JP2012162684A - Processed pigment, pigment dispersion composition using the same, colored actinic ray-sensitive or radiation-sensitive composition, color filter, pattern forming method, method for manufacturing color filter for solid state imaging element, color filter for solid state imaging element and solid state imaging element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a processed pigment exhibiting excellent dispersion stability for stably maintaining dispersed primary particles even in finely pulverized pigment, and capable of producing a color filter of good color characteristics with reduced variation in color density when the color filter is produced from a colored actinic ray-sensitive or radiation-sensitive composition containing a pigment dispersion composition using the processed pigment.SOLUTION: The processed pigment is prepared by coating a heterocyclic azo pigment of the specific structure having an average primary particle diameter of 5-50 nm with a polymer compound. The pigment dispersion composition using the same, the colored actinic ray-sensitive or radiation-sensitive composition, the color filter, the pattern forming method, the method for manufacturing the color filter for the solid state imaging element, the color filter for the solid state imaging element, and the solid state imaging element are also disclosed.

Description

  The present invention relates to a processed pigment, a pigment dispersion composition using the processed pigment, a colored actinic ray-sensitive or radiation-sensitive composition, a color filter, a pattern forming method, a method for producing a color filter for a solid-state image sensor, and a solid-state image sensor The present invention relates to a color filter and a solid-state imaging device.

  The color filter contains a pigment dispersion composition in which an organic pigment or an inorganic pigment is dispersed, a polyfunctional monomer, a polymerization initiator, an alkali-soluble resin, and other components to form a colored photosensitive composition. It is manufactured by forming a colored pattern by a photolithography method, an ink jet method or the like.

  In recent years, color filters tend to be used not only for monitors but also for televisions (TVs) in liquid crystal display (LCD) applications. Along with this trend of expanding applications, color filters are required to have high color characteristics in terms of chromaticity and contrast. Similarly, color filters for use in image sensors (solid-state imaging devices) are also required to have high color characteristics such as reduction in color unevenness and improvement in color resolution.

  In response to the above requirements, the pigment contained in the colored photosensitive composition is dispersed in a finer state (good dispersibility), and is dispersed in a stable state (good dispersion stability). Is required. When the dispersibility of the pigment is insufficient, fringes (jagged edges) and surface irregularities occur in the colored pixels formed by the photolithographic method, and there are many undeveloped residues (residues) on the substrate. There are problems that the chromaticity and dimensional accuracy of the color filter are lowered and the contrast is remarkably deteriorated. In addition, when the dispersion stability of the pigment is insufficient, in the color filter manufacturing process, in particular, the uniformity of the film thickness in the coating process of the colored curable composition is reduced, or the sensitivity in the exposure process. Or the alkali solubility in the development process is likely to be reduced. Furthermore, when the dispersion stability of the pigment is poor, there is also a problem that the constituent components of the colored curable composition are aggregated to increase the viscosity with time and the pot life is extremely shortened. In order to improve color characteristics such as the contrast of color filters, it is effective to reduce the particle diameter of the pigment. However, if the particle diameter of the pigment is reduced, the surface area of the pigment particles increases, so the aggregation between the pigment particles It is often difficult to increase the strength and achieve both a high level of dispersibility and dispersion stability.

The following are known regarding the refinement of pigment particles and improvement of dispersibility.
In general, the primary particles of the pigment are made fine by a method of kneading a pigment, a water-soluble inorganic salt, or a water-soluble organic solvent that does not substantially dissolve the inorganic salt with a kneader (a salt milling method). Are known. The obtained mixture of primary particles of fine pigment is put into water and stirred with a mixer or the like to form a slurry. Next, the slurry is filtered, washed with water, and dried to obtain a fine pigment as a secondary aggregate that is an aggregate of primary particles of the pigment. The dispersion step in a normal disperser such as a sand mill or a ball mill is a step of loosening a secondary aggregate that is an aggregate of primary particles of a pigment to obtain a dispersion close to the primary particles.

  However, when the primary particles of the pigment are made finer, aggregation tends to occur, and aggregates (secondary aggregates) are likely to be generated during slurry or drying. Further, as the primary particles of the pigment become finer, strong secondary aggregation tends to occur. For this reason, it is generally very difficult to redisperse the refined pigment to primary particles. A color filter formed using a dispersion containing a large amount of secondary aggregates has a large light scattering, and the contrast is remarkably lowered and color density unevenness occurs. Therefore, the pigment dispersion composition aggregates. It is desirable that the primary particles are stably dispersed and the properties are easy to handle.

In order to suppress the strong secondary aggregation of the refined pigment, a rosin, a rosin derivative, or a water-insoluble monomer or oligomer is added in the salt milling process to treat the pigment. There has been proposed a technique for obtaining a color filter having a high contrast by using it (for example, see Patent Documents 1 and 2).
Also, a pigment dispersion composition that uses a polymer compound having a heterocyclic ring in the side chain during the dispersion step as a dispersant in the pigment dispersion step, and has excellent dispersion stability and can form a high-contrast color pattern for color filters. In addition, a technique for obtaining a colored photosensitive composition and a color filter has also been proposed (see, for example, Patent Document 3).
Furthermore, in order to provide a color filter with high contrast and good color characteristics with little unevenness in color density, a polymer compound having a heterocyclic ring in the side chain is added in the pigment refining step and coated. Produced processed pigments have also been proposed. (For example, Patent Document 4)
Moreover, as a pigment used for the coloring composition for color filters, the specific heterocyclic azo pigment is disclosed by patent document 5, for example.
However, these methods cannot provide a color filter having high dispersion stability in a fine pigment and having good color characteristics with small color density unevenness, and an improvement thereof has been desired.

Japanese Patent No. 3130217 JP 2004-233727 A JP 2003-26950 A JP 2009-062457 A International Publication No. 10/008081 Pamphlet

That is, the subject of the present invention is a processed pigment having excellent dispersion stability in which the dispersed primary particles are stably maintained even in a fine pigment, and the processed pigment is used. A processed pigment capable of producing a color filter having good color characteristics (spectral characteristics) with small color density unevenness when a color filter is produced from a colored actinic ray-sensitive or radiation-sensitive composition containing a pigment dispersion composition It is to provide.
A further object of the present invention is to use such a processed pigment, a pigment dispersion composition having excellent pigment dispersion stability, and a colored actinic ray-sensitive or radiation-sensitive composition containing such a pigment composition. Is to provide.
Another object of the present invention is to provide a color filter having good color characteristics with small color density unevenness using the colored actinic ray-sensitive or radiation-sensitive composition of the present invention, a pattern forming method, and solid-state imaging. An object of the present invention is to provide a device color filter manufacturing method, a solid-state image sensor color filter, and a solid-state image sensor.

  As a result of intensive studies, the present inventors have obtained a processed pigment obtained by coating a azo pigment having a specific structure of a heterocyclic azo pigment having an average primary particle diameter of 5 to 50 nm with a polymer compound. When primary particles are stably maintained and not only excellent in dispersion stability, but also when a color filter is produced from a colored actinic ray-sensitive or radiation-sensitive composition containing a pigment dispersion composition using the processed pigment Furthermore, it was found that a color filter having good color characteristics with small color density unevenness can be produced.

That is, the object of the present invention is achieved by the following means.
[1]
A processed pigment obtained by coating an azo pigment represented by the following general formula (Az) and having an average primary particle diameter of 5 to 50 nm with a polymer compound.

(In the general formula (Az),
A represents an aromatic 5- or 6-membered heterocyclic group.
B represents a structure represented by any one of the following general formulas (1) to (3) and (1-1) to (1-10).
n represents an integer of 1 to 4. )
(In the general formulas (1) to (3) and (1-1) to (1-10),
Each G independently represents a hydrogen atom, an aliphatic group, an aryl group, a heterocyclic group, an acyl group, an aliphatic oxycarbonyl group, a carbamoyl group, an aliphatic sulfonyl group or an arylsulfonyl group.
Each R ₁ independently represents a hydrogen atom, —C (═O) NR ₄ R ₅ , —NR ₆ C (═O) —R ₇ , —C (═O) R ₈ , —C (═O); Represents OR ₈ , —OR ₈ , —SR ₈ , an amino group, an aliphatic group, an aryl group, a halogen atom, or a heterocyclic group;
R ₂ each independently represents a substituent, and when a plurality of R ₂ are present, they may be the same as or different from each other.
Each R ₃ independently represents —C (═O) NR ₄ R ₅ or —C (═O) OR ₈ .
R ₄ each independently represents a hydrogen atom or an alkyl group.
R ₅ each independently represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, or —N (R ₉ ) (R ₁₀ ).
R ₆ each independently represents a hydrogen atom or an alkyl group.
R ₇ each independently represents an alkyl group, an aryl group, a heterocyclic group, an acyl group, an alkoxy group, or —N (R ₉ ) (R ₁₀ ).
R ₈ each independently represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group or an acyl group.
R ₉ each independently represents a hydrogen atom or an alkyl group.
R ₁₀ each independently represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. R ₄ and R ₅ , and R ₉ and R ₁₀ may be bonded to each other to form a 5- or 6-membered ring.
R ₁₁ each independently represents an amino group, an aliphatic oxy group, an aliphatic group, an aryl group or a heterocyclic group.
R ₁₂ each independently represents a hydrogen atom, an aliphatic group, an aryl group or a heterocyclic group.
R ₁₃ each independently represents a hydrogen atom, an aliphatic group, an aryl group or a heterocyclic group.
Y each independently represents a divalent group that forms a heterocyclic ring with —N═C—N—.
Each m independently represents an integer of 0 or more, and when m is 2 or more, R ₂ may be connected to each other to be condensed.
* Represents a bonding position with the azo group of the general formula (Az).
When n in the general formula (Az) is 2, it represents a dimer via R _{1 to} R ₁₃ , A or G. When n is 3, it represents a trimer via R _{1 to} R ₁₃ , A or G. When n is 4, it represents a tetramer via R _{1 to} R ₁₃ , A or G. )
[2]
The processed pigment according to the above [1], wherein the polymer compound is a polymer compound having a heterocyclic ring in a side chain.
[3]
The processed pigment according to [2] above, wherein the polymer compound having a heterocyclic ring in the side chain contains a polymer unit derived from a monomer represented by the following general formula (H-1).
In the general formula (H-1), R ¹ represents a hydrogen atom or an alkyl group. R ² represents a single bond or a divalent linking group. Y represents -CO-, -C (= O) O-, -CONH-, -OC (= O)-, or a phenylene group. Z represents a group having a nitrogen-containing heterocyclic structure.
[4]
The processed pigment according to any one of the above [1] to [3], which is produced by adding the polymer compound in a pigment refining step.
[5]
A pigment dispersion composition obtained by dispersing the processed pigment according to any one of the above [1] to [4] in an organic solvent.
[6]
The pigment dispersion composition according to [5], further including a pigment dispersant.
[7]
A colored actinic ray-sensitive or radiation-sensitive composition comprising the pigment dispersion composition according to [5] or [6], a polymerizable compound, and a photopolymerization initiator.
[8]
The colored actinic ray-sensitive or radiation-sensitive composition according to the above [7], wherein the photopolymerization initiator is an oxime photopolymerization initiator.
[9]
A color filter formed using the colored actinic ray-sensitive or radiation-sensitive composition according to [7] or [8].
[10]
On the support, the step of applying the colored actinic ray-sensitive or radiation-sensitive composition according to [7] or [8] to form a colored actinic ray-sensitive or radiation-sensitive composition layer; A step of exposing the colored actinic ray-sensitive or radiation-sensitive composition layer through a mask; and a step of developing the colored actinic-ray-sensitive or radiation-sensitive composition layer after exposure to form a colored pattern. , Pattern formation method.
[11]
On the support, the step of applying the colored actinic ray-sensitive or radiation-sensitive composition according to [7] or [8] to form a colored actinic ray-sensitive or radiation-sensitive composition layer; A step of exposing the colored actinic ray-sensitive or radiation-sensitive composition layer through a mask; and a step of developing the colored actinic-ray-sensitive or radiation-sensitive composition layer after exposure to form a colored pattern. The manufacturing method of the color filter for solid-state image sensors.
[12]
A solid-state image sensor color filter produced by the method for producing a solid-state image sensor color filter described in [11] above.
[13]
The solid-state image sensor provided with the color filter for solid-state image sensors as described in said [12].

The present invention preferably further has the following configuration.
[14]
In the general formula (Az), B is a structure represented by any one of the general formulas (1) to (3) and (1-1) to (1-4). [4] The processed pigment according to any one of [4].
[15]
In the general formula (Az), the processed pigment according to the above [14], wherein B is a structure represented by any one of the general formulas (1) to (3).

According to the present invention, even a finer pigment is a processed pigment excellent in dispersion stability in which dispersed primary particles are stably maintained, and a pigment dispersion composition using the processed pigment is obtained. When a color filter is produced from the contained colored actinic ray-sensitive or radiation-sensitive composition, a processed pigment capable of producing a color filter having good color characteristics with small color density unevenness can be provided.
In addition, according to the present invention, a pigment dispersion composition having excellent pigment dispersion stability using such a processed pigment, and a colored actinic ray-sensitive or radiation-sensitive composition containing such a pigment composition Can provide.
Further, according to the present invention, a color filter having good color characteristics with small color density unevenness using the colored actinic ray-sensitive or radiation-sensitive composition of the present invention, a pattern forming method, and a solid-state image sensor A method for producing a color filter, a color filter for a solid-state image sensor, and a solid-state image sensor can be provided.

6 is an infrared absorption spectrum diagram of Pigment 3 synthesized according to Synthesis Example 5. FIG. It is a figure of the infrared absorption spectrum of the pigment 4 synthesize | combined according to the synthesis example 6. FIG.

Hereinafter, the present invention will be described in detail.
In addition, in the description of the group (atomic group) in this specification, the description which does not describe substitution and non-substitution includes the thing which has a substituent with the thing which does not have a substituent. . For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In addition, “active light” or “radiation” in the present specification means, for example, an emission line spectrum of a mercury lamp, far ultraviolet rays represented by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, electron beams, and the like. In the present invention, light means actinic rays or radiation. Unless otherwise specified, “exposure” in this specification is not only exposure with far-ultraviolet rays such as mercury lamps and excimer lasers, X-rays, EUV light, but also drawing with particle beams such as electron beams and ion beams. Are also included in the exposure.
The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments. In the present specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
In the present specification, “(meth) acrylate” represents acrylate and methacrylate, “(meth) acryl” represents acryl and methacryl, and “(meth) acryloyl” represents acryloyl and methacryloyl. In the present specification, “monomer” and “monomer” are synonymous.The monomer in the present invention is distinguished from oligomer and polymer, and refers to a compound having a mass average molecular weight of 2,000 or less. In the specification, a polymerizable compound means a compound having a polymerizable group, and may be a monomer or a polymer, and a polymerizable group is a group involved in a polymerization reaction. say.
The “colored layer” in the present invention means a layer composed of pixels and / or a black matrix used for a color filter.

  Hereinafter, the processed pigment, the pigment dispersion composition, the colored actinic ray-sensitive or radiation-sensitive composition, the color filter and the production method (pattern formation method), the solid-state imaging device, and the liquid crystal display device of the present invention will be described in detail. The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.

Hereinafter, the processed pigment will be described in detail.
<Processed pigment>
The processed pigment of the present invention is a heterocyclic azo pigment having a specific structure represented by the general formula (Az) described later, and an azo pigment having an average primary particle diameter of 5 to 50 nm is coated with a polymer compound It is characterized by becoming.
Although the reason why the above effect is obtained by the processed pigment of the present invention is not clear, the heterocyclic azo pigment having a specific structure according to the present invention has a very high color gamut and sensitivity required in recent years for color filter applications. The pigment is refined so that the average primary particle diameter of such a pigment is 5 to 50 nm, and then the polymer is coated with a polymer compound, whereby secondary aggregates of primary particles are formed. The generation of aggregates can be suppressed, and the pigment can be stably dispersed in a fine state. As a result, while maintaining the excellent color reproduction range and sensitivity characteristics of the heterocyclic azo pigment having a specific structure according to the present invention (that is, having excellent spectral characteristics), a pigment dispersion composition is obtained. It is considered that not only the dispersion stability of the pigment is excellent, but also the color density unevenness (zara performance) is reduced when applied to a color filter.
The processed pigment of the present invention is preferably used for a color filter because the above-described effects are remarkably exhibited.

  Such microfabricated pigments can be produced, for example, by i) a pigment, ii) a water-soluble inorganic salt, iii) a small amount of a water-soluble organic solvent that does not substantially dissolve ii), and iv) a polymer compound. A step of mechanically kneading with a kneader or the like (this step is referred to as salt milling), a step of adding this mixture into water, stirring it with a high speed mixer or the like to form a slurry, and filtering the slurry, It is carried out through a step of washing with water and drying if necessary. By such a production method, the processed pigment of the present invention is obtained which is fine and has little aggregation of the pigment during drying.

The salt milling described above will be described more specifically. First, a small amount of iii) water-soluble organic solvent is added as a wetting agent to a mixture of i) pigment and ii) water-soluble inorganic salt, and after kneading with a kneader or the like, the mixture is poured into water. Stir with a speed mixer to make a slurry. Next, the slurry is filtered, washed with water, and dried if necessary to obtain a finer pigment. When used by dispersing in an oily varnish, it is also possible to disperse the treated pigment before drying (referred to as a filter cake) in the oily varnish while removing water by a method generally called flushing. When dispersed in an aqueous varnish, the treated pigment does not need to be dried, and the filter cake can be dispersed in the varnish as it is.
In the present invention, the above iii) organic solvent is used in combination with iv) a polymer compound at the time of salt milling, so that the surface is further finely coated with the polymer compound and the pigment is less agglomerated during drying. A pigment is obtained.
As a method of preventing dry aggregation, an alkali-soluble resin dissolved in an alkaline aqueous solution is added to the slurry, and after sufficiently stirring and mixing, neutralized with an acidic aqueous solution such as hydrochloric acid or sulfuric acid to deposit the polymer compound on the pigment, It is also possible to prevent dry aggregation by adding an aqueous solution of a water-soluble polyvalent metal salt such as calcium chloride or barium chloride to precipitate a polymer compound and deposit it on the pigment.
Note that iv) the polymer compound may be added at the initial stage of the salt milling step, or may be added separately.

[I) Azo pigment]

First, the aliphatic group, aryl group, heterocyclic group, acyl group and substituent in the present invention will be described.
In the aliphatic group in the present invention, 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 may be a single ring or a condensed ring. Further, it may be unsubstituted or may have a substituent. Moreover, the heterocyclic group should just have a hetero atom (for example, a nitrogen atom, a sulfur atom, an oxygen atom) in the ring, and even if it is a saturated ring, it is an unsaturated ring. Also good. Further, it may be a single ring or a condensed ring, and may be unsubstituted or may have a substituent.
The acyl group may be an aliphatic carbonyl group, an arylcarbonyl group, a heterocyclic carbonyl group, may have a substituent, and may be substituted. Any group can be used as long as it is a substitutable group among the groups described in the following substituent group. For example, acetyl, propanoyl, benzoyl, 3-pyridinecarbonyl and the like can be mentioned.

  Further, the substituent in the present invention may be any group that 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, an aryloxy group, a hetero group Ring oxy group, aliphatic oxycarbonyl group, aryloxycarbonyl group, heterocyclic oxycarbonyl group, carbamoyl group, aliphatic sulfonyl group, arylsulfonyl group, heterocyclic sulfonyl group, aliphatic sulfonyloxy group, arylsulfonyloxy group, hetero Ring sulfonyloxy group, sulfamoyl group, aliphatic sulfonamide group, aryl sulfonamide group, heterocyclic sulfonamide group, amino group, aliphatic amino group, arylamino group, heterocyclic amino group, aliphatic oxycarbonylamino group, aryl Oxycarbonylamino group, heterocycle Xoxycarbonylamino 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, sulfo group Examples include a famoylamino group, a halogen atom, a sulfamoylcarbamoyl group, a carbamoylsulfamoyl group, a dialiphatic oxyphosphinyl group, and a diaryloxyphosphinyl group.

  The azo pigment of the present invention does not contain an ionic hydrophilic group (for example, carboxyl group, sulfo group, phosphono group and quaternary ammonium group) as a substituent from the viewpoint of solubility. When it contains an ionic hydrophilic group, it is preferably a salt with a polyvalent metal cation (eg, magnesium, calcium, barium), more preferably a lake pigment.

Here, Hammett's substituent constant σp value used in the present specification will be described briefly.
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). 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 compound represented by the general formula (Az) of 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.

The azo pigment according to the present invention is an azo pigment represented by the following general formula (Az), and has an average primary particle diameter of 5 to 50 nm. The compound represented by the general formula (Az) 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.
The average primary particle diameter of the azo pigment represented by the general formula (Az) is preferably 10 to 50 nm, and more preferably 10 to 40 nm. The average primary particle diameter of the azo pigment can be determined by a transmission electron microscope (TEM).
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.
In addition, by having a specific structure represented by the following general formula (Az), it exhibits excellent characteristics in color characteristics such as tinting strength and hue, and is excellent in durability such as light resistance and ozone resistance. Characteristics 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 (Az) exhibits good spectral characteristics as red.
Here, “spectral characteristics favorable as red” refers to at least one of the following properties, for example. Spectral characteristics that satisfy all of the following three properties are the best.
-The transmittance in the wavelength region of 650 nm to 750 nm is high.
-The transmittance curve rises sharply in the wavelength region of 540 nm or more.
-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 (Az) will be described.

(In the general formula (Az),
A represents an aromatic 5- or 6-membered heterocyclic group.
B represents a structure represented by any one of the following general formulas (1) to (3) and (1-1) to (1-10).
n represents an integer of 1 to 4. )

(In the general formulas (1) to (3) and (1-1) to (1-10),
Each G independently represents a hydrogen atom, an aliphatic group, an aryl group, a heterocyclic group, an acyl group, an aliphatic oxycarbonyl group, a carbamoyl group, an aliphatic sulfonyl group or an arylsulfonyl group.
Each R ₁ independently represents a hydrogen atom, —C (═O) NR ₄ R ₅ , —NR ₆ C (═O) —R ₇ , —C (═O) R ₈ , —C (═O); Represents OR ₈ , —OR ₈ , —SR ₈ , an amino group, an aliphatic group, an aryl group, a halogen atom, or a heterocyclic group;
R ₂ each independently represents a substituent, and when a plurality of R ₂ are present, they may be the same as or different from each other.
Each R ₃ independently represents —C (═O) NR ₄ R ₅ or —C (═O) OR ₈ .
R ₄ each independently represents a hydrogen atom or an alkyl group.
R ₅ each independently represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, or —N (R ₉ ) (R ₁₀ ).
R ₆ each independently represents a hydrogen atom or an alkyl group.
R ₇ each independently represents an alkyl group, an aryl group, a heterocyclic group, an acyl group, an alkoxy group, or —N (R ₉ ) (R ₁₀ ).
R ₈ each independently represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group or an acyl group.
R ₉ each independently represents a hydrogen atom or an alkyl group.
R ₁₀ each independently represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. R ₄ and R ₅ , and R ₉ and R ₁₀ may be bonded to each other to form a 5- or 6-membered ring.
R ₁₁ each independently represents an amino group, an aliphatic oxy group, an aliphatic group, an aryl group or a heterocyclic group.
R ₁₂ each independently represents a hydrogen atom, an aliphatic group, an aryl group or a heterocyclic group.
R ₁₃ each independently represents a hydrogen atom, an aliphatic group, an aryl group or a heterocyclic group.
Y each independently represents a divalent group that forms a heterocyclic ring with —N═C—N—.
Each m independently represents an integer of 0 or more, and when m is 2 or more, R ₂ may be connected to each other to be condensed.
* Represents a bonding position with the azo group of the general formula (Az).
When n in the general formula (Az) is 2, it represents a dimer via R _{1 to} R ₁₃ , A or G. When n is 3, it represents a trimer via R _{1 to} R ₁₃ , A or G. When n is 4, it represents a tetramer via R _{1 to} R ₁₃ , A or G. )

  The aliphatic group represented by G may have a substituent and may be saturated or unsaturated. The group that may be substituted may be any group as long as it is a group that can be substituted with the groups described in the above-mentioned substituent group. Preferred substituents include a hydroxy group, an aliphatic oxy group, a carbamoyl group, and an aliphatic group. An 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.

  The aryl group represented by G may be condensed or may have a substituent. As the group which may be substituted, any group can be used as long as it can be substituted with the groups described in the above-mentioned substituent group. Preferred substituents include nitro group, halogen atom, aliphatic oxy group, 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.

  The heterocyclic group represented by G may have a substituent, may be saturated or unsaturated, and may be condensed. The group that may be substituted may be any group as long as it is a group that can be substituted with the groups described in the above-mentioned substituent group. Preferred substituents include halogen atoms, hydroxy groups, aliphatic oxy groups, carbamoyl groups, 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.

  The acyl group represented by G may be an aliphatic carbonyl group, an arylcarbonyl group, a heterocyclic carbonyl group, or may have a substituent. The group that may be substituted may be any group as long as it is a group that can be substituted with the groups described in the above-mentioned substituent group. Preferred substituents include a hydroxy group, a halogen atom, an aryl group, and an aliphatic oxy group. Carbamoyl group, aliphatic oxycarbonyl group, aliphatic thio group, amino group, aliphatic amino group, acylamino group, carbamoylamino group. The acyl group represented by G is preferably an acyl group having 2 to 8 carbon atoms in total, more preferably an acyl group having 2 to 4 carbon atoms in total, such as acetyl, propanoyl, benzoyl, 3-pyridine. Examples include carbonyl and the like.

