JP2014149506A - Red coloring composition for color filter, and color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a stable coloring composition for a color filter having a high flowability, and to provide a color filter having a high color characteristic and high heat resistance that is formed using a red composition having a high brightness and high contrast ratio.SOLUTION: The red coloring composition for a color filter includes a colorant, a resin, a resin type dispersant, and a solvent. The colorant contains a specific naphthol azo pigment [A1], and the resin type dispersant contains a resin type dispersant (c) having a basic substituent.

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.

  In general, two or more kinds of pigments are used in combination in the red filter segment, which is one of the three primary colors (red, green, blue; RGB) of the color filter substrate. I. Pigment red 254 and C.I. I. Pigment Red 177 is also a yellow pigment for toning. I. Pigment yellow 150, C.I. I. Pigment yellow 138, or C.I. I. Pigment Yellow 139 or the like is used.

  Here, C.I. I. Pigment Red 254 is a pigment that is particularly excellent in luminance when used as a colored composition. Further, since the coloring power is high, it is advantageous when adjusting the chromaticity and film thickness of the color filter. However, C.I. I. Pigment Red 254 has a problem in heat resistance when used in a refined form, and has a drawback that the contrast ratio is lowered when a refined product is used as a colored coating film.

  As a method for obtaining a color filter having a high contrast ratio, C.I. I. Pigment Red 254, C.I. I. A technique for producing a colored composition by adding Pigment Red 177 is used. However, C.I. I. Pigment Red 177 itself has low luminance and coloring power, so it cannot be used at a high content rate. I. Pigment Red 254 and C.I. I. When Pigment Red 177 is contained, the luminance, coloring power, and contrast are lowered in terms of arithmetic average, and as long as the combination of these conventionally used red pigments and yellow pigments can be used, the high contrast ratio and the high brightness are the limits. This is the current situation.

  In Patent Documents 1 to 3, in order to further improve the brightness of the red filter segment, C.I. I. Pigment red 176, C.I. I. Pigment red 242, and C.I. I. 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.

  Naphthol azo pigments have C.I. affinity for the solvent itself and the acidity of the pigment surface. I. Pigment red 254 and C.I. I. Since it is different from CI Pigment Red 177 and the like, it has been impossible to obtain a colored composition that is excellent in dispersibility, fluidity, storage stability, and has high brightness and contrast ratio.

JP 2009-237462 A Japanese Patent Laid-Open No. 11-14824 Japanese Patent Laid-Open No. 10-115709

  The present invention is a stable color filter coloring composition having high brightness and contrast ratio and excellent fluidity, and has good color characteristics and heat resistance formed using the color filter coloring composition. It is to provide an excellent color filter.

  As a result of intensive studies to solve the above problems, the present inventors have found that a colorant containing a naphtholazo pigment [A1] represented by the general formula (1) and a resin-type dispersant having a basic substituent It has been found that the above problems can be solved by a coloring composition containing a resin-type dispersant containing (c).

［一般式（１）中、Ａは、それぞれ独立して、水素原子、メチル基、ベンズイミダゾロン基、置換基を有してもよいフェニル基、または置換基を有してもよい複素環基を表す。
Ｒ¹は、水素原子、ハロゲン原子、トリフルオロメチル基、炭素数１〜４のアルキル基、−ＯＲ⁷、または−ＣＯＯＲ⁸を表す。Ｒ²〜Ｒ⁶は、それぞれ独立して、水素原子、ハロゲン原子、シアノ基、ニトロ基、トリフルオロメチル基、炭素数１〜４のアルキル基、−ＯＲ⁹、−ＣＯＯＲ¹⁰、−ＣＯＮＨＲ¹¹、または−ＳＯ₂ＮＨＲ¹²を表し、Ｒ²〜Ｒ⁶のうち少なくとも１つはトリフルオロメチル基を表す。Ｒ⁷〜Ｒ¹²は、それぞれ独立して、水素原子、または炭素数１〜４のアルキル基を表す。］ That is, the present invention relates to a red coloring composition for a color filter containing a colorant, a resin, a resin-type dispersant, and a solvent, wherein the colorant is a naphthol azo pigment represented by the following general formula (1): It is related with the red coloring composition for color filters characterized by including the resin type dispersing agent (c) which contains [A1] and this resin type dispersing agent has a basic substituent.
General formula (1)

[In General Formula (1), each A independently represents a hydrogen atom, a methyl group, a benzimidazolone group, a phenyl group which may have a substituent, or a heterocyclic group which may have a substituent. Represents.
R ¹ represents a hydrogen atom, a halogen atom, a trifluoromethyl group, an alkyl group having 1 to 4 carbon atoms, —OR ⁷ , or —COOR ⁸ . R ^{2 to} R ⁶ are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, a trifluoromethyl group, an alkyl group having 1 to 4 carbon atoms, —OR ⁹ , —COOR ¹⁰ , —CONHR ¹¹ , or an -SO ₂ NHR ^12, representative of at least one trifluoromethyl group among R ² to R ^6. R ^{7 to} R ¹² each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ]

  The present invention also relates to the red coloring composition for a color filter, wherein A is a phenyl group which may have a substituent.

  In addition, the present invention relates to the red coloring composition for a color filter, wherein the resin type dispersant (c) having a basic substituent is a resin type dispersant containing a nitrogen atom.

  The present invention further includes a dye derivative (e), wherein the dye derivative (e) includes a pigment derivative having an acidic substituent, a β-naphthol derivative having an acidic substituent, and a triazine derivative having an acidic substituent. It contains the pigment derivative which has at least 1 or more types of acidic substituent selected from the group which consists of the said red coloring composition for color filters characterized by the above-mentioned.

［一般式（６）中、Ａ¹は、それぞれ独立して、水素原子、置換基を有してもよいフェニル基または置換基を有してもよい複素環基を表す。Ｒ⁵¹は、水素原子、トリフルオロメチル基、炭素数１〜４のアルキル基、−ＯＲ⁵⁷または−ＣＯＯＲ⁵⁸を表す。Ｒ⁵⁷、Ｒ⁵⁸は、それぞれ独立して、水素原子または炭素数１〜４のアルキル基を表す。］ In the present invention, the colorant further includes a naphthol azo pigment [A ′] represented by the following general formula (6), an azo pigment [C], a diketopyrrolopyrrole pigment, and an anthraquinone pigment. It contains the coloring composition for the said color filter characterized by including at least 1 sort (s) chosen.
General formula (6)

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

  The present invention further relates to the red coloring composition for a color filter, further comprising a photopolymerizable monomer and / or a photopolymerization initiator.

  Furthermore, the present invention comprises a color filter comprising a red filter segment formed from the red coloring composition for a color filter on a substrate.

  According to the present invention, by using the naphtholazo pigment [A1] represented by the general formula (1) as the colorant and the resin type dispersant (c) having a basic substituent as the resin type dispersant, Color filter coloring composition with high contrast ratio, high fluidity and good stability. By using this, it is possible to form color filters with good color characteristics, high brightness and high contrast ratio. It becomes.

  By using the azo pigment represented by the general formula (1) of the present invention, it is possible to provide a color filter having excellent lightness and excellent heat resistance and light resistance. Moreover, the same effect can be acquired even if it expand | deploys to the coloring composition for inkjet, printing ink, a resin colorant, and a coating material.

Hereinafter, the present invention will be described in detail.
The red coloring composition for a color filter of the present invention is a colorant containing a naphtholazo pigment [A1] represented by the general formula (1), a resin, and a resin-type dispersant (c) having a basic substituent. It is a coloring composition containing a resin-type dispersant and a solvent.

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

［一般式（１）中、Ａは、それぞれ独立して、水素原子、メチル基、ベンズイミダゾロン基、置換基を有してもよいフェニル基、または置換基を有してもよい複素環基を表す。
Ｒ¹は、水素原子、ハロゲン原子、トリフルオロメチル基、炭素数１〜４のアルキル基、−ＯＲ⁷、または−ＣＯＯＲ⁸を表す。Ｒ²〜Ｒ⁶は、それぞれ独立して、水素原子、ハロゲン原子、シアノ基、ニトロ基、トリフルオロメチル基、炭素数１〜４のアルキル基、−ＯＲ⁹、−ＣＯＯＲ¹⁰、−ＣＯＮＨＲ¹¹、または−ＳＯ₂ＮＨＲ¹²を表し、Ｒ²〜Ｒ⁶のうち少なくとも１つはトリフルオロメチル基を表す。Ｒ⁷〜Ｒ¹²は、それぞれ独立して、水素原子、または炭素数１〜４のアルキル基を表す。］ General formula (1):

[In General Formula (1), each A independently represents a hydrogen atom, a methyl group, a benzimidazolone group, a phenyl group which may have a substituent, or a heterocyclic group which may have a substituent. Represents.
R ¹ represents a hydrogen atom, a halogen atom, a trifluoromethyl group, an alkyl group having 1 to 4 carbon atoms, —OR ⁷ , or —COOR ⁸ . R ^{2 to} R ⁶ are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, a trifluoromethyl group, an alkyl group having 1 to 4 carbon atoms, —OR ⁹ , —COOR ¹⁰ , —CONHR ¹¹ , or an -SO ₂ NHR ^12, representative of at least one trifluoromethyl group among R ² to R ^6. R ^{7 to} R ¹² each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ]

  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 group 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 Group, 2-thiazolyl group, piperidino group, 4-piperidyl group, morpholino group, 2-morpholinyl group, N-indolyl group, 2-indolyl group, 2-benzofuryl group, 2-benzothienyl group, 2-quinolino group, N -Carbazolyl group etc. are mentioned.

Examples of the halogen atom in R ^{1 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 ¹² 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 the colorant of the present invention,
A is preferably independently a hydrogen atom, a methyl group, a benzimidazolone group, or an optionally substituted phenyl group,
R ¹ is preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or —OR ⁷ .
R ⁷ is preferably an alkyl group having 1 to 4 carbon atoms,
R ^{2 to} R ⁶ are each independently preferably a hydrogen atom, a halogen atom, or a trifluoromethyl group, and at least one of R ^{2 to} R ⁶ is a trifluoromethyl group.
From the viewpoint of lightness, it is preferable that A is a phenyl group which may have a substituent. 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.

In addition, since at least one of R ^{2 to} R ⁶ is a trifluoromethyl group, miniaturization is facilitated.
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.

  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.

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

(Method for producing naphtholazo pigment [A1])
The naphthol azo pigment [A1] of the present invention can be produced by a coupling reaction of a diazonium salt and a β-naphthol, 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 [A1] is prepared by first adding an amine (diazo component) represented by the following general formula (3) 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 (4) obtained by diazotization with a nitrite is produced.

General formula (3)

[一般式（３）および（４）中、ＡおよびＲ¹は、一般式（１）におけるものと同義である。Ｘ^-は、無機または有機アニオンを表す。］ General formula (4)

[In General Formulas (3) and (4), A and R ¹ have the same meanings as in General Formula (1). X ⁻ represents an inorganic or organic anion. ]

Examples of the inorganic or organic anion include fluoride ion, chloride ion, bromide ion, iodide ion, perchlorate ion, hypochlorite ion, CH ₃ COO ⁻ , C ₆ H ₅ COO ^{−, and the} like. Preferred are chloride ion, bromide ion, and CH ₃ COO 2 ^— .

  Next, the diazonium salt represented by the general formula (4) and the β-naphthols (coupling component) represented by the following general formula (5) are usually reacted at 5 ° C. to 70 ° C. in an aqueous solvent. And post-treatment by a conventional method to produce a naphtholazo pigment [A1] of the general formula (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 naphthol azo pigment [A1] of this invention is not limited to these methods.

