JP6822273B2 - Coloring compositions and color filters for color filters - Google Patents

Description

The present invention is a color liquid crystal display device having a backlight portion using quantum dots, a coloring composition for a color filter used for manufacturing a color filter used for a color image pickup tube element, and the like, and a coloring composition for a color filter formed by using the same. It relates to a color filter having a filter segment of

In recent years, in the field of color filters, in order to realize high contrast ratio, high brightness, and high coloring power, C.I. I. Pigment Red 176 and C.I. I. It has been proposed to use a naphthol azo pigment such as Pigment Red 242 as a main pigment (Patent Document 1). However, the naphthol azo pigment has an affinity for the solvent of the pigment, the acidity of the pigment surface, and the like. I. Pigment Red 254 and C.I. I. Since it is different from Pigment Red 177 and the like, it is inferior in dispersibility, fluidity and storage stability, and also has inferior heat resistance and solvent resistance, so that a practical color filter has not been obtained.

Recently, the development of a backlight unit using quantum dot technology is also underway (Patent Document 2 and Non-Patent Documents 1 and 2). Here, the quantum dot means a nanometer-sized fine particle of a semiconductor. In addition, quantum dots exhibit specific optical and electrical properties due to the quantum confinement effect (quantum size effect) in which electrons and exciters are confined in small nanometer-sized crystals, and semiconductor nanoparticles. , Also called Semiconductor Nanocrystal. Examples of the quantum dots include semiconductor fine particles whose emission color is regulated by their own particle size and semiconductor fine particles having a dopant. As a backlight unit using the quantum dots, for example, a backlight unit having a blue light emitting element, a green quantum dot, and a red quantum dot has been proposed, and the backlight unit has a sharp peak wavelength in the emission spectrum. It has the characteristic of high color purity. It should be noted that a method for achieving higher color reproducibility and power saving in a liquid crystal display device having a backlight portion using quantum dots has not yet been found.

JP-A-1999-119019 Special Table 2013-539598

John Van Derlofske Ph.D., Gilles Benoit Ph.D., Art Lathrop, Dave Lamb Ph.D., “Quauntum Dot Enhancement of Color For LCD Systems”, IDW’13 FMC8-1 (USA), p548-551 Naoki Tanaka, "To Quantum Dot Display," Nikkei Electronics, March 3, 2014, p53-59

An object of the present invention is to color a color filter having excellent fastness such as heat resistance, light resistance, and chemical resistance, not only high brightness and contrast, but also excellent hue even in a thin film of 2-3 μm and high coloring power. To provide a composition.

As a result of diligent research to solve the above problems, the present inventors have been used in the manufacture of color filters used in color liquid crystal displays, color imaging tube elements, etc., which have a backlight portion using quantum dots. It has been found that the above-mentioned problems can be solved by a coloring composition containing a coloring agent containing a naphthol azo pigment [A1] represented by the general formula (1) in the coloring composition for a color filter.

That is, the present invention is a coloring composition for a color filter containing a colorant, an acidic resin type dispersant, a binder resin and an organic solvent.
The colorant contains the pigment [A1] represented by the following general formula (1) and contains.
The chromaticity coordinates of the coating film in the XYZ color system measured using a light source containing quantum dots as a light emitting element form a coating film having chromaticity coordinates x = 0.680 and chromaticity coordinates y = 0.318. when the thickness is 2.0~3.0μm der is, a light source including quantum dots as light-emitting element, a first peak wavelength in 430 to 480 nm, a second peak wavelength in 510 to 560 nm, 600 to The present invention relates to a coloring composition for a color filter, which is a light source having a third peak wavelength at 660 nm .

General formula (1)

[In general formula (1),
A represents a hydrogen atom, a benzimidazolone group, a phenyl group which may have a substituent or a heterocyclic group which may have a substituent.
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, -Represents NHCOR ¹² or 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.
However, this excludes cases where R ⁴ is -NHCOR ¹² , A, R ² , R ³ , R ⁵ and R ⁶ are hydrogen atoms, and R ¹ is a halogen atom. ]

The present invention also relates to the above-mentioned coloring composition for a color filter, which further contains at least one selected from the group consisting of a photopolymerization initiator and a photopolymerizable monomer.

The present invention also relates to a color filter including a filter segment formed by using the coloring composition for a color filter.

Furthermore, the present invention relates to a display device including the color filter and a light emitting element including quantum dots.

According to the present invention, a coloring composition for a color filter having excellent fastness such as heat resistance, light resistance, and chemical resistance, high brightness and contrast, and excellent hue even in a thin film of 2-3 μm and high coloring power. It has the excellent effect of being able to provide objects and color filters.

The emission spectrum shown in FIG. 1 is obtained from a light emitting device containing InP / ZnS core-shell type quantum dots manufactured according to the method described in Example B1 of JP2011-202148. This emission spectrum has a first peak wavelength at 450 nm, a second peak wavelength at 542 nm, and a third peak wavelength at 629 nm, and the half width of the first peak wavelength is 20 nm and the second peak. The half width of the wavelength is 40 nm, and the half width of the third peak wavelength is 39 nm.

Hereinafter, the present invention will be described in detail. In this specification, when it is described as "(meth) acryloyl", "(meth) acrylic", "(meth) acrylic acid", "(meth) acrylate", or "(meth) acrylamide", Unless otherwise stated, "acryloyl and / or methacrylic acid", "acrylic and / or methacrylic acid", "acrylic acid and / or methacrylic acid", "acrylate and / or methacrylate", or "acrylamide and / or methacrylic acid", respectively. It shall represent. Further, "CI" mentioned in the present specification means a color index (CI).

<Colorant>
[Naftor azo pigment represented by the general formula (1) [A1]]
The colorant in the coloring composition for a color filter of the present invention is characterized by containing a naphthol azo pigment [A1] represented by the general formula (1).

General formula (1):

[In the general formula (1), A is independently a hydrogen atom, a methyl group, a benzimidazolone group, a phenyl group which may have a substituent, or a heterocyclic group which may have a substituent. Represents.
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, Alternatively, it represents SO ₂ NHR ^12, and at least one of R ^{2 to} R ⁶ represents a trifluoromethyl group. R ^{7 to} R ¹² each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ]

In the general formula (1), in A, the "substituted group" of the phenyl group which may have a substituent includes a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, and a cyano. Monovalent 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. Examples thereof include trivalent metal salts (for example, sodium salt, potassium salt, aluminum salt, etc.). Therefore, specific examples of the phenyl group that 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, and an o-tri. 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 Examples thereof include −methoxy-4-carbamoylphenyl group, 2-methoxy-4-methyl-3-sulfamoylphenyl group, 4-sulfophenyl group, 4-carboxyphenyl group, 2-methyl-4-sulfophenyl group and the like. However, it is not limited to these.

Further, in A, the "substituted group" of the heterocyclic group which may have a substituent includes a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, a cyano group and a trifluoro. A monovalent to trivalent metal of an acidic group selected from a methyl 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. Examples include salts (eg, sodium salt, potassium salt, aluminum salt, etc.). Further, the "heterocycle" means an atom containing one or more heteroatoms other than carbon atoms among the atoms constituting the ring system, and may be a saturated ring or an unsaturated ring. Further, it may be a monocyclic ring or a fused ring. Therefore, the heterocycles include pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, triazine ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, pyrazole ring, oxazole ring, thiazole ring, isooxazole ring, and isothiazole ring. , Triazole ring, thiazazole ring, oxazole ring, quinoline ring, benzofuran ring, indole ring, morpholin ring, pyrrolidine ring, piperidine ring, tetrahydrofuran ring and the like. Therefore, the heterocyclic group means a monovalent group derived by removing a hydrogen atom from these heterocycles, and therefore, as a specific example of a heterocyclic group which may have a substituent, 2-pyridyl Group, 3-pyridyl group, 4-pyridyl group, 2-pyrrolill group, 3-pyrrolill 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-indrill group, 2-indrill group, 2-benzofuryl group, 2-benzothienyl group, 2-quinolino group, N − Carbazolyl groups and the like.

Further, examples of the halogen atom in R ^{1 to} R ⁶ include fluorine, chlorine, bromine and iodine.

The alkyl group having 1 to 4 carbon atoms in R ^{1 to} R ¹² may be linear or branched, and specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, or an isobutyl group. , The sec-butyl group and the tert-butyl group.

The colorant of the present invention includes
It is preferable that A is a phenyl group which may independently have a hydrogen atom, a methyl group, a benzimidazolone group, or a substituent.
R ¹ is preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or OR ⁷ .
R ⁷ is preferably an alkyl group having 1 to 4 carbon atoms.
R ² to R ⁶ are each independently a hydrogen atom, a halogen atom, preferably a trifluoromethyl group, at least one of R ² to R ⁶ is trifluoromethyl group.
From the viewpoint of lightness, it is preferable that A is a phenyl group which may have a substituent. Further, from the viewpoint of lightness and dispersibility, R ¹ is preferably an alkyl group having 1 to 4 carbon atoms or OR ⁷ , and R ¹ is more preferably a methyl group or a methoxy group.

Also, preferably, be at least one of R ² to R ⁶ is a trifluoromethyl group is preferred for miniaturization is easy. Among them, R ⁵ is - preferably a trifluoromethyl group, that R ² is -Cl group, preferred. By satisfying these conditions, the pigment can be miniaturized, so that high contrast can be achieved.

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

Specific examples of the azo compound used in the colorant of the present invention include, but are not limited to, the azo compounds shown in Tables 1 to 3 below. In Tables 1 to 3, Ph represents a phenyl group.

(Manufacturing method of naphthol azo pigment [A1])
The naphthol azo pigment [A1] of the present invention can be produced by coupling a diazonium salt with β-naphthols, as is well known in the pigment field. Further, as described below, two or more kinds of naphthol azo pigments are simultaneously synthesized by using aromatic amines (diazo component), β-naphthols (coupler component), or both in two kinds of reactions. , A plurality of naphthol azo pigment species may be contained together. In this case, it is more preferable because it may be possible to obtain a pigment composition which is excellent in miniaturization and gives excellent brightness.

By synthesizing two or more kinds of naphthol azo pigments at the same time, the crystal growth can be inhibited, fine pigment particles can be obtained, and the brightness can be improved for reasons such as improvement in transparency.

To produce the naphthol azo pigment [A1], first, amines (diazo components) represented by the following general formula (3) are mixed with hydrochloric acid, sulfuric acid, acetic acid or the like in an acidic aqueous solution containing nitrite, nitrite or A diazonium salt represented by the following general formula (4) obtained by diazotization with a nitrite is produced.

General formula (3)

General formula (4)

[In the general formulas (3) and (4), A and R ¹ are synonymous with those in the 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. Chloride ion, bromide ion, CH ₃ COO ⁻ are preferable.

Next, the diazonium salt represented by the above general formula (4) and β-naphthols (coupling component) represented by the following general formula (5) are usually reacted at 5 ° C to 70 ° C in an aqueous solvent. Then, post-treatment by a conventional method is performed to produce the naphthol azo pigment [A1] of the general formula (1). Further, the coupling reaction may be carried out in the presence of a surfactant, a resin, a dye derivative, or an inert solvent. Further, the method for producing the naphthol azo pigment [A1] of the present invention is not limited to these methods.

General formula (5)

[In the general formula (5), R ^{2 to} R ⁶ are synonymous with those in the general formula (1). ]

Further, when two or more kinds of naphthol azo pigments are produced at the same time, for example, the following methods can be mentioned.
First, at least one mixture of aromatic amines (diazo components) represented by the following general formula (3) is mixed with hydrochloric acid, sulfuric acid, acetic acid or the like in an acidic aqueous solution containing nitrite, nitrite or nitrite. A mixture of diazonium salts represented by the following general formula (4) obtained by diazotization with an ester is produced.

General formula (3)

General formula (4)

[In the general formulas (3) and (4), A and R ¹ are synonymous with those in the 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. Chloride ion, bromide ion, CH ₃ COO ⁻ are preferable.

Next, the diazonium salt represented by the general formula (4), the β-naphthols (coupling component) represented by the following general formula (5), and the β-naphthols represented by the following general formula (10). The mixture with (coupling component) is usually reacted at 5 ° C. to 70 ° C. in an aqueous solvent and post-treated by a conventional method to obtain the naphthol azo pigment [A1] of the general formula (1) and the general formula. A pigment composition containing the naphthol azo pigment [A'] represented by (6) can be produced. At this time, A ¹ in the general formula (6) is the same as A in the general formula (1), and R ¹⁵¹ is the same pigment as R ¹ . Further, the coupling reaction may be carried out in the presence of a surfactant, a resin, a dye derivative, or an inert solvent. Further, the method for producing the naphthol azo pigment [A1] of the present invention is not limited to these methods.

General formula (5)

[In the general formula (5), R ^{2 to} R ⁶ are synonymous with those in the general formula (1). ]

General formula (10)

The mixing ratio of aromatic amines of the general formula (3) used in the reaction and the mixing ratio of β-naphthols of the general formula (5) and the general formula (10) are set between 60:40 and 100: 0, respectively. can do. By adjusting these mixing ratios, a pigment composition having a desired mass ratio can be obtained.

As described above, the coupler component composed of a mixture of the naphthol compound represented by the general formula (5) and the naphthol compound represented by the general formula (10) and the diazo compound of the aromatic amine represented by the general formula (3). Can be reacted to produce a colorant containing an azo pigment represented by the general formula (1) and the general formula (6). Such a colorant is preferable because it has excellent brightness and contrast ratio. At this time, the mass ratio of the mixture of the naphthol compound represented by the general formula (5) and the naphthol compound represented by the general formula (10) is preferably 60:40 to 100: 0, preferably 100: 0. In this case, the naphthol azo pigment [A1] represented by the general formula (1) is the only product.

