WO2013081140A1 - Quinophthalone compound and pigment for color filter including said compound - Google Patents

Abstract

A quinophthalone compound indicated by formula (1), that is useful as a pigment for a color filter as a result of having excellent solvent solubility and high color purity.　In particular, in formula, X5 is formula (3) (in formula (3), Y is a non-aromatic annular structure having a C4-16 unsubstituted or substituted group, and the ring may include a hetero atom) or formula (4) (in formula (4), Z1 and Z2 are each independently a hydrogen atom, a halogen atom, or a straight-chain or branched-chain C1-8 alkyl group, alkoxy group, alkylthio group, or alkylamino group. Alternatively, Z1 and Z2 may form a non-aromatic ring together).

Description

Quinophthalone compound and colorant for color filter containing the compound

The present invention relates to a quinophthalone compound. Specifically, the present invention relates to a quinophthalone compound having a high transmittance at 500 nm, a low transmittance at 470 nm (high light shielding rate), and a high solubility in an organic solvent.

Dyes have long been used as dyes for dyeing various fibers. In recent years, ink sheets for inkjet inks, synthetic resin and dyes for synthetic fiber materials, colorants for polymer materials, and thermal transfer type image forming materials have been used. It is used in various fields such as toner for electrophotography, magnetic recording material, and optical recording material. For this reason, the development of dyes that combine these performances is desired, including the performance required of dyes, not only for color development but also for light resistance, heat resistance, solubility in solvents, and compatibility with resins. .

The quinophthalone compound is generally known as a yellow pigment that is excellent in heat resistance, moisture resistance, and light resistance (see, for example, Patent Document 1).

JP 2008-81565 A

However, the quinophthalone compound described in Patent Document 1 has room for improvement in terms of color purity, is difficult to dissolve in a solvent, and is difficult to apply to uses that need to be dissolved in a solvent. In particular, color filter colorants include oil-based inks in which pigments or dyes are dissolved or dispersed in a solvent. In such applications, high solubility in the solvent is required.

Therefore, the present invention has been made in view of the above circumstances, and an object thereof is to provide a quinophthalone compound having excellent solvent solubility and high color purity.

Another object of the present invention is to provide a high-intensity color filter excellent in color, particularly a color filter used for a liquid crystal display.

As a result of intensive studies, the present inventors have found that the above-mentioned problems can be solved by the following compounds. That is, the object of the present invention is to formula (1) below;

In equation (1),
Each R ₁ independently represents a halogen atom or an alkyl group having 1 to 12 carbon atoms, n represents an integer of 0 to 5;
X ₁ to X ₄ each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, —COOR ₂ , —CONHR ₃ , —CONR ₃ R ₄ , —OR ₅ , —SR ₆ , — NHR ₇ , —NR ₇ R ₈ , or the following formula (2):

(In Formula (2), X ₆ is an oxygen atom or a sulfur atom, and m is an integer of 0 to 5)
A substituent represented by
Here, R ₂ to R ₈ are each independently an alkyl group having 1 to 12 carbon atoms, an alkoxyalkyl group having 2 to 8 carbon atoms which may be substituted with an arbitrary substituent, — (CH ₂ ) _p —CO—R ₁₀ (R ₁₀ is a linear or branched alkyl group having 1 to 8 carbon atoms, —COOR _a , —OCOR _b , —NHR _c , —NR _d R _e or —OR _f. In this case, R _a , R _b , R _c , R _d , R _e , and R _f are each independently an alkyl group having 1 to 8 carbon atoms, and p is an integer of 1 to 4 -(R ₁₁ O) _q -R ₁₂ (R ₁₁ is a linear or branched alkylene group having 1 to 3 carbon atoms, and R ₁₂ is a straight chain having 1 to 8 carbon atoms or Branched alkyl group, —COOR _a , —OCOR _b , —NHR _c , or —NR _d R _e , wherein R _a , R _b , R _c , R _d , and R _e are each independently an alkyl group having 1 to 8 carbon atoms, and q is an integer of 1 to 4 Or — (CH ₂ CH (OH) CH ₂ ) —R ₁₃ (R ₁₃ is a halogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, —COOR _a , —OCOR _b , —NHR _c , or —NR _d R _e , wherein R _a , R _b , R _c , R _d , and R _e are each independently an alkyl group having 1 to 8 carbon atoms) Yes,
R ₉ each independently represents a halogen atom, an alkyl group having 1 to 12 carbon atoms which may be substituted with an arbitrary substituent, — (CH ₂ ) _p —CO—R ₁₀ (R ₁₀ represents carbon A linear or branched alkyl group having 1 to 8 atoms, —COOR _a , —OCOR _b , —NHR _c , —NR _d R _e, or —OR _f , wherein R _a , R _b , R _c , R _d , R _e and R _f are each independently an alkyl group having 1 to 8 carbon atoms, and p is an integer of 1 to 4), — (R ₁₁ O) _q —R ₁₂ ( R ₁₁ is a linear or branched alkylene group having 1 to 3 carbon atoms, R ₁₂ is a linear or branched alkyl group having 1 to 8 carbon atoms, —COOR _a , —OCOR _b , an -NHR _c or _-NR d _{R e,,} this _{time, R a,} R _b, R , _R d, _{R e} are each independently an alkyl group having a carbon number of 1 ~ 8, q is an integer of _{1 ~ 4), - (CH} 2 CH (OH) CH 2) -R 13 (R ₁₃ is a halogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, —COOR _a , —OCOR _b , —NHR _c , or —NR _d R _e , where R _a , R _b , R _c , R _d and R _e are each independently an alkyl group having 1 to 8 carbon atoms), —COOR ₁₄ (R ₁₄ is a straight chain having 1 to 8 carbon atoms or A branched alkyl group or an alkoxyalkyl group having 2 to 8 carbon atoms), —CONHR ₁₅ (R ₁₅ is a linear or branched alkyl group having 1 to 8 carbon atoms, or 2 to 8 carbon atoms) alkoxyalkyl group), or -CONR ₁ R _{16 (R 15} and _{R 16} are each independently a linear or branched alkyl group or alkoxyalkyl group having 2 to 8 carbon atoms, 1 to 8 carbon atoms), and
X ₅ represents the following formula (3):

(In Formula (3), Y is an unsubstituted or substituted non-aromatic cyclic structure having 4 to 16 carbon atoms, and the ring may contain a hetero atom),
Or the following formula (4):

(In the formula (4), Z ₁ and Z ₂ are each independently a hydrogen atom, a halogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, an alkoxy group, an alkylthio group, or an alkylamino group. Or Z ₁ and Z ₂ may form a non-aromatic ring together)
A substituent represented by:
It is solved by a quinophthalone compound represented by:

The quinophthalone compound of the present invention has a high transmittance at 500 nm and a low transmittance at 470 nm (high light shielding rate). Therefore, the light absorption spectrum from the long wavelength side rises sharply. high. Moreover, the quinophthalone compound of the present invention has high solvent solubility in cyclohexanone. Furthermore, the quinophthalone compound of the present invention is excellent in heat resistance.

2 is a graph showing an absorption spectrum of a quinophthalone compound obtained in Example 1. FIG. 4 is a graph showing an absorption spectrum of a quinophthalone compound obtained in Example 2. FIG. 6 is a graph showing an absorption spectrum of a quinophthalone compound obtained in Example 3. FIG. 6 is a graph showing an absorption spectrum of a quinophthalone compound obtained in Example 4. FIG. 6 is a graph showing an absorption spectrum of a quinophthalone compound obtained in Example 5. FIG.

Hereinafter, the present invention will be described in detail.

The quinophthalone compound of the present invention is represented by the formula (1).

The compound represented by the formula (1) has a skeleton derived from (anhydrous) phthalic acid (substituent of 1,3-indandione skeleton) at the 2-position of the quinoline ring and 3- to 8-positions of the quinoline ring. Either has a substituent of an imide skeleton. By having a substituent of an imide skeleton having a large steric hindrance at any of the 3 to 8 positions of the quinoline ring, a decrease in solubility and a decrease in color purity due to the association between the dye molecules are effectively suppressed. It is preferable from the viewpoint of color purity. Further, the compound represented by the formula (1) has a stable structure in which the hydroxyl group of the 1,3-indandione skeleton and the nitrogen of the quinoline ring are hydrogen-bonded, and the quinoline ring 3 Since it has a substituent of imide skeleton at any of ˜8-positions, it has excellent heat resistance. On the other hand, the compound disclosed in Patent Document 1 further has a substituent of an aminoalkylsulfonamide skeleton at any of positions 3 to 7 of the quinoline ring.

Due to the difference in the structure, the quinophthalone compound represented by the formula (1) has high solubility in an organic solvent, particularly cyclohexanone, and is excellent in heat resistance. In addition, the compound represented by the formula (1) has a sharp absorption wavelength spectrum and high transmittance at 500 nm, so that the color purity as a yellow pigment is high, and the transmittance at 470 nm is low (the light shielding rate is high). Therefore, coloring power as a yellow pigment is high. The quinophthalone compound represented by the formula (1) has high color developability and exhibits yellow with high color purity. In the present specification, “high coloring power” means that the color density as a yellow dye is high, that is, the blue light shielding power per unit mass of the dye is high. That is, when the transmittance of light (blue light) at 470 nm is low (the light shielding rate is high), a yellow pigment with high coloring power is obtained. The present invention is not limited by the above estimation.

Next, the compound represented by the formula (1) will be specifically described.

In formula (1), each R ₁ independently represents a halogen atom or an alkyl group having 1 to 12 carbon atoms, and n represents an integer of 0 to 5.

In the present specification, the alkyl group includes any of straight chain, branched chain and cyclic unless otherwise specified.

Examples of the halogen atom for R ₁ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Of these, a fluorine atom, a chlorine atom, and a bromine atom are preferable.

The alkyl group in R ₁ is a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, preferably a linear or branched alkyl group having 1 to 8 carbon atoms. Specifically, methyl group, ethyl group, n-propyl group, isopropyl group, cyclopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, cyclobutyl group, n-pentyl group, isopentyl group Group, neopentyl group, 1,2-dimethylpropyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, 1,3-dimethylbutyl group, 1-isopropylpropyl group, 1,2-dimethylbutyl group, n-heptyl group 1,4-dimethylpentyl group, 2-methyl-1-isopropylpropyl group, 1-ethyl-3-methylbutyl group, cycloheptyl group, n-octyl group, 2-ethylhexyl group, nonyl group, decyl group, undecyl group And dodecyl group.

In the formula (1), n is an integer of 0 to 5, preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and further preferably 0 or 1.

In the formula (1), X ₁ to X ₄ each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, —COOR ₂ , —CONHR ₃ , —CONR ₃ R ₄ , —OR ₅ , -SR ₆ , -NHR ₇ , -NR ₇ R ₈ , or the following formula (2):

(In Formula (2), X ₆ is an oxygen atom or a sulfur atom, and m is an integer of 0 to 5)
It is a substituent represented by these.