  The aliphatic oxycarbonyl group represented by G may be saturated or unsaturated, and may have a substituent. The group that may be substituted may be any group as long as it is a group that can be substituted with the groups described in the above-mentioned substituent group. Preferred substituents include a hydroxy group, an aliphatic oxy group, a carbamoyl group, and an aliphatic group. An oxycarbonyl group, an aliphatic thio group, an amino group, an aliphatic amino group, an acylamino group, and a carbamoylamino group. The aliphatic oxycarbonyl group represented by G is preferably an alkoxycarbonyl group having 2 to 8 carbon atoms in total, more preferably an alkoxycarbonyl group having 2 to 4 carbon atoms in total, such as methoxycarbonyl, ethoxy Examples include carbonyl and (t) -butoxycarbonyl.

  The carbamoyl group represented by G may have a substituent. As the group which may be substituted, any group can be used as long as it is a group that can be substituted with the groups described in the above-mentioned substituent group. Preferred examples of the substituent include an aliphatic group, an aryl group, and a heterocyclic group. preferable. The carbamoyl group which may have a substituent represented by G is preferably an unsubstituted carbamoyl group, an alkylcarbamoyl group having 2 to 9 carbon atoms, or a total carbon number of 7 to 11, more preferably none. A substituted carbamoyl group and an alkylcarbamoyl group having 2 to 5 carbon atoms in total, such as N-methylcarbamoyl, N, N-dimethylcarbamoyl, N-phenylcarbamoyl and the like.

  The aliphatic sulfonyl group represented by G may be saturated or unsaturated, and may have a substituent. As the group which may be substituted, any group may be used as long as it can be substituted with the groups described in the above-mentioned substituent group. Preferred substituents include a hydroxy group, an aryl group, an aliphatic oxy group, and 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 sulfonyl group represented by G is preferably an alkylsulfonyl group having 1 to 6 carbon atoms, more preferably an alkylsulfonyl group having 1 to 4 carbon atoms, such as methanesulfonyl. It is done.

  The arylsulfonyl group represented by G may have a substituent. The group that may be substituted may be any group as long as it is a group that can be substituted with the groups described in the above-mentioned substituent group. Preferred substituents include a hydroxy group, an aliphatic group, an aliphatic oxy group, and a carbamoyl group. A group, an aliphatic oxycarbonyl group, an aliphatic thio group, an amino group, an aliphatic amino group, an acylamino group, and a carbamoylamino group. The arylsulfonyl group represented by G is preferably an arylsulfonyl group having 6 to 10 carbon atoms in total, and examples thereof include benzenesulfonyl.

  G is preferably a hydrogen atom, an aliphatic group, an aryl group or a heterocyclic group, more 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, and the group which may be substituted may be any of the groups described in the above-mentioned substituent group, and may be substituted. Any substituent may be used, and preferred examples of the substituent include an aliphatic group, an aryl group, and a heterocyclic group. As the amino group which may have a substituent represented by R ₁ , 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, An arylamino group having 6 to 12 carbon atoms in total, a heterocyclic amino group which may be saturated or unsaturated having 2 to 12 carbon atoms in total, more preferably an unsubstituted amino group, Even if the alkylamino group having 1 to 8 carbon atoms, the dialkylamino group having 2 to 8 carbon atoms, the arylamino group having 6 to 10 carbon atoms, or the saturation having 2 to 12 carbon atoms, A heterocyclic amino group which may be unsaturated, for example, methylamino, N, N-dimethylamino, N-phenylamino, N- (2-pyrimidyl) amino and the like.

The aliphatic group represented by R ₁ may have a substituent and may be saturated or unsaturated. As the substituent, any group can be used as long as it is a group that can be substituted as described in the above-mentioned substituent group. Preferred substituents include a hydroxy group, an aliphatic oxy group, a carbamoyl group, and an aliphatic oxycarbonyl. A group, an aliphatic thio group, an amino group, an aliphatic amino group, an acylamino group, and a carbamoylamino group. The aliphatic group for 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)- Examples include butyl, methoxyethyl, carbamoylmethyl and the like.

The aryl group represented by R ₁ may be condensed or may have a substituent. As the substituent, any group can be used as long as it is a group that can be substituted as described in the above-mentioned substituent group. Preferred substituents include a nitro group, a halogen atom, an aliphatic oxy group, a carbamoyl group, an aliphatic group. Group oxycarbonyl group, aliphatic thio group, amino group, aliphatic amino group, acylamino group, carbamoylamino group, and alkoxy group. The aryl group for 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- Examples include chlorophenyl.

Examples of the halogen atom represented by R ₁ include a fluorine atom, a chlorine atom, and a bromine atom.

The heterocyclic group represented by R ₁ may be a saturated heterocyclic ring or an unsaturated heterocyclic group, may have a substituent, or may be condensed. As the substituent, any group can be used as long as it is a group that can be substituted as described in the above-mentioned substituent group. Preferred substituents include a halogen atom, a hydroxy group, an aliphatic oxy group, a carbamoyl group, an aliphatic group. An oxycarbonyl group, an aliphatic thio group, an amino group, an aliphatic amino group, an acylamino group, and a carbamoylamino group. The heterocyclic group of R ₁ is preferably a heterocyclic group having 2 to 10 carbon atoms in total, more preferably a saturated heterocyclic group bonded with a nitrogen atom having 2 to 8 carbon atoms in total, for example, Examples include 1-piperidyl, 4-morpholinyl, 2-pyrimidyl, 4-pyridyl and the like.

R ₁ is preferably —C (═O) NR ₄ R ₅ , —NR ₆ C (═O) —R ₇ , —C (═O) OR ₈ or —OR ₈ , more preferably —C _{(= O) NR 4 R 5} , -C (= O) is oR ₈ or -OR _8, more preferably from _{-C (= O) NR 4 R} 5.

R ₄ and R ₆ each represent a hydrogen atom or an alkyl group.
The alkyl group represented by R ₄ and R ₆ may have a substituent, and the group that may be substituted is a group that can be substituted with a group that can be substituted with the groups described in the above-mentioned substituents section. Anything is fine. The alkyl group represented by R ₄ and R ₆ may be linear, branched or cyclic. The alkyl group represented by R ₄ and R ₆ is preferably an alkyl group having 1 to 8 carbon atoms in total, more preferably an alkyl group having 1 to 4 carbon atoms in total, for example, methyl, ethyl, vinyl Cyclohexyl, carbamoylmethyl and the like.

R ₅ represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, or —N (R ₉ ) (R ₁₀ ).
The alkyl group represented by R ₅ may have a substituent, and the group that may be substituted is any group that can be substituted with the groups described in the above-mentioned substituents section. Good. The alkyl group represented by R ₅ may be linear, branched or cyclic. The alkyl group represented by R ₅ is preferably an alkyl 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, And carbamoylmethyl.
The aryl group represented by R ₅ may be condensed, may have a substituent, and the group that may be substituted is the group described in the above-mentioned substituent section, Any group that can be substituted is acceptable. The aryl group represented by R ₅ is preferably an aryl group having 6 to 12 carbon atoms, more preferably an aryl group having 6 to 10 carbon atoms in total, such as phenyl, 4-nitrophenyl, 4-acetyl. Aminophenyl, 4-methanesulfonylphenyl, etc. are mentioned.
The heterocyclic group represented by R ₅ may have a substituent, may be saturated or unsaturated, and may be condensed. The heterocyclic group represented by R ₅ is preferably a heterocyclic group bonded with carbon atoms having 2 to 12 carbon atoms in total, more preferably 5 to 5 having 2 to 10 carbon atoms bonded with carbon atoms. 6-membered heterocycle, for example, 2-tetrahydrofuryl, 2-pyrimidyl and the like.

R ₇ represents an alkyl group, an aryl group, a heterocyclic group, an acyl group, an alkoxy group, or —N (R ₉ ) (R ₁₀ ).
Specific examples and preferred ranges of the alkyl group, aryl group and heterocyclic group represented by R ₇ are the same as the specific examples and preferred ranges of the alkyl group, aryl group and heterocyclic group represented by R ₅ .
The acyl group represented by R ₇ 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 may be used as long as it is a group which can be substituted with the groups described in the above-mentioned substituent group. The acyl group represented by R ₇ is preferably an acyl group having 2 to 8 carbon atoms in total, more preferably an acyl group having 2 to 4 carbon atoms in total, such as acetyl, benzoyl, 3-pyridinecarbonyl Etc.
The alkoxy group represented by R ₇ may have a substituent, and the substituent may be any group as long as it is the group described in the above-mentioned substituent group and can be substituted. The alkoxy group represented by R ₇ 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.

R ₈ represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group or an acyl group.
Specific examples and preferred ranges of the alkyl group, aryl group, heterocyclic group and acyl group represented by R ₈ are specific examples and preferred ranges of the alkyl group, aryl group, heterocyclic group and acyl group represented by R _7. It is the same.

R ₉ represents a hydrogen atom or an alkyl group, and R ₁₀ represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.
Specific examples and preferred ranges of the alkyl group represented by R ₉ and R ₁₀ are the same as the specific examples and preferred ranges of the alkyl group represented by R ₅ .
Specific examples and preferred ranges of the aryl group and heterocyclic group represented by R ₁₀ are the same as the specific examples and preferred ranges of the aryl group and heterocyclic group represented by R ₅ .

R ₄ and R ₅ , and R ₉ and R ₁₀ may be bonded to each other to form a 5- or 6-membered ring.
The 5- or 6-membered ring formed by combining R ₄ and R ₅ or R ₉ and R ₁₀ may have a substituent, may be saturated or unsaturated, and may be condensed. For example, morpholine, piperidine and the like can be mentioned.
R ₄ is preferably a hydrogen atom, R ₅ is preferably a hydrogen atom, an alkyl group or an aryl group, and R ₆ is preferably a hydrogen atom, and R ₇ is preferably an alkyl group or an aryl group. R ₈ is preferably a hydrogen atom, an alkyl group, or an aryl group. R ₉ is preferably a hydrogen atom, and R ₁₀ is preferably a hydrogen atom, an alkyl group, or an aryl group.

R ₂ represents a substituent, and when a plurality of R ₂ are present, they may be the same as or different from each other. When m is 2 or more, R ₂ may be linked to each other and condensed.
The substituent represented by R ₂ may be any group as long as it is a group that can be substituted with the groups described in the above-mentioned substituent group, and is preferably an aliphatic group, an aryl group, a heterocyclic group, an aliphatic oxycarbonyl. Group, carboxyl group, optionally substituted carbamoyl group, acylamino group, sulfonamide group, optionally substituted carbamoylamino group, optionally substituted sulfamoyl group, fatty acid An oxy group, an aliphatic thio group, a cyano group, a halogen atom, and a hydroxy group, more preferably an aliphatic oxycarbonyl group, an optionally substituted carbamoyl group, an acylamino group, and a substituent. A carbamoylamino group, an aliphatic oxy group and a halogen atom which may be present, 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 heteroatom-hydrogen atom bond is preferable. The group is more preferable from the viewpoint of facilitating intermolecular interaction such as intermolecular hydrogen bonding.

The aliphatic group represented by R ₂ may have a substituent, may be saturated or unsaturated, and the group that may be substituted includes the above-mentioned substituent group. Any group can be used as long as it is a substitutable group. The aliphatic group for 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-propyl, cyclohexyl, t-butyl etc. are mentioned.

The aryl group represented by R ₂ may have a substituent, and the group that may be substituted is any group that can be substituted with the groups described in the above-mentioned substituents section. Good. The aryl group for 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, such as phenyl, 3-methoxyphenyl, 4-carbamoylphenyl. Etc.

The heterocyclic group represented by R ₂ may have a substituent, may be saturated or unsaturated, may be condensed, and may be substituted. Can be any group as long as it is a group that can be substituted with the groups described in the above-mentioned substituent group. The heterocyclic group of 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, such as 1- Examples include pyrrolidinyl, 4-morpholinyl, 2-pyridyl, 1-pyrrolyl, 1-imidazolyl, 1-benzoimidazolyl and the like.

The aliphatic oxycarbonyl group represented by R ₂ may have a substituent, may be saturated or unsaturated, and the group that may be substituted includes the above-described substituents Any group can be used as long as it is a substitutable group among the groups described in the section. The aliphatic oxycarbonyl group for 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 or i-propyl. Examples include oxycarbonyl, carbamoylmethoxycarbonyl and the like.

The carbamoyl group represented by R ₂ may have a substituent, and as the group that may be substituted, any group can be used as long as it is a group that can be substituted with the groups described in the above-mentioned substituent group. Of these, an aliphatic group, an aryl group, a heterocyclic group and the like are preferable. The carbamoyl group optionally having a substituent for 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 in total, and a total carbon atom number of 7 -13 arylcarbamoyl group, 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 a dialkylcarbamoyl group having 3 to 6 carbon atoms. Group, an arylcarbamoyl group having 7 to 11 carbon atoms in total, and a heterocyclic carbamoyl group having 3 to 10 carbon atoms in total, such as carbamoyl, methylcarbamoyl, dimethylcarbamoyl, phenylcarbamoyl, 4-pyridinecarbamoyl, and the like. .

The acylamino group represented by R ₂ may have a substituent, may be aliphatic, aromatic, heterocyclic, or may be substituted. Can be any group as long as it is a group that can be substituted with the groups described in the above-mentioned substituent group. The acylamino group for R ₂ is preferably an acylamino group having 2 to 12 carbon atoms, more preferably an acylamino group having 2 to 8 carbon atoms, and still more preferably an alkyl having 2 to 8 carbon atoms. Examples of the carbonylamino group include acetylamino, benzoylamino, 2-pyridinecarbonylamino, propanoylamino and the like.

The sulfonamide group represented by R ₂ may have a substituent, may be aliphatic, aromatic, heterocyclic, or may be substituted. As the above, 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. 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, and as the group that may be substituted, any group can be used as long as it is a group that can be substituted with the groups described in the above-mentioned substituents section. Of these, an aliphatic group, an aryl group, a heterocyclic group and the like are preferable. 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.

As the sulfamoyl group which may have a substituent represented by R ₂ , the group which may be substituted may be any group as long as it can be substituted with the groups described in the above-mentioned substituent section, An aliphatic group, an aryl group, a heterocyclic group and the like are preferable. 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, may be saturated or unsaturated, and may be substituted. Any group can be used as long as it is a substitutable group. The aliphatic oxy group for 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, Examples include cyclohexyloxy and methoxyethoxy.

The aliphatic thio group represented by R ₂ may have a substituent, may be saturated or unsaturated, and may be substituted. Any group can be used as long as it is a substitutable group. The aliphatic thio group for R ₂ is preferably an alkylthio group having 1 to 8 carbon atoms, more preferably an alkylthio group having 1 to 6 carbon atoms, such as methylthio, ethylthio, carbamoylmethylthio, t- Examples include 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.
From the viewpoint of the effect of the present invention, R ₂ is preferably an aliphatic oxy group, an aliphatic oxycarbonyl group, or an optionally substituted carbamoyl group, and more preferably an aliphatic oxy group. .

When m is 2 or more, the ring formed by connecting R ₂ to each other may be an aliphatic ring, an aliphatic hetero ring, an aromatic ring, an aromatic hetero ring It may be a ring. The number of carbon atoms in the ring formed by connecting R ₂ to each other is preferably 2 to 20, and more preferably 3 to 10.

R ₃ represents —C (═O) NR ₄ R ₅ or —C (═O) OR ₈ . Specific examples and preferred ranges of R _{4, R 5} and _{R 8} are the same as _R 4, _{R 5} and _{R 8} described above. R ₃ preferably represents —C (═O) NR ₄ R ₅ .

R ₁₁ represents an amino group, aliphatic oxy group, aliphatic group, aryl group or heterocyclic group.
The amino group represented by R ₁₁ may have a substituent, and the group which may be substituted may be any of the groups described in the above-mentioned substituent group and may be substituted. Any substituent may be used, and preferred examples of the substituent include an aliphatic group, an aryl group, and a heterocyclic group.
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.
As the amino group which may have a substituent represented by R ₁₁ , 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, An arylamino group having 6 to 13 carbon atoms in total, a heterocyclic amino group which may be saturated or unsaturated having 2 to 12 carbon atoms in total, more preferably an unsubstituted amino group, An alkylamino group having 1 to 8 carbon atoms in total, an arylamino group having 6 to 13 carbon atoms in total, a heterocyclic amino group having 2 to 12 carbon atoms that may be saturated or unsaturated. Yes, for example, methylamino, N, N-dimethylamino, N-phenylamino, N- (2-pyrimidyl) amino and the like.
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 ₁₁ 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. The substituent may be any group that can be substituted with the group described in the above-mentioned substituent group, and preferably has 1 to 7 carbon atoms in total, more preferably 1 to 4 carbon atoms in total. An aliphatic group which may have a group (for example, methyl, ethyl, allyl, (i) -propyl, (t) -butyl, etc.), 1 to 7 carbon atoms, more preferably 1 to 1 carbon atoms in total. An aliphatic oxy group (for example, methoxy, ethoxy, (i) -propyloxy, allyloxy, etc.) optionally having 4 substituents, a halogen atom (for example, fluorine, chlorine, bromine, etc.), 7, more preferably a carbamoyl group (for example, carbamoyl, N-phenylcarbamoyl, N-methylcarbamoyl, etc.) which may have a substituent having 1 to 4 carbon atoms, more preferably 1 to 7 carbon atoms Is the total carbon field A ureido group (for example, ureido, N-methylureido, N, N-dimethylureido, N-4-pyridylureido, N-phenylureido, etc.) optionally having a substituent of formulas 1-4, nitro group, total It has a heterocyclic ring condensed with the aryl group having 1 to 7 carbon atoms (for example, imidazolone), a hydroxy group, a substituent having 1 to 7 total carbon atoms, more preferably 1 to 4 carbon atoms in total. A good aliphatic thio group (for example, methylthio, ethylthio, (i) -propylthio, allylthio, (t) -butylthio, etc.), a substituent having 2 to 7 total carbon atoms, more preferably 2 to 4 total carbon atoms. An acylamino group which may have (for example, acetoamino, propionylamino, pivaloylamino, benzoylamino, etc.), 1 to 7 carbon atoms in total, more preferably 1 to 4 carbon atoms in total An optionally substituted 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. An optionally substituted aliphatic oxycarbonyl group (for example, methoxycarbonyl, ethoxycarbonyl, etc.), an acyl optionally having a substituent of 2 to 7 carbon atoms, more preferably 2 to 4 carbon atoms in total Group (which may be an aliphatic carbonyl group, an arylcarbonyl group, a heterocyclic carbonyl group, may have a substituent, and the group that may be substituted includes Any group can be used as long as it is a group that can be substituted among the groups described in the section of the substituent, preferably an acyl group having 2 to 7 carbon atoms, more preferably an acyl group having 2 to 4 carbon atoms. And examples thereof include acetyl, propanoyl, benzoyl, 3-pyridinecarbonyl, and the like. Etc.
When the substituent on the aryl group is substituted from the bonding position with the amino group to the para position, since the substituent is at the end of the molecule, intermolecular interaction such as intermolecular hydrogen bonding is likely to occur. 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 ₁₁ is a heterocyclic amino group, the substituent may be any group that can be substituted with the group described in the above-mentioned substituent group, and preferably the same substituent as in the case of the arylamino group. Groups are preferred. When the substituent on the heterocyclic 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. A substituent having a bond is more preferable from the viewpoint of facilitating intermolecular interaction such as intermolecular hydrogen bonding.

More preferred substituents when R ₁₁ is an arylamino group or a heterocyclic amino group include an aliphatic group, an aliphatic oxy group, a halogen atom, a carbamoyl group, a heterocycle fused with the aryl group, an aliphatic group It is an 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 carbamoyl group having 1 to 4 carbon atoms, a nitro group, or a total carbon. It is an aliphatic oxycarbonyl group having 2 to 4 atoms.

The aliphatic oxy group represented by R ₁₁ may have a substituent and may be saturated or unsaturated. As the substituent, any group can be used as long as it is a group that can be substituted as described in the above-mentioned substituent group. Preferred substituents include a hydroxy group, an aliphatic oxy group, a carbamoyl group, and an aliphatic oxycarbonyl. A group, an aliphatic thio group, an amino group, an aliphatic amino group, an acylamino group, and a carbamoylamino group. The aliphatic oxy group for R ₁₁ is preferably an alkoxy group having 1 to 8 carbon atoms, more preferably an alkoxy group having 1 to 4 carbon atoms, and still more preferably 1 to 1 carbon atoms. 2, for example, methoxy, ethoxy, (t) -butoxy, methoxyethoxy, carbamoylmethoxy and the like.

The aliphatic group represented by R ₁₁ may have a substituent and may be saturated or unsaturated. Any group can be used as long as it is a group that can be substituted, as described in the above-mentioned substituent group. Preferred substituents include a hydroxy group, an aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thiol group. A group, an amino group, an aliphatic amino group, an acylamino group, and a carbamoylamino group. The aliphatic group for R ₁₁ is preferably an alkyl 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, (s)- Examples include butyl, methoxyethyl, carbamoylmethyl and the like.

The aryl group represented by R ₁₁ may have a substituent, and the substituent may be any group as long as it is the group described in the above-mentioned substituent group and can be substituted. Preferred examples of the substituent include an aliphatic group, an aliphatic oxy group, a halogen atom, a carbamoyl group, a hetero ring fused with the aryl group, and an aliphatic oxycarbonyl group. The aryl group for R ₁₁ 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- Examples include chlorophenyl.

The heterocyclic group represented by R ₁₁ may be a saturated heterocyclic ring or an unsaturated heterocyclic group, may have a substituent, or may be condensed. As the substituent, any group can be used as long as it is a group that can be substituted as described in the above-mentioned substituent group. Preferred substituents include aliphatic groups, aliphatic oxy groups, carbamoyl groups, and heteroatoms. A heterocyclic ring fused to the group, or an aliphatic oxycarbonyl group. The heterocyclic group of R ₁₁ is preferably a heterocyclic group having 2 to 10 carbon atoms in total, more preferably a saturated heterocyclic group bonded with a nitrogen atom having 2 to 8 carbon atoms in total, for example, Examples include 1-piperidyl, 4-morpholinyl, 2-pyrimidyl, 4-pyridyl and the like.

R ₁₁ is preferably an amino group which may have a substituent, an aliphatic oxy group, or a saturated heterocyclic group bonded with a nitrogen atom, more preferably a substituent. An amino group, an aliphatic oxy group, and more preferably an amino group which may have a substituent.

R ₁₁ is also preferably an amino group represented by —N (R ₀₁ ) —R ₀₂ —N (R ₀₃ ) (R ₀₄ ) or —N (R ₀₁ ) —R ₀₅ .
Here, R ₀₁ represents a hydrogen atom, an aliphatic group, an aryl group, or a heterocyclic group, preferably a hydrogen atom. R ₀₂ represents an alkylene group, an arylene group, a carbonyl group or a thiocarbonyl group, preferably a carbonyl group. R _{03 to} R ₀₅ each independently represents a hydrogen atom, an aliphatic group, an aryl group, or a heterocyclic group, and R ₀₁ and R ₀₅ or R ₀₃ and R ₀₄ are connected to each other to form a heterocyclic ring. It may be formed. Heterocycles that may be formed include pyrrole, pyrroline, pyrrolidine, pyrrolidone, indole, indoline, isoindole, carbazole, benzoindole, imidazole, pyrazole, pyrazoline, oxazine, phenoxazine, benzocarbazole, thiomorpholine, etc. A ring of an amino group can be mentioned.
Each group as R _{01 to} R ₀₅ may further have a substituent.

R ₀₃ is preferably a hydrogen atom because it easily forms an intramolecular hydrogen bond or an intramolecular cross-hydrogen bond.
R ₀₄ is preferably an alkyl group or an aryl group from the viewpoint of hue and durability (heat resistance / light resistance), more preferably an aryl group, and still more preferably a phenyl group.
R ₀₅ is preferably an aryl group or a heterocyclic group. The aryl group and heterocyclic group are preferably substituted or unsubstituted groups with an aliphatic group, an alkoxy group, a halogen atom, or an alkylthio group. The aryl group is preferably a phenyl group or a naphthyl group. The heterocyclic group is preferably a nitrogen-containing heteroaryl group, and more preferably a pyridyl group.

R ₁₂ represents a hydrogen atom, an aliphatic group, an aryl group or a heterocyclic group.
As the aliphatic group, aryl group and heterocyclic group for R _12, the same groups as those for R ₁₁ can be mentioned. R ₁₂ is preferably a hydrogen atom or an aliphatic group.

R ₁₃ represents a hydrogen atom, an aliphatic group, an aryl group or a heterocyclic group.
As the aliphatic group, aryl group and heterocyclic group for R _13, the same groups as those for R ₁₁ can be mentioned. R ₁₃ is preferably a hydrogen atom or an aliphatic group.

Y is a divalent group that forms a heterocyclic ring with —N═C—N—, an alkylene group (preferably having 1 to 5 carbon atoms), an alkenylene group (preferably having 2 to 5 carbon atoms), an arylene group ( Preferably, it has 6 to 10 carbon atoms, and a heteroarylene group (preferably 4 to 10 carbon atoms).
Y is preferably an alkenylene group or an arylene group, and more preferably an arylene group.
The heterocyclic ring formed by Y together with —N═C—N— is preferably a ring consisting of a nitrogen atom, an oxygen atom and a carbon atom, or a ring consisting of a nitrogen atom and a carbon atom, and a nitrogen atom and a carbon atom More preferably, the ring consists of Moreover, it is preferable that it is a 5 or 6 membered ring, and it is more preferable to form the benzimidazole ring or the naphthimidazole ring.

m is an integer greater than or equal to 0, and the upper limit is 5 in the general formulas (1), (2) and (1-1) to (1-3), and the general formulas (3) and (1-4). ) Is 7, and in general formulas (1-5) to (1-10), it is 4, but is preferably an integer of 0 to 4, more preferably an integer of 0 to 3, and 0 or The case of 1 is more preferable, and the case of 0 is still more preferable.
n is preferably 1 or 2.

