JP2011252065A - Pigment dispersion composition, colored curable composition, color filter for solid state imaging device, its manufacturing method, and solid state imaging device - Google Patents

Abstract

[PROBLEMS] To provide a colored curable composition capable of both maintaining adhesion of a colored pattern to a support and suppressing generation of a residue even when development conditions are strengthened when forming a colored pattern on the support. A simple pigment dispersion composition.
A pigment containing an azo pigment represented by the general formula (1), at least one compound selected from organic dye derivatives, anthraquinone derivatives, and triazine derivatives having an acidic functional group, and a dispersant. Dispersion composition [G: hydrogen atom, aliphatic group, aryl group, heterocyclic group; R ₁ : amino group, aliphatic oxy group, aliphatic group, aryl group, or heterocyclic group; R ₂ : substituent group; A : Heterocyclic group; m: an integer of 0 to 5; n: an integer of 1 to 4; the general formula (1) does not have an ionic hydrophilic group. ]

[Selection figure] None

Description

  The present invention relates to a pigment dispersion composition, a colored curable composition, a color filter for a solid-state imaging device, a method for producing the same, and a solid-state imaging device.

  As a color filter used for colorizing a solid-state imaging device or a liquid crystal display device, a color filter composed of a red filter layer, a green filter layer, and a blue filter layer formed adjacent to each other on the same plane on a substrate In addition, a color filter composed of a yellow filter layer, a magenta filter layer, and a cyan filter layer is known (in the present specification, the colored filter layers of the respective colors are also referred to as “colored patterns”).

In recent years, further high definition has been desired for color filters.
However, the conventional pigment dispersion system does not improve resolution, and has problems such as color unevenness due to coarse pigment particles, so that a fine pattern such as a solid-state image sensor is required. It was not suitable for use. In order to solve this problem, the use of dyes has been conventionally proposed (for example, see Patent Document 1).
For example, it is known that a red dye is used for a red filter array of a color filter (see, for example, Patent Document 2).

However, since the coloring pattern obtained with the dye does not have sufficient heat resistance and light resistance, a color filter using an organic pigment having excellent heat resistance and light resistance has been studied.
As a method for producing a color filter using an organic pigment, for example, a photolithography method (for example, performing a patterning process by exposing and developing a composition in which an organic pigment is dispersed in a photosensitive resin is repeated a required number of times. And Patent Document 3), and printing methods such as offset printing and ink jet printing using an ink containing an organic pigment.

As organic pigments for color filters, the use of organic pigments with excellent heat resistance and light resistance such as anthraquinone, diketopyrrolopyrrole, quinacridone, isoindoline, perinone, perylene, and condensed azo has been studied. Yes.
Patent Document 4 proposes a red ink composition for a color filter containing a monoazo compound containing a naphthalene ring. Studies have been made to obtain color filters having good spectral characteristics using such various pigments.

  On the other hand, miniaturization of color filters in recent years has progressed further than ever. In such a fine color filter manufacturing process, residues are easily generated due to the small colored pattern formed, and such residues often adversely affect the performance of the color filter and often cause problems. It was.

JP-A-6-75375 Japanese Patent Laid-Open No. 5-5067 Japanese Patent Laid-Open No. 1-152449 International Publication No. 05/052074 Pamphlet

  Under these circumstances, as a means of reducing the amount of residue when forming a colored pattern, when reducing the residue by strengthening the development process (using a developer with a high alkali concentration, extending the development time, repeating the development process several times, etc.) There is. However, when such a development process is strengthened, there is a problem that the colored pattern is easily peeled off from the substrate and the yield is deteriorated.

This invention is made | formed in view of said situation, and makes it a subject to achieve the following objectives.
That is, the object of the present invention is a color curing that can maintain both the adhesion of the colored pattern to the support and suppress the generation of residues even when the development conditions are strengthened when forming the colored pattern on the support. Another object of the present invention is to provide a pigment dispersion composition suitable for the color composition, and a colored curable composition containing the pigment dispersion composition.
Another object of the present invention is to provide a color filter for a solid-state image sensor having a colored pattern with few peeling defects and residual defects, and a solid-state image sensor provided with the color filter.

Specific means for solving the above problems are as follows.
<1> At least one selected from the group consisting of an azo pigment represented by the general formula (1), an organic dye derivative having an acidic functional group, an anthraquinone derivative having an acidic functional group, and a triazine derivative having an acidic functional group A pigment dispersion composition comprising a compound and a dispersant.

In General Formula (1), G represents a hydrogen atom, an aliphatic group, an aryl group, or a heterocyclic group, and R ₁ represents an amino group, an aliphatic oxy group, an aliphatic group, an aryl group, or a heterocyclic group. R ₂ represents a substituent.
A represents any of the groups represented by the following general formulas (A-1) to (A-32).
m represents an integer of 0 to 5, and n represents an integer of 1 to 4.
When n = 2, the general formula (1) represents a dimer via R ₁ , R ₂ , A or G.
In the case of n = 3, the general formula (1) represents a trimer via R ₁ , R ₂ , A or G.
When n = 4, the general formula (1) represents a tetramer through R ₁ , R ₂ , A or G.
There is no ionic hydrophilic group in the general formula (1).

In general formulas (A-1) to (A-32), R _{51 to} R ₅₉ each independently represent a hydrogen atom or a substituent, and adjacent substituents are bonded to each other to form a 5- to 6-membered ring. It may be formed. * Represents the bonding position with the azo group in the general formula (1).

<2> The pigment dispersion composition according to <1>, wherein the azo pigment represented by the general formula (1) is an azo pigment represented by the following general formula (2).

In General Formula (2), R ₂₁ represents an amino group, an aliphatic oxy group, an aliphatic group, an aryl group, or a heterocyclic group, and R ₂₂ represents a substituent. R ₅₅ and R ₅₉ each independently represent a hydrogen atom or a substituent.
m represents an integer of 0 to 5, and n represents an integer of 1 to 4.
Z represents an electron withdrawing group having a Hammett's σp value of 0.2 or more.
When n = 2, general formula (2) represents a dimer via R ₂₁ , R ₂₂ , R ₅₅ , R ₅₉ or Z.
When n = 3, general formula (2) represents a trimer via R ₂₁ , R ₂₂ , R ₅₅ , R ₅₉ or Z.
When n = 4, the general formula (2) represents a tetramer through R ₂₁ , R ₂₂ , R ₅₅ , R ₅₉ or Z.
There is no ionic hydrophilic group in the general formula (2).

<3> A triazine derivative in which at least one compound selected from the group consisting of an organic dye derivative having an acidic functional group, an anthraquinone derivative having an acidic functional group, and a triazine derivative having an acidic functional group has a sulfo group or a carboxy group. <1> to <2>, wherein the pigment dispersion composition is.
<4> The pigment dispersion composition according to <1> to <3>, wherein the dispersant is a dispersant containing a nitrogen atom.
<5> The former dispersant has (i) a main chain portion having a nitrogen atom, and (ii) a functional group having a pKa of 14 or less, and a group bonded to the nitrogen atom present in the main chain portion. The pigment according to <1> to <4>, which is a resin having X ”and (iii) a side chain containing an oligomer chain or polymer chain“ Y ”having a number average molecular weight of 500 to 1,000,000 Dispersion composition.
<6> The pigment dispersion composition according to any one of <1> to <5>, wherein the azo pigment represented by the general formula (1) is a solvent salt milled azo pigment.
<7> The pigment dispersion composition according to any one of <1> to <6>, further including a pigment having a hue selected from red, yellow, orange, and violet.

<8> A colored curable composition containing the pigment dispersion composition according to any one of <1> to <7>, a photopolymerization initiator, and a polymerizable compound.
<9> The colored curable composition according to <8>, wherein the photopolymerization initiator is an oxime photopolymerization initiator.

<10> A step of forming a colored curable composition layer by applying the colored curable composition according to <8> or <9> on a support, and the colored curable composition layer through a mask. And a step of developing the colored curable composition layer after exposure to form a colored pattern. A method for producing a color filter for a solid-state imaging device, comprising:
<11> A color filter for a solid-state imaging device manufactured by the method for manufacturing a color filter for a solid-state imaging device according to <10>.
<12> A solid-state imaging device comprising the solid-state imaging device color filter according to <11>.

According to the present invention, even when the development conditions are strengthened when forming a colored pattern on a support, a colored curable composition capable of both maintaining the adhesion of the colored pattern to the support and suppressing the occurrence of residues. A pigment dispersion composition suitable for a product, and a colored curable composition containing the pigment dispersion composition can be provided.
In addition, according to the present invention, it is possible to provide a color filter for a solid-state imaging device having a colored pattern with few peeling defects and residual defects, and a solid-state imaging device including the color filter.

[Pigment dispersion composition]
The pigment dispersion composition of the present invention comprises the group consisting of an azo pigment represented by the general formula (1), an organic dye derivative having an acidic functional group, an anthraquinone derivative having an acidic functional group, and a triazine derivative having an acidic functional group. And at least one compound selected from the group consisting of a dispersant and a dispersant.

In General Formula (1), G represents a hydrogen atom, an aliphatic group, an aryl group, or a heterocyclic group, and R ₁ represents an amino group, an aliphatic oxy group, an aliphatic group, an aryl group, or a heterocyclic group. R ₂ represents a substituent.
A represents any of the groups represented by the following general formulas (A-1) to (A-32).
m represents an integer of 0 to 5, and n represents an integer of 1 to 4.
When n = 2, the general formula (1) represents a dimer via R ₁ , R ₂ , A or G.
In the case of n = 3, the general formula (1) represents a trimer via R ₁ , R ₂ , A or G.
When n = 4, the general formula (1) represents a tetramer through R ₁ , R ₂ , A or G.
There is no ionic hydrophilic group in the general formula (1).

In general formulas (A-1) to (A-32), R _{51 to} R ₅₉ each independently represent a hydrogen atom or a substituent, and adjacent substituents are bonded to each other to form a 5- to 6-membered ring. It may be formed. * Represents the bonding position with the azo group in the general formula (1).

  The pigment dispersion composition of the present invention is suitable as a colored curable composition that can be used for forming a colored pattern of a color filter or the like, and one of the characteristic constitutions thereof is a specific derivative having an acidic functional group. It is to contain. By having such a configuration, the colored curable composition (the colored curable composition of the present invention) containing the pigment dispersion composition of the present invention is used for developing conditions when a colored pattern is formed on a support using the composition. Even if it is a case where the intensity | strength is strengthened, generation | occurrence | production of a residue can be suppressed, maintaining the adhesiveness of the coloring pattern with respect to a support body.

  By applying the pigment dispersion composition of the present invention, it is not certain about the compatible action even when the development conditions are strengthened by maintaining the adhesion of the colored pattern to the support and suppressing the occurrence of residues, A specific derivative having an acidic functional group, which is one of the characteristic components in the present invention, contributes greatly to the improvement of developability due to the presence of the acidic functional group in the non-formation region of the colored pattern. On the other hand, in the region where the colored pattern (cured film) is formed, the acidic functional group of the specific derivative interacts with the support so that the substrate is colored. It is estimated that the adhesion of the pattern is improved.

<Azo pigment represented by the general formula (1)>
The pigment dispersion composition and colored curable composition of the present invention contain an azo pigment represented by the following general formula (1).

In General Formula (1), G represents a hydrogen atom, an aliphatic group, an aryl group, or a heterocyclic group, and R ₁ represents an amino group, an aliphatic oxy group, an aliphatic group, an aryl group, or a heterocyclic group. R ₂ represents a substituent.
A represents any of the groups represented by the following general formulas (A-1) to (A-32).
m represents an integer of 0 to 5, and n represents an integer of 1 to 4.
When n = 2, the general formula (1) represents a dimer via R ₁ , R ₂ , A or G.
In the case of n = 3, the general formula (1) represents a trimer via R ₁ , R ₂ , A or G.
When n = 4, the general formula (1) represents a tetramer through R ₁ , R ₂ , A or G.
There is no ionic hydrophilic group in the general formula (1).

In general formulas (A-1) to (A-32), R _{51 to} R ₅₉ each independently represent a hydrogen atom or a substituent, and adjacent substituents are bonded to each other to form a 5- to 6-membered ring. You may do it. * Represents a bonding position with the azo group of the general formula (1).

The compound represented by the general formula (1) can easily form an intermolecular interaction of dye molecules due to its specific structure, has low solubility in water or an organic solvent, and can be an azo pigment.
A pigment is used by being finely dispersed as solid particles such as molecular aggregates in a solvent, unlike a dye used by being dissolved in water or an organic solvent in a molecular dispersion state.

Here, the pigment containing an azo pigment will be described.
A pigment is a state in which molecules are firmly bonded to each other by cohesive energy due to strong interaction between dye molecules. In order to create this state, it is described in, for example, Journal of Imaging Society of Japan, Vol. 43, page 10 (2004) that van der Waals force between molecules and hydrogen bonding between molecules are necessary.
In order to increase the van der Waals force between molecules, introduction of an aromatic group, a polar group and / or a hetero atom into the molecule can be considered. In order to form an intermolecular hydrogen bond, introduction of a substituent containing a hydrogen atom bonded to a hetero atom and / or introduction of an electron donating substituent into the molecule can be considered. Further, it is considered preferable that the polarity of the whole molecule is high. For this purpose, in the azo pigment, for example, a shorter chain group such as an alkyl group is preferable, and a smaller molecular weight / azo group value is preferable.
From these viewpoints, the pigment molecule preferably contains an amide bond, a sulfonamide bond, an ether bond, a sulfone group, an oxycarbonyl group, an imide group, a carbamoylamino group, a hetero ring, a benzene ring and the like.

In addition, the azo pigment represented by the following general formula (1) has a specific structure, thereby exhibiting excellent characteristics in color characteristics such as coloring power and hue, and durability such as light resistance and ozone resistance. The characteristic which was excellent also in the property can be shown.
Specifically, the red pattern of the color filter formed using the pigment dispersion composition of the present invention containing the azo pigment represented by the general formula (1) exhibits good spectral characteristics as red.
Here, “spectral characteristics favorable as red” refers to at least one of the following properties, for example. The spectral characteristics that satisfy all of the following two properties are the best.
-The transmittance in the wavelength region of 650 nm to 750 nm is high.
-The transmittance | permeability in a wavelength range (especially 350 nm-400 nm) below 540 nm is low.

Hereinafter, the azo pigment represented by the general formula (1) will be described in detail.
First, the aliphatic group, aryl group, heterocyclic group, and substituent in general formula (1) will be described.

  As the aliphatic group in the general formula (1), the aliphatic moiety may be linear, branched or cyclic. Moreover, it may be saturated or unsaturated. Specific examples include an alkyl group, an alkenyl group, a cycloalkyl group, and a cycloalkenyl group. Furthermore, the aliphatic group may be unsubstituted or may have a substituent.

The aryl group in the general formula (1) may be a single ring or a condensed ring. The aryl group may be unsubstituted or may have a substituent.
The heterocyclic group in the general formula (1) only needs to have a hetero atom (for example, a nitrogen atom, a sulfur atom, or an oxygen atom) in the ring portion. It may be a ring. The heterocyclic moiety may be a single ring or a condensed ring. Furthermore, the heterocyclic group may be unsubstituted or may have a substituent.

  Moreover, the substituent in General formula (1) should just be a group which can be substituted, for example, an aliphatic group, an aryl group, a heterocyclic group, an acyl group, an acyloxy group, an acylamino group, an aliphatic oxy group, aryl Oxy group, heterocyclic oxy group, aliphatic oxycarbonyl group, aryloxycarbonyl group, heterocyclic oxycarbonyl group, carbamoyl group, aliphatic sulfonyl group, arylsulfonyl group, heterocyclic sulfonyl group, aliphatic sulfonyloxy group, arylsulfonyl Oxy group, heterocyclic sulfonyloxy group, sulfamoyl group, aliphatic sulfonamide group, aryl sulfonamide group, heterocyclic sulfonamide group, amino group, aliphatic amino group, arylamino group, heterocyclic amino group, aliphatic oxycarbonyl An amino group, an aryloxycarbonylamino group, Telocyclic oxycarbonylamino group, aliphatic sulfinyl group, arylsulfinyl group, aliphatic thio group, arylthio group, hydroxy group, cyano group, sulfo group, carboxy group, aliphatic oxyamino group, aryloxyamino group, carbamoylamino group Sulfamoylamino group, halogen atom, sulfamoylcarbamoyl group, carbamoylsulfamoyl group, dialiphatic oxyphosphinyl group, diaryloxyphosphinyl group and the like. These substituents may be further substituted, and examples of the further substituent include groups selected from the substituents described above.

  When the substituent is an acyl group, the acyl group may be an aliphatic carbonyl group, an arylcarbonyl group, a heterocyclic carbonyl group, or may have a substituent. As the group which may be substituted, any group can be used as long as it is a group which can be substituted with the groups described in the above-mentioned substituent group. For example, acetyl, propanoyl, benzoyl, 3-pyridinecarbonyl and the like can be mentioned.

  The azo pigment represented by the general formula (1) does not contain an ionic hydrophilic group (for example, carboxy group, sulfo group, phosphono group and quaternary ammonium group) as a substituent from the viewpoint of solubility.

  In the general formula (1), the aliphatic group represented by G may have a substituent and may be saturated or unsaturated. The substituent may be any group as long as it is a group described in the above-mentioned substituent group and can be substituted for the aliphatic group represented by G. Preferred substituents include a hydroxy group and an aliphatic group. An oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thio group, an amino group, an aliphatic amino group, an acylamino group, and a carbamoylamino group. The aliphatic group represented by G is preferably an aliphatic group having 1 to 8 carbon atoms in total, more preferably an alkyl group having 1 to 4 carbon atoms in total, such as methyl, ethyl, vinyl, cyclohexyl. , Carbamoylmethyl and the like.

  In general formula (1), the aryl group represented by G may be condensed or may have a substituent. The substituent may be any group as long as it is a group described in the above-mentioned substituent group and can be substituted for the aryl group represented by G. Preferred substituents include a nitro group, a halogen atom, An aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thio group, an amino group, an aliphatic amino group, an acylamino group, and a carbamoylamino group. The aryl group represented by G is preferably an aryl group having 6 to 12 carbon atoms, more preferably an aryl group having 6 to 10 carbon atoms, such as phenyl, 4-nitrophenyl, 4-acetylamino. Phenyl, 4-methanesulfonylphenyl and the like.

  In the general formula (1), the heterocyclic group represented by G may have a substituent, may be saturated or unsaturated, and may be condensed. As the substituent, any group can be used as long as it is a group described in the above-mentioned substituent group and can be substituted with the heterocyclic group represented by G. Preferred substituents include a halogen atom, a hydroxy group, An aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thio group, an amino group, an aliphatic amino group, an acylamino group, and a carbamoylamino group. The heterocyclic group represented by G is preferably a heterocyclic group bonded with carbon atoms having 2 to 12 carbon atoms in total, more preferably 5 to 6 having 2 to 10 carbon atoms bonded with carbon atoms. It is a membered heterocycle, and examples thereof include 2-tetrahydrofuryl and 2-pyrimidyl.

  G is preferably a hydrogen atom. This is because it is easy to form an intramolecular hydrogen bond or an intramolecular cross hydrogen bond.

The amino group represented by R ₁ may have a substituent. The substituent may be any group as long as it is a group described in the above-mentioned substituent group and can be substituted with the amino group represented by R _1. Preferred substituents include aliphatic groups, aryl Group, heterocyclic group and the like.
These substituents may further have a substituent, and the substituent is preferably a substituent having an aliphatic group, a hydroxy group, an amide bond, an ether bond, an oxycarbonyl bond, a thioether bond, and the like. A substituent having a bond between a hetero atom and a hydrogen atom is more preferable from the viewpoint of facilitating intermolecular interaction such as intermolecular hydrogen bonding.
The amino group which may have a substituent represented by R ₁ is preferably an unsubstituted amino group, an alkylamino group having 1 to 10 carbon atoms in total, a dialkylamino group having 2 to 10 carbon atoms in total ( Dialkyl groups may be bonded to each other to form a 5- to 6-membered ring), an arylamino group having 6 to 12 carbon atoms in total, saturated even if having 2 to 12 carbon atoms in total, A heterocyclic amino group which may be present, more preferably an unsubstituted amino group, an alkylamino group having 1 to 8 carbon atoms in total, a dialkylamino group having 2 to 8 carbon atoms in total, and 6 carbon atoms in total. -10 arylamino group, a heterocyclic amino group which may be saturated or unsaturated having 2 to 12 carbon atoms in total, such as methylamino, N, N-dimethylamino, N-phenylamino N- (2-pyrimidyl) a Mino etc. are mentioned.
More preferably, the arylamino group having 6 to 13 carbon atoms which may have a substituent and the saturated or unsaturated group having 2 to 12 total carbon atoms which may have a substituent A heterocyclic amino group which may be

When R ₁ is an arylamino group, the substituent on the aryl group preferably has a substituent at the para position from the bonding position with the amino group, and most preferably has a substituent only at the para position. As the substituent, any group can be used as long as it is a group described in the above-mentioned substituent group and can be substituted on the arylamino group represented by R ₁ , and preferably has 1 to 7 carbon atoms in total. More preferably an aliphatic group optionally having a substituent having 1 to 4 carbon atoms (for example, methyl, ethyl, allyl, (i) -propyl, (t) -butyl, etc.), the total number of carbon atoms 1 to 7 optionally substituted aliphatic oxy groups (for example, methoxy, ethoxy, (i) -propyloxy, allyloxy, etc.), halogen atoms (for example, fluorine, chlorine, bromine, etc.), total carbon A carbamoyl group (for example, carbamoyl, N-phenylcarbamoyl, N-methylcarbamoyl, etc.) which may have a substituent of 1 to 7 atoms, 1 to 7 total carbon atoms, more preferably 1 total carbon atoms With ~ 4 substituents Ureido group (for example, ureido, N-methylureido, N, N-dimethylureido, N-4-pyridylureido, N-phenylureido, etc.), nitro group, aryl having 1 to 7 carbon atoms in total A heterocyclic ring condensed with a group (e.g., imidazolone), a hydroxy group, an aliphatic thio group (e.g., having a substituent having 1 to 7 carbon atoms in total, more preferably 1 to 4 carbon atoms in total) , Methylthio, ethylthio, (i) -propylthio, allylthio, (t) -butylthio, etc.), acylamino which may have a substituent having 2 to 7 total carbon atoms, more preferably 2 to 4 total carbon atoms A group (for example, acetamino, propionylamino, pivaloylamino, benzoylamino, etc.) having a substituent of 2 to 7 carbon atoms, more preferably 2 to 4 carbon atoms in total. May have an aliphatic oxycarbonylamino group (for example, methoxycarbonylamino, propyloxycarbonylamino, etc.), a substituent having 2 to 7 carbon atoms in total, more preferably 2 to 4 carbon atoms in total. A good aliphatic oxycarbonyl group (for example, methoxycarbonyl, ethoxycarbonyl, etc.), an acyl group (aliphatic group) which may have a substituent having 2 to 7 total carbon atoms, more preferably 2 to 4 total carbon atoms It may be a carbonyl group, an arylcarbonyl group, a heterocyclic carbonyl group, or may have a substituent, and the substituent is described in the above-mentioned substituents section. Any acyl group having 2 to 7 carbon atoms in total, more preferably an acyl group having 2 to 4 carbon atoms in total, may be used as long as it is a group that can be substituted on the acyl group. There, for example, acetyl, propanoyl, benzoyl, 3-pyridine carbonyl, and the like. ) And the like.

