JP2016114940A - Color filter coloring composition and color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a color filter coloring composition that is superior in terms of brightness, a contrast ratio, heat resistance and light resistance, and to provide a color filter using the same.SOLUTION: The above problem is cleared by a color filter coloring composition containing a colorant, metal complex compound, binder resin, and organic solvent, where the colorant contains a naphthol-azo pigment [A] represented by a general formula (1) and the metal complex compound is a metal complex compound [B] whose central metal is at least one selected from vanadium (V), chrome (Cr), manganese (Mn), iron (Fe), cobalt (Co), and copper (Cu).SELECTED DRAWING: None

Description

  The present invention relates to a color liquid crystal display device, a color composition for a color filter used for producing a color filter used for a color image pickup tube element, and the like, and a color filter including a filter segment formed using the same. It is.

  In the liquid crystal display device, a liquid crystal layer sandwiched between two polarizing plates controls the amount of light passing through the first polarizing plate by controlling the degree of polarization of light passing through the first polarizing plate. The type using twisted nematic (TN) type liquid crystal is the mainstream. Other typical liquid crystal display devices include an in-plane switching (IPS) method in which a pair of electrodes is provided on one substrate and electrolysis is applied in a direction parallel to the substrate, negative dielectric anisotropy Vertical alignment (VA) method for vertically aligning nematic liquid crystal with optical properties, and Optical Convencence Bend (OCB) method in which the optical axes of uniaxial retardation films are orthogonal to each other to perform optical compensation Etc., and each has been put to practical use.

  A liquid crystal display device is capable of color display by providing a color filter between two polarizing plates, and has recently been used in televisions, personal computer monitors, and the like. Increasing demands are being made.

  A color filter is a surface of a transparent substrate such as glass, in which two or more kinds of fine band (striped) filter segments of different hues are arranged in parallel or crossing each other, or fine filter segments are arranged vertically and horizontally. It is made up of those arranged in The filter segments are as fine as several microns to several hundreds of microns, and are regularly arranged in a predetermined arrangement for each hue.

  Generally, in a color liquid crystal display device, a transparent electrode for driving a liquid crystal is formed on a color filter by vapor deposition or sputtering, and an alignment film for aligning the liquid crystal in a certain direction is further formed thereon. Yes. In order to sufficiently obtain the performance of these transparent electrodes and alignment films, the formation thereof must generally be performed at a high temperature of 200 ° C. or higher, preferably 230 ° C. or higher. For this reason, at present, as a method for producing a color filter, a method called a pigment dispersion method using a pigment having excellent light resistance and heat resistance as a colorant is mainly used.

  Quality items required for the color filter include brightness and contrast ratio. When a color filter with a low contrast ratio is used, the degree of polarization controlled by the liquid crystal is disturbed, and when light must be blocked (OFF state), light must leak or be transmitted (ON) In other words, the transmitted light is attenuated in the state), resulting in a blurred screen. Therefore, in order to realize a high-quality liquid crystal display device, high contrast is indispensable.

  If a color filter with low brightness is used, the light transmittance is low, resulting in a dark screen. In order to obtain a bright screen, it is necessary to increase the number of backlights as light sources. For this reason, from the viewpoint of suppressing an increase in power consumption, increasing the brightness of color filters has become a trend. Furthermore, as described above, since the color liquid crystal device has been used for televisions, personal computer monitors, and the like, the demand for high reliability and high lightness and contrast for color filters has also increased.

  The red filter segment, which is one of the three primary colors (red, green, blue; RGB) of the color filter substrate, has light resistance and heat resistance such as diketopyrrolopyrrole pigment, anthraquinone pigment, perylene pigment or disazo pigment as a colorant. It is common to use pigments that are excellent in singly or in combination.

  Among the pigment types, C.I. which is a diketopyrrolopyrrole pigment from the viewpoint of lightness. I. Pigment Red 254 is an anthraquinone pigment from the viewpoint of contrast ratio. I. Pigment Red 177 is used as the main pigment. Among these, C.I. I. Pigment Red 177 has a spectral transmittance of C.I. I. Since it is lower than CI Pigment Red 254 and the spectral shape is poor, C.I. I. As Pigment Red 177 was added, there was a drawback of causing a decrease in brightness. Therefore, C.I. I. Development of an alternative material for Pigment Red 177 is desired.

  C. I. As an example of studying an alternative material for Pigment Red 177, as described in Patent Documents 1 to 3, C.I. I. Pigment red 176, C.I. I. Pigment red 242, and C.I. I. It has been proposed to use an azo pigment such as CI Pigment Orange 38 as a main pigment, but the brightness is not sufficient, and further improvement has been demanded.

In addition, it is known that a part of the azo dye emits fluorescence, and the contrast ratio is lowered by disturbing the degree of polarization controlled by the liquid crystal.
Therefore, there is a demand for a coloring composition that has both high brightness and a high contrast ratio and is excellent in heat resistance and light resistance.

JP 2002-131521 A JP 2002-250812 A JP 2002-338841 A

  The problem to be solved by the present invention is to provide a color filter coloring composition excellent in lightness, contrast ratio, heat resistance and light resistance, and a color filter using the same.

  As a result of intensive studies, the present inventors have found that the above-described problems can be solved by using a naphtholazo pigment [A] having a specific structure and a specific metal complex compound. It came to.

That is, the present invention is a color filter coloring composition comprising a colorant, a metal complex compound, a binder resin, and an organic solvent,
The colorant contains a naphthol azo pigment [A] represented by the following general formula (1):
A metal having a metal complex compound as a central metal of at least one selected from the group consisting of vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), and copper (Cu) It is related with the coloring composition for color filters characterized by being complex compound [B].

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

In the present invention, the central metal of the metal complex compound [B] is chromium (Cr), cobalt (C
o) The above-mentioned coloring composition for a color filter, which is copper (Cu).

  In addition, the present invention relates to the coloring composition for a color filter, wherein the metal complex compound [B] is a metal complex dye.

  In the present invention, the content [B] / ([B] + [A]) of the metal complex compound [B] relative to the total of the naphtholazo pigment [A] and the metal complex compound [B] is 0.01 to It is 0.5, It is related with the said coloring composition for color filters characterized by the above-mentioned.

In the invention, the colorant is at least one selected from the group consisting of a naphthol azo pigment [A ′], an azo pigment [C], a diketopyrrolopyrrole pigment, and an anthraquinone pigment represented by the following general formula (6). The present invention relates to a coloring composition for a color filter comprising a seed.
[In General Formula (6), A ¹ represents a hydrogen atom, a phenyl group which may have a substituent, or a heterocyclic group which may have a substituent. R ⁵¹ represents a hydrogen atom, a trifluoromethyl group, an alkyl group having 1 to 4 carbon atoms, —OR ⁵⁷ or —COOR ⁵⁸ . R ⁵⁷ and R ⁵⁸ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ]

  Further, the present invention relates to the color composition for color filters, further comprising a photopolymerizable monomer and / or a photopolymerization initiator.

  The present invention also relates to a color filter comprising a filter segment formed on the base material from the color filter coloring composition.

  With the coloring composition for a color filter of the present invention, a color filter excellent in lightness and contrast ratio, and excellent in heat resistance and light resistance can be obtained.

Hereinafter, the present invention will be described in detail.
In the present specification, when expressed as “(meth) acryloyl”, “(meth) acryl”, “(meth) acrylic acid”, “(meth) acrylate”, or “(meth) acrylamide” Unless otherwise specified, “acryloyl and / or methacryloyl”, “acrylic and / or methacrylic”, “acrylic acid and / or methacrylic acid”, “acrylate and / or methacrylate”, or “acrylamide and / or methacrylamide”, respectively. ".
Further, “CI” mentioned in the present specification means a color index (CI).

《Colorant》
<Naphthol azo pigment [A]>
The colorant of the present invention contains a naphthol azo pigment [A] represented by the general formula (1).

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

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

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

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

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

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

In addition, the alkyl group having 1 to 4 carbon atoms in R ^{1 to} R ¹³ may be linear or branched, and specifically includes a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and an isobutyl group. , Sec-butyl group, and tert-butyl group.

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

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

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

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

(Naphthol azo pigment [A1])
Among the naphthol azo pigments [A] represented by the general formula (1), the naphthol azo pigment [A1], in which at least one of R ^{2 to} R ⁶ is a trifluoromethyl group, is easily refined. Yes, because it is excellent in brightness and contrast ratio.

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

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

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

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

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

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

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

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

Examples of the inorganic or organic anion include fluoride ion, chloride ion, bromide ion, iodide ion, perchlorate ion, hypochlorite ion, CH ₃ COO ⁻ , C ₆ H ₅ COO ^−.
Preferred examples include chloride ion, bromide ion, and CH ₃ COO ⁻ .

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

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

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

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

Examples of the inorganic or organic anion include fluoride ion, chloride ion, bromide ion, iodide ion, perchlorate ion, hypochlorite ion, CH ₃ COO ⁻ , C ₆ H ₅ COO ^−.
Preferred examples include chloride ion, bromide ion, and CH ₃ COO ⁻ .

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

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

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

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

<Other colorants>
The color composition for color filter of the present invention includes other pigments or dyes other than the naphtholazo pigment [A] of the general formula (1) within the range of not impairing the effects of the present invention in order to adjust chromaticity. These 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 colorants that can be used in combination include pigments such as diketopyrrolopyrrole pigments, azo pigments other than the naphtholazo pigment [A] of the general formula (1) such as azo, disazo, or polyazo, aminoanthraquinone, diaminodianthraquinone. , Anthrapyrimidine, flavantron, anthanthrone, indanthrone, pyranthrone, violanthrone, anthraquinone pigment, quinacridone pigment, perinone pigment, perylene pigment, thioindigo pigment, isoindoline pigment, isoindolinone pigment, quinophthalone pigment, or selenium pigment Is mentioned.
Examples of the dye include xanthene dyes, azo (pyridone series, barbituric acid series, etc.) dyes, disazo dyes, anthraquinone dyes, and methine dyes. In addition, lake pigments obtained by lake- ing these dyes, inorganic salts of acidic dyes having acidic groups such as sulfonic acid and carboxylic acid, salt-forming compounds of acidic dyes and nitrogen-containing compounds, sulfonic acid amides of acidic dyes It may be in the form of a compound or the like.

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

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

(Naphthol azo pigment [A '])
The naphthol azo pigment [A ′] is a naphthol azo pigment represented by the general formula (6).

[In General Formula (6), A ¹ represents a hydrogen atom, a phenyl group which may have a substituent, or a heterocyclic group which may have a substituent. R ⁵¹ represents a hydrogen atom, a trifluoromethyl group, an alkyl group having 1 to 4 carbon atoms, —OR ⁵⁷ or —COOR ⁵⁸ . R ⁵⁷ and R ⁵⁸ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ]

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

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

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

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

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

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

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

  Specific examples of red pigments that can be used in combination are 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, Use 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 together Can do. 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, 82,185,187,188,193,194,198,199,213, and 214, and the like.
Examples of the orange pigment include C.I. I. Pigment orange 38, 43, 71, or 73.
Among these, C.I. can be expanded in that the chromaticity region can be expanded. I. Pigment yellow 138, 139, 150, C.I. I. Pigment Orange 38 is preferable.

The dyes that can be used in combination are red and purple, and preferably have any form of oil-soluble dyes, acid dyes, direct dyes, and basic dyes.
Among these, use of a xanthene oil-soluble dye, a xanthene basic dye, and a xanthene acid dye is preferable because of excellent hue. In addition, lake pigments obtained by lake- ing these dyes, inorganic salts of acidic dyes having acidic groups such as sulfonic acid and carboxylic acid, salt-forming compounds of acidic dyes and nitrogen-containing compounds, sulfonic acid amides of acidic dyes It may be in the form of a compound or the like.

Xanthene 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. CI 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. Among them, CI solvent red 35, CI solvent red 36, CI solvent red 49, CI solvent red 109, CI solvent red, which are rhodamine-based oil-soluble dyes having high color development Red 237, CI Solvent Red 246, and CI Solvent Violet 2 are more preferable.
Examples of xanthene basic dyes 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 these, C.I. I. Basic Red 1, C.I. I. Basic violet 10 is preferably used.
Examples of xanthene acid dyes include C.I. I. Acid Red 51 (erythrosin (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 Phloxin 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 these, in terms of heat resistance and light resistance, C.I. 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., which is a rhodamine acid dye, is particularly excellent in terms of color developability, heat resistance and light resistance. I. Most preferably, Acid Red 52 is used.

  When used in combination with the above-mentioned red pigment, yellow pigment, orange pigment, and dye, the content of the naphtholazo pigment [A] described by the general formula (1) is 10 to 90 wt% in a total of 100 wt% of the colorant. %, Preferably 20 to 80% by weight. By being in this content range, the chromaticity region can be expanded.

<Miniaturization of colorant>
The pigment used in the present invention can be used after being refined. The naphtholazo pigment [A] is also preferably used after being refined, but the refinement method is not particularly limited. For example, any of wet grinding, dry grinding, and dissolution precipitation can be used. As illustrated, a salt milling process by a kneader method, which is a kind of wet grinding, can be performed. Any commercially available product may be used as the naphthol azo pigment [A] to be refined, and a naphthol azo pigment [A] produced by a coupling reaction between a diazonium salt corresponding to the naphthol azo pigment [A] and β-naphthols is used. Also good.

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

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

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

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

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

<< Metal Complex Compound [B] >>
The metal complex compound [B] of the present invention is at least one selected from the group consisting of vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), and copper (Cu). Is a metal complex compound with a central metal, and has a fluorescence quenching ability, so that the fluorescence emission of the naphtholazo pigment [A] can be suppressed, the contrast ratio of the colored composition can be increased, and the heat resistance is also improved. It can be excellent.
A particularly preferred central metal is chromium (C) because of its particularly excellent contrast ratio and heat resistance.
r), cobalt (Co) or copper (Cu).

  Further, among such metal complex compounds [B], the metal complex dye not only has a high contrast ratio, but also has little color change due to heating, so that both brightness and contrast ratio can be achieved. Moreover, it is preferable.

  The content [B] / ([B] + [A]) of the metal complex compound [B] with respect to the total of the naphtholazo pigment [A] and the metal complex compound [B] is 0.01 to 0.5. Is preferable from the viewpoint of the balance between brightness, contrast, heat resistance, and light resistance, and more preferably 0.01 to 0.3.

  The molecular weight of one ligand in the metal complex compound [B] is preferably 20 or more and less than 300. If it is 300 or more, the molecular weight increases, and the contrast ratio improving effect may be diminished.

