JP2012197428A - Additive, pigment dispersion liquid, colored resin composition, color filter, liquid crystal display device, and organic el display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a pigment dispersion liquid and a colored resin composition, improved in dispersion stability and suppressed in generation of crystal foreign matters in a microparticulating step, a dispersion step or after firing.SOLUTION: The pigment dispersion liquid contains a pigment, a solvent and a compound represented by formula (1) as an additive, and the colored resin composition contains in the dispersion liquid, a binder resin and the like. In the formula, Ais a nitrogen-containing condensed ring group which may have a substituent; Bis a 6-10C aromatic ring group which may have a substituent or a 2-12C heterocyclic group which may have a substituent; Ris a 1-5C alkyl group which may have a substituent; n is an integer of 0 to 2; and Z is a direct bond or a divalent group selected from a sulfonamide group, a sulfone ester group, an amide group and an ester group.

Description

  The present invention relates to an additive, 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 addition, in order to produce a high-intensity color filter, it is necessary to highly atomize a pigment having a high transmittance, and further to disperse the pigment with a narrow particle size distribution in a small particle size region. The control technology is rapidly developing.

For example, as red pigments, dianthraquinone pigments, perylene pigments, diketopyrrolopyrrole pigments and the like have been used. In particular, diketopyrrolopyrrole pigments are used in combination with various yellow pigments because of their high permeability, excellent light resistance and heat resistance. A quinophthalone pigment is used as the yellow pigment.
However, in recent years, a pigment system with higher permeability has been demanded, and further improvement in permeability has been studied by searching for new pigments and further reducing the primary particle size of pigments and narrowing the particle size distribution. .

As a method for atomizing the pigment, for example, the pigment, the water-soluble inorganic salt such as salt and the water-soluble organic solvent are mechanically kneaded together with a kneader or the like, and then the inorganic salt and the organic solvent are removed by washing with water. There is a method such as a salt milling method for obtaining a pigment that has been converted into a pigment.
However, the pigment atomized by the above method tends to cause aggregation and crystallization. Therefore, in order to obtain a high-intensity color filter, it has been a problem to maintain dispersion stability and suppress pigment crystallization as a pigment dispersion.

In order to solve such problems, for example, Patent Documents 1 to 5 disclose mixing a pigment derivative into which a sulfo group or a salt thereof is introduced when preparing a pigment dispersion.
However, even with the above-described method, the stability of the pigment dispersion and the suppression of crystallization of the pigment are not sufficient, and therefore, further improvement in the luminance of the obtained color filter has been desired.

JP 2000-160084 A JP 2006-265528 A JP 2007-23266 A JP-T-2004-505157 JP 2009-186835 A

In view of the above problems, the present invention has an object to provide a pigment dispersion and a colored resin composition that improve dispersion stability and suppress generation of crystal foreign matter after the atomization step, the dispersion step, or the firing. To do.
Another object of the present invention is to provide a color filter with high luminance, 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 a pigment derivative mixed for the purpose of suppressing crystal transition has high orientation itself and has not been able to effectively suppress the crystal transition of the pigment. It has been found that the coloring of the derivative itself is one factor that causes a decrease in luminance of the obtained pixel.
In other words, mixing for the purpose of suppressing crystal transition is not easy to cause crystallization by agglomeration and reorientation like pigment derivatives. In addition, by using a material that is not easily crystallized by reorientation, it is possible to suppress the crystal transition of the pigment that occurs when the resist is formed using the dispersion or the colored resin composition. Moreover, 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, the inventors have found that the above-mentioned problems can be solved by using an additive having a specific structure, and have reached the present invention.
That is, the present invention resides in an additive, a pigment dispersion, a colored resin composition, a color filter, a liquid crystal display device, and an organic EL display device characterized by comprising a compound represented by the following formula (1).

(The formula (1), A ¹ represents a nitrogen-containing condensed ring group which may have a substituent.
B ¹ has an optionally substituted alkyl group having 1 to 5 carbon atoms, an optionally substituted aromatic ring group having 6 to 10 carbon atoms, or a substituent. Or a C2-C12 heterocyclic group.
R ¹¹ 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.

n represents an integer of 0 to 2.
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 with A ¹ or an adjacent phenyl group.)