Here, R ₂ to R ₈ are each independently an alkyl group having 1 to 12 carbon atoms, an alkoxyalkyl group having 2 to 8 carbon atoms which may be substituted with an arbitrary substituent, — (CH ₂ ) _p —CO—R ₁₀ (R ₁₀ is a linear or branched alkyl group having 1 to 8 carbon atoms, —COOR _a , —OCOR _b , —NHR _c , —NR _d R _e or —OR _f. In this case, R _a , R _b , R _c , R _d , R _e , and R _f are each independently an alkyl group having 1 to 8 carbon atoms, and p is an integer of 1 to 4 -(R ₁₁ O) _q -R ₁₂ (R ₁₁ is a linear or branched alkylene group having 1 to 3 carbon atoms, and R ₁₂ is a straight chain having 1 to 8 carbon atoms or Branched alkyl group, —COOR _a , —OCOR _b , —NHR _c , or —NR _d R _e , wherein R _a , R _b , R _c , R _d , and R _e are each independently an alkyl group having 1 to 8 carbon atoms, and q is an integer of 1 to 4 Or — (CH ₂ CH (OH) CH ₂ ) —R ₁₃ (R ₁₃ is a halogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, —COOR _a , —OCOR _b , —NHR _c , or —NR _d R _e , wherein R _a , R _b , R _c , R _d , and R _e are each independently an alkyl group having 1 to 8 carbon atoms) Yes,
R ₉ each independently represents a halogen atom, an alkyl group having 1 to 12 carbon atoms which may be substituted with an arbitrary substituent, — (CH ₂ ) _p —CO—R ₁₀ (R ₁₀ represents carbon A linear or branched alkyl group having 1 to 8 atoms, —COOR _a , —OCOR _b , —NHR _c , —NR _d R _e, or —OR _f , wherein R _a , R _b , R _c , R _d , R _e and R _f are each independently an alkyl group having 1 to 8 carbon atoms, and p is an integer of 1 to 4), — (R ₁₁ O) _q —R ₁₂ ( R ₁₁ is a linear or branched alkylene group having 1 to 3 carbon atoms, R ₁₂ is a linear or branched alkyl group having 1 to 8 carbon atoms, —COOR _a , —OCOR _b , an -NHR _c or _-NR d _{R e,,} this _{time, R a,} R _b, R , _R d, _{R e} are each independently an alkyl group having a carbon number of 1 ~ 8, q is an integer of _{1 ~ 4), - (CH} 2 CH (OH) CH 2) -R 13 (R ₁₃ is a halogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, —COOR _a , —OCOR _b , —NHR _c , or —NR _d R _e , where R _a , R _b , R _c , R _d and R _e are each independently an alkyl group having 1 to 8 carbon atoms), —COOR ₁₄ (R ₁₄ is a straight chain having 1 to 8 carbon atoms or A branched alkyl group or an alkoxyalkyl group having 2 to 8 carbon atoms), —CONHR ₁₅ (R ₁₅ is a linear or branched alkyl group having 1 to 8 carbon atoms, or 2 to 8 carbon atoms) alkoxyalkyl group), or -CONR ₁ R _{16 (R 15} and _{R 16} are each independently a linear or branched alkyl group or alkoxyalkyl group having 2 to 8 carbon atoms, having 1 to 8 carbon atoms) it is.

Here, specific examples of the halogen atom in X ₁ to X ₄ , R ₉ and R ₁₃ , and the alkyl group having 1 to 12 carbon atoms in X ₁ to X ₄ and R ₂ to R ₉ are given in the above R ₁ column. What has been described.

Examples of the alkoxyalkyl group having 2 to 8 carbon atoms in R ₂ to R ₈ (—R—OR ′, R = alkylene group, R ′ = alkyl group) include methoxymethyl group, methoxyethyl group, methoxybutyl group, ethoxy Methyl group, butoxymethyl group, n-propyloxymethyl group, n-pentyloxymethyl group, n-hexyloxymethyl group, n-heptyloxymethyl group, 1-ethyl-3-methylbutyloxymethyl group, methoxyethyl group , Ethoxyethyl group, n-propyloxyethyl group, isopropyloxymethyl group, isopropyloxyethyl group, n-butyloxyethyl group, isobutyloxyethyl group, sec-butyloxyethyl group, n-pentyloxyethyl group, isopentyl Oxyethyl group, neopentyloxyethyl group, 1,2-dimethyl Propyloxyethyl group, n-hexyloxyethyl group, 1,3-dimethylbutyloxyethyl group, 1,2-dimethylbutyloxyethyl group, methoxypropyl group, ethoxypropyl group, n-propyloxypropyl group, 1- Examples include methoxy-n-propyl group, 2-ethoxy-n-propyl group, 1-butoxy-n-propyl group, n-propyloxybutyl group, tert-butyloxybutyl group and the like. As the alkoxyalkyl group, the alkyl group (including the alkyl part of alkoxy) may be linear or branched.

R ₁₀ , R ₁₂ , R _13, R ₁₄ , R _15, R _16, R _a , R _b , R _c , R _d , R _e , R _f linear or branched alkyl having 1 to 8 carbon atoms Specific examples of groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, and neopentyl. Group, 1,2-dimethylpropyl group, n-hexyl group, 1,3-dimethylbutyl group, 1-isopropylpropyl group, 1,2-dimethylbutyl group, n-heptyl group, 1,4-dimethylpentyl group, Examples include 2-methyl-1-isopropylpropyl group, 1-ethyl-3-methylbutyl group, n-octyl group, 2-ethylhexyl group and the like.

Examples of the linear or branched alkylene group having 1 to 3 carbon atoms in R ₁₁ include a methylene group, an ethylene group, a methylmethylene group, a propylene group, a dimethylmethylene group, and a methylethylene group. p represents the number of repeating units of a methylene group (— (CH ₂ ) —) and is an integer of 1 to 4. In consideration of coloring power, p is preferably 1 or 2. q represents the number of repeating units of the oxyalkylene group (—R ₁₁ O—) and is an integer of 1 to 4. In consideration of coloring power, q is preferably 1 or 2.

Examples of the alkoxyalkyl group having 2 to 8 carbon atoms in R ₁₄ , R _{15 and} R ₁₆ include those described in the above R ₂ to R ₈ column.

In the formula (2), m is an integer of 0 to 5, preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and further preferably 0 or 1. Further, the bonding position of R ₉ is preferably the 2-position or the 3-position, and more preferably the 3-position.

In the present invention, at least one of X ₁ to X ₄ is an alkyl group having 1 to 12 carbon atoms, —COOR ₂ , —CONHR ₃ , —CONR ₃ R ₄ , —OR ₅ , —SR ₆ , —NHR ₇ , -NR ₇ R ₈ or the following formula (2):

It is preferable that it is a substituent represented by these. When at least one of X ₁ to X ₄ has the above substituent, the solubility of the quinophthalone compound can be further improved. In particular, among X ₁ to X ₄ , X ₂ or / and X ₃ are more preferably a substituent represented by the above substituent.

In the present invention, at least one of X ₁ to X ₄ is more preferably a halogen atom, —COOR ₂ , —SR ₆ , or a substituent represented by the above formula (2). In particular, among X ₁ to X ₄ , X ₂ or / and X ₃ is more preferably —COOR ₂ , —SR ₆ , or a substituent represented by the above formula (2). In this case, R ₂ is — (CH ₂ ) _p —CO—R ₁₀ (R ₁₀ is preferably a linear or branched alkyl group having 1 to 8 carbon atoms, and p is preferably 1 or 2). — (R ₁₁ O) _q —R ₁₂ (R ₁₁ is preferably a linear or branched alkylene group having 1 to 3 carbon atoms, and R ₁₂ is a linear or branched chain group having 1 to 8 carbon atoms. Preferably an alkyl group, q is preferably 1 or 2, or — (CH ₂ CH (OH) CH ₂ ) —R ₁₃ (R ₁₃ is preferably —OCOR _b and R _b is 1 carbon atom) Are preferred). R ₆ is — (CH ₂ ) _p —CO—R ₁₀ (R ₁₀ is preferably —OR _f , R _f is an alkyl group having 1 to 8 carbon atoms, and p is 1 or 2 Preferably).

When X ₁ to X ₄ are a substituent represented by the above formula (2), X ₆ is a sulfur atom or an oxygen atom, and the solubility of the compound represented by the formula (1) is further improved. From the viewpoint of coloring power, R ₉ is preferably 0 or 1, and when m is 1, —COOR ₁₄ (R ₁₄ is preferably an alkoxyalkyl group having 2 to 8 carbon atoms). ) Is preferred.

At least one of X ₁ to X ₄ is an alkyl group having 1 to 12 carbon atoms, —COOR ₂ , —CONHR ₃ , —CONR ₃ R ₄ , —OR ₅ , —SR ₆ , —NHR ₇ , —NR ₇ R ₈ Or a substituent represented by the above formula (2), and when at least one of the remaining X ₁ to X ₄ is a halogen atom, chlorine and fluorine are preferred from the viewpoint of coloring power and solubility, More preferred. In particular, when X ₁ to X ₄ have a halogen atom, the number of halogen atoms is preferably 1 to 3 and more preferably 1 or 2 from the viewpoint of solubility. Alternatively, when all of X ₁ to X ₄ are halogen atoms, from the viewpoint of coloring power and solubility, the halogen atom is preferably chlorine or fluorine, and more preferably fluorine.

The total number of carbon atoms present in X ₁ to X ₄ and R ₁ is preferably 3 or more. In consideration of solubility in cyclohexanone, the total number of carbon atoms is preferably 5 or more, and more preferably 7 or more. Presence of a certain number or more of carbon atoms in the compound increases the hydrophobicity of the compound and increases the solvent solubility.

In the formula (1), X ₅ is a substituent represented by the following formula (3) or (4).

In the formula (3), Y is an unsubstituted or substituted non-aromatic cyclic structure having 4 to 16 carbon atoms, and the ring may contain a hetero atom. Examples of the unsubstituted or substituted non-aromatic cyclic structure having 4 to 16 carbon atoms in Y include cycloalkanes such as cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane and cyclodecane; cyclobutene, cyclohexene Cycloalkenes such as cycloheptene and cyclooctene; Bicyclic alkanes such as bicyclohexane; Norbornane (bicyclo [2.2.1] heptane), Norbornene (bicyclo [2.2.1] hept-2-ene), Bicyclo [2.2.2] octane, bicyclo [2.2.2] oct-2-ene, tricyclo [2.2.1.0] heptane, 7-oxabicyclo [2.2.1] hepta-5 Ene, 7-azabicyclo [2.2.1] heptane, 1,4-diazabicyclo [2. .2] Polycyclic compounds such as octane (DABCO); azetidine (azacyclobutane), pyrrolidine, piperidine, piperazine, hexamethyleneimine, octacene (1,3-propylene oxide), tetrahydrofuran, tetrahydropyran, dioxane, hexamethylene oxide , Non-aromatic heterocycles containing oxygen, sulfur or / and nitrogen atoms, such as thietane (trimethylene sulfide), thiolane (tetrahydrothiophene), thiane, 1,4-dithiane, hexamethylene sulfide, etc. .

In the formula (4), Z ₁ and Z ₂ are each independently a hydrogen atom, a halogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, an alkoxy group, an alkylthio group, or an alkylamino group. Or Z ₁ and Z ₂ together may form a non-aromatic ring.

