JP5919689B2 - Pigment dispersion, colored resin composition, color filter, liquid crystal display device and organic EL display device - Google Patents

Description

  The present invention relates to a pigment dispersion, a colored resin composition (hereinafter sometimes referred to as “resist”), a color filter, a liquid crystal display device, and an organic EL display device.

Conventionally, a pigment dispersion method, a dyeing method, an electrodeposition method, a printing method, and the like are known as methods for producing a color filter used for a liquid crystal display device or the like. Among these, from the viewpoint of spectral characteristics, durability, pattern shape, accuracy, etc., a pigment dispersion method having excellent characteristics on average is most widely adopted.
In recent years, the trend of technological innovation is rapid, and color filters are required to have higher transmittance (hereinafter sometimes referred to as “brightness”), higher contrast, and higher color density. It was. As the color material for determining the color of the color filter, a pigment is generally used from the viewpoint of heat resistance, light resistance and the like. As the pigment, a pigment whose intrinsic absorption spectrum in the visible light wavelength region matches the phosphor emission spectrum of the backlight is preferably used. In order to produce a high-contrast, high-luminance color filter, it is necessary to highly atomize a pigment having a high transmittance, and further to control and disperse the pigment particle size distribution in a small particle size region. The pigment particle size control technology is also rapidly developing.

  For example, dianthraquinone pigments, perylene pigments, diketopyrrolopyrrole pigments and the like have been used as red pigments. In particular, diketopyrrolopyrrole pigments are used in combination with various yellow pigments because of their high permeability, excellent light resistance and heat resistance. However, in recent years, pigment systems with higher transparency and contrast have been demanded, and further improvement in permeability has been studied by searching for new pigments as well as making the primary particle size of pigments finer and narrowing the particle size distribution. ing. In particular, in order to obtain a high contrast, atomization of the pigment is a key process.

As a method of atomizing the pigment by the atomization step, for example, the pigment, the water-soluble inorganic salt, and the water-soluble organic solvent are both mechanically kneaded with a kneader, etc., and then the inorganic salt and the organic solvent are removed by washing with water and atomized. There is a method such as a salt milling method for obtaining a pigment.
However, the pigment atomized by the above method tends to cause aggregation and crystallization. Therefore, how to suppress the crystallization of the pigment and obtain uniform fine particles has been a problem for many years.

In order to solve such a problem, for example, in Patent Documents 1 to 3, when preparing a pigment dispersion, a diketopyrrolopyrrole pigment derivative into which a sulfo group or a salt thereof is introduced is mixed into a diketopyrrolopyrrole pigment. It is disclosed.
Patent Document 4 discloses that a composition containing a sulfonated diketopyrrolopyrrole and a Mannich type substituted dihydroquinaclone is used.

JP 2000-160084 A JP 2006-265528 A JP 2007-23266 A JP-T-2004-505157

However, even with the methods described in Patent Documents 1 to 4, the obtained pixel contrast is insufficient.
In view of the above problems, the present invention has an object to provide a pigment dispersion and a colored resin composition capable of suppressing aggregation and crystallization of a pigment after the atomization step, the dispersion step, or the baking and obtaining a pixel having a high contrast. And

  Another object of the present invention is to provide a color filter having high contrast pixels, a high-quality liquid crystal display device, and an organic EL display device.

As a result of intensive studies, the present inventors have found that the pigment derivatives mixed for the purpose of suppressing the crystal growth of the pigment have a high cohesive force and have a crystal transition preventing function by effectively adsorbing to the pigment surface. It was found that the brightness was lowered due to coloring of the pigment derivative itself, and as a result, the above-mentioned problems were caused.
In other words, mixing for the purpose of suppressing crystal growth is not easy to inhibit the ability to suppress crystallization of pigments due to aggregation like pigment derivatives. It is effective to use a pigment that does not cause crystallization of the pigment by aggregation.

Therefore, it was speculated that by adding two or more additives, the aggregation of the pigment itself, which is generated when the additives are added individually, is effectively inhibited, thereby further suppressing the aggregation of the pigment.
Further, it was speculated that the above-mentioned problem could be solved as a result of the additive having a maximum absorption wavelength in the short wavelength region, that is, not having a maximum absorption wavelength in the visible light region.
As a result of further intensive studies based on these assumptions, the present inventors have found that the above-mentioned problems can be solved by using two or more compounds having a specific structure in combination.

  That is, the present invention is characterized in that a pigment dispersion containing (A) a pigment, (B) a solvent, and (D) a dispersant further contains two or more compounds represented by the following formula (1). Present in pigment dispersions, colored resin compositions, color filters, liquid crystal display devices and organic EL display devices.

(The formula (1), A ¹ represents a nitrogen-containing condensed ring group which may have a substituent.
R ¹ is an optionally substituted alkyl group having 1 to 5 carbon atoms, an optionally substituted alkoxy group having 1 to 4 carbon atoms, or an optionally substituted carbon. An aromatic ring group of several 6 to 10 is represented.
B ¹ represents an arbitrary substituent.
However, B ¹ in at least one compound is a group represented by —Z—X.
Z represents a direct bond or a divalent group selected from the following <divalent linking group group>.
<Divalent linking group group>

(In the above formula, * represents a linking site.)
X represents a group represented by any of the following formulas.

In the above formula, * represents a connecting site with Z.
M ¹ and M ² each independently represent a hydrogen atom, an alkali metal atom, or an alkaline earth metal atom.
R ^a1 and R ^a2 each independently represent a hydrogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or an aromatic ring group which may have a substituent. )

When a color filter is formed using a colored resin composition containing the pigment dispersion liquid of the present invention, the contrast is high because the pigment hardly aggregates.
In addition, by including the color filter of the present invention, it is possible to provide a high-quality liquid crystal display device and organic EL display device.

It is a section schematic diagram showing an example of an organic EL device which has a color filter of the present invention.

The constituent requirements and embodiments of the present invention will be described in detail below, but these are examples of the embodiments of the present invention, and the present invention is not limited to these contents.
“(Meth) acryl” and the like mean “at least one of acryl and methacryl” and “(meth) acrylate” and the like mean “at least one of acrylate and methacrylate”. “Meth) acrylic acid” means “at least one of acrylic acid and methacrylic acid”.

Further, “total solid content” means all components other than the solvent components described later, which are contained in the pigment dispersion or the colored resin composition.
In the present invention, unless otherwise specified, the weight average molecular weight refers to a polystyrene-reduced weight average molecular weight (Mw) by GPC (gel permeation chromatography). “C.I.” means a color index (C.I.).

Furthermore, in the present invention, the “amine value” means an amine value in terms of effective solid content unless otherwise specified, and is a value represented by the amount of base and the equivalent weight of KOH per 1 g of the solid content of the dispersant. is there. The measuring method will be described later. On the other hand, the “acid value” represents an acid value in terms of effective solid content unless otherwise specified, and is calculated by neutralization titration.
In the present invention, “aromatic ring” refers to both “aromatic hydrocarbon ring” and “aromatic heterocycle”.

The pigment dispersion of the present invention contains (A) a pigment, (B) a solvent, and (D) a dispersant, and further contains two or more compounds represented by the formula (1).
First, the compound represented by the formula (1) will be described in detail.
[Regarding Compound Represented by Formula (1)]

(The formula (1), A ¹ represents a nitrogen-containing condensed ring group which may have a substituent.
R ¹ is an optionally substituted alkyl group having 1 to 5 carbon atoms, an optionally substituted alkoxy group having 1 to 4 carbon atoms, or an optionally substituted carbon. An aromatic ring group of several 6 to 10 is represented.
B ¹ represents an arbitrary substituent.

However, B ¹ in at least one compound is a group represented by —Z—X.
Z represents a direct bond or a divalent group selected from the following <divalent linking group group>.
<Divalent linking group group>

(In the above formula, * represents a linking site.)
X represents a group represented by any of the following formulas.

In the above formula, * represents a connecting site with Z.
M ¹ and M ² each independently represent a hydrogen atom, an alkali metal atom, or an alkaline earth metal atom.
R ^a1 and R ^a2 each independently represent a hydrogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or an aromatic ring group which may have a substituent. )
(For ^{A 1)}
A ¹ represents a nitrogen-containing fused ring group which may have a substituent.

Examples of the nitrogen-containing condensed ring include a condensed ring of a cyclic aliphatic amine and an aromatic hydrocarbon ring.
Examples of the cycloaliphatic amine include a pyrrolidine ring, an imidazoline ring, a pyrazolidine ring, a piperidine ring, a piperazine ring, and a morpholine ring.
Examples of the aromatic hydrocarbon ring include a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring, acenaphthene ring, fluoranthene ring, and fluorene ring. Etc.

Preferable examples including a ring in which the cycloaliphatic amine and the aromatic hydrocarbon ring are condensed, that is, a substituent of the nitrogen-containing condensed ring, include those of the following <nitrogen-containing condensed ring group A>.
<Nitrogen-containing fused ring group A>

(In the above formula, * represents a linking site.)
Among them, the group exemplified in <Nitrogen-Condensed Ring Group A1> is particularly preferable in that it easily forms an intermolecular hydrogen bond with the pigment and has strong adsorption to the pigment surface.
<Nitrogen-containing fused ring group A1>

(In the above formula, * represents a linking site.)
Examples of the substituent that the nitrogen-containing fused ring group in A ¹ may have include, but are not limited to, the following <Substituent Group W>.
In addition, the benzene ring contained in the said structure may have a substituent other than a coupling group.
<Substituent group W>
Alkyl group which may have a substituent, alkoxy group which may have a substituent, amino group, alkylamino group which may have a substituent, aryl which may have a substituent An amino group, an acylamino group which may have a substituent, an alkylsulfonylamino group which may have a substituent, an arylsulfonylamino group which may have a substituent, a carbamoyl group, and a substituent. An optionally substituted alkylcarbamoyl group, an optionally substituted arylcarbamoyl group, a sulfamoyl group, an optionally substituted alkylsulfamoyl group or an optionally substituted aryl Examples include sulfamoyl group, hydroxyl group, nitro group, sulfo group, sulfonate group, carboxy group, carboxylate group, oxo group, cyano group and halogen atom. That.

  The alkyl group which may have a substituent has a total carbon number including the substituent of usually 1 or more, usually 6 or less, preferably 4 or less. Examples of the group that may be substituted on the alkyl group include an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, a halogen atom, a sulfo group, and a carboxy group. Specific examples of the alkyl group include a lower alkyl group which may have a substituent such as a methyl group, an ethyl group, an n-propyl group, a hydroxyethyl group, or a 1,2-dihydroxypropyl group.

