JP2018159749A - Red coloring composition for organic el display device, color filter for organic el display device, and organic el display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coloring composition which can provide a color filter that is thin while having high color purity and has good flatness and chemical resistance when a specific pigment is used with a specific ratio, in an organic EL display device using a white light-emitting organic EL element as a light source.SOLUTION: A red coloring composition for organic EL display device contains a red pigment, a yellow pigment, an alkali-soluble resin, a photopolymerizable monomer and a photopolymerization initiator, where the red pigment contains C.I.pigment red 177 and/or a naphthol azo pigment [A] represented by the following general formula (1), the yellow pigment contains C.I pigment yellow 185, and a content of any one of the C.I. pigment red 177 and the naphthol azo pigment [A] represented by the following general formula (1) is 77 wt.% or more in 100 wt.% of the red pigment.SELECTED DRAWING: Figure 1

Description

The present invention relates to a red coloring composition for an organic EL display device, a color filter, which is preferably used for a color display device using a white light emitting organic EL (electroluminescence) element (hereinafter sometimes referred to as “organic EL element”). And a color display device. White means a broad concept including pseudo white.

Examples of color display devices using color filters include (i) a backlight as a light source, a liquid crystal as an optical shutter, and a combination of color filters having color adjustment functions (color conversion function, color separation function, color correction function, etc.) And (ii) a synthetic white organic EL light source, and an organic EL display device comprising a combination of color filters having a color adjustment function (color conversion function, color separation function, color correction function, etc.).

Currently, liquid crystal displays (i) are the mainstream for flat panel displays. Due to the advantages of low power consumption and space saving, there are various types of monitors such as personal computer monitors, mobile phone displays, notebook personal computers, and personal digital assistants. In recent years, it has been used for liquid crystal televisions instead of conventional CRT televisions. For LCD TV applications, color reproducibility is important. The color reproducibility of the color liquid crystal display device is determined by the color of light emitted from the red, green, and blue filter segments, and the chromaticity points of the respective filter segments are (xR, yR), (xG, yG), When (xB, yB), the standard three primary colors, red, evaluated by the area of the triangle surrounded by these three points on the xy chromaticity diagram and defined by the US National Television System Committee (NTSC) (0.67, 0.33), ratio to the area surrounded by green (0.21, 0.71), blue (0.14, 0.08) (unit:%, hereinafter abbreviated as NTSC ratio) Expressed. This value is 40 to 100% for a general notebook computer, 50 to 100% for a monitor for a personal computer, and 70% to 100% for a liquid crystal television.

As the backlight in the liquid crystal display device of (i), a cold cathode tube type backlight, a two-wavelength peak pseudo-white backlight and a three-wavelength peak backlight using a light emitting diode or an organic EL element using an inorganic material. and so on. In the liquid crystal display device, a liquid crystal layer sandwiched between two polarizing plates controls the amount of light passing through the first polarizing plate by controlling the degree of polarization of light passing through the first polarizing plate. The VA mode, the IPS mode, etc., and the type using a TN (twisted nematic) mode type liquid crystal is the mainstream. However, these liquid crystal display devices have a problem that energy is wasted because the backlight unit continues to emit the same light as white display even in black display.

As the synthetic white light source of the organic EL display device of (ii), there are a light source having a two-wavelength peak, a light source having a three-wavelength peak, and a light source having a large number of peaks in the visible light region. Synthetic white light is obtained by mixing or layering.

Since the organic EL display device can directly turn on / off the light source of the pixel by a TFT (thin film transistor) or the like, it is possible to perform black display by turning off the light emission of the designated pixel. Therefore, the deflecting plate used in the liquid crystal display device is not required in the light emitting device, and it is not necessary to control the liquid crystal body. For this reason, the amount of transmitted light in the display device increases, and energy consumption can be greatly reduced by turning off the light emitting device in black display. In addition, it is possible to reproduce true dark black, and the contrast ratio can be increased. As an organic EL color display device in which the problems in the liquid crystal display device are solved, for example, a product such as “XEL-1” manufactured by SONY is already on the market. (For example, see Patent Document 1)

However, a light emitting device using such an organic EL element has a light emission spectrum different from that of a conventionally used light source. For example, a conventional light source has a peak in the vicinity of 420 to 430 nm, but a light source using an organic EL element has no peak in the vicinity of 420 to 430 nm due to the characteristics of the material, and has a peak in the vicinity of 460 nm. In addition, the emission spectrum of the light source using the organic EL element has a broad peak as compared with the conventional light source, and therefore, even after passing the peak around 460 nm, the conventional light source reaches about 500 nm. The spectrum is higher. For these reasons, currently used color filters cannot be used as they are in display devices using light sources using organic EL elements. For this reason, it is necessary to select and develop a color filter material that can be used for a light source using an organic EL element and has an optimum hue and transmittance characteristics.

An organic EL display device having such a light source is also required to have a high NTSC ratio, as in a liquid crystal display device. In order to increase the NTSC ratio, it is necessary to increase the color purity of each filter segment. However, if the color purity is increased, the light use efficiency (represented by the brightness Y value) of the light source is decreased. There is a problem that increases.

In order to obtain a color filter having a large NTSC ratio, C.I. I. Pigment red 177, C.I. I. Pigment Red 179, a red pigment, and C.I. I. Often, yellow pigments such as CI Pigment Yellow 139 are used.

Here, when the said pigment | dye is used individually or in combination, there exists a problem that the brightness is low.

In Patent Documents 2 to 4, in order to further improve the brightness of the red filter segment, C.I. I. Pigment red 176, C.I. I. Pigment red 242, and C.I. I. Although it has been proposed to use an azo pigment such as CI Pigment Orange 38 as a main pigment, brightness and color purity are not sufficient, and further improvement has been demanded.

Patent Document 5 proposes to achieve both color purity and lightness by using an azo pigment having a specific structure.

However, in order to obtain a color filter having a high NTSC ratio, it is necessary to increase the pigment content in the coloring composition or to increase the film thickness. When the content of the pigment is increased, there is a problem that the pigment concentration in the coating film increases and the unevenness degree (flatness) of the filter segment surface is deteriorated. When the flatness of the filter segment is deteriorated, the surface of the transparent electrode formed on the filter segment also follows the surface and becomes uneven, causing dark spots (light emitting defect points) and short circuits.
In addition, the demand for thin color display devices is increasing and the film thickness tends to be reduced. As a result, the components that contribute to the curing of the coating film are reduced as the pigment concentration increases. As a result, a problem may arise in the chemical resistance of the coating film.

Japanese Patent Laid-Open No. 2005-10091 JP 2009-237462 A Japanese Patent Laid-Open No. 11-14824 Japanese Patent Laid-Open No. 10-115709 JP 2014-112527 A

In the organic EL display device using a white light-emitting organic EL element as a light source, the colored composition of the present invention becomes a thin film with high color purity when a specific dye is used at a specific ratio, and has flatness and chemical resistance. A good color filter can be provided.

As a result of intensive studies, the present inventors have determined that C.I. I. It has been found that the above-mentioned problems can be solved by using Pigment Yellow 185, and the present invention has been achieved.

That is, the present invention is a red coloring composition for an organic EL display device containing a red pigment, a yellow pigment, an alkali-soluble resin, a photopolymerizable monomer, and a photopolymerization initiator, C. I. Pigment Red 177 and / or a naphthol azo pigment [A] represented by the following general formula (1): I. Pigment Yellow 185, and C.I. I. The organic EL display device, wherein the content of any one of CI Pigment Red 177 and the naphtholazo pigment [A] represented by the following general formula (1) is 77% by weight or more in 100% by weight of the red dye The present invention relates to a red coloring composition.

[In General Formula (1), A represents a hydrogen atom, a benzimidazolone group, an optionally substituted phenyl group, or an optionally substituted heterocyclic group. R ¹ represents a hydrogen atom, a halogen atom, a trifluoromethyl group, an alkyl group having 1 to 4 carbon atoms, —OR ⁷ or —COOR ⁸ . R ^{2 to} R ⁶ are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, a trifluoromethyl group, an alkyl group having 1 to 4 carbon atoms, —OR ⁹ , —COOR ¹⁰ , —CONHR ¹¹ , -NHCOR ¹² or an _-SO 2 ^{NHR 13.} R ^{7 to} R ¹³ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ]

The present invention also provides C.I. I. The present invention relates to the red coloring composition for organic EL display devices, wherein the content of pigment yellow 185 is 12 to 35% by weight in 100% by weight of the total content of red pigment and yellow pigment.

The present invention also includes a naphthol azo pigment [A] in which the red dye is represented by the general formula (1), and the naphthol azo pigment [A] represented by the general formula (1) is C.I. I. The present invention relates to the red coloring composition for organic EL display devices, which is CI Pigment Red 269.

The present invention also relates to the red coloring composition for an organic EL display device, wherein the photopolymerization initiator contains an oxime ester compound.

The present invention also relates to the red coloring composition for an organic EL display device, wherein the alkali-soluble resin is a resin having a structural unit derived from methyl methacrylate.

The present invention also relates to a color filter for an organic EL display device comprising a filter segment formed on the substrate from the red coloring composition for an organic EL display device.

The present invention also relates to an organic EL display device comprising the color filter for an organic EL display device and a white organic EL light source.

  With the red coloring composition for organic EL display devices of the present invention, it is possible to obtain a coloring composition for a color filter which is a thin film while having high color purity and is excellent in flatness and chemical resistance of a coating film.

It is an example of the emission spectrum of a white organic EL light source (EL-1).

Hereinafter, the present invention will be described in detail.
In the present application, when “(meth) acryloyl”, “(meth) acryl”, “(meth) acrylic acid”, “(meth) acrylate”, or “(meth) acrylamide” is particularly described, Unless otherwise indicated, “acryloyl and / or methacryloyl”, “acrylic and / or methacrylic”, “acrylic acid and / or methacrylic acid”, “acrylate and / or methacrylate”, or “acrylamide and / or methacrylamide”, respectively. It shall represent.
Further, “CI” in this specification means a color index (CI).

<Red coloring composition>
First, the red coloring composition for organic EL display devices of the present invention will be described.
The red coloring composition of the present invention contains a red pigment, a yellow pigment, an alkali-soluble resin, a photopolymerizable monomer, and a photopolymerization initiator, and particularly includes a white organic EL light source. It is a red coloring composition preferably used for a color filter of a color display device. First, other components such as a red pigment, a yellow pigment, an alkali-soluble resin, a photopolymerizable monomer, a photopolymerization initiator, a sensitizer, an antioxidant, and an organic solvent used in the red coloring composition will be sequentially described. .

<Red pigment>
The red pigment contained in the red coloring composition for organic EL display devices of the present invention is C.I. I. Pigment Red 177 and / or a naphthol azo pigment [A] represented by the general formula (1), and C.I. I. The content of any one of Pigment Red 177 and the naphtholazo pigment [A] represented by the general formula (1) is in a range of 77% by weight or more in 100% by weight of the red pigment. By being in this range, the flatness and chemical resistance of the coating film become good.
It is speculated that this can be explained in terms of the strength of interaction between the red dye and the binder resin described below and the structure of the red dye itself.

C. I. Pigment Red 177 and naphtholazo pigment [A] represented by the general formula (1) are C.I. I. Pigment red 254 and C.I. I. Compared with a red pigment such as CI Pigment Red 179, it has a feature that it has abundant functional groups such as an amide group, a hydroxyl group, an amino group, and a carbonyl group. On the other hand, C.I. I. Pigment red 254 and C.I. I. The red dye such as CI Pigment Red 179 has a feature that the intermolecular interaction works strongly because of its stacking structure between the dye molecules.
For the above reasons, among the red pigments, C.I. I. Pigment Red 177 and the naphthol azo pigment [A] represented by the general formula (1) have a functional group that easily interacts with a carboxylic acid possessed by an alkali-soluble resin, and also has an intermolecular interaction between pigments. Since it is weak, the interaction with the alkali-soluble resin becomes strong, and it is assumed that the flatness and chemical resistance of the coating film are improved.

C. in 100% by weight of red pigment. I. When the content of either Pigment Red 177 or the naphtholazo pigment [A] represented by the general formula (1) is less than 77% by weight, a large number of dyes having different structures are present in the system. As a result, the surface area of the dye molecules is increased, and sufficient interaction with the alkali-soluble resin cannot be obtained, so that the flatness of the coating film and chemical resistance are deteriorated.

As a red dye, the naphthol azo pigment [A] represented by the general formula (1) has a weak intermolecular interaction between dyes and can have a strong interaction with a resin because of its structure. This is preferable because chemical resistance is improved.

(Naphthol azo pigment [A])
The red coloring composition of the present invention contains a naphthol azo pigment [A] represented by the general formula (1) as a red pigment.

[In General Formula (1), A represents a hydrogen atom, a benzimidazolone group, an optionally substituted phenyl group, or an optionally substituted heterocyclic group. R ¹ represents a hydrogen atom, a trifluoromethyl group, an alkyl group having 1 to 4 carbon atoms, —OR ⁷ or —COOR ⁸ . R ^{2 to} R ⁶ are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, a trifluoromethyl group, an alkyl group having 1 to 4 carbon atoms, —OR ⁹ , —COOR ¹⁰ , —CONHR ¹¹ , -NHCOR ¹² or an _-SO 2 ^{NHR 13.} R ^{7 to} R ¹³ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ]

Among the naphthol azo pigments [A] represented by the general formula (1), naphthol azo pigments [A1] in which at least one of R ^{2 to} R ⁶ is a trifluoromethyl group, or R ^{2 to} R ^{6 are} preferable. A naphtholazo pigment [A2] in which at least one of them is —NHCOR ¹² is preferable because the pigment particles are easily made finer and the contrast ratio is excellent.

  As a naphthol azo pigment [A] represented by the general formula (1), when represented by a color index (CI) number, C.I. I. Pigment Red 31, 32, 146, 147, 150, 184, 187, 188, 210, 238.2245.247, 266, 268, 269, C.I. I. Violet 25, 50, etc. are mentioned. Among these, from the viewpoint of hue and lightness, C.I. I. Pigment Red 150, 170, 187, 266, 268, 269 are preferred, and C.I. I. Pigment Red 269 is particularly preferable.

  In the general formula (1), in A, the “substituent” of the phenyl group which may have a substituent is a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, cyano Of an acidic group selected from a group, a trifluoromethyl group, a nitro group, a hydroxyl group, a carbamoyl group, an N-substituted carbamoyl group, a sulfamoyl group, an N-substituted sulfamoyl group, a carboxyl group, a sulfo group, a carboxyl group or a sulfo group Trivalent metal salts (for example, sodium salt, potassium salt, aluminum salt, etc.) and the like can be mentioned. Therefore, specific examples of the phenyl group which may have a substituent include a phenyl group, a p-methylphenyl group, a 4-tert-butylphenyl group, a p-nitrophenyl group, a p-methoxyphenyl group, an o-triphenyl group. Fluoromethylphenyl group, p-chlorophenyl group, p-bromophenyl group, 2,4-dichlorophenyl group, 3-carbamoylphenyl group, 2-chloro-4-carbamoylphenyl group, 2-methyl-4-carbamoylphenyl group, 2 -Methoxy-4-carbamoylphenyl group, 2-methoxy-4-methyl-3-sulfamoylphenyl group, 4-sulfophenyl group, 4-carboxyphenyl group, 2-methyl-4-sulfophenyl group, etc. However, it is not limited to these.

  In A, the “substituent” of the heterocyclic group which may have a substituent is a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, a cyano group, or trifluoro group. Monovalent to trivalent metal of an acidic group selected from methyl group, nitro group, hydroxyl group, carbamoyl group, N-substituted carbamoyl group, sulfamoyl group, N-substituted sulfamoyl group, carboxyl group, sulfo group, carboxyl group or sulfo group Salt (for example, sodium salt, potassium salt, aluminum salt etc.) etc. are mentioned. “Heterocycle” means an atom in which one or more heteroatoms other than carbon atoms are contained in the atoms constituting the ring system, and may be a saturated ring or an unsaturated ring. Further, it may be a single ring or a condensed ring. Therefore, the heterocyclic ring includes pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, triazine ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, pyrazole ring, oxazole ring, thiazole ring, isoxazole ring, isothiazole ring. , Triazole ring, thiadiazole ring, oxadiazole ring, quinoline ring, benzofuran ring, indole ring, morpholine ring, pyrrolidine ring, piperidine ring, tetrahydrofuran ring and the like. Therefore, the heterocyclic group means a monovalent radical derived by removing a hydrogen atom from these heterocycles. Therefore, specific examples of the heterocyclic group which may have a substituent include 2- Pyridyl group, 3-pyridyl group, 4-pyridyl group, 2-pyrrolyl group, 3-pyrrolyl group, 2-furyl group, 3-furyl group, 2-thienyl group, 3-thienyl group, 2-imidazolyl group, 2- Oxazolyl group, 2-thiazolyl group, piperidino group, 4-piperidyl group, morpholino group, 2-morpholinyl group, N-indolyl group, 2-indolyl group, 2-benzofuryl group, 2-benzothienyl group, 2-quinolino group, N-carbazolyl group etc. are mentioned.

Examples of the halogen atom in R ^{2 to} R ⁶ and R ¹⁴ include fluorine, chlorine, bromine, and iodine.

In addition, the alkyl group having 1 to 4 carbon atoms in R ^{1 to} R ¹⁴ may be linear or branched, and specifically includes a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and an isobutyl group. , Sec-butyl group, and tert-butyl group.

As a pigment, it is preferable that A is a phenyl group which may have a substituent from a viewpoint of brightness. Furthermore, from the viewpoints of lightness and dispersibility, R ¹ is preferably an alkyl group having 1 to 4 carbon atoms or —OR ⁷ , and more preferably R ¹ is a methyl group or a methoxy group.

  The colorant of the present invention may have a chemical structure of the general formula (1) or a tautomer thereof, and may be a pigment having any crystal form, and any crystal called a so-called polymorph. It may be a mixed crystal of pigments having a form. The crystal form of these pigments can be confirmed by powder X-ray diffraction measurement or X-ray crystal structure analysis.

  The naphtholazo pigment [A] of the present invention is a water-insoluble pigment having excellent fastness to solvents and light, and by using this pigment, both brightness and contrast ratio are excellent. A colored composition for a color filter can be obtained.

  In the colorant of the present invention, the naphtholazo pigment [A] can be used alone or in admixture of two or more.

(Naphthol azo pigment [A1])
Among the naphthol azo pigments [A] represented by the general formula (1), the azo pigment (A1) in which at least one of R ^{2 to} R ⁶ is a trifluoromethyl group is easily miniaturized. Therefore, it is preferable.

Among these, R ⁵ is preferably a -trifluoromethyl group, and R ² is preferably a -Cl group. By satisfying these requirements, the pigment can be made finer, so that high contrast can be achieved.

  Specific examples of the naphthol azo pigment [A1] include the following naphthol azo pigments, but the present invention is not limited thereto.

(Naphthol azo pigment [A2])
Among the naphthol azo pigments [A] represented by the general formula (1), the azo pigment (A2) in which at least one of R ^{2 to} R ⁶ is —NHCOR ¹² is excellent in lightness. preferable.
Among these, R ⁴ is preferably —NHCOR ¹² and R ¹ is more preferably a methoxy group.

Specific examples of the naphthol azo pigment [A2] include the following naphthol azo pigments, but the present invention is not limited thereto.

(Method for producing naphtholazo pigment [A])
The naphthol azo pigment [A] of the present invention can be produced by coupling reaction of a diazonium salt and β-naphthols, as is well known in the pigment field. Also, as described below, two or more naphthol azo pigments can be synthesized simultaneously by using aromatic amines (diazo component), β-naphthols (coupler component), or both in the reaction. A plurality of naphthol azo pigment species may be included. In this case, a pigment composition that is excellent in miniaturization and gives excellent lightness may be obtained, which is more preferable.

  By simultaneously synthesizing two or more naphthol azo pigments, crystal growth can be inhibited, fine pigment particles can be obtained, and lightness can be improved for reasons such as improved transparency.

  The naphtholazo pigment [A] is produced by firstly adding an amide (diazo component) represented by the following general formula (7) in an acidic aqueous solution to which hydrochloric acid, sulfuric acid, acetic acid or the like is added, nitrous acid, nitrite or A diazonium salt represented by the following general formula (8) obtained by diazotization with a nitrite is produced.

[In General Formulas (7) and (8), A and R ¹ have the same meanings as in General Formula (1). X ⁻ represents an inorganic or organic anion. ]

Examples of the inorganic or organic anion include fluoride ion, chloride ion, bromide ion, iodide ion, perchlorate ion, hypochlorite ion, CH ₃ COO ⁻ , C ₆ H ₅ COO ^{−, and the} like. preferably chloride, _bromide, CH 3 COO ^- and the like.

  Next, the diazonium salt represented by the general formula (8) and the β-naphthols (coupling component) represented by the following general formula (9) are usually reacted at 5 ° C. to 70 ° C. in an aqueous solvent. The naphthol azo pigment [A] of the general formula (1) is produced by post-treatment by a conventional method. Further, the coupling reaction may be performed in the presence of a surfactant, a resin, a pigment derivative, or an inert solvent. Moreover, the manufacturing method of the naphthol azo pigment [A] of this invention is not limited to these methods.