The additive of the present invention inhibits pigment aggregation and reorientation, and does not impair pigment permeability. Therefore, when a color filter is formed using the pigment dispersion or the colored resin composition of the present invention, the transmittance of the pigment is not impaired, and thus the luminance of the obtained color filter is high. Moreover, since the additive of the present invention has a maximum absorption wavelength in a short wavelength region, it is difficult to cause a decrease in luminance due to the addition.
Furthermore, since the viscosity of the resulting pigment dispersion is low, production yield due to high viscosity is unlikely to occur.

  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”.

Hereinafter, the additive in this invention is demonstrated first.
<Additives>
The additive in the present invention is an additive composed of a compound represented by the following formula (1).

(The formula (1), A ¹ represents a nitrogen-containing condensed ring group which may have a substituent.
B ¹ has an optionally substituted alkyl group having 1 to 5 carbon atoms, an optionally substituted aromatic ring group having 6 to 10 carbon atoms, or a substituent. Or a C2-C12 heterocyclic group.
R ¹¹ 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.

n represents an integer of 0 to 2.
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 with A ¹ or an adjacent phenyl group.)
(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 an aromatic hydrocarbon ring condensed with a cyclic amide bond. For example, the aromatic hydrocarbon ring which (beta) -lactam, (gamma) -lactam, (delta) -lactam etc. condensed is mentioned. On the other hand, examples of the aromatic hydrocarbon ring include a benzene ring and a naphthyl ring.

  Preferable examples including the aromatic hydrocarbon ring condensed with the cycloaliphatic cyclic amide bond, that is, the substituent of the nitrogen-containing condensed ring include the following <nitrogen-containing condensed ring group A>. <Nitrogen-containing fused ring group A>

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 with Z or a phenyl group.)
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.
Examples of the substituents that may be included in the total carbon number including the substituent of the alkyl group in R ⁵³ R ⁵⁴ are the same as those exemplified for the alkyl groups 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 and the like), carboxy-substituted lower alkylamines having 1 to 6 carbon atoms (for example, carboxymethylamine, carboxyethylamine, carboxypropylamine, dicarboxymethylamine and the like) 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 has an optionally substituted alkyl group having 1 to 5 carbon atoms or an aromatic ring group having 6 to 10 carbon atoms that may have a substituent, and a substituent. Or a C2-C12 heterocyclic group.
The number of carbon atoms of the alkyl group in B ¹ represents generally from 1 to 5, preferably 1 to 3. Within the above range, when used as an atomization aid or dispersion aid, dissolution of the additive of the present invention in an organic solvent is suppressed, and this is preferable in that efficient adsorption to the pigment surface is possible.
Examples of the substituent that the alkyl group in B ¹ may have include those described in the section of <Substituent group W>.

Specific examples of the alkyl group for B ¹ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and a methoxyethyl group.
The number of carbon atoms of the aromatic ring group for B ¹ represents a normally 6-10. Within the above range, the hue of the compound represented by the formula (1) tends to have maximum absorption in a short wavelength region, and this is preferable in that a desired color can be easily obtained in the obtained color filter.

The aromatic ring group for B ¹ is preferably an aromatic hydrocarbon group such as a phenyl group or a naphthyl group, or a group containing 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 dipyridyl group, a quinolinyl group, an isoquinolinyl group, a benzothiazoyl group, a thiadiazoyl group, and the like. Among them, a benzothiazoyl 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 thiadiazoyl group is preferred.

The aromatic ring group in B ¹ may have a substituent.
The aromatic substituent which may be ring group optionally having at B ^1, the total number of carbon atoms including the preferred substituents on the aromatic ring group of B ^1, and and examples of even substituent preferably have Specific examples and preferred numbers of substituents include those described in the section of <Substituent group W>.
In addition, when it has a sulfo group and its derivative, a carboxyl group and its derivative as a substituent, the dispersion aids adsorbed on the pigment surface by having repulsion between the dispersion aids adsorbed on the pigment surface due to steric hindrance and polarity. This makes it easy to suppress the aggregation of the pigment. In particular, it is preferable that B ¹ is contained as a substituent because the above-mentioned effect can be easily obtained.

