthermore, from the viewpoint of excellent storage stability of the colored curable resin composition, (b1-2) is more preferred.

[0459] Examples of (c) include (meth)acrylate monomers, unsaturated carboxylic acid esters such as unsaturated dicarboxylic acid esters, and vinyl monomers having an unsaturated aliphatic hydrocarbon ring, an unsaturated heterocyclic ring, or an aromatic ring.

[0460] Examples of the (meth)acrylate monomer include (meth)acrylates having a linear or branched aliphatic saturated hydrocarbon group such as methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, and cyclopentyl (meth)acrylate;

[0461] (Meth)acrylates having a linear or branched aliphatic unsaturated hydrocarbon group such as allyl (meth)acrylate and propargyl (meth)acrylate;

[0462] Cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclohexyl (meth)acrylate [5.2.1.0 2,6 ] (meth)acrylates having a cyclic saturated hydrocarbon group, such as decane-8-yl ester (in the technical field, it is commonly known as "dicyclopentanyl (meth)acrylate". In addition, it is sometimes referred to as "tricyclodecyl (meth)acrylate"), isobornyl (meth)acrylate, and adamantyl (meth)acrylate;

[0463] (Meth)acrylic acid tricyclic [5.2.1.0 2,6 ] (meth)acrylates having a cyclic unsaturated aliphatic hydrocarbon group, such as decen-8-yl ester (in the technical field, it is commonly known as "dicyclopentenyl (meth)acrylate") and dicyclopentyloxyethyl (meth)acrylate;

[0464] (Meth)acrylates having an aromatic ring, such as phenyl (meth)acrylate, naphthyl (meth)acrylate, benzyl (meth)acrylate, and phenoxybenzyl (meth)acrylate;

[0465] (Meth)acrylates containing a hydroxyl group, such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate.

[0466] Examples of the unsaturated dicarboxylic acid ester include dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, and diethyl itaconate.

[0467] Among these unsaturated carboxylic acid esters, (meth)acrylic acid C such as methyl methacrylate and 2-ethylhexyl acrylate are preferred. 1-10 Alkyl ester; (meth)acrylic acid tricyclic [5.2.1.0 2,6 ] decane-8-yl ester and other (meth)acrylates having a cyclic saturated hydrocarbon group; (meth)acrylate tricyclic [5.2.1.0 2,6 ] (meth)acrylates having a cyclic unsaturated aliphatic hydrocarbon group such as decen-8-yl ester; (meth)acrylates having an aromatic ring such as benzyl (meth)acrylate and phenoxybenzyl (meth)acrylate, etc.

[0468] Examples of the vinyl monomer having an unsaturated aliphatic hydrocarbon ring include bicyclo[2.2.1]hept-2-ene (also referred to as 2-norbornene), 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxybicyclo[2.2.1]hept-2-ene, 5-hydroxymethylbicyclo[2.2.1]hept-2-ene, 5-(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5-methoxybicyclo[2.2.1]hept-2-ene, 5-ethoxybicyclo[2.2.1]hept-2-ene, 5,6-dihydroxybicyclo[2.2.1]hept-2-ene, 5,6-bis(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6-bis(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene. 2.1]hept-2-ene, 5,6-dimethoxybicyclo[2.2.1]hept-2-ene, 5,6-diethoxybicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxymethyl-5-methylbicyclo[2.2.1]hept-2-ene, 5 Bicyclic unsaturated compounds such as tert-butyloxycarbonylbicyclo[2.2.1]hept-2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]hept-2-ene, 5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-bis(tert-butyloxycarbonyl)bicyclo[2.2.1]hept-2-ene and 5,6-bis(cyclohexyloxycarbonyl)bicyclo[2.2.1]hept-2-ene.

[0469] Examples of the vinyl monomer having an unsaturated heterocyclic ring include dicarbonyl imide derivatives such as N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidohexanoate, N-succinimidyl-3-maleimidopropionate, and N-(9-acridinyl)maleimide.

[0470] Examples of the vinyl monomer having an aromatic ring include styrene-based monomers such as styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, and p-methoxystyrene.

[0471] Examples of other vinyl monomers include monomers containing a nitrile group such as acrylonitrile and methacrylonitrile; monomers containing a halogen atom such as vinyl chloride and vinylidene chloride; acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, and 2,3-dimethyl-1,3-butadiene.

[0472] Among these vinyl monomers, preferred are styrene-based monomers such as styrene and vinyltoluene, dicarbonyl imide derivatives such as N-phenylmaleimide, N-cyclohexylmaleimide, and N-benzylmaleimide, and bicyclic unsaturated compounds such as bicyclo[2.2.1]hept-2-ene (also referred to as 2-norbornene) from the viewpoint of copolymerization reactivity and heat resistance.

[0473] The structural unit derived from (a) to which the structural unit (b) is added refers to a unit formed by addition bonding of (b) to the structural unit derived from (a) constituting the main chain of the copolymer, and has a side chain unsaturated group derived from (b). In this structural unit, (a) can be any of the compounds exemplified above, and (b) can also be any of the compounds exemplified above. As (a), unsaturated monocarboxylic acids such as (meth)acrylic acid are preferred. As (b), monomers (b1) having an oxirane group and an ethylenically unsaturated bond are preferred, and monomers (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized are more preferred.

[0474] The structural unit derived from (b) to which the structural unit derived from (a) is added refers to a unit formed by addition bonding of (a) to the structural unit derived from (b) constituting the main chain of the copolymer, and has a side chain unsaturated group derived from (a). In this structural unit, (b) can be any of the compounds exemplified above, and (a) can also be any of the compounds exemplified above. As (b), a monomer (b1) having an oxirane group and an ethylenically unsaturated bond is preferred, and a monomer (b1-1) having a structure in which a straight-chain or branched aliphatic unsaturated hydrocarbon is epoxidized is more preferred. As (a), an unsaturated monocarboxylic acid such as (meth)acrylic acid is preferred.

[0475] The structural unit to which (a) is added and further to which carboxylic anhydride is added is a structural unit in which (a) is bonded to the structural unit from (b) constituting the main chain of the copolymer to generate a hydroxyl group, and the carboxylic anhydride is bonded to the hydroxyl group by half-esterification, and has a side chain carboxyl group from the carboxylic anhydride and a side chain unsaturated group from (a). In this structural unit, (b) can be any of the compounds exemplified above, and (a) can also be any of the compounds exemplified above. As (b), a monomer (b1) having an oxirane group and an ethylenically unsaturated bond is preferred, and a monomer (b1-1) having a structure in which a straight-chain or branched aliphatic unsaturated hydrocarbon is epoxidized is more preferred. As (a), an unsaturated monocarboxylic acid such as (meth)acrylic acid is preferred.

[0476] Examples of the carboxylic acid anhydride include saturated aliphatic polycarboxylic acid anhydrides such as malonic anhydride, succinic anhydride, glutaric anhydride, and adipic anhydride; unsaturated aliphatic polycarboxylic acid anhydrides such as maleic anhydride, citraconic anhydride, and itaconic anhydride; aromatic polycarboxylic acid anhydrides such as 3-vinylphthalic anhydride and 4-vinylphthalic anhydride; and polycarboxylic acid anhydrides such as alicyclic polycarboxylic acid anhydrides such as 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride and 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride.

[0477] In resin [K1], the ratio of the structural units derived from each unit is preferably 2 to 60 mol% of the structural units derived from (a) and 40 to 98 mol% of the structural units derived from (b), and more preferably 10 to 50 mol% of the structural units derived from (a) and 50 to 90 mol% of the structural units derived from (b), among all the structural units constituting resin [K1].

[0478] In addition, it is preferred that the structural unit derived from (c) is not substantially contained.

[0479] The total amount of the structural units derived from (a) and (b) in all the structural units constituting the resin [K1] is, for example, 90 mol % or more, preferably 95 mol % or more, more preferably 98 mol % or more, particularly preferably 100 mol %.

[0480] When the ratio of the structural unit of the resin [K1] is within the above range, the storage stability of the colored curable resin composition, the developability when forming a colored pattern, and the solvent resistance of the obtained color filter tend to be excellent.

[0481] The resin [K1] can be produced, for example, by the method described in the document "Experimental Methods for Polymer Synthesis" (Otsu Takayuki Publishing Co., Ltd., Chemical Dojin, 1st edition, 1st printing, published on March 1, 1972) and the references described in the document.

[0482] Specifically, the following method can be cited: a predetermined amount of (a) and (b), a polymerization initiator, a solvent, etc. are added to a reaction container, and a deoxygenated atmosphere is formed by replacing oxygen with nitrogen, for example, and heating and heat preservation are performed while stirring. It should be noted that the polymerization initiator and solvent used here are not particularly limited, and polymerization initiators and solvents commonly used in this field can be used. For example, as a polymerization initiator, an azo compound (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile)), an organic peroxide (benzoyl peroxide, etc.) can be cited, and as a solvent, as long as it is a solvent that dissolves each monomer, the solvent described later as the solvent (E) of the colored curable resin composition of the present invention can be cited.

[0483] In addition, the obtained copolymer may be used as a solution after the reaction, or may be used as a concentrated or diluted solution, or may be used as a solid (powder) obtained by a method such as reprecipitation. In particular, by using the solvent contained in the colored curable resin composition of the present invention as a solvent during the polymerization, the solution after the reaction can be used directly for preparing the colored curable resin composition of the present invention, so that the production process of the colored curable resin composition of the present invention can be simplified.

[0484] In resin [K2], the ratio of the structural unit derived from each unit is preferably 1 to 70 mol% of the structural unit derived from (a), 1 to 60 mol% of the structural unit derived from (b), and 20 to 95 mol% of the structural unit derived from (c) in all the structural units constituting resin [K2]. It is more preferred that the structural unit derived from (a) is 3 to 50 mol%, the structural unit derived from (b) is 3 to 40 mol%, and the structural unit derived from (c) is 30 to 90 mol%. It is even more preferred that the structural unit derived from (a) is 5 to 40 mol%, the structural unit derived from (b) is 5 to 30 mol%, and the structural unit derived from (c) is 40 to 80 mol%.

[0485] The total amount of the structural units derived from (a), the structural units derived from (b) and the structural units derived from (c) in all the structural units constituting the resin [K2] is, for example, 90 mol% or more, preferably 95 mol% or more, more preferably 98 mol% or more, and particularly preferably 100 mol%.

[0486] When the ratio of the structural unit of the resin [K2] is within the above range, the storage stability of the colored curable resin composition, the developability when forming a colored pattern, and the solvent resistance, heat resistance and mechanical strength of the obtained color filter tend to be excellent.

[0487] In the resin [K2], (a) is preferably an unsaturated monocarboxylic acid such as (meth)acrylic acid. As (b), a monomer (b1) having an oxirane group and an ethylenically unsaturated bond is preferred, and a monomer (b1-2) having a structure in which an alicyclic unsaturated hydrocarbon is epoxidized is more preferred. As (c), (meth)acrylates having a cyclic unsaturated aliphatic hydrocarbon group, (meth)acrylates having an aromatic ring, and dicarbonyl imide derivatives are preferred.