[R < ² > -R < ⁶ > is synonymous with the thing in General formula (1) in General formula (9). ]

Moreover, when manufacturing simultaneously 2 or more types of naphthol azo pigment seed | species, the method described below is mentioned, for example.
First, a mixture of at least one aromatic amine (diazo component) represented by the following general formula (7) is added to a nitrous acid, a nitrite or a nitrous acid in an acidic aqueous solution to which hydrochloric acid, sulfuric acid or acetic acid is added. A mixture of diazonium salts represented by the following general formula (8) obtained by diazotization with an ester is produced.

[In General Formulas (7) and (8), A and R ¹ have the same meanings as in General Formula (1). X- represents an inorganic or organic anion. ]

Examples of the inorganic or organic anion include fluoride ion, chloride ion, bromide ion, iodide ion, perchlorate ion, hypochlorite ion, CH ₃ COO ⁻ , C ₆ H ₅ COO ^{−, and the} like. preferably chloride, _bromide, CH 3 COO ^- and the like.

Next, the mixture of the diazonium salt represented by the general formula (8) is converted into β-naphthols (coupler component) represented by the following general formula (9) and β-naphthols represented by the following chemical formula (10). The mixture of (coupler component) is usually reacted in an aqueous solvent at 5 ° C. to 70 ° C. and subjected to post-treatment by a conventional method to obtain a naphthol azo pigment [A] represented by the general formula (1) and the general formula A pigment composition containing the naphtholazo pigment [A ′] represented by (6) can be produced.
At this time, A ¹ in the general formula (6) is the same as A, and R ⁵¹ is the same pigment as R ¹ .
Further, the coupling reaction may be performed in the presence of a surfactant, a resin, a pigment derivative, or an inert solvent. Moreover, the manufacturing method of the pigment composition of this invention is not limited to these methods.

[R < ² > -R < ⁶ > is synonymous with the thing in General formula (1) in General formula (9). ]

  The mixing ratio of the aromatic amines of the general formula (7) used in the reaction and the mixing weight ratio of the β-naphthols of the general formula (9) and the chemical formula (10) are respectively set between 60:40 and 100: 0. can do. By adjusting these mixing ratios, a pigment composition having a target weight ratio can be obtained.

Thus, a coupler component composed of a mixture of a naphthol compound represented by the general formula (9) and a naphthol compound represented by the chemical formula (10), a diazo compound of an aromatic amine represented by the general formula (7), Can be reacted to produce a colorant containing the azo pigments represented by the general formula (1) and the general formula (6).
Such a colorant is excellent in lightness and contrast ratio, and is preferable.
At this time, the weight ratio of the mixture of the naphthol compound represented by the general formula (9) and the naphthol compound represented by the chemical formula (10) is preferably 60.0: 40.0 to 100.0: 0. In the case of 100.0: 0, the naphthol azo pigment [A] represented by the general formula (1) is the only product.

(Yellow pigment)
The yellow pigment contained in the red coloring composition for organic EL display devices of the present invention is C.I. I. Pigment yellow 185. C. is generally used for color filters. I. Pigment Yellow 138, 139, 150, and 185 all have a ring structure. I. Pigment Yellow 185 is characterized by low molecular structure symmetry compared to other yellow pigments. Therefore, the intermolecular interaction between the yellow dyes is small, and the degree of freedom of the functional group possessed is high. From this structural feature, C.I. I. Pigment Yellow 185 has a ring structure of C.I. I. It interacts with Pigment Red 177 or the naphtholazo pigment [A] represented by the general formula (1), and the functional group part interacts with an alkali-soluble resin, so that it is specifically flat compared with other yellow dyes. And chemical resistance is estimated to be good.

C. I. The content of Pigment Yellow 185 is preferably 12 to 35% by weight in 100% by weight of the total content of red pigment and yellow pigment. In the case of less than 12% by weight, C.I. I. Pigment Yellow 185, C.I. I. Interaction with the ring structure with Pigment Red 177 or the naphtholazo pigment [A] represented by the general formula (1) and interaction with the alkali-soluble resin due to the functional group are not sufficiently obtained, and flatness and chemical resistance are not obtained. Since it gets worse, it is not preferable.
If it is higher than 35% by weight, the ratio of the red pigment is low, and therefore the film thickness of the red filter segment produced using the red coloring composition is undesirably increased.

(Other pigments)
In the coloring composition of the present invention, in order to adjust the chromaticity, the above-mentioned C.I. I. Pigment Red 177, a naphtholazo pigment represented by the general formula (1) [A], C.I. I. Other pigments such as pigments or dyes other than Pigment Yellow 185 may be used in combination. These pigments / dyes can be used alone or in admixture of two or more at any ratio as required.

Examples of pigments that can be used in combination include diketopyrrolopyrrole pigments, azo pigments other than the naphtholazo pigment [A] of the general formula (1) such as azo, disazo, or polyazo, aminoanthraquinone, diaminodianthraquinone, anthra Anthraquinone pigments such as pyrimidine, flavantron, anthanthrone, indanthrone, pyranthrone, violanthrone, quinacridone pigment, perinone pigment, perylene pigment, thioindigo pigment, isoindoline pigment, isoindolinone pigment, quinophthalone And pigments, selenium pigments, benzimidazolone pigments, and metal complex pigments.
As dyes, xanthene dyes, azo (pyridone, barbituric acid, metal complex, etc.) dyes, disazo dyes, anthraquinone dyes, methine dyes and the like may be included. In addition, lake pigments obtained by lake- ing these dyes, inorganic salts of acidic dyes having acidic groups such as sulfonic acid and carboxylic acid, salt-forming compounds of acidic dyes and nitrogen-containing compounds, sulfonic acid amides of acidic dyes It may be in the form of a compound or the like.

  Preferred red dyes to be used in combination are azo pigments other than the naphthol azo pigment [A] of the general formula (1), diketopyrrolopyrrole, anthraquinone, quinophthalone, isoindoline, from the viewpoint of brightness and tinting strength. , Perinone-based, perylene-based, and benzimidazolone-based dyes.

  Examples of the azo pigments other than the naphthol azo pigment [A] of the general formula (1) include the naphthol azo pigment [A ′] represented by the general formula (6), and other azo pigments [C]. The naphthol azo pigment [A ′] represented by the general formula (6) is preferable because of its high brightness.

[Naphthol azo pigment [A ']]
The naphthol azo pigment [A ′] is a naphthol azo pigment represented by the general formula (6).
[In General Formula (6), A ¹ each independently represents a hydrogen atom, a phenyl group which may have a substituent, or a heterocyclic group which may have a substituent. R ⁵¹ represents a hydrogen atom, a trifluoromethyl group, an alkyl group having 1 to 4 carbon atoms, —OR ⁵⁷ or —COOR ⁵⁸ . R ⁵⁷ and R ⁵⁸ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ]

In A ¹ , the “substituent” of the phenyl group which may have a substituent and the “substituent” of the heterocyclic group which may have a substituent are the “substituent” in A of the general formula (1). Is the same.

In addition, the alkyl group having 1 to 4 carbon atoms in R ⁵¹ , R ⁵⁷ and R ⁵⁸ may be linear or branched, and specifically includes a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group. , Isobutyl group, sec-butyl group, and tert-butyl group.

As a pigment, from the viewpoint of brightness, A ¹ is preferably a phenyl group which may have a substituent. Furthermore, from the viewpoints of lightness and dispersibility, R ⁵¹ is preferably an alkyl group having 1 to 4 carbon atoms or —OR ⁵⁷ , and more preferably R ⁵¹ is a methyl group or a methoxy group.

  The dye of the present invention may have a chemical structure of the general formula (6), or a tautomer thereof, may be a pigment having any crystal form, and may be any crystal form called a polymorph. It may be a mixed crystal of pigments having the same. The crystal form of these pigments can be confirmed by powder X-ray diffraction measurement or X-ray crystal structure analysis.

  When the dye contains a naphthol azo pigment [A ′] represented by the general formula (6), it is represented by the naphthol azo pigment [A] represented by the general formula (1) and the general formula (6). The weight ratio of the naphthol azo pigment [A ′] is preferably in the range of 60.0: 40.0 to 95.0: 5.0. More preferably, it is the range of 70.0: 30.0-90.0: 10.0. When the content of the naphtholazo pigment [A] is 60 or more or 95 or less, it is preferable because more excellent brightness can be obtained.

  Examples of the naphthol azo pigment represented by the general formula (6) include C.I. I. And CI Pigment Red 176.

[Other azo pigments [C]]
The other azo pigment [C] is an azo such as azo, disazo or polyazo other than the naphthol azo pigment [A] represented by the general formula (1) and the azo pigment [A ′] represented by the general formula (6). And pigments.
Examples of such pigments include C.I. I. Pigment Red 2, 5, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 21, 22, 23, 95, 112, 114, 119, 136, 144, 164, 166, 170, 171, 175, 185, 208, 213, 214, 220, 221, 242, 253, 256, 258, C.I. I. Pigment Orange 1, 4, 15, 16, 22, 24, 38, 74, C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 9, 10, 12, 13, 14, 15, 16, 17, 49, 55, 60, 63, 65, 73, 74, 75, 77, 81, 83, 87, 97, 98, 105, 106, 111, 113, 114, 116, 124, 126, 127, 130, 152, 155, 165, 167, 170, 172, 174, 176, 205, 214, 219 or the like. Among these, from the viewpoint of hue, brightness, and contrast ratio, C.I. I. Pigment red 185, 242 and C.I. I. Pigment Orange 38 is desirable.

   Specific examples of other red pigments that can be used in combination include C.I. I. Pigment Red 41, 48: 1, 48: 2, 48: 3, 48: 4, 57: 1, 81, 81: 1, 81: 2, 81: 3, 81: 4, 122, 146, 168, 169, 178, 179, 184, 187, 200, 202, 210, 246, 254, 255, 264, 270, 272, 273, 274, 276, 277, 278, 279, 280, 281, 282, 283, 284, 285, Mention may be made of red pigments such as 286 or 287. Examples of red dyes include xanthene series, azo series (pyridone series, barbituric acid series, metal complex series, etc.), disazo series, and anthraquinone series. Specifically, C.I. I. And salt forming compounds of xanthene acid dyes such as Acid Red 52, 87, 92, 289 and 338.

  In addition, C.I. I. Pigment Orange 43, 64, 71, or 73, and / or C.I. I. Pigment Yellow 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 61, 62, 93, 94, 95, 100, 101, 104, 108, 109, 110, 115, 117, 118, 119, 120, 123, 128, 129, 138, 139, 147, 150, 151, 153, 154, 156, 161, 162, 164, 166, 168, 169, 171, 173, 175, 177, 179, 180, 181, 182, 187, 188, 193, 194, 198, 199, 213, 218, 220, or 221 can be used in combination. . Examples of the orange dye and / or yellow dye include quinoline series, azo series (pyridone series, barbituric acid series, metal complex series, etc.), disazo series, and methine series.

  Preferred dyes to be used in combination include diketopyrrolopyrrole, anthraquinone, quinophthalone, isoindoline, perylene, perinone, and benzimidazolone dyes from the viewpoint of brightness and tinting strength. Specifically, C.I. I. Pigment red 176, 179, 254, 242, C.I. I. Pigment yellow 138, 139, 150, 231, C.I. I. Pigment oranges 38, 43 and 64.

(Miniaturization of pigment)
The pigment used in the present invention can be used after being refined. The azo pigment [A] is also preferably used after being refined, but the refinement method is not particularly limited. For example, any of wet grinding, dry grinding, and dissolution precipitation can be used, and is exemplified in the present invention. Thus, a salt milling process by a kneader method, which is a kind of wet grinding, can be performed. As the azo pigment [A] to be refined, any commercially available product may be used, or an azo pigment [A] produced by a coupling reaction of a diazonium salt corresponding to the azo pigment [A] and β-naphthols may be used. .
By making these colorants finer, they can be suitably used as red coloring compositions for organic EL display devices.

The primary particle size of the refined pigment is preferably 20 nm or more because of good dispersion in the colorant carrier. Moreover, since it can form a filter segment with high contrast ratio, it is preferable that it is 100 nm or less. A particularly preferable range is a range of 25 to 85 nm.
The primary particle diameter of the pigment was measured by directly measuring the size of the primary particle from an electron micrograph of the pigment using a TEM (transmission electron microscope). Specifically, the minor axis diameter and major axis diameter of the primary particles of each pigment were measured, and the average was taken as the particle diameter of the pigment particles. Next, for 100 or more pigment particles, the volume of each particle is approximated to a cube having the obtained particle diameter to obtain an average volume, and the length of one side of the cube having this average volume is determined as the average primary The particle size.

  Salt milling is a process of heating a mixture of pigment, water-soluble inorganic salt and water-soluble organic solvent using a kneader such as a kneader, trimix, two-roll mill, three-roll mill, ball mill, attritor or sand mill. Then, after mechanically kneading, the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water. The water-soluble inorganic salt serves as a crushing aid, and the pigment is crushed using the high hardness of the inorganic salt during salt milling. By optimizing the conditions for salt milling the pigment, it is possible to obtain a pigment having a sharp particle size distribution with a very fine primary particle diameter and a wide distribution range.

  As the water-soluble inorganic salt, sodium chloride, barium chloride, potassium chloride, sodium sulfate and the like can be used, but sodium chloride (salt) is preferably used from the viewpoint of cost. The water-soluble inorganic salt is preferably used in an amount of 50 to 2000 parts by weight, and most preferably 300 to 1000 parts by weight with respect to 100 parts by weight of the pigment, from the viewpoint of both processing efficiency and production efficiency.

  The water-soluble organic solvent functions to wet the pigment and the water-soluble inorganic salt, and is not particularly limited as long as it dissolves (mixes) in water and does not substantially dissolve the inorganic salt to be used. However, a high boiling point solvent having a boiling point of 120 ° C. or higher is preferable from the viewpoint of safety because the temperature rises during salt milling and the solvent is easily evaporated. For example, 2-methoxyethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, Liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid polypropylene glycol and the like are used. The water-soluble organic solvent is preferably used in an amount of 5 to 1000 parts by weight, and most preferably 50 to 500 parts by weight, based on 100 parts by weight of the pigment.

  When the salt is milled, a resin may be added as necessary. The type of resin used is not particularly limited, and natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, and the like can be used. The resin used is solid at room temperature, preferably insoluble in water, and more preferably partially soluble in the organic solvent. The amount of the resin used is preferably in the range of 5 to 200 parts by weight with respect to 100 parts by weight of the pigment.

<Alkali-soluble resin>
The alkali-soluble resin in the present invention is for imparting development solubility in an alkali development step at the time of producing a color filter and has an acid group. Further, in order to further improve the photosensitivity, a resin having an ethylenically unsaturated double bond can be used.

  In particular, by using an active energy ray-curable resin into which an ethylenically unsaturated double bond has been introduced by the method (i) or (ii) shown below, the resin is used to form a coating film by exposure with active energy rays. Is three-dimensionally cross-linked to increase cross-linking density and improve chemical resistance.

[Method (i)]
As the method (i), for example, a side chain epoxy group of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having an epoxy group and one or more other monomers is used. Addition reaction of a carboxyl group of an unsaturated monobasic acid having an ethylenically unsaturated double bond, and further reacting a polybasic acid anhydride with the generated hydroxyl group to convert an ethylenically unsaturated double bond and a carboxyl group. There is a way to introduce.

  Examples of the ethylenically unsaturated monomer having an epoxy group include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, 2-glycidoxyethyl (meth) acrylate, and 3,4-epoxybutyl (meth) acrylate. And 3,4-epoxycyclohexyl (meth) acrylate, which may be used alone or in combination of two or more. From the viewpoint of reactivity with the unsaturated monobasic acid in the next step, glycidyl (meth) acrylate is preferred.

  Examples of unsaturated monobasic acids include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-haloalkyl of (meth) acrylic acid, alkoxyl, halogen, nitro, cyano substituted products, etc. Monocarboxylic acid etc. are mentioned, These may be used independently or may use 2 or more types together.

  Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, etc., and these may be used alone or in combination of two or more. It doesn't matter. If necessary, use a tricarboxylic anhydride such as trimellitic anhydride or a tetracarboxylic dianhydride such as pyromellitic dianhydride to increase the number of carboxyl groups. The group can be hydrolyzed. Further, when tetrahydrophthalic anhydride or maleic anhydride having an ethylenically unsaturated double bond is used as the polybasic acid anhydride, the ethylenically unsaturated double bonds can be further increased.

  As a method similar to the method (i), for example, a side chain of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having a carboxyl group and one or more other monomers. There is a method in which an ethylenically unsaturated monomer having an epoxy group is added to a part of a carboxyl group to introduce an ethylenically unsaturated double bond and a carboxyl group.

[Method (ii)]
As the method (ii), an ethylenically unsaturated monomer having a hydroxyl group is used, and an unsaturated monobasic acid monomer having another carboxyl group or another monomer is copolymerized. There is a method of reacting the isocyanate group of an ethylenically unsaturated monomer having an isocyanate group with the side chain hydroxyl group of the obtained copolymer.

Examples of the ethylenically unsaturated monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3
-Or 4-hydroxybutyl (meth) acrylate, glycerol (meth) acrylate, or hydroxyalkyl methacrylates such as cyclohexanedimethanol mono (meth) acrylate, and these may be used alone or in combination of two or more. It may be used in combination. In addition, polyether mono (meth) acrylate obtained by addition polymerization of ethylene oxide, propylene oxide, and / or butylene oxide to the above hydroxyalkyl (meth) acrylate, polyγ-valerolactone, polyε-caprolactone, and / or Polyester mono (meth) acrylate added with poly-12-hydroxystearic acid or the like can also be used. From the viewpoint of suppressing foreign matter on the coating film, 2-hydroxyethyl methacrylate or glycerol methacrylate is preferable.

  Examples of the ethylenically unsaturated monomer having an isocyanate group include 2- (meth) acryloyloxyethyl isocyanate or 1,1-bis [methacryloyloxy] ethyl isocyanate, but are not limited thereto. Two or more types can be used in combination.

The following are mentioned as a monomer which comprises alkali-soluble resin. For example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) Acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, or ethoxypolyethylene Glycol (meth) acrylate of (meth) acrylates,
Alternatively, (meth) acrylamide (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, diacetone (meth) acrylamide, acryloylmorpholine, etc. Acrylamide styrene, styrenes such as α-methylstyrene, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, vinyl ethers such as isobutyl vinyl ether, fatty acid vinyls such as vinyl acetate or vinyl propionate Is mentioned.
Alternatively, cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimide ethane 1,6-bismaleimidehexane, 3-maleimidopropionic acid, 6,7-methylenedioxy-4-methyl-3-maleimide Coumarin, 4,4′-bismaleimide diphenylmethane, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, N, N′-1,3-phenylenedimaleimide, N, N′-1,4- Phenylene dimaleimide, N- (1-pyrenyl) maleimide, N- (2,4,6-trichlorophenyl) maleimide, N- (4-aminophenyl) maleimide, N- (4-nitrophenyl) maleimide, N-benzyl Maleimide, N-bromomethyl-2,3-dichloromaleimide, N-succin Midyl-3-maleimidobenzoate, N-succinimidyl-3-maleimidopropionate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidohexanoate, N- [4- (2-benzimidazolyl) phenyl N-substituted maleimides such as maleimide and 9-maleimide acridine.

Among them, the acrylic soluble resin of the present invention is preferably a resin having a structural unit derived from methyl methacrylate. Use of a resin having a structural unit derived from methyl methacrylate is preferable because the packing property of the resin chain is improved and the chemical resistance is improved.

A carboxyl group-containing ethylenically unsaturated monomer can also be used. Examples of the carboxyl group-containing ethylenically unsaturated monomer include acrylic acid, methacrylic acid, ε-caprolactone-added acrylic acid, ε-caprolactone-added methacrylic acid, itaconic acid, maleic acid, fumaric acid, and crotonic acid.

Moreover, a hydroxyl-containing ethylenically unsaturated monomer can also be used. Examples of the hydroxyl group-containing ethylenically unsaturated monomer include 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3- or 4-hydroxybutyl (meth) acrylate, or cyclohexane. And hydroxyalkyl (meth) acrylates such as dimethanol mono (meth) acrylate. Also, polyether mono (meth) acrylates obtained by addition polymerization of the above hydroxyalkyl (meth) acrylates with ethylene oxide, propylene oxide, and / or butylene oxide, (poly) γ-valerolactone, (poly) ε-caprolactone And / or (poly) ester mono (meth) acrylate added with (poly) 12-hydroxystearic acid and the like.

A phosphoric ester group-containing ethylenically unsaturated monomer can also be used. As the phosphoric ester group-containing ethylenically unsaturated monomer, for example, a monomer that can be obtained by reacting the hydroxyl group of the hydroxyl group-containing ethylenically unsaturated monomer with a phosphoric acid esterifying agent such as phosphorus pentoxide or polyphosphoric acid. Is mentioned.

