KR20090122126A - Azo compound or salt thereof, and manufacturing method thereof - Google Patents

Abstract

PURPOSE: An azo compound or its salt is provided to be produced high yield, and to be suitable for a coloring agent of a color filter used in a display device such as an LCD panel, electroluminescence, and plasma display panel. CONSTITUTION: An azo compound or its salt has a structure of chemical formula (I). A method for preparing the azo compound comprises a step of reacting an azo compound represented by chemical formula (III) and acylating agent. In chemical formulae, R^1 is an organic group with an azo group; R^2 and R^3 are independently substituted or unsubstituted C1-16 aliphatic hydrocarbon group, substituted or unsubstituted C3-16 alicyclic hydrocarbon group, substituted or unsubstituted C7-20 aralkyl group, or substituted or unsubstituted C6-14 aryl group.

Description

Azo compound or its salt, and its manufacturing method {AZO COMPOUND OR SALT THEREOF, AND MANUFACTURING METHOD THEREOF}

The present invention relates to an azo compound or a salt thereof useful as a dye.

Dye is used as a coloring agent of the color filter used for display apparatuses, such as a liquid crystal display panel, an electroluminescence, and a plasma display panel.

As the dye, for example, Patent Document 1 describes an azo compound represented by formula (A-4).

[Preceding technical literature]

[Patent Documents]

[Patent Document 1]

Japanese Patent Publication No. 2003-510398

[Patent Document 2]

Japanese Patent Application Publication No. 7-88633

[Patent Document 3]

Japanese Patent Application Laid-Open No. 2006-124634

[Patent Document 4]

Japanese Patent Application Laid-Open No. 2007-99840

The objective of this invention is providing the azo compound or its salt which can form the coating film excellent in heat resistance and light resistance.

MEANS TO SOLVE THE PROBLEM The present inventors discovered this invention as a result of examining the azo compound or its salt which can form the coating film excellent in heat resistance and light resistance.

That is, this invention provides the following [1]-[6].

[1] Azo compounds represented by formula (I) or salts thereof.

[In Formula (I), R <^1> represents the organic group which has an azo group,

R ² and R ³ are each independently C _1-16 aliphatic hydrocarbon group which may have a substituent, C _3-16 alicyclic hydrocarbon group which may have a substituent, or C ₇ which may have a substituent _-20 Aralkyl group or C _6-14 aryl group which may have a substituent.]

[2] The azo compound or salt thereof according to [1], wherein the azo compound or salt thereof represented by formula (I) is an azo compound or salt thereof represented by formula (II).

[In formula (II), R <^2> and R <^3> represent the same meaning as the case of formula (I),

A is at least one group selected from the group consisting of a C _1-8 aliphatic hydrocarbon group, a C _1-8 alkoxy group, a carboxyl group, an N-substituted azo group, a sulfone group, a sulfamoyl group and an N-substituted sulfamoyl group. A phenylene group which may have a dog or two, or a naphthylene group which may have 1 to 3 groups selected from the group consisting of N-substituted azo groups, sulfone groups, sulfamoyl groups and N-substituted sulfamoyl groups. Indicate,

R ⁴ and R ⁵ are each independently a hydrogen atom, a C _1-16 aliphatic hydrocarbon group which may have a substituent, a C _3-16 alicyclic hydrocarbon group which may have a substituent, or a C _7-20 which may have a substituent Aralkyl group or C _6-l4 aryl group which may have a substituent,

R ⁶ represents a hydrogen atom, a cyano group, or a carbamoyl group.]

[3] A method for producing an azo compound represented by formula (I), which has a step of reacting the azo compound represented by formula (III) with an acylating agent.

[In Formula (I) and Formula (III), R <^1> represents the organic group which has an azo group,

R ² and R ³ are each independently a C _1-16 aliphatic hydrocarbon group which may have a substituent, a C _3-16 alicyclic hydrocarbon group which may have a substituent, a C _7-20 aralkyl group which may have a substituent, or C _6-14 aryl group which may have a substituent.]

[4] The method for producing an azo compound according to [3], wherein the acylating agent is an acid chloride or an acid anhydride.

[5] A dimer of the azo compound or salt thereof according to [1].

[6] A dimer of the azo compound or salt thereof according to [2].

The azo compound or its salt of this invention can form the coating film excellent in heat resistance and light resistance. Moreover, the azo compound of this invention or the manufacturing method of its salt can obtain the target azo compound with high yield.

This invention is a compound represented by Formula (I) (henceforth an azo compound (I).).

In formula (I), R <^1> represents the organic group which has an azo group.

R ² and R ³ are each independently a C _1-16 aliphatic hydrocarbon group which may have a substituent, a C _3-16 alicyclic hydrocarbon group which may have a substituent, a C _7-20 aralkyl group which may have a substituent, or The C _6-14 aryl group which may have a substituent is shown.

The compound represented by Formula (I) may form the dimer or more multimer at arbitrary positions.

Below, the compound represented by Formula (I) is demonstrated in detail.

In formula (I), R <^1> is an organic group which has an azo group, Specifically, group derived from a pyridone azo compound, group derived from a pyrazolone azo compound, group derived from a pyridine azo compound, pyrimidine azo The group derived from a compound, the group derived from an oxyindole azo compound, etc. are mentioned. In addition, the group derived from a compound means the group in which one hydrogen atom was missing from the compound.

