JP5578812B2 - Coloring composition for color filter, adjustment method thereof, and color filter - Google Patents

Description

  The present invention relates to a coloring composition for a color filter useful as a color material for a color filter used in a liquid crystal display device or a solid-state imaging device, an adjustment method thereof, and a color filter.

In recent years, image display devices have been required to be smaller, thinner, lighter, larger in screen, higher in definition, and the like. The application has expanded to displays for personal computers, television receivers, game machines, etc., and the demand for color liquid crystal displays is rapidly increasing.
Against this background, color filters used in liquid crystal display elements are also required to have high color purity.

  The color filter formed on the element for colorizing the solid-state image sensor or the liquid crystal display element is composed of a yellow filter layer, a magenta filter layer, and a cyan filter layer formed adjacent to each other on the same plane on the substrate. A color filter including a color filter, a red filter layer, a green filter layer, and a blue filter layer is known.

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

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

As organic pigments for color filters, the use of organic pigments with excellent heat resistance and light resistance such as anthraquinone, diketopyrrolopyrrole, quinacridone, isoindoline, perinone, perylene, and condensed azo has been studied. Yes. However, these pigments are generally difficult to disperse in a color filter, and it is difficult to obtain a highly transparent color filter.
Similarly, in a color filter composed of a yellow filter layer, a magenta filter layer, and a cyan filter layer, further improvement in fastness has been desired for the yellow dye used in the yellow filter layer.

  Patent Document 4 proposes a red ink composition for a color filter containing a monoazo compound containing a naphthalene ring. However, the color filter using the compound described in Patent Document 4 is not sufficient in terms of contrast, and high contrast is desired.

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

The purpose of the present invention is to have a good hue, to exhibit good fastness to light, heat and ozone, and to have good dispersibility, high transparency, spectral characteristics, contrast, stable dispersion over time An object of the present invention is to provide a coloring composition for a color filter that can provide a color filter having excellent properties.
A further object of the present invention is to provide a color filter obtained by using the above-mentioned coloring composition for a color filter, having high transparency, and excellent spectral characteristics, contrast, and dispersion stability over time.

（一般式（１）中、Ｇは、水素原子、脂肪族基、アリール基、又はヘテロ環基を表し、Ｒ_１は、アミノ基、脂肪族オキシ基、脂肪族基、アリール基、又はヘテロ環基を表し、Ｒ_２は置換基を表す。Ａは、下記一般式（Ａ−１３）〜（Ａ−２０）、（Ａ−２５）〜（Ａ−２９）及び（Ａ−３２）のいずれかを表す。ｍは０〜５の整数を表し、ｎは１を表す。一般式（１）がイオン性親水性基を有することはない。）

（一般式（Ａ−１３）〜（Ａ−２０）、（Ａ−２５）〜（Ａ−２９）及び（Ａ−３２）中、Ｒ_５５〜Ｒ_５９は水素原子、置換基を表し、隣接する置換基は互いに結合し、５〜６員環を形成していてもよい。＊は一般式（１）のアゾ基との結合位置を表す。）
＜２＞
前記一般式（１）におけるＡが下記一般式（Ａ−１３）〜（Ａ−１７）、（Ａ−１９）、（Ａ−２０）、（Ａ−２５）〜（Ａ−２９）及び（Ａ−３２）のいずれかを表すことを特徴とする＜１＞に記載のカラーフィルター用着色組成物。

（一般式（Ａ−１３）〜（Ａ−１７）、（Ａ−１９）、（Ａ−２０）、（Ａ−２５）〜（Ａ−２９）及び（Ａ−３２）中、Ｒ_５５〜Ｒ_５９は水素原子、置換基を表し、隣接する置換基は互いに結合し、５〜６員環を形成していてもよい。＊は一般式（１）のアゾ基との結合位置を表す。）
＜３＞
前記一般式（１）で表されるアゾ顔料が、下記一般式（２）で表わされることを特徴とする＜１＞又は＜２＞に記載のカラーフィルター用着色組成物。

（一般式（２）中、Ｒ_２１、Ｒ_２２、Ｒ_５５、Ｒ_５９、ｍ、及びｎは一般式（１）で定義したＲ_１、Ｒ_２、Ｒ_５５、Ｒ_５９、ｍ、及びｎと同じである。Ｚはハメットのσｐ値が０．２以上の電子求引性基を表す。一般式（２）がイオン性親水性基を有することはない。）
＜４＞
さらに重合性化合物および溶剤を含むことを特徴とする＜１＞〜＜３＞のいずれかに記載のカラーフィルター用着色組成物。
＜５＞
一般式（１）で表されるアゾ顔料を、重合性化合物１質量部に対し、０．０１〜２質量部含む＜４＞に記載のカラーフィルター用着色組成物。
＜６＞
重合性化合物が感光性化合物であることを特徴とする＜４＞又は＜５＞に記載のカラーフィルター用着色組成物。
＜７＞
さらに、界面活性剤、シリコーン系添加剤、顔料系の添加剤、シラン系カップリング剤およびチタン系カップリング剤から選択される１種以上の分散剤を含むことを特徴とする＜１＞〜＜６＞のいずれかに記載のカラーフィルター用着色組成物。
＜８＞
＜１＞〜＜７＞のいずれかに記載のカラーフィルター用着色組成物を用いて形成されたことを特徴とするカラーフィルター。
＜９＞
フォトリソグラフィー法、またはインクジェット法によって形成されたことを特徴とする＜８＞に記載のカラーフィルター。
＜１０＞
界面活性剤、シリコーン系添加剤、顔料系の添加剤、シラン系カップリング剤およびチタン系カップリング剤から選択される１種以上の分散剤および、一般式（１）で表されるアゾ顔料を、溶剤の一部に分散して顔料分散体を得る工程、および、該顔料分散体を重合性化合物および残余の溶剤と混合する工程を含む、＜７＞に記載のカラーフィルター用着色組成物の調製方法。
本発明は、前記＜１＞〜＜１０＞に係る発明であるが、以下、それ以外の事項（例えば、下記〔１〕〜〔１０〕）についても記載している。 As a result of intensive studies, the present inventors have obtained knowledge that a specific nitrogen-containing heterocyclic azo pigment can solve the above problems.
Specific means for solving the above problems will be described below.
<1>
A coloring composition for a color filter comprising an azo pigment represented by the general formula (1).

(In the general formula (1), G represents a hydrogen atom, an aliphatic group, an aryl group, or a heterocyclic group, and R ₁ represents an amino group, an aliphatic oxy group, an aliphatic group, an aryl group, or a heterocyclic ring. R ₂ represents a substituent, and A represents any one of the following general formulas (A-13) to (A-20), (A-25) to (A-29), and (A-32). the representative .m is an integer of 0 to 5, n is. one general formula (1) can not have an ionic hydrophilic group representing 1.)

(Formula (A-13) ~ (A -20), represents (A-25) ~ (A -29) and (A-32) _in, R 55 _{to R 59} is a hydrogen atom, a substituent, adjacent The substituents may be bonded to each other to form a 5- to 6-membered ring. * Represents the bonding position with the azo group of the general formula (1).
<2>
A in the general formula (1) is represented by the following general formulas (A-13) to (A-17), (A-19), (A-20), (A-25) to (A-29) and (A -The coloring composition for color filters as described in <1> characterized by representing either.

(In the general formula (A-13) ~ (A -17), (A-19), (A-20), (A-25) ~ (A-29) and _{(A-32), R 55} ~R ₅₉ represents a hydrogen atom or a substituent, and adjacent substituents may be bonded to each other to form a 5- to 6-membered ring, and * represents a bonding position with the azo group of the general formula (1).
<3>
The coloring composition for a color filter according to <1> or <2>, wherein the azo pigment represented by the general formula (1) is represented by the following general formula (2).

(In the general formula (2), R ₂₁ , R ₂₂ , R ₅₅ , R ₅₉ , m, and n are the same as R ₁ , R ₂ , R ₅₅ , R ₅₉ , m, and n defined in the general formula (1). is the same .Z the σp value of Hammett's. one general formula (2) will not have an ionic hydrophilic group representing 0.2 or more electron-withdrawing group.)
<4>
The colored composition for a color filter according to any one of <1> to <3>, further comprising a polymerizable compound and a solvent.
<5>
The coloring composition for color filters as described in <4> which contains 0.01-2 mass parts of azo pigments represented by General formula (1) with respect to 1 mass part of polymeric compounds.
<6>
The coloring composition for a color filter according to <4> or <5>, wherein the polymerizable compound is a photosensitive compound.
<7>
<1> to <1>, further comprising at least one dispersant selected from a surfactant, a silicone-based additive, a pigment-based additive, a silane-based coupling agent, and a titanium-based coupling agent. The coloring composition for color filters in any one of 6>.
<8>
<1>-<7> The color filter formed using the coloring composition for color filters in any one of.
<9>
The color filter according to <8>, which is formed by a photolithography method or an inkjet method.
<10>
One or more dispersants selected from surfactants, silicone-based additives, pigment-based additives, silane-based coupling agents, and titanium-based coupling agents, and an azo pigment represented by the general formula (1) A coloring composition for a color filter according to <7>, comprising a step of dispersing in part of a solvent to obtain a pigment dispersion, and a step of mixing the pigment dispersion with a polymerizable compound and the remaining solvent. Preparation method.
Although this invention is invention which concerns on said <1>-<10>, below, other matters (for example, following [1]-[10]) are also described.

[1]
A coloring composition for a color filter comprising an azo pigment represented by the general formula (1).

(In the general formula (1), G represents a hydrogen atom, an aliphatic group, an aryl group, or a heterocyclic group, and R ₁ represents an amino group, an aliphatic oxy group, an aliphatic group, an aryl group, or a heterocyclic ring. represents a group, .A _{R 2} is representative of the substituents, .m represent any of the following formulas (a-1) ~ (a -32) represents an integer of 0 to 5, n is 1 to 4 In the case of n = 2, it represents a dimer via R ₁ , R ₂ , A or G. In the case of n = 3, a trimer via R ₁ , R ₂ , A or G. In the case of n = 4, it represents a tetramer through R ₁ , R ₂ , A or G. General formula (1) does not have an ionic hydrophilic group.)