(For ^{R 11)}
R ¹¹ 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.
R ¹¹ 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 in the alkyl group in R ¹¹ is, usually 1 to 5, preferably 1 to 3. Within the above range, when used as an atomization aid or dispersion aid, dissolution of the additive of the present invention in an organic solvent is suppressed, and this is preferable in that efficient adsorption to the pigment surface is possible.
As the alkyl group for R ^11, 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, an isopropyl group, and a methoxyethyl group.

Examples of the substituent that the alkyl group in R ¹¹ may have include 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.

Specific examples of the alkyl group for R ¹¹ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and a methoxyethyl group.
The number of carbon atoms of the alkoxy group in R ¹¹ is usually 1-5, preferably 1-3. Within the above range, when used as an atomization aid or dispersion aid, dissolution of the additive of the present invention in an organic solvent is suppressed, and this is preferable in that efficient adsorption to the pigment surface is possible.

The substituent that the alkoxy group in R ¹¹ may have includes 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 ¹¹ include a methoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group, a hydroxyethoxy group, and a 1,2-dihydroxypropoxy group.
The number of carbon atoms of the aromatic ring group for R ¹¹ is usually 6-10. 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 ¹¹ 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 ¹¹ , examples of the substituents that may be present, and preferred specific examples thereof, and the preferred number of substituents are given in the section <Substituent group W>. What has been described.

(About n)
n represents an integer of 0 to 2.
Since the number of divalent linking groups affects the planarity, n is particularly preferably 0 in terms of excellent planarity and easier adsorption with the pigment.
(About Z)
Z represents a direct bond or a divalent group selected from the following <divalent linking group group B>.
<Divalent linking group B>

(In the above formula, * represents a linking site with A ¹ or an adjacent phenyl group.)
The <divalent linking group B> shields the electronic effect (electron donating property and electron withdrawing property) of the nitrogen-containing condensed ring in A ¹ and does not electronically affect the adjacent phenyl group.
Therefore, when n is 1 or more, the compound represented by Formula (1) does not depend on the structure of the nitrogen-containing fused ring group in A ¹ and has a structure in which the color tone has a maximum absorption in a shorter wavelength region. be able to.

In particular, when the sulfur atom in groups selected from the <divalent linking group B>, and the carbon atoms comprising the structure that binds to A ^1, ring A ¹ will have an electron withdrawing group as a substituent This is preferable because the maximum absorption wavelength of the compound represented by the formula (1) can be further shortened.
In addition, -NH-CO- is particularly preferable in that it is excellent in the group selected from the <divalent linking group B>, compound stability, heat resistance, and light resistance.

The phenyl group linked to Z may have a substituent in addition to the linking site, and specific examples of the substituent include those described in the above <Substituent group W> section. Can be mentioned.
However, in order to keep the flatness better, the phenyl group linked to Z is preferably unsubstituted.
(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.

<Reason for obtaining the effect of the present invention>
The reason why the luminance of the obtained color filter is particularly increased when the additive of the present invention is used as a dispersion aid and an atomization aid 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 does not impair the transparency in the long wavelength region, particularly with a red pigment, resulting in high brightness.

On the other hand, as a dispersion liquid for obtaining a pixel with high luminance, it is necessary to stably disperse pigment particles to a size near the primary particles. As described above, the additive has high planarity, 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.

That is, when the additive of the present invention is added in the atomization step or the dispersion step, it can be easily taken into the pigment surface or inside, and the crystallinity of the pigment can be inhibited. Therefore, when the additive of the present invention is used in the pigment dispersion step and atomization step, the pigment dispersion can stably disperse to the vicinity of the temporary particle size.
From the above, the pixel obtained using the additive of the present invention has high luminance.

<Application>
The additive of the present invention is preferably used for a color filter, and more preferably used as a atomization aid or a dispersion aid contained in a pigment dispersion or a colored resin composition. More specifically, the additive of the present invention is preferably added during the atomization step or dispersion step of the pigment. When used in the atomization step, the additive is a atomization aid, and when used in the dispersion step, Dispersing aid.

  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 process is likely to occur, but this phenomenon can be suppressed in the presence of the additive of the present invention.