The aliphatic hydrocarbon group for R ² and R ³ may be either linear or branched. The carbon number of an aliphatic hydrocarbon group does not contain the carbon number of a substituent, The carbon number is 1-16, Preferably it is 6-10. As said aliphatic hydrocarbon group, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert- butyl group, methyl butyl group (1, 1, 3, for example) , 3-tetramethylbutyl group, etc.), methylhexyl group (1, 5-dimethylhexyl group etc.), and ethylhexyl group (2-ethylhexyl group etc.) are mentioned.

The aliphatic hydrocarbon group may be substituted with substituents such as a C _1-8 alkoxy group and a carboxyl group. As an aliphatic hydrocarbon group which has a substituent, a propoxypropyl group (3- (isopropoxy) propyl group etc.), 2- (carboxy) ethyl group, 3- (carboxy) ethylpropyl group, and 4- (carboxy), for example Butyl group etc. are mentioned.

Carbon number of a substituent is not contained in the carbon number of the alicyclic hydrocarbon group of R <^2> and R <^3> , and the carbon number is 3-16. Examples of the alicyclic hydrocarbon group include a cyclopentyl group, a cyclohexyl group, a methylcyclohexyl group (such as 2-methylcyclohexyl group), a cyclohexylalkyl group, and the like. As a substituent of the said alicyclic hydrocarbon group, the group similar to the substituent of the said aliphatic hydrocarbon group is mentioned.

Portions other than the aromatic ring of the aralkyl group of R ² and R ³ may be linear, branched or ring-shaped. Aralkyl group has 7 to 20 carbon atoms, preferably 7 to 10 carbon atoms. Examples of the aralkyl group include benzyl group, phenylethyl group (2-phenylethyl group, 2- (4-hydroxyphenyl) ethyl group, and the like), phenylethylene group (such as 2-phenylethylene group), and phenylbutyl group (3-amino-1 Phenyl alkyl groups such as -phenyl butyl group and the like.

Unsubstituted may be sufficient as the aryl group of R <^2> and R <^3> , and you may have substituents, such as an aliphatic hydrocarbon group or a carboxyl group. Carbon number of the said aryl group is counted including carbon number of a substituent, and is 6-14 normally, Preferably it is 6-10. As these aryl groups, a phenyl group, a carboxyphenyl group (2-carboxyphenyl group, 2, 4- dicarboxyphenyl group etc.), a trifluoromethylphenyl group (4-trifluoromethylphenyl group etc.), a methoxyphenyl group (4, for example) Unsubstituted or substituted phenyl groups, such as -methoxyphenyl group), etc. are mentioned.

It is preferable that azo compound (I) is a compound represented by Formula (II) [Hereinafter, it may be called azo compound (II).].

[Formula (II), R <^2> and R <^3> represents the same meaning as the case of Formula (I).

A is at least one group selected from the group consisting of a C _1-8 aliphatic hydrocarbon group, a C _1-8 alkoxy group, a carboxyl group, an N-substituted azo group, a sulfone group, a sulfamoyl group and an N-substituted sulfamoyl group. A phenylene group which may have a dog or two, or a naphthylene group which may have 1 to 3 groups selected from the group consisting of N-substituted azo groups, sulfone groups, sulfamoyl groups and N-substituted sulfamoyl groups. Indicates.

R ⁴ and R ⁵ are each independently a hydrogen atom, a C _1-16 aliphatic hydrocarbon group which may have a substituent, a C _3-16 alicyclic hydrocarbon group which may have a substituent, or a C _7-20 aral which may have a substituent The C _6-14 aryl group which may have a _kill group or a substituent is shown.

R ⁶ represents a hydrogen atom, a cyano group, or a carbamoyl group.

The compound represented by Formula (II) may form a dimer or more multimer at arbitrary positions.]

In formula (lI), A is selected from the group consisting of C _1-8 aliphatic hydrocarbon group, C _1-8 alkoxy group, carboxyl group, N-substituted azo group, sulfone group, sulfamoyl group and N-substituted sulfamoyl group 1 to 3 groups selected from the group consisting of a phenylene group or an N-substituted azo group, a sulfone group, a sulfamoyl group and an N-substituted sulfamoyl group which may have one or two or at least one group. It is preferable that it is a naphthylene group which may have. The azo compound of the present invention or a salt thereof has a C _1-8 aliphatic hydrocarbon group, a C _1-8 alkoxy group, a sulfone group, a sulfamoyl group, and an N-substituted sulfamoyl group, thereby providing water solubility and solubility in an organic solvent. It can be combined. In order to improve the solubility in an organic solvent, in formula (II), A is selected from the group consisting of a C _1-8 aliphatic hydrocarbon group, a C _1-8 alkoxy group, a sulfamoyl group and an N-substituted sulfamoyl group. It is preferable to have at least 1 type of group.

As the N- substituted sulfamoyl group, -SO ^₂ NHR ₂ group (R ² represents the above-described substituent group.), Or -SO ^₂ NHR ₂ (COR ³⁾ groups (R ² and R ^3, the above-described substituent Is preferred. The azo compound or its salt of this invention can have water solubility and the solubility with respect to the organic solvent by having N-substituted sulfamoyl group.