  In the azo pigment represented by the general formula (Az), B represents the above general formulas (1) to (3) and (1-1) from the viewpoint of various properties (heat resistance, color characteristics, etc.) as the pigment. It is preferable that it is a structure represented by either of (1-4), and it is especially preferable that it is a structure represented by either of the said general formula (1)-(3).

The aromatic 5- or 6-membered heterocyclic group represented by A removes any one hydrogen atom bonded to the carbon atom constituting the ring of the aromatic 5- or 6-membered heterocyclic ring, and bonds with the azo group. The aromatic 5- or 6-membered heterocyclic ring may be condensed or monocyclic, and the condensed ring may be a carbocyclic ring or a heterocyclic ring. It may be an aromatic ring or a non-aromatic ring, and is preferably an aromatic 5- or 6-membered ring containing 1 to 3 heteroatoms. As the aromatic 5- or 6-membered hetero ring which may be condensed in A, a pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, triazine ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, pyrazole A condensed heterocyclic group of a ring, an oxazole ring, a thiazole ring, an isoxazole ring, an isothiazole ring, a triazole ring, a thiadiazole ring, an oxadiazole ring and the like and a benzene ring derivative and a heterocyclic derivative.
The aromatic 5- or 6-membered heterocyclic group represented by A is an aromatic 5- or 6-membered heterocyclic group represented by any one of the following general formulas (A-1) to (A-34). Is preferable from the viewpoint of various properties (heat resistance, color properties, etc.) as a pigment.

(In the general formulas (A-1) to (A-34), R _{51 to} R ₅₈ each independently represent a hydrogen atom or a substituent, and the adjacent substituents are bonded to each other to form a 5- or 6-membered ring. (* Represents the bonding position with the azo group of the general formula (Az).)

The substituent represented by R _{51 to} R ₅₄ may be any group as long as it is a group that can be substituted with the groups described in the above-mentioned substituent group. As a substituent for 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 group An oxy group, an aliphatic thio group, a cyano group, and the like, more preferably an aliphatic group, an aliphatic oxycarbonyl group, an optionally substituted carbamoyl group, an aliphatic oxy group, a cyano group, and the like.

R _{51 to} R ₅₄ are hydrogen atoms, aliphatic groups, aryl groups, heterocyclic groups, aliphatic oxycarbonyl groups, carbamoyl groups which may have a substituent, acylamino groups, sulfonamides in terms of the effects of the present invention. Group, an aliphatic oxy group, an aliphatic thio group, a cyano group, etc., preferably a hydrogen atom, an aliphatic group, an aliphatic oxycarbonyl group, an optionally substituted carbamoyl group, an aliphatic oxy group More preferably, it is a cyano group.

The substituent represented by R ₅₅ may be any group as long as it is a group that can be substituted with the groups described in the above-mentioned substituent group. The substituent for R ₅₅ is preferably an aliphatic group, an aryl group, a heterocyclic group or the like, more preferably an aromatic group, an aryl group, or an aromatic group containing a nitrogen atom adjacent to the bonding site with the nitrogen atom. It is a 5-6 membered heterocyclic group.

From the viewpoint of the effects of the present invention, R ₅₅ is preferably an aliphatic group, an aryl group, or a heterocyclic group, and contains a nitrogen atom at a position adjacent to the bonding site with the aliphatic group, aryl group, or nitrogen atom. The aromatic 5- to 6-membered heterocyclic group is more preferable, and the aromatic 5- to 6-membered heterocyclic group containing a nitrogen atom adjacent to the binding site with the nitrogen atom is more preferable. R ₅₅ is an aromatic 5- to 6-membered heterocyclic group containing a nitrogen atom adjacent to the binding site with the nitrogen atom, thereby strengthening not only the intermolecular interaction of the dye molecule but also the intramolecular interaction. Easy to form. 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.).

The aromatic 5- to 6-membered heterocyclic group containing a nitrogen atom adjacent to the binding site with the nitrogen atom, which is preferable as R ₅₅ in terms of the effects of the present invention, 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. An aromatic oxycarbonyl group, an aliphatic thio group, an amino group, an aliphatic amino group, an acylamino group, a carbamoylamino group, whether it is a saturated or unsaturated heterocycle, a condensed heterocycle Preferably, it is an aromatic 5- to 6-membered heterocyclic group containing a nitrogen atom adjacent to the binding site with the nitrogen atom having 2 to 12 carbon atoms, more preferably a total carbon atom. Bonding part with the nitrogen atom of several 2-10 It is an aromatic 5- to 6-membered heterocyclic group containing a nitrogen atom at the adjacent position. 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 view of the effects of the present invention, the aryl group preferable as R ₅₅ may have a substituent, and the group which may be substituted may be substituted with the group described in the above-mentioned substituent group. As long as it is a group, preferred substituents are hydroxy group, nitro group, aliphatic oxy group, carbamoyl group, aliphatic oxycarbonyl group, aliphatic thio group, amino group, aliphatic amino group, acylamino group, It is 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 general formula (1), R ₅₅ is preferably any one of the following (Y-1) to (Y-13), and is a 6-membered ring in order to make it easy to form an intramolecular hydrogen bond structure. More preferably, it is any of the following (Y-1) to (Y-6), and any of the following (Y-1), (Y-3), (Y-4), or (Y-6) In some cases, it is more preferable, and in the following (Y-1) or (Y-4), it is particularly preferable. * In the general formulas (Y-1) to (Y-13) represents a bonding site with the N atom of the pyrazole ring. Y _{1 to} Y ₁₁ represent a hydrogen atom or a substituent. G ₁₁ in (Y-13) represents a nonmetallic atom group that can form a 5- to 6-membered heterocycle, and the heterocycle represented by G ₁₁ has a substituent even if it is unsubstituted. The heterocycle may be monocyclic or condensed. Formulas (Y-1) to (Y-13) may have tautomeric structures together with substituents.

Y ₁ to Y ₁₁ are hydrogen atoms, aliphatic groups, aryl groups, heterocyclic groups, aliphatic oxycarbonyl groups, carbamoyl groups optionally having substituents, acylamino groups, sulfonamides in terms of the effects of the present invention. Group, an aliphatic oxy group, an aliphatic thio group, a cyano group, etc., preferably a hydrogen atom, an aliphatic group, an aliphatic oxycarbonyl group, an optionally substituted carbamoyl group, an aliphatic oxy group More preferably, it is a cyano group.

As the substituent represented by R ₅₆ or R ₅₇ , any group can be used as long as it is a group that can be substituted with the groups described in the above-mentioned substituent group. As a substituent for R ₅₆ and R _57, 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 group An oxy group, an aliphatic thio group, a cyano group, and the like, more preferably an aliphatic group, an aliphatic oxy group, an aliphatic thio group, a cyano group, and the like.

In terms of the effects of the present invention, R ₅₆ and R ₅₇ 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, A sulfonamide group, an aliphatic oxy group, an aliphatic thio group, a cyano group and the like are preferable, and a hydrogen atom, an aliphatic group, an aliphatic oxy group, an aliphatic thio group, and a cyano group are more preferable.

The substituent represented by R ₅₈ may be any group as long as it is a group that can be substituted with the groups described in the above-mentioned substituent group. 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. If the σp value is within this range, R ₅₈ can be synthesized by the same synthesis method, and the same effect can be obtained in terms of increasing the hue wavelength.

Specific examples of R ₅₈ which is an electron withdrawing group having a σp value of 0.2 or more include an acyl group, an acyloxy group, a carbamoyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a cyano group, a nitro group, and a dialkylphospho 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 0.2 or more, heterocyclic groups, Halogen atom, azo group, or selenasia Include the over door group.

  In one embodiment, the azo pigment represented by the general formula (Az) has an A of (A-10), (A-14) to (A-16), (A-25) or (A-26). It is preferable that A is (A-10), (A-14) to (A-16), or (A-26), more preferably (A-16). preferable.

  In view of the effect of the present invention, the azo pigment represented by the general formula (Az) is preferably an azo pigment represented by the following general formula (Az-1).

(In the general formula (Az-1),
G ₂ each independently represents a hydrogen atom, an aliphatic group, an aryl group or a heterocyclic group.
R ₂₁ each independently represents an amino group, an aliphatic oxy group, or a saturated heterocyclic group bonded with a nitrogen atom.
R ₂₂ each independently represents a substituent, and when a plurality of R ₂₂ are present, they may be the same as or different from each other.
A ₂ each independently represents an aromatic 5- or 6-membered heterocyclic group represented by any one of the following general formulas (A-1) to (A-34).
Each m independently represents an integer of 0 or more. When m is 2 or more, R ₂₂ may be connected to each other to form a condensed ring.
n represents an integer of 1 to 4.
When n in the general formula (Az-1) is 2, it represents a dimer through R ₂₁ , R ₂₂ , A ₂ or G ₂ . When n is 3, it represents a trimer via R ₂₁ , R ₂₂ , A ₂ or G ₂ . When n is 4, it represents a tetramer via R ₂₁ , R ₂₂ , A ₂ or G ₂ . )

(In the general formulas (A-1) to (A-34), R _{51 to} R ₅₈ each independently represent a hydrogen atom or a substituent, and the adjacent substituents are bonded to each other to form a 5- or 6-membered ring. (* Represents a bonding position with the azo group of the general formula (Az-1).)

G ₂ represents a hydrogen atom, an aliphatic group, an aryl group or a heterocyclic group.
Specific examples and preferred ranges of the aliphatic group, aryl group and heterocyclic group represented by G ₂ are the same as the specific examples and preferred ranges of the aliphatic group, aryl group and heterocyclic group represented by G ₂ .
G ₂ is preferably a hydrogen atom. This is because it is easy to form an intramolecular hydrogen bond or an intramolecular cross hydrogen bond.

R ₂₁ represents an amino group, an aliphatic oxy group, or a saturated heterocyclic group bonded with a nitrogen atom.
Specific examples and preferred ranges of the amino group, aliphatic oxy group and saturated heterocyclic group bonded with a nitrogen atom represented by R ₂₁ include the amino group, aliphatic oxy group and nitrogen atom bonded with R ₁₁ . The specific examples and preferred ranges of the saturated heterocyclic group are the same.

R ₂₂ each independently represents a substituent, and when a plurality of R ₂₂ are present, they may be the same as or different from each other.
Specific examples and preferred ranges of the substituent represented by R ₂₂ are the same as the specific examples and preferred ranges of the substituent represented by R ₂ .

A ₂ each independently represents an aromatic 5- or 6-membered heterocyclic group represented by any one of the general formulas (A-1) to (A-34). Specific examples and preferred ranges of R _{51 to} R _{58 in} the general formulas (A-1) to (A-34) are the same as the specific examples and preferred ranges described above.
In one embodiment, in the azo pigment represented by the general formula (Az-1), A ₂ is (A-10), (A-14) to (A-16), (A-25) or ( A-26) is preferred, and A ₂ is more preferably (A-10), (A-14) to (A-16), or (A-26), and (A-16) More preferably it is.

m is synonymous with m in the general formulas (1) to (3) and (1-1) to (1-10), and the preferred range is also the same.
n is synonymous with n in the said general formula (Az), and its preferable range is also the same.

  Specific examples of the azo pigment represented by the general formula (Az) include compounds described in paragraphs [0132] to [0153] of WO 10/008081, and paragraph [0115] of JP 2010-155983 A. To [0130], compounds described in paragraphs [0123] to [0129] of JP2010-43255A, compounds described in paragraphs [0128] to [0142] of JP2010-84135A, However, the azo pigments used in the present invention are not limited to these. 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 pigment represented by the general formula (Az) of the present invention only needs to have a chemical structural formula of the general formula (Az) or a tautomer thereof, and may be a pigment in any crystal form also called a polymorph.

  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 crystal polymorph exists in the pigment represented by the general formula (Az) of the present invention, any polymorph may be used, and a mixture of two or more polymorphs may be used. It is preferable to use a single component as the main component. 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.

  In the present invention, when the azo pigment represented by the general formula (Az) has an acid group, 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 that may be substituted with alkyl groups or hydroxyalkyl groups, 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 (Az) may be a hydrate containing water molecules in the crystal.

The exemplified compounds D-29 to D-37 can be obtained by subjecting the amine compound corresponding to A in the exemplified compounds D-29 to D-37 to a diazo coupling reaction with the compound corresponding to B. It is.
For example, the heterocyclic amine compound represented by A-NH ₂ (A is A in the formula (Az)) is diazoniumized with non-aqueous acidity. In the structure represented by general formulas (1) to (3) and (1-1) to (1-10) of B, a compound in which the bond represented by * is a hydrogen atom is in an acidic state. The azo pigment can be produced by carrying out a coupling reaction and after-treatment by a conventional method.

Heterocyclic amines corresponding to the amino form of A in the above general formula (Az) can be obtained as commercial products, but are generally described in known and commonly used methods, for example, Japanese Patent No. 4022221. It can be manufactured by the method.
Although couplers corresponding to the structures represented by the above general formulas (1) to (3) and (1-1) to (1-10) can be obtained as commercial products, JP-A-63-264762. Can be produced by the method described in JP-A No. 5-323634, JP-A No. 1-179158 and the like, 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. It can be carried out by reacting for about minutes to 6 hours.
In the coupling reaction, the diazonium salt obtained by the above-described method and the compounds represented by the general formulas (1) to (3) and (1-1) to (1-10) are 40 ° C. or less, preferably It can carry out by making it react for 10 minutes-about 12 hours at 25 degrees C or less.
The synthesis method in the case where n in the general formula (Az) is 2 or more includes, for example, the general formulas (1) to (3) and (1-1) to (1- In R _{1 to} R ₁₃ in 10), R _{51 to} R ₅₈ in general formulas (A-1) to (A-34), etc., a divalent, trivalent or tetravalent substituent capable of being substituted was introduced. The raw materials 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 collected crystals can be washed and dried as necessary to obtain an azo pigment represented by the general formula (Az).

Although the pigment represented by the general formula (Az) is obtained as a crude azo pigment (crude) by the above production method, it is desirable to perform post-treatment when used as the pigment of 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 exemplified compounds D-1 to D-20 can also be synthesized by, for example, the synthesis method described in International Publication No. 10/008081. The exemplified compounds D-21 to D-28 can also be synthesized, for example, by the synthesis method described in JP2010-155983A. Other compounds can also be synthesized by methods known in the art.

  Although the azo pigment represented by the general formula (Az) is obtained as a crude azo pigment (crude) by the above production method, it is desirable to perform post-treatment when used as the pigment of 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 (Az) of the present invention is preferably subjected to solvent heat treatment and / or solvent salt milling as a post-treatment.
By performing solvent salt milling, the average primary particle diameter of the azo pigment represented by the general formula (Az) can be easily adjusted within the above 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 diameter 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 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 JP-A-2009-263501.
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.

  The content of the azo pigment represented by the general formula (Az) in the processed pigment of the present invention is preferably 1 to 99% by mass, more preferably 10 to 95% by mass, and 20 to 95% by mass. % Is more preferable. This is for balance with color density and other components.

<Other pigments>
The pigment dispersion composition of the present invention is a pigment other than the azo pigment represented by the general formula (Az), together with the azo pigment represented by the general formula (Az), 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.

Examples of the 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). Listed are numbers.
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, 58
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 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, 58
C. I. Pigment Black 1

  Specific examples of the inorganic pigment include titanium oxide, barium sulfate, calcium carbonate, zinc white, lead sulfate, yellow lead, zinc yellow, red bean (red iron (III) oxide), cadmium red, ultramarine blue, bitumen, and oxidation. Examples thereof include chrome 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.

  Particularly 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), in addition to the azo pigment represented by the general formula (Az), red It is preferable to contain at least one pigment having a hue selected from (Red), yellow (Yellow), orange (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 another pigment other than the azo pigment represented by the general formula (Az) (particularly, a pigment having a hue selected from red, yellow, orange, and violet) is 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%.

[Ii) Water-soluble inorganic salt]
The water-soluble inorganic salt used in the present invention is not particularly limited as long as it is soluble in water, and sodium chloride, barium chloride, potassium chloride, sodium sulfate and the like can be used. Alternatively, sodium sulfate is preferably used.
The amount of the inorganic salt used for salt milling is preferably 1 to 30 times, particularly 5 to 25 times the amount of the organic pigment, from the viewpoint of both processing efficiency and production efficiency. This is because the finer efficiency is higher as the amount ratio of the inorganic salt to the organic pigment is larger, but the amount of treatment of one pigment is reduced.

[Iii) A small amount of a water-soluble organic solvent that does not substantially dissolve ii)
The water-soluble organic solvent functions to wet the organic pigment and the inorganic salt, and is not particularly limited as long as it dissolves (mixes) in water and does not substantially dissolve the inorganic salt to be used. However, a high boiling point solvent having a boiling point of 120 ° C. or higher is preferable from the viewpoint of safety because the temperature rises during salt milling and the solvent easily evaporates. Examples of the water-soluble organic solvent include 2-methoxyethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, ethylene glycol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether. Acetate, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol Monoethyl ether, liquid polypropylene glycol or the like is used.

  The addition amount of the water-soluble organic solvent is preferably 5% by mass to 50% by mass with respect to the inorganic salt. More preferably, it is 10 mass%-40 mass% with respect to an inorganic salt, and optimally it is 15 mass%-35 mass% with respect to an inorganic salt. When the addition amount is less than 5% by mass, uniform kneading becomes difficult, and the particle size distribution becomes large, which is not preferable. When the addition amount is 50% by mass or more, the kneaded composition becomes too soft and the kneaded composition is less likely to be sheared, so that a sufficient refinement effect cannot be obtained. iii) The water-soluble organic solvent may be added in the initial stage of salt milling, or may be added separately. A water-soluble organic solvent may be used independently and can also use 2 or more types together.

[Iv) Polymer compound]
The polymer compound of the present invention is a polymer compound introduced when forming a processed pigment. Thereby, the strong secondary aggregation of the refined | miniaturized pigment can be suppressed and a processed pigment with high contrast can be obtained.

The polymer compound of the present invention is preferably added in the pigment refinement step to produce a processed pigment. Therefore, it is not particularly limited as long as it is a polymer compound that dissolves in the solvent used in the miniaturization step. Preferably, it should be solid at room temperature, insoluble in water, and at least partially soluble in a water-soluble organic solvent used as a wetting agent during salt milling. A modified synthetic resin or the like is used.
When using a dried treated pigment, the compound used is preferably solid at room temperature. 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 processed pigment of the present invention thus obtained is a processed pigment excellent in dispersibility and dispersion stability because the pigment surface is firmly coated with the polymer compound and does not release even when immersed in an organic solvent. The application range is wide, and it is particularly useful for the preparation of a pigment dispersion composition.

  Therefore, the polymer compound preferably has an aryl group or a heterocyclic group included in the pigment structure. When a polymer compound having a similar structure is used, the pigment surface can be efficiently coated. Specific examples include a benzyl group, a phenyl group, a naphthalene group, and a pyridinyl group. A polymer compound having a heterocyclic structure in the immediate chain, which will be described later, is particularly preferable.

  The molecular weight of the polymer compound is preferably in the range of 1,000 to 100,000 in terms of weight average molecular weight (Mw) and in the range of 400 to 50,000 in terms of number average molecular weight (Mn). More preferably, the weight average molecular weight (Mw) is in the range of 5,000 to 50,000, and the number average molecular weight (Mn) is in the range of 2,000 to 30,000. In particular, the weight average molecular weight (Mw) is most preferably in the range of 8,000 to 30,000, and the number average molecular weight (Mn) is in the range of 4,000 to 12,000. When the weight average molecular weight (Mw) is 100,000 or less, the polymer compound can be prevented from being insolubilized in the solvent, and when the weight average molecular weight (Mw) is 1,000 or more, the pigment is sufficiently coated. Can do.

  The polymer compound of the present invention is preferably a polymer compound having a heterocyclic ring in the side chain. By introducing a heterocyclic structure, a fine pigment can be obtained. The heterocyclic ring contained in the polymer compound promotes adsorption to the azo pigment having the specific heterocyclic group according to the present invention (heterocyclic azo pigment), and the pigment is coated with a large amount of the polymer. Estimated effect. In this way, when the pigment is specifically coated with a polymer compound having a heterocyclic ring in the side chain, the pigment tends to stay in the film via the polymer compound, and a coating film layer of another color is applied. It is considered that the pigment is prevented from oozing out when heated or heated. In particular, when the azo pigment according to the present invention is applied to an image sensor, the conventional method has a problem of color mixing when another color is applied on the color filter. It has been found that the use of a processed pigment coated with a polymer compound having a heterocyclic ring in the side chain improves unexpectedly.

  The polymer compound having a heterocyclic ring in the side chain includes a polymer unit derived from a monomer represented by the following general formula (H-1), or a monomer composed of maleimide or a maleimide derivative. A polymer is preferable, and a polymer including a polymer unit derived from a monomer represented by the following general formula (H-1) is particularly preferable.

In the general formula (H-1), R ¹ represents a hydrogen atom or an alkyl group. R ² represents a single bond or a divalent linking group. Y represents -CO-, -C (= O) O-, -CONH-, -OC (= O)-, or a phenylene group. Z represents a group having a nitrogen-containing heterocyclic structure.
As the alkyl group for R ¹ , an alkyl group having 1 to 12 carbon atoms is preferable, an alkyl group having 1 to 8 carbon atoms is more preferable, and an alkyl group having 1 to 4 carbon atoms is particularly preferable. The alkyl group of R ¹ may have a substituent.
When the alkyl group represented by R ¹ has a substituent, examples of the substituent include a hydroxy group and an alkoxy group (preferably having 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms). A methoxy group, an ethoxy group, a cyclohexyloxy group, etc. are mentioned.

Specific examples of the preferred alkyl group represented by R ¹ include, for example, methyl group, ethyl group, propyl group, n-butyl group, i-butyl group, t-butyl group, n-hexyl group, cyclohexyl group, 2 -Hydroxyethyl group, 3-hydroxypropyl group, 2-hydroxypropyl group, 2-methoxyethyl group can be mentioned.
R ¹ is most preferably a hydrogen atom or a methyl group.

In General Formula (H-1), R ² represents a single bond or a divalent linking group. The divalent linking group is preferably a substituted or unsubstituted alkylene group. The alkylene group is preferably an alkylene group having 1 to 12 carbon atoms, more preferably an alkylene group having 1 to 12 carbon atoms, still more preferably an alkylene group having 1 to 8 carbon atoms, and an alkylene group having 1 to 4 carbon atoms. Particularly preferred.
The alkylene group represented by R ² may be one in which two or more are connected via a hetero atom (for example, an oxygen atom, a nitrogen atom, or a sulfur atom).
Specific examples of the preferable alkylene group represented by R ² include a methylene group, an ethylene group, a propylene group, a trimethylene group, and a tetramethylene group.
When the preferable alkylene group represented by R ² has a substituent, examples of the substituent include a hydroxy group.

Examples of the divalent linking group represented by R ² include —O—, —S—, —C (═O) O—, —CONH—, and —C (═O) S at the terminal of the alkylene group. A heteroatom or a heteroatom selected from-, -NHCONH-, -NHC (= O) O-, -NHC (= O) S-, -OC (= O)-, -OCONH-, and -NHCO- It may have a partial structure and be linked to Z via the heteroatom or a partial structure containing a heteroatom.

  In General Formula (H-1), Z represents a group having a heterocyclic structure. Examples of the group having a heterocyclic structure include phthalocyanine, insoluble azo, azo lake, anthraquinone, quinacridone, dioxazine, diketopyrrolopyrrole, anthrapyridine, ansanthrone, indanthrone, and flavan. Throne, perinone, perylene, thioindigo dye structures, such as thiophene, furan, xanthene, pyrrole, pyrroline, pyrrolidine, dioxolane, pyrazole, pyrazoline, pyrazolidine, imidazole, oxazole, thiazole, oxadiazole, triazole, Thiadiazole, pyran, pyridine, piperidine, dioxane, morpholine, pyridazine, pyrimidine, piperazine, triazine, trithiane, isoindoline, isoindolinone, benzimidazolone, Heterocycles such as zothiazole, succinimide, phthalimide, naphthalimide, hydantoin, indole, quinoline, carbazole, acridine, acridone, anthraquinone, pyrazine, tetrazole, phenothiazine, phenoxazine, benzimidazole, benztriazole, cyclic amide, cyclic urea, cyclic imide Structure is mentioned. These heterocyclic structures may have a substituent, and examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, an aliphatic ester group, an aromatic ester group, an alkoxycarbonyl group, and the like. Can be mentioned.

  Z is more preferably a group having a nitrogen-containing heterocyclic structure having 6 or more carbon atoms, and particularly preferably a group having a nitrogen-containing heterocyclic structure having 6 to 12 carbon atoms. Specific examples of the nitrogen-containing heterocyclic structure having 6 or more carbon atoms include phenothiazine ring, phenoxazine ring, acridone ring, anthraquinone ring, benzimidazole structure, benztriazole structure, benzthiazole structure, cyclic amide structure, cyclic urea structure And a cyclic imide structure are preferable, and a structure represented by the following (H-2), (H-3) or (H-4) is particularly preferable.