(In the general formulas (A-1) to (A-32), R _{51 to} R ₅₉ represent a hydrogen atom and a substituent, and adjacent substituents may be bonded to each other to form a 5- to 6-membered ring. * Represents the bonding position with the azo group of the general formula (1).
[2]
A in the general formula (1) is represented by the following general formulas (A-1), (A-4) to (A-11), (A-13) to (A-17), (A-19) to (A −23), (A-25) to (A-32) any one of the coloring compositions for color filters characterized by the above-mentioned.

(General Formulas (A-1), (A-4) to (A-11), (A-13) to (A-17), (A-19) to (A-23), (A-25) In (A-32), R _{51 to} R ₅₉ each represent a hydrogen atom or a substituent, and the adjacent substituents may be bonded to each other to form a 5- to 6-membered ring. ) Represents the bonding position with the azo group.)
[3]
The coloring composition for a color filter according to [1] or [2], wherein the azo pigment represented by the general formula (1) is represented by the following general formula (2).

(In the general formula (2), R ₂₁ , R ₂₂ , R ₅₅ , R ₅₉ , m, and n are the same as R ₁ , R ₂ , R ₅₅ , R ₅₉ , m, and n defined in the general formula (1). Z represents an electron-withdrawing group having a Hammett's σp value of 0.2 or more, and when n = 2, a dimer via R ₂₁ , R ₂₂ , R ₅₅ , R ₅₉ or Z. _R 21 for .n = 3 representing _a, R _22, R _55, in the case of .n = 4 representing a trimer formed through _{R 59,} or _{Z R 21, R 22, R} 55, R 59 or Z (The general formula (2) does not have an ionic hydrophilic group.)
[4]
The colored composition for a color filter according to any one of [1] to [3], further comprising a polymerizable compound and a solvent.
[5]
The coloring composition for color filters as described in [4] which contains 0.01-2 mass parts of azo pigments represented by General formula (1) with respect to 1 mass part of polymeric compounds.
[6]
The coloring composition for a color filter as described in [4] or [5], wherein the polymerizable compound is a photosensitive compound.
[7]
Furthermore, it contains one or more dispersants selected from surfactants, silicone-based additives, pigment-based additives, silane-based coupling agents, and titanium-based coupling agents [1] to [1] 6] The coloring composition for color filters according to any one of [6].
[8]
A color filter formed using the color filter coloring composition according to any one of [1] to [7].
[9]
The color filter according to [8], which is formed by a photolithography method or an inkjet method.
[10]
One or more dispersants selected from surfactants, silicone-based additives, pigment-based additives, silane-based coupling agents, and titanium-based coupling agents, and an azo pigment represented by the general formula (1) The coloring composition for a color filter according to [7], comprising a step of dispersing in part of a solvent to obtain a pigment dispersion, and a step of mixing the pigment dispersion with a polymerizable compound and the remaining solvent. Preparation method.

  According to the present invention, high dispersibility, dispersion stability over time, heat resistance and light resistance are obtained to obtain a color filter that achieves high contrast and excellent transparency required for color liquid crystal displays and camera modules in various applications. Another object of the present invention is to provide a coloring composition for a color filter.

It is a figure of the infrared absorption spectrum of the specific compound example D-1 synthesize | combined according to the synthesis example 1. FIG. It is a figure of the infrared absorption spectrum of specific compound example D-33 synthesize | combined according to the synthesis example 2. FIG. It is a figure of the infrared absorption spectrum of specific compound example D-20 synthesize | combined according to the synthesis example 3. FIG. It is a figure of the infrared absorption spectrum of specific compound example D-22 synthesize | combined according to the synthesis example 4. FIG. FIG. 11 is an infrared absorption spectrum diagram of specific compound example D-222 synthesized according to synthesis example 5. It is a figure of the infrared absorption spectrum of the specific compound example D-228 synthesize | combined according to the synthesis example 6. FIG.

The coloring composition for a color filter of the present invention contains an azo pigment represented by the general formula (1).
First, the aliphatic group, aryl group, heterocyclic 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 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 Examples include a famoylamino group, a halogen atom, a sulfamoylcarbamoyl group, a carbamoylsulfamoyl group, a dialiphatic oxyphosphinyl group, and a diaryloxyphosphinyl group. These substituents may be further substituted, and examples of the further substituent include groups selected from the substituents described above.

  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) ing. In the present invention, each substituent is limited or explained by Hammett's substituent constant σp, but this means that it is limited to only a substituent having a value known in the literature, which can be found in the above-mentioned book. Needless to say, even if the value is unknown, it includes a substituent that would be included in the range when measured based on Hammett's rule. Although the pigment represented by the general formula (1) or (2) 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.

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

The azo pigment according to the present invention is represented by the following general formula (1).
The compound represented by the general formula (1) can easily form an intermolecular interaction of dye molecules due to its specific structure, has low solubility in water or an organic solvent, and can be an azo pigment.
A pigment is used by being finely dispersed as solid particles such as molecular aggregates in a solvent, unlike a dye used by being dissolved in water or an organic solvent in a molecular dispersion state.
In addition, by having a specific structure represented by the following general formula (1), it exhibits excellent characteristics in color characteristics such as coloring power and hue, and is excellent in durability such as light resistance and ozone resistance. Characteristics can be shown.
Next, the pigment represented by the general formula (1) will be described.

(In the general formula (1), G represents a hydrogen atom, an aliphatic group, an aryl group, or a heterocyclic group, and R ₁ represents an amino group, an aliphatic oxy group, an aliphatic group, an aryl group, or a heterocyclic ring. represents a group, .A _{R 2} is representative of the substituents, .m represent any of the following formulas (a-1) ~ (a -32) represents an integer of 0 to 5, n is 1 to 4 In the case of n = 2, it represents a dimer via R ₁ , R ₂ , A or G. In the case of n = 3, a trimer via R ₁ , R ₂ , A or G. In the case of n = 4, it represents a tetramer through R ₁ , R ₂ , A or G. General formula (1) does not have an ionic hydrophilic group.)

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

  The aliphatic group represented by G may have a substituent, may be saturated or unsaturated, and the group that may be substituted is described in the above-mentioned substituent group. Any substituent can be used as long as it is a group that can be substituted. Preferred substituents include a hydroxy group, an aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thio group, an amino group, and 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, and the group that may be substituted is the group described in the above-mentioned substituent group. Any possible group may be used, and preferred substituents include a nitro group, a halogen atom, an aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thio group, an amino group, an aliphatic amino group, and an acylamino group. , 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.

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

The amino group represented by R ₁ may have a substituent, 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.
The amino group which may have a substituent represented by R ₁ is preferably an unsubstituted amino group, an alkylamino group having 1 to 10 carbon atoms in total, a dialkylamino group having 2 to 10 carbon atoms in total ( A dialkyl group may be bonded to each other to form a 5- or 6-membered ring), an arylamino group having 6 to 12 carbon atoms in total, a saturated group having 2 to 12 carbon atoms, or unsaturated. A heterocyclic amino group which may be present, more preferably an unsubstituted amino group, an alkylamino group having 1 to 8 carbon atoms in total, a dialkylamino group having 2 to 8 carbon atoms in total, and 6 carbon atoms in total. -10 arylamino group, a heterocyclic amino group which may be saturated or unsaturated having 2 to 12 carbon atoms in total, such as methylamino, N, N-dimethylamino, N-phenylamino N- (2-pyrimidyl) a Mino etc. are mentioned.
More preferably, the arylamino group having 6 to 13 carbon atoms which may have a substituent and the saturated or unsaturated group having 2 to 12 total carbon atoms which may have a substituent A heterocyclic amino group which may be
When R ₁ is an arylamino group, the substituent on the aryl group preferably has a substituent at the para position from the bonding position with the amino group, and most preferably has a substituent only at the para position. 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 and the like) and a substituent having 1 to 7 carbon atoms in total It may have an aliphatic oxy group (for example, methoxy, ethoxy, (i) -propyloxy, allyloxy, etc.), a halogen atom (for example, fluorine, chlorine, bromine, etc.), or a substituent having 1 to 7 carbon atoms in total. A carbamoyl group (for example, carbamoyl, N-phenylcarbamoyl, N-methylcarbamoyl, etc.), a ureido group (for example, an optionally substituted group having 1 to 7 carbon atoms, more preferably 1 to 4 carbon atoms in total) Ureido, N- Tilureido, N, N-dimethylureido, N-4-pyridylureido, N-phenylureido, etc.), nitro group, heterocyclic ring condensed with the aryl group having 1 to 7 carbon atoms in total (for example, imidazolone), hydroxy group An aliphatic thio group (for example, methylthio, ethylthio, (i) -propylthio, allylthio, (t)) which may have a substituent having 1 to 7 carbon atoms in total, more preferably 1 to 4 carbon atoms in total. -Butylthio, etc.), an acylamino group (for example, acetamino, propionylamino, pivaloylamino, benzoylamino, etc.) which may have a substituent having 2 to 7 carbon atoms in total, more preferably 2 to 4 carbon atoms in total, An aliphatic oxycarbonylamino group (e.g. methato) which may have a substituent of 2 to 7 carbon atoms, more preferably 2 to 4 carbon atoms in total. Cicarbonylamino, propyloxycarbonylamino and the like), an aliphatic oxycarbonyl group (for example, methoxycarbonyl, ethoxy) which may have a substituent having 2 to 7 total carbon atoms, more preferably 2 to 4 total carbon atoms Carbonyl, etc.), an acyl group (which may be an aliphatic carbonyl group or an arylcarbonyl group) which may have a substituent having 2 to 7 total carbon atoms, more preferably 2 to 4 total carbon atoms, May be a heterocyclic carbonyl group, may have a substituent, and may be substituted as long as it is a group that can be substituted with the groups described in the above-mentioned substituents section. Any acyl group having 2 to 7 carbon atoms in total, more preferably an acyl group having 2 to 4 carbon atoms in total, such as acetyl, propanoyl, benzoyl, 3-pyridinecarbox Nil and the like. ) And the like.
When the substituent on the aryl group of the arylamino group is substituted from the bonding position with the amino group to the para position, the substituent is located at the end of the molecule, so intermolecular interactions such as intermolecular hydrogen bonding are likely to occur. Because of this, the hue becomes sharper. When the substituent on the aryl group further has a substituent, a substituent having an aliphatic group, a hydroxy group, an amide bond, an ether bond, an oxycarbonyl bond, a thioether bond or the like is preferable, and a bond between a hetero atom and a hydrogen atom Is more preferable from the viewpoint of facilitating intermolecular interaction such as intermolecular hydrogen bonding.
When R ₁ is a heterocyclic amino group, the substituent 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. Group is preferable, but 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 between an atom and a hydrogen atom is more preferable from the viewpoint of facilitating intermolecular interaction such as intermolecular hydrogen bonding.