Specific examples of the halogen atom in Z ₁ and Z ₂ include those described in the above R ₁ column.

Specific examples of the alkyl group having 1 to 8 carbon atoms in Z ₁ and Z ₂ include those described in the above R ₁₀ , R ₁₂ , R _{13 and} R _a to R _e columns.

Specific examples of the alkoxy group having 1 to 8 carbon atoms in Z ₁ and Z ₂ include a methyloxy (methoxy) group, an ethyloxy (ethoxy) group, an n-propyloxy group, an isopropyloxy group, and an n-butyloxy group. , Isobutyloxy group, sec-butyloxy group, tert-butyloxy group, n-pentyloxy group, isopentyloxy group, neopentyloxy group, 1,2-dimethylpropyloxy group, n-hexyloxy group, 1,3- Dimethylbutyloxy group, 1-isopropylpropyloxy group, 1,2-dimethylbutyloxy group, n-heptyloxy group, 1,4-dimethylpentyloxy group, 2-methyl-1-isopropylpropyloxy group, 1-ethyl -3-methylbutyloxy group, n-octyloxy group, 2-ethylhexyloxy group Such as a group, and the like.

The alkylthio group having 1 to 8 carbon atoms (—SR, R = alkylene) in Z ₁ and Z ₂ specifically includes a methylthio group, an ethylthio group, an n-propylthio group, an isopropylthio group, and an n-butylthio group. , Isobutylthio group, sec-butylthio group, tert-butylthio group, n-pentylthio group, isopentylthio group, neopentylthio group, 1,2-dimethylpropylthio group, n-hexylthio group, 1,3-dimethylbutyl Thio group, 1-isopropylpropylthio group, 1,2-dimethylbutylthio group, n-heptylthio group, 1,4-dimethylpentylthio group, 2-methyl-1-isopropylpropylthio group, 1-ethyl-3- Examples thereof include a methylbutylthio group, an n-octyl group, and a 2-ethylhexylthio group.

The alkylamino group having 1 to 8 carbon atoms (—NHR or —NRR ′, R and R ′ = alkyl) in Z ₁ and Z ₂ specifically includes a methylamino group, a dimethylamino group, an ethylamino group Methylethylamino group, n-propylamino group, n-butylamino group, pentylamino group, n-hexylamino group, n-octylamino group, 2-ethylhexylamino group and the like.

When Z ₁ and Z ₂ together form a non-aromatic ring, examples of the non-aromatic ring include cycloalkenes such as cyclobutene, cyclohexene, cycloheptene, and cyclooctene; norbornene (bicyclo [ 2.2.1] hept-2-ene), bicyclic alkenes such as bicyclo [2.2.2] oct-2-ene; 1,4-dioxane-2-ene, 1,4-dithian-2 -Non-aromatic heterocycles containing oxygen, sulfur or / and nitrogen atoms such as -ene, 2-pyrroline, dihydropyran; and the like.

In the present invention, when X ₅ is represented by the formula (3), Y preferably has a cyclohexane skeleton, more preferably a cyclohexane skeleton and a bridged cyclic structure (which is a polycyclic compound). preferable. In particular, Y is preferably a bicyclic alkene such as norbornene (bicyclo [2.2.1] hept-2-ene), bicyclo [2.2.2] oct-2-ene. When X ₅ is represented by the formula (4), it is preferable that Z ₁ and Z ₂ are a hydrogen atom, or Z ₁ and Z ₂ are combined to form a non-aromatic ring. The non-aromatic ring is preferably a bicyclic alkene (preferably cyclohexene) or a non-aromatic heterocycle (preferably 1,4-dithian-2-ene).

In addition, the alkyl group and the substituent present in the non-aromatic cyclic structure are not particularly limited, and examples thereof include a halogen atom, a nitro group, a cyano group, an alkoxy group, a heterocyclic group, and an aryl group. , Hydroxy group, acyl group, alkyl group, phenyl group, halogenated alkyl group, halogenated alkoxyl group, amino group, alkylamino group, alkylcarbonylamino group, arylamino group, arylcarbonylamino group, carbonyl group, alkoxycarbonyl group An alkylaminocarbonyl group, an alkoxysulfonyl group, an alkylthio group, a carbamoyl group, an aryloxycarbonyl group, an oxyalkyl ether group and the like can be exemplified, but are not limited thereto. When a plurality of these substituents are present, they may be the same or different. Some of the above substituents are shown below with more specific examples.

First, among the substituents optionally present in the alkyl group and the non-aromatic cyclic structure, the halogen atom is a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, preferably a fluorine atom or a chlorine atom, and more Preferred is a fluorine atom.

Among the substituents optionally present in the alkyl group and non-aromatic cyclic structure, the alkoxy group includes, for example, an alkoxy group having 1 to 8 carbon atoms, specifically, a methoxy group, an ethoxy group, Examples thereof include linear, branched or cyclic alkoxy groups such as propoxy group, isopropoxy group, butoxy group, pentyloxy group, hexyloxy group, 2-ethylhexyloxy group and octyloxy group.

Of the substituents optionally present in the alkyl group and the non-aromatic cyclic structure, the heterocyclic group has 2 to 10 carbon atoms and is at least one selected from a nitrogen atom, an oxygen atom and a sulfur atom A heterocyclic group containing a heteroatom, and not limited to a monocyclic heterocyclic group, a condensed heterocyclic group in which a plurality of heterocyclic rings are condensed, a heterocyclic ring and a hydrocarbon ring (non-aromatic hydrocarbon ring or aromatic ring) A condensed heterocyclic group obtained by condensation (orthocondensation, orthoandpericondensation, etc.). The heterocyclic group may be non-aromatic or aromatic. Furthermore, in the condensed heterocyclic group in which the heterocyclic ring and the hydrocarbon ring are condensed, either the heterocyclic ring or the hydrocarbon ring may have a bond. As the heterocyclic group having a nitrogen atom as a hetero atom, a 5-membered or 6-membered monocyclic heterocyclic group such as a pyrrolyl group, an imidazolyl group, a pyridyl group, a pyrazinyl group, an indolyl group, a quinolyl group, an isoquinolyl group, a quinazolyl group, Examples thereof include a condensed heterocyclic group in which a 5-membered or 6-membered heterocyclic ring such as a carbazolyl group, a carbolinyl group, a phenanthridinyl group, an acridinyl group, or a phenazinyl group is condensed with a hydrocarbon ring. As the cyclic group, a 5-membered or 6-membered monocyclic heterocyclic group such as a furyl group (for example, a tetrahydrofurfuryl group), a 5-membered or 6-membered heterocyclic ring such as an isobenzofuranyl group or a chromenyl group is a hydrocarbon ring. Examples thereof include a condensed heterocyclic group condensed with the above. The heterocyclic group having a sulfur atom as a hetero atom includes a condensed heterocyclic ring in which a 5- or 6-membered monocyclic heterocyclic group such as a thienyl group or a 5- or 6-membered heterocyclic ring such as a thiantenyl group is condensed to a hydrocarbon ring Group etc. are included. In addition, examples of the heterocyclic group having different heteroatoms include 5-membered or 6-membered monocyclic groups such as morpholinyl group, isothiazolyl group and isoxazolyl group, and 5-membered or 6-membered heterocyclic rings such as phenoxathiinyl group. And a condensed heterocyclic group in which is condensed to a hydrocarbon ring. Preferred heterocyclic groups include 5- or 6-membered heterocyclic groups having at least a nitrogen atom as a hetero atom (pyrrolyl, pyridyl, etc.), 5- or 6-membered heterocyclic groups having at least a nitrogen atom as a hetero atom, and aromatic carbonization A heterocyclic group condensed with hydrogens (for example, a carbazolyl group) and the like are included. Of these, when considering particularly heat resistance such as heat resistance and solubility in organic solvents, specifically, a tetrahydrofurfuryl group, a 4-picolyl group, and the like are preferable.

Among the substituents optionally present in the above alkyl group and non-aromatic cyclic structure, the aryl group includes a phenyl group and a naphthyl group.

Examples of the acyl group include an acetyl group, an ethylcarbonyl group, a propylcarbonyl group, a butylcarbonyl group, a pentylcarbonyl group, a hexylcarbonyl group, a benzoyl group, and a pt-butylbenzoyl group. Among these, acetyl, An ethylcarbonyl group is preferred.

Among the above-mentioned alkyl groups and substituents optionally present in the non-aromatic cyclic structure, the alkyl group is a straight chain, branched chain or cyclic group having 1 to 20 carbon atoms, preferably 1 to 8 carbon atoms. A methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a neopentyl group, 1 , 2-dimethylpropyl group, n-hexyl group, cyclohexyl group, 1,3-dimethylbutyl group, 1-isopropylpropyl group, 1,2-dimethylbutyl group, n-heptyl group, 1,4-dimethylpentyl group, Examples include 2-methyl-1-isopropylpropyl group, 1-ethyl-3-methylbutyl group, n-octyl group, 2-ethylhexyl group and the like. Of these, a methyl group and an ethyl group are preferred.

Among the substituents optionally present in the above alkyl group and non-aromatic cyclic structure, the halogenated alkyl group is a linear or branched chain having 1 to 20 carbon atoms, preferably 1 to 8 carbon atoms. Alternatively, a part of the cyclic alkyl group is halogenated, and chloromethyl group, bromomethyl group, trifluoromethyl group, chloroethyl group, 2,2,2-trichloroethyl group, bromoethyl group, chloropropyl group, bromo A propyl group etc. are mentioned.

Among the substituents optionally present in the above alkyl group and non-aromatic cyclic structure, the halogenated alkoxyl group is a linear or branched chain having 1 to 20 carbon atoms, preferably 1 to 8 carbon atoms. Alternatively, a part of the cyclic alkoxyl group is halogenated, and chloromethoxy group, bromomethoxy group, trifluoromethoxy group, chloroethoxy group, 2,2,2-trichloroethoxy group, bromoethoxy group, chloropropoxy group Group, bromopropoxy group and the like.

Among the substituents optionally present in the above alkyl group and non-aromatic cyclic structure, the alkylamino group is an alkylamino having an alkyl moiety having 1 to 20 carbon atoms, preferably 1 to 8 carbon atoms. Methylamino, ethylamino, n-propylamino, n-butylamino, sec-butylamino, n-pentylamino, n-hexylamino, n-heptylamino, n- Examples include octylamino group, 2-ethylhexylamino group and the like. Of these, methylamino group, ethylamino group, n-propylamino group and n-butylamino group are preferred.

Of the substituents optionally present in the above-mentioned alkyl group and non-aromatic cyclic structure, the alkylcarbonylamino group includes an acetylamino group, an ethylcarbonylamino group, an n-propylcarbonylamino group, an iso-propylcarbonylamino group, n-butylcarbonylamino group, iso-butylcarbonylamino group, sec-butylcarbonylamino group, t-butylcarbonylamino group, n-pentylcarbonylamino group, n-hexylcarbonylamino group, cyclohexylcarbonylamino group, n-heptyl Examples thereof include a carbonylamino group, a 3-heptylcarbonylamino group, and an n-octylcarbonylamino group.