  The alkoxy group which may have a substituent has a total carbon number including the substituent of usually 1 or more, usually 6 or less, preferably 3 or less. Examples of the group that may be substituted on the alkoxy group include an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, a halogen atom, a sulfo group, and a carboxy group. Specific examples of the alkoxy group include a lower alkoxy group which may have a substituent such as a methoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group, a hydroxyethoxy group, and a 1,2-dihydroxypropoxy group. Can be mentioned.

The alkylamino group which may have a substituent is represented by —NR ⁵¹ R ⁵² , R ⁵¹ represents an alkyl group which may have a substituent, and R ⁵² represents a hydrogen atom or a substituent. It represents an alkyl group that may have. The alkyl group has a total carbon number including substituents of usually 1 or more, usually 4 or less, preferably 2 or less. Examples of the group that may be substituted on the alkyl group include an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, a sulfo group, a carboxy group, and a halogen atom. Specific examples of the alkylamino group include a methylamino group, an ethylamino group, a propylamino group, and a dimethylamino group.

The arylamino group which may have a substituent is represented by —NR ⁵³ R ⁵⁴ , R ⁵³ represents a phenyl group or a naphthyl group which may have a substituent, and R ⁵⁴ represents a hydrogen atom. Represents an alkyl group which may have a substituent, a phenyl group which may have a substituent, or a naphthyl group which may have a substituent.
The total carbon number including the substituent of the alkyl group in R ⁵³ and R ⁵⁴ and examples of the substituent which may be present are the same as those exemplified for the alkyl group of R ⁵¹ and R ⁵² . The phenyl group has a total carbon number including substituents of usually 6 or more, usually 10 or less, preferably 8 or less. The naphthyl group has a total carbon number including a substituent of usually 10 or more, usually 14 or less, preferably 12 or less. Examples of the group that may be substituted on the phenyl group and the naphthyl group include an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, a sulfo group, a carboxy group, and a halogen atom. Specific examples of the arylamino group include a phenylamino group, a diphenylamino group, a phenylmethylamino group, and a naphthylamino group.

The acylamino group which may have a substituent is represented by —NH—COR ⁵⁵ , and R ⁵⁵ is an alkyl group which may have a substituent, a phenyl group which may have a substituent, or a substituted group. A naphthyl group which may have a group is represented. The alkyl group has a total carbon number including substituents of usually 1 or more, usually 4 or less, preferably 2 or less. The phenyl group generally has 6 or more, usually 10 or less, preferably 8 or less carbon atoms in the substituent. The naphthyl group has a total carbon number including a substituent of usually 10 or more, usually 14 or less, preferably 12 or less. Examples of the group that may be substituted on the alkyl group, the phenyl group, and the naphthyl group include an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, a sulfo group, a carboxy group, and a halogen atom. Specific examples of the acylamino group include an acetylamino group and a benzoylamino group.

The alkylsulfonylamino group which may have a substituent is represented by —NH—SO ₂ R ⁶¹ , and R ⁶¹ represents an alkyl group which may have a substituent. Examples of the total carbon number including preferred substituents of the alkyl group and the substituents that may be present are the same as those exemplified for the alkyl groups of R ⁵¹ and R ⁵² . Specific examples of the alkylsulfonylamino group include a methylsulfonylamino group and an ethylsulfonylamino group.

The arylsulfonylamino group which may have a substituent is represented by —NH—SO ₂ R ⁶² , and R ⁶² may have a phenyl group which may have a substituent or a substituent. Represents a naphthyl group. Examples of the total carbon number including preferred substituents of the phenyl group and naphthyl group, and the substituents that may be present are the same as those exemplified for the phenyl group and naphthyl group of R ⁵³ and R ^54. It is. Specific examples of the arylsulfonylamino group include a benzenesulfonylamino group and a p-tolylsulfonylamino group.

The alkylcarbamoyl group which may have a substituent is represented by —CO—NHR ⁵⁶ , and R ⁵⁶ represents an alkyl group which may have a substituent. Examples of the total carbon number including preferred substituents of the alkyl group and the substituents that may be present are the same as those exemplified for the alkyl groups of R ⁵¹ and R ⁵² . Specific examples of the alkylcarbamoyl group include a methylcarbamoyl group and an ethylcarbamoyl group.

The arylcarbamoyl group which may have a substituent is represented by —CO—NHR ⁵⁷ , and R ⁵⁷ is a phenyl group which may have a substituent or a naphthyl group which may have a substituent. Represents. Examples of the total carbon number including preferred substituents of the phenyl group and naphthyl group, and the substituents that may be present are the same as those exemplified for the phenyl group and naphthyl group of R ⁵³ and R ^54. It is. Specific examples of the arylcarbamoyl group include a phenylcarbamoyl group and a naphthylcarbamoyl group.

The alkylsulfamoyl group which may have a substituent is represented by —SO ₂ —NHR ⁵⁸ , and R ⁵⁸ represents an alkyl group which may have a substituent. Examples of the total carbon number including preferred substituents of the alkyl group and the substituents that may be present are the same as those exemplified for the alkyl groups of R ⁵¹ and R ⁵² . Specific examples of the alkylsulfamoyl group include a methylsulfamoyl group and an ethylsulfamoyl group.

The arylsulfamoyl group which may have a substituent is represented by —SO ₂ —NHR ⁵⁹ , and R ⁵⁹ may have a phenyl group which may have a substituent or a substituent. Represents a good naphthyl group. Examples of the total carbon number including preferred substituents of the phenyl group and naphthyl group, and the substituents that may be present are the same as those exemplified for the phenyl group and naphthyl group of R ⁵³ and R ^54. It is. Specific examples of the arylsulfamoyl group include a phenylsulfamoyl group and a naphthylsulfamoyl group.

  Examples of salts of sulfonate groups and carboxylate groups include alkali metal salts such as lithium salts, sodium salts and potassium salts, alkaline earth metal salts such as calcium salts and barium salts, aluminum salts, copper Examples thereof include various metal salts such as salts, ammonium salts, ammonium salts optionally substituted with alkyl groups or hydroxyalkyl groups, and salts of organic amines.

Examples of the alkyl group or hydroxyalkyl group that is a substituent that the ammonium salt may have include a lower alkyl group having 1 to 6 carbon atoms and a hydroxy-substituted lower alkyl group having 1 to 6 carbon atoms. .
Examples of organic amines include lower alkyl amines having 1 to 6 carbon atoms (for example, methylamine, ethylamine, dimethylamine, trimethylamine, etc.), hydroxy-substituted lower alkylamines having 1 to 6 carbon atoms (for example, ethanolamine, Diethanolamine, triethanolamine, etc.), carboxy-substituted lower alkylamines having 1 to 6 carbon atoms (for example, carboxymethylamine, carboxyethylamine, carboxypropylamine,
Dicarboxymethylamine) and the like.

In the case of these salts, the type is not limited to one type, and a plurality of types may be mixed. Moreover, multiple types may be mixed in one molecule of a compound, and multiple types may be mixed in the pigment dispersion or the colored resin composition.
Preferred salts for the sulfonate and carboxylate groups are free acid forms or calcium salts when low solubility in water is required (eg, added to the atomization step). Alkaline earth metal salts such as barium salts and aluminum salts are preferable. In order to have affinity with organic solvents, dispersants and resins, ammonium salts, ammonium salts which may have a substituent, organic salts Amine salts are preferred.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and among them, a fluorine atom, a chlorine atom and a bromine atom are preferable.
(For ^{B 1)}
B ¹ represents an arbitrary substituent.
Examples of the optional substituent include those described in the section of <Substituent group W>.
However, B ¹ in at least one compound is a group represented by —Z—X (note that a compound in which B ¹ is a group represented by —Z—X is hereinafter referred to as “compound (1- A) ").

Z represents a direct bond or a divalent group selected from the following <divalent linking group group>.
<Divalent linking group group>

(In the above formula, * represents a linking site.)
X represents a group represented by any of the following formulas.

In the above formula, * represents a connecting site with Z.
M ¹ and M ² each independently represent a hydrogen atom, an alkali metal atom, or an alkaline earth metal atom.
R ^a1 and R ^a2 each independently represent a hydrogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or an aromatic ring group which may have a substituent. )
Z may be only one kind mentioned in <Divalent linking group group>, or may be a group combining two or more kinds. Further, the number is preferably 5 or less.
M ¹ and M ² each independently represent a hydrogen atom, an alkali metal atom, or an alkaline earth metal atom. As the alkali metal atom, sodium is preferable. As the alkaline earth metal, calcium is preferable.

The hydrocarbon group for R ^a1 and R ^a2 is not particularly limited as long as it has 1 to 12 carbon atoms, and may be linear, branched or cyclic, and may be a saturated group or an unsaturated group. Methyl group, ethyl group, propyl group, butyl group, cyclohexyl group and the like.
In addition, examples of the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group.
The aromatic hydrocarbon ring group may be a single ring or a condensed ring, and is not particularly limited as long as the number of carbon atoms forming the ring is 6 to 18, but for example, one free valence Benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring, acenaphthene ring, fluoranthene ring, fluorene ring and the like.

  In addition, the aromatic heterocyclic group may be a single ring or a condensed ring, and is not particularly limited as long as the number of carbon atoms forming the ring is 3 to 10, but for example, one free atom Having a valence, furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole Ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzisoxazole ring, benzoisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, Synoline ring, quinoxaline ring, phenanthridine ring, Zone imidazole ring, perimidine ring, a quinazoline ring, a quinazolinone ring, groups such as azulene ring.

The free valence in the present invention is based on the description in “Organic Chemistry / Biochemical Nomenclature” (Nanedo, published May 20, 1992, translated by Kenzo Hirayama and Kazuo Hirayama, pages 11-12). It is.
(About R ¹ )
R ¹ is an optionally substituted alkyl group having 1 to 5 carbon atoms, an optionally substituted alkoxy group having 1 to 4 carbon atoms, or an optionally substituted carbon. An aromatic ring group of several 6 to 10 is represented.

The number of carbon atoms of the alkyl group in R ¹ is typically 1-5, preferably 1-3. Within the above range, when used as an atomization aid or dispersion aid, dissolution of the compound represented by the formula (1) in an organic solvent is suppressed, and efficient adsorption onto the pigment surface is possible. It is preferable in a certain point.
As the alkyl group for R ^1, an alkyl group having 1 to 3 carbon atoms is preferable in order to maintain the planarity of the whole molecule. Examples thereof include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group.