  The alkali-soluble resin in the present invention is preferably a resin having a spectral transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region.

The weight average molecular weight (Mw) of the alkali-soluble resin in the present invention is from 2000 to 40000, preferably from 3000 to 30000, more preferably from 4000 to 20000, in order to impart alkali development solubility. Moreover, it is preferable that the value of Mw / Mn is 10 or less. When the weight average molecular weight (Mw) is less than 2000, the adhesion to the substrate is lowered, and the exposure pattern is less likely to remain. If it exceeds 40,000, the alkali developing solubility is lowered, a residue is generated, and the linearity of the pattern is deteriorated.
The acid value of the alkali-soluble resin in the present invention is from 50 to 200 (KOHmg / g) in order to impart alkali development solubility, preferably in the range from 70 to 180, more preferably from 90 to 170. It is a range. When the acid value is less than 50, the alkali development solubility is lowered, a residue is generated, and the linearity of the pattern is deteriorated. If it exceeds 200, the adhesion to the substrate is lowered, and the exposure pattern is less likely to remain.

[Thermosetting compound]
In the present invention, a thermosetting compound may be further contained in combination with the acrylic soluble resin.

  Examples of the thermosetting compound include epoxy compounds and / or resins, benzoguanamine compounds and / or resins, rosin-modified maleic acid compounds and / or resins, rosin-modified fumaric acid compounds and / or resins, melamine compounds and / or resins, Examples include urea compounds and / or resins, phenol compounds and / or resins, but the present invention is not limited thereto.

<Photopolymerizable monomer>
Photopolymerizable monomers that may be added to the colored composition of the present invention include monomers or oligomers that are cured by ultraviolet rays or heat to produce a transparent resin.

Examples of monomers and oligomers that are cured by ultraviolet rays or heat to produce a transparent resin include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 2-hydroxypropyl (meth) acrylate. , Cyclohexyl (meth) acrylate, β-carboxyethyl (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di ( (Meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1,6-hexanediol diglycy Luether di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tricyclodeca Nyl (meth) acrylate, ester acrylate, methylolated melamine (meth) acrylate ester, epoxy (meth) acrylate, urethane acrylate and other acrylic esters and methacrylate esters, (meth) acrylic acid, styrene, vinyl acetate, Hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl Examples include, but are not necessarily limited to, til (meth) acrylamide, N-vinylformamide, acrylonitrile and the like.
These photopolymerizable compounds can be used singly or in combination of two or more at any ratio as required.

  The content of the photopolymerizable monomer is preferably 5 to 400 parts by weight with respect to 100 parts by weight of the dye, and more preferably 10 to 300 parts by weight from the viewpoint of photocurability and developability.

<Photopolymerization initiator>
In the colored composition of the present invention, a photopolymerization initiator is added to form a filter segment by photolithography by curing the composition by ultraviolet irradiation, and a solvent development type or alkali development type photosensitive coloring composition is added. It can be prepared in the form of

(Oxime ester compounds)
The photosensitive coloring composition for a color filter of the present invention can contain an oxime ester-based compound as a photopolymerization initiator.
The oxime ester-based compound absorbs ultraviolet rays to cleave the N—O bond of the oxime to generate an iminyl radical and an alkyloxy radical. Since these radicals are further decomposed to generate radicals with high activity, a pattern can be formed with a small exposure amount. When the concentration of the colorant in the photosensitive coloring composition is high, the ultraviolet transmittance of the coating film may be low and the curing degree of the coating film may be low. The More preferably, when it has a carbazole group, it can be set as the composition excellent in the brightness and color purity. Particularly preferred is an oxime ester photopolymerization initiator represented by the general formula (3).

(Oxime ester photopolymerization initiator represented by the general formula (3))
General formula (3)

In general formula (3),
Y ¹ is a hydrogen atom or an optionally substituted alkenyl group, alkyl group, alkyloxy group, aryl group, aryloxy group, heterocyclic group, heterocyclic oxy group, alkylsulfanyl group, arylsulfanyl group An alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, an acyloxy group, an amino group, a phosphinoyl group, a carbamoyl group, or a sulfamoyl group,
Y ² is a hydrogen atom or an optionally substituted alkenyl group, alkyl group, alkyloxy group, aryl group, aryloxy group, heterocyclic group, heterocyclic oxy group, alkylsulfanyl group, arylsulfanyl group , An alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyloxy group, or an amino group.
Z is a direct bond or a -CO- group,
Y ³ is a monovalent organic group including a carbazole group which may have a substituent, a Ph-S-Ph- group (Ph represents a phenyl group or a phenylene group which may have a substituent). Etc.

Examples of the alkenyl group which may have a substituent in Y ¹ include a linear, branched, monocyclic or condensed polycyclic alkenyl group having 1 to 18 carbon atoms, and these include a plurality of carbon atoms in the structure. -It may have a carbon double bond, and specific examples include vinyl group, 1-propenyl group, allyl group, 2-butenyl group, 3-butenyl group, isopropenyl group, isobutenyl group, 1-pentenyl group. 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group, cyclopentenyl group, cyclohexenyl group, 1 , 3-butadienyl group, cyclohexadienyl group, cyclopentadienyl group and the like, but are not limited thereto.

The alkyl group which may have a substituent for Y ¹ is a linear, branched, monocyclic or condensed polycyclic alkyl group having 1 to 18 carbon atoms, or 2 to 18 carbon atoms and optionally 1 Examples include a linear, branched, monocyclic or condensed polycyclic alkyl group interrupted by one or more —O—. Specific examples of the linear, branched, monocyclic or condensed polycyclic alkyl group having 1 to 18 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group. Group, nonyl group, decyl group, dodecyl group, octadecyl group, isopropyl group, isobutyl group, isopentyl group, sec-butyl group, tert-butyl group, sec-pentyl group, tert-pentyl group, tert-octyl group, neopentyl group , Cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, adamantyl group, norbornyl group, boronyl group, 4-decylcyclohexyl group and the like, but are not limited thereto. Specific examples of the linear or branched alkyl group having 2 to 18 carbon atoms and optionally interrupted by one or more of —O— include —CH ₂ —O—CH ₃ , —CH _2. —CH ₂ —O—CH ₂ —CH ₃ , —CH ₂ —CH ₂ —CH ₂ —O—CH ₂ —CH ₃ , — (CH ₂ —CH ₂ —O) _n —CH ₃ (where n is 1) To 8), — (CH ₂ —CH ₂ —CH ₂ —O) _m —CH ₃ (where m is 1 to 5), —CH ₂ —CH (CH ₃ ) —O—CH ₂ —. _{CH 3 -, - CH 2 -CH-} (OCH 3) but ₂ and the like, but is not limited thereto.

  Specific examples of the monocyclic or condensed polycyclic alkyl group having 2 to 18 carbon atoms and optionally interrupted by one or more of -O- include the following, but are not limited thereto. Is not to be done.

The alkyloxy group which may have a substituent for Y ¹ is a linear, branched, monocyclic or condensed polycyclic alkyloxy group having 1 to 18 carbon atoms, or 2 to 18 carbon atoms. Examples include linear, branched, monocyclic or condensed polycyclic alkyloxy groups optionally interrupted by one or more —O—. Specific examples of the linear, branched, monocyclic or condensed polycyclic alkyloxy group having 1 to 18 carbon atoms include methyloxy group, ethyloxy group, propyloxy group, butyloxy group, pentyloxy group, hexyloxy Group, heptyloxy group, octyloxy group, nonyloxy group, decyloxy group, dodecyloxy group, octadecyloxy group, isopropyloxy group, isobutyloxy group, isopentyloxy group, sec-butyloxy group, tert-butyloxy group, sec-pentyl Oxy group, tert-pentyloxy group, tert-octyloxy group, neopentyloxy group, cyclopropyloxy group, cyclobutyloxy group, cyclopentyloxy group, cyclohexyloxy group, adamantyloxy group, norbornyloxy group, boroni Group, 4-decyl cyclohexyl although group and the like, but is not limited thereto. Specific examples of the linear or branched alkyloxy group having 2 to 18 carbon atoms and optionally interrupted by one or more —O— include —O—CH ₂ —O—CH ₃ , _{-O-CH 2 -CH 2 -O-} CH 2 -CH 3, -O-CH 2 -CH 2 -CH 2 -O-CH 2 -CH 3, -O- (CH 2 -CH 2 -O) n -CH ₃ (wherein n is 1 to _{8), - O- (CH 2} -CH 2 -CH 2 -O) m -CH 3 ( here m is 5 1), - O-CH _{2 -CH (CH 3) -O-} CH 2 -CH 3 -, - OCH 2 -CH- (OCH 3) can be cited _2, etc., but is not limited thereto.

  Specific examples of the monocyclic or condensed polycyclic alkyloxy group having 2 to 18 carbon atoms and optionally interrupted by one or more of —O— include the following. It is not limited.

Examples of the aryl group that may have a substituent in Y ¹ include a monocyclic or condensed polycyclic aryl group having 6 to 24 carbon atoms, and specific examples thereof include a phenyl group, a 1-naphthyl group, and 2-naphthyl. Group, 1-anthryl group, 9-anthryl group, 2-phenanthryl group, 3-phenanthryl group, 9-phenanthryl group, 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azurenyl group, 1-acenaphthyl group Group, 2-fluorenyl group, 9-fluorenyl group, 3-perylenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 2,3-xylyl group, 2,5-xylyl group, mesityl group, p -Cumenyl group, p-dodecylphenyl group, p-cyclohexylphenyl group, 4-biphenyl group, o-fluorophenyl group, m-chlorophenyl group, p-bromopheny Group, p-hydroxyphenyl group, m-carboxyphenyl group, o-mercaptophenyl group, p-cyanophenyl group, m-nitrophenyl group, m-azidophenyl group, etc., but are not limited thereto. It is not something.

Examples of the aryloxy group which may have a substituent for Y ¹ include a monocyclic or condensed polycyclic aryloxy group having 4 to 18 carbon atoms, and specific examples include a phenoxy group, a 1-naphthyloxy group, 2- Naphtyloxy group, 9-anthryloxy group, 9-phenanthryloxy group, 1-pyrenyloxy group, 5-naphthacenyloxy group, 1-indenyloxy group, 2-azurenyloxy group, 1-acenaphthyloxy group , 9-fluorenyloxy group and the like, but are not limited thereto.

Examples of the heterocyclic group which may have a substituent for Y ¹ include aromatic or aliphatic heterocyclic groups having 4 to 24 carbon atoms, including a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom. 2-thienyl group, 2-benzothienyl group, naphtho [2,3-b] thienyl group, 3-thianthrenyl group, 2-thianthrenyl group, 2-furyl group, 2-benzofuryl group, pyranyl group, isobenzofuranyl Group, chromenyl group, xanthenyl group, phenoxathiinyl group, 2H-pyrrolyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, pyridyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, indolizinyl group, isoindolyl group, 3H-indolyl group 2-indolyl group, 3-indolyl group, 1H-indazolyl group, purinyl group, 4H-quinolidinyl group, isoquino Lyl group, quinolyl group, phthalazinyl group, naphthyridinyl group, quinoxanilyl group, quinazolinyl group, cinnolinyl group, pteridinyl group, 4aH-carbazolyl group, 2-carbazolyl group, 3-carbazolyl group, β-carbolinyl group, phenanthridinyl group, 2-acridinyl group, perimidinyl group, phenanthrolinyl group, phenazinyl group, phenalsadinyl group, isothiazolyl group, phenothiazinyl group, isoxazolyl group, furazanyl group, 3-phenixazinyl group, isochromanyl group, chromanyl group, pyrrolidinyl group, pyrrolinyl group, Imidazolidinyl group, imidazolinyl group, pyrazolidinyl group, pyrazolinyl group, piperidyl group, piperazinyl group, indolinyl group, isoindolinyl group, quinuclidinyl group, morpholinyl group, thioxanthryl group 4-quinolinyl group, 4-isoquinolyl group, 3-phenothiazinyl group, 2-phenoxathiinyl group, 3-coumarinyl of the group and the like, but is not limited thereto.

Examples of the heterocyclic oxy group that may have a substituent for Y ¹ include a monocyclic or condensed polycyclic heterocyclic oxy group having 4 to 18 carbon atoms, including a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom. Specific examples include 2-furanyloxy group, 2-thienyloxy group, 2-indolyloxy group, 3-indolyloxy group, 2-benzofuryloxy group, 2-benzothienyloxy group, 2-carbazolyl. Examples thereof include, but are not limited to, a ruoxy group, a 3-carbazolyloxy group, a 4-carbazolyloxy group, and a 9-acridinyloxy group.

Examples of the alkylsulfanyl group which may have a substituent in Y ¹ include a linear, branched, monocyclic or condensed polycyclic alkylthio group having 1 to 18 carbon atoms. Specific examples include a methylthio group. , Ethylthio group, propylthio group, butylthio group, pentylthio group, hexylthio group, octylthio group, decylthio group, dodecylthio group, octadecylthio group and the like, but are not limited thereto.

Examples of the arylsulfanyl group which may have a substituent in Y ¹ include a monocyclic or condensed polycyclic arylthio group having 6 to 18 carbon atoms, and specific examples thereof include a phenylthio group, a 1-naphthylthio group, 2- Examples thereof include, but are not limited to, a naphthylthio group, a 9-anthrylthio group, and a 9-phenanthrylthio group.

The alkylsulfinyl group which may have a substituent in Y ¹ is preferably an alkylsulfinyl group having 1 to 20 carbon atoms, and specific examples include a methylsulfinyl group, an ethylsulfinyl group, a propylsulfinyl group, an isopropylsulfinyl group, Butylsulfinyl group, hexylsulfinyl group, cyclohexylsulfinyl group, octylsulfinyl group, 2-ethylhexylsulfinyl group, decanoylsulfinyl group, dodecanoylsulfinyl group, octadecanoylsulfinyl group, cyanomethylsulfinyl group, methyloxymethylsulfinyl group, etc. Although it is mentioned, it is not limited to these.

The arylsulfinyl group which may have a substituent in Y ¹ is preferably an arylsulfinyl group having 6 to 30 carbon atoms, and specific examples thereof include a phenylsulfinyl group, a 1-naphthylsulfinyl group, a 2-naphthylsulfinyl group, 2-chlorophenylsulfinyl group, 2-methylphenylsulfinyl group, 2-methyloxyphenylsulfinyl group, 2-butyloxyphenylsulfinyl group, 3-chlorophenylsulfinyl group, 3-trifluoromethylphenylsulfinyl group, 3-cyanophenylsulfinyl group 3-nitrophenylsulfinyl group, 4-fluorophenylsulfinyl group, 4-cyanophenylsulfinyl group, 4-methyloxyphenylsulfinyl group, 4-methylsulfanylphenylsulfinyl group, 4- Examples thereof include, but are not limited to, a phenylsulfanylphenylsulfinyl group and a 4-dimethylaminophenylsulfinyl group.

The alkylsulfonyl group which may have a substituent in Y ¹ is preferably an alkylsulfonyl group having 1 to 20 carbon atoms, and specific examples include a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, an isopropylsulfonyl group, Butylsulfonyl group, hexylsulfonyl group, cyclohexylsulfonyl group, octylsulfonyl group, 2-ethylhexylsulfonyl group, decanoylsulfonyl group, dodecanoylsulfonyl group, octadecanoylsulfonyl group, cyanomethylsulfonyl group, methyloxymethylsulfonyl group, etc. Although it is mentioned, it is not limited to these.

The arylsulfonyl group which may have a substituent for Y ¹ is preferably an arylsulfonyl group having 6 to 30 carbon atoms, and specific examples include a phenylsulfonyl group, a 1-naphthylsulfonyl group, a 2-naphthylsulfonyl group, 2-chlorophenylsulfonyl group, 2-methylphenylsulfonyl group, 2-methyloxyphenylsulfonyl group, 2-butyloxyphenylsulfonyl group, 3-chlorophenylsulfonyl group, 3-trifluoromethylphenylsulfonyl group, 3-cyanophenylsulfonyl group 3-nitrophenylsulfonyl group, 4-fluorophenylsulfonyl group, 4-cyanophenylsulfonyl group, 4-methyloxyphenylsulfonyl group, 4-methylsulfanylphenylsulfonyl group, 4-phenylsulfanylphenylsulfo Examples thereof include, but are not limited to, a nyl group and a 4-dimethylaminophenylsulfonyl group.

Examples of the acyl group which may have a substituent for Y ¹ include a hydrogen atom or a carbonyl group to which a linear, branched, monocyclic or condensed polycyclic aliphatic group having 1 to 18 carbon atoms is bonded, A carbonyl group substituted by an alkyloxy group having 2 to 20 carbon atoms, a carbonyl group to which a monocyclic or condensed polycyclic aryl group having 6 to 18 carbon atoms is bonded, or a monocyclic or condensed polycyclic aryloxy group having 6 to 18 carbon atoms. Examples include a carbonyl group to which a monocyclic or condensed polycyclic heterocyclic group having 4 to 18 carbon atoms including a substituted carbonyl group, a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom is bonded. Specific examples include formyl Group, acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group, isovaleryl group, pivaloyl group, lauroyl group, myristoyl group, palmitoyl Group, stearoyl group, cyclopentylcarbonyl group, cyclohexylcarbonyl group, acryloyl group, methacryloyl group, crotonoyl group, isocrotonoyl group, oleoyl group, cinnamoyl group benzoyl group, methyloxycarbonyl group, ethyloxycarbonyl group, propyloxycarbonyl group, butyl Oxycarbonyl group, hexyloxycarbonyl group, octyloxycarbonyl group, decyloxycarbonyl group, octadecyloxycarbonyl group, trifluoromethyloxycarbonyl group, benzoyl group, toluoyl group, 1-naphthoyl group, 2-naphthoyl group, 9-an Thrylcarbonyl group, phenyloxycarbonyl group, 4-methylphenyloxycarbonyl group, 3-nitrophenyloxycarbonyl group, 4-dimethylaminopheny Oxycarbonyl group, 2-methylsulfanylphenyloxycarbonyl group, 1-naphthoyloxycarbonyl group, 2-naphthoyloxycarbonyl group, 9-anthrylyloxycarbonyl group, 3-furoyl group, 2-thenoyl group, nicotinoyl group, Although an isonicotinoyl group etc. can be mentioned, it is not limited to these.

Examples of the acyloxy group which may have a substituent in Y ¹ include an acyloxy group having 2 to 20 carbon atoms, and specific examples include an acetyloxy group, a propanoyloxy group, a butanoyloxy group, and a pentanoyloxy group. Group, trifluoromethylcarbonyloxy group, benzoyloxy group, 1-naphthylcarbonyloxy group, 2-naphthylcarbonyloxy group and the like.

Examples of the amino group which may have a substituent in Y ¹ include an amino group, an alkylamino group, a dialkylamino group, an arylamino group, a diarylamino group, an alkylarylamino group, a benzylamino group, and a dibenzylamino group. Can be mentioned.

  Here, as the alkylamino group, methylamino group, ethylamino group, propylamino group, butylamino group, pentylamino group, hexylamino group, heptylamino group, octylamino group, nonylamino group, decylamino group, dodecylamino group , Octadecylamino group, isopropylamino group, isobutylamino group, isopentylamino group, sec-butylamino group, tert-butylamino group, sec-pentylamino group, tert-pentylamino group, tert-octylamino group, neopentyl Amino group, cyclopropylamino group, cyclobutylamino group, cyclopentylamino group, cyclohexylamino group, cycloheptylamino group, cyclooctylamino group, cyclododecylamino group, 1-adamantamino group, 2-adamantami Group, and the like, but not limited thereto.

  Dialkylamino groups include dimethylamino group, diethylamino group, dipropylamino group, dibutylamino group, dipentylamino group, dihexylamino group, diheptylamino group, dioctylamino group, dinonylamino group, didecylamino group, didodecylamino group, Dioctadecylamino group, diisopropylamino group, diisobutylamino group, diisopentylamino group, methylethylamino group, methylpropylamino group, methylbutylamino group, methylisobutylamino group, cyclopropylamino group, pyrrolidino group, piperidino group, Examples include, but are not limited to, piperazino groups.

  As an arylamino group, an anilino group, 1-naphthylamino group, 2-naphthylamino group, o-toluidino group, m-toluidino group, p-toluidino group, 2-biphenylamino group, 3-biphenylamino group, 4- A biphenylamino group, a 1-fluoreneamino group, a 2-fluoreneamino group, a 2-thiazoleamino group, a p-terphenylamino group, and the like are exemplified, but the invention is not limited thereto.

  Examples of the diarylamino group include, but are not limited to, a diphenylamino group, a ditolylamino group, an N-phenyl-1-naphthylamino group, and an N-phenyl-2-naphthylamino group.

  Examples of the alkylarylamino group include N-methylanilino group, N-methyl-2-pyridino group, N-ethylanilino group, N-propylanilino group, N-butylanilino group, N-isopropyl, N-pentylanilino group, N -Ethylanilino group, N-methyl-1-naphthylamino group and the like are exemplified, but not limited thereto.