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

The aliphatic oxy group represented by R ₁ may have a substituent, and the substituent is any of the groups described in the above-mentioned substituent group and can be substituted. Of these, preferred substituents are a hydroxy group, an aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thio group, an amino group, an aliphatic amino group, an acylamino group, and a carbamoylamino group. The aliphatic oxy group for R ₁ is preferably an alkoxy group having 1 to 8 carbon atoms in total, more preferably an alkoxy group having 1 to 4 carbon atoms in total, such as methoxy, ethoxy, (t) -Butoxy, methoxyethoxy, carbamoylmethoxy and the like.

The aliphatic group represented by R ₁ may have a substituent, and the substituent may be any group as long as it is a group described in the above-mentioned substituent group and can be substituted. Preferred substituents are a hydroxy group, an aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thio group, an amino group, an aliphatic amino group, an acylamino group, and a carbamoylamino group. The aliphatic 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 have a substituent, and the substituent may be any group as long as it is a group described in the above-mentioned substituent section 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 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.

The heterocyclic group represented by R ₁ may be a saturated heterocyclic ring or an unsaturated heterocyclic group, and may have a substituent. Examples of the substituent include the substituents described above. And any group that can be substituted, and preferred substituents include aliphatic groups, aliphatic oxy groups, carbamoyl groups, hetero rings condensed with the hetero groups, It is an aliphatic oxycarbonyl group. The heterocyclic group for R ₁ is preferably a heterocyclic group having 2 to 10 carbon atoms in total, more preferably a 5- to 6-membered non-aromatic group bonded by a nitrogen atom having 2 to 8 carbon atoms in total. Examples of the heterocyclic group include 1-piperidyl, 4-morpholinyl, 1-quinoyl, 2-pyrimidyl, 4-pyridyl, and the like.

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

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

The substituent represented by R ₂ may be any group as long as it is a group that can be substituted 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. Group, carboxyl group, optionally substituted carbamoyl group, acylamino group, sulfonamide group, optionally substituted carbamoylamino group, optionally substituted sulfamoyl group, fatty acid Group oxy group, aliphatic thio group, cyano group, and halogen atom, more preferably aliphatic oxycarbonyl group, optionally substituted carbamoyl group, acylamino group, optionally substituted A good carbamoylamino group, aliphatic oxy group and halogen atom are preferred, and an aliphatic oxy group is most preferred.
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.

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

The aliphatic group represented by R ₂ may have a substituent, 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 in total, more preferably an acylamino group having 1 to 8 carbon atoms in total, and still more preferably an alkyl having 1 to 8 carbon atoms in total. 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 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. 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.

The sulfamoyl group represented by R ₂ may have a substituent, and the group that may be substituted may be any group as long as it 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 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.
In view of the effect of the present invention, R ₂ is preferably an aliphatic oxycarbonyl group or a carbamoyl group which may have a substituent. In view of the effect of the present invention, m is preferably 0 or 1, and more preferably 0.

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

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 effect of the present invention, R ₅₅ is preferably an aliphatic group, an aryl group, or a heterocyclic group, and an aromatic group containing an aromatic group, aryl group, or aromatic group containing a nitrogen atom adjacent to the binding site with the nitrogen atom. The group is more preferably a 5- to 6-membered heterocyclic group, and more preferably an aromatic 5- to 6-membered heterocyclic group containing a nitrogen atom adjacent to the binding site with the nitrogen atom. _R55 is an aromatic 5- to 6-membered heterocyclic group containing a nitrogen atom adjacent to the binding site with the nitrogen atom, so that not only the intermolecular interaction of the dye molecule but also the intramolecular interaction is firmly formed. It becomes easy to do. This makes it easy to construct a pigment having a stable molecular arrangement, which is preferable in terms of showing good hue and high fastness (light resistance, gas, heat, water, etc.).
In terms of the effect of the present invention, 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 , 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, 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 a nitrogen atom having 2 to 12 carbon atoms in total, more preferably 2 carbon atoms in total. Next to 10 to 10 nitrogen atoms It is an aromatic 5- to 6-membered heterocyclic group containing a nitrogen atom at the coordinate 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 group, aliphatic oxy group, carbamoyl group, aliphatic oxycarbonyl group, aliphatic thio group, amino group, aliphatic amino group An acylamino group and a carbamoylamino group. The aryl group for R ₅₅ is preferably an aryl group having 6 to 12 carbon atoms in total, more preferably an aryl group having 6 to 10 carbon atoms in total, such as phenyl, 3-methoxyphenyl, 4-carbamoylphenyl. The phenyl group is preferable.
From the viewpoint of the effects of the present invention, the aliphatic group preferable as R ₅₅ may have a substituent, and the group which may be substituted includes the group described in the above-mentioned substituent group. Any possible group may be used, and preferred substituents include a hydroxy group, a nitro group, an aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thio group, an amino group, an aliphatic amino group, and an acylamino group. , A carbamoylamino group. The aliphatic group for R ₅₅ is preferably an alkyl group having 1 to 6 carbon atoms in total, more preferably an aliphatic group having 1 to 4 carbon atoms in total, such as methyl, ethyl, methoxyethyl, carbamoylmethyl. And a methyl 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.

The substituent represented by Y _{1 to} Y ₁₁ 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 the substituent for Y _{1 to} Y _11, 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. Two adjacent substituents in Y _{1 to} Y ₁₁ may form a 5- to 6-membered ring.
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.
In view of the effect of the present invention, A is preferably a 5-membered heterocycle from the viewpoint of hue, more preferably a nitrogen-containing or sulfur-containing 5-membered heterocycle, and it contains 2 or more heteroatoms. More preferably, it is a 5-membered heterocycle.

As the substituent represented by R _{56 to} R ₅₇ and R ₅₉ , any group may 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 to} R ₅₇ and R _59, 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, 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 to} R ₅₇ and R ₅₉ are aliphatic groups, aryl groups, heterocyclic groups, aliphatic oxycarbonyl groups, carbamoyl groups optionally having substituents, acylamino groups, sulfones. An amide group, aliphatic oxy group, aliphatic thio group, cyano group and the like are preferable, and an aliphatic group, aliphatic oxy group, aliphatic thio group, and 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.

Specific examples of R ₅₈ which is an electron-attracting group having a σp value of 0.2 or more include acyl group, acyloxy group, carbamoyl group, alkyloxycarbonyl group, aryloxycarbonyl group, cyano group, nitro group, dialkylphosphonic group Group, diarylphosphono group, diarylphosphinyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfonyloxy group, acylthio group, sulfamoyl group, thiocyanate group, thiocarbonyl group, alkyl halide Groups, halogenated alkoxy groups, halogenated aryloxy groups, halogenated alkylamino groups, halogenated alkylthio groups, aryl groups substituted with other electron-withdrawing groups having a σp value of 0.20 or more, heterocyclic groups, Halogen atom, azo group, or selenoshi Include sulfonate groups.
From the viewpoint of the effect of the present invention, R ₅₈ is preferably (Y-1) to (Y-13) described above, and a 6-membered ring described below is used in order to make it easy to take an intramolecular hydrogen bond structure. More preferably, it is any one of (Y-1) to (Y-6), and any one of (Y-1), (Y-3), (Y-4), and (Y-6). The case is more preferable, and the case of (Y-1) or (Y-4) is particularly preferable.
Among the heterocycles of (A-1) to (A-32) listed as A, if the atom adjacent to the carbon atom bonded to the azo group is a heteroatom, light and heat fastness are high. A pigment having such a structural feature is preferably used for a color filter because a color filter exhibiting high contrast can be obtained.

In terms of the effects of the present invention, the pigment represented by the general formula (1) is a saturated heterogeneous group in which G is a hydrogen atom and R ₁ is an amino group which may have a substituent, or a nitrogen atom. When m is 0 or 1 and m is 1, R ₂ is an aliphatic oxycarbonyl group, an optionally substituted carbamoyl group, and A is ( A-1), (A-10) to (A-17), (A-20) to (A-23), (A-27), (A-28), (A-30) to (A-) 32), where n is preferably 1 or 2, G is a hydrogen atom, R ₁ is an amino group which may have a substituent, and a saturated hetero bond bonded with a nitrogen atom. a Hajime Tamaki, a m is 0 or 1, when m is 1, R ₂ is which may have an aliphatic oxycarbonyl group, a substituted carbamoyl And A is (A-1), (A-10), (A-11), (A-13) to (A-17), (A-20), (A-22) to (A A-23), (A-27), (A-28), (A-30) to (A-32), wherein n is 1 or 2, and G is hydrogen. An atom, an amino group that R ₁ may have a substituent, a saturated heterocyclic group bonded by a nitrogen atom, m is 0, and A is (A-10), ( A-11), (A-13) to (A-17), (A-20), (A-22) to (A-23), (A-27), (A-28), (A- 30) to (A-32), wherein n is more preferably 1 or 2, G is a hydrogen atom, and R ₁ is an amino group which may have a substituent. Where m is 0 and A is , (A-16) to (A-17), (A-20), (A-28), (A-32), where n is 1 or 2, particularly preferably G Is a hydrogen atom, R ₁ is an amino group which may have a substituent, m is 0, A is (A-16) and n is 1 or 2 Is most preferred.

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

  Hereinafter, the azo pigment represented by the general formula (2), a tautomer thereof, a salt or a hydrate thereof will be described in detail.

(In the general formula (2), R ₂₁ , R ₂₂ , R ₅₅ , R ₅₉ , m, and n are the same as R ₁ , R ₂ , R ₅₅ , R ₅₉ , m, and n defined in the general formula (1). Z represents an electron-withdrawing group having a Hammett's σp value of 0.2 or more, and when n = 2, a dimer via R ₂₁ , R ₂₂ , R ₅₅ , R ₅₉ or Z. _R 21 for .n = 3 representing _a, R _22, R _55, in the case of .n = 4 representing a trimer formed through _{R 59,} or _{Z R 21, R 22, R} 55, R 59 or Z (The general formula (2) does not have an ionic hydrophilic group.)