[0488] The resin [K2] can be produced, for example, in the same manner as described as the method for producing the resin [K1].

[0489] In resin [K3], the ratio of the structural units derived from each unit is preferably 2 to 60 mol% of the structural units derived from (a) and 40 to 98 mol% of the structural units derived from (c) in all the structural units constituting resin [K3]. It is more preferred that the structural units derived from (a) are 10 to 50 mol% and the structural units derived from (c) are 50 to 90 mol%. It is even more preferred that the structural units derived from (a) are 35 to 45 mol% and the structural units derived from (c) are 55 to 65 mol%.

[0490] In addition, it is preferred that the structural unit derived from (b) is not substantially contained.

[0491] The total amount of the structural units derived from (a) and (c) in all the structural units constituting the resin [K3] is, for example, 90 mol% or more, preferably 95 mol% or more, more preferably 98 mol% or more, particularly preferably 100 mol%.

[0492] Among the resins [K3], (a) is preferably an unsaturated monocarboxylic acid such as (meth)acrylic acid, and (c) is preferably a (meth)acrylate having an aromatic ring.

[0493] The resin [K3] can be produced, for example, in the same manner as described as the method for producing the resin [K1].

[0494] In the resin [K4], the ratio of the structural unit derived from each unit is preferably 1 to 60 mol% of the structural unit derived from (a) (without addition of (b)), 1 to 50 mol% of the structural unit obtained by adding (b) to the structural unit derived from (a), and 30 to 90 mol% of the structural unit derived from (c), more preferably 5 to 50 mol% of the structural unit derived from (a) (without addition of (b)), 5 to 40 mol% of the structural unit obtained by adding (b) to the structural unit derived from (a), and 35 to 80 mol% of the structural unit derived from (c), and even more preferably 10 to 40 mol% of the structural unit derived from (a) (without addition of (b)), 10 to 25 mol% of the structural unit obtained by adding (b) to the structural unit derived from (a), and 40 to 75 mol% of the structural unit derived from (c).

[0495] The total amount of the structural units derived from (a) (without addition of (b)), the structural units derived from (a) to which (b) is added, and the structural units derived from (c) is, for example, 90 mol% or more, preferably 95 mol% or more, more preferably 98 mol% or more, and particularly preferably 100 mol% in all the structural units constituting the resin [K4].

[0496] As the structural unit derived from (a) (without addition of (b)), a structural unit derived from an unsaturated monocarboxylic acid such as (meth)acrylic acid is preferred. As the structural unit obtained by adding (b) to the structural unit derived from (a), a structural unit obtained by adding a monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized to the structural unit derived from an unsaturated monocarboxylic acid such as (meth)acrylic acid is preferred. As the structural unit derived from (c), one or more selected from (meth)acrylates having a linear or branched aliphatic saturated hydrocarbon group, (meth)acrylates having a cyclic saturated hydrocarbon group, (meth)acrylates having an aromatic ring, bicyclic unsaturated compounds and styrene-based monomers are preferred, and two or more are more preferred. When there are two constituent units derived from (c), (c) is preferably two selected from unsaturated carboxylates such as (meth)acrylates, (meth)acrylates having a cyclic saturated hydrocarbon group, and (meth)acrylates having an aromatic ring, and two or more selected from vinyl monomers such as bicyclic unsaturated compounds and styrene-based monomers.

[0497] The resin [K4] can be produced by obtaining a copolymer of (a) and (c), and adding the cyclic ether having 2 to 4 carbon atoms contained in (b) to the carboxylic acid and / or carboxylic anhydride contained in (a).

[0498] First, a copolymer of (a) and (c) is produced in the same manner as described as the method for producing resin [K1]. In this case, the ratio of the structural units derived from each is preferably the same ratio as that exemplified in resin [K3].

[0499] Next, a part of the carboxylic acid and / or carboxylic anhydride derived from (a) in the above copolymer is reacted with the cyclic ether having 2 to 4 carbon atoms contained in (b).

[0500] After producing the copolymer of (a) and (c), the atmosphere in the flask is replaced from nitrogen to air, and (b), a reaction catalyst of carboxylic acid or carboxylic anhydride and cyclic ether (e.g., tris(dimethylaminomethyl)phenol, etc.), and a polymerization inhibitor (e.g., hydroquinone, etc.) are placed in the flask and reacted at, for example, 60 to 130° C. for 1 to 10 hours, thereby producing resin [K4].

[0501] The amount of (b) used is preferably 5 to 80 mol, more preferably 10 to 75 mol, relative to 100 mol of (a). By being within this range, there is a tendency that the storage stability of the colored curable resin composition, the developability when forming a pattern, and the balance of the solvent resistance, heat resistance, mechanical strength and sensitivity of the obtained pattern become good.

[0502] The amount of the reaction catalyst used is preferably 0.001 to 5 parts by mass relative to 100 parts by mass of the total amount of (a), (b) and (c). The amount of the polymerization inhibitor used is preferably 0.001 to 5 parts by mass relative to 100 parts by mass of the total amount of (a), (b) and (c).

[0503] The reaction conditions such as the charging method, reaction temperature and time can be appropriately adjusted in consideration of the production equipment, the calorific value based on the polymerization, etc. It should be noted that the charging method and reaction temperature can be appropriately adjusted in consideration of the production equipment, the calorific value based on the polymerization, etc., similarly to the polymerization conditions.

[0504] In the resin [K4'], the ratio of the structural units derived from each unit is preferably 5 to 95 mol% of the structural units derived from (a) and (b) in all the structural units constituting the resin [K4'], and 5 to 95 mol% of the structural units derived from (c). It is more preferred that the structural units derived from (a) and (b) are added to each other, and the structural units derived from (c) are 15 to 90 mol%, and 10 to 85 mol%. It is even more preferred that the structural units derived from (a) and (b) are added to each other, and the structural units derived from (c) are 20 to 80 mol%, and 20 to 80 mol%.

[0505] Furthermore, the structural unit derived from (a) to which (b) is not added is substantially not contained.

[0506] The total amount of the structural units derived from (a) to which the structural units derived from (b) are added and the structural units derived from (c) is, for example, 90 mol% or more, preferably 95 mol% or more, more preferably 98 mol% or more, particularly preferably 100 mol% of all the structural units constituting the resin [K4'].

[0507] As the structural unit derived from (a) to which (b) is added, preferably, a structural unit derived from an unsaturated monocarboxylic acid such as (meth)acrylic acid to which a monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized is added. As the structural unit derived from (c), preferably, at least one selected from (meth)acrylates having a linear or branched aliphatic saturated hydrocarbon group and (meth)acrylates having a cyclic saturated hydrocarbon group, more preferably at least two selected.

[0508] The resin [K4′] can be produced by referring to the production method of the above-mentioned resin [K4], and the amount of (b) used is preferably 100 mol relative to 100 mol of (a).

[0509] In the resin [K5], the ratio of the structural unit derived from each unit is preferably 0 to 30 mol% of the structural unit derived from (b) (without addition of (a)), 5 to 95 mol% of the structural unit derived from (b) with (a) added, and 5 to 95 mol% of the structural unit derived from (c), more preferably 0 to 10 mol% of the structural unit derived from (b) (without addition of (a)), 15 to 90 mol% of the structural unit derived from (b) with (a) added, and 10 to 85 mol% of the structural unit derived from (c), and even more preferably 0 to 5 mol% of the structural unit derived from (b) (without addition of (a)), 20 to 80 mol% of the structural unit derived from (b) with (a) added, and 20 to 80 mol% of the structural unit derived from (c).

[0510] The total amount of the structural units derived from (b) (without addition of (a)), the structural units derived from (b) to which (a) is added, and the structural units derived from (c) is, for example, 90 mol% or more, preferably 95 mol% or more, more preferably 98 mol% or more, and particularly preferably 100 mol% in all the structural units constituting the resin [K5].

[0511] As the structural unit derived from (b) (without addition of (a)), a structural unit derived from a monomer (b1-1) having a structure in which a straight-chain or branched aliphatic unsaturated hydrocarbon is epoxidized is preferred. As the structural unit obtained by adding (a) to the structural unit derived from (b), a structural unit obtained by adding an unsaturated monocarboxylic acid such as (meth)acrylic acid to the structural unit derived from the monomer (b1-1) having a structure in which a straight-chain or branched aliphatic unsaturated hydrocarbon is epoxidized is preferred. As the structural unit derived from (c), one or more selected from (meth)acrylates having a straight-chain or branched aliphatic saturated hydrocarbon group and (meth)acrylates having a cyclic saturated hydrocarbon group are preferred, and two or more are more preferred.

[0512] As a first step, the resin [K5] is subjected to the same method as the above-mentioned method for producing the resin [K1] to obtain a copolymer of (b) and (c). As described above, the obtained copolymer may be used directly as a solution after the reaction, or may be used after a concentration or dilution, or may be used after being taken out in a solid (powder) form by a method such as reprecipitation.

[0513] The ratio of the structural units derived from (b) and (c) to the total molar number of all structural units constituting the above-mentioned copolymer is preferably 5 to 95 mol% for the structural units derived from (b) and 5 to 95 mol% for the structural units derived from (c), and more preferably 10 to 90 mol% for the structural units derived from (b) and 10 to 90 mol% for the structural units derived from (c).

[0514] Furthermore, resin [K5] can be obtained by reacting the cyclic ether derived from (b) contained in the copolymer of (b) and (c) with the carboxylic acid or carboxylic anhydride contained in (a) under the same conditions as those in the method for producing resin [K4] or resin [K4′].

[0515] The amount of (a) to be reacted with the copolymer is preferably 5 to 100 mol per 100 mol of (b). Since cyclic ethers have high reactivity and unreacted (b) is less likely to remain, (b1) is preferred as (b) to be used in the resin [K5], and (b1-1) is more preferred.

[0516] In the resin [K6], the ratio of the structural unit derived from each unit is preferably 0 to 30 mol% of the structural unit derived from (b) (without addition of (a)), 20 to 85 mol% of the structural unit derived from (b) to which (a) is added (without addition of carboxylic acid anhydride), 2 to 40 mol% of the structural unit derived from (b) to which (a) and further carboxylic acid anhydride are added, and 10 to 60 mol% of the structural unit derived from (c), and more preferably 0 to 10 mol% of the structural unit derived from (b) (without addition of (a)), and 20 to 85 mol% of the structural unit derived from (b) to which (a) and further carboxylic acid anhydride are added. The content of the structural units (without addition of carboxylic acid anhydride) is 40 to 80 mol%, the content of the structural units derived from (b) to which (a) and further carboxylic acid anhydride are added is 3 to 30 mol%, and the content of the structural units derived from (c) is 15 to 50 mol%. More preferably, the content of the structural units derived from (b) (without addition of (a)) is 0 to 5 mol%, the content of the structural units (without addition of carboxylic acid anhydride) obtained by adding (a) to the structural units derived from (b) is 50 to 70 mol%, the content of the structural units derived from (b) to which (a) and further carboxylic acid anhydride are added is 5 to 20 mol%, and the content of the structural units derived from (c) is 20 to 40 mol%.