  When the substituent on the aryl group of the arylamino group is substituted from the bonding position with the amino group to the para position, the substituent is located at the end of the molecule, so intermolecular interactions such as intermolecular hydrogen bonding are likely to occur. Because of this, the hue becomes sharper. When the substituent on the aryl group further has a substituent, a substituent having an aliphatic group, a hydroxy group, an amide bond, an ether bond, an oxycarbonyl bond, a thioether bond or the like is preferable, and a bond between a hetero atom and a hydrogen atom Is more preferable from the viewpoint of facilitating intermolecular interaction such as intermolecular hydrogen bonding.

When R ₁ is a heterocyclic amino group, the substituent is the group described in the above-mentioned substituent group, and can be any group that can be substituted for the heterocyclic amino group represented by R _1. Any substituent may be used, and the same substituent as in the case of the arylamino group is preferable. When the substituent on the heterocyclic group further has a substituent, an aliphatic group, a hydroxy group, an amide bond, an ether bond, an oxycarbonyl bond In addition, a substituent having a thioether bond or the like is preferable, and a substituent having a bond between a hetero atom and a hydrogen atom is more preferable from the viewpoint of facilitating intermolecular interaction such as intermolecular hydrogen bonding.

More preferable substituents when R ₁ is an arylamino group or a heterocyclic amino group include an aliphatic group, an aliphatic oxy group, a halogen atom, a carbamoyl group, a heterocyclic ring condensed with the aryl group, It is an aliphatic oxycarbonyl group. More preferably, the substituent is preferably an aliphatic group having 1 to 4 carbon atoms, an aliphatic oxy group having 1 to 4 carbon atoms, a halogen atom, a nitro group, a carbamoyl group having 1 to 4 carbon atoms, or a total carbon atom. It is an aliphatic oxycarbonyl group having 2 to 4 atoms.

The aliphatic oxy group represented by R ₁ may have a substituent, and the substituent is the group described in the above-mentioned substituent group, and the aliphatic oxy group represented by R ₁ Any group can be used as long as it can be substituted with an aliphatic oxy group. Preferred substituents include a hydroxy group, an aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thio group, an amino group, an aliphatic amino group, An acylamino group and a carbamoylamino group. The aliphatic oxy group represented by R ₁ is preferably an alkoxy group having 1 to 8 carbon atoms in total, more preferably an alkoxy group having 1 to 4 carbon atoms in total, such as methoxy, ethoxy, ( t) -butoxy, methoxyethoxy, carbamoylmethoxy and the like.

The aliphatic group represented by R ₁ may have a substituent, and the substituent is the group described in the above-mentioned substituent group, and the aliphatic group represented by R _1. Any group can be used as long as the group can be substituted. Preferred substituents include a hydroxy group, an aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thio group, an amino group, an aliphatic amino group, and an acylamino group. , A carbamoylamino group. The aliphatic group represented by R ₁ is preferably an alkyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, such as methyl, ethyl, (s) -Butyl, methoxyethyl, carbamoylmethyl and the like.

The aryl group represented by R ₁ may have a substituent, and the substituent is the group described in the above-mentioned substituent group, and includes the aryl group represented by R _1. Any substituent can be used, and preferred substituents include an aliphatic group, an aliphatic oxy group, a halogen atom, a carbamoyl group, a heterocycle condensed with the aryl group, and an aliphatic oxycarbonyl group. The aryl group represented by R ₁ is preferably an aryl group having 6 to 12 carbon atoms in total, more preferably an aryl group having 6 to 10 carbon atoms in total, such as phenyl, 4-methylphenyl, 3-chlorophenyl and the like can be mentioned.

The heterocyclic group represented by R ₁ may be a saturated heterocyclic ring, an unsaturated heterocyclic group, or may have a substituent. The substituent may be any group as long as it is the group described in the above-mentioned substituent group and can be substituted on the heterocyclic group represented by R _1. Preferred substituents include aliphatic groups, An aliphatic oxy group, a carbamoyl group, a hetero ring condensed with the hetero group, and an aliphatic oxycarbonyl group. The heterocyclic group represented by R ₁ is preferably a heterocyclic group having 2 to 10 carbon atoms in total, more preferably a 5- to 6-membered non-ring bonded with a nitrogen atom having 2 to 8 carbon atoms in total. An aromatic heterocyclic group such as 1-piperidyl, 4-morpholinyl, 1-quinoyl, 2-pyrimidyl, 4-pyridyl and the like.

R ₁ is preferably an amino group which may have a substituent, an aliphatic oxy group, or a 5- to 6-membered non-aromatic heterocyclic group bonded by a nitrogen atom, more preferably a substituted group. An amino group which may have a group, an aliphatic oxy group, and more preferably an amino group which may have a substituent.

R ₁ is more preferably an amino group which may have a substituent.

The substituent represented by R ₂ may be any group as long as it is a group that can be substituted as R ₂ , and is preferably an aliphatic group, an aryl group, or a heterocyclic group. A group, an aliphatic oxycarbonyl group, a carboxy group, an optionally substituted carbamoyl group, an acylamino group, a sulfonamide group, an optionally substituted carbamoylamino group, and a substituent. A sulfamoyl group, an aliphatic oxy group, an aliphatic thio group, a cyano group, and a halogen atom, more preferably an aliphatic oxycarbonyl group, an optionally substituted carbamoyl group, an acylamino group, and a substituent. A carbamoylamino group, an aliphatic oxy group, or a halogen atom, which may have an aliphatic group, most preferably an aliphatic oxy group.
When these substituents further have a substituent, a substituent having an aliphatic group, a hydroxy group, an amide bond, an ether bond, an oxycarbonyl bond, a thioether bond or the like is preferable, and a substituent having a bond of a hetero atom and a hydrogen atom The group is more preferable from the viewpoint of facilitating intermolecular interaction such as intermolecular hydrogen bonding.

m is preferably 0 to 3, more preferably 0 to 1, and even more preferably 0.
n is preferably 1 or 2.

The aliphatic group represented by R ₂ may have a substituent and may be saturated or unsaturated. The substituent may be any group as long as it is a group described in the above-mentioned substituent group and can be substituted for the aliphatic group represented by R ₂ . The aliphatic group represented by R ₂ is preferably an alkyl group having 1 to 8 carbon atoms in total, more preferably an alkyl group having 1 to 6 carbon atoms in total, such as methyl, ethyl, i- And propyl, cyclohexyl, t-butyl and the like.

The aryl group represented by R ₂ may have a substituent. As the substituent, any group can be used as long as it is the group described in the above-mentioned substituent group and can be substituted for the aryl group represented by R ₂ . The aryl group represented by R ₂ is preferably an aryl group having 6 to 12 carbon atoms in total, more preferably an aryl group having 6 to 10 carbon atoms in total, such as phenyl, 3-methoxyphenyl, 4-carbamoylphenyl and the like can be mentioned.

The heterocyclic group represented by R ₂ may have a substituent, may be saturated or unsaturated, and may be condensed. As the substituent, any group can be used as long as it is a group described in the above-mentioned substituent group and can be substituted for the heterocyclic group represented by R ₂ . The heterocyclic group represented by R ₂ is preferably a heterocyclic group having 2 to 16 carbon atoms in total, more preferably a 5 to 6-membered heterocyclic group having 2 to 12 carbon atoms in total, For example, 1-pyrrolidinyl, 4-morpholinyl, 2-pyridyl, 1-pyrrolyl, 1-imidazolyl, 1-benzoimidazolyl and the like can be mentioned.

The aliphatic oxycarbonyl group represented by R ₂ may have a substituent and may be saturated or unsaturated. As the substituent, any group can be used as long as it is the group described in the above-mentioned substituent group and can be substituted for the aliphatic oxycarbonyl group represented by R ₂ . The aliphatic oxycarbonyl group represented by R ₂ is preferably an alkoxycarbonyl group having 1 to 8 carbon atoms in total, more preferably an alkoxycarbonyl group having 1 to 6 carbon atoms in total, such as methoxycarbonyl , I-propyloxycarbonyl, carbamoylmethoxycarbonyl and the like.

The carbamoyl group represented by R ₂ may have a substituent. The substituent may be any group as long as it is a group described in the above-mentioned substituent group and can be substituted for the carbamoyl group represented by R ₂ , and is preferably an aliphatic group, an aryl group, a hetero group. A cyclic group and the like. The carbamoyl group optionally having a substituent represented by R ₂ is preferably a carbamoyl group, an alkylcarbamoyl group having 2 to 9 carbon atoms in total, a dialkylcarbamoyl group having 3 to 10 carbon atoms, or a total carbon atom. An arylcarbamoyl group having 7 to 13 atoms and a heterocyclic carbamoyl group having 3 to 12 carbon atoms, more preferably a carbamoyl group, an alkylcarbamoyl group having 2 to 7 carbon atoms, and 3 to 6 carbon atoms. Dialkylcarbamoyl group, arylcarbamoyl group having 7 to 11 carbon atoms in total, and heterocyclic carbamoyl group having 3 to 10 carbon atoms in total, such as carbamoyl, methylcarbamoyl, dimethylcarbamoyl, phenylcarbamoyl, 4-pyridinecarbamoyl, etc. Is mentioned.

The acylamino group represented by R ₂ may have a substituent, and may be aliphatic, aromatic, or heterocyclic. As the substituent, any group can be used as long as it is the group described in the above-mentioned substituent section and can be substituted with the acylamino group represented by R ₂ . The acylamino group represented by R ₂ is preferably an acylamino group having 2 to 12 carbon atoms, more preferably an acylamino group having 1 to 8 carbon atoms, and still more preferably 1 to 1 carbon atoms. 8 alkylcarbonylamino group, and examples thereof include acetylamino, benzoylamino, 2-pyridinecarbonylamino, propanoylamino and the like.

The sulfonamide group represented by R ₂ may have a substituent, and may be aliphatic, aromatic, or heterocyclic. The substituent is any group as long as it is a group described in the above-mentioned substituent group and can be substituted for the sulfonamide group represented by R ₂ . The sulfonamide group of R ₂ is preferably a sulfonamide group having 1 to 12 carbon atoms in total, more preferably a sulfonamide group having 1 to 8 carbon atoms in total, and still more preferably 1 to 1 carbon atoms in total. 8 alkylsulfonamide groups such as methanesulfonamide, benzenesulfonamide, 2-pyridinesulfonamide and the like.

The carbamoylamino group represented by R ₂ may have a substituent. The substituent may be any group as long as it is a group described in the above-mentioned substituent group and can be substituted on the carbamoylamino group represented by R ₂ , and is preferably an aliphatic group, an aryl group, A heterocyclic group or the like; The carbamoylamino group optionally having a substituent for R ₂ is preferably a carbamoylamino group, an alkylcarbamoylamino group having 2 to 9 carbon atoms in total, a dialkylcarbamoylamino group having 3 to 10 carbon atoms in total, An arylcarbamoylamino group having 7 to 13 carbon atoms and a heterocyclic carbamoylamino group having 3 to 12 carbon atoms, more preferably a carbamoylamino group, an alkylcarbamoylamino group having 2 to 7 carbon atoms, and a total carbon A dialkylcarbamoylamino group having 3 to 6 atoms, an arylcarbamoylamino group having 7 to 11 carbon atoms, and a heterocyclic carbamoylamino group having 3 to 10 carbon atoms, such as carbamoylamino, methylcarbamoylamino, N , N-dimethylcarbamoylamino, phenylcarbamoylamino And 4-pyridinecarbamoylamino.

The sulfamoyl group represented by R ₂ may have a substituent. The substituent may be any group as long as it is a group described in the above-mentioned substituent group and can be substituted on the sulfamoyl group represented by R ₂ , and is preferably an aliphatic group, an aryl group, a hetero group. A cyclic group and the like. The sulfamoyl group optionally having a substituent for R ₂ is preferably a sulfamoyl group, an alkylsulfamoyl group having 1 to 9 carbon atoms in total, a dialkylsulfamoyl group having 2 to 10 carbon atoms in total, An arylsulfamoyl group having 7 to 13 carbon atoms and a heterocyclic sulfamoyl group having 2 to 12 carbon atoms, more preferably a sulfamoyl group, an alkylsulfamoyl group having 1 to 7 carbon atoms, and a total carbon A dialkylsulfamoyl group having 3 to 6 atoms, an arylsulfamoyl group having 6 to 11 carbon atoms, and a heterocyclic sulfamoyl group having 2 to 10 carbon atoms, such as sulfamoyl, methylsulfamoyl, N, N-dimethylsulfamoyl, phenylsulfamoyl, 4-pyridinesulfamoyl and the like can be mentioned.

The aliphatic oxy group represented by R ₂ may have a substituent, and may be saturated or unsaturated. The substituent may be any group as long as it is a group described in the above-mentioned substituent group and can be substituted for the aliphatic oxy group represented by R ₂ . The aliphatic oxy group represented by R ₂ is preferably an alkoxy group having 1 to 8 carbon atoms in total, more preferably an alkoxy group having 1 to 6 carbon atoms in total, such as methoxy, ethoxy, i -Propyloxy, cyclohexyloxy, methoxyethoxy and the like.

The aliphatic thio group represented by R ₂ may have a substituent and may be saturated or unsaturated. As the substituent, any group can be used as long as it is the group described in the above-mentioned substituent section and can be substituted with the aliphatic thio group represented by R ₂ . The aliphatic thio group represented by R ₂ is preferably an alkylthio group having 1 to 8 carbon atoms in total, more preferably an alkylthio group having 1 to 6 carbon atoms in total, for example, methylthio, ethylthio, carbamoyl Examples thereof include methylthio and t-butylthio.

The halogen atom represented by R ₂ is preferably a fluorine atom, a chlorine atom, or a bromine atom, and more preferably a chlorine atom.
In view of the effect of the present invention, R ₂ is preferably an aliphatic oxycarbonyl group or a carbamoyl group which may have a substituent.

  General formulas (A-1) to (A-32) represented by A will be described. The groups represented by the general formulas (A-1) to (A-32) preferably have 2 to 15 total carbon atoms, and more preferably 2 to 12 total carbon atoms.

As the substituent represented by R _{51 to} R ₅₄ , any group can be used as long as it is the group described in the above-mentioned substituent group and can be substituted as R _{51 to} R ₅₄ . As the substituent represented by R _{51 to} R ₅₄ , an aliphatic group, an aryl group, a heterocyclic group, an aliphatic oxycarbonyl group, an optionally substituted carbamoyl group, an acylamino group, a sulfonamide group An aliphatic oxy group, an aliphatic thio group, a cyano group, etc., more preferably an aliphatic group, an aliphatic oxycarbonyl group, an optionally substituted carbamoyl group, an aliphatic oxy group, a cyano group, etc. It is.

In terms of the effects of the present invention, R _{51 to} R ₅₄ are a hydrogen atom, an aliphatic group, an aryl group, a heterocyclic group, an aliphatic oxycarbonyl group, an optionally substituted carbamoyl group, an acylamino group, Preferred is a sulfonamide group, an aliphatic oxy group, an aliphatic thio group, a cyano group, etc., a hydrogen atom, an aliphatic group, an aliphatic oxycarbonyl group, an optionally substituted carbamoyl group, an aliphatic group The case where it is an oxy group and a cyano group is more preferable.

As the substituent represented by R ₅₅ , any group can be used as long as it is the group described in the above-mentioned substituent section and can be substituted as R ₅₅ . The substituent represented by R _55, preferably an aliphatic group, an aryl group, a heterocyclic group, more preferably contains an aliphatic group, an aryl group, the nitrogen atom in the position adjacent to the position connected to the nitrogen atom It is an aromatic 5- to 6-membered heterocyclic group.

From the viewpoint of the effect of the present invention, R ₅₅ is preferably an aliphatic group, an aryl group, or a heterocyclic group, and contains a nitrogen atom adjacent to the bonding site with the aliphatic group, aryl group, or nitrogen atom. More preferably, it is an aromatic 5 to 6-membered heterocyclic group, and more preferably an aromatic 5 to 6-membered heterocyclic group containing a nitrogen atom at the position adjacent to the binding site with the nitrogen atom. _R55 is an aromatic 5- to 6-membered heterocyclic group containing a nitrogen atom adjacent to the binding site with the nitrogen atom, so that not only the intermolecular interaction of the dye molecule but also the intramolecular interaction is firmly formed. It becomes easy to do. This makes it easy to construct a pigment having a stable molecular arrangement, which is preferable in terms of showing good hue and high fastness (light resistance, gas, heat, water, etc.).

In terms of the effects of the present invention, the aromatic 5- to 6-membered heterocyclic group containing a nitrogen atom at the position adjacent to the binding site with the nitrogen atom, which is preferable as R ₅₅ , may have a substituent. The substituent may be any group as long as it is a group described in the above-mentioned substituent section and can be substituted on the aromatic 5- to 6-membered heterocyclic group. Preferred substituents include a hydroxy group, An aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thio group, an amino group, an aliphatic amino group, an acylamino group, and a carbamoylamino group. Or an aromatic 5- to 6-membered heterocyclic group containing a nitrogen atom at the position adjacent to the binding site with the nitrogen atom having 2 to 12 carbon atoms in total. And more preferably an aromatic 5- to 6-membered heterocyclic group containing a nitrogen atom at the position adjacent to the binding site with the nitrogen atom having 2 to 10 carbon atoms in total. For example, 2-thiazolyl, 2-benzothiazolyl, 2-oxazolyl, 2-benzoxazolyl, 2-pyridyl, 2-pyrazinyl, 3-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 2-imidazolyl, 2-benzimidazolyl, 2-triazinyl and the like can be mentioned, and these heterocyclic groups may have a tautomeric structure together with a substituent.

In terms of the effects of the present invention, the aryl group preferable as R ₅₅ may have a substituent. The substituent may be any group as long as it is a group described in the above-mentioned substituent group and can be substituted for the aryl group. Preferred substituents include a hydroxy group, a nitro group, an aliphatic group, An aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thio group, an amino group, an aliphatic amino group, an acylamino group, and a carbamoylamino group. The aryl group for R ₅₅ is preferably an aryl group having 6 to 12 carbon atoms in total, more preferably an aryl group having 6 to 10 carbon atoms in total, such as phenyl, 3-methoxyphenyl, 4-carbamoylphenyl. The phenyl group is preferable.

In terms of the effects of the present invention, the aliphatic group preferable as R ₅₅ may have a substituent. The substituent may be any group as long as it is a group described in the above-mentioned substituent group and can be substituted for the aliphatic group. Preferred substituents include a hydroxy group, a nitro group, and an aliphatic oxy group. A carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thio group, an amino group, an aliphatic amino group, an acylamino group, and a carbamoylamino group.
Preferred aliphatic groups as R ₅₅ are preferably alkyl groups having 1 to 6 carbon atoms, more preferably aliphatic groups having 1 to 4 carbon atoms, such as methyl, ethyl, methoxyethyl, carbamoyl. Methyl etc. are mentioned, A methyl group is preferable.

In general formula (1), R ₅₅ is preferably any one of groups represented by the following general formulas (Y-1) to (Y-13), and has a structure that easily takes an intramolecular hydrogen bond structure. Therefore, it is more preferable that it is any of the groups represented by the following general formulas (Y-1) to (Y-6) which are 6-membered rings, and the following general formulas (Y-1) and (Y-3) ), (Y-4), and (Y-6) are more preferred, and the following (Y-1) or (Y-4) may be preferred. Particularly preferred.
* In the following general formulas (Y-1) to (Y-13) represents a binding site with the N atom of the pyrazole ring. Y _{1 to} Y ₁₁ represent a hydrogen atom or a substituent. G ₁₁ in the following general formula (Y-13) represents a nonmetallic atom group capable of constituting a 5- to 6-membered heterocycle, and the heterocycle represented by G ₁₁ is substituted even if the heterocycle is unsubstituted. The heterocycle may be monocyclic or condensed. General formulas (Y-1) to (Y-13) may have tautomeric structures together with substituents.

The substituents represented by Y ₁ to Y _11, a group described in the aforesaid paragraph on substituents may be any substitutable group as in Y ₁ to Y _11. The substituent represented by Y _{1 to} Y ₁₁ is preferably an aliphatic group, an aryl group, a heterocyclic group, an aliphatic oxycarbonyl group, an optionally substituted carbamoyl group, an acylamino group, or a sulfonamide. Group, aliphatic oxy group, aliphatic thio group, cyano group and the like, more preferably aliphatic group, aliphatic oxy group, aliphatic thio group, cyano group and the like. In Y _{1 to} Y ₁₁ , two adjacent substituents may form a 5- to 6-membered ring.
In terms of the effect of the present invention, Y _{1 to} Y ₁₁ are each a hydrogen atom, an aliphatic group, an aryl group, a heterocyclic group, an aliphatic oxycarbonyl group, an optionally substituted carbamoyl group, an acylamino group, Preferred is a sulfonamide group, an aliphatic oxy group, an aliphatic thio group, a cyano group, etc., a hydrogen atom, an aliphatic group, an aliphatic oxycarbonyl group, an optionally substituted carbamoyl group, an aliphatic group In the case of an oxy group or a cyano group, it is more preferable.
From the viewpoint of the effect of the present invention, A is preferably a 5-membered heterocycle from the viewpoint of hue, more preferably a nitrogen-containing or sulfur-containing 5-membered heterocycle, and two or more heteroatoms. More preferably, it is a 5-membered heterocycle.