In formula (II), R ⁴ and R ⁵ are each independently a hydrogen atom or a linear or branched C _1-16 aliphatic hydrocarbon group which may have a substituent, or a C _3-16 alicyclic hydrocarbon group which may have a substituent. , C _7-20 aralkyl group which may have a substituent, or C _6-14 aryl group which may have a substituent. The carbon number of the aliphatic hydrocarbon group does not include the carbon number of the substituent. The carbon number is 1-16, Preferably it is 2-8, More preferably, it is 3-6. Examples of the aliphatic hydrocarbon group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group and tert-butyl group. Carbon number of the said alicyclic hydrocarbon group is 3-16, Preferably it is 5-10. As said alicyclic hydrocarbon group, a cyclohexyl group, a cyclopentyl group, etc. are mentioned, for example. The aliphatic hydrocarbon group and alicyclic hydrocarbon group of R ⁴ and R ⁵ may be substituted with a substituent such as a C _1-8 alkoxy group. As an aliphatic hydrocarbon group and alicyclic hydrocarbon group which have a substituent, a 3- (ethylhexyloxy) propyl group etc. are mentioned, for example.

The portion other than the aromatic ring of the aralkyl group of R ⁴ and R ⁵ may be linear, branched or cyclic, as in the case of R ² and R ³ , and the carbon number thereof is 7 to 20, preferably Is 7 to 10. The specific example of the aralkyl group of R <^4> and R <^5> is the same as that of R <^2> and R <^3> .

The aryl group of R ⁴ and R ⁵ may be unsubstituted, as in the case of R ² and R ³ , or may have a substituent such as an aliphatic hydrocarbon group or a hydroxyl group. The carbon number is counted including carbon number of a substituent, and is 6-14, Preferably it is 6-10. The specific example of the aralkyl group of R <^4> and R <^5> is the same as that of R <^2> and R <^3> .

R ⁶ represents a hydrogen atom, a cyano group, or a carbamoyl group. The hydrogen atom or cyano group is particularly preferable because the solubility in color density and organic solvent can be improved.

In order to increase the color density, it is preferable that R ³ is an aliphatic hydrocarbon group having 5 or less (preferably 3 or less) carbon atoms (for example, methyl group, ethyl group, isopropyl group, 2- (carboxy) ethyl group, etc.). . Moreover, in order to improve the solubility with respect to the organic solvent, it is preferable that R <^2> is a C6-C12 aliphatic hydrocarbon group.

Moreover, in order to raise a color density, it is preferable that R <^5> is a C3 or less aliphatic hydrocarbon group (for example, methyl group, such as a methyl group and an ethyl group, especially). Moreover, in order to improve the solubility with respect to the organic solvent, it is preferable that R <^4> is a C2-C12 aliphatic hydrocarbon group.

Moreover, in order to raise a color density, it is preferable that A is a para substituted phenylene group or a meta substituted phenylene group. Para-substituted here means that the azo group and sulfamoyl group in Formula (II) have a positional relationship of para on a phenylene group.

When two or more types of azo compounds (I) are used in combination, the amount of dissolution in an organic solvent tends to be greater than that in the case of using one of them alone. As a pigment for a liquid crystal display device, two types of azo compounds (I) are used. It is also preferable to use the above combination. As an example of the combination which improves the solubility to an organic solvent, the azo compound (disulfonamide) which has two N-substituted sulfamoyl groups, and the azo compound which has one N-substituted sulfamoyl group and one sulfone group (mono And sulfonamides).

Moreover, since a monosulfone amide has a low molecular weight, it is especially preferable from a viewpoint of color density.

In order to improve the solubility in the organic solvent, R ² to R ⁵ are preferably a branched aliphatic hydrocarbon group and an aliphatic hydrocarbon group bonded by two or more halogen atoms, and are tertiary aliphatic hydrocarbon groups such as tert-butyl groups and trifluoro. Particularly preferred are aliphatic hydrocarbon groups in which three or more halogen atoms such as a methyl group are bonded.

By selecting a bulky group, the azo pigment stacking can be reduced, and the solubility in an organic solvent can be improved. Moreover, by selecting a bulky group, azo groups can be protected and light resistance can be improved.

Preferred examples of formula (I) include formulas (I-1) to (I-35) and formulas (II-1) to (II-116).

In the azo compound (I), a pyridone azo compound like the compound represented by the formula (II) is more preferable in terms of chromaticity.

This invention is not limited to the compound represented by Formula (I) and Formula (II), It also includes the salt. As a salt, the sulfonate in the case of having a sulfone group in a molecule | numerator, the carboxylate in the case of having a carboxyl group is mentioned. Moreover, the cation which forms these salts is not specifically limited, In view of solubility in a solvent, Alkali metal salts, such as a lithium salt, a sodium salt, and potassium salt; Ammonium salts; And organic amine salts such as ethanolamine salts and alkylamine salts. In particular, an alkali metal salt (preferably sodium salt) is useful when it contains in a polarizing film base material. Moreover, since an organic amine salt is useful when it is made to contain in curable resin composition, and since it is a nonmetal salt, it is useful also in the field where insulation is important.

As a method for producing the azo compound (I), for example, the method described in Japanese Patent Application Laid-Open No. 7-88633, represented by Formula (VI), and the azo compound represented by Formula (III) [hereinafter referred to as azo compound (III) And the acylating agent. Among these, a method of reacting the azo compound (III) with the acylating agent is preferable.