As the ligand in the metal complex compound [B], all general ligands can be used, and any of monodentate ligands and polydentate ligands can be suitably used.
Specific examples of the ligand include fluoro, chloro, bromo, iodo, hydroxo, aqua, tetrahydrofuran, ethylene glycol dimethyl ether, acetonitrile, benzonitrile, oxo, peroxo, carbonyl, carbonate, oxalato, acetato, ethanolato, 1-butanethiolato. Thiophenolato, 2,2′-thiobis (4-t-octyl) phenolate, acetylacetonate, 2,2,6,6-tetramethyl-3,5-heptanedionate, trifluoroacetylacetonate, hexafluoroacetylacetate Nato, ethyl acetoacetonate, thiocyanato, isothiocyanato, diethyl dithiocarbamate, di-n-butyldithiocarbamate, cyano, amine, dimethylamine, diethylamine, tetraethylammonium Piperidine, N-methylaniline, pyridine, 2-phenylpyridine, ethylenediamine, N, N, N ′, N′-tetramethylethylenediamine, 1,2-diaminocyclohexane, 2,2′-bipyridine, 1,10-phenanthroline , Ethylenediaminetetraacetato, 1,4,8,11-tetraazacyclotetradecane, tris (2-aminoethyl) amine, sulfato, nitro, nitrito, phosphato, diisopropyldithiophosphate, diethyldithiophosphate, triethylphosphine, tributylphosphine, Tricyclohexylphosphine, dimethylphenylphosphine, triphenylphosphine, diphenylphosphine, tricyclohexylphosphine, cyclopentadiene, pentamethylcyclopentadiene, cyclo Punctuation, 1,5-cyclooctadiene, bicyclo [2.2.1] hepta-2,5-diene, benzene, naphthalene, allyl and the like.

Preferred ligands include fluoro, chloro, bromo, iodo, hydroxo, aqua, tetrahydrofuran, ethylene glycol dimethyl ether, acetonitrile, oxo, peroxo, carbonyl, carbonate, oxalato, acetato, ethanolato, 1-butanethiolato, acetylacetate. Nato, 2,2,6,6-tetramethyl-3,5-
Heptanedionate, trifluoroacetylacetonate, hexafluoroacetylacetonate, ethylacetoacetonate, thiocyanate, isothiocyanato, diethyldithiocarbamate, di-n-butyldithiocarbamate, cyano, amine, dimethylamine, diethylamine, tetraethylammonium, ethylenediamine, N , N, N ′, N′-tetramethylethylenediamine, 1,2-diaminocyclohexane, ethylenediaminetetraacetate, 1,4,8,11-tetraazacyclotetradecane, tris (2-aminoethyl) amine, sulfato, nitro , Nitrito, phosphate, diisopropyldithiophosphate, diethyldithiophosphate, triethylphosphine, tributylphosphine, tricyclohexylphosphine, Kurookuten, 1,5-cyclooctadiene, bicyclo [2.2.1] hepta-2,5-diene, allyl, and the like.

More preferable examples of the ligand include acetate, acetylacetonato, hexafluoroacetylacetonate, thiocyanate, diethyldithiocarbamate, and di-n-butyldithiocarbamate.
Further, as described later, a dye containing a group capable of complexing with a metal atom can be used as a ligand.

Furthermore, as the metal complex compound [B] other than the above, a metal complex compound having the following cation moiety can be used. The counter-anion species is not particularly limited, but any one selected from Cl ⁻ , Br ⁻ , I ⁻ , ClO ₄ ⁻ , PF ₆ ⁻ , BF ₄ ⁻ , SO ₄ ²⁻ , and CF ₂ SO ₃ ^−.
Species are preferred.

<Metal complex dye>
The metal complex compound [B] of the present invention is particularly preferably a metal complex dye obtained by complexing a dye molecule containing a group capable of complexing with a metal atom in the molecule with the metal atom. Among these, the ligand is preferably an azo dye, and the central metal is preferably chromium or cobalt.
Such a metal complex dye not only has excellent resistance, but also has excellent color characteristics due to the fact that the spectral spectrum is yellow to red, so that there is little decrease in brightness when combined with the naphtholazo pigment [A]. can do.

  Examples of the metal complex dye include a 1: 1 type metal complex dye in which the bond ratio between the metal atom and the dye molecule is 1: 1, and a 1: 2 type metal complex dye in which the ratio is 1: 2. A 1: 2 form metal complex dye is preferred.

Examples of the metal complex dye include C.I. I. Solvent Yellow 13, 19, 21, 25, 25: 1, 62, 79, 81, 82, 83, 83: 1, 88, 89, 90, 151, 161, C.I. I. Solvent Orange 5, 11, 20, 40: 1, 41, 45, 54, 56, 58, 62, 70, 81, 99, C.I. I. Solvent Red 8, 35, 83: 1, 84: 1, 90, 90: 1, 91, 92, 118, 119, 122, 124, 125, 127, 130, 132, 160, 208, 212, 214, 225, 233, 234, 243; C.I. I. Solvent Violet 2, 21, 21: 1, 46, 49, 58, 61; I. Solvent Blue 137; C.I. I. Solvent Brown 28, 42, 43, 44, 53, 62, 63; C.I. I. Acid Yellow 59, 121; C.I. I. Acid Orange 74, 162; C.I. I. Acid Red 211 is exemplified.
These metal complex dyes may be used alone or in combination of two or more.

  Among these, C.I. from the viewpoint of suppressing the fluorescence emission of the naphtholazo pigment [A]. I. Solvent Yellow 21, 79, 81, 82, 151, C.I. I. Solvent Orange 41, 45, 54, 56, 62, 99, C.I. I. Solvent Red 8, 118, 122, 127 are preferable, and C.I. I. Solvent oranges 41, 45, 56, 62 and 99 are particularly preferred.

  The most preferable form of the metal complex dye [B] is a compound represented by the following general formula (11), a compound represented by the following general formula (12), or a compound represented by the following general formula (13). Preferably there is.

[Compound represented by formula (11)]

[In General Formula (11), R _{510 to} R ₅₂₇ each independently represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 8 carbon atoms, a nitro group, —SO ₂ NHR ₅₃₀ , —SO ₃ H or —SO ₂ CH ₃ represents a halogen group.
R ₅₂₈ and R ₅₂₉ each independently represent a hydrogen atom, a methyl group or an ethyl group, —SO ₂ NHR ₅₃₀ , —SO ₃ H or —SO ₂ CH ₃ , or a halogen group.
R ₅₃₀ each independently represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 8 carbon atoms, or 2 carbon atoms.
Represents an alkoxyalkyl group of ˜15.
A _{1 to} A ₄ each independently represent * —O—, * —O—CO—, or * —CO—O—.
* Represents a bond with M.
M represents Cr or Co.
n represents an integer of 1 to 5.
D ⁺ represents hydrone and a monovalent metal cation. ]

Examples of the monovalent saturated hydrocarbon group having 1 to 8 carbon atoms represented by R _{510 to} R ₅₂₇ and R ₅₃₀ include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n -Linear alkyl groups such as hexyl group, n-heptyl group, n-octyl group; isopropyl group, sec-butyl group, tert-butyl group, 1-methylbutyl group, 1,1,3,3-tetramethylbutyl Groups, branched alkyl groups such as 1,5-dimethylhexyl group, 1,6-dimethylheptyl group, 2-ethylhexyl group and 1,1,5,5-tetramethylhexyl group.
It is preferable that at least one of R _{510 to} R ₅₂₇ is a nitro group. By having a nitro group, the spectral concentration of the compound tends to increase.
R ₅₂₈ and R ₅₂₉ are preferably a methyl group or —SO ₃ H.

Examples of the alkoxyalkyl group having 2 to 15 carbon atoms represented by R ₅₃₀ include a methoxymethyl group, a methoxyethyl group, a methoxypropyl group, a methoxybutyl group, a methoxypentyl group, a 1-ethoxypropyl group, a 2-ethoxypropyl group, 1-ethoxy-1-methylethyl group, 2-ethoxy-1-methylethyl group, 1-isopropoxypropyl group, 2-isopropoxypropyl group, 1-isopropoxy-1-methylethyl group, 2-isopropoxy- Examples include 1-methylethyl group, octyloxypropyl group, 3-ethoxypropyl group, 3- (2-ethylhexyloxy) propyl group and the like.

In the general formula (11), preferred combinations of groups other than D are as follows. That is, one of R _{510 to} R ₅₁₈ is a hydrogen atom or a nitro group, and one is one selected from a hydrogen atom, SO ₂ NHR ₅₃₀ , —SO ₃ H, —SO ₂ CH ₃ , and a halogen group. The rest are hydrogen atoms,
One of R _{519 to} R ₅₂₇ is a hydrogen atom or a nitro group, one is one selected from a hydrogen atom, SO ₂ NHR ₅₃₀ , —SO ₃ H, —SO ₂ CH ₃ , and a halogen group, and the rest Is a hydrogen atom,
R ₅₂₈ and R ₅₂₉ are a methyl group or —SO ₃ H;
R ₅₃₀ is a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 4 carbon atoms, or an alkoxyalkyl group having 2 to 8 carbon atoms,
Two of A _{1 to} A ₄ are * —O—, and the rest are the same * —O— or * —O—CO—,
M is Cr,
A combination in which n is 1 is preferable.

  Examples of such a metal complex dye represented by the general formula (11) include C.I. I. Solvent Red 130, C.I. I. Solvent Orange 41, C.I. I. Solvent orange 62 etc. are mentioned.

[Compound represented by formula (12)]

[In General Formula (12), R _{60 to} R ₆₈ are each independently a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, a nitro group, —SO ₂ NHR ₆₄₁ , —SO ₃ H. or -SO ₂ CH _3, a halogen radical.
R ₆₉ each independently represents a hydrogen atom, a methyl group or an ethyl group, —SO ₂ NHR ₆₄₁ , —SO ₃ H or —SO ₂ CH ₃ , or a halogen group.
R ₆₄₁ each independently represents a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, or an alkoxyalkyl group having 2 to 15 carbon atoms.
A ₅ and A ₆ each independently represent * —O—, * —O—CO— or * —CO—O—.
* Represents a bond with M1.
M1 represents Cr or Co.
n1 represents the integer of 0-2.
D1 ⁺ represents hydrone and a monovalent metal cation. ]

Examples of the monovalent saturated hydrocarbon group having 1 to 8 carbon atoms represented by R _{60 to} R ₆₈ and R ₆₄₁ include a methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n -Linear alkyl groups such as hexyl group, n-heptyl group, n-octyl group; isopropyl group, sec-butyl group, tert-butyl group, 1-methylbutyl group, 1,1,3,3-tetramethylbutyl Groups, branched alkyl groups such as 1,5-dimethylhexyl group, 1,6-dimethylheptyl group, 2-ethylhexyl group and 1,1,5,5-tetramethylhexyl group.
It is preferable that at least one of R _{60 to} R ₆₈ is a nitro group. By having a nitro group, the spectral concentration of the compound tends to increase.

Examples of the alkoxyalkyl group having 2 to 15 carbon atoms represented by R ₆₄₁ include a methoxymethyl group, a methoxyethyl group, a methoxypropyl group, a methoxybutyl group, a methoxypentyl group, a 1-ethoxypropyl group, a 2-ethoxypropyl group, 1-ethoxy-1-methylethyl group, 2-ethoxy-1-methylethyl group, 1-isopropoxypropyl group, 2-isopropoxypropyl group, 1-isopropoxy-1-methylethyl group, 2-isopropoxy- Examples include 1-methylethyl group, octyloxypropyl group, 3-ethoxypropyl group, 3- (2-ethylhexyloxy) propyl group and the like.

In the general formula (12), preferred combinations of groups other than D1 are as follows. That is, one of R _{60 to} R ₆₈ is a nitro group, and one is SO ₂ NHR ₆₄₁ or —SO ₃ H.
, And SO ₂ CH ₃ , one selected from a halogen group, the remaining is a hydrogen atom, R ₆₉ is a methyl group,
R ₆₄₁ is a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 4 carbon atoms, or an alkoxyalkyl group having 2 to 8 carbon atoms,
One of A _{5 to} A ₆ is * -O-, the rest is * -O- or * -O-CO-,
M1 is Cr or Co;
n1 is preferably a combination of 0 or 1.

  Examples of such a metal complex dye represented by the general formula (12) include C.I. I. Solvent orange 56 etc. are mentioned.

[Compound represented by formula (13)]

[In the general formula (13), R ₇₀ represents a monovalent saturated hydrocarbon group having 1 to 12 carbon atoms, hydrogen atoms contained in the saturated hydrocarbon group, -OH, -OR _77, -CO- OR ₇₇ , —O—COR ₇₇ , —CONR ₇₇ R ₇₈ , a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, or —CH contained in the saturated hydrocarbon group, optionally substituted with a halogen atom ₂ — may be replaced by at least one of —O— and —CO—.
R ₇₁ represents a hydrogen atom, —CN, or —CONH ₂ .
R ₇₂ represents an alkyl group having 1 to 4 carbon atoms which may be substituted with a halogen atom.
R _{73 to} R ₇₆ are, independently of each other, —R ₇₇ , —OR ₇₇ , —CO—OR ₇₇ , —COR ₇₇ , —OCO—OR ₇₇ , —O—COR ₇₇ , —CN, —NO ₂ , halogen atom , -SO ₃ H, -SO ₃ N
a, represents the _{-SO 3 K, -SO 2 NR 77} R 78 or -NR ₇₉₂ R _793. R ₇₃ and R ₇₄ , R ₇₄ and R ₇₅ , and R ₇₅ and R ₇₆ may be bonded to each other to form a 6 to 7 membered ring containing a benzene ring carbon.
R ₇₇ and R ₇₈ are each independently a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or a monovalent aromatic group having 6 to 10 carbon atoms. Represents a hydrocarbon group, and a hydrogen atom contained in the aliphatic hydrocarbon group, the aralkyl group and the aromatic hydrocarbon group may be substituted with —OR ₇₉ .
R ₇₉ represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 8 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms.
R ₇₉₂ and R ₇₉₃ each independently represent a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, an acyl group having 2 to 8 carbon atoms, or a tetrahydrofurfuryl group. R ₇₉₂ and R ₇₉₃ may combine with each other to form a ring containing a nitrogen atom.
A _{7 to} A ₁₀ each independently represent * —O—, * —O—CO—, or * —CO—O—. *
Represents a bond with M2.
M2 represents Cr or Co.
n2 represents an integer of 1 to 5.
D2 ⁺ represents hydrone and a monovalent metal cation. ]

The monovalent saturated hydrocarbon group having 1 to 12 carbon atoms represented by R _70, a methyl group, an ethyl group, n- propyl group, n- butyl group, n- pentyl group, n- hexyl, n- Linear saturated hydrocarbon groups such as heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group;
Isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isopentyl group, methylpentyl group, ethylbutyl group, methylhexyl group, ethylpentyl group, propylbutyl group, (methylethyl) butyl group, (methylethyl) ( Methyl) propyl, methylheptyl, ethylhexyl, propylpentyl, (methylethyl) pentyl, butylbutyl, (butyl) (methyl) butyl, (dimethylethyl) (butyl) butyl, dimethylpropyl, dimethyl Butyl, (ethyl) (methyl) propyl, dimethylpentyl, (ethyl) (methyl) butyl, dimethylhexyl, (ethyl) (methyl) pentyl, (propyl) (methyl) butyl, (methylethyl) ) (Methyl) butyl group, diethyl butyl group, etc. Chain saturated hydrocarbon group;
Examples thereof include alicyclic saturated hydrocarbon groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, and cyclodecyl group.