[0517] The total amount of the structural units derived from (b) (without addition of (a)), the structural units obtained by adding (a) to the structural units derived from (b) (without addition of carboxylic acid anhydride), the structural units obtained by adding (a) to the structural units derived from (b) and further adding carboxylic acid anhydride, and the structural units derived from (c) is, for example, 90 mol% or more, preferably 95 mol% or more, more preferably 98 mol% or more, and particularly preferably 100 mol% in all the structural units constituting the resin [K6].

[0518] As the structural unit derived from (b) (without addition of (a)), a structural unit derived from a monomer (b1-1) having a structure in which a straight-chain or branched aliphatic unsaturated hydrocarbon is epoxidized is preferred. As the structural unit derived from (b) to which (a) is added (without addition of carboxylic anhydride), a structural unit derived from a monomer (b1-1) having a structure in which an unsaturated monocarboxylic acid such as (meth)acrylic acid is added is preferred. As the structural unit derived from (b) to which (a) is added and a carboxylic anhydride is further added, a structural unit derived from a monomer (b1-1) having a structure in which a straight-chain or branched aliphatic unsaturated hydrocarbon is epoxidized is preferably added and an unsaturated monocarboxylic acid such as (meth)acrylic acid is added and a saturated aliphatic polycarboxylic anhydride such as succinic anhydride is further added is preferably added. The structural unit derived from (c) is preferably one or more selected from (meth)acrylates having a linear or branched aliphatic saturated hydrocarbon group and (meth)acrylates having a cyclic saturated hydrocarbon group, and more preferably two or more selected from (meth)acrylates.

[0519] As a first step, the resin [K6] is subjected to the same method as the above-mentioned method for producing the resin [K1] to obtain a copolymer of (b) and (c). As described above, the obtained copolymer may be used directly as a solution after the reaction, or may be used after a concentration or dilution, or may be used after being taken out in a solid (powder) form by a method such as reprecipitation.

[0520] The ratio of the structural units derived from (b) and (c) to the total molar number of all structural units constituting the above-mentioned copolymer is preferably 5 to 95 mol% for the structural units derived from (b) and 5 to 95 mol% for the structural units derived from (c), and more preferably 10 to 90 mol% for the structural units derived from (b) and 10 to 90 mol% for the structural units derived from (c).

[0521] In addition, under the same conditions as the method for producing resin [K4], the cyclic ether derived from (b) in the copolymer of (b) and (c) is reacted with the carboxylic acid or carboxylic anhydride in (a). The amount of (a) used is preferably 80 to 100 mol relative to 100 mol of (b).

[0522] The carboxylic acid anhydride is reacted with the hydroxyl group generated by the reaction of the cyclic ether and the carboxylic acid or carboxylic acid anhydride possessed by (a). The amount of the carboxylic acid anhydride used is preferably 0.05 to 1 mol, more preferably 0.10 to 0.8 mol, and even more preferably 0.13 to 0.7 mol, relative to 1 mol of the amount of (a) used (in other words, 1 mol of the hydroxyl group generated by using (a)).

[0523] Specific examples of the resin (B) include 3,4-epoxycyclohexylmethyl (meth)acrylate / (meth)acrylic acid copolymers, 3,4-epoxytricyclo[5.2.1.0 2,6 ] Decyl ester / (meth)acrylic acid copolymer resin [K1];

[0524] (Meth) acrylate glycidyl / (meth) acrylate benzyl / (meth) acrylic acid copolymer, (meth) acrylate glycidyl / styrene / (meth) acrylic acid copolymer, acrylic acid 3,4-epoxy tricyclic [5.2.1.0 2,6 ]decyl ester / (meth)acrylic acid / N-cyclohexylmaleimide copolymer, 3,4-epoxytricyclo[5.2.1.0 2,6 ] decyl ester / (meth) acrylic acid / N-cyclohexyl maleimide / (meth) acrylic acid 2-hydroxyethyl ester copolymer, 3,4-epoxytricyclo[5.2.1.0 2,6 ]decyl ester / (meth)acrylic acid / N-cyclohexylmaleimide / (meth)acrylic acid tricyclic[5.2.1.0 2,6 ]Decene-8-yl ester copolymer, acrylic acid 3,4-epoxy tricyclic [5.2.1.0 2,6 ]decyl ester / (meth)acrylic acid / benzyl (meth)acrylate copolymer, 3,4-epoxytricyclo[5.2.1.0 2,6 ] decyl ester / (meth)acrylic acid / phenoxybenzyl(meth)acrylate copolymer, 3-methyl-3-(meth)acryloyloxymethyloxetane / (meth)acrylic acid / styrene copolymer and other resins [K2];

[0525] Resins such as benzyl (meth)acrylate / (meth)acrylic acid copolymer and styrene / (meth)acrylic acid copolymer [K3];

[0526] Resins including a resin in which glycidyl (meth)acrylate is added to a part of the carboxylic acid groups of a benzyl (meth)acrylate / (meth)acrylic acid copolymer, a resin in which glycidyl (meth)acrylate is added to a part of the carboxylic acid groups of a tricyclodecyl (meth)acrylate / styrene / (meth)acrylic acid copolymer, a resin in which glycidyl (meth)acrylate is added to a part of the carboxylic acid groups of a tricyclodecyl (meth)acrylate / benzyl (meth)acrylate / (meth)acrylic acid copolymer, a resin in which glycidyl (meth)acrylate is added to a part of the carboxylic acid groups of a norbornene / vinyltoluene / (meth)acrylic acid copolymer, a resin in which glycidyl (meth)acrylate is added to a part of the carboxylic acid groups of a norbornene / styrene / (meth)acrylic acid copolymer, and the like [K4];

[0527] Resins such as a resin obtained by reacting a copolymer of tricyclodecyl (meth)acrylate / (meth)acrylic acid with glycidyl (meth)acrylate, and a resin obtained by reacting a copolymer of tricyclodecyl (meth)acrylate / styrene / (meth)acrylic acid with glycidyl (meth)acrylate [K4'];

[0528] Resins such as a resin obtained by reacting a copolymer of tricyclodecyl (meth)acrylate / glycidyl (meth)acrylate with (meth)acrylic acid, and a resin obtained by reacting a copolymer of tricyclodecyl (meth)acrylate / styrene / glycidyl (meth)acrylate with (meth)acrylic acid [K5];

[0529] Resins obtained by further reacting a copolymer of tricyclodecyl (meth)acrylate / glycidyl (meth)acrylate with (meth)acrylic acid with tetrahydrophthalic anhydride, a resin obtained by further reacting a copolymer of 2-ethylhexyl (meth)acrylate / tricyclodecyl (meth)acrylate / glycidyl (meth)acrylate with (meth)acrylic acid with succinic anhydride, a resin obtained by further reacting a part of the hydroxyl groups of a resin obtained by further reacting a copolymer of 2-ethylhexyl (meth)acrylate / tricyclodecyl (meth)acrylate / glycidyl (meth)acrylate with (meth)acrylic acid with succinic anhydride, a resin obtained by further reacting a copolymer of methyl (meth)acrylate / 2-ethylhexyl (meth)acrylate / tricyclodecyl (meth)acrylate / glycidyl (meth)acrylate with (meth)acrylic acid with succinic anhydride, and the like [K6], etc.

[0530] Resins [K1] to [K6] may be one kind or a combination of two or more kinds. Among them, as resin (B), at least one kind selected from resin [K1] and resin [K2] is preferred, and resin [K1] is particularly preferred.

[0531] The polystyrene-equivalent weight average molecular weight of the resin (B) is preferably 3000 to 100000, more preferably 5000 to 50000, and even more preferably 5000 to 30000. When the molecular weight is within the above range, the hardness of the color filter is improved, the residual film rate is high, the solubility of the unexposed portion in the developer is good, and the resolution of the colored pattern tends to be improved.

[0532] The dispersion degree [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (B) is preferably 1.1-6, more preferably 1.2-4.

[0533] The acid value of the resin (B) is preferably 20 mg-KOH / g to 170 mg-KOH / g, more preferably 25 mg-KOH / g to 150 mg-KOH / g, and further preferably 73 mg-KOH / g to 135 mg-KOH / g, calculated on a solid content basis. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin (B), and can be determined, for example, by titration using an aqueous potassium hydroxide solution.

[0534] The content of the resin (B) is preferably 7% to 85% by mass, more preferably 13% to 80% by mass, and further preferably 15% to 70% by mass relative to the total amount of the solid component. If the content of the resin (B) is within the above range, a colored pattern can be formed, and the resolution and residual film rate of the colored pattern tend to be improved.

[0535] <Polymerizable compound (C)>

[0536] The polymerizable compound (C) is a compound that can be polymerized by active radicals and / or acids generated from the polymerization initiator (D), and examples thereof include compounds having a polymerizable ethylenically unsaturated bond, and are preferably (meth)acrylate compounds.

[0537] Among them, the polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenically unsaturated bonds. Examples of such polymerizable compounds include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol octa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tetrapentaerythritol deca(meth)acrylate, tetrapentaerythritol nona(meth)acrylate, tris(2-(meth)acryloyloxyethyl)isocyanurate, ethylene glycol-modified pentaerythritol tetra(meth)acrylate, ethylene glycol-modified dipentaerythritol hexa(meth)acrylate, propylene glycol-modified pentaerythritol tetra(meth)acrylate, propylene glycol-modified dipentaerythritol hexa(meth)acrylate, caprolactone-modified pentaerythritol tetra(meth)acrylate, and caprolactone-modified dipentaerythritol hexa(meth)acrylate.

[0538] Among them, at least one selected from dipentaerythritol penta(meth)acrylate and dipentaerythritol hexa(meth)acrylate is preferred.

[0539] The weight average molecular weight of the polymerizable compound (C) is preferably 150 to 2,900, more preferably 250 to 1,500.

[0540] The content of the polymerizable compound (C) is preferably 5% to 75% by mass, more preferably 7% to 70% by mass, and further preferably 15% to 70% by mass relative to the total amount of the solid component. When the content of the polymerizable compound (C) is within the above range, there is a tendency for the residual film rate during color pattern formation and the chemical resistance of the color filter to be improved.

[0541] <Polymerization initiator (D)>

[0542] The polymerization initiator (D) is not particularly limited as long as it is a compound that can generate active free radicals, acids, etc. under the action of light or heat and initiate polymerization, and a known polymerization initiator can be used. Examples of polymerization initiators that generate active free radicals include alkylphenone compounds, triazine compounds, acylphosphine oxide compounds, O-acyloxime compounds, and biimidazole compounds.