Examples of the phosphinoyl group which may have a substituent in Y ¹ include phosphinoyl groups having 2 to 50 carbon atoms, and specific examples thereof include dimethylphosphinoyl group, diethylphosphinoyl group, dipropylphosphinoyl group. Group, diphenylphosphinoyl group, dimethoxyphosphinoyl group, diethoxyphosphinoyl group, dibenzoylphosphinoyl group, bis (2,4,6-trimethylphenyl) phosphinoyl group, etc. Is not to be done.

Examples of the carbamoyl group which may have a substituent for Y ¹ include carbamoyl groups having 1 to 30 carbon atoms, and specific examples thereof include an N-methylcarbamoyl group, an N-ethylcarbamoyl group, and an N-propylcarbamoyl group. N-butylcarbamoyl group, N-hexylcarbamoyl group, N-cyclohexylcarbamoyl group, N-octylcarbamoyl group, N-decylcarbamoyl group, N-octadecylcarbamoyl group, N-phenylcarbamoyl group, N-2-methylphenylcarbamoyl group Group, N-2-chlorophenylcarbamoyl group, N-2-isopropoxyphenylcarbamoyl group, N-2- (2-ethylhexyl) phenylcarbamoyl group, N-3-chlorophenylcarbamoyl group, N-3-nitrophenylcarbamoyl group, N-3-cyanoph Enylcarbamoyl group, N-4-methoxyphenylcarbamoyl group, N-4-cyanophenylcarbamoyl group, N-4-methylsulfanylphenylcarbamoyl group, N-4-phenylsulfanylphenylcarbamoyl group, N-methyl-N-phenylcarbamoyl Group, N, N-dimethylcarbamoyl group, N, N-dibutylcarbamoyl group, N, N-diphenylcarbamoyl group, and the like, but are not limited thereto.

Examples of the sulfamoyl group which may have a substituent in Y ¹ include a sulfamoyl group having 0 to 30 carbon atoms, and specific examples thereof include a sulfamoyl group, an N-alkylsulfamoyl group, and an N-arylsulfamoyl group. Group, N, N-dialkylsulfamoyl group, N, N-diarylsulfamoyl group, N-alkyl-N-arylsulfamoyl group and the like. More specifically, N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-butylsulfamoyl group, N-hexylsulfamoyl group, N-cyclohexylsulfur group. Famoyl group, N-octylsulfamoyl group, N-2-ethylhexylsulfamoyl group, N-decylsulfamoyl group, N-octadecylsulfamoyl group, N-phenylsulfamoyl group, N-2- Methylphenylsulfamoyl group, N-2-chlorophenylsulfamoyl group, N-2-methoxyphenylsulfamoyl group, N-2-isopropoxyphenylsulfamoyl group, N-3-chlorophenylsulfamoyl group, N-3-nitrophenylsulfamoyl group, N-3-cyanophenylsulfamoyl group, N-4-methoxyphenyl Nylsulfamoyl group, N-4-cyanophenylsulfamoyl group, N-4-dimethylaminophenylsulfamoyl group, N-4-methylsulfanylphenylsulfamoyl group, N-4-phenylsulfanylphenylsulfamoyl Group, N-methyl-N-phenylsulfamoyl group, N, N-dimethylsulfamoyl group, N, N-dibutylsulfamoyl group, N, N-diphenylsulfamoyl group and the like. It is not limited to.

Y ² may have a substituent, an alkenyl group, an alkyl group, an alkyloxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfinyl group, As the arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, acyloxy group, and amino group, the aforementioned alkenyl group that may have a substituent in R1, an alkyl group that may have a substituent, and a substituent An alkyloxy group that may have, an aryl group that may have a substituent, an aryloxy group that may have a substituent, a heterocyclic group that may have a substituent, and a substituent A good heterocyclic oxy group, an alkylsulfanyl group which may have a substituent, an arylsulfanyl group which may have a substituent, a substituent An alkylsulfinyl group which may have a substituent, an arylsulfinyl group which may have a substituent, an alkylsulfonyl group which may have a substituent, an arylsulfonyl group which may have a substituent, and a substituent. It is synonymous with the acyloxy group which may be sufficient, and the amino group which may have a substituent.

Examples of these substituents for Y ¹ and Y ² include halogen groups such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group, ethoxy group and tert-butoxy group, phenoxy group and p-tolyloxy. Aryloxy groups such as methoxycarbonyl groups, butoxycarbonyl groups, alkoxycarbonyl groups such as phenoxycarbonyl groups, acyloxy groups such as acetoxy groups, propionyloxy groups, benzoyloxy groups, acetyl groups, benzoyl groups, isobutyryl groups, acryloyl groups , Acyl groups such as methacryloyl group, methoxalyl group, alkylsulfanyl groups such as methylsulfanyl group, tert-butylsulfanyl group, arylsulfanyl groups such as phenylsulfanyl group, p-tolylsulfanyl group, methylamino , Alkylamino groups such as cyclohexylamino group, dialkylamino groups such as dimethylamino group, diethylamino group, morpholino group and piperidino group, arylamino groups such as phenylamino group and p-tolylamino group, methyl group, ethyl group, tert- Alkyl groups such as butyl, dodecyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclooctadecyl, phenyl, p-tolyl, xylyl, cumenyl, naphthyl Group, anthryl group, aryl group such as phenanthryl group, heterocyclic group such as furyl group, thienyl group, etc., hydroxy group, carboxy group, formyl group, mercapto group, sulfo group, mesyl group, p-toluenesulfonyl group, Amino group, nitro group, cyano group, tri Examples thereof include a fluoromethyl group, a trichloromethyl group, a trimethylsilyl group, a phosphinico group, a phosphono group, a trimethylammoniumum group, a dimethylsulfoniumyl group, and a triphenylphenacylphosphoniumyl group.
One or more of these substituents may be present, or one or more of these substituents may be present, and the hydrogen atom of these substituents may be further substituted with another substituent.

  Among these, the oxime ester photopolymerization initiator represented by the following general formula (4) or (5) is excellent in sensitivity and is preferable.

[Oxime ester photopolymerization initiator represented by formula (4)]
General formula (4)

The general formula (4) corresponds to the case where Z in the general formula (3) is a —CO— group and Y ³ is a Ph—S—Ph— group, and Y ⁴ to Y ^{6 each} represents a hydrogen atom or a substituent. An alkyl group or an aryl group which may be contained is preferable.

Furthermore the aryl group which may have a substituent as Y ^1, alkyl group having 1 to 20 carbon atoms that may have a substituent as Y ² is preferably a hydrogen atom as Y ⁴ to Y ⁶ .

The alkyl group that may have a substituent or the aryl group that may have a substituent in Y ^{4 to} Y ⁶ has the same meaning as the alkyl group or aryl group in Y ¹ and Y ² .

The alkyl group which may have a substituent or the substituent of the aryl group which may have a substituent has the same meaning as the substituent in Y ¹ and Y ² .

Y ² is preferably an alkyl group having 1 to 20 carbon atoms that may have a substituent, and the substituent is preferably a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, A cycloalkyl group such as a cyclooctadecyl group;

Specific examples of the oxime ester photopolymerization initiator represented by the general formula (4) include a photopolymerization initiator represented by the following chemical formula (4-1) or (4-2).

[Oxime ester photopolymerization initiator represented by general formula (5)]
General formula (5)

The general formula (5) corresponds to the case where Y ³ in the general formula (3) is a monovalent organic group including a carbazole group which may have a substituent, and Y ⁷ to Y ¹⁴ are Y ¹ and Y It is synonymous with the substituent in ² .

Further, the alkyl group having 1 to 20 carbon atoms which may have a substituent as Y ¹ may have an alkyl group having 1 to 20 carbon atoms which may have a substituent as Y ² or a substituent. A good aryl group is preferably a hydrogen atom as Y ^{7 to} Y ¹⁴ , an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aryl group which may have a substituent.

  When Z in the general formula (5) is a direct bond, an oxime ester photopolymerization initiator represented by the following general formula (5a) is preferable.

"Oxime ester photopolymerization initiator represented by formula (5a)"
General formula (5a)

The general formula (5a) corresponds to the case where Z in the general formula (3) is a direct bond and Y ³ is a monovalent organic group including a carbazole group which may have a substituent. Y < ⁷ > -Y < ¹⁰ > and Y < ¹² > -Y < ¹³ > are hydrogen atoms.
Y ¹¹ is preferably a Y ¹⁵ —CO— group or a nitro group. Y ¹⁵ is synonymous with the substituent in Y ¹ and Y ² and is preferably an aryl group which may have a substituent. The Y ¹⁵ —CO— group is preferably an acyl group such as an acetyl group, a benzoyl group, an isobutyryl group, an acryloyl group, a methacryloyl group, or a methoxalyl group, which may further have a substituent. More preferred is a benzoyl group or nitro group which may have a substituent. Y ¹⁴ is preferably an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aryl group which may have a substituent.

Moreover, as a substituent in the benzoyl group which may have a substituent, a C1-C20 alkyl group or an alkyloxy group is preferable. Further, the alkyl group is preferably a methyl group or an ethyl group, and among the alkyloxy groups, a linear or branched chain having 2 to 18 carbon atoms and optionally interrupted by one or more —O— Monocyclic or condensed polycyclic alkyloxy groups are preferred, linear, branched, monocyclic or condensed polycyclic having 2 to 18 carbon atoms in Y ¹ and optionally interrupted by one or more —O— Synonymous with alkyloxy group.

Y ² is preferably an alkyl group having 1 to 20 carbon atoms that may have a substituent, and the substituent is preferably a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, A cycloalkyl group such as a cyclooctadecyl group; Further, an aryl group which may have a substituent is preferable, and as the substituent, an alkyl group having 1 to 20 carbon atoms which may further have a substituent, a methoxy group, an ethoxy group, or a tert-butoxy group Etc. are preferred.

Specific examples of the oxime ester photopolymerization initiator represented by the general formula (5a) include photopolymerization initiators represented by the following chemical formulas (5a-1) to (5a-4).

"Oxime ester photopolymerization initiator represented by general formula (5b)"
When Z in the general formula (5) is a -CO- group, an oxime ester photopolymerization initiator represented by the following general formula (5b) is preferable.

General formula (5b)

The general formula (5b) corresponds to the case where Z in the general formula (3) is a -CO- group and Y ³ is a monovalent organic group including a carbazole group which may have a substituent. Is an oxime ester photopolymerization initiator.
Y ^{7 to} Y ¹³ are preferably a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aryl group which may have a substituent, and Y ¹⁴ may have a substituent. A good aryl group is preferred.
As the substituent of the aryl group which may have a substituent, an acyl group such as an acetyl group, a benzoyl group, an isobutyryl group, an acryloyl group, a methacryloyl group and a methoxalyl group is preferable, and a benzoyl group is more preferable.

Specific examples of the oxime ester photopolymerization initiator represented by the general formula (5b) include photopolymerization initiators represented by the following chemical formulas (5b-1) to (5b-4).

  Commercially available products of these oxime ester compounds include 1,2-octanedione, 1- [4- (phenylthio) phenyl-, 2- (O-benzoyloxime)] (IRGACURE OXE-01), and ethanone from BASF. , 1- [9-Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) (IRGACURE OXE 02) is commercially available. In addition to these, oximes described in JP2007-210991A, JP2009-179619A, JP2010-037223A, JP2010-215575A, JP2011-020998A, and the like. It is also possible to use an ester photopolymerization initiator.

  The content of the oxime ester compound is preferably 2 to 50 parts by weight with respect to 100 parts by weight of the dye, and more preferably 2 to 30 parts by weight from the viewpoint of photocurability and developability. When the amount is less than 2 parts by weight, the adhesion of the formed pattern to the base material is deteriorated. When the amount exceeds 50 parts by weight, there is a problem in developability or a decrease in brightness after heat treatment at 230 ° C.

(Other photopolymerization initiators)
Other photopolymerization initiators include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] Acetophenone compounds such as -1- [4- (4-morpholinyl) phenyl] -1-butanone or 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one; benzoin , Benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, Or benzoin compounds such as benzyldimethyl ketal; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl)- 4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloromethyl)- s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4 -Methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, and Triazine compounds such as 2,4-trichloromethyl- (4′-methoxystyryl) -6-triazine; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)] Or an oxime ester compound such as O- (acetyl) -N- (1-phenyl-2-oxo-2- (4′-methoxy-naphthyl) ethylidene) hydroxylamine; bis (2,4,6-trimethylbenzoyl) ) Phosphine compounds such as phenylphosphine oxide or 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone and ethylanthraquinone; borate compounds; carbazole compounds Imidazole compound; or titanocene Thing, or the like is used.
These photoinitiators can be used individually by 1 type or in mixture of 2 or more types by arbitrary ratios as needed.

  The content of the photopolymerization initiator is preferably 2 to 200 parts by weight with respect to 100 parts by weight of the dye, and more preferably 3 to 150 parts by weight from the viewpoint of photocurability and developability.

<Sensitizer>
Furthermore, the coloring composition for a color filter of the present invention can contain a sensitizer.
Sensitizers include chalcone derivatives, unsaturated ketones such as dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives , Xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives, and other polymethine dyes, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, Azulene derivatives, azurenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, Trapirazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphylline derivatives, annulene derivatives, spiropyran derivatives, spirooxazine Derivatives, thiospiropyran derivatives, metal arene complexes, organoruthenium complexes, or Michler's ketone derivatives, α-acyloxy esters, acylphosphine oxides, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethyl Anthraquinone, 4,4'-diethylisophthalophenone, 3,3 ', or 4,4'-tetra (t-butylperoxycarbonyl) benzopheno And 4,4′-diethylaminobenzophenone.
These sensitizers can be used singly or in combination of two or more at any ratio as necessary.

  More specifically, edited by Shin Okawara et al., “Dye Handbook” (1986, Kodansha), edited by Shin Okawara et al., “Chemistry of Functional Dye” (1981, CMC), edited by Tadasaburo Ikemori et al. Examples include, but are not limited to, sensitizers described in "Special Functional Materials" (1986, CMC). In addition, a sensitizer that absorbs light from the ultraviolet region to the near infrared region can also be contained.

  The content of the sensitizer is preferably 3 to 60 parts by weight with respect to 100 parts by weight of the photopolymerization initiator contained in the colored composition, and 5 to 50 parts by weight from the viewpoint of photocurability and developability. It is more preferable that

<Antioxidant>
The coloring composition for a color filter of the present invention can contain an antioxidant. Antioxidants are used to prevent the photopolymerization initiators and thermosetting compounds contained in the color filter coloring composition from oxidizing and yellowing due to thermal processes during thermal curing and ITO annealing. Can be high. Therefore, by including an antioxidant, yellowing due to oxidation during the heating step can be prevented, and high coating film transmittance can be obtained.

  The “antioxidant” in the present invention may be a compound having an ultraviolet absorbing function, a radical scavenging function, or a peroxide decomposing function. Specifically, as an antioxidant, a hindered phenol type, a hindered amine type are used. , Phosphorus-based, sulfur-based, benzotriazole-based, benzophenone-based, hydroxylamine-based, salicylate-based, and triazine-based compounds, and known ultraviolet absorbers, antioxidants, and the like can be used.

  Among these antioxidants, a hindered phenol antioxidant, a hindered amine antioxidant, a phosphorus antioxidant, or a sulfur antioxidant is preferable from the viewpoint of achieving both transmittance and sensitivity of the coating film. Agents. More preferably, they are hindered phenolic antioxidants, hindered amine antioxidants, or phosphorus antioxidants.

  As the hindered phenol-based antioxidant, 2,4-bis [(laurylthio) methyl] -o-cresol, 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl), 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl), 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di- -T-butylanilino) -1,3,5-triazine, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2,6-di-t-butyl-4- Nonylphenol, 2,2′-isobutylidene-bis- (4,6-dimethyl-phenol), 4,4′-butylidene-bis- (2-tert-butyl-5-methylphenol), 2,2′-thio -Bis- (6-tert-butyl-4-methylphenol), 2,5-di-tert-amyl-hydroquinone, 2,2'thiodiethylbis- (3,5-di-tert-butyl-4-hydroxy Phenyl) -propionate, 1,1,3-tris- (2′-methyl-4′-hydroxy-5′-t-butylphenyl) -butane, 2,2′-methylene-bis- (6- (1- Methyl-cyclohexyl) -p-cresol), 2,4-dimethyl-6- (1-methyl-cyclohexyl) -phenol, N, N-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-) Hydrocinnamamide) and the like. In addition, oligomer-type and polymer-type compounds having a hindered phenol structure can also be used.

  Examples of hindered amine-based antioxidants include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (N-methyl-2,2,6,6-tetramethyl-4-piperidyl) sebacate, N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) -1,6-hexamethylenediamine, 2-methyl-2- (2,2,6,6-tetramethyl-4 -Piperidyl) amino-N- (2,2,6,6-tetramethyl-4-piperidyl) propionamide, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) (1,2,3, 4-butanetetracarboxylate, poly [{6- (1,1,3,3-tetramethylbutyl) imino-1,3,5-triazine-2,4-diyl} {(2,2,6,6 -Tetramethyl-4-piperidi ) Imino} hexamethyl {(2,2,6,6-tetramethyl-4-piperidyl) imino}], poly [(6-morpholino-1,3,5-triazine-2,4-diyl) {(2, 2,6,6-tetramethyl-4-piperidyl) imino} hexamethine {(2,2,6,6-tetramethyl-4-piperidyl) imino}], dimethyl succinate and 1- (2-hydroxyethyl)- Polycondensate with 4-hydroxy-2,2,6,6-tetramethylpiperidine, N, N′-4,7-tetrakis [4,6-bis {N-butyl-N- (1,2,2 , 6,6-pentamethyl-4-piperidyl) amino} -1,3,5-triazin-2-yl] -4,7-diazadecane-1,10-diamine, etc. Other oligomer type having a hindered amine structure as well as Rimmer type of compounds and the like can also be used.

  Phosphorous antioxidants include tris (isodecyl) phosphite, tris (tridecyl) phosphite, phenyl isooctyl phosphite, phenyl isodecyl phosphite, phenyl di (tridecyl) phosphite, diphenyl isooctyl phosphite, diphenyl isodecyl Phosphite, diphenyltridecyl phosphite, triphenyl phosphite, tris (nonylphenyl) phosphite, 4,4 ′ isopropylidenediphenol phosphite, trisnonylphenyl phosphite, trisdinonylphenyl phosphite, tris (2 , 4-di-t-butylphenyl) phosphite, tris (biphenyl) phosphite, distearyl pentaerythritol diphosphite, di ( , 4-di-t-butylphenyl) pentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, tetratridecyl 4,4′-butylidenebis (3-methyl-) 6-t-butylphenol) diphosphite, hexatridecyl 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane triphosphite, 3,5-di-t-butyl -4-hydroxybenzyl phosphite diethyl ester, sodium bis (4-t-butylphenyl) phosphite, sodium-2,2-methylene-bis (4,6-di-t-butylphenyl) -phosphite, 1,3 -Bis (diphenoxyphosphonoxy)- Benzene, phosphorous acid ethyl bis (2,4-di-tert- butyl-6-methylphenyl), and the like. In addition, oligomer type and polymer type compounds having a phosphite structure can also be used.

  As sulfur-based antioxidants, 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,4-bis [(octylthio) methyl]- o-cresol, 2,4-bis [(laurylthio) methyl] -o-cresol and the like. In addition, oligomer type and polymer type compounds having a thioether structure can also be used.

  As the benzotriazole-based antioxidant, oligomer-type and polymer-type compounds having a benzotriazole structure can be used.

  Specific examples of the benzophenone antioxidant include 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2 -Hydroxy-4-octadecyloxybenzophenone, 2,2'dihydroxy-4-methoxybenzophenone, 2,2'dihydroxy-4,4'-dimethoxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2, -Hydroxy-4-methoxy-5sulfobenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, 2-hydroxy-4-chlorobenzophenone and the like. In addition, oligomer type and polymer type compounds having a benzophenone structure can also be used.

  Examples of the triazine antioxidant include 2,4-bis (allyl) -6- (2-hydroxyphenyl) 1,3,5-triazine. In addition, oligomer-type and polymer-type compounds having a triazine structure can also be used.

  Examples of the salicylate ester antioxidant include phenyl salicylate, p-octylphenyl salicylate, p-tertbutylphenyl salicylate, and the like. In addition, oligomer-type and polymer-type compounds having a salicylate structure can also be used.

  These antioxidants can be used singly or in combination of two or more at any ratio as required.

  Further, the content of the antioxidant is more preferably 0.5 to 5.0% by weight based on the solid content weight of the photosensitive coloring composition for a color filter because the brightness and sensitivity are good.

<Organic solvent>
In the coloring composition for color filter of the present invention, a dye is sufficiently dispersed and permeated in a dye carrier, and coated on a substrate such as a glass substrate so as to have a dry film thickness of 0.2 to 5 μm. In order to make it easier to form, an organic solvent is included. The organic solvent is selected in consideration of good applicability of the coloring composition, solubility of each component of the coloring composition, and safety.