Among the substituents optionally present in the alkyl group and non-aromatic cyclic structure, the arylamino group includes a phenylamino group, a p-methylphenylamino group, a pt-butylphenylamino group, a diphenylamino group, Examples thereof include a di-p-methylphenylamino group and a di-pt-butylphenylamino group.

Among the substituents optionally present in the above alkyl group and non-aromatic cyclic structure, the arylcarbonylamino group includes a benzoylamino group, a p-chlorobenzoylamino group, a p-methoxybenzoylamino group, and a pt-butyl group. Examples thereof include a benzoylamino group, a p-trifluoromethylbenzoylamino group, and an m-trifluoromethylbenzoylamino group.

Among the substituents optionally present in the above alkyl group and non-aromatic cyclic structure, the alkoxycarbonyl group means 1 to 8 carbon atoms, preferably 1 which may contain a hetero atom in the alkyl group part of the alkoxyl group. Represents -5 alkoxycarbonyl, or cyclic alkoxycarbonyl having 3 to 8, preferably 5 to 8 carbon atoms which may contain heteroatoms. Specific examples include a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, an isopropoxycarbonyl group, an n-butoxycarbonyl group, an isobutoxycarbonyl group, a sec-butoxycarbonyl group, and a tert-butoxycarbonyl group. . Of these, a methoxycarbonyl group and an ethoxycarbonyl group are preferred.

Of the substituents optionally present in the above-mentioned alkyl group and non-aromatic cyclic structure, the alkylaminocarbonyl group includes a methylaminocarbonyl group, an ethylaminocarbonyl group, an n-propylaminocarbonyl group, and an n-butylaminocarbonyl group. Sec-butylaminocarbonyl group, n-pentylaminocarbonyl group, n-hexylaminocarbonyl group, n-heptylaminocarbonyl group, n-octylaminocarbonyl group, 2-ethylhexylaminocarbonyl group, dimethylaminocarbonyl group, diethylaminocarbonyl Group, di-n-propylaminocarbonyl group, di-n-butylaminocarbonyl group, di-sec-butylaminocarbonyl group, di-n-pentylaminocarbonyl group, di-n-hexylaminocarbonyl group, di-n - Heptyl aminocarbonyl group, di -n- octyl amino group and the like.

Among the substituents optionally present in the above alkyl group and non-aromatic cyclic structure, the alkylthio group includes methylthio group, ethylthio group, n-propylthio group, isopropylthio group, n-butylthio group, isobutylthio group, sec -Butylthio group, tert-butylthio group, n-pentylthio group, isopentylthio group, neopentylthio group, 1,2-dimethylpropylthio group, n-hexylthio group, 1,3-dimethylbutylthio group, 1-isopropyl Propylthio group, 1,2-dimethylbutylthio group, n-heptylthio group, 1,4-dimethylpentylthio group, 2-methyl-1-isopropylpropylthio group, 1-ethyl-3-methylbutylthio group, n -Octyl group, 2-ethylhexylthio group and the like.

In addition, the substituent which exists depending on the case does not become the same as the substituted group. For example, an alkyl group is not substituted with an alkyl group.

In the present invention, X _{5 of the} quinophthalone compound represented by the formula (1) is preferably substituted at the 4-position or 8-position of the quinoline ring. That is, the compound represented by the formula (1) is represented by the following formula (1-A) or the following formula (1-B):

(In the formulas (1-A) and (1-B), R ₁ , X ₁ to X ₅ , and n are as defined in the formula (1)).
It is preferable that it is a compound represented by these. If the quinophthalone compound has the above structure, the lower steric hindrance group X ₅ is substituted at the 4th or 8th position of the quinoline ring, so that the decrease in solubility and the decrease in color purity due to the association between the dye molecules are particularly suppressed. Therefore, it is preferable from the viewpoint of solubility and color purity.

In addition, the compound of the formula (1) has tautomers having the following structures in the common structure, and these tautomers are also within the scope of the right of the present invention.

As preferred embodiments of the compound represented by the formula (1), preferred embodiments of R ₁ and X ₁ to X ₅ are exemplified below.

In R _1, n is preferably 0.

In one preferred embodiment, X ₁ and X ₄ are a hydrogen atom or a halogen atom (preferably a fluorine atom or a chlorine atom).

In one preferred embodiment, X ₃ is a hydrogen atom, a halogen atom (preferably a fluorine atom or a chlorine atom), or a compound represented by the following formula:

A substituent selected from the group consisting of

In one preferred embodiment, X ₂ is a halogen atom (preferably a fluorine atom or a chlorine atom), or the following formula:

A substituent selected from the group consisting of

In one preferred embodiment, X ₅ is represented by the following formula:

A substituent selected from the group consisting of

As the above combination, the following compounds are exemplified as the compound represented by (1).

The method for producing the quinophthalone compound of the present invention is not particularly limited, and a conventionally known method can be appropriately used. Hereinafter, an embodiment of a method for producing a quinophthalone compound will be described.

First, an 8-amino-2-methylquinoline derivative represented by the following formula (I) (hereinafter also simply referred to as “aminoquinoline derivative”);

And a succinic anhydride derivative (II-1) or a maleic anhydride derivative (II-2);

And the following formula (III-1) or (III-2):

Is obtained. In the above formulas (I) to (III-2), R ₁ , Y, Z ₁ , Z ₂ , and n are defined by the structure of the desired quinophthalone compound. Specifically, these definitions are defined by the formula (I Since it is the same definition as the compound represented by 1), description thereof is omitted here.

At this time, the reaction molar ratio between the aminoquinoline derivative and the succinic anhydride derivative or maleic anhydride derivative (hereinafter, the two compounds are also referred to as “dicarboxylic anhydride”) is appropriately set depending on the compound. Usually, aminoquinoline derivative: dicarboxylic anhydride = 1: 0.95 to 1.50.

The above reaction may be performed in the absence of a solvent or in an organic solvent, but is preferably performed in an organic solvent. Examples of the solvent used at this time include dimethylformamide, dimethylacetamide, N-methylpyrrolidone, sulfolane, benzoic acid, benzonitrile, tetralin, dichlorobenzene, trichlorobenzene, toluene, xylene, and trimethylbenzene. The amount of the solvent used is appropriately adjusted depending on the reaction, but is such an amount that the total concentration of the aminoquinoline derivative and the dicarboxylic acid anhydride is usually 10 to 50% by weight.

In addition, the reaction conditions of the aminoquinoline derivative and the dicarboxylic acid anhydride are not particularly limited as long as the reaction proceeds to obtain the compound represented by the formula (III-1) or (III-2). Specifically, the reaction temperature is usually 40 to 200 ° C., preferably 40 to 160 ° C., and the reaction time is usually about 3 to 60 hours, preferably 5 to 45 hours.

If necessary, a catalyst such as acid or alkali may be used.

Next, a compound represented by (III-1) or (III-2) (hereinafter, the two compounds are also collectively referred to as “quinophthalone intermediate”), a substituted phthalic anhydride or a substituted phthalic acid, Can be reacted to obtain a quinophthalone compound. For example, as phthalic anhydride, trimellitic anhydride:

And the following formula (IV-1):

Is obtained. In the above formula (IV-1), R ₁ , X ₅ , and n are defined by the structure of the desired quinophthalone compound. Specifically, these definitions are the same as in the compound represented by the formula (1) Therefore, the description is omitted here.

At this time, the reaction molar ratio of the quinophthalone intermediate and trimellitic anhydride is appropriately set depending on the compound. Usually, the quinophthalone intermediate: trimellitic anhydride = 1: 0.95 to 1.50. is there.

The above reaction may be performed in the absence of a solvent or in an organic solvent, but is preferably performed in an organic solvent. Examples of the solvent used in this case include sulfolane, benzoic acid, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, benzonitrile, tetralin, dichlorobenzene, trichlorobenzene, trimethylbenzene, nitrobenzene and the like. The amount of the solvent used is appropriately adjusted depending on the reaction, but is such an amount that the total concentration of the quinophthalone intermediate and trimellitic anhydride is usually 10 to 50% by weight.

In addition, the reaction conditions of the quinophthalone intermediate and trimellitic anhydride are not particularly limited as long as the reaction proceeds to obtain the compound represented by the formula (IV-1). Specifically, the reaction temperature is usually 120 to 240 ° C., preferably 130 to 200 ° C., and the reaction time is usually about 1 to 50 hours, preferably 1.5 to 30 hours.

If necessary, a catalyst such as a metal salt may be used.

Next, a compound represented by the formula (IV-1), R _x —OH (R _x is an alkyl group having 1 to 12 carbon atoms), R _x —X (R _x is 1 to 12 carbon atoms) An alkyl group in which X is a halogen atom), R ₁₀ —CO— (CH ₂ ) _p-1 —CH ₂ —X (where R ₁₀ is as defined above, X is a halogen atom), and in some cases NH ₂ (R ₃ ) or NH (R ₃ ) (R ₄ ) (hereinafter “R _x —OH, R _x —X, R ₁₀ —CO— (CH ₂ ) _p−1 —CH ₂ —X, NH ₂ (R ₃ ) and NH (R ₃ ) (R ₄ ) ”, also simply referred to as“ reaction precursor ”), to give the following formula:

Can be obtained. In the above formula, R ₂ is defined by the structure of the desired quinophthalone compound. Specifically, R ₂ is —R _x (R _x is an alkyl group having 1 to 12 carbon atoms), —CH ₂ — (CH ₂ ) _p-1 —CO—R ₁₀ , —NH (R ₃ ), or —N (R ₃ ) (R ₄ ), wherein R ₃ , R ₄ , R ₁₀ , and p are of the formula ( The definition is the same as the compound represented by 1).

The reaction between the compound represented by the formula (IV-1) and the reaction precursor is an acid-catalyzed Fischer ester synthesis reaction, R _x —X or R ₁₀ —CO— (CH ₂ ) _p-1 —CH ₂ —. A reaction between X and a carboxylic acid, a dehydration condensation reaction between an amine compound (NH ₂ (R ₃ ) or NH (R ₃ ) (R ₄ )) and a carboxylic acid can be used. When performing the Fischer ester synthesis reaction by an acid catalyst, in order to advance an ester reaction, it is preferable to heat and reflux while dehydrating. As a dehydration method, a conventionally known method can be used. For example, water generated using a Dean-Stark trap or the like can be removed from the reaction system. The acid catalyst used is not particularly limited, and a conventionally known catalyst can be used. For example, p-toluenesulfonic acid monohydrate, acetic acid, hydrochloric acid, sulfuric acid, trifluoroacetic acid and the like can be used. When reacting R _x —X or R ₁₀ —CO— (CH ₂ ) _p-1 —CH ₂ —X with a carboxylic acid, potassium carbonate, sodium carbonate, sodium hydrogen carbonate or the like is preferably used as a base. When performing a dehydration condensation reaction between an amine compound and a carboxylic acid, a dehydration condensation agent (N, N′-dicyclohexylcarbodiimide, 1-hydroxybenzotriazole, etc.) is used, or a Fischer ester synthesis reaction using an acid catalyst is performed. It is necessary to perform the same treatment as before.