(Other colorants)
The coloring composition for a color filter of the present invention includes pigments or dyes other than the naphthol azo pigment [A1] of the above general formula (1) as long as the effects of the present invention are not impaired in order to adjust the chromaticity. Colorants 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 the colorant that can be used in combination include diketopyrrolopyrrole pigments, azo pigments such as azo, disuazo, and polyazo, and azo pigments other than the naphthol azo pigment [A1] of the general formula (1), aminoanthraquinone, and diamino. Anthraquinone pigments such as dianthraquinone, anthrapyrimidine, flavantron, antoanthron, indantron, pyranthron, or biolantron, quinacridone pigments, perinone pigments, perylene pigments, thioindigo pigments, isoindolin pigments, isoindolinone pigments Examples thereof include pigments, quinophthalone pigments, slene pigments and metal complex pigments.

Examples of the dye include xanthene dyes, azo dyes (pyridone dyes, barbituric acid dyes, metal complex dyes, etc.), disazo dyes, anthraquinone dyes, and methine dyes. In addition, rake pigments made from these dyes, inorganic salts of acid dyes having acidic groups such as sulfonic acid and carboxylic acid, salt-forming compounds of acid dyes and nitrogen-containing compounds, and sulfonic acid amides of acid dyes. It may be in the form of a compound or the like.

Among these, azo pigments other than the naphthol azo pigment [A1] of the general formula (1), diketopyrrolopyrrole pigments, quinophthalone pigments, and anthraquinone pigments are preferable from the viewpoint of lightness and coloring power. ..

(Azo pigments other than the naphthol azo pigment [A1] of the general formula (1))
Examples of the azo pigment other than the naphthol azo pigment [A1] 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 and contrast ratio.

<< Naftor azo pigment [A'] >>
The naphthol azo pigment [A'] is a naphthol azo pigment represented by the general formula (6).
General formula (6)

[In the general formula (6), A ¹ independently represents a hydrogen atom, a phenyl group which may have a substituent, or a heterocyclic group which may have a substituent. R ¹⁵¹ represents a hydrogen atom, a trifluoromethyl group, an alkyl group having 1 to 4 carbon atoms, -OR ¹⁵⁷ or COOR ¹⁵⁸ . R ¹⁵⁷ and R ¹⁵⁸ 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 "substituents" in A of the general formula (1). Similar to the substituent.

The alkyl group having 1 to 4 carbon atoms in R ¹⁵¹ , R ¹⁵⁷ , and R ¹⁵⁸ may be linear or branched, and specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, or a butyl group. , Isobutyl group, sec-butyl group, tert-butyl group.

As the pigment, from the viewpoint of lightness, A ¹ is preferably a phenyl group which may have a substituent. Further, from the viewpoint of lightness and ^{dispersibility,} it is preferable that ^{R 151} is an alkyl group or ^{OR 157} 1 to 4 carbon ^atoms, and more preferably ^{R 151} is a methyl group or a methoxy group.

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

When the colorant contains a naphthol azo pigment [A'] represented by the general formula (6), it is represented by the naphthol azo pigment [A1] 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 in the range of 70.0: 30.0 to 90.0: 10.0. When the content of the naphthol azo 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. Pigment Red 176 and the like.

<< Other azo pigments [C] >>
Other azo pigments [C] include azos other than the naphthol azo pigment [A1] represented by the general formula (1) and the azo pigment [A'] represented by the general formula (6), azos such as azo, disazo, and polyazo. Examples include system 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. Pigmen 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 and the like can be mentioned. Among these, from the viewpoint of hue, lightness, and contrast ratio, C.I. I. Pigment Red 185, 242, C.I. I. Pigment Orange 38 is preferred.

Specific examples of the red pigment that can be used in combination as described above include, for example, C.I. I. Pigment Red 7, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 57: 1, 81, 81: 1, 81: 2, 81: 3, 81: 4, 122, 146, Concomitant use of red pigments such as 166, 168, 176, 177, 178, 179, 184, 185, 187, 200, 202, 210, 221 242, 246, 254, 255, 264, 270, 272, and 279. Can be done. Among these, from the viewpoint of obtaining a high contrast ratio and high brightness, C.I. I. Pigment Red 177, C.I. I. Pigment Red 254, C.I. I. Pigment Red 242 is preferably used, and these may be used together.

Examples of orange pigments and yellow pigments that can be used in combination 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, 182, 185, 187, 188, 193, 194, 198, 199, 213, and 214 and the like can be mentioned. Examples of the orange pigment include C.I. I. Pigment Orange 38, 43, 71, 73 and the like. Among these, C.I. I. Pigment Yellow 138, 139, 150, C.I. I. Pigment Orange 38 is preferred.

Further, as the quinophthalone-based pigment, those described in Japanese Patent No. 4993026 can be used, but the pigment is not particularly limited thereto.

Further, as the dye to be used in combination, a diketopyrrolopyrrole pigment represented by the following general formula (2) is preferable.
General formula (2)

[In general formula (2),
B, C, D and E may independently have a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, an alkyl group having 1 to 12 carbon atoms, and a substituent. Group, -CF ₃ , -OR ¹³ , -SR ¹⁴ , -N (R ¹⁵ ) R ¹⁶ , -COOR ¹⁷ , -CONH ₂ , -CONHR ¹⁸ , -CON (R ¹⁹ ) R ²⁰ , -SO ₂ NH ₂ , -SO ₂ NHR ²¹ or -SO ₂ N (R ²² ) R ²³ .
R ^{13 to} R ²³ are independently alkyl groups having 1 to 12 carbon atoms, phenyl groups which may have a substituent, or aralkyl groups which may have a substituent. ]

Specific examples of the diketopyrrolopyrrole pigment represented by the general formula (2) that can be used in the present invention are given below, but the present invention is not limited thereto.

Among the diketopyrrolopyrrole pigments represented by the general formula (2) that can be used in the present invention, formulas (2-1), formulas (2-2), formulas (2-3), and formulas (2-4). ), Formula (2-19), and Formula (2-20) are preferable from the viewpoint of brightness, contrast, and crystal precipitation suppressing effect. In particular, the formulas (2-19) and (2-20) are preferable from the viewpoint of brightness. Further, in R ^{18 to} R ²⁰ of the formulas (2-3) and (2-4), an alkyl group having 4 or more carbon atoms or a phenyl group which may have a substituent has an effect of suppressing contrast and crystal precipitation. It is preferable from the viewpoint of. The reason why these are effective in increasing the contrast and suppressing crystal precipitation is that the pigment is affected by the steric hindrance effect of bulky substituents such as carboamide group, phenyl group and t-butyl group having an alkyl group having 4 or more carbon atoms. It is considered that this is because the aggregation of phenyl group is suppressed. Further, the diketopyrrolopyrrole pigment having a carboamide group, a phenyl group and a t-butyl group is also excellent in color characteristics.

The dye that can be used in combination is a dye that exhibits red or purple, and preferably has any form of an oil-soluble dye, an acid dye, a direct dye, and a basic dye. Among these, it is preferable to use a xanthene-based oil-soluble dye, a xanthene-based basic dye, or a xanthene-based acid dye because of its excellent hue. In addition, rake pigments made from these dyes, inorganic salts of acid dyes having acidic groups such as sulfonic acid and carboxylic acid, salt-forming compounds of acid dyes and nitrogen-containing compounds, and sulfonic acid amides of acid dyes. It may be in the form of a compound or the like.

Examples of xanthene-based oil-soluble dyes include CI Solvent Red 35, CI Solvent Red 36, CI Solvent Red 42, CI Solvent Red 43, CI Solvent Red 44, and C.I. I. Solvent Red 45, CI Solvent Red 46, CI Solvent Red 47, CI Solvent Red 48, CI Solvent Red 49, CI Solvent Red 72, CI. Solvent Red 73, CI Solvent Red 109, CI Solvent Red 140, CI Solvent Red 141, CI Solvent Red 237, CI Solvent Red 246, CI Solvent Violet 2. CI Solvent Violet 10 and the like can be mentioned. Among them, CI Solvent Red 35, CI Solvent Red 36, CI Solvent Red 49, CI Solvent Red 109, and CI Solvent Red, which are rhodamine-based oil-soluble dyes with high color development. Red 237, CI Solvent Red 246, and CI Solvent Violet 2 are more preferred.

Examples of the xanthene-based basic dye include C.I. I. Basic Red 1 (Rhodamine 6 GCP), 8 (Rhodamine G), C.I. I. Basic Violet 10 (Rhodamine B) and the like. Among them, in terms of excellent color development, C.I. I. Basic Red 1, C.I. I. It is preferable to use Basic Violet 10.

Examples of xanthene-based acid dyes include C.I. I. Acid Red 51 (erythrosine (edible red No. 3)), C.I. I. Acid Red 52 (Acid Rhodamine), C.I. I. Acid Red 87 (Eosin G (Edible Red No. 103)), C.I. I. Acid Red 92 (Acid Phloxine PB (Edible Red No. 104)), C.I. I. Acid Red 289, C.I. I. Acid Red 388, Rose Bengal B (Edible Red No. 5), Acid Rhodamine G, C.I. I. It is preferable to use Acid Violet 9.

Among them, C.I., which is a xanthene-based acid dye, has heat resistance and light resistance. I. Acid Red 87, C.I. I. Acid Red 92, C.I. I. Acid Red 388 or Rhodamine acid dye C.I. I. Acid Red 52 (Acid Rhodamine), C.I. I. Acid Red 289, Acid Rhodamine G, C.I. I. It is more preferable to use Acid Violet 9. Among these dyes, C.I., a rhodamine-based acid dye, is particularly excellent in color development, heat resistance, and light resistance. I. It is most preferable to use Acid Red 52.

When used in combination with the above red pigments, yellow pigments, orange pigments, and dyes, the content of the naphthol azo pigment [A1] described in the general formula (1) is 10 to 90% by weight based on 100% by weight of the total colorant. %, Preferably 20 to 80% by weight. By being in this content range, the chromaticity region can be expanded.

(Miniaturization of colorants)
The colorant for a color filter of the present invention is used for a color filter by finening the colorant particles by salt milling treatment or the like as necessary in order to obtain high brightness and high contrast when the coloring composition is used. It can be suitably used as a colorant. The primary particle size of the colorant is preferably 10 nm or more in order to enhance the dispersibility in the colorant carrier. Further, in order to obtain a filter segment having high contrast, it is preferably 50 nm or less.

Salt milling is a process of heating a mixture of a colorant, a water-soluble inorganic salt, and a water-soluble organic solvent using a kneader such as a kneader, a 2-roll mill, a 3-roll mill, a ball mill, an attritor, or a sand mill. 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 acts as a crushing aid, and the colorant is crushed by utilizing the high hardness of the inorganic salt during salt milling. By optimizing the conditions for salt milling the colorant, it is possible to obtain a colorant having a very fine primary particle size, a narrow distribution width, and a sharp particle size distribution.

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 price. From the viewpoint of both treatment efficiency and production efficiency, the water-soluble inorganic salt is preferably used in an amount of 50 to 2000% by weight, most preferably 300 to 1000% by weight, based on the total weight of the pigment (100% by weight).

The water-soluble organic solvent has a function of wetting the colorant 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 used. However, since the temperature rises during salt milling and the solvent easily evaporates, a high boiling point having a boiling point of 120 ° C. or higher is preferable from the viewpoint of safety. Such examples include, 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, etc. Is used. These water-soluble organic solvents are preferably used in an amount of 5 to 1000% by weight, most preferably 50 to 500% by weight, based on the total weight of the colorant (100% by weight).

When the colorant is salt-milled, a resin may be added if necessary. Here, the type of resin used is not particularly limited, and a natural resin, a modified natural resin, a synthetic resin, a synthetic resin modified with a natural resin, or the like can be used. The resin used is preferably solid at room temperature, water-insoluble, and more preferably partially soluble in the water-soluble organic solvent. The amount of the resin used is preferably in the range of 2 to 200% by weight based on the total weight of the colorant (100% by weight).

<Dye derivative>
A dye derivative may be used in the coloring composition for a color filter of the present invention. It is presumed that the dye derivative functions as a crystal transition inhibitor or a crystal growth inhibitor, and by containing the compound represented by the general formula (X), as a result, finer particles are promoted and the particle size distribution is improved. The sharpening effect works, and it is possible to improve the brightness and the viscosity stability. Examples of the dye derivative of the present invention include compounds represented by the following general formula (X).

General formula (X) P-Ln
(However, P: organic pigment residue, anthraquinone residue, acridone residue or triazine residue, L: phthalimide methyl group which may have a basic substituent, an acidic substituent, or a substituent, n: 1 ~ 4 integer)

Examples of the organic pigment constituting the organic pigment residue of P include diketopyrrolopyrrole pigments;
Azo pigments such as azo, disazo, polyazo; phthalocyanine pigments such as copper phthalocyanine, halogenated copper phthalocyanine, and metal-free phthalocyanine;
Anthraquinone pigments such as aminoanthraquinone, diaminodianthraquinone, anthrapyrimidine, flavantron, anthraquinone, indanetron, pyranthron, and biolantron;
Kinaclidene pigments; dioxazine pigments; perinone pigments; perylene pigments; thioindigo pigments; isoindolin pigments; isoindolinone pigments; quinophthalone pigments; slene pigments; metal complex pigments and the like.

As a specific example of the substituent of L, a phthalimide methyl group which may have a substituent such as a phthalimide methyl group, a 4-nitrophthalimide methyl group, a 4-chlorophthalimide methyl group, a tetrachlorophthalimide methyl group, etc.
Carbamoyl group, sulfamoyl group, aminomethyl group, dimethylaminomethyl group, diethylaminomethyl group, dibutylaminomethyl group, piperidinomethyl group, dimethylaminopropylaminosulfonyl group, diethylaminopropylaminosulfonyl group, dibutylaminopropylaminosulfonyl group, morpholinoethylamino Sulfonyl group, dimethylaminopropylaminocarbonyl group, 4- (diethylaminopropylaminocarbonyl) phenylaminocarbonyl group, dimethylaminomethylcarbonylaminomethyl group, diethylaminopropylaminomethylcarbonylaminomethyl group, dibutylaminopropylaminomethylcarbonylaminomethyl group, etc. Basic substituents,
Sulphonic acid group, sodium sulphonato group, calcium sulphonato group, aluminum sulphonato group, dodecylammoniosulphonato group, octadecylammoniosulphonato group, trimethyloctadesylammoniosulphonato group, dimethyldidecylammoniosulphonato group, Acidic substituents such as carboxylic acid groups,
There are 2-aluminum carboxylate-5-nitrobenzamide methyl group, and the like.