Examples of the alkyl group having 1 to 4 carbon atoms represented by R ₇₂ include a linear saturated hydrocarbon group having 4 or less carbon atoms and a branched chain having 4 or less carbon atoms among the groups exemplified for R _70. A saturated saturated hydrocarbon group can be exemplified.

Examples of the monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms represented by R ₇₇ , R ₇₈ , R ₇₉₂ and R ₇₉₃ include those having 8 or less carbon atoms among the above groups exemplified as R _70. It can be illustrated. Furthermore, a vinyl group, a propenyl group, an isopropenyl group, a butenyl group, a 2-methylpropenyl group, and the like are also included.

Examples of the aralkyl group having 7 to 12 carbon atoms in R ₇₇ and R ₇₈ include a benzyl group, a phenylethyl group, a phenylpropyl group, a naphthylmethyl group, and a naphthylethyl group. Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in R ₇₇ , R ₇₈ and R ₇₉ include a phenyl group, a toluyl group, a xylyl group and a naphthyl group.
Examples of the monovalent saturated hydrocarbon group having 1 to 8 carbon atoms represented by R ₇₉ include those having 8 or less carbon atoms among the groups exemplified for R ₇₀ .

Examples of the acyl group having 2 to 8 carbon atoms in R ₇₉₂ and R ₇₉₃ include formyl group, acetyl group, propionyl group, butanoyl group, pentanoyl group, hexanoyl group, heptanoyl group, octanoyl group and the like.

Examples of the saturated hydrocarbon group in which —CH ₂ — is replaced by —O— or —CO— in R ₇₀ include a saturated hydrocarbon group containing an oxo group such as an acetyl group, an oxobutyl group, an oxopentyl group, and an oxohexyl group. A hydrocarbon group;
Fragrance such as phenacyl group, oxo (naphthyl) ethyl group, oxo (hydroxyphenyl) ethyl group, oxo (hydroxynaphthyl) ethyl group, oxo (methoxyphenyl) ethyl group, oxo (phenyl) propyl group, oxo (naphthyl) propyl group An oxo group-containing saturated hydrocarbon group substituted with a group; a saturated hydrocarbon group in which one —CH ₂ — is replaced with —CO—, and the like, and a 2- [2- (acetyloxy) acetoxy] ethyl group, Groups formed by alkyl groups such as 2- (2-ethylhexanoyloxy) ethyl group, 2- [2- (methoxycarbonyl) ethylcarbonyloxy] ethyl group, alkylene groups, and ester bonds;
2-benzoyl alkylene group such as methacryloyloxyethyl group, an aromatic ring, and a group formed by an ester bond; one -CH ₂ such - is replaced by -CO-, one -CH ₂ - is -O A saturated hydrocarbon group replaced by-.

In the general formula (13), a preferable combination of groups other than D2 is
R ₇₀ is an alkyl group having 1 to 4 carbon atoms; a hydroxyalkyl group having 1 to 4 carbon atoms; a group formed by an alkyl group, an alkylene group, and two ester bonds, an alkylene group, an aromatic ring, and one ester Any of the groups formed with the bond,
R ₇₁ is -CN;
R ₇₂ is an alkyl group having 1 to 4 carbon atoms,
Three of the R ₇₃ to R ₇₆ is an R ₇₇ is a hydrogen atom, an R ₇₇ or -NR ₇₉₂ R _793, one is a hydrogen atom remains, R ₇₉₂ and R ₇₉₃ constitute the -NR ₇₉₂ R ₇₉₃ One of them is a hydrogen atom, the other is an acyl group having 2 to 4 carbon atoms,
Two of A _{7 to} A ₁₀ are * —O—, and the rest are the same * —O— or * —O—CO—;
M2 is Cr,
n2 is a combination that becomes 1.

Examples of monovalent metal cations represented by D ⁺ , D1 ⁺ , and D2 ⁺ include lithium cations, sodium cations, and potassium cations.

  Examples of the metal complex dye represented by the general formula (13) include compounds represented by the formulas (13-1) to (13-6).

(Salt forming compound of metal complex dye)
In order to use the metal complex dye of the present invention in an image display device using a color filter that requires high reliability, as a technique for making it more excellent in light resistance and heat resistance, (1) If anionic, quaternary ammonium salt compounds (cationic compounds), tertiary amine compounds, secondary amine compounds, primary amine compounds, etc., and resin components having these functional groups and metal complex dyes are salified. (2) used as a salt-forming compound obtained by salting a metal complex dye and an inorganic acid salt of fatty acid amide, and (3) when the metal complex dye has a sulfonic acid group, Amidation and use as a sulfonic acid amide compound.

[Cationic compound]
When the metal complex dye of this invention is a pigment | dye which has an anionic group, it can use as a form of a salt-forming compound by salt-forming with the compound which has a cationic group. In that case, as the compound having a cationic group, a compound represented by the following general formula (14) can be used.

In General Formula (14), R _{1 to} R ₄ each independently represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group. , R _{1 to} R ₃ may be bonded to each other to form a ring. Y ^- is representative of an inorganic or organic anion. The substituents, alkyl groups, alkenyl groups, and aryl groups mentioned here are those described below.

  Substituents include halogen atoms, alkyl groups, cycloalkyl groups, alkenyl groups, cycloalkenyl groups, alkynyl groups, aryl groups, heterocyclic groups, cyano groups, hydroxyl groups, nitro groups, carboxyl groups, alkoxy groups, aryloxy groups , Silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group (including alkylamino group and anilino group), acylamino group, aminocarbonylamino group, alkoxycarbonyl Amino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl or arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkyl group Or arylsulfinyl group, alkyl or arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, aryl or heterocyclic azo group, imide group, phosphino group, phosphinyl group, phosphinyloxy group, phosphini Examples include a ruamino group and a silyl group. Details are described below.

Halogen atoms (for example, fluorine atom, chlorine atom, bromine atom, iodine atom),
A linear or branched alkyl group (a linear or branched substituted or unsubstituted alkyl group, preferably an alkyl group having 1 to 30 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, t-butyl, n-octyl, 2-chloroethyl, 2-cyanoethyl, 2-ethylhexyl),
A cycloalkyl group (preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms such as cyclohexyl and cyclopentyl, and a multicycloalkyl group such as a bicycloalkyl group (preferably having 5 to 30 carbon atoms). Substituted or unsubstituted bicycloalkyl groups such as, for example, polycyclo [1,2,2] heptan-2-yl, bicyclo [2,2,2] octane-3-yl) and tricycloalkyl groups A group having a structure is preferable, and a monocyclic cycloalkyl group and a bicycloalkyl group are preferable, and a monocyclic cycloalkyl group is particularly preferable.)

A linear or branched alkenyl group (a linear or branched substituted or unsubstituted alkenyl group, preferably an alkenyl group having 2 to 30 carbon atoms, such as vinyl, allyl, prenyl, geranyl, oleyl),
A cycloalkenyl group (preferably a substituted or unsubstituted cycloalkenyl group having 3 to 30 carbon atoms such as 2-cyclopenten-1-yl and 2-cyclohexen-1-yl, and a polycycloalkenyl group such as A bicycloalkenyl group (preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms such as bicyclo [2,2,1] hept-2-en-1-yl, bicyclo [2,2, 2] Oct-2-en-4-yl) and tricycloalkenyl groups, and monocyclic cycloalkenyl groups are particularly preferred.
An alkynyl group (preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, such as ethynyl, propargyl, trimethylsilylethynyl group),

An aryl group (preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms such as phenyl, p-tolyl, naphthyl, m-chlorophenyl, o-hexadecanoylaminophenyl),
Heterocyclic group (preferably a 5- or 7-membered substituted or unsubstituted, saturated or unsaturated, aromatic or non-aromatic, monocyclic or condensed heterocyclic group, more preferably a ring-constituting atom is a carbon atom A heterocyclic group selected from a nitrogen atom and a sulfur atom and having at least one heteroatom of any one of a nitrogen atom, an oxygen atom and a sulfur atom, more preferably a 5- or 6-membered member having 3 to 30 carbon atoms Aromatic heterocyclic groups such as 2-furyl, 2-thienyl, 2-pyridyl, 4-pyridyl, 2-pyrimidinyl, 2-benzothiazolyl), cyano group, hydroxyl group, nitro group, carboxyl group,

An alkoxy group (preferably a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms such as methoxy, ethoxy, isopropoxy, t-butoxy, n-octyloxy, 2-methoxyethoxy),
An aryloxy group (preferably a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms such as phenoxy, 2-methylphenoxy, 2,4-di-t-amylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 2-tetradecanoylaminophenoxy),
A silyloxy group (preferably a silyloxy group having 3 to 20 carbon atoms, for example, trimethylsilyloxy, t-butyldimethylsilyloxy),
Heterocyclic oxy group (preferably a substituted or unsubstituted heterocyclic oxy group having 2 to 30 carbon atoms, wherein the heterocyclic part is preferably the heterocyclic part described above for the heterocyclic group, for example, 1-phenyltetrazole -5-oxy, 2-tetrahydropyranyloxy),

An acyloxy group (preferably a formyloxy group, a substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms, such as formyloxy, acetyloxy Pivaloyloxy, stearoyloxy, benzoyloxy, p-methoxyphenylcarbonyloxy),
A carbamoyloxy group (preferably a substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms such as N, N-dimethylcarbamoyloxy, N, N-diethylcarbamoyloxy, morpholinocarbonyloxy, N, N-di -N-octylaminocarbonyloxy, Nn-octylcarbamoyloxy),
An alkoxycarbonyloxy group (preferably a substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms, such as methoxycarbonyloxy, ethoxycarbonyloxy, t-butoxycarbonyloxy, n-octylcarbonyloxy),
Aryloxycarbonyloxy group (preferably a substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms such as phenoxycarbonyloxy, p-methoxyphenoxycarbonyloxy, pn-hexadecyloxyphenoxycarbonyloxy ),

An amino group (preferably an amino group, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, or a heterocyclic amino group having 0 to 30 carbon atoms); And, for example, amino, methylamino, dimethylamino, anilino, N-methyl-anilino, diphenylamino, N-1,3,5-triazin-2-ylamino),
An acylamino group (preferably a formylamino group, a substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms, such as formylamino, acetyl Amino, pivaloylamino, lauroylamino, benzoylamino, 3,4,5-tri-n-octyloxyphenylcarbonylamino),
Aminocarbonylamino group (preferably a substituted or unsubstituted aminocarbonylamino group having 1 to 30 carbon atoms, such as carbamoylamino, N, N-dimethylaminocarbonylamino, N, N-diethylaminocarbonylamino, morpholinocarbonylamino) ,
An alkoxycarbonylamino group (preferably a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms such as methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, n-octadecyloxycarbonylamino, N-methyl- Methoxycarbonylamino),

Aryloxycarbonylamino group (preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms, such as phenoxycarbonylamino, p-chlorophenoxycarbonylamino, mn-octyloxyphenoxycarbonylamino) ,
Sulfamoylamino group (preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms such as sulfamoylamino, N, N-dimethylaminosulfonylamino, Nn-octylaminosulfonyl amino),
An alkyl or arylsulfonylamino group (preferably a substituted or unsubstituted alkylsulfonylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfonylamino group having 6 to 30 carbon atoms, such as methylsulfonylamino, butyl Sulfonylamino, phenylsulfonylamino, 2,3,5-trichlorophenylsulfonylamino, p-methylphenylsulfonylamino),
Mercapto group,

An alkylthio group (preferably a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms such as methylthio, ethylthio, n-hexadecylthio),
An arylthio group (preferably a substituted or unsubstituted arylthio group having 6 to 30 carbon atoms, such as phenylthio, p-chlorophenylthio, m-methoxyphenylthio),
Heterocyclic thio group (preferably a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms, wherein the heterocyclic part is preferably the heterocyclic part described above for the heterocyclic group, for example, 2-benzothiazolyl Luthio, 1-phenyltetrazol-5-ylthio),
Sulfamoyl group (preferably a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms such as N-ethylsulfamoyl, N- (3-dodecyloxypropyl) sulfamoyl, N, N-dimethylsulfamoyl, N -Acetylsulfamoyl, N-benzoylsulfamoyl, N- (N′-phenylcarbamoyl) sulfamoyl), sulfo group,

An alkyl or arylsulfinyl group (preferably a substituted or unsubstituted alkylsulfinyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfinyl group having 6 to 30 carbon atoms, such as methylsulfinyl, ethylsulfinyl, phenylsulfinyl, p-methylphenylsulfinyl),
An alkyl or arylsulfonyl group (preferably a substituted or unsubstituted alkylsulfonyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfonyl group having 6 to 30 carbon atoms, such as methylsulfonyl, ethylsulfonyl, phenylsulfonyl, p-methylphenylsulfonyl),
Acyl group (preferably formyl group, substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, such as acetyl, pivaloyl, 2-chloroacetyl , Stearoyl, benzoyl, pn-octyloxyphenylcarbonyl),
Aryloxycarbonyl group (preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms such as phenoxycarbonyl, o-chlorophenoxycarbonyl, m-nitrophenoxycarbonyl, pt-butylphenoxycarbonyl) ,

An alkoxycarbonyl group (preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, n-octadecyloxycarbonyl),
A carbamoyl group (preferably a substituted or unsubstituted carbamoyl having 1 to 30 carbon atoms such as carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N, N-di-n-octylcarbamoyl, N- (methyl Sulfonyl) carbamoyl),
An aryl or heterocyclic azo group (preferably a substituted or unsubstituted arylazo group having 6 to 30 carbon atoms, a substituted or unsubstituted heterocyclic azo group having 3 to 30 carbon atoms (the heterocyclic portion is described in the above heterocyclic group) Heterocycles that are preferred), for example, phenylazo, p-chlorophenylazo, 5-ethylthio-1,3,4-thiadiazol-2-ylazo),
An imide group (preferably a substituted or unsubstituted imide group having 2 to 30 carbon atoms such as N-succinimide and N-phthalimide),
A phosphino group (preferably a substituted or unsubstituted phosphino group having 2 to 30 carbon atoms, such as dimethylphosphino, diphenylphosphino, methylphenoxyphosphino),
A phosphinyl group (preferably a substituted or unsubstituted phosphinyl group having 2 to 30 carbon atoms, such as phosphinyl, dioctyloxyphosphinyl, diethoxyphosphinyl),

A phosphinyloxy group (preferably a substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms, such as diphenoxyphosphinyloxy, dioctyloxyphosphinyloxy),
A phosphinylamino group (preferably a substituted or unsubstituted phosphinylamino group having 2 to 30 carbon atoms, such as dimethoxyphosphinylamino, dimethylaminophosphinylamino),
Examples thereof include a silyl group (preferably a substituted or unsubstituted silyl group having 3 to 30 carbon atoms such as trimethylsilyl, t-butyldimethylsilyl, and phenyldimethylsilyl).