[0543] The O-acyl oxime compound is a compound having a partial structure represented by formula (d1).

[0544]

[0545] Examples of the O-acyl oxime compounds include N-benzoyloxy-1-(4-phenylthiophenyl)butane-1-one-2-imine, N-benzoyloxy-1-(4-phenylthiophenyl)octane-1-one-2-imine, N-benzoyloxy-1-(4-phenylthiophenyl)-3-cyclopentylpropane-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4-( 3,3-dimethyl-2,4-dioxolanylmethoxy)benzoyl}-9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropane-1-imine, N-benzoyloxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropane-1-one-2-imine, N-acetoxy-1-(4-phenylthiophenyl)-3-cyclohexylpropane-1-one-2-imine, etc. Commercially available products such as Irgacure (registered trademark) OXE01, OXE02 (all manufactured by BASF), N-1919 (manufactured by ADEKA), and PBG-327 (manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.) may also be used. Among them, the O-acyl oxime compound is preferably at least one selected from N-benzoyloxy-1-(4-phenylthiophenyl)butane-1-one-2-imine, N-benzoyloxy-1-(4-phenylthiophenyl)octane-1-one-2-imine, N-acetoxy-1-(4-phenylthiophenyl)-3-cyclohexylpropane-1-one-2-imine and N-benzoyloxy-1-(4-phenylthiophenyl)-3-cyclopentylpropane-1-one-2-imine, and more preferably N-benzoyloxy-1-(4-phenylthiophenyl)octane-1-one-2-imine and N-acetoxy-1-(4-phenylthiophenyl)-3-cyclohexylpropane-1-one-2-imine. When these O-acyl oxime compounds are used, there is a tendency that a color filter with high brightness can be obtained.

[0546] The alkylphenone compound is preferably a compound having a partial structure represented by formula (d2) or a partial structure represented by formula (d3). In these partial structures, the benzene ring may have a substituent.

[0547]

[0548] Examples of the compound having a partial structure represented by formula (d2) include 2-methyl-2-morpholino-1-(4-methylthiophenyl)propane-1-one, 2-dimethylamino-1-(4-morpholinophenyl)-2-benzylbutane-1-one, and 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholino)phenyl]butane-1-one. Commercially available products such as Irgacure (registered trademark) 369, 907, and 379 (all manufactured by BASF) can also be used.

[0549] Examples of the compound having a partial structure represented by formula (d3) include 2-hydroxy-2-methyl-1-phenylpropane-1-one, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propane-1-one, 1-hydroxycyclohexyl phenyl ketone, oligomers of 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propane-1-one, α,α-diethoxyacetophenone, and benzil dimethyl ketal.

[0550] In terms of sensitivity, the alkylphenone compound is preferably a compound having a partial structure represented by formula (d2).

[0551] Examples of the triazine compound include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, and 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine. [2-(5-methylfuran-2-yl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-triazine, and the like.

[0552] Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, etc. Commercially available products such as Irgacure (registered trademark) 819 (manufactured by BASF Corporation) can be used.

[0553] Examples of the biimidazole compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (see, for example, Japanese Patent Application Laid-Open Nos. 6-75372 and 6-75373), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxyphenyl)biimidazole, and 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxyphenyl)biimidazole. (2-Chlorophenyl)-4,4',5,5'-tetrakis(dialkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(trialkoxyphenyl)biimidazole (see, for example, JP-B-48-38403, JP-A-62-174204, etc.), biimidazole compounds in which the phenyl groups at the 4,4',5,5'-positions are substituted with carboalkoxy groups (see, for example, JP-A-7-10913, etc.), and the like.

[0554] In addition, examples of the polymerization initiator (D) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone compounds such as benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, and 2,4,6-trimethylbenzophenone; quinone compounds such as 9,10-phenanthrenequinone, 2-ethylanthraquinone, and camphorquinone; 10-butyl-2-chloroacridone, benzil, methyl benzoylformate, and titanocene compounds, etc. These are preferably used in combination with the polymerization initiator aid (D1) (particularly amines) described later.

[0555] Examples of the acid generator include onium salts such as 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4-acetoxyphenylmethylbenzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, and diphenyliodonium hexafluoroantimonate, nitrobenzyl toluenesulfonates, and benzoin toluenesulfonates.

[0556] The polymerization initiator (D) preferably contains at least one selected from an alkylphenone compound, a triazine compound, an acylphosphine oxide compound, an O-acyloxime compound and a biimidazole compound, and more preferably contains an O-acyloxime compound.

[0557] The content of the polymerization initiator (D) is preferably 0.1 to 30 parts by mass, and more preferably 1 to 20 parts by mass, relative to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). When the content of the polymerization initiator (D) is within the above range, there is a tendency to increase sensitivity and shorten exposure time, thereby improving the productivity of the color filter.

[0558] <Polymerization initiator aid (D1)>

[0559] The polymerization initiator aid (D1) is a compound or sensitizer for accelerating the polymerization of the polymerizable compound to be polymerized by the polymerization initiator. When the polymerization initiator aid (D1) is contained, it is usually used in combination with the polymerization initiator (D).

[0560] Examples of the polymerization initiation aid (D1) include amine compounds, alkoxyanthracene compounds, thioxanthone compounds, and carboxylic acid compounds.

[0561] Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isopentyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl-p-toluidine, 4,4'-bis(dimethylamino)benzophenone (commonly known as Michler's ketone), 4,4'-bis(diethylamino)benzophenone, and 4,4'-bis(ethylmethylamino)benzophenone. Among them, 4,4'-bis(diethylamino)benzophenone is preferred. Commercially available products such as EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.) may also be used.

[0562] Examples of the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, and 2-ethyl-9,10-dibutoxyanthracene.

[0563] Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthone.

[0564] Examples of the carboxylic acid compound include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, and naphthoxyacetic acid.

[0565] When these polymerization initiation aids (D1) are used, their content is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, relative to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). When the amount of the polymerization initiation aid (D1) is within this range, a colored pattern can be formed with higher sensitivity, and there is a tendency to improve the productivity of the color filter.

[0566] <Solvent (E)>

[0567] The solvent (E) is not particularly limited, and a solvent commonly used in this field can be used. For example, ester solvents (solvents containing -COO- and not containing -O- in the molecule), ether solvents (solvents containing -O- and not containing -COO- in the molecule), ether ester solvents (solvents containing -COO- and -O- in the molecule), ketone solvents (solvents containing -CO- and not containing -COO- in the molecule), alcohol solvents (solvents containing OH and not containing -O-, -CO- and -COO- in the molecule), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide, etc. can be mentioned.

[0568] Specific examples of the ester solvent include the same solvents as those exemplified as the ester solvent in the above-mentioned solvent (Z).

[0569] Specific examples of the ether solvent include the same solvents as those exemplified as the ether solvent in the above-mentioned solvent (Z).

[0570] Specific examples of the ether ester solvent include the same solvents as those exemplified as the ether ester solvent in the above-mentioned solvent (Z).

[0571] Specific examples of the ketone solvent include the same solvents as those exemplified as the ketone solvent in the above-mentioned solvent (Z).

[0572] Specific examples of the alcohol solvent include the same solvents as those exemplified as the alcohol solvent in the above solvent (Z).

[0573] Specific examples of the aromatic hydrocarbon solvent include the same solvents as those exemplified as the aromatic hydrocarbon solvent in the above-mentioned solvent (Z).

[0574] Specific examples of the amide solvent include the same solvents as those exemplified as the amide solvent in the above-mentioned solvent (Z).

[0575] Among the above-mentioned solvents, an organic solvent having a boiling point of 120° C. to 180° C. at 1 atm is preferred from the viewpoint of coating properties and drying properties. As the solvent (E), a solvent containing at least one selected from propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 4-hydroxy-4-methyl-2-pentanone and N,N-dimethylformamide is preferred, and a solvent containing at least one selected from propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, ethyl 3-ethoxypropionate and 4-hydroxy-4-methyl-2-pentanone is more preferred.

[0576] The content of the solvent (E) is preferably 55% to 95% by mass, and more preferably 60% to 92% by mass, relative to the total amount of the colored curable resin composition of the present invention. In other words, the total content of the solid content of the colored curable resin composition is preferably 5% to 45% by mass, and more preferably 8% to 40% by mass. When the content of the solvent (E) is within the above range, the flatness during coating becomes good, and the color density is not insufficient when forming a color filter, so there is a tendency for the display characteristics to become good.

[0577] <Leveling agent (F)>

[0578] Examples of the leveling agent (F) include silicone-based surfactants, fluorine-based surfactants, and silicone-based surfactants having fluorine atoms, etc. These may have a polymerizable group in a side chain.

[0579] Examples of the silicone-based surfactant include surfactants having a siloxane bond in the molecule. Specific examples include Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (trade name: manufactured by Dow Corning Toray Co., Ltd.), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, and TSF4460 (manufactured by Momentive Performance Materials Japan Co., Ltd.).

[0580] Examples of the fluorine-based surfactant include surfactants having a fluorine carbon chain in the molecule. Specifically, examples include FLUORAD (registered trademark) FC430, FLUORAD FC431 (manufactured by Sumitomo 3M Co., Ltd.), MEGAFAC (registered trademark) F142D, MEGAFAC F171, MEGAFAC F172, MEGAFAC F173, MEGAFAC F177, MEGAFAC F183, MEGAFAC F554, MEGAFAC R30, MEGAFAC RS-718-K (manufactured by DIC Corporation), F-top (registered trademark) EF301, F-top EF303, F-top EF351, F-top EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), Surflon (registered trademark) S381, Surflon S382, Surflon SC101, Surflon SC105 (manufactured by Asahi Glass Co., Ltd.) and E5844 (manufactured by Daikin Fine Chemicals Laboratories, Ltd.), etc.

[0581] Examples of the above-mentioned organosilicon-based surfactants having fluorine atoms include surfactants having a siloxane bond and a fluorocarbon chain in the molecule, and more specifically, MEGAFAC (registered trademark) R08, MEGAFAC BL20, MEGAFAC F475, MEGAFAC F477, and MEGAFAC F443 (manufactured by DIC Corporation).

[0582] The content of the leveling agent (F) is preferably 0.00001% to 0.2% by mass, more preferably 0.00005% to 0.1% by mass, and further preferably 0.0001% to 0.05% by mass relative to the total amount of the colored curable resin composition. It should be noted that the content of the above-mentioned dispersant is not included in this content. When the content of the leveling agent (F) is within the above range, the flatness of the color filter can be improved.

[0583] <Other ingredients>

[0584] The colored curable resin composition of the present invention may contain additives known in the technical field such as a filler, other polymer compounds, an adhesion promoter, an antioxidant, a light stabilizer, and a chain transfer agent, as required.

[0585] <Method for producing colored curable resin composition>

[0586] The colored curable resin composition of the present invention can be prepared by mixing, for example, an azo dye (Aa), a resin (B), a polymerizable compound (C), a polymerization initiator (D), and a solvent (E), and optionally, a dye (A1-1), a pigment (A1-2), a leveling agent (F), and other components. The mixing can be performed by a known or customary device and conditions.