Examples of the organic solvent include ethyl lactate, benzyl alcohol, 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane. 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3- Methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N, N-dimethylacetamide, N, N- Dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, Ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol Monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate , Diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether , Dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol Monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, Louis Seo ketone, methyl cyclohexanol, acetic acid n- amyl acetate n- butyl, isoamyl acetate, isobutyl acetate, propyl acetate, and dibasic acid esters.
These solvents can be used alone or in admixture of two or more at any ratio as required.

  Among them, the dispersibility of the dye, the penetrability, and the coating property of the coloring composition are good, so that ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether It is preferable to use glycol acetates such as acetate, alcohols such as benzyl alcohol and diacetone alcohol, and ketones such as cyclohexanone.

  In addition, the organic solvent can be used in an amount of 500 to 4000 parts by weight with respect to 100 parts by weight of the dye because the colored composition can be adjusted to an appropriate viscosity to form a desired filter segment having a uniform film thickness. preferable.

(Leveling agent)
In order to improve the leveling property of the composition on the transparent substrate, it is preferable to add a leveling agent to the coloring composition for a color filter of the present invention. As the leveling agent, dimethylsiloxane having a polyether structure or a polyester structure in the main chain is preferable. Specific examples of dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Toray Dow Corning, BYK-333 manufactured by Big Chemie. Specific examples of dimethylsiloxane having a polyester structure in the main chain include BYK-310 and BYK-370 manufactured by BYK Chemie. Dimethylsiloxane having a polyether structure in the main chain and dimethylsiloxane having a polyester structure in the main chain can be used in combination. In general, the content of the leveling agent is preferably 0.003 to 0.5% by mass in 100% by mass of the total mass of the coloring composition.

  Particularly preferred as a leveling agent is a kind of so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule, having a hydrophilic group but low solubility in water, and when added to a coloring composition, It has the characteristics of low surface tension reduction ability, and it is useful to have good wettability to the glass plate despite its low surface tension reduction ability. Those that can sufficiently suppress the chargeability can be preferably used. As a leveling agent having such preferable characteristics, dimethylpolysiloxane having a polyalkylene oxide unit can be preferably used. Examples of the polyalkylene oxide unit include a polyethylene oxide unit and a polypropylene oxide unit, and dimethylpolysiloxane may have both a polyethylene oxide unit and a polypropylene oxide unit.

  In addition, the bonding form of the polyalkylene oxide unit with dimethylpolysiloxane includes a pendant type in which the polyalkylene oxide unit is bonded in the repeating unit of dimethylpolysiloxane, a terminal-modified type in which the end of dimethylpolysiloxane is bonded, and dimethylpolysiloxane. Any of linear block copolymer types in which they are alternately and repeatedly bonded may be used. Dimethylpolysiloxane having a polyalkylene oxide unit is commercially available from Toray Dow Corning Co., Ltd., for example, FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, FZ. -2207, but is not limited thereto.

An anionic, cationic, nonionic or amphoteric surfactant can be supplementarily added to the leveling agent. Two or more kinds of surfactants may be mixed and used.
Anionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkyl naphthalene sulfonate, alkyl diphenyl ether disulfonic acid Sodium, lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate Examples include esters.

  Examples of the chaotic surfactant that is supplementarily added to the leveling agent include alkyl quaternary ammonium salts and their ethylene oxide adducts. Nonionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate ester, polyoxyethylene sorbitan monostearate And amphoteric surfactants such as alkyl dimethylamino acetic acid betaine and alkylimidazolines, and fluorine-based and silicone-based surfactants.

(Curing agent, curing accelerator)
Moreover, in order to assist hardening of a thermosetting resin, the coloring composition for color filters of this invention may contain the hardening | curing agent, the hardening accelerator, etc. as needed. As the curing agent, phenolic resins, amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds and the like are effective, but are not particularly limited to these, and thermosetting resins. Any curing agent may be used as long as it can react with the. Among these, a compound having two or more phenolic hydroxyl groups in one molecule and an amine curing agent are preferable. Examples of the curing accelerator include amine compounds (for example, dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl). -N, N-dimethylbenzylamine etc.), blocked isocyanate compounds (eg dimethylamine etc.), imidazole derivatives bicyclic amidine compounds and salts thereof (eg imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl) -4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole, etc.), phosphorus compounds (for example tri Phenylphosphine ), Guanamine compounds (for example, melamine, guanamine, acetoguanamine, benzoguanamine, etc.), S-triazine derivatives (for example, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino) -S-triazine, 2-vinyl-4,6-diamino-S-triazine / isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine / isocyanuric acid adduct, etc.) Can do. These may be used alone or in combination of two or more. As content of the said hardening accelerator, 0.01-15 mass parts is preferable with respect to 100 mass parts of thermosetting resins.

(Other additive components)
The coloring composition for a color filter of the present invention can contain a storage stabilizer in order to stabilize the viscosity with time. Moreover, in order to improve adhesiveness with a transparent substrate, adhesion improving agents, such as a silane coupling agent, can also be contained.

(Storage stabilizer)
Examples of the storage stabilizer include organic acids such as lactic acid and oxalic acid and methyl ether thereof, organic phosphines such as t-butylpyrocatechol, tetraethylphosphine and tetraphenylphosphine, and phosphites. The storage stabilizer can be used in an amount of 0.1 to 10 parts by mass with respect to 100 parts by mass of the dye.

(Adhesion improver)
Examples of the adhesion improver include vinyl silanes such as vinyltris (β-methoxyethoxy) silane, vinylethoxysilane and vinyltrimethoxysilane, (meth) acrylsilanes such as γ-methacryloxypropyltrimethoxysilane, β- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) Epoxysilanes such as methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (amino Ethyl) γ-aminopropyltrie Xisilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl Examples include silane coupling agents such as aminosilanes such as -γ-aminopropyltriethoxysilane, and thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane. The adhesion improver can be used in an amount of 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the pigment in the colored composition.

(Multifunctional thiol)
The coloring composition for a color filter of the present invention may contain a compound having two or more thiol (SH) groups as a polyfunctional thiol.
By using a polyfunctional thiol together with a photopolymerization initiator, a thiyl radical that acts as a chain transfer agent and is less susceptible to polymerization inhibition by oxygen is generated in the radical polymerization process after light irradiation, so the resulting colored composition is highly sensitive. It becomes. In particular, a polyfunctional aliphatic thiol in which an SH group is bonded to an aliphatic group such as methylene or ethylene group is preferable. Examples of the polyfunctional thiol include hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, and ethylene glycol bisthiopropioate. , Trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, trimercaptopropionic acid Tris (2-hydroxyethyl) isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2- (N, N-dibu Arylamino) -4,6-dimercapto--s- triazine and the like, preferably ethylene glycol bisthiopropionate, trimethylolpropane tris thiopropionate, pentaerythritol tetrakis thiopropionate.

These polyfunctional thiols can be used individually by 1 type or in mixture of 2 or more types.
The content of the polyfunctional thiol is preferably 0.05 to 100 parts by mass, more preferably 1.0 to 50.0 parts by mass with respect to 100 parts by mass of the dye. When the polyfunctional thiol content is less than 0.05 parts by mass, the effect of the chain transfer agent is small. .

<The manufacturing method of a red coloring composition>

(Miniaturization of pigment)
When the pigment used in the colored composition of the present invention is a pigment, it can be refined by a salt milling process or the like. It is preferable that the average primary particle diameter calculated | required by TEM (transmission electron microscope) of a pigment is the range of 5-90 nm. When the thickness is smaller than 5 nm, dispersion in an organic solvent becomes difficult. When the thickness is larger than 90 nm, a sufficient contrast ratio cannot be obtained. For these reasons, a more preferable average primary particle size is in the range of 10 to 70 nm.

  Salt milling is a process in which a mixture of pigment, water-soluble inorganic salt and water-soluble organic solvent is heated using a kneader such as a kneader, two-roll mill, three-roll mill, ball mill, attritor, or sand mill. After kneading, the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water. The water-soluble inorganic salt serves as a crushing aid, and the pigment is crushed using the high hardness of the inorganic salt during salt milling. By optimizing the conditions for salt milling the pigment, it is possible to obtain a pigment having a sharp particle size distribution with a very fine primary particle diameter and a wide distribution range.

  As the water-soluble inorganic salt, sodium chloride, barium chloride, potassium chloride, sodium sulfate and the like can be used, but sodium chloride (salt) is preferably used from the viewpoint of cost. The water-soluble inorganic salt is preferably used in an amount of 50 to 2000 parts by weight, and most preferably 300 to 1000 parts by weight with respect to 100 parts by weight of the pigment, from the viewpoint of both processing efficiency and production efficiency.

  The water-soluble organic solvent functions to wet the pigment and the water-soluble inorganic salt, and is not particularly limited as long as it dissolves (mixes) in water and does not substantially dissolve the inorganic salt to be used. However, a high boiling point solvent having a boiling point of 120 ° C. or higher is preferable from the viewpoint of safety because the temperature rises during salt milling and the solvent is easily evaporated. For example, 2-methoxyethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, Liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid polypropylene glycol and the like are used. The water-soluble organic solvent is preferably used in an amount of 5 to 1000 parts by weight, and most preferably 50 to 500 parts by weight, based on 100 parts by weight of the pigment.

  When the salt is milled, a resin may be added as necessary. The type of resin used is not particularly limited, and natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, and the like can be used. The resin used is solid at room temperature, preferably insoluble in water, and more preferably partially soluble in the organic solvent. The amount of the resin used is preferably in the range of 5 to 200 parts by weight with respect to 100 parts by weight of the pigment.

<Removal of coarse particles>
The coloring composition for color filter of the present invention is 5 μm or larger, preferably 1 μm or larger, more preferably 0.5 μm or larger by means of centrifugation, filtration with a sintered filter or a membrane filter. It is preferable to remove coarse particles and mixed dust. Thus, it is preferable that a coloring composition does not contain a particle | grain of 0.5 micrometer or more substantially. More preferably, it is 0.3 μm or less.

<Color filter>
The color filter for organic EL display devices of the present invention will be described.
The color filter of the present invention comprises at least one red filter segment, at least one green filter segment, and at least one blue filter segment, and the at least one red filter segment is made of the red coloring composition of the present invention. Preferably there is.
Moreover, the green coloring composition which forms a green filter segment can be produced similarly to the above-mentioned red coloring composition by replacing with a green pigment or dye. The same applies to the blue coloring composition forming the blue filter segment.

  The green filter segment can be formed using a normal green coloring composition. Examples of the green coloring composition include C.I. I. It is a composition obtained by using a green pigment such as CI Pigment Green 7, 10, 36, 37, or 58. Green coloring compositions include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 82,185,187,188,193,194,198,199,213, or a yellow pigment 214 and the like can be used in combination.

  The blue filter segment can be formed using a normal blue coloring composition containing a blue pigment and a colorant carrier. Examples of blue pigments include C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64 or the like is used.

  In addition, C.I. I. Purple pigments such as CI Pigment Violet 23, C.I. I. A metal lake pigment of a rhodamine dye such as CI Pigment Red 81, 81: 1, 81: 2, 81: 3, 81: 4, 81: 5 can be used in combination. Further, a basic dye or a salt forming compound of an acidic dye that exhibits blue or purple can be used.

<Color filter manufacturing method>
The color filter of the present invention can be produced by using a coloring composition by a printing method or a photolithography method.

  Formation of a colored film by a printing method can be performed by simply repeating printing and drying of a colored composition prepared as a printing ink, so that the color filter manufacturing method is low cost and excellent in mass productivity. Furthermore, it is possible to print a fine pattern having high dimensional accuracy and smoothness by the development of printing technology. In order to perform printing, it is preferable that the ink does not dry and solidify on the printing plate or on the blanket. Control of ink fluidity on a printing press is also important, and ink viscosity can be adjusted with a dispersant or extender pigment.

  When forming a colored film by photolithography, the colored composition prepared as a solvent developing type or alkali developing type colored resist material is applied on a transparent substrate, such as spray coating, spin coating, slit coating, roll coating, etc. By a method, it applies so that a dry film thickness may be set to 0.2-5 micrometers. If necessary, the dried film is exposed to ultraviolet light through a mask having a predetermined pattern provided in contact with or non-contact with the film. Then, after immersing in a solvent or alkali developer or spraying the developer by spraying or the like to remove the uncured portion to form a desired pattern, the same operation is repeated for other colors to produce a color filter. be able to. Furthermore, in order to accelerate the polymerization of the colored resist material, heating can be performed as necessary. According to the photolithography method, a color filter with higher accuracy than the above printing method can be manufactured.

In development, an aqueous solution such as sodium carbonate or sodium hydroxide is used as an alkali developer, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Moreover, an antifoamer and surfactant can also be added to a developing solution.
In order to increase the UV exposure sensitivity, after coating and drying the colored resist, a water-soluble or alkaline water-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin is applied and dried to form a film that prevents polymerization inhibition by oxygen. Thereafter, ultraviolet exposure can also be performed.

  The color filter of the present invention can be produced by an electrodeposition method, a transfer method, an ink jet method or the like in addition to the above method, but the colored composition of the present invention can be used in any method. The electrodeposition method is a method for manufacturing a color filter by using a transparent conductive film formed on a substrate and forming a colored film on the transparent conductive film by electrodeposition of colloidal particles. . The transfer method is a method in which a colored film is formed in advance on the surface of a peelable transfer base sheet, and this colored film is transferred to a desired substrate.

If the black matrix is formed in advance before forming the filter segment on the transparent substrate or the reflective substrate, the contrast of the display panel can be further increased. As the black matrix, a chromium, chromium / chromium oxide multilayer film, an inorganic film such as titanium nitride, or a resin film in which a light-shielding agent is dispersed is used, but is not limited thereto. Further, a thin film transistor (TFT) may be formed in advance on the transparent substrate or the reflective substrate, and then a filter segment may be formed. By forming the filter segment on the TFT substrate, the aperture ratio of the panel can be increased and the luminance can be improved.
On the color filter of the present invention, an overcoat film or a transparent conductive film is formed as necessary.

<Organic EL display device>
The organic EL display device in the present invention is a display device having a color filter formed of the red coloring composition for an organic EL display device of the present invention and a white light emitting organic EL element (hereinafter referred to as an organic EL element) as a light source. Preferably there is.

(Organic EL element (white light-emitting organic EL element))

  An organic EL element is comprised from the element which formed the organic layer of one layer or a multilayer between the anode and the cathode. Here, the single-layer organic EL element refers to an element composed of only a light emitting layer between an anode and a cathode, while the multilayer organic EL element refers to a hole or a hole in the light emitting layer in addition to the light emitting layer. Hole injection layer, hole transport layer, hole blocking layer, electron injection for the purpose of facilitating electron injection and smooth recombination of holes and electrons in the light emitting layer It refers to a laminate of layers. Therefore, typical element configurations of the multilayer organic EL element include (1) anode / hole injection layer / light emitting layer / cathode, and (2) anode / hole injection layer / hole transport layer / light emitting layer / cathode. (3) Anode / hole injection layer / light emitting layer / electron injection layer / cathode, (4) Anode / hole injection layer / hole transport layer / light emitting layer / electron injection layer / cathode, (5) Anode / positive Hole injection layer / light emitting layer / hole blocking layer / electron injection layer / cathode, (6) anode / hole injection layer / hole transport layer / light emitting layer / hole blocking layer / electron injection layer / cathode, (7) Examples include an anode / light emitting layer / hole blocking layer / electron injection layer / cathode, and (8) an element configuration laminated in a multilayer structure such as anode / light emitting layer / electron injection layer / cathode. However, the organic EL element used in the present invention is not limited to these.

  Moreover, each organic layer mentioned above may be formed by the layer structure of 2 or more layers, respectively, and several layers may be laminated | stacked repeatedly. As such an example, an element configuration called “multi-photon emission” in which a part of the multilayer organic EL element is multilayered has been proposed in recent years for the purpose of improving light extraction efficiency. For example, in an organic EL device composed of a glass substrate / anode / hole transport layer / electron transporting light emitting layer / electron injection layer / charge generating layer / light emitting unit / cathode, the charge generating layer and the light emitting unit There is a method of laminating a plurality of portions.

  First, materials that can be used for each of these layers are specifically exemplified. However, materials that can be used in the present invention are not limited to these.

As a material that can be used for the hole injection layer, a phthalocyanine-based compound is effective, and copper phthalocyanine (abbreviation: CuPc), vanadyl phthalocyanine (abbreviation: VOPc), or the like can be used. There are also materials obtained by chemically doping conductive polymer compounds, such as polyethylenedioxythiophene (abbreviation: PEDOT) doped with polystyrene sulfonic acid (abbreviation: PSS), polyaniline (abbreviation: PANI), or the like. You can also. Further, thin films of inorganic semiconductors such as molybdenum oxide (abbreviation: MoO _x ), vanadium oxide (abbreviation: VO _x ), nickel oxide (abbreviation: NiO _x ), and inorganic insulation such as aluminum oxide (abbreviation: Al ₂ O ₃ ) An ultra-thin body film is also effective. In addition, 4,4 ′, 4 ″ -tris (N, N-diphenyl-amino) -triphenylamine (abbreviation: TDATA), 4,4 ′, 4 ″ -tris [N- (3-methylphenyl) -N -Phenyl-amino] -triphenylamine (abbreviation: MTDATA), N, N'-bis (3-methylphenyl) -N, N'-diphenyl-1,1'-biphenyl-4,4'-diamine (abbreviation) : TPD), 4,4′-bis [N- (1-naphthyl) -N-phenyl-amino] -biphenyl (abbreviation: α-NTPD), 4,4′-bis [N- (4- (N, Aromatic amine compounds such as (N-di-m-tolyl) amino) phenyl-N-phenylamino] biphenyl (abbreviation: DNTPD) can also be used. Further, a substance showing acceptability with respect to these aromatic amine compounds may be added to the aromatic amine compound, specifically, 2,3,5,6-tetrafluoro-7 which is an acceptor for VOPc. , 7,8,8-tetracyanoquinodimethane (abbreviation: F4-TCNQ), or α-NPD to which acceptor MoO _x is added may be used.

  As a material that can be used for the hole transport layer, an aromatic amine compound is preferable, and TDATA, MTDATA, TPD, α-NPD, DNTPD, and the like described for the hole injection material can be used.

  Examples of the electron transport material that can be used for the electron transport layer include tris (8-quinolinolato) aluminum (abbreviation: Alq3), tris (4-methyl-8-quinolinolato) aluminum (abbreviation: Almq3), bis (10-hydroxybenzo). [H] -quinolinato) beryllium (abbreviation: BeBq2), bis (2-methyl-8-quinolinolato) (4-phenylphenolato) aluminum (abbreviation: BAlq), bis [2- (2-hydroxyphenyl) benzoxazola And metal complexes such as zinc (substantially: Zn (BOX) 2) and bis [2- (2-hydroxyphenyl) benzothiazolate] zinc (substantially: Zn (BTZ) 2). In addition to metal complexes, 2- (4-biphenylyl) -5- (4-tert-butylphenyl) -1,3,4-oxadiazole (abbreviation: PBD), 1,3-bis [5- Oxadiazole derivatives such as (p-tert-butylphenyl) -1,3,4-oxadiazol-2-yl] benzene (abbreviation: OXD-7), 3- (4-tert-butylphenyl) -4 -Phenyl-5- (4-biphenylyl) -1,2,4-triazole (abbreviation: TAZ), 3- (4-tert-butylphenyl) -4- (4-ethylphenyl) -5- (4-biphenylyl) ) -1,2,4-triazole (abbreviation: p-EtTA Z) and other triazole derivatives, 2,2 ′, 2 ″-(1,3,5-benzenetriyl) tris [1-phenyl-1H-benz Imidazole] (abbreviated Imidazole derivatives such as TPBI), bathophenanthroline (abbreviation: can be used phenanthroline derivatives such as BCP): BPhen), bathocuproine (abbreviation.

Materials that can be used for the electron injection layer include Alq3, Almq3, BeBq2, BAlq, Zn (BOX) ₂ , Zn (BTZ) ₂ , PBD, OXD-7, TAZ, p-EtTAZ, TPBI, Electron transport materials such as BPhen and BCP can be used. In addition, an ultra-thin film of an insulator such as an alkali metal halide such as LiF or CsF, an alkaline earth halide such as CaF ₂ , or an alkali metal oxide such as Li ₂ O is often used. In addition, alkali metal complexes such as lithium acetylacetonate (abbreviation: Li (acac)) and 8-quinolinolato-lithium (abbreviation: Liq) are also effective. Further, a substance exhibiting a donor property with respect to these electron injection materials may be added to the electron injection material, and alkali metals, alkaline earth metals, rare earth metals, and the like can be used as donors. Specifically, a material obtained by adding lithium as a donor to BCP or a material obtained by adding lithium as a donor to Alq ₃ can be used.