<Acid resin type dispersant>
The composition of the present invention contains a resin-type dispersant (acid-resin-type dispersant) having an acidic substituent. The acidic resin-type dispersant of the present invention has a pigment-affinitive unit containing an acidic substituent adsorbed on the pigment [A1] represented by the following general formula (1) and a unit compatible with the pigment carrier. However, it functions to stabilize the dispersion of the pigment [A1] represented by the following general formula (1) in the pigment carrier.

In particular, when the pigment [A1] represented by the following general formula (1), the resin-type dispersant having an acidic substituent, and the dye derivative having a basic substituent are used, the fluidity and dispersibility are improved. Not only is it good, but it is also preferable because it exhibits excellent effects such as both optical properties and heat resistance and light resistance.

The basic structure of the resin type dispersant is not particularly limited, and examples thereof include general resins such as acrylic resin, polyester resin, polyether resin, urethane resin, silicon resin, epoxy resin, and vinyl acetate resin.

Examples of the acidic substituent include a phosphoric acid group, a sulfonic acid group, and a carboxyl group. In addition, trimellitic acid and / or pyromellitic acid partially esterified are preferably used. Further, in some cases, the aromatic ring having two or more acidic substituents may be a unit having one acidic substituent by a plurality of direct bonds and / or linking groups. Among them, it is preferable to have two or more carboxyl groups in one molecule. A dispersant having two or more carboxyl groups in one molecule is a colorant because it has more adsorbing groups to the colorant than a resin-type dispersant having 0 or 1 carboxyl groups in one molecule. It is preferable because it has a strong function of stabilizing dispersion on the carrier, the polarity of the dispersant is increased, and higher dispersion stability can be ensured.

As the resin type dispersant, those having a block or randomly acidic substituent, aromatic group or the like in the main chain or the end of the linear resin and the main chain or the side chain of the comb-shaped resin are preferable. Specifically, polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, modified products thereof, and poly ( An amide formed by the reaction of a lower alkyleneimine) and a polyester having a free carboxyl group, a salt thereof, or the like is used. In addition, water-soluble resins such as (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, and polyvinylpyrrolidone, and water-soluble. Polymer compounds, polyesters, modified poly (meth) acrylates, ethylene oxide / propylene oxide adducts, phosphoric acid esters and the like are used. These can be used alone or in combination of two or more, but are not necessarily limited to these.

At least one polymer unit selected from polyester, polyether, and poly (meth) acrylate is preferable as the site of the resin-type dispersant of the present invention having a high affinity for the dispersion medium.

For example, as polyester, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol , 1,4-bis (Hydroxymethyl) cyclohesane, bisphenol A, hydrogenated bisphenol A, hydroxypivalyl hydroxypivalate, trimethylolethane, trimethylolpropane, 2,2,4-trimethyl-1,3-pentanediol, One or more alcohols such as glycerin or hexanetriol, succinic acid, adipic acid, sebacic acid, azelaic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid , Glutaconic acid, 1,2,5-hexanetricarboxylic acid, 1,4-cyclohexanehycarboxylic acid, 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2,4-cyclohexyl Examples thereof include polyester polyols obtained by co-condensation with one or more kinds of carboxylic acids such as satricarboxylic acid or 2,5,7-naphthalene tricarboxylic acid.

For example, as the polyether, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexane Diol, 1,4-bis (hydroxymethyl) cyclohesane, bisphenol A, hydrogenated bisphenol A, hydroxypivalyl hydroxypivalate, trimethylol ethane, trimethylol propane, 2,2,4-trimethyl-1,3-pentanediol , Glycerin or alcohols such as hexanetriol, and various (cyclic) ether bond-containing compounds such as ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether or allyl glycidyl ether. Examples thereof include modified polyether polyols obtained by ring-opening polymerization of.

For example, examples of the poly (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) acrylate. t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, tetrahydrofurfreel (meth) acrylate, isobornyl (meth) acrylate, phenyl Acrylate such as (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, oxetane (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, ethoxypolyethylene glycol (meth) acrylate, etc. Polyalkylene glycol (meth) acrylates, (meth) acrylamide, and N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, diacetone (meth) acrylamide, N-substituted (meth) acrylamides such as acryloylmorpholin, amino group-containing (meth) acrylates such as N, N-dimethylaminoethyl (meth) acrylates and N, N-diethylaminoethyl (meth) acrylates, (meth) acrylonitrile Examples thereof include homopolymers and copolymers such as nitriles such as. These may be used alone, may be used in combination, or may be in the form of a block polymer, a graft polymer or a random polymer.

Commercially available resin-type pigment dispersants having an acidic functional group include, for example, Solspurth 3000, Solsperse 21000, Solsperse 26000, Solsperse 36600, Solsperse 41000, Solsperse 44000, Solsperse 46000, Solsperse 55000, (manufactured by Abyssia); Big 108, Disperbic 110, Disperbic 111, Disperbic 112, Disperbic 116, Disperbic 142, Disperbic 180, Disperbic 2001, (manufactured by BIC Chemie); Disparon 3600N, Disparon 1850 (manufactured by Kusumoto Kasei); PA111 (Manufactured by Ajinomoto Fine Techno Co., Ltd.); EFKA4401, EFKA4550 (manufactured by Fuka Additives Co., Ltd.) and the like, but are not limited thereto.

<Binder resin>
The binder resin is for dispersing, dyeing, or permeating a colorant, and examples thereof include thermoplastic resins. When used in the form of an alkali-developable colored resist material, it is preferable to use an alkali-soluble vinyl-based resin copolymerized with an acidic group-containing ethylenically unsaturated monomer. Further, in order to further improve the photosensitivity, an active energy ray-curable resin having an ethylenically unsaturated double bond can also be used.

In particular, by using an active energy ray-curable resin having an ethylenically unsaturated double bond in the side chain as an alkali-developable colored resist material, the resin is three-dimensionally crosslinked when exposed to active energy rays to form a coating film. By doing so, the colorant is fixed, the heat resistance is improved, and fading (deterioration of spectral characteristics) due to the heat of the colorant can be suppressed. It also has the effect of suppressing aggregation and precipitation of colorant components in the developing process.

The binder resin 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 binder resin is preferably in the range of 10,000 to 100,000, more preferably in the range of 10,000 to 80,000 in order to preferably disperse the colorant. The number average molecular weight (Mn) is preferably in the range of 5,000 to 50,000, and the Mw / Mn value is preferably 10 or less.

When the binder resin is used as a photosensitive coloring composition for a color filter, a carboxyl group that acts as a colorant adsorbent group and an alkali-soluble group during development, an aliphatic group that acts as an affinity group for a colorant carrier and a solvent, and an aliphatic group. The balance of aromatic groups is important for the dispersibility, permeability, developability, and durability of the colorant, and it is preferable to use a resin having an acid value of 20 to 300 mgKOH / g. If the acid value is less than 20 mgKOH / g, the solubility in a developing solution is poor and it is difficult to form a fine pattern. If it exceeds 300 mgKOH / g, no fine pattern remains.

Since the binder resin has good film forming properties and various resistances, it is preferable to use it in an amount of 20 parts by weight or more with respect to 100 parts by weight of the total weight of the colorant, and the colorant concentration is high and good color characteristics are obtained. Since it can be expressed, it is preferably used in an amount of 1000 parts by weight or less.

Examples of the thermoplastic resin used for the binder resin include acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, and polyvinyl acetate. , Polyurethane resin, polyester resin, vinyl resin, alkyd resin, polystyrene resin, polyamide resin, rubber resin, cyclized rubber resin, celluloses, polyethylene (HDPE, LDPE), polybutadiene, polyimide resin and the like. .. Above all, it is preferable to use an acrylic resin.

Examples of the vinyl-based alkali-soluble resin obtained by copolymerizing an acidic group-containing ethylenically unsaturated monomer include a resin having an acidic group such as a carboxyl group and a sulfone group.
Specifically, as the alkali-soluble resin, an acrylic resin having an acidic group, an α-olefin / (maleic anhydride) maleic anhydride copolymer, a styrene / styrene sulfonic acid copolymer, an ethylene / (meth) acrylic acid copolymer, or Examples thereof include isobutylene / (maleic anhydride) copolymer. Among them, an acrylic resin having an acidic group and at least one resin selected from a styrene / styrene sulfonic acid copolymer, particularly an acrylic resin having an acidic group, is preferably used because of its high heat resistance and transparency.

Examples of the active energy ray-curable resin having an ethylenically unsaturated double bond include a resin in which an unsaturated ethylenically double bond is introduced by the methods (i) and (ii) shown below.

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

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

Examples of unsaturated monobasic acids include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-position haloalkyl of (meth) acrylic acid, alkoxyls, halogens, nitros, and cyano-substituted products. Examples thereof include monocarboxylic acids, which may be used alone or in combination of two or more.

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

As a method similar to the method (i), for example, a side chain of a copolymer obtained by copolymerizing an unsaturated ethylenic monomer having a carboxyl group with one or more other monomers. There is a method of introducing an unsaturated ethylenic double bond and a carboxyl group by addition-reacting an unsaturated ethylenic monomer having an epoxy group to a part of the carboxyl group.

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

Examples of the unsaturated ethylenic monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3- or 4-hydroxybutyl (meth) acrylate, and glycerol. Examples thereof include hydroxyalkyl (meth) acrylates such as (meth) acrylate and cyclohexanedimethanol mono (meth) acrylate, and these may be used alone or in combination of two or more. Further, a polyether mono (meth) acrylate obtained by addition-polymerizing ethylene oxide, propylene oxide, and / or butylene oxide to the above hydroxyalkyl (meth) acrylate, (poly) γ-valerolactone, and (poly) ε-caprolactone. , And / or (poly) ester mono (meth) acrylate to which (poly) 12-hydroxystearic acid or the like is added can also be used. 2-Hydroxyethyl (meth) acrylate or glycerol (meth) acrylate is preferable from the viewpoint of suppressing foreign matter in the coating film.

Examples of the unsaturated ethylenic monomer having an isocyanate group include 2- (meth) acryloyloxyethyl isocyanate and 1,1-bis [(meth) acryloyloxy] ethyl isocyanate, but the present invention is limited thereto. However, two or more types can be used together.

<Organic solvent>
In the coloring composition of the present invention, the colorant is sufficiently dispersed and permeated into the colorant carrier, and the filter segment is applied onto a substrate such as a glass substrate so that the dry film thickness is 0.2 to 5 μm. An organic solvent is included to facilitate the formation. The organic solvent is selected in consideration of the solubility of each component of the coloring composition and the safety in addition to the good coatability of the coloring composition.

Examples of the organic solvent include 1,2,3-trichloropropane, 1-methoxy-2-propanol, ethyl lactate, 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-cyclohexene-1-one, 3,3,5-trimethylcyclohexanone, 3-ethoxypropionic acid Ethylene, 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, N-methylpyrrolidone, 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 monotersial 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, dipro Pylene 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, methyl Examples thereof include isobutyl ketone, methylcyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, dibasic acid ester and the like. These solvents can be used alone or in admixture of two or more in any ratio as required.

The solvent can be used in an amount of 100 to 10000 parts by weight, preferably 500 to 5000 parts by weight, based on 100 parts by weight of the colorant in the coloring composition.

<Photopolymerizable monomer>
The photopolymerizable monomer that may be added to the coloring composition of the present invention includes a monomer or an oligomer that is cured by ultraviolet rays, heat, or the like 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 ( Meta) Acrylate, Trimethylol Propanetri (Meta) Acrylate, Pentaerythritol Tri (Meta) Acrylate, Pentaerythritol Tetra (Meta) Acrylate, 1,6-Hexanediol Diglycidyl Ether Di (Meta) Acrylate, Bisphenol A Diglycidyl Etherdi (Meta) acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tricyclodecanyl (meth) acrylate, ester acrylate, methylolated melamine (Meta) acrylic acid ester, epoxy (meth) acrylate, various acrylic acid esters such as urethane acrylate and methacrylic acid ester, (meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol tri Examples thereof include vinyl ether, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-vinylformamide, acrylonitrile, and the like, but the present invention is not limited thereto. These photopolymerizable compounds may be used alone or in admixture of two or more at any ratio as required.

The content of the photopolymerizable monomer is preferably 5 to 500 parts by weight, and more preferably 10 to 400 parts by weight from the viewpoint of photocurability and developability with respect to 100 parts by weight of the colorant. ..

<Photopolymerization initiator>
A solvent-developed or alkali-developed photosensitive coloring composition is added to the coloring composition of the present invention by adding a photopolymerization initiator in order to cure the composition by ultraviolet irradiation and form a filter segment by a photolithography method. It can be prepared in the form of.

Examples of the photopolymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1-. Hydroxycyclohexylphenylketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1 -Acetophenone compounds such as 4- (4-morpholinyl) phenyl] -1-butanone or 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1-one; benzophenone, benzoin Benzophenones such as methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzyl dimethyl ketal; benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylicized benzophenone, 4-benzoyl-4' -Methyldiphenyl sulfide, or benzophenone compounds such as 3,3', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorthioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4 Thioxanthone compounds such as −diisopropylthioxanthone or 2,4-diethylthioxanthone; 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- (naphtho-1-yl) -4,6-bis (trichloromethyl) -s- Triazine, 2- (4-methoxy-naphtho-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, or 2,4- Triazine compounds such as trichloromethyl- (4'-methoxystyryl) -6-triazine; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime) )], Or oxime ester compounds such as O- (acetyl) -N- (1-phenyl-2-oxo-2- (4'-methoxy-naphthyl) ethylidene) hydroxylamine; bis (2,4,6- Trimethylbenzoyl) phenylphosphine oxide, or phosphine compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrene quinone, camphorquinone, ethylanthraquinone; borate compounds; carbazole A system compound; an imidazole system compound; or a titanosen system compound or the like is used. These photopolymerization initiators can be used alone or in admixture of two or more at any ratio as required.