[0587] The colorant (A1) can be used in a state where it is pre-mixed with a part or all of the solvent (E) and dispersed to an average particle size of about 0.2 μm or less using a bead mill or the like. At this time, a part or all of the above-mentioned dispersant and resin (B) can be combined as needed. It is preferred to prepare the target colored curable resin composition by mixing the remaining components in the dispersion thus obtained in a manner to achieve a specified concentration. When a bead mill is used, the diameter of the grinding beads is preferably 0.05 mm to 0.5 mm, and the material of the grinding beads can include glass, ceramics, metals, etc.

[0588] <Method for manufacturing color filter>

[0589] As a method for manufacturing a color pattern of a color filter by the colored curable resin composition of the present invention, photolithography, inkjet method, printing method, etc. can be cited. Among them, photolithography is preferred. Photolithography is a method in which the above-mentioned colored curable composition is applied to a substrate and dried to form a composition layer, and the composition layer is exposed through a photomask and developed. In the photolithography, a colored coating film as a cured product of the above-mentioned composition layer can be formed without using a photomask and / or developing during exposure.

[0590] The film thickness of the color filter (cured film) is not particularly limited and may be appropriately adjusted depending on the purpose and application, and is, for example, 0.1 μm to 30 μm, preferably 0.1 μm to 20 μm, and more preferably 0.5 μm to 6 μm.

[0591] As the substrate, a glass plate such as quartz glass, borosilicate glass, aluminosilicate glass, soda-lime glass with silicon dioxide coated on the surface, a resin plate such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate, silicon, or a substrate having aluminum, silver, or a silver / copper / palladium alloy thin film formed thereon can be used. Other color filter layers, resin layers, transistors, circuits, etc. can be formed on these substrates. In addition, a substrate treated with HMDS on a silicon substrate can also be used.

[0592] The formation of pixels of each color based on the photolithography method can be carried out using known or customary devices and conditions. For example, it can be produced as described below. First, a curable colored resin composition is applied to a substrate, and heat-dried (pre-baked) and / or dried under reduced pressure to remove volatile components such as solvents and dry them to obtain a smooth composition layer. As coating methods, spin coating, slit coating, slit and spin coating, etc. can be cited. The temperature during heating and drying is preferably 30 to 120°C, more preferably 50 to 110°C. In addition, as a heating time, it is preferably 10 seconds to 60 minutes, more preferably 30 seconds to 30 minutes. When drying under reduced pressure, it is preferably carried out at a temperature range of 20 to 25°C under a pressure of 50 to 150 Pa. The film thickness of the composition layer is not particularly limited, as long as it is appropriately selected according to the film thickness of the target color filter.

[0593] Next, the composition layer is exposed through a photomask for forming a target coloring pattern. The pattern on the photomask is not particularly limited, and a pattern corresponding to the target application is used. As the light source used in the exposure, a light source that produces light with a wavelength of 250 to 450 nm is preferably used. For example, light less than 350 nm can be cut off using a filter that cuts off the wavelength region, or light near 436 nm, near 408 nm, and near 365 nm can be selectively extracted using a bandpass filter that extracts these wavelength regions. Specifically, mercury lamps, light emitting diodes, metal halide lamps, and halogen lamps can be cited. In order to be able to uniformly irradiate parallel light to the entire exposure surface and accurately align the photomask with the substrate, it is preferred to use a reduced projection exposure device or a proximity exposure device such as a mask aligner and a stepper.

[0594] The exposed composition layer is brought into contact with a developer and developed to form a colored pattern on the substrate. By developing, the unexposed portion of the composition layer is dissolved in the developer and removed. As the developer, for example, aqueous solutions of alkaline compounds such as potassium hydroxide, sodium bicarbonate, sodium carbonate and tetramethylammonium hydroxide are preferred. The concentration of these alkaline compounds in the aqueous solution is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass. Furthermore, the developer may contain a surfactant. The developing method may be any one of a rotary immersion method, an immersion method and a spray method. Furthermore, the substrate may be tilted at any angle during development.

[0595] After development, water washing is preferably performed.

[0596] The obtained colored pattern is preferably post-baked. The post-baking temperature is preferably 80 to 250° C., more preferably 100 to 245° C. The post-baking time is preferably 1 to 120 minutes, more preferably 2 to 30 minutes.

[0597] The colored pattern and colored coating film thus obtained are useful as a color filter, and the color filter is useful as a color filter used in a display device (for example, a liquid crystal display device, an organic EL device, etc.), electronic paper, a solid-state imaging element, and the like.

[0598] Example

[0599] Hereinafter, the present invention will be described in more detail by giving examples, but the present invention is not limited to the following examples, and can certainly be implemented by adding appropriate changes within the scope of the above-mentioned and later-described purports, which are all included in the technical scope of the present invention. It should be noted that, below, "parts" means "parts by mass", and "%" means "% by mass", unless otherwise specified.

[0600] The chemical structure of the compound was confirmed by mass spectrometry (LC; Model 1200 manufactured by Agilent, MASS; Model LC / MSD6130 manufactured by Agilent).

[0601] The determination of the crystal structure of the azo dye is carried out by powder X-ray measurement. The conditions of the powder X-ray measurement are as follows. Aluminum oxide as an internal standard is added in a ratio of 50 parts to 50 parts of the azo dye and mixed. As the above-mentioned aluminum oxide, aluminum oxide made by Fujifilm and Wako Pure Chemical Industries, Ltd. is used. For the obtained X-ray diffraction pattern, the difference spectrum with the X-ray diffraction pattern of only the glass sample plate is calculated. In addition, since the thickness of the sample depends on the intensity of the X-ray diffraction pattern, each peak intensity is obtained based on the X-ray diffraction pattern in which the peak intensity I3 of aluminum oxide as an internal standard is standardized to 100,000.

[0602] Device: RINT2000, manufactured by Rigaku Co., Ltd.

[0603] Internal standard: Alumina

[0604] X-ray: Cu-Kα ray

[0605] Device control: centralized method

[0606] Measuring angle: 5~50°

[0607] Voltage:40kV

[0608] Current: 40mA

[0609] The polystyrene-equivalent weight average molecular weight (Mw) and number average molecular weight (Mn) of the resin were measured by GPC (gel permeation chromatography) under the following conditions.

[0610] Equipment: HLC-8120GPC (manufactured by Tosoh Corporation)

[0611] Column:TSK-GELG2000HXL

[0612] Column temperature: 40℃

[0613] Solvent:Tetrahydrofuran

[0614] Flow rate: 1.0mL / min

[0615] Solid content concentration of the analysis sample: 0.001 to 0.01 mass%

[0616] Injection volume: 50μL

[0617] Detector: RI

[0618] Calibration standard substances: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corporation)

[0619] The ratio of the polystyrene-equivalent weight average molecular weight to the number average molecular weight (Mw / Mn) obtained above was defined as the degree of dispersion.

[0620] <Synthesis example 1>

[0621] 33 parts of water and 3.3 parts of 35% hydrochloric acid were added to 2.0 parts of 3-amino-4-methoxybenzanilide and stirred. An aqueous solution prepared by dissolving 0.7 parts of sodium nitrite in 1.8 parts of water was added to the reaction solution under ice cooling and stirred for 2 hours to obtain a suspension containing a diazonium salt. On the other hand, 10 parts of acetic acid, 10 parts of water and 55 parts of methanol were added to 30 parts of 3-methyl-1-phenyl-5-pyrazolone, and then 19 parts of a 25% aqueous sodium hydroxide solution were added under ice cooling and stirred. The suspension containing the diazonium salt was added dropwise thereto. After the addition was completed, the mixture was further stirred at room temperature for 1 hour to obtain a yellow suspension. The yellow solid obtained by filtration was dried at 60°C under reduced pressure to obtain 2.2 parts of azo dye (1-1) composed of a compound represented by formula (AI-1) (yield 64%). MS (ESI) m / z = 427.8 [M] +

[0622] The X-ray diffraction pattern of azo dye (1-1) is shown in Figure 2 , and the X-ray diffraction parameters are shown in Table 6. Figure 2 In the X-ray diffraction spectrum, the peaks at diffraction angles (2θ±0.2°) = 25.5, 35.1, 37.8, 43.3, and 43.4° are derived from aluminum oxide as an internal standard ( Figure 1 and 3 The same is true for ~10). In addition, Figure 2The spectrum shown is a difference spectrum between the azo dye and the glass sample plate, and is a spectrum obtained by normalizing the peak intensity at the diffraction angle (2θ±0.2°)=35.1° from aluminum oxide as an internal standard to 100,000 ( Figure 1 and 3 The same is true for ~10).

[0623]

[0624] <Example 1>

[0625] 0.5 parts of the azo dye (1-1) obtained in Synthesis Example 1, 3.0 parts of N-methylpyrrolidone and 10.5 parts of xylene were mixed, and the mixture in a slurry state was stirred at an internal temperature of 125° C. for 3 hours. After cooling to room temperature, the obtained mixture was filtered, and the obtained residue was dried under reduced pressure at 60° C., thereby obtaining 0.39 parts of azo dye (1) composed of a compound represented by formula (AI-1) (yield 78%).

[0626] The X-ray diffraction pattern of the azo dye (1) is shown in Figure 1 , and the X-ray diffraction parameters are shown in Table 6.

[0627] <Synthesis example 2>

[0628] To 4.4 parts of 4,4'-diaminobenzophenone, 24 parts of acetic acid, 81 parts of water and 8.2 parts of 35% hydrochloric acid were added and stirred. Under ice cooling, an aqueous solution prepared by dissolving 3.6 parts of sodium nitrite in 5.3 parts of water was added to the reaction solution and stirred for 2 hours to obtain a suspension containing a diazonium salt. On the other hand, after adding 132 parts of methanol to 7.2 parts of 3-methyl-1-phenyl-5-pyrazolone, 69 parts of a 25% aqueous sodium hydroxide solution were added and stirred under ice cooling. The suspension containing the diazonium salt was added dropwise thereto. After the addition was completed, the mixture was further stirred at room temperature for 1 hour to obtain a yellow suspension. The yellow solid obtained by filtration was dried at 60°C under reduced pressure to obtain 10 parts (yield 86%) of azo dye (2-1) composed of a compound represented by formula (AI-274). MS (ESI) m / z = 581.0 [M-H] -

[0629] The X-ray diffraction pattern of azo dye (2-1) is shown in Figure 4 , and the X-ray diffraction parameters are shown in Table 6.

[0630]

[0631] <Example 2>

[0632] 0.9 parts of the azo dye (2-1) obtained in Synthesis Example 2 and 24 parts of xylene were mixed, and the mixture in a slurry state was stirred at an internal temperature of 125°C for 3 hours. After cooling to room temperature, 21 parts of methanol were added dropwise and stirred for 1 hour. The obtained mixture was filtered, and the obtained residue was dried under reduced pressure at 60°C, thereby obtaining 0.8 parts of azo dye (2) composed of a compound represented by formula (AI-274) (yield 89%).