As the substituent that the alkyl group in R ¹ may have, an alkoxy group that may have a substituent, an amino group, an alkylamino group that may have a substituent, and a substituent An arylamino group, a hydroxyl group, a halogen atom and the like which may be included are exemplified.
Examples of the total number of carbon atoms including preferred substituents of the alkoxy group, alkylamino group, and acylamino group, and examples of preferred substituents and preferred specific examples thereof are described in the above section <Substituent group W>. Things.

The number of carbon atoms of the alkoxy group in R ¹ is typically 1-5, preferably 1-3. Within the above range, when used as an atomization aid or dispersion aid, dissolution of the compound represented by the formula (1) in an organic solvent is suppressed, and efficient adsorption onto the pigment surface is possible. It is preferable in a certain point.
Examples of the substituent that the alkoxy group in R ¹ may have include an alkyl group that may have a substituent, an amino group, an alkylamino group that may have a substituent, and a substituent. An arylamino group, a hydroxyl group, a halogen atom and the like which may be included are exemplified.

Examples of the total carbon number including preferred substituents of the alkyl group, alkylamino group, and acylamino group, and examples and preferred specific examples of the substituents that may be included are described in the above <Substituent group W> section. Things.
Specific examples of the alkoxy group for R ¹ include methoxy group, ethoxy group, n-propoxy group, n-butoxy group, hydroxyethoxy group, 1,2-dihydroxypropoxy group and the like.

The carbon number of the aromatic ring group in R ¹ is usually 6 to 10. Within the above range, it is preferable in that the color of the auxiliary agent itself can be controlled to have maximum absorption in the short wavelength region.
The aromatic ring group for R ¹ is preferably an aromatic hydrocarbon group such as a phenyl group or a naphthyl group, or a group derived from a monocyclic or bicyclic heterocyclic ring. Examples of the atoms other than carbon constituting the heterocyclic group include a nitrogen atom, a sulfur atom, and an oxygen atom. When the heterocyclic group has a plurality of atoms constituting a ring other than carbon, these may be the same or different. Specific examples include a pyridinyl group, a quinolinyl group, an isoquinolinyl group, a benzothiazolinyl group, a phthalimidoyl group, a benzimidazolonyl group, and the like. Among them, a phenyl group naphthyl group which may have a substituent in that it has excellent planarity and can be more strongly adsorbed on the pigment surface by causing a π-π interaction with the pigment. A phthalimidoyl group and a benzimidazolonyl group are preferable from the viewpoint of flatness and strong hydrogen bonding with a pigment or a dispersant.

The aromatic ring group in R ¹¹ may have a substituent, and examples of the substituent include those described in the section of <Substituent group W>.
The total number of carbon atoms including preferred substituents of the aromatic ring group of R ¹ , examples of the substituents that may be present, and preferred specific examples thereof, and the preferred number of substituents are as described in the above <Substituent group W>. What has been described.

(Molecular weight)
The molecular weight of the compound represented by the formula (1) is preferably 200 or more, more preferably 300 or more, and preferably 2500 or less, more preferably 1800 or less.
Within the above range, not only the decomposition of the compound represented by the formula (1) at the time of firing and the deterioration of color characteristics due to sublimation are prevented, but also the number of molecules per unit weight is optimized, so that fine particles can be effectively formed. And dispersion are possible.

[Concrete example]
Hereinafter, preferred specific examples of the compound represented by the formula (1) are shown below, but the present invention is not limited thereto.
(Specific Example of Compound (1-A))

  (Specific examples other than compound (1-A))

(Synthesis method)
The compound represented by the formula (1) can be produced according to a known method, and for example, it can be synthesized by a diazotization reaction.
When synthesizing by a diazotization reaction, for example, a primary amine is mixed with nitrite (mainly sodium nitrite) in an acidic aqueous solution to quickly produce a diazonium salt and react with the corresponding coupler.

Other methods include a method of dissolving in concentrated sulfuric acid and diazotizing using nitrosylsulfuric acid.
(combination)
The pigment dispersion of the present invention contains two or more compounds represented by the formula (1). Here, two or more types may be any compound in which at least ^one of A ¹ , B ¹ and R ¹ is different from each other. For example, any two or more types from the compounds described in the above (specific examples) are used. However, it is preferable to contain two or more compounds having different B ^{1 from the} viewpoint that the effects of the present invention can be satisfactorily obtained.

When B ¹ is a compound different from each other, two or more compounds in the compound (1-A), that is, two or more compounds having different groups represented by —Z—X may be used.
(Content ratio of two different compounds)
In the pigment dispersion of the present invention, among the compounds represented by the formula (1), the weight ratio of the compound having the highest content to the compound having the lowest content is usually 1.0 times. In addition, it is usually 3.0 times or less, preferably 2.0 times or less.

Within the above range, it is preferable in that the effect of the present invention can be obtained satisfactorily.
(Content)
In the pigment dispersion of the present invention, the content of the compound represented by the formula (1) is a total amount, and usually 0.001 times or more, preferably 0.01 by weight with respect to the pigment (A). It is more than twice, and usually less than 0.025 times, preferably less than 0.018 times.

Within the above range, there is an auxiliary agent that is sufficiently adsorbed on the pigment surface, so that aggregation of pigments or subsequent crystal growth is effectively inhibited, which is preferable.
<Reason for effect>
The reason why the contrast of the pixel formed using the colored resin composition containing the pigment dispersion of the present invention is increased is estimated as follows.

The compound represented by the formula (1) has an azo bond, an amide bond, and a carbonyl bond in the vicinity, and has a maximum absorption in a short wavelength region by forming an intramolecular hydrogen bond between these groups. However, it has high flatness. This maximum absorption in the short wavelength region makes it difficult to impair the transparency in the long wavelength region such as a red pigment.
Furthermore, as a dispersion liquid for obtaining a pixel having a high contrast, it is necessary to stably disperse the pigment particles to a size near the primary particles. The compound represented by the formula (1) has high planarity as described above, and at the same time has a portion where π-π interaction occurs between molecules.

Furthermore, there is a structure having a nitrogen-containing heterocyclic group at the azo bond site, and this structure effectively functions as an intermolecular hydrogen bond site.
Here, in order to disperse and atomize the pigment more efficiently, the affinity of the additive to the pigment is important.
The compound represented by the formula (1) has a high planarity due to a π-π interaction with the pigment and an intermolecular hydrogen bond with the pigment due to the structure having a nitrogen-containing heterocyclic group at the azo bond site. , Has increased affinity with pigments.

As described above, while having affinity for the pigment, when the compound represented by the formula (1) is adsorbed on the pigment surface, the compounds represented by the formula (1) are electrostatically bonded to each other. Repulsion or steric repulsion is caused, and the pigment is dispersed or atomized.
Since the compounds represented by the formula (1) are more repulsive to each other, B ¹ is preferably a group represented by —Z—X because of having polarity.

However, when a kind of the compound represented by the formula (1) is used, the compounds represented by the formula (1) may aggregate while repelling.
Here, when another compound represented by the formula (1) is present, compared to the case where only one compound is used, aggregation of the compounds by the same species is inhibited, and the rate at which the compounds repel each other increases.
Thereby, the pixel formed using the colored resin composition containing the pigment dispersion of the present invention has a high contrast.

(Use)
As described above, the compound represented by the formula (1) is preferably used particularly during the step of atomizing the pigment, and two or more kinds of compounds represented by the formula (1) are used during the atomization step. Is preferred.
Examples of the atomization step include a grinding method in which pigments and additives are mechanically pulverized to reduce the particle size. The grinding method uses a ball mill, sand mill or kneader to grind the pigment and additives together with a water-soluble inorganic salt such as salt as a grinding agent, and if necessary, a water-soluble organic solvent that does not dissolve them, followed by washing with water, etc. In this way, relatively uniform pigment and / or additive particles can be obtained by removing the grinding agent and the water-soluble organic solvent to make the primary particles finer. However, the phenomenon that the pigment fine particles undergo crystal transition due to energy such as heat generated during the atomization step is likely to occur, but this phenomenon can be suppressed by adopting the configuration of the present invention.

<Pigment dispersion>
Below, each component of the pigment dispersion liquid of this invention is demonstrated. The pigment dispersion of the present invention contains an additive represented by the formula (1), (A) a pigment, and (B) a solvent.
Furthermore, you may contain other additives other than these components.
Hereinafter, each component will be described.

[(A) Pigment]
The pigment dispersion of the present invention contains (A) a pigment, and from the viewpoint of the effects of the invention, as the (A) pigment, various types such as a red pigment, a green pigment, a yellow pigment, a purple pigment, an orange pigment, and a brown pigment are usually used. Colors of pigments can be used.
Examples of the chemical structure of various pigments include organic pigments such as azo, quinacridone, benzimidazolone, isoindolinone, dioxazine, indanthrene, and perylene. In addition to these, various inorganic pigments can also be used.

Specific examples of pigments that can be used in the present invention are shown below by pigment numbers, but are not limited to these examples.
First, as a red pigment, C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53, 53: 1, 53: 2, 53: 3, 57, 57: 1, 57: 2, 58: 4, 60, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81: 1, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 17 , 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267 268, 269, 270, 271, 272, 273, 274, 275, 276 and the like. Of these, C.I. I. Pigment Red 48: 1, 122, 168, 177, 202, 206, 207, 209, 224, 242, 254, etc., more preferably C.I. I. Pigment red 177, 209, 224, 242, 254, and the like.

Examples of green pigments include C.I. I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55, 58 and the like. Of these, C.I. I. Pigment green 7, 36, 58, and the like.
Examples of yellow pigments include C.I. I. Pigment Yellow 1, 1: 1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62: 1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127: 1, 128, 129, 133, 134, 136, 138, 139, 142, 147, 148, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 173, 17 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191: 1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202, 203 , 204, 205, 206, 207, 208, and a pigment defined by <Pigment Y> below (hereinafter referred to as “Pigment Y”).

<Pigment Y>
A compound obtained by inserting another compound into a 1: 1 complex of azobarbituric acid with nickel represented by the following structural formula or a compatible isomer thereof.

  Examples of the other compounds include compounds represented by the following formula (I-1).

Of these, C.I. I. Pigment yellow 83, 117, 129, 138, 139, 154, 155, 180, 185, pigment Y, and the like, more preferably C.I. I. Pigment yellow 83, 138, 139, 180, pigment Y, and the like.
Examples of purple pigments include C.I. I. Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50 and the like. Of these, C.I. I. Pigment violet 19, 23, etc., more preferably C.I. I. Pigment violet 23 and the like.