The content of the photopolymerization initiator is preferably 1 to 500 parts by weight, and more preferably 5 to 400 parts by weight from the viewpoint of photocurability and developability with respect to 100 parts by weight of the colorant.

<Sensitizer>
Further, the coloring composition for a color filter of the present invention may contain a sensitizer.
Examples of the sensitizer include unsaturated ketones such as chalcone derivatives and dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, and anthraquinone derivatives. , Xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonoal derivatives and other polymethine dyes, aclysine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indolin derivatives, Azulene derivative, azurenium derivative, squarylium derivative, porphyrin derivative, tetraphenylporphyrin derivative, triarylmethane derivative, tetrabenzoporphyrin derivative, tetrapyrazinoporphyrazine derivative, phthalocyanine derivative, tetraazaporphyrazine derivative, tetraquinoxalyloporphyrazine derivative , Naphthalocyanine derivative, Subphthalocyanine derivative, Pyrylium derivative, Thiopyrylium derivative, Tetraphyllin derivative, Anuren derivative, Spiropyran derivative, Spiroxazine derivative, Thiospiropirane derivative, Metal allene complex, Organic ruthenium complex, Michler ketone derivative and the like. These sensitizers can be used alone or in admixture of two or more at any ratio, if necessary.

More specific examples include Nobu Ogawara et al., "Dye Handbook" (1986, Kodansha), Nobu Ogawara et al., "Chemistry of Functional Dyes" (1981, CMC), Chuzaburo Ikemori et al., "Special". The sensitizers described in "Functional Materials" (1986, CMC) can be mentioned, but the present invention is not limited thereto. In addition, a sensitizer that absorbs light from the ultraviolet to the near infrared region can also be contained. Among the above sensitizers, particularly suitable sensitizers include thioxanthone derivatives, Michler ketone derivatives, and carbazole derivatives. More specifically, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone, 4,4'-bis (Dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4,4'-bis (ethylmethylamino) benzophenone, N-ethylcarbazole, 3-benzoyl-N-ethylcarbazole, 3,6-dibenzoyl- N-ethylcarbazole or the like is used.

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

<Multifunctional thiol>
The coloring composition for a color filter of the present invention can contain a polyfunctional thiol. A polyfunctional thiol is a compound having two or more thiol (SH) groups. When the polyfunctional thiol is used together with the above-mentioned photopolymerization initiator, it acts as a chain transfer agent in the radical polymerization process after light irradiation and generates chile radicals that are less susceptible to polymerization inhibition by oxygen. The composition becomes highly sensitive. In particular, a polyfunctional aliphatic thiol in which the SH group is bonded to an aliphatic group such as methylene or ethylene group is preferable.

Examples of the polyfunctional thiol include hexanedithiol, decandithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, and ethylene glycol bisthiopropio. Nate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolethanetris (3-mercaptobutyrate), trimethylolpropane tris (3-mercaptobutyrate), trimethylolpropane tris (3-mercaptobutyrate) Mercaptopropionate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetraxthiopropionate, pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), trimethylolpropane propion Tris (2-hydroxyethyl) isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2- (N, N-dibutylamino) -4,6-dimercapto-s -Triazine and the like. These polyfunctional thiols can be used alone or in admixture of two or more at any ratio as required.

The content of the polyfunctional thiol is preferably 0.05 to 100 parts by weight, more preferably 1.0 to 50.0 parts by weight, based on 100 parts by weight of the colorant. Better development resistance can be obtained by using 0.05 parts by weight or more of the polyfunctional thiol. When a monofunctional thiol having one thiol (SH) group is used, such an improvement in development resistance cannot be obtained.

<Leveling agent>
It is preferable to add a leveling agent to the coloring composition of the present invention in order to improve the leveling property of the composition on the transparent substrate. As the leveling agent, dimethylsiloxane having a polyether structure or a polyester structure in the main chain is preferable. Specific examples of the dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Toray Dow Corning Co., Ltd. and BYK-333 manufactured by Big Chemie Co., Ltd. Specific examples of dimethylsiloxane having a polyester structure in the main chain include BYK-310 and BYK-370 manufactured by Big Chemie. Dimethylsiloxane having a polyether structure in the main chain and dimethylsiloxane having a polyester structure in the main chain can also be used in combination. The content of the leveling agent is usually preferably 0.003 to 1.0 parts by weight with respect to 100 parts by weight of the total weight of the coloring composition.

A particularly preferable leveling agent is a kind of so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule, which has a hydrophilic group but has low solubility in water, and when added to a coloring composition, the same. It is useful to have a feature of low surface tension lowering ability and good wettability to the glass plate despite low surface tension lowering ability, and the amount of addition does not cause defects in the coating film due to foaming. Those capable of sufficiently suppressing chargeability can be preferably used. As a leveling agent having such preferable properties, dimethylpolysiloxane having a polyalkylene oxide unit can be preferably used. The polyalkylene oxide unit includes a polyethylene oxide unit and a polypropylene oxide unit, and dimethylpolysiloxane may have both a polyethylene oxide unit and a polypropylene oxide unit.

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 polyalkylene oxide unit is bonded to the terminal of dimethylpolysiloxane, and dimethylpolysiloxane. It may be any of the linear block copolymer types that are alternately and repeatedly bonded. Didimethylpolysiloxane 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 to these.

Anionic, cationic, nonionic, or amphoteric surfactants can be added as an adjunct to the leveling agent. Two or more kinds of surfactants may be mixed and used. Anionic surfactants to be added as an auxiliary to the leveling agent include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkylnaphthalin sulfonate, and alkyldiphenyl ether disulfonic acid. Sodium, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate Examples include ester.

Examples of the chaotic surfactant added as a supplement to the leveling agent include alkyl quaternary ammonium salts and their ethylene oxide adducts. Nonionic surfactants to be added as a supplement to the leveling agent include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate, and polyoxyethylene sorbitan monostearate. , Polyethylene glycol monolaurate and the like; alkyl betaines such as alkyldimethylaminoacetic acid betaine, amphoteric surfactants such as alkylimidazoline, and fluorine-based and silicone-based surfactants.

<UV absorber, polymerization inhibitor>
The coloring composition for a color filter of the present invention may contain an ultraviolet absorber or a polymerization inhibitor. By containing an ultraviolet absorber or a polymerization inhibitor, the shape and resolution of the pattern can be controlled.

Examples of the ultraviolet absorber include 2- [4-[(2-hydroxy-3- (dodecyl and tridecyl) oxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl). -1,3,5-triazine, 2- (2-hydroxy-4- [1-octyloxycarbonylethoxy] phenyl) -4,6-bis (4-phenylphenyl) -1,3,5-triazine, etc. Hydroxyphenyltriazine, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (2H-benzotriazole-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol, Bentriazoles such as 2- (3-t butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2,4-dihydroxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2,2' , Benzopenone type such as 4,4'-tetrahydroxybenzophenone, phenyl salicylate, salicylate type such as p-tert-butylphenyl salicylate, cyanoacrylate such as ethyl-2-cyano-3,3'-diphenylacrylate. System, 2,2,6,6, -tetramethylpiperidin-1-oxyl (triacetone-amine-N-oxyl), bis (2,2,6,6-tetramethyl-4-piperidyl) -sevacate, poly [[6-[(1,1,3,3-tetrabutyl) amino] -1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidinyl) Imino] and other hindered amines are mentioned. These UV absorbers can be used alone or in admixture of two or more at any ratio as required.

Examples of the polymerization inhibitor include hydroquinones such as methyl hydroquinone, t-butyl hydroquinone, 2,5-di-t-butyl hydroquinone, 4-benzoquinone, 4-methoxyphenol, 4-methoxy-1-naphthol, and t-butyl catechol. Derivatives and phenol compounds, amine compounds such as phenothiazine, bis- (1-dimethylbenzyl) phenothiazine, 3,7-dioctylphenothiazine, copper dibutyldithiocarbamate, copper diethyldithiocarbamate, manganese diethyldithiocarbamate, manganese diphenyldithiocarbamate And nitroso compounds such as manganese salt compounds, 4-nitrosophenol, N-nitrosodiphenylamine, N-nitrosocyclohexylhydroxylamine, N-nitrosophenylhydroxylamine and ammonium salts or aluminum salts thereof. These polymerization inhibitors may be used alone or in admixture of two or more at any ratio as required.

The ultraviolet absorber and the polymerization inhibitor can be used in an amount of 0.01 to 20 parts by weight, preferably 0.05 to 10 parts by weight, based on 100 parts by weight of the colorant in the coloring composition. Better resolution can be obtained by using 0.01 part by weight or more of the ultraviolet absorber or the polymerization inhibitor.

<Antioxidant>
The coloring composition for a color filter of the present invention may contain an antioxidant in order to increase the transmittance of the coating film. The antioxidant may increase the transmittance of the coating film in order to prevent the photopolymerization initiator contained in the coloring composition for a color filter from being oxidized and yellowed by the thermal process at the time of thermosetting or ITO annealing. it can. Therefore, by including an antioxidant, yellowing due to oxidation during the heating step can be prevented, and a high transmittance of the coating film can be obtained.

Preferred antioxidants include hindered phenol-based antioxidants, hindered amine-based antioxidants, phosphorus-based antioxidants, sulfide-based antioxidants, and the like. Further, more preferably, it is a hindered phenol-based antioxidant, a hindered amine-based antioxidant, or a phosphorus-based antioxidant. These antioxidants may be used alone or in admixture of two or more at any ratio as required.

Examples of the hindered phenolic antioxidant include 2,4-bis [(laurylthio) methyl] -o-cresol, 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl), and the like. 1,3,5-Tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) and 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 and the like can be mentioned.

For hindered amine antioxidants, 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-) Piperidine) 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-piperidyl) imino} hexamethyl {(2,2,6,6-tetramethyl-4-piperidyl) imino}], poly [(6-morpholino-1,3,5-triazin-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) -4-hydroxy-2,2,6,6-polycondensate with tetramethylpiperidine, N, N'-4,7-tetrakis [4,6-bis {N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino} -1,3,5-triazine-2-yl] -4,7-diazadecan-1,10-diamine and the like can be mentioned.

As a phosphorus-based antioxidant, tris [2-[[2,4,8,10-tetrakis (1,1-dimethylethyl) dibenzo [d, f] [1,3,2] dioxaphosphepine- 6-yl] oxy] ethyl] amine, tris [2-[(4,6,9,11-tetra-tert-butyldibenzo [d, f] [1,3,2] dioxaphosfepin-2- Il) oxy] ethyl] amine, ethylbis phosphite (2,4-ditert-butyl-6-methylphenyl) can be mentioned.

Examples of the sulfide-based antioxidant include 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] and 2,4-bis [(octylthio) methyl]-. Examples thereof include o-cresol and 2,4-bis [(laurylthio) methyl] -o-cresol.

The content of the antioxidant is preferably 0.1 to 5% by weight based on 100% by weight of the total solid content of the coloring composition for a color filter. When the amount of the antioxidant is less than 0.1% by weight, the effect of increasing the transmittance is small, and when it is more than 5% by weight, the hardness is greatly reduced and the sensitivity of the coloring composition for a color filter is greatly reduced.

<Other ingredients>
The coloring composition for a color filter of the present invention contains an adhesion improver such as a silane coupling agent in order to enhance the adhesion to a transparent substrate, or an amine compound having a function of reducing dissolved oxygen. Can be made to.

Examples of the silane coupling agent include vinylsilanes such as vinyltris (β-methoxyethoxy) silane, vinylethoxysilane and vinyltrimethoxysilane, (meth) acrylic silanes such as γ-methacryloxypropyltrimethoxysilane, and β- ( 3,4-Epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxy) Epoxysilanes such as cyclohexyl) methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (Aminoethyl) γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysisilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ Examples thereof include aminosilanes such as −aminopropyltrimethoxysilane and N-phenyl-γ-aminopropyltriethoxysilane, and thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane.

The silane coupling agent can be used in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, based on 100 parts by weight of the colorant in the coloring composition.

Examples of amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 4 -Dimethylaminobenzoate 2-ethylhexyl, N, N-dimethylparatoluidine and the like can be mentioned.

<Manufacturing method of coloring composition for color filter>
The coloring composition for a color filter of the present invention comprises a kneader, a 2-roll mill, a 3-roll mill, a ball mill, in which a colorant is placed in a colorant carrier such as a resin and / or a solvent together with a dispersion aid, if necessary. It can be produced by finely dispersing it using various dispersion means such as a horizontal sand mill, a vertical sand mill, an annual bead mill, or an attritor (colorant dispersion). At this time, two or more kinds of colorants and the like may be dispersed in the colorant carrier at the same time, or those dispersed separately in the colorant carrier may be mixed. The epoxy compound may be added at the stage of preparing the colorant dispersion, or the same effect can be obtained by adding the epoxy compound to the prepared colorant dispersion later. If the colorant such as a dye is highly soluble, specifically, if it is highly soluble in the solvent used, dissolved by stirring, and no foreign matter is confirmed, it is manufactured by finely dispersing as described above. There is no need.

When used as a photosensitive coloring composition (resist material) for a color filter, it can be prepared as a solvent-developing type or alkali-developing type coloring composition. The solvent-developed or alkali-developed coloring composition includes the colorant dispersion, a photopolymerizable monomer and / or a photopolymerization initiator, and if necessary, a solvent, other pigment dispersants, and additives. Etc. can be mixed and adjusted. The photopolymerization initiator may be added at the stage of preparing the coloring composition, or may be added later to the prepared coloring composition.