Examples of the dispersion step include a finely divided pigment composition obtained by the above method, an additive of the present invention, and a method of dispersing the resin together with a solvent with a dispersing machine such as a sand mill as necessary. A dispersion can be obtained. At this time, as described above, the pigment and additives are mixed in advance and refined, and then dispersed or dissolved in an organic solvent, and the resulting dispersion or solution may be mixed, or the refined pigment And the additive may be added and dispersed separately in the organic solvent. The disperser used when dispersing the atomized pigment and the dispersant in the organic solvent is not particularly limited. For example, a known disperser such as a kneader, a roll mill, a sand mill, an attritor, or a homomixer may be used. Can be mentioned. It becomes possible to improve the dispersion state of the pigment dispersion obtained by adding an appropriate amount of an additive as a dispersion aid during the dispersion step, resulting in a decrease in the viscosity of the resulting pigment dispersion. .
As described above, the colored resin composition containing the additive of the present invention is particularly preferably used as a color filter application (that is, a colored resin composition for a color filter).

<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 pigment Y represented by the following definitions.

<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.

Of these, C.I. I. Pigment yellow 83, 117, 129, 138, 139, 154, 155, 180, 185, and pigment Y, and more preferably C.I. I. Pigment yellow 83, 138, 139, 180, and pigment Y.
In particular, C.I. is particularly advantageous in that the effect of the present invention that the viscosity of the pigment dispersion is greatly reduced can be obtained. I. Particularly preferred is CI Pigment Yellow 138.

  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 it has a high affinity with the additive of the present invention and an effect can be easily obtained.
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 present invention is usually 80% by weight or less, preferably 70% by weight or less, more preferably 60% by weight or less, and usually 0.1% by weight or more with respect to the total solid content. , Preferably 0.5% by weight or more, more preferably 1% by weight or more.

  (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 ratio 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% considering the viscosity suitable for coating.
% By weight or more, 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 further contain an 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, but the additive of the present invention is particularly preferable because the luminance of the obtained pixel is high. It is preferable to use it as an atomization aid.
The content of the atomization aid in the pigment dispersion and colored resin composition of the present invention is usually 0.01% by weight or more, preferably 1% by weight or more, and usually 40% by weight or less based on the pigment (A). It is preferably 30% by weight 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 mgKOH / g or more and 150 mgKOH / g. The following (in terms of effective solid content) is particularly preferable. More preferably, it is 100-140 mgKOH / 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 C 1 -C
These are the above alkylene groups, and 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 [mgKOH / 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 group that is the basis of the acid value, and is usually 50 mgKOH / g or less, preferably 40 or less, more preferably 30. It is as follows.

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). Hereinafter, it is more preferably 10% by weight or less, still more preferably 5% by 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.

Even when other dispersion aids are contained, the total amount of the dispersion aids is set within the above range.
When the pigment dispersion and colored resin composition of the present invention contains a dispersion aid, the dispersion aid is preferably contained from the additive of the present invention.

[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 mgKOH / g or more, more preferably 1 mgKOH / g or more, most preferably 5 mgKOH / g or more, more preferably 300 mgKOH / g or less, more preferably 200 mgKOH / g or less, and 150 mgKOH / g. The following are most preferred. 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.

[(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. Alkali-soluble resin obtained by adding a polybasic acid anhydride to at least a part of the hydroxyl group produced by the addition reaction

  As a particularly preferred resin of the resin (C-1), a copolymer of 5 to 90 mol% of an epoxy group-containing (meth) acrylate and 10 to 95 mol% of another radical polymerizable monomer, A resin obtained by adding an unsaturated monobasic acid to 10 to 100 mol% of the epoxy group of the copolymer, or a polybasic acid anhydride is added to 10 to 100 mol% of a hydroxyl group generated by the addition reaction. And alkali-soluble resins obtained.

  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 system 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 diisocyanates; aromatic diisocyanates such as tolylene diisocyanate and diphenylmethane diisocyanate, and (meth) acryloyl such as 2-hydroxyethyl (meth) acrylate and 3-hydroxy [1,1,1-tri (meth) acryloyloxymethyl] propane A reaction product with a group-containing hydroxy compound is exemplified.