  Furthermore, a hole blocking material that can prevent holes from passing through the light emitting layer from reaching the electron injection layer and form a layer having excellent thin film formability is used for the hole blocking layer. Examples of such hole blocking materials include aluminum complex compounds such as bis (8-hydroxyquinolinato) (4-phenylphenolato) aluminum, and bis (2-methyl-8-hydroxyquinolina). -To) (4-phenylphenolato) gallium complex compounds such as gallium, nitrogen-containing condensed aromatic compounds such as 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (abbreviation: BCP) Can be mentioned.

  Although there is no restriction | limiting in particular as a light emitting layer which obtains white light emission, For example, the following can be used. That is, the energy level of each layer of the organic EL laminated structure is defined and light is emitted using tunnel injection (European Patent No. 0390551). Similarly, a white light-emitting element is an example of an element using tunnel injection. What is described (JP-A-3-230584), a light-emitting layer having a two-layer structure (JP-A-2-220390 and JP-A-2-216790), and a plurality of light-emitting layers A layered material composed of materials having different emission wavelengths (Japanese Patent Laid-Open No. 4-51491), a blue light emitter (fluorescent peak 380 to 480 nm) and a green light emitter (480 to 580 nm), Further, a red phosphor is included (Japanese Patent Laid-Open No. 6-207170), the blue light emitting layer contains a blue fluorescent dye, and the green light emitting layer is a red fluorescent dye. It has contained area, such as construction of those (JP-A-7-142169) and the like further containing a green phosphor.

  Further, as the light emitting material used in the present invention, a material known as a conventional light emitting material may be used. Examples of compounds suitably used for blue, green, orange to red light emission are shown below. However, the light emitting material is not limited to those specifically exemplified below.

  Blue light emission can be obtained by using perylene, 2,5,8,11-tetra-t-butylperylene (abbreviation: TBP), 9,10-diphenylanthracene derivative, or the like as a guest material, for example. Further, styrylarylene derivatives such as 4,4′-bis (2,2-diphenylvinyl) biphenyl (abbreviation: DPVBi), 9,10-di-2-naphthylanthracene (abbreviation: DNA), 9,10-bis It can also be obtained from an anthracene derivative such as (2-naphthyl) -2-tert-butylanthracene (abbreviation: t-BuDNA). A polymer such as poly (9,9-dioctylfluorene) may also be used.

  Further preferred specific examples are shown in Table 1.

Green light is emitted from coumarin dyes such as coumarin 30 and coumarin 6, bis [2- (2,4-difluorophenyl) pyridinato] picolinatoiridium (abbreviation: FIrpic), bis (2-phenylpyridinato) acetyl. It can be obtained by using acetonatoiridium (abbreviation: Ir (ppy) (acac)) or the like as a guest material. In addition, metal complexes such as tris (8-hydroxyquinoline) aluminum (abbreviation: Alq ₃ ), BAlq, Zn (BTZ), bis (2-methyl-8-quinolinolato) chlorogallium (abbreviation: Ga (mq) ₂ Cl) Can also be obtained from A polymer such as poly (p-phenylene vinylene) may also be used.

Further preferred specific examples are shown in Table 2.

  Light emission from orange to red is caused by rubrene, 4- (dicyanomethylene) -2- [p- (dimethylamino) styryl] -6-methyl-4H-pyran (abbreviation: DCM1), 4- (dicyanomethylene) -2- Methyl-6- (9-julolidyl) ethynyl-4H-pyran (abbreviation: DCM2), 4- (dicyanomethylene) -2,6-bis [p- (dimethylamino) styryl] -4H-pyran (abbreviation: BisDCM) Bis [2- (2-thienyl) pyridinato] acetylacetonatoiridium (abbreviation: Ir (thp) 2 (acac)), bis (2-phenylquinolinato) acetylacetonatoiridium (abbreviation: Ir (pq) (acac) )) Etc. as a guest material. It can also be obtained from a metal complex such as bis (8-quinolinolato) zinc (abbreviation: Znq2) or bis [2-cinnamoyl-8-quinolinolato] zinc (abbreviation: Znsq2). A polymer such as poly (2,5-dialkoxy-1,4-phenylenevinylene) may be used.

  Further preferred specific examples are shown in Table 3.

Furthermore, the material used for the anode of the organic EL element used in the present invention is preferably a material having a work function (4 eV or more) metal, alloy, electrically conductive compound or a mixture thereof as an electrode substance. Specific examples of such an electrode substance include metals such as Au, and conductive materials such as CuI, ITO, SNO ₂ , and ZNO. In order to form this anode, a thin film can be formed from these electrode materials by a method such as vapor deposition or sputtering. The anode desirably has such a characteristic that when light emitted from the light emitting layer is extracted from the anode, the transmittance of the anode for light emission is greater than 10%. The sheet resistance of the anode is preferably several hundred Ω / cm ² or less. Further, although the film thickness of the anode depends on the material, it is usually selected in the range of 10 nm to 1 μm, preferably 10 to 200 nm.

The material used for the cathode of the organic EL device used in the present invention is a material having a work function (4 eV or less) metal, alloy, electrically conductive compound and a mixture thereof as an electrode substance. Specific examples of such electrode materials include sodium, sodium-potassium alloy, magnesium, lithium, magnesium / silver alloy, aluminum / aluminum oxide, aluminum / lithium alloy, indium, and rare earth metals. This cathode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering. Here, when light emitted from the light-emitting layer is extracted from the cathode, the transmittance of the cathode for light emission is preferably greater than 10%. Further, the sheet resistance as the cathode is preferably several hundred Ω / cm ² or less, and the film thickness is usually 10 nm to 1 μm, preferably 50 to 200 Nm.

  Regarding the method for producing the organic EL device used in the present invention, an anode, a light emitting layer, a hole injection layer as necessary, and an electron injection layer as necessary are formed by the above materials and methods, and finally a cathode is formed. What is necessary is just to form. Moreover, an organic EL element can also be produced from the cathode to the anode in the reverse order.

  This organic EL element is manufactured on a translucent substrate. This translucent substrate is a substrate that supports the organic EL element, and for the translucency, it is desirable that the transmittance of light in the visible region of 400 to 700 nm is 50% or more, preferably 90% or more, Further, it is preferable to use a smooth substrate.

  These substrates have mechanical and thermal strengths and are not particularly limited as long as they are transparent. For example, glass plates, synthetic resin plates and the like are preferably used. Examples of the glass plate include plates made of soda-lime glass, barium / strontium-containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, quartz, and the like. Examples of the synthetic resin plate include plates such as polycarbonate resin, acrylic resin, polyethylene terephthalate resin, polyether sulfide resin, and polysulfone resin.

  As a method for forming each layer of the organic EL element used in the present invention, a dry film forming method such as vacuum deposition, electron beam beam irradiation, sputtering, plasma, ion plating, or spin coating, dipping, flow coating, inkjet A wet film-forming method such as a method, a method of vapor-depositing a light emitter on a donor film, JP-A-2002-534882, and S. T.A. Lee, et al. , Proceedings of SID'02, p. LITI (Laser Induced Thermal Imaging) method described in 784 (2002), printing (offset printing, flexographic printing, gravure printing, screen printing), inkjet, and the like can also be applied.

  The organic layer is particularly preferably a molecular deposited film. Here, the molecular deposited film is a thin film formed by deposition from a material compound in a gas phase state or a film formed by solidifying from a material compound in a solution state or a liquid phase state. Can be classified from a thin film (accumulated film) formed by the LB method according to a difference in an agglomerated structure and a higher-order structure and a functional difference resulting therefrom. Also, as disclosed in JP-A-57-51781, a binder such as a resin and a material compound are dissolved in a solvent to form a solution, and then this is thinned by a spin coat method or the like. Also, an organic layer can be formed. The film thickness of each layer is not particularly limited, but if the film thickness is too thick, a large applied voltage is required to obtain a constant light output, resulting in poor efficiency. Conversely, if the film thickness is too thin, the pinhole is used. Or the like, and even when an electric field is applied, it is difficult to obtain sufficient light emission luminance. Accordingly, the thickness of each layer is suitably in the range of 1 nm to 1 μm, but more preferably in the range of 10 nm to 0.2 μm.

  Further, in order to improve the stability of the organic EL element against temperature, humidity, atmosphere, etc., a protective layer may be provided on the surface of the element, or the entire element may be covered or sealed with a resin or the like. In particular, when the entire element is covered or sealed, a photocurable resin that is cured by light is preferably used.

  The current applied to the organic EL element used in the present invention is usually a direct current, but a pulse current or an alternating current may be used. The current value and the voltage value are not particularly limited as long as they are within the range that does not destroy the element. However, considering the power consumption and life of the element, it is desirable to efficiently emit light with as little electrical energy as possible.

  The driving method of the organic EL element used in the present invention can be driven not only by the passive matrix method but also by the active matrix method. Further, the method for extracting light from the organic EL device of the present invention is applicable not only to the method of bottom emission for extracting light from the anode side but also to the method of top emission for extracting light from the cathode side. These methods and techniques are described in Shinji Kido, “All about organic EL”, published by Nihon Jitsugyo Shuppansha (published in 2003).

  The main method of the full color method of the organic EL element used in the present invention is a color filter method. The color filter method uses a white light emitting organic EL element to extract light of three primary colors through a color filter. In addition to these three primary colors, a part of white light is extracted as it is and used for light emission. In addition, the luminous efficiency of the entire device can be increased.

  Furthermore, the organic EL element used in the present invention may adopt a microcavity structure. This is because the organic EL device has a structure in which the light emitting layer is sandwiched between the anode and the cathode, and the emitted light causes multiple interference between the anode and the cathode, but the reflectance and transmission of the anode and the cathode This is a technology that actively uses the multiple interference effect and controls the emission wavelength extracted from the device by appropriately selecting the optical characteristics such as the rate and the film thickness of the organic layer sandwiched between them. . Thereby, it is also possible to improve the emission chromaticity. For the mechanism of this multiple interference effect, see J.A. Yamada et al., AM-LCD Digest of Technical Papers, OD-2, p. 77-80 (2002).

  As described above, an RGB color filter layer is produced in parallel with a glass substrate, and a light emitting layer (backlight) produced using the ITO electrode layer and the organic EL element is placed on the color filter layer. As a result, color display is possible, and a color display device is obtained. At this time, a color display device having a high contrast ratio can be realized by controlling the current flow during light emission by the TFT.

  Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. In the examples, “parts” and “%” represent “parts by weight” and “% by weight”, respectively.

  Moreover, the measuring method of the average primary particle diameter of a pigment, the identification method of an azo pigment, and the measuring method of the weight average molecular weight (Mw) of resin are as follows.

(Average primary particle diameter of pigment)
The average primary particle diameter of the pigment was measured by a method of directly measuring the size of primary particles from an electron micrograph using a transmission electron microscope (TEM). Specifically, the minor axis diameter and major axis diameter of the primary particles of each pigment were measured, and the average was taken as the particle diameter of the primary pigment particles. Next, for 100 or more pigment particles, the volume (weight) of each particle was obtained by approximating the obtained particle size cube, and the volume average particle size was defined as the average primary particle size.

(Azo pigment identification method)
The identification of the azo pigment of the present invention was carried out using a MALDI mass spectrometer autoflex III (hereinafter referred to as TOF-MS) manufactured by Bruker Daltonics, and the molecular ion peak of the obtained mass spectrum, the mass number obtained by calculation, Identified with the agreement.

(Weight average molecular weight of resin (Mw))
The weight average molecular weight (Mw) of the resin was measured in terms of polystyrene measured using TSKgel column (manufactured by Tosoh Corporation) and GPC (manufactured by Tosoh Corporation, HLC-8120GPC) equipped with an RI detector using THF as a developing solvent. It is a weight average molecular weight (Mw).

    Subsequently, the organic EL elements, alkali-soluble resin solutions, naphthol azo pigments [A], other dyes, dye dispersions, photosensitive green coloring compositions, and photosensitive blue coloring compositions used in Examples and Comparative Examples were used. A manufacturing method will be described.

<Example of manufacturing organic EL element>
The production example of the organic EL element used as a white light source is specifically shown below. In the production examples of organic EL elements, all the mixing ratios are weight ratios unless otherwise specified. Vapor deposition (vacuum deposition) was performed in a vacuum of 10 ⁻⁶ Torr and under conditions without temperature control such as substrate heating and cooling. In the evaluation of the light emission characteristics of the element, the characteristics of an organic EL element having an electrode area of 2 mm × 2 mm were measured.

(Manufacture of organic EL element 1 (EL-1))
After the cleaned glass plate with the ITO electrode was treated with oxygen plasma for about 1 minute, 4,4′-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (α-NPD) was vacuum deposited, A hole injection layer having a thickness of 150 nm was obtained. On the hole injection layer, the compound (R-2) and the compound (R-3) shown in Table 3 are further co-evaporated at a composition ratio of 100: 2 to form a first light emitting layer having a thickness of 10 nm. did. Furthermore, the compound (B-1) and the compound (B-4) in Table 1 were co-evaporated at a composition ratio of 100: 3 to form a second light emitting layer having a thickness of 20 nm. On this light emitting layer, 5 nm of α-NPD and 20 nm of the compound (G-3) in Table 2 were further evaporated to form a third light emitting layer. Further, a tris (8-hydroxyquinoline) aluminum complex was vacuum-deposited to form an electron injection layer having a film thickness of 35 nm, and then an electrode was formed by first depositing 1 nm of lithium fluoride and then 200 nm of aluminum. The organic EL element 1 was obtained.

Furthermore, in order to protect this organic EL element from the surrounding environment, it was hermetically sealed in a dry glow box filled with pure nitrogen. This device produced white light emission with a direct current voltage of 5 V and an emission luminance of 950 (cd / m ² ), a maximum emission luminance of 55000 (cd / m ² ), and an emission efficiency of 3.9 (lm / W). FIG. 1 shows an emission spectrum of the obtained EL device (EL-1).

<Method for producing alkali-soluble resin solution>
(Alkali-soluble resin solution (P-1))
[Step 1: Polymerization of resin main chain]
Place 100 parts of propylene glycol monomethyl ether acetate (PGMAC) in a reaction vessel equipped with a thermometer, cooling tube, nitrogen gas inlet tube, and stirrer in a separable four-necked flask, and heat to 120 ° C while injecting nitrogen gas into the vessel. At the same temperature, 12.0 parts of methyl methacrylate, 15.0 parts of styrene, 33.0 parts of glycidyl methacrylate, and 4.0 parts of azobisisobutyronitrile as a catalyst required for the reaction of the precursor at this stage The mixture was added dropwise over 2.5 hours to conduct a polymerization reaction.

[Step 2: Reaction to epoxy group]
Next, the inside of the flask was purged with air, and 19.0 parts of acrylic acid and 0.3 parts of trisdimethylaminomethylphenol and 0.3 parts of hydroquinone were added as catalysts required for the reaction of the precursor at this stage, The reaction was performed for 5 hours. Since the added acrylic acid is ester-bonded to the end of the epoxy group of the glycidyl methacrylate structural unit, no carboxyl group is generated in the resin structure.

(Step 3: Reaction to hydroxyl group)
Further, 21.0 parts of tetrahydrophthalic anhydride and 0.5 parts of triethylamine as a catalyst required for the reaction of the precursor at this stage were added and reacted at 120 ° C. for 4 hours. In the added tetrahydrophthalic anhydride, one of two carboxyl groups generated by cleavage of the carboxylic anhydride moiety is ester-bonded to a hydroxyl group in the resin structure, and the other produces a carboxyl group terminal.

(Step 4: Adjustment of nonvolatile content)
Propylene glycol monomethyl ether acetate was added so that the nonvolatile content was 20% to obtain an alkali-soluble resin solution (P-1). The weight average molecular weight (Mw) was 12000.

(Alkali-soluble resin solution (P-2))
An alkali-soluble resin solution (P-2) was obtained in the same manner except that the methyl methacrylate in Step 1 of the alkali-soluble resin solution (P-1) was changed to benzyl methacrylate. The weight average molecular weight (Mw) was 12000.

<Method for producing naphtholazo pigment [A]>
(Red pigment (PR-1))
Below, the specific synthesis | combining method of the said azo pigment (A1-1) is shown with the reaction scheme (the following reaction scheme A). Other azo pigments according to the present invention can be synthesized according to a similar scheme. In addition, the manufacturing method (synthesis method) of an azo pigment is not limited to the following method.

(1) Synthesis of Compound (B) 90 parts of 2,3-hydroxynaphthoic acid and 1.2 parts of N, N-dimethylformamide were added to 573 parts of toluene, heated to 85 ° C., and 556.3 parts of thionyl chloride. Was added dropwise over 15 minutes. After completion of the dropwise addition, the mixture was refluxed for 1 hour. The above reaction solution was added dropwise over 30 minutes to a solution in which 80.9 parts of separately prepared compound (A) and 264 parts of toluene were heated to 85 ° C., and the mixture was heated to reflux for 2 hours. After cooling this reaction liquid to 95 ° C., 8.0 parts of 28% ammonia aqueous solution and 20 parts of water were added and stirred at 95-100 ° C. for 15 minutes, and then toluene and unreacted compound (A) were removed by steam distillation. did. The precipitated reaction product was collected by filtration, washed with hot water, and dried to obtain 152 parts (yield: 95.8%) of compound (B).

(2) Synthesis of Azo Pigment (A1-1) After adding 36.3 parts of Compound (C) to 252.2 parts of glacial acetic acid, 39.1 parts of 35% hydrochloric acid is added so that the temperature becomes −2 to 0 ° C. Cooled down. After adding 42.2 parts of 25% aqueous sodium nitrite solution to this solution, the mixture was stirred for 30 minutes while maintaining at 0-5 ° C. This reaction solution was added to a mixed solution consisting of 50.7 parts of the compound (B) prepared separately by the previous method, 67.1 parts of 25% sodium hydroxide solution, 772 parts of water and 680 parts of isopropyl alcohol for 15 minutes. It was dripped at. After completion of the dropwise addition, the mixture was stirred at room temperature for 30 minutes, and further stirred while maintaining at 80 ° C. The precipitated reaction product was collected by filtration, washed with hot water and methanol, and dried to obtain 85.9 parts of azo dye 1. (Yield: 98%) was obtained. As a result of mass spectrometry by TOF-MS, it was identified as an azo pigment (A1-1).

  Next, 80 parts of the azo pigment (A1-1), 800 parts of sodium chloride, and 90 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho), kneaded at 60 ° C. for 6 hours, and subjected to salt milling treatment. did. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 78 parts of red pigment (PR-1) were obtained. The average primary particle size was 38 nm.

(Red pigment (PR-2))
The red colorant (PR-1) was used except that 66.8 parts of 3-aminobenztrifluoride was used instead of 80.9 parts of the compound (A) used in the production of the red pigment (PR-1). Operation similar to manufacture was performed and 80.0 parts (yield 98%) of azo pigments (A1-2) were obtained. As a result of mass spectrometry by TOF-MS, it was identified as an azo pigment (A1-2).

  Next, 80 parts of the azo pigment (A1-2), 800 parts of sodium chloride, and 90 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho), kneaded at 60 ° C. for 6 hours, and subjected to salt milling treatment. did. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 78 parts of red pigment (PR-2) were obtained. The average primary particle size was 42 nm.

(Red pigment (PR-3))
A red dye (except for using 34.9 parts of 3-amino-4-methoxybenzanilide used in the production of the red dye (PR-1), except that 24.9 parts of 3-amino-4-methoxybenzamide was used. Operation similar to manufacture of PR-1) was performed, and 80.0 parts (yield 97%) of azo pigments (A1-3) were obtained. As a result of mass spectrometry by TOF-MS, it was identified as an azo pigment (A1-3).

Next, 80 parts of the azo pigment (A1-3), 800 parts of sodium chloride and 90 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho), kneaded at 60 ° C. for 6 hours, and subjected to a salt milling treatment. did. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 78 parts of a red pigment (PR-3) were obtained. The average primary particle size was 45 nm.

(Red pigment (PR-4))
Instead of 80.9 parts of compound (A) used in the production of the red dye (PR-1), 66.8 parts of 3-aminobenztrifluoride, and instead of 3-amino-4-methoxybenzanilide Except for using 24.9 parts of 3-amino-4-methoxybenzamide, the same operation as in the production of the red colorant (PR-1) was carried out to obtain 80.0 parts (inclusive of azo pigment (A1-4)). 97%). As a result of mass spectrometry by TOF-MS, it was identified as an azo pigment (A1-4).

  Next, 80 parts of the azo pigment (A1-4), 800 parts of sodium chloride, and 90 parts of diethylene glycol were charged in a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho), kneaded at 60 ° C. for 6 hours, and subjected to salt milling treatment. did. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 78 parts of red pigment (PR-4) were obtained. The average primary particle size was 39 nm.

(Red pigment (PR-5))
Instead of the compound (A) used in the production of the red dye (PR-1), 66.8 parts of 2-aminobenztrifluoride and 3-amino-4-methoxybenzanilide instead of 3-amino Except for using 24.9 parts of -4-methoxybenzamide, the same operation as in the production of the red dye (PR-1) was performed to obtain 80.0 parts (yield 95%) of the azo pigment (A1-5). It was. As a result of mass spectrometry by TOF-MS, it was identified as an azo pigment (A1-5).