As the azo compound (III), azo compounds described in Japanese Patent Application Laid-Open No. 7-88633 and the like can be suitably used, in addition to the dyes commonly distributed (C. I. Solvent Yellow 162 manufactured by BASF).

As an acylating agent, well-known substances, such as an acid anhydride and an acid chloride, can be used, An acid anhydride is more preferable at the point of reactivity.

As the acid chloride, preferably acetic acid chloride, propionic acid chloride, butyric acid chloride, benzoyl chloride and the like can be exemplified.

As the acid anhydride, anhydrides of aliphatic carboxylic acids and aromatic carboxylic acids may be used, and may be chain or cyclic anhydrides, specifically, acetic anhydride, propionic anhydride, maleic anhydride, butyric anhydride, succinic anhydride, and hydroic acid anhydride. , Phthalic anhydride and the like are preferably used. There is no restriction | limiting in particular in the kind of acylating agent used, You may use together 2 or more types of acylating agents. As for the usage-amount of an acylating agent, about 1-3 mol is preferable with respect to 1 mol of azo compounds (III). In addition, when water has in a reaction system, it is preferable to use an acid anhydride excessively with respect to an azo compound.

Generally available organic amines can be used, and aliphatic amines and aromatic amines are particularly preferable. Preferably, triethylamine, piperidine, 1,4-diazabicyclo [2,2,2] octane, 1,8-diazabicyclo [5,4,0] -7-undecene, pyridine, 4-dimethylaminopyridine, 4-pyrrolidinopyridine, and the like can be exemplified. In view of improving the reaction rate, 4-dimethylaminopyridine and 4-pyrrolidinopyridine are particularly preferred. The use amount of organic amine is 0.05-50 mol with respect to 1 mol of azo compounds (III), for example. There is no restriction | limiting in particular in the kind of organic amine to be used, You may use together two or more types of organic amines.

It is preferable to perform reaction of an azo compound (III) and an acylating agent in an organic solvent. As a solvent, For example, ether, such as 1, 4- dioxane (especially cyclic ether); Halogenated hydrocarbons such as chloroform, methylene chloride, carbon tetrachloride, 1,2-dichloroethane, dichloroethylene, trichloroethylene, perchloroethylene, dichloropropane, amyl chloride and 1,2-dibromoethane;

Ketones such as acetone, methyl isobutyl ketone and cyclohexanone;

Carbon type aromatics, such as benzene, toluene, and xylene, etc. are mentioned, You may use two or more types of solvent together. The usage-amount of a solvent is about 1 mass part or more (preferably 5 mass parts or more), and 20 mass parts or less (preferably 10 mass parts or less) with respect to 1 mass part of azo compounds (III).

The reaction between the azo compound (III) and the acylating agent is carried out in a nitrogen atmosphere or in an argon atmosphere, but the reaction proceeds even in air dried with calcium chloride or the like.

Reaction temperature is 0 degreeC or more (preferably 10 degreeC or more), and 70 degrees C or less (preferably 60 degrees C or less). The reaction time is, for example, 0.5 hours or more (preferably 3 hours or more) and 25 hours or less (preferably 15 hours or less).

The order of addition of the acid anhydride and the organic amine is not particularly limited, but it is preferable to add (drop) the acid anhydride to the reaction solution composed of the azo compound (III), the organic amine, and the organic solvent.

The method for obtaining the azo compound (I) as the target compound from the reaction mixture is not particularly limited, and various known methods can be employed, and the method of purifying by extracting the reaction mixture with an organic solvent, the reaction mixture, the organic solvent and water. And azo compound (I) by elution to an organic phase, and a solvent distillation of the organic phase fractionated by a separation lot etc. is mentioned, and the method of obtaining an azo compound (I), etc. are mentioned. As for extraction temperature, 10 degreeC or more (preferably 20 degreeC or more) and 50 degreeC or less (preferably 30 degreeC or less) are preferable. In addition, the extraction is preferably stirred at the same temperature for 0.5 to 4 hours. The azo compound (I) after extraction is normally washed with alcohol or the like and then dried. Moreover, you may refine | purify further by well-known methods, such as recrystallization as needed.

(Example)

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. In the examples, "%" and "parts" indicating the content and the amount of use are mass% and mass parts unless otherwise specified.

(Example 1)

The following reaction was performed in nitrogen atmosphere. To 32 parts of Solvent Yellow 162 (manufactured by BASF) represented by the formula (A-1), 0.6 parts of 4-dimethylaminopyridine, 20 parts of triethylamine and 200 parts of chloroform were added, followed by stirring for 30 minutes to adjust the reaction solution. It was. Under ice-cooling, 9 parts of acetic anhydride was added dropwise over 30 minutes while stirring the reaction solution. After completion of the dropwise addition, the mixture was stirred for 12 hours while returning to room temperature. The reaction solution was poured into 2 liters of water, and then 1 liter of ethyl acetate was added and stirred for 2 hours. The organic phase was aliquoted using a separating lot, followed by further washing with 2 liters of water. Solvent distillation was removed from the separated organic phase to obtain 32.8 parts of a crude product. The crude product was washed with 1 liter of methanol to obtain 30.2 parts of the azo compound represented by formula (II-1). Yield 86%.