In general formula (H-2), X represents a single bond, an alkylene group (for example, a methylene group, an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, etc.), -O-, -S-, -NR ^A-. , And -C (= O)-. Here, R ^A represents a hydrogen atom or an alkyl group. When R ^A represents an alkyl group, the alkyl group is preferably an alkyl group having 1 to 18 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, such as a methyl group, an ethyl group, or an n-propyl group. I-propyl group, n-butyl group, t-butyl group, n-hexyl group, n-octyl group, 2-ethylhexyl group, n-octadecyl group and the like.
Among the above, as X in the general formula (H-2), a single bond, a methylene group, —O—, or —C (═O) — is preferable, and —C (═O) — is particularly preferable.

In formula (H-4), Y and Z are each independently, -N =, - NH -, - N (R B) -, - S-, or an -O-. R ^B represents an alkyl group, and when R ^B represents an alkyl group, the alkyl group is preferably an alkyl group having 1 to 18 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, for example, a methyl group , Ethyl group, n-propyl group, i-propyl group, n-butyl group, t-butyl group, n-hexyl group, n-octyl group, 2-ethylhexyl group, n-octadecyl group and the like.
Among the above, as Y and Z in the general formula (H-4), —N═, —NH—, and —N (R ^B ) — are particularly preferable. Examples of the combination of Y and Z include a combination in which one of Y and Z is —N═ and the other is —NH—, and an imidazolyl group.

  In general formulas (H-2), (H-3), and (H-4), ring A, ring B, ring C, and ring D each independently represent an aromatic ring. Examples of the aromatic ring include a benzene ring, naphthalene ring, indene ring, azulene ring, fluorene ring, anthracene ring, pyridine ring, pyrazine ring, pyrimidine ring, pyrrole ring, imidazole ring, indole ring, quinoline ring, acridine ring, Examples include phenothiazine ring, phenoxazine ring, acridone ring, anthraquinone ring, among others, benzene ring, naphthalene ring, anthracene ring, pyridine ring, phenoxazine ring, acridine ring, phenothiazine ring, phenoxazine ring, acridone ring, anthraquinone ring Are preferable, and a benzene ring, a naphthalene ring, and a pyridine ring are particularly preferable.

  Specifically, examples of the ring A and the ring B in the general formula (H-2) include a benzene ring, a naphthalene ring, a pyridine ring, and a pyrazine ring. Examples of the ring C in the general formula (H-3) include a benzene ring, a naphthalene ring, a pyridine ring, and a pyrazine ring. Examples of the ring D in the general formula (H-4) include a benzene ring, a naphthalene ring, a pyridine ring, and a pyrazine ring.

  Among the structures represented by the general formulas (H-2), (H-3), and (H-4), a benzene ring and a naphthalene ring are more preferable from the viewpoint of dispersibility and the temporal stability of the dispersion. In general formula (H-2) or (H-4), a benzene ring is more preferable, and in general formula (H-3), a naphthalene ring is more preferable.

  In the polymer compound having a heterocyclic ring in the side chain of the present invention, preferred specific examples of the monomer, maleimide and maleimide derivative represented by the following general formula (H-1) are listed below. It is not limited.

The polymer compound having a heterocyclic ring in the side chain used in the present invention contains only one type of copolymer unit derived from the monomer represented by formula (H-1), maleimide, and maleimide derivative. There may be two or more kinds.
In the polymer compound having a heterocyclic ring in the side chain of the present invention, the content of the copolymer unit derived from the monomer represented by formula (H-1), maleimide, and maleimide derivative is not particularly limited. When the total structural unit contained in the polymer compound having a heterocyclic ring in the side chain of the present invention is 100% by mass, the monomer represented by the general formula (H-1), maleimide, maleimide derivative It is preferable to contain 5% by mass or more of derived copolymer units, and more preferably 10 to 50% by mass. Among the monomers represented by the general formula (H-1), maleimide, and maleimide derivatives, the monomer represented by the general formula (H-1) is preferable because of its high adsorptivity to the pigment.

  That is, in order to effectively suppress the formation of secondary aggregates, which are aggregates of primary particles of pigment, or to effectively weaken the cohesive force of secondary aggregates, the general formula (H-1) is used. The content of the copolymer unit derived from the monomer, maleimide, and maleimide derivative represented is preferably 5% by mass or more. From the viewpoint of developability when producing a color filter with a photocurable composition containing a pigment dispersion composition, copolymer units derived from the monomer represented by formula (H-1) are used. The content is preferably 50% by mass or less.

The polymer compound having a heterocyclic ring in the side chain of the present invention preferably further contains a copolymer unit derived from a monomer having an acid group or a basic group. When the polymer compound further contains a copolymer unit derived from a monomer having an acid group, when the pigment dispersion composition is applied to the photosensitive composition, the development removability of the unexposed area is excellent.
As monomers having an acid group, unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid; maleic acid, maleic anhydride, fumaric acid, itaconic acid, anhydrous Unsaturated dicarboxylic acids such as itaconic acid, citraconic acid, citraconic anhydride and mesaconic acid or their anhydrides; trivalent or higher unsaturated polycarboxylic acids or their anhydrides; succinic acid mono (2-acryloyloxyethyl) ), Succinic acid mono (2-methacryloyloxyethyl), phthalic acid mono (2-acryloyloxyethyl), phthalic acid mono (2-methacryloyloxyethyl) monovalent polyvalent carboxylic acid mono [ (Meth) acryloyloxyalkyl] esters; ω-carboxy-polycaprolactone monoacrylate, ω-carboxy-polycaprolactone monoacrylate Mono (meth) acrylates such as both terminal carboxy polymers methacrylate and the like.
As the monomer having a basic group, a monomer having an amino group is preferable, and examples thereof include dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, dimethylaminoethyl acrylate, and dimethylaminopropyl methacrylate. it can.
The polymer compound of the present invention may contain only one type of copolymer unit derived from a monomer having an acid group or basic group, or may contain two or more types.

In the polymer compound having a heterocyclic ring in the side chain of the present invention, the content of the copolymer unit derived from the monomer having an acid group is preferably 50 to 200 mgKOH / g, particularly preferably 80 to 200 mgKOH / g. g. A more preferable range is 100 to 180 mgKOH / g. That is, in terms of suppressing the formation of precipitates in the developer, the content of copolymer units derived from the monomer having an acid group is preferably 50 mgKOH / g or more. An acid value of 200 mgKOH / g or less is preferable because aggregation between acid groups is suppressed from becoming too strong, and aggregation between processed pigments and dispersibility are suppressed. In order to effectively suppress the formation of secondary aggregates, which are aggregates of primary particles of the pigment, or to effectively weaken the cohesive force of the secondary aggregates, it is derived from a monomer having an acid group. The content of the copolymerized unit is preferably in the above range.
The content of the copolymer unit derived from the monomer having a basic group is preferably an amine value of 10 to 300 mgKOH / g, more preferably 20 to 300 mgKOH / g, and a particularly preferred range of 30 to 280 mg KOH / g. When the amine value is 300 mgKOH / g or less, the aggregation between the basic groups is suppressed from becoming too strong, and the aggregation between the processed pigments or the dispersibility is suppressed from being suppressed. Therefore, it is preferable. In order to effectively suppress the formation of secondary aggregates, which are aggregates of primary particles of pigment, or to effectively weaken the cohesive strength of secondary aggregates, a monomer having a basic group The content of the copolymer unit derived from is preferably in the above range.

The polymer compound having a heterocyclic ring in the side chain in the present invention may further contain copolymer units derived from a copolymerizable vinyl monomer as long as the effect is not impaired.
Although it does not restrict | limit especially as a vinyl monomer which can be used here, For example, (meth) acrylic acid esters, crotonic acid esters, vinyl esters, maleic acid diesters, fumaric acid diesters, itaconic acid diesters, ( Preference is given to meth) acrylamides, vinyl ethers, esters of vinyl alcohol, styrenes, (meth) acrylonitrile and the like. Specific examples of such vinyl monomers include the following compounds. In addition, in this specification, when showing either or both of "acryl and methacryl", it may describe as "(meth) acryl".

  Examples of (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n-butyl (meth) acrylate. , Isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, (meth) acrylic acid 2- Ethylhexyl, t-octyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, acetoxyethyl (meth) acrylate, phenyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-Methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate 2- (2-methoxyethoxy) ethyl (meth) acrylate, 3-phenoxy-2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, diethylene glycol monomethyl ether (meth) acrylate, (meth) acrylic acid Diethylene glycol monoethyl ether, (meth) acrylic acid triethylene glycol monomethyl ether, (meth) acrylic acid triethylene glycol monoethyl ether, (meth) acrylic acid polyethylene glycol monomethyl ether, (meth) acrylic acid polyethylene glycol monoethyl ether, ( Β-phenoxyethoxyethyl (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclo (meth) acrylate Pentenyloxyethyl, trifluoroethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, tribromophenyl (meth) acrylate And (meth) acrylic acid tribromophenyloxyethyl.

Examples of crotonic acid esters include butyl crotonate and hexyl crotonate.
Examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl methoxyacetate, vinyl benzoate, and the like.
Examples of maleic acid diesters include dimethyl maleate, diethyl maleate, and dibutyl maleate.
Examples of the fumaric acid diesters include dimethyl fumarate, diethyl fumarate, and dibutyl fumarate.
Examples of itaconic acid diesters include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.

  (Meth) acrylamides include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, and Nn-butyl. Acrylic (meth) amide, Nt-butyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N- (2-methoxyethyl) (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N -Diethyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-benzyl (meth) acrylamide, (meth) acryloylmorpholine, diacetone acrylamide, etc. are mentioned.

Examples of vinyl ethers include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, and methoxyethyl vinyl ether.
Examples of styrenes include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, butyl styrene, hydroxy styrene, methoxy styrene, butoxy styrene, acetoxy styrene, chlorostyrene, dichlorostyrene, bromostyrene, chloromethyl Examples thereof include styrene, hydroxystyrene protected with a group that can be deprotected by an acidic substance (for example, t-Boc and the like), methyl vinylbenzoate, and α-methylstyrene.

  The preferred molecular weight of the polymer compound having a heterocyclic ring in the side chain according to the present invention is in the range of 1,000 to 100,000 in terms of weight average molecular weight (Mw), and in the range of 400 to 50,000 in terms of number average molecular weight (Mn). It is preferable that More preferably, the weight average molecular weight (Mw) is in the range of 5,000 to 50,000, and the number average molecular weight (Mn) is in the range of 2,000 to 30,000. In particular, the weight average molecular weight (Mw) is most preferably in the range of 8,000 to 30,000, and the number average molecular weight (Mn) is in the range of 4,000 to 12,000.

That is, from the viewpoint of effectively suppressing the formation of secondary aggregates, which are aggregates of primary particles of pigment, or effectively reducing the cohesive force of secondary aggregates, The weight average molecular weight (Mw) of the polymer compound having a heterocyclic ring is preferably 1,000 or more. Further, from the viewpoint of developability when producing a color filter with a colored actinic ray-sensitive or radiation-sensitive composition containing a pigment dispersion composition, the weight of the polymer compound having a heterocyclic ring in the side chain of the present invention The average molecular weight (Mw) is preferably 100,000 or less.
In the pigment dispersion composition of the present invention, the content of the polymer compound having a heterocyclic ring in the side chain according to the present invention is, by mass ratio, i) pigment: the polymer compound having a heterocyclic ring in the side chain = 1: 0. .01 to 1: 2 is preferable, more preferably 1: 0.05 to 1: 1, and still more preferably 1: 0.1 to 1: 0.6.

The polymer compound having a heterocyclic ring in the side chain includes, for example, a monomer represented by the general formula (H-1), a polymerizable oligomer (macromonomer), and another radical polymerizable compound as a copolymerization component. And can be produced by an ordinary radical polymerization method. In general, a suspension polymerization method or a solution polymerization method is used. Solvents used in the synthesis of such polymers include, for example, ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, propanol, butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl. Examples include acetate, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, toluene, ethyl acetate, methyl lactate, and ethyl lactate. . These solvents may be used alone or in combination of two or more.
In the radical polymerization, a radical polymerization initiator can be used, and a chain transfer agent (eg, 2-mercaptoethanol and dodecyl mercaptan) can be further used.

A preferred form of the processed pigment of the present invention is characterized in that i) the pigment particles are coated with a polymer compound having a heterocyclic ring in the side chain, and the polymer compound is firmly attached to part or all of the pigment particle surface. The effect of the present invention is further exerted by being coated on the surface, which is different from that obtained by adsorbing a general polymer dispersant to a pigment. This covering state can be confirmed by measuring the free amount (release rate) of the polymer compound by washing with an organic solvent described below. That is, almost all of the polymer compound simply adsorbed is washed and washed with an organic solvent, specifically 65% by mass or more. In the case of a processed pigment whose surface is coated as in the present invention, The liberation rate is extremely small and is 30% by mass or less.
The processed pigment of the present invention is washed with 1-methoxy-2-propanol, and the free amount is calculated. In this method, 10 g of the processed pigment was put into 100 ml of 1-methoxy-2-propanol and shaken at room temperature for 3 hours with a shaker. Thereafter, the pigment was allowed to settle for 8 hours at 80,000 rpm in a centrifuge, and the solid content of the supernatant was determined from the drying method. The mass of the polymer compound released from the pigment was determined, and the liberation rate (%) was calculated from the ratio to the mass of the polymer compound used in the initial treatment.

The liberation rate of commercially available processed pigments can be measured by the following method. That is, after dissolving the entire processed pigment with a solvent that dissolves the pigment (for example, dimethyl sulfoxide, dimethylformamide, formic acid, sulfuric acid, etc.), the polymer compound and the pigment are separated by an organic solvent using the difference in solubility. Then, it is calculated as “mass of the polymer compound used in the initial treatment”. Separately, the processed pigment was washed with 1-methoxy-2-propanol, and the obtained release amount was divided by this “mass of the polymer compound used in the initial treatment” to obtain the release rate (%). Ask.
The smaller the liberation rate, the higher the coverage of the pigment, and the better the dispersibility and dispersion stability. A preferable range of the liberation rate is 30% by mass or less, more preferably 20% by mass or less, and most preferably 15% by mass or less. Ideally 0%, that is, the polymer compound is not liberated.

  Two or more of the above polymer compounds may be used in combination. When two or more kinds of polymer compounds are used in combination, at least one kind is preferably a polymer compound having a heterocyclic ring in the side chain, and two or more kinds of polymer compounds having a heterocyclic ring in the side chain are used in combination. Is more preferable.

  In the processed pigment of the present invention, the content of the polymer compound (when two or more types are used in combination) is preferably 1 to 90% by mass, and preferably 5 to 70% by mass, More preferably, it is 5-50 mass%. This is to ensure a sufficient color density.

The processed pigment of the present invention can be dispersed in an organic solvent to form a pigment dispersion composition.
In the dispersion step, it is preferable to use a pigment derivative and a dispersant in addition to the processed pigment. When the pigment derivative used at this time is acidic, the polymer compound of the present invention is preferably neutral or acidic, and the dispersant is preferably a basic dispersant. Dispersibility can be imparted by acid-base interaction. As a preferable acid group, a sulfonic acid and a carboxyl group are preferable, and a carboxyl group is preferable because it is easy to dissolve in a solvent. Moreover, it is preferable to have a carboxyl group in the range of 50-200 mgKOH / g, and dispersion | distribution of a pigment becomes favorable in this range.

  On the other hand, when the pigment derivative used in the dispersion step is basic, the polymer compound of the present invention is preferably neutral or basic, and the dispersant is preferably acidic. Examples of the basic group include an amino group and an aromatic group containing a basic nitrogen atom.

<Pigment dispersion composition>
Next, the pigment dispersion composition of the present invention using the processed pigment of the present invention will be described.
The pigment dispersion composition of the present invention is obtained by dispersing the processed pigment of the present invention in an organic solvent.
Moreover, when dispersing the processed pigment of this invention in the organic solvent, it is also a preferable aspect to use (A) a pigment derivative and (B) a dispersing agent suitably as needed.

[(A) Pigment derivative]
A pigment derivative is suitably used for the pigment dispersion composition of the present invention.
In the present invention, a part having affinity with the dispersant or a pigment derivative having a polar group introduced is adsorbed on the surface of the treated pigment, and this is used as an adsorption point of the dispersant, whereby the pigment is made into fine particles. It can be dispersed in the dispersion composition and re-aggregation can be prevented. That is, the pigment derivative has an effect of promoting the adsorption of the dispersant by modifying the pigment surface.

Specifically, the pigment derivative is a compound in which an organic pigment is used as a base skeleton, and an acidic group, a basic group, or an aromatic group is introduced into a side chain as a substituent. Specific examples of organic pigments serving as a base skeleton include quinacridone pigments, phthalocyanine pigments, azo pigments, quinophthalone pigments, isoindoline pigments, isoindolinone pigments, quinoline pigments, diketopyrrolopyrrole pigments, benzoic pigments. Examples include imidazolone pigments.
The host skeleton also includes light yellow aromatic polycyclic compounds such as naphthalene, anthraquinone, triazine, and quinoline that are not generally called pigments.

  Examples of the pigment derivative in the present invention include JP-A Nos. 11-49974, 11-189732, 10-245501, 2006-265528, 8-295810, and JP-A. Those described in JP-A-11-199796, JP-A-2005-234478, JP-A-2003-240938, JP-A-2001-356210, and the like can be used.

When a pigment derivative is used in the pigment dispersion composition of the present invention, the amount used is preferably in the range of 1% by mass to 80% by mass with respect to the pigment, and 3% by mass to 65% by mass. More preferably, it is in the range of 5% by mass to 50% by mass. When the content is within this range, the pigment can be favorably dispersed while keeping the viscosity low, and the dispersion stability after dispersion can be improved.
By applying this pigment dispersion composition to the production of a color filter, a color filter having high transmittance, excellent color characteristics, and high contrast can be obtained.

[(B) Dispersant]
For the purpose of further improving the dispersibility of the pigment, conventionally known dispersants such as pigment dispersants and surfactants, and other components may be added.
The pigment dispersion composition of the present invention preferably contains a dispersant (pigment dispersant).
Known dispersants (pigment dispersants) include polymer dispersants such as polyamidoamines and salts thereof, polycarboxylic acids and salts thereof, high molecular weight unsaturated acid esters, modified polyurethanes, modified polyesters, and modified poly (meth). Acrylate, (meth) acrylic copolymer, naphthalenesulfonic acid formalin condensate], polyoxyethylene alkyl phosphate ester, polyoxyethylene alkylamine, alkanolamine and the like.

The polymer dispersant acts to adsorb on the pigment surface and prevent reaggregation. Therefore, a terminal-modified polymer, a graft polymer and a block polymer having an anchor site to the pigment surface can be mentioned as preferred structures. On the other hand, the pigment derivative has an effect of promoting the adsorption of the polymer dispersant by modifying the pigment surface.
The polymer dispersant acts on the surface of the pigment so as to prevent reaggregation in the dispersion step, like the polymer compound that coats the pigment of the present invention. For this reason, a block polymer, a graft polymer, and a terminal-modified polymer having an anchor site to the pigment surface can be cited as preferred structures. On the other hand, the pigment derivative has an effect of promoting the adsorption of the polymer dispersant by modifying the pigment surface.

The polymer dispersant is not particularly limited, and linear polymers, graft polymers, star polymers, block polymers and the like can be used.
Specific examples of the block-type polymer include Disperbyk-2000, the same -2001 (above BYK Chemie), EFKA 4330, the same 4340 (above EFKA) and the like.
As graft type polymers, commercially available products such as Solsperse 24000, 28000, 32000, 38500, 39000, 35000 (above Lubrizol), Disperbyk-161, -171, -174 (above BYK) Chemie)).
Examples of the terminal-modified polymer include polymers having a functional group at the end of the polymer described in JP-A-9-77994, JP-A-2002-273191, and the like.
Examples of the terminal-modified polymer include commercially available products such as Solsperse 3000, 17000, and 27000 (manufactured by Lubrizol).

  As the dispersant, a graft polymer is preferable from the viewpoint of dispersion stability.

  The main chain structure of the graft polymer is not particularly limited, and poly (meth) acrylic structures, polyesters, polyurethanes, polyureas, and the like can be used. Solubility in a solvent used as a polymer dispersion medium and ease of synthesis Therefore, a poly (meth) acrylic structure is preferable.

  The graft polymer is not particularly limited, but is a compound obtained by reacting a polyalkyleneimine and a polyester compound described in JP-A No. 54-37082, JP-A No. 61-174939, etc., and JP-A No. 9-169821. Preferred examples include a compound in which the amino group of the side chain of polyallylamine described in Japanese Patent Publication No. 5 is modified with a polyester, and a polyester polyol-added polyurethane described in JP-A No. 60-166318, and further, JP-A No. 9-171253. A graft type polymer having a polymerizable oligomer (hereinafter referred to as a macromonomer) as a copolymerization component is also preferable, as described in the publication and the chemistry and industry of macromonomer (IPC Publishing Department, 1989). Can do.

  Examples of the branch part of the graft type polymer include polystyrene, polyethylene oxide, polypropylene oxide, poly (meth) acrylic acid ester, polycaprolactone, and the like, and the following general formula (I), formula (II), and formula (III) ) Or a graft type polymer having at least a structural unit represented by formula (IV) in the branch.

In general formulas (I) to (IV), R ^{1 to} R ¹³ each independently represents a hydrogen atom or a monovalent organic group. X ^{1 to} X ⁴ each independently represent —CO—, —C (═O) O—, —CONH—, —OC (═O) —, or a phenylene group, and L ^{1 to} L ⁴ each represents Independently, it represents a single bond or a divalent organic linking group. A ^{1 to} A ³ each independently represents a monovalent organic group, and A ⁴ represents a radical polymerization initiation terminal. Q is a cyano group, an aryl group having 6 to 30 carbon atoms, or —COOR ⁷⁵ (wherein R ⁷⁵ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms). Represents. m and n each independently represents an integer of 2 to 8, p, q and t each independently represent an integer of 1 to 100, and r and s each independently represents an integer of 0 to 100 Represents. However, one of r and s is 1 or more.

  Among the general formulas (I) to (IV), the general formulas (I) and (II) are particularly preferable.

  One type or two types of repeating units of the general formulas (I) to (IV) may be used, and repeating units having different graft chain lengths may be used in combination.

R ^{1 to} R ⁶ each independently represents a hydrogen atom or a monovalent organic group. As the monovalent organic group, a substituted or unsubstituted alkyl group is preferable. As an alkyl group, a C1-C12 alkyl group is preferable, a C1-C8 alkyl group is more preferable, and a C1-C4 alkyl group is especially preferable.
When the alkyl group has a substituent, examples of the substituent include a hydroxy group, an alkoxy group (preferably having 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms), a methoxy group, an ethoxy group, Examples include a cyclohexyloxy group.
Specific examples of preferred alkyl groups include methyl, ethyl, propyl, n-butyl, i-butyl, t-butyl, n-hexyl, cyclohexyl, 2-hydroxyethyl, A 3-hydroxypropyl group, a 2-hydroxypropyl group, and a 2-methoxyethyl group are exemplified.
R ¹ , R ² , R ⁴ , and R ⁵ are preferably hydrogen atoms, and R ³ and R ⁶ are most preferably hydrogen atoms or methyl groups from the viewpoint of adsorption efficiency on the pigment surface.

X ¹ and X ² each independently represent —CO—, —C (═O) O—, —CONH—, —OC (═O) —, or a phenylene group. Among them, —C (═O) O—, —CONH—, and a phenylene group are preferable from the viewpoint of adsorptivity to the pigment, and —C (═O) O— is most preferable.

L ¹ and L ² each independently represents a single bond or a divalent organic linking group. The divalent organic linking group is preferably a substituted or unsubstituted alkylene group or a divalent organic linking group comprising the alkylene group and a hetero atom or a partial structure containing a hetero atom. Here, the alkylene group is preferably an alkylene group having 1 to 12 carbon atoms, more preferably an alkylene group having 1 to 8 carbon atoms, and particularly preferably an alkylene group having 1 to 4 carbon atoms. Moreover, as a hetero atom in the partial structure containing a hetero atom, an oxygen atom, a nitrogen atom, and a sulfur atom are mentioned, for example, Among these, an oxygen atom and a nitrogen atom are preferable.
Specific examples of preferable alkylene groups include a methylene group, an ethylene group, a propylene group, a trimethylene group, and a tetramethylene group.
When the alkylene group has a substituent, examples of the substituent include a hydroxy group.
The divalent organic linking group includes a heteroatom or a heteroatom selected from —C (═O) —, —OC (═O) —, and —NHC (═O) — at the end of the above alkylene group. A compound having a partial structure and linked to an adjacent oxygen atom via the heteroatom or a partial structure containing a heteroatom is preferable from the viewpoint of adsorptivity to the pigment. Here, the adjacent oxygen atom means an oxygen atom that binds to L ¹ in the general formula (I) and L ² in the general formula (II) on the side chain end side.

A ¹ and A ² each independently represents a monovalent organic group. As the monovalent organic group, a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group is preferable.
Examples of preferable alkyl groups include linear, branched, and cyclic alkyl groups having 1 to 20 carbon atoms. Specific examples thereof include a methyl group, an ethyl group, a propyl group, Butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, hexadecyl, octadecyl, eicosyl, isopropyl, isobutyl, s-butyl, Examples thereof include t-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclohexyl group, cyclopentyl group and 2-norbornyl group.