The reaction molar ratio between the compound represented by the formula (IV-1) and the reaction precursor is appropriately set depending on the desired compound. For example, the compound represented by the formula (IV-1): reaction precursor = 1: 0.95 to 1:10.

The reaction between the compound represented by the formula (IV-1) and the reaction precursor is preferably performed in an organic solvent. The solvent used in this case is not particularly limited, and benzene, toluene, xylene, dimethylformamide, sulfolane and the like can be used. The amount of the solvent used is appropriately adjusted depending on the reaction, but is such an amount that the total concentration of the compound represented by the formula (IV) and the reaction precursor is usually 5 to 50% by weight.

In addition, the reaction conditions for the compound represented by the formula (IV-1) and the reaction precursor are not particularly limited as long as the reaction proceeds to obtain the compound represented by the formula (IV-1). In the case of the Fischer ester synthesis reaction, specifically, the reaction temperature is usually 50 to 200 ° C., preferably 70 to 160 ° C., and the reaction time is usually about 0.5 to 48 hours, preferably 1 to 24 hours. is there. In the case of reaction of R _x —X or R ₁₀ —CO— (CH ₂ ) _p-1 —CH ₂ —X with a carboxylic acid, specifically, the reaction temperature is usually 40 to 150 ° C., preferably 60 to At 120 ° C., the reaction time is usually about 0.5 to 24 hours, preferably 1 to 12 hours. In the case of a dehydration condensation reaction between an amine compound and a carboxylic acid, specifically, the reaction temperature is usually 90 to 200 ° C., preferably 100 to 160 ° C., and the reaction time is usually about 1 to 30 hours, preferably 2 ~ 24 hours.

After the reaction, filtration, washing and drying may be performed according to a conventionally known method. Moreover, you may refine | purify well-known purification methods, such as recrystallization, reprecipitation, crystallization, and silica gel column chromatography, if needed, combining 1 type or multiple types. By such an operation, the quinophthalone compound can be obtained efficiently and with high purity.

Further, as a reaction precursor, a compound represented by the following formula (VI-1):

Is used, the compound represented by the formula (IV-1) is reacted with the compound represented by the formula (VI-1) to give the following formula:

Can be obtained. Here, in the above formula, R ₂ is — (CH ₂ CH (OH) CH ₂ ) —R ₁₃ , R ₁₃ is defined by the structure of the desired quinophthalone compound, and specifically, R ₁₃ is represented by the formula It is the same definition as the compound represented by (1).

The reaction of the compound represented by the formula (IV-1) and the compound represented by the formula (VI-1) can be performed by a known method.

The reaction molar ratio between the compound represented by the formula (IV-1) and the compound represented by the formula (VI-1) is appropriately set depending on the desired compound. For example, the compound represented by formula (IV-1): the compound represented by formula (VI-1) = 1: 0.95 to 1.50.

The reaction conditions of the compound represented by the formula (IV-1) and the compound represented by the formula (VI-1) are the same as those obtained by the reaction proceeding to obtain the compound represented by the formula (IV-1). If it is conditions, it will not restrict | limit in particular. Specifically, the reaction temperature is usually 40 to 150 ° C., preferably 50 to 120 ° C., and the reaction time is usually about 0.5 to 24 hours, preferably 1 to 12 hours. In carrying out the reaction, it is preferable to use tetrabutylammonium bromide, sodium hydrogen carbonate or the like as a catalyst.

The above reaction using the compound represented by the formula (VI-1) is preferably performed in an organic solvent. The solvent used in this case is not particularly limited, and dimethylformamide, dimethylacetamide, dimethyl sulfoxide, benzonitrile, acetonitrile and the like can be used. The amount of the solvent used is appropriately adjusted depending on the reaction, but the total concentration of the compound represented by the formula (IV) and the compound represented by the formula (VI-1) is usually 5 to 50% by weight. It is an amount.

In the above, trimellitic anhydride was used as an example. For example, quinophthalone intermediate and tetrachlorophthalic anhydride:

And the following formula (IV-2):

Is obtained. In the above formula (IV-2), R ₁ , X ₅ , and n are defined by the structure of the desired quinophthalone compound. Specifically, these definitions are the same as in the compound represented by the formula (1) Therefore, the description is omitted here.

At this time, the reaction molar ratio between the quinophthalone intermediate and the tetrachlorophthalic anhydride is appropriately set depending on the compound, but usually the quinophthalone intermediate: tetrachlorophthalic anhydride = 1: 0.95 to 1. 50.

The compound represented by the formula (IV-2) is still the quinophthalone compound of the present invention, but the compound represented by the formula (IV-2) may be reacted with a reaction precursor. In this case, examples of the reaction precursor include alkylthiol, benzenethiol, and phenol, each of which may have a substituent.

As described above, trimellitic acid anhydride and tetrachlorophthalic acid anhydride were used as examples. However, instead of the compound, pyromellitic acid anhydride, tetrafluorophthalic acid anhydride, etc. were used as appropriate. By using a synthetic method, a desired quinophthalone compound can be produced.

In addition, since each reaction described above has few by-products and the target compound can be obtained in high yield, the quinophthalone compound of the present invention can be obtained by OnePot (one pot) synthesis.

The quinophthalone compound of the present invention as described above has an absorption peak at 400 to 440 nm as the first absorption peak and at 450 to 480 nm as the second absorption peak. In the present invention, since the second absorption peak has a sharp rise from the long wavelength side and strong absorption, the transmittance at 470 nm is low, and it is suitably used as a yellow dye (yellow dye compound). it can.

Since the quinophthalone compound of the present invention has a high transmittance at 500 nm and a low transmittance at 470 nm (high light shielding rate), it is suitable as a color filter colorant having high yellow purity and high luminance. In the quinophthalone compound of the present invention, the transmittance at 470 nm is preferably 45% or less, more preferably 40% or less, still more preferably 35% or less, and particularly preferably 30% or less. In addition, since the one where the transmittance | permeability in 470 nm is smaller is preferable, a minimum in particular is not restrict | limited, However, It is 0% or more substantially. Further, the transmittance at 500 nm is preferably 70% or more, more preferably 75% or more, still more preferably 78% or more, and particularly preferably 80% or more. In addition, since the one where the transmittance | permeability in 500 nm is larger is preferable, an upper limit in particular is not restrict | limited, However, It is 100% or less substantially.

In the quinophthalone compound of the present invention, the transmittance at 470 nm (T ₄₇₀ ) and the transmittance at 500 nm (T ₅₀₀ ) are preferably 35% or more, more preferably 45% or more, The difference is preferably 55% or more, particularly preferably 60% or more, and most preferably 62% or more. In addition, since the one where the transmittance | permeability difference is larger is preferable, an upper limit in particular is not restrict | limited, but it is 100% or less substantially. Since the absorption wavelength has such a relationship, it can be a quinophthalone compound with high yellow purity, which is preferable.

In addition, the absorption peak and transmittance of the absorption spectrum of the quinophthalone compound described above mean values measured using a UV-visible spectrophotometer with a yellow color filter containing a quinophthalone compound prepared by the method described later.

The quinophthalone compound of the present invention is a solvent, particularly cyclohexanone (CHN) or N-methylpyrrolidone (NMP), propylene glycol 1-monomethyl ether 2-acetate, propylene glycol monomethyl ether, acetone, dimethylformamide, dimethyl sulfoxide, chloroform, Excellent solubility (compatibility) with toluene, ethyl acetate, tetrahydrofuran and the like, more preferably excellent solubility (compatibility) with cyclohexanone and N-methylpyrrolidone. The solvent solubility of the quinophthalone compound of the present invention is not particularly limited, and the higher the better. For example, the concentration of the quinophthalone compound relative to the amount of CHN required to dissolve the quinophthalone compound of the present invention is preferably 0.5% by weight or more, more preferably 1% by weight or more, and 2% by weight. More preferably, it is the above. Further, the concentration of the quinophthalone compound relative to the amount of NMP necessary for dissolving the quinophthalone compound of the present invention is preferably 0.5% by weight or more, more preferably 1% by weight or more, and 2% by weight. Is more preferable.

Thus, since the quinophthalone compound of the present invention is excellent in heat resistance and solvent solubility, it can be suitably used for various applications, particularly colorants for color filters.

Hereinafter, the use of the quinophthalone compound of the present invention will be described by taking a color filter colorant as an example. That is, the other form of this invention is the coloring agent for color filters using the quinophthalone compound of this invention.

The color filter colorant of the present invention is the same color filter colorant as in the past, such as JP 2011-197669 A and JP 2011-197670 A, except that it contains the quinophthalone compound of the present invention as a pigment. sell.

The composition of the colorant for a color filter of the present invention can be the same as a known composition except that it contains the quinophthalone compound of the present invention as a pigment. For example, the colorant for a color filter of the present invention contains a pigment, a resin, and a solvent.

The colorant for color filter of the present invention must contain the quinophthalone compound of the present invention as a pigment. Here, the amount of the quinophthalone compound of the present invention is not particularly limited, but is preferably 1 to 40% by weight, more preferably 3 to 30% by weight, based on the total weight of the colorant. Within such a range, a colorant having an appropriate color density can be obtained. In addition, the quinophthalone compound of the present invention may be used alone or in the form of a mixture of two or more.

The color filter colorant of the present invention may be used in combination with other pigments or dyes. Other pigments or dyes are not particularly limited, and known pigments or dyes can be used. The other pigments or dyes may be used alone or in the form of a mixture of two or more.

Examples of other pigments or dyes used in the color filter colorant of the present invention include green dyes. By using a green pigment, when used as a color filter, its color purity and brightness can be improved. At this time, the quinophthalone compound used in the present invention can be used for the complementary color of the green dye. The green colorant that can be used is not particularly limited, and specifically, International Publication No. 2011/010733, International Publication No. 2011/105603, JP 2010-265254 A, JP 2009-108135 A, The phthalocyanine pigments and phthalocyanine dyes described in Japanese Patent Application Laid-Open No. 2003-161827 can be suitably used as the phthalocyanine compound.

The green pigment may be used alone or in the form of a mixture of two or more. Further, the amount of the green colorant when using the green colorant is not particularly limited as long as it does not inhibit the effect of the quinophthalone compound of the present invention, and is appropriately determined in consideration of the desired color purity, luminance, and the like. You can choose. The amount of the green pigment is preferably 2 to 20 parts by weight, more preferably 4 to 10 parts by weight, based on 100 parts by weight of the color filter colorant.

In addition, the color filter colorant of the present invention may contain a compound of a known resin (photosensitive resin composition) as necessary. The resin (photosensitive resin composition) that can be used in the present invention undergoes a chemical reaction by the action of light, resulting in a change in solubility or affinity for the solvent, or a change from liquid to solid. I just need it. For example, light obtained by using an acrylic or maleimide resin liquid as a binder resin (base polymer), and adding a photosensitive monomer (photopolymerizable monomer) or photopolymerization initiator composed of various acrylic esters or methacrylic esters. A photopolymerization type photosensitive resin composition or a photodimerization type photopolymer resin composition using an acrylic resin liquid that undergoes photodimerization may be mentioned. Among these, a photopolymerization type photopolymer resin composition is preferred.