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

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

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

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

In another embodiment, the azo compound represented by the general formula (1) has an A of (A-1) to (A-9), (A-11) to (A-13), or (A-17). ), (A-20) to (A-23), (A-27), (A-28), (A-30) to (A-32), preferably (A-11) to (A A-13), (A-17), (A-20) to (A-23), (A-27), (A-28), (A-30) to (A-32). More preferably, (A-17), (A-20), (A-22) to (A-23), (A-27), (A-28), (A-31), (A-32) It is more preferable that (A-20), (A-28), and (A-32) are more preferable, and (A-20) is most preferable. Further, particularly preferably _{R 56} is _{R 59} in (A-20).

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

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

  Of the azo pigments represented by the general formula (1), examples of the particularly preferred azo pigments represented by the general formula (1) are represented by the following general formulas (3-1) to (3-4). Mention may be made of azo pigments. The pigment represented by the general formula (1) is preferably an azo pigment represented by the following general formula (3-1) to general formula (3-4).

  Hereinafter, the azo pigments represented by the general formulas (3-1) to (3-4), tautomers thereof, salts or hydrates thereof will be described in detail.

(In General Formula (3-1) to General Formula (3-4), R ₁ , R ₂ , m, and n are the same as those defined in General Formula (1) and General Formula (2). Represents a carbon atom or a nitrogen atom, Ax and Bx represent an aromatic 5- to 6-membered heterocyclic group together with X and the carbon atom, and are specifically defined by A in the general formula (1) (A-1) to (a-32) applicable .Yx representing those that are .R ₂₃ representing those falling within the heterocyclic group as defined in R ₅₅ in the general formula (1) together with the nitrogen and carbon atoms are generally in the Among the substituents such as R ₅₁ , R ₅₄ , R ₅₇ , and R ₅₈ defined in Formula (1), this represents a substituent corresponding to a group obtained by removing the carbonyl group from the corresponding substituent.

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

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

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

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

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

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

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

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

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

  In the present invention, the azo pigments represented by the general formulas (1) and (2) may be hydrates containing water molecules in the crystals.

  Next, an example of a method for producing the azo pigment represented by the general formula (1) will be described. For example, a heterocyclic amine represented by the following general formula (4) is diazonium with non-aqueous acidity, a coupling reaction is performed with a compound represented by the following general formula (5) in an acidic state, and post-treatment by a conventional method is performed. It can carry out and can manufacture the azo pigment represented by General formula (6) of this invention. The azo pigment represented by the general formula (1) can be produced by performing the same operation using a heterocyclic amine corresponding to A of the general formula (1) instead of the general formula (4).

(In the formula, R ₅₅ , R ₅₈ and R ₅₉ have the same meaning as defined in the general formula (2).)

(In the formula, R ₁ , R ₂ and m are as defined in the general formula (1).)
The reaction scheme is shown below.

(In the formula, G, R ₁ , R ₂ , R, R ₅₅ , R ₅₈ , R ₅₉ and m have the same meanings as defined in general formula (1) or general formula (2).)

Heterocyclic amines represented by the amino compounds of the above general formulas (4) and (A-1) to (A-32) can be obtained as commercial products, but are generally known and commonly used. It can be produced by a method, for example, the method described in Japanese Patent No. 4022221. Although the heterocyclic coupler represented by the general formula (5) can be obtained as a commercial product, it can be produced by the method described in JP-A-2008-13472 and a method analogous thereto. The diazoniumation reaction of the heterocyclic amine represented by the above reaction scheme is carried out at a temperature of 15 ° C. or less with a reagent such as sodium nitrite, nitrosylsulfuric acid, isoamyl nitrite in an acidic solvent such as sulfuric acid, phosphoric acid, and acetic acid. The reaction can be carried out for about 6 minutes to 6 minutes. The coupling reaction is carried out by reacting the diazonium salt obtained by the above-described method with the compound represented by the general formula (5) at 40 ° C. or less, preferably 25 ° C. or less for about 10 minutes to 12 hours. Can do.
The synthesis method in the case where n in general formula (1) and general formula (2) is 2 or more is R _{1 to} R ₂ , R ₅₅ , R ₅₉ , R ₅₈ in general formula (4) or general formula (5), etc. The raw material into which a divalent, trivalent or tetravalent substituent capable of substitution can be synthesized can be synthesized in the same manner as in the above scheme.
In some cases, crystals are precipitated in this way, but in general, water or an alcohol solvent is added to the reaction solution to precipitate the crystals, and the crystals can be collected by filtration. it can. In addition, an alcohol solvent, water or the like can be added to the reaction solution to precipitate crystals, and the precipitated crystals can be collected by filtration. The crystals collected by filtration can be washed and dried as necessary to obtain an azo pigment represented by the general formula (1).

  Although the pigment represented by the general formula (1) and the general formula (2) 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 pigments represented by the general formulas (1) and (2) of the present invention are preferably subjected to solvent heat treatment and / or solvent salt milling as a post-treatment.
Examples of the solvent used in the solvent heat treatment include water, aromatic hydrocarbon solvents such as toluene and xylene, halogenated hydrocarbon solvents such as chlorobenzene and o-dichlorobenzene, and alcohols such as isopropanol and isobutanol. Examples thereof include solvents, polar aprotic organic solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, glacial acetic acid, pyridine, and mixtures thereof. An inorganic or organic acid or base may be further added to the solvents mentioned above. The temperature of the solvent heat treatment varies depending on the desired primary particle size of the pigment, but is preferably 40 to 150 ° C, more preferably 60 to 100 ° C. The treatment time is preferably 30 minutes to 24 hours.
As solvent salt milling, for example, a crude azo pigment, an inorganic salt, and an organic solvent that does not dissolve the crude azo pigment are charged into a kneader and kneaded and ground therein. As the inorganic salt, a water-soluble inorganic salt can be preferably used. For example, an inorganic salt such as sodium chloride, potassium chloride, sodium sulfate is preferably used. Moreover, it is more preferable to use an inorganic salt having an average particle size of 0.5 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.

[Coloring composition for color filter]
The colored composition for color filters of the present invention (hereinafter sometimes simply referred to as a colored composition) means a colored composition containing at least one azo pigment represented by the general formula (1).
The colored composition of the present invention preferably further contains a polymerizable compound and a solvent.
Moreover, when manufacturing the coloring composition of this invention, the azo pigment obtained by making it above may be mix | blended as it is, or the pigment dispersion disperse | distributed in the solvent may be mix | blended. An azo pigment is preferably a pigment dispersion because it has excellent color characteristics, durability and dispersion stability, light resistance and weather resistance.

  The amount of the azo pigment represented by the general formula (1) in the colored composition of the present invention (the total amount of pigment used when other pigments are used in combination) is 1 part by weight of the polymerizable compound. , 0.01 to 2 parts by weight, preferably 0.1 to 1 part by weight.

(Polymerizable compound)
The polymerizable compound may be appropriately selected in consideration of the production process of the color filter. Examples of the polymerizable compound include a photosensitive compound and / or a thermosetting compound, and the photosensitive compound is particularly preferable.

The photosensitive compound is preferably selected from at least one of a photopolymerizable resin, a photopolymerizable monomer and a photopolymerizable oligomer and having an ethylenically unsaturated bond. What is necessary is just to include what becomes resin in the state which hardened | cured in the coloring composition for color filters, and includes the case where only the component which is not resin-ized is contained in the uncured state.
Examples of the photopolymerizable compound, photopolymerizable monomer, and photopolymerizable oligomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and ethylene glycol di (meth). Acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, pentaerythritol di (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) Acrylate, bisphenol A type epoxy di (meth) acrylate, bisphenol F type epoxy di (meth) acrylate, bisphenol fluorene type epoxy di (meth) acrylate Rate (meth) acrylic acid esters such as and the like. Also, vinyl resins such as acrylic acid (co) polymer, (meth) acrylic acid (co) polymer, maleic acid (co) polymer, polyethylene oxide, polyvinylpyrrolidone, polyamide, polyurethane, polyether, polyester, etc. Resins having an ethylenic double bond in the side chain can also be mentioned. These may be used alone or in combination of two or more. The compounding quantity of a polymeric compound is 20-90 mass%, Preferably the range of 40-80 mass% is good.
The blending ratio of the polymerizable compound is preferably 40 to 95% by mass, more preferably 50 to 90% by mass, based on the total solid content in the color filter composition. In the composition, other resins and the like can be blended as necessary. In this case, it is desirable that the total amount of the other resins falls within the above range. The total solid content means a component that remains as a solid content after drying and curing, does not include a solvent, and includes a monomer.

(Photopolymerization initiator)
When a photosensitive compound is used as the polymerizable compound, a photopolymerization initiator is used together with the monomer and / or oligomer of the photosensitive compound. Examples of the photopolymerization initiator include one or more selected from compounds such as benzophenone derivatives, acetophenone derivatives, benzoin derivatives, benzoin ether derivatives, thioxanthone derivatives, anthraquinone derivatives, naphthoquinone derivatives, and triazine derivatives. A known photosensitizer may be used together with these photopolymerization initiators.

  Examples of the thermosetting resin include melamine resin, urea resin, alkyd resin, epoxy resin, phenol resin, and cyclopentadiene resin.

  In the present specification and claims, “photosensitive resin” and “thermosetting resin” include not only a cured resin but also a polymerizable monomer and / or oligomer.

  In addition to the photosensitive resin and / or thermosetting resin, as other polymerizable compound, a binder resin having an acidic group and a resin generally used for inks such as an acrylic resin and a urethane resin may be used. Good.