  Next, 80 parts of the azo pigment (A1-5), 800 parts of sodium chloride, and 90 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho), kneaded at 60 ° C. for 6 hours, and subjected to a salt milling treatment. did. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 78 parts of a red pigment (PR-5) were obtained. The average primary particle size was 38 nm.

(Red pigment (PR-6))
Instead of the compound (A) used in the production of the red dye (PR-1), instead of 5-chloro-2-aminobenztrifluoride and 3-amino-4-methoxybenzanilide, 3-amino- The same operation as in the production of the red dye (PR-1) was performed except that 24.9 parts of 4-methoxybenzamide was used to obtain 80.0 parts of an azo pigment (A1-6). As a result of mass spectrometry by TOF-MS, it was identified as an azo pigment (A1-6).

  Next, 80 parts of the azo pigment (A1-6), 800 parts of sodium chloride, and 90 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho), kneaded at 60 ° C. for 6 hours, and subjected to salt milling treatment. did. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 78 parts of red pigment (PR-6) were obtained. The average primary particle size was 42 nm.

(Red pigment (PR-7))
Instead of the compound (A) used in the production of the red dye (PR-1), 95.1 parts of 3,5-bis (trifluoromethyl) aniline and 3-amino-4-methoxybenzanilide In addition, except that 24.9 parts of 3-amino-4-methoxybenzamide were used, the same operation as in the production of the red dye (PR-1) was carried out to obtain 80.0 parts (inclusive of azo pigment (A1-7)). Rate 96%). As a result of mass spectrometry by TOF-MS, it was identified as an azo pigment (A1-7).

  Next, 80 parts of the azo pigment (A1-7), 800 parts of sodium chloride, and 90 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho), kneaded at 60 ° C. for 6 hours, and subjected to salt milling treatment. did. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 78 parts of red pigment (PR-7) were obtained. The average primary particle size was 47 nm.

(Red pigment (PR-8))
Instead of the compound (A) used in the production of the red dye (PR-1), 0.050 mol amount of 4-fluoro-3-aminobenztrifluoride, and instead of 3-amino-4-methoxybenzanilide , Except that 0.015 mol amount of 3-amino-4-methoxybenzamide was used, the same operation as in the production of the red dye (PR-1) was carried out to obtain 7.97 g (yield 96) of the azo pigment (A1-8). %)Obtained. As a result of mass spectrometry by TOF-MS, it was identified as an azo pigment (A1-8).

  Next, 80 parts of the azo pigment (A1-8), 800 parts of sodium chloride, and 90 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho), kneaded at 60 ° C. for 6 hours, and subjected to salt milling treatment. did. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 78 parts of red pigment 8 (PR-8) were obtained. The average primary particle size was 42 nm.

(Red dye (PR-9))
Instead of the compound (A) used in the production of the red dye (PR-1), 74.3 parts of 2-chloro-5-aminobenztrifluoride and instead of 3-amino-4-methoxybenzanilide Except for using 24.9 parts of 3-amino-4-methoxybenzamide, the same operation as in the production of the red dye (PR-1) was carried out to obtain 80.0 parts (yield) of the azo pigment (A1-9). 97%). As a result of mass spectrometry by TOF-MS, it was identified as an azo pigment (A1-9).

  Next, 80 parts of the azo pigment (A1-9), 800 parts of sodium chloride, and 90 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho), kneaded at 60 ° C. for 6 hours, and subjected to salt milling treatment. did. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 78 parts of red pigment (PR-9) were obtained. The average primary particle size was 41 nm.

(Red pigment (PR-10))
Instead of the compound (A) used in the production of the red dye (PR-1), 66.8 parts of 4-aminobenztrifluoride, and 3-amino-4-methoxybenzanilide instead of 3-amino Except for using 24.9 parts of -4-methoxybenzamide, the same operation as in the production of the red colorant (PR-1) was performed, and 80.0 parts (95% yield) of the azo pigment (A1-10) was obtained. Obtained. As a result of mass spectrometry by TOF-MS, it was identified as an azo pigment (A1-10).

  Next, 80 parts of the azo pigment (A1-10), 800 parts of sodium chloride, and 90 parts of diethylene glycol are charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho), kneaded at 60 ° C. for 6 hours, and subjected to salt milling treatment. did. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 78 parts of red pigment (PR-10) were obtained. The average primary particle size was 48 nm.

(Red pigment (PR-11))
Red dye (PR-1) except that 24.9 parts of 3-amino-4-methylbenzamide were used instead of 3-amino-4-methoxybenzanilide used in the production of red dye (PR-1) The same operation as in the production of was performed to obtain 80.0 parts (yield 97%) of an azo pigment (A1-11). As a result of mass spectrometry by TOF-MS, it was identified as an azo pigment (A1-11).

  Next, 80 parts of the azo pigment (A1-11), 800 parts of sodium chloride, and 90 parts of diethylene glycol were charged into a stainless gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.), kneaded at 60 ° C. for 6 hours, and subjected to salt milling treatment. did. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 78 parts of red pigment (PR-11) were obtained. The average primary particle size was 50 nm.

(Red pigment (PR-12))
Instead of 3-amino-4-methoxybenzanilide used in the production of the red dye (PR-1), 3-amino-4-methoxybenz- (2′-chloro-5′-trifluoromethyl) anilide is 51 The same operation as in the production of the red dye (PR-1) was carried out except that 6 parts were used to obtain 80.0 parts (yield 96%) of the azo pigment (A1-12). As a result of mass spectrometry by TOF-MS, it was identified as an azo pigment (A1-12).

  Next, 80 parts of the azo pigment (A1-12), 800 parts of sodium chloride, and 90 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho), kneaded at 60 ° C. for 6 hours, and subjected to salt milling treatment. did. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 78 parts of red pigment (PR-12) were obtained. The average primary particle size was 38 nm.

(Red pigment (PR-13))
Instead of the compound (A) used in the production of the red dye (PR-1), 66.8 parts of 3-aminobenztrifluoride and 3-amino-4-methoxybenzanilide instead of 3-amino Except for using 46.5 parts of -4-methoxybenz- (3′-trifluoromethyl) anilide, the same operation as in the production of the red dye (PR-1) was carried out, and 80 parts of the azo pigment (A1-13) was obtained. 0.0 part (yield 95%) was obtained. As a result of mass spectrometry by TOF-MS, it was identified as an azo pigment (A1-13).

  Next, 80 parts of the azo pigment (A1-13), 800 parts of sodium chloride, and 90 parts of diethylene glycol were charged into a stainless gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.), kneaded at 60 ° C. for 6 hours, and subjected to salt milling treatment. did. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 78 parts of a red pigment (PR-13) were obtained. The average primary particle size was 36 nm.

(Red pigment (PR-14))
In place of 3-amino-4-methoxybenzanilide used in the production of the red pigment (PR-1), except that 44.7 parts of the following compound (D) was used, the production of the red pigment (PR-1) The same operation was performed to obtain 80.0 parts (yield 95%) of an azo pigment (A1-14). As a result of mass spectrometry by TOF-MS, it was identified as an azo pigment (A1-14).

  Next, 80 parts of the azo pigment (A1-14), 800 parts of sodium chloride, and 90 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho), kneaded at 60 ° C. for 6 hours, and subjected to a salt milling treatment. did. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 78 parts of red pigment (PR-14) were obtained. The average primary particle size was 40 nm.

(Red pigment (PR-15))
Instead of (A) used in the production of the red dye (PR-1), 66.8 parts of 3-aminobenztrifluoride and compound (D) instead of 3-amino-4-methoxybenzanilide Was used in the same manner as in the production of the red dye (PR-1), to obtain 80.0 parts (97% yield) of the azo pigment (A1-15). As a result of mass spectrometry by TOF-MS, it was identified as an azo pigment (A1-15).

  Next, 80 parts of the azo pigment (A1-15), 800 parts of sodium chloride, and 90 parts of diethylene glycol are charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho), kneaded at 60 ° C. for 6 hours, and subjected to a salt milling treatment. did. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 78 parts of a red pigment (PR-15) were obtained. The average primary particle size was 43 nm.

(Red pigment (PR-16))
A red colorant (PR-1) except that 27.0 parts of 3-amino-N-methylbenzamide was used instead of 3-amino-4-methoxybenzanilide used in the production of the red dye (PR-1). ) To give 80.0 parts (97% yield) of azo pigment (A1-16). As a result of mass spectrometry by TOF-MS, it was identified as an azo pigment (A1-16).

  Next, 80 parts of the azo pigment (A1-16), 800 parts of sodium chloride, and 90 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho), kneaded at 60 ° C. for 6 hours, and subjected to salt milling treatment. did. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 78 parts of a red pigment (PR-16) were obtained. The average primary particle size was 43 nm.

(Red pigment (PR-17))
80 parts of the azo pigment (A1-1) obtained in the production of the red dye (PR-1) was added to 1200 parts of concentrated sulfuric acid, and the mixture was stirred at 40 ° C. for 3 hours, and then this sulfuric acid solution was added to 24,000 parts of cold water at 3 ° C. Injected. The produced precipitate was filtered and washed with water, and then dried at 80 ° C. for a whole day and night to obtain 78 parts of a red pigment (PR-17). The average primary particle size was 65 nm.

(Red pigment (PR-18))
63.4 parts of 3-amino-4-methoxybenzanilide are dispersed in 900 parts of water, adjusted to a temperature of 5 ° C. by adding ice, added with 104.0 parts of 35% aqueous hydrochloric acid and stirred for 1 hour, and then added with nitrous acid. An aqueous solution prepared by adding 19.9 parts of sodium to 50 parts of water was added and stirred for 3 hours. After adding 3.2 parts of sulfamic acid to eliminate excess sodium nitrite, an aqueous solution comprising 192 parts of 80% acetic acid aqueous solution, 210 parts of 25% sodium hydroxide aqueous solution, and 180 parts of water was added, and the diazonium salt aqueous solution was added. did.
On the other hand, 88.4 parts of N- [4- (acetylamino) phenyl] -3-hydroxy-2-naphthalenecarboxamide and 174.0 parts of 25% aqueous sodium hydroxide solution were dissolved in 1500 parts of water at 50 ° C. to prepare a coupler. It was set as the solution.
This coupler solution was poured into the 5 ° C. diazonium salt aqueous solution over 30 minutes to carry out a coupling reaction. The pH at this time was 4.5. After stirring for 3 hours and confirming the disappearance of the diazonium salt, the mixture was heated to 70 ° C., filtered, washed with water, and dried at 90 ° C. for 24 hours to obtain 141 parts of a naphthol azo pigment represented by the formula (A2-1). . As a result of mass spectrometry by TOF-MS, it was identified as a naphthol azo pigment of the formula (A2-1).

  Subsequently, a salt milling process was performed. 100 parts of a naphthol azo pigment represented by the formula (A2-1), 1200 parts of sodium chloride and 120 parts of diethylene glycol are charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho), kneaded at 60 ° C. for 6 hours, and salt milling. Processed. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 97 parts of a red pigment (PR-18) were obtained.

(Red pigment (PR-19)
Disperse 39.3 parts of 3-amino-4-methylbenzamide in 900 parts of water, add ice to adjust the temperature to 5 ° C., add 104.0 parts of 35% aqueous hydrochloric acid and stir for 1 hour, then sodium nitrite. 19.9 parts was added to 50 parts of water, the prepared aqueous solution was added, and the mixture was stirred for 3 hours. After adding 3.2 parts of sulfamic acid to eliminate excess sodium nitrite, an aqueous solution comprising 192 parts of 80% acetic acid aqueous solution, 210 parts of 25% sodium hydroxide aqueous solution, and 180 parts of water was added, and the diazonium salt aqueous solution was added. did. On the other hand, 88.4 parts of N- [4- (acetylamino) phenyl] -3-hydroxy-2-naphthalenecarboxamide and 174.0 parts of 25% aqueous sodium hydroxide solution were dissolved in 1500 parts of water at 50 ° C. to prepare a coupler. It was set as the solution.

  This coupler solution was poured into the 5 ° C. diazonium salt aqueous solution over 30 minutes to carry out a coupling reaction. The pH at this time was 4.4. After stirring for 3 hours and confirming the disappearance of the diazonium salt, the mixture was heated to 70 ° C., filtered, washed with water, and dried at 90 ° C. for 24 hours to obtain 118 parts of an azo pigment represented by the formula (A2-4). . As a result of mass spectrometry by TOF-MS, it was identified as an azo pigment of the formula (A2-4).

  Next, 100 parts of the azo pigment of the formula (A2-4), 1200 parts of sodium chloride and 120 parts of diethylene glycol are charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho), kneaded at 60 ° C. for 6 hours, and subjected to a salt milling process. did. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 98 parts of red pigment (PR-19) were obtained. The average primary particle size was 38 nm.

(Red pigment (PR-20))
Disperse 43.5 parts of 3-amino-4-methoxybenzamide in 900 parts of water, add ice to adjust the temperature to 5 ° C., add 104.0 parts of 35% aqueous hydrochloric acid and stir for 1 hour, then sodium nitrite. 19.9 parts was added to 50 parts of water, the prepared aqueous solution was added, and the mixture was stirred for 3 hours. After adding 3.2 parts of sulfamic acid to eliminate excess sodium nitrite, an aqueous solution comprising 192 parts of 80% acetic acid aqueous solution, 210 parts of 25% sodium hydroxide aqueous solution, and 180 parts of water was added, and the diazonium salt aqueous solution was added. did. On the other hand, 88.4 parts of N- [4- (acetylamino) phenyl] -3-hydroxy-2-naphthalenecarboxamide and 174.0 parts of 25% aqueous sodium hydroxide solution were dissolved in 1500 parts of water at 50 ° C. to prepare a coupler. It was set as the solution.

This coupler solution was poured into the 5 ° C. diazonium salt aqueous solution over 30 minutes to carry out a coupling reaction. The pH at this time was 4.4. After stirring for 3 hours and confirming the disappearance of the diazonium salt, the mixture was heated to 70 ° C., filtered, washed with water, and dried at 90 ° C. for 24 hours to obtain 118 parts of an azo pigment represented by the formula (A2-3). . As a result of mass spectrometry by TOF-MS, it was identified as an azo pigment of the formula (A2-3).

Next, 100 parts of the azo pigment of the formula (A2-3), 1200 parts of sodium chloride, and 120 parts of diethylene glycol are charged into a stainless 1 gallon kneader (manufactured by Inoue Seisakusho), kneaded at 60 ° C. for 6 hours, and subjected to salt milling treatment. did. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 98 parts of red pigment (PR-20) were obtained. The average primary particle size was 38 nm.

(Red dye (PR-21))
74.6 parts of the amine compound of the following chemical formula (11) was dispersed in 900 parts of water, ice was added to adjust the temperature to 5 ° C., 104.0 parts of 35% hydrochloric acid aqueous solution was added and stirred for 1 hour, and then sodium nitrite. 19.9 parts was added to 50 parts of water, the prepared aqueous solution was added, and the mixture was stirred for 3 hours. After adding 3.2 parts of sulfamic acid to eliminate excess sodium nitrite, an aqueous solution comprising 192 parts of 80% acetic acid aqueous solution, 210 parts of 25% sodium hydroxide aqueous solution, and 180 parts of water was added, and the diazonium salt aqueous solution was added. did. On the other hand, 88.4 parts of N- [4- (acetylamino) phenyl] -3-hydroxy-2-naphthalenecarboxamide and 174.0 parts of 25% aqueous sodium hydroxide solution were dissolved in 1500 parts of water at 50 ° C. to prepare a coupler. It was set as the solution.
This coupler solution was poured into the 5 ° C. diazonium salt aqueous solution over 30 minutes to carry out a coupling reaction. The pH at this time was 4.5. After stirring for 3 hours and confirming the disappearance of the diazonium salt, the mixture was heated to 70 ° C., filtered, washed with water, and dried at 90 ° C. for 24 hours to obtain 145 parts of a naphtholazo pigment represented by the formula (A2-8). . As a result of mass spectrometry by TOF-MS, it was identified as a naphthol azo pigment of the formula (A2-8).

Next, 100 parts of the azo pigment of the formula (A2-8), 1200 parts of sodium chloride, and 120 parts of diethylene glycol are charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.), kneaded at 60 ° C. for 6 hours, and subjected to salt milling treatment. did. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 98 parts of red pigment (PR-21) were obtained. The average primary particle size was 49 nm.

Chemical formula (11)

(Red pigment (PR-22))
Commercially available C.I. I. 100 parts of Pigment Red 269 (PR269) (“Toner Magenta F8B” manufactured by Clariant), 800 parts of sodium chloride, and 180 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70 ° C. for 5 hours. The mixture was poured into 4000 parts of warm water, stirred at a high speed mixer for about 1 hour while being heated to about 80 ° C. to form a slurry, filtered and washed repeatedly to remove salt and solvent, and then at 80 ° C. for 24 hours. It dried and obtained 100 parts of red pigment | dye (PR-22). The average primary particle size was 45 nm.

(Red pigment (PR-23))
66.1 parts of 3-amino-4-methoxybenzanilide are dispersed in 1027 parts of water, adjusted to a temperature of 5 ° C. by adding ice, added with 108.3 parts of 35% aqueous hydrochloric acid and stirred for 1 hour, and then added with nitrous acid. An aqueous solution prepared by adding 19.9 parts of sodium to 50 parts of water was added and stirred for 3 hours. After adding 3.2 parts of sulfamic acid to eliminate excess sodium nitrite, an aqueous solution comprising 192 parts of 80% acetic acid aqueous solution, 210 parts of 25% sodium hydroxide aqueous solution, and 180 parts of water was added, and the diazonium salt aqueous solution was added. did. Meanwhile, 70.7 parts of N- [4-acetylaminophenyl] -3-hydroxy-2-naphthalenecarboxamide, N- [4- (2-oxo-2,3-dihydro-1H-benzimidazol-5-yl] )]-3-Hydroxy-2-naphthalenecarboxamide (17.6 parts) and 25% aqueous sodium hydroxide solution (174.0 parts) were dissolved in methanol (1500 parts) at 50 ° C. to obtain a coupler solution.

This coupler solution was poured into the 5 ° C. diazonium salt aqueous solution over 30 minutes to carry out a coupling reaction. The pH at this time was 4.2. After stirring for 3 hours and confirming the disappearance of the diazonium salt, it was heated to 70 ° C., filtered, washed with water, and dried at 90 ° C. for 24 hours, and the azo pigment represented by the formula (A2-1) and the chemical formula (12) 142 parts of a mixture of the azo pigments represented are obtained. As a result of mass spectrometry by TOF-MS, it was confirmed that the weight ratio of the mixture of the azo pigments of the formula (A2-1) and the chemical formula (12) was 80.1: 19.9.

  Next, 100 parts of a mixture of the azo pigments of the formula (A2-1) and chemical formula (12) obtained by the above reaction, 1200 parts of sodium chloride, and 120 parts of diethylene glycol were made of 1 gallon kneader made of stainless steel (manufactured by Inoue Seisakusho). The mixture was kneaded at 60 ° C. for 6 hours and subjected to salt milling. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 97 parts of a red pigment (PR-23) were obtained. The average primary particle size was 35 nm.

(Red pigment (PR-24))
66.1 parts of 3-amino-4-methoxybenzanilide are dispersed in 1027 parts of water, ice is added to adjust the temperature to 5 ° C., 108.3 parts of 35% aqueous hydrochloric acid is added, and the mixture is stirred and stirred for 1 hour. An aqueous solution prepared by adding 19.9 parts of sodium nitrate to 50 parts of water was added and stirred for 3 hours. After adding 3.2 parts of sulfamic acid to eliminate excess sodium nitrite, an aqueous solution comprising 192 parts of 80% acetic acid aqueous solution, 210 parts of 25% sodium hydroxide aqueous solution, and 180 parts of water was added, and the diazonium salt aqueous solution was added. did. On the other hand, 72.4 parts of N- [5-chloro-2-methoxyphenyl] -3-hydroxy-2-naphthalenecarboxamide, N- [4- (2-oxo-2,3-dihydro-1H-benzimidazole] 5-yl)]-3-hydroxy-2-naphthalenecarboxamide (17.6 parts) and 25% aqueous sodium hydroxide solution (174.0 parts) were dissolved in methanol (1500 parts) at 50 ° C. to obtain a coupler solution.

  This coupler solution was poured into the 5 ° C. diazonium salt aqueous solution over 30 minutes to carry out a coupling reaction. The pH at this time was 4.3. After stirring for 3 hours and confirming the disappearance of the diazonium salt, the mixture was heated to 70 ° C., filtered, washed with water, and dried at 90 ° C. for 24 hours, and the azo pigment represented by the chemical formula (13) and the chemical formula (12) were represented. 143 parts of a mixture of azo pigments were obtained. As a result of mass spectrometry by TOF-MS, it was confirmed that the weight ratio of the mixture of the azo pigments of the chemical formula (13) and the chemical formula (12) was 80.4: 19.6.