(Dispersion aid)
When the colorant is dispersed in the colorant carrier, not only the dispersant but also a dispersion aid such as a dye derivative and a surfactant may be appropriately contained. Since the dispersion aid has a great effect of preventing the reaggregation of the colorant after dispersion, the coloring composition obtained by dispersing the colorant in the colorant carrier using the dispersion aid has high lightness and viscosity stability. Become good.

Examples of the dye derivative include compounds in which an organic pigment, anthraquinone, acridone or triazine is introduced with a basic substituent, an acidic substituent, or a phthalimidemethyl group which may have a substituent. No. 63-305173, No. 57-15620, No. 59-40172, No. 63-17102, No. 5-9469, No. 2001-335717, No. 2003-2003. 128669, 2004-091497, 2007-156395, 2008-094873, 2008-094986, 2008-095007, 2008-195916 Those described in Japanese Patent Publication No. 4585781, etc. can be used, and these can be used alone or in combination of two or more kinds.

From the viewpoint of improving dispersibility, the content of the dye derivative is preferably 0.5 parts by weight or more, more preferably 1 part by weight or more, and most preferably 3 parts by weight or more with respect to 100 parts by weight of the colorant. Further, from the viewpoint of heat resistance and light resistance, it is preferably 40 parts by weight or less, more preferably 35 parts by weight or less.

Examples of the surfactant include sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkylnaphthalin sulfonate, and sodium alkyldiphenyl ether disulfonate. , Monoethanolamine lauryl sulfate, Triethanolamine lauryl sulfate, Ammonium lauryl sulfate, Monoethanolamine stearate, Monoethanolamine styrene-acrylic acid copolymer, Anionic surfactants such as polyoxyethylene alkyl ether phosphate; Nonionic surfactants such as polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate, polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate; alkyl Chaotic surfactants such as quaternary ammonium salts and their ethylene oxide adducts; alkyl betaines such as alkyldimethylaminoacetic acid betaine and amphoteric surfactants such as alkylimidazolin, which may be used alone or in combination of two or more. They can be mixed and used, but are not necessarily limited to these.

When a surfactant is added, it is preferably 0.1 to 55 parts by weight, more preferably 0.1 to 45 parts by weight, based on 100 parts by weight of the colorant. If the content of the surfactant is less than 0.1 parts by weight, it is difficult to obtain the effect of addition, and if the content is more than 55 parts by weight, the dispersion may be affected by the excess dispersant. ..

<Removal of coarse particles>
The colored composition of the present invention has coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably 0.5 μm or more of coarse particles by means of centrifugation, filtration with a sintering filter or a membrane filter, and the like. It is preferable to remove the mixed dust. As described above, it is preferable that the coloring composition does not substantially contain particles of 0.5 μm or more. More preferably, it is 0.3 μm or less.

<Color filter>
Next, the color filter of the present invention will be described. The color filter of the present invention includes a red filter segment, a green filter segment, and a blue filter segment on a base material, and further includes a magenta color filter segment, a cyan color filter segment, or a yellow filter segment. It may be, and the at least one filter segment is formed from the coloring composition of the present invention.

<Manufacturing method of color filter>
The color filter of the present invention can be manufactured by a printing method or a photolithography method. The formation of the filter segment by the printing method can be patterned only by repeating printing and drying of the coloring composition prepared as the printing ink, and therefore, as a manufacturing method of the color filter, it is excellent in mass productivity at low cost. Further, with the development of printing technology, it is possible to print a fine pattern having high dimensional accuracy and smoothness. In order to perform printing, it is preferable that the composition is such that the ink does not dry or solidify on the printing plate or on the blanket. It is also important to control the fluidity of the ink on the printing machine, and the viscosity of the ink can be adjusted with a dispersant or an extender pigment.

When the filter segment is formed by the photolithography method, the coloring composition prepared as the solvent-developing type or alkali-developing type colored resist material is applied onto a transparent substrate by spray coating, spin coating, slit coating, roll coating or the like. By the method, the coating is applied so that the dry film thickness is 0.2 to 5 μm. If necessary, the dried film is exposed to ultraviolet rays through a mask having a predetermined pattern provided in contact with or without contact with the film. Then, after immersing in a solvent or an alkaline developer or spraying the developer with a spray or the like to remove the uncured portion to form a desired pattern, the same operation is repeated for other colors to manufacture a color filter. be able to. Further, in order to promote the polymerization of the colored resist material, heating can be applied as needed. According to the photolithography method, a color filter having higher accuracy than the above printing method can be manufactured.

At the time of development, an aqueous solution of sodium carbonate, sodium hydroxide or the like is used as the alkaline developer, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Further, an antifoaming agent or a surfactant can be added to the developing solution.
In order to increase the UV exposure sensitivity, the colored resist material is applied and dried, and then 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. After that, ultraviolet exposure can be performed.

The color filter of the present invention can be produced by an electrodeposition method, a transfer method, an inkjet method, or the like in addition to the above methods, and the coloring composition of the present invention can be used in any method. The electrodeposition method is a method of manufacturing a color filter by electrodepositing each color filter segment on the transparent conductive film by electrophoresis of colloidal particles using the transparent conductive film formed on the substrate. .. Further, the transfer method is a method in which a filter segment is formed in advance on the surface of a peelable transfer base sheet, and the filter segment is transferred to a desired substrate.

A black matrix can be formed in advance before each color filter segment is formed on a substrate such as a transparent substrate or a reflective substrate. As the black matrix, a multilayer film of chromium or chromium / chromium oxide, an inorganic film such as titanium nitride, or a resin film in which a light-shielding agent is dispersed is used, but the black matrix is not limited thereto. It is also possible to form a thin film transistor (TFT) on the transparent substrate or the reflective substrate in advance, and then form each color filter segment. Further, an overcoat film, a transparent conductive film, or the like is formed on the color filter of the present invention, if necessary.

The color filter is bonded to the opposite substrate using a sealing agent, liquid crystal is injected from the injection port provided in the sealing portion, the injection port is sealed, and a polarizing film or a retardation film is placed on the outside of the substrate as necessary. A liquid crystal display panel is manufactured by laminating.

Such liquid crystal display panels include Twisted Nematic (TN), Super Twisted Nematic (STN), In-Plane Switching (IPS), Vertical Alignment (VA), and Optically Convencend Bend (OCB). It can be used in the liquid crystal display mode in which colorization is performed using a color filter such as.

As the transparent substrate, a glass plate such as soda-lime glass, low-alkali borosilicate glass, or non-alkali aluminoborosilicate glass, or a resin plate such as polycarbonate, polymethylmethacrylate, or polyethylene terephthalate is used. Further, on the surface of the glass plate or the resin plate, a transparent electrode made of indium oxide, tin oxide or the like may be formed for driving the liquid crystal after the panelization.

If a black matrix is formed in advance before the filter segment is formed on the transparent substrate, the contrast of the liquid crystal display panel can be further enhanced. As the black matrix, a multilayer film of chromium or chromium / chromium oxide, an inorganic film such as titanium nitride, or a resin film in which a light-shielding agent is dispersed is used, but the coloring composition for a color filter of the present invention is not limited thereto. A black matrix made of is preferred. 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 thereafter. By forming the filter segment and / or the black matrix on the TFT substrate, the aperture ratio of the liquid crystal display panel can be increased and the brightness can be improved.

The dry film thickness of the filter segment and the black matrix is preferably 0.2 to 10 μm, more preferably 0.2 to 5 μm. When drying the coating film, a vacuum dryer, a convection oven, an IR oven, a hot plate or the like may be used.

The formation of each color filter segment and the black matrix by the photolithography method is performed by the following method. That is, the coloring composition for a color filter prepared as a coloring composition for a solvent-developing type or an alkali-developing type coloring color filter is dried on a transparent substrate by a coating method such as spray coating, spin coating, slit coating, or roll coating. Apply so that the film thickness is 0.2 to 10 μm. If necessary, the dried film is exposed to ultraviolet rays through a mask having a predetermined pattern provided in contact with or without contact with the film.

After that, the filter segment and the black matrix can be formed by immersing in a solvent or an alkaline developer, or spraying the developer with a spray or the like to remove the uncured portion and form a desired pattern. Further, in order to promote the polymerization of the filter segment and the black matrix formed by the development, heating can be applied if necessary. According to the photolithography method, a filter segment and a black matrix with higher accuracy than the printing method can be formed.

At the time of development, an aqueous solution of sodium carbonate, sodium hydroxide or the like is used as the alkaline developer, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Further, an antifoaming agent or a surfactant can be added to the developing solution.
As the development processing method, a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid filling) development method and the like can be applied. In order to increase the ultraviolet exposure sensitivity, the coloring composition for a color filter is applied and dried, and then a water-soluble or alkali-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin is applied and dried to prevent polymerization inhibition by oxygen. After forming the film, ultraviolet exposure can also be performed.

An overcoat film, a columnar spacer, a transparent conductive film, a liquid crystal alignment film, or the like is formed on the color filter, if necessary.

The color filter is bonded to the opposite substrate using a sealing agent, liquid crystal is injected from the injection port provided in the sealing portion, the injection port is sealed, and a polarizing film or a retardation film is placed on the outside of the substrate as necessary. A liquid crystal display panel is manufactured by laminating.

Such liquid crystal display panels include Twisted Nematic (TN), Super Twisted Nematic (STN), In-Plane Switching (IPS), Vertical Alignment (VA), and Optically Convencend Bend (OCB). It can be used in the liquid crystal display mode in which colorization is performed using a color filter such as.

<Display device>
The display device of the present invention includes the color filter of the present invention and a light emitting element including quantum dots. The display device of the present invention displays the conventional vivid hue by wavelength-converting the light from the light emitting source included in the light emitting element using quantum dots and passing the obtained light through the color filter of the present invention. It will be possible.

The emission spectrum of the light emitting device containing the quantum dots of the present invention has a first peak wavelength at 430 to 480 nm, a second peak wavelength at 510 to 560 nm, and a third peak wavelength at 600 to 660 nm, respectively. Is preferable. The first peak wavelength is preferably further 435-470 nm, further 440-460 nm, particularly preferably 445-455 nm. The second peak wavelength is preferably further 515 to 555 nm, further preferably 520 to 550 nm, and particularly preferably 525 to 550 nm. It is preferable that the third peak wavelength is further provided at 610 to 650 nm, further preferably at 615 to 645 nm, and particularly preferably at 620 to 640 nm. According to the above aspects, in the display device of the present invention, the color filter of the present invention, which is a component thereof, can display more vivid hues. The coloring composition for a color filter of the present invention has a film thickness of 2.0 to 2.0 when the coating film in the XYZ color system measured using a light source containing quantum dots as a light emitting element has specific chromaticity coordinates. The light emitting element may be 3.0 μm, and any known light emitting element containing quantum dots can be used without limitation.

Further, the first peak wavelength preferably has a half width of 70 nm or less. It is more preferably 60 nm or less, further preferably 50 nm or less, and particularly preferably 40 nm or less. The second peak wavelength preferably has a half width of 80 nm or less. It is more preferably 70 nm or less, further preferably 60 nm or less, and particularly preferably 50 nm or less. The third peak wavelength preferably has a half width of 80 nm or less. It is more preferably 70 nm or less, further preferably 60 nm or less, and particularly preferably 50 nm or less. According to the above aspects, in the display device of the present invention, the color filter of the present invention, which is a component thereof, can display more vivid hues.

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 mass" and "% by mass", respectively. Further, "PGMAc" means propylene glycol monomethyl ether acetate.

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

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

<Contrast ratio of coating film>
The light emitted from the backlight unit for a liquid crystal display passes through a polarizing plate, is polarized, passes through a dry coating film of a coloring composition applied on a glass substrate, and reaches the polarizing plate. If the polarizing plate and the polarizing planes of the polarizing plate are parallel, light passes through the polarizing plate, but if the polarizing planes are orthogonal, the light is blocked by the polarizing plate. However, when the light polarized by the polarizing plate passes through the dry coating film of the coloring composition, scattering by pigment particles or the like occurs and a part of the polarizing surface is displaced. When the polarizing plates are parallel, the polarized light is polarized. The amount of light transmitted through the plate is reduced, and when the polarizing plate is orthogonal, part of the light is transmitted through the polarizing plate. This transmitted light was measured as the brightness on the polarizing plate, and the ratio (contrast ratio) between the brightness when the polarizing plates were parallel and the brightness when the polarizing plates were orthogonal was calculated.
(Contrast ratio) = (Brightness when parallel) / (Brightness when orthogonal)
A color luminance meter (“BM-5A” manufactured by Topcon Corporation) was used as the luminance meter, and a polarizing plate (“NPF-G1220DUN” manufactured by Nitto Denko Corporation) was used as the polarizing plate. At the time of measurement, a black mask having a 1 cm square hole was applied to the measurement portion in order to block unnecessary light.

First, a method for producing an acrylic resin solution, a fine pigment, a pigment dispersion, a green photosensitive coloring composition, and a blue photosensitive coloring composition used in Examples and Comparative Examples will be described.

<Manufacturing method of acrylic resin solution>
(Preparation of acrylic resin solution)
70.0 parts of PGMAc was charged into a reaction vessel equipped with a thermometer, a cooling pipe, a nitrogen gas introduction pipe, and a stirrer in a separable 4-neck flask, the temperature was raised to 80 ° C., nitrogen was replaced in the reaction vessel, and then the dropping tube 13.3 parts of n-butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 4.3 parts of methacrylic acid, 7.4 parts of paracumylphenol ethylene oxide-modified acrylate (“Aronix M110” manufactured by Toa Synthetic Co., Ltd.), 2 parts, 2 , 2'-A mixture of 0.4 parts of azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropping, the reaction was continued for another 3 hours to obtain a solution of an acrylic resin having a weight average molecular weight (Mw) of 26000. After cooling to room temperature, about 2 g of the resin solution was sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content, and PGMAc was added to the previously synthesized resin solution so that the non-volatile content was 20% by weight. Acrylic resin solution was prepared.