As the acrylic or maleimide resin, at least 10% by weight of monomers and oligomers constituting the acrylic resin or maleimide resin are selected from compounds having acrylic acid, methacrylic acid, acrylic acid ester, methacrylic acid ester and maleimide group. The compound having an acrylic acid, methacrylic acid or maleimide group is preferably 1 to 50% by weight, more preferably 5 to 35% by weight, and acrylic acid ester or methacrylic acid is preferably 10 to 90 parts by weight, more preferably 30%. Contains up to 80% by weight.

As monomers constituting the acrylic system, (meth) acrylic acid, methyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, benzyl (meth) ) Acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (meth) acrylamide, N-hydroxymethylacrylamide, acrylonitrile, styrene, vinyl acetate, maleic acid, fumaric acid, N-phenylmaleimide, Polyethylene glycol diacrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipen Hexa (meth) acrylate dipentaerythritol hexa (meth) caprolactone adduct acrylate, melamine (meth) acrylate, epoxy (meth) acrylate prepolymer and the like.

As monomers constituting the maleimide resin, fragrances such as N-phenylmaleimide, N-benzylmaleimide, N-hydroxyphenylmaleimide, N-methylphenylmaleimide, N-methoxyphenylmaleimide, N-chlorophenylmaleimide, N-naphthylmaleimide, etc. In addition to group-substituted maleimides, alkyl-substituted maleimides such as N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide and N-cyclohexylmaleimide can be exemplified.

In addition, examples of the photosensitive monomer that can be a component of the photosensitive resin composition of the present invention include monomers that constitute the acrylic resin, and preferably trimethylolpropane trimethacrylate, dipentaerythritol hexaacrylate, pentaerythritol. Examples include polyfunctional (meth) acrylates such as triacrylate and pentaerythritol tetraacrylate.

Examples of the photopolymerization initiator that can be a composition component of the photopolymerizable photosensitive resin composition include, for example, benzoin alkyl ether compounds, acetophenone compounds, benzophenone compounds, phenyl ketone compounds, thioxanthone compounds, triazine compounds, Examples include imidazole compounds and anthraquinone compounds. More specifically, acetophenone compounds such as Irgacure 369 and Irgacure 907 (both manufactured by Nippon Ciba Geigy Co., Ltd.) can be used.

The addition amount of the photopolymerization initiator is not particularly limited, but for acetophenone compounds (IRGACURE (Irgacure) 369, etc.), the non-volatile content (component excluding the solvent) in the colorant composition is 100 wt. It is desirable that 0.1 to 15 parts by weight, more preferably 0.5 to 10 parts by weight is added.

In addition, an optional component such as a thermal polymerization inhibitor can be added to the color filter colorant composition of the present invention, if necessary. The thermal polymerization inhibitor is added for the purpose of improving storage stability. For example, hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4 , 4′-thiobis (3-methyl-6-tert-butylphenol), 2,2′-methylene (4-methyl-6-tert-butylphenol), 2- (mercaptobenzimidazole), and the like. Moreover, you may add a photodegradation prevention agent as needed.

The blending amount of the resin (photosensitive resin composition) in the color filter colorant of the present invention is not particularly limited, but is preferably 1 to 50 parts by weight with respect to 100 parts by weight of the colorant, and 5 to 30 parts by weight. Is more preferable.

The colorant for color filter of the present invention can further contain a solvent.

The solvent is not particularly limited as long as it can dissolve a yellow dye compound. For example, toluene, xylene, benzene, ethylbenzene, tetralin, cyclohexane, cyclohexanol, methyl cellosolve, n-propanol, n-butanol, 2-ethylbutanol, n-heptanol, 2-ethylhexanol, butoxyethanol, diacetone alcohol, benzaldehyde , Γ-butyrolactone, acetone, methyl ethyl ketone, dibutyl ketone, methyl-i-butyl ketone, methyl-i-amyl ketone, acetophenone, methylal, furan, dioxane, tetrahydrofuran, ethyl acetate, n-butyl acetate, amyl acetate, cyclohexylamine, ethanolamine , Dimethylformamide, acetonitrile, nitromethane, nitroethane, 2-nitropropane, nitrobenzene, dimethylsulfoxide Diethylene glycol dimethyl ether, diethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol 1-monomethyl ether 2-acetate, cyclohexanone, N- methylpyrrolidone and the like. Among these, from the viewpoint of boiling point and viscosity, propylene glycol 1-monomethyl ether 2-acetate, propylene glycol monomethyl ether, diethylene glycol dimethyl ether, cyclohexanone, N-methylpyrrolidone and the like are preferable.

The amount of the solvent in the colorant for the color filter is not particularly limited, but is preferably 0 to 85 parts by weight and more preferably 0 to 80 parts by weight with respect to 100 parts by weight of the colorant. Moreover, the said solvent means the total amount including the said solvent, when it melt | dissolves in the solvent with the component of the resin shown above, for example.

Further, the color filter colorant of the present invention may further contain a dispersant. In particular, when a pigment is used as the coloring matter, it is preferable to include a dispersant since the dispersion stability of the colorant is increased by using the dispersant. Moreover, since the dye containing a yellow pigment or a green pigment is usually dissolved in the polymer resin, a dispersant is not essential. However, since the dye may have a high concentration (for example, about 30 wt%) in the color filter, if a dispersant is used to prevent the aggregation and precipitation, an effect of improving luminance and contrast can be obtained.

Here, as the dispersant used in the present invention, a known dispersant can be used. Representative examples of such dispersants include, for example, polyurethane-based high molecular weight wetting and dispersing agents in organic solvent systems, carboxylic acid esters such as polyacrylates, unsaturated polyamides, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, By reaction of polycarboxylic acid alkylamine salt, polysiloxane, long-chain polyaminoamide phosphate, hydroxyl group-containing polycarboxylic acid ester and their modified products, poly (lower alkyleneimine) and polyester having a free carboxylic acid group Formed amides and salts thereof; in water, (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinyl Water-soluble polymer compounds such as pyrrolidone; sodium lauryl sulfate , Polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkyl naphthalene sulfonate, sodium alkyl diphenyl ether disulfonate, lauryl sulfate monoethanolamine, lauryl Anionic surfactants such as triethanolamine sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate; Polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate ester Nonionic surfactants such as polyoxyethylene sorbitan monostearate and polyethylene glycol monolaurate; alkylbetaines such as alkyldimethylaminoacetic acid betaine and amphoteric surfactants such as alkylimidazoline, which may be used alone or in combination. A mixture of seeds or more can be used.

In addition, the color filter colorant composition of the present invention may contain a compound such as a known dispersion aid, if necessary. These compounds are compounds that mediate between the pigment and the dispersant, and are considered to have a function of improving dispersion stability by being electrically and chemically adsorbed to the pigment surface and the dispersant.

Examples of such a dispersion aid include anionic active agents such as polycarboxylic acid type polymer activators and polysulfonic acid type polymer activators, and nonionic activators such as polyoxyethylene and polyoxylene block polymers. Are preferable, anthraquinone, phthalocyanine, metal phthalocyanine, quinacridone, azo chelate, azo, isoindolinone, pyranthrone, indanthrone, anthrapyrimidine, dibromoanthanthrone, flavanthrone And pigment derivatives based on organic pigments such as perylene-based, perinone-based, quinophthalone-based, thioindigo-based, dioxazine-based, etc., and introduced with substituents such as hydroxyl group, carboxyl group, sulfonic acid group, carbonamide group, and sulfonamide group. It is done. Of these, phthalocyanine-based and metal phthalocyanine sulfonamide compounds are particularly effective.

The color filter colorant of the above form can be produced by a known method. For example, the colorant for a color filter of the present invention contains the quinophthalone compound of the present invention as an essential component, and if necessary, other dyes (pigments or dyes), solvents, resins, dispersants, dispersion aids, and the like. Other additives and the like may be blended. The colorant for the color filter preferably contains a quinophthalone compound, and further contains a solvent, another pigment (pigment or dye), and a resin (photosensitive resin composition) containing a polymerization initiator. In this case, since each component is the same as the above definition, the description is omitted here. The method for producing the colorant for a color filter of the present invention is not particularly limited, but can be obtained by mixing and dissolving the above components.

As explained in the Background section, color filters used in liquid crystal displays and imaging devices are generally composed of a transparent substrate such as glass, red, green, and blue primary color pixels and a light-shielding layer provided between these pixels. It is manufactured by forming a black matrix.

The method for producing a color filter can be applied by referring to known knowledge as appropriate or in combination. For example, the method disclosed in Japanese Patent Application Laid-Open No. 10-160921 is preferable for producing a color filter, but is not limited thereto.

Next, a process for applying a color filter colorant on a glass substrate will be described. First, a black matrix is formed on a glass substrate. Next, a colorant comprising the quinophthalone compound of the present invention and, if necessary, other green pigment, solvent, resin (photosensitive resin composition), dispersant, etc., is spin coated on a glass substrate, etc. Apply and dry. Next, after that, exposure is performed through a photomask as necessary. Thereafter, alkali development is performed as necessary to obtain a colored pattern (colored layer). Thereafter, if necessary, a transparent overcoat layer (protective film) is formed to protect the colored layer and flatten the surface. Furthermore, a transparent conductive film is formed as needed. In this way, a color filter can be obtained.

The quinophthalone compound of the present invention has sufficient heat resistance to withstand the drying process at the time of producing a color filter, has a high transmittance at 500 nm after the drying process, and a low transmittance at 470 nm (high light shielding rate). . Therefore, whether the quinophthalone compound of the present invention is used alone as a yellow pigment or as a yellow pigment for toning green pixels, the quinophthalone contained in the color filter colorant of the present invention is used. Depending on the compound, the color filter produces a bright yellow color. In addition, since the quinophthalone compound contained in the color filter colorant of the present invention is excellent in solvent solubility, a stable dissolved state can be maintained in the color filter colorant.

Note that this application is based on Japanese Patent Application No. 2011-265188 filed on December 2, 2011, the disclosure of which is incorporated by reference in its entirety.

The effect of the present invention will be described using the following examples and comparative examples. However, the technical scope of the present invention is not limited only to the following examples.

<Synthesis of Intermediate>
(Synthesis of Intermediate (1))

In a 100 mL two-necked reaction vessel, 5.00 g of 5-norbornene-2,3-dicarboxylic anhydride, 4.81 g of 8-amino-2-methylquinoline, and 39 g of dimethylformamide were added. After stirring at 40 ° C. for 2 hours, the temperature was raised to 100 ° C. and reacted for another 40 hours. The reaction solution was slowly discharged into water, and the precipitate was collected by filtration. The filtrate was transferred to a beaker, stirred and washed with a small amount of methanol, further added with water, stirred and filtered to obtain the desired intermediate (1) in 8.85 g in a yield of 95.6%. It was.

(Synthesis of intermediate (2))

In a 100 mL two-necked reaction vessel, 8.71 g of methyl-5-norbornene-2,3-dicarboxylic acid anhydride (manufactured by Hitachi Chemical: MHAC-P), 6.39 g of 8-amino-2-methylquinoline, dimethylformamide The target intermediate (2) was obtained in the same manner as in the intermediate (1) except that 36 g was added, in an amount of 11.39 g in a yield of 88.4%.