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 system and / or thermal polymerization initiation system]
The colored resin composition of the present invention preferably contains (F) a photopolymerization initiation system and / or a thermal polymerization initiation system 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 system having a function of generating a polymerization active radical and / or a thermal polymerization initiating system for generating a polymerization active radical by heat. In the present invention, the component (F) as the photopolymerization initiation system is a photopolymerization initiator (hereinafter arbitrarily referred to as (F1) component) to 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 system)
The colored resin composition of the present invention preferably contains a photopolymerization initiation system. The photopolymerization initiating system 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 photopolymerization initiator constituting the photopolymerization initiation system (F1) include titanocene derivatives described in JP-A Nos. 59-152396 and 61-151197, etc .; 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 initiation systems is usually 0.1% by weight or more, preferably 0.2% by weight or more, more preferably 0.8% by weight in 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 system)
Specific examples of the thermal polymerization initiation system (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 the preparation method, (A) a solvent containing a pigment, (D) a dispersant, represented by the above formula (1). In the presence of a compound to be added, and a dispersion aid to be further added as necessary, (C) optionally together with a part of the binder resin, for example, paint shaker, sand grinder, ball mill, roll mill, stone mill, jet mill, Using a homogenizer or the like, a colored 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 and mixed with the colored dispersion. The method of preparing by 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.

  A light source for using radiation having a wavelength of 190 to 450 nm used for image exposure is not particularly limited. For example, a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, 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, more preferably 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 examples and comparative examples. In addition, this invention is not limited to description of a following example, unless the summary is exceeded.
[Synthesis of additives]
(Synthesis Example 1: Synthesis of Compound 1)

5-Amino-2-benzimidazolinone (2.61 g, 17.5 mmol) was added to 70% NMP water (100 mL) and cooled to 10 ° C., then concentrated hydrochloric acid (8.0 g) and sodium nitrite ( 1.98 g, 28.7 mmol) was added and stirred at 10 ° C. for 1 hour.
N- [4- [3- (Diethylamino) propylsulfamoyl] phenyl] -3-oxobutanamide (6.99 g, 17.5 mmol) is added with water (100 g), and the liquid containing the diazonium salt is carbonated. While adding an aqueous sodium solution, the solution was added dropwise at pH = 8.0 and 5 ° C. over 30 minutes.

The resulting precipitate was filtered and washed with water (200 g) to obtain a yellow cake. The cake was dried to obtain the compound 1. (8.35 g, 90% yield)
<Synthesis Example 2: Synthesis of Compound 2>

  5-Amino-2-benzimidazolinone (14.9 g, 100 mmol), sodium carbonate (5.26 g, 50 mmol), 4-dimethylaminopyridine (60 mg, 500 mmol) was added to NMP (200 mL) to give 4-nitrobenzoyl. Chloride (18.5 g, 100 mmol) was added and stirred at room temperature for 3 hours. The obtained reaction solution was discharged into water (800 ml) and filtered to obtain a cake.

The cake obtained above was added to water (400 ml), and a sodium hydroxide aqueous solution was added to adjust the pH to 10. After the liquid temperature was adjusted to 50 ° C., sodium hydrosulfide (46 g) was added and stirred for 30 minutes. The resulting precipitate was filtered and washed with water (800 g) to obtain a brown cake. This cake was dried to obtain a precursor of compound 2. (21.4 g, 80% yield)
The same synthesis was performed using the present precursor instead of 5-amino-2-benzimidazolinone in Synthesis Example 1 to obtain Compound 2 (10.1 g, yield 89%).
<Synthesis Example 3: Synthesis of Compound 3>

In Synthesis Example 1, N- [4- [3- (diethylamino) propylsulfamoyl] phenyl] -3-oxobutanamide was changed to sodium 3-oxobutanoylaminophenyl-6-methylbenzothiazole-7-sulfonate In the same manner as above, a wet cake Na salt azo compound was obtained.