〔solvent〕
The pigment dispersion may be aqueous or non-aqueous, but differs depending on the method of producing the color filter. For example, the photolithography method is preferably non-aqueous, and the inkjet method may be either.
Examples of the solvent used in the coloring composition of the present invention include fatty acid esters such as ethyl acetate, butyl acetate, ethylene glycol monomethyl ether acetate, and propylene glycol monomethyl ether acetate; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diacetone alcohol, and the like. Ketones; aromatics such as benzene, toluene, 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 Glycerin; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and other alkylene glycol monoalkyl ethers; triethylene Alkylene glycol dialkyl ethers such as glycol dimethyl ether, triethylene glycol diethyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether; ethers such as tetrahydrofuran, dioxane, diethylene glycol diethyl ether; monoethanolamine, diethanol Alkanolamines such as amine and triethanolamine; N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, 2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, etc. Nitrogen-containing polar organic solvent; water and the like.

  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.

  An azo pigment made into a pigment dispersion has excellent light resistance and weather resistance compared to an azo pigment not made into a pigment dispersion.

  The coloring composition of the present invention may contain two or more azo pigments represented by the general formula (1). In addition to the azo pigment represented by the general formula (1), other types of pigments such as azo pigments, disazo pigments, benzimidazolone pigments, and condensed azo pigments may be used without departing from the object of the present invention. One or more pigments selected from azo lake pigments, anthraquinone pigments, diketopyrrolopyrrole pigments, quinacridone pigments, isoindoline pigments, isoindolinone pigments, perinone pigments, perylene pigments, and / or the like Alternatively, derivatives thereof may be used.

The pigment that may be used in combination in the present invention is not particularly limited. Specifically, a compound classified as a pigment in a color index (CI; issued by The Society of Dyers and Colorists), that is, a color index (CI) number as shown below. What is attached can be mentioned.
C. I. Pigment yellow 1, C.I. I. Pigment yellow 3, C.I. I. Pigment yellow 12, C.I. I. Pigment yellow 13, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 180, C.I. I. Yellow pigments such as C.I. Pigment Yellow 185; I. Pigment red 1, C.I. I. Pigment red 2, C.I. I. Pigment red 3, C.I. I. Pigment red 177, C.I. I. Red pigments such as CI Pigment Red 254; and C.I. I. Pigment blue 15, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. C.I. Blue pigments such as CI Pigment Blue 15: 6; I. Pigment green 7, C.I. I. Green pigments such as C.I. Pigment Green 36; I. Pigment violet 23, C.I. I. Pigment violet 23:19 and the like.

  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.

  When other pigments other than the azo pigment represented by the general formula (1) are used in combination, the content thereof is preferably 50% by mass or less, and 20% by mass in the total mass of the pigment in the coloring composition. It is particularly preferred that

  Hereinafter, in the present specification, the term “azo pigment represented by the general formula (1)” refers to not only an azo pigment represented by one kind of the general formula (1) but also two or more kinds of general formulas ( It is used in the meaning including the combination of the azo compound represented by 1) and the combination of the azo pigment represented by the general formula (1) and other pigments.

[Pigment dispersion]
The pigment dispersion is preferably obtained by dispersing the azo pigment and the aqueous or non-aqueous medium using a dispersing device. 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.

  In the present invention, the volume average particle diameter of the pigment is preferably 10 nm or more and 250 nm or less. The volume average particle diameter of the pigment particles refers to the particle diameter of the pigment itself or the particle diameter to which the additive has adhered when an additive such as a dispersant is attached to the pigment. In the present invention, a Nanotrac UPA particle size analyzer (UPA-EX150; manufactured by Nikkiso Co., Ltd.) was used as a measuring device for the volume average particle diameter of the pigment. The measurement was performed according to a predetermined measuring method by putting 3 ml of the pigment dispersion in a measuring cell. As parameters to be input at the time of measurement, ink viscosity was used as the viscosity, and pigment density was used as the density of the dispersed particles.

  A more preferable volume average particle diameter is 20 nm or more and 250 nm or less, and further preferably 30 nm or more and 230 nm or less. When the number average particle size of the particles in the pigment dispersion is less than 20 nm, there are cases where the storage stability cannot be ensured, whereas when it exceeds 250 nm, the optical density may be lowered.

  The concentration of the pigment contained in the pigment dispersion 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 azo pigment of the present invention is used by adjusting physical properties such as solvent resistance, dispersibility, and heat mobility suitable for the application with a substituent. Further, the azo pigment of the present invention can be used in an emulsified and dispersed state and further in a solid dispersed state depending on the system used.

Moreover, in order to disperse | distribute a component favorably in a short time, you may include a dispersing agent in a composition.
The coloring composition for color filters in the present invention further includes one or more dispersants selected from surfactants, silicone additives, pigment additives, silane coupling agents, and titanium coupling agents. It is preferable to contain. Two or more of these dispersants may be used in combination.

Specific examples of the dispersant will be described below.
The surfactant is not particularly limited as long as it has a surface active action, and examples thereof include cationic, anionic, nonionic, and amphoteric surfactants. Specific examples thereof include alkanes. Sulfonate, linear alkylbenzene sulfonate, branched alkylbenzene sulfonate, alkyl naphthalene sulfonate, naphthalene sulfonate formaldehyde condensate, alkyl sulfate, polyoxyethylene alkyl ether sulfate, alkyl phosphate, poly Anionic surfactants such as oxyethylene alkyl ether phosphates and aliphatic monocarboxylates; cationic surfactants such as alkylamine salts and quaternary amine salts; glycerin fatty acid esters, sorbitan fatty acid esters, Polyoxyethylene alkyl ether, polyoxy Nonionic surfactants such as ethylene alkylphenyl ether, polyethylene glycol fatty acid esters, and polyoxyethylene sorbitan fatty acid esters; amphoteric surfactants such as alkylbetaines; any of cationic, anionic, nonionic, or amphoteric Examples thereof may include a high molecular weight surfactant.

  Specific examples of the silicone-based additive include polyalkylsiloxane, polyalkylphenylsiloxane, polyorganosiloxane, polydimethylsiloxane, polyorganosiloxane polyether copolymer, polyfluorosiloxane, and organosilane. These silicone additives may be used in combination of two or more.

  The pigment-based additive is a pigment derivative in which a substituent such as a basic group, an acidic group, a linear alkyl group, a branched alkyl group, or a polyoxyethylene group is introduced into the pigment skeleton. Preferred pigment skeletons include monoazo pigments, disazo pigments, benzimidazolone pigments, condensed azo pigments, azo lake pigments, anthraquinone pigments, diketopyrrolopyrrole pigments, quinacridone pigments, isoindoline pigments, and isoindoline pigments. Indolinone pigments, perinone pigments, perylene pigments and the like can be mentioned.

  Among these pigment-based additives, those in which the above substituent is introduced into the skeleton of the azo pigment are preferable because of their good affinity with the azo compound represented by the general formula (1).

  Specific examples of the silane coupling agent include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and γ-glycidoxy. Propyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, Methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane n- butyl trimethoxysilane, isobutyl trimethoxysilane, trimethyl methoxysilane, hydroxypropyl Ritori silane, n- hexadecyl trimethoxysilane, and the like n- octadecyl trimethoxysilane.

  Specific examples of the titanium coupling agent include isopropyl tri (N-aminoethylaminoethyl) titanate and dibutoxybistriethanolamine titanate.

  The amount of the dispersant used is preferably 0.1 to 100 parts by mass with respect to 100 parts by mass of the azo compound represented by the general formula (1), although it depends on the type of dispersant to be used. It is particularly preferable to use 0.5 to 80 parts by mass.

The method for using the dispersant is not particularly limited, and may be a known method for preparing a coloring composition for photolithography.
The present invention also relates to a method for preparing a colored composition for a color filter. The method for preparing the coloring composition for a color filter of the present invention includes one or more dispersants selected from surfactants, silicone additives, pigment additives, silane coupling agents and titanium coupling agents, and And a step of dispersing the azo compound represented by the general formula (1) in a part of a solvent to obtain a pigment dispersion, and a step of mixing the pigment dispersion with a polymerizable compound and the remaining solvent.
The method of the present invention is preferably used as a method for preparing the color filter coloring composition.

  The present invention also provides a color filter obtained using the above-described coloring composition for a color filter. The color filter exhibits high contrast and good light transmission. Specifically, at a wavelength of 650 nm, the light transmittance is preferably 85% or more, more preferably 90% or more.

  In order to produce the color filter of the present invention, any known method may be used, and preferred examples include a photolithography method and an ink jet method. Hereinafter, the photolithography method and the inkjet method will be described in detail.

1) Photolithographic method When a color filter is formed by a photolithography method, a photosensitive resin is used as the polymerizable compound of the coloring composition for a color filter of the present invention. The photosensitive resin is blended in the coloring composition together with the photopolymerization initiator as a monomer and / or oligomer, and is cured by light irradiation to form a film on the transparent substrate.

  As the photosensitive resin, a polymer or copolymer of a polymerizable monomer having one or more ethylenic double bonds in the molecule is preferably used.

  As these photosensitive resins (polymerizable monomers), acrylic acid esters and methacrylic acid esters are particularly preferable. Specifically, methyl acrylate, methyl methacrylate, butyl methacrylate, butyl acrylate, pentaerythritol tetraacrylate, pentaerythritol tetra Methacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, glycerol diacrylate, glycerol dimethacrylate, 1,4-butanediol Diacrylate, 1,4-butanediol dimethacrylate, vinyl Phenol A diacrylate, and bisphenol A dimethacrylate.

  In the case of using a photolithography method, a binder resin having an acidic group is used in the colored composition of the present invention in addition to the above-described photosensitive resin. Examples of the binder resin having an acidic group include resins having a carboxyl group, a hydroxyl group, a sulfonic acid group, and the like, and a binder resin having a carboxyl group and / or a hydroxyl group is preferable.

  Examples of the binder resin having an acidic group include monomers having an ethylenic double bond selected from acrylic esters, methacrylic esters, styrene, vinyl acetate, vinyl chloride, N-vinylpyrrolidone, acrylamide, and the like. , Acrylic acid, methacrylic acid, p-styrene carboxylic acid, p-styrene sulfonic acid, p-hydroxystyrene, maleic anhydride and the like, and a monomer having an ethylenic double bond having an acidic group Polymers are preferably used.

  The binder resin having an acidic group is preferably used in an amount of 0.5 to 4 parts by mass, particularly preferably 1 to 3 parts by mass with respect to 1 part by mass of the photosensitive resin (polymerizable monomer).