The structure of the azo compound (II-1) was determined by ¹ H-NMR, ¹³ C-NMR, and mass spectrometry. The NMR apparatus used ECA-500 (made by Nihon Bunco Co., Ltd.), and the mass spectrometer used JMS-700 (made by Nihon Denshi Co., Ltd.). :

¹ H-NMR (500 MHz, δ value in ppm, TMS), DMSO); 0.86-0.92 (9H, m), 1.23-1.36 (10 H, m), 1.54 (2H, qq, J = 6.9, 6.9 Hz), 1.73 (1H, m), 2.22 (3H, s), 2.54 (3H, s), 3.74 (2H, d, J = 7.7 Hz), 3.84 (2H, br.t, J = 6.9 Hz), 7.91 (2H, br, d, J = 8.4 Hz) , 7.98 (2H, broad doublet, J = 8.4 Hz), 14.9 (1H, s)

¹³ C-NMR (125 MHz, δ value in ppm, TMS), DMSO): 10.47, 13.61, 13.86, 16.43, 19.67, 22.41, 23.09, 24.47, 27.96, 29.16, 29.64, 38.72, 39.17, 50.61, 102.54, 114.74, 117.54, 124.96, 129.39, 135.77, 145.43, 159.13, 159.87, 160.15, 170.42

Mass spectrometry:

Ionization Mode = FD +: m / z = 543

0.35 g of the obtained azo compound (II-1) was dissolved in ethyl lactate to make a volume of 250 cm 3, 2 cm 3 of which was diluted with ethyl lactate to make a volume of 100 cm 3 (concentration: 0.028 g / L), Absorption spectra were measured using a spectrophotometer (quartz cell, 1 cm in length). This compound showed the absorbance 2.48 (arbitrary unit) at (lambda) max = 423 nm.

(Example 2)

The following reaction was performed in nitrogen atmosphere. 0.2 parts of 4-dimethylaminopyridine, 6.1 parts of triethylamine and 62 parts of chloroform were added to 10.0 parts of Solvent Yellow 162 (manufactured by BASF) represented by the formula (A-1), followed by stirring for 30 minutes to adjust the reaction solution. It was. Under ice-cooling, 2.2 parts of amber anhydride was added while stirring the reaction solution. After completion of the dropwise addition, the mixture was stirred for 12 hours while returning to room temperature. The reaction solution was poured into 2 liters of water, and 0.5 liters of ethyl acetate was added and stirred for 2 hours. The organic phase was aliquoted using a separating lot, followed by further washing with 1 liter of water. The solvent-distilled organic phase was distilled off and 8.5 parts of crude products were obtained. The crude product was washed with 0.2 liter of methanol to obtain 7.6 parts of azo compound represented by formula (II-4). Yield 63%.

The structure of the azo compound (II-4) was determined by ¹ H-NMR, ¹³ C-NMR, and mass spectrometry. The NMR apparatus used ECA-500 (made by Nihon Bunco Co., Ltd.), and the mass spectrometer used JMS-700 (made by Nihon Denshi Co., Ltd.). :

¹ H-NMR (500 MHz, δ value in ppm, TMS), DMSO); 0.88-0.94 (9 H, m), 1.23- 1.37 (11 H, m), 1.54 (2 H, qq, J = 6.8, 6.9 Hz), 1.73 (1 H, m), 2.62 (3 H, s) , 2.85-2.87 (4H, m), 3.76 (2H, d, J = 7.7 Hz), 3.96 (2H, br.t, J = 6.8 Hz), 7.91 (2H, br.d, J = 8.4 Hz), 7,98 (2 H, br.d, J = 8.4 Hz), 14.9 (1 H, s)

¹³ C-NMR (125 MHz, δ value in ppm, TMS), DMSO): 10.48, 13.59, 13.89, 16.52, 20.00, 22.75, 23.43, 28.37, 28.42, 29.58, 30.10, 31.35, 38.97, 39.02, 50.85, 103.48, 113.82, 116.83, 124.65, 129.54, 136.62, 143.77, 158.28, 159.50, 161.3, 171.91, 177.12

Mass spectrometry:

Ionization Mode = FD +: m / z = 601

0.35 g of the obtained azo compound (II-4) was dissolved in ethyl lactate to make a volume of 250 cm 3, 2 cm 3 of which was diluted with ethyl lactate to make a volume of 100 cm 3 (concentration: 0.028 g / L), Absorption spectra were measured using a spectrophotometer (quartz cell, 1 cm in length). This compound showed an absorbance of 2.46 (arbitrary unit) at lambda max = 426 nm.

(Example 3)

150 parts of water were added to 25.0 parts of 3-methylaniline-4-sulfonic acid represented by formula (B-1), and it adjusted to pH 7-8 with 30% sodium hydroxide aqueous solution under ice-cooling. The following operation was performed under ice cooling. 27.6 parts of sodium nitrite was added and stirred for 30 minutes. 97.4 parts of 35% hydrochloric acid was added little by little to make a brown solution, and it stirred for 2 hours. The aqueous solution which melt | dissolved 25.1 parts of amic sulfuric acid in 250 parts of water was added to the reaction solution, it stirred, and the suspension containing a diazonium salt was obtained.

260 parts of water was added to 28.9 parts of 1-butyl-3-cyano-4-methyl-6-hydroxypyrid-2-one represented by the formula (C-1), and then the pH was adjusted with 30% sodium hydroxide aqueous solution under ice cooling. It adjusted to 8-9.