[一般式（５）中、Ｒ²〜Ｒ⁶は、一般式（１）におけるものと同義である。］ General formula (5)

[In General Formula (5), R < ² > -R < ⁶ > is synonymous with the thing in General formula (1). ]

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 (3) is added to a nitrous acid, a nitrite or a nitrous acid in an acidic aqueous solution to which hydrochloric acid, sulfuric acid, acetic acid or the like is added. A mixture of diazonium salts represented by the following general formula (4) obtained by diazotization with an ester is produced.

General formula (3)

[一般式（３）および（４）中、ＡおよびＲ¹は、一般式（１）におけるものと同義である。Ｘ^-は、無機または有機アニオンを表す。］ General formula (4)

[In General Formulas (3) and (4), A and R ¹ have the same meanings as in General Formula (1). X ⁻ represents an inorganic or organic anion. ]

Examples of the inorganic or organic anion include fluoride ion, chloride ion, bromide ion, iodide ion, perchlorate ion, hypochlorite ion, CH ₃ COO ⁻ , C ₆ H ₅ COO ^{−, and the} like. Preferred are chloride ion, bromide ion, and CH ₃ COO 2 ^— .

Subsequently, the diazonium salt represented by the general formula (4), the β-naphthols (coupling component) represented by the following general formula (5), and the β-naphthols represented by the following general formula (10) The mixture with (coupling component) is usually reacted in an aqueous solvent at 5 ° C. to 70 ° C. and subjected to a post-treatment by a conventional method to obtain a naphthol azo pigment [A1] of 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 in the general formula (1), 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 naphthol azo pigment [A1] of this invention is not limited to these methods.

[一般式（５）中、Ｒ²〜Ｒ⁶は、一般式（１）におけるものと同義である。］ General formula (5)

[In General Formula (5), R < ² > -R < ⁶ > is synonymous with the thing in General formula (1). ]

General formula (10)

  The mixing ratio of the aromatic amines of the general formula (3) used in the reaction and the mixing ratio of the β-naphthols of the general formulas (5) and (10) are set between 60:40 and 100: 0, respectively. can do. 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 (5) and a naphthol compound represented by the general formula (10), and a diazo compound of an aromatic amine represented by the general formula (3) To produce a colorant containing an azo pigment 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 (5) and the naphthol compound represented by the general formula (10) is preferably 60:40 to 100: 0, In some cases, the naphthol azo pigment [A1] 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 naphthol azo pigment [A1] of the above 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.

Colorants that can be used in combination include pigments such as diketopyrrolopyrrole pigments, azo pigments other than the naphtholazo pigment [A1] of the general formula (1) such as azo, disazo, or polyazo, aminoanthraquinone, diamino Anthraquinone pigments such as dianthraquinone, anthrapyrimidine, flavantron, anthanthrone, indanthrone, pyranthrone, violanthrone, quinacridone pigment, perinone pigment, perylene pigment, thioindigo pigment, isoindoline pigment, isoindolinone pigment Examples thereof include pigments, quinophthalone pigments, selenium pigments, and metal complex pigments.
Examples of the dye include xanthene dyes, azo (pyridone, barbituric acid, metal complex, 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 [A1] of the general formula (1), diketopyrrolopyrrole pigments, and anthraquinone pigments are preferable from the viewpoint of brightness and coloring power.

  Examples of the azo pigment other than the naphthol azo pigment [A1] represented by the general formula (1) include the 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).

［一般式（６）中、Ａ¹は、それぞれ独立して、水素原子、置換基を有してもよいフェニル基または置換基を有してもよい複素環基を表す。Ｒ⁵¹は、水素原子、トリフルオロメチル基、炭素数１〜４のアルキル基、−ＯＲ⁵⁷または−ＣＯＯＲ⁵⁸を表す。Ｒ⁵⁷、Ｒ⁵⁸は、それぞれ独立して、水素原子または炭素数１〜４のアルキル基を表す。］ General formula (6)

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

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

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 [A1] 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])
Other azo pigments [C] include naphthol azo pigments [A1] represented by the general formula (1), azos other than the azo pigments [A ′] represented by the general formula (6), disazo, or polyazo 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.

  Moreover, as a pigment | dye used together, the diketopyrrolopyrrole pigment represented by following General formula (2) is preferable.

[一般式（２）中、
Ｂ、Ｃ、ＤおよびＥは、それぞれ独立して、水素原子、フッ素原子、塩素原子、臭素原子、ヨウ素原子、シアノ基、炭素数１〜１２のアルキル基、置換基を有してもよいフェニル基、−ＣＦ₃、−ＯＲ¹³、−ＳＲ¹⁴、−Ｎ（Ｒ¹⁵）Ｒ¹⁶、−ＣＯＯＲ¹⁷、−ＣＯＮＨ₂、−ＣＯＮＨＲ¹⁸、−ＣＯＮ（Ｒ¹⁹）Ｒ²⁰、−ＳＯ₂ＮＨ₂、−ＳＯ₂ＮＨＲ²¹、または、−ＳＯ₂Ｎ（Ｒ²²）Ｒ²³であり、
Ｒ¹³〜Ｒ²³は、それぞれ独立して、炭素数１〜１２のアルキル基、置換基を有してもよいフェニル基、または、置換基を有してもよいアラルキル基である。] General formula (2)

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

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

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

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. I. Solvent Red 45, C.I. Solvent Red 46, C.I. Solvent Red 47, C.I. Solvent Red 48, C.I. Solvent Red 49, C.I. Solvent Red 72, C.I. 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 [A1] 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 color filter colorant of the present invention provides high brightness and high contrast in the case of a colored composition. Therefore, if necessary, the color filter particle is refined by a salt milling process or the like, if necessary. It can be suitably used as a colorant. The primary particle diameter of the colorant is preferably 10 nm or more in order to improve dispersibility in the colorant carrier. Moreover, in order to obtain a filter segment with high contrast, the thickness is preferably 50 nm or less.

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

  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% by weight, and most preferably 300 to 1000% by weight based on the total weight of the pigment (100% by weight) from the viewpoint of both processing efficiency and production efficiency.

  The water-soluble organic solvent functions to wet the colorant and 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, since the temperature rises during salt milling and the solvent is likely to evaporate, those having a high boiling point of 120 ° C. or higher are preferable from the viewpoint of safety. Such as, for example, 2-methoxyethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol , Triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid polypropylene glycol, etc. Is used. These water-soluble organic solvents are preferably used in an amount of 5 to 1000% by weight, and most preferably 50 to 500% by weight, based on the total weight of the colorant (100% by weight).

  When salt milling the colorant, a resin may be added as necessary. Here, 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 water-soluble organic solvent. The amount of resin used is preferably in the range of 2 to 200% by weight based on the total weight of the colorant (100% by weight).

<Resin>
The 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 the isocyanate group of an ethylenically unsaturated monomer having an isocyanate group with the side chain hydroxyl group of the obtained copolymer.

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

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

  In order to disperse the colorant preferably, the weight average molecular weight (Mw) of the resin is preferably in the range of 10,000 to 100,000, more preferably in the range of 10,000 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, it is 100-400 weight part. More preferably, it is 160-320 weight part. The chromaticity region can be expanded by such a composition ratio of the pigment.

<Resin type dispersant>
The resin-type dispersant in the present invention contains a resin-type dispersant (c) having a basic substituent. The resin-type dispersant of the present invention has a pigment-affinity unit containing a basic substituent that adsorbs to the naphthol azo pigment [A1] and a unit compatible with the pigment carrier, and the naphthol azo pigment [A1]. This serves to stabilize the dispersion of the pigment in the pigment carrier.

  In particular, when a naphthol azo pigment [A1], a resin-type dispersant (c) having a basic substituent, and a dye derivative having an acidic substituent described later are used, excellent fluidity and dispersibility are achieved. It is preferable in order to exhibit the effect.

  Among the resin-type dispersants, the resin-type dispersant having a basic substituent containing a nitrogen atom is more excellent in the dispersion stability of the colored composition and is preferable.

  As a weight average molecular weight of the resin type dispersing agent used by this invention, 500-50000 are preferable normally, 700-30000 are especially preferable, Furthermore, 700-20000 are preferable. When the number average molecular weight is less than 500, the effect of steric repulsion due to the pigment affinity group, the effect of compatibility with the pigment carrier, and the effect of compatibility with the pigment carrier and solvent when using a solvent are small, It may be difficult to prevent aggregation of the pigment, and the viscosity of the dispersion may increase. On the other hand, if the number average molecular weight is 50000 or more, the amount of resin added for dispersion increases, and the pigment concentration in the coating film may be lowered.

The amine value of the resin-type dispersant is preferably 2 to 80 mgKOH / g, particularly preferably 3 to 60 mgKOH / g, and further preferably 4 to 25 mgKOH / g.
If the amine value is less than 2 mgKOH / g, the pigment may not be sufficiently adsorbed and may result in poor dispersion. If the amine value exceeds 80 mgKOH / g, the naphtholazo pigment [A1] may be adsorbed or reacted with an acidic component in the pigment carrier. In some cases, the adsorption efficiency with respect to the liquid becomes poor, resulting in poor dispersion.

  Various resin types such as vinyl, urethane, polyester, polyether, or polyamide can be used as the resin-type dispersant. However, the resin-based dispersant is easy to design and has excellent resistance to vinyl monomers. The coalescence type is preferable, specifically, a copolymer resin of an N, N-disubstituted amino group-containing vinyl monomer unit, an alkyl (meth) acrylate monomer unit, and other vinyl monomer units is preferable. As described later, these block copolymers are particularly preferable from the viewpoint of not only contrast but also brightness.

  As N, N-disubstituted amino group-containing vinyl monomer units, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, Examples thereof include N, N-diethylaminopropyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylamide, and N, N-diethylaminoethyl (meth) acrylamide, but are not necessarily limited thereto. These monomer units are adsorbed to the naphthol azo pigment [A1] as basic group-containing monomer units.

  As alkyl (meth) acrylate monomer units, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, It is obtained by the reaction of unsaturated monocarboxylic acid such as 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, stearyl (meth) acrylate, or lauryl (meth) acrylate with alkyl alcohol having 1 to 18 carbon atoms (meta ) Acrylic esters and the like, but are not necessarily limited thereto. These monomer units act as pigment carrier affinity groups.

  Other vinyl monomer units include nitro group-containing vinyl monomers such as (meth) acrylonitrile, vinyl aromatic monomers such as styrene, α-methylstyrene, or benzyl (meth) acrylate, 2-hydroxyethyl ( Hydroxyl group-containing vinyl monomers such as (meth) acrylate, hydroxypropyl (meth) acrylate, or polyethylene glycol (meth) acrylate, (meth) acrylamide, N, N-dimethylacrylamide, N-isopropylacrylamide, diacetone acrylamide, etc. Amide group-containing vinyl monomers, vinyl monomers such as N-methylol (meth) acrylamide or dimethylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, or N-butoxime Alkoxymethyl group-containing vinyl monomers such as ru (meth) acrylamide, olefins such as ethylene, propylene or isoprene, dienes such as chloroprene or butadiene, methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, Examples thereof include vinyl ethers such as n-butyl vinyl ether or isobutyl vinyl ether, and fatty acid vinyls such as vinyl acetate or vinyl propionate, which are appropriately used according to the purpose, but are not necessarily limited thereto.