Water (600 ml) was added to the azo compound obtained by the above method and stirred for 1 hour, and then 20% aqueous calcium chloride solution (4.2 g, 8.0 mmol) was added and stirred for 3 hours. The obtained precipitate was filtered, washed with water (600 ml), and then dried to obtain calcium salt 3 (4.8 g, yield 90%).
<Synthesis Example 4: Synthesis of Compound 4>

Synthetic Example 3 except that sodium 3-oxobutanoylaminophenyl-6-methylbenzothiazole-7-sulfonate was used in Synthesis Example 3 as potassium 4- (1,3-dioxobutylamino) benzenesulfonate. In the same manner, compound 4 was obtained (6.48 g, yield 85%).
<Synthesis Example 5: Synthesis of Compound 5>

Compound 5 was obtained in the same manner as in Compound 4 except that the precursor synthesized in Synthesis Example 2 was used instead of 5-amino-2-benzimidazolinone, to obtain Compound 5 (8.26 g, yield 85%).
<Synthesis Example 6: Synthesis of Compound 6>

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 is precipitated in ice water (10000 ml), the precipitate is filtered and washed with water, dried, suspended in water, added with 20% aqueous calcium chloride, and then filtered and washed to obtain a water paste. It was. This water paste was dried to obtain a diketopyrrolopyrrole derivative having a calcium sulfonate group introduced therein, that is, compound 6 (70 g). The introduction of sulfo group was 0.8 to 1 on average per molecule.
<Synthesis Example 7: Synthesis of Compound 7>

Instead of adding the calcium chloride aqueous solution in Synthesis Example 6, aqueous ammonia was added to obtain Compound 7 (70 g).
[Synthesis of binder resin]
(Reference Synthesis Example 1: 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 further 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 mgKOH / g.

<Dispersant BYK-LPN6919 (manufactured by Big Chemie)>
It is a methacrylic acid AB block copolymer, the amine value is 121 mgKOH / g, and the acid value is 1 mgKOH / g or less.
Of the repeating units having a nitrogen atom-containing functional group contained in the B block, about 100 mol% has a structure represented by the following formula (i), and the repeating unit represented by the following formula (ii) The ratio in one molecule in terms of the monomer composing the acid AB block copolymer was 7.5 mol%.

<Preparation of atomized pigment and preparation of pigment dispersion>
Example 1
[Production of Red Atomized Pigment (R-1) Using Compound 1]
Compound 1 (3.0 parts by weight) obtained in Synthesis Example 1 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. to obtain a red atomized pigment (R-1). Obtained.

[Preparation of pigment dispersion]
<Preparation of Red Pigment Dispersion (1) Using Red Atomized Pigment (R-1) Containing Compound 1>
Red atomized pigment (R-1) obtained in Example 1 (100 parts by weight) as a pigment, Compound 7 (9.6 parts by weight) obtained in Synthesis Example 7 as a dispersion aid, obtained in Reference Synthesis Example The obtained resin S (34.1 parts by weight), “BYK-LPN6919” (manufactured by Big Chemie) (38.6 parts by weight) as a dispersant, and PGMEA (669 parts by weight) as a solvent were mixed with stirring, and zirconia beads (400 Parts by weight) and dispersion was carried out for 6 hours with a bead mill to prepare a red pigment dispersion (1).

The red pigment dispersion (1) was prepared, and it was visually confirmed that the dispersion after 1 hour had fluidity.
[Preparation of colored resin composition (1) containing red pigment dispersion (1)]
Subsequently, each component shown in Table 1 below was mixed with the red pigment dispersion (1) obtained in [Preparation of Pigment Dispersion] to prepare various colored resin compositions.

(Examples 2 to 5, Comparative Example 1)
[Production of Red Atomized Pigments (R-2) to (R-6) Using Compounds 2 to 6]
In Example 1, red atomized pigments (R-2) to (R-6) were obtained in the same manner except that compounds 2 to 6 were used instead of compound 1.
[Preparation of Red Pigment Dispersion Liquid (2-6) Using Red Atomized Pigments (R-2) to (R-6) containing Compounds 2 to 6]

The same procedure as in Example 1 was conducted except that the red atomized pigment (R-1) used in Example 1 was changed to red atomized pigments (R-2) to (R-6). 2) to (6) were obtained.
[Preparation of colored resin compositions (2) to (6) containing red pigment dispersions (2) to (6)]
Except that the red pigment dispersion liquid (1) in Example 1 [Preparation of colored resin composition (1) containing red pigment dispersion liquid (1)] was changed to red pigment dispersion liquids (2) to (6), this was carried out. In the same manner as in Example 1, colored resin compositions (2) to (6) were prepared.