  Examples of orange pigments include C.I. I. Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79 and the like. Of these, C.I. I. Pigment orange 38, 71 and the like.

Alternatively, the pigment dispersion of the present invention may be used to prepare a colored resin composition as will be described later to form a resin black matrix of a color filter. In that case, a black pigment can be used. . In addition, a black pigment may be used independently and may mix and use pigments, such as red, green, and blue. Further, it may be an inorganic pigment or an organic pigment.
The pigment in the present invention is preferably C.I. I. (Color Index) Pigment Red 177, Pigment Red 242, Pigment Red 254, Pigment Red 255, Pigment Red 264, and Pigment Red 272, Pigment Yellow 138, Pigment Yellow 139, Pigment Yellow 180, Pigment Green 7, Pigment Green 36, and It is preferable to use at least one pigment selected from the group consisting of CI Pigment Green 58 and Pigment Y.

The pigment in the present invention is C.I. I. (Color Index) Pigment Red 254 is particularly preferable because of its high affinity with the compound represented by the formula (1) and a more effective effect.
Examples of inorganic pigments that can be used in the present invention include barium sulfate, lead sulfate, titanium oxide, yellow lead, red iron oxide, and chromium oxide.

In addition, the above-mentioned various pigments can be used in combination. For example, in order to adjust the chromaticity, as the (A) pigment, a red pigment and a yellow pigment can be used in combination, or a green pigment and a yellow pigment can be used in combination.
The average primary particle size of the pigment (A) according to the present invention is usually 100 nm or less, preferably 80 nm or less, more preferably 20 nm or more and 70 nm or less. Since the present invention is particularly effective in the case of a composition containing a highly atomized pigment, the case of containing a pigment having an average primary particle size of 20 nm to 60 nm is particularly preferable.

By making the average primary particle size of the pigment (A) used within the above range, the depolarization characteristics are kept good, high contrast and transmittance are realized, dispersion stability is good, heat resistance and light resistance A pigment dispersion and a colored resin composition having excellent properties can be obtained.
The primary particle diameter of the pigment can be determined by the following method.
First, the pigment is ultrasonically dispersed in chloroform, dropped onto a collodion film-attached mesh, dried, and a primary particle image of the pigment is obtained by observation with a transmission electron microscope (TEM). However, in the case of organic pigments, the particle diameter of each pigment particle is the diameter corresponding to the area circle converted to the diameter of a circle having the same area, and the particle diameter of each of plural (usually about 200 to 300) pigment particles. Ask for. Using the obtained primary particle size value, the number average value is calculated according to the following formula to obtain the average particle size.

The pigment (A) thus obtained may be used alone, but one or two or more pigments can be mixed and used within a range not impairing the effects of the present invention.
The content of the pigment (A) in the pigment dispersion of the present invention is usually 80% by weight or less, preferably 70% by weight or less, more preferably 60% by weight or less, based on the total solid content. It is 1% by weight or more, preferably 0.5% by weight or more, more preferably 1% by weight or more.
The content of the pigment (A) in the colored resin composition of the present invention is usually 3% by weight or more, preferably 5% by weight or more, more preferably 10% by weight or more, and usually 50% by weight, based on the total solid content. % Or less, preferably 40% by weight or less, more preferably 30% by weight or less.

(A) By setting the pigment content within the above range, the film thickness with respect to the color density does not become too large, and there is no adverse effect on the gap control during the formation of a liquid crystal cell, and sufficient image formability is obtained. In addition, the dispersed state of the pigment is maintained, and aggregation and sedimentation are unlikely to occur. As a result, problems such as thickening and lowering of brightness and contrast can be solved.
[(B) Solvent]
In the present invention, the solvent has a function of adjusting the viscosity by dissolving or dispersing components other than the above-described components in addition to the above components.

The solvent is not particularly limited as long as it can dissolve or disperse each component. As such a solvent, the solvent etc. which are described in international publication WO2009 / 107734 etc. are mentioned, for example.
Commercially available products corresponding to these solvents include mineral spirits, valsol # 2, Apco # 18 solvent, apco thinner, and soak solvent no. 1 and no. 2, Solvesso # 150, Shell TS28 Solvent, carbitol, ethyl carbitol, butyl carbitol, methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, methyl cellosolve acetate, diglyme (all trade names) and the like. These solvents may be used alone or in combination of two or more.

The content of the solvent in the entire colored resin composition of the present invention is not particularly limited, but the upper limit is usually 99% by weight or less, and preferably 50% by weight in consideration of viscosity suitable for coating. Above, more preferably 60% by weight or more, particularly preferably 70% by weight or more.
[Atomization aid]
The pigment dispersion and the colored resin composition of the present invention preferably contain a atomization aid.

The atomization aid is not particularly limited as long as it can suppress the crystal transition of the pigment fine particles, which occurs during the atomization step. In particular, in the above-described formula (1), the obtained pixel has a high contrast. It is preferable to use two or more compounds represented.
The content of the atomization aid in the pigment dispersion and colored resin composition of the present invention is usually 0.001 times or more, preferably 0.01 times or more, and usually 0.01 times or more by weight with respect to the (A) pigment. It is 0.025 times or less, preferably 0.018 times or less.

Within the above range, it is preferable in that the effect of the present invention can be obtained satisfactorily.
[(D) Dispersant]
The dispersant in the present invention is not particularly limited as long as the pigment is dispersed and can maintain stability. For example, cationic, anionic, nonionic or amphoteric dispersants can be used, but polymer dispersants are preferred. Specifically, a modified acrylic copolymer, an acrylic copolymer, polyurethane, polyester, a polymer copolymer alkylammonium salt or phosphate ester salt, a cationic comb graft polymer, and the like can be given. Among these dispersants, modified acrylic copolymers, polyurethane, and cationic comb graft polymers are preferable. In particular, a modified acrylic copolymer is preferable. Among these, a block copolymer composed of an A block having a solvophilic property and a B block having a functional group containing a nitrogen atom has an amine value of 80 mg-KOH / g or more and 150 mg. What is -KOH / g or less (effective solid content conversion) is especially preferable. More preferably, it is 100-140 mg-KOH / g.

Within the above range, the adsorptive power to the pigment surface is sufficient and the dispersion stability is good.
Of these, the (meth) acrylic block copolymer described in JP-A-2009-025813 is preferable. The acrylic block copolymer can disperse the pigment (A) very efficiently. This is presumably because the molecular arrangement is controlled, so that there are few structures that obstruct the dispersant when adsorbing to the pigment.

In the present invention, the acrylic block copolymer is preferably an AB block comprising an A block and a B block and / or an ABA block copolymer.
The B block constituting the acrylic block copolymer has an amino group, and the amino group is preferably —NR ⁴¹ R ⁴² (provided that R ⁴¹ and R ⁴² each independently have a substituent). A cyclic or chain alkyl group which may be substituted, an aryl group which may have a substituent, or an aralkyl group which may have a substituent. A preferable example is represented by the following formula, for example.

^{(However, R 41} and ^{R 42} has the same meaning as above ^{R 41} and ^{R 42, R 43} is one or more alkylene groups having a carbon ^{number, R 44} represents a hydrogen atom or a methyl group.)
Among them, R ⁴¹ and R ⁴² are preferably methyl groups, R ⁴³ is preferably a methylene group or an ethylene group, and R ⁴⁴ is preferably a methyl group. Examples of such a compound include a partial structure represented by the following formula.

Two or more kinds of the partial structure containing an amino group as described above may be contained in one B block. In that case, two or more amino group-containing partial structures may be contained in the B block in any form of random copolymerization or block copolymerization. In addition, a partial structure not containing an amino group may be partially contained in the B block within a range not impairing the effects of the present invention. Examples of such a partial structure include (meth) acrylic acid esters. And a partial structure derived from a monomer.

On the other hand, in the present invention, the A block of the (D) dispersant is not particularly limited as long as it is solvophilic and is composed of a monomer that can be copolymerized with the monomer constituting the B block described above.
Examples of the A block include polymer structures obtained by copolymerizing comonomers such as styrene monomers, (meth) acrylate monomers, (meth) acrylate monomers, vinyl acetate monomers, glycidyl ether monomers, and the like. It is done.

The (D) dispersant in the present invention is an AB block or ABA block copolymeric polymer compound composed of an A block and a B block as described above. Of these, AB block copolymers are preferred. Such a block copolymer is prepared, for example, by a living polymerization method.
The living polymerization method includes an anion living polymerization method, a cation living polymerization method, and a radical living polymerization method. Specifically, for example, a method described in JP-A-2007-270147 can be mentioned.

The amine value of the dispersant (in terms of effective solid content) is represented by the weight of KOH equivalent to the amount of base per gram of solid content excluding the solvent in the dispersant sample, and is measured by the following method. Disperse 0.5-1.5 g of the dispersant sample in a 100 mL beaker and dissolve with 50 mL of acetic acid. This solution is neutralized with a 0.1 mol / L HClO ₄ acetic acid solution using an automatic titrator equipped with a pH electrode. Using the inflection point of the titration pH curve as the end point of titration, the amine value is determined by the following formula.

Amine value [mg-KOH / g] = (561 × V) / (W × S)
(W: represents the amount of the dispersant sample weighed [g], V: represents the titration amount at the end of titration [mL], and S represents the solid content concentration [wt%] of the dispersant sample.)
Further, the acid value of this block copolymer is preferably lower, although it depends on the presence and type of acidic groups that form the acid value, and is usually 50 mg-KOH / g or less, preferably 40 or less, more preferably. Is 30 or less.

When the average primary particle size of the pigment is small, the specific surface area increases and the amount of adsorbing dispersant per unit area decreases. In this case, the dispersant made of the copolymer is preferably used because it is more effective than the other dispersants.
The dispersant in the present invention is preferably 5% by weight or more, more preferably 10% by weight or more, and usually 200% by weight or less, more preferably 100% by weight or less, based on the total amount of the pigment in the colored resin composition.
The pigment dispersion and colored resin composition of the present invention may contain other dispersants as long as the effects of the present invention are not impaired. Examples of other dispersants include those described in JP-A-2006-343648, for example.

[Dispersion aid]
In the pigment dispersion or colored resin composition of the present invention, the additive of the present invention may be used as a dispersion aid, or may contain other dispersion aids. The dispersion aid here may be a pigment derivative. Examples of the pigment derivative include JP-A Nos. 2001-220520, 2001-271004, 2002-179976, and 2007-. Various compounds described in Japanese Patent Application Publication No. 113000 and Japanese Patent Application Publication No. 2007-186681 can be used.