  Solvents used in the coloring composition for photolithography include fatty acid esters, ketones, aromatics, alcohols, glycols, glycerin, alkylene glycol monoalkyl ethers, alkylene glycol dialkyl ethers, ethers, and One or more oily media selected from nitrogen-containing polar organic solvents can be mentioned.

  The amount of these solvents used is preferably 3 to 30 times, and particularly preferably 4 to 15 times, the total mass of components other than the solvent in the colored composition.

  In addition to the above-described components, the coloring composition for the photolithography method in the present invention, if necessary, wetting agent, anti-fading agent, emulsion stabilizer, ultraviolet absorber, preservative, antifungal agent, pH adjustment And known additives (described in JP-A-2003-306623) such as an agent, a surface tension modifier, an antifoaming agent, a viscosity modifier, a dispersion stabilizer, a rust inhibitor, and a chelating agent. These various additives may be added to the oil phase or the aqueous phase at the time of preparation.

  The coloring composition for a color filter of the present invention includes an azo compound represented by the general formula (1), a polymerizable compound, a solvent, and other various additives such as a bead mill, a ball mill, a sand mill, a two-roll mill, and three Using a device such as a roll mill, a homogenizer, a kneader, or a shaker, it can be prepared by a method including a step of uniformly mixing and dispersing, and a step of adjusting the viscosity using the solvent.

As a method for forming a color filter on a substrate using the coloring composition for a color filter of the present invention, a known photolithography method may be used. For example, the step of uniformly applying the colored composition of the present invention onto a display substrate by a known method such as a printing method, a spray method, a bar coating method, a roll coating method, or a spin coating method, and removing the solvent in the ink by heating. The color filter can be obtained by a method including a step of exposing the color filter pattern on the display substrate using a high-pressure mercury lamp, an alkali developing step, a cleaning step, and a baking step.
As the developer used in the method for producing a color filter of the present invention, any developer can be used as long as it dissolves the composition of the present invention and does not dissolve the radiation irradiated portion. Specifically, a combination of various organic solvents or an alkaline aqueous solution can be used.
Examples of the organic solvent include the aforementioned solvents used in preparing the composition of the present invention.
Examples of the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, Concentration of an alkaline compound such as choline, pyrrole, piperidine, 1,8-diazabicyclo- [5.4.0] -7-undecene is 0.001 to 10% by mass, preferably 0.01 to 1% by mass. An alkaline aqueous solution dissolved in this manner is used. When a developer composed of such an alkaline aqueous solution is used, it is generally washed with water after development.

2) Inkjet method When a color filter is formed using an inkjet method, the polymerizable compound of the coloring composition for a color filter of the present invention is not particularly limited as long as it is conventionally used for an inkjet ink. Any of them may be used. A monomer of a photosensitive resin and / or a thermosetting resin is preferably used.

  Examples of these photosensitive resins include acrylic resins, methacrylic resins, and epoxy resins, and acrylic resins and methacrylic resins are preferably used. Acrylic resins and methacrylic resins are photopolymerizable monomers selected from acrylic esters, methacrylic esters, urethane acrylates, urethane methacrylates, acrylic amides, methacrylic amides, alkyl acrylates, benzyl methacrylates, benzyl acrylates, aminoalkyl methacrylates, and the like. A combination of a monomer and a photopolymerization initiator selected from compounds such as a benzophenone derivative, an acetophenone derivative, a benzoin derivative, a benzoin ether derivative, a thioxanthone derivative, an anthraquinone derivative, a naphthoquinone derivative, and a triazine derivative is preferable. In addition to the above photopolymerizable monomer, a photopolymerizable monomer having a hydrophilic group such as acrylic acid, methacrylic acid, maleic acid, and vinyl acetate may be added.

  Examples of the thermosetting resin include melamine resin, urea resin, alkyd resin, epoxy resin, phenol resin, and cyclopentadiene resin.

  When the inkjet method is used, the solvent used for the coloring composition may be an oily medium or an aqueous medium, but an aqueous medium is more preferably used. As the aqueous medium, water or a mixed solvent of water and a water-soluble organic solvent is used, and a mixed solvent of water and a water-soluble organic solvent is preferable. Moreover, it is desirable to use what was deionized.

  Although the oil-based medium used in said coloring composition is not specifically limited, For example, what was mentioned as a solvent for coloring compositions used for the photolithographic method etc. can be used.

  The solvent used in the aqueous medium is selected from alcohols, ketones, ethers, glycols, glycerin, alkylene glycol monoalkyl ethers, alkylene glycol dialkyl ethers, alkanolamines, and nitrogen-containing polar organic solvents. And those having water solubility. These water-soluble organic solvents may be used alone or in combination of two or more.

  The amount of these solvents used is not particularly limited, but the amount used may be appropriately adjusted so that the viscosity of the colored composition is 20 mPa · s or less, preferably 10 mPa · s or less at room temperature.

  The inkjet coloring composition of the present invention can be prepared by a method including a step of dispersing and mixing components in the same manner as the coloring composition for photolithography. If necessary, a dispersing agent may be added at the time of dispersion as in the case of the photolithography method.

  In addition to the above-described components, the coloring composition for inkjet according to the present invention, if necessary, a wetting agent, an antifading agent, an emulsion stabilizer, an ultraviolet absorber, an antiseptic, an antifungal agent, a pH adjuster, Various known additives such as a surface tension adjusting agent, an antifoaming agent, a viscosity adjusting agent, and a dispersion stabilizer may be included.

  A method for forming a color filter using the colored composition obtained as described above is not particularly limited as long as it is a method for forming a color filter by a known inkjet method. For example, a step of forming a predetermined color filter pattern in the form of droplets on the substrate, a step of drying this, and a step of curing and forming a film on the color filter pattern on the substrate by performing heat treatment or light irradiation or both of them A color filter can be formed by a method including:

  Although the photolithography method and the ink jet method have been described above, the color filter of the present invention may be obtained by other methods.

  Even when a color filter forming method other than the above (for example, various printing methods such as an offset printing method) is used, the coloring composition contains the polymerizable compound and the solvent described above and is represented by the general formula (1). As long as an azo compound is used as a colorant, both the color filter coloring composition and the obtained color filter are included in the scope of the present invention.

  For example, the components such as the polymerizable compound, the solvent, and the additive, and the formulation at the time of forming the color filter may be selected according to conventional examples, and are not limited to those described in the description of the photolithography method and the inkjet method described above.

The color filter of the present invention obtained as described above forms pixels together with G (green) and B (blue) color filter patterns by a known method. Such a filter can provide a liquid crystal display that can display a clear image with very high transparency, excellent spectral characteristics, and a small depolarization effect. Further, when a device in which this color filter is formed is used, a camera module having good spectral characteristics can be provided.
The color filter of the present invention can be used for a liquid crystal display element, a solid-state imaging element such as a CCD or a CMOS, and is also suitable for a high-resolution CCD element or a CMOS element that exceeds 1 million pixels.

  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 1]
Synthesis of Specific Compound Example D-1 Specific compound example D-1 was synthesized by the following route.

Synthesis of D-1 1.0 g of compound (1) was dissolved in 10 ml of phosphoric acid (Wako Pure Chemical Industries, Ltd .; reagent special purity 85%, the same applies hereinafter). This solution was ice-cooled and kept at −5 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 acetonitrile was added to 1.30 g of compound (0), and the above diazonium salt solution was added at 8 ° C. or lower with stirring. Upon completion of the addition, the ice bath was removed and the mixture was further stirred for 3 hours. 50 ml of acetonitrile was added to the reaction solution, and the mixture was stirred for 30 minutes. The precipitated crystals were separated by filtration and washed with 30 ml of acetonitrile. The crystals were added to 100 ml of water without drying, and a solution of 0.5 g of sodium bicarbonate dissolved in 30 ml of water was added, followed by stirring at 20 to 25 ° C. for 30 minutes. The precipitated crystals were separated by filtration, and further thoroughly washed with water. The obtained crystals were added to 50 ml of dimethylacetamide without drying and heated and stirred at 100 ° C. for 30 minutes. The mixture was stirred at room temperature for 30 minutes, and the precipitated crystals were filtered and washed with 30 ml of dimethylacetamide. The obtained crystals were added to 50 ml of dimethylacetamide without drying, 25 ml of water was gradually added dropwise, stirred at 80 ° C. for 1 hour, and further stirred at room temperature for 30 minutes. The precipitated crystals were filtered and washed with 20 ml of dimethylacetamide / water = 2/1 and 20 ml of methanol. The obtained crystals were dried to obtain 1.2 g of the compound D-1 of the present invention. Yield 52%.
FIG. 1 shows an infrared absorption chart.

[Synthesis Example 2]
Synthesis of Specific Compound Example D-33 Specific compound example D-33 was synthesized by the following route.

Synthesis of D-33 1.0 g of compound (2) was added to 10 ml of phosphoric acid (Wako Pure Chemical Industries, Ltd .; reagent grade 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 obtained by dissolving 1.4 g of compound (0) in 5 ml of dimethylacetamide while maintaining at 5 to 10 ° C., and then stirred for 1 hour while maintaining at 5 to 10 ° C. Thereafter, the ice bath was removed, and the mixture was further stirred for 0.5 hour. 50 ml of ethyl acetate was added to the reaction solution, and it was completely dissolved by heating at 80 ° C. Thereto was added 50 ml of hexane, and the mixture was further stirred at 80 ° C. for 20 minutes and at room temperature for 40 minutes. The precipitated crystals were separated by filtration and washed with 50 ml of hexane. The crystals were neutralized by adding 200 ml of water and 0.1 ml of saturated sodium bicarbonate without drying. 100 ml of acetonitrile was added to the crystals, and the mixture was stirred at 80 ° C. for 3 hours and at room temperature for 1 hour. The precipitated crystals were filtered and washed with 50 ml of acetonitrile. The obtained crystals were dried to obtain 0.51 g of the compound D-33 of the present invention. Yield 21%.
λmax: 504 nm, ε: 1.59 × 10 ⁴ (CHCl ₃ )
FIG. 2 shows an infrared absorption chart.

[Synthesis Example 3]
Synthesis of Specific Compound Example D-20 Specific Compound Example D-20 was synthesized by the following route.