  Polymers having primary amino group-containing monomer units such as allylamine, or polyethyleneimine, polyethylene polyamine, polyxylylene poly (hydroxypropylene) polyamine, or poly (aminomethylated) epoxy resin, polyester resin, acrylic resin Alternatively, a resin-type dispersant having a comb-shaped basic substituent modified with a polyether resin or the like can also be mentioned.

  Commercially available products of such resin-type dispersants include, for example, DISPERBYK 161, 162, 163, 164, 166, 167, 168, 174, 182, 183, 184, 185, 2000, 2001, 2050, 2150 from Big Chemie Japan. , 2163, 2164, BYK-LPN6919, 21116, 21324, SOLPERSE 11200, 13240, 13650, 13940, Nippon Lubrizol Corporation 24000, 26000, 28000, 32000, 32500, 32550, 32600, 33000, 34750, 35100, 35200, 37500, 38500, 39000, 53095, 56000, 71000, EFKA4300, 4330, 4046, 4060, 4080 from BASF, Ajinomoto Fa Ntekuno Co. AJISPER PB711, PB821, PB822, PB824, and the like.

As the resin-type dispersant for the red coloring composition for a color filter of the present invention, a block copolymer consisting of a basic copolymer block (A) and a pigment carrier affinity copolymer block (B) is particularly preferable. It is a coalesced resin, and the basic copolymer block (A) preferably contains a nitrogen atom.
Hereinafter, the resin type dispersant which is a block copolymer will be described.

(Block copolymer)
The resin-type dispersant is a part that adsorbs to the pigment (hereinafter abbreviated as an adsorbing part) and a part having a high affinity for the pigment carrier (hereinafter referred to as affinity) that has the effect of preventing aggregation of the pigments and improving dispersibility. Abbreviated as sex part). A basic copolymer block (A) that is an adsorbing part for the naphtholazo pigment [A1] and a pigment carrier affinity copolymer block (B) that is an affinity part for the pigment carrier are present on the same molecule. By using the block copolymer used as a resin-type dispersant, a red colored composition in which the naphtholazo pigment [A1] is finely and low-viscosity and stably dispersed without impairing its color characteristics is provided. can do.

  Various resin systems can be selected for the basic copolymer block (A) and the pigment carrier affinity copolymer block (B) constituting the block copolymer, but the resin design is easy and A vinyl copolymer having excellent resistance is desirable. Hereinafter, each copolymer block will be described.

"Basic copolymer block (A)"
Specific examples of the basic copolymer block (A) include N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N N, N-diethylaminopropyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylamide, N, N-diethylaminoethyl (meth) acrylamide and the like having N, N-disubstituted amino group-containing vinyl monomer units Polymers, polymers having primary amino group-containing monomer units such as allylamine, polyethyleneimine, polyethylene polyamine, polyxylylene poly (hydroxypropylene) polyamine, poly (aminomethylated) epoxy resin, etc. Yes, but not necessarily limited to these Not.

  Among these, a copolymer having an N, N-disubstituted amino group-containing vinyl monomer unit, which is easy to design a resin of the block copolymer and excellent in various resistances, is preferable. The N, N-disubstituted amino group-containing vinyl monomer unit contained in the combined block (A) is 60 to 100% by weight, more preferably 80 to 100% by weight, and the N, N-disubstituted amino group is contained. The vinyl monomer unit other than the vinyl monomer unit is preferably a vinyl monomer unit described in the pigment carrier affinity copolymer block (B).

  More preferably, it has a structural unit represented by the following structural formula from the viewpoint of the stability of the coloring composition.

[一般式（７）中、Ｒ³⁴は水素原子又はメチル基、Ｒ³⁵は炭素数１〜１０のアルキレン基、アリーレン基、−ＣＯＮＨ−Ｒ^g−基、−ＣＯＯ−Ｒ^h−基（但し、Ｒ^g及びＲ^hは直接結合、炭素数１〜１０のアルキレン基、又は炭素数１〜１０のエーテル基（−Ｒ'−Ｏ−Ｒ"−：Ｒ'及びＲ"は、各々独立にアルキレン基）である）を表す。ｎ３は０又は１の整数であって、Ｒ³⁶〜Ｒ³⁸は置換基を有していてもよい環状又は鎖状のアルキル基、置換基を有していてもよいアリール基、又は置換基を有していてもよいアラルキル基を表し、Ｘ^1-はｎ３＝１である場合のカウンターアニオンを表す。] General formula (7)

[In General Formula (7), R ³⁴ is a hydrogen atom or a methyl group, R ³⁵ is an alkylene group having 1 to 10 carbon atoms, an arylene group, a —CONH—R ^g — group, a —COO—R ^h — group (provided that R ^g and R ^h are a direct bond, an alkylene group having 1 to 10 carbon atoms, or an ether group having 1 to 10 carbon atoms (—R′—O—R ″ —: R ′ and R ″ are each independently an alkylene group) ). n3 is an integer of 0 or 1, and R ^{36 to} R ³⁸ each represents a cyclic or chain-like alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. Represents an aralkyl group which may be present, and X ¹⁻ represents a counter anion in the case of n3 = 1. ]

Examples of the counter anion X ¹⁻ include Cl ⁻ , Br ⁻ , I ⁻ , ClO ₄ −, BF ₄ ⁻ , CH ₃ COO ⁻ , and PF ₆ ⁻ .

Among them, R ^{36 to} R ³⁸ are preferably a methyl group, an ethyl group, a benzyl group, X ¹⁻ is preferably a Cl 2 ⁻ , and R ³⁵ is preferably a methylene group, an ethylene group or the like.
Moreover, it is preferable to have a quaternary ammonium base in which n3 = 1, and it is also preferable to have a tertiary amino group in which n = 0.

  Two or more repeating units containing an amino group as described above may be contained in one B block. In that case, the repeating unit containing 2 or more types of amino groups may be contained in the B block in any form of random copolymerization or block copolymerization.

In —N ⁺ R ³⁶ R ³⁷ R ³⁸ of the general formula (7), two or more of R ³⁶ , R ³⁷ and R ³⁸ may be bonded to each other to form a cyclic structure, for example, 5 to 7 Examples thereof include a membered nitrogen-containing heterocyclic monocycle or a condensed ring formed by condensing two of them. The nitrogen-containing heterocycle preferably has no aromaticity, more preferably a saturated ring. Specifically, the thing of a following formula (C) is mentioned, for example.

Formula (C)

These cyclic structures may further have a substituent. As R ³⁶ to R ³⁸ in ^{-N + R 36 R 37 R 38} , more preferred are an alkyl group having 1 to 3 carbon atoms which may have a substituent, which may have a substituent aralkyl Or a phenyl group which may have a substituent.

In the general formula (7), examples of the divalent linking group R ³⁵ include, for example, an alkylene group having 1 to 10 carbon atoms, an arylene group, a —CONH—R ^g — group, a —COO—R ^h — group (provided that R ^g and R ^h are a direct bond, an alkylene group having 1 to 10 carbon atoms, or an ether group having 1 to 10 carbon atoms (—R′—O—R ″ —: R ′ and R ″ are each independently an alkylene group) And is preferably a —COO—R ^h — group. Among the —COO—R ^h — groups, R ^h is more preferably a methylene group, an ethylene group, a propylene group, or a butylene group, and particularly preferably an ethylene group.

The structural unit represented by the general formula (7) includes (meth) acryloylaminopropyltrimethylammonium chloride, (meth) acryloyloxyethyltrimethylammonium chloride, (meth) acryloyloxyethyl (4-benzoylbenzyl) dimethylammonium bromide. (Meth) acryloyloxyethylbenzyldimethylammonium chloride is preferred, and (meth) acryloyloxyethylbenzyldimethylammonium chloride is particularly preferred from the viewpoint of pigment dispersibility.
Two or more of these structural units may be contained.

Moreover, it can be confirmed by the following method that the quaternary ammonium halogen salt which is one of the general formula (7) is contained in the pigment dispersant according to the present invention. The presence of ionic halogen can be detected by vigorously stirring the sample alone or the organic solvent solution of the sample with pure water, adding an aqueous silver nitrate solution to the aqueous layer, and generating insoluble matter. Also, quaternary ammonium to be paired can be detected by showing absorption in 2900～3300Cm ^-1 and 1300～1500Cm ^-1 in the infrared absorption spectrum analysis.

"Pigment carrier affinity copolymer block (B)"
The monomer that is a precursor of the pigment carrier affinity copolymer block (B) does not have a functional group containing a nitrogen atom such as an amino group and can be copolymerized with a monomer constituting the A-block. There is no particular limitation.
For example, styrene monomers such as styrene and α-methylstyrene; methyl (meth) acrylate, ethyl (meth) acrylate (propyl) (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, (meth ) Octyl acrylate, 2-ethylhexyl (meth) acrylate, glycidyl (meth) acrylate, benzyl (meth) acrylate, hydroxyethyl (meth) acrylate, glycidyl ethyl acrylate, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) (Meth) acrylic acid ester monomers such as acrylates; (meth) acrylic acid salt monomers such as (meth) acrylic acid chlorides; vinyl acetate monomers; allyl glycidyl ether, crotonic acid glycidyl ether Any polymer structure obtained by copolymerizing comonomers including glycidyl ether monomers.

  In particular, the B-block contains a polyalkylene glycol (meth) acrylate such as polyethylene glycol (meth) acrylate and polypropylene glycol (meth) acrylate as a copolymerization component (that is, a partial structure derived from polyalkylene glycol (meth) acrylate). In particular, and preferably has a partial structure represented by the following general formula (I).

[一般式（Ｉ）中、ｎは１〜５の整数を表し、Ｒ³⁹は水素原子又はメチル基を表す。] Formula (I)

[In General Formula (I), n represents an integer of 1 to 5, and R ³⁹ represents a hydrogen atom or a methyl group. ]

  As for the partial structure represented by general formula (I), it is especially preferable that 5-40 mol% is contained in B-block.

  Further, from the viewpoint of enhancing the dispersion stability, the B-block further contains 50 to 90 mol of a structural unit having a (meth) acrylic acid ester monomer other than the partial structure represented by the general formula (I) as a precursor. It is preferable to contain%, More preferably, it is 60-80 mol%. Among them, (meth) acrylic acid ester monomers include (meth) methyl acrylate, (meth) ethyl acrylate (propyl meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, (meth) It is preferable to use octyl acrylate because the dispersibility and stability of the coloring composition are excellent.

  By including the partial structure represented by the general formula (I) in the B-block, hydrophilicity is imparted and the solubility in the developer is improved. On the other hand, the compatibility with the binder resin is increased and the dispersion stability is improved by further including a structural unit having a (meth) acrylate monomer other than the partial structure represented by the general formula (I) as a precursor. .

  The pigment carrier affinity copolymer block (B) preferably contains 0% by weight of vinyl monomer units containing amino groups, but may be contained if it is less than 10% by weight.

"Production method of block copolymer"
The block copolymer can be produced by a known method. In particular, (1) a method using living polymerization, or (2) a precursor of a basic copolymer block (A) having a functional group at the terminal. A polymer coupling method in which (a) and a precursor (b) of a pigment carrier affinity copolymer block (B) having a functional group at the terminal are reacted is preferable. Among these, (1) a method using living polymerization is particularly preferable.