<Manufacturing method of finely divided pigments>
(Production of red colorant (R-1): Azo compound 1)
The specific method for synthesizing the azo compound 1 is shown below together with its reaction scheme (reaction scheme A below). Other azo compounds according to the present invention can also be synthesized according to a similar scheme. The method for producing the azo compound (synthesis method) is not limited to the following method.

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

<< Synthesis of azo compound 1 >>
After adding 36.3 parts of compound (C) to 252.2 parts of glacial acetic acid, 39.1 parts of 35% hydrochloric acid was added, and the mixture was cooled to -2 to 0 ° C. After adding 42.2 parts of a 25% aqueous sodium nitrite solution to this solution, the mixture was stirred for 30 minutes while maintaining the temperature at 0 to 5 ° C. This reaction solution was added to a mixed solution consisting of 50.7 parts of compound (B) prepared separately in the previous method, 67.1 parts of 25% sodium hydroxide solution, 772 parts of water, and 680 parts of isopropyl alcohol for 15 minutes. Dropped in. After completion of the dropping, the mixture was stirred at room temperature for 30 minutes, further stirred while maintaining at 80 ° C., the precipitated reactant was collected by filtration, washed with boiling water and methanol, and dried to add 85.9 parts of azo dye 1. (Yield: 98%) was obtained. As a result of mass spectrometry by TOF-MS, it was identified as azo compound 1.

Next, 80 parts of the azo compound 1, 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. The obtained kneaded product was put into 3 liters of warm water, stirred for 1 hour while heating at 70 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. for 24 hours. , 78 parts of red colorant (R-1) was obtained. The average primary particle size was 38 nm.

(Production of red colorant (R-2): Azo compound 2)
Red colorant (R-1) except that 66.8 parts of 3-aminobenztrifloride was used instead of 80.9 parts of compound (A) used in the production of red colorant (R-1). The same operation as in the production of azo compound 2 was carried out to obtain 80.0 parts (yield 98%) of azo compound 2. As a result of mass spectrometry by TOF-MS, it was identified as azo compound 2.

Next, 80 parts of the azo compound 2, 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. The obtained kneaded product was put into 3 liters of warm water, stirred for 1 hour while heating at 70 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. for 24 hours. , 78 parts of red colorant (R-2) was obtained. The average primary particle size was 42 nm.

(Production of red colorant (R-3): Azo compound 3)
Red coloring except that 24.9 parts of 3-amino-4-methoxybenzamide was used instead of 36.3 parts of 3-amino-4-methoxybenzanilide used in the production of the red colorant (R-1). The same operation as in the production of the agent (R-1) was carried out to obtain 80.0 parts (yield 97%) of azo compound 3. As a result of mass spectrometry by TOF-MS, it was identified as azo compound 3.

Next, 80 parts of the azo compound 3, 800 parts of sodium chloride, and 90 parts of diethylene glycol were charged in 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. The obtained kneaded product was put into 3 liters of warm water, stirred for 1 hour while heating at 70 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. for 24 hours. , 78 parts of red colorant (R-3) was obtained. The average primary particle size was 45 nm.

(Production of red colorant (R-4): Azo compound 4)
Instead of 80.9 parts of compound (A) used in the production of the red colorant (R-1), 66.8 parts of 3-aminobenztrifloride, and instead of 3-amino-4-methoxybenzanilide The same operation as in the production of the red colorant (R-1) was carried out except that 24.9 parts of 3-amino-4-methoxybenzamide was used, and 80.0 parts of azo compound 4 (yield 97%) was used. )Obtained. As a result of mass spectrometry by TOF-MS, it was identified as azo compound 4.

Next, 80 parts of the azo compound 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 Co., Ltd.), kneaded at 60 ° C. for 6 hours, and subjected to salt milling treatment. The obtained kneaded product was put into 3 liters of warm water, stirred for 1 hour while heating at 70 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. for 24 hours. , 78 parts of red colorant (R-4) was obtained. The average primary particle size was 39 nm.

(Production of red colorant (R-5): Azo compound 5)
Instead of compound (A) used in the production of the red colorant (R-1), 66.8 parts of 2-aminobenztrifloride, and instead of 3-amino-4-methoxybenzanilide, 3- The same operation as in the production of the red colorant (R-1) was carried out except that 24.9 parts of amino-4-methoxybenzamide was used to obtain 80.0 parts (yield 95%) of azo compound 5. As a result of mass spectrometry by TOF-MS, it was identified as azo compound 5.

Next, 80 parts of the azo compound 5, 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. The obtained kneaded product was put into 3 liters of warm water, stirred for 1 hour while heating at 70 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. for 24 hours. , 78 parts of red colorant (R-5) was obtained. The average primary particle size was 38 nm.

(Production of red colorant (R-6): Azo compound 6)
Instead of compound (A) used in the production of the red colorant (R-1), 5-chloro-2-aminobenztrifloride, and instead of 3-amino-4-methoxybenzanilide, 3-amino The same operation as in the production of the red colorant (R-1) was carried out except that 24.9 parts of -4-methoxybenzamide was used to obtain 80.0 parts of azo compound 6. As a result of mass spectrometry by TOF-MS, it was identified as azo compound 6.

Next, 80 parts of the azo compound 6, 800 parts of sodium chloride, and 90 parts of diethylene glycol were charged in 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. The obtained kneaded product was put into 3 liters of warm water, stirred for 1 hour while heating at 70 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. for 24 hours. , 78 parts of red colorant (R-6) was obtained. The average primary particle size was 42 nm.

(Production of red colorant (R-7): Azo compound 7)
Instead of compound (A) used in the production of the red colorant (R-1), 95.1 parts of 3,5-bis (trifluoromethyl) aniline and 3-amino-4-methoxybenzanilide Instead, the same operation as in the production of the red colorant (R-1) was carried out except that 24.9 parts of 3-amino-4-methoxybenzamide was used, and 80.0 parts of azo compound 7 (yield 96) was used. %)Obtained. As a result of mass spectrometry by TOF-MS, it was identified as azo compound 7.

Next, 80 parts of the azo compound 7, 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. The obtained kneaded product was put into 3 liters of warm water, stirred for 1 hour while heating at 70 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. for 24 hours. , 78 parts of red colorant (R-7) was obtained. The average primary particle size was 47 nm.

(Production of red colorant (R-8): Azo compound 8)
Instead of compound (A) used in the production of the red colorant (R-1), 0.050 mol of 4-fluoro-3-aminobenztrifloride and instead of 3-amino-4-methoxybenzanilide The same procedure as in the production of the red colorant (R-1) was carried out except that 0.015 mol of 3-amino-4-methoxybenzamide was used, and 7.97 g (yield 96%) of azo compound 8 was used. Obtained. As a result of mass spectrometry by TOF-MS, it was identified as azo compound 8.

Next, 80 parts of the azo compound 8, 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. The obtained kneaded product was put into 3 liters of warm water, stirred for 1 hour while heating at 70 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. for 24 hours. , 78 parts of red colorant (R-8) was obtained. The average primary particle size was 42 nm.

(Production of red colorant (R-9): Azo compound 9)
Instead of compound (A) used in the production of the red colorant (R-1), 74.3 parts of 2-chloro-5-aminobenztrifloride and 3-amino-4-methoxybenzanilide In addition, 24.9 parts of 3-amino-4-methoxybenzamide was used, but the same operation as in the production of the red colorant (R-1) was carried out, and 80.0 parts of azo compound 9 (yield 97%) was used. )Obtained. As a result of mass spectrometry by TOF-MS, it was identified as azo compound 9.

Next, 80 parts of the azo compound 9, 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. The obtained kneaded product was put into 3 liters of warm water, stirred for 1 hour while heating at 70 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. for 24 hours. , 78 parts of red colorant (R-9) was obtained. The average primary particle size was 41 nm.

(Production of Red Colorant (R-10): Azo Compound 10)
Instead of compound (A) used in the production of the red colorant (R-1), 66.8 parts of 4-aminobenztrifloride, and instead of 3-amino-4-methoxybenzanilide, 3- The same operation as in the production of the red colorant (R-1) was carried out except that 24.9 parts of amino-4-methoxybenzamide was used to obtain 80.0 parts (yield 95%) of the azo compound 10. As a result of mass spectrometry by TOF-MS, it was identified as azo compound 10.

Next, 80 parts of the azo compound 10, 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. The obtained kneaded product was put into 3 liters of warm water, stirred for 1 hour while heating at 70 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. for 24 hours. , 78 parts of red colorant (R-10) was obtained. The average primary particle size was 48 nm.

(Production of Red Colorant (R-11): Azo Compound 11)
Red colorant (R-) except that 24.9 parts of 3-amino-4-methylbenzamide was used in place of 3-amino-4-methoxybenzanilide used in the production of the red colorant (R-1). The same operation as in the production of 1) was carried out to obtain 80.0 parts (yield 97%) of the azo compound 11. As a result of mass spectrometry by TOF-MS, it was identified as azo compound 11.

Next, 80 parts of the azo compound 11, 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. The obtained kneaded product was put into 3 liters of warm water, stirred for 1 hour while heating at 70 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. for 24 hours. , 78 parts of red colorant (R-11) was obtained. The average primary particle size was 50 nm.

(Production of Red Colorant (R-12): Azo Compound 12)
Instead of the 3-amino-4-methoxybenzanilide used in the production of the red colorant (R-1), 3-amino-4-methoxybenz- (2'-chloro-5'-trifluoromethyl) anilide was used. The same operation as in the production of the red colorant (R-1) was carried out except that 51.6 parts were used, and 80.0 parts (yield 96%) of the azo compound 12 was obtained. As a result of mass spectrometry by TOF-MS, it was identified as azo compound 12.

Next, 80 parts of the azo compound 12, 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. The obtained kneaded product was put into 3 liters of warm water, stirred for 1 hour while heating at 70 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. for 24 hours. , 78 parts of red colorant (R-12) was obtained. The average primary particle size was 38 nm.

(Production of Red Colorant (R-13): Azo Compound 13)
Instead of compound (A) used in the production of the red colorant (R-1), 66.8 parts of 3-aminobenztrifloride, and instead of 3-amino-4-methoxybenzanilide, 3- The same operation as in the production of the red colorant (R-1) was carried out except that 46.5 parts of amino-4-methoxybenz- (3'-trifluoromethyl) anilide was used, and the azo compound 13 was added to 80.0. Part (yield 95%) was obtained. As a result of mass spectrometry by TOF-MS, it was identified as azo compound 13.

Next, 80 parts of the azo compound 13, 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. The obtained kneaded product was put into 3 liters of warm water, stirred for 1 hour while heating at 70 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. for 24 hours. , 78 parts of red colorant (R-13) was obtained. The average primary particle size was 36 nm.

(Production of Red Colorant (R-14): Azo Compound 14)
Of the red colorant (R-1), except that 44.7 parts of the following compound (D) was used in place of the 3-amino-4-methoxybenzanilide used in the production of the red colorant (R-1). The same operation as in the production was carried out to obtain 80.0 parts (yield 95%) of the azo compound 14. As a result of mass spectrometry by TOF-MS, it was identified as azo compound 14.

Next, 80 parts of the azo compound 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 salt milling treatment. The obtained kneaded product was put into 3 liters of warm water, stirred for 1 hour while heating at 70 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. for 24 hours. , 78 parts of red colorant (R-14) was obtained. The average primary particle size was 40 nm.

Compound (D)

(Production of Red Colorant (R-15): Azo Compound 15)
Instead of (A) used in the production of the red colorant (R-1), 66.8 parts of 3-aminobenztrifloride, and instead of 3-amino-4-methoxybenzanilide, compound (D). The same operation as in the production of the red colorant (R-1) was carried out except that 44.7 parts of azo compound 15 was used to obtain 80.0 parts (yield 97%) of azo compound 15. As a result of mass spectrometry by TOF-MS, it was identified as azo compound 15.

Next, 80 parts of the azo compound 1, 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. The obtained kneaded product was put into 3 liters of warm water, stirred for 1 hour while heating at 70 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. for 24 hours. , 78 parts of red colorant (R-15) was obtained. The average primary particle size was 43 nm.

(Production of Red Colorant (R-16): Azo Compound 16)
Red colorant (R-) except that 27.0 parts of 3-amino-N-methylbenzamide was used in place of 3-amino-4-methoxybenzanilide used in the production of the red colorant (R-1). The same operation as in the production of 1) was carried out to obtain 80.0 parts (yield 97%) of the azo compound 16. As a result of mass spectrometry by TOF-MS, it was identified as azo compound 16.

Next, 80 parts of the azo compound 16, 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. The obtained kneaded product was put into 3 liters of warm water, stirred for 1 hour while heating at 70 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. for 24 hours. , 78 parts of red colorant (R-16) was obtained. The average primary particle size was 43 nm.

(Production of red colorant (R-17): Miniaturization of azo compound 1 by acid pacing method)
80 parts of the azo compound 1 obtained in the production of the red colorant (R-1) was added to 1200 parts of concentrated sulfuric acid, and the mixture was stirred at 40 ° C. for 3 hours, and then the sulfuric acid solution was injected into 24000 parts of cold water at 3 ° C. .. The formed precipitate was filtered and washed with water, and then dried at 80 ° C. for 24 hours to obtain 78 parts of a red colorant (R-17). The average primary particle size was 65 nm.