The content of the dispersion aid in the pigment dispersion and colored resin composition of the present invention is usually 0.1% by weight or more, usually 30% by weight or less, preferably 20% by weight, based on the pigment (A). Less than,
More preferably, it is 10 weight% or less, More preferably, it is 5 weight% or less.
Within the above range, the effect as a dispersion aid is effectively obtained, and this is preferable in terms of good dispersibility and dispersion stability.

[Dispersion resin]
The pigment dispersion and colored resin composition of the present invention may contain a part or all of a resin selected from (C) binder resin or other binder resin described later as the following dispersion resin.
Specifically, in the dispersion treatment step to be described later, the (C) binder resin is added to the (D) dispersant by adding the (C) binder resin together with the components such as the (D) dispersant described above. It contributes to the dispersion stability of the pigment (A) by a synergistic effect. As a result, there is a possibility that the amount of (D) dispersant added can be reduced, which is preferable. Further, it is preferable because the developability is improved, the undissolved matter does not remain in the non-pixel portion of the substrate, and the adhesion of the pixel to the substrate is improved.

Thus, the (C) binder resin used in the dispersion treatment step may be referred to as a dispersion resin. The dispersion resin is preferably used in an amount of about 0 to 200% by weight, more preferably about 10 to 100% by weight, based on the total amount of pigment in the pigment dispersion.
As the dispersion resin, various (C) binder resins described later can be used.
The acid value of the dispersion resin is preferably 0.5 mg-KOH / g or more, more preferably 1 mg-KOH / g or more, most preferably 5 mg-KOH / g or more, and preferably 300 mg-KOH / g or less, 200 mg-KOH / G or less is more preferable, and 150 mg-KOH / g or less is most preferable. By controlling the acid value within the above range, the alkali developability is improved, and the handling becomes easy in synthesis and the like.

  The weight average molecular weight in terms of polystyrene measured by GPC of the dispersion resin is preferably 1000 or more, more preferably 1500 or more, most preferably 2000 or more, more preferably 200000 or less, more preferably 50000 or less, and 30000 or less. Most preferred. By controlling the molecular weight within the above range, the alkali developability can be improved and the dispersion stability can be prevented from being lowered.

[Colored resin composition]
The colored resin composition of the present invention further comprises (C) a binder resin in the pigment dispersion of the present invention, more preferably (E) a polymerizable monomer, (F) a photopolymerization initiating component and / or a thermal polymerization initiating component. Further, it contains other components as required.
That is, the colored resin composition of the present invention contains at least (A) a pigment, (B) a solvent, (C) a binder resin, and (D) a dispersant, and further includes a compound represented by the formula (1). It is a composition containing 2 or more types.

Hereinafter, (C) the binder resin will be described.
[(C) Binder resin]
(C) The preferred resin for the binder resin differs depending on the curing means.
When the colored resin composition of the present invention is a photopolymerizable resin composition, examples of the (C) binder resin include JP-A-7-207211, JP-A-8-259876, JP-A-10-300922, 11-14144, JP-A No. 11-174224, JP-A No. 2000-56118, JP-A No. 2003-233179, and the like can be used. C-1) to (C-5) resins and the like.

(C-1): With respect to a copolymer of an epoxy group-containing (meth) acrylate and another radical polymerizable monomer, an unsaturated monobasic acid is added to at least a part of the epoxy group of the copolymer. Resin to be added, or an alkali-soluble resin (hereinafter referred to as “resin (C-1)”) obtained by adding a polybasic acid anhydride to at least a part of the hydroxyl group generated by the addition reaction. .)
(C-2): Carboxyl group-containing linear alkali-soluble resin (C-2) (hereinafter sometimes referred to as “resin (C-2)”)
(C-3): a resin obtained by adding an epoxy group-containing unsaturated compound to the carboxyl group portion of the resin (C-2) (hereinafter sometimes referred to as “resin (C-3)”).
(C-4): (Meth) acrylic resin (hereinafter sometimes referred to as “resin (C-4)”)
(C-5): Epoxy acrylate resin having a carboxyl group (hereinafter sometimes referred to as “resin (C-5)”)
Of these, the resin (C-1) is particularly preferable, and the resin will be described below.

The resins (C-2) to (C-5) may be any ones that are dissolved in an alkaline developer and have solubility to the extent that the desired development processing is performed. This is the same as that described as the same item in Japanese Patent No. 025813. The preferred embodiment is also the same.
(C-1): With respect to a copolymer of an epoxy group-containing (meth) acrylate and another radical polymerizable monomer, an unsaturated monobasic acid is added to at least a part of the epoxy group of the copolymer. As one of particularly preferable resins of the alkali-soluble resin resin (C-1) obtained by adding a polybasic acid anhydride to at least a part of the hydroxyl group generated by the addition reaction, or an epoxy group, Unsaturated in 10 to 100 mol% of the epoxy group of the copolymer with respect to the copolymer of 5 to 90 mol% of (meth) acrylate and 10 to 95 mol% of other radical polymerizable monomer Examples thereof include a resin obtained by adding a monobasic acid, or an alkali-soluble resin obtained by adding a polybasic acid anhydride to 10 to 100 mol% of a hydroxyl group generated by the addition reaction.

  Examples of the epoxy group-containing (meth) acrylate include glycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, (3,4-epoxycyclohexyl) methyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. ) Acrylate glycidyl ether and the like. Of these, glycidyl (meth) acrylate is preferred. These epoxy group-containing (meth) acrylates may be used alone or in combination of two or more.

The other radical polymerizable monomer copolymerized with the epoxy group-containing (meth) acrylate is not particularly limited as long as the effects of the present invention are not impaired. For example, vinyl aromatics, dienes, (meth) Examples include acrylic acid esters, (meth) acrylic acid amides, vinyl compounds, unsaturated dicarboxylic acid diesters, monomaleimides, and the like, and in particular, mono (meth) having a structure represented by the following formula (7) Acrylate is preferred.
The repeating unit derived from the mono (meth) acrylate having the structure represented by the following formula (7) contains 5 to 90 mol% among the repeating units derived from “other radical polymerizable monomers”. The content is preferably 10 to 70 mol%, more preferably 15 to 50 mol%.

In the above formula (7), R ⁸⁹ represents a hydrogen atom or a methyl group, and R ⁹⁰ represents a structure represented by the following formula (8).

The formula ^{(8), R} 91 ~R ⁹⁸ each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. R ⁹⁶ and R ⁹⁸ may be connected to each other to form a ring.
The ring formed by connecting R ⁹⁶ and R ⁹⁸ is preferably an aliphatic ring, may be saturated or unsaturated, and preferably has 5 to 6 carbon atoms.
Among these, among the structures represented by the formula (8), those represented by the following structural formulas (8a), (8b), or (8c) are particularly preferable.

In addition, the mono (meth) acrylate which has a structure represented by the said Formula (8) may be used individually by 1 type, and may use 2 or more types together.
As "other radical polymerizable monomers" other than the mono (meth) acrylate having the structure represented by the formula (8), the heat resistance and strength excellent in the colored resin composition can be improved. , Styrene, (n-butyl) (meth) acrylate, tert-butyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, benzyl (meth) acrylate , (Meth) acrylic acid-2-hydroxyethyl, N-phenylmaleimide, N-cyclohexylmaleimide.

The content ratio of repeating units derived from at least one selected from the above monomer group is preferably 1 to 70 mol%, more preferably 3 to 50 mol%.
A known solution polymerization method is applied to the copolymerization reaction between the epoxy group-containing (meth) acrylate and the other radical polymerizable monomer.
In the present invention, as a copolymer of the epoxy group-containing (meth) acrylate and the other radical polymerizable monomer, 5 to 90 mol% of repeating units derived from the epoxy group-containing (meth) acrylate, and others Is preferably composed of 10 to 95 mol% of repeating units derived from the radically polymerizable monomer, more preferably composed of 20 to 80 mol% of the former and 80 to 20 mol% of the latter. What consists of 70 mol% and the latter 70-30 mol% is especially preferable.

Within the above range, the addition amount of the polymerizable component and alkali-soluble component described later is sufficient, and the heat resistance and strength are sufficient, which is preferable.
The epoxy group portion of the epoxy group-containing copolymer synthesized as described above is reacted with an unsaturated monobasic acid (polymerizable component) and a polybasic acid anhydride (alkali-soluble component).
Here, as an unsaturated monobasic acid added to an epoxy group, a well-known thing can be used, For example, unsaturated carboxylic acid which has an ethylenically unsaturated double bond is mentioned.

Specific examples include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-position substituted with a haloalkyl group, an alkoxyl group, a halogen atom, a nitro group, or a cyano group. And monocarboxylic acids such as (meth) acrylic acid. Of these, (meth) acrylic acid is preferred. These may be used alone or in combination of two or more.

By adding such components, polymerizability can be imparted to the binder resin used in the present invention.
These unsaturated monobasic acids are usually added to 10 to 100 mol% of the epoxy group of the copolymer, preferably 30 to 100 mol%, more preferably 50 to 100 mol%. It is preferable for it to be in the above range since the colored resin composition is excellent in stability over time. In addition, a well-known method is employable as a method of adding unsaturated monobasic acid to the epoxy group of a copolymer.

Furthermore, a well-known thing can be used as a polybasic acid anhydride added to the hydroxyl group produced when an unsaturated monobasic acid is added to the epoxy group of a copolymer.
For example, dibasic acid anhydrides such as maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, chlorendic anhydride; trimellitic anhydride, pyromellitic anhydride, benzophenone Examples thereof include anhydrides of three or more bases such as tetracarboxylic acid anhydride and biphenyltetracarboxylic acid anhydride. Of these, succinic anhydride and tetrahydrophthalic anhydride are preferred. These polybasic acid anhydrides may be used individually by 1 type, and may use 2 or more types together.

By adding such a component, alkali solubility can be imparted to the binder resin used in the present invention.
These polybasic acid anhydrides are usually added to 10 to 100 mol% of the hydroxyl group generated by adding an unsaturated monobasic acid to the epoxy group of the copolymer, preferably 20 to 90 mol. %, More preferably 30 to 80 mol%.