(1) Living polymerization method In the living polymerization method, side reactions occurring in general radical polymerization are suppressed, and further, the growth of polymerization occurs uniformly, so that a block polymer or a resin having a uniform molecular weight can be easily synthesized.
Above all, the atom transfer radical polymerization method using organic halides and sulfonyl halide compounds as initiators and transition metal complexes as catalysts can be applied to a wide range of monomers and employs a polymerization temperature applicable to existing equipment. It is preferable in that it can be performed. An atom transfer radical polymerization method can be performed by the method described in the following references 1 to 8 and the like.
(Reference 1) Fukuda et al., Prog. Polym. Sci. 2004, 29, 329
(Reference 2) Matyjaszewski et al., Chem. R ev. 2001, 101, 2921
(Reference 3) Matyjaszewski et al. Am. Chem. Soc. 1995, 117, 5614
(Reference 4) Macromolecules 1995, 28, 7901, Science, 1996, 272, 866
(Reference 5) Pamphlet of International Publication No. 96/30421 (Reference 6) Pamphlet of International Publication No. 97/18247 (Reference 7) JP-A-9-208616 (Reference 8) JP-A-8-411117

  In the atom transfer radical polymerization method, a transition metal complex such as copper, ruthenium, iron and nickel is used as a redox catalyst. Specific examples of the transition metal complex include low-valent halogenated transition metals such as copper (I) chloride and copper (I) bromide. In order to control the polymerization rate, a well-known method is used. High valent transition metals such as copper (II) chloride and copper (II) bromide may be added to the polymerization system.

  An organic ligand is used for the metal complex. Organic ligands are used to allow reversible changes in solubility in the polymerization solvent and redox conjugated complexes. Examples of the metal coordination atom include a nitrogen atom, an oxygen atom, a phosphorus atom, and a sulfur atom, and a nitrogen atom or a phosphorus atom is preferable. Specific examples of the organic ligand include sparteine, 2,2′-bipyridyl and derivatives thereof, 1,10-phenanthroline and derivatives thereof, tetramethylethylenediamine, pentamethyldiethylenetriamine, tris (dimethylaminoethyl) amine, hexamethyl ( 2-aminoethyl) amine, triphenylphosphine, and tributylphosphine. Among the above catalysts, polymerization is preferably performed using a combination of copper halide and tetraethylenediamine in view of controlling the polymerization rate and the molecular weight of the block resin.

The transition metal and the organic ligand may be added separately to form a metal complex in the polymer, or the metal complex may be synthesized in advance and added to the polymerization system. In particular, when the transition metal is copper, the former method is preferable, and for the ruthenium, iron, and nickel, the latter method is preferable.
Specific examples of ruthenium, iron and nickel complexes synthesized in advance include tristriphenylphosphinoniruthenium chloride (Ru (Cl) ₂ (PPh ₃ ) ₃ , bistrisphenylphosphinoniiron chloride (Fe (Cl) ₂ (PPh ₃ ) ₂ ), nickel bistrisphenylphosphinonichloride (Ni (Cl) ₂ (PPh ₃ ) ₂ ), nickel bistributylphosphinonibromide (NiBr ₂ (PBu ₃ ) ₂ ), etc. .

  As the initiator used in the atom transfer radical polymerization method, known initiators can be used, and organic halides having a highly reactive carbon halogen bond, sulfonyl halide compounds and the like are mainly used. Specific examples include ethyl bromoisobutyrate, ethyl bromobutyrate, ethyl chloroisobutyrate, ethyl chlorobutyrate, p-toluenesulfonic acid chloride, bromoethylbenzene, and chloroethylbenzene. These are used alone or in combination.

  In the above atom transfer radical polymerization, the initiator of the atom transfer radical polymerization is appropriately selected according to the molecular weight of the resin to be synthesized, but is preferably 0.001 to 10 mol% based on the total amount of the radical polymerizable monomer. Preferably it is used in a proportion of 0.01 to 1 mol%.

  The amount of transition metal used is preferably 0.03 to 3 moles, more preferably 0.1 to 2 moles per mole of initiator as a form of halide or the like. Further, the ligand is used in a proportion of usually 1 to 5 mol, preferably 1.2 to 3 mol, per 1 mol of the transition metal (form of halide, etc.). When the above-mentioned atom transfer radical polymerization initiator, transition metal and ligand are used in such proportions, it is preferable in terms of the reactivity of living radical polymerization, the molecular weight of the produced polymer, and the like.

  In addition, due to the characteristics of atom transfer radical polymerization, the resulting resin has an active carbon-halogen bond at the terminating end, which can be modified by a known method to introduce a functional group. Moreover, it can superpose | polymerize with the polymerization initiator which has a functional group, can introduce | transduce a functional group to the resin terminal, and can utilize for various reactions.

  Atom transfer radical polymerization can be carried out without a solvent, or may be carried out in the presence of a solvent such as butyl acetate, toluene, xylene, anisole, methyl ethyl ketone, or cyclohexanone. In particular, a ketone solvent is preferable from the viewpoint of polymerization rate, and methyl ethyl ketone is particularly preferable. In the case of using a solvent, in order to prevent a decrease in polymerization rate, the amount of the solvent used after the polymerization is preferably 50% by weight or less. Even when there is no solvent or a small amount of solvent, there is no particular safety problem with respect to control of polymerization heat and the like.

  The polymerization conditions are 60 to 130 ° C. polymerization temperature from the point of polymerization rate and catalyst deactivation, and depending on the final molecular weight and polymerization temperature, the polymerization time may be about 1 to 100 hours. . The polymerization reaction is preferably performed in an inert gas atmosphere such as nitrogen or argon in order to prevent deactivation of the polymerization catalyst by oxygen.

  After completion of the polymerization reaction, the polymerization reaction system is preferably cooled to 0 ° C. or less, more preferably about −78 ° C. to stop the reaction, and the remaining monomer and / or solvent is removed according to a well-known method. Reprecipitation in the medium and filtration of the precipitated polymer can be performed by centrifugation, washing of the polymer and drying. The block resin used in the present invention can be obtained by removing the transition metal and the like contained in the polymerization system by a known method, if necessary, and then evaporating the volatile components. As the removal method, the reaction mixture is diluted with an organic solvent such as tetrahydrofuran, toluene, or methyl ethyl ketone, washed with water / dilute hydrochloric acid or an aqueous amine solution, and the resin solution is contacted with a cation exchange resin or a chelate resin. There are a method of passing through a silica or clay column or pad, a method of filtering and centrifuging after adding an adsorbent such as a reducing agent or hydrotalcite. From the viewpoint of ease of processing, it is preferable to add a cation exchange resin and an acid adsorbent such as hydrotalcite to the diluted resin solution and stir, and filter the ion exchange resin and the acid adsorbent to obtain a resin solution. .

  When water is mixed into the resin solution by the purification treatment, the reaction between the block resin used in the present invention and the curing agent may be hindered. For example, a solvent miscible with water may be added to the resin solution and subjected to azeotropic dehydration, etc. It is desirable to remove moisture from the resin solution by treatment.

  In the atom transfer radical polymerization used in the present invention, in order to suppress side reactions that occur during general radical polymerization, depending on the charging ratio of the initiator of the atom transfer radical polymerization added during polymerization and the radical polymerizable monomer, The molecular weight of the resin and the ratio of the basic copolymer block (A) or the pigment carrier affinity copolymer block (B) can be freely controlled.

(2) Polymer coupling method Functional group at the terminal of the precursor (a) of the basic copolymer block (A) and the precursor (b) of the pigment carrier affinity copolymer block (B) in the polymer coupling method Specific examples of preferable examples include a carboxyl group, a primary amino group, a hydroxyl group, and an alkoxysilyl group.

  As a method for introducing a terminal functional group into the precursor (a) of the basic copolymer block (A) and the precursor (b) of the pigment carrier affinity copolymer block (B), the functional groups listed above are used. A method of radical polymerization using a chain transfer agent having a thiol group is preferred. The chain transfer agent having a carboxyl group is mercaptopropionic acid, the chain transfer agent having a primary amino group is cysteamine, the chain transfer agent having a hydroxyl group is mercaptoethanol, and the chain transfer agent having an alkoxysilyl group is 3- Examples include mercaptopropylmethylmethoxysilane and 3-mercaptopropyltrimethoxysilane.

  The reaction between the precursor (a) and the precursor (b) can be performed by a known reaction with a combination shown in Table 4 below, for example.

  Examples of the binder polyisocyanate compound include aromatic polyisocyanate, aliphatic polyisocyanate, araliphatic polyisocyanate, and alicyclic polyisocyanate. Examples of the aromatic polyisocyanate include 1,3-phenylene diisocyanate, 4,4′-diphenyl diisocyanate, 1,4-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6 -Tolylene diisocyanate, 4,4'-toluidine diisocyanate, 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate benzene, dianisidine diisocyanate, 4,4'-diphenyl ether diisocyanate, or 4,4 ' , 4 "-triphenylmethane triisocyanate, etc. Examples of the aliphatic polyisocyanate include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, Examples include tamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, or 2,4,4-trimethylhexamethylene diisocyanate. Examples of the polyisocyanate include ω, ω′-diisocyanate-1,3-dimethylbenzene, ω, ω′-diisocyanate-1,4-dimethylbenzene, ω, ω′-diisocyanate-1,4-diethylbenzene, 1, Examples include 4-tetramethylxylylene diisocyanate or 1,3-tetramethylxylylene diisocyanate, etc. Examples of the alicyclic polyisocyanate include 3-isocyanate methyl-3,5,5-trimethylcyclohexane. Xyl isocyanate, 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4′-methylenebis ( Cyclohexyl isocyanate), 1,4-bis (isocyanate methyl) cyclohexane, 1,4-bis (isocyanate methyl) cyclohexane, etc., but are not necessarily limited to these, and some of the above poly A trimethylolpropane adduct of isocyanate, a burette reacted with water, a trimer having an isocyanurate ring, and the like can also be used in combination.

  As the polyepoxy compound of the binder, a polyepoxy compound having at least two glycidyl groups is preferable. Specifically, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether, trimethylolethane triglycidyl ether, sorbitol polyglycidyl ether, or penta Aliphatic polyepoxy compounds such as erythritol polyglycidyl ether, aromatic polyepoxy compounds of the bisphenol A or bisphenol F type, tetraglycidylaminophenylmethane, triglycidyl isocyanurate, or 1,3-bis (N, N-glycidylaminomethyl) ) Glycidylamine type epoxy compounds such as cyclohexane, but are not necessarily limited to these Not intended to be.

  The constitutional weight ratio of the basic copolymer block (A) and the pigment carrier affinity copolymer block (B) and the weight average molecular weight of each block are the same as the weight average molecular weight and amine value of the resin type dispersant as a whole. It is preferable that it can be designed arbitrarily so as to be in the preferable range.

  In the red coloring composition of the present invention, the content of the resin-type dispersant (c) having a basic substituent is preferably 5 to 70 parts by weight, more preferably 10 to 50 parts by weight with respect to 100 parts by weight of the colorant. Part. If it is less than 5 parts by weight, the dispersibility may be deteriorated, and if it exceeds 70 parts by weight, the heat resistance and light resistance may be deteriorated.

  In the present invention, in addition to the above resin type dispersant, other resin type dispersants may be included, and a resin type dispersant having an acidic group may be used in combination.

<Solvent>
The solvent sufficiently disperses the colorant in the resin, and the filter composition is formed by applying the colored composition of the present invention on a transparent substrate such as a glass substrate so that the dry film thickness is 0.2 to 5 μm. Used to make things easier.
As the solvent, 1,2,3-trichloropropane, 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, N- Methylpyrrolidone, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, P-chlorotoluene, P-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene Glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl Ether, ethylene glycol monohexyl ether, ethylene glycol Recall 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 Pill ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, Propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methylcyclohexanol, n-amyl acetate, n-acetate Chill, isoamyl acetate, isobutyl acetate, propyl acetate, and dibasic acid esters.
These solvents can be used singly or in combination of two or more at any ratio as required.