[0633] The X-ray diffraction pattern of azo dye (2) is shown in Figure 3 , and the X-ray diffraction parameters are shown in Table 6.

[0634] <Synthesis example 3>

[0635] To 1.0 part of 4,4'-diaminodiphenyl ether, 20 parts of water and 2.0 parts of 35% hydrochloric acid were added and stirred. Under ice cooling, an aqueous solution prepared by dissolving 0.9 parts of sodium nitrite in 1.1 parts of water was added to the reaction solution and stirred for 2 hours to obtain a suspension containing a diazonium salt. On the other hand, after adding 34 parts of methanol, 6.0 parts of acetic acid and 6.5 parts of water to 1.8 parts of 3-methyl-1-phenyl-5-pyrazolone, 12 parts of a 25% aqueous sodium hydroxide solution were added and stirred under ice cooling. The suspension containing the diazonium salt was added dropwise thereto. After the addition was completed, the mixture was further stirred at room temperature for 1 hour to obtain a yellow suspension. The yellow solid obtained by filtration was dried at 60°C under reduced pressure to obtain 2.9 parts of azo dye (3-1) composed of a compound represented by formula (AI-169) (yield 98%). MS (ESI) m / z = 569.2 [M-H] -

[0636] The X-ray diffraction pattern of azo dye (3-1) is shown in Figure 6 , and the X-ray diffraction parameters are shown in Table 6.

[0637]

[0638] <Example 3>

[0639] 0.5 parts of the azo dye (3-1) obtained in Synthesis Example 3, 3.0 parts of N-methylpyrrolidone and 10.5 parts of xylene were mixed, and the mixture in a slurry state was stirred at an internal temperature of 125°C for 3 hours. After cooling to room temperature, 5 parts of acetonitrile were added dropwise and stirred for 1 hour. The obtained mixture was filtered, and the obtained residue was dried under reduced pressure at 60°C to obtain 0.4 parts of azo dye (3) composed of a compound represented by formula (AI-169) (yield 71%).

[0640] The X-ray diffraction pattern of azo dye (3) is shown in Figure 5 , and the X-ray diffraction parameters are shown in Table 6.

[0641] <Synthesis example 4>

[0642] 20 parts of water, 8.0 parts of methanol, 2.0 parts of acetic acid and 5.0 parts of 98% sulfuric acid were added to 2.0 parts of 2,5-dichloro-4-nitroaniline and stirred. Under ice cooling, an aqueous solution prepared by dissolving 1.2 parts of sodium nitrite in 1.8 parts of water was added to the reaction solution and stirred for 2 hours to obtain a suspension containing a diazonium salt. On the other hand, 11 parts of methanol were added to 1.8 parts of 3-cyano-1-butyl-6-hydroxy-4-methyl-2-pyridone, and then 14 parts of a 25% aqueous sodium hydroxide solution were added under ice cooling and stirred. The suspension containing a diazonium salt was added dropwise thereto. After the addition was completed, the suspension was further stirred at room temperature for 1 hour to obtain an orange suspension. The orange solid obtained by filtration was dried at 60°C under reduced pressure to obtain a compound represented by formula (b).

[0643]

[0644] Next, 39 parts of water, 8.0 parts of methanol, 1.6 parts of sodium bicarbonate and 4.7 parts of sodium sulfide nonahydrate were added to 4.1 parts of the compound represented by formula (b), and the mixture was stirred at 85°C for 2 hours. After the reaction solution was cooled to room temperature, the reaction solution was neutralized to pH 6 with 35% hydrochloric acid, and the precipitated solid was filtered out. The obtained solid was washed with water, and the filtered red solid was dried at 60°C under reduced pressure to obtain a compound represented by formula (c).

[0645]

[0646] Next, 16 parts of water, 3.8 parts of acetic acid and 19 parts of 98% sulfuric acid were added to 3.8 parts of the compound represented by formula (c) and stirred. Under ice cooling, an aqueous solution prepared by dissolving 2.0 parts of sodium nitrite in 3.0 parts of water was added to the reaction solution and stirred for 2 hours to obtain a suspension containing a diazonium salt. On the other hand, 11 parts of methanol was added to 1.4 parts of 3-cyano-1-butyl-6-hydroxy-4-methyl-2-pyridone, and then 54 parts of a 25% aqueous sodium hydroxide solution were added under ice cooling and stirred. The suspension containing the diazonium salt was added dropwise thereto. After the addition was completed, the mixture was further stirred at room temperature for 1 hour to obtain a red suspension. The filtered red solid was dispersed and washed with water and methanol for 30 minutes respectively, then filtered and dried at 60°C under reduced pressure to obtain 3.9 parts of azo dye (4-1) composed of a compound represented by formula (AI-22) (yield 66%). MS (ESI) m / z = 609.2 [M-H] -

[0647] The X-ray diffraction pattern of azo dye (4-1) is shown in Figure 8 , and the X-ray diffraction parameters are shown in Table 6.

[0648]

[0649] <Example 4>

[0650] 0.5 parts of the azo dye (4-1) obtained in Synthesis Example 4, 3.0 parts of N-methylpyrrolidone and 10.5 parts of xylene were mixed, and the mixture in a slurry state was stirred at an internal temperature of 125° C. for 3 hours. After cooling to room temperature, the obtained mixture was filtered, and the obtained residue was dried under reduced pressure at 60° C. to obtain 0.4 parts of azo dye (4) composed of a compound represented by formula (AI-22) (yield 75%).

[0651] The X-ray diffraction pattern of azo dye (4) is shown in Figure 7 , and the X-ray diffraction parameters are shown in Table 6.

[0652] <Synthesis example 5>

[0653] 90 parts of methanol, 60 parts of acetic acid, 194 parts of 35% hydrochloric acid and 150 parts of water were added to 30 parts of 2,5-dichloro-1,4-phenylenediamine and stirred. Under ice cooling, an aqueous solution in which 14 parts of sodium nitrite was dissolved in 21 parts of water was added to the reaction solution and stirred for 2 hours to obtain a suspension containing a diazonium salt. On the other hand, 105 parts of methanol were added to 30 parts of 3-methyl-1-phenyl-5-pyrazolone, and 412 parts of a 25% aqueous sodium hydroxide solution were added under ice cooling and stirred. The suspension containing the diazonium salt was added dropwise thereto. After the addition was completed, the suspension was further stirred at room temperature for 1 hour to obtain an orange suspension. The orange solid obtained by filtration was dried at 60°C under reduced pressure to obtain a compound represented by formula (d).

[0654]

[0655] Next, 20 parts of water, 6.7 parts of acetic acid and 3.3 parts of 98% sulfuric acid were added to 2.1 parts of the compound represented by formula (d) and stirred. An aqueous solution prepared by dissolving 0.6 parts of sodium nitrite in 3.3 parts of water was added to the reaction solution under ice cooling and stirred for 2 hours to obtain a suspension containing a diazonium salt. On the other hand, 0.8 parts of methanol was added to 3-methyl-1-phenyl-5-pyrazolone, and 15 parts of a 25% aqueous sodium hydroxide solution was added under ice cooling and stirred. The suspension containing the diazonium salt was added dropwise thereto. After the addition was completed, the mixture was further stirred at room temperature for 1 hour to obtain a red suspension. The filtered red solid was dispersed and washed with water and methanol for 30 minutes respectively, filtered, and dried at 60°C under reduced pressure to obtain 0.8 parts of azo dye (5-1) composed of a compound represented by formula (AI-19) (yield 53%). MS (ESI) m / z = 545.0 [M-H] - The X-ray diffraction pattern of azo dye (5-1) is shown in Fig.14, and the X-ray diffraction parameters are shown in Table 6.

[0656]

[0657] <Synthesis example 6>

[0658] Next, 10 parts of the azo dye (5-1) obtained in Synthesis Example 5, 23 parts of tetramethylammonium hydroxide (25% aqueous solution) and 70 parts of methanol are mixed and stirred at room temperature for 1 hour. On the other hand, 24 parts of methanol are added to 7.3 parts of 35% hydrochloric acid and stirred under ice cooling. The above-mentioned solution containing the azo dye is added dropwise thereto. After the addition is completed, it is further stirred at room temperature for 1 hour to obtain an orange suspension. The filtered orange solid is dispersed and washed with water, filtered, and dried at 60°C under reduced pressure to obtain 9.8 parts of azo dye (5-2) composed of a compound represented by formula (AI-19) (yield 98%).

[0659] Table 6 shows the X-ray diffraction parameters of the azo dye (5-2).

[0660] <Synthesis Example 7>

[0661] Mix 3.0 parts of the azo dye (5-1) obtained in Synthesis Example 5, 12.7 parts of tetraethylammonium hydroxide (35% aqueous solution), and 51.0 parts of methanol, and stir at room temperature for 1 hour. On the other hand, add 7.2 parts of methanol to 3.4 parts of 35% hydrochloric acid and stir under ice cooling. Add dropwise the solution containing the above-mentioned azo dye. After the addition is completed, stir further at room temperature for 1 hour to obtain an orange suspension. After the filtered orange solid is dispersed and washed with water, it is filtered and dried at 60°C under reduced pressure to obtain 2.8 parts of azo dye (5-3) composed of a compound represented by formula (AI-19) (yield 94%).

[0662] Table 6 shows the X-ray diffraction parameters of the azo dye (5-3).

[0663] <Synthesis example 8>

[0664] Mix 2.0 parts of the azo dye (5-1) obtained in Synthesis Example 5, 4.7 parts of tetramethylammonium hydroxide (25% aqueous solution), and 14 parts of acetonitrile, and stir at room temperature for 1 hour. On the other hand, add 4.8 parts of water to 1.5 parts of 35% hydrochloric acid and stir under ice cooling. Add dropwise the solution containing the above-mentioned azo dye. After the addition is completed, stir further at room temperature for 1 hour to obtain an orange suspension. After the filtered orange solid is dispersed and washed with water, it is filtered and dried at 60°C under reduced pressure to obtain 1.9 parts of azo dye (5-4) composed of a compound represented by formula (AI-19) (yield 96%).

[0665] Table 6 shows the X-ray diffraction parameters of the azo dye (5-4).

[0666] <Synthesis Example 9>

[0667] 1 part of the azo dye (5-1) obtained in Synthesis Example 5 and 40 parts of 90% sulfuric acid were mixed and stirred at 23°C for 1 hour. 45 parts of acetonitrile were added thereto and stirred at the same temperature for 1 hour to obtain a suspension. The filtered solid was dispersed and washed with water, filtered and dried at 60°C under reduced pressure to obtain 0.9 parts of azo dye (5-5) composed of a compound represented by formula (AI-19) (yield 90%).