The substituent represented by R _{56 to} R ₅₇ and R ₅₉ may be any group as long as it is the group described in the above-mentioned substituent group and can be substituted as R _{56 to} R ₅₇ and R ₅₉ . As the substituent represented by R _{56 to} R ₅₇ and R ₅₉ , an aliphatic group, an aryl group, a heterocyclic group, an aliphatic oxycarbonyl group, an optionally substituted carbamoyl group, and an acylamino group are preferable. , Sulfonamido group, aliphatic oxy group, aliphatic thio group, cyano group and the like, more preferably aliphatic group, aliphatic oxy group, aliphatic thio group, cyano group and the like.

In terms of the effects of the present invention, R _{56 to} R ₅₇ and R ₅₉ are an aliphatic group, an aryl group, a heterocyclic group, an aliphatic oxycarbonyl group, an optionally substituted carbamoyl group, an acylamino group, A sulfonamide group, an aliphatic oxy group, an aliphatic thio group, a cyano group and the like are preferable, and an aliphatic group, an aliphatic oxy group, an aliphatic thio group, and a cyano group are more preferable.

As the substituent represented by R ₅₈ , any group can be used as long as it is the group described in the above-mentioned substituent section and can be substituted as R ₅₈ . In view of the effect of the present invention, R ₅₈ is preferably a heterocyclic group or an electron-withdrawing group having Hammett's substituent constant σp value of 0.2 or more, and σp value of 0.3 or more. It is preferably an attractive group. The upper limit is 1.0 or less electron withdrawing group.

Here, Hammett's substituent constant σp value used in this specification will be described.
Hammett's rule is a method described in 1935 in order to quantitatively discuss the effect of substituents on the reaction or equilibrium of benzene derivatives. P. A rule of thumb proposed by Hammett, which is widely accepted today. Substituent constants determined by Hammett's rule include a σp value and a σm value, and these values can be found in many general books. A. Dean, “Lange's Handbook of Chemistry”, 12th edition, 1979 (Mc Graw-Hill) and “Chemicals” special edition, 122, 96-103, 1979 (Nankodo) ing. In the present invention, each substituent is limited or explained by Hammett's substituent constant σp, but this means that it is limited to only a substituent having a value known in the literature, which can be found in the above-mentioned book. Needless to say, even if the value is unknown, it includes a substituent that would be included in the range when measured based on Hammett's rule. Although the azo pigment represented by the general formula (1) in the present invention is not a benzene derivative, the σp value is used as a scale indicating the electronic effect of the substituent regardless of the substitution position. In the present invention, the σp value will be used in this sense.

Specific examples of R ₅₈ which is an electron-attracting group having a σp value of 0.2 or more include acyl group, acyloxy group, carbamoyl group, alkyloxycarbonyl group, aryloxycarbonyl group, cyano group, nitro group, dialkylphosphonic group Group, diarylphosphono group, diarylphosphinyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfonyloxy group, acylthio group, sulfamoyl group, thiocyanate group, thiocarbonyl group, alkyl halide Groups, halogenated alkoxy groups, halogenated aryloxy groups, halogenated alkylamino groups, halogenated alkylthio groups, aryl groups substituted with other electron-withdrawing groups having a σp value of 0.20 or more, heterocyclic groups, Halogen atom, azo group, or selenoshi Include sulfonate groups.

From the viewpoint of the effects of the present invention, R ₅₈ is preferably a group represented by the general formulas (Y-1) to (Y-13), which makes it easy to take an intramolecular hydrogen bond structure. Therefore, it is more preferable that it is any of the groups represented by the following general formulas (Y-1) to (Y-6) of a 6-membered ring, and the general formulas (Y-1), (Y-3), The case represented by (Y-4) or (Y-6) is more preferred, and the case represented by the general formula (Y-1) or (Y-4) is preferred. Particularly preferred.
Among the heterocyclic groups represented by the general formulas (A-1) to (A-32) listed as A, if the atom adjacent to the carbon atom bonded to the azo group is a heteroatom, light and heat fastness It is preferable to use a pigment having such a structural characteristic in a color filter because a color filter exhibiting high contrast can be obtained.

In view of the effects of the present invention, the azo pigment represented by the general formula (1), G is a hydrogen atom, R ₁ is attached by an amino group which may have a substituent, or a nitrogen atom A saturated heterocyclic group, when m is 0 or 1 and m is 1, R ₂ is an aliphatic oxycarbonyl group, an optionally substituted carbamoyl group, or an aliphatic oxy group And A is represented by the general formulas (A-1), (A-10) to (A-17), (A-20) to (A-23), (A-27), (A-28). , (A-30) to (A-32), wherein n is preferably 1 or 2, G is a hydrogen atom, and R ₁ has a substituent. an amino group which may have, or a saturated heterocyclic group connected at the nitrogen atom, a m is 0 or 1, when m is 1, R ₂ is an aliphatic oxy A sulfonyl group, an optionally substituted carbamoyl group, or an aliphatic oxy group, wherein A is a group represented by the general formulas (A-1), (A-10), (A-11), (A- 13) to (A-17), (A-20), (A-22) to (A-23), (A-27), (A-28), (A-30) to (A-32) It is more preferable that n is 1 or 2, and G is a hydrogen atom, and R ₁ may have a substituent, or a nitrogen atom Embedded image wherein m is 0, and A is represented by formulas (A-10), (A-11), (A-13) to (A-17), (A- 20), any one of the groups represented by (A-22) to (A-23), (A-27), (A-28), (A-30) to (A-32), When n is 1 or 2 But more preferably, a G is a hydrogen atom, an amino group which may R ₁ is substituted, a m is 0, A is represented by the general formula (A-16) ~ (A -17), (A-20), (A-28), (A-32), wherein n is particularly preferably 1 or 2, and G is a hydrogen atom. R ₁ is an amino group which may have a substituent, m is 0, A is a group represented by the general formula (A-16), and n is 1 or Most preferred is 2.

From the viewpoint of the effect of the present invention, the azo pigment represented by the general formula (1) is more preferably an azo pigment represented by the following general formula (2). The azo pigment represented by the general formula (2) includes tautomers, salts or hydrates thereof.
The azo pigment represented by the general formula (2) forms a cross-hydrogen bond between Z or R ₅₅ and the hydroxy group of the naphthalene ring and the azo group to improve the planarity of the pigment structure, and the intramolecular and intermolecular interactions. As a result, light fastness, heat fastness, solvent resistance and the like are greatly improved.

  Hereinafter, the azo pigment represented by the general formula (2), tautomers thereof, salts or hydrates thereof will be described in detail.

In the general formula (2), R ₂₁ , R ₂₂ , R ₅₅ , R ₅₉ , m, and n are the same as R ₁ , R ₂ , R ₅₅ , R ₅₉ , m, and n defined in the general formula (1). The same. Z represents an electron withdrawing group having a Hammett's σp value of 0.2 or more. In the case of n = 2, it represents a dimer through the general formula (2), R ₂₁ , R ₂₂ , R ₅₅ , R ₅₉ or Z. When n = 3, general formula (2) represents a trimer via R ₂₁ , R ₂₂ , R ₅₅ , R ₅₉ or Z. When n = 4, the general formula (2) represents a tetramer through R ₂₁ , R ₂₂ , R ₅₅ , R ₅₉ or Z. There is no ionic hydrophilic group in the general formula (2).

Examples of the substituent having a Hammett σp value represented by Z of 0.2 or more include the groups described in the description of R _{58 in} the general formula (1).

Preferred substituents and ranges for R ₂₁ , R ₂₂ , R ₅₅ , R ₅₉ , m, and n of the azo pigment represented by the general formula (2) are R ₁ , R ₂ , R ₅₅ , Same as R ₅₉ , m, and n.
From the viewpoint of the effects of the present invention, Z is preferably an acyl group, a carbamoyl group, an alkyloxycarbonyl group, a cyano group, an alkylsulfonyl group, or a sulfamoyl group, more preferably a carbamoyl group, an alkyloxycarbonyl group, or a cyano group. Most preferred is the group.

In terms of the effects of the present invention, the azo pigment represented by the general formula (2) is an amino group in which R ₂₁ may have a substituent, m is 0 or 1, and m is In the case of 1, R ₂₂ is an aliphatic oxycarbonyl group, an optionally substituted carbamoyl group, or an aliphatic oxy group, and R ₅₅ contains a nitrogen atom adjacent to the binding site. An aromatic 5- to 6-membered heterocyclic group, wherein R ₅₉ is a hydrogen atom or an aliphatic group, and Z is an acyl group, a carbamoyl group, an alkyloxycarbonyl group, a cyano group, an alkylsulfonyl group, or a sulfamoyl group And n is preferably 1 or 2, R ₂₁ is an amino group which may have a substituent, m is 0, and R ₅₅ is represented by the general formula (Y-1 ) To (Y-13), and R ₅₉ Is more preferably a hydrogen atom or an aliphatic group, Z is a carbamoyl group, an alkyloxycarbonyl group, or a cyano group, and n is 1 or 2, and R ₂₁ has a substituent. An amino group in which m is 0, R ₅₅ is any one of the groups represented by formulas (Y-1) to (Y-6), and R ₅₉ is a hydrogen atom or More preferably, it is an aliphatic group, Z is a carbamoyl group, an alkyloxycarbonyl group, or a cyano group, and n is 1 or 2, and R ₂₁ is an amino group that may have a substituent. M is 0, R ₅₅ is a group represented by the general formula (Y-1), (Y-4), or (Y-6), and R ₅₉ is a hydrogen atom. More preferably, Z is a cyano group and n is 1 or 2.

  In terms of the effects of the present invention, the azo pigment represented by the general formula (1) or the general formula (2) preferably has “total carbon number / number of azo groups” of 40 or less, and 30 or less. The case is more preferable. In terms of the effects of the present invention, the azo pigment represented by the general formula (1) or the general formula (2) preferably has “molecular weight / number of azo groups” of 700 or less. In view of the effect of the present invention, the azo pigment represented by the general formula (1) or the general formula (2) is preferably not substituted with an isoionic substituent of a sulfo group or a carboxy group.

In another embodiment, the azo compound represented by the general formula (1) has a general formula (A-1) to (A-9), (A-11) to (A-13), (A- 17), preferably a group represented by (A-20) to (A-23), (A-27), (A-28), (A-30) to (A-32), Formula (A-11)-(A-13), (A-17), (A-20)-(A-23), (A-27), (A-28), (A-30)-( A-32) is more preferable, and (A-17), (A-20), (A-22) to (A-23), (A-27), (A-28), (A- 31) and a group represented by (A-32) are more preferred, and a group represented by formulas (A-20), (A-28) and (A-32) is more preferred. And a group represented by formula (A-20) There it is most preferable. In general formula (A-20) group _{R 56} represented by is particularly preferably an _{R 59} in the general formula (2).

The present invention includes in its scope tautomers of the azo pigments represented by the general formula (1) or the general formula (2). The general formula (1) or the general formula (2) is shown in the form of an extreme structural formula among several tautomers that can be taken in terms of chemical structure, but is a tautomer other than the described structure. It may be used as a mixture containing a plurality of tautomers.
For example, the azo pigment represented by the general formula (1) includes an azo-hydrazone tautomer represented by the following general formula (1 ′).
The present invention includes within its scope the pigment represented by the following general formula (1 ′), which is a tautomer of the azo pigment represented by the general formula (1).

In general formula (1 ′), G, R ₁ , R ₂ , m, n, and A are the same as those defined in general formula (1).

Of the azo pigments represented by the general formula (1), examples of the particularly preferred azo pigments represented by the general formula (1) are represented by the following general formulas (3-1) to (3-4). Mention may be made of azo pigments. The azo pigment represented by the general formula (1) is preferably an azo pigment represented by the following general formula (3-1) to general formula (3-4).
The azo pigments represented by general formula (3-1) to general formula (3-4) include tautomers, salts or hydrates thereof.
Hereinafter, the azo pigments represented by the general formulas (3-1) to (3-4), tautomers thereof, salts or hydrates thereof will be described in detail.

In general formula (3-1) to general formula (3-4), R ₁ , R ₂ , m, and n are the same as those defined in general formula (1) and general formula (2). X represents a carbon atom or a nitrogen atom, Ax and Bx together with X and the carbon atom represent an aromatic 5- to 6-membered heterocyclic group, and more specifically, a general formula (A- 1) to the group represented by (A-32). Yx represents that fall out of the heterocyclic group as defined in R ₅₅ in the general formula (1) together with the nitrogen atom and carbon atoms. R ₂₃ represents a substituent corresponding to a group obtained by removing a carbonyl group from the corresponding substituent among substituents such as R ₅₁ , R ₅₄ , R ₅₇ , and R ₅₈ defined in the general formula (1). R ′ ₁ represents a corresponding substituent obtained by removing —NH— from the amino group of R ₁ defined by the general formula (1). )

In the azo pigments represented by the general formulas (1), (2), and (3-1) to (3-4), many tautomers can be considered.
In the present invention, the azo pigment represented by the general formula (1) preferably has a substituent that forms an intramolecular hydrogen bond or an intramolecular cross-hydrogen bond. It is more preferable to have at least one substituent that forms an intramolecular hydrogen bond, and it is particularly preferable to have at least one substituent that forms an intramolecular cross-hydrogen bond.

Factors in which this structure is preferable include, as shown by the general formulas (3-1) to (3-4), a nitrogen atom constituting a heterocyclic group contained in the azo pigment structure and a hydrogen atom of the hydroxy group of the naphthalene substituent And an oxygen atom, a nitrogen atom of a hydrazone group which is an azo group or a tautomer thereof, or a carbonyl group substituted for an azo component contained in an azo pigment structure, a hydrogen atom and an oxygen atom of a hydroxy group of a naphthalene substituent, and It is mentioned that the nitrogen atom of the azo group or hydrazone group which is a tautomer thereof easily forms a cross-hydrogen bond in the molecule.
As a result, the planarity of the molecule is improved, the intramolecular / intermolecular interaction is improved, and the crystallinity of the azo pigment represented by the general formula (3-1) or the general formula (3-4) is increased ( It is more preferable because it is easy to form a higher order structure), and the required performance as a pigment is greatly improved in light fastness, heat stability, wet heat stability, water resistance, gas resistance and / or solvent resistance. An example.
Also from this viewpoint, the azo pigment represented by the general formula (1) is preferably a pigment represented by the general formula (2) or (3-1) to (3-4). ), (3-1) or a pigment represented by (3-2) is more preferred, and an azo pigment represented by the general formula (2) is particularly preferred.

  Specific examples of the azo pigment represented by the general formula (1) are shown below, but the azo pigment used in the present invention is not limited to the following examples. The structures of the following specific examples are shown in the form of an ultimate structural formula among several tautomers that can be taken in terms of chemical structure, but may be tautomeric structures other than those described. Needless to say.

  The azo pigment represented by the general formula (1) may have any crystal form as long as the chemical structural formula is the general formula (1), the general formula (2), or a tautomer thereof, and is also called a polymorph. May be.

  Crystal polymorphs refer to the same chemical composition but different arrangement of building blocks (molecules or ions) in the crystal. The crystal structure determines the chemical and physical properties, and each polymorph can be distinguished by its rheology, color, and other color characteristics. Different polymorphs can also be confirmed by X-Ray Diffraction (powder X-ray diffraction measurement result) or X-Ray Analysis (X-ray crystal structure analysis result).

When a crystalline polymorph exists in the azo pigment represented by the general formula (1) or the general formula (2), any polymorph may be used, and a mixture of two or more polymorphs may be used. The main component is preferably a single crystal type. That is, it is preferable that the crystalline polymorph is not mixed, and the content of the azo pigment having a single crystal type is 70% to 100%, preferably 80% to 100%, more preferably 90% with respect to the entire azo pigment. -100%, more preferably 95% -100, particularly preferably 100%. By using an azo pigment having a single crystal form as a main component, the regularity of the dye molecule arrangement is improved, the intramolecular / intermolecular interaction is strengthened, and a higher-order three-dimensional network is easily formed. . As a result, it is preferable in terms of performance required for pigments such as improvement of hue, light fastness, heat fastness, humidity fastness, oxidizing gas fastness and solvent resistance.
The mixing ratio of crystal polymorphs in azo pigments is based on solid physicochemical measurements such as single crystal X-ray crystal structure analysis, powder X-ray diffraction (XRD), crystal micrograph (TEM), IR (KBr method), etc. I can confirm.

  The tautomerism and / or crystal polymorphism described above can be controlled by the production conditions during the coupling reaction.

  Further, in the present invention, when the azo pigment represented by the general formula (1) has an acid group, a part or all of the acid group may be in a salt form. Acid type pigments may be mixed. Examples of the salt type include salts of alkali metals such as Na, Li and K, ammonium salts optionally substituted with an alkyl group or hydroxyalkyl group, and organic amine salts. Examples of organic amines include lower alkyl amines, hydroxy-substituted lower alkyl amines, carboxy-substituted lower alkyl amines, and polyamines having 2 to 10 alkyleneimine units having 2 to 4 carbon atoms. In the case of these salt types, the type is not limited to one type, and a plurality of types may be mixed.

  Further, in the structure of the pigment used in the present invention, when a plurality of acid groups are contained in one molecule, the plurality of acid groups may be salt type or acid type and may be different from each other.

  In the present invention, the azo pigment represented by the general formula (1) may be a hydrate containing water molecules in the crystal.

The pigment dispersion composition of the present invention may contain two or more azo pigments represented by the general formula (1).
In the present specification, the term “azo pigment represented by the general formula (1)” is not limited to one kind of azo pigment represented by the general formula (1), but also two or more kinds of the general formula (1). And a combination of the azo pigment represented by the general formula (1) and other pigments described later.

Next, an example of a method for producing the azo pigment represented by the general formula (1) will be described.
The azo pigment represented by the general formula (1) is, for example, a diazonium non-acidic heterocyclic amine represented by the following general formula (4) and an acidic state with the compound represented by the following general formula (5) The azo pigment represented by the general formula (6) of the present invention can be produced by performing a coupling reaction with the above and performing a post-treatment by a conventional method. The azo pigment represented by the general formula (1) is obtained by performing the same operation using the heterocyclic amine corresponding to A in the general formula (1) instead of the heterocyclic amine represented by the general formula (4). Can be manufactured.

In the general formula (4), R ₅₅ , R ₅₈ and R ₅₉ are synonymous with those defined in the general formula (2).

In the general formula (5), R ₁ , R ₂ and m have the same definitions as those defined in the general formula (1).
The reaction scheme is shown below.

In the general formulas (4) to (6), G, R ₁ , R ₂ , R ₅₅ , R ₅₈ , R ₅₉ , m, and n are defined by the general formula (1) or the general formula (2). It is synonymous.

Heterocyclic amines represented by the amino compounds of the general formulas (4) and (A-1) to (A-32) can be obtained as commercial products, but generally known methods are commonly used. For example, it can manufacture by the method of patent 4022271 gazette. The heterocyclic coupler represented by the general formula (5) can be obtained as a commercial product, but can be produced by the method described in JP-A-2008-13472 and a method analogous thereto.
The diazoniumation reaction of the heterocyclic amine represented by the above reaction scheme is carried out at a temperature of 15 ° C. or less with a reagent such as sodium nitrite, nitrosylsulfuric acid, isoamyl nitrite in an acidic solvent such as sulfuric acid, phosphoric acid, and acetic acid. The reaction can be carried out for about 6 minutes to 6 minutes. The coupling reaction is carried out by reacting the diazonium salt obtained by the above-described method with the compound represented by the general formula (5) at 40 ° C. or less, preferably 25 ° C. or less for about 10 minutes to 12 hours. it can.
In the general formula (1) or the general formula (2), the method for synthesizing the azo pigment in the form where n is 2 or more is represented by R _{1 to} R ₂ , R ₅₅ in the general formula (4) or the general formula (5). In R ₅₉ , R _{58 and the} like, raw materials into which a substitutable divalent, trivalent or tetravalent substituent is introduced can be synthesized and synthesized in the same manner as in the above scheme.
In some cases, crystals are precipitated in this way, but in general, water or an alcohol solvent is added to the reaction solution to precipitate the crystals, and the crystals can be collected by filtration. it can. In addition, an alcohol solvent, water or the like can be added to the reaction solution to precipitate crystals, and the precipitated crystals can be collected by filtration. The crystals collected by filtration can be washed and dried as necessary to obtain an azo pigment represented by the general formula (1).

  Although the azo pigment represented by the general formula (1) or the general formula (2) is obtained as a crude azo pigment (crude) by the above production method, it is desirable to perform a post-treatment when used as a pigment in the present invention. . Examples of post-treatment methods include solvent salt milling, salt milling, dry milling, solvent milling, pigment particle control step by grinding treatment such as acid pasting, solvent heating treatment, resin, surfactant and dispersant. The surface treatment process by etc. is mentioned.

The azo pigment represented by the general formula (1) or the general formula (2) obtained as a crude azo pigment is preferably subjected to solvent heating treatment and / or solvent salt milling as post-treatment.
By performing solvent salt milling, the average primary particle diameter of the azo pigment represented by the general formula (1) can be easily adjusted within the above preferred range.
Examples of the solvent used in the solvent heat treatment include water, aromatic hydrocarbon solvents such as toluene and xylene, halogenated hydrocarbon solvents such as chlorobenzene and o-dichlorobenzene, and alcohols such as isopropanol and isobutanol. Examples thereof include solvents, polar aprotic organic solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, glacial acetic acid, pyridine, and mixtures thereof. An inorganic or organic acid or base may be further added to the solvents mentioned above. The temperature of the solvent heat treatment varies depending on the desired primary particle size of the pigment, but is preferably 40 to 150 ° C, more preferably 60 to 100 ° C. The treatment time is preferably 30 minutes to 24 hours.