(Synthesis of intermediate (3))

An intermediate was obtained except that 2.30 g of 1-cyclohexene-1,2-dicarboxylic anhydride, 2.00 g of 8-amino-2-methylquinoline, and 6.00 g of dimethylformamide were added to a 50 mL two-necked reaction vessel. By the same method as (1), 2.40 g of the target intermediate (3) was obtained in a yield of 79.7%.

(Synthesis of intermediate (4))

In the same manner as in Intermediate (1), except that 1.36 g of maleic anhydride, 2.00 g of 8-amino-2-methylquinoline, and 6.01 g of dimethylformamide were added to a 50 mL two-necked reaction vessel. 2.50 g of the target intermediate (4) was obtained in a yield of 83.0%.

(Synthesis of intermediate (5))

Except that 2.31 g of cis-4-cyclohexene-1,2-dicarboxylic anhydride, 2.00 g of 8-amino-2-methylquinoline, and 6.01 g of dimethylformamide were added to a 50 mL two-necked reaction vessel, By a method similar to that for the intermediate (1), 3.38 g of the target intermediate (5) was obtained in a yield of 91.3%.

(Synthesis of intermediate (6))

An intermediate (except for the addition of 1.94 g of cis-1,2-cyclohexanedicarboxylic acid anhydride, 2.00 g of 8-amino-2-methylquinoline, and 15 g of N-methylpyrrolidone was added to a 50 mL two-necked reaction vessel. By the same method as in 1), 3.16 g of the target intermediate (6) was obtained in a yield of 84.9%.

<Synthesis of quinophthalone compound>
(Synthesis of quinophthalone compound (1))

In a 25 ml reaction vessel, 2.00 g of intermediate (1), 1.33 g of trimellitic anhydride and 13.3 g of sulfolane were added, and the temperature was raised to 158 ° C. and reacted for 18 hours. After completion of heating, the mixture was allowed to cool and then slowly discharged into water, and the precipitate was collected by filtration. The filtrate was transferred to a beaker, washed with a small amount of methanol, stirred, added with water, and filtered. The residue was dried under reduced pressure at 70 ° C. overnight to obtain 2.59 g of quinophthalone compound (1) in a yield of 82.4%.

(Synthesis of quinophthalone compound (1) -1)

A 25 ml three-necked reaction vessel was charged with 0.7 g of quinophthalone compound (1), 0.98 g of 1-chloropinacholine, 0.31 g of sodium bicarbonate, and 10.1 g of dimethylformamide and heated at 120 ° C. for 1 hour. After completion of the reaction, the mixture was allowed to cool and then slowly discharged into water, and the precipitate was collected by filtration. The filtrate was transferred to a beaker, washed with a small amount of methanol, stirred, added with water, and filtered. The residue was dried under reduced pressure at 70 ° C. overnight and purified by silica gel column chromatography (solvent: ethyl acetate) to obtain 0.62 g of quinophthalone compound (1) -1 in a yield of 73.5%.

(Synthesis of quinophthalone compound (1) -2)

A 25 ml three-necked reaction vessel was charged with 0.5 g of quinophthalone compound (1), 0.72 g of n-bromobutane, 0.22 g of sodium bicarbonate, and 7.3 g of dimethylformamide and heated at 120 ° C. for 1 hour. After completion of the reaction, the mixture was allowed to cool and then slowly discharged into water, and the precipitate was collected by filtration. The filtrate was transferred to a beaker, washed with a small amount of methanol, stirred, added with water, and filtered. The residue was dried under reduced pressure at 70 ° C. overnight to obtain 0.46 g of quinophthalone compound (1) -2 in a yield of 87.6%.

(Synthesis of quinophthalone compound (1) -3)

A 50 ml three-necked reaction vessel was charged with 1.41 g of quinophthalone compound (1), 0.51 g of butyric acid (S) -glycidyl, 0.10 g of tetrabutylammonium bromide, and 15 g of dimethylformamide and heated at 120 ° C. for 2 hours and 30 minutes. . After completion of the reaction, the mixture was allowed to cool and then slowly discharged into water, and the precipitate was collected by filtration. The residue was dried and purified by silica gel column chromatography (solvent: 50% ethyl acetate-50% hexane mixed solvent) to obtain 1.15 g of quinophthalone compound (1) -3 in a yield of 62.7%. It was.

(Synthesis of quinophthalone compound (2))

In a 25 ml reaction vessel, 2.50 g of intermediate (1), 2.36 g of tetrachlorophthalic anhydride and 20 g of sulfolane were added, and the temperature was raised to 138 ° C. and reacted for 8 hours. After heating, the mixture was allowed to cool and then slowly discharged into water. After stirring for 1 hour, the precipitate was collected by filtration. The dried product was dried and then transferred to a beaker, and ethyl acetate was added thereto, followed by stirring and washing, followed by filtration. The residue was dried under reduced pressure at 70 ° C. overnight to obtain 1.47 g of quinophthalone compound (2) in a yield of 33%.

(Synthesis of quinophthalone compound (2) -1)

A 50 ml three-necked reaction vessel was charged with 0.45 g of quinophthalone compound (2), 0.23 g of ethyl thioglycolate, 0.30 g of potassium carbonate, and 5 g of N-methylpyrrolidone, and heated at 100 ° C. for 3 hours. After completion of the reaction, the mixture was allowed to cool and then slowly discharged into water, extracted with ethyl acetate, and washed with water. After concentration, purification by silica gel column chromatography (solvent: 50% ethyl acetate-50% hexane mixed solvent) gave 0.18 g of quinophthalone compound (2) -1 in a yield of 12.7%.

(Synthesis of quinophthalone compound (3))

Intermediate (2) 5.00 g, trimellitic anhydride 3.16 g, and sulfolane 32 g were added to a 25 ml reaction vessel, heated to 158 ° C. and reacted for 20 hours. After completion of heating, the mixture was allowed to cool and then slowly discharged into water, and the precipitate was collected by filtration. The filtrate was transferred to a beaker, washed with a small amount of methanol, stirred, added with water, and filtered. The residue was dried under reduced pressure at 70 ° C. overnight to obtain 3.98 g of quinophthalone compound (3) in a yield of 51.5%.

(Synthesis of quinophthalone compound (3) -1)

A 25 ml three-necked reaction vessel was charged with 1.5 g of quinophthalone compound (3), 2.1 g of 1-chloropinacholine, 0.66 g of sodium hydrogen carbonate and 21 g of dimethylformamide, and heated at 120 ° C. for 2 hours. After completion of the reaction, the mixture was allowed to cool and then slowly discharged into water, extracted with ethyl acetate, and washed with water. After drying with sodium sulfate, it is concentrated and purified by silica gel column chromatography (solvent: 50% ethyl acetate-50% hexane) to obtain 0.8 g of quinophthalone compound (3) -1 in a yield of 43.2%. Obtained.

(Synthesis of quinophthalone compound (4))

In a 50 ml reaction vessel, 0.96 g of intermediate (3), 0.98 g of tetrachlorophthalic anhydride and 6 g of sulfolane were charged, heated to 140 ° C. and reacted for 10 hours. After heating, the mixture was allowed to cool and then slowly discharged into water. After stirring for 1 hour, the precipitate was collected by filtration. The dried product was dried and then transferred to a beaker, and ethyl acetate was added thereto, followed by stirring and washing, followed by filtration. The residue was dried under reduced pressure at 60 ° C. overnight to obtain 0.40 g of quinophthalone compound (4) in a yield of 21.7%.

(Synthesis of quinophthalone compound (4) -1)

A 25 ml reaction vessel was charged with 0.30 g of quinophthalone compound (4), 0.11 g of p-hydroxybenzoic acid methoxyethyl ester, 0.11 g of sodium bicarbonate and 1.00 g of acetonitrile, heated at 40 ° C. for 2 hours, and then heated to 60 ° C. The temperature was raised to and the reaction was further continued for 2 hours. After completion of the reaction, the mixture was filtered, and the filtrate was slowly discharged into water. After stirring for 1 hour, the precipitate was collected by filtration. The residue was dried under reduced pressure at 60 ° C. overnight to obtain 0.13 g of quinophthalone compound (4) -1 in a yield of 33.7%.

(Synthesis of quinophthalone compound (5))

In a 50 ml reaction vessel, 1.00 g of intermediate (3), 0.78 g of tetrofluorophthalic anhydride and 5 g of sulfolane were charged, heated to 140 ° C., and reacted for 8 hours. After heating, the mixture was allowed to cool and then slowly discharged into water. After stirring for 1 hour, the precipitate was collected by filtration. The dried product was dried and then transferred to a beaker, and ethyl acetate was added thereto, followed by stirring and washing, followed by filtration. The residue was dried under reduced pressure at 60 ° C. overnight to obtain 0.73 g of quinophthalone compound (5) in a yield of 43.2%.

(Synthesis of quinophthalone compound (5) -1)

A 25 ml reaction vessel was charged with 0.50 g of quinophthalone compound (5), 0.21 g of methoxyethyl p-hydroxybenzoate, 0.10 g of potassium fluoride and 1.58 g of acetone, heated at 40 ° C. for 2 hours, and then heated to 60 ° C. The temperature was raised to and the reaction was further continued for 2 hours. After completion of the reaction, the mixture was filtered, and the filtrate was slowly discharged into water. After stirring for 1 hour, the precipitate was collected by filtration. The residue was dried under reduced pressure at 60 ° C. overnight to obtain 0.08 g of quinophthalone compound (5) -1 in a yield of 11.8%.

(Synthesis of quinophthalone compound (6))

Intermediate (4) 0.40 g, pyromellitic anhydride 0.44 g and sulfolane 1.68 g were added to a 25 ml reaction vessel, heated to 160 ° C. and reacted for 18 hours. After completion of heating, the mixture was allowed to cool and then slowly discharged into water, and the precipitate was collected by filtration. The filtrate was transferred to a beaker, washed with a small amount of methanol, stirred, added with water, and filtered. The residue was dried under reduced pressure at 60 ° C. overnight to obtain 0.51 g of quinophthalone compound (6) in a yield of 69.3%.

(Synthesis of quinophthalone compound (6) -1)

To a 25 ml reaction vessel were added 0.20 g of quinophthalone compound (6), 1.44 g of 2-methoxypropanol and 0.12 g of paratoluenesulfonic acid monohydrate, and the temperature was raised to 140 ° C. and reacted for 6 hours. After completion of heating, the mixture was allowed to cool and then slowly discharged into water, and the precipitate was collected by filtration. The filtrate was transferred to a beaker, washed with a small amount of methanol, stirred, added with water, and filtered. The residue was dried under reduced pressure at 60 ° C. overnight to obtain 0.08 g of quinophthalone compound (6) -1 in a yield of 29.2%.