[0668] Table 6 shows the X-ray diffraction parameters of the azo dye (5-5).

[0669] <Synthesis Example 10>

[0670] 1.3 parts of the azo dye (5-1) obtained in Synthesis Example 5 and 19.6 parts of trifluoroacetic acid were mixed, heated to 40°C and stirred for 1 hour. 5.2 parts of methanol were added thereto, stirred for 0.5 hours, cooled to room temperature, 15.6 parts of methanol were added, and stirred to obtain an orange suspension. The filtered orange solid was dispersed and washed with water, filtered, and dried at 60°C under reduced pressure to obtain 1.2 parts of azo dye (5-6) composed of a compound represented by formula (AI-19) (yield 92%).

[0671] Table 6 shows the X-ray diffraction parameters of the azo dye (5-6).

[0672] <Example 5>

[0673] 0.5 parts of the azo dye (5-2) obtained in Synthesis Example 6, 3.0 parts of N-methylpyrrolidone and 10.5 parts of xylene were mixed, and the mixture in a slurry state was stirred at an internal temperature of 125° C. for 3 hours. After cooling to room temperature, the obtained mixture was filtered, and the obtained residue was dried under reduced pressure at 60° C. to obtain 0.45 parts of azo dye (5a) composed of a compound represented by formula (AI-19) (yield 90%).

[0674] The X-ray diffraction pattern of the azo dye (5a) is shown in Fig. 9 , and the X-ray diffraction parameters are shown in Table 6.

[0675] <Example 6>

[0676] 0.5 parts of the azo dye (5-2) obtained in Synthesis Example 6, 0.5 parts of N-methylpyrrolidone, 5.0 parts of xylene and 0.5 parts of ethanolamine were mixed, and the slurry mixture was stirred at an internal temperature of 125°C for 3 hours. After cooling to room temperature, 1 part of methanol was added dropwise and stirred for 1 hour. The obtained mixture was filtered, and the obtained residue was dried under reduced pressure at 60°C to obtain 0.4 parts of azo dye (5b) composed of a compound represented by formula (AI-19) (yield 88%).

[0677] The X-ray diffraction pattern of the azo dye (5b) is shown in Fig.10 , and the X-ray diffraction parameters are shown in Table 6.

[0678] <Example 7>

[0679] 1.4 parts of the azo dye (5-1) obtained in Synthesis Example 5 and 84 parts of N-methylpyrrolidone were mixed, and the mixture in a slurry state was stirred at an internal temperature of 125°C for 3 hours. After cooling to an internal temperature of 60°C, 6 parts of acetonitrile were added dropwise, and after further cooling to room temperature, 30 parts of acetonitrile were added dropwise and stirred for 1 hour. The obtained mixture was filtered, and the obtained residue was dried under reduced pressure at 60°C to obtain 1.2 parts of azo dye (5c) composed of a compound represented by formula (AI-19) (yield 86%).

[0680] The X-ray diffraction pattern of the azo dye (5c) is shown in Fig.11 , and the X-ray diffraction parameters are shown in Table 6.

[0681] <Example 8>

[0682] 25 parts of the azo dye (5-1) obtained in Synthesis Example 5 and 375 parts of xylene were mixed, and the mixture in a slurry state was stirred at an internal temperature of 125° C. for 3 hours. After cooling to room temperature, the obtained mixture was filtered, and the obtained residue was dried under reduced pressure at 60° C. to obtain 22 parts (yield 90%) of an azo dye (5d) composed of a compound represented by formula (AI-19).

[0683] The X-ray diffraction pattern of azo dye (5d) is shown in Fig.12 , and the X-ray diffraction parameters are shown in Table 6.

[0684] <Example 9>

[0685] 1 part of the azo dye (5-1) obtained in Synthesis Example 5 and 100 parts of toluene were mixed, and the mixture in a slurry state was stirred at an internal temperature of 100° C. for 3 hours. After cooling to room temperature, the obtained mixture was filtered, and the obtained residue was dried under reduced pressure at 60° C. to obtain 0.9 parts (yield 90%) of an azo dye (5e) composed of a compound represented by formula (AI-19).

[0686] The X-ray diffraction pattern of azo dye (5e) is shown in Fig.13 , and the X-ray diffraction parameters are shown in Table 6.

[0687] <Example 10>

[0688] 1.0 part of the azo dye (5-2) obtained in Synthesis Example 6, 1.7 parts of N-methylpyrrolidone, 10.0 parts of xylene, and 0.3 parts of ethanolamine were mixed, and the slurry mixture was stirred at an internal temperature of 125°C for 3 hours. After cooling to room temperature, 2 parts of methanol were added dropwise and stirred for 1 hour. The obtained mixture was filtered, and the obtained residue was dried under reduced pressure at 60°C to obtain 0.78 parts of azo dye (5f) composed of a compound represented by formula (AI-19) (yield 78%).

[0689] The X-ray diffraction pattern of azo dye (5f) is shown in Fig.14 , and the X-ray diffraction parameters are shown in Table 6.

[0690] <Example 11>

[0691] 1.0 part of the azo dye (5-2) obtained in Synthesis Example 6, 3.4 parts of N-methylpyrrolidone, 10.0 parts of xylene, and 0.6 parts of ethanolamine were mixed, and the slurry mixture was stirred at an internal temperature of 125°C for 3 hours. After cooling to room temperature, 2 parts of methanol were added dropwise and stirred for 1 hour. The obtained mixture was filtered, and the obtained residue was dried under reduced pressure at 60°C to obtain 0.76 parts of azo dye (5g) composed of a compound represented by formula (AI-19) (yield 76%).

[0692] The X-ray diffraction pattern of azo dye (5 g) is shown in Fig.15 , and the X-ray diffraction parameters are shown in Table 6.

[0693] <Example 12>

[0694] 0.5 parts of the azo dye (5-2) obtained in Synthesis Example 6, 1.0 parts of cyclohexanone, 5.0 parts of xylene, and 1.0 parts of ethanolamine were mixed, and the mixture in a slurry state was stirred at an internal temperature of 125° C. for 3 hours. After cooling to room temperature, the obtained mixture was filtered, and the obtained residue was dried under reduced pressure at 60° C. to obtain 0.44 parts of azo dye (5h) composed of a compound represented by formula (AI-19) (yield 88%).

[0695] The X-ray diffraction pattern of azo dye (5h) is shown in Fig.16 , and the X-ray diffraction parameters are shown in Table 6.

[0696] <Example 13>

[0697] 1.0 part of the azo dye (5-3) obtained in Synthesis Example 7, 6.0 parts of N-methylpyrrolidone, and 21.0 parts of xylene were mixed, and the mixture in a slurry state was stirred at an internal temperature of 125° C. for 3 hours. After cooling to room temperature, the obtained mixture was filtered, and the obtained residue was dried under reduced pressure at 60° C. to obtain 0.8 part of azo dye (5i) composed of a compound represented by formula (AI-19) (yield 80%).

[0698] The X-ray diffraction pattern of azo dye (5i) is shown in Fig.17 , and the X-ray diffraction parameters are shown in Table 6.

[0699] <Example 14>

[0700] 1.5 parts of the azo dye (5-4) obtained in Synthesis Example 8, 1.5 parts of N-methylpyrrolidone, 15.0 parts of xylene, and 1.5 parts of ethanolamine were mixed, and the slurry mixture was stirred at an internal temperature of 125°C for 3 hours. After cooling to room temperature, 3 parts of methanol were added dropwise and stirred for 1 hour. The obtained mixture was filtered, and the obtained residue was dried under reduced pressure at 60°C to obtain 1.3 parts of azo dye (5j) composed of a compound represented by formula (AI-19) (yield 87%).

[0701] The X-ray diffraction pattern of azo dye (5j) is shown in Fig.18 , and the X-ray diffraction parameters are shown in Table 6.

[0702] <Example 15>

[0703] 1.0 part of the azo dye (5-5) obtained in Synthesis Example 9 and 60 parts of N-methylpyrrolidone were mixed, and the mixture in a slurry state was stirred at an internal temperature of 125°C for 3 hours. After cooling to 60°C, 5.0 parts of acetonitrile were added dropwise and stirred for 1 hour. After cooling to room temperature, 25.0 parts of acetonitrile were added dropwise and stirred for 1 hour. The obtained mixture was filtered, and the obtained residue was dried under reduced pressure at 60°C to obtain 0.75 parts of azo dye (5k) composed of a compound represented by formula (AI-19) (yield 75%).

[0704] The X-ray diffraction pattern of azo dye (5k) is shown in Fig.19 , and the X-ray diffraction parameters are shown in Table 6.

[0705] <Example 16>

[0706] 0.5 parts of the azo dye (5-6) obtained in Synthesis Example 10 and 15.0 parts of N-methylpyrrolidone were mixed, and the mixture in a slurry state was stirred at an internal temperature of 125°C for 3 hours. After cooling to 60°C, 2.4 parts of acetonitrile were added dropwise and stirred for 1 hour. After cooling to room temperature, 19.9 parts of acetonitrile were added dropwise and stirred for 1 hour. The obtained mixture was filtered, and the obtained residue was dried under reduced pressure at 60°C to obtain 0.38 parts of azo dye (5l) composed of a compound represented by formula (AI-19) (yield 75%).

[0707] The X-ray diffraction pattern of azo dye (5l) is shown in Fig. 20 , and the X-ray diffraction parameters are shown in Table 6.

[0708] [Table 6]

[0709]

[0710] 2θmax in Table 6 is a diffraction angle at which the maximum peak is detected within the range of diffraction angle (2θ±0.2°)=5° to 25°.

[0711] <Synthesis Example 11>

[0712] <Synthesis of Colorant (a)>

[0713] The compound represented by the formula (a) was synthesized according to the contents described in Japanese Unexamined Patent Publication No. 2002-179979.

[0714]

[0715] <Synthesis Example 12>

[0716] An appropriate amount of nitrogen was flowed into a flask equipped with a reflux condenser, a dropping funnel, and a stirrer to create a nitrogen atmosphere, and 280 parts of propylene glycol monomethyl ether acetate was added, and heated to 80°C while stirring. Next, 38 parts of acrylic acid, 3,4-epoxytricyclo[5.2.1.0 2,6 ]decane-8-yl ester and 3,4-epoxytricyclic acrylate [5.2.1.0 2,6] A mixed solution of 289 parts of a mixture of decane-9-yl ester (containing a ratio of 1:1 in molar ratio) and 125 parts of propylene glycol monomethyl ether acetate. On the other hand, a solution of 33 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) dissolved in 235 parts of propylene glycol monomethyl ether acetate was added dropwise over 6 hours. After the addition was completed, the mixture was kept at 80°C for 4 hours and then cooled to room temperature to obtain a copolymer (resin B-1) solution with a solid content of 35.1% and a viscosity of 125 mPas measured by a B-type viscometer (23°C). The weight average molecular weight Mw of the resulting copolymer was 9200, the degree of dispersion was 2.08, and the acid value converted to solid content was 77 mg-KOH / g. Resin B-1 has the following structural units.