Within the above range, the remaining film ratio and solubility during development are sufficient, which is preferable.
In addition, a well-known method is employable as a method of adding a polybasic acid anhydride to this hydroxyl group.
Furthermore, in order to improve photosensitivity, after adding the above-mentioned polybasic acid anhydride, glycidyl (meth) acrylate or a glycidyl ether compound having a polymerizable unsaturated group is added to a part of the generated carboxyl group. May be. Such a resin structure is described in, for example, Japanese Patent Application Laid-Open Nos. 8-297366 and 2001-89533.

  The polystyrene-reduced weight average molecular weight (Mw) of the above-described binder resin (C-1) measured by GPC (gel permeation chromatography) is preferably 3000 to 100,000, and particularly preferably 5000 to 50000. If the molecular weight is less than 3000, heat resistance and film strength may be inferior, and if it exceeds 100,000, the solubility in a developer tends to be insufficient. Moreover, as a standard of molecular weight distribution, the ratio of weight average molecular weight (Mw) / number average molecular weight (Mn) is preferably 2.0 to 5.0.

In addition, the acid value of binder resin (C-1) is 10-200 mg-KOH / g normally, Preferably it is 15-150 mg-KOH / g, More preferably, it is 25-100 mg-KOH / g.
Within the above range, the solubility in a developer is good and film roughness is not likely to occur, which is preferable.

Moreover, the content rate of (C) binder resin is 0.1-80 weight% normally in a total solid, Preferably it is 1-60 weight%.
Within the above range, the adhesion to the substrate is good, the permeability of the developer to the exposed area is moderate, and the surface smoothness and sensitivity of the pixels are good.
[(E) Polymerizable monomer]
The colored resin composition of the present invention preferably contains (E) a polymerizable monomer. (E) The polymerizable monomer is not particularly limited as long as it is a polymerizable low molecular compound, but it may be an addition-polymerizable compound having at least one ethylenic double bond (hereinafter referred to as “ethylenic compound”). Is preferred).

The ethylenic compound is a compound having an ethylenic double bond that undergoes addition polymerization and cures by the action of the photopolymerization initiation component when the colored resin composition of the present invention is irradiated with actinic rays. In addition, the (E) polymerizable monomer in this invention means the concept opposite to what is called a polymeric substance, and also includes a dimer, a trimer, and an oligomer other than a monomer in a narrow sense.
(E) Examples of the ethylenic compound in the polymerizable monomer include unsaturated carboxylic acids such as (meth) acrylic acid; esters of monohydroxy compounds and unsaturated carboxylic acids; aliphatic polyhydroxy compounds and unsaturated carboxylic acids; Esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids; Esterification of unsaturated carboxylic acids with polyvalent carboxylic acids and polyhydric hydroxy compounds such as aliphatic polyhydroxy compounds and aromatic polyhydroxy compounds described above An ester obtained by the reaction; an ethylenic compound having a urethane skeleton obtained by reacting a polyisocyanate compound and a (meth) acryloyl group-containing hydroxy compound;

  Esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids include ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate , Pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) Examples include (meth) acrylic acid esters such as acrylate and glycerol (meth) acrylate. In addition, the (meth) acrylic acid portion of these (meth) acrylic acid esters is replaced with an itaconic acid portion, a crotonic acid portion replaced with a crotonic acid portion, or a maleic acid ester replaced with a maleic acid portion, etc. Is mentioned.

Examples of the ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid include hydroquinone di (meth) acrylate, resorcin di (meth) acrylate, pyrogallol tri (meth) acrylate, and the like.
The ester obtained by the esterification reaction of an unsaturated carboxylic acid with a polyvalent carboxylic acid and a polyvalent hydroxy compound is not necessarily a single substance but may be a mixture. Representative examples are condensates of (meth) acrylic acid, phthalic acid, and ethylene glycol; condensates of (meth) acrylic acid, maleic acid, and diethylene glycol; condensation of (meth) acrylic acid, terephthalic acid, and pentaerythritol A condensate of (meth) acrylic acid, adipic acid, butanediol, and glycerin.

Examples of the ethylenic compound having a urethane skeleton obtained by reacting a polyisocyanate compound and a (meth) acryloyl group-containing hydroxy compound include aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate; alicyclic rings such as cyclohexane diisocyanate and isophorone diisocyanate. Formula diisocyanate; aromatic diisocyanate such as tolylene diisocyanate, diphenylmethane diisocyanate, 2-hydroxyethyl (meth) acrylate, 3-hydroxy [1,1,1-tri (
And a reaction product with a (meth) acryloyl group-containing hydroxy compound such as (meth) acryloyloxymethyl] propane.

In addition, examples of the ethylenic compound used in the present invention include (meth) acrylamides such as ethylene bis (meth) acrylamide; allyl esters such as diallyl phthalate; vinyl group-containing compounds such as divinyl phthalate. .
Among these, esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids are preferred, pentaerythritol or (meth) acrylic acid esters of dipentaerythritol are more preferred, and dipentaerythritol hexa (meth) acrylate is particularly preferred.

  The ethylenic compound may be a monomer having an acid value. The monomer having an acid value is, for example, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and a non-aromatic carboxylic acid anhydride is reacted with an unreacted hydroxyl group of the aliphatic polyhydroxy compound. A polyfunctional monomer having a group is preferable, and in this ester, the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol.

These monomers may be used alone, but since it is difficult to obtain a single compound in production, a mixture of two or more kinds may be used.
Moreover, you may use together the polyfunctional monomer which does not have an acid group, and the polyfunctional monomer which has an acid group as (E) polymeric monomer as needed.
A preferable acid value of the polyfunctional monomer having an acid group is 0.1 to 40 mg-KOH / g, and particularly preferably 5 to 30 mg-KOH / g.

When it is within the above range, the development and dissolution characteristics are hardly deteriorated, and the production and handling are easy. Furthermore, it is preferable because the photopolymerization performance is hardly lowered and the curability such as the surface smoothness of the pixel is good.
In the present invention, a more preferred polyfunctional monomer having an acid group is, for example, a mixture containing succinic acid ester of dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentaacrylate as a main component. It is also possible to use this polyfunctional monomer in combination with another polyfunctional monomer.

In the colored resin composition of the present invention, the content ratio of these (E) polymerizable monomers is usually 1% by weight or more, preferably 5% by weight or more, more preferably 10% by weight or more in the total solid content. Further, it is usually 80% by weight or less, preferably 70% by weight or less, more preferably 50% by weight or less, and particularly preferably 40% by weight or less.
The ratio of the (E) polymerizable monomer to the total colorant is usually 1% by weight or more, preferably 5% by weight or more, more preferably 10% by weight or more, and particularly preferably 20% by weight or more. It is 200% by weight or less, preferably 150% by weight or less, more preferably 110% by weight or less.

Within the above range, photocuring is appropriate, poor adhesion during development is difficult to place, the cross-section after development is difficult to reverse taper, and further, peeling phenomenon and omission failure due to lower solubility are difficult to place. preferable.
[(F) Photopolymerization initiation component and / or thermal polymerization initiation component]
The colored resin composition of the present invention preferably contains (F) a photopolymerization initiation component and / or a thermal polymerization initiation component for the purpose of curing the coating film. However, the curing method may be other than those using these initiators.

In particular, when the colored resin composition of the present invention includes a resin having an ethylenic double bond as the component (C), or includes an ethylenic compound as the component (E), it directly absorbs light, or It is preferable to contain a photopolymerization initiating component that has a function of generating a polymerization active radical and / or a thermal polymerization initiating component that generates a polymerization active radical by heat. In the present invention, the component (F) as a photopolymerization initiation component refers to a photopolymerization initiator (hereinafter arbitrarily referred to as (F1) component) and a polymerization accelerator (hereinafter arbitrarily referred to as (F2) component). , Means a mixture in which an additive such as a sensitizing dye (hereinafter, arbitrarily referred to as component (F3)) is used in combination.

(Photopolymerization initiation component)
The colored resin composition of the present invention preferably contains a photopolymerization initiation component. The photopolymerization initiating component is usually used as a mixture of (F1) a photopolymerization initiator and an additive such as (F3) a sensitizing dye and (F2) a polymerization accelerator which are added as necessary. It is a component having a function of generating a polymerization active radical by directly absorbing or photosensitizing to cause a decomposition reaction or a hydrogen abstraction reaction.

  Examples of the (F1) photopolymerization initiator constituting the photopolymerization initiating component include titanocene derivatives described in JP-A Nos. 59-152396 and 61-151197; JP-A-10-300922 Hexaarylbiimidazole derivatives described in JP-A-11-174224, JP-A-2000-56118, etc .; halomethylated oxadiazole derivatives described in JP-A-10-39503, etc., halomethyl-s -Radical activators such as triazine derivatives, N-aryl-α-amino acids such as N-phenylglycine, N-aryl-α-amino acid salts, N-aryl-α-amino acid esters, α-aminoalkylphenone derivatives And oxime ester derivatives described in JP-A No. 2000-80068 and the like.

Specific examples include photopolymerization initiators described in International Publication No. 2009/107734 pamphlet and the like.
Among these photopolymerization initiators, α-aminoalkylphenone derivatives, oxime ester derivatives, biimidazole derivatives, acetophenone derivatives, and thioxanthone derivatives are more preferable.

The oxime ester derivatives include 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (o-benzoyloxime), ethanone, 1- [9-ethyl-6- ( 2-methylbenzoyl) -9H-carbazol-3-yl], 1- (o-acetyloxime), and the like.
In addition, benzoin alkyl ethers, anthraquinone derivatives; acetophenone derivatives such as 2-methyl- (4′-methylthiophenyl) -2-morpholino-1-propanone, 2-ethylthioxanthone, 2,4-diethylthioxanthone, etc. Examples also include thioxanthone derivatives, benzoate derivatives, acridine derivatives, phenazine derivatives, anthrone derivatives and the like.

Among these photopolymerization initiators, α-aminoalkylphenone derivatives, thioxanthone derivatives, and oxime ester derivatives are more preferable. In particular, oxime ester derivatives are preferable.
Examples of the (F2) polymerization accelerator used as necessary include N, N-dialkylaminobenzoic acid alkyl esters such as N, N-dimethylaminobenzoic acid ethyl ester; 2-mercaptobenzothiazole, 2-mercapto Examples thereof include mercapto compounds having a heterocyclic ring such as benzoxazole and 2-mercaptobenzimidazole; mercapto compounds such as aliphatic polyfunctional mercapto compounds.