As the substituent of the substituted alkyl group, a monovalent non-metallic atomic group other than hydrogen is used. Preferred examples include halogen atoms (—F, —Br, —Cl, —I), hydroxyl groups, alkoxy groups. Group, aryloxy group, mercapto group, alkylthio group, arylthio group, alkyldithio group, aryldithio group, amino group, N-alkylamino group, N, N-dialkylamino group, N-arylamino group, N, N-diaryl Amino group, N-alkyl-N-arylamino group, acyloxy group, carbamoyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, N, N-dialkylcarbamoyloxy group, N, N-diarylcarbamoyloxy Group, N-alkyl-N-arylcarbamoyloxy group, alkylsulfoxy , Arylsulfoxy group, acyloxy group, acylthio group, acylamino group, N-alkylacylamino group, N-arylacylamino group, ureido group, N′-alkylureido group, N ′, N′-dialkylureido group, N '-Arylureido group, N', N'-diarylureido group, N'-alkyl-N'-arylureido group, N-alkylureido group, N-arylureido group, N'-alkyl-N-alkylureido group N′-alkyl-N-arylureido group, N ′, N′-dialkyl-N-alkylureido group, N ′, N′-dialkyl-N-arylureido group, N′-aryl-N-alkylureido group N′-aryl-N-arylureido group, N ′, N′-diaryl-N-alkylureido group, N ′, N′-diaryl-N-aryluree Id group, N′-alkyl-N′-aryl-N-alkylureido group, N′-alkyl-N′-aryl-N-arylureido group, alkoxycarbonylamino group, aryloxycarbonylamino group, N-alkyl- N-alkoxycarbonylamino group, N-alkyl-N-aryloxycarbonylamino group, N-aryl-N-alkoxycarbonylamino group, N-aryl-N-aryloxycarbonylamino group, formyl group, acyl group, carboxyl group , Alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N, N-diarylcarbamoyl group, N-alkyl-N-arylcarbamoyl group An alkylsulfinyl group, Arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfo group (—SO ₃ H) and its conjugate base group (hereinafter referred to as sulfonate group), alkoxysulfonyl group, aryloxysulfonyl group, sulfinamoyl group, N-alkyls Rufinamoyl group, N, N-dialkylsulfinamoyl group, N-arylsulfinamoyl group, N, N-diarylsulfinamoyl group, N-alkyl-N-arylsulfinamoyl group, sulfamoyl group, N-alkyl Sulfamoyl group, N, N-dialkylsulfamoyl group, N-arylsulfamoyl group, N, N-diarylsulfamoyl group, N-alkyl-N-arylsulfamoyl group, phosphono group (—PO ₃ H ₂₎ and its conjugated base group (hereinafter referred to as phosphonato group), Alkyl phosphono group _{(-PO 3 (alkyl) 2)} , diaryl phosphono group _{(-PO 3 (aryl) 2)} , alkyl aryl phosphono group _{(-PO 3 (alkyl) (aryl} )), monoalkyl phosphono group (—PO ₃ H (alkyl)) and its conjugate base group (hereinafter referred to as alkylphosphonate group), monoarylphosphono group (—PO ₃ H (aryl)) and its conjugate base group (hereinafter referred to as arylphosphonate) Group), phosphonooxy group (—OPO ₃ H ₂ ) and its conjugate base group (hereinafter referred to as phosphonatoxy group), dialkylphosphonooxy group (—OPO ₃ (alkyl) ₂ ), diarylphosphonooxy group (— OPO _{3 (aryl) 2),} alkylaryl phosphono group _{(-OPO 3 (alkyl) (aryl} )) Monoalkyl phosphono group _(-OPO 3 H (alkyl)) and its conjugated base group (hereinafter referred to as alkylphosphonato group), monoarylphosphono group _(-OPO 3 H (aryl)) and its conjugate Examples thereof include a base group (hereinafter referred to as an arylphosphonatoxy group), a cyano group, a nitro group, an aryl group, a heteroaryl group, an alkenyl group, an alkynyl group, and a silyl group.
Specific examples of the alkyl group in these substituents include the alkyl groups described above, and these may further have a substituent.
Examples of the substituent include an alkoxy group, aryloxy group, alkylthio group, arylthio group, N, N-dialkylamino group, N, N-diarylamino group, N-alkyl-N-arylamino group, acyloxy group, aryl group, hetero An aryl group, an alkenyl group, an alkynyl group, and a silyl group are preferable from the viewpoint of dispersion stability.

  Specific examples of the aryl group include phenyl, biphenyl, naphthyl, tolyl, xylyl, mesityl, cumenyl, chlorophenyl, bromophenyl, chloromethylphenyl, hydroxyphenyl, methoxyphenyl, ethoxy Phenyl group, phenoxyphenyl group, acetoxyphenyl group, benzoyloxyphenyl group, methylthiophenyl group, phenylthiophenyl group, methylaminophenyl group, dimethylaminophenyl group, acetylaminophenyl group, carboxyphenyl group, methoxycarbonylphenyl group, Ethoxyphenylcarbonyl group, phenoxycarbonylphenyl group, N-phenylcarbamoylphenyl group, phenyl group, cyanophenyl group, sulfophenyl group, sulfonatophenyl group, phosphonophenyl group It can be exemplified phosphonophenyl phenyl group.

As A ¹ and A ² , from the viewpoint of dispersion stability and developability, a straight chain having 1 to 20 carbon atoms, a branched structure having 3 to 20 carbon atoms, and a number having 5 to 20 carbon atoms Cyclic alkyl groups are preferable, linear alkyl groups having 4 to 15 carbon atoms, branched alkyl groups having 4 to 15 carbon atoms, and cyclic alkyl groups having 6 to 10 carbon atoms are more preferable. Even more preferred are linear alkyl groups of 6 to 10 and branched alkyl groups of 6 to 12 carbon atoms.

  m and n each independently represents an integer of 2 to 8. In view of dispersion stability and developability, 4 to 6 is preferable, and 5 is most preferable.

  p and q each independently represent an integer of 1 to 100. Two or more different p and different q may be mixed. p and q are preferably 5 to 60, more preferably 5 to 40, and still more preferably 5 to 20 from the viewpoints of dispersion stability and developability.

  The specific polymer in the present invention is preferably a polymer containing a repeating unit represented by the general formula (I) from the viewpoint of dispersion stability.

  Moreover, as a repeating unit represented by general formula (I), it is more preferable that it is a repeating unit represented by the following general formula (I) -2.

In the general formula (I) -2, R ^{1 to} R ³ each independently represent a hydrogen atom or a monovalent organic group, La represents an alkylene group having 2 to 10 carbon atoms, and Lb represents —C (═O) — or —NHC (═O) —, A ¹ represents a monovalent organic group, m represents an integer of 2 to 8, and p represents an integer of 1 to 100. Represents.

  The repeating unit represented by the general formula (I), (II), or (I) -2 is a simple unit represented by the following general formula (i), (ii), or (i) -2, respectively. The polymer is introduced as a repeating unit of the polymer compound by polymerization or copolymerization.

In the general formulas (i), (ii), and (i) -2, R ^{1 to} R ⁶ each independently represent a hydrogen atom or a monovalent organic group, and X ¹ and X ² are each Independently represents —CO—, —C (═O) O—, —CONH—, —OC (═O) —, or a phenylene group, and L ¹ and L ² each independently represent a single bond or 2 A valent organic linking group, La represents an alkylene group having 2 to 10 carbon atoms, Lb represents -C (= O)-, or -NHC (= O)-, and A ¹ and A ² represent Each independently represents a monovalent organic group, m and n each independently represents an integer of 2 to 8, and p and q each independently represents an integer of 1 to 100.

  Below, the preferable specific example [monomer (A-1)-(A-13)] of the monomer represented by general formula (i), (ii), or (i) -2 is given below. However, the present invention is not limited to these.

  The specific polymer in the present invention only needs to contain at least one type of repeating unit selected from the repeating units represented by any of the general formulas (I) and (II). It may also include two or more.

  In the specific polymer, the content of the repeating unit represented by any one of the general formulas (I) and (II) is not particularly limited, but the total repeating unit contained in the polymer is 100% by mass. In this case, the repeating unit represented by any one of the general formulas (I) and (II) is preferably contained in an amount of 5% by mass or more, more preferably 50% by mass, and 50% by mass to 80% by mass. It is more preferable to contain.

The specific polymer in the present invention is represented by the above-described general formulas (i), (ii), and (i) -2 with a monomer having a functional group that can be adsorbed to the pigment for the purpose of enhancing the adsorption to the pigment. It is preferably a polymer compound obtained by copolymerization with a monomer to be prepared.
Specific examples of the monomer having a functional group capable of adsorbing to the pigment include a monomer having an organic dye structure or a heterocyclic structure, a monomer having an acidic group, a monomer having a basic nitrogen atom, and an ionic group. A monomer etc. can be mentioned. Among these, a monomer having an organic dye structure or a heterocyclic structure is preferable from the viewpoint of the adsorptive power to the pigment.

The specific polymer in the present invention may contain only one type of repeating unit derived from a monomer having an acidic group, or may contain two or more types.
In the specific polymer, the content of the repeating unit derived from the monomer having an acidic group is preferably 50 mgKOH / g or more, particularly preferably 50 mgKOH / g to 200 mgKOH / g. That is, in terms of suppressing the formation of precipitates in the developer, the content of the repeating unit derived from the monomer having an acidic group is preferably 50 mgKOH / g or more. In order to effectively suppress the formation of secondary aggregates, which are aggregates of primary particles of pigment, or to effectively weaken the cohesive force of secondary aggregates, repeating units derived from monomers having acidic groups The content of is preferably 50 mgKOH / g to 200 mgKOH / g.

  As a monomer having a basic nitrogen atom, (meth) acrylic acid ester, (meth) acrylic acid N, N-dimethylaminoethyl, (meth) acrylic acid N, N-dimethylaminopropyl, (meth) acrylic acid 1 -(N, N-dimethylamino) -1,1-dimethylmethyl, (meth) acrylic acid N, N-dimethylaminohexyl, (meth) acrylic acid N, N-diethylaminoethyl, (meth) acrylic acid N, N -Diisopropylaminoethyl, N, N-di-n-butylaminoethyl (meth) acrylate, N, N-di-i-butylaminoethyl (meth) acrylate, morpholinoethyl (meth) acrylate, (meth) Piperidinoethyl acrylate, 1-pyrrolidinoethyl (meth) acrylate, N, N-methyl-2-pyrrolidyl (meth) acrylate And (meth) acrylamides include N- (N ′, N′-dimethylaminoethyl) acrylamide, N- (N ′, N ′), and the like. -Dimethylaminoethyl) methacrylamide, N- (N ', N'-diethylaminoethyl) acrylamide, N- (N', N'-diethylaminoethyl) methacrylamide, N- (N ', N'-dimethylaminopropyl) Acrylamide, N- (N ′, N′-dimethylaminopropyl) methacrylamide, N- (N ′, N′-diethylaminopropyl) acrylamide, N- (N ′, N′-diethylaminopropyl) methacrylamide, 2- ( N, N-dimethylamino) ethyl (meth) acrylamide, 2- (N, N-diethylamino) ) Ethyl (meth) acrylamide, 3- (N, N-diethylamino) propyl (meth) acrylamide, 3- (N, N-dimethylamino) propyl (meth) acrylamide, 1- (N, N-dimethylamino) -1 , 1-dimethylmethyl (meth) acrylamide and 6- (N, N-diethylamino) hexyl (meth) acrylamide, morpholino (meth) acrylamide, piperidino (meth) acrylamide, N-methyl-2-pyrrolidyl (meth) acrylamide and the like Examples of styrenes include N, N-dimethylaminostyrene, N, N-dimethylaminomethylstyrene, and the like.

  Moreover, it is also possible to use a monomer having a urea group, a urethane group, a coordinating oxygen atom, a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, an epoxy group, an isocyanate group, or a hydroxyl group. Specific examples include monomers having the following structure.

  Examples of the monomer having an ionic group include vinyl monomers having an ionic group (anionic vinyl monomers and cationic vinyl monomers). Examples of the anionic vinyl monomer include alkali metal salts of vinyl monomers having an acidic group, salts with organic amines (eg, tertiary amines such as triethylamine and dimethylaminoethanol), and the like. As the vinyl monomer, the nitrogen-containing vinyl monomer is an alkyl halide (alkyl group: C1-18, halogen atom: chlorine atom, bromine atom or iodine atom); benzyl halide such as benzyl chloride or benzyl bromide; Alkylsulfonic acid esters such as acids (alkyl groups: C1-18); arylsulfonic acid alkyl esters such as benzenesulfonic acid and toluenesulfonic acid (alkyl groups: C1-18); dialkyl sulfates (alkyl groups: C1-4), etc. Quaternized with dialkyldiallylane Such as salt, and the like.

  The monomer having a functional group capable of adsorbing to the pigment can be appropriately selected according to the type of pigment to be dispersed, and these may be used alone or in combination of two or more.

  The specific polymer in the present invention may further contain a repeating unit derived from a copolymerizable vinyl monomer as long as the effect is not impaired.

  Although it does not restrict | limit especially as a vinyl monomer which can be used here, For example, (meth) acrylic acid esters, crotonic acid esters, vinyl esters, maleic acid diesters, fumaric acid diesters, itaconic acid diesters, ( Preference is given to meth) acrylamides, vinyl ethers, esters of vinyl alcohol, styrenes, (meth) acrylonitrile and the like. Specific examples of such vinyl monomers include the following compounds. In addition, in this specification, when showing either or both of "acryl and methacryl", it may describe as "(meth) acryl".

  Examples of (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n-butyl (meth) acrylate. , Isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, (meth) acrylic acid 2- Ethylhexyl, t-octyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, acetoxyethyl (meth) acrylate, phenyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-Methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate 2- (2-methoxyethoxy) ethyl (meth) acrylate, 3-phenoxy-2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, diethylene glycol monomethyl ether (meth) acrylate, (meth) acrylic acid Diethylene glycol monoethyl ether, (meth) acrylic acid triethylene glycol monomethyl ether, (meth) acrylic acid triethylene glycol monoethyl ether, (meth) acrylic acid polyethylene glycol monomethyl ether, (meth) acrylic acid polyethylene glycol monoethyl ether, ( Β-phenoxyethoxyethyl (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclo (meth) acrylate Pentenyloxyethyl, trifluoroethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, tribromophenyl (meth) acrylate And (meth) acrylic acid tribromophenyloxyethyl.

Examples of crotonic acid esters include butyl crotonate and hexyl crotonate.
Examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl methoxyacetate, vinyl benzoate, and the like.
Examples of maleic acid diesters include dimethyl maleate, diethyl maleate, and dibutyl maleate.
Examples of the fumaric acid diesters include dimethyl fumarate, diethyl fumarate, and dibutyl fumarate.
Examples of itaconic acid diesters include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.

  (Meth) acrylamides include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, and Nn-butyl. Acrylic (meth) amide, Nt-butyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N- (2-methoxyethyl) (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N -Diethyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-benzyl (meth) acrylamide, (meth) acryloylmorpholine, diacetone acrylamide, etc. are mentioned.

Examples of vinyl ethers include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, and methoxyethyl vinyl ether.
Examples of styrenes include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, butyl styrene, hydroxy styrene, methoxy styrene, butoxy styrene, acetoxy styrene, chlorostyrene, dichlorostyrene, bromostyrene, chloromethyl Examples thereof include styrene, hydroxystyrene protected with a group that can be deprotected by an acidic substance (for example, t-Boc and the like), methyl vinylbenzoate, and α-methylstyrene.

Preferred embodiments of the specific polymer in the present invention include at least a monomer represented by the general formula (i), (ii), or (i) -2, a monomer having an organic dye structure or a heterocyclic structure, and an acidic function. A copolymer obtained by copolymerizing at least one monomer selected from a monomer having a group in a side chain and a monomer having a basic nitrogen atom in a side chain.
According to this embodiment, it is possible to provide a pigment dispersion composition having excellent pigment adsorption and excellent developability.

The preferred molecular weight of the specific polymer in the present invention is preferably in the range of 5000 to 100,000 in terms of weight average molecular weight (Mw) and in the range of 2500 to 50000 in terms of number average molecular weight (Mn). More preferably, the weight average molecular weight (Mw) is in the range of 10,000 to 50,000, and the number average molecular weight (Mn) is in the range of 5,000 to 30,000.
In particular, the weight average molecular weight (Mw) is most preferably in the range of 10,000 to 30000, and the number average molecular weight (Mn) is in the range of 5000 to 15000.
That is, the weight average molecular weight (Mw) of the specific polymer is 1000 or more from the viewpoint of effectively loosening the secondary aggregate, which is an aggregate of primary particles of the pigment, or effectively weakening the reaggregation. It is preferable that Further, from the viewpoint of developability when producing a color filter from a colored photosensitive composition containing a pigment dispersion composition, the weight average molecular weight (Mw) of the specific polymer is preferably 30000 or less.

The specific polymer in the present invention includes, for example, a monomer represented by the general formula (i), (ii), or (i) -2 and another radical polymerizable compound (as described above) as a copolymerization component. And various monomers), and can be produced by an ordinary radical polymerization method.
In general, a suspension polymerization method or a solution polymerization method is used. Examples of the solvent used when synthesizing such a specific polymer include ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, propanol, butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxy. Examples include ethyl acetate, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, toluene, ethyl acetate, methyl lactate, and ethyl lactate. It is done. These solvents may be used alone or in combination of two or more.
In the radical polymerization, a radical polymerization initiator can be used, and a chain transfer agent (eg, 2-mercaptoethanol and dodecyl mercaptan) can be further used.

  In the pigment dispersion composition of the present invention, the content of the specific polymer is preferably a mass ratio of pigment: specific polymer = 1: 0.1 to 1: 2, more preferably 1: 0.2 to 1. : 1, more preferably 1: 0.4 to 1: 0.7.

Moreover, in the range which does not impair the effect of this invention, you may use another high molecular compound simultaneously with the above-mentioned specific polymer as needed.
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.

In the case of a polymer dispersant, the addition amount of the dispersant is preferably 0.5 to 100% by mass, more preferably 3 to 100% by mass, and more preferably 5 to 80% by mass with respect to the pigment. % Is particularly preferred. When the amount of the pigment dispersant is within the above range, a sufficient pigment dispersion effect can be obtained. However, the optimum addition amount of the dispersant is appropriately adjusted depending on the combination of the type of pigment used, the type of solvent, and the like.
The ratio of the polymer compound of the present invention coated with a pigment and the dispersant is not particularly limited, but when the dispersant is a polymer dispersant, a 10/90 to 90/10 mass ratio is preferable, and in particular, 20/80. An 80/20 mass ratio is preferred.

〔solvent〕
The pigment dispersion composition of the present invention can be suitably prepared using a solvent.
Examples of the solvent include fatty acid esters such as ethyl acetate, butyl acetate, ethylene glycol monomethyl ether acetate, and propylene glycol monomethyl ether acetate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and diacetone alcohol; benzene, toluene, Aromatics such as xylene; alcohols 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 Glycerol; alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether; triethylene glycol dimethyl ether, Alkylene glycol dialkyl ethers such as triethylene glycol diethyl ether, tetraethylene glycol dimethyl ether and tetraethylene glycol diethyl ether; ethers such as tetrahydrofuran, dioxane and diethylene glycol diethyl ether; monoethanolamine, diethanolamine and triethanol Alkanolamines such as min; nitrogen-containing polar organics such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, 2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone Solvent; 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.

The volume average particle diameter of the pigment (a pigment containing at least the azo pigment represented by the general formula (Az)) in the pigment dispersion composition of the present invention is preferably 5 nm or more and 50 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 to be input at the time of measurement, the ink viscosity was used as the viscosity, and the pigment density was used as the density of the dispersed particles.

  A more preferable volume average particle diameter is 5 nm or more and 40 nm or less. If the volume average particle diameter of the particles in the pigment dispersion composition is 40 nm or less, the optical density will be higher.

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 will be easy to adjust the physical-property values of dispersion, such as surface tension and a viscosity, and it is preferable.
The total concentration of solids contained in the pigment dispersion composition of the present invention is preferably in the range of 1 to 50% by mass, and more preferably in the range of 2 to 40% by mass.

<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, for example, by dispersing the azo pigment, the dispersant, the azo pigment derivative, and the solvent represented by the general formula (Az) using a dispersion apparatus. Is preferred.
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 (Az), a dispersant, an azo pigment derivative, and a solvent in a vertical or horizontal sand grinder, pin mill, Using a slit mill, an ultrasonic disperser or the like, fine dispersion can be performed with beads made of glass, zirconia or the like having a particle diameter of 0.01 mm to 1 mm.
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 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 and Pigment Dispersion” by Patton (published by John Wiley and Sons, 1964) and the like, and the method described herein can also be applied to the present invention.

  The colored actinic ray-sensitive or radiation-sensitive composition of the present invention comprises a processed pigment obtained by coating the above-described pigment of the present invention with a polymer compound, a polymerizable compound, and a photopolymerization initiator (preferably together with a solvent). It can be prepared by mixing and dispersing additives such as alkali-soluble resins and surfactants as necessary, and mixing and dispersing using various mixers and dispersers. it can.

  The pigment dispersion composition of the present invention is suitably used for a colored actinic ray-sensitive or radiation-sensitive composition used for producing a color filter.

<Colored actinic ray-sensitive or radiation-sensitive composition>
The colored actinic ray-sensitive or radiation-sensitive composition of the present invention comprises the above-described pigment dispersion composition of the present invention, a polymerizable compound, and a photopolymerization initiator, and other components as necessary. (Alkali-soluble resin, surfactant, etc.) may be included. The details of the pigment dispersion composition of the present invention are as described above. Hereinafter, each component will be described in detail.

<Alkali-soluble resin>
The colored actinic ray-sensitive or radiation-sensitive composition of the present invention preferably further contains an alkali-soluble resin. By containing an alkali-soluble resin, developability and pattern formation are improved.

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 suitably selected from alkali-soluble resins having a group. From the viewpoint of heat resistance, polyhydroxystyrene resins, polysiloxane resins, acrylic resins, acrylamide resins, and acryl / acrylamide copolymer resins are preferable. From the viewpoint of development control, acrylic resins and acrylamide resins are preferable. Resins and acrylic / acrylamide copolymer resins are preferred.
Examples of the group that promotes alkali solubility (hereinafter also referred to as an acid group) include a carboxyl group, a phosphoric acid group, a sulfonic acid group, and a phenolic hydroxyl group. The group is soluble in an organic solvent and developed with a weak alkaline aqueous solution. Possible are preferable, and (meth) acrylic acid is particularly preferable. These acid groups may be used alone or in combination of two or more.
Examples of the monomer capable of imparting an acid group after the polymerization include a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, a monomer having an epoxy group such as glycidyl (meth) acrylate, and 2-isocyanatoethyl (meta ) Monomers having an isocyanate group such as acrylate. These monomers for introducing an acid group may be only one type or two or more types. In order to introduce an acid group into an alkali-soluble binder, for example, a monomer having an acid group and / or a monomer capable of imparting an acid group after polymerization (hereinafter sometimes referred to as “monomer for introducing an acid group”) .) May be polymerized as a monomer component.
In addition, when introducing an acid group using a monomer capable of imparting an acid group after polymerization as a monomer component, for example, a treatment for imparting an acid group as described later is required after the polymerization.

  For production of the alkali-soluble resin, for example, a known radical polymerization method can be applied. 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 used as the alkali-soluble resin, a polymer having a carboxylic acid in the side chain is preferable, such as a methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, and a crotonic acid copolymer. , Maleic acid copolymers, partially esterified maleic acid copolymers, alkali-soluble phenolic resins such as novolak resins, etc., acid cellulose derivatives having a carboxylic acid in the side chain, and acid anhydrides added to polymers having a hydroxyl group. Can be mentioned. In particular, a copolymer of (meth) acrylic acid and another monomer copolymerizable therewith is suitable as the alkali-soluble resin. Examples of other monomers copolymerizable with (meth) acrylic acid include alkyl (meth) acrylates, aryl (meth) acrylates, and vinyl compounds. As alkyl (meth) acrylate and aryl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, Examples of vinyl compounds such as hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, styrene, α-methylstyrene, vinyltoluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene monomer Romonoma, polymethyl methacrylate macromonomer, as N-position-substituted maleimide monomer described in JP-A-10-300922, N- phenylmaleimide, mention may be made of N- cyclohexyl maleimide and the like. In addition, only 1 type may be sufficient as the other monomer copolymerizable with these (meth) acrylic acids, and 2 or more types may be sufficient as it. Resist performance can be adjusted by combining two or more.

  As an alkali-soluble resin, the following general formula (ED)

(In the formula (ED), R ¹ and R ² each independently represents a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent) It is also preferable to include a polymer (a) obtained by polymerizing a monomer component that may be referred to as “ether dimer”. Thereby, the colored actinic ray-sensitive or radiation-sensitive composition of the present invention can form a cured coating film that is extremely excellent in heat resistance and transparency. In the general formula (ED) showing the ether dimer, the hydrocarbon group having 1 to 25 carbon atoms which may have a substituent represented by R ¹ and R ² is not particularly limited, A linear or branched alkyl group such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, t-amyl, stearyl, lauryl, 2-ethylhexyl; an aryl group such as phenyl; Alicyclic groups such as cyclohexyl, t-butylcyclohexyl, dicyclopentadienyl, tricyclodecanyl, isobornyl, adamantyl, 2-methyl-2-adamantyl; substituted with alkoxy such as 1-methoxyethyl, 1-ethoxyethyl An alkyl group substituted with an aryl group such as benzyl; and the like. Among these, an acid such as methyl, ethyl, cyclohexyl, benzyl or the like, or a primary or secondary carbon substituent which is difficult to be removed by heat is preferable from the viewpoint of heat resistance.