  Among the above functional groups, those having a hydrogen atom may have a hydrogen atom portion in the functional group substituted with any of the above groups. Examples of functional groups that can be introduced as a substituent include an alkylcarbonylaminosulfonyl group, an arylcarbonylaminosulfonyl group, an alkylsulfonylaminocarbonyl group, and an arylsulfonylaminocarbonyl group. Specifically, methylsulfonylaminocarbonyl, Examples include p-methylphenylsulfonylaminocarbonyl, acetylaminosulfonyl, and benzoylaminosulfonyl groups.

  A preferred form of the compound represented by the general formula (14) (quaternary ammonium salt compound) is colorless or white. Here, colorless or white means a so-called transparent state, and is defined as a state in which the transmittance is 95% or more, preferably 98% or more in the entire wavelength region of 400 to 700 nm in the visible light region. Is. That is, it is necessary not to inhibit color development of the dye component and to cause no color change.

The molecular weight of the cation moiety serving as a counter for the quaternary ammonium salt compound is preferably in the range of 190 to 900. Here, the cation moiety corresponds to the (NR ₁ R ₂ R ₃ R ₄ ) ⁺ moiety in the following general formula (14). When the molecular weight is smaller than 190, light resistance and heat resistance are lowered, and the solubility in a solvent may be further lowered. On the other hand, when the molecular weight is larger than 900, the ratio of the coloring component in the molecule is lowered, so that the color developability is lowered and the lightness is also lowered. More preferably, the molecular weight of the cation moiety is in the range of 240 to 850, and particularly preferably in the range of 350 to 800.
Here, the molecular weight was calculated based on the structural formula. The atomic weight of C was 12, the atomic weight of H was 1, and the atomic weight of N was 14.

The solubility with respect to a solvent becomes favorable because the number of C of the side chain of at least 2 or more of R < ¹ > -R < ⁴ > in General formula (14) shall be 5-20. When R ^{1 to} R ⁴ have 3 or more alkyl groups having a C number smaller than 5, the solubility in a solvent is deteriorated, and coating film foreign matter is likely to be generated. Further, if an alkyl group having a C number exceeding 20 is present in the side chain, the color forming property of the salt-forming compound may be impaired.

The Y-component constituting the anion of the quaternary ammonium salt compound may be an inorganic or organic anion, but is preferably a halogen, more preferably chlorine.

Specific examples of such quaternary ammonium salt compounds include tetramethylammonium chloride (with a molecular weight of the cation moiety of 74), tetraethylammonium chloride (with a molecular weight of the cation moiety of 122), and monostearyltrimethylammonium chloride (with a molecular weight of the cation moiety). 312), distearyldimethylammonium chloride (cation part molecular weight 550), tristearyl monomethylammonium chloride (cation part molecular weight 788), cetyltrimethylammonium chloride (cation part molecular weight 284), trioctylmethylammonium chloride ( The molecular weight of the cation moiety is 368), dioctyldimethylammonium chloride (the molecular weight of the cation moiety is 270), monolauryltrimethyla Monium chloride (cation part molecular weight 228), dilauryldimethylammonium chloride (cation part molecular weight 382), trilaurylmethylammonium chloride (cation part molecular weight 536), triamylbenzylammonium chloride (cation part molecular weight 318), trihexylbenzylammonium chloride (cation part molecular weight 360), trioctylbenzylammonium chloride (cation part molecular weight 444), trilaurylbenzylammonium chloride (cation part molecular weight 612), benzyldimethylstearylammonium chloride (Molecular weight of the cation moiety is 388) and benzyldimethyloctyl ammonium chloride (molecular weight of the cation moiety is 248) , Or dialkyl (alkyl C ₁₄ -C ₁₈₎ dimethyl ammonium chloride (hydrogenated tallow) (molecular weight of the cationic moiety is from 438 to 550) is preferably used and the like.

As products, Cotamin 24P, Cotamin 86P Conch, Cotamin 60W, Cotamin 86W, Cotamin D86P, Sanizole C, Sanizole B-50, etc. manufactured by Kao Corporation, Lion Corporation's Arcade 210-80E, 2C-75, 2HT-75, 2HT flakes, 2O-75I, 2HP-75 or 2HP flakes and the like, among others QUARTAMIN D86P (distearyldimethylammonium chloride), or Arquad 2HT-75 (di (alkyl C ₁₄ -C ₁₈₎ dimethyl ammonium chloride) Etc. are preferable.

[Acrylic resin containing cationic group structural unit]
Moreover, you may use the acrylic resin containing cationic group structural units, such as a quaternary ammonium salt, as a compound which has a cationic group. The acrylic resin containing a cationic group structural unit is an acrylic resin prepared by copolymerizing an ethylenically unsaturated monomer having an ammonium base or an ethylenically unsaturated monomer having an amino group as a monomer component.

  The ethylenically unsaturated monomer suitable for preparing the acrylic resin containing the cationic group structural unit of the present invention is shown below. In addition, in this specification, when showing either or both of "acryl, methacryl", it may describe as "(meth) acryl". Similarly, when one or both of “acryloyl and methacryloyl” are indicated, it may be described as “(meth) acryloyl”.

[Ethylenically unsaturated monomer having ammonium base]
Examples of the ethylenically unsaturated monomer having an ammonium base include (meth) acryloyloxyethyltrimethylammonium chloride, (meth) acryloyloxyethyltriethylammonium chloride, (meth) acryloyloxyethyldimethylbenzylammonium chloride, and (meth) acryloyl. Alkyl (meth) acrylate quaternary ammonium salts such as oxyethylmethylmorpholino ammonium chloride, (meth) acryloylaminopropyltrimethylammonium chloride, (meth) acryloylaminoethyltriethylammonium chloride, (meth) acryloylaminoethyldimethylbenzylammonium chloride Alkyl (meth) acryloylamide quaternary ammonium salts such as dimethyl Allyl ammonium methyl sulfate, trimethyl vinyl phenyl ammonium chloride.

[Ethylenically unsaturated monomer having amino group]
Examples of the ethylenically unsaturated monomer having an amino group include dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dipropylaminoethyl (meth) acrylate, diisopropylaminoethyl (meth) acrylate, and dibutylamino. Ethyl (meth) acrylate, diisobutylaminoethyl (meth) acrylate, di-t-butylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylamide, diethylaminopropyl (meth) acrylamide, dipropylaminopropyl (meth) acrylamide, diisopropyl Aminopropyl (meth) acrylamide, dibutylaminopropyl (meth) acrylamide, diisobutylaminopropyl (meth) acrylamide, di-t-butyl Examples include (meth) acrylic acid esters having a dialkylamino group such as minopropyl (meth) acrylamide or (meth) acrylamide, and styrenes having a dialkylamino group such as dimethylaminostyrene and dimethylaminomethylstyrene, diallylmethylamine, diallylamine And amino group-containing aromatic vinyl monomers such as N-vinylpyrrolidine, N-vinylpyrrolidone and N-vinylcarbazole.

[Other copolymerizable ethylenically unsaturated monomers]
Other examples of monomers that can be used include (meth) acrylic acid esters, crotonic acid esters, vinyl esters, maleic acid diesters, fumaric acid diesters, itaconic acid diesters, (meth) acrylamides, Vinyl ethers, esters of vinyl alcohol, styrenes, (meth) acrylonitrile and the like are preferable.

The amount of the ammonium base present in the acrylic resin containing the cationic group structural unit is not particularly limited, but the ammonium salt value of the resin is preferably 10 to 200 mgKOH / g, and 20 to 130 mgKOH / g. More preferably.
In order for the ammonium salt value of the resin to satisfy the above range, the preferred content of the structural unit having a quaternary ammonium base is 2-50% by weight out of a total of 100% by weight of the structural units constituting the resin. It is preferable that it is a polymer, More preferably, it is a copolymer containing 10 to 40 weight%.

  The molecular weight of the acrylic resin containing a cationic group structural unit used in the present invention is not particularly limited, but the converted weight average molecular weight measured by gel permeation chromatography (GPC) is 1,000 to 500,000. It is preferable that it is 3,000 to 15,000.

  Moreover, it is preferable that the acrylic resin containing a cationic group structural unit suitable for the present invention has a property of being dissolved in a solvent widely used for a color filter coloring composition. Thereby, the coating film without a foreign material generation | occurrence | production can be obtained. In particular, it is preferable to dissolve in glycol acetates, especially propylene glycol monomethyl ether acetate.

[Inorganic acid salt of fatty acid amide]
The inorganic acid salt of fatty acid amide in the present invention is a salt-forming compound of fatty acid amide and an inorganic acid such as hydrochloric acid, sulfuric acid, acetic acid or nitric acid. The fatty acid amide is roughly classified into a saturated fatty acid amide, an unsaturated fatty acid amide, and an alkylene bis unsaturated fatty acid amide.
Representative fatty acid amides include lauric acid amide, myristic acid amide, palmitic acid amide, stearic acid amide, isostearic acid amide, ethylhexanoic acid amide, triethylhexanoic acid amide, and the like.
Examples of unsaturated fatty acid amides include succinic acid amide, lindelic acid amide, tuzuic acid amide, palmitooleic acid amide, oleic acid amide, vaccenic acid amide, linoleic acid amide, linolenic acid amide, eleostearic acid amide and arachidonic acid. Amide, nervonic acid amide, erucic acid amide, etc.
Typical alkylene bis-unsaturated fatty acid amides include methylene bissuccinic acid amide, methylene bis-lindelic acid amide, methylene bis-tuzumic acid amide, methylene bispalmitoleic acid amide, methylene bis oleic acid amide, methylene bis vaccenic acid amide, methylene Bislinoleic acid amide, methylene bis linolenic acid amide, methylene bis eleostearic acid amide, methylene bis arachidonic acid amide, methylene bisnerbonic acid amide, methylene biserucic acid amide, etc., or ethylene bissuccinic acid amide, ethylene bis Lindelic acid amide, Ethylene bis tungstate amide, Ethylene bis palmitooleic acid amide, Ethylene bis oleic acid amide, Ethylene bis vaccenic acid amide, Ethylene Bis linoleic acid amide, ethylene bis-linolenic acid amide, ethylene bis Jer osteoprotegerin stearic acid amide ethylene bis arachidonic acid amide, ethylenebis nervonic acid amide, and ethylene bis-erucic acid amide, and the like.
In particular, stearic acid amide, oleic acid amide, erucic acid amide, methylene bis oleic acid amide, ethylene bis oleic acid amide, methylene bis erucic acid amide, and ethylene bis erucic acid amide are preferably used.

(Salt formation of metal complex dyes)
[Salt formation between a metal complex dye and a compound having a cationic group]
The salt-forming compound of a metal complex dye is composed of a solution in which a metal complex dye is dissolved, a compound having a cationic group stirred or vibrated, or a solution in which a metal complex dye is dissolved and a compound having a cationic group. A salt-forming compound can be easily obtained by mixing the solution with stirring or vibration. In the solution, when the anionic group of the solution in which the metal complex dye is dissolved and the cationic group of the compound having a cationic group are ionized and these are ionically bonded, and the ion-bonded portion becomes water-insoluble, A salt-forming compound is precipitated. In that case, a salt composed of a counter anion of a compound having a cationic group and a counter cation of a metal complex dye is water-soluble, and therefore can be removed by washing or the like. As the compound having a cationic group and the dye having an anionic group (having fluorescence), only a single kind or a plurality of kinds having different structures may be used.
When the salt-forming compound does not precipitate, the solution is appropriately dropped in a large amount of poor solvent to obtain a precipitate. The precipitate is washed with water to remove a salt composed of a counter anion of a compound having a cationic group and a counter cation of a metal complex dye. As the compound having an anionic group and the metal complex dye to be used, only a single type or a plurality of types having different structures may be used.

The metal complex dye salt compound is a mixture of a compound having a cationic group and a metal complex dye in an aqueous solution to remove a salt composed of a counter anion of the compound having a cationic group and a counter cation of the metal complex dye. It is preferable from the viewpoint of heat resistance and storage stability. When a by-product (for example, NaCl) generated by salt formation exists in the salt-forming compound, the salt-forming compound may precipitate over time in the colored composition.

As a solution used at the time of salt formation, a mixed solution of water and a water-soluble organic solvent may be used as a solvent for dissolving the compound having a cationic group and the metal complex dye (BX). Examples of the water-soluble organic solvent include methanol, ethanol, n-propanol, isopropanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, n-butanol, isobutanol, 2- (methoxymethoxy) ethanol, 2- Butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, ethylene glycol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene Glycol, propylene glycolic monomethyl ether acetate, dipropylene glycol, dipropylene glycol Monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol, triethylene glycol monomethyl ether, polyethylene glycol, glycerin, tetraethylene glycol, dipropylene glycol, acetone, diacetone alcohol, aniline, pyridine, ethyl acetate, isopropyl acetate, methyl ethyl ketone , N, N-dimethylformamide, dimethyl sulfoxide, tetrahydrofuran (THF), dioxane, 2-pyrrolidone, 2-methylpyrrolidone, N-methyl-2-pyrrolidone, 1,2-hexanediol, 2,4,6-hexanetriol , Tetrafurfuryl alcohol, 4-methoxy-4-methylpentanone and the like.
These water-soluble organic solvents are preferably used in an amount of 5 to 90% by weight, and most preferably 5 to 20% by weight, based on the total weight (100% by weight) of the aqueous solution.