(Production of red colorant (R-18): Azo compound 1 / PR176)
Disperse 125 parts of 3-amino-4-methoxybenzanilide in 2000 parts of water, add ice to adjust the temperature to 5 ° C., add 205 parts of a 35% hydrochloric acid aqueous solution, stir for 1 hour, and then sodium nitrite 37.5. The prepared aqueous solution was added to 110 parts of water, and the mixture was stirred for 2 hours. An aqueous solution consisting of 380 parts of an 80% acetic acid aqueous solution, 418 parts of a 25% sodium hydroxide aqueous solution, and 413 parts of water was added to prepare a diazonium salt aqueous solution. On the other hand, N- [2-chloro-5-trifluoromethylphenyl] -3-hydroxy-2-naphthalene carboamide 154 parts, N- [4- (2-oxo-2,3-dihydro-1H-benzimidazole-) 5-Il)]-3-hydroxy-2-naphthalene carboamide (33.5 parts) and 25% sodium hydroxide aqueous solution (1344 parts) were dissolved in 3500 parts of methanol to prepare a coupler solution. This coupler solution was injected into the above 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 is heated to 70 ° C., filtered, washed with water, and dried at 90 ° C. for 24 hours. The azo pigment of azo compound 1 and the azo represented by the general formula (6) C.I. I. 309 parts of a mixture with Pigment Red 176 was obtained. As a result of mass spectrometry by TOF-MS, the azo pigment of azo compound 1 and C.I. I. It was confirmed that the mass ratio of the mixture of the naphthol azo pigment of Pigment Red 176 was 82.1: 17.9. The obtained azo compound was subjected to a salt milling treatment method similar to that of the red colorant (R-1) to obtain a red colorant (R-18). The average primary particle size was 32 nm.

(Production of Red Colorant (R-19-30): Azo Compound 19-30)
The same operation as in the production of the red colorant (R-1) was performed except that the compound (B) or (C) used in the production of the red colorant (R-1) was changed as shown in Table 4. Compounds 19-30 were obtained. The compound (B) and the compound (C) in Table 4 are shown in Table 5.

<Manufacturing method of other colorants>
(Manufacturing of red colorant 1: PR254)
Commercially available C.I. I. Pigment Red 254 (PR254) (BASF's "Irgafore Red B-CF"), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and 6 at 60 ° C. It was kneaded for a long time and treated with salt milling. The obtained kneaded product was put into 3 liters of warm water, stirred for 1 hour while heating at 70 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. for 24 hours. , 98 parts of red colorant 1 was obtained. The average primary particle size was 33 nm.

(Manufacturing of red colorant 2: PR177)
C. I. Pigment Red 254 (BASF's "Irgafore Red B-CF"), C.I. I. Pigment Red 177 (PR177) (“CROMOPHTAL RED A2B” manufactured by BASF Ltd.) was changed in the same manner as in the production of the red colorant 1, and 97 parts of the red colorant 2 was obtained. The average primary particle size was 37 nm.

(Manufacturing of red colorant 3: PR242)
C. I. Pigment Red 254 (BASF's "Irgafore Red B-CF"), C.I. I. Pigment Red 242 (PR242) (“Sandorin Scarlet 4RF” manufactured by Clariant AG) was changed in the same manner as in the production of the red colorant 1 to obtain 98 parts of the red colorant 3. The average primary particle size was 39 nm.

(Manufacturing of red colorant 4: PR176)
C. I. Pigment Red 254 (BASF's "Irgafore Red B-CF"), C.I. I. Pigment Red 176 (PR176) (“Novoperm Carmine HF3C” manufactured by Clariant AG) was changed in the same manner as in the production of the red colorant 1 to obtain 98 parts of the red colorant 4. The average primary particle size was 35 nm.

(Production of Red Colorant 5: Formula (2-19))
(Brominated diketopyrrolopyrrole pigment formula (2-19))
To a stainless steel reaction vessel equipped with a reflux tube, 200 parts of molecular sieve-dehydrated tert-amyl alcohol and 140 parts of sodium-tert-amyl alkoxide were added under a nitrogen atmosphere and heated to 100 ° C. with stirring to prepare an alcoholate solution. Prepared. On the other hand, 88 parts of diisopropyl succinate and 153.6 parts of 4-bromobenzonitrile were added to a glass flask and heated to 90 ° C. with stirring to dissolve them to prepare a solution of a mixture thereof. The heated solution of this mixture was slowly added dropwise to the alcoholate solution heated to 100 ° C. at a constant rate over 2 hours with vigorous stirring. After completion of the dropping, heating and stirring were continued at 90 ° C. for 2 hours to obtain an alkali metal salt of a diketopyrrolopyrrole compound. Further, 600 parts of methanol, 600 parts of water, and 304 parts of acetic acid were added to a reaction vessel with a glass jacket, and the mixture was cooled to −10 ° C. The cooled mixture was cooled to 75 ° C. using a high-speed stirring disperser while rotating a share disk having a diameter of 8 cm at 4000 rpm, and the alkali metal salt of the previously obtained diketopyrrolopyrrole compound was obtained. The solution was added in small portions. At this time, the rate at which the alkali metal salt of the diketopyrrolopyrrole compound is added at 75 ° C. while cooling so that the temperature of the mixture consisting of methanol, acetic acid, and water is always maintained at −5 ° C. or lower. Was added in small portions over approximately 120 minutes while adjusting. After the addition of the alkali metal salt, red crystals were precipitated and a red suspension was formed. Subsequently, the obtained red suspension was washed with an ultrafiltration device at 5 ° C. and then filtered to obtain a red paste. This paste was redispersed in 3500 parts of methanol cooled to 0 ° C. to prepare a suspension having a methanol concentration of about 90%, and the paste was stirred at 5 ° C. for 3 hours to perform particle sizing and washing with crystal transition. Subsequently, the water paste of the diketopyrrolopyrrole compound obtained by filtration filtration with an ultrafilter was dried at 80 ° C. for 24 hours and pulverized to form bromine represented by the formula (2-19). 150.8 parts of diketopyrrolopyrrole pigment was obtained.

100 parts of the brominated diketopyrrolopyrrole pigment represented by the above formula (2-19), 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. Kneaded with salt for 6 hours and subjected to salt milling treatment. The obtained kneaded product was put into 3 liters of warm water, stirred for 1 hour while heating at 70 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. for 24 hours. , 98 parts of red colorant 5 was obtained. The average primary particle size was 45 nm.

(Manufacturing of Yellow Colorant 1: PY138)
Kinoftalone yellow pigment C.I. I. Pigment Yellow 138 (BASF's "Pariotor Yellow K0960-HD"), 500 parts of sodium chloride, and 250 parts of diethylene glycol were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 120 ° C. for 8 hours. Next, this kneaded product was put into 5 liters of warm water, stirred for 1 hour while heating at 70 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. for 24 hours. Then, 490 parts of the yellow colorant 1 was obtained. The average primary particle size was 63 nm.

(Manufacture of Yellow Colorant 2: PY139)
Kinoftalone yellow pigment C.I. I. Pigment Yellow 139 (BASF's "Pariotor Yellow K1841"), 500 parts of sodium chloride, and 250 parts of diethylene glycol were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 120 ° C. for 8 hours. Next, this kneaded product was put into 5 liters of warm water, stirred for 1 hour while heating at 70 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. for 24 hours. Then, 510 parts of yellow colorant 2 was obtained. The average primary particle size was 68 nm.

(Manufacture of Yellow Colorant 3: PY150)
Kinoftalone yellow pigment C.I. I. Pigment Yellow 150 (BASF's "Pariotor Yellow K1841"), 500 parts of sodium chloride, and 250 parts of diethylene glycol were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 120 ° C. for 8 hours. Next, this kneaded product was put into 5 liters of warm water, stirred for 1 hour while heating at 70 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. for 24 hours. Then, 500 parts of the yellow colorant 3 was obtained. The average primary particle size was 60 nm.

(Production of Yellow Colorant 4: Formula (3-1))
To 200 parts of methyl benzoate, 40 parts of 8-aminoquinaldine, 150 parts of 2,3-naphthalenedicarboxylic acid anhydride, and 154 parts of benzoic acid were added, heated to 180 ° C., and stirred for 4 hours. Further, after cooling to room temperature, the reaction mixture was added to 5440 parts of acetone and stirred at room temperature for 1 hour. The product was filtered off, washed with methanol and dried to obtain 116 parts of quinophthalone compound (q). As a result of mass spectrometry by TOF-MS, it was identified as a quinophthalone compound (q).

Kinoftalone compound (q)

Further, using the quinophthalone compound (q) as a raw material, the compound (q-2) was obtained according to the synthesis method described in JP-A-2008-81566.

Compound (q-2)

To 300 parts of methyl benzoate, 100 parts of compound (q-2), 108 parts of tetrachlorophthalic anhydride, and 143 parts of benzoic acid were added, heated to 180 ° C., and reacted for 4 hours. By TOF-MS, the formation of the quinophthalone compound (formula (3-1)) and the disappearance of the raw material compound (q-2) were confirmed. Further, after cooling to room temperature, the reaction mixture was added to 3510 parts of acetone and stirred at room temperature for 1 hour. The product was separated by filtration, washed with methanol, and dried to obtain 120 parts of a quinophthalone compound represented by the following formula (3-1). As a result of mass spectrometry by TOF-MS, it was identified as a quinophthalone compound (formula (3-1)).
Equation (3-1)

500 parts of the quinophthalone compound represented by the formula (3-1), 500 parts of sodium chloride, and 250 parts of diethylene glycol obtained above were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 120 ° C. for 8 hours. Next, this kneaded product was put into 5 liters of warm water, stirred for 1 hour while heating at 70 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. for 24 hours. Then, 480 parts of the yellow colorant 4 was obtained. The average primary particle size was 62 nm.

(Manufacturing of green colorant 1: PG58)
Phthalocyanine-based green pigment C.I. I. Pigment Green 58 (“FASTOGEN GREEN A110” manufactured by DIC Corporation), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. The kneaded product was put into 8000 parts of warm water, stirred for 2 hours while heating at 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. for 24 hours and 190 parts. The green colorant 1 of No. 1 was obtained. The average primary particle size was 69 nm.

(Preparation of blue colorant 1: PB15: 6)
Phthalocyanine blue pigment C.I. I. Pigment Blue 15: 6 (“LIONOL BLUE ES” manufactured by Toyo Color Co., Ltd.), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. .. Next, this kneaded product was put into 8000 parts of warm water, stirred for 2 hours while heating at 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. for 24 hours. , 190 parts of blue colorant 1 was obtained. The average primary particle size was 74 nm.

(Preparation of purple colorant 1: PV23)
Dioxazine-based purple pigment C.I. I. Pigment Violet 23 (“LIONOGEN VIOLET RL” manufactured by Toyo Color Co., Ltd.), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, this kneaded product was put into 8000 parts of warm water, stirred for 2 hours while heating at 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. for 24 hours. , 190 parts of purple colorant 1 was obtained. The average primary particle size was 69 nm.

<Manufacturing method of pigment dispersion>
(Pigment dispersion (DC-1): PR254)
The following mixture is stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini model M-250 MKII” manufactured by Eiger Japan) for 3 hours using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. The pigment dispersion (DC-1) having a non-volatile component content of 20% by weight was prepared by filtering with the filter of.
Red colorant 1 (PR254): 12.0 parts Acrylic resin solution: 36.4 parts Propylene glycol monomethyl ether acetate (PGMAc): 50.2 parts Acid resin type dispersant solution ("Disperbic 110" manufactured by BIC Chemie): 1.4 copies

(Pigment dispersion (DC-2): PR177)
The following mixture is stirred and mixed so as to be uniform, and then dispersed for 3 hours with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan Co., Ltd.) using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. The pigment dispersion (DC-2) having a non-volatile component content of 20% by weight was prepared by filtering with the filter of.
Red colorant 2 (PR177): 12.0 parts Acrylic resin solution: 36.4 parts Propylene glycol monomethyl ether acetate (PGMAc): 50.2 parts Acid resin type dispersant solution ("Disperbic 110" manufactured by BIC Chemie): 1.4 copies

(Pigment dispersion (DC-3): PR242)
The following mixture is stirred and mixed so as to be uniform, and then dispersed for 3 hours 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 (DC-3) having a non-volatile component content of 20% by weight was prepared by filtering with the filter of.
Red colorant 3 (PR242): 12.0 parts Acrylic resin solution: 36.4 parts Propylene glycol monomethyl ether acetate (PGMAc): 50.2 parts Acid resin type dispersant solution ("Disperbic 110" manufactured by BIC Chemie): 1.4 copies

(Pigment dispersion (DC-4): PR176)
The following mixture is stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini model M-250 MKII” manufactured by Eiger Japan) for 3 hours using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. The pigment dispersion (DC-4) having a non-volatile component content of 20% by weight was prepared by filtering with the filter of.
Red colorant 4 (PR176): 12.0 parts Acrylic resin solution: 36.4 parts Propylene glycol monomethyl ether acetate (PGMAc): 50.2 parts Acid resin type dispersant solution ("Disperbic 110" manufactured by BIC Chemie): 1.4 copies

(Pigment dispersion (DC-5): formula (2-19))
The following mixture is stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini model M-250 MKII” manufactured by Eiger Japan) for 3 hours using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. The pigment dispersion (DC-5) having a non-volatile component content of 20% by weight was prepared by filtering with the filter of.
Red colorant 6 (Formula (2-19)): 12.0 parts Acrylic resin solution: 36.4 parts Propylene glycol monomethyl ether acetate (PGMAc): 50.2 parts Acid resin type dispersant solution ("Disper" manufactured by Big Chemie BIC 110 "): 1.4 copies

(Pigment dispersion (DC-6): PY138)
The following mixture is stirred and mixed so as to be uniform, and then dispersed for 3 hours 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 (DC-6) having a non-volatile component content of 20% by weight was prepared by filtering with the filter of.
Yellow colorant 1 (PY138): 12.0 parts Acrylic resin solution: 36.4 parts Propylene glycol monomethyl ether acetate (PGMAc): 50.2 parts Acid resin type dispersant solution ("Disperbic 110" manufactured by BIC Chemie): 1.4 copies

(Pigment dispersion (DC-7): PY139)
The following mixture is stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini model M-250 MKII” manufactured by Eiger Japan) for 3 hours using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. The pigment dispersion (DC-7) having a non-volatile component content of 20% by weight was prepared by filtering with the filter of.
Yellow colorant 2 (PY139): 12.0 parts Acrylic resin solution: 36.4 parts Propylene glycol monomethyl ether acetate (PGMAc): 50.2 parts Acid resin type dispersant solution ("Disperbic 110" manufactured by BIC Chemie): 1.4 copies

(Pigment dispersion (DC-8): PY150)
The following mixture is stirred and mixed so as to be uniform, and then dispersed for 3 hours on 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 (DC-8) having a non-volatile component content of 20% by weight was prepared by filtering with the filter of.
Yellow colorant 3 (PY150): 12.0 parts Acrylic resin solution: 36.4 parts Propylene glycol monomethyl ether acetate (PGMAc): 50.2 parts Acid resin type dispersant solution ("Disperbic 110" manufactured by BIC Chemie): 1.4 copies

(Pigment dispersion (DC-9): Equation (3-1))
The following mixture is stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini model M-250 MKII” manufactured by Eiger Japan) for 3 hours using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. A pigment dispersion (DC-9) having a non-volatile component content of 20% by weight was prepared by filtering with the filter of.
Yellow colorant 4 (formula (3-1)): 12.0 parts Acrylic resin solution: 36.4 parts Propylene glycol monomethyl ether acetate (PGMAc): 50.2 parts Acid resin type dispersant solution ("Disper" manufactured by Big Chemie BIC 110 "): 1.4 copies

<Manufacturing method of pigment dispersion>
[Production Example 1] (Pigment dispersion (D-1))
The following mixture is stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini model M-250 MKII” manufactured by Eiger Japan) for 3 hours using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. The pigment dispersion (D-1) having a non-volatile component content of 20% by weight was prepared by filtering with the filter of.
Red colorant (R-1): 12.0 parts Acrylic resin solution: 36.4 parts Propylene glycol monomethyl ether acetate (PGMAc): 50.2 parts Acid resin type dispersant solution ("Disperbic 110" manufactured by BIC Chemie) : 1.4 copies

[Production Examples 2 to 30] (Pigment dispersion (D-2 to 30))
Hereinafter, the pigment dispersions (D-2 to 30) were prepared in the same manner as the pigment dispersion (D-1) except that the compositions were changed to those shown in Table 6.