Synthesis of D-20 1.0 g of the compound (3) was added to 10 ml of phosphoric acid and heated to 30 ° C. to dissolve. This solution was ice-cooled and kept at 0 to 5 ° C., 0.35 g of sodium nitrite was added and stirred for 2 hours to obtain a diazonium salt solution. The diazonium salt solution was added dropwise to a solution of 1.3 g of compound (0) in 5 ml of dimethylacetamide while keeping the temperature at 5 to 10 ° C., then kept at 5 to 10 ° C. for 20 minutes, and then the ice bath was removed. Stir for another 20 minutes. 100 ml of dimethylacetamide was added to the reaction solution and stirred at 40 ° C. for 20 minutes. Acetonitrile 100ml was added there and it stirred at room temperature for 10 minutes. The precipitated crystals were separated by filtration and washed with 50 ml of acetonitrile. Without drying the crystals, 200 ml of water and 0.1 ml of saturated sodium bicarbonate were added for neutralization, and the obtained crystals were dried to obtain 0.49 g of Compound D-20 of the present invention. Yield 21%.
λmax: 493 nm, ε: 1.93 × 10 ⁴ (CHCl ₃ )
FIG. 3 shows an infrared absorption chart.

[Synthesis Example 4]
Synthesis of Specific Compound Example D-22 Specific Compound Example D-22 was synthesized by the following route.

Synthesis of D-22 4.5 g of compound (4) was added to 45 ml of phosphoric acid and heated to 30 ° C. to dissolve. This solution was ice-cooled and kept at 0 to 5 ° C., 1.47 g of sodium nitrite was added and stirred for 1 hour to obtain a diazonium salt solution. The diazonium salt solution was added dropwise to a solution of 4.5 g of compound (0) in 70 ml of dimethylacetamide while maintaining the temperature at 5 to 10 ° C., then maintained at 5 to 10 ° C. for 30 minutes, and then the ice bath was removed. The mixture was further stirred for 1 hour. 200 ml of water was added to the reaction solution, and the precipitated crystals were separated by filtration and washed with 200 ml of water. 200 ml of acetonitrile was added to the crystals and stirred at 80 ° C. for 2 hours. Then, after stirring at room temperature for 2 hours, the precipitated crystals were separated by filtration. The crystals were neutralized by adding 0.1 ml of saturated sodium bicarbonate, and the obtained crystals were dried to obtain 6.9 g of Compound D-22 of the present invention. Yield 82%.
λmax: 494 nm, ε: 1.91 × 10 ⁴ (CHCl ₃ )
FIG. 4 shows an infrared absorption chart.

[Synthesis Example 5]
Synthesis of Specific Compound Example D-222 Specific compound example D-222 was synthesized by the following route.

1.0 g of the compound (1 ′) was dissolved in 10 ml of phosphoric acid (Wako Pure Chemical Industries, Ltd .; reagent special grade purity 85%, the same applies hereinafter). This solution was ice-cooled and kept at -5 to 0 ° C., 0.55 g of sodium nitrite was added and stirred for 1 hour to obtain a diazonium salt solution. Separately, 20 ml of NMP (N-methylpyrrolidone) was added to 1.60 g of compound (0), and the above diazonium salt solution was added at 8 ° C. or lower with stirring. Upon completion of the addition, the ice bath was removed and the mixture was further stirred for 3 hours. 50 ml of methanol was added to the reaction solution and stirred for 30 minutes. The precipitated crystals were filtered off and washed with 30 ml of methanol. The crystals were added to 100 ml of water without drying, and a solution of 0.5 g of sodium bicarbonate dissolved in 30 ml of water was added, followed by stirring at 20 to 25 ° C. for 30 minutes. The precipitated crystals were separated by filtration, and further thoroughly washed with water. The obtained crystals were added to 20 ml of NMP and 10 ml of water without drying, and heated and stirred at 100 ° C. for 30 minutes. The mixture was stirred at room temperature for 30 minutes, and the precipitated crystals were filtered and washed with 20 ml of NMP / water = 2/1 and 20 ml of water. The obtained crystals were dried to obtain 1.8 g of the compound D-222 of the present invention. Yield 72%.
FIG. 5 shows an infrared absorption chart.

[Synthesis Example 6]
Synthesis of Specific Compound Example D-228 Specific compound example D-228 was synthesized by the following route.

1.0 g of compound (2 ′) was dissolved in 10 ml of phosphoric acid. This solution was ice-cooled and kept at -5 to 0 ° C, 0.54 g of sodium nitrite was added and stirred for 1 hour to obtain a diazonium salt solution. Separately, 20 ml of NMP (N-methylpyrrolidone) was added to 1.60 g of compound (3 ′), and the above diazonium salt solution was added at 8 ° C. or lower with stirring. Upon completion of the addition, the ice bath was removed and the mixture was further stirred for 1 hour. 40 ml of methanol was added to the reaction solution, and the mixture was stirred for 30 minutes. The precipitated crystals were separated by filtration and washed with 30 ml of methanol. The crystals were added to 100 ml of water without drying and stirred at 20-25 ° C. for 30 minutes. The precipitated crystals were separated by filtration, and further thoroughly washed with water. The obtained crystals were added to 20 ml of NMP and 10 ml of water without drying, and heated and stirred at 100 ° C. for 30 minutes. The mixture was stirred at room temperature for 30 minutes, and the precipitated crystals were filtered and washed with 20 ml of NMP / water = 2/1 and 20 ml of water. The obtained crystals were dried to obtain 2.0 g of the compound D-228 of the present invention. Yield 80%.
FIG. 6 shows an infrared absorption chart.
Other compounds were synthesized in the same manner as Compound Example 228.

[Example 1]
[Production of color filters by photolithography]
The pigment represented by Compound D-1 synthesized in Synthesis Example 1 was used. The material shown below was put into a 70 cc mayonnaise bottle and shaken with a shaker (DAS200 manufactured by LAU) for 6 hours to obtain pigment dispersion 1.

  The following materials were added to the pigment dispersion 1, and the mixture was further shaken for 30 minutes with the above shaker to prepare a colored composition 1 for a color filter for photolithography.

The obtained colored composition 1 for a color filter was placed on a slide glass with a bar coater Rod No. 10 was applied and dried in an oven at 80 ° C. for 5 minutes to obtain an ink coating film.
The above-mentioned coating film was exposed by irradiating under a condition of 200 mJ / cm ² using a high-pressure mercury lamp after appropriately masking a part of the coating film. Thereafter, development was performed at 25 ° C. using a 0.5% sodium carbonate aqueous solution, followed by drying in an oven at 220 ° C. for 20 minutes to produce a color filter. The light transmittance of this film was measured using a spectrophotometer (manufactured by Hitachi, Ltd., U-3310). The results are shown in FIG. Moreover, the wavelength which shows the minimum transmission of the obtained color filter was calculated | required between wavelengths 540-610 nm. The results are shown in Table 3.

[Example 2]
Instead of the pigment used in Example 1, the pigment represented by Compound D-33 synthesized in Synthesis Example 2 was used, and the solvent (1,2-propanediol 1-monomethyl ether 2- A colored composition was prepared in the same manner as in Example 1 except that the amount of acetate) was changed to the amount shown in Table 1. A color filter was prepared using the obtained colored composition, and the light transmittance was measured. The results are shown in FIG. Moreover, the wavelength which shows the minimum transmittance | permeability of the obtained color filter was calculated | required between wavelengths 540-610 nm. The results are shown in Table 3.

[Examples 3 to 11]
The amount of solvent 1 (1,2-propanediol-1-monomethyl ether-2-acetate) in the composition of pigment dispersion 1 was used instead of the pigment used in Example 1, using the pigments listed in Table 1. A colored composition was prepared in the same manner as in Example 1 except that the amount was as described in Table 1. A color filter was prepared using the obtained colored composition. Moreover, the wavelength which shows the minimum transmittance | permeability of the obtained color filter was calculated | required between wavelengths 540-610 nm. The results are shown in Table 3.

Example 21
In Example 1, 0.5 g of a surfactant (pigment wetting and dispersing agent BYK-161 manufactured by Big Chemie Co., Ltd.) was added as a dispersant to 0.6 g of the pigment, and dispersion was performed. The dispersion time was 6 hours. Thus, a color filter having the same performance as in Example 1 was obtained.

[Examples 22 to 26]
A pigment dispersion was prepared by dispersing the pigment using a shaking disperser (DAS200 manufactured by LAU) in the same manner as in Example 1 except that the amount used was changed using the dispersant shown in Table 2. A color filter having the same performance as in Example 1 was obtained with a dispersion time of 6 hours.

[Comparative Examples 1 and 2]
Instead of the pigment used in Example 1, C.I. I. A colored film was prepared in exactly the same manner as in Example 1 except that Pigment Red 254 (IRGAPHORE DPP RED, manufactured by Ciba Specialty Chemicals) and a pigment represented by the following formula [I] were used. The light transmittance of the obtained film was measured, and the minimum wavelength of the light transmittance, the light transmittance of 650 nm, and the light transmittance of 540 nm were obtained. The results are shown in Table 3.

  The color filter prepared using the coloring composition for a color filter of the present invention containing the compounds represented by Compound D-1 and Compound D-33 as a colorant has a sharply rising transmittance curve and has a wavelength of 650 to 750 nm. In this region, the transmittance was high and an excellent transmittance curve was exhibited. Furthermore, although the color filter of Comparative Example 1 had a portion with a high transmittance at 540 nm, the color filters of Examples 1 to 11 had a low transmittance at 540 nm and were excellent.

  Moreover, the color filter produced using the coloring composition for a color filter of the present invention has a very low transmittance of blue light of 350 to 400 nm as compared with the color filters obtained in Comparative Examples 1 and 2. In other words, it is possible to display red with high color purity.

  That is, the coloring composition for a color filter of the present invention has a wavelength at which the transmittance changes rapidly between about 540 nm and about 590 nm by selecting the structure of the azo pigment represented by the general formula (1). This is useful in that it can be adjusted and an optimum hue of red can be obtained according to the light source wavelength of the backlight of the display.