  The ratio of the compound having a cationic group to the metal complex dye is such that the molar ratio of the total cationic unit of the compound having a cationic group to the total anionic group of the metal complex dye is in the range of 10/1 to 1/4. If it exists, the salt-forming compound of the metal complex dye of this invention can be adjusted suitably, and if it is the range of 2/1-1/2, it is more preferable.

[Salt formation between metal complex dyes and fatty acid amide inorganic acid salts]
In order to prepare a salt-forming compound of a metal complex dye and an inorganic acid salt of fatty acid amide, it is necessary to first obtain an inorganic acid salt of fatty acid amide by reacting the fatty acid amide with an inorganic acid. As the inorganic acid, any one selected from hydrochloric acid, acetic acid, nitric acid and the like is preferable, and hydrochloric acid is most preferable. This reaction is carried out by adding and mixing an aqueous solution of fatty acid amide or an organic solvent solution containing an aqueous solution containing 1 to 20 moles of hydrogen chloride of fatty acid amide. Moreover, it is preferable to implement reaction at -100-100 degreeC. The reaction time is about 0.1 to 100 hours, and an inorganic acid salt aqueous solution of an aliphatic acid amide or an organic solvent solution can be obtained.
Use the obtained inorganic acid salt aqueous solution of fatty acid amide or organic solvent solution instead of the compound having a cationic group described in “Salt formation between a metal complex dye and a compound having a cationic group”. A salt-forming compound can be easily obtained by the same method except that.
As an example of salt formation between a metal complex dye and an inorganic acid salt of fatty acid amide, C.I. I. The salt formation process of Solvent Red 130 and hydrochloride of erucic acid amide is shown.

<Binder resin>
The binder resin contained in the coloring composition for a color filter of the present invention disperses a colorant, and examples thereof include a thermoplastic resin and a thermosetting resin. The resin is preferably a transparent 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. Moreover, when using with the form of an alkali image development type photosensitive coloring composition, it is preferable to use the alkali-soluble vinyl resin which copolymerized the acidic substituent containing ethylenically unsaturated monomer. In order to further improve the photosensitivity, an active energy ray-curable resin having an ethylenically unsaturated double bond can also be used.

  Examples of the thermoplastic resin include acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, and polyurethane resin. Polyester resins, vinyl resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resins.

  Examples of the thermosetting resin include epoxy resins, benzoguanamine resins, rosin-modified maleic acid resins, rosin-modified fumaric acid resins, melamine resins, urea resins, and phenol resins.

  Examples of the vinyl-based alkali-soluble resin copolymerized with an acidic substituent-containing ethylenically unsaturated monomer include resins having an acidic substituent such as a carboxyl group and a sulfone group. Specific examples of the alkali-soluble resin include an acrylic resin having an acidic substituent, an α-olefin / (anhydrous) maleic acid copolymer, a styrene / styrene sulfonic acid copolymer, an ethylene / (meth) acrylic acid copolymer, Or an isobutylene / (anhydrous) maleic acid copolymer etc. are mentioned. Among them, at least one resin selected from an acrylic resin having an acidic substituent and a styrene / styrene sulfonic acid copolymer, particularly an acrylic resin having an acidic substituent, is preferably used because of its high heat resistance and transparency. It is done.

  Examples of the active energy ray-curable resin having an ethylenically unsaturated double bond include resins into which an ethylenically unsaturated double bond has been introduced by the following methods (i) and (ii).

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

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

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

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

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

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

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

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

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

  In addition, from the viewpoint of dispersibility, stability, developability, and heat resistance of the colorant, a carboxyl group that functions as a colorant adsorption group and an alkali-soluble group during development, an aliphatic group that functions as an affinity group for the colorant carrier and the solvent. The balance between the group and the aromatic group is important for the dispersibility of the pigment, the permeability of the developer in the coating film, the solubility of the developer in the uncured part, and the durability, and a resin having an acid value of 20 to 300 mgKOH / g. It is preferable to use it. When the acid value is less than 20 mgKOH / g, the solubility in the developing solution is poor and it is difficult to form a fine pattern. If it exceeds 300 mgKOH / g, a fine pattern may not remain.

  The resin is preferably used in an amount of 30 parts by weight or more based on 100 parts by weight of the total weight of the colorant because the film formability and various resistances are good, 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 500 parts by weight or less. More preferably 30 to 400 parts by weight. More preferably, it is 30-300 weight part. The chromaticity region can be expanded by such a composition ratio of the pigment.

"Organic solvent"
In the coloring composition of the present invention, the colorant is sufficiently dispersed and permeated in the colorant carrier, and is applied on 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 good applicability of the coloring composition, solubility of each component of the coloring composition, and safety.

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

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

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

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

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

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

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

Examples of the photopolymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- Hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1 − [
Acetophenone compounds such as 4- (4-morpholinyl) phenyl] -1-butanone or 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one; benzoin, benzoin methyl ether Benzoin compounds such as benzoin ethyl ether, benzoin isopropyl ether or benzyldimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyl Benzophenone compounds such as diphenyl sulfide or 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methyl Thioxanthone compounds such as thioxanthone, isopropylthioxanthone, 2,4-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- (naphth-1-yl) -4,6- Bis (trichloromethyl) -s-triazine, 2- (4-methoxy-naphth-1-yl) -4,6-bis (trick Triazine compounds such as (romethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, or 2,4-trichloromethyl- (4′-methoxystyryl) -6-triazine; -Octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], or O- (acetyl) -N- (1-phenyl-2-oxo-2- (4'-methoxy- Oxime ester compounds such as naphthyl) ethylidene) hydroxylamine; phosphine compounds such as bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide or 2,4,6-trimethylbenzoyldiphenylphosphine oxide; 9,10- Quinone compounds such as phenanthrenequinone, camphorquinone and ethylanthraquinone Borate compounds; carbazole compounds; imidazole compounds; or titanocene compounds.
These photoinitiators can be used individually by 1 type or in mixture of 2 or more types by arbitrary ratios as needed.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

<Amine compound>
Moreover, the coloring composition of this invention can be made to contain the amine compound which has a function which reduces the dissolved oxygen.

  Such amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminobenzoate. Examples include ethyl, 2-ethylhexyl 4-dimethylaminobenzoate, and N, N-dimethylparatoluidine.

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

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

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

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

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

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

《Other additive ingredients》
The coloring composition of the present invention may contain a storage stabilizer in order to stabilize the viscosity with time. Moreover, in order to improve adhesiveness with a transparent substrate, adhesion improving agents, such as a silane coupling agent, can also be contained.

  Examples of storage stabilizers include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid, and methyl ethers thereof, t-butylpyrocatechol, tetraethylphosphine, and tetraphenylphosphine. Organic phosphines, phosphites and the like can be mentioned. The storage stabilizer can be used in an amount of 0.1 to 10 parts by weight with respect to 100 parts by weight of the colorant.

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

<< Method for producing colored composition >>
The coloring composition of the present invention comprises a kneader, a two-roll mill, a coloring agent containing a naphtholazo pigment [A] in a coloring agent carrier such as a binder resin and / or a solvent, preferably together with a dispersion aid. It can be produced by finely dispersing (pigment dispersion) using various dispersing means such as a roll mill, a ball mill, a horizontal sand mill, a vertical sand mill, an annular bead mill, or an attritor. At this time, the metal complex compound [B] may be dispersed in the colorant carrier simultaneously with the colorant, or may be mixed separately in the colorant carrier. That is, the metal complex compound [B] may be added at the stage of preparing the pigment dispersion. Even if it is added later to the prepared pigment dispersion, the same fluorescence quenching effect can be obtained, but from the viewpoint of solubility. It is preferable to add at the stage of adjusting the pigment dispersion.
In addition, when the colorant has high solubility, specifically, it is highly soluble in the solvent to be used, and if it is dissolved by stirring and no foreign matter is confirmed, it is necessary to manufacture by finely dispersing as described above. There is no.

  Moreover, when using as a photosensitive coloring composition (resist material) for color filters, it can prepare as a solvent developing type or an alkali developing type coloring composition. The solvent development type or alkali development type coloring composition includes the pigment dispersion, a photopolymerizable monomer and / or a photopolymerization initiator, and, if necessary, a solvent, other pigment dispersants, additives, and the like. Can be mixed and adjusted. The photopolymerization initiator may be added at the stage of preparing the colored composition, or may be added later to the prepared colored composition.

(Dispersing aid)
When dispersing the colorant in the colorant carrier, a dispersion aid such as a pigment derivative, a resin-type dispersant, or a surfactant may be appropriately contained. Since the dispersion aid has a large effect of preventing reaggregation of the colorant after dispersion, the color composition obtained by dispersing the colorant in the colorant carrier using the dispersion aid has lightness and viscosity stability. Become good.

  Examples of the dye derivative include a compound obtained by introducing a basic substituent, an acidic substituent, or a phthalimidomethyl group which may have a substituent into an organic pigment, anthraquinone, acridone, or triazine. 63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, JP-A-2001-335717, JP-A-2003 128669, JP-A-2004-091497, JP-A-2007-156395, JP-A-2008-094773, JP-A-2008-094986, JP-A-2008-095007, JP-A-2008-195916 Gazettes, Japanese Patent No. 4585781 etc. can be used. These may be used alone or in combination of two or more.

  The content of the pigment derivative is preferably 0.5 parts by weight or more, more preferably 1 part by weight or more, most preferably 3 parts by weight or more with respect to 100 parts by weight of the colorant from the viewpoint of improving dispersibility. 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.

  The resin-type dispersant has a colorant-affinity part having the property of adsorbing to the colorant and a part compatible with the colorant carrier, and adsorbs to the colorant to disperse the colorant to the colorant carrier. It works to stabilize. Specific examples of resin-type dispersants include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acid alkylamine salts. , Polysiloxane, long-chain polyaminoamide phosphate, hydroxyl group-containing polycarboxylic acid ester, modified products thereof, amides formed by reaction of poly (lower alkyleneimine) and polyester having a free carboxyl group, and salts thereof Oil-soluble dispersants such as, (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone, etc. Resin, water-soluble polymer, polyester, modified poly Acrylate-based, ethylene oxide / propylene oxide addition compound, phosphate ester-based and the like are used, they can be used alone or in admixture of two or more, not necessarily limited thereto.

  Commercially available resin-type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, and 170 manufactured by Big Chemie Japan. 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150, 2155, or Anti-Terra-U, 203, 204, or BYK -SOLPERSE-3000, 9000, 13000, 13240, 13650, 13940, 160 manufactured by Nippon Lubrizol Corporation, such as P104, P104S, 220S, 6919, or Lactimon, Lactimon-WS or Bykumen, etc. 0, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500, etc., BASF EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320 , 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554 1101,120,150,1501,1502,1503, etc., Ajinomoto Fine-Techno Co., Ltd. of AJISPER PA111, PB711, PB821, PB822, PB824, and the like.

  Surfactants include sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkyl naphthalene sulfonate, sodium alkyl diphenyl ether disulfonate Anionic surfactants such as lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate; Polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene Nonionic surfactants such as alkyl ether phosphates, polyoxyethylene sorbitan monostearate and polyethylene glycol monolaurate; chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; alkyldimethylamino Examples include amphoteric surfactants such as alkylbetaines such as betaine acetate and alkylimidazolines, and these can be used alone or in admixture of two or more, but are not necessarily limited thereto.

  When a resin-type dispersant and a surfactant are added, the amount is preferably 0.1 to 55 parts by weight, more preferably 0.1 to 45 parts by weight with respect to 100 parts by weight of the colorant. When the blending amount of the resin-type dispersant and the surfactant is less than 0.1 parts by weight, it is difficult to obtain the added effect. When the content is more than 55 parts by weight, the dispersion is affected by an excessive dispersant. May affect.

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

《Color filter》
Next, the color filter of the present invention will be described.
The color filter of the present invention is a color filter comprising at least one filter segment formed from the coloring composition for a color filter of the present invention.
The color filter comprises at least one red filter segment, at least one green filter segment, and at least one blue filter segment, and the at least one red filter segment is a red coloring composition for a color filter of the present invention. It is preferable to use a product. The color filter may further include a magenta filter segment, a cyan filter segment, and a yellow filter segment.

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

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

  In addition, C.I. I. Purple pigments such as CI Pigment Violet 23, C.I. I. A metal lake pigment of a rhodamine dye such as CI Pigment Red 81, 81: 1, 81: 2, 81: 3, 81: 4, 81: 5 can be used in combination. Also, basic dyes exhibiting blue or purple, acidic dyes, salt forming compounds of acidic dyes, and the like can be used.

《Color filter manufacturing method》
The color filter of the present invention can be produced by a printing method or a photolithography method.

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

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

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

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

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

  The color filter is bonded to the counter substrate using a sealant, and after injecting liquid crystal from the injection port provided in the seal part, the injection port is sealed, and if necessary, a polarizing film or a retardation film is placed outside the substrate. A liquid crystal display panel is manufactured by bonding.

  Such liquid crystal display panels include twisted nematic (TN), super twisted nematic (STN), in-plane switching (IPS), vertical alignment (VA), and optically convented bend (OCB). It can be used for the liquid crystal display mode that performs colorization using color filters such as

  Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. In the examples, “parts” and “%” represent “parts by weight” and “% by weight”, respectively. “PGMAC” means propylene glycol monomethyl ether acetate.

  Also, a method for measuring the average primary particle diameter of the pigment, a method for identifying the azo pigment, a method for measuring the weight average molecular weight (Mw) of the resin, a method for measuring the acid value of the resin, and a method for measuring the contrast ratio (CR) of the coating film Is as follows.

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

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

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

(Resin acid value)
To 0.5 to 1.0 part of the resin solution, 80 ml of acetone and 10 ml of water are added and stirred to dissolve uniformly, and a 0.1 mol / L KOH aqueous solution is used as a titrant and an automatic titrator (“COM-555”). Titration using Hiranuma Sangyo) and the acid value of the resin solution was measured. Then, the acid value per solid content of the resin was calculated from the acid value of the resin solution and the solid content concentration of the resin solution.