  Specific examples of the ether dimer include dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, (N-propyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (isopropyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (n-butyl) ) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (isobutyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (t-butyl) -2, 2 ′-[oxybis (methylene)] bis-2-propenoate, di (t-amyl) -2,2 ′-[oxybis (methylene)] bis-2-propeno , Di (stearyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (lauryl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (2 -Ethylhexyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (1-methoxyethyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (1- Ethoxyethyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, dibenzyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diphenyl-2,2 ′-[oxybis ( Methylene)] bis-2-propenoate, dicyclohexyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (t- Tilcyclohexyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (dicyclopentadienyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (tri Cyclodecanyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (isobornyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, diadamantyl-2,2 Examples include '-[oxybis (methylene)] bis-2-propenoate and di (2-methyl-2-adamantyl) -2,2'-[oxybis (methylene)] bis-2-propenoate. Among these, dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, dicyclohexyl-2,2′- [Oxybis (methylene)] bis-2-propenoate and dibenzyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate are preferred. These ether dimers may be only one kind or two or more kinds. The structure derived from the compound represented by the general formula (ED) may be copolymerized with other monomers.

  In order to improve the crosslinking efficiency of the colored actinic ray-sensitive or radiation-sensitive composition in the present invention, an alkali-soluble resin having a polymerizable group may be used. As the alkali-soluble resin having a polymerizable group, an alkali-soluble resin containing an allyl group, a (meth) acryl group, an allyloxyalkyl group or the like in the side chain is useful. Examples of the above-described polymer containing a polymerizable group include: NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (produced by COOH-containing polyurethane acrylic oligomer. Diamond Shamrock Co. Ltd.), Viscoat R-264, Examples thereof include KS resist 106 (all manufactured by Osaka Organic Chemical Industry Co., Ltd.), Cyclomer P series, Plaxel CF200 series (all manufactured by Daicel Chemical Industries, Ltd.), Ebecryl 3800 (manufactured by Daicel UCB Co., Ltd.), and the like. As an alkali-soluble resin containing these polymerizable groups, an isocyanate group and an OH group are reacted in advance to leave one unreacted isocyanate group and a compound containing a (meth) acryloyl group and an acrylic resin containing a carboxyl group; Urethane-modified polymerizable double bond-containing acrylic resin obtained by the above reaction, unsaturated group-containing acrylic obtained by reaction of an acrylic resin containing a carboxyl group and a compound having both an epoxy group and a polymerizable double bond in the molecule Resin, acid pendant type epoxy acrylate resin, OH group-containing acrylic resin and polymerizable double bond-containing acrylic resin obtained by reacting a polymerizable double bond, OH group-containing acrylic resin and isocyanate Resin obtained by reacting a compound having a polymerizable group, JP 2002-229207 A And a resin obtained by performing a basic treatment on a resin having an ester group having a leaving group such as a halogen atom or a sulfonate group at the α-position or β-position described in JP-A-2003-335814 Etc. are preferable.

  As the alkali-soluble resin, in particular, a benzyl (meth) acrylate / (meth) acrylic acid copolymer and a multi-component copolymer composed of benzyl (meth) acrylate / (meth) acrylic acid / other monomers are suitable. In addition, a copolymer of 2-hydroxyethyl methacrylate, a 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer described in JP-A-7-140654, 2-hydroxy -3-phenoxypropyl acrylate / polymethyl methacrylate 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.

The acid value of the alkali-soluble resin is preferably 10 mgKOH / g to 200 mgKOH / g, more preferably 20 mgKOH / g to 150 mgKOH / g, and most preferably 20 to 130 mgKOH / g.
Moreover, as a weight average molecular weight (Mw) of alkali-soluble resin, 2,000-50,000 are preferable and 5,000-30,000 are still more preferable.

  The content of the alkali-soluble resin in the colored actinic ray-sensitive or radiation-sensitive composition is preferably 1 to 30% by mass, more preferably 2 to 20% by mass, based on the total solid content of the composition. And particularly preferably 3 to 10% by mass.

<Polymerizable compound>
The colored actinic ray-sensitive or radiation-sensitive composition of the present invention can be suitably constituted by containing at least one polymerizable compound. The polymerizable compound is mainly contained when the colored photosensitive composition is configured as a negative type. Here, the polymerizable compound is a compound that causes polymerization by an active species. Examples of the active species include radicals, acids, and bases.
When the radical is an active species, a compound having a terminal ethylenically unsaturated bond as a polymerizable group is usually used as the polymerizable compound.
On the other hand, when the active species is an acid such as sulfonic acid, phosphoric acid, sulfinic acid, carboxylic acid, sulfuric acid, and sulfuric monoester, examples of the polymerizable compound include cyclic groups such as an epoxy group, an oxetanyl group, and a tetrahydrofuranyl group. A compound having an ether group or a vinylbenzene group is used.
When the active species is a base such as an amino compound, the polymerizable compound is, for example, a compound having a cyclic ether group such as an epoxy group, oxetanyl group or tetrahydrofuranyl group or a vinylbenzene group. The

  The polymerizable compound is preferably selected from compounds having at least one terminal ethylenically unsaturated bond, more preferably two or more. Such a compound group is widely known in the industrial field, and these can be used without particular limitation in the present invention. These may be in any chemical form such as, for example, monomers, prepolymers, ie dimers, trimers and oligomers, or mixtures thereof and multimers thereof. The polymeric compound in this invention may be used individually by 1 type, and may use 2 or more types together.

More specifically, examples of monomers and prepolymers thereof include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, amides, And multimers thereof, preferably esters of unsaturated carboxylic acids and aliphatic polyhydric alcohol compounds, amides of unsaturated carboxylic acids and aliphatic polyhydric amine compounds, and multimers thereof. is there. Also, addition reaction products of monofunctional or polyfunctional isocyanates or epoxies with unsaturated carboxylic acid esters or amides having a nucleophilic substituent such as hydroxyl group, amino group, mercapto group, 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 isocyanate group or an epoxy group with a monofunctional or polyfunctional alcohol, amine or thiol, and further a halogen group A substitution reaction product of an unsaturated carboxylic acid ester or amide having a detachable 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 compound group in which an unsaturated phosphonic acid, a vinylbenzene derivative such as styrene, vinyl ether, allyl ether or the like is used instead of the unsaturated carboxylic acid.
As these specific compounds, the compounds described in paragraphs 0095 to 0108 of JP-A-2009-288705 can also be suitably used in the present invention.

The polymerizable compound is also preferably a compound having at least one addition-polymerizable ethylene group as a polymerizable monomer and having an ethylenically unsaturated group having a boiling point of 100 ° C. or higher under normal pressure. Examples include monofunctional acrylates and methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, trimethylolethanetri (Meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (Meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) iso (Meth) acrylate obtained by adding ethylene oxide or propylene oxide to polyfunctional alcohols such as annulate, glycerin and trimethylolethane; Urethane (meth) acrylates as described in JP-B-37193, polyester acrylates described in JP-A-48-64183, JP-B-49-43191, JP-B-52-30490, Mention may be made of polyfunctional acrylates and methacrylates such as epoxy acrylates and the like, which are reaction products of epoxy resins and (meth) acrylic acid, and mixtures thereof.
A polyfunctional (meth) acrylate obtained by reacting a polyfunctional carboxylic acid with a compound having a cyclic ether group such as glycidyl (meth) acrylate and an ethylenically unsaturated group can also be used.
As other preferable polymerizable compounds, compounds having a fluorene ring and having two or more functional ethylenic polymerizable groups described in JP 2010-160418 A, JP 2010-129825 A, JP 4364216 A, and cardo resins. Can also be used.

  Further, compounds having a boiling point of 100 ° C. or higher under normal pressure and having at least one addition-polymerizable ethylenically unsaturated group are disclosed in paragraphs [0254] to [0257] of JP-A-2008-292970. The compounds described are also suitable.

  In addition to the above, radically polymerizable monomers represented by the following general formulas (MO-1) to (MO-5) can also be suitably used. In the formula, when T is an oxyalkylene group, the terminal on the carbon atom side is bonded to R.

In the said general formula, n is 0-14 and m is 1-8. A plurality of R and T present in one molecule may be the same or different.
In each of the radical polymerizable monomers represented by the general formulas (MO-1) to (MO-5), at least one of the plurality of Rs is —OC (═O) CH═CH ₂ , or represents an _{-OC (= O) C (CH} 3) = groups represented by CH _2.
Specific examples of the radical polymerizable monomer represented by the above general formulas (MO-1) to (MO-5) include compounds described in paragraph numbers 0248 to 0251 of JP2007-26979A. Can also be suitably used in the present invention.

  In addition, a compound which has been (meth) acrylated after adding ethylene oxide or propylene oxide to the polyfunctional alcohol described in JP-A-10-62986 as general formulas (1) and (2) together with specific examples thereof. Can be used as a polymerizable compound.

  Among them, as the polymerizable compound, dipentaerythritol triacrylate (KAYARAD D-330 as a commercial product; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (as a commercial product, KAYARAD D-320; Nippon Kayaku Co., Ltd.) Dipentaerythritol penta (meth) acrylate (commercially available product: KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (commercially available product: KAYARAD DPHA; Nippon Kayaku Co., Ltd.) And a structure in which these (meth) acryloyl groups are interposed via ethylene glycol and propylene glycol residues. These oligomer types can also be used.

The polymerizable compound is a polyfunctional monomer and may have an acid group such as a carboxyl group, a sulfonic acid group, and a phosphoric acid group. For example, ethylenically unsaturated compounds having an acid group are preferably used. Can be mentioned. The ethylenically unsaturated compounds having an acid group can be obtained by, for example, converting (meth) acrylate a part of the hydroxy group of the polyfunctional alcohol and adding an acid anhydride to the remaining hydroxy group to form a carboxy group. can get.
If the ethylenic compound has an unreacted carboxyl group as in the case of a mixture as described above, this can be used as it is. Non-aromatic carboxylic acid anhydrides may be reacted to introduce acid groups. In this case, specific examples of the non-aromatic carboxylic anhydride used include tetrahydrophthalic anhydride, alkylated tetrahydrophthalic anhydride, hexahydrophthalic anhydride, alkylated hexahydrophthalic anhydride, succinic anhydride, anhydrous Maleic acid is mentioned.

  In the present invention, the monomer having an acid group is an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and a non-aromatic carboxylic acid anhydride is reacted with an unreacted hydroxyl group of the aliphatic polyhydroxy compound. A polyfunctional monomer having an acid group is preferable, and in this ester, the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol. Examples of commercially available products include M-510 and M-520 as polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.

These monomers may be used alone, but since it is difficult to use a single compound in production, two or more kinds may be used in combination. Moreover, you may use together the polyfunctional monomer which does not have an acid group as a monomer, and the polyfunctional monomer which has an acid group as needed.
A preferable acid value of the polyfunctional monomer having an acid group is 0.1 to 40 mg-KOH / g, and particularly preferably 5 to 30 mg-KOH / g. If the acid value of the polyfunctional monomer is too low, the developing dissolution properties are lowered, and if it is too high, the production and handling are difficult, the photopolymerization performance is lowered, and the curability such as the surface smoothness of the pixel is deteriorated. Accordingly, when two or more polyfunctional monomers having different acid groups are used in combination, or when a polyfunctional monomer having no acid group is used in combination, the acid groups as the entire polyfunctional monomer should be adjusted so as to fall within the above range. Is essential.

  In addition, the polymerizable compound in the present invention is preferably at least one selected from the group of compounds represented by the following general formula (i) or (ii).

In the general formulas (i) and (ii), each E independently represents — ((CH ₂ ) yCH ₂ O) — or — ((CH ₂ ) yCH (CH ₃ ) O) —, and y Each independently represents an integer of 0 to 10, and each X independently represents an acryloyl group, a methacryloyl group, a hydrogen atom, or a carboxyl group.
In said general formula (i), the sum total of acryloyl group and 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. However, when the total of each m is 0, any one of X is a carboxyl group.
In said general formula (ii), the sum total of acryloyl group and methacryloyl group is 5 or 6, n represents the integer of 0-10 each independently, and the sum total of each n is an integer of 0-60. However, when the total of each n is 0, any one of X is a carboxyl group.

In the general formula (i), 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 the general formula (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 (i) or formula (ii) in the _{- ((CH 2) yCH 2} O) - or _{- ((CH 2) yCH (} CH 3) O) - , the terminal oxygen atom side X The form which couple | bonds with is preferable.

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

  Moreover, as a total content in the polymeric compound of the compound represented by general formula (i) or (ii), 20 mass% or more is preferable and 50 mass% or more is more preferable.

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

Among the compounds represented by the general formulas (i) and (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), (e) and (f) are preferred.

  Examples of commercially available polymerizable compounds represented by the general formulas (i) and (ii) include SR-494, a tetrafunctional acrylate having four ethyleneoxy chains manufactured by Sartomer, manufactured by Nippon Kayaku Co., Ltd. DPCA-60, which is a hexafunctional acrylate having six pentyleneoxy chains, and TPA-330, which is a trifunctional acrylate having three isobutyleneoxy chains.

Examples of the polymerizable compound include urethane acrylates described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765, Also suitable are urethane compounds having an ethylene oxide-based skeleton described in 58-49860, JP-B 56-17654, JP-B 62-39417, and JP-B 62-39418. Further, as polymerizable compounds, addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238 are exemplified. By using it, it is possible to obtain a curable composition having an extremely excellent photosensitive speed.
Commercially available polymerizable compounds include urethane oligomers UAS-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp Co., Ltd.), UA-7200 "(manufactured by Shin-Nakamura Chemical Co., Ltd., DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA- 306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha) and the like.

  About these polymerizable compounds, the details of the usage method such as the structure, single use or combination, addition amount, etc. can be arbitrarily set in accordance with the final performance design of the colored actinic ray-sensitive or radiation-sensitive composition. . For example, from the viewpoint of sensitivity, a structure having a high unsaturated group content per molecule is preferable, and in many cases, a bifunctional or higher functionality is preferable. Also, from the viewpoint of increasing the strength of the colored cured film, those having three or more functionalities are preferable, and those having different functional numbers and different polymerizable groups (for example, acrylic acid esters, methacrylic acid esters, styrene compounds, vinyl ether compounds). It is also effective to adjust both sensitivity and intensity by using together. Furthermore, it is possible to control the developability of the colored actinic ray-sensitive or radiation-sensitive composition by using a tri- or more functional polymerizable compound having different ethylene oxide chain length, and has excellent pattern forming ability. It is preferable in that it is obtained. In addition, compatibility with other components (for example, photopolymerization initiator, alkali-soluble resin, colorant (pigment), binder polymer, etc.) contained in the colored actinic ray-sensitive or radiation-sensitive composition On the other hand, the selection and use method of the polymerizable compound is an important factor. For example, the compatibility may be improved by using a low-purity compound or using two or more kinds in combination. In addition, a specific structure may be selected from the viewpoint of improving adhesion to a hard surface such as a support.

  Hereinafter, although the specific example of a polymeric compound is given, it is not limited to this.

  A polymeric compound may be used by 1 type, or may be used in combination of 2 or more type.

  The content of the polymerizable compound in the colored actinic ray-sensitive or radiation-sensitive composition of the present invention is 0.1% by mass to 90% with respect to the solid content in the colored actinic ray-sensitive or radiation-sensitive composition. % By mass is preferable, 1.0% by mass to 80% by mass is more preferable, and 2.0% by mass to 70% by mass is particularly preferable.

  In the colored actinic ray-sensitive or radiation-sensitive composition of the present invention, the content ratio by mass of the specific colorant and the polymerizable monomer (compound represented by the general formula (Az): polymerizable monomer) is a layer thinning viewpoint. Therefore, the ratio is preferably 1: 2 to 20: 1, and more preferably 1: 1 to 10: 1.

<Photopolymerization initiator>
The colored actinic ray-sensitive or radiation-sensitive composition of the present invention preferably further contains a photopolymerization initiator from the viewpoint of further improving sensitivity.
The photopolymerization initiator is preferably contained because it imparts photosensitivity to the composition, can be used as a photosensitive composition, and can be suitably used for a color resist or the like. The colored actinic ray-sensitive or radiation-sensitive composition is provided with photosensitivity by containing a photopolymerization initiator, and contains the above-described polymerizable compound and an alkali-soluble resin. After the coating layer is formed by radiation sensitivity, the coating layer can be exposed and developed to form a pattern. The pattern thus obtained can be used as a color filter for a solid-state imaging device or a liquid crystal display device color filter.
The photopolymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of the polymerizable compound, and can be appropriately selected from known photopolymerization initiators, for example, visible from the ultraviolet region. Those having photosensitivity to light are preferable, and may be an activator that generates an active radical by causing some action with a photoexcited sensitizer, and initiates cationic polymerization according to the type of monomer. It may be an initiator.
The photopolymerization initiator preferably contains at least one component having a molecular extinction coefficient of at least about 50 within a range of about 300 to 800 nm (more preferably 330 to 500 nm).

  Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, oxime. Examples include oxime compounds such as derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, and hydroxyacetophenones.

  Examples of the halogenated hydrocarbon compound having a triazine skeleton include those described in Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), a compound described in British Patent 1388492, a compound described in JP-A-53-133428, a compound described in German Patent 3337024, F.I. C. J. Schaefer et al. Org. Chem. 29, 1527 (1964), compounds described in JP-A-62-258241, compounds described in JP-A-5-281728, compounds described in JP-A-5-34920, US Pat. No. 4,221,976 And the compounds described in the book.

  Examples of the compound described in US Pat. No. 4,221,976 include compounds having an oxadiazole skeleton (for example, 2-trichloromethyl-5-phenyl-1,3,4-oxadiazole, 2- Trichloromethyl-5- (4-chlorophenyl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (1-naphthyl) -1,3,4-oxadiazole, 2-trichloromethyl-5 -(2-naphthyl) -1,3,4-oxadiazole, 2-tribromomethyl-5-phenyl-1,3,4-oxadiazole, 2-tribromomethyl-5- (2-naphthyl) -1,3,4-oxadiazole; 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- (4-chlorostyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (4-methoxystyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (1-naphthyl) -1, 3,4-oxadiazole, 2-trichloromethyl-5- (4-n-butoxystyryl) -1,3,4-oxadiazole, 2-tripromomethyl-5-styryl-1,3,4 Oxadiazole, etc.).

  In addition, as photopolymerization initiators other than those described above, polyhalogen compounds (for example, 9-phenylacridine, 1,7-bis (9,9′-acridinyl) heptane, etc.), N-phenylglycine (for example, Carbon tetrabromide, phenyl tribromomethyl sulfone, phenyl trichloromethyl ketone, etc.), coumarins (for example, 3- (2-benzofuroyl) -7-diethylaminocoumarin, 3- (2-benzofuroyl) -7- (1-pyrrolidinyl) ) Coumarin, 3-benzoyl-7-diethylaminocoumarin, 3- (2-methoxybenzoyl) -7-diethylaminocoumarin, 3- (4-dimethylaminobenzoyl) -7-diethylaminocoumarin, 3,3′-carbonylbis (5 , 7-di-n-propoxycoumarin), 3,3′-carbo Rubis (7-diethylaminocoumarin), 3-benzoyl-7-methoxycoumarin, 3- (2-furoyl) -7-diethylaminocoumarin, 3- (4-diethylaminocinnamoyl) -7-diethylaminocoumarin, 7-methoxy-3 -(3-pyridylcarbonyl) coumarin, 3-benzoyl-5,7-dipropoxycoumarin, 7-benzotriazol-2-ylcoumarin, JP-A-5-19475, JP-A-7-271028, JP 2002-363206, JP-A 2002-363207, JP-A 2002-363208, JP-A 2002-363209, etc.), acylphosphine oxides (for example, bis (2,4 , 6-Trimethylbenzoyl) -phenylphosphite Oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphenylphosphine oxide, Lucirin TPO, etc.), metallocenes (for example, bis (η5-2,4-cyclopentadien-1-yl)- Bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium, η5-cyclopentadienyl-η6-cumenyl-iron (1 +)-hexafluorophosphate (1-), etc.) Examples thereof include compounds described in JP-A-53-133428, JP-B-57-1819, JP-A-57-6096, and US Pat. No. 3,615,455.

  Examples of the ketone compound include benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 4-methoxybenzophenone, 2-chlorobenzophenone, 4-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone, 2-ethoxycarbonylbenzolphenone, benzophenonetetracarboxylic acid or tetramethyl ester thereof, 4,4′-bis (dialkylamino) benzophenone (for example, 4,4′-bis (dimethylamino) benzophenone, 4,4′- Bisdicyclohexylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4,4′-bis (dihydroxyethylamino) benzophenone, 4-methoxy-4′-dimethylamino Nzophenone, 4,4'-dimethoxybenzophenone, 4-dimethylaminobenzophenone, 4-dimethylaminoacetophenone, benzyl, anthraquinone, 2-t-butylanthraquinone, 2-methylanthraquinone, phenanthraquinone, xanthone, thioxanthone, 2-chloro -Thioxanthone, 2,4-diethylthioxanthone, fluorenone, 2-benzyl-dimethylamino-1- (4-morpholinophenyl) -1-butanone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino -1-propanone, 2-hydroxy-2-methyl- [4- (1-methylvinyl) phenyl] propanol oligomer, benzoin, benzoin ethers (for example, benzoin methyl ether, benzoin ethyl ether, In propyl ether, benzoin isopropyl ether, benzoin phenyl ether, benzyl dimethyl ketal), acridone, chloro acridone, N- methyl acridone, N- butyl acridone, N- butyl - such as chloro acrylic pyrrolidone.

As the photopolymerization initiator, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds can also be suitably used. More specifically, for example, aminoacetophenone initiators described in JP-A-10-291969 and acylphosphine oxide initiators described in Japanese Patent No. 4225898 can also be used.
As the hydroxyacetophenone-based initiator, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, IRGACURE-127 (trade names: all manufactured by BASF Japan Ltd.) can be used. As the aminoacetophenone-based initiator, commercially available products IRGACURE-907, IRGACURE-369, and IRGACURE-379 (trade names: all manufactured by BASF Japan Ltd.) can be used. As the aminoacetophenone-based initiator, a compound described in JP-A-2009-191179 in which an absorption wavelength is matched with a long wave light source such as 365 nm or 405 nm can also be used. As the acylphosphine initiator, commercially available products such as IRGACURE-819 and DAROCUR-TPO (trade names: both manufactured by BASF Japan Ltd.) can be used.

  More preferred examples of the photopolymerization initiator include oxime photopolymerization initiators (oxime compounds). Specific examples of the oxime photopolymerization initiator include oxime compounds described in JP-A No. 2001-233842, oxime compounds described in JP-A No. 2000-80068, and oxime compounds described in JP-A No. 2006-342166.

  Examples of oxime compounds such as oxime derivatives that are preferably used as a photopolymerization initiator in the present invention include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutane-2-one, and 3-propionyloxyimino. Butan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4 -Toluenesulfonyloxy) iminobutan-2-one, 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one and the like.

Examples of oxime ester compounds include J.M. C. S. Perkin II (1979) pp. 1653-1660), J.M. C. S. Perkin II (1979) pp. 156-162, Journal of Photopolymer Science and Technology (1995) pp. 202-232, compounds described in JP-A No. 2000-66385, compounds described in JP-A No. 2000-80068, JP-T 2004-534797, JP-A No. 2006-342166, and the like.
IRGACURE-OXE01 (manufactured by BASF Japan) and IRGACURE-OXE02 (manufactured by BASF Japan) are also preferably used as commercial products.

  Further, as oxime ester compounds other than those described above, compounds described in JP-T 2009-519904, in which an oxime is linked to the N-position of carbazole, compounds described in US Pat. No. 7,626,957 in which a hetero substituent is introduced into the benzophenone moiety, Compounds described in Japanese Patent Application Laid-Open No. 2010-15025 and US Patent Publication No. 2009-292209, in which a nitro group is introduced into the dye moiety, and ketoxime compounds described in International Patent Publication No. 2009-131189, triazine skeleton and oxime skeleton are the same molecule A compound described in U.S. Pat. No. 7,556,910, a compound described in JP-A-2009-221114 having an absorption maximum at 405 nm and good sensitivity to a g-line light source, and the like may be used.

Preferably, it can also be suitably used for the cyclic oxime compounds described in JP-A-2007-231000 and JP-A-2007-322744. Among the cyclic oxime compounds, the cyclic oxime compounds fused to the carbazole dyes described in JP2010-32985A and JP2010-185072A in particular have high light absorptivity from the viewpoint of high sensitivity. preferable.
Further, the compound described in JP-A-2009-242469 having an unsaturated bond at a specific site of the oxime compound can be preferably used because it can achieve high sensitivity by regenerating active radicals from polymerization inert radicals. it can.

Most preferably, the oxime compound which has a specific substituent shown by Unexamined-Japanese-Patent No. 2007-267979 and the oxime compound which has a thioaryl group shown by Unexamined-Japanese-Patent No. 2009-191061 are mentioned.
Specifically, the oxime photopolymerization initiator is preferably a compound represented by the following formula (1). The N—O bond of the oxime may be an (E) oxime compound, a (Z) oxime compound, or a mixture of (E) and (Z) isomers. .

(In formula (1), R and B each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group.)
The monovalent substituent represented by R is preferably a monovalent nonmetallic atomic group.
Examples of the monovalent nonmetallic atomic group include an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, an alkylthiocarbonyl group, and an arylthiocarbonyl group. Moreover, these groups may have one or more substituents. Moreover, the substituent mentioned above may be further substituted by another substituent.
Examples of the substituent include a halogen atom, an aryloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group, an acyloxy group, an acyl group, an alkyl group, and an aryl group.

  As the alkyl group which may have a substituent, an alkyl group having 1 to 30 carbon atoms is preferable, and specifically, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a decyl group. , Dodecyl group, okdadecyl group, isopropyl group, isobutyl group, sec-butyl group, t-butyl group, 1-ethylpentyl group, cyclopentyl group, cyclohexyl group, trifluoromethyl group, 2-ethylhexyl group, phenacyl group, 1- Naphthoylmethyl group, 2-naphthoylmethyl group, 4-methylsulfanylphenacyl group, 4-phenylsulfanylphenacyl group, 4-dimethylaminophenacyl group, 4-cyanophenacyl group, 4-methylphenacyl group, 2- Methylphenacyl group, 3-fluorophenacyl group, 3-trifluoromethylphenacyl group, and , 3 Nitorofenashiru group can be exemplified.