  Among them, since the dispersibility of the colorant of the present invention is good, glycol acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, benzyl alcohol, etc. It is preferable to use ketones such as aromatic alcohols and cyclohexanone.

  The solvent is preferably used in an amount of 800 to 4000 parts by weight with respect to 100 parts by weight of the colorant because the solvent can adjust the coloring composition to an appropriate viscosity and form a filter segment having a desired uniform film thickness.

<Dye derivative (e)>
The coloring composition for a color filter of the present invention can preferably use a pigment derivative (e). The dye derivative is excellent in the dispersion of the naphthol azo pigment and has a great effect of preventing reaggregation of the naphthol azo pigment after the dispersion.
As a pigment derivative, a basic substituent, an acidic substituent, or an optionally substituted phthalimidomethyl group is introduced into an organic pigment, a benzimidazolone compound, an acridone compound, a β-naphthol compound, or a triazine compound. And the like.

  In particular, the organic pigment preferably contains a pigment derivative having an acidic substituent or a metal salt thereof. Dye derivatives that have acidic substituents or their metal salts in organic pigments promote the pigment adsorption of pigments and resin-type dispersants, and improve the dispersibility of pigments, thus preventing re-aggregation of pigments after dispersion Is big. Therefore, when using a coloring composition in which a pigment is dispersed in a pigment carrier using a dye derivative having an acidic substituent or a metal salt thereof, a color filter having excellent stability can be obtained. Furthermore, it is preferable to use the resin-type dispersant having a basic substituent containing a nitrogen atom at the same time because dispersibility is further improved. This is considered to promote the pigment adsorption of the dispersant by the acid-base interaction between the acidic substituent of the dye derivative arranged in the vicinity of the pigment and the basic substituent of the dispersant.

That is, the structure of the pigment derivative (e) that can be used in the present invention is a compound represented by the following general formula (52).
P-Ln Formula (52)
[In general formula (52),
P: Organic pigment residue, benzimidazolone residue, acridone residue, β-naphthol residue or triazine residue L: basic substituent, acidic substituent, or optionally substituted phthalimidomethyl group , N is an integer of 1 to 4. ]

  Examples of the organic pigment constituting the organic pigment residue of P include, for example, diketopyrrolopyrrole pigments; azo pigments such as azo, disazo and polyazo; phthalocyanine pigments such as copper phthalocyanine, halogenated copper phthalocyanine and metal-free phthalocyanine Anthraquinone pigments such as aminoanthraquinone, diaminodianthraquinone, anthrapyrimidine, flavantron, anthanthrone, indanthrone, pyranthrone, violanthrone; quinacridone pigment; dioxazine pigment; perinone pigment; perylene pigment; thiaindigo pigment; Indoline pigments; isoindolinone pigments; quinophthalone pigments; selenium pigments; metal complex pigments.

Among them, organic pigments constituting the organic pigment residue of P are diketopyrrolopyrrole pigments, azo pigments such as azo, disazo, polyazo, aminoanthraquinone, diaminodianthraquinone, anthrapyrimidine, flavantron, anthanthrone, indane. Anthraquinone pigments such as Throne, Pyrantron, Biolantron, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thiaindigo pigments, isoindoline pigments, isoindolinone pigments, quinophthalone pigments, selenium pigments, In the case of a metal complex pigment, it is more preferable because the color is close to the main pigment and easy toning,
Diketopyrrolopyrrole pigments, azo pigments such as azo, disazo, and polyazo, aminoanthraquinones, diaminodianthraquinones, anthrapyrimidines, flavantrons, anthanthrone, indanthrone, pyranthrone, violanthrone, and other anthraquinone pigments, quinacridone pigments, Particularly preferred are thiaindigo pigments and quinophthalone pigments.

  Β-naphthol constituting the β-naphthol residue of P is an alkyl group (methyl group, ethyl group, butyl group, etc.), amino group, alkylamino group (dimethylamino group, diethylamino group, dibutylamino group, etc.), nitro Group, hydroxyl group, alkoxy group (methoxy group, ethoxy group, butoxy group, etc.), halogen (chlorine, bromine, etc.), phenyl group (alkyl group, amino group, alkylamino group, nitro group, hydroxyl group, alkoxy group, halogen, etc.) And a substituent such as a phenylamino group (which may be substituted with an alkyl group, amino group, alkylamino group, nitro group, hydroxyl group, alkoxy group, halogen, etc.) It is also a good β-naphthol.

  Examples of the acidic substituent for L include sulfonic acid, carboxylic acid, and phosphoric acid.

By including a pigment derivative, even in the case of a pigment that is difficult to disperse without a pigment derivative, a pigment composition excellent in dispersibility, fluidity, and storage stability can be obtained, and the fluidity and storage stability are excellent. It can be made into a pigment composition.

  Furthermore, since the colorant of the present invention is an azo dye, the dye derivative is also preferably an azo dye derivative. It is considered that the combination of the azo dye and the dye derivative increases the adsorptivity of the dye derivative to the pigment, and fine pigment particles exist in a more stable state.

  In the present invention, the amount of the pigment derivative (e) is preferably 1 part by weight or more, more preferably 5 parts by weight or more, and most preferably 10 parts by weight with respect to 100 parts by weight of the colorant from the viewpoint of improving dispersibility. That's it. Further, from the viewpoint of heat resistance and light resistance, the amount is preferably 25 parts by weight or less, and most preferably 20 parts by weight or less with respect to 100 parts by weight of the colorant.

  The coloring composition for a color filter of the present invention can be used as a photosensitive coloring composition (resist material) for a color filter by further adding a photopolymerizable monomer and / or a photopolymerization initiator.

<Photopolymerizable monomer>
The photopolymerizable monomer used in the present invention includes monomers or oligomers that are cured by ultraviolet rays or heat to form a resin, and these can be used alone or in combination of two or more.

  Examples of the photopolymerizable monomer include methyl methacrylate, ethyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, cyclohexyl methacrylate, β-carboxyethyl methacrylate, polyethylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, triethylene glycol dimethacrylate, tripropylene glycol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, 1,6-hexanediol di Glycidyl ether dimethacrylate, bisphenol A diglycidyl ether dimethacrylate, neopentyl grease Diglycidyl ether dimethacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol pentamethacrylate, tricyclodecanyl methacrylate, ester acrylate, methylolated melamine methacrylate, epoxy methacrylate, urethane acrylate, etc. Acrylic acid ester and methacrylic acid ester, acrylic acid, methacrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, methacrylamide, N-hydroxymethylmethacrylamide, N-vinylformamide, acrylonitrile However, it is not necessarily limited to these.

  The content 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 coloring composition for a color filter of the present invention, when the composition is cured by ultraviolet irradiation and a filter segment is formed by a photolithography method, a photopolymerization initiator or the like is added to add a solvent development type or an alkali development type photosensitive. Can be prepared in the form of an ionic coloring composition.

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 ethyl ether, benzoin isopropyl ether, or ben Benzoin compounds such as rudimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, or 3,3 ′, 4 Benzophenone compounds such as 4,4′-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, 2,4-diethylthioxanthone, etc. 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloromethyl) -S-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- ( 4-methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, or 2,4-trichloromethyl- (4 Triazine compounds such as' -methoxystyryl) -6-triazine; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], or O Oxime ester compounds such as (acetyl) -N- (1-phenyl-2-oxo-2- (4′-methoxy-naphthyl) ethylidene) hydroxylamine; bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide Or phosphine compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone and ethylanthraquinone; borate compounds; carbazole compounds; imidazole compounds Or a titanocene compound or the like is used.
These photoinitiators can be used individually by 1 type or in mixture of 2 or more types by arbitrary ratios as needed.

  The content of the photopolymerization initiator is preferably 5 to 200 parts by weight with respect to 100 parts by weight of the colorant, and more preferably 10 to 150 parts by weight from the viewpoint of photocurability and developability.

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

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

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

<Antioxidant>
The coloring composition for a color filter of the present invention can contain an antioxidant. Antioxidants are used to prevent the photopolymerization initiators and thermosetting compounds contained in the color filter coloring composition from oxidizing and yellowing due to thermal processes during thermal curing and ITO annealing. Can be high. Therefore, by including an antioxidant, yellowing due to oxidation during the heating step can be prevented, and 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- Su- (6-t-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-hydro Cinnamamide) 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. 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 for color filters 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 coloring composition for a color filter of the present invention. As the leveling agent, dimethylsiloxane having a polyether structure or a polyester structure in the main chain is preferable. Specific examples of dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Toray Dow Corning, BYK-333 manufactured by Big Chemie. Specific examples of dimethylsiloxane having a polyester structure in the main chain include BYK-310 and BYK-370 manufactured by BYK Chemie. Dimethylsiloxane having a polyether structure in the main chain and dimethylsiloxane having a polyester structure in the main chain can be used in combination. The content of the leveling agent is usually preferably 0.003 to 0.5% by weight in 100% by weight of the total weight of the coloring composition.

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

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

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

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

<Curing agent, curing accelerator>
Moreover, in order to assist hardening of a thermosetting resin, the coloring composition for color filters of this invention may contain the hardening | curing agent, the hardening accelerator, etc. as needed. As the curing agent, phenolic resins, amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds and the like are effective, but are not particularly limited to these, and thermosetting resins. Any curing agent may be used as long as it can react with the. Among these, a compound having two or more phenolic hydroxyl groups in one molecule and an amine curing agent are preferable. Examples of the curing accelerator include amine compounds (for example, dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl). -N, N-dimethylbenzylamine etc.), 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- D Ru-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. The content of the curing accelerator is preferably 0.01 to 15 parts by weight based on the total weight of the thermosetting resin (100 parts by weight).

<Other additive components>
The coloring composition for a color filter of the present invention can contain a storage stabilizer in order to stabilize the viscosity with time of the composition. 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 total 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, based on 100 parts by weight of the total weight of the colorant.

<Method for producing colored composition>
The coloring composition for a color filter of the present invention comprises a coloring agent containing a naphtholazo pigment [A1], a resin-type dispersant, and, if necessary, a resin, a solvent (e), and a dye derivative (e). It can be produced by finely dispersing (pigment dispersion) using various dispersing means such as a present roll mill, a two-roll mill, a sand mill, a kneader, a trimix, or an attritor. Moreover, the coloring composition for color filters of this invention may disperse | distribute the naphthol azo pigment [A1], and other colorants, such as a red pigment and a yellow pigment used together, separately mixed. Can also be manufactured

  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 comprises the pigment dispersion, a photopolymerizable monomer and / or a photopolymerization initiator, and, if necessary, a solvent, other dispersants, and additives. 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.

<Removal of coarse particles>
The colored composition for a color filter of the present invention is a coarse particle having a size of 5 μm or more, preferably a coarse particle having a size of 1 μm or more, more preferably a coarse particle having a size of 0.5 μm or more. It is preferable to remove the mixed dust. Thus, it is preferable that the coloring composition for color filters substantially does not contain particles of 0.5 μm or more. More preferably, it is 0.3 μm or less.

<Color filter>
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 green filter segment can be formed using a normal green coloring composition. Examples of the green coloring composition include C.I. I. Pigment Green 7, 10, 36, 37, 58, and the like. 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 It can be used in combination with the yellow pigments such as 181,182,185,187,188,193,194,198,199,213,214.

  Moreover, a blue filter segment can be formed using a normal blue coloring composition. Examples of the blue coloring composition include C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, and the like. Blue coloring compositions include C.I. I. Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, 50, and other purple pigments can be used in combination.