The following operation was performed under ice cooling. The pyridone aqueous solution was stirred to give a colorless solution, and the suspension containing the diazonium salt was added dropwise by pump over 2 hours while adjusting the pH to 8-9 with 30% aqueous sodium hydroxide solution. After completion of the dropwise addition, the mixture was stirred for 2 hours to obtain a yellow suspension. The yellow solid obtained by filtration was dried at 60 degreeC under reduced pressure, and 46.7 parts (yield 79%) of an azo compound represented by a formula (D-1) were obtained.

The following reaction was performed in nitrogen atmosphere. To the flask equipped with a cooling tube and a stirring device, 30 parts of azo compound (D-1), 300 parts of chloroform and 11.9 parts of N, N-dimethylformamide were charged, and the mixture was kept at 20 ° C. or lower while stirring. 16.6 parts of O'Neill were added dropwise. After completion of the dropwise addition, the temperature was raised to 50 ° C, held at the same temperature for 5 hours for reaction, and then cooled to 20 ° C. A mixture of 47.9 parts of 2-ethylhexylamine and 90.1 parts of triethylamine was added dropwise while keeping the reaction solution after cooling at 20 ° C. or lower under stirring. Thereafter, the reaction was stirred at the same temperature for 5 hours. Subsequently, the solvent was distilled off from the reaction mixture by a rotary evaporator, and then a small amount of methanol was added and the mixture was stirred vigorously. This mixture was added to a mixture of 60 parts of acetic acid and 600 parts of ion-exchanged water with stirring to precipitate crystals. Precipitated crystals were separately filtered, washed well with ion exchanged water, and dried under reduced pressure at 60 ° C to obtain 27.0 parts (yield 71%) of azo compound represented by formula (A-2).

The following reaction was performed in nitrogen atmosphere. 0.1 part of 4-dimethylaminopyridine, 2.0 parts of triethylamine, and 26.9 parts of chloroform were added to the azo compound represented by Formula (A-2), and it stirred for 30 minutes, and adjusted the reaction solution. Under ice-cooling, 1.1 parts of acetic anhydride was added dropwise over 30 minutes while stirring the reaction solution. After completion of the dropwise addition, the mixture was stirred for 12 hours while returning to room temperature. The reaction solution was poured into 2 liters of water, and 0.5 liters of ethyl acetate was added and stirred for 2 hours. The organic phase was aliquoted using a separating lot, followed by further washing with 1 liter of water. The solvent-distilled organic phase was distilled off and 4.0 parts of crude products were obtained. The crude product was washed with 1 liter of methanol to obtain 3.7 parts of azo compound represented by formula (II-43). Yield 79%.

The structure of the azo compound (II-43) was determined by ¹ H-NMR, ¹³ C-NMR, and mass spectrometry. The NMR apparatus used ECA-500 (made by Nihon Bunco Co., Ltd.), and the mass spectrometer used JMS-700 (made by Nihon Denshi Co., Ltd.). :

¹ H-NMR (500 MHz, δ value in ppm, TMS), DMSO); 0.90-0.97 (9 H, m), 1.26-1.48 (10 H, m), 1.60 (2 H, qq, J = 6.8, 6.8 Hz), 1.81 (1 H, m), 2.23 (3 H, s) , 2.58 (3H, s), 2.62 (3H, s), 3.78 (2H, d, J = 7.5 Hz), 3.88 (2H, br.t, J = 6.8 Hz), 7.31 (1H, s), 7.44 (2H, broad doublet, J = 8.7 Hz), 8.03 (1H, broadened, J = 8.7 Hz), 14.8 (1 H, s)

¹³ C-NMR (125 MHz, δ value in ppm, TMS), DMSO): 10.33, 13.50, 13.85, 16.43, 20.00, 20.20, 22.76, 23.36, 24.70, 28.24, 29.50, 30.00, 38.96, 39.77, 50.85, 103.84, 113.84, 120.04, 124.55, 132.17, 135.36, 139.72, 144.25, 158.08, 159.39, 161.24, 170.10

Mass spectrometry:

Ionization Mode = FD +: m / z = 557

0.35 g of the obtained azo compound (II-43) was dissolved in ethyl lactate to give a volume of 250 cm 3, 2 cm 3 of which was diluted with ethyl lactate to make a volume of 100 cm 3 (concentration: 0.028 g / L), followed by a spectrophotometer. Absorption spectra were measured using [quartz cell, cell length is 1 cm]. This compound showed an absorbance of 2.41 (arbitrary unit) at lambda max = 425 nm.

(Example 4)

The following reaction is performed in nitrogen atmosphere. 0.9 parts of 4-dimethylaminopyridine, 20.0 parts of triethylamine and 200 parts of chloroform were added to 35.0 parts of Solvent Yellow 162 (made by BASF) represented by Formula (A-1), and it stirred, and adjusted the reaction solution. Under ice-cooling, 6.0 parts of acetate acetate was added dropwise while stirring the reaction solution. After completion of dropping, the mixture is stirred while returning to room temperature. The reaction solution is poured into 2 liters of water, and then 1 liter of ethyl acetate is added and stirred. After separating the organic phase using a separating lot, it is also washed with 2 liters of water. The solvent-distilled organic phase is distilled off and 24.9 parts of crude products are obtained. The crude product is washed with 1 liter of methanol to obtain an azo compound represented by formula (II-1).