(Synthesis of quinophthalone compound (7))

To a 25 ml reaction vessel, 2.0 g of intermediate (5), 1.45 g of pyromellitic anhydride and 10 g of benzoic acid were added, heated to 180 ° C. and reacted for 10 hours. After heating, the mixture was allowed to cool and then slowly discharged into methanol, and the precipitate was collected by filtration. The filtrate was transferred to a beaker, stirred and washed with a small amount of methanol, and then filtered. The residue was dried under reduced pressure at 60 ° C. overnight to obtain 2.01 g of quinophthalone compound (7) in a yield of 63%.

(Synthesis of quinophthalone compound (7) -1)

A 25 ml three-necked reaction vessel was charged with 1.5 g of quinophthalone compound (7), 2.16 g of 1-chloropinacholine, 0.81 g of sodium hydrogen carbonate and 10 g of dimethylformamide, and heated at 120 ° C. for 2 hours. After completion of the reaction, the mixture was allowed to cool and then slowly discharged into water, extracted with ethyl acetate, and washed with water. After drying with sodium sulfate, it is concentrated and purified by silica gel column chromatography (solvent: 50% ethyl acetate-50% hexane) to obtain 0.97 g of quinophthalone compound (7) -1 in a yield of 53.5%. Obtained.

(Synthesis of quinophthalone compound (8))

In a 25 ml reaction vessel, 2.0 g of intermediate (6), 1.44 g of pyromellitic anhydride and 15 g of benzoic acid were added, and the temperature was raised to 180 ° C. and reacted for 10 hours. After heating, the mixture was allowed to cool and then slowly discharged into methanol, and the precipitate was collected by filtration. The filtrate was transferred to a beaker, stirred and washed with a small amount of methanol, and then filtered. The residue was dried under reduced pressure at 60 ° C. overnight to obtain 1.87 g of quinophthalone compound (8) in a yield of 59.5%.

(Synthesis of quinophthalone compound (8) -1)

A 25 ml three-necked reaction vessel was charged with 1.5 g of quinophthalone compound (8), 2.16 g of 1-chloropinacholine, 0.81 g of sodium hydrogen carbonate and 10 g of dimethylformamide, and heated at 120 ° C. for 2 hours. After completion of the reaction, the mixture was allowed to cool and then slowly discharged into water, extracted with ethyl acetate, and washed with water. After drying with sodium sulfate, it is concentrated and purified by silica gel column chromatography (solvent: 50% ethyl acetate-50% hexane) to obtain 1.24 g of quinophthalone compound (8) -1 in a yield of 84.3%. Obtained.

(Synthesis of quinophthalone compound (2)) (OnePot synthesis)

In a 100 mL two-necked reaction vessel, 3.90 g of 5-norbornene-2,3-dicarboxylic acid, 3.02 g of 8-amino-2-methylquinoline, and 25 g of dimethylformamide were added. After stirring at 40 ° C. for 2 hours, the temperature was raised to 100 ° C. and reacted for another 40 hours. Thereafter, 5.45 g of tetrachlorophthalic anhydride and 10 g of sulfolane were further added to the reaction vessel, and the temperature was raised to 150 ° C. and reacted for 12 hours. After completion of the reaction, the reaction mixture was allowed to cool and discharged into water, and the precipitate was collected by filtration. The filtrate was transferred to a beaker, stirred and washed with methanol, and filtered. Further, the filtrate was transferred to a beaker, stirred and washed with ethyl acetate, filtered, and dried under reduced pressure at 70 ° C. overnight to obtain 5.1 g of the desired quinophthalone compound (2), yield 37.5%. Got in.

[Evaluation]
For the synthesized quinophthalone compound, transmittance measurement, heat resistance evaluation, and solubility test were performed by the methods described below.

Example 1
A color filter containing a quinophthalone compound was prepared according to the following method, and the transmittance of the obtained filter was measured. The results are shown in Table 2.

(A) Preparation of resist solution (colorant composition for color filter) A resist solution (colorant composition) was prepared by mixing and dissolving the compositions shown in Table 1 below.

(B) Preparation of coating film plate The surface of a glass substrate was previously wiped with acetone. The resist solution obtained in (a) was spin-coated on this glass substrate under the conditions of 1600 rpm and 1.5 seconds, and prebaked at 80 ° C. for 30 minutes. Then, after being cured by UV irradiation, it was post-baked at 230 ° C. for 30 minutes.

(C) Evaluation of color filter <Measurement of transmittance>
The absorption spectrum of the post-baked coating glass plate obtained above was measured using an Hitachi spectrophotometer U-2910, and the transmittance% T (470 nm) at a wavelength of 470 nm and the transmittance% at a wavelength of 500 nm were measured. T (500 nm) was determined.

<Evaluation of heat resistance>
Absorption spectra were measured for the pre-baked coating film and the post-baked cured film, and the heat resistance was evaluated as ΔE as follows. ΔE is the area in the wavelength range of 380 to 520 nm in the absorption spectrum measured for the coating film after pre-baking, and is the area in the wavelength range of 380 to 520 nm in the absorption spectrum measured for the cured film after post-baking. Is a value given by the formula [(Pr−Pos) / Pr] × 100 (%). It can be said that the smaller the ΔE, the higher the heat resistance of the colorant composition.

<Solubility test>
30 mg of quinophthalone compound (1) -1 was placed in a vial, cyclohexanone (CHN) was added at room temperature (20 ° C.), and the weight of the minimum amount of CHN required to dissolve the quinophthalone compound was determined. The concentration (wt%) of the quinophthalone compound in the determined solvent weight (wt% of the quinophthalone compound relative to 100 wt% of the solvent) was calculated and used as the solubility (solubility).

Table 2 shows the results obtained.

(Examples 2 to 10)
About the other quinophthalone compound, the transmittance | permeability measurement, the heat resistance evaluation, and the solubility test were done like the case of Example 1. FIG. Table 2 shows the correspondence between the example numbers and the compound numbers and the results obtained.

The compounds of Examples 1 to 10 had high solubility in cyclohexanone. In addition, the compounds of Examples 1 to 5 and Example 9 had high transmittance at 500 nm, low transmittance at 470 nm, and high color purity.

Claims (5)

1. Following formula (1);
   

   

   In equation (1),
   Each R ₁ independently represents a halogen atom or an alkyl group having 1 to 12 carbon atoms, n represents an integer of 0 to 5;
   X ₁ to X ₄ each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, —COOR ₂ , —CONHR ₃ , —CONR ₃ R ₄ , —OR ₅ , —SR ₆ , — NHR ₇ , —NR ₇ R ₈ , or the following formula (2):
   

   

   (In Formula (2), X ₆ is an oxygen atom or a sulfur atom, and m is an integer of 0 to 5)
   A substituent represented by
   Here, R ₂ to R ₈ are each independently an alkyl group having 1 to 12 carbon atoms, an alkoxyalkyl group having 2 to 8 carbon atoms which may be substituted with an arbitrary substituent, — (CH ₂ ) _p —CO—R ₁₀ (R ₁₀ is a linear or branched alkyl group having 1 to 8 carbon atoms, —COOR _a , —OCOR _b , —NHR _c , —NR _d R _e or —OR _f. In this case, R _a , R _b , R _c , R _d , R _e , and R _f are each independently an alkyl group having 1 to 8 carbon atoms, and p is an integer of 1 to 4 -(R ₁₁ O) _q -R ₁₂ (R ₁₁ is a linear or branched alkylene group having 1 to 3 carbon atoms, and R ₁₂ is a straight chain having 1 to 8 carbon atoms or Branched alkyl group, —COOR _a , —OCOR _b , —NHR _c , or —NR _d R _e , wherein R _a , R _b , R _c , R _d , and R _e are each independently an alkyl group having 1 to 8 carbon atoms, and q is an integer of 1 to 4 Or — (CH ₂ CH (OH) CH ₂ ) —R ₁₃ (R ₁₃ is a halogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, —COOR _a , —OCOR _b , —NHR _c , or —NR _d R _e , wherein R _a , R _b , R _c , R _d , and R _e are each independently an alkyl group having 1 to 8 carbon atoms) Yes,
   R ₉ each independently represents a halogen atom, an alkyl group having 1 to 12 carbon atoms which may be substituted with an arbitrary substituent, — (CH ₂ ) _p —CO—R ₁₀ (R ₁₀ represents carbon A linear or branched alkyl group having 1 to 8 atoms, —COOR _a , —OCOR _b , —NHR _c , —NR _d R _e, or —OR _f , wherein R _a , R _b , R _c , R _d , R _e and R _f are each independently an alkyl group having 1 to 8 carbon atoms, and p is an integer of 1 to 4), — (R ₁₁ O) _q —R ₁₂ ( R ₁₁ is a linear or branched alkylene group having 1 to 3 carbon atoms, R ₁₂ is a linear or branched alkyl group having 1 to 8 carbon atoms, —COOR _a , —OCOR _b , an -NHR _c or _-NR d _{R e,,} this _{time, R a,} R _b, R , _R d, _{R e} are each independently an alkyl group having a carbon number of 1 ~ 8, q is an integer of _{1 ~ 4), - (CH} 2 CH (OH) CH 2) -R 13 (R ₁₃ is a halogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, —COOR _a , —OCOR _b , —NHR _c , or —NR _d R _e , where R _a , R _b , R _c , R _d and R _e are each independently an alkyl group having 1 to 8 carbon atoms), —COOR ₁₄ (R ₁₄ is a straight chain having 1 to 8 carbon atoms or A branched alkyl group or an alkoxyalkyl group having 2 to 8 carbon atoms), —CONHR ₁₅ (R ₁₅ is a linear or branched alkyl group having 1 to 8 carbon atoms, or 2 to 8 carbon atoms) alkoxyalkyl group), or -CONR ₁ R _{16 (R 15} and _{R 16} are each independently a linear or branched alkyl group or alkoxyalkyl group having 2 to 8 carbon atoms, 1 to 8 carbon atoms), and
   X ₅ represents the following formula (3):
   

   

   (In Formula (3), Y is an unsubstituted or substituted non-aromatic cyclic structure having 4 to 16 carbon atoms, and the ring may contain a hetero atom),
   Or the following formula (4):
   

   

   (In the formula (4), Z ₁ and Z ₂ are each independently a hydrogen atom, a halogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, an alkoxy group, an alkylthio group, or an alkylamino group. Or Z ₁ and Z ₂ may form a non-aromatic ring together)
   A substituent represented by:
   A quinophthalone compound represented by:
2. At least one of the X ₁ to X ₄ is an alkyl group having 1 to 12 carbon atoms, —COOR ₂ , —CONHR ₃ , —CONR ₃ R ₄ , —OR ₅ , —SR ₆ , —NHR ₇ , —NR ₇ R ₈ or the following formula (2):
   

   

   (In Formula (2), X ₆ is an oxygen atom or a sulfur atom, and m is an integer of 0 to 5)
   Here, R ₂ to R ₉ are as defined in claim 1.
   The quinophthalone compound of Claim 1 which is a substituent represented by these.
3. The quinophthalone compound according to claim 1 or 2, wherein X _{5 of the} quinophthalone compound represented by the formula (1) is substituted at the 4-position or the 8-position of the quinoline ring.
4. A colorant for a color filter comprising the compound according to any one of claims 1 to 3.
5. The colorant for a color filter according to claim 4, further comprising phthalocyanine.

Images