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

[Photolithography]
When forming a filter segment by a photolithography method, the photosensitive coloring composition prepared as the solvent development type or alkali development type coloring composition is spray coated, spin coated, slit coated, roll coated, etc. on a transparent substrate. The coating method is applied so that the dry film thickness is 0.2 to 5 μm. If necessary, the dried film is exposed to ultraviolet rays, which are active energy rays, 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 | stimulate superposition | polymerization of a coloring composition, it can also heat as needed. 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 composition, a water-soluble or alkaline water-soluble resin such as polyvinyl alcohol or water-soluble acrylic resin is applied and dried to form a film that prevents polymerization inhibition by oxygen. Then, ultraviolet exposure can be performed.

  The color filter of the present invention can be produced by an electrodeposition method, a transfer method, etc. 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.

  The colored composition of the present invention can be used in any of the methods described above, but is most suitable for the photolithography method.

  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. In addition, 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. On the color filter of the present invention, an overcoat film, a columnar spacer, a transparent conductive film, a liquid crystal alignment film, and the like are formed 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 in a liquid crystal display mode in which colorization is performed using a color filter such as the above.

  EXAMPLES The present invention will be described more specifically with reference to the following examples. However, the present invention is not limited to the following examples unless it exceeds the gist. In the examples and comparative examples, “parts” and “%” mean “parts by weight” and “% by weight”, respectively.

  Also, identification method of azo pigment, acid value of resin and resin type dispersant, weight average molecular weight (Mw) and number average molecular weight (Mn) of resin, amine value of resin type dispersant, resin type dispersant The quaternary ammonium salt value, the average primary particle diameter of the pigment, the specific surface area of the pigment, and the contrast ratio of the coating film are as follows.

<Azo pigment identification method>
The identification of the azo pigment of the present invention is carried out using the 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 and the mass number obtained by calculation. Identified with agreement.

<Acid value of resin and resin type dispersant>
The acid values of the resin and the resin-type dispersant were determined by potentiometric titration using a 0.1N potassium hydroxide / ethanol solution. The acid value of the resin and the resin-type dispersant indicates the acid value of the solid content.

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

<Amine value of resin-type dispersant>
The amine value of the resin-type dispersant was determined by potentiometric titration using a 0.1N hydrochloric acid aqueous solution, and then converted to an equivalent of potassium hydroxide. The amine value of the resin-type dispersant indicates the amine value of the solid content.

<Quaternary ammonium salt value of resin-type dispersant>
The quaternary ammonium salt value of the resin-type dispersant was determined by titrating with a 0.1N silver nitrate aqueous solution using a 5% potassium chromate aqueous solution as an indicator, and then converted into an equivalent of potassium hydroxide. The quaternary ammonium salt value of the following resin type dispersant indicates the quaternary ammonium salt value of the solid content.

<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 (TEM) 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 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.

<Specific surface area of pigment>
The specific surface area of the pigment was measured by an automatic vapor adsorption amount measuring apparatus (“BELSORP18” manufactured by Nippon Bell Co., Ltd.) using the nitrogen adsorption BET method.

<Measurement method of contrast ratio of coating film>
The light emitted from the backlight unit for liquid crystal display passes through the polarizing plate, is polarized, passes through the dried coating film of the colored composition applied on the glass substrate, and reaches the polarizing plate. If the polarizing planes of the polarizing plate and the polarizing plate are parallel, light is transmitted through the polarizing plate, but if the polarizing plane is perpendicular, the light is blocked by the polarizing plate. However, when the light polarized by the polarizing plate passes through the dried coating film of the colored composition, scattering by the pigment particles occurs, resulting in deviation in a part of the polarization plane. When the amount of light transmitted through the plate is reduced and the polarizing plate is perpendicular, a part of the light is transmitted through the polarizing plate. This transmitted light was measured as the luminance on the polarizing plate, and the ratio (contrast ratio) between the luminance when the polarizing plate was parallel and the luminance when it was orthogonal was calculated.
(Contrast ratio) = (Luminance when parallel) / (Luminance when direct)
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, a black mask with a 1 cm square hole was applied to the measurement portion in order to block unnecessary light.

First, the used pigment derivative will be described.
<Structural formula of pigment derivative>
Table 5 summarizes the basic skeleton and terminal skeleton of the derivatives having acidic substituents used, and appends the structural formula of the organic pigment residue. The structural formula of the derivative is obtained by replacing the acidic group A bonded to the organic pigment residue with the terminal skeleton in Table 5.

Azo pigment general formula (60)

Quinophthalone pigment general formula (61)

Diketopyrrolopyrrole pigment general formula (62)

Anthraquinone pigments general formula (63)

Azo pigment general formula (64)

Thiaindigo pigment general formula (65)

Quinacridone pigment general formula (66)

Anthraquinone pigments general formula (67)

Azo pigment general formula (68)

  Then, the manufacturing method of the acrylic resin solution used for the Example and the comparative example, the resin-type dispersant solution, the refinement | purification pigment, the pigment dispersion, the green photosensitive coloring composition, and the blue photosensitive coloring composition is demonstrated.

<Method for producing acrylic resin solution>
(Adjustment of 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.

(Adjustment of 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.

<Method for producing resin-type dispersant>
(Resin type dispersant D solution)
A four-necked separable flask equipped with a thermometer, stirrer, distillation tube, and condenser was charged with 70 parts of methyl ethyl ketone, 96.1 parts of n-butyl acrylate, 2.8 parts of sparteine, and 1.9 parts of ethyl bromoisobutyrate. The temperature was raised to 40 ° C. under a nitrogen stream. 1.1 parts of cuprous chloride was added and the temperature was raised to 75 ° C. to initiate polymerization. After polymerization for 3 hours, the polymerization solution is sampled, and it is confirmed that the polymerization yield is 95% or more from the solid content of the polymerization, and 3.9 parts of N, N-dimethylaminoethyl methacrylate and 30.0 parts of MEK are added. Further, polymerization was performed. After 2 hours, it was confirmed that the polymerization yield was 97% or more from the solid content of the polymerization solution, and the polymerization was stopped by cooling to room temperature. 100 parts of the obtained resin solution was diluted with 100 parts of methyl ethyl ketone, 60 parts of cation exchange resin “Diaion PK228LH (Mitsubishi Chemical Corporation)” was added and stirred at room temperature for 1 hour. Part of "KYOWARD 500SN" (manufactured by Kyowa Chemical Industry Co., Ltd.) was added and stirred for 30 minutes. The polymerization catalyst residue was removed by removing the cation exchange resin and the adsorbent by filtration. Further, the resin solution is concentrated and substituted with ethylene glycol monomethyl ether acetate to form a block copolymer having an amine value of 76 mgKOH / g per solid, a weight average molecular weight (Mw) of 9000, and a nonvolatile content of 40% by weight. A resin type dispersant D solution having a substituent was obtained.

<Method for producing red colorant>
(Production of Red Colorant 1 (R-1): Azo Compound 1)
Below, the specific synthesis method of the said azo compound 1 is shown with the reaction scheme (the following reaction scheme A). Other azo compounds according to the present invention can be synthesized according to a similar scheme. In addition, the manufacturing method (synthesis method) of an azo compound is not limited to the following method.

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

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

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

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

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

(Production of Red Colorant 3 (R-3): Azo Compound 3)
Red except that 34.9 parts of 3-amino-4-methoxybenzanilide used in the production of red colorant 1 (R-1) was used, except that 24.9 parts of 3-amino-4-methoxybenzamide were used. Operation similar to manufacture of the coloring agent 1 (R-1) was performed, and 80.0 parts (yield 97%) of azo compounds 3 were obtained. As a result of mass spectrometry by TOF-MS, it was identified as azo compound 3.

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

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

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

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

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

(Production of Red Colorant 6 (R-6): Azo Compound 6)
Instead of compound (A) used in the production of red colorant 1 (R-1), instead of 5-chloro-2-aminobenztrifluoride and 3-amino-4-methoxybenzanilide, 3- Except for using 24.9 parts of amino-4-methoxybenzamide, the same operation as in the production of Red Colorant 1 (R-1) was performed to obtain 80.0 parts of azo compound 6. As a result of mass spectrometry by TOF-MS, it was identified as azo compound 6.

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

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

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

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

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

(Production of Red Colorant 9 (R-9): Azo Compound 9)
Instead of the compound (A) used in the production of the red colorant 1 (R-1), 74.3 parts of 2-chloro-5-aminobenztrifluoride, and 3-amino-4-methoxybenzanilide Instead, except that 24.9 parts of 3-amino-4-methoxybenzamide were used, the same operation as in the production of red colorant 1 (R-1) was performed, and 80.0 parts of azo compound 9 (yield) 97%). As a result of mass spectrometry by TOF-MS, it was identified as azo compound 9.

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

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

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

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

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

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

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

(Production of Red Colorant 13 (R-13): Azo Compound 13)
Instead of compound (A) used in the preparation of red colorant 1 (R-1), 66.8 parts 3-aminobenztrifluoride and 3 amino-3 instead of 3-amino-4-methoxybenzanilide Except for using 46.5 parts of -amino-4-methoxybenz- (3'-trifluoromethyl) anilide, the same operation as in the production of red colorant 1 (R-1) was performed, and azo compound 13 was converted to 80 0.0 part (yield 95%) was obtained. As a result of mass spectrometry by TOF-MS, it was identified as azo compound 13.

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

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

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

Compound (D)

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

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

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

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

(Production of Red Colorant 17 (R-17): Azo Compound 1 Refined by Acid Pasting Method)
Add 80 parts of azo compound 1 obtained in the production of red colorant 1 (R-1) to 1200 parts of concentrated sulfuric acid, stir at 40 ° C. for 3 hours, and then inject this sulfuric acid solution into 24000 parts of cold water at 3 ° C. did. The produced precipitate was filtered, washed with water, and dried overnight at 80 ° C. to obtain 78 parts of red colorant 17 (R-17). The average primary particle size was 65 nm.

(Production of Red Colorant 18 (R-18): Azo Compound 1 / PR176)
125 parts of 3-amino-4-methoxybenzanilide are dispersed in 2000 parts of water, ice is added to adjust the temperature to 5 ° C., 205 parts of 35% aqueous hydrochloric acid is added, and the mixture is stirred for 1 hour. A water solution prepared by adding 110 parts to water was added, and the mixture was stirred for 2 hours. An aqueous solution consisting of 380 parts of an 80% aqueous acetic acid solution, 418 parts of a 25% aqueous sodium hydroxide solution, and 413 parts of water was added to form an aqueous diazonium salt solution.
Meanwhile, 154 parts of N- [2-chloro-5-trifluoromethylphenyl] -3-hydroxy-2-naphthalenecarboxamide, N- [4- (2-oxo-2,3-dihydro-1H-benzimidazole] 5-yl)]-3-hydroxy-2-naphthalenecarboxamide 33.5 parts and 25% aqueous sodium hydroxide solution 1344 parts were dissolved in 3500 parts of methanol to obtain a coupler solution.
This coupler solution was poured into the 5 ° C. diazonium salt aqueous solution over 30 minutes to carry out a coupling reaction. The pH at this time was 4.4. After stirring for 3 hours and confirming the disappearance of the diazonium salt, the mixture was heated to 70 ° C., filtered, washed with water, and dried at 90 ° C. for 24 hours. The azo pigment of azo compound 1 and the azo compound represented by the general formula (6) C. a pigment. I. 309 parts of a mixture with Pigment Red 176 were obtained. As a result of mass spectrometry by TOF-MS, an azo pigment of azo compound 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 azo compound was subjected to the same salt milling method as red colorant 1 (R-1) to obtain red colorant 18 (R-18). The average primary particle size was 32 nm.