(Contrast ratio of coating film (CR))
The light emitted from the backlight unit for liquid crystal display passes through the polarizing plate, is polarized, passes through the coating film of the colored composition applied on the glass substrate, and reaches the other polarizing plate. At this time, if the polarizing planes of the polarizing plate and the polarizing plate are parallel, the light is transmitted 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 coating film of the colored composition, scattering or the like occurs by the colorant particles, and when a part of the polarization plane is displaced, the polarizing plate is transmitted in parallel. When the polarizing plate is orthogonal, part of the light is transmitted. This transmitted light was measured as the luminance on the polarizing plate, and the ratio between the luminance when the polarizing plates were parallel and the luminance when they were orthogonal was calculated as the contrast ratio.

(Contrast ratio) = (Luminance when parallel) / (Luminance when orthogonal)

Therefore, when scattering occurs due to the colorant in the coating film, the luminance when parallel is reduced and the luminance when orthogonal is increased, the contrast ratio becomes low.

  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. In the measurement, the measurement was performed through a black mask having a 1 cm square hole in the measurement portion.

  Subsequently, the naphthol azo pigment [A] used in Examples and Comparative Examples, other pigments, a method for producing a binder resin, a method for preparing a resin-type dispersant solution, a pigment dispersion, and a green photosensitive coloring composition The method for producing the blue photosensitive coloring composition and the structure of the metal complex compound or dye will be described.

<Method for producing naphtholazo pigment [A]>
(Production of naphtholazo pigment (a-1))
N- [2-chloro-5-trifluoromethylphenyl] -3-hydroxy-2-naphthalenecarboxamide (191 parts) and 25% aqueous sodium hydroxide solution (580 parts) were dissolved in methanol (2000 parts) to prepare a coupler solution.
On the other hand, 125 parts of 3-amino-4-methoxybenzanilide was dispersed in 2000 parts of water, ice was added to adjust the temperature to 5 ° C., 228 parts of 35% aqueous hydrochloric acid solution was added and stirred for 1 hour, and then sodium nitrite 42 The aqueous solution prepared by adding parts to 126 parts of water was added and stirred for 2 hours. An aqueous solution consisting of 581 parts of an 80% aqueous acetic acid solution, 664 parts of a 25% aqueous sodium hydroxide solution, and 734 parts of water was added to form an aqueous diazonium salt solution.
This coupler solution was poured into the 5 ° C. diazonium salt aqueous solution over 30 minutes to carry out a coupling reaction. The pH at this time was 5.4. After stirring for 3 hours and confirming disappearance of the diazonium salt, the mixture was heated to 70 ° C., filtered, washed with water, and dried at 90 ° C. for 24 hours to obtain 307 parts of an azo pigment represented by the formula (A1-1). . As a result of mass spectrometry by TOF-MS, it was identified to be a naphthol azo pigment described by the formula (A1-1).

  Subsequently, a salt milling process was performed. 100 parts of a naphthol azo pigment represented by the formula (A1-1), 1200 parts of sodium chloride and 120 parts of diethylene glycol are charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho), kneaded at 60 ° C. for 6 hours, and salt milling. Processed. The obtained kneaded product was put into 3000 parts of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 97 parts of a refined naphthol azo pigment (a-1) were obtained. The average primary particle size was 43 nm.

(Production of naphtholazo pigment (a-2))
In preparing the coupler solution, instead of 191 parts of N- [2-chloro-5-trifluoromethylphenyl] -3-hydroxy-2-naphthalenecarboxamide, N- [3-trifluoromethylphenyl] -3- The same operation as in the production of the naphthol azo pigment (a-1) was carried out except that 173 parts of hydroxy-2-naphthalenecarboxamide was used to obtain 290 parts of azo compound 2. As a result of mass spectrometry by TOF-MS, it was identified to be a naphthol azo pigment described in formula (A1-2).

  The obtained naphthol azo pigment represented by the formula (A1-2) was subjected to the same salt milling method as the naphthol azo pigment (a-1) to obtain a refined naphthol azo pigment (a-2). The average primary particle size was 42 nm.

(Production of naphtholazo pigment (a-3))
In preparing the diazonium salt solution, 86 parts of 3-amino-4-methoxybenzamide were used instead of 125 parts of 3-amino-4-methoxybenzanilide used in the production of the naphtholazo pigment (a-1). The same operation as in the production of the naphthol azo pigment (a-1) was performed to obtain 269 parts of a naphthol azo pigment described in the formula (A1-3). As a result of mass spectrometry by TOF-MS, it was identified to be a naphthol azo pigment described in formula (A1-3).

  The obtained naphthol azo pigment represented by the formula (A1-3) was subjected to the same salt milling method as the naphthol azo pigment (a-1) to obtain a refined naphthol azo pigment (a-3). The average primary particle size was 45 nm.

(Production of naphtholazo pigment (a-4))
In preparing the coupler solution, instead of 191 parts of N- [2-chloro-5-trifluoromethylphenyl] -3-hydroxy-2-naphthalenecarboxamide, N- [3,5-trifluoromethylphenyl]- 208 parts of 3-hydroxy-2-naphthalenecarboxamide was used, and 86 parts of 3-amino-4-methoxybenzamide were used instead of 125 parts of 3-amino-4-methoxybenzanilide when preparing the diazonium salt solution. Except for the above, the same operation as in the production of the naphthol azo pigment (a-1) was carried out to obtain 285 parts of a naphthol azo pigment described in the formula (A1-7). As a result of mass spectrometry by TOF-MS, it was identified to be a naphthol azo pigment azo compound 7 described in formula (A1-7).

  The obtained naphthol azo pigment represented by the formula (A1-7) was subjected to the same salt milling method as the naphthol azo pigment (a-1) to obtain a refined naphthol azo pigment (a-4). The average primary particle size was 47 nm.

(Production of naphtholazo pigment (a-5))
In preparing the coupler solution, N- [2-chloro-5-trifluoromethylphenyl]
Instead of 191 parts of 3-hydroxy-2-naphthalenecarboxamide, 182 parts of N- [2-fluoro-5-trifluoromethylphenyl] -3-hydroxy-2-naphthalenecarboxamide was used, and a diazonium salt solution In the production, the same operation as in the production of the naphthol azo pigment (a-1) was carried out except that 86 parts of 3-amino-4-methoxybenzamide was used instead of 125 parts of 3-amino-4-methoxybenzanilide. 261 parts of a naphthol azo pigment described in formula (A1-8) were obtained. As a result of mass spectrometry by TOF-MS, it was identified to be a naphthol azo pigment described in formula (A1-8).

  The obtained naphthol azo pigment represented by the formula (A1-8) was subjected to the same salt milling method as the naphthol azo pigment (a-1) to obtain a refined naphthol azo pigment (a-5). The average primary particle size was 42 nm.

(Production of naphtholazo pigment (a-6))
In preparing the diazonium salt solution, 77 parts of 3-amino-4-methylbenzamide were used in place of 125 parts of 3-amino-4-methoxybenzanilide used in the production of the naphtholazo pigment (a-1). The same operation as in the production of the naphthol azo pigment (a-1) was performed to obtain 260 parts of a naphthol azo pigment described in the formula (A1-11). As a result of mass spectrometry by TOF-MS, it was identified to be a naphthol azo pigment described in formula (A1-11).

    The obtained naphthol azo pigment represented by the formula (A1-11) was subjected to a salt milling treatment similar to that for the naphthol azo pigment (a-1) to obtain a refined naphthol azo pigment (a-6). The average primary particle size was 50 nm.

(Production of naphtholazo pigment (a-7))
In preparing the diazonium salt solution, naphtholazo was used except that 154 parts of the following compound (D) was used instead of 125 parts of 3-amino-4-methoxybenzanilide used in the production of the naphtholazo pigment (a-1). The same operation as in the production of the pigment (a-1) was carried out to obtain 334 parts of a naphthol azo pigment described in the formula (A1-14). As a result of mass spectrometry by TOF-MS, it was identified to be naphtholazo described in formula (A1-14).

  The obtained naphthol azo pigment represented by the formula (A1-14) was subjected to a salt milling method similar to that for the naphthol azo pigment (a-1) to obtain a refined naphthol azo pigment (a-7). The average primary particle size was 40 nm.

(Production of naphtholazo pigment (a-8))
In the preparation of the diazonium salt solution, 77 parts of 3-amino-N-methylbenzamide were used instead of 125 parts of 3-amino-4-methoxybenzanilide used in the production of the naphtholazo pigment (a-1). In the same manner as in the production of the naphthol azo pigment (a-1), 259 parts of a naphthol azo pigment described in the formula (A1-16) were obtained. As a result of mass spectrometry by TOF-MS, it was identified to be a naphthol azo pigment described in formula (A1-16).

  The obtained naphthol azo pigment represented by the formula (A1-16) was subjected to the same salt milling method as the naphthol azo pigment (a-1) to obtain a refined naphthol azo pigment (a-8). The average primary particle size was 43 nm.

(Production of naphtholazo pigment (a-9))
In preparing the coupler solution, N- [2-chloro-5-trifluoromethylphenyl]
Instead of 191 parts of -3-hydroxy-2-naphthalenecarboxamide, 167 parts of N- [4- (acetylamino) phenyl] -3-hydroxy-2-naphthalenecarboxamide was used except that naphtholazo pigment (a The same operation as in the production of -1) was performed to obtain 284 parts of a naphthol azo pigment described in the formula (A2-1). As a result of mass spectrometry by TOF-MS, it was identified to be a naphthol azo pigment described in formula (A2-1).

  The obtained naphthol azo pigment represented by the formula (A2-1) was subjected to the same salt milling method as the naphthol azo pigment (a-1) to obtain a refined naphthol azo pigment (a-9). The average primary particle size was 50 nm.

(Production of naphtholazo pigment (a-10))
In preparing the coupler solution, N- [2-chloro-5-trifluoromethylphenyl]
In place of 191 parts of -3-hydroxy-2-naphthalenecarboxamide, 167 parts of N- [4- (acetylamino) phenyl] -3-hydroxy-2-naphthalenecarboxamide was used, and when the diazonium salt solution was prepared. , Except that 117 parts of 3-amino-4-methylbenzanilide was used instead of 125 parts of 3-amino-4-methoxybenzanilide, the same operation as in the production of naphtholazo pigment (a-1) was carried out, and the formula 276 parts of the naphthol azo pigment described in (A2-2) were obtained. As a result of mass spectrometry by TOF-MS, it was identified as a naphthol azo pigment described in formula (A2-2).

  The obtained naphthol azo pigment represented by the formula (A2-2) was subjected to a salt milling treatment similar to that for the naphthol azo pigment (a-1) to obtain a refined naphthol azo pigment (a-10). The average primary particle size was 52 nm.

(Production of naphthol azo pigment (a-11))
In preparing the coupler solution, N- [2-chloro-5-trifluoromethylphenyl]
In place of 191 parts of -3-hydroxy-2-naphthalenecarboxamide, 167 parts of N- [4- (acetylamino) phenyl] -3-hydroxy-2-naphthalenecarboxamide was used, and when the diazonium salt solution was prepared. , Except for using 86 parts of 3-amino-4-methoxybenzamide instead of 125 parts of 3-amino-4-methoxybenzanilide, 246 parts of a naphthol azo pigment described in A2-3) were obtained. As a result of mass spectrometry by TOF-MS, it was identified to be a naphthol azo pigment described in formula (A2-3).

  The obtained naphthol azo pigment represented by the formula (A2-3) was subjected to the same salt milling method as the naphthol azo pigment (a-1) to obtain a refined naphthol azo pigment (a-11). The average primary particle size was 53 nm.

(Production of naphtholazo pigment (a-12))
In preparing the coupler solution, N- [2-chloro-5-trifluoromethylphenyl]
In place of 191 parts of -3-hydroxy-2-naphthalenecarboxamide, 167 parts of N- [4- (acetylamino) phenyl] -3-hydroxy-2-naphthalenecarboxamide was used, and when the diazonium salt solution was prepared. In the same manner as in the production of the naphthol azo pigment (a-1) except that 147 parts of the following chemical formula (15-b) was used instead of 125 parts of 3-amino-4-methoxybenzanilide, the compound represented by the formula (A2 -8) 305 parts of the naphthol azo pigment described in the above was obtained. As a result of mass spectrometry by TOF-MS, it was identified to be a naphthol azo pigment described in formula (A2-8).

  The obtained naphthol azo pigment represented by the formula (A2-8) was subjected to a salt milling method similar to that for the naphthol azo pigment (a-1) to obtain a refined naphthol azo pigment (a-12). The average primary particle size was 49 nm.

(Production of naphtholazo pigment (a-13))
In preparing the coupler solution, N- [2-chloro-5-trifluoromethylphenyl]
Instead of 191 parts of 3-hydroxy-2-naphthalenecarboxamide, 152 parts of N- [2-chloro-5-trifluoromethylphenyl] -3-hydroxy-2-naphthalenecarboxamide, N- [4- (2 -Oxo-2,3-dihydro-1H-benzimidazol-5-yl)]-3-hydroxy-2-naphthalenecarboxamide Same as the preparation of naphtholazo pigment (a-1) except that 33 parts are used. C. is an azo pigment represented by the formula (A1-1) and an azo pigment represented by the general formula (6). I. 302 parts of a mixture with Pigment Red 176 were obtained. As a result of mass spectrometry by TOF-MS, formula (A1-1) and C.I. I. It was confirmed that the mass ratio of the pigment red 176 mixture of naphthol azo pigments was 82.1: 17.9.

  The obtained naphthol azo pigment mixture was subjected to the same salt milling method as that of the naphthol azo pigment (a-1) to obtain a refined naphthol azo pigment (a-13). The average primary particle size was 32 nm.

(Production of naphtholazo pigment (a-14))
Other than using 117 parts of 3-amino-4-methylbenzanilide instead of 125 parts of 3-amino-4-methoxybenzanilide used in the production of the naphtholazo pigment (a-1) when preparing the diazonium salt solution Performed the same operation as in the production of the naphthol azo pigment (a-1) to obtain 299 parts of a naphthol azo pigment described in the formula (A1-17). As a result of mass spectrometry by TOF-MS, it was identified as a naphthol azo pigment described in formula (A1-17).

  The obtained naphthol azo pigment represented by the formula (A1-17) was subjected to the same salt milling method as the naphthol azo pigment (a-1) to obtain a refined naphthol azo pigment (a-14). The average primary particle size was 44 nm.

(Production of naphtholazo pigment (a-15))
In preparing the diazonium salt solution, except that 125 parts of 3-amino-4-methoxybenzanilide used in the production of the naphtholazo pigment (a-1) was used, 109 parts of 3-amino-N-phenylbenzamide were used. In the same manner as in the production of the naphthol azo pigment (a-1), 292 parts of a naphthol azo pigment represented by the formula (A1-23) were obtained. As a result of mass spectrometry by TOF-MS, it was identified to be a naphthol azo pigment described in formula (A1-23).