These (F1) photopolymerization initiators and (F2) polymerization accelerators may be used alone or in combination of two or more.
Further, (F3) sensitizing dye is used for the purpose of increasing the sensitivity as required. As the sensitizing dye, an appropriate one is used according to the wavelength of the image exposure light source. For example, xanthene dyes described in JP-A-4-221958 and JP-A-4-219756; No. 239703, JP-A-5-289335, etc. Coumarin dyes having a heterocyclic ring; JP-A-3-239703, JP-A-5-289335, etc .; 3-ketocoumarin dyes; Pyrromethene dyes described in JP-A-6-19240 and the like; JP-A-47-2528, JP-A-54-155292, JP-B-45-37377, JP-A-48-84183, JP-A-52-112681 JP, 58-15503, JP 60-88005, JP 59-56403, JP 2-69, JP 57-168088, JP 5-10. 761 No., JP-A-5-210240, dyes having a dialkyl aminobenzene skeleton described in JP-A 4-288818 Patent JP-like.

(F3) A sensitizing dye may also be used alone or in combination of two or more.
In the colored resin composition of the present invention, the content ratio of these (F) photopolymerization initiating components is usually 0.1% by weight or more, preferably 0.2% by weight or more, more preferably 0.8% by weight based on the total solid content. It is 5% by weight or more, usually 40% by weight or less, preferably 30% by weight or less, and more preferably 20% by weight or less. If this content is extremely low, the sensitivity to exposure light may be reduced. Conversely, if it is extremely high, the solubility of the unexposed portion in the developer may be reduced, leading to poor development.

(Thermal polymerization initiation component)
Specific examples of the thermal polymerization initiation component (thermal polymerization initiator) that may be contained in the colored resin composition of the present invention include azo compounds, organic peroxides, and hydrogen peroxide. Of these, azo compounds are preferably used. More specifically, for example, a thermal polymerization initiator described in International Publication No. 2009/107734 pamphlet or the like can be used.

These thermal polymerization initiators may be used individually by 1 type, and may use 2 or more types together.
[Preparation Method of Colored Resin Composition]
In the present invention, the colored resin composition can be prepared by an appropriate method. For example, as a preparation method, (A) a solvent containing a pigment, (D) a dispersant, two or more of the above formulas ( In the presence of the compound represented by 1) and a dispersion aid to be further added as necessary, (C) a part of the binder resin, for example, paint shaker, sand grinder, ball mill, roll mill, stone mill Using a jet mill, a homogenizer or the like, a pigment dispersion is prepared by mixing and dispersing while pulverizing. (C) Binder resin, and, if necessary, (E) a polymerizable monomer and (F) an additive such as a photopolymerization initiator and / or a thermal polymerization initiator are added to the pigment dispersion and mixed. The method of preparing by can be mentioned.

More preferably, as described above, after passing through the atomization step using two or more compounds represented by the formula (1), (D) the dispersant and (C) are dispersed together with a part of the binder resin. A method of preparing a colored resin composition by adding other additives after preparing the pigment dispersion can be mentioned.
[Application of colored resin composition]
The colored resin composition of the present invention is usually in a state where all the constituent components are dissolved or dispersed in a solvent. This colored resin composition is supplied onto the substrate to form components such as a color filter, a liquid crystal display device, and an organic EL display device.

Hereinafter, as an application example of the colored resin composition of the present invention, an application as a color filter, and a liquid crystal display device (panel) and an organic EL display device using them will be described.
<Color filter>
The color filter of the present invention has a pixel formed from the colored resin composition of the present invention.

The method for forming the color filter of the present invention will be described below.
The pixel of the color filter can be formed by various methods. Here, although the case where it forms by the photolithographic method using a photopolymerizable colored resin composition is demonstrated to an example, a manufacturing method is not limited to this.
First, on the surface of the substrate, if necessary, a black matrix is formed so as to partition a portion for forming pixels, and after applying the colored resin composition of the present invention on this substrate, pre-baking is performed. The solvent is evaporated to form a coating film. Then, after exposing this coating film through a photomask, developing with an alkali developer, dissolving and removing the unexposed portion of the coating film, and then post-baking, each of red, green, and blue A color filter can be manufactured by forming a pixel pattern.

The substrate used for forming the pixel is not particularly limited as long as it is transparent and has an appropriate strength. For example, a polyester resin, a polyolefin resin, a polycarbonate resin, an acrylic resin, or a thermoplastic resin is used. A sheet, an epoxy resin, a thermosetting resin, various glass, etc. are mentioned.
In addition, these substrates may be appropriately subjected to pretreatment as desired, such as thin film formation treatment with a silane coupling agent or urethane resin, surface treatment such as corona discharge treatment or ozone treatment, if desired.

When applying the colored resin composition to the substrate, a spinner method, a wire bar method, a flow coating method, a slit and spin method, a die coating method, a roll coating method, a spray coating method, and the like can be given. Of these, the slit and spin method and the die coating method are preferable.
The thickness of the coating film is usually 0.2 to 20 μm, preferably 0.5 to 10 μm, particularly preferably 0.8 to 5.0 μm as the film thickness after drying.

Within the above range, it is preferable in that the gap can be easily adjusted in the pattern development or liquid crystal cell forming step, and a desired color can be easily expressed.
For example, visible rays, ultraviolet rays, far ultraviolet rays, electron beams, X-rays, and the like can be used as the radiation used when forming the pixels, but radiation having a wavelength in the range of 190 to 450 nm is preferable.

  The light source used for image exposure for using radiation having a wavelength of 190 to 450 nm is not particularly limited. Lamp light sources such as medium pressure mercury lamp, low pressure mercury lamp, carbon arc, fluorescent lamp; laser light sources such as argon ion laser, YAG laser, excimer laser, nitrogen laser, helium cadmium laser, semiconductor laser, and the like. An optical filter can also be used when used by irradiating light of a specific wavelength.

Exposure of radiation, 10~10,000J / ^{m 2} is preferred.
Examples of the alkaline developer include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, Inorganic alkaline compounds such as potassium phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide; mono-di- or tri-ethanolamine, mono-di-, or tri -Methylamine, mono-, di-, or tri-ethylamine, mono-, or di-isopropylamine, n-butylamine, mono-, di-, or tri-isopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium Hydroxide (TMAH) Aqueous solution of an organic alkaline compound choline are preferred.

An appropriate amount of a water-soluble organic solvent such as isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone alcohol, or the like can be added to the alkali developer. In addition, it is usually washed with water after alkali development.
As the development processing method, any method such as an immersion development method, a spray development method, a brush development method, and an ultrasonic development method can be used. The development conditions are preferably 5 to 300 seconds at room temperature (23 ° C.).

There are no particular restrictions on the conditions of the development processing, but the development temperature is usually 10 ° C. or higher, especially 15 ° C. or higher, more preferably 20 ° C. or higher, and usually 50 ° C. or lower, especially 45 ° C. or lower, further 40 ° C. or lower. Is preferred.
The developing method can be any one of immersion developing method, spray developing method, brush developing method, ultrasonic developing method and the like.

  When the color filter thus produced is used in a liquid crystal display device, a transparent electrode such as ITO is formed on the image as it is, and is used as a part of a color display, a liquid crystal display device, or the like. Although used, in order to improve surface smoothness and durability, a top coat layer such as polyamide or polyimide can be provided on the image as necessary. Further, in some applications such as a planar alignment type drive system (IPS mode), the transparent electrode may not be formed. In the vertical alignment type driving method (MVA mode), ribs may be formed. Also, a column structure (photo spacer) made of photolithography may be formed instead of the bead dispersion type spacer.

<Liquid crystal display device>
The liquid crystal display device of the present invention uses the above-described color filter of the present invention. There is no restriction | limiting in particular about the model and structure of the liquid crystal display device of this invention, It can assemble in accordance with a conventional method using the color filter of this invention.
For example, the liquid crystal display device of the present invention can be formed by the method described in “Liquid Crystal Device Handbook” (Nikkan Kogyo Shimbun, September 29, 1989, Japan Society for the Promotion of Science 142nd Committee).

<Organic EL display device>
When producing an organic EL display device including the color filter of the present invention, for example, as shown in FIG. 1, on a blue color filter in which pixels 20 are formed on a transparent support substrate 10 by the colored resin composition of the present invention. A multicolor organic EL element is manufactured by laminating the organic light-emitting body 500 through the organic protective layer 30 and the inorganic oxide film 40.

  As a method for laminating the organic light emitter 500, a transparent anode 50, a hole injection layer 51, a hole transport layer 52, a light emitting layer 53, an electron injection layer 54, and a cathode 55 are sequentially formed on the upper surface of the color filter. For example, a method of adhering the organic light-emitting body 500 formed on another substrate onto the inorganic oxide film 40 can be used. The organic EL element 100 manufactured as described above can be applied to both a passive drive type organic EL display device and an active drive type organic EL display device.

Hereinafter, the present invention will be described more specifically with reference to synthesis examples, examples and comparative examples. In addition, this invention is not limited to description of a following example, unless the summary is exceeded.
(Synthesis Example 1: Synthesis of Compound 1)

5-Amino-2-benzimidazolone (5.96 g, 40 mmol) was dissolved in 50% aqueous N-methylpyrrolidone solution (162 mL) and cooled to 10 ° C., then concentrated hydrochloric acid (14.6 g) and sodium nitrite were added. (3.04 g, 44 mmol) was added and stirred at 10 ° C. for 30 minutes.
Acetoacetanilide (7.08 g, 40 mmol) was dissolved in methanol (60 g), water (120 g) was added, and the solution containing the diazonium salt was added at 30 ° C. at pH = 8.0 and 5 ° C. while adding an aqueous sodium carbonate solution. Dropped in minutes.
The resulting precipitate was filtered and washed with water (300 g) to obtain a yellow cake. The cake was dried to obtain the compound 1. (11.1 g, 83% yield)
(Synthesis Example 2: Synthesis of Compound 2)

The same procedure as in Synthesis Example 1 was repeated except that acetoacetanilide was changed to sodium 3-oxobutanoylaminophenyl-6-methylbenzothiazole-7-sulfonate to obtain a wet cake Na salt azo compound.
After adding water (2350 ml) to the azo compound obtained by the above method and stirring for 1 hour, 20% aqueous calcium chloride solution (13.3 g, 24 mmol) was added and stirred for 3 hours. The obtained precipitate was filtered, washed with water (2350 ml), and dried to obtain the compound 2 (20.4 g, 90%).