<Method for producing other red colorant>
(Production of red colorant 19 (RC-1): PR254)
Commercially available C.I. I. 100 parts of Pigment Red 254 (PR254) ("Irgafore Red B-CF" manufactured by BASF), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) at 6O 0 C. The mixture was kneaded for a time and subjected to salt milling. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 98 parts of red colorant 19 (RC-1) were obtained. The average primary particle size was 33 nm.

(Production of red colorant 20 (RC-2): PR177)
C. I. Pigment Red 254 (“Irgafore Red B-CF” manufactured by BASF) I. Except for changing to CI Pigment Red 177 (PR177) ("CROMOPHTAL RED A2B" manufactured by BASF), the same procedure as in the production of Red Colorant 1 (RC-1) was carried out, and 97 parts of Red Colorant 20 (RC-2) was added. Obtained. The average primary particle size was 37 nm.

(Production of red colorant 21 (RC-3): PR242)
C. I. Pigment Red 254 (“Irgafore Red B-CF” manufactured by BASF) I. Except having changed to pigment red 242 (PR242) (Clariant's SandorinScallet4RF), it carried out similarly to manufacture of the red coloring agent 1 (RC-1), and obtained 98 parts of red coloring agent 21 (RC-3). The average primary particle size was 39 nm.

(Production of red colorant 22 (RC-4): PR176)
C. I. Pigment Red 254 (“Irgafore Red B-CF” manufactured by BASF) I. Pigment Red 176 (PR176) (“Novoperm Carmine HF3C” manufactured by Clariant) was used in the same manner as in the production of Red Colorant 1 (RC-1), and 98 parts of Red Colorant 22 (RC-4) were used. Obtained. The average primary particle size was 35 nm.

(Production of red colorant 23 (RC-5): PO38)
C. I. Pigment Red 254 (“Irgafore Red B-CF” manufactured by BASF) I. Pigment Orange 38 (PO38) (“Novoperm Red HF part” manufactured by Clariant) was performed in the same manner as in the production of Red Colorant 1 (RC-1), and 97 parts of Red Colorant 23 (RC-5) Got. The average primary particle size was 39 nm.

(Production of Red Colorant 24 (RC-6): Formula (2-19))
To a stainless steel reaction vessel equipped with a reflux tube, 200 parts of tert-amyl alcohol dehydrated with molecular sieves and 140 parts of sodium-tert-amyl alkoxide are added in a nitrogen atmosphere and heated to 100 ° C. with stirring to obtain an alcoholate solution. Prepared. On the other hand, 88 parts of diisopropyl succinate and 153.6 parts of 4-bromobenzonitrile were added to a glass flask and dissolved by heating to 90 ° C. with stirring to prepare a solution of these mixtures. The heated solution of the mixture was slowly dropped into the alcoholate solution heated to 100 ° C. at a constant rate over 2 hours with vigorous stirring. After completion of the dropwise addition, heating and stirring were continued for 2 hours at 90 ° C. to obtain an alkali metal salt of a diketopyrrolopyrrole compound. Furthermore, 600 parts of methanol, 600 parts of water and 304 parts of acetic acid were added to a reaction vessel with a glass jacket, and cooled to -10 ° C. While cooling this mixture with a high-speed stirring disperser and rotating a shear disk having a diameter of 8 cm at 4000 rpm, the alkali metal salt of the diketopyrrolopyrrole compound obtained above was cooled to 75 ° C. The solution was added in small portions. At this time, the rate of addition of the alkali metal salt of the diketopyrrolopyrrole compound at 75 ° C. while cooling so that the temperature of the mixture consisting of methanol, acetic acid and water is always kept at −5 ° C. or lower. Was added in small portions over approximately 120 minutes. After addition of the alkali metal salt, red crystals were precipitated to form a red suspension. Subsequently, the obtained red suspension was washed with an ultrafiltration device at 5 ° C. and then filtered to obtain a red paste. This paste was re-dispersed in 3500 parts of methanol cooled to 0 ° C. to make a suspension with a methanol concentration of about 90%, and stirred at 5 ° C. for 3 hours to perform particle sizing and washing with crystal transition. Subsequently, the resulting diketopyrrolopyrrole compound aqueous paste was filtered off with an ultrafiltration machine, dried at 80 ° C. for 24 hours, and pulverized, thereby bromination represented by the formula (2-19). 150.8 parts of diketopyrrolopyrrole pigment were obtained.

  100 parts of the brominated diketopyrrolopyrrole pigment represented by the formula (2-19) obtained above, 1200 parts of sodium chloride and 120 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) at 60 ° C. And kneaded for 6 hours and subjected to salt milling. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 98 parts of red colorant 24 (RC-6) were obtained. The average primary particle size was 45 nm.

<Manufacturing method of other colorants>
(Production of green colorant 1: PG58)
Phthalocyanine green pigment C.I. I. 200 parts of Pigment Green 58 (“FASTOGEN GREEN A110” manufactured by DIC), 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. The product was put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, then dried overnight at 85 ° C., 190 parts of A green colorant 1 was obtained, and the specific surface area of the green colorant 1 was 75 m ² / g.

(Preparation of blue colorant 1: PB15: 6)
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. 190 parts of blue colorant 1 were obtained. The specific surface area of the blue colorant 1 was 80 m ² / g.

(Preparation of purple colorant 1: PV23)
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. 190 parts of purple colorant 1 were obtained. The specific surface area of the purple colorant 1 was 95 m ² / g.

<Method for producing pigment dispersion>
(Pigment dispersion (DC-1): PR254)
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 (DC-1) whose non-volatile component is 20 weight% was produced.
Red colorant 19 (RC-1): 11.0 parts (CI Pigment Red 254)
Acrylic resin solution 1: 35.0 parts propylene glycol monomethyl ether acetate (PGMAC): 49.0 parts resin-type dispersant solution (dispersant A): 5.0 parts “DISPERBYK2000” (manufactured by Big Chemie Japan)
Non-volatile content 40% by weight Propylene glycol monomethyl ether acetate / butoxyethanol solution

(Pigment dispersion (DC-2): PR177)
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 (DC-2) whose non-volatile component is 20 weight% was produced.
Red colorant 20 (RC-2): 11.0 parts (CI Pigment Red 177)
Acrylic resin solution 1: 35.0 parts Propylene glycol monomethyl ether acetate (PGMAC): 49.0 parts Resin type dispersant solution (dispersant A): 5.0 parts

(Pigment dispersion (DC-3): PR242)
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 (DC-3) whose non-volatile component is 20 weight% was produced.
Red colorant 21 (RC-3): 11.0 parts (CI Pigment Red 242)
Acrylic resin solution 1: 35.0 parts Propylene glycol monomethyl ether acetate (PGMAC): 49.0 parts Resin type dispersant solution (dispersant A): 5.0 parts

(Pigment dispersion (DC-4): PR176)
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 (DC-4) whose non-volatile component is 20 weight% was produced.
Red colorant 22 (RC-4): 11.0 parts (CI Pigment Red 176)
Acrylic resin solution 1: 35.0 parts Propylene glycol monomethyl ether acetate (PGMAC): 49.0 parts Resin type dispersant solution (dispersant A): 5.0 parts

(Pigment dispersion (DC-5): PO38)
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 (DC-5) whose non-volatile component is 20 weight% was produced.
Red colorant 23 (RC-5): 11.0 parts (CI Pigment Orange 38)
Acrylic resin solution 1: 35.0 parts Propylene glycol monomethyl ether acetate (PGMAC): 49.0 parts Resin type dispersant solution (dispersant A): 5.0 parts

(Pigment dispersion (DC-6): Brominated diketopyrrolopyrrole pigment Formula (2-19))
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 (DC-6) whose non-volatile component is 20 weight% was produced.
Red colorant 24 (RC-6): 11.0 parts (brominated diketopyrrolopyrrole pigment formula (2-19))
Acrylic resin solution 1: 35.0 parts Propylene glycol monomethyl ether acetate (PGMAC): 49.0 parts Resin type dispersant solution (dispersant A): 5.0 parts

  Table 6 shows pigment dispersions using other red colorants.

<Green photosensitive coloring composition, blue photosensitive coloring composition production method>
(Green photosensitive coloring composition 1: PG58 / PO38)
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. A green pigment dispersion having a nonvolatile content of 20% by weight was prepared.
Green colorant 1 (CI Pigment Green 58): 11.0 parts acrylic resin solution 1: 35.0 parts propylene glycol monomethyl ether acetate (PGMAC): 49.0 parts resin type dispersant solution (dispersant A) : 5.0 parts

Subsequently, a mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to prepare a green photosensitive coloring composition 1.
Green pigment dispersion: 32.0 parts Pigment dispersion (DC-5): 18.0 parts Acrylic resin solution 2: 7.5 parts Photopolymerizable monomer (“Aronix M-402” manufactured by Toagosei Co., Ltd.): 2.0 parts dipentaerythritol hexaacrylate photopolymerization initiator (“OXE-02” manufactured by BASF): 1.5 parts Etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole 3-yl]-, 1- (0-acetyloxime)
Cyclohexanone: 39.0 parts

(Blue photosensitive coloring composition 1: PB15: 6 / PV23)
The non-volatile content is 20% by weight in the same manner as the green pigment dispersion except that the green colorant 1 (CI Pigment Green 58) is changed to the blue colorant 1 (CI Pigment Blue 15: 6). Of blue pigment dispersion was obtained.

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

  Subsequently, a total of 50.0 parts of 32.0 parts of the green pigment dispersion and 18.0 parts of the pigment dispersion (DC-5) was converted to 46.0 parts of the blue dispersion and 4.0 parts of the purple dispersion 50. A blue photosensitive coloring composition 1 was obtained in the same manner as the green photosensitive coloring composition 1 except that 0 part was replaced.

[Example 1]
(Pigment dispersion (D-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 (D-1) whose non-volatile component is 20 weight% was produced.
Red colorant 1 (R-1): 10.0 parts acrylic resin solution 1: 35.0 parts propylene glycol monomethyl ether acetate (PGMAC): 49.0 parts resin type dispersant solution (dispersant A): 5.0 Part derivative (derivative A): 1.0 part

[Examples 2-39, Comparative Examples 1-4]
(Pigment dispersion (D-2 to 43))
Hereinafter, the pigment dispersions (D-2 to 43) were prepared in the same manner as the pigment dispersion (D-1) except that the pigment, the resin-type dispersant, and the derivative were changed to the compositions shown in Table 7.

Abbreviations in the table are described below.
<Resin type dispersant having basic group>
Resin-type dispersant A: DISPERBYK2000 (manufactured by Big Chemie Japan) Nonvolatile content: 40% by weight Propylene glycol monomethyl ether acetate / butoxyethanol solution, amine value: 4 mgKOH / g
Resin type dispersant B: SOLPERSE 76500 (manufactured by Lubrizol) Non-volatile content 50% by weight butyl acetate solution, amine value 10 mgKOH / g
Resin type dispersant C: BYK-LPN21116 (manufactured by Big Chemie Japan) Nonvolatile content 40% by weight Propylene glycol monomethyl ether acetate / ethylene glycol monobutyl ether / ethanol solution, amine value 29 mgKOH / g
-Resin type dispersant D: as described above. Amine value 76 mgKOH / g, Mw9000
Resin type dispersant E: BYK-LPN21715 (manufactured by Big Chemie Japan) Nonvolatile content 60% by weight Propylene glycol monomethyl ether acetate / ethylene glycol monobutyl ether solution, amine value 44 mgKOH / g
Resin type dispersant F: EFKA-4300 (manufactured by BSAF) Non-volatile content 80 wt% propylene glycol monomethyl ether acetate solution, amine value 56 mgKOH / g
Resin type dispersant G: BYK-LPN6919 (manufactured by Big Chemie Japan) Nonvolatile content 60% by weight propylene glycol monomethyl ether acetate / ethanol solution, amine value 74 mgKOH / g

[Evaluation of coloring composition (pigment dispersion) for color filter]
The viscosity characteristics, color characteristics, and contrast ratio of the pigment dispersions (D-1 to 43) obtained in Examples and Comparative Examples were evaluated by the following methods. Table 8 shows the evaluation results.