  The aryl group which may have a substituent is preferably an aryl group having 6 to 30 carbon atoms, specifically, a phenyl group, a biphenyl group, a 1-naphthyl group, a 2-naphthyl group, or a 9-anthryl group. 9-phenanthryl group, 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azurenyl group, 9-fluorenyl group, terphenyl group, quarterphenyl group, o-, m- and p-tolyl group, Xylyl group, o-, m- and p-cumenyl group, mesityl group, pentarenyl group, binaphthalenyl group, tarnaphthalenyl group, quarternaphthalenyl group, heptaenyl group, biphenylenyl group, indacenyl group, fluoranthenyl group, acenaphthylenyl group, ASEAN Trirenyl group, phenalenyl group, fluorenyl group, anthryl group, bianthracenyl group, ter Nthracenyl group, quarteranthracenyl group, anthraquinolyl group, phenanthryl group, triphenylenyl group, pyrenyl group, chrysenyl group, naphthacenyl group, preadenyl group, picenyl group, perylenyl group, pentaphenyl group, pentacenyl group, tetraphenylenyl group, Examples include a hexaphenyl group, a hexacenyl group, a rubicenyl group, a coronenyl group, a trinaphthylenyl group, a heptaphenyl group, a heptacenyl group, a pyranthrenyl group, and an ovalenyl group.

  The acyl group which may have a substituent is preferably an acyl group having 2 to 20 carbon atoms, specifically, an acetyl group, a propanoyl group, a butanoyl group, a trifluoroacetyl group, a pentanoyl group, a benzoyl group, 1-naphthoyl group, 2-naphthoyl group, 4-methylsulfanylbenzoyl group, 4-phenylsulfanylbenzoyl group, 4-dimethylaminobenzoyl group, 4-diethylaminobenzoyl group, 2-chlorobenzoyl group, 2-methylbenzoyl group, 2 -Methoxybenzoyl group, 2-butoxybenzoyl group, 3-chlorobenzoyl group, 3-trifluoromethylbenzoyl group, 3-cyanobenzoyl group, 3-nitrobenzoyl group, 4-fluorobenzoyl group, 4-cyanobenzoyl group, and And 4-methoxybenzoyl group.

  The alkoxycarbonyl group which may have a substituent is preferably an alkoxycarbonyl group having 2 to 20 carbon atoms, specifically, a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a butoxycarbonyl group, or a hexyloxy group. Examples thereof include a carbonyl group, an octyloxycarbonyl group, a decyloxycarbonyl group, an octadecyloxycarbonyl group, and a trifluoromethyloxycarbonyl group.

  Specific examples of the aryloxycarbonyl group which may have a substituent include phenoxycarbonyl group, 1-naphthyloxycarbonyl group, 2-naphthyloxycarbonyl group, 4-methylsulfanylphenyloxycarbonyl group, 4-phenylsulfanyl. Phenyloxycarbonyl group, 4-dimethylaminophenyloxycarbonyl group, 4-diethylaminophenyloxycarbonyl group, 2-chlorophenyloxycarbonyl group, 2-methylphenyloxycarbonyl group, 2-methoxyphenyloxycarbonyl group, 2-butoxyphenyloxy Carbonyl group, 3-chlorophenyloxycarbonyl group, 3-trifluoromethylphenyloxycarbonyl group, 3-cyanophenyloxycarbonyl group, 3-nitrophenyloxycarbonyl , 4-fluorophenyl oxycarbonyl group, 4-cyanophenyl oxycarbonyl group, and a 4-methoxy phenyloxy carbonyl group can be exemplified.

The heterocyclic group which may have a substituent is preferably an aromatic or aliphatic heterocyclic ring containing a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom.
Specifically, thienyl group, benzo [b] thienyl group, naphtho [2,3-b] thienyl group, thiantenyl group, furyl group, pyranyl group, isobenzofuranyl group, chromenyl group, xanthenyl group, phenoxathiyl Nyl, 2H-pyrrolyl, pyrrolyl, imidazolyl, pyrazolyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, indolizinyl, isoindolyl, 3H-indolyl, indolyl, 1H-indazolyl, purinyl 4H-quinolidinyl group, isoquinolyl group, quinolyl group, phthalazinyl group, naphthyridinyl group, quinoxanilyl group, quinazolinyl group, cinnolinyl group, pteridinyl group, 4aH-carbazolyl group, carbazolyl group, β-carbolinyl group, phenanthridinyl group, acridinyl Group Midinyl group, phenanthrolinyl group, phenazinyl group, phenalsadinyl group, isothiazolyl group, phenothiazinyl group, isoxazolyl group, furazanyl group, phenoxazinyl group, isochromanyl group, chromanyl group, pyrrolidinyl group, pyrrolinyl group, imidazolidinyl group, imidazolinyl group, pyrazolidinyl group, pyrazolidinyl group Examples include a group, pyrazolinyl group, piperidyl group, piperazinyl group, indolinyl group, isoindolinyl group, quinuclidinyl group, morpholinyl group, and thioxanthryl group.

  Specific examples of the optionally substituted alkylthiocarbonyl group include a methylthiocarbonyl group, a propylthiocarbonyl group, a butylthiocarbonyl group, a hexylthiocarbonyl group, an octylthiocarbonyl group, a decylthiocarbonyl group, and an octadecylthiocarbonyl group. Examples thereof include a group and a trifluoromethylthiocarbonyl group.

  Specific examples of the arylthiocarbonyl group which may have a substituent include a 1-naphthylthiocarbonyl group, a 2-naphthylthiocarbonyl group, a 4-methylsulfanylphenylthiocarbonyl group, and a 4-phenylsulfanylphenylthiocarbonyl group. 4-dimethylaminophenylthiocarbonyl group, 4-diethylaminophenylthiocarbonyl group, 2-chlorophenylthiocarbonyl group, 2-methylphenylthiocarbonyl group, 2-methoxyphenylthiocarbonyl group, 2-butoxyphenylthiocarbonyl group, 3 -Chlorophenylthiocarbonyl group, 3-trifluoromethylphenylthiocarbonyl group, 3-cyanophenylthiocarbonyl group, 3-nitrophenylthiocarbonyl group, 4-fluorophenylthiocarbonyl group, 4-cyanophenyl Two thiocarbonyl group, and a and a 4-methoxyphenylthiocarbonyl group.

  The monovalent substituent represented by B represents an aryl group, a heterocyclic group, an arylcarbonyl group, or a heterocyclic carbonyl group. These groups may have one or more substituents. Examples of the substituent include the above-described substituents. Moreover, the substituent mentioned above may be further substituted by another substituent.

Of these, the structures shown below are particularly preferred.
In the following structure, Y, X, and n have the same meanings as Y, X, and n in formula (2) described later, and preferred examples are also the same.

Examples of the divalent organic group represented by A include an alkylene group (preferably an alkylene group having 1 to 12 carbon atoms), a cyclohexylene group (preferably a cyclohexylene group having 6 to 12 carbon atoms), and an alkynylene group (preferably Is an alkynylene group having 2 to 12 carbon atoms. These groups may have one or more substituents. Examples of the substituent include the above-described substituents. Moreover, the substituent mentioned above may be further substituted by another substituent.
Among them, A is an alkylene substituted with an unsubstituted alkylene group or an alkyl group (for example, a methyl group, an ethyl group, a tert-butyl group, or a dodecyl group) from the viewpoint of increasing sensitivity and suppressing coloration due to heating. Group, alkylene group substituted with alkenyl group (for example, vinyl group, allyl group), aryl group (for example, phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl group, phenanthryl group, styryl group) An alkylene group substituted with

The aryl group represented by Ar is preferably an aryl group having 6 to 30 carbon atoms and may have a substituent. Examples of the substituent include the same substituents as those introduced into the substituted aryl group mentioned above as specific examples of the aryl group which may have a substituent.
Among these, a substituted or unsubstituted phenyl group is preferable from the viewpoint of increasing sensitivity and suppressing coloring due to heating.

  In the formula (1), it is preferable in terms of sensitivity that the structure of “SAr” formed by Ar and adjacent S is the following structure. Me represents a methyl group, and Et represents an ethyl group.

  The oxime compound is preferably a compound represented by the following formula (2).

(In formula (2), R and X each independently represent a monovalent substituent, A and Y each independently represent a divalent organic group, Ar represents an aryl group, and n represents 0-5. (It is an integer.)
R, A, and Ar in formula (2) have the same meanings as R, A, and Ar in formula (1), and preferred examples are also the same.

  Examples of the monovalent substituent represented by X include an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyloxy group, an acyl group, an alkoxycarbonyl group, an amino group, a heterocyclic group, and a halogen atom. These groups may have one or more substituents. Examples of the substituent include the above-described substituents. Moreover, the substituent mentioned above may be further substituted by another substituent.

Among these, X is preferably an alkyl group from the viewpoints of solvent solubility and improvement in absorption efficiency in the long wavelength region.
Moreover, n in Formula (2) represents the integer of 0-5, and the integer of 0-2 is preferable.

Examples of the divalent organic group represented by Y include the structures shown below. In the groups shown below, “*” represents a bonding position between Y and an adjacent carbon atom in the formula (2).

  Among these, from the viewpoint of increasing sensitivity, the following structures are preferable.

  Furthermore, the oxime compound is preferably a compound represented by the following formula (3).

(In formula (3), R and X each independently represent a monovalent substituent, A represents a divalent organic group, Ar represents an aryl group, and n is an integer of 0 to 5.)
R, X, A, Ar, and n in Formula (3) have the same meanings as R, X, A, Ar, and n in Formula (2), respectively, and preferred examples are also the same.

  Specific examples (C-1) to (C-10) of oxime compounds that can be suitably used are shown below, but the present invention is not limited thereto.

  The oxime compound has a maximum absorption wavelength in a wavelength region of 350 nm to 500 nm, preferably has an absorption wavelength in a wavelength region of 360 nm to 480 nm, and particularly preferably has high absorbance at 365 nm and 455 nm.

The molar extinction coefficient at 365 nm or 405 nm of the oxime compound is preferably 1,000 to 300,000, more preferably 2,000 to 300,000, more preferably 5,000 to 200, from the viewpoint of sensitivity. Is particularly preferred.
A known method can be used for the molar extinction coefficient of the compound. Specifically, for example, 0.01 g of an ultraviolet-visible spectrophotometer (Varian Inc., Carry-5 spctrophotometer) is used with an ethyl acetate solvent. It is preferable to measure at a concentration of / L.

  The radical photopolymerization initiator used in the present invention may be used in combination of two or more as required.

  The content of the photopolymerization initiator based on the total solid content of the colored actinic ray-sensitive or radiation-sensitive composition of the present invention is preferably 0.1 to 20% by mass, and 0.3 to 10% by mass. It is preferably 0.4 to 5% by mass.

  The colored actinic ray-sensitive or radiation-sensitive composition may contain a sensitizer for the purpose of improving the radical generation efficiency of the radical initiator and increasing the photosensitive wavelength. As the sensitizer that can be used in the present invention, a sensitizer that sensitizes the above-mentioned photo radical polymerization initiator by an electron transfer mechanism or an energy transfer mechanism is preferable.

Examples of the sensitizer used in the colored actinic ray-sensitive or radiation-sensitive composition include compounds described in paragraph numbers [0101] to [0154] of JP-A-2008-32803.
The content of the sensitizer in the colored actinic ray-sensitive or radiation-sensitive composition is 0.1% by mass to 20% by mass in terms of solid content from the viewpoint of light absorption efficiency to the deep part and initiation decomposition efficiency. It is preferable that there is 0.5% by mass to 15% by mass.
A sensitizer may be used individually by 1 type and may use 2 or more types together.

<Solvent>
In general, the colored actinic ray-sensitive or radiation-sensitive 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 actinic ray-sensitive or radiation-sensitive composition of the present invention from the viewpoint of further improving coatability. 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, since the colored actinic ray-sensitive or radiation-sensitive composition of the present invention contains a fluorosurfactant, liquid properties (particularly, fluidity) when prepared as a coating liquid are further improved. The uniformity of coating thickness and liquid-saving properties can be further improved.
That is, when a film is formed using a coating liquid to which a colored actinic ray-sensitive or radiation-sensitive composition containing a fluorosurfactant is applied, the interfacial tension between the surface to be coated and the coating liquid is reduced. As a result, the wettability to the coated surface 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 fluorosurfactant having a fluorine content within this range is effective in terms of uniformity of coating film thickness and liquid-saving properties, and is soluble in colored actinic ray-sensitive or radiation-sensitive compositions. The property is also good.

  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, SC-103, SC-104, SC-105, SC1068, SC-381, SC-383, S393, and KH-40 (above, manufactured by Asahi Glass Co., Ltd.).

  Specific examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates thereof (for example, glycerol propoxylate, glycerin ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene Stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, Pluronic L10, L31, L61, L62 manufactured by BASF 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1, Sol Perth 20000 (manufactured by Nippon Lubrizol Corporation), and the like.

  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 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 the silicone surfactant include “Toray Silicone DC3PA”, “Toray Silicone SH7PA”, “Toray Silicone DC11PA”, “Tore Silicone SH21PA”, “Tore Silicone SH28PA”, “Toray Silicone” manufactured by Toray Dow Corning Co., Ltd. “Silicone SH29PA”, “Toresilicone SH30PA”, “Toresilicone SH8400”, “TSF-4440”, “TSF-4300”, “TSF-4445”, “TSF-4460”, “TSF” manufactured by Momentive Performance Materials, Inc. -4552 "," KP341 "," KF6001 "," KF6002 "manufactured by Shin-Etsu Silicone Co., Ltd.," BYK307 "," BYK323 "," BYK330 "manufactured by Big Chemie.
Only one type of surfactant may be used, or two or more types may be combined.
The addition amount of the surfactant is preferably 0.001% by mass to 5.0% by mass, more preferably 0.005% by mass to 3% with respect to the total mass of the colored actinic ray-sensitive or radiation-sensitive composition. 0.0% by mass.

<Polymerization inhibitor>
In the colored actinic ray-sensitive or radiation-sensitive composition of the present invention, in order to prevent unnecessary thermal polymerization of the polymerizable compound during the production or storage of the colored actinic ray-sensitive or radiation-sensitive composition. It is desirable to add a small amount of a polymerization inhibitor.
Examples of the polymerization inhibitor that can be used in the present invention 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), N-nitrosophenylhydroxyamine primary cerium salt and the like.
The addition amount of the polymerization inhibitor is preferably about 0.01% by mass to about 5% by mass with respect to the mass of the whole composition.

<Other ingredients>
In the colored actinic ray-sensitive or radiation-sensitive 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, the above alkali-soluble resin. Other additives such as a polymer compound other than the above, an adhesion promoter, an antioxidant, an ultraviolet absorber, an aggregation inhibitor, an organic carboxylic acid having a molecular weight of 1000 or less, and / or an organic carboxylic acid anhydride 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 actinic ray-sensitive or radiation-sensitive composition of the present invention comprises a polymerizable compound, a photopolymerization initiator, and, if necessary, an alkali-soluble resin with respect to the pigment dispersion composition of the present invention described above. And can be prepared by adding additives such as solvents and surfactants.
The total concentration of solids contained in the colored actinic ray-sensitive or radiation-sensitive composition of the present invention is preferably in the range of 1 to 70% by mass, and more preferably in the range of 2 to 50% by mass. .

Since the colored actinic ray-sensitive or radiation-sensitive composition of the present invention includes a pigment dispersion composition containing an azo pigment represented by the general formula (Az), it has excellent pigment dispersibility and also has color characteristics. Excellent.
Therefore, it is preferably used for forming a colored region of a color filter (especially a color filter for a solid-state image sensor) that requires good color characteristics. That is, this invention relates also to the color filter (especially color filter for solid-state image sensors) formed using the coloring actinic-ray-sensitive or radiation-sensitive composition of this invention.

[Color filter for solid-state imaging device or liquid crystal display device and manufacturing method thereof]
The manufacturing method (pattern formation method) of the color filter for solid-state image sensors or liquid crystal display elements of this invention apply | coats the coloring actinic-ray-sensitive or radiation-sensitive composition of this invention mentioned above on a support body. A step of forming a colored actinic ray-sensitive or radiation-sensitive composition layer (hereinafter also referred to as a “colored actinic ray-sensitive or radiation-sensitive composition layer forming step”), and the colored actinic ray-sensitive or radiation-sensitive layer. A step of exposing the composition layer through a mask (hereinafter also referred to as “exposure step”), and developing the colored actinic ray-sensitive or radiation-sensitive composition layer after exposure to develop a colored pattern (hereinafter referred to as “colored pixel”). A step (hereinafter also referred to as “development step”).
The color filter for a solid-state image sensor or liquid crystal display device of the present invention is manufactured by the method for manufacturing a color filter for a solid-state image sensor or liquid crystal display device of the present invention. The present invention is more preferably a solid-state image sensor color filter manufactured by the method for manufacturing a solid-state image sensor color filter of the present invention.
The color filter for a solid-state image sensor or liquid crystal display element of the present invention has at least a red pattern (red pixel) manufactured by the method for manufacturing a color filter for solid-state image sensor or liquid crystal display device of the present invention. Good. As a specific form of the color filter for the solid-state imaging device or the liquid crystal display 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, blue color) A color filter having three or more colors having at least a pattern and a green pattern is preferable.
Hereinafter, the color filter for the solid-state imaging device or the liquid crystal display device may be simply referred to as “color filter”.

<Coloring actinic ray-sensitive or radiation-sensitive composition layer forming step>
In the colored actinic ray-sensitive or radiation-sensitive composition layer forming step, the colored actinic ray-sensitive or radiation-sensitive composition of the present invention is applied to the support to give the colored actinic-ray-sensitive or radiation-sensitive composition. Form a layer.
In the case of a solid-state imaging device, the support that can be used in this step is, for example, an imaging device (such as a charge coupled device (CCD) or a complementary metal-oxide semiconductor (CMOS)) on a substrate (for example, a silicon substrate) ( A solid-state image sensor substrate provided with a light receiving element) can be used. In the case of a liquid crystal display device, a glass substrate can be used as a support.
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.

  Examples of the method for applying the colored actinic ray-sensitive or radiation-sensitive composition of the present invention on a support include various coating methods such as slit coating, ink jet method, spin coating, cast coating, roll coating, and screen printing. Can be applied.

  The thickness of the colored actinic ray-sensitive or radiation-sensitive composition layer is preferably 0.1 μm to 10 μm, more preferably 0.2 μm to 5 μm, and still more preferably 0.2 μm to 3 μm.

  The colored actinic ray-sensitive or radiation-sensitive 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 actinic ray-sensitive or radiation-sensitive composition layer formed in the colored actinic ray-sensitive or radiation-sensitive composition layer forming step is subjected to a predetermined mask pattern using an exposure device such as a stepper, for example. Pattern exposure through a mask having
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>
Subsequently, by carrying out an alkali development treatment, the colored actinic ray-sensitive or radiation-sensitive 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 actinic ray-sensitive or radiation-sensitive composition layer forming step, exposure step, and development step, if necessary, a curing step in which the formed colored pattern is cured by heating and / or exposure. May be included.

  Even when the colored actinic ray-sensitive or radiation-sensitive composition of the present invention adheres to, for example, a nozzle of a coating apparatus discharge section, a piping section of a coating apparatus, or the inside of a coating apparatus, it is easily cleaned using a known cleaning liquid Can be removed. In this case, in order to perform more efficient cleaning and removal, it is preferable to use the solvent described above as the solvent contained in the colored actinic ray-sensitive or radiation-sensitive composition of the present invention 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 JP 2007-2101 A, JP 2007-2102 A, JP 2007-281523 A, etc. are also cleaning liquids for cleaning and removing the colored actinic ray-sensitive or radiation-sensitive composition of the present invention. Can be suitably used.
As the cleaning liquid, it is preferable to use alkylene glycol monoalkyl ether carboxylate or alkylene glycol monoalkyl ether.
These solvents that can be used as the cleaning liquid may be used alone or in combination of two or more.
When mixing 2 or more types of solvent, the mixed solvent formed by mixing the solvent which has a hydroxyl group, and the solvent which does not have a hydroxyl group is preferable. 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. The mixed solvent is a mixed solvent of propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME), and the mass ratio is particularly preferably 60/40.
In addition, in order to improve the permeability of the cleaning liquid to the colored actinic ray-sensitive or radiation-sensitive composition, the cleaning liquid is listed above as a surfactant that the colored actinic-ray-sensitive or radiation-sensitive composition can contain. A surfactant may be added.

Since the color filter for a solid-state imaging device of the present invention uses the colored actinic ray-sensitive or radiation-sensitive 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 general formula (Az), it is excellent in 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.

<Liquid crystal display element>
Since the color filter of the present invention has colored pixels that are excellent in hue and excellent in light resistance, it is particularly suitable as a color filter for liquid crystal display devices. A liquid crystal display device provided with such a color filter can display a high-quality image having a good display image color and excellent display characteristics.

  For the definition of display devices and details of each display device, refer to, for example, “Electronic Display Devices (Akio Sasaki, published by Industrial Research Institute 1990)”, “Display Devices (Junaki Ibuki, Industrial Books Co., Ltd.) Issued in the first year). The liquid crystal display device is described in, for example, “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, published by Kogyo Kenkyukai 1994)”. The liquid crystal display device to which the present invention can be applied is not particularly limited, and can be applied to, for example, various types of liquid crystal display devices described in the “next generation liquid crystal display technology”.

The color filter of the present invention is particularly effective for a color TFT liquid crystal display device. The color TFT liquid crystal display device is described in, for example, “Color TFT liquid crystal display (issued in 1996 by Kyoritsu Publishing Co., Ltd.)”. Furthermore, the present invention is applied to a liquid crystal display device with a wide viewing angle such as a lateral electric field driving method such as IPS, a pixel division method such as MVA, STN, TN, VA, OCS, FFS, and R-OCB. it can.
The color filter of the present invention can also be used for a bright and fine COA (Color-filter On Array) system. In a COA type liquid crystal display device, the required characteristics for the color filter layer require the required characteristics for the interlayer insulating film in addition to the normal required characteristics as described above, that is, low dielectric constant and peeling liquid resistance. Sometimes. In order to satisfy the required characteristics of a low dielectric constant, a resin film may be provided on the color filter layer.
Further, the colored layer formed by the COA method has a side length of about 1 to 15 μm in order to connect the ITO electrode disposed on the colored layer and the terminal of the driving substrate below the colored layer. It is necessary to form a conduction path such as a rectangular through hole or a U-shaped depression, and the dimension of the conduction path (that is, the length of one side) is preferably 5 μm or less, but the present invention is used. Thus, it is possible to form a conduction path of 5 μm or less. These image display methods are described, for example, on page 43 of "EL, PDP, LCD display-Technology and latest trends in the market (issued by Toray Research Center Research Division 2001)".

The liquid crystal display element of the present invention includes various members such as an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, and a viewing angle guarantee film in addition to the color filter of the present invention. The color filter of the present invention can be applied to a liquid crystal display element composed of these known members. Regarding these materials, for example, “'94 Liquid Crystal Display Peripheral Materials / Chemicals Market (Kentaro Shima, CMC 1994)”, “2003 Liquid Crystal Related Markets Current Status and Future Prospects (Volume 2)” Fuji Chimera Research Institute, Ltd., published in 2003) ”.
Regarding the backlight, SID meeting Digest 1380 (2005) (A. Konno et.al), Monthly Display December 2005, pages 18-24 (Yasuhiro Shima), pages 25-30 (Takaaki Yagi), etc. Are listed.

  When the color filter of the present invention is used for a liquid crystal display element, a high contrast can be realized when combined with a conventionally known three-wavelength tube of a cold cathode tube, and further, red, green and blue LED light sources (RGB-LED). By using as a backlight, a liquid crystal display device having high luminance and high color purity and good color reproducibility can be provided.

  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.

<Synthesis example of polymer compound>
[Synthesis Example 1]
(Synthesis of polymer compound 1)
The following compound M-6 27.0 g, dimethylaminoethyl methacrylate 126.0 g, methyl methacrylate 27.0 g, and 1-methoxy-2-propanol 420.0 g were introduced into a nitrogen-substituted three-necked flask, and a stirrer (Shinto) The mixture was stirred with a scientific (three-motor) and heated to 90 ° C. while flowing nitrogen into the flask. To this was added 1.80 g of 2,2-azobis (2,4-dimethylvaleronitrile) (V-65 manufactured by Wako Pure Chemical Industries, Ltd.), and the mixture was heated and stirred at 90 ° C. for 2 hours. After 2 hours, 1.80 g of V-65 was further added, and after 3 hours of heating and stirring, a 30% by mass solution of polymer compound 1 (structure is shown below) (hereinafter also referred to as “polymer compound solution 1”) was obtained. It was.
As a result of measuring the weight average molecular weight of the obtained polymer compound 1 by gel permeation chromatography (GPC) using polystyrene as a standard substance, it was 21,000 and the degree of dispersion was 2.6. From the titration with hydrochloric acid, the amine value per solid content was 250 mgKOH / g. The ¹ H-NMR measurement results of calculating the composition ratio of the polymer compound 1 (molar ratio) was 8/69/23 left to the following structure.
The polymer compound 1 is a polymer compound having a heterocyclic ring in the side chain.