  (Synthesis Example 3: Synthesis of Compound 3)

A yellow cake was obtained in the same manner as in Synthesis Example 1 except that acetoacetanilide was changed to N- [4- [3- (diethylamino) propylsulfamoyl] phenyl] -3-oxobutanamide. The cake was dried to obtain the compound 3. (19.1 g, 83% yield)
<Synthesis Example 4: Synthesis of Compound 4>

C. I. Pigment Red 254 (100 g) was added to 25% fuming sulfuric acid (900 g) and reacted at 50 ° C. for 4 hours. After cooling, the reaction mixture was precipitated in ice water (10000 ml), the precipitate was filtered and washed with water, dried, suspended in water, added with aqueous ammonia, then filtered and washed to obtain a water paste. This water paste was dried to obtain Compound 4 (70 g) which is a diketopyrrolopyrrole derivative having an ammonium sulfonate group introduced therein.
The introduction of sulfo group was 0.8 to 1 on average per molecule.

(Synthesis Example 5: Synthesis of Resin S)
145 parts by weight of propylene glycol monomethyl ether acetate was stirred while purging with nitrogen, and the temperature was raised to 120 ° C. 10 parts by weight of styrene, 85.2 parts by weight of glycidyl methacrylate and 66 parts by weight of monoacrylate FA-513M (manufactured by Hitachi Chemical Co., Ltd.) having a tricyclodecane skeleton were added dropwise thereto, and 2.2'-azobis-2-methyl 8.47 parts by weight of butyronitrile was added dropwise over 3 hours, and stirring was continued at 90 ° C. for 2 hours. Next, the inside of the reaction vessel was changed to air substitution, 0.7 part by weight of trisdimethylaminomethylphenol and 0.12 part by weight of hydroquinone were added to 43.2 parts by weight of acrylic acid, and the reaction was continued at 100 ° C. for 12 hours. Thereafter, 56.2 parts by weight of tetrahydrophthalic anhydride (THPA) and 0.7 parts by weight of triethylamine were added and reacted at 100 ° C. for 3.5 hours. The binder resin thus obtained had a weight average molecular weight Mw measured by GPC of about 8400 and an acid value of 80 mg-KOH / g.

[1] Preparation of red atomized pigment composition (Preparation of red atomized pigment composition (R-1) using compounds 1 and 2)
Compounds 1 and 2 obtained in Synthesis Examples 1 and 2 (3.0 parts by weight, respectively) as an atomization aid were used. I. Pigment Red 254 (50 parts by weight), sodium chloride (550 parts by weight), diethylene glycol (110 parts by weight), resin S obtained in Synthesis Example 5 (15 parts by weight in solid content) were charged into a double-arm kneader, Atomization was performed by a solvent salt milling method at 50 ° C. for 4 hours. This kneaded product was put into 7000 parts by weight of water, stirred for 30 minutes, filtered and washed with water, after removing sodium chloride and diethylene glycol, dried and pulverized at 50 ° C. to obtain a red atomized pigment composition (R-1 )

(Preparation of red atomized pigment composition (R-2) using compounds 1 and 3)
Production of the red atomized pigment composition (R-1) was carried out in the same manner except that the compound 2 was changed to the compound 3 to obtain a red atomized pigment composition (R-2).
(Preparation of red atomized pigment composition (R-3) using Compound 2)
Compound 2 (6.0 parts by weight) as an atomization aid, C.I. I. Pigment Red 254 (50 parts by weight), sodium chloride (550 parts by weight), diethylene glycol (110 parts by weight), and resin S obtained in Synthesis Example 2 (15 parts by weight in solid content) were charged into a double-arm kneader, Atomization was performed by a solvent salt milling method at 50 ° C. for 4 hours. This kneaded product is put into 7000 parts by weight of water, stirred for 30 minutes, filtered and washed with water, after removing sodium chloride and diethylene glycol, dried and pulverized at 50 ° C., and the red atomized pigment composition (R-3 )

(Preparation of red atomized pigment composition (R-4) using Compound 2)
In the production of the red atomized pigment composition (R-3), the amount of compound 2 used as the atomization aid was changed from 6.0 parts by weight to 3.0 parts by weight in the same manner. A red atomized pigment composition (R-4) was obtained.
(Preparation of red atomized pigment composition (R-5) using Compound 3)
Preparation of the red atomized pigment composition (R-4) was carried out in the same manner as in the case where the compound 2 was changed to the compound 3, and a red atomized pigment composition (R-5) was obtained.

(Comparative Example 4: Production of red atomized pigment composition (R-6) using Compound 1)
Preparation of the red atomized pigment composition (R-4) was carried out in the same manner except that the compound 2 was changed to the compound 1, to obtain a red atomized pigment composition (R-6).
[2] Preparation of pigment dispersion (Examples 1 and 2, Comparative Examples 1 to 4: Red pigment dispersions (1) to (1) using the red atomized pigment compositions (R-1) to (R-6)) 6) Preparation)
9.6 parts by weight of the compound 4 obtained in Synthesis Example 4 as a dispersion aid, 100 parts by weight of the red atomized pigment composition (R-1) as a pigment, and the resin S obtained in Synthesis Example 5 34.1 parts by weight in terms of solid content, 38.6 parts by weight of “BYK-LPN6919” (produced by Big Chemie; equivalent to (D-2) dispersant) as a dispersant, and propylene glycol monomethyl ether acetate (hereinafter referred to as “the solvent”). 669 parts by weight of the mixture (which may be referred to as “PGMEA”) was stirred and mixed, 400 parts by weight of zirconia beads were added, and dispersed for 6 hours by a bead mill to prepare a red pigment dispersion (1).

Similarly, using the red atomized pigment compositions (R-2) to (R-6) in place of the red fine pigment composition (R-1), red pigment dispersions (2) to (6) are used. ) Was prepared.
The red pigment dispersions (1) to (6) were prepared, and it was visually confirmed that the dispersion after 1 hour had fluidity.
[3] Preparation of colored resin composition Subsequently, the components described in Table 1 below were mixed with the red pigment dispersions (1) to (6) obtained in [2] above, and various colored resin compositions were prepared. Was prepared.
Examples 1 and 2 use colored resin compositions containing pigment dispersions (1) and (2), and Comparative Examples 1 to 4 use colored resin compositions containing pigment dispersions (3) to (6). Things were used.

[4] Preparation of colored resin film and colored plate On the transparent glass substrate “AN-100” (manufactured by Asahi Glass Co., Ltd.), each of the colored resin compositions obtained in [3] above was spin-coated and applied at 80 ° C. Was pre-baked on a hot plate for 3 minutes to obtain a dried coating film.
Subsequently, the obtained dried coating film was exposed at 60 mJ / cm ² with a high-pressure mercury lamp, and then post-baked in an oven at 230 ° C. for 30 minutes to prepare various colored resin films.

In the application, after the post-baking, the rotation speed was adjusted so that the color coordinates of the dry coating film obtained would be a film thickness where x = 0.648.
The thickness of the obtained colored resin film was about 2.4 μm. Thus, various colored plates having a colored resin film on a transparent glass substrate were produced.
[5] Measurement of contrast value Various colored plates obtained in the above [4] were measured using a color luminance meter “BM-5AS” (manufactured by Topcon Corporation). Table 2 shows the results of contrast values.

About Table 2, when compound 1 and compound 2 are used in combination rather than the case where only compound 1 is used as the atomization aid (Comparative Example 4) or the case where only Compound 2 is used (Comparative Example 1) It can be seen that the contrast in Example 1) is improved.
Also, contrast is higher when Compound 1 and Compound 3 are used in combination (Example 2) than when Compound 1 alone is used (Comparative Example 4) or only Compound 3 is used (Comparative Example 3). It can be seen that is improved.

That is, the pixel formed using the colored resin composition containing the pigment dispersion of the present invention has a high contrast.
Therefore, the color filter of the present invention has high contrast, and the liquid crystal display device and the organic EL display device have high quality.

DESCRIPTION OF SYMBOLS 100 Organic EL element 20 Pixel 30 Organic protective layer 40 Inorganic oxide film 500 Organic light-emitting body 51 Hole injection layer 54 Electron injection layer

Claims (9)

In a pigment dispersion containing (A) a pigment, (B) a solvent and (D) a dispersant,
Furthermore, it contains two or more compounds represented by the following formula (1) ,
The pigment (A) is C.I. I. (Color Index) Pigment Red 177, Pigment Red 242, Pigment Red 254, Pigment Yellow 138, Pigment Yellow 139, Pigment Yellow 180, Pigment Green 7, Pigment Green 36, Pigment Green 58 and Pigment Y represented by the following definition A pigment dispersion comprising at least one pigment selected from the group .

(In the above formula (1), A ¹ represents a nitrogen-containing fused ring group which may have a substituent.
R ¹ is an optionally substituted alkyl group having 1 to 5 carbon atoms, an optionally substituted alkoxy group having 1 to 4 carbon atoms, or an optionally substituted carbon. An aromatic ring group of several 6 to 10 is represented.
B ¹ represents an arbitrary substituent.
However, B < ¹ > in at least 1 type of compound is group represented by -ZX. Z represents a direct bond or a divalent group selected from the following <divalent linking group group>.
<Divalent linking group group>

(In the above formula, * represents a linking site.)
X represents a group represented by any of the following formulas.

In the above formula, * represents a connecting site with Z.
M ¹ and M ² each independently represents a hydrogen atom, an alkali metal atom, or an alkaline earth metal atom.
R ^a1 and R ^a2 each independently represent a hydrogen atom, an optionally substituted hydrocarbon group having 1 to 12 carbon atoms, or an optionally substituted aromatic ring group. )
<Pigment Y>
A compound obtained by inserting another compound into a 1: 1 complex of azobarbituric acid with nickel represented by the following structural formula or a compatible isomer thereof.

  Among the compounds represented by the formula (1), the weight ratio of the compound having the largest content to the compound having the smallest content is 1 to 3.0 times. The pigment dispersion according to claim 1, characterized in that it is characterized in that   The total amount of the compound represented by the formula (1) is 0.001 times or more and 0.025 times or less by weight ratio with respect to the pigment (A). Or the pigment dispersion liquid of 2. A colored resin composition comprising the pigment dispersion according to any one of claims 1 to 3 and (C) a binder resin. The colored resin composition according to claim 4 , further comprising (E) a polymerizable monomer. And (F) a photopolymerization initiating component and / or a thermal polymerization initiating component.
The colored resin composition according to claim 4 or 5 . It characterized by having a pixel formed by using a colored resin composition according to any one of claims 4-6, the color filter. A liquid crystal display device comprising the color filter according to claim 7 . An organic EL display device comprising the color filter according to claim 7 .

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