As solvent salt milling, for example, a crude azo pigment, an inorganic salt, and an organic solvent that does not dissolve the crude azo pigment are charged into a kneader and kneaded and ground therein.
As the inorganic salt, a water-soluble inorganic salt can be preferably used. For example, an inorganic salt such as sodium chloride, potassium chloride, sodium sulfate is preferably used.
Moreover, it is more preferable to use an inorganic salt having an average particle size of 0.5 μm to 50 μm. The amount of the inorganic salt used is preferably 3 to 20 times by mass, more preferably 5 to 15 times by mass with respect to the crude azo pigment.
As the organic solvent, a water-soluble organic solvent can be suitably used, and the solvent easily evaporates due to a temperature rise during kneading, so that a high boiling point solvent is preferable from the viewpoint of safety. Examples of such organic solvents include diethylene glycol, glycerin, ethylene glycol, propylene glycol, liquid polyethylene glycol, liquid polypropylene glycol, 2- (methoxymethoxy) ethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, diethylene glycol Propylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene Glycol or mixtures thereof. The amount of the water-soluble organic solvent used is preferably 0.1 to 5 times by mass with respect to the crude azo pigment. The kneading temperature is preferably 20 to 130 ° C, particularly preferably 40 to 110 ° C. As a kneader, for example, a kneader or a mix muller can be used.

As the solvent salt milling, it is also preferable to use the method described in paragraphs 0007 to 0071 of JP2009-263501A.
That is, this preferred solvent salt milling uses, as an attrition agent, anhydrous sodium sulfate for pigment attrition having an average particle size of 5.5 μm or less and a content of particle size of 10.0 μm or more of 5 vol% or less. Solvent salt milling used.
Here, it is preferable that the anhydrous sodium sulfate for pigment grinding has an average particle size of 2.0 μm or more and 4.0 μm or less, and a content of particle size of 10.0 μm or more is 1% by volume or less. The anhydrous sodium sulfate for pigment grinding preferably has a water content of 1.0% by mass or less. Moreover, it is preferable that the anhydrous sodium sulfate for pigment grinding contains an anti-caking agent.

<Other pigments>
The pigment dispersion composition of the present invention is a pigment other than the azo pigment represented by the general formula (1), together with the azo pigment represented by the general formula (1), as long as the object of the present invention is not hindered. May be included.
The other pigments are not particularly limited. For example, azo pigments, disazo pigments, benzimidazolone pigments, condensed azo pigments, azo lake pigments, anthraquinone pigments, diketopyrrolopyrrole pigments, quinacridone pigments. One or more pigments selected from isoindoline pigments, isoindolinone pigments, perinone pigments, perylene pigments, and / or derivatives thereof may be used.

Other pigments include compounds classified as Pigments in the Color Index (CI; issued by The Society of Dyers and Colorists), that is, the following Color Index (CI) numbers: Can be mentioned.
C. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48: 1, 48: 2, 48: 3, 48: 4 49, 49: 1, 49: 2, 52: 1, 52: 2, 53: 1, 57: 1, 60: 1, 63: 1, 66, 67, 81: 1, 81: 2, 81: 3 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 270, 272, 279,
C. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 17 , 175,176,177,179,180,181,182,185,187,188,193,194,199,213,214,
C. I. Pigment Orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73,
C. I. Pigment Green 7, 10, 36, 37,
C. I. Pigment Blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66, 79, 79 were changed to OH. Things, 80,
C. I. Pigment Violet 1, 19, 23, 27, 32, 37, 42,
C. I. Pigment Brown 25, 28,
C. I. Pigment Black 1, 7 and the like.
However, the present invention is not limited to these.

Among these, the pigments that can be preferably used include the following.
C. I. Pigment Yellow 11, 24, 108, 109, 110, 138, 139, 150, 151, 154, 167, 180, 185,
C. I. Pigment Orange 36, 71,
C. I. Pigment Red 122, 150, 171, 175, 177, 209, 224, 242, 254, 255, 264,
C. I. Pigment Violet 19, 23, 29, 32,
C. I. Pigment Blue 15: 1, 15: 3, 15: 6, 16, 22, 60, 66,
C. I. Pigment Green 7, 36, 37,
C. I. Pigment Black 1, 7

  Inorganic pigments may also be used. Specific examples thereof include titanium oxide, barium sulfate, calcium carbonate, zinc white, lead sulfate, yellow lead, zinc yellow, red bean (red iron oxide (III)), cadmium red, Examples include ultramarine blue, bitumen, chromium oxide green, cobalt green, amber, titanium black, synthetic iron black, and carbon black. In this invention, a pigment can be used individually or in mixture of 2 or more types.

  In particular, in the pigment dispersion composition of the present invention, from the viewpoint of further improving the spectral characteristics (hue) as a red pattern (red color filter), together with the azo pigment represented by the general formula (1), It is preferable to contain at least one pigment having a hue selected from red, yellow, orange, and violet. These pigments include C.I. exemplified above. I. At least one pigment can be selected from the numbered pigments. Thereby, the transmittance on the short wavelength side (for example, a wavelength of 500 nm or less (more preferably, a wavelength of 400 nm or less)) can be further suppressed, and a better red hue can be obtained.

When other pigments other than the azo pigment represented by the general formula (1) (particularly, a pigment having a hue selected from red, yellow, orange, and violet) are used in combination, the content of the pigment of the present invention The total mass of the pigment in the dispersion composition (or the colored curable composition of the present invention) is preferably 50% by mass or less, more preferably 40% by mass or less, and 30% by mass or less. It is particularly preferred.
The lower limit of the content of other pigments (particularly pigments having a hue selected from red, yellow, orange, and violet) is not particularly limited, but 5% by mass is preferable from the viewpoint of adjusting spectral characteristics, More preferably, it is 10 mass%.

The volume average particle diameter of the pigment (a pigment containing at least the azo pigment represented by the general formula (1)) in the pigment dispersion composition of the present invention is preferably 1 nm or more and 250 nm or less. The volume average particle diameter of the pigment particles refers to the particle diameter of the pigment itself or the particle diameter to which the additive has adhered when an additive such as a dispersant is attached to the pigment.
In the present invention, a Nanotrac UPA particle size analyzer (UPA-EX150; manufactured by Nikkiso Co., Ltd.) was used as a measuring device for the volume average particle diameter of the pigment. The measurement was performed according to a predetermined measurement method by placing 3 ml of the pigment dispersion composition in a measurement cell. As parameters input at the time of measurement, the viscosity of the pigment dispersion composition was used as the viscosity, and the density of the pigment was used as the density of the dispersed particles.

A more preferable volume average particle size of the pigment is 1 nm or more and 200 nm or less, and more preferably 1 nm or more and 150 nm or less. If the volume average particle diameter of the particles in the pigment dispersion composition is 250 nm or less, the optical density will be higher.
Furthermore, the particularly preferable volume average particle diameter of the pigment is 2 nm or more and 100 nm or less from the viewpoint of further improving the dispersion stability, and the most preferable volume average particle diameter is 2 nm or more and 50 nm or less.

  The total concentration of the pigments contained in the pigment dispersion composition of the present invention is preferably in the range of 1 to 35% by mass, and more preferably in the range of 2 to 25% by mass. If it is the said range, it is easy to adjust the physical-property values of dispersion, such as surface tension and a viscosity, and it is preferable.

<At least one compound selected from the group consisting of an organic dye derivative having an acidic functional group, an anthraquinone derivative having an acidic functional group, and a triazine derivative having an acidic functional group>
The pigment dispersion composition of the present invention comprises at least one compound selected from the group consisting of an organic dye derivative having an acidic functional group, an anthraquinone derivative having an acidic functional group, and a triazine derivative having an acidic functional group (hereinafter referred to as “acidic” as appropriate). In some cases, it is generically referred to as a “functional group-containing derivative”.

Examples of the acidic functional group possessed by the acidic functional group-containing derivative include a sulfo group, a carboxy group, a phosphoric acid group, and an acetylacetonato group, and those having a sulfo group or a carboxy group are preferable from the viewpoint of residue control. . These acidic functional groups may take a salt structure.
Hereinafter, the acidic functional group-containing derivative in the present invention will be described in detail.

(Organic dye derivatives having acidic functional groups)
Examples of the organic dye derivative having an acidic functional group include organic dye derivatives represented by the following general formula (I).

P- [X _1- (Y ₁ ) k] m (I)
In general formula (I), P represents an organic dye residue. X ₁ represents a single bond, —O—, —S—, —CO—, —SO ₂ —, —NR ₁ —, —CONR ₁ —, —SO ₂ NR ₁ —, —NR ₁ CO—, —NR _1. SO ₂ — (wherein R ₁ represents a hydrogen atom, an alkyl group, or a hydroxyalkyl group), a linear or branched alkylene group having 1 to 12 carbon atoms, an alkyl group, an amino group, a nitro group, A hydroxyl group, an alkoxy group, a benzene residue or a triazine residue which may be substituted with a halogen atom, or a linking group constituted by combining two or more of these groups is represented. Y ₁ represents —SO ₃ · M / n or —COO · M / n, where M is a hydrogen ion, a 1 to 3 metal ion, or an ammonium ion in which at least one is substituted with an alkyl group N represents the valence of M. k represents an integer of 1 or 2, and m represents an integer of 1 to 4.

In the general formula (I), examples of the organic dye residue represented by P include diketopyrrolopyrrole dyes, azo dyes such as azo, disazo, polyazo, phthalocyanine dyes, diaminodianthraquinone, anthrapyrimidine, Anthraquinone dyes such as flavantron, anthanthrone, indanthrone, pyratron, violanthrone, quinacridone dye, dioxazine dye, perinone dye, perylene dye, thioindigo dye, isoindoline dye, isoindolinone dye, quinophthalone And dye residues such as a system dye, a selenium dye, and a metal complex dye.
Among these, as P, a dye residue of a diketopyrrolopyrrole dye, an azo, a disazo dye, or a quinacridone dye is more preferable.

In the general formula (I), when Y ₁ is —SO ₃ · M / n, specific examples thereof include, for example, a sulfo group, a sodium sulfonate group, a calcium sulfonate group, a strontium sulfonate group, and a barium sulfo group. Nato group, aluminum sulfonate group, 4- (aluminum sulfonate group) phenylcarbamoylmethyl group, dodecylammoniosulfonato group, octadecylammoniosulfonato group, trimethyloctadecylammoniosulfonato group, dimethyldidecylammoniosulfonato group Etc.

In the general formula (I), when Y ₁ is —COO · M / n, specific examples thereof include, for example, carboxy group, 2-ammoniumcarboxylato-5-nitrobenzamidomethyl group, 4-carboxyphenylamino. A carbonyl group etc. are mentioned.

As the organic dye derivative represented by the general formula (I), Y ₁ is preferably —SO ₃ .M / n. Among them, Y ₁ is a sulfo group, a sodium sulfonate group, or an aluminum sulfonate group. It is preferable that Among these, a combination in which P is a diketopyrrolopyrrole dye or an azo dye and Y ₁ is a sulfo group or a sodium sulfonate group is particularly preferable.

(Anthraquinone derivatives having acidic functional groups)
Examples of the anthraquinone derivative having an acidic functional group include anthraquinone derivatives represented by the following general formula (II).
_{Q- [X 2 - (Y 2} ) k] m (II)
In general formula (II), Q represents an anthraquinone residue which may be substituted with an alkyl group, an amino group, a nitro group, a hydroxyl group, an alkoxy group, or a halogen atom. X ₂ represents a single bond, —O—, —S—, —CO—, —SO ₂ —, —NR ₁ —, —CONR ₁ —, —SO ₂ NR ₁ —, —NR ₁ CO—, —NR _1. SO ₂ — (wherein R ₁ represents a hydrogen atom, an alkyl group, or a hydroxyalkyl group), a linear or branched alkylene group having 1 to 12 carbon atoms, an alkyl group, an amino group, a nitro group, A hydroxyl group, an alkoxy group, a benzene residue or a triazine residue which may be substituted with a halogen atom, or a linking group constituted by combining two or more of these groups is represented. Y ₂ represents —SO ₃ · M / n or —COO · M / n, M represents a hydrogen ion, a 1-3 valent metal ion, or an ammonium ion in which at least one is substituted with an alkyl group, n represents the valence of M. k represents an integer of 1 or 2, and m represents an integer of 1 to 4.

  In general formula (II), the anthraquinone residue represented by Q includes alkyl groups such as methyl and ethyl groups, amino groups, nitro groups, hydroxyl groups or methoxy groups, alkoxy groups such as ethoxy groups, and halogens such as chlorine. And anthraquinone residues which may be substituted with atoms.

In the general formula (II), when Y ₂ is —SO ₃ · M / n, specific examples thereof include, for example, a sulfo group, a sodium sulfonate group, a calcium sulfonate group, a strontium sulfonate group, and a barium sulfo group. Nato group, aluminum sulfonate group, 4- (aluminum sulfonate group) phenylcarbamoylmethyl group, dodecylammoniosulfonato group, octadecylammoniosulfonato group, trimethyloctadecylammoniosulfonato group, dimethyldidecylammoniosulfonato group Etc.

In the general formula (II), when Y ₂ is —COO · M / n, specific examples thereof include a carboxy group and a 4- (aluminum carboxylato) phenylaminocarbonyl group.

In the anthraquinone derivative represented by the general formula (II), Y ₂ is preferably —SO ₃ · M / n, and among them, a sulfo group, a sodium sulfonate group, and an aluminum sulfonate group are preferable. Among them, a combination in which Q is anthraquinone is particularly preferable.

(Triazine derivative having acidic functional group)
Examples of the triazine derivative having an acidic functional group include triazine derivatives represented by the following general formula (III).

In general formula (III), R represents a triazine residue. X ³ , X ⁴ and X ⁵ are each independently a single bond, —O—, —S—, —CO—, —SO ₂ —, —NR ¹ —, —CONR ¹ —, —SO ₂ NR ¹ —. ^{, -NR 1 CO -, - NR} 1 SO 2 - ( wherein ^{R 1} represents a hydrogen atom, an alkyl group, a hydroxyalkyl group), an alkylene group number is 1 to 12 linear or branched carbon atoms, And an alkyl group, a nitro group, a hydroxyl group, an alkoxy group, a benzene residue optionally substituted with a halogen atom, or a linking group formed by combining two or more of these groups. Y ³ represents —SO ₃ · M / n, or —COO · M / n, M represents a hydrogen ion, a 1-3 valent metal ion, or an ammonium ion in which at least one is substituted with an alkyl group, n Represents the valence of M. Y ⁴ and Y ⁵ are each independently the same as Y ³ , or may be substituted with an alkyl group, a nitro group, a hydroxyl group, an alkoxy group, a halogen atom, or a methyl group, a methoxy group, a hydroxyl group, or the like Represents a good phenyl group. p, q and r each independently represent an integer of 1 or 2.

  The triazine in the triazine residue represented by R is preferably 1,3,5-triazine.

When Y ³ , Y ⁴ or Y ⁵ is —SO ₃ · M / n, specific examples thereof include an aluminum sulfonatoethylamino group and a 4-sulfophenylamino group.
In addition, when Y ³ , Y ⁴ or Y ⁵ is —COO · M / n, specific examples thereof are as follows, and specific examples thereof include a 4-carboxyphenylamino group.

The triazine derivative represented by the general formula (III) is preferably a case where at least one of Y ₃ , Y ₄ , and Y ₅ is —SO ₃ .M / n, among which a sulfo group, a sodium sulfonate group, or An aluminum sulfonate group is preferred. Among these, a combination in which at least one of Y ₃ , Y ₄ , and Y ₅ is —SO ₃ · M / n and R is 1,3,5-triazine is particularly preferable.

  Specific examples of the organic dye derivative represented by the general formula (I), the anthraquinone derivative represented by the general formula (II), and the triazine derivative represented by the general formula (III) include the following compounds: Although it is mentioned, it is not limited to these.

  Examples of the organic dye derivative represented by the general formula (I), the anthraquinone derivative represented by the general formula (II), and the triazine derivative represented by the general formula (III) include, for example, JP-B-39-28884 and JP-B-58- No. 028303, JP-B 63-17101, JP-A 56-81371, JP-B 01-34268, JP-B 01-34269, JP-B 05-9496, JP-B 02-62893 No. 07-33485, Japanese Patent No. 2584515, Japanese Patent No. 2906833, and Japanese Patent No. 3518300.

  In the pigment dispersion composition, the acidic functional group-containing derivative may contain only one type, or two or more types may be used in combination.

  Among the acidic functional group-containing derivatives, a triazine derivative represented by the general formula (III) having a sulfo group or a carboxy group is most preferable because a residue is extremely small.

  The content of the acidic functional group-containing derivative in the pigment dispersion composition of the present invention is in the range of 0.1% by mass to 80% by mass with respect to all pigments including at least the azo pigment represented by the general formula (1). Preferably, it is in the range of 1% to 65% by weight, more preferably in the range of 3% to 50% by weight. When the content of the acidic functional group-containing derivative is within this range, the pigment dispersion can be improved while the viscosity of the pigment dispersion composition is kept low, and the dispersion stability after dispersion can be improved.

  By applying such a pigment dispersion composition to the manufacture of a color filter, the heat resistance of the color filter can be improved. Further, a color filter having high transmittance, excellent color characteristics, and high contrast can be obtained.

<Dispersant>
The pigment dispersion composition of the present invention contains at least one dispersant.
The dispersant is not particularly limited, and a known pigment dispersant can be used.
As the dispersant in the present invention, a nitrogen atom-containing dispersant is preferable.
As the nitrogen atom-containing dispersant, surfactants, polymer dispersants and the like are usually used, and polymer dispersants are particularly preferable.
Examples of suitable polymer dispersants include urethane dispersants, graft copolymer type dispersants containing nitrogen atoms, block copolymer type dispersants containing nitrogen atoms, and the like.
In the present invention, in particular, (i) a main chain portion having a nitrogen atom and (ii) a group “X” having a functional group having a pKa of 14 or less and bonded to the nitrogen atom present in the main chain portion And (iii) a side chain including an oligomer chain or polymer chain “Y” having a number average molecular weight of 500 to 1,000,000 (hereinafter, also referred to as “specific resin” as appropriate) is high. Suitable as a molecular dispersant. In addition, amphoteric dispersants such as Hinoact T-8000E (manufactured by Kawaken Fine Chemical Co., Ltd.) can also be suitably used.
Hereinafter, the polymer dispersant suitable for the present invention will be described in detail.

<Urethane-based dispersant>
Urethane dispersants include (1) polyisocyanate compounds, (2) compounds having one or two hydroxyl groups in the same molecule, and (3) compounds having active hydrogen and tertiary amino groups in the same molecule. It is preferable that it is a urethane type dispersion resin obtained by making it react.

(1) Polyisocyanate compound Examples of the polyisocyanate compound include paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthalene-1,5-diisocyanate, Aromatic diisocyanates such as tolidine diisocyanate, hexamethylene diisocyanate, lysine methyl ester diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, dimer acid diisocyanate and other aliphatic diisocyanates, isophorone diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate) , Ω, ω'-diisocyanate dimethylcyclohexane, alicyclic diisocyanates, xylylene diisocyanate, α , Α, α ′, α′-tetramethylxylylene diisocyanate, etc., aliphatic diisocyanates, lysine ester triisocyanates, 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane 1,3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate, triisocyanate such as tris (isocyanatephenylmethane), tris (isocyanatephenyl) thiophosphate, and trimers thereof, water adducts, and these Examples include polyol adducts. Preferred as the polyisocyanate is a trimer of an organic diisocyanate, and most preferred is a trimer of tolylene diisocyanate and a trimer of isophorone diisocyanate, which may be used alone or in combination.

  As a method for producing an isocyanate trimer, the polyisocyanate may be converted into an isocyanate group using an appropriate trimerization catalyst such as tertiary amines, phosphines, alkoxides, metal oxides, carboxylates and the like. And the trimerization is stopped by adding a catalyst poison, and then the unreacted polyisocyanate is removed by solvent extraction and thin-film distillation to obtain the desired isocyanurate group-containing polyisocyanate.

(2) Compounds having one or two hydroxyl groups in the same molecule Examples of compounds having one or two hydroxyl groups in the same molecule include polyether glycol, polyester glycol, polycarbonate glycol, polyolefin glycol, and the like, and these compounds. And a mixture of two or more of these having one end hydroxyl group alkoxylated with an alkyl group having 1 to 25 carbon atoms.

Polyether glycols include polyether diols, polyether ester diols, and mixtures of two or more of these.
Examples of the polyether diol include those obtained by homopolymerizing or copolymerizing alkylene oxide, such as polyethylene glycol, polypropylene glycol, polyethylene-propylene glycol, polyoxytetramethylene glycol, polyoxyhexamethylene glycol, polyoxyoctamethylene glycol, and the like. The mixture of 2 or more types of those is mentioned.
Polyether ester diols include those obtained by reacting mixtures of ether group-containing diols or other glycols with dicarboxylic acids or their anhydrides, or reacting polyester glycols with alkylene oxides, such as poly ( And polyoxytetramethylene) adipate.
The most preferable polyether glycol is polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol, or a compound in which one terminal hydroxyl group of these compounds is alkoxylated with an alkyl group having 1 to 25 carbon atoms.

  Polyester glycol includes dicarboxylic acid (succinic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid, maleic acid, phthalic acid, etc.) or anhydrides thereof and glycol (ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, Dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 3-methyl-1,5-pentanediol, neopentyl glycol 2-methyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl-2,4- Nanthanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2,5-dimethyl-2,5-hexanediol, 1,8-octamethylene glycol, Aliphatic glycols such as 2-methyl-1,8-octamethylene glycol and 1,9-nonanediol, alicyclic glycols such as bishydroxymethylcyclohexane, aromatic glycols such as xylylene glycol and bishydroxyethoxybenzene, N -N-alkyl dialkanolamines such as methyldiethanolamine) obtained by polycondensation, such as polyethylene adipate, polybutylene adipate, polyhexamethylene adipate, polyethylene / propylene adipate, etc., or the diol or carbon number 1 to 25 monovalent Polylactone diol or polylactone monool obtained by using an alcohol as an initiator, for example, polycaprolactone glycol, polymethyl valerolactone and mixtures of two or more thereof. Most preferred as the polyester glycol is polycaprolactone glycol or polycaprolactone starting with an alcohol having 1 to 25 carbon atoms, more specifically, a compound obtained by ring-opening addition polymerization of ε-caprolactone to a monool. .