(Comparative Example 1)

400 parts of water was added to 40.0 parts of sulfanylic acid represented by Formula (B-2), and it adjusted to pH 7-8 with 30% sodium hydroxide aqueous solution under ice-cooling. The following operation was performed under ice cooling. 19.1 parts of sodium nitrite were added, and it stirred for 30 minutes. A small amount of 72.2 parts of 35% hydrochloric acid was added to make a brown solution, followed by stirring for 2 hours. An aqueous solution in which 4.4 parts of amidic sulfuric acid was dissolved in 30 parts of water was added to the reaction solution, followed by stirring to obtain a suspension containing a diazonium salt.

800 parts of water was added to 54.4 parts of 1-ethyl-3-cyano-4-methyl-6-hydroxypyrid-2-one represented by the formula (C-2), and then the pH was adjusted with 30% sodium hydroxide aqueous solution under ice-cooling. It adjusted to 8-9.

The following operation was performed under ice cooling. The pyridone aqueous solution was stirred to give a colorless solution, and the suspension containing the diazonium salt was added dropwise by pump over 2 hours while adjusting the pH to 8-9 with 30% aqueous sodium hydroxide solution. After completion of the dropwise addition, the dark solution was obtained by stirring for 2 hours. The yellow solid obtained by filtration was dried at 60 degreeC under reduced pressure, and 80.5 parts (yield 92%) of an azo compound represented by a formula (D-2) were obtained.

Thionyl chloride while adding 5 parts of azo compound (D-2), 50 parts of chloroform and 2.1 parts of N, N-dimethylformamide to a flask equipped with a cooling tube and a stirring device, and keeping the temperature below 20 ° C under stirring. 6 parts were added dropwise. After completion of the dropwise addition, the temperature was raised to 50 ° C, held at the same temperature for 5 hours for reaction, and then cooled to 20 ° C. A mixture of 4 parts of 3-isopropoxypropylamine and 14 parts of triethylamine was added dropwise while maintaining the reaction solution after cooling at 20 ° C. or lower while stirring. Thereafter, the reaction was stirred at the same temperature for 5 hours. Subsequently, the obtained reaction mixture was distilled off the solvent by an evaporator rotator, and a small amount of methanol was added thereto, followed by vigorous stirring. This mixture was added to a mixture of 29 parts of acetic acid and 300 parts of ion-exchanged water with stirring to precipitate crystals. Precipitated crystals were separately filtered, washed well with ion-exchanged water, and dried under reduced pressure at 60 ° C to obtain 3.5 parts (yield 56%) of azo compound represented by formula (A-3).

0.35 g of the obtained azo compound (A-3) was dissolved in ethyl lactate to obtain a volume of 250 cm 3, 2 cm 3 of which was diluted with ion-exchanged water to a volume of 100 cm 3 (concentration: 0.028 g / L), and spectroscopy. Absorption spectra were measured using a photometer (quartz cell, optical path length; 1 cm). This compound showed an absorbance of 2.77 (arbitrary unit) at lambda max = 430 nm.

(Comparative Example 2)

The following azo compound was synthesize | combined by the method of patent document 2. 0.35 g of azo compound (A-4) was dissolved in ethyl lactate to make a volume of 250 cm 3, 2 cm 3 of which was diluted with ion-exchanged water to a volume of 100 cm 3 (concentration: 0.028 g / L), and a spectrophotometer Absorption spectrum was measured using (quartz cell, optical path length; 1 cm). This compound showed an absorbance of 2.6 (arbitrary unit) at lambda max = 425 nm.

The component used by the following example is as follows, and may abbreviate | omit and display it below.

(II-1) Colorant: Azo compound synthesized in Example 1

(II-4) Colorant: Azo compound synthesized in Example 2

(II-43) Colorant: Azo compound synthesized in Example 3

(A-1) Colorant: Solvent Yellow 162 (manufactured by BASF)

(A-3) Colorant: Azo compound synthesized in Comparative Example 1

(A-4) Colorant: Azo compound synthesized in Comparative Example 2

(F-1) Resin: HN-122 (manufactured by Takaoka Chemical Co., Ltd.)

(G-1) Solvent: N, N-dimethylformamide

(Example 5)

[Preparation of Colored Composition 1]

(II-1) 0.51 parts by mass

(F-1) 1.19 parts by mass

(G-1) 8.30 parts by mass

It mixed and obtained the coloring composition 1.

Next, after apply | coating the coloring composition 1 obtained above by the spin coat method on glass (# 1737: Corning), volatile matter was volatilized for 3 minutes at 100 degreeC, and the coating film of coloring composition 1 was formed.

In the coating film described above, the C light source is used to measure the xy chromaticity of the CIE's XYZ colorimeter [OSP-SP-200; OLYMPUS Co., Ltd.] was used for the measurement.

[Evaluation 1] Heat resistance evaluation method

The obtained coating film was heated at 230 degreeC for 120 minutes, the chromaticity after heating was measured similarly to the above, and the color difference ((DELTA) Eab *) before and behind heating was calculated | required.

As the evaluation criteria for the color difference, almost no color change is observed when ΔEab * is 6 or less, and exhibits good characteristics as a color filter, and when ΔEab * is more than 6 and 10 or less, a slight color change is confirmed, but the practical use of the color filter If ΔEab * is 10 or more, the color change can be clearly confirmed, and the level is a problem as the color filter.