  The obtained naphthol azo pigment represented by the formula (A1-23) was subjected to the same salt milling method as the naphthol azo pigment (a-1) to obtain a refined naphthol azo pigment (a-15). The average primary particle size was 48 nm.

(Production of naphtholazo pigment (a-16))
In preparing the coupler solution, instead of 191 parts of N- [2-chloro-5-trifluoromethylphenyl] -3-hydroxy-2-naphthalenecarboxamide, N- [3-trifluoromethylphenyl] -3- Except for using 173 parts of hydroxy-2-naphthalenecarboxamide and 117 parts of 3-amino-4-methylbenzanilide instead of 125 parts of 3-amino-4-methoxybenzanilide when preparing the diazonium salt solution Performed the same operation as in the production of naphthol azo pigment (a-1) to obtain 282 parts of a naphthol azo pigment described in formula (A1-24). As a result of mass spectrometry by TOF-MS, it was identified to be a naphthol azo pigment described in formula (A1-24).

  The obtained naphthol azo pigment represented by the formula (A1-24) was subjected to the same salt milling method as the naphthol azo pigment (a-1) to obtain a refined naphthol azo pigment (a-16). The average primary particle size was 41 nm.

(Production of naphtholazo pigment (a-17))
In preparing the coupler solution, instead of 191 parts of N- [2-chloro-5-trifluoromethylphenyl] -3-hydroxy-2-naphthalenecarboxamide, N- [3-trifluoromethylphenyl] -3- Except for using 173 parts of hydroxy-2-naphthalenecarboxamide and 109 parts of 3-amino-N-phenylbenzamide instead of 125 parts of 3-amino-4-methoxybenzanilide when preparing the diazonium salt solution. In the same manner as in the production of the naphthol azo pigment (a-1), 275 parts of a naphthol azo pigment represented by the formula (A1-25) were obtained. As a result of mass spectrometry by TOF-MS, it was identified to be a naphthol azo pigment described in formula (A1-25).

  The obtained naphthol azo pigment represented by the formula (A1-25) was refined naphthol azo pigment (a-17) by the same salt milling method as naphthol azo pigment (a-15). The average primary particle size was 43 nm.

(Production of naphtholazo pigment (a-18))
Naphtholazo red pigment C.I. I. Pigment Red 269 (“Pigment Red 269” manufactured by Tokyo Color Material Industries Co., Ltd.), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. . Next, the kneaded product is put into 8000 parts of warm water, stirred for 2 hours while heating to 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. overnight. A refined naphthol azo pigment (a-18) was obtained. The average primary particle size was 52 nm.

<Method for producing other pigments>
(Production of fine red pigment (PR254-1))
Diketopyrrolopyrrole pigment C.I. I. 200 parts of Pigment Red 254 (“B-CF” manufactured by BASF), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a stainless gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is put into 8000 parts of warm water, stirred for 2 hours while heating to 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. overnight. Diketopyrrolopyrrole-based fine red pigment (PR254-1) was obtained.

(Production of refined red pigment (PR177-1))
Anthraquinone red pigment C.I. I. 200 parts of Pigment Red 177 (“chromophthaled red A2B” manufactured by BASF), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is put into 8000 parts of warm water, stirred for 2 hours while heating to 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. overnight. Anthraquinone-based fine red pigment (PR177-1) was obtained.

(Production of refined red pigment (PR176-1))
Naphtholazo red pigment C.I. I. 200 parts of Pigment Red 176 ("Permanent Carmine H3C" manufactured by BASF), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C for 6 hours. Next, the kneaded product is put into 8000 parts of warm water, stirred for 2 hours while heating to 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. overnight. A naphtholazo-based fine red pigment (PR176-1) was obtained.

(Production of refined red pigment (PO38-1))
Naphtholazo red pigment C.I. I. 200 parts of Pigment Orange 38 (“Grafol Red HFG” manufactured by Clariant), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is put into 8000 parts of warm water, stirred for 2 hours while heating to 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. overnight. A naphtholazo-based fine red pigment (PO38-1) was obtained.

(Miniaturized green pigment (PG58-1))
Phthalocyanine green pigment C.I. I. 200 parts of Pigment Green 58 (“FASTOGEN GREEN A110” manufactured by DIC Corporation), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is put into 8000 parts of warm water, stirred for 2 hours while heating to 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. overnight. A phthalocyanine-based fine green pigment (PG58-1) was obtained.

(Miniaturized yellow pigment (PY150-1))
Nickel complex yellow pigment C.I. I. 200 parts of Pigment Yellow 150 (“E-4GN” manufactured by LANXESS), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a stainless gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is put into 8000 parts of warm water, stirred for 2 hours while heating to 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. overnight. A nickel complex-based fine yellow pigment (PY150-1) was obtained.

(Miniaturized blue pigment (PB15: 6-1))
Phthalocyanine blue pigment C.I. I. Pigment Blue 15: 6 (“LIONOL BLUE ES” manufactured by Toyocolor Co., Ltd., specific surface area 60 m 2 / g) 200 parts, sodium chloride 1400 parts and diethylene glycol 360 parts were charged into a stainless steel 1 gallon kneader (Inoue Seisakusho), 80 The mixture was kneaded at 6 ° C. for 6 hours. Next, the kneaded product is put into 8000 parts of warm water, stirred for 2 hours while heating to 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. overnight. A phthalocyanine-based fine blue pigment (PB15: 6-1) was obtained.

(Miniaturized purple pigment (PV23-1))
Dioxazine-based purple pigment C.I. I. 200 parts of Pigment Violet 23 (“LIONOGEN VIOLET RL” manufactured by Toyocolor Co., Ltd.), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is put into 8000 parts of warm water, stirred for 2 hours while heating to 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. overnight. A dioxazine-based purple refined purple pigment (PV23-1) was obtained.

<Method for producing acrylic resin solution>
(Acrylic resin solution 1)
A reaction vessel equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirrer was charged with 70.0 parts of cyclohexanone, heated to 80 ° C., and the inside of the reaction vessel was purged with nitrogen. 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 Toagosei Co., Ltd.), A mixture of 0.4 part of 2,2′-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was continued for 3 hours to obtain an acrylic resin solution having a weight average molecular weight (Mw) of 26000. After cooling to room temperature, about 2 g of the resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content. Propylene glycol monoethyl was added to the previously synthesized resin solution so that the nonvolatile content was 20% by weight. Acrylic resin solution 1 was prepared by adding ether acetate.

(Acrylic resin solution 2)
A separable four-necked flask equipped with a thermometer, a cooling pipe, a nitrogen gas introduction pipe, a dropping pipe and a stirring device was charged with 370 parts of cyclohexanone, heated to 80 ° C., and the atmosphere in the flask was replaced with nitrogen. 18 parts of milphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.), 10 parts of benzyl methacrylate, 18.2 parts of glycidyl methacrylate, 25 parts of methyl methacrylate, and 2,2′-azobisisobutyronitrile 2.0 Part of the mixture was added dropwise over 2 hours. After dropping, the reaction was further carried out at 100 ° C. for 3 hours, and then 1.0 part of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and the reaction was further continued at 100 ° C. for 1 hour. Next, the inside of the container is replaced with air, and 0.5 part of trisdimethylaminophenol and 0.1 part of hydroquinone are put into 9.3 parts of acrylic acid (100% of glycidyl group) and the container is placed at 120 ° C. The reaction was continued for 6 hours, and when the acid value of the solid content reached 0.5, the reaction was terminated to obtain an acrylic resin solution. Further, 19.5 parts of tetrahydrophthalic anhydride (100% of the generated hydroxyl group) and 0.5 parts of triethylamine were added and reacted at 120 ° C. for 3.5 hours to obtain a solution of an acrylic resin having a weight average molecular weight (Mw) of 19000. Obtained. After cooling to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and cyclohexanone was added to the previously synthesized resin solution so that the nonvolatile content was 20% by weight. Then, an acrylic resin solution 2 which is an active energy ray curable resin was prepared.

<Preparation of resin-type dispersant solution>
A commercially available resin type dispersant, EFKA4300 manufactured by BASF, and ethylene glycol monomethyl ether acetate were used to prepare a 40% by weight non-volatile solution and used as the resin type dispersant solution 1.

<Method for producing pigment dispersion>
(PR254 / Pigment dispersion (PP254-1))
The following mixture was stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. The pigment dispersion (PP254-1) whose non-volatile component is 20 weight% was produced.

Refined red pigment (PR254-1): 12.0 parts Acrylic resin solution 1: 30.0 parts Propylene glycol monomethyl ether acetate (PGMAC): 53.0 parts Resin-type dispersant solution 1: 5.0 parts

(PR177 / Pigment dispersion (PP177-1))
The PR177 / pigment dispersion (PP254-1) was prepared in the same manner as the pigment dispersion (PP254-1) except that the refined red pigment (PR254-1) pigment was changed to PR177-1 in the production method of the pigment dispersion (PP254-1). PP1777-1) was produced.

(PR176 / Pigment dispersion (PP176-1))
PR176 / Pigment in the same manner as the pigment dispersion (PP254-1), except that the refined red pigment (PR254-1) in the method for producing the pigment dispersion (PP254-1) was changed to (PR176-1). A dispersion (PP176-1) was produced.

(PO38 / pigment dispersion (PP38-1))
The PO38 / pigment dispersion is the same as the pigment dispersion (PP254-1) except that the refined red pigment (PR254-1) pigment is changed to (PO38-1) in the method for producing the pigment dispersion (PP254-1). A body (PP38-1) was produced.

(PG58 / Pigment Dispersion (PP58-1))
PG58 / pigment dispersion was the same as pigment dispersion (PP254-1) except that the refined red pigment (PR254-1) pigment was changed to (PG58-1) in the method for producing pigment dispersion (PP254-1). A body (PP58-1) was produced.

(PY150 / Pigment dispersion (PP150-1))
PY150 / Pigment dispersion in the same manner as the pigment dispersion (PP254-1), except that the refined red pigment (PR254-1) pigment was changed to (PY150-1) in the production method of the pigment dispersion (PP254-1). A body (PP150-1) was produced.

(PB15: 6, pigment dispersion (PP15: 6-1))
PB15: In the same manner as the pigment dispersion (PP254-1), except that the refined red pigment (PR254-1) pigment was changed to (PB15: 6-1) in the production method of the pigment dispersion (PP254-1). 6. A pigment dispersion (PP15: 6-1) was prepared.

(PV23 / Pigment Dispersion (PP23-1))
PV23 / pigment dispersion in the same manner as the pigment dispersion (PP254-1) except that the refined red pigment (PR254-1) pigment was changed to (PV23-1) in the production method of the pigment dispersion (PP254-1). A body (PP23-1) was produced.

<Method for producing green and blue photosensitive coloring composition>
(Green photosensitive coloring composition (RG-1))
A mixture having the following composition was stirred and mixed to be uniform, and then filtered through a 1 μm filter to prepare a green photosensitive coloring composition (RG-1).

PG58 / Pigment dispersion (PP58-1): 32.0 parts PY150 / Pigment dispersion (PP150-1): 18.0 parts Acrylic resin solution 1: 7.5 parts Photopolymerizable monomer (manufactured by Toagosei Co., Ltd.) "Aronix M-402"): 2.0 parts dipentaerythritol hexaacrylate photopolymerization initiator ("OXE-02" manufactured by BASF): 1.5 parts Etanone, 1- [9-ethyl-6- (2- Methylbenzoyl) -9H-carbazol-3-yl]-, 1- (0-acetyloxime)
Cyclohexanone: 39.0 parts

(Blue photosensitive coloring composition (RB-1))
A mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to produce a blue photosensitive coloring composition (RB-1).

PB15: 6 · Pigment dispersion (PP15: 6-1): 45.0 parts PV23 · Pigment dispersion (PP23-1): 5.0 parts Acrylic resin solution 1: 7.5 parts Photopolymerizable monomer ( "Aronix M-402" manufactured by Toagosei Co., Ltd.): 2.0 parts photopolymerization initiator ("OXE-02" manufactured by BASF): 1.5 parts cyclohexanone: 39.0 parts

<Metal complex compound or dye structure>
The structure of the metal complex compound or dye used is shown below.
In addition, all the metal complex compounds (B-7 to 13) are metal complex dyes, and the ligand is an azo dye.

<Method for producing metal complex compound>
(Metal complex Cu-1)

  1.1 parts of copper (II) chloride (manufactured by Kanto Chemical) are dissolved in 10 parts of water, and then 2.5 parts of 2,6-dimethyl-3,5-heptanedione (manufactured by Tokyo Chemical Industry) What was dissolved in a portion of methanol was added. Further, 1.3 parts of sodium acetate (manufactured by Kanto Chemical) dissolved in 5 parts of water was added and refluxed for 30 minutes. After cooling, the target product was filtered and washed with water. It was made to dry at 80 degreeC for 24 hours, and 2.3 parts of metal complexes Cu-1 were obtained.

(Metal complex Cu-2)

  0.8 parts of copper (II) chloride (manufactured by Kanto Chemical Co.) is dissolved in 10 parts of water, and then 2.2 parts of 2,2,6,6-tetramethyl-3,5-heptanedione (Tokyo) (Chemical conversion) dissolved in 3 parts of methanol was added. Further, 1.0 part of sodium acetate (manufactured by Kanto Chemical) dissolved in 5 parts of water was added and refluxed for 30 minutes. After cooling, 25 parts of ethyl acetate was added and the organic layer was extracted. The organic layer was washed with 10 parts of water, dried over magnesium sulfate, and evap. The target was obtained. And it dried for 24 hours with the 40 degreeC vacuum dryer. 1.8 parts of metal complex Cu-2 were obtained.

(Metal complex Cu-3)

0.7 parts of copper (II) chloride (manufactured by Kanto Chemical) is dissolved in 5 parts of water, and then 2.3 parts of 1,3-diphenyl-1,3-propanedione (manufactured by Tokyo Chemical Industry Co., Ltd.) What was dissolved in a portion of tetrahydrofuran was added. Further, 0.8 part of sodium acetate (manufactured by Kanto Chemical) dissolved in 5 parts of water was added and refluxed for 30 minutes. After cooling, the target product was filtered and washed with water. It was made to dry at 80 degreeC for 24 hours, and 2.4 parts of metal complexes Cu-3 were obtained.

[Example 1]
(Naphthol azo pigment dispersion (P-1))
The following mixture was stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. The naphthol azo pigment dispersion (P-1) having a non-volatile component of 20% by weight was obtained.