Examples of the polycarbonate glycol include poly (1,6-hexylene) carbonate and poly (3-methyl-1,5-pentylene) carbonate.
Examples of the polyolefin glycol include polybutadiene glycol, hydrogenated polybutadiene glycol, and hydrogenated polyisoprene glycol.
Of the compounds having one or two hydroxyl groups in the same molecule, polyether glycol and polyester glycol are particularly preferable.
The number average molecular weight of the compound having one or two hydroxyl groups in the same molecule is usually 300 to 10,000, preferably 500 to 6,000, and more preferably 1,000 to 4,000.

(3) Compound having active hydrogen and tertiary amino group in the same molecule Active hydrogen, that is, hydrogen atom directly bonded to oxygen atom, nitrogen atom or sulfur atom includes hydroxyl group, amino group, thiol group, etc. The hydrogen atom in a functional group is mentioned, Especially, the hydrogen atom of an amino group, especially a primary amino group is preferable.
The tertiary amino group is not particularly limited. For example, a dialkylamino group having an alkyl group having 1 to 4 carbon atoms such as methyl, ethyl, isopropyl and n-butyl, or the dialkylamino group is linked to form a heterocyclic structure. The group which forms, More specifically, an imidazole ring or a triazole ring is mentioned.

  Examples of such compounds having an active hydrogen and a tertiary amino group in the same molecule include N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, N , N-dipropyl-1,3-propanediamine, N, N-dibutyl-1,3-propanediamine, N, N-dimethylethylenediamine, N, N-diethylethylenediamine, N, N-dipropylethylenediamine, N, N -Dibutylethylenediamine, N, N-dimethyl-1,4-butanediamine, N, N-diethyl-1,4-butanediamine, N, N-dipropyl-1,4-butanediamine, N, N-dibutyl-1 , 4-butanediamine and the like.

  In addition, the tertiary amino group is a nitrogen-containing heterocycle, such as pyrazole ring, imidazole ring, triazole ring, tetrazole ring, indole ring, carbazole ring, indazole ring, benzimidazole ring, benzotriazole ring, benzoxazole ring, benzo Examples thereof include N-containing hetero 5-membered rings such as thiazole ring and benzothiadiazole ring, nitrogen-containing hetero 6-membered rings such as pyridine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, acridine ring, and isoquinoline ring. Preferred as these nitrogen-containing heterocycles are an imidazole ring or a triazole ring.

  Specific examples of these compounds having an imidazole ring and a primary amino group include 1- (3-aminopropyl) imidazole, histidine, 2-aminoimidazole, 1- (2-aminoethyl) imidazole and the like. . Specific examples of the compound having a triazole ring and a primary amino group include 3-amino-1,2,4-triazole, 5- (2-amino-5-chlorophenyl) -3-phenyl-1H- 1,2,4-triazole, 4-amino-4H-1,2,4-triazole-3,5-diol, 3-amino-5-phenyl-1H-1,3,4-triazole, 5-amino- Examples include 1,4-diphenyl-1,2,3-triazole, 3-amino-1-benzyl-1H-2,4-triazole and the like. Among them, N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, 1- (3-aminopropyl) imidazole, 3-amino-1,2,4-triazole Is preferred.

  The preferable blending ratio of the raw materials for obtaining the urethane-based dispersion resin described above is usually 10 to 200 parts by mass, preferably 20 to 20 parts by mass of the compound having one or two hydroxyl groups in the same molecule with respect to 100 parts by mass of the polyisocyanate compound. -190 mass parts, More preferably, it is 30-180 mass parts, The compound which has an active hydrogen and a tertiary amino group in the same molecule is 0.2-25 mass parts normally, Preferably it is 0.3-24 mass parts.

  The polystyrene-reduced weight average molecular weight measured by GPC of the urethane-based dispersion resin is usually 1,000 to 200,000, preferably 2,000 to 200 from the viewpoints of dispersibility and dispersion stability, solubility, and reaction controllability. The range is 100,000, more preferably 3,000 to 50,000.

Manufacture of a urethane type dispersion resin is performed in accordance with the well-known method of polyurethane resin manufacture.
As a solvent for production, usually, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, isophorone, esters such as ethyl acetate, butyl acetate, cellosolve acetate, benzene, toluene, xylene, hexane Hydrocarbons such as diacetone alcohol, isopropanol, sec-butanol, tert-butanol, etc., chlorides such as methylene chloride and chloroform, ethers such as tetrahydrofuran and diethyl ether, dimethylformamide, N-methyl Aprotic polar solvents such as pyrrolidone and dimethyl sulfoxide are used.

  As the catalyst for production, a usual urethanization reaction catalyst is used. Examples of the catalyst include tin-based compounds such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctoate, stannous octoate, iron-based compounds such as iron acetylacetonate and ferric chloride, triethylamine, and triethylenediamine. Secondary amine type and the like can be mentioned.

The introduction amount of the compound having active hydrogen and tertiary amino group in the same molecule is 1 to 100 mg in terms of amine value of the dispersion resin after the reaction.
It is preferable to control within the range of OH / g. More preferably, it is the range of 5-95 mgKOH / g. When the amine value is less than the above range, the dispersing ability tends to decrease, and when it exceeds the above range, the developability tends to decrease. In addition, when an isocyanate group remains in the dispersion resin by the above reaction, it is preferable to crush the isocyanate group with an alcohol or an amino compound because the dispersion resin has high temporal stability.

(Graft copolymer containing nitrogen atoms)
As the graft copolymer containing a nitrogen atom, those having a repeating unit containing a nitrogen atom in the main chain are preferred. Among them, those having a repeating unit represented by the following formula (A) and / or a repeating unit represented by the formula (B) are preferable.

In the formula (A), R ₁ represents an alkylene group having 1 to 5 carbon atoms, and A represents a hydrogen atom or a group represented by the following formulas (C) to (E).
In the formula (A), R ₁ represents a linear or branched alkylene group having 1 to 5 carbon atoms such as methylene, ethylene or propylene, preferably 2 to 3 carbon atoms, more preferably an ethylene group. It is. A represents either a hydrogen atom or a group represented by the following formulas (C) to (E), preferably a group represented by the following formula (C).

Wherein (B), _{R 1} and A have the same meanings as _{R 1} and A in the formula (A).

In the formula (C), W ₁ represents a linear or branched alkylene group having 2 to 10 carbon atoms, and among them, an alkylene group having 4 to 7 carbon atoms such as butylene, pentylene, hexylene and the like is preferable. p represents an integer of 1 to 20, preferably an integer of 5 to 10.

In formula (D), Y ₁ represents a divalent linking group, among which an alkylene group having 1 to 4 carbon atoms such as ethylene and propylene, and an alkyleneoxy group having 1 to 4 carbon atoms such as ethyleneoxy and propyleneoxy. preferable. W ₂ represents a linear or branched alkylene group having 2 to 10 carbon atoms such as ethylene, propylene, or butylene, and among them, an alkylene group having 2 to 3 carbon atoms such as ethylene or propylene is preferable. Y ₂ represents a hydrogen atom or CO—R ₂ (R ₂ represents an alkyl group having 1 to 10 carbon atoms such as ethyl, propyl, butyl, pentyl, hexyl, etc., among which carbon numbers 2 to 2 such as ethyl, propyl, butyl, pentyl, etc. 5 is preferred). q represents an integer of 1 to 20, preferably an integer of 5 to 10.

In the formula (E), W ₃ represents an alkyl group having 1 to 50 carbon atoms or a hydroxyalkyl group having 1 to 50 carbon atoms having 1 to 5 hydroxyl groups. Among them, an alkyl group having 10 to 20 carbon atoms such as stearyl, mono A C10-20 hydroxyalkyl group having 1-2 hydroxyl groups such as hydroxystearyl is preferred.

The content of the repeating unit represented by the formula (A) or (B) in the “graft copolymer containing nitrogen atom” is preferably higher, and is usually 50 mol% or more, preferably 70 mol%. That's it. The repeating unit represented by the formula (A) and the repeating unit represented by the formula (B) may both be present, and the content ratio is not particularly limited, but preferably the formula (A) It is preferable to contain a larger number of repeating units. The total number of repeating units represented by formula (A) or formula (B) is usually 1 to 100, preferably 10 to 70, and more preferably 20 to 50. Moreover, repeating units other than Formula (A) and Formula (B) may be included, and examples of other repeating units include an alkylene group and an alkyleneoxy group. The above-mentioned “graft copolymer containing a nitrogen atom” preferably has a terminal of —NH ₂ and —R ₁ —NH ₂ (R ₁ is the same as R ₁ ).

The “graft copolymer containing nitrogen atom” may have a main chain which is linear or branched. The amine value of the graft copolymer is usually 5 to 100 mgKOH / g, preferably 10 to 70 mgKOH / g, more preferably 15 to 40 mgKOH / g or less.
When the amine value is 5 mgKOH / g or more, the dispersion stability can be further improved, and the viscosity can be further stabilized. When the amine value is 100 mgKOH / g or less, the residue can be further suppressed, and the deterioration of the electrical characteristics after the liquid crystal panel is formed can be further suppressed.

  As a weight average molecular weight measured by GPC of the said "graft copolymer containing a nitrogen atom", 3000-100000 are preferable and 5000-50000 are especially preferable. When the weight average molecular weight is 3000 or more, aggregation of the coloring material can be further suppressed, and higher viscosity and gelation can be further suppressed. When it is 100,000 or less, the viscosity increase of the copolymer itself can be further suppressed, and the lack of solubility in the organic solvent can be further suppressed.

  As a method for synthesizing the dispersant, a known method can be adopted, and for example, a method described in JP-B-63-30057 can be used.

(Block copolymer type dispersant containing nitrogen atom)
As a copolymer that can be used as a block copolymer type dispersant containing a nitrogen atom, an A-block comprising an A block having a quaternary ammonium base in its side chain and a B block having no quaternary ammonium base, B block copolymer and / or BAB block copolymer are mentioned.

The A block constituting the block copolymer is a quaternary ammonium base, preferably -N ⁺ R _1a R _2a R _3a · Y ⁻ (where R _1a , R _2a and R _3a are each independently a hydrogen atom, Alternatively, it represents an optionally substituted cyclic or chain hydrocarbon group, or two or more of R _1a , R _2a and R _3a may be bonded to each other to form a cyclic structure. -Represents a counter anion.) And has a quaternary ammonium base. The quaternary ammonium base may be directly bonded to the main chain, but may be bonded to the main chain via a divalent linking group.

In -N ⁺ R _1a R _2a R _3a , as a cyclic structure formed by combining two or more of R _1a , R _2a and R _3a with each other, for example, a 5- to 7-membered nitrogen-containing heterocyclic monocycle or A condensed ring formed by condensing two of these may be mentioned. The nitrogen-containing heterocycle preferably has no aromaticity, more preferably a saturated ring. Specifically, the nitrogen-containing heterocyclic ring shown below is mentioned, for example.

In the nitrogen-containing heterocyclic ring, R represents any group of R _{1a to} R _3a .
These cyclic structures may further have a substituent.
As _R 1a _{to R 3a} in the ^{_{-N + R 1a R 2a R 3a}} , and more preferred may have an alkyl group, or a substituent having carbon atoms of 1 to 3 may have a substituent It is a phenyl group.
As the A block, those containing a partial structure represented by the following general formula (1A) are particularly preferable.

In General Formula (1A), R _1a , R _2a , and R _3a each independently represent a hydrogen atom or an optionally substituted cyclic or chain hydrocarbon group. Alternatively, two or more of R _1a , R _2a and R _3a may be bonded to each other to form a cyclic structure. R _4a represents a hydrogen atom or a methyl group. X represents a divalent linking group, and Y ⁻ represents a counter anion.
In the general formula (1A), examples of the divalent linking group X include, for example, an alkylene group having 1 to 10 carbon atoms, an arylene group, —CONH—R _5a —, —COO—R _6a — (provided that R _5a and R _{5 6a} represents a direct bond, an alkylene group having 1 to 10 carbon atoms, or an ether group having 1 to 10 carbon atoms (—R _7a —O—R _8a —: R _7a and R _8a are each independently an alkylene group). And the like, preferably —COO—R _6a —.

Examples of Y ⁻ which is a counter anion include Cl ⁻ , Br ⁻ , I ⁻ −, ClO ₄ ⁻ , BF ₄ ⁻ , CH ₃ COO ⁻ and PF ₆ ⁻ .
Two or more kinds of partial structures containing the specific quaternary ammonium base as described above may be contained in one A block. In that case, two or more quaternary ammonium base-containing partial structures may be contained in the A block in any form of random copolymerization or block copolymerization. Moreover, the partial structure which does not contain this quaternary ammonium base may be contained in the A block, and examples of the partial structure include a partial structure derived from a (meth) acrylic acid ester monomer described later. It is done. The content in the A block of the partial structure not containing the quaternary ammonium base is preferably 0 to 50% by mass, more preferably 0 to 20% by mass, but the partial structure not containing the quaternary ammonium base is in the A block. It is most preferable that it is not contained in.

  On the other hand, as the B block constituting the block copolymer, for example, styrene monomers such as styrene and α-methylstyrene; methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, ( Such as isopropyl (meth) acrylate, butyl (meth) acrylate, glycidyl (meth) acrylate, benzyl (meth) acrylate, hydroxyethyl (meth) acrylate, glycidyl ethyl acrylate, N, N-dimethylaminoethyl (meth) acrylate, etc. (Meth) acrylic acid ester monomer; (meth) acrylic acid salt monomer such as (meth) acrylic acid chloride; (meth) acrylamide, N-methylolacrylamide, N, N-dimethylacrylamide, N, N-dimethylaminoethyl Acrylamide Which (meth) acrylamide monomer; vinyl acetate; acrylonitrile; allyl glycidyl ether, crotonic acid glycidyl ether; N- methacryloyl morpholine, polymer structure obtained by copolymerizing comonomers such.

  The B block is particularly preferably a partial structure derived from a (meth) acrylic acid ester monomer represented by the following general formula (1B). In the present specification, “(meth) acryl”, “(meth) acrylate” and the like mean “acryl or methacryl”, “acrylate or methacrylate” and the like, for example, “(meth) acrylic acid” It shall mean “acrylic acid or methacrylic acid”.

In General Formula (1B), R _9a represents a hydrogen atom or a methyl group. R _10a represents a cyclic or chain alkyl group which may have a substituent, an allyl group which may have a substituent, or an aralkyl group which may have a substituent.

Two or more types of partial structures derived from (meth) acrylic acid ester monomers may be contained in one B block. Of course, the B block may further contain a partial structure other than these. When a partial structure derived from two or more monomers is present in a B block that does not contain a quaternary ammonium base, each partial structure is contained in the B block in any form of random copolymerization or block copolymerization. May be.
When the B block contains a partial structure other than the partial structure derived from the (meth) acrylate monomer, the content in the B block of the partial structure other than the (meth) acrylate monomer is preferably Is 0 to 50% by mass, more preferably 0 to 20% by mass, but it is most preferable that a partial structure other than the meth) acrylic acid ester monomer is not included in the B block.

  An AB block or a B-A-B block copolymer composed of such an A block and a B block is prepared, for example, by the living polymerization method shown below.

  The living polymerization method includes an anion living polymerization method, a cation living polymerization method, and a radical living polymerization method. In the anion living polymerization method, the polymerization active species is an anion, for example, shown in the following scheme.

  In the radical living polymerization method, the polymerization active species is a radical, and is represented by the following scheme, for example.

  In the synthesis of the block copolymer, JP-A-9-62002, P. Lutz, P. Masson et al, Polym. Bull. 12, 79 (1984), BC Anderson, GD Andrews et al. , Macromolecules, 14, 1601 (1981), K. Hatada, K. Ute, et al, Polym. J. 17, 977 (1985), 18, 1037 (1986), Koichi Right hand, Koichi Hatada, Polymer processing, 36 366 (1987), Toshinobu Higashimura, Mitsuo Sawamoto, Polymer Journal, 46, 189 (1989), M. Kuroki, T. Aida, J. Am. Chem. Sic, 109, 4737 (1987), Takuzo Aida Inoue Shohei, Synthetic Organic Chemistry, 43, 300 (1985), DY Sogoh, WR Hertler et al, Macromolecules, 20, 1473 (1987), etc. can be employed.

  The block copolymer may be an AB block copolymer or a B-A-B block copolymer, from the viewpoint of better heat resistance and dispersibility. The A block / B block ratio (mass ratio) that constitutes is usually 1/99 or more, preferably 5/95 or more, and usually 80/20 or less, preferably 60/40 or less.

The amount of the quaternary ammonium base in 1 g of the AB block copolymer and the BAB block copolymer is usually 0.1 to 10 mmol from the viewpoint of better heat resistance and dispersibility. Preferably there is.
Such a block copolymer usually contains an amino group produced in the production process, but its amine value is about 1 to 100 mg-KOH / g. The amine value is a value expressed in mg of KOH corresponding to the acid value after neutralization titration of a basic amino group with an acid.

(Specific resin)
The most preferable dispersant in the present invention includes (i) a main chain portion having a nitrogen atom, and (ii) a group having a functional group having a pKa of 14 or less and bonded to a nitrogen atom present in the main chain portion. A resin (specific resin) having “X” and (iii) a side chain including an oligomer chain or a polymer chain “Y” having a number average molecular weight of 500 to 1,000,000 is mentioned.
Hereinafter, the specific resin will be described in detail.

(I) Main chain portion having nitrogen atom The specific resin is composed of (i) a main chain portion having a nitrogen atom. Thereby, the adsorptive power to the pigment surface can be improved and the interaction between the pigments can be reduced.
The specific resin preferably has a main chain portion composed of an oligomer or polymer containing a known amino group, more preferably a primary or secondary amino group. More specifically, examples of the oligomer or polymer containing an amino group include poly (lower alkyleneimine), polyallylamine, polydiallylamine, metaxylenediamine-epichlorohydrin polycondensate, polyvinylamine, and 2-dialkyl (meth) acrylate. A main chain structure selected from aminoethyl- (meth) acrylic acid ester copolymers and the like is preferable.
The poly (lower alkyleneimine) may be chain-like or network-like, but the dispersion stability and the material supply ability are particularly improved by being network-like.

  The number average molecular weight of the main chain portion in the specific resin is preferably from 100 to 10,000, more preferably from 200 to 5,000, more preferably from 300 to 2,000, and particularly in the range of the number average molecular weight from 500 to 1500. It is most preferable from the viewpoint of both dispersion stability and developability. The molecular weight of the main chain is determined from the ratio of the terminal group and the hydrogen atom integral value of the main chain measured by nuclear magnetic resonance spectroscopy, or by measuring the molecular weight of the oligomer or polymer containing the amino group as the raw material. Can do.

  The main chain portion of the specific resin is particularly preferably composed of a poly (lower alkylene imine) or a polyallylamine skeleton. In the present invention, the term “lower” in poly (lower alkyleneimine) indicates that the number of carbon atoms is 1 to 5, and the term “lower alkyleneimine” refers to an alkyleneimine having 1 to 5 carbon atoms.

  The specific resin is a structure having a repeating unit represented by the general formula (I-1) and a repeating unit represented by the general formula (I-2), or a repeating unit represented by the general formula (II-1). And a structure containing a repeating unit represented by formula (II-2).

<< Repeating unit represented by general formula (I-1) and repeating unit represented by general formula (I-2) >>
The repeating unit represented by the general formula (I-1) and the repeating unit represented by the general formula (I-2), which are preferable components of the specific resin, will be described in detail.

In general formulas (I-1) and (I-2), R ¹ and R ² represent a hydrogen atom, a halogen atom, or an alkyl group. a represents an integer of 1 to 5. * Represents a connecting part between repeating units. X represents a group containing a functional group having a pKa of 14 or less. Y represents an oligomer chain or a polymer chain having a number average molecular weight of 500 to 1,000,000.

  The specific resin has a repeating unit represented by the general formula (I-3) as a copolymer component in addition to the repeating unit represented by the general formula (I-1) or the general formula (I-2). Is preferred. By using such a repeating unit in combination, the dispersion performance is further improved when this resin is used as a fine particle dispersant such as a pigment.

In general formula (I-3), R ¹ , R ² and a have the same meaning as in general formula (I-1). Y ′ represents an oligomer chain or a polymer chain having an anionic group and a number average molecular weight of 500 to 1,000,000. The repeating unit represented by the general formula (I-3) is obtained by adding an oligomer or polymer having a group that reacts with an amine to form a salt to a resin having a primary or secondary amino group in the main chain. It can be formed by reacting. Examples of the anionic group, CO ₂ ^- or SO ₃ ^- are preferred, CO ₂ ^- is most preferred. The anionic group is preferably at the terminal position of the oligomer chain or polymer chain of Y ′.

In General Formula (I-1), General Formula (I-2), and General Formula (I-3), R ¹ and R ² are particularly preferably hydrogen atoms. a is preferably 2 from the viewpoint of raw material availability.

  In addition to the repeating units represented by the general formula (I-1), general formula (I-2) and general formula (I-3), the specific resin includes a lower alkyleneimine containing a primary or tertiary amino group. It may be included as a repeating unit. The nitrogen atom in such a lower alkyleneimine repeating unit further includes a group represented by X, Y or Y ′ in the general formula (I-1), (I-2) or (I-3). It may be bonded. Resins containing both a repeating unit having a group represented by X and a repeating unit having Y bonded to the main chain structure are also included in the specific resin.

  The repeating unit represented by the general formula (I-1) is a repeating unit having a group X containing a functional group having a pKa of 14 or less. Such a repeating unit is a viewpoint of storage stability and developability. Therefore, the content is preferably 1 to 80 mol%, and most preferably 3 to 50 mol% in all repeating units contained in the resin of the present invention.