[Creation of colored resin film and colored plate]
On the transparent glass substrate “AN-100” (manufactured by Asahi Glass Co., Ltd.), the various colored resin compositions obtained in the above [Preparation of colored resin composition] were each spin-coated, and 3 on an 80 ° C. hot plate. Pre-baking was performed for a minute 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.
[Measurement of luminance (Y value)]
Using the spectrophotometer “U-3310” (manufactured by Hitachi High-Technologies Corporation), the chromaticity (Y, x, y) of the various colored plates obtained in [Creation of colored resin film and colored plate] with a spectrophotometer “U-3310” Was measured. The results of Y value are shown in Table 2.

  As shown in Table 2, it can be seen that the permeability is remarkably improved by including the additive of the present invention. That is, it can be seen that the pixel formed using the colored resin composition containing the additive of the present invention has high luminance.

[Preparation of yellow pigment dispersion]
<Preparation of yellow pigment dispersion (7) using compound 1 as dispersion aid>
C.I. I. Pigment Yellow 138 (100 parts by weight), Compound 1 (9.6 parts by weight) obtained in Synthesis Example 1 as a dispersion aid, Resin S (34.1 parts by weight) obtained in Reference Synthesis Example 1, and a dispersant "BYK-LPN6919" (by Big Chemie) (38.6 parts by weight), PGMEA (669 parts by weight) as a solvent was stirred and mixed, zirconia beads (400 parts by weight) were added, and dispersed in a bead mill for 6 hours. A pigment dispersion (7) was prepared. The fluidity was good.

<Preparation of yellow pigment dispersion (8)>
A yellow pigment dispersion (8) was prepared in the same manner as in <Preparation of Yellow Pigment Dispersion (7) Using Compound 1 as Dispersing Aid >>, except that Compound 1 was not used. The fluidity was extremely poor and viscosity measurement was impossible.

[3] Viscosity of Pigment Dispersion After the yellow pigment dispersions (7) and (8) obtained above were stored at room temperature (23 ° C.) for one day, an E-type viscometer “RE-80L” (Toki The viscosity was measured at room temperature (23 ° C.) and 20 rpm.
The results are shown in Table 3.

As shown in Table 3, it can be seen that the use of the additive of the present invention as a dispersion aid greatly reduces the viscosity of the pigment dispersion.
Accordingly, it is possible to suppress a decrease in manufacturing yield due to the high viscosity of the pigment dispersion.

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 (13)

An additive comprising a compound represented by the following formula (1).

(The formula (1), A ¹ represents a nitrogen-containing condensed ring group which may have a substituent.
B ¹ has an optionally substituted alkyl group having 1 to 5 carbon atoms, an optionally substituted aromatic ring group having 6 to 10 carbon atoms, or a substituent. Or a C2-C12 heterocyclic group.
R ¹¹ 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.
n represents an integer of 0 to 2.
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 with A ¹ or an adjacent phenyl group.) 2. The additive according to claim 1, wherein the nitrogen-containing fused ring group in A ¹ is a group selected from the following <nitrogen-containing fused ring group A>.
<Nitrogen-containing fused ring group A>

  A pigment dispersion comprising the additive according to claim 1, (A) a pigment, and (B) a solvent. 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, and Pigment Green 58, from Pigment Y represented by the following definition The pigment dispersion according to claim 3, comprising at least one pigment selected from the group consisting of:
<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.

  Furthermore, (D) A dispersing agent is contained, The pigment dispersion liquid of Claim 3 or 4 characterized by the above-mentioned.   A colored resin composition comprising the pigment dispersion according to any one of claims 3 to 5 and (C) a binder resin.   A colored resin composition comprising (A) a pigment, (B) a solvent, (C) a binder resin, and the additive according to claim 1 or 2.   The colored resin composition according to claim 7, further comprising (D) a dispersant.   Furthermore, (E) polymeric monomer is contained, The colored resin composition as described in any one of Claims 6-8 characterized by the above-mentioned.   The colored resin composition according to any one of claims 6 to 9, further comprising (F) a photopolymerization initiation system and / or a thermal polymerization initiation system.   It has a pixel formed using the colored resin composition as described in any one of Claims 6-10, The color filter characterized by the above-mentioned.   A liquid crystal display device comprising the color filter according to claim 11.   An organic EL display device comprising the color filter according to claim 11.

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