<Viscosity characteristics>
As for the viscosity of the pigment dispersion, an initial viscosity at 25 ° C. was measured using an E type viscometer (“ELD type viscometer” manufactured by Toki Sangyo Co., Ltd.). Separately, 25 g of the pigment dispersion was allowed to stand at 40 ° C. for 24 hours in a sealed state in a glass container, and then the viscosity was measured by the same method as described above to obtain the viscosity over time.

<Color characteristic evaluation>
The obtained photosensitive coloring composition is applied onto a glass substrate, dried at 70 ° C. for 20 minutes, and further heated at 230 ° C. for 60 minutes, so that the chromaticity of the substrate is x = 0. A coated substrate was obtained such that 640, y = 0.322. The brightness (Y) of the obtained substrate was measured with a microspectrophotometer (“OSP-SP200” manufactured by Olympus Optical Co., Ltd.).

<Contrast ratio (CR)>
Using the obtained pigment dispersion, a spin coater was used to produce three coated substrates so that the dry film thickness was about 1 μm by changing the number of rotations. After coating, the film was dried in a hot air oven at 80 ° C. for 30 minutes, and the film thickness and the contrast ratio were measured. The contrast ratio (CR) at a film thickness of 1 μm was determined from the three points of data by the primary correlation method.

  The coloring composition for a color filter of the present invention comprising a coloring agent containing the naphtholazo pigment [A1] represented by the general formula (1) and a resin-type dispersant having an acidic substituent is a coloring composition of a comparative example. On the other hand, the viscosity was low and the brightness and CR were high. In particular, the naphthol azo pigment [A1] of the coloring composition of the present invention is an existing pigment C.I. I. Compared to Pigment Orange 38, C.I. I. Pigment Red 254, bluer, C.I. I. It is yellowish than CI Pigment Red 177, and the rising wavelength of the transmission spectrum is in the range of 570 to 590 nm. Therefore, it effectively acts on the bright line of the backlight generally used in liquid crystal display devices, and high brightness is obtained. It was. Moreover, by using a naphtholazo pigment and a resin-type dispersant in combination, the pigment can be stably present in a primary particle state, and a high contrast ratio can be obtained at the same time.

  In particular, when the polyester skeleton contains an acidic resin-type dispersant having an aromatic carboxylic acid group as an acidic substituent and a pigment derivative having a basic substituent, the viscosity was lower and the CR was higher. .

  In particular, when A is a phenyl group which may have a substituent, superiority was observed in brightness and CR.

[Example 40]
(Photosensitive coloring composition (DR-1))
The following mixture (100 parts in total) was stirred and mixed so as to be uniform, and then filtered through a 1.0 μm filter to obtain a photosensitive colored composition (DR-1).
(Pigment dispersion) (Total 50 parts)
Pigment dispersion (D-1): 20.0 parts Pigment dispersion (RC-1): 30.0 parts Acrylic resin solution 2: 7.5 parts Photopolymerizable monomer ("Aronix M-" manufactured by Toagosei Co., Ltd.) 402 "): 2.0 parts dipentaerythritol hexaacrylate photopolymerization initiator (" OXE-02 "manufactured by BASF): 1.5 parts ethanone, 1- [9-ethyl-6- (2-methylbenzoyl)- 9H-carbazol-3-yl]-, 1- (0-acetyloxime)
Cyclohexanone: 39.0 parts

[Examples 41 to 84, Comparative Examples 5 to 8]
(Photosensitive coloring composition (DR-2 to 49))
Photosensitive coloring compositions (DR-2 to 49) were obtained in the same manner as the photosensitive coloring composition (DR-1) except that the pigment dispersion was changed to the type and blending amount of the pigment dispersion shown in Table 9. . In each photosensitive coloring composition adjustment, it added so that the sum total of a pigment dispersion might be 50 parts, and adjusted 100 parts of photosensitive coloring compositions.

[Evaluation of Color Filter Coloring Composition (Photosensitive Coloring Composition)]
The color characteristics, contrast ratio, heat resistance, light resistance, and foreign matter evaluation of the photosensitive coloring compositions (DR-1 to 49) obtained in Examples and Comparative Examples were performed by the following methods. Table 9 shows the evaluation results.

<Color characteristic evaluation>
The photosensitive coloring composition (DR1 to 49) is applied on a 100 mm × 100 mm, 1.1 mm thick glass substrate using a spin coater, then dried at 70 ° C. for 20 minutes, and an ultrahigh pressure mercury lamp is used. Then, UV exposure was performed with an integrated light amount of 150 mJ / cm ² , development was performed with an alkaline developer at 23 ° C., and then heated and allowed to cool at 230 ° C. for 60 minutes to obtain a coated substrate. After heat treatment at 230 ° C., a coated substrate having x = 0.658 and y = 0.325 in a C light source was obtained. The brightness (Y) of the obtained substrate was measured with a microspectrophotometer (“OSP-SP200” manufactured by Olympus Optical Co., Ltd.).

<Contrast ratio (CR)>
An evaluation substrate was prepared in the same manner as the color characteristic evaluation of the coating film. The CR of the obtained coated substrate was measured.

<Heat resistance evaluation>
On a 100 mm × 100 mm, 1.1 mm thick glass substrate, a spin coater was used to apply a dry film thickness of 2.0 μm, followed by drying at 70 ° C. for 20 minutes, and using an ultrahigh pressure mercury lamp. Then, UV exposure was performed with an integrated light amount of 150 mJ / cm ² , development was performed with an alkaline developer at 23 ° C., and then the coating substrate was prepared by heating at 230 ° C. for 60 minutes and allowing to cool. 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 250 ° C. for 1 hour, and the chromaticity ([L * (2), a * (2), b * (2)]) with a C light source was measured. The color difference ΔEab * was determined and evaluated in the following three stages.
ΔEab * = √ ((L * (2)-L * (1)) 2+ (a * (2)-a * (1)) 2+ (b * (2)-b * (1)) 2)
○: ΔEab * is less than 2.5 Δ: ΔEab * is 2.5 or more and less than 5.0 ×: ΔEab * is 5.0 or more

<Light resistance evaluation>
A coated substrate is prepared in the same manner as in the heat resistance evaluation, and the chromaticity ([L * (1), a * (1), b * (1)]) with a C light source is measured with a microspectrophotometer ( Measurement was performed using “OSP-SP100” manufactured by Olympus Optical Co., Ltd. Subsequently, an ultraviolet cut filter (“COLORED OPTICAL part LASS L38” manufactured by Hoya Co., Ltd.) was applied on the substrate, and irradiated with ultraviolet rays for 100 hours using a 470 W / m ² xenon lamp, and then the chromaticity ( [L * (2), a * (2), b * (2)]) were measured, and the color difference ΔEab * was determined by the above formula and evaluated according to the same criteria as for heat resistance.

<Coating foreign material evaluation>
On a 100 mm × 100 mm, 1.1 mm thick glass substrate, a spin coater was used to apply a dry film thickness of 2.0 μm, followed by drying at 70 ° C. for 20 minutes, and using an ultrahigh pressure mercury lamp. Then, UV exposure was performed with an integrated light amount of 150 mJ / cm ² , development was performed with an alkaline developer at 23 ° C., and then the coating substrate was prepared by heating at 230 ° C. for 60 minutes and allowing to cool. The evaluation was performed using a Olympus system metal microscope “BX60”). The magnification was 500 times, and the number of particles that were observable in arbitrary 5 fields of view through transmission was counted. Evaluation was made in the following three stages. ○ indicates that the number of foreign matters is small and good, and Δ indicates that there is a large number of foreign matters but there is no problem in use, and × indicates that the coating cannot be used because of uneven coating due to foreign matters.
○: Number of foreign matter is less than 10 Δ: Number of foreign matter is 10 or more, less than 60 ×: Number of foreign matter is 60 or more

  Coloring for a color filter of the present invention comprising a colorant containing a naphtholazo pigment [A1] represented by the general formula (1) and a resinous dispersant (c) which is a resinous dispersant having a basic substituent. All the compositions had high brightness and CR, and had good results in heat resistance, light resistance, and coating film foreign matter.

  Further, the photosensitive coloring composition further containing a dye derivative had a better CR than the photosensitive coloring composition not containing the dye derivative.

  On the other hand, the photosensitive coloring composition containing no naphtholazo pigment [A1] had poor resistance and low brightness.

[Example of color filter production]
Using the red photosensitive coloring composition 1, the green photosensitive coloring composition 1 and the blue photosensitive coloring composition 1 of the present invention, the dry film thickness is 1.7 μm by spin coating on the substrate. It is applied, dried, and exposed to UV light through a mask having a predetermined pattern provided in a non-contact state with the coating film. After that, an alkaline developer is sprayed to remove the uncured portion and form a desired pattern. After that, it was heated at 230 ° C. for 1 hour. By repeating the same operation for green and blue to produce a color filter, it was possible to produce an RGB three-color filter with high brightness and excellent resistance.

Claims (7)

In the red coloring composition for a color filter containing a colorant, a resin, a resin-type dispersant, and a solvent, the colorant contains a naphtholazo pigment [A1] represented by the following general formula (1): The red colored composition for a color filter, wherein the resin type dispersant contains a resin type dispersant (c) having a basic substituent.
General formula (1)

[In General Formula (1), each A independently represents a hydrogen atom, a methyl group, a benzimidazolone group, a phenyl group which may have a substituent, or a heterocyclic group which may have a substituent. Represents.
R ¹ represents a hydrogen atom, a halogen atom, a trifluoromethyl group, an alkyl group having 1 to 4 carbon atoms, —OR ⁷ , or —COOR ⁸ . R ^{2 to} R ⁶ are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, a trifluoromethyl group, an alkyl group having 1 to 4 carbon atoms, —OR ⁹ , —COOR ¹⁰ , —CONHR ¹¹ , or an -SO ₂ NHR ^12, representative of at least one trifluoromethyl group among R ² to R ^6. R ^{7 to} R ¹² each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ]   The red coloring composition for a color filter according to claim 1, wherein A is a phenyl group which may have a substituent.   The red coloring composition for a color filter according to claim 1 or 2, wherein the resin-type dispersant (c) having a basic substituent is a resin-type dispersant containing a nitrogen atom.   Furthermore, the dye derivative (e) is included, and the dye derivative (e) is at least selected from the group consisting of a pigment derivative having an acidic substituent, a β-naphthol derivative having an acidic substituent, and a triazine derivative having an acidic substituent. The red coloring composition for a color filter according to any one of claims 1 to 3, comprising a pigment derivative having one or more kinds of acidic substituents. The colorant further comprises at least one selected from the group consisting of a naphthol azo pigment [A ′] represented by the following general formula (6), an azo pigment [C], a diketopyrrolopyrrole pigment, and an anthraquinone pigment. The coloring composition for color filters according to any one of claims 1 to 4, which is contained.
General formula (6)

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