The repeating unit represented by the general formula (I-2) is a repeating unit having an oligomer chain or a polymer chain Y having a number average molecular weight of 500 to 1,000,000. Such a repeating unit is storage stable. From the viewpoint of property, it is preferable to contain 10 to 90 mol%, and most preferably 30 to 70 mol% in all repeating units of the resin of the present invention.
In order to examine the content ratio between the two, from the viewpoint of the balance between dispersion stability and hydrophilicity / hydrophobicity, the repeating unit (I-1) :( I-2) has a molar ratio in the range of 10: 1 to 1: 100. And is more preferably in the range of 1: 1 to 1:10.

In addition, the repeating unit represented by the general formula (I-3) used in combination as desired has a partial structure containing an oligomer chain or a polymer chain having a number average molecular weight of 500 to 1,000,000 as the main chain nitrogen. In terms of the effect, it is preferably contained in an amount of 0.5 to 20 mol%, and preferably in an amount of 1 to 10 mol% in all repeating units of the specific resin. Most preferred.
It can be confirmed that the polymer chain “Y” is ionically bonded by infrared spectroscopy, acid value titration or base titration.

<< Repeating unit represented by general formula (II-1) and repeating unit represented by general formula (II-2) >>
The repeating unit represented by the general formula (II-1) and the repeating unit represented by the general formula (II-2), which are other preferable components of the specific resin, will be described in detail.

In general formulas (II-1) and (II-2), R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom, a halogen atom or an alkyl group. *, X and Y have the same meanings as *, X and Y in formulas (I-1) and (I-2).

  In addition to the repeating unit represented by the general formula (II-1) and the repeating unit represented by the general formula (II-2), the specific resin further includes the repeating unit represented by the general formula (II-3). It is preferable to contain as a copolymerization component. By using such a repeating unit in combination, the dispersion performance is improved.

In general formula (II-3), R ³ , R ⁴ , R ⁵ and R ⁶ have the same meaning as in general formula (II-1). Y ′ has the same meaning as Y ′ in formula (I-3).

In the general formulas (II-1), (II-2) and (II-3), R ³ , R ⁴ , R ⁵ and R ⁶ are preferably hydrogen atoms from the viewpoint of availability of raw materials.

The general formula (II-1) is a repeating unit having a group containing a functional group X having a pKa of 14 or less. Such a repeating unit is added to the resin of the present invention from the viewpoint of storage stability and developability. It is preferable to contain 1-80 mol% in all the repeating units contained, and it is most preferable to contain 3-50 mol%.
The general formula (II-2) is a repeating unit having an oligomer chain or a polymer chain Y having a number average molecular weight of 500 to 1,000,000. Such a repeating unit is represented by the present invention from the viewpoint of storage stability. It is preferable to contain 10-90 mol% in all the repeating units of this resin, and it is most preferable to contain 30-70 mol%.

In order to examine the content ratio of both, from the viewpoint of dispersion stability and hydrophilicity / hydrophobicity balance, the repeating unit (II-1) :( II-2) is in the range of 10: 1 to 1: 100 in molar ratio. And is more preferably in the range of 1: 1 to 1:10.
The repeating unit represented by the general formula (II-3) used in combination is preferably contained in an amount of 0.5 to 20 mol%, preferably 1 to 10 mol%, in all repeating units of the specific resin. Most preferred.
In particular resin, it is most preferable to include both the repeating unit represented by the general formula (I-1) and the repeating unit represented by the general formula (I-2) from the viewpoint of dispersibility.

(Ii) a group “X” containing a functional group with a pKa of 14 or less
X represents a group containing a functional group having a pKa of 14 or less at a water temperature of 25 ° C. Here, “pKa” has the definition described in Chemical Handbook (II) (4th revised edition, 1993, edited by The Chemical Society of Japan, Maruzen Co., Ltd.).
The “functional group having a pKa of 14 or less” is not particularly limited as long as its physical properties satisfy this condition, and examples thereof include a known functional group having a pKa that satisfies the above range. the, for example, (about pKa 3 to 5) carboxylic acids, sulfonic acid (about pKa -3 to-2), phosphoric acid (about 2 _pKa), - COCH 2 CO- (about pKa 8 to 10), - COCH ₂ CN (about pKa 8 to 11), —CONHCO—, phenolic hydroxyl group, —R _F CH ₂ OH or — (R _F ) ₂ CHOH (R _F represents a perfluoroalkyl group, pKa about 9 to 11)), sulfonamide group mentioned (pKa about 9 to 11), etc., especially (about pKa 3 to 5) carboxylic acids, sulfonic acid (about _{pKa -3~-2), - COCH} 2 CO- ( about pKa 8 to 10 It is preferred.

The group “X” containing a functional group having a pKa of 14 or less is usually bonded directly to a nitrogen atom contained in the main chain structure. In addition to the covalent bond, they may be linked in a form that forms a salt by ionic bond.
The molecular weight of the group “X” containing a functional group having a pKa of 14 or less is preferably 50 to 1000, and most preferably 50 to 500. When the molecular weight is within this range, developability and dispersibility become better.

As the group “X” containing a functional group having a pKa of 14 or less, in particular, a structure represented by the following general formula (V-1), general formula (V-2) or general formula (V-3) is used. What has is preferable.

  In General Formula (V-1) and General Formula (V-2), U represents a single bond or a divalent linking group. d and e each independently represents 0 or 1; In general formula (V-3), W represents an acyl group or an alkoxycarbonyl group.

Examples of the divalent linking group represented by U include alkylene (more specifically, for example, —CH ₂ —, —CH ₂ CH ₂ —, —CH ₂ CHMe—, — (CH ₂ ) ₅ —. , —CH ₂ CH (n—C ₁₀ H ₂₁ ) —, etc.), oxygen-containing alkylene (more specifically, for example, —CH ₂ OCH ₂ —, —CH ₂ CH ₂ OCH ₂ CH ₂ —, etc.) , A cycloalkylene group (eg, cyclobutylene, cyclopentylene, cyclohexylene, cyclooctylene, etc.), an arylene group (eg, phenylene, tolylene, biphenylene, naphthylene, furylene, pyrrolylene, etc.), alkyleneoxy (eg, ethyleneoxy, Propyleneoxy, phenyleneoxy, etc.), etc., in particular, an alkylene group having 1 to 30 carbon atoms and a cyclohexane having 5 to 20 carbon atoms. Alkylene group, or preferably an arylene group having 6 to 20 carbon atoms, alkylene group having 1 to 20 carbon atoms, an arylene group of a cycloalkylene group or a C6-15 having 5 to 10 carbon atoms most preferred. Further, from the viewpoint of productivity, d is preferably 1, and e is preferably 0.

  W represents an acyl group or an alkoxycarbonyl group. As the acyl group in W, an acyl group having 1 to 30 carbon atoms (for example, formyl, acetyl, n-propanoyl, benzoyl and the like) is preferable, and acetyl is particularly preferable. As the alkoxycarbonyl group in W, W is particularly preferably an acyl group, and an acetyl group is preferable from the viewpoint of ease of production and availability of a raw material (precursor X ′ of X).

  “X” is characterized by being bonded to a nitrogen atom in the main chain. Thereby, the dispersibility and dispersion stability of the pigment are dramatically improved. The reason for this is unknown, but it is thought as follows. That is, the nitrogen atom in the main chain part exists in the structure of an amino group, an ammonium group or an amide group, and these are adsorbed by interacting with the acidic part on the pigment surface, such as a hydrogen bond or an ionic bond. Conceivable. Furthermore, since “X” of the present invention functions as an acid group, it can interact with a basic part (such as a nitrogen atom) or a metal atom (such as copper of copper phthalocyanine) of the pigment. In other words, since the resin of the present invention can adsorb both the basic part and the acidic part of the pigment with nitrogen atoms and “X”, the adsorbing ability is improved, and the dispersibility and storage stability are dramatically improved. It is thought to have improved.

  Furthermore, since “X” includes a functional group having a pKa of 14 or less as a partial structure, “X” also functions as an alkali-soluble group. Therefore, when this specific resin is used for a curable composition, etc., it is partially cured by imparting energy to the coating film, and when used for applications such as forming a pattern by dissolving and removing unexposed areas, The developability of the region into an alkaline developer is improved, and in a colored curable composition using a pigment dispersion containing an ultrafine pigment, a pigment dispersion having a high pigment content, and a colored curable composition, It is thought that dispersion stability and developability can be established.

The content of the functional group having a pKa of 14 or less in X is not particularly limited, but is preferably 0.01 to 5 mmol, and most preferably 0.05 to 1 mmol, with respect to 1 g of the specific resin. Within this range, the dispersibility and dispersion stability of the pigment in the pigment dispersion composition are improved, and when the pigment dispersion composition is used in the curable composition, the developability of the uncured portion is excellent. Further, from the viewpoint of the acid value, the amount that the acid value of the specific resin is about 5 to 50 mgKOH / g is included, from the viewpoint of developability when the specific resin is used in the pattern-forming curable composition. To preferred.
The acid value titration can be performed by a known method. For example, an indicator method (a method for determining a neutralization point with an indicator), a potentiometric method, or the like can be used. The titration solution used for the acid value titration may be a commercially available sodium hydroxide aqueous solution, but water such as a functional group having a relatively high pKa (for example, —COCH ₂ CO—, phenolic hydroxyl group, etc.). When it is difficult to measure the acid value with an aqueous sodium oxide solution, it is possible to prepare a nonaqueous titrant such as a sodium methoxide-dioxane solution and measure the acid value in a nonaqueous solvent system.

(Iii) Oligomer chain or polymer chain “Y” having a number average molecular weight of 500 to 100,000
“Y” represents an oligomer chain or a polymer chain having a number average molecular weight of 500 to 100,000. Examples of Y include known polymer chains such as polyester, polyamide, polyimide, and poly (meth) acrylic acid ester that can be connected to the main chain portion of the specific resin. The binding site with the main chain portion of the specific resin of Y is preferably a terminal.

  Y is preferably bonded to a nitrogen atom in the main chain. The bonding mode between Y and the main chain is covalent bond, ionic bond, or a mixture of covalent bond and ionic bond. The ratio of the binding mode between Y and the main chain is covalent bond: ionic bond = 100: 0 to 0: 100, preferably 95: 5 to 5:95, more preferably 90:10 to 10:90, The range of 95: 5 to 80:20 is most preferred. By setting the bonding mode between the covalent bond and the ionic bond within this preferable range, the dispersibility and dispersion stability are improved, and the solvent solubility is improved.

  Y is preferably ionically bonded to the nitrogen atom in the main chain portion as an amide bond or carboxylate.

The number average molecular weight of Y can be measured by the polystyrene conversion value by GPC method. The number average molecular weight of Y is particularly preferably 1,000 to 50,000, and most preferably 1,000 to 30,000 from the viewpoints of dispersibility, dispersion stability, and developability.
It is preferable that two or more side chain structures represented by Y are connected to the main chain portion in one molecule of the specific resin, and most preferably five or more are connected.

  In particular, Y preferably has a structure represented by the general formula (III-1).

  In general formula (III-1), Z is a polymer or oligomer having a polyester chain as a partial structure, and a residue obtained by removing a carboxy group from a polyester having a free carboxylic acid represented by the following general formula (IV): To express.

  In general formula (IV), Z is synonymous with Z in general formula (III-1).

  When specific resin contains the repeating unit represented by general formula (I-3) or (II-3), it is preferable that Y 'is general formula (III-2).

  In General Formula (III-2), Z has the same meaning as Z in General Formula (III-1).

  Polyester having a carboxy group at one end (polyester represented by the general formula (IV)) includes (IV-1) polycondensation of carboxylic acid and lactone, (IV-2) polycondensation of hydroxy group-containing carboxylic acid, (IV -3) It can be obtained by polycondensation of a dihydric alcohol and a divalent carboxylic acid (or a cyclic acid anhydride).

(IV-1) The carboxylic acid used in the polycondensation reaction of carboxylic acid and lactone is an aliphatic carboxylic acid (preferably a linear or branched carboxylic acid having 1 to 30 carbon atoms, such as formic acid, acetic acid, propionic acid, butyric acid, Valeric acid, n-hexanoic acid, n-octanoic acid, n-decanoic acid, n-dodecanoic acid, palmitic acid, 2-ethylhexanoic acid, cyclohexane acid, etc.), hydroxy group-containing carboxylic acid (C1-C30 direct) A chain or branched hydroxy group-containing carboxylic acid is preferable, for example, glycolic acid, lactic acid, 3-hydroxypropionic acid, 4-hydroxydodecanoic acid, 5-hydroxydodecanoic acid, ricinoleic acid, 12-hydroxydodecanoic acid, 12-hydroxystearic acid. Acid, 2,2-bis (hydroxymethyl) butyric acid, etc.), in particular, straight chain aliphatic having 6 to 20 carbon atoms. A carboxylic acid or a C1-C20 hydroxy group-containing carboxylic acid is preferred. These carboxylic acids may be used as a mixture. As the lactone, known lactones can be used, for example, β-propiolactone, β-butyrolactone, γ-butyrolactone, γ-hexanolactone, γ-octanolactone, δ-valerolactone, δ-hexalanolactone. , Δ-octanolactone, ε-caprolactone, δ-dodecanolactone, α-methyl-γ-butyrolactone, and the like, and ε-caprolactone is particularly preferable from the viewpoint of reactivity and availability.
These lactones may be used as a mixture of plural kinds.
The charging ratio at the time of the reaction between the carboxylic acid and the lactone cannot be uniquely determined because it depends on the molecular weight of the target polyester chain, but is preferably carboxylic acid: lactone = 1: 1 to 1: 1,000, and 1: 3 to 1: 500 is most preferred.

(IV-2) The hydroxy group-containing carboxylic acid in the polycondensation of the hydroxy group-containing carboxylic acid is the same as the hydroxy group-containing carboxylic acid in (IV-1), and the preferred range is also the same.
(IV-3) As the dihydric alcohol in the polycondensation reaction of the dihydric alcohol and the divalent carboxylic acid (or cyclic acid anhydride), a linear or branched aliphatic diol (a diol having 2 to 30 carbon atoms is preferable, For example, ethylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, 1,2-propanediol, 1,3-propanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, etc. In particular, aliphatic diols having 2 to 20 carbon atoms are preferred.
As the divalent carboxylic acid, a linear or branched divalent aliphatic carboxylic acid (preferably a divalent aliphatic carboxylic acid having 1 to 30 carbon atoms is preferable. For example, succinic acid, maleic acid, adipic acid, sebacic acid, Dodecanedioic acid, glutaric acid, suberic acid, tartaric acid, oxalic acid, malonic acid, etc.), and in particular, a divalent carboxylic acid having 3 to 20 carbon atoms is preferred. Further, acid anhydrides equivalent to these divalent carboxylic acids (for example, succinic anhydride, glutaric anhydride, etc.) may be used.
The divalent carboxylic acid and the dihydric alcohol are preferably charged at a molar ratio of 1: 1. This makes it possible to introduce a carboxylic acid at the terminal.

The polycondensation during the production of the polyester is preferably performed by adding a catalyst. As the catalyst, a catalyst that functions as a Lewis acid is preferable. For example, a Ti compound (eg, Ti (OBu) ₄ , Ti (O—Pr) _4, etc.), a Sn compound (eg, tin octylate, dibutyltin oxide, dibutyltin laurate) Monobutyltin hydroxybutyl oxide, stannic chloride, butyltin dioxide, etc.), protonic acids (for example, sulfuric acid, paratoluenesulfonic acid, etc.) and the like. The catalyst amount is preferably from 0.01 to 10 mol%, most preferably from 0.1 to 5 mol%, based on the number of moles of all monomers. The reaction temperature is preferably 80 to 250 ° C, and most preferably 100 to 180 ° C. Although reaction time changes with reaction conditions, it is 1 to 24 hours in general.

  The number average molecular weight of the polyester can be measured as a polystyrene converted value by the GPC method. The number average molecular weight of the polyester is 1,000 to 1,000,000, preferably 2,000 to 100,000, and most preferably 3,000 to 50,000. When the molecular weight is in this range, both dispersibility and developability can be achieved.

  The polyester partial structure forming the polymer chain in Y is in particular a polyester obtained by (IV-1) polycondensation of carboxylic acid and lactone and (IV-2) polycondensation of hydroxy group-containing carboxylic acid. Is preferable from the viewpoint of ease of manufacture.

In addition, in the pigment dispersion composition of the present invention, in addition to the above-described polymer dispersant, other polymer compounds shown below may be used.
As other polymer compounds, natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, and the like are used.
The natural resin is typically rosin, and the modified natural resin includes rosin derivatives, fiber derivatives, rubber derivatives, protein derivatives and oligomers thereof. Examples of the synthetic resin include an epoxy resin, an acrylic resin, a maleic acid resin, a butyral resin, a polyester resin, a melamine resin, a phenol resin, and a polyurethane resin. Examples of synthetic resins modified with natural resins include rosin-modified maleic acid resins and rosin-modified phenolic resins.
Synthetic resins include polyamidoamine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, polyurethane, polyester, poly (meth) acrylate, (meth) acrylic copolymer, naphthalenesulfonic acid formalin condensate Is mentioned.

  The content of the dispersant in the pigment dispersion composition of the present invention is, as a mass ratio, pigment (all pigments including at least the azo pigment represented by the general formula (1)): dispersant = 1: 0.1 1: 2 is preferable, More preferably, it is 1: 0.2-1: 1, More preferably, it is 1: 0.4-1: 0.7.

<Solvent etc.>
The pigment dispersion composition of the present invention can be suitably prepared using a solvent.
Solvents include fatty acid esters such as ethyl acetate, butyl acetate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diacetone alcohol; benzene, toluene, xylene Aromatics such as methanol, ethanol, n-propanol, isopropanol, n-butanol; ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol , Polypropylene glycol, trimethylene glycol, hexanetriol, etc. Recalls; Glycerin; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and other alkylene glycol monoalkyl ethers; triethylene glycol dimethyl ether, tri Alkylene glycol dialkyl ethers such as ethylene glycol diethyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether; ethers such as tetrahydrofuran, dioxane, diethylene glycol diethyl ether; monoethanolamine, diethanolamine, triethanolamine Nitrogen-containing polar organic solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, 2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone ; Water etc. are mentioned.

Among these solvents, those which are water-soluble may be mixed with water and used as an aqueous medium. Moreover, you may mix and use 2 or more types chosen from said solvent except water, and may use it as an oil-based medium.
The pigment dispersion composition of the present invention may contain other components as necessary.

<Preparation of pigment dispersion composition>
The pigment dispersion composition of the present invention can be prepared by passing through a mixing and dispersing step of mixing and dispersing using various mixers and dispersers.
The mixing and dispersing step preferably comprises kneading and dispersing followed by fine dispersion treatment, but kneading and dispersing can be omitted.

Specifically, the pigment dispersion composition of the present invention is obtained by, for example, dispersing the azo pigment represented by the general formula (1), the acidic functional group-containing derivative, the dispersant, and the solvent using a dispersion apparatus. It is preferable to obtain.
Dispersing devices include simple stirrer, impeller stirring method, in-line stirring method, mill method (for example, colloid mill, ball mill, sand mill, bead mill, attritor, roll mill, jet mill, paint shaker, agitator mill, etc.), ultrasonic method Further, a high-pressure emulsification dispersion system (high-pressure homogenizer; specific commercially available devices such as gorin homogenizer, microfluidizer, DeBEE2000, etc.) can be used.

More specifically, the pigment dispersion composition of the present invention includes, for example, an azo pigment represented by the general formula (1), an acidic functional group-containing derivative, a dispersant, and a solvent in a vertical or horizontal sand grinder, Using a pin mill, a slit mill, an ultrasonic disperser or the like, fine dispersion can be performed with beads made of glass having a particle diameter of 0.01 mm to 1 mm, zirconia, or the like.
In addition, before carrying out fine dispersion with beads, use a two-roll, three-roll, ball mill, tron mill, disper, kneader, kneader, homogenizer, blender, single-screw or twin-screw extruder, etc. It is also possible to carry out the kneading and dispersing process while giving.

For details on kneading and dispersing, see T.W. C. “Paint Flow” by Patton
and Pigment Dispersion "(published by John Wiley and Sons, 1964), etc., and the method described herein can also be applied to the present invention.

[Colored curable composition]
The colored curable composition of the present invention contains the above-described pigment dispersion composition of the present invention, a photopolymerization initiator, and a polymerizable compound.
Since the colored curable composition of the present invention has the above-described configuration, even when the development conditions are strengthened when forming the colored pattern on the support, the adhesion of the colored pattern to the support and the residue It is possible to achieve both generation suppression.
Further, in the colored curable composition of the present invention, the dispersion stability of the azo pigment represented by the general formula (1) is improved, and the heat resistance of the colored pattern can be improved when the colored pattern is obtained. . The reason why the heat resistance of the formed colored pattern can be improved by improving the dispersion stability is not clear, but it is presumed that the decrease in transmittance due to the aggregation of the pigment can be suppressed. However, the present invention is not limited by this estimation.

<Photopolymerization initiator>
The colored curable composition of the present invention contains a photopolymerization initiator.
Examples of the photopolymerization initiator include a benzophenone photopolymerization initiator, an acetophenone photopolymerization initiator, a benzoin photopolymerization initiator, a benzoin ether photopolymerization initiator, a thioxanthone photopolymerization initiator, and an anthraquinone photopolymerization initiator. 1 or more types selected from an agent, a naphthoquinone photopolymerization initiator, a triazine photopolymerization initiator, and an oxime photopolymerization initiator. A known photosensitizer may be used together with these photopolymerization initiators.
Among these, an oxime photopolymerization initiator is preferable from the viewpoint of improving pattern formability (pattern curability) and suppressing development residue.

  As the oxime photopolymerization initiator, a compound that is decomposed by light and initiates and accelerates a polymerization reaction of a radical polymerizable monomer is preferable, and a compound having absorption in a wavelength region of 300 to 500 nm is more preferable. The reason why the oxime photopolymerization initiator is good is presumed that a rectangular pattern can be formed after development because the decomposition efficiency by light is extremely high and higher curability is obtained.