Naphthol azo pigment (a-1): 11.4 parts Metal complex compound (B-1): 0.6 parts Bis (hexafluoroacetylacetonato) Co (II) hydrate acrylic resin solution 1 manufactured by Tokyo Chemical Industry Co., Ltd. 30.0 parts propylene glycol monomethyl ether acetate (PGMAC): 53.0 parts Resin-type dispersant solution 1: 5.0 parts

[Examples 2-32, 34-37, Comparative Examples 1-2]
(Naphthol azo pigment dispersion (P-2 to 32, 34 to 37, 38, 39))
The naphthol azo pigment dispersion (P-1) and the composition of the naphthol azo pigment (a-1) and the metal complex compound (B-1) and the amount (parts by weight) were changed as shown in Table 3. Pigment dispersions (P-2 to 32, 34 to 37, 38, 39) were prepared in the same manner.
In Example 25, the blending amount of the naphthol azo pigment (a-13) is 11.4 parts, and the content of the naphthol azo pigment [A] contained is 9.36 parts.

[Example 33]
(Naphthol azo pigment dispersion (P-33))
The following mixture was stirred and mixed so as to be uniform, and then dispersed with an Eiger mill ("Mini Model M-250 MKII" manufactured by Eiger Japan) for 3 hours using zirconia beads having a diameter of 0.5 mm. To this pigment dispersion, 0.60 part of metal complex compound (B-11) (Valifast Yellow 3180, manufactured by Orient Co., Ltd.) was added, mixed well with stirring, filtered through a 5.0 μm filter, and the non-volatile component was 20 wt. % Naphthol azo pigment dispersion (P-33) was prepared.

Naphthol azo pigment (a-1): 11.4 parts Acrylic resin solution 1: 30.0 parts Propylene glycol monomethyl ether acetate (PGMAC): 53.0 parts Resin-type dispersant solution 1: 5.0 parts

[Evaluation of coloring composition]
<Coating preparation and evaluation>
A red coating film was prepared using the obtained naphtholazo pigment dispersion (P-1 to 35), and the contrast ratio (CR) and heat resistance were evaluated by the following methods. Table 4 shows the evaluation results.

[Evaluation of coloring composition]
<Coating preparation and evaluation>
A red coating film was prepared using the obtained naphtholazo pigment dispersion (P-1 to 39), and the contrast ratio (CR) and heat resistance were evaluated by the following methods. Table 4 shows the evaluation results.

(Contrast ratio)
The pigment dispersion (P-1 to 39) was applied on a glass substrate of 100 mm × 100 mm and 1.1 mm thickness using a spin coater, then dried at 70 ° C. for 20 minutes, and then at 220 ° C. for 60 minutes. The coated substrate was prepared by heating and allowing to cool. The contrast ratio (CR) of the obtained coated substrate was measured. The prepared coated substrate was adjusted to a chromaticity of x = 0.620 with a C light source after heat treatment at 220 ° C.

  In order to compare the quenching effect, the rate of change (= (b) / (a)) was determined from the measured value (a) when no metal complex compound was added and the measured value (b) when added. It can be said that the larger the value of (b) / (a), the greater the effect of fluorescence quenching. The measured value (a) when the metal complex compound [B] is not added is a measured value of the pigment dispersion when the metal complex compound [B] is replaced with a naphthol azo pigment [A].

(Heat resistance evaluation)
The pigment dispersion (P-1 to 39) was applied on a glass substrate of 100 mm × 100 mm and 1.1 mm thickness using a spin coater, then dried at 70 ° C. for 20 minutes, and then at 220 ° C. for 60 minutes. The coated substrate was prepared by heating and allowing to cool. The prepared coated substrate was adjusted to a chromaticity of x = 0.620 with a C light source after heat treatment at 220 ° C. The chromaticity ([L * (1), a * (1), b * (1)]) of the obtained coating film with a C light source was measured with a microspectrophotometer ("OSP-SP100" manufactured by Olympus Optical Co., Ltd.). And measured. Further, as a heat resistance test, the sample was heated at 230 ° C. for 1 hour, and the chromaticity ([L * (2), a * (2), b * (2)]) with a C light source was measured. The color difference ΔE * ab was determined and evaluated in the following three stages.

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 pigment dispersion (P-1 to 39) was applied on a glass substrate of 100 mm × 100 mm and 1.1 mm thickness using a spin coater, then dried at 70 ° C. for 20 minutes, and then at 220 ° C. for 60 minutes. The coated substrate was prepared by heating and allowing to cool. The prepared coated substrate was adjusted to a chromaticity of x = 0.620 with a C light source after heat treatment at 220 ° C. After measuring the chromaticity [L * (1), a * (1), b * (1)] using a microspectrophotometer ("OSP-SP100" manufactured by Olympus), the spectral distribution equivalent to sunlight Using this xenon lamp, an accelerated exposure test at 470 W / m @ 2 was conducted for 200 hours. 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 color change due to light irradiation, and a colored composition with good light resistance. 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

As shown in Table 4, by containing the naphtholazo pigment [A] represented by the general formula (1) and the metal complex compound [B], the fluorescence emission is suppressed and the contrast ratio is greatly improved. It could be confirmed.
In particular, when a metal complex compound in which the central metal of the metal complex compound [B] is chromium (Cr) or cobalt (Co) is used, the color characteristics and the contrast ratio are balanced. In the case of a metal complex compound of an azo dye, excellent results were obtained. In addition, when the ligand is a metal complex compound of an azo dye, which is classified as Solvent Orange (SO) or Solvent Red (SR), the color difference at the time of light resistance evaluation is small, and light resistance is improved. The result was particularly excellent.

  Further, when a metal complex compound whose central metal of the metal complex compound [B] is chromium (Cr), cobalt (Co), or copper (Cu) is used, the contrast ratio is particularly excellent, and the heat resistance is also good. It was a result.

  In addition, the colored compositions for color filters of the present invention were not only high contrast ratios, but also excellent heat resistance and light resistance.

[Example 38]
(Red photosensitive coloring composition (RR-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 red photosensitive coloring composition (RR-1).

(Pigment dispersion) (Total 50 parts)
PR254 pigment dispersion (PP254-1): 25.0 parts naphtholazo pigment dispersion (P-1): 25.0 parts acrylic resin solution 2: 7.5 parts photopolymerizable monomer (Toagosei Co., Ltd.) "Aronix M-402" manufactured): 2.0 parts photopolymerization initiator ("OXE-02" manufactured by BASF): 1.5 parts PGMAC: 39.0 parts

[Examples 39 to 73, Comparative Examples 3 and 4]
(Red photosensitive coloring composition (RR-2 to 38))
A red photosensitive coloring composition (RR-2 to 42) was obtained in the same manner as the red photosensitive coloring composition (RR-1) except that the pigment dispersion was changed to the type of pigment dispersion shown in Table 5. . In each photosensitive coloring composition, a total of 50 parts of the pigment dispersion is divided into x = 0.658 and y = 0.325 when the coating film substrate for evaluating the brightness of each coloring composition is C light source. Thus, the ratio of the pigment dispersion was adjusted to prepare 100 parts of a red photosensitive coloring composition.

[Evaluation of photosensitive coloring composition]
<Coating preparation and evaluation>
The contrast ratio, heat resistance, and light resistance of the coating film prepared using the obtained red photosensitive coloring composition (RR-1 to 42) were evaluated by the following methods. Table 6 shows the evaluation results.

(Contrast ratio)
The red photosensitive coloring composition (RR-1 to 42) was applied onto a 100 mm × 100 mm, 1.1 mm thick glass substrate using a spin coater, and then dried at 70 ° C. for 20 minutes to obtain ultrahigh pressure mercury. Using a lamp, UV exposure was performed with an integrated light amount of 150 mJ / cm ² and development was performed with an alkaline developer at 23 ° C. to obtain a coated substrate. Then, after heating at 220 ° C. for 30 minutes and allowing to cool, the contrast ratio (CR) of the obtained coating film substrate was measured by the same method as the evaluation of the colored composition. The prepared coated substrate was adjusted to a chromaticity of y = 0.600 with a C light source after heat treatment at 220 ° C. The alkali developer was 1.5% by weight of sodium carbonate, 0.5% by weight of sodium hydrogen carbonate, 8.0% by weight of an anionic surfactant (“Perex NBL” manufactured by Kao Corporation), and 90% by weight of water. The thing which consists of was used.

(Lightness evaluation)
The red photosensitive coloring composition (RR-1 to 42) was applied onto a 100 mm × 100 mm, 1.1 mm thick glass substrate using a spin coater, dried at 70 ° C. for 20 minutes, and then further heated to 230 ° C. at 60 ° C. A coated substrate was obtained in which the chromaticity of the substrate obtained by partial heating was such that x = 0.658 and y = 0.325 in a C light source. The brightness (Y) of the obtained substrate was measured with a microspectrophotometer (“OSP-SP200” manufactured by Olympus Optical Co., Ltd.).

(Evaluation of heat resistance of coating film)
The red photosensitive coloring composition (RR-1 to 42) was applied onto a glass substrate of 100 mm × 100 mm and 1.1 mm thickness using a spin coater, then dried at 70 ° C. for 20 minutes, and then 220 ° C. The coated substrate was prepared by heating and cooling for 60 minutes. The prepared coated substrate was adjusted to a chromaticity of x = 0.600 with a C light source after heat treatment at 220 ° C. The chromaticity ([L * (1), a * (1), b * (1)]) of the obtained coating film with a C light source was measured with a microspectrophotometer ("OSP-SP100" manufactured by Olympus Optical Co., Ltd.). And measured. Further, as a heat resistance test, the sample was heated at 230 ° C. for 1 hour, and the chromaticity ([L * (2), a * (2), b * (2)]) with a C light source was measured. The color difference ΔE * ab was determined and evaluated in the following three stages.

ΔE * ab = √ ((L * (2)-L * (1)) ² + (a * (2)-a * (1)) ² + (b * (2)-b * (1)) ² )
A: 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 of coating film)
The red photosensitive coloring composition (RR-1 to 42) was applied onto a glass substrate of 100 mm × 100 mm and 1.1 mm thickness using a spin coater, then dried at 70 ° C. for 20 minutes, and then 220 ° C. The coated substrate was prepared by heating and cooling for 60 minutes. The prepared coated substrate was adjusted to a chromaticity of x = 0.600 with a C light source after heat treatment at 220 ° C. After measuring the chromaticity [L * (1), a * (1), b * (1)] using a microspectrophotometer ("OSP-SP100" manufactured by Olympus), the spectral distribution equivalent to sunlight The accelerated exposure test at 470 W / m ² was performed for 200 hours using the following 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 color change due to light irradiation, and the better the light resistance. 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

  By including the naphtholazo pigment [A] represented by the general formula (1) of the present invention and the specific metal complex compound [B], a high contrast ratio that could not be achieved in the past was achieved. In addition, various properties such as lightness, heat resistance and light resistance were improved, and the colored composition for a color filter of the present invention obtained high-level evaluation results in all evaluations.

  In particular, when a metal complex compound whose central metal is chromium (Cr), cobalt (Co), or copper (Cu) is used, suppression of a decrease in brightness due to the addition of the metal complex compound is observed, and high performance is exhibited. A colored composition was obtained.

<Production of color filter>
The red photosensitive coloring composition (RR-1) of the present invention was applied by spin coating to a glass substrate on which a black matrix was previously formed, and then prebaked at 70 ° C. for 20 minutes in a clean oven. Next, the substrate was cooled to room temperature, and then exposed to ultraviolet rays through a photomask using an ultrahigh pressure mercury lamp.
Thereafter, the substrate was spray-developed with a 0.2 wt% sodium carbonate aqueous solution at 23 ° C. for 30 seconds, washed with ion-exchanged water, and air-dried. Further, post-baking was performed at 230 ° C. for 30 minutes in a clean oven to form a striped colored pixel layer on the substrate.
Next, the green photosensitive coloring composition (RG-1) is used, the green coloring pixel layer is formed in the same manner as the red coloring pixel layer, and further the blue photosensitive coloring composition (RB-1) is used. In the same manner as the red colored pixel layer, a blue colored pixel layer was formed to obtain a color filter (CF-1). The formed film thickness of each colored pixel layer was 2.0 μm.

  The color filter using the red coloring composition of the present invention has high brightness and excellent contrast ratio, and the effect of the present invention has been proved.

Claims (7)

A color filter coloring composition comprising a colorant, a metal complex compound, a binder resin, and an organic solvent,
The colorant contains a naphthol azo pigment [A] represented by the following general formula (1):
A metal having a metal complex compound as a central metal of at least one selected from the group consisting of vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), and copper (Cu) A coloring composition for a color filter, which is a complex compound [B].

[In General Formula (1), A is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a benzimidazolone group, an optionally substituted phenyl group, or an optionally substituted heterocyclic group. Represents. R ¹ represents a hydrogen atom, a trifluoromethyl group, an alkyl group having 1 to 4 carbon atoms, —OR ⁷ or —COOR ⁸ . R ^{2 to} R ⁶ are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, a trifluoromethyl group, an alkyl group having 1 to 4 carbon atoms, —OR ⁹ , —COOR ¹⁰ , —CONHR ¹¹ , -NHCOR ¹² or an -SO ₂ NHR ^13. R ^{7 to} R ¹³ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ]   The coloring composition for a color filter according to claim 1, wherein the central metal of the metal complex compound [B] is chromium (Cr), cobalt (Co), or copper (Cu).   The coloring composition for a color filter according to claim 1 or 2, wherein the metal complex compound [B] is a metal complex dye.   The content [B] / ([B] + [A]) of the metal complex compound [B] with respect to the total of the naphtholazo pigment [A] and the metal complex compound [B] is 0.01 to 0.5. The colored composition for a color filter according to any one of claims 1 to 3. The colorant further contains at least one selected from the group consisting of a naphthol azo pigment [A ′], an azo pigment [C], a diketopyrrolopyrrole pigment, and an anthraquinone pigment represented by the following general formula (6). The coloring composition for a color filter according to any one of claims 1 to 4, wherein the coloring composition is used.

[In General Formula (6), A ¹ represents a hydrogen atom, a phenyl group which may have a substituent, or a heterocyclic group which may have a substituent. R ⁵¹ represents a hydrogen atom, a trifluoromethyl group, an alkyl group having 1 to 4 carbon atoms, —OR ⁵⁷ or —COOR ⁵⁸ . R ⁵⁷ and R ⁵⁸ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ]   Furthermore, the coloring composition for color filters of any one of Claims 1-5 containing a photopolymerizable monomer and / or a photoinitiator.   A color filter comprising a filter segment formed from the colored composition for a color filter according to claim 1 on a substrate.