[Production Example 31] (Pigment Dispersion (D-31))
The following mixture is stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini model M-250 MKII” manufactured by Eiger Japan) for 3 hours using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. The pigment dispersion (D-31) having a non-volatile component content of 20% by weight was prepared by filtering with the filter of.
Red colorant (R-1): 12.0 parts Acrylic resin solution: 35.0 parts Propylene glycol monomethyl ether acetate (PGMAc): 52.0 parts Basic resin type dispersant solution (BASF "EFKA4300"): 1.0 copy

[Production Example 32] (Pigment Dispersion (D-32))
The following mixture is stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini model M-250 MKII” manufactured by Eiger Japan) for 3 hours using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. The pigment dispersion (D-32) having a non-volatile component content of 20% by weight was prepared by filtering with the filter of.
Red colorant (R-1): 12.0 parts Acrylic resin solution: 46.6 parts Propylene glycol monomethyl ether acetate (PGMAc): 42.1 parts Acid resin type dispersant solution ("Disperbic 110" manufactured by BIC Chemie) : 1.3 copies

<Manufacturing method of photosensitive coloring composition for color filter>
[Example 1]
(Photosensitive coloring composition (DR-1))
The following mixture (100 parts in total) was stirred and mixed so as to be uniform, and then filtered through a 1.0 μm filter to obtain a photosensitive coloring composition (DR-1).
Pigment dispersion (D-1): 27.0 parts Pigment dispersion (DC-1): 23.0 parts Acrylic resin solution: 7.5 parts Photopolymerizable monomer (Aronix M-402 manufactured by Toa Synthetic Co., Ltd.) ”): 2.0 parts Dipentaerythritol hexaacrylate photopolymerization initiator (BASF“ OXE-02 ”): 1.5 parts Etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H -Carbazole-3-yl]-, 1- (0-acetyloxime)
Cyclohexanone: 39.0 parts

[Examples 2-38, Comparative Examples 1-5]
(Photosensitive coloring composition (DR-2 to 43))
Photosensitive coloring compositions (DR-2 to 43) were obtained in the same manner as the photosensitive coloring composition (DR-1) except that the pigment dispersion was changed to the type and blending amount of the pigment dispersion shown in Table 7. .. In each adjustment of the photosensitive coloring composition, 100 parts of the photosensitive coloring composition was adjusted by adding so that the total amount of the pigment dispersion was 50 parts.

<Evaluation of photosensitive coloring composition for color filters>
The brightness, heat resistance, and light resistance of the obtained photosensitive coloring composition were measured by the following methods. Table 7 shows the evaluation results.

[brightness]
The obtained photosensitive coloring composition is applied onto a glass substrate, dried at 70 ° C. for 20 minutes, and then heated at 230 ° C. for 60 minutes. The chromaticity of the obtained substrate contains quantum dots as a light emitting element. A coated substrate was obtained such that x = 0.680 and y = 0.318 at the light source. The brightness (Y) of the obtained substrate was measured with a microspectrophotometer (“OSP-SP200” manufactured by Olympus Optical Co., Ltd.).

[Contrast ratio (CR)]
The contrast ratio was measured using the substrate whose brightness was measured.

[Film thickness]
The film thickness was measured using the substrate whose brightness was measured. A surface shape measuring instrument DEKTAK150 (manufactured by ULVAC ES) was used for measuring the film thickness.

[Heat resistance evaluation]
The obtained photosensitive coloring composition was applied onto a 100 mm × 100 mm, 1.1 mm thick glass substrate using a spin coater so that the film thickness after firing was 1 μm, and then at 70 ° C. for 20 minutes. A coated substrate was prepared by drying, then heating at 220 ° C. for 20 minutes, and allowing to cool. The chromaticity ([L * (1), a * (1), b * (1)]) of the obtained coating film at a light source containing quantum dots as a light emitting element is measured by a spectrophotometer (manufactured by Olympus Optical Co., Ltd.). It was measured using "OSP-SP100"). After that, as a heat resistance test, it is heated at 230 ° C. for 1 hour, and the chromaticity ([L * (2), a * (2), b * (2)]) with a light source containing quantum dots as a light emitting element is measured. Then, the color difference ΔE * ab was calculated by the following formula and evaluated according to the following criteria.
ΔE * ab = √ ((L * (2) -L * (1)) 2+ (a * (2) -a * (1)) 2+ (b * (2) -b * (1)) 2 )
⊚: ΔE * ab is less than 3.0 ○: ΔE * ab is 3.0 or more and less than 4.5 Δ: ΔE * ab is 4.5 or more and less than 10.0 ×: ΔE * ab is 10.0 or more

[Light resistance evaluation]
The obtained photosensitive coloring composition was applied onto a 100 mm × 100 mm, 1.1 mm thick glass substrate using a spin coater so that the film thickness after firing was 1 μm, and then at 70 ° C. for 20 minutes. A coated substrate was prepared by drying, then heating at 220 ° C. for 20 minutes, and allowing to cool. After measuring the chromaticity [L * (1), a * (1), b * (1)] using a microscopic photometric meter (“OSP-SP100” manufactured by Olympus Corporation), the spectral distribution is equivalent to that of sunlight. An accelerated exposure test at 470 W / m2 was performed for 200 hours using a xenon lamp. The chromaticity [L * (2), a * (2), b * (2)] after light irradiation was measured, and the color difference ΔE * ab was calculated by the following formula.
ΔE * ab = √ ((L * (2) -L * (1)) 2+ (a * (2) -a * (1)) 2+ (b * (2) -b * (1)) 2 )
The smaller the color difference ΔE * ab, the smaller the discoloration due to light irradiation, and the better the light resistance of the colored composition. Each sample was evaluated according to the following criteria.
⊚: ΔE * ab is less than 3.0 ○: ΔE * ab is 3.0 or more and less than 4.5 Δ: ΔE * ab is 4.5 or more and less than 10.0 ×: ΔE * ab is 10.0 or more

The coloring composition for a color filter of the present invention containing the naphthol azo pigment [A1] represented by the general formula (1) has a higher brightness and CR than the photosensitive coloring composition of the comparative example, is a thin film, and has heat resistance. -The result of solvent resistance was good. Further, when the basic resin type dispersant was used, the brightness, CR, heat resistance and light resistance were deteriorated as compared with the case where the acidic resin type dispersant was used. Further, when the pigment concentration in the pigment dispersion becomes low, the brightness, CR, heat resistance and light resistance deteriorate, and the film thickness becomes thicker than 3 μm, resulting in inferior coloring power. It can be said that the thinner the film thickness, the higher the hue of red with high color purity can be displayed even with thin-film pixels.

<Manufacturing and evaluation of color filters>
(Green Photosensitive Coloring Composition 1: PG58 / PY138)
The following mixture is stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) for 5 hours using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. The mixture was filtered through the above filter to prepare a green pigment dispersion having a non-volatile content of 20% by weight.
Green Colorant 1 (CI Pigment Green 58): 12.0 parts Acrylic resin solution: 36.4 parts Propylene glycol monomethyl ether acetate (PGMAc): 50.2 parts Acid resin type dispersant solution (manufactured by BIC Chemie) Disperbic 110 "): 1.4 copies

The following mixture is stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) for 5 hours using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. The mixture was filtered through the above filter to prepare a yellow pigment dispersion having a non-volatile content of 20% by weight.
Yellow Colorant 1 (CI Pigment Yellow 138): 12.0 parts Acrylic resin solution: 36.4 parts Propylene glycol monomethyl ether acetate (PGMAc): 50.2 parts Acid resin type dispersant solution (manufactured by BIC Chemie) Disperbic 110 "): 1.4 copies

Subsequently, the mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to prepare a green photosensitive coloring composition 1.
Green pigment dispersion: 32.0 parts Yellow pigment dispersion: 18.0 parts Acrylic resin solution: 7.5 parts Photopolymerizable monomer ("Aronix M-402" manufactured by Toa Synthetic Co., Ltd.): 2.0 parts Pentaerythritol hexaacrylate photopolymerization initiator (BASF "OXE-02"): 1.5 parts Etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl]- , 1- (O-acetyloxime)
Cyclohexanone: 39.0 parts

(Blue Photosensitive Coloring Composition 1: PB15: 6 / PV23)
Similar to the green pigment dispersion, the non-volatile content is 20% by weight, except that the green colorant 1 (CI Pigment Green 58) is changed to the blue colorant 1 (CI Pigment Blue 15: 6). Blue pigment dispersion was obtained.

Similar to the green pigment dispersion, purple with a non-volatile content of 20% by weight, except that the green colorant 1 (CI Pigment Green 58) was changed to the purple colorant 1 (CI Pigment Violet 23). A pigment dispersion was obtained.

Subsequently, 32.0 parts of the green pigment dispersion and 18.0 parts of the yellow pigment dispersion were replaced with 46.0 parts of the blue dispersion and 4.0 parts of the purple dispersion, totaling 50.0 parts. A blue photosensitive coloring composition 1 was obtained in the same manner as the green photosensitive coloring composition 1 except for the above.

(Manufacturing and evaluation of color filters)
The red photosensitive coloring composition (DR-1) is applied onto a glass substrate on which a black matrix is formed using a slit die coater, and then prebaked on a hot plate at 90 ° C. for 2 minutes to form a coating film. Formed. Next, after cooling the substrate on which the coating film was formed to room temperature, using a high-pressure mercury lamp, the coating film was irradiated with radiation containing wavelengths of 365 nm, 405 nm, and 436 nm at 1,000 J / m via a striped photomask. ^It was exposed with an exposure amount of ² . After performing alkaline development, the cells were washed with ultrapure water and post-baked at 230 ° C. for 20 minutes to form red striped pixels having a film thickness of 2.3 μm on the substrate. The film thickness of 2.3 μm corresponds to the film thickness at the chromaticity coordinate value x = 0.680 obtained in Example 1.
Then, by the same method, the green photosensitive coloring composition 1 was used to form green striped pixels having a film thickness of 2.5 μm next to the red striped pixels. Further, using the blue photosensitive coloring composition 1, similarly, blue striped pixels having a film thickness of 2.6 μm adjacent to the red and green pixels were formed. The film thickness of the green striped pixel of 2.5 μm corresponds to the film thickness of the chromaticity coordinate value y = 0.710 obtained in Example 6, and the film thickness of the blue striped pixel is 2.6 μm. Corresponds to the film thickness at the chromaticity coordinate value y = 0.080 obtained in Reference Example 1. Next, a protective film was formed on the pixels composed of the three colors of red, green, and blue using the photocurable resin composition. In this way, the color filter substrate having the red pixels and the green pixels of the present invention was produced. By using the light of the emission spectrum shown in FIG. 1 as a light source for the obtained color filter, it was possible to produce an RGB 3-color color filter having high brightness and excellent resistance.

Claims (4)

A coloring composition for a color filter containing a colorant, an acidic resin type dispersant, a binder resin and an organic solvent, wherein the colorant contains a pigment [A1] represented by the following general formula (1).
The chromaticity coordinates of the coating film in the XYZ color system measured using a light source containing quantum dots as a light emitting element form a coating film having chromaticity coordinates x = 0.680 and chromaticity coordinates y = 0.318. when the thickness is 2.0~3.0μm der is, a light source including quantum dots as light-emitting element, a first peak wavelength in 430 to 480 nm, a second peak wavelength in 510 to 560 nm, 600 to A coloring composition for a color filter, which is a light source having a third peak wavelength at 660 nm .
[In general formula (1),
A represents a hydrogen atom, a benzimidazolone group, a phenyl group which may have a substituent or a heterocyclic group which may have a substituent.
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, -Represents NHCOR ¹² or 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.
However, this excludes cases where R ⁴ is -NHCOR ¹² , A, R ² , R ³ , R ⁵ and R ⁶ are hydrogen atoms, and R ¹ is a halogen atom. ] The coloring composition for a color filter according to claim 1, further containing at least one selected from the group consisting of a photopolymerization initiator and a photopolymerizable monomer. A color filter comprising a filter segment formed by using the coloring composition for a color filter according to claim 1 or 2. A display device including the color filter according to claim 3 and a light emitting element including quantum dots.