[0717]

[0718] <Examples 17 to 21, Comparative Examples 1 to 5>

[0719] (1) Preparation of dispersion

[0720] (Dispersion Preparation Example 1)

[0721] 4.5 parts of the azo dye (1) obtained in Example 1, 0.5 parts of the compound represented by formula (a), 3.5 parts of a dispersant (BYK LPN-6919 manufactured by BYK) (converted to solid content), 3.5 parts of resin B-1 (converted to solid content), 83 parts of propylene glycol monomethyl ether acetate, and 5.0 parts of diacetone alcohol are mixed, 300 parts of 0.2 mm zirconium oxide grinding beads are added, the mixture is shaken, and the zirconium oxide grinding beads are removed by filtration to obtain a dispersion (P-1).

[0722] (Dispersion Preparation Examples 2 to 10)

[0723] Dispersions (P-2) to (P-10) were obtained by the same method as in Dispersion Preparation Example 1 except that the azo dye (1) in Dispersion Preparation Example 1 was changed to the following azo dye.

[0724] Dispersion liquid (P-2): azo dye (1-1) obtained in Synthesis Example 1

[0725] Dispersion liquid (P-3): azo dye (2) obtained in Example 2

[0726] Dispersion liquid (P-4): azo dye (2-1) obtained in Synthesis Example 2

[0727] Dispersion liquid (P-5): azo dye (3) obtained in Example 3

[0728] Dispersion liquid (P-6): azo dye (3-1) obtained in Synthesis Example 3

[0729] Dispersion liquid (P-7): azo dye (4) obtained in Example 4

[0730] Dispersion liquid (P-8): azo dye (4-1) obtained in Synthesis Example 4

[0731] Dispersion liquid (P-9): azo dye (5a) obtained in Example 5

[0732] Dispersion liquid (P-10): azo dye (5-1) obtained in Synthesis Example 5

[0733] (2) Preparation of colored curable resin composition

[0734] The dispersion (P), the resin (B), the polymerizable compound (C), the polymerization initiator (D), the solvent (E), and the leveling agent (F) were mixed to have the composition shown in Table 7, thereby obtaining a colored curable resin composition.

[0735] [Table 7]

[0736]

[0737] In Table 7, each component represents the following compound.

[0738] Resin (B-1): Resin B-1 (solid content conversion)

[0739] Polymerizable compound (C-1): dipentaerythritol polyacrylate (trade name "A-9570", manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)

[0740] Polymerization initiator (D-1): N-acetoxy-1-(4-phenylthiophenyl)-3-cyclohexylpropane-1-one-2-imine (trade name "PBG-327"; O-acyl oxime compound, manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.)

[0741] Solvent (E-1): Propylene glycol monomethyl ether acetate

[0742] Leveling agent (F-1): polyether-modified silicone oil (trade name "Toray Silicone SH8400", manufactured by DowCorning Toray Co., Ltd.)

[0743] (3) Production of color coating

[0744] The colored curable resin composition was applied onto a 5 cm square glass substrate (EAGLE XG; manufactured by CORNING) by spin coating so that the film thickness after post-baking was 2.0 μm, and then pre-baked at 100°C for 3 minutes to form a colored composition layer. After cooling, an exposure machine (TME-150RSK; manufactured by TOPCON Co., Ltd.) was used to expose the composition at 80 mJ / cm2 Irradiate the colored composition layer formed on the substrate with an exposure amount (365 nm standard). After the irradiation, bake it in an oven at 230 °C for 30 minutes to obtain a colored coating film. Measure the film thickness of the obtained colored coating film using DEKTAK3 ((株)ULVAC).

[0745] (4) Heat resistance evaluation

[0746] Heat the obtained colored coating film in an oven at 230 °C for 120 minutes. Measure the xy chromaticity coordinates (x, y) and the stimulus value Y based on the spectral data measured for the colored coating film before and after heating using a colorimeter (OSP-SP-200; manufactured by OLYMPUS(株)). Calculate the color difference ΔE*ab using the method described in JIS Z8730:2009 (7. Calculation method of color difference). The smaller ΔE*ab is, the smaller the color change is. The results are shown in Table 8.

[0747] (5) Light resistance evaluation

[0748] Place an ultraviolet cut-off filter (COLORED OPTICAL GLASS L38; manufactured by HOYA Corporation; cuts off light below 380 nm) on the obtained colored coating film, and irradiate xenon lamp light from its upper surface for 48 hours using a light resistance testing machine (SUNTEST CPS+: manufactured by Toyo Seiki Co., Ltd.). Measure the xy chromaticity coordinates (x, y) and the stimulus value Y based on the spectral data measured for the colored coating film before and after the light irradiation using a colorimeter (OSP-SP-200; manufactured by OLYMPUS(株)). Calculate the color difference ΔE*ab using the method described in JIS Z 8730:2009 (7. Calculation method of color difference). The smaller ΔE*ab is, the smaller the color change is. The results are shown in Table 8.

[0749] [Table 8]

[0750]

[0751] Based on the results of Examples 17 to 21 and Comparative Examples 1 to 5, even for azo pigments having the same chemical structure, color filters with improved heat resistance and light resistance can be formed by having the specified crystal structure of the present invention.

Claims

1. An azo dye represented by the following formula (I): The azo dye has a diffraction pattern of powder X-ray diffraction using CuKα rays of a mixture of 50 parts of the azo dye and 50 parts of aluminum oxide. There is a peak in the diffraction angle range of 2θ±0.2° from 5° to 25°. The maximum peak among 5° to 25° exists at 9.8° to 16.0°. There is one or more peaks at 11.0° to 11.8°. The maximum peak intensity I1 at 9.8° to 16.0° and the maximum peak intensity I2 at 11.0° to 11.8° satisfy I2 / I1≥0.05, and The peak intensity I3 at the diffraction angle of 2θ±0.2° from aluminum oxide is 35.1° and I1 satisfies I1 / I3≥0.

35. A-L1(I) In formula (I), L 1 represents a group represented by formula (ph1-1), formula (ph1-2), formula (ph11-1) or formula (ph11-2), A represents a group represented by formula (ia), In formula (ph1-1), formula (ph1-2), formula (ph11-1) and formula (ph11-2), X 1 a.X 1b , X 10 , X 11 a.X 11b Each independently represents a substituent or a hydrocarbon group which may have a substituent, n1 represents an integer of 0 to 5, n2 represents an integer of 0 to 4, and when n1 represents an integer greater than 2, a plurality of X 1 a may be the same or different, and when n2 represents an integer greater than 2, multiple X 1b may be the same or different, n1 represents an integer greater than 2 and X 1 When a is bonded to an adjacent carbon atom, X bonded to the adjacent carbon atom 1a may be bonded to each other to form a ring, n2 represents an integer greater than 2 and X 1b When bonded to an adjacent carbon atom, X bonded to the adjacent carbon atom 1b can bond to each other to form a ring, p represents an integer of 0 to 4. When p represents an integer greater than 2, a plurality of X 10 may be the same or different, p represents an integer greater than 2 and X 10 When bonded to an adjacent carbon atom, X bonded to the adjacent carbon atom 10 can bond to each other to form a ring, q1 represents an integer from 0 to 5, q2 represents an integer from 0 to 4, and when q1 represents an integer greater than 2, multiple X 11a may be the same or different. When q2 represents an integer greater than 2, multiple X 11b may be the same or different, q1 represents an integer greater than 2 and X 11a When bonded to an adjacent carbon atom, X bonded to the adjacent carbon atom 11a may be bonded to each other to form a ring, q2 represents an integer greater than 2 and X 11b When bonded to an adjacent carbon atom, X bonded to the adjacent carbon atom 11b can bond to each other to form a ring, Y represents -O-, -CO-, -SO2- or -C(CF3)2-, * indicates the bonding site with A, ** represents the bonding site to the group represented by formula (ib), In formula (ia) and formula (ib), X 6 ~X 9 Each independently represents a hydrocarbon group which may have a substituent, wherein -CH2- contained in the hydrocarbon group may be substituted by -O-, -CO- or -NH-, wherein -CH= contained in the hydrocarbon group may be substituted by -N=, wherein -C< contained in the hydrocarbon group may be substituted by -N<, X 6 With X 7 Can bond to each other to form a ring, X 8 With X 9 can bond to each other to form a ring, *Indicates the same as L 1 bonding site.

2. The azo dye according to claim 1, wherein The group represented by the formula (ph1-2) is the group represented by the formula (ph2-2), the group represented by the formula (ph11-1) is the group represented by the formula (ph12-1), and the group represented by the formula (ph11-2) is the group represented by the formula (ph12-2), In formula (ph2-2), formula (ph12-1), and formula (ph12-2), X 2b ~X 5b , X 12a ~X 15a , X 21a ~X 25a , X 12b ~X 15b , X 22b ~X 25b each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an amino group, an amide group, a carboxamide group, a carboxyl group, an alkoxy group having 1 to 4 carbon atoms, an alkylthio group having 1 to 4 carbon atoms, a cyano group, or a halogen atom, X 2b With X 3b , X 4b With X 5b , X 12a With X 13a , X 14a With X 15a , X 22a With X 23a , X 21a With X 23a , X 21a With X 25a , X 24a With X 25a , X 12b With X 13b , X 14b With X 15b , X 22b With X 23b , X 24b With X 25b can bond to each other to form a ring, Y has the same meaning as above, * indicates the bonding site with A, ** represents a bonding site to the group represented by formula (ib).

3. The azo dye according to claim 1, wherein The groups represented by formula (ia) and formula (ib) are each independently any one of the groups represented by formula (t1) to formula (t5), In formula (t1) to formula (t5), R 1 ~R 16 each independently represents a hydrogen atom, a hydrocarbon group which may have a substituent, a heterocyclic group, a cyano group or a halogen atom, *Indicates the same as L 1 bonding site. 4 . A colored curable resin composition comprising the azo dye according to claim 1 , a resin, a polymerizable compound, a polymerization initiator, and a solvent. 5 . A color filter formed from the colored curable resin composition according to claim 4 . A display device comprising the color filter according to claim 5 . 7 . A solid-state imaging element comprising the color filter according to claim 5 .

8. A method for producing an azo dye, comprising a contact step of bringing an azo dye (A) into contact with a solvent (Z) in a slurry state at a temperature of 80 to 200° C. and a separation step of taking out the azo dye (A) in contact with the solvent (Z) by solid-liquid separation, wherein the solvent (Z) comprises at least one selected from an ester solvent, an ether solvent, an ether ester solvent, a ketone solvent, a nitrile solvent, an alcohol solvent, an amide solvent, an aromatic hydrocarbon solvent, a sulfoxide solvent, a sulfone solvent, a halogen solvent and an amine solvent, and the amount of the solvent (Z) in the contact step is 0.1 to 120.0 times by mass relative to the azo dye (A).

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