  Next, 100 parts of the mixture of the azo pigments of the chemical formula (12) and chemical formula (13) obtained by the above reaction, 1200 parts of sodium chloride, and 120 parts of diethylene glycol are charged into a stainless 1 gallon kneader (manufactured by Inoue Seisakusho). The mixture was kneaded at 60 ° C. for 6 hours and subjected to salt milling. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 96 parts of red pigment (PR-24) were obtained. The average primary particle size was 35 nm.

(Red pigment (PR-25))
A mixture of 52.9 parts of 3-amino-4-methoxybenzanilide and 16.3 parts of the amine compound of the chemical formula (14) is dispersed in 1027 parts of water, adjusted to a temperature of 5 ° C. by adding ice, and 35% aqueous hydrochloric acid solution After adding 108.3 parts and stirring for 1 hour, an aqueous solution prepared by adding 19.9 parts of sodium nitrite to 50 parts of water was added and stirred for 3 hours. After adding 3.2 parts of sulfamic acid to eliminate excess sodium nitrite, an aqueous solution comprising 192 parts of 80% acetic acid aqueous solution, 210 parts of 25% sodium hydroxide aqueous solution, and 180 parts of water was added, and a diazonium salt aqueous solution was added. did. On the other hand, 88.4 parts of N- [4-acetylaminophenyl] -3-hydroxy-2-naphthalenecarboxamide and 174.0 parts of 25% aqueous sodium hydroxide solution were dissolved in 1500 parts of methanol at 50 ° C. did.

  This coupler solution was poured into the 5 ° C. diazonium salt aqueous solution over 30 minutes to carry out a coupling reaction. The pH at this time was 4.3. After stirring for 3 hours and confirming the disappearance of the diazonium salt, the mixture was heated to 70 ° C., filtered, washed with water, and dried at 90 ° C. for 24 hours. The azo pigment represented by the formula (A2-1) and the chemical formula (A2- 141 parts of a mixture of azo pigments represented by 6) were obtained. As a result of mass spectrometry by TOF-MS, it was confirmed that the weight ratio of the mixture of the azo pigments of the formula (A2-1) and the chemical formula (A2-6) was 80.3: 19.7.

  Next, 100 parts of a mixture of the azo pigments of the formula (A2-1) and chemical formula (15) obtained by the above reaction, 1200 parts of sodium chloride, and 120 parts of diethylene glycol were made of 1 gallon kneader made of stainless steel (manufactured by Inoue Seisakusho). The mixture was kneaded at 60 ° C. for 6 hours and subjected to salt milling. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 97 parts of a red pigment (PR-25) were obtained. The average primary particle size was 37 nm.

(Red pigment (PR-26))
66.1 parts of 3-amino-4-methoxybenzanilide are dispersed in 1027 parts of water, adjusted to a temperature of 5 ° C. by adding ice, added with 108.3 parts of 35% aqueous hydrochloric acid and stirred for 1 hour, and then added with nitrous acid. An aqueous solution prepared by adding 19.9 parts of sodium to 50 parts of water was added and stirred for 3 hours. After adding 3.2 parts of sulfamic acid to eliminate excess sodium nitrite, an aqueous solution comprising 192 parts of 80% acetic acid aqueous solution, 210 parts of 25% sodium hydroxide aqueous solution, and 180 parts of water was added, and the diazonium salt aqueous solution was added. did. Meanwhile, 80.7 parts of N- [2-chloro-5-trifluoromethylphenyl] -3-hydroxy-2-naphthalenecarboxamide, N- [4- (2-oxo-2,3-dihydro-1H-benz] Imidazole-5-yl)]-3-hydroxy-2-naphthalenecarboxamide (17.6 parts) and 25% aqueous sodium hydroxide solution (174.0 parts) were dissolved in methanol (1500 parts) at 50 ° C. to obtain a coupler solution.
This coupler solution was poured into the 5 ° C. diazonium salt aqueous solution over 30 minutes to carry out a coupling reaction. The pH at this time was 4.4. After stirring for 3 hours and confirming the disappearance of the diazonium salt, it was heated to 70 ° C., filtered, washed with water, and dried at 90 ° C. for 24 hours, and the azo pigment represented by the formula (A1-1) and the chemical formula (12) 158 parts of a mixture of azo pigments represented by the formula: As a result of mass spectrometry by TOF-MS, it was confirmed that the weight ratio of the mixture of the azo pigments represented by the formula (A1-1) and the chemical formula (12) was 82.1: 17.9.
Next, 100 parts of a mixture of azo pigments of the formula (A1-1) and chemical formula (12) obtained by the above reaction, 1200 parts of sodium chloride, and 120 parts of diethylene glycol were made of 1 gallon kneader made of stainless steel (manufactured by Inoue Seisakusho). The mixture was kneaded at 60 ° C. for 6 hours and subjected to salt milling. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 98 parts of red pigment (PR-26) were obtained. The average primary particle size was 38 nm.

(Red pigment (PR-27))
61.7 parts of 3-amino-4-methylbenzanilide are dispersed in 1027 parts of water, ice is added to adjust the temperature to 5 ° C., 108.3 parts of 35% aqueous hydrochloric acid solution is added, and the mixture is stirred for 1 hour. An aqueous solution prepared by adding 19.9 parts of sodium to 50 parts of water was added and stirred for 3 hours. After adding 3.2 parts of sulfamic acid to eliminate excess sodium nitrite, an aqueous solution comprising 192 parts of 80% acetic acid aqueous solution, 210 parts of 25% sodium hydroxide aqueous solution, and 180 parts of water was added, and the diazonium salt aqueous solution was added. did. Meanwhile, 80.7 parts of N- [2-chloro-5-trifluoromethylphenyl] -3-hydroxy-2-naphthalenecarboxamide, N- [4- (2-oxo-2,3-dihydro-1H-benz] Imidazole-5-yl)]-3-hydroxy-2-naphthalenecarboxamide (17.6 parts) and 25% aqueous sodium hydroxide solution (174.0 parts) were dissolved in methanol (1500 parts) at 50 ° C. to obtain a coupler solution.
This coupler solution was poured into the 5 ° C. diazonium salt aqueous solution over 30 minutes to carry out a coupling reaction. The pH at this time was 4.5. After stirring for 3 hours and confirming the disappearance of the diazonium salt, the mixture was heated to 70 ° C., filtered, washed with water, and dried at 90 ° C. for 24 hours, and the azo pigment represented by formula (A1-17) and formula (16) 149 parts of a mixture of azo pigments represented by the formula: As a result of mass spectrometry by TOF-MS, it was confirmed that the weight ratio of the mixture of the azo pigments of formula (A1-17) and formula (16) was 82.1: 17.9.
Next, 100 parts of a mixture of the azo pigments of the formula (A1-17) and the formula (16) obtained by the above reaction, 1200 parts of sodium chloride, and 120 parts of diethylene glycol were made of 1 gallon kneader made of stainless steel (manufactured by Inoue Seisakusho). The mixture was kneaded at 60 ° C. for 6 hours and subjected to salt milling. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 97 parts of a red pigment (PR-27) were obtained. The average primary particle size was 36 nm.

(Red pigment (PR-28))
A mixture of 52.8 parts of 3-amino-4-methoxybenzanilide and 16.3 parts of the amine compound of the chemical formula (14) is dispersed in 1027 parts of water, adjusted to a temperature of 5 ° C. by adding ice, and 35% aqueous hydrochloric acid solution After adding 108.3 parts and stirring for 1 hour, the aqueous solution prepared by adding 19.9 parts of sodium nitrite to 50 parts of water was added and stirred for 3 hours. After adding 3.2 parts of sulfamic acid to eliminate excess sodium nitrite, an aqueous solution comprising 192 parts of 80% acetic acid aqueous solution, 210 parts of 25% sodium hydroxide aqueous solution, and 180 parts of water was added, and the diazonium salt aqueous solution was added. did. On the other hand, 100.9 parts of N- [2-chloro-5-trifluoromethylphenyl] -3-hydroxy-2-naphthalenecarboxamide and 174.0 parts of 25% aqueous sodium hydroxide solution were dissolved in 1500 parts of methanol at 50 ° C. To obtain a coupler solution.
This coupler solution was poured into the 5 ° C. diazonium salt aqueous solution over 30 minutes to carry out a coupling reaction. The pH at this time was 4.3. After stirring for 3 hours and confirming the disappearance of the diazonium salt, the mixture was heated to 70 ° C., filtered, washed with water, and dried at 90 ° C. for 24 hours, and the azo pigment represented by the formula (A1-1) and the formula (A1- 14) A mixture of azo pigments represented by 14) was obtained. As a result of mass spectrometry by TOF-MS, it was confirmed that the weight ratio of the mixture of the azo pigments of the formula (A1-1) and the formula (A1-14) was 76.5: 23.5.
Next, 100 parts of a mixture of the azo pigments of the formulas (A1-1) and (A1-14) obtained by the above reaction, 1200 parts of sodium chloride, and 120 parts of diethylene glycol were added to a 1 gallon kneader made of stainless steel (Inoue Manufacturing Co., Ltd.). And kneaded at 60 ° C. for 6 hours and subjected to salt milling. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 97 parts of red pigment (PR-28) were obtained. The average primary particle size was 34 nm.

<Other dye production methods>
(Red pigment (PR-29))
Commercially available C.I. I. 100 parts of Pigment Red 177 (PR177) (“chromophthaled red A2B” manufactured by BASF), 1200 parts of sodium chloride and 120 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60 ° C. for 6 hours. Then, salt milling was performed. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 98 parts of a red pigment (PR-29) were obtained. The average primary particle size was 33 nm.

(Red colorant (PR-30))
Commercially available C.I. I. 100 parts of Pigment Red 254 (PR254) (“Irgafore Red B-CF” manufactured by BASF), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) at 6 ° C. The mixture was kneaded for a time and subjected to salt milling. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 98 parts of red pigment (PR-30) were obtained. The average primary particle size was 33 nm.

(Red colorant (PR-31))
Commercially available C.I. I. 100 parts of Pigment Red 179 (PR179) (“Pariogen Maroon L-3920” manufactured by BASF), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) at 60 ° C. for 6 hours. Kneaded and salt milled. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 98 parts of red pigment (PR-31) were obtained. The average primary particle size was 40.8 nm.

(Yellow pigment (PY-1))
C. I. 100 parts of Pigment Yellow 185 (PY185) (“Pariogen Yellow D1155” manufactured by BASF), 700 parts of sodium chloride, and 180 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. . The mixture was poured into 2000 parts of warm water and stirred for 1 hour while heating to 80 ° C. to form a slurry, filtered, washed with water repeatedly to remove salt and solvent, dried at 80 ° C. overnight, and 95 parts of yellow A dye (PY-1) was obtained. The average primary particle size was 45.7 nm.

(Yellow pigment (PY-2))
C. I. 100 parts of Pigment Yellow 138 (PY138) (“Pariotor Yellow K0960-HD” manufactured by BASF), 700 parts of sodium chloride, and 180 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) at 80 ° C. for 6 hours. Kneaded. The mixture was poured into 2000 parts of warm water and stirred for 1 hour while heating to 80 ° C. to form a slurry, filtered, washed with water repeatedly to remove salt and solvent, dried at 80 ° C. overnight, and 95 parts of yellow A dye (PY-2) was obtained. The average primary particle size was 40.2 nm.

(Yellow pigment (PY-3))
C. I. 100 parts of Pigment Yellow 139 (PY139) ("Irgafore Yellow 2R-CF" manufactured by BASF), 700 parts of sodium chloride, and 180 parts of diethylene glycol were charged into a stainless gallon kneader (manufactured by Inoue Seisakusho) at 80 ° C for 6 hours. Kneaded. The mixture was poured into 2000 parts of warm water and stirred for 1 hour while heating to 80 ° C. to form a slurry, filtered, washed with water repeatedly to remove salt and solvent, dried at 80 ° C. overnight, and 95 parts of yellow A dye (PY-3) was obtained. The average primary particle size was 43.2 nm.

(Yellow pigment (PY-4))
C. I. 100 parts of Pigment Yellow 150 (PY150) (“E-4GN” manufactured by LANXESS), 700 parts of sodium chloride, and 180 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. The mixture was poured into 2000 parts of warm water and stirred for 1 hour while heating to 80 ° C. to form a slurry, filtered, washed with water repeatedly to remove salt and solvent, dried at 80 ° C. overnight, and 95 parts of yellow A dye (PY-4) was obtained. The average primary particle size was 36.2 nm.

<Method for producing pigment dispersion>
(Dye dispersion (DR-1))
The following mixture was stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. The pigment dispersion (DR-1) was produced by filtering with a filter.

Red pigment (PR-1): 12.0 parts (Azo pigment formula (A1-1))
Resin type dispersant: 1.0 part ("EFKA4300" manufactured by BASF)
Alkali-soluble resin solution (P-2): 35.0 parts Solvent: 52.0 parts Propylene glycol monomethyl ether acetate (PGMAC)

(Dye dispersion (DR-2 to 31, DY-1 to 4))
Except having changed to the mixture of the composition (part by weight) shown in Table 5 and Table 6, it was the same as the dye dispersion (DR-1), and the dye dispersions (DR-2 to 31), (DY-1 to DY-1) 4) was produced.

In Tables 5 and 6, EFKA4300 and PGMAC are as follows.
EFKA4300: PGMAC manufactured by BASF: Propylene glycol monomethyl ether acetate

<Preparation of red coloring composition for organic EL display device>
[Example 1]
(Photosensitive red coloring composition (RR-1))
The following mixture was stirred and mixed so as to be uniform, and then filtered through a 1.0 μm filter to prepare a photosensitive coloring composition (RR-1).

Dye dispersion (DR-1): 50.0 parts (Azo pigment formula (A1-1))
Dye dispersion (DY-1): 16.7 parts (CI Pigment Yellow 185 (PY185))
Alkali-soluble resin solution (P-1): 4.3 parts Photopolymerizable monomer: 4.2 parts (“Aronix M402” manufactured by Toagosei Co., Ltd.)
Photopolymerization initiator: 1.2 parts (“OXE-02” manufactured by BASF)
Sensitizer: 0.4 parts ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.)
Solvent: 23.2 parts (propylene glycol monomethyl ether acetate (PGMAC))

[Examples 2-46, Comparative Examples 1-7]
(Photosensitive coloring composition (RR-2 to 53)
Hereinafter, except that the dye dispersion, alkali-soluble resin solution, photopolymerizable monomer, photopolymerization initiator, sensitizer, and solvent were changed to the types shown in Tables 6 and 7 and the blending amount (parts by weight). The photosensitive red coloring composition (RR-2 to 53) was prepared in the same manner as the photosensitive red coloring composition (RR-1). Moreover, “Aronix M402” manufactured by Toa Gosei Co., Ltd. was used as the photopolymerizable monomer described in Tables 6 and 7, and “EAB-F” manufactured by Hodogaya Chemical Co., Ltd. was used as the sensitizer.

Abbreviations in Tables 6 and 7 are described below.
<Photopolymerization initiator>
(Oxime ester compounds)
I-1: Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime)
("IRGACURE OXE 02" manufactured by BASF)
I-2: Compound having the structure of the following chemical formula (5b-1)

Chemical formula (5b-1)
I-3: Compound chemical formula (5b-2) having the structure of the following chemical formula (5b-2)
(Other photopolymerization initiators)
・ Irg. 369 ("IRGACURE 369" manufactured by BASF)

[Evaluation of photosensitive red coloring composition]
The color characteristics and film thickness of the photosensitive red coloring compositions obtained in Examples and Comparative Examples were evaluated by the following methods. Tables 8 and 9 show the evaluation results.

<Formation of filter segment>
A black matrix is patterned on a glass substrate, and the value of chromaticity x is 0 in an organic EL device (EL-1) as a light source using the coloring composition shown in Tables 6 and 7 on the substrate with a spin coater. Each film was coated to a thickness of 680 to form a colored composition film. The film was irradiated with ultraviolet rays of 150 mJ / cm ² using a super high pressure mercury lamp through a photomask. Next, sprayed with an alkali developer consisting of 0.15% by weight of sodium carbonate, 0.05% by weight of sodium hydrogen carbonate, 0.05% by weight of an anionic surfactant ("Perex NBL" manufactured by Kao Corporation) and 99.7% by weight of water. After developing and removing the unexposed portion, the substrate was washed with ion exchange water, and the substrate was heated at 230 ° C. for 20 minutes to form a red filter segment.

(Flatness)
About the obtained red filter segment, the surface roughness (Ra) of the coating film was measured using the three-dimensional structural analysis microscope (made by ZYGO system Canon Marketing Japan Co., Ltd.). The surface roughness (Ra) indicates an arithmetic average roughness defined in JIS B0601 and JIS B0031.
Evaluation was made based on the following criteria.

A: Surface roughness of less than 100 mm O: Surface roughness of 100 mm to less than 150 mm Δ: Surface roughness of 150 mm to less than 200 mm X: Surface roughness of 200 mm or more

(Chemical resistance)
<NMP resistance test evaluation>
About the obtained red filter segment, chromaticity ([L * (1), a * (1), b * (1)]) with a C light source was measured with a microspectrophotometer ("OSP-SP100" manufactured by Olympus Optics). ). Further, the substrate on which the filter segment is formed is immersed in NMP for 15 minutes, washed with water, dried, and then chromaticity with a C light source ([L * (2), a * (2), b * (2)]) The color difference ΔE * ab was determined by the following calculation formula and evaluated in the following four stages.

ΔE * ab = √ ((L * (2) -L * (1)) ² + (a * (2) -a * (1)) ² + (b * (2) -b * (1)) ² )

A: ΔE * ab is less than 1.0
○: ΔE * ab is 1.0 or more and less than 1.5
Δ: ΔE * ab is 1.5 or more and less than 3.0 ×: ΔE * ab is 3.0 or more

(Thickness evaluation)
The film thickness of the obtained red filter segment was measured using a surface shape measuring device DEKTAK150 (manufactured by ULVAC-ES).

  As shown in Tables 8 and 9, C.I. I. Pigment Red 177 and / or a naphthol azo pigment [A] represented by the following general formula (1): I. Pigment Yellow 185, and C.I. I. The photosensitive coloring composition in which the content of either Pigment Red 177 or the naphtholazo pigment [A] represented by the following general formula (1) is 77% by weight or more in 100% by weight of the red pigment is a thin film It was finished and showed good coating flatness and chemical resistance. Among them, a naphthol azo pigment [A] represented by the general formula (1) as a red dye, particularly C.I. I. When CI Pigment Red 269 was contained, the coating film became a thin film, which was a preferable result.

Since the flatness of the coating film is obtained as described above, chemical resistance is obtained, and since it is a thin film, even when used for an organic EL display, the organic EL element is not damaged. It was possible to use it suitably.

Claims (7)

A red coloring composition for an organic EL display device comprising a red dye, a yellow dye, an alkali-soluble resin, a photopolymerizable monomer, and a photopolymerization initiator, wherein the red dye is C.I. I. Pigment Red 177 and / or a naphthol azo pigment [A] represented by the following general formula (1): I. Pigment Yellow 185, and C.I. I. The organic EL display device, wherein the content of any one of CI Pigment Red 177 and the naphtholazo pigment [A] represented by the following general formula (1) is 77% by weight or more in 100% by weight of the red dye Red coloring composition.


[In General Formula (1), A represents a hydrogen atom, a benzimidazolone group, an optionally substituted phenyl group, or an optionally substituted heterocyclic group. R ¹ represents a hydrogen atom, a halogen atom, a trifluoromethyl group, an alkyl group having 1 to 4 carbon atoms, —OR ⁷ or —COOR ⁸ . R ^{2 to} R ⁶ are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, a trifluoromethyl group, an alkyl group having 1 to 4 carbon atoms, —OR ⁹ , —COOR ¹⁰ , —CONHR ¹¹ , -NHCOR ¹² or an _-SO 2 ^{NHR 13.} R ^{7 to} R ¹³ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ] C. I. 2. The red coloring composition for an organic EL display device according to claim 1, wherein the content of Pigment Yellow 185 is 12 to 35% by weight in 100% by weight of the total content of red pigment and yellow pigment. The red dye contains a naphthol azo pigment [A] represented by the general formula (1), and the naphthol azo pigment [A] represented by the general formula (1) is C.I. I. The red coloring composition for organic EL display devices according to claim 1, wherein the red coloring composition is Pigment Red 269. The red coloring composition for an organic EL display device according to any one of claims 1 to 3, wherein the photopolymerization initiator contains an oxime ester compound. The red coloring composition for an organic EL display device according to any one of claims 1 to 4, wherein the alkali-soluble resin is a resin having a structural unit derived from methyl methacrylate. A color filter for an organic EL display device, comprising a filter segment formed on the base material from the red coloring composition for an organic EL display device according to any one of claims 1 to 5. An organic EL display device comprising the color filter for an organic EL display device according to claim 6 and a white organic EL light source.