  Examples of the oxime photopolymerization initiator in the present invention include J.I. C. S. Perkin II (1979) 1653-1660), J. MoI. C. S. Perkin II (1979) 156-162, Journal of Photopolymer Science and Technology (1995) 202-232, JP 2000-66385 A, JP 2000-80068 A (paragraph numbers 0004-0296), Special Table 1004-534797 And the compounds described in JP-A-2001-233842, WO-02 / 100903A1, JP-A-2006-342166 (paragraph numbers 0004-0264), and the like.

  Moreover, as an oxime system initiator, the compound represented by the following general formula (O-I) is preferable from a viewpoint of obtaining the effect of pattern formation improvement and development residue suppression more effectively.

In General Formula (O-I), R ¹ represents an alkyl group or an aryl group which may have a substituent. R ² represents an acyl group that may have a substituent, an alkyl group that may have a substituent, an aryl group that may have a substituent, an alkenyl group that may have a substituent, or a substituent. Represents an alkynyl group which may have a substituent or an acetyl group which may have a substituent. R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ each independently represent a hydrogen atom or a monovalent organic group. R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ may be bonded to each other to form a 5-membered ring or a 6-membered ring.
Here, examples of the substituent that can be introduced into the alkyl group, aryl group, and acyl group include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an i-propyl group, a t-butyl group, A chloro group, a bromo group, etc. are mentioned.

Preferred R ¹ is an alkyl group having 1 to 12 carbon atoms or a 4- (alkylthio having 1 to 4 carbon atoms) phenyl group. Preferred R ² is an acetyl group or an acyl group.
Preferred organic groups when R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ represent a monovalent organic group include a methyl group, an ethyl group, a methoxy group, an ethoxy group, a phenoxy group, and a thiophenoxy group. Among them, a phenoxy group and a thiophenoxy group are preferable.
R ³ , R ⁴ , R ⁶ and R ⁷ are preferably hydrogen atoms. R ⁵ is preferably a group represented by —SR ⁸ , wherein R ⁸ represents a phenyl group which may have a substituent. More preferred R ⁵ is a group represented by the following formula.

  Among the oxime initiators represented by the general formula (O-I), examples of suitable oxime initiators include compounds represented by the following general formula (O-II).

In general formula (O-II), R ⁹ has the same meaning as R ² in general formula (O-I). X ³ represents a monovalent substituent, and when n 2 represents an integer of 2 to 5, a plurality of X ³ may be the same or different from each other. A ⁰ represents a divalent organic group, and Ar represents an aryl group. n2 is an integer of 1-5.

In the general formula (O-II), examples of the monovalent organic group represented by X ³ include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an i-propyl group, and a t-butyl group. , A methoxy group, an ethoxy group, and the like.
In the general formula (O-II), examples of the divalent organic group represented by A ⁰ include alkylene having 1 to 12 carbon atoms, cyclohexylene, and alkynylene.

In general formula (O-II), the aryl group represented by Ar is preferably an aryl group having 6 to 30 carbon atoms, and the aryl group may have a substituent. Examples of the substituent that can be introduced into the aryl group include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an i-propyl group, a t-butyl group, a methoxy group, and an ethoxy group.
Among these, Ar is preferably a substituted or unsubstituted phenyl group from the viewpoint of increasing sensitivity and suppressing coloring due to heating.

  In the present invention, specific examples of the oxime photoinitiator include the following compounds (I-1) to (I-6). Particularly preferred compounds are included in the general formula (O-I). (I-2) to (I-6). Among them, (I-2) is most preferable because the development residue at the time of pattern formation is particularly small.

  Specific names of oxime photopolymerization initiators that can be used in the present invention include 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-butanedione, 2 -(O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-pentanedione, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2- Hexanedione, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-heptanedione, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl]- 1,2-octanedione, 2- (O-benzoyloxime) -1- [4- (methylphenylthio) phenyl] -1,2-butanedione, 2- (O-ben Iloxime) -1- [4- (ethylphenylthio) phenyl] -1,2-butanedione, 2- (O-benzoyloxime) -1- [4- (butylphenylthio) phenyl] -1,2-butanedione, 1- (O-acetyloxime) -1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone, 1- (O-acetyloxime) -1- [9-methyl -6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone, 1- (O-acetyloxime) -1- [9-propyl-6- (2-methylbenzoyl) -9H-carbazole-3 -Yl] ethanone, 1- (O-acetyloxime) -1- [9-ethyl-6- (2-ethylbenzoyl) -9H-carbazol-3-yl] ethanone, 1- (O- Cetyl) -1- [9-ethyl-6- (2-butyl benzoyl) -9H- carbazol-3-yl] ethanone and the like. However, it is not limited to these.

  Particularly preferred specific examples of the oxime photopolymerization initiator include 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 1- (O-acetyloxime)- 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone. Examples of such oxime photopolymerization initiators include CGI-124 and CGI-242 (manufactured by Ciba Specialty Chemicals).

  As content of the photoinitiator (for example, oxime system photoinitiator) in the colored curable composition of this invention, it is 1.0 mass%-15.0 mass% in a total solid. Preferably, it is 1.0% by mass to 12.5% by mass, more preferably 1.0% by mass to 10.0% by mass, and 1.0% by mass to 5.0% by mass. It is particularly preferred. Within this range, better sensitivity, pattern formability, and coating film uniformity can be obtained.

  Here, in the present specification, the solid content of the colored curable composition for specifying the blending ratio includes all components contained in the composition excluding the solvent, and is liquid at normal temperature (25 ° C.). These components (for example, a liquid polymerizable compound) are also included in the solid content.

<Polymerizable compound>
The colored curable composition of the present invention contains at least one polymerizable compound.
As the polymerizable compound, a known polymerizable compound may be used, and a monofunctional polymerizable compound may be used, but from the viewpoint of further improving pattern formation, a polyfunctional polymerizable compound is preferable. A trifunctional or higher functional polymerizable compound is more preferable.
The polymerizable compound is preferably an addition polymerizable compound having at least one ethylenically unsaturated double bond, and is selected from compounds having at least one terminal ethylenically unsaturated bond, preferably two or more. It is more preferable. Such a compound group is widely known in the industrial field, and can be used without any particular limitation in the present invention. The polymerizable compound has a chemical form such as a monomer, a prepolymer, that is, a dimer, a trimer and an oligomer, or a mixture thereof and a copolymer thereof.

Examples of monomers and copolymers thereof include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), and esters and amides thereof. In this case, an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, or an amide of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound is used. In addition, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxyl group, amino group or mercapto group with a monofunctional or polyfunctional isocyanate or epoxy, and monofunctional or polyfunctional A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an epoxy group or an epoxy group with a monofunctional or polyfunctional alcohol, amine or thiol, a halogen group or In addition, a substitution reaction product of an unsaturated carboxylic acid ester or amide having a leaving substituent such as a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable. As another example, it is also possible to use a group of compounds substituted with unsaturated phosphonic acid, styrene, vinyl ether or the like instead of the unsaturated carboxylic acid.
Moreover, as a polymeric compound, you may use the polymeric compound described in Unexamined-Japanese-Patent No. 2009-256572 paragraph number 0118-0128.

  In addition, the polymerizable compound in the present invention is described in paragraph numbers 0029 to 0056 of JP2009-244807A and paragraphs 0038 to 0051 of JP2009-229761 from the viewpoint of pattern formation and the like. A photocurable compound (polymerizable compound), for example, at least one polymerizable compound selected from the group of compounds represented by the following general formula (Mi) or (M-ii) preferable.

In general formulas (M-i) and (M-ii), each E independently represents — ((CH ₂ ) _y CH ₂ O) — or — ((CH ₂ ) _y CH (CH ₃ ) O). -Represents each independently an integer of 0 to 10, and each X independently represents an acryloyl group, a methacryloyl group, a hydrogen atom, or a carboxy group.
In general formula (Mi), the sum total of the acryloyl group and the methacryloyl group is 3 or 4, m represents the integer of 0-10 each independently, and the sum of each m is an integer of 0-40. is there. However, when the sum of each m is 0, any one of X is a carboxy group.
In general formula (M-ii), the sum total of acryloyl group and methacryloyl group is 5 or 6, each n independently represents an integer of 0 to 10, and the sum of each n is an integer of 0 to 60. is there. However, when the total of each n is 0, any one of X is a carboxy group.

In general formula (Mi), m is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4. Moreover, the integer of 2-40 is preferable, the integer of 2-16 is more preferable, and the integer of 4-8 is especially preferable as the sum total of each m.
In general formula (M-ii), n is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4. Further, the total of each n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and particularly preferably an integer of 6 to 12.
In general formula (M-i) or the general formula (M-ii) in the _{- ((CH 2) y CH} 2 O) - or _{- ((CH 2) y CH} (CH 3) O) - , the oxygen A form in which the end on the atom side is bonded to X is preferred.

  The compounds represented by the general formula (M-i) or (M-ii) may be used alone or in combination of two or more. In particular, in the general formula (M-ii), a form in which all six Xs are acryloyl groups is preferable.

  The compound represented by the general formula (M-i) or (M-ii) is obtained by a ring-opening addition reaction of ethylene oxide or propylene oxide with pentaerythritol or dipentaerythritol, which is a conventionally known process. It can be synthesized from a step of bonding a ring-opening skeleton and a step of introducing a (meth) acryloyl group by reacting, for example, (meth) acryloyl chloride with a terminal hydroxyl group of the ring-opening skeleton. Each step is a well-known step, and a person skilled in the art can easily synthesize a compound represented by the general formula (Mi) or (M-ii).

  Among the compounds represented by the general formulas (M-i) and (M-ii), pentaerythritol derivatives and / or dipentaerythritol derivatives are more preferable. Specific examples include compounds represented by the following formulas (a) to (f) (hereinafter also referred to as “exemplary compounds (a) to (f)”), and among them, exemplary compounds (a) and (b) ), (C), (f) are preferred.

    Examples of commercially available compounds represented by the general formulas (M-i) and (M-ii) include SR-494, Nippon Kayaku, which is a tetrafunctional acrylate having four ethyleneoxy groups manufactured by Sartomer. Examples thereof include DPCA-60, which is a hexafunctional acrylate having 6 pentyleneoxy groups, and TPA-330, which is a trifunctional acrylate having 3 isobutyleneoxy groups.

  As content of the polymeric compound in the colored curable composition of this invention, it is preferable that it is 5 mass%-70 mass% with respect to the total solid, and it is more preferable that it is 10 mass%-60 mass%. preferable.

<Alkali-soluble resin>
The colored curable composition of the present invention preferably contains an alkali-soluble resin.
When the colored curable composition contains an alkali-soluble resin, the pattern forming property can be further improved when the colored curable composition is applied to pattern formation by a photolithography method.

  The alkali-soluble resin is a linear organic polymer, and promotes at least one alkali-solubility in a molecule (preferably a molecule having an acrylic copolymer or a styrene copolymer as a main chain). It can be appropriately selected from alkali-soluble resins having a group (for example, a carboxy group, a phosphoric acid group, a sulfonic acid group, etc.). Of these, more preferred are those which are soluble in an organic solvent and can be developed with a weak alkaline aqueous solution.

  For example, a known radical polymerization method can be applied to the production of the alkali-soluble resin. Polymerization conditions such as temperature, pressure, type and amount of radical initiator, type of solvent, etc. when producing an alkali-soluble resin by radical polymerization can be easily set by those skilled in the art, and the conditions are determined experimentally. It can also be done.

  As the linear organic polymer, a polymer having a carboxylic acid in the side chain is preferable. For example, JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, JP-B-54-25957, JP-A-59-53836, JP-A-59-71048 As described, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, etc., and side chain Preferred examples also include acidic cellulose derivatives having a carboxylic acid, and polymers having a hydroxyl group and an acid anhydride added to the polymer, and a polymer having a (meth) acryloyl group in the side chain.

Among these, benzyl (meth) acrylate / (meth) acrylic acid copolymers and multi-component copolymers composed of benzyl (meth) acrylate / (meth) acrylic acid / other monomers are particularly suitable.
In addition, those obtained by copolymerizing 2-hydroxyethyl methacrylate are also useful.

  In addition to the above, 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxy-3-phenoxypropyl acrylate / polymethyl methacrylate described in JP-A-7-140654 Macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer Etc.

  As a suitable thing of alkali-soluble resin in this invention, the copolymer of (meth) acrylic acid and the other monomer copolymerizable with this is mentioned especially. Here, (meth) acrylic acid is a general term that combines acrylic acid and methacrylic acid, and (meth) acrylate is also a general term for acrylate and methacrylate.

Examples of other monomers copolymerizable with (meth) acrylic acid include alkyl (meth) acrylates, aryl (meth) acrylates, and vinyl compounds. Here, the hydrogen atom of the alkyl group and the aryl group may be substituted with a substituent.
Specific examples of alkyl (meth) acrylate and aryl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) ) Acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, and the like. .

Examples of the vinyl compound include styrene, α-methylstyrene, vinyl toluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinyl pyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene macromonomer, polymethyl methacrylate macromonomer, CH ₂ = CR ¹ R ² , CH ₂ = C (R ¹ ) (COOR ³ ) [wherein R ¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ² represents an aromatic carbon atom having 6 to 10 carbon atoms. Represents a hydrogen ring, and R ³ represents an alkyl group having 1 to 8 carbon atoms or an aralkyl group having 6 to 12 carbon atoms. And the like.

These other copolymerizable monomers can be used singly or in combination of two or more.
Preferred other copolymerizable monomers are selected from CH ₂ ═CR ¹ R ² , CH ₂ ═C (R ¹ ) (COOR ³ ), phenyl (meth) acrylate, benzyl (meth) acrylate, and styrene. At least one selected from the group consisting of CH ₂ ═CR ¹ R ² and / or CH ₂ ═C (R ¹ ) (COOR ³ ).

  When the alkali-soluble resin is contained, the content in the colored curable composition is preferably 1% by mass to 30% by mass, more preferably 1% by mass to 25%, based on the total solid content of the composition. % By mass, particularly preferably 2% by mass to 20% by mass.

<Solvent>
In general, the colored curable composition of the present invention can be suitably prepared by using a solvent together with the aforementioned components.
Examples of the solvent used include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, and lactic acid. Methyl, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate; methyl 3-oxypropionate, ethyl 3-oxypropionate Alkyl 3-esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, 2-oxy Ethyl propionate, propyl 2-oxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-oxy- Methyl 2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, pyruvate Propyl, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc .; ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol No ethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, etc .; ketones such as methyl ethyl ketone , Cyclohexanone, 2-heptanone, 3-heptanone and the like; aromatic hydrocarbons such as toluene and xylene.

Among these, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, propylene glycol methyl ether acetate, etc. Is preferred.
You may use a solvent in combination of 2 or more types besides using independently.

<Surfactant>
Various surfactants may be added to the colored curable composition of the present invention from the viewpoint of further improving applicability. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used.

In particular, the colored curable composition of the present invention contains a fluorosurfactant, so that the liquid properties (particularly fluidity) when prepared as a coating liquid are further improved, so that the coating thickness is uniform. And the liquid-saving property can be further improved.
That is, when a film is formed using a coating liquid to which a colored curable composition containing a fluorosurfactant is applied, by reducing the interfacial tension between the coated surface and the coating liquid, The wettability is improved, and the coating property to the coated surface is improved. For this reason, even when a thin film of about several μm is formed with a small amount of liquid, it is effective in that it is possible to more suitably form a film having a uniform thickness with small thickness unevenness.

  The fluorine content in the fluorosurfactant is preferably 3% by mass to 40% by mass, more preferably 5% by mass to 30% by mass, and particularly preferably 7% by mass to 25% by mass. A fluorine-based surfactant having a fluorine content in this range is effective in terms of uniformity of coating film thickness and liquid-saving properties, and has good solubility in a colored curable composition.

  Examples of the fluorosurfactant include Megafac F171, F172, F173, F176, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, F780, F781 (above DIC Corporation), Florard FC430, FC431, FC171 (above, Sumitomo 3M Limited), Surflon S-382, SC-101, Same SC-103, Same SC-104, Same SC-105, Same SC1068, Same SC-381, Same SC-383, Same S393, Same KH-40 (above, manufactured by Asahi Glass Co., Ltd.), Solsperse 20000 (Geneca Corporation) Manufactured) and the like.

  Specific examples of nonionic surfactants include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol dilaurate. Stearate, sorbitan fatty acid ester (pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2, manufactured by BASF, Tetronic 304, 701, 704, 901, 904, 150R1, etc. are mentioned.

  Specific examples of the cationic surfactant include phthalocyanine derivatives (trade name: EFKA-745, manufactured by Morishita Sangyo Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid ( Co) polymer polyflow no. 75, no. 90, no. 95 (manufactured by Kyoeisha Yushi Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.), and the like.

  Specific examples of the anionic surfactant include W004, W005, W017 (manufactured by Yusho Co., Ltd.) and the like.

Examples of silicone surfactants include Toray Dow Corning Co., Ltd. “Torre Silicone DC3PA”, “Torre Silicone SH7PA”, “Torre Silicone DC11PA”, “Torre Silicone SH21PA”, “Torre Silicone SH28PA”, “Torre Silicone” “SH29PA”, “Tore Silicone SH30PA”, “Tore Silicone SH8400”, “TSF-4440”, “TSF-4300”, “TSF-4445”, “TSF-4460”, “TSF-” manufactured by Momentive Performance Materials, Inc. 4452 ”,“ KP341 ”,“ KF6001 ”,“ KF6002 ”manufactured by Shin-Etsu Silicone Co., Ltd.,“ BYK323 ”,“ BYK330 ”manufactured by Big Chemie.
Only one type of surfactant may be used, or two or more types may be combined.

<Thermal polymerization inhibitor>
Furthermore, a thermal polymerization inhibitor (polymerization inhibitor) may be added to the colored curable composition of the present invention.
Examples of the thermal polymerization inhibitor include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6-t- Butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2-mercaptobenzimidazole, and the like are useful.

<Other ingredients>
In the colored curable composition of the present invention, if necessary, a sensitizing dye, an epoxy resin, a fluorine-based organic compound, a thermal polymerization initiator, a thermal polymerization component, a filler, a polymer compound other than the alkali-soluble resin, Various additives such as an adhesion promoter, an antioxidant, an ultraviolet absorber, and an aggregation inhibitor can be contained.
As other components, for example, each component described in paragraphs 0155 to 0217 of JP-A-2009-256572 can be used.

  The colored curable composition of the present invention comprises a polymerizable compound, a photopolymerization initiator, and, if necessary, an alkali-soluble resin, a solvent, and a surfactant with respect to the pigment dispersion composition of the present invention described above. It can prepare by adding additives, such as.

The colored curable composition of the present invention achieves both maintaining the adhesion of the colored pattern to the support and suppressing the occurrence of residues even when the development conditions are strengthened when forming the colored pattern on the support. Therefore, it is possible to form a fine colored region in which the occurrence of residue defects or the like is suppressed. Moreover, since the pigment dispersion composition containing the azo pigment represented by the general formula (1) is included, the pigment dispersibility is excellent and the color characteristics are also excellent.
Therefore, it is preferably used for forming a colored region of a color filter (particularly a color filter for a solid-state imaging device) that requires fine and good color characteristics.

[Color filter for solid-state imaging device and manufacturing method thereof]
The method for producing a color filter for a solid-state imaging device of the present invention comprises a step of forming a colored curable composition layer by applying the above-described colored curable composition of the present invention on a support (hereinafter referred to as “colored curing”). Development of the colored curable composition layer after exposure), a step of exposing the colored curable composition layer through a mask (hereinafter also referred to as “exposure process”), and developing the colored curable composition layer after exposure. Forming a colored pattern (hereinafter also referred to as “colored pixel”) (hereinafter also referred to as “developing step”).
Moreover, the color filter for solid-state image sensors of this invention is manufactured by the manufacturing method of the color filter for solid-state image sensors of this invention.
The color filter for solid-state image sensor of the present invention only needs to have at least a red pattern (red pixel) manufactured by the method for manufacturing a color filter for solid-state image sensor of the present invention. As a specific form of the color filter for a solid-state imaging device of the present invention, for example, a form of a multicolored color filter that combines the red pattern and another colored pattern (for example, the red pattern, the blue pattern, and the green pattern) 3 or more color filters having at least
Hereinafter, the color filter for the solid-state imaging device may be simply referred to as “color filter”.

<Colored curable composition layer forming step>
In the colored curable composition layer forming step, the colored curable composition layer of the present invention is applied to the support to form the colored curable composition layer.
As a support that can be used in this step, for example, a solid-state imaging in which an imaging element (light receiving element) such as a CCD (Charge Coupled Device) or a CMOS (Complementary Metal-Oxide Semiconductor) is provided on a substrate (for example, a silicon substrate). An element substrate can be used.
The colored pattern in the present invention may be formed on the imaging element forming surface side (front surface) of the solid-state imaging element substrate, or may be formed on the imaging element non-forming surface side (back surface).
A light-shielding film may be provided between the image sensors on the solid-state image sensor substrate or on the back surface of the solid-state image sensor substrate.
Further, if necessary, an undercoat layer may be provided on the support for improving adhesion with the upper layer, preventing diffusion of substances, or flattening the substrate surface.

  As a method for applying the colored curable composition of the present invention to the support, various coating methods such as slit coating, ink jet method, spin coating, cast coating, roll coating, screen printing method and the like can be applied. .

  The film thickness of the colored curable composition layer is preferably 0.1 μm to 10 μm, more preferably 0.2 μm to 5 μm, and further preferably 0.2 μm to 3 μm.

  The colored curable composition layer coated on the support can be dried (prebaked) at a temperature of 50 ° C. to 140 ° C. for 10 seconds to 300 seconds using a hot plate, oven, or the like.

<Exposure process>
In the exposure step, the colored curable composition layer formed in the colored curable composition layer forming step is subjected to pattern exposure through a mask having a predetermined mask pattern using an exposure apparatus such as a stepper, for example.
As radiation (light) that can be used for exposure, ultraviolet rays such as g-line and i-line are particularly preferable (particularly preferably i-line). Irradiation dose (exposure amount) is more preferably preferably ^{50~1000mJ / cm 2 30~1500mJ / cm 2} , 80~500mJ / cm 2 being most preferred.