[Synthesis Example 2]
(Synthesis of polymer compound 2)
The following compound M-11 27.0 g, methyl methacrylate 126.0 g, methacrylic acid 27.0 g, and 1-methoxy-2-propanol 420.0 g were introduced into a nitrogen-substituted three-necked flask, and a stirrer (Shinto) The mixture was stirred with a scientific (three-motor) and heated to 90 ° C. while flowing nitrogen into the flask. To this was added 1.69 g of 2,2-azobis (2,4-dimethylvaleronitrile) (V-65 manufactured by Wako Pure Chemical Industries, Ltd.), and the mixture was stirred with heating at 90 ° C. for 2 hours. Two hours later, 1.69 g of V-65 was further added, and after 3 hours of heating and stirring, a 30% by mass solution of polymer compound 2 (structure is shown below) (hereinafter also referred to as “polymer compound solution 2”) was obtained. It was.
As a result of measuring the weight average molecular weight of the obtained polymer compound 2 by a gel permeation chromatography method (GPC) using polystyrene as a standard substance, it was 20,000 and the dispersity was 2.0. From the titration with sodium hydroxide, the acid value per solid content was 98 mgKOH / g. The ¹ H-NMR measurement results of calculating the composition ratio of the polymer compound 2 (molar ratio) was 5/75/20 left to the following structure.
The polymer compound 2 is a polymer compound having a heterocyclic ring in the side chain.

[Synthesis Example 3]
(Synthesis of polymer compound 3)
24 g of diethylene glycol is introduced into a nitrogen-substituted three-necked flask and stirred with a stirrer (Shinto Kagaku Co., Ltd .: Three-One Motor). To this, 70.5 g of benzyl methacrylate, 29.5 g of methacrylic acid, 210 g of diethylene glycol, 1.3 g of dodecyl mercaptan, 2,2-azobis (2,4-dimethylisobutyrate) (V-made by Wako Pure Chemical Industries, Ltd.) 601) A solution in which 1.5 g was dissolved was dropped over 2 hours. The mixture was further stirred for 2 hours to obtain a 30% by mass solution of polymer compound 3 (structure below) (hereinafter also referred to as “polymer compound solution 3”).
As a result of measuring the weight average molecular weight of the obtained polymer compound 3 by gel permeation chromatography (GPC) using polystyrene as a standard substance, it was 17,000 and the dispersity was 1.9. Moreover, the acid value per solid content was 192 mgKOH / g from the titration using sodium hydroxide. The ¹ H-NMR measurement results of calculating the composition ratio of the polymer compound 3 (molar ratio) was 54/46 in order from the left of the following structure.
The polymer compound 3 is a polymer compound having no heterocyclic ring in the side chain.

[Synthesis Example 4]
(Synthesis of polymer compound 4)
A 30% by mass solution of polymer compound 4 (structure shown below) (hereinafter referred to as “polymer compound”) in the same manner as in Synthesis Example 3 except that benzyl methacrylate (benzyl methacrylate) was changed to methyl methacrylate (methyl methacrylate). Solution 4 ") was also obtained.
As a result of measuring the weight average molecular weight of the obtained polymer compound 4 by gel permeation chromatography (GPC) using polystyrene as a standard substance, it was 15,000 and the degree of dispersion was 1.8. Moreover, the acid value per solid content was 192 mgKOH / g from the titration using sodium hydroxide. The ¹ H-NMR measurement results of calculating the composition ratio of the polymer compound 4 (molar ratio) was 67/33 in order from the left of the following structure.
The polymer compound 4 is a polymer compound having no heterocyclic ring in the side chain.

<Example of pigment synthesis>
Pigment 1 having the following structure was synthesized according to Synthesis Example 1 described in paragraphs [0171] to [0173] of JP 2010-47750 A. Pigment 2 having the following structure was synthesized according to Synthesis Example 1 described in paragraphs [0244] to [0246] of JP2010-155983A. Pigment 5 having the following structure was synthesized according to Synthesis Example 1 described in paragraphs [0181] to [0183] of JP 2010-043255 A. Pigment 6 having the following structure was synthesized according to Synthesis Example 1 described in paragraphs [0247] to [0249] of JP 2010-084135 A. In addition, pigments 3 and 4 having the following structures were synthesized as in the following synthesis examples.

[Synthesis Example 5]
(Synthesis of Pigment 3)
The pigment 3 was synthesized by the following route.

1.0 g of the compound (1) was dissolved in 7.5 ml of phosphoric acid (Wako Pure Chemical Industries, Ltd .; reagent grade, purity 85%). This solution was ice-cooled and kept at −2 to 0 ° C., 0.38 g of sodium nitrite was added and stirred for 1 hour to obtain a diazonium salt solution. Separately, 25 ml of N-methylpyrrolidone was added to 1.50 g of compound (0), and the above-mentioned diazonium salt solution was added at 5 to 12 ° C. with dissolution and stirring. Upon completion of the addition, the ice bath was removed and the mixture was further stirred for 2 hours. 100 ml of methanol was added to the reaction solution and stirred for 30 minutes, and the precipitated crystals were filtered and washed with 50 ml of methanol. The obtained crystals were stirred with 100 ml of water for 1 hour, and the crystals were filtered. To the obtained crystals, 25 ml of N-methylpyrrolidone and 25 ml of water were added, stirred at 80 ° C. for 1 hour, and stirred at room temperature for 2 hours. The crystals were filtered and washed with 20 ml of N-methylpyrrolidone / water = 1/1 and 20 ml of water. The obtained crystals were dried to obtain 1.8 g of the pigment 3 of the present invention. Yield 76.3%.
FIG. 1 shows an infrared absorption chart.

[Synthesis Example 6]
(Synthesis of Pigment 4)
Pigment 4 was synthesized by the following route.

1.0 g of the compound (1-2) was added to 10 ml of phosphoric acid (Wako Pure Chemical Industries, Ltd .; reagent special purity 85%, the same applies hereinafter) and heated to 30 ° C. to dissolve. This solution was ice-cooled and kept at 0 to 5 ° C., 0.38 g of sodium nitrite was added and stirred for 1.5 hours to obtain a diazonium salt solution. This diazonium salt solution was added dropwise to a solution prepared by dissolving 1.4 g of compound (2-2) in 5 ml of dimethylacetamide while maintaining the temperature at 5 to 10 ° C., and then stirred for 1 hour while maintaining the temperature at 5 to 10 ° C. Thereafter, the ice bath was removed, and the mixture was further stirred for 0.5 hour. 50 ml of water was added to the reaction solution, and it was completely dissolved by heating at 80 ° C. The precipitated crystals were separated by filtration and washed with 50 ml of water. After drying the crystals, 500 ml of dimethylacetamide was added and stirred at 80 ° C. for 3 hours and at room temperature for 1 hour. The precipitated crystals were filtered and washed with 500 ml of methanol. The obtained crystals were dried to obtain 1.0 g of pigment 4. Yield 50%.
FIG. 2 shows an infrared absorption chart of the pigment 4 obtained.

<Manufacture of processed pigments>
[Processed pigment 1]
50 g of pigment 1 listed in Table 1 below, 500 g of sodium chloride, 25 g of a 30% by mass solution of polymer compound 1 obtained above (polymer compound solution 1), and 100 g of diethylene glycol are made of stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho). And kneaded for 9 hours. Next, this mixture is poured into about 3 liters of water, stirred for about 1 hour with a high speed mixer, filtered, washed with water to remove sodium chloride and solvent, dried and processed pigment coated with a polymer compound. 1 was obtained.

[Processed pigments 2 to 10, Comparative processed pigments 1 to 3, Non-processed pigment 1]
In the processed pigment 1, processed pigments 2 to 10 and comparative processed pigments 1 to 3 were obtained in the same manner as the processed pigment 1 except that the pigments and polymer compound solution described in Table 1 below were used. Comparative processed pigments 2 and 3 mean that they were kneaded without introducing a polymer compound.
Further, when the pigment 1 shown in Table 1 below was used as it was without kneading, it was designated as non-processed pigment 1.
In addition, as hydrogenated rosin ester ("Ester gum HP" manufactured by Arakawa Chemical Co., Ltd.) used in processed pigment 5, one prepared in a diethylene glycol solution having a solid content of 30% by mass was used. The hydrogenated rosin ester is a high molecular compound having no heterocyclic ring in the side chain.

(Measurement of average primary particle diameter of pigment)
The average primary particle diameter of the pigment was determined by observing the obtained processed pigment and non-processed pigment with a transmission electron microscope (TEM) and calculating the average value of the particle diameters of 50 pigment particles. Since the average primary particle diameter of the pigment is not substantially affected by the coating with the polymer compound, the average primary particle diameter of the pigment after coating with the polymer compound is in the range of 5 to 50 nm. The average primary particle diameter of the pigment before being coated with is also in the range of 5 to 50 nm.

(Evaluation of pigment coverage)
10 g of the obtained processed pigment was put into 100 mL of 1-methoxy-2-propanol, and shaken at room temperature for 3 hours with a shaker. Thereafter, the pigment was precipitated with a centrifugal separator at 50,000 rpm for 8 hours. The solid content of the supernatant was determined from the drying method. The amount of the polymer compound released from the pigment was determined, and the liberation rate (% by mass) was calculated from the ratio with the polymer compound used in the treatment. The smaller the liberation rate, the higher the degree of coverage on the pigment.

The details of the pigment used in comparative processed pigment 1 are as follows.
PR254; C.I. I. Pigment Red 254 (compound with the following structure)

  As is apparent from the results in Table 1, when the pigment according to the present invention is coated with a polymer compound having a heterocyclic ring in the side chain, the amount of the polymer compound released from the pigment is small and the coverage to the pigment is reduced. It turns out that it is excellent. On the other hand, when a pigment other than the pigment according to the present invention (PR254) was coated with a polymer compound having a heterocyclic ring in the side chain, the liberation rate of the polymer compound was higher than in the above case. .

<Preparation of pigment dispersion composition>

A mixed liquid having the following composition was mixed and dispersed by a bead mill for 2 hours to prepare a red pigment dispersion composition P-1.
-Composition-
A mixture of the above processed pigment 1 and Pigment Yellow 139 (PY139) (mass ratio [processed pigment 1 / PY139] = 100/30) 11.8 parts, pigment derivative 2 below 1.2 parts, dispersant below 1 (weight average molecular weight 23000, acid value 98 mgKOH / g) ... 5.8 parts propylene glycol monomethyl ether acetate (PGMEA) 80.3 parts

  In the pigment mixture, processed pigment 1 is the main pigment and pigment yellow 139 is the sub-pigment. Pigment Yellow 139 is a compound having the following structure.

  Red pigment dispersion compositions P-2 to P-10 in the same manner as red pigment dispersion composition P-1, except that processed pigments or non-processed pigments, pigment derivatives and dispersants listed in Table 2 below were used. Comparative red pigment dispersion compositions PC-1 to PC-4 were prepared.

  Details of the pigment derivatives and dispersants described in Table 2 are as follows.

The weight average molecular weight of the dispersant 1 is 23000, the dispersity is 1.6, the acid value is 98 mgKOH / g, and the composition ratio (in order from the left of the structure) is 40/60% by mass.
The weight average molecular weight of the dispersant 2 is 25000, the dispersity is 1.6, the acid value is 30 mgKOH / g, and the composition ratio (in order from the left of the above structure) is 5/5/90 mass%.
Dispersant 3: Disperbyk-2091 manufactured by Big Chemie

<Measurement of volume average particle diameter>
About the obtained red pigment dispersion compositions P-1 to P-10 and PC-1 to PC-4, the volume average particle diameter is measured using a Nanotrac UPA particle size analyzer (UPA-EX150; manufactured by Nikkiso Co., Ltd.). As a result, it was 10 nm.

<Dispersion stability evaluation>
About red pigment dispersion composition P-1 to P-10 and PC-1 to PC-4, using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd., RE-85L), the viscosity η1 ( Unit mPa · s), and after dispersion, the viscosity η2 (unit mPa · s) after standing at room temperature (25 ° C., the same shall apply hereinafter) for 1 week was measured at room temperature, and the amount of thickening [η2−η1] Was calculated. Furthermore, based on the calculated thickening amount, the dispersion stability of the red pigment dispersion composition was evaluated according to the following evaluation criteria. The evaluation results are shown in Table 2.
The smaller the amount of thickening, the better the dispersion stability.
-Evaluation criteria-
A: Thickening amount is 5 mPa · s or less ○: Thickening amount is greater than 5 mPa · s and 8 mPa · s or less ×: Thickening amount is greater than 8 mPa · s

  As is apparent from the results in Table 2, the pigment dispersion compositions P-1 to P-10 using the pigment coated with the polymer compound are not coated with the polymer compound and have an average primary particle size of 5 to 50 nm. It was found that the dispersion stability was good as compared with pigment dispersion compositions PC-2 to PC-3 using a pigment. Although the pigment dispersion composition PC-4 was not coated with the polymer compound, the dispersion stability result was ◯. This is the unprocessed pigment 1 used in the pigment dispersion composition PC-4. This is considered to be because the average primary particle diameter was large and easy to disperse.

<Preparation of red colored actinic ray-sensitive or radiation-sensitive composition>
Using the pigment dispersion composition P-1, the mixture was stirred and mixed so as to have the following composition to prepare a red colored actinic ray-sensitive or radiation-sensitive composition R-1.
(composition)
Pigment dispersion composition P-1 10.28 parts Polymerizable compound (Exemplary compound (MC-3)) 0.15 parts Oxime-based photopolymerization initiator (IRGACURE-OXE01 manufactured by BASF Japan Ltd.)
... 0.07 parts · Polymerization inhibitor (p-methoxyphenol) · 0.01 parts · Alkali-soluble resin (benzyl methacrylate / methacrylic acid / -2-hydroxyethyl methacrylate copolymer, molar ratio 60/22/18) , Acid value 30 mgKOH / g, weight average molecular weight 15000)) ... 1.14 parts Fluorosurfactant (1.0% by mass PGMEA solution of Megafic F781 manufactured by DIC)
... 0.63 parts, solvent (propylene glycol monomethyl ether acetate) ... 2.73 parts

  The red colored actinic ray sensitive or radiation sensitive composition R- was the same as the red colored actinic ray sensitive or radiation sensitive composition R-1, except that the pigment dispersion composition described in Table 3 below was used. 2 to R-10, red colored actinic ray sensitive or radiation sensitive compositions RC-1 to RC-4 for comparison were prepared.

<Production of red color filter>
Applying the red-colored actinic ray-sensitive or radiation-sensitive composition prepared above to the device-forming surface side of an 8-inch device-formed silicon wafer (solid-state imaging device substrate) previously sprayed with hexamethyldisilazane, A photocurable coating film was formed. 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 150 mJ / cm ² through a photomask for forming a 1.0 μm square red pixel at a wavelength of 365 nm. Exposure was performed.
Thereafter, 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 an alkali developer CD-2000 ( Paddle development was carried out at 23 ° C. for 180 seconds using a 40% diluted solution of FUJIFILM Electronics Materials Co., Ltd. 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 then rinsed and then spray dried.
Next, it heated for 5 minutes with a 200 degreeC hotplate, and obtained the red pattern (red color filter) on the silicon wafer.

When the obtained silicon wafer with a red color filter was observed with an optical microscope (1000 times magnification), development residues were suppressed in the colored pattern non-formation region.
Moreover, when the pattern shape of the red color filter was observed with an optical microscope (magnification 1000 times) and a scanning electron microscope (SEM) (magnification 20000 times), the pattern shape was good and the pattern formability was good.

<Evaluation of uneven color>
In the same manner as the preparation of the silicon wafer with the undercoat layer described above, a glass substrate with an undercoat layer is prepared by applying a resist solution on the glass plate, and the red colored actinic ray-sensitive or radiation-sensitive composition is applied with the undercoat layer. It apply | coated on glass and the colored layer (coating film) was formed. Heat treatment (pre-baking) was performed for 120 seconds using a hot plate at 100 ° C. so that the dry film thickness of the coating film became 0.7 μm. The luminance distribution of the coated glass plate was analyzed from an image taken with a microscope MX-50 (Olympus).
The luminance distribution was analyzed, and the color unevenness was evaluated based on the ratio of the pixels whose deviation from the average is within ± 5% to the total number of pixels. The evaluation criteria are as follows. In practice, an evaluation of Δ or more is required.

-Evaluation criteria-
○: Pixels whose deviation from the average is within ± 5% is 99% or more of the total number of pixels. Δ: Pixels whose deviation from the average is within ± 5% is 95% or more and less than 99% of the total number of pixels. : Pixels whose deviation from the average is within ± 5% is less than 95% of the total number of pixels

<Evaluation of defects>
A green pattern was formed on the red pattern (red color filter) created by the above method by the same method as described above.
The green pattern has the same components except that a mixed pigment of PG36 (CI Pigment Green 36) / PY139 = 90/10 (mass ratio) is used instead of the pigment in the pigment dispersion composition P-1. A dispersion consisting of was formed with the same formulation as described above.
It analyzed from the image image | photographed with microscope MX-50 (made by Olympus) on the green pattern, and it was confirmed whether it was mixed colors. The evaluation criteria are as follows. In practice, an evaluation of Δ or more is required.

-Evaluation criteria-
○: There are no defects such as bleeding and protrusion on the green pattern, color mixture with adjacent pixels, and white spots. Δ: Bleeding and protrusion on the green pattern, and slightly mixed colors with adjacent pixels, but no white spots. : Red color oozes and protrudes on the green pattern

<Dispersion stability evaluation (thickening with time)>
Red pigment in Table 2 for red colored actinic ray sensitive or radiation sensitive compositions R-1 to R-10 and comparative red colored actinic ray sensitive or radiation sensitive compositions RC-1 to RC-4 In the same manner as in the dispersion compositions P-1 to P-10 and PC-1 to PC-4, from the thickening amount between the viscosity after adjustment of the composition and after standing for 1 week after adjustment, the same as above The dispersion stability was evaluated. The evaluation results are shown in Table 3.

<Measurement of spectral characteristics>
In the production of the red color filter, a silicon wafer having an 8-inch device formed thereon is replaced with a glass substrate, the pattern exposure is changed to full exposure, and a red film having a dry film thickness of 0.6 μm (colored) is formed on the glass substrate. A permeable membrane) was formed.
The spectral characteristics (transmittance at each wavelength) of the obtained red film were measured by MCPD-3000 (manufactured by Otsuka Electronics Co., Ltd.).
As the spectral characteristics of the red film formed in Example 1, the transmittance at 400 nm was 9%, the transmittance at 525 nm was 3%, the transmittance at 600 nm was 81%, and the transmittance at 700 nm was 99%. . From this, it was confirmed that the red film exhibits good spectral characteristics as red.
Regarding the transmittance at 400 nm, 525 nm, 600 nm, and 700 nm, those satisfying the characteristics shown in Table 3 are indicated by “◎”, and those not satisfying are indicated by “x”.

  As is apparent from the results in Table 3, colored active light rays containing pigment dispersion compositions P-1 to P-10 using the processed pigment of the present invention in which the specific pigment according to the present invention is coated with a polymer compound The radiation-sensitive or radiation-sensitive compositions R-1 to R-10 were all good in color unevenness, dispersion stability and spectral characteristics at the same time (Examples 1 to 10). On the other hand, a comparative colored actinic ray-sensitive or radiation-sensitive composition RC-1 containing a pigment dispersion composition PC-1 using a comparatively processed pigment 1 that does not use the specific pigment according to the present invention, a polymer Colored actinic ray-sensitive or radiation-sensitive compositions RC-2 and RC-3 for comparison containing pigment dispersion compositions PC-2 and PC-3 using comparatively processed pigments 2 and 3 not coated with the compound, and The comparative colored actinic ray-sensitive or radiation-sensitive composition RC-4 containing the pigment dispersion composition PC-4 using the unprocessed pigment 1 obtained without going through the kneading step is as in the above examples. All of good color unevenness, dispersion stability and spectral characteristics could not be satisfied at the same time.

  Also, pigment dispersion compositions P-1, P-2, and P using processed pigments 1, 2, and 6 to 10 obtained by coating the specific pigment according to the present invention with a polymer compound having a heterocyclic ring in the side chain. The colored actinic ray-sensitive or radiation-sensitive compositions R-1, R-2 and R-6 to R-10 containing -6 to P-10 were free from defects such as color mixing (Example 1, 2 and 6-10). Further, as is clear from the comparison between these Examples and Examples 3 to 5 and Comparative Examples 1 to 4, such an effect is obtained by the specific pigment according to the present invention and the polymer compound having a heterocyclic ring in the side chain. It was only unexpectedly seen when using.

In addition, although the said Example demonstrated the example which formed the red color filter on the silicon wafer with which the device was formed, this invention is not limited by the said Example.
For example, by producing a red color filter in the same manner as in the above embodiment, a green color filter by a known method using a green color resist, and a blue color filter by a known method using a blue color resist, Three color filters can be produced on a silicon wafer on which devices have been formed. A solid-state imaging device having these three color filters has excellent heat resistance and good spectral characteristics.

Claims (13)

A processed pigment obtained by coating an azo pigment represented by the following general formula (Az) and having an average primary particle diameter of 5 to 50 nm with a polymer compound.
(In the general formula (Az),
A represents an aromatic 5- or 6-membered heterocyclic group.
B represents a structure represented by any one of the following general formulas (1) to (3) and (1-1) to (1-10).
n represents an integer of 1 to 4. )
(In the general formulas (1) to (3) and (1-1) to (1-10),
Each G independently represents a hydrogen atom, an aliphatic group, an aryl group, a heterocyclic group, an acyl group, an aliphatic oxycarbonyl group, a carbamoyl group, an aliphatic sulfonyl group or an arylsulfonyl group.
Each R ₁ independently represents a hydrogen atom, —C (═O) NR ₄ R ₅ , —NR ₆ C (═O) —R ₇ , —C (═O) R ₈ , —C (═O); Represents OR ₈ , —OR ₈ , —SR ₈ , an amino group, an aliphatic group, an aryl group, a halogen atom, or a heterocyclic group;
R ₂ each independently represents a substituent, and when a plurality of R ₂ are present, they may be the same as or different from each other.
Each R ₃ independently represents —C (═O) NR ₄ R ₅ or —C (═O) OR ₈ .
R ₄ each independently represents a hydrogen atom or an alkyl group.
R ₅ each independently represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, or —N (R ₉ ) (R ₁₀ ).
R ₆ each independently represents a hydrogen atom or an alkyl group.
R ₇ each independently represents an alkyl group, an aryl group, a heterocyclic group, an acyl group, an alkoxy group, or —N (R ₉ ) (R ₁₀ ).
R ₈ each independently represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group or an acyl group.
R ₉ each independently represents a hydrogen atom or an alkyl group.
R ₁₀ each independently represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. R ₄ and R ₅ , and R ₉ and R ₁₀ may be bonded to each other to form a 5- or 6-membered ring.
R ₁₁ each independently represents an amino group, an aliphatic oxy group, an aliphatic group, an aryl group or a heterocyclic group.
R ₁₂ each independently represents a hydrogen atom, an aliphatic group, an aryl group or a heterocyclic group.
R ₁₃ each independently represents a hydrogen atom, an aliphatic group, an aryl group or a heterocyclic group.
Y each independently represents a divalent group that forms a heterocyclic ring with —N═C—N—.
Each m independently represents an integer of 0 or more, and when m is 2 or more, R ₂ may be connected to each other to be condensed.
* Represents a bonding position with the azo group of the general formula (Az).
When n in the general formula (Az) is 2, it represents a dimer via R _{1 to} R ₁₃ , A or G. When n is 3, it represents a trimer via R _{1 to} R ₁₃ , A or G. When n is 4, it represents a tetramer via R _{1 to} R ₁₃ , A or G. )   The processed pigment according to claim 1, wherein the polymer compound is a polymer compound having a heterocyclic ring in a side chain. The processed pigment according to claim 2, wherein the polymer compound having a heterocyclic ring in the side chain contains a polymer unit derived from a monomer represented by the following general formula (H-1).

In the general formula (H-1), R ¹ represents a hydrogen atom or an alkyl group. R ² represents a single bond or a divalent linking group. Y represents -CO-, -C (= O) O-, -CONH-, -OC (= O)-, or a phenylene group. Z represents a group having a nitrogen-containing heterocyclic structure.   The processed pigment according to any one of claims 1 to 3, which is produced by adding the polymer compound in a pigment refining step.   The pigment dispersion composition formed by disperse | distributing the processed pigment of any one of Claims 1-4 in the organic solvent.   The pigment dispersion composition according to claim 5, further comprising a pigment dispersant.   A colored actinic ray-sensitive or radiation-sensitive composition comprising the pigment dispersion composition according to claim 5 or 6, a polymerizable compound, and a photopolymerization initiator.   The colored actinic ray-sensitive or radiation-sensitive composition according to claim 7, wherein the photopolymerization initiator is an oxime photopolymerization initiator.   A color filter formed using the colored actinic ray-sensitive or radiation-sensitive composition according to claim 7 or 8.   Applying the colored actinic ray-sensitive or radiation-sensitive composition according to claim 7 or 8 on a support to form a colored actinic ray-sensitive or radiation-sensitive composition layer; Pattern formation including a step of exposing a light-sensitive or radiation-sensitive composition layer through a mask and a step of developing a colored actinic-ray-sensitive or radiation-sensitive composition layer after exposure to form a colored pattern Method.   Applying the colored actinic ray-sensitive or radiation-sensitive composition according to claim 7 or 8 on a support to form a colored actinic ray-sensitive or radiation-sensitive composition layer; Solid imaging including a step of exposing a light-sensitive or radiation-sensitive composition layer through a mask, and a step of developing the colored active light-sensitive or radiation-sensitive composition layer after exposure to form a colored pattern Manufacturing method of color filter for element.   The color filter for solid-state image sensors produced by the manufacturing method of the color filter for solid-state image sensors of Claim 11.   The solid-state image sensor provided with the color filter for solid-state image sensors of Claim 12.