[Heat resistance evaluation]
A heat resistance test was performed using the color filters obtained in Examples 1 to 11 and Comparative Examples 1 and 2.
<Heat resistance test method>
The color filter was exposed at 250 ° C. for 90 minutes in the atmosphere, and the color difference before and after that (ΔE * ab) was measured with a spectrophotometer (Macbeth Colorey-3000 manufactured by Sakata Inx Corporation). Evaluation was made according to the following criteria, and these results are shown in Table 4.
<Criteria>
○: ΔE * ab <1.0
Δ1.0 ≦ ΔE * ab <1.1
×: 1.1 ≦ ΔE * ab

  The color filters of Examples 1 to 11 prepared using the coloring composition for a color filter of the present invention containing the azo compound represented by the general formula (1) as a colorant are obtained by using the pigment of Comparative Example 1. In comparison, the heat resistance was equivalent or better.

<Light resistance evaluation>
The coated product having an image density of 1.0 used for evaluation of coloring power was irradiated with xenon light (170000 lux .; Suga test machine in the presence of a cut filter of 325 nm or less) for 20 days using a fade meter, and the color difference before and after that (ΔE * Ab) was measured with a spectrophotometer (Macbeth Colorey-3000 manufactured by Sakata Inx Corporation). Evaluation was made according to the following criteria, and these results are shown in Table 5.
<Criteria>
○: ΔE * ab ≦ 3.0
Δ: 3.0 <ΔE * ab ≦ 6.0
X: 6.0 <ΔE * ab

  The color filters of Examples 1 to 11 prepared using the coloring composition for a color filter of the present invention containing the azo compound represented by the general formula (1) as the colorant used the pigments of Comparative Examples 1 and 2. Compared to those, the light resistance was equivalent or better.

(Contrast evaluation)
The contrast of the obtained color filter was measured using a contrast tester CT-1 manufactured by Aisaka Electric Co., Ltd. In the evaluation, contrast ≧ 23000 is indicated by “◯”, 23000> contrast ≧ 18000 is indicated by “Δ”, and 18000> contrast is indicated by “x”.

  The color filters of Examples 1 to 11 prepared using the coloring composition for a color filter of the present invention containing the compound represented by the general formula (1) as the colorant are compared with those using the pigment of Comparative Example 2. And showed excellent contrast.

(Evaluation of dispersion stability over time)
Examples 1-11, Colored Compositions 1-11 created in Comparative Examples 1 and 2, and Comparative Colored Compositions 1 and 2 were stored for 2 weeks at room temperature in the dark, and then the degree of precipitation of foreign matters was visually observed according to the following criteria. evaluated.
<Criteria>
○: No precipitation was observed.
Δ: Slight precipitation was observed.
X: Precipitation was recognized.

  Pigment dispersions 1 to 11 prepared using the color filter coloring composition of the present invention containing the compound represented by the general formula (1) as the colorant are compared with those using the pigments of Comparative Examples 1 and 2. Thus, no foreign matter was observed over time, and the dispersion was excellent in stability over time.

(Example 101)
<Preparation of Green pigment dispersion>
-Preparation of Green pigment dispersion P1-
As a pigment, C.I. I. Pigment Green 36 and C.I. I. 12.6 parts of a 100/55 (mass ratio) mixture with Pigment Yellow 139, 5.2 parts of a dispersing agent, BYK2001 (Disperbyk: manufactured by BYK Corporation, solid content concentration: 45.1% by mass), and dispersion A mixed solution consisting of 2.7 parts of benzyl methacrylate / methacrylic acid copolymer (acid value 134 mgKOH / g, Mw = 30,000) as a resin and 78.3 parts of propylene glycol monomethyl ether acetate as a solvent was obtained by a bead mill. Green pigment dispersion P1 was prepared by mixing and dispersing for 15 hours.

<Preparation of Red pigment dispersion>
-Preparation of Red pigment dispersion P2-
D-1 and C.I. I. 12.1 parts of 100/45 (mass ratio) mixture with Pigment Yellow 139, and 10.4 parts of BYK2001 (Disperbyk: BYK Corporation (solid content concentration: 45.1% by mass)) as a dispersing agent A mixed solution consisting of 3.8 parts of benzyl methacrylate / methacrylic acid copolymer (acid value 134 mgKOH / g, Mw = 30,000) as resin and 73.7 parts of propylene glycol monomethyl ether acetate as solvent was By mixing and dispersing for 15 hours, a Red pigment dispersion P2 was prepared.

<Preparation of Blue Pigment Dispersion>
-Preparation of Blue pigment dispersion P3-
As a pigment, C.I. I. Pigment blue 15: 6 and C.I. I. 14 parts of a 100/25 (mass ratio) mixture with CI Pigment Violet 23, 4.7 parts of BYK2001 (Disperbyk: BYK Corporation (solid content concentration: 45.1% by mass)) as a dispersant, and a dispersion resin A mixed solution composed of 3.5 parts of a benzyl methacrylate / methacrylic acid copolymer (acid value 134 mgKOH / g, Mw = 30,000) and 77.8 parts of propylene glycol monomethyl ether acetate as a solvent was mixed with a bead mill for 15 hours. By mixing and dispersing, a blue pigment dispersion P3 was prepared.

<Preparation of Green Colored Photosensitive Composition (Coating Solution) A-1>
A colored photosensitive composition A-1 was prepared by mixing and stirring the above Green pigment dispersion so as to have the following composition.

<Preparation of Red colored photosensitive composition (coating liquid) B-1>
Using the above-mentioned Red pigment dispersion P2, the photosensitive composition B-1 was prepared by mixing and stirring so as to have the following composition.

<Preparation of Blue colored photosensitive composition (coating liquid) C-1>
Using the above-mentioned Blue pigment dispersion P3, the photosensitive composition C-1 was prepared by mixing and stirring so as to have the following composition.

The green colored photosensitive composition A-1 prepared above was applied onto an 8-inch device-formed silicon wafer previously sprayed with hexamethyldisilazane to form a photocurable coating film. Then, heat treatment (pre-baking) was performed for 180 seconds using a hot plate at 100 ° C. so that the dry film thickness of the coating film became 1.0 μm. Then, using an i-line stepper exposure apparatus FPA-3000i5 + (Canon (Ltd.)), it was irradiated in 50~1000mJ / cm ² through 1.0μm square Bayer pattern mask at a wavelength of 365nm (50mJ / cm ² The amount of exposure changes in steps). Then, the silicon wafer on which the irradiated coating film is formed is placed on a horizontal rotary table of a spin shower developing machine (DW-30 type; manufactured by Chemitronics), and CD-2000 (Fuji Film Electronics). Paddle development was performed at 23 ° C. for 180 seconds using a 40% diluted solution (manufactured by Materials Co., Ltd.) to form a colored pattern on the silicon wafer.

A silicon wafer on which a colored 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 ejected from above the rotation center from a jet nozzle. And then rinsed and then spray dried.
Next, it was heated for 5 minutes on a 200 ° C. hot plate to obtain a color filter on which a pattern was formed.

Furthermore, by repeating the same process as Green except that the red colored photosensitive composition B-1 and the Blue photosensitive composition C-1 are used and the exposure pattern is exposed through a 1.0 μm square island pattern mask, A color filter formed with an RGB pattern was formed.
It was confirmed that when a camera module was produced using a device in which this color filter was formed, it had good spectral characteristics.

  When D-26, D-136, D-209, and D-236 are used instead of D-1 in Example 101 to create a color filter and a camera module, good spectral characteristics are obtained as in Example 101. It was confirmed that the

Claims (10)

A coloring composition for a color filter comprising an azo pigment represented by the general formula (1).

(In the general formula (1), G represents a hydrogen atom, an aliphatic group, an aryl group, or a heterocyclic group, and R ₁ represents an amino group, an aliphatic oxy group, an aliphatic group, an aryl group, or a heterocyclic ring. R ₂ represents a substituent, and A represents any one of the following general formulas (A-13) to (A-20), (A-25) to (A-29), and (A-32). the representative .m is an integer of 0 to 5, n is. one general formula (1) can not have an ionic hydrophilic group representing 1.)

(Formula (A-13) ~ (A -20), represents (A-25) ~ (A -29) and (A-32) _in, R 55 _{to R 59} is a hydrogen atom, a substituent, adjacent The substituents may be bonded to each other to form a 5- to 6-membered ring. * Represents the bonding position with the azo group of the general formula (1). A in the general formula (1) is represented by the following general formulas (A-13) to (A-17), (A-19), (A-20), (A-25) to (A-29) and (A The coloring composition for a color filter according to claim 1, which represents any one of -32).

(In the general formula (A-13) ~ (A -17), (A-19), (A-20), (A-25) ~ (A-29) and _{(A-32), R 55} ~R ₅₉ represents a hydrogen atom or a substituent, and adjacent substituents may be bonded to each other to form a 5- to 6-membered ring, and * represents a bonding position with the azo group of the general formula (1). The coloring composition for a color filter according to claim 1 or 2, wherein the azo pigment represented by the general formula (1) is represented by the following general formula (2).

(In the general formula (2), R ₂₁ , R ₂₂ , R ₅₅ , R ₅₉ , m, and n are the same as R ₁ , R ₂ , R ₅₅ , R ₅₉ , m, and n defined in the general formula (1). is the same .Z the σp value of Hammett's. one general formula (2) will not have an ionic hydrophilic group representing 0.2 or more electron-withdrawing group.)   The coloring composition for a color filter according to any one of claims 1 to 3, further comprising a polymerizable compound and a solvent.   The coloring composition for color filters of Claim 4 which contains 0.01-2 mass parts of azo pigments represented by General formula (1) with respect to 1 mass part of polymeric compounds.   The coloring composition for a color filter according to claim 4 or 5, wherein the polymerizable compound is a photosensitive compound.   Furthermore, 1 or more types of dispersing agents selected from surfactant, a silicone type additive, a pigment type additive, a silane type coupling agent, and a titanium type coupling agent are included, The 1-6 characterized by the above-mentioned. The coloring composition for color filters in any one of.   A color filter formed using the coloring composition for a color filter according to claim 1.   The color filter according to claim 8, wherein the color filter is formed by a photolithography method or an inkjet method.   One or more dispersants selected from surfactants, silicone-based additives, pigment-based additives, silane-based coupling agents, and titanium-based coupling agents, and an azo pigment represented by the general formula (1) A coloring composition for a color filter according to claim 7, comprising: a step of dispersing in part of a solvent to obtain a pigment dispersion; and a step of mixing the pigment dispersion with a polymerizable compound and the remaining solvent. Preparation method.

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