<Development process>
Next, by carrying out an alkali development treatment, the colored curable composition layer of the non-light-irradiated portion in the exposure step is eluted in the alkaline aqueous solution, and only the photocured portion remains.
The developer is preferably an organic alkali developer that does not cause damage to the underlying image sensor or circuit. The development temperature is usually 20 ° C. to 30 ° C., and the development time is conventionally 20 seconds to 90 seconds. In order to remove the residue more, in recent years, it may be carried out for 120 seconds to 180 seconds. Furthermore, in order to further improve residue removability, the process of shaking off the developer every 60 seconds and further supplying a new developer may be repeated several times.

Examples of the alkaline agent used in the developer include ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5, 4, 0] -7-undecene and the like, and an alkaline aqueous solution obtained by diluting these alkaline agents with pure water so as to have a concentration of 0.001 to 10% by mass, preferably 0.01 to 1% by mass. Is preferably used as a developer.
In addition, an inorganic alkali may be used for the developer, and as the inorganic alkali, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium oxalate, sodium metaoxalate and the like are preferable.
In the case where a developer composed of such an alkaline aqueous solution is used, it is generally washed (rinsed) with pure water after development.

Next, it is preferable to perform heat treatment (post-bake) after drying.
If a multicolor coloring pattern is to be formed, a cured film can be produced by sequentially repeating the above steps for each color. Thereby, a color filter is obtained.
Post-baking is a heat treatment after development for complete curing, and a heat curing treatment is usually performed at 100 ° C. to 240 ° C., preferably 200 ° C. to 240 ° C.
This post-bake treatment is performed continuously or batchwise using a heating means such as a hot plate, a convection oven (hot air circulation dryer), a high-frequency heater, or the like so that the coating film after development is in the above-described condition. be able to.

  In addition, the manufacturing method of this invention may have a well-known process as a manufacturing method of the color filter for solid-state image sensors as processes other than the above as needed. For example, after performing the above-described colored curable composition layer forming step, exposure step, and development step, a curing step of curing the formed colored pattern by heating and / or exposure may be included as necessary. .

In addition, when using the colored curable composition according to the present invention, for example, clogging of nozzles and pipes of the coating apparatus discharge unit, contamination due to adhesion, sedimentation, and drying of the colored curable composition and pigment in the coating machine, etc. May occur. Therefore, in order to efficiently clean the contamination caused by the colored curable composition of the present invention, it is preferable to use the solvent related to the present composition as the cleaning liquid. JP-A-7-128867, JP-A-7-146562, JP-A-8-278737, JP-A-2000-273370, JP-A-2006-85140, JP-A-2006-291191, The cleaning liquids described in JP2007-2101A, JP2007-2102A, JP2007-281523A, and the like can also be suitably used for cleaning and removing the colored curable composition according to the present invention.
Of the above, alkylene glycol monoalkyl ether carboxylate and alkylene glycol monoalkyl ether are preferred.
These solvents may be used alone or in combination of two or more. When mixing 2 or more types, it is preferable to mix the solvent which has a hydroxyl group, and the solvent which does not have a hydroxyl group. The mass ratio of the solvent having a hydroxyl group and the solvent having no hydroxyl group is from 1/99 to 99/1, preferably from 10/90 to 90/10, more preferably from 20/80 to 80/20. In a mixed solvent of propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME), the ratio is particularly preferably 60/40. In addition, in order to improve the permeability of the cleaning liquid with respect to contaminants, a surfactant related to the present composition described above may be added to the cleaning liquid.

Since the color filter for a solid-state imaging device of the present invention uses the colored curable composition of the present invention, there are few peeling defects and residual defects, and the color pattern has excellent heat resistance. Moreover, since it is formed using the azo pigment represented by the general formula (1), it has excellent spectral characteristics as red.
The color filter for a solid-state imaging device of the present invention can be suitably used for a solid-state imaging device such as a CCD or CMOS, and is particularly suitable for a CCD or CMOS having a high resolution exceeding 1 million pixels. The color filter for a solid-state image sensor of the present invention can be used as a color filter disposed between, for example, a light receiving portion of each pixel constituting a CCD or CMOS and a microlens for condensing light.

The film thickness of the colored pattern (colored pixel) in the color filter for the solid-state imaging device is preferably 2.0 μm or less, and more preferably 1.0 μm or less.
Further, the size (pattern width) of the colored pattern (colored pixel) is preferably 2.5 μm or less, more preferably 2.0 μm or less, and particularly preferably 1.7 μm or less.

[Solid-state imaging device]
The solid-state image sensor of the present invention includes the above-described color filter for a solid-state image sensor of the present invention.
The configuration of the solid-state imaging device of the present invention is a configuration provided with the color filter for the solid-state imaging device of the present invention, and is not particularly limited as long as the configuration functions as a solid-state imaging device. A configuration is mentioned.

A transfer electrode made of a plurality of photodiodes and polysilicon constituting a light receiving area of a solid-state imaging device (CCD image sensor, CMOS image sensor, etc.) is provided on the support, and the transfer electrodes are formed on the photodiodes and the transfer electrodes. Having a light-shielding film made of tungsten or the like that is opened only in the light-receiving part of the photodiode, and having a device protective film made of silicon nitride or the like formed on the light-shielding film so as to cover the entire surface of the light-shielding film and the photodiode light-receiving part, It is the structure which has the color filter for solid-state image sensors of this invention on a device protective film.
Further, a configuration having light collecting means (for example, a microlens, etc., the same shall apply hereinafter) on the device protective layer and under the color filter (on the side close to the support), or a structure having the light collecting means on the color filter. Etc.

  The present invention will be described more specifically with reference to the following examples. The materials, reagents, ratios, equipment, operations, and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. In the following examples, “%” and “parts” represent “% by mass” and “parts by mass” unless otherwise specified, and the molecular weight indicates the weight average molecular weight.

[Example 1]
<Preparation of pigment dispersion composition P>
(Preparation of pulverized sodium sulfate (crushed sodium sulfate))
Dry air was fed into a 0.65 MPa jet mill (Nisshin Engineering Co., Ltd., air-flow pulverizer, Super Jet Mill), and raw material mirabilite (Mitajiri Chemical Industry Co., Ltd., neutral anhydrous mirabilite, average particle size) Was supplied at a rate of 20 kg / hr and pulverized continuously. The pulverized salt cake discharged from the pulverizer was collected in a lump with a bag filter.
Add powder frame mirabilite to isobutyl alcohol, disperse with ultrasonic waves (for 1 minute), measure the particle size distribution with a particle size measuring device (manufactured by Nikkiso Co., Ltd., Microtrac particle size distribution measuring device, MT-3300II), and average The particle diameter D50 was determined to be 3.19 μm. Furthermore, the volume% of large particles having a size of 10 μm or more was read from the particle size distribution data and found to be 0.00 volume%.

(Polent solvent salt milling)
The following pigment 1 (red pigment), which is an azo pigment represented by the general formula (1), was refined by solvent salt milling. Details will be described below.

Solvent salt milling of Pigment 1 was performed according to the following procedure.
First, 3000 g of the pulverized mirabilite was added to a double-arm kneader (manufactured by Moriyama, 5 L kneader Σ type, hereinafter referred to as “kneader”), and 300 g of pigment 1 was further added and mixed for 5 minutes. 900 g of diethylene glycol (DEG) (manufactured by Nippon Shokubai Co., Ltd.) was added to the mixture and kneaded. The temperature is controlled so that the temperature of the kneaded material in the kneader is 50 ° C., and the kneaded material is kneaded for 10 hours (hereinafter, the kneaded material is referred to as magma). The above operation was defined as a miniaturization process.

Next, the magma which completed the refinement | miniaturization process was taken out, and it moved to the tank which can be temperature-controlled. 20 L of deionized water was previously stored in the tank. The magma was dispersed by stirring with a stirrer at 150 rpm for 2 hours. The resulting dispersion was transferred to Nutsche and filtered. After filtration, it was washed with deionized water until the electrical conductivity of the washing wastewater was 3 μS / cm or less (a fine pigment containing a large amount of water that has been washed is referred to as a pigment paste).
The pigment paste after washing with water was taken out, placed on a drying shelf (material SUS304), further transferred to a dryer and dried at 80 to 105 ° C. for 15 hours (the dried finer pigment is referred to as a drying block).
The dried block was pulverized with a pulverizer (manufactured by Kyoritsu Riko Co., Ltd., small pulverizer, sample mill SK-M2).
As described above, solvent salt milling of the pigment 1 was performed. For the preparation of the following pigment dispersion composition P, the pigment 1 after the above solvent salt milling was used.

(Preparation of pigment dispersion composition P)
A mixed liquid having the following composition was mixed and dispersed for 2 hours by a bead mill to prepare a red pigment dispersion composition P.
-Composition-
A mixture of Pigment 1 after solvent salt milling and Pigment Yellow 139 (PY139) (mass ratio [pigment 1 / PY139] = 100/30) 11.80 parts. Compound 1 below (triazine having an acidic functional group) Derivatives)… 1.31 parts · Dispersant 1 below · 6.59 parts · Propylene glycol monomethyl ether acetate (PGMEA)
... 80.29 parts

  In the pigment dispersion composition P, the pigment 1 is a main pigment and the pigment yellow 139 is a sub-pigment.

Dispersant 1

  In addition, the said dispersing agent 1 is compoundable according to the synthesis example described in paragraph number [0245]-[0247] of Unexamined-Japanese-Patent No. 2009-203462.

  With respect to the obtained red pigment dispersion composition P, the volume average particle diameter was measured using a Nanotrac UPA particle size analyzer (UPA-EX150; manufactured by Nikkiso Co., Ltd.).

<Preparation of red colored curable composition R>
Using the above-mentioned pigment dispersion composition P, a red colored curable composition R was prepared by mixing and stirring so as to have the following composition.
(composition)
Pigment dispersion composition P: 10.28 parts Polymerizable compound: Compound listed above as exemplary compound (b) 0.15 parts Oxime-based photopolymerization initiator: CGI-124 manufactured by Ciba Specialty Chemicals
... 0.07 parts · Polymerization inhibitor: p-methoxyphenol · 0.01 parts · Resin: benzyl methacrylate / methacrylic acid / -2-hydroxyethyl methacrylate copolymer, molar ratio 60/20/20, weight average 1.14 parts · Fluorosurfactant: 1.0% propylene glycol monomethyl ether acetate solution of Megafac F781 manufactured by DIC Corp. · 0.63 parts · Solvent: propylene glycol monomethyl ether acetate (hereinafter, "PGMEA") .) 2.73 parts

<Preparation of substrate with undercoat layer>
An 8-inch device-formed silicon wafer (solid-state imaging device substrate) was heat-treated in an oven at 200 ° C. for 30 minutes. Next, a curable resin solution “Cyclomer P ACA Z230AA” manufactured by Daicel Chemical Industries, Ltd. is applied on this substrate so as to have a dry film thickness of 0.3 μm, and further heated and dried on a 230 ° C. hot plate for 5 minutes. An undercoat layer was formed to obtain a substrate with an undercoat layer.

<Production of red color filter>
The red colored curable composition R prepared above was applied to the device forming surface side of the substrate with the undercoat layer prepared above to form a photocurable coating film. And the heat processing (prebaking) were performed for 120 second using a 100 degreeC hotplate so that the dry film thickness of this coating film might be set to 1.0 micrometer.
Next, using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.), a pattern is formed at a dose of 200 mJ / cm ² through a photomask for forming red pixels of 1.0 μm square at a wavelength of 365 nm. Exposure was performed.
Then, the silicon wafer on which the irradiated coating film is formed is placed on a horizontal rotary table of a spin shower developing machine (DW-30 type; manufactured by Chemitronics), and CD-2000 (Fuji Film Electronics). Paddle development was repeated three times at 23 ° C. for 60 seconds using a 60% dilution solution (manufactured by Materials) to form a red pattern on the silicon wafer.

A silicon wafer on which a red pattern is formed is fixed to the horizontal rotary table by a vacuum chuck method, and the silicon wafer is rotated at a rotation speed of 50 rpm by a rotating device, and pure water is sprayed from the upper part of the rotation center from a jet nozzle. And rinsed, and then spray-dried.
Next, it heated for 5 minutes with a 220 degreeC hotplate, and obtained the red pattern (red color filter) on the silicon wafer.

<Evaluation of adhesion (peeling of colored pattern)>
The obtained silicon wafer with a red color filter is observed with an optical microscope (100 times magnification), 50 fields of view are randomly extracted per wafer, the number of peeled patterns is actually counted, and peeling of colored patterns occurs. The rate was calculated. The results are shown in Table 1.
As shown in Table 1, the color pattern peeling rate is less than 1%. From this, the red color filter obtained in this example sufficiently suppresses the peeling of the colored pattern. Was confirmed.
The occurrence rate of color pattern peeling is 3% or less, which is a level that does not cause a problem in practice.

<Evaluation of residue>
The obtained silicon wafer with a red color filter is inspected with a defect inspection apparatus ComPLUS3 manufactured by Applied Materials technology, and a defective portion is detected, and the amount of residual defects (pieces / cm ² ) in a microscopic image of these defective portions. Was calculated.
It is a level which does not become a problem practically that the abundance of a residue defect is 3.0 piece / cm < ² > or less. The results are shown in Table 1 below.

<Confirmation of spectroscopy>
In the production of the red color filter, the 8-inch device-formed silicon wafer is replaced with a glass substrate, the pattern exposure is changed to the entire surface exposure, a red film is formed, and the spectral characteristics of the resulting red film (transmittance at each wavelength) ) Was measured by MCPD-3000 (manufactured by Otsuka Electronics Co., Ltd.).
In the measured spectral characteristics, the transmittance at 350 nm to 400 nm was reduced, and the transmittance in the wavelength region of 650 nm to 750 nm was high.
That is, it was confirmed that the color pattern of the color filter obtained in this example shows good spectral characteristics as red.

<Evaluation of heat resistance>
In the production of the red color filter, the 8-inch device-formed silicon wafer was replaced with a glass substrate, and the pattern exposure was changed to the entire surface exposure to form a red film.
The obtained red film was exposed at 220 ° C. for 60 minutes in the atmosphere, and the color difference before and after that (ΔE * ab) was measured with a spectrophotometer MCPD-3000 (manufactured by Otsuka Electronics Co., Ltd.). The heat resistance was evaluated based on the measured color difference (ΔE * ab).
It shows that heat resistance is so favorable that the value of color difference (DELTA) E * ab is small. The evaluation results are shown in Table 1 below.

[Examples 2 to 15, Comparative Example 1]
In Example 1, the pigment dispersion composition, the colored curable composition, the same as in Example 1 except that the types of the main pigment, sub-pigment, pigment derivative and dispersant were changed as shown in Table 1 below. And the red color filter was produced and the same evaluation as Example 1 was performed.
The evaluation results are shown in Table 1 below.

  The detail of each component described in Table 1 is as follows.

Pigment 4: Pigment Yellow 139
Pigment 5: Pigment Yellow 150
Pigment 6: Pigment Yellow 185
Pigment 7: Pigment Red 254
Pigment 8: Pigment Orange 71
Pigment 9: Pigment Violet 29

Dispersant 2: 100/50/2 reaction product (molecular weight 10,000) of 2,4-tolylene diisocyanate, polybutylene adipate (molecular weight 2000) and N, N-diethyl-1,3-propanediamine
Dispersant 3: benzyl methacrylate / 2-ethylhexyl methacrylate / 2-dimethylaminoethyl methacrylate (weight ratio 30/30/40) copolymer (weight average molecular weight 12,000)
Dispersant 4: Methacrylic acid / 2-hydroxyethyl methacrylate / N-phenylmaleimide / styrene / n-butyl methacrylate copolymer (copolymerization ratio = 15/15/15/15/12/23/20, weight average molecular weight = 12,000)
Dispersant 5: Dispersant having the above structure (weight average molecular weight 25,000)

  As shown in Table 1, the colored curable composition using the pigment dispersion of Examples 1 to 15 containing an azo pigment, an acidic functional group derivative, and a dispersant has good adhesion of the formed colored pattern. And good pattern forming property with little residue.

  In the above embodiment, an example in which a red color filter is formed on a device-formed silicon wafer has been described. However, the present invention is not limited to the above embodiment.

Example 16
A solid-state image sensor was produced as follows.
<Preparation of colored curable composition>
A green colored curable composition was prepared in the same manner as in Example 1 except that in Example 1, Pigment 1 was changed to Pigment Green 36.
A blue colored curable composition was prepared in the same manner as in Example 1 except that in Example 1, Pigment 1 was changed to Pigment Blue 15: 6 and Pigment 4 was changed to Pigment Violet 23.
As the red colored curable composition, the red colored curable composition R prepared in Example 1 was used.

<Preparation of silicon wafer with pre-coated device>
An undercoat layer was formed on a silicon wafer on which a device was previously formed by a known method in the same manner as in the production of the substrate with the undercoat layer in Example 1, and a silicon wafer with a device with an undercoat layer formed thereon.

<Production of solid-state image sensor>
In the production of the red color filter in Example 1, the green colored curable composition prepared above was used instead of the red colored curable composition R, and a 1.0 μm square checkered pattern was formed on the photomask used for exposure. Except for changing to a mask that can be used, exposure, development, rinsing, and post-baking were performed in the same manner as in Example 1 to form a green pattern on a silicon wafer with a device with an undercoat layer formed thereon.
Next, a red pattern was formed on the silicon wafer on which the green pattern was formed in the same manner as the green pattern except that the red colored curable composition R was used.
Next, a blue pattern was formed on the silicon wafer on which the green pattern and the red pattern were formed in the same manner as the green pattern except that the blue colored curable composition prepared above was used.
As described above, a color filter for a solid-state imaging device having a green pattern, a red pattern, and a blue pattern was produced.
Furthermore, according to a known method, a solid-state image sensor incorporating a solid-state image sensor color filter was produced.
As a result of capturing and confirming an image with the obtained solid-state imaging device, it was confirmed that the image was good.

Claims (12)

At least one compound selected from the group consisting of an azo pigment represented by the general formula (1), an organic dye derivative having an acidic functional group, an anthraquinone derivative having an acidic functional group, and a triazine derivative having an acidic functional group; A pigment dispersion composition containing a dispersant.


[In General Formula (1), G represents a hydrogen atom, an aliphatic group, an aryl group, or a heterocyclic group, and R ₁ represents an amino group, an aliphatic oxy group, an aliphatic group, an aryl group, or a heterocyclic ring. Represents a group, and R ₂ represents a substituent.
A represents any of the groups represented by the following general formulas (A-1) to (A-32).
m represents an integer of 0 to 5, and n represents an integer of 1 to 4.
When n = 2, the general formula (1) represents a dimer via R ₁ , R ₂ , A or G.
In the case of n = 3, the general formula (1) represents a trimer via R ₁ , R ₂ , A or G.
When n = 4, the general formula (1) represents a tetramer through R ₁ , R ₂ , A or G.
There is no ionic hydrophilic group in the general formula (1). ]


[In General Formulas (A-1) to (A-32), R _{51 to} R ₅₉ each independently represent a hydrogen atom or a substituent, and the adjacent substituents are bonded to each other to form a 5- to 6-membered ring. May be formed. * Represents the bonding position with the azo group in the general formula (1). ] The pigment dispersion composition according to claim 1, wherein the azo pigment represented by the general formula (1) is an azo pigment represented by the following general formula (2).


[In General Formula (2), R ₂₁ represents an amino group, an aliphatic oxy group, an aliphatic group, an aryl group, or a heterocyclic group, and R ₂₂ represents a substituent. R ₅₅ and R ₅₉ each independently represent a hydrogen atom or a substituent.
m represents an integer of 0 to 5, and n represents an integer of 1 to 4.
Z represents an electron withdrawing group having a Hammett's σp value of 0.2 or more.
When n = 2, general formula (2) represents a dimer via R ₂₁ , R ₂₂ , R ₅₅ , R ₅₉ or Z.
When n = 3, general formula (2) represents a trimer via R ₂₁ , R ₂₂ , R ₅₅ , R ₅₉ or Z.
When n = 4, the general formula (2) represents a tetramer through R ₂₁ , R ₂₂ , R ₅₅ , R ₅₉ or Z.
There is no ionic hydrophilic group in the general formula (2). ]   The at least one compound selected from the group consisting of an organic dye derivative having an acidic functional group, an anthraquinone derivative having an acidic functional group, and a triazine derivative having an acidic functional group is a triazine derivative having a sulfo group or a carboxy group. Item 3. A pigment dispersion composition according to item 1 or 2.   The pigment dispersion composition according to any one of claims 1 to 3, wherein the dispersant is a dispersant containing a nitrogen atom.   The dispersant is (i) a main chain portion having a nitrogen atom, and (ii) a group “X” having a functional group having a pKa of 14 or less and bonded to the nitrogen atom present in the main chain portion; (Iii) A resin having an oligomer chain having a number average molecular weight of 500 to 1,000,000 or a side chain containing a polymer chain “Y”. 5. The resin according to claim 1. Pigment dispersion composition.   The pigment dispersion composition according to any one of claims 1 to 5, wherein the azo pigment represented by the general formula (1) is a solvent salt milled azo pigment.   The pigment dispersion composition according to any one of claims 1 to 6, further comprising a pigment having a hue selected from red, yellow, orange, and violet.   The colored curable composition containing the pigment dispersion composition of any one of Claims 1-7, a photoinitiator, and a polymeric compound.   The colored curable composition according to claim 8, wherein the photopolymerization initiator is an oxime photopolymerization initiator.   A step of forming a colored curable composition layer by applying the colored curable composition according to claim 8 or 9 on a support, and exposing the colored curable composition layer through a mask. The manufacturing method of the color filter for solid-state image sensors including a process and the process of developing the colored curable composition layer after exposure, and forming a colored pattern.   The color filter for solid-state image sensors manufactured by the manufacturing method of the color filter for solid-state image sensors of Claim 10.   The solid-state image sensor provided with the color filter for solid-state image sensors of Claim 11.