[Evaluation 2] Light resistance evaluation method

UV cut filter [COLORED OPTlCAL GLASS L38; on the obtained coating film; Hoya Corporation] was laminated | stacked, and the xenon lamp light was irradiated for 48 hours with the light resistance test machine (SUNTEST CPS +: Toyo Seiki Seisakusho Co., Ltd.).

Next, the chromaticity after a light resistance test was measured, and the color difference ((DELTA) Eab *) before and after a light resistance test was calculated | required.

[Evaluation of Coating Film]

As a result of evaluating the obtained coating film in the same manner to the above, the color difference ((DELTA) Eab *) in heat resistance evaluation was 4.0, and the color difference ((DELTA) Eab *) in light resistance evaluation was 0.5.

(Example 6)

[Preparation of Colored Composition 2]

Except changing the coloring agent (II-1) of Example 5 into coloring agent (II-4), it mixed similarly to Example 5 and obtained the coloring composition 2.

[Formation and Evaluation of Coating Film]

When the coating film was produced and evaluated similarly to Example 5, the color difference ((DELTA) Eab *) in heat resistance evaluation was 4.9 and the color difference (ΔEab *) in light resistance evaluation was 0.6.

(Example 7)

[Preparation of Colored Composition 3]

Except changing the coloring agent (II-1) of Example 5 into coloring agent (II-43), it mixed similarly to Example 5 and obtained the coloring composition 3.

[Formation and Evaluation of Coating Film]

The coating film was produced and evaluated in the same manner as in Example 5, and as a result, the color difference (ΔEab *) in the heat resistance evaluation was 5.3, and the color difference (ΔEab *) in the light resistance evaluation was 0.3.

(Comparative Example 3)

[Preparation of Colored Composition 4]

Except changing the coloring agent (II-1) of Example 5 into a coloring agent (A-1), it mixed similarly to Example 5 and obtained the coloring composition 4.

[Formation and Evaluation of Coating Film]

When the coating film was produced and evaluated in the same manner as in Example 5, the color difference (ΔEab *) in the heat resistance evaluation was 10.8, and the color difference (ΔEab *) in the light resistance evaluation was 0.8.

(Comparative Example 4)

[Preparation of Colored Composition 5]

Except changing the coloring agent (II-1) of Example 5 into a coloring agent (A-3), it mixed similarly to Example 5 and obtained the coloring composition 5.

[Formation and Evaluation of Coating Film]

The coating film was produced and evaluated in the same manner as in Example 5, and the color difference (ΔEab *) in the heat resistance evaluation was 7.5, and the color difference (ΔEab *) in the light resistance evaluation was 1.3.

(Comparative Example 5)

[Preparation of Colored Composition 6]

Except changing the coloring agent (II-1) of Example 5 into a coloring agent (A-4), it mixed like Example 5 and obtained the coloring composition 6.

[Formation and Evaluation of Coating Film]

When the coating film was produced and evaluated in the same manner as in Example 5, the color difference (ΔEab *) in the heat resistance evaluation was 117.6, and the color difference (ΔEab *) in the light resistance evaluation was 1.5.

From the above result, it turns out that the azo compound of this invention improves heat resistance and light resistance compared with the conventional azo compound.

Since the azo compound or its salt of this invention can form the coating film excellent in heat resistance and light resistance, it can be used suitably as a coloring agent of the color filter used for display apparatuses, such as a liquid crystal display panel, an electroluminescence, and a plasma display panel. Can be.

Claims (6)

Azo compound or its salt represented by Formula (I).

[In Formula (I), R <^1> represents the organic group which has an azo group, R ² and R ³ are each independently a C _1-16 aliphatic hydrocarbon group which may have a substituent, a C _3-16 alicyclic hydrocarbon group which may have a substituent, a C _7-20 aralkyl group which may have a substituent, Or a C _6-14 aryl group which may have a substituent.] The method of claim 1, Azo compound or its salt whose azo compound represented by Formula (I) or its salt is an azo compound or its salt represented by Formula (II).

[In Formula (II), R <^2> and R <^3> represent the same meaning as the case of Formula (I), A is at least one group selected from the group consisting of a C _1-8 aliphatic hydrocarbon group, a C _1-8 alkoxy group, a carboxyl group, an N-substituted azo group, a sulfone group, a sulfamoyl group and an N-substituted sulfamoyl group. A phenylene group which may have a dog or two, or a naphthylene group which may have 1 to 3 groups selected from the group consisting of N-substituted azo groups, sulfone groups, sulfamoyl groups and N-substituted sulfamoyl groups. Indicate, R ⁴ and R ⁵ are each independently a hydrogen atom, a C _1-16 aliphatic hydrocarbon group which may have a substituent, a C _3-16 alicyclic hydrocarbon group which may have a substituent, or a C _7-20 which may have a substituent Aralkyl group or C _6-l4 aryl group which may have a substituent, R ⁶ represents a hydrogen atom, a cyano group, or a carbamoyl group.] The manufacturing method of the azo compound represented by Formula (I) which has the process of making the azo compound represented by Formula (III) and acylating agent react.

[In Formula (I) and Formula (III), R <^1> represents the organic group which has an azo group, R ² and R ³ are each independently a C _1-16 aliphatic hydrocarbon group which may have a substituent, a C _3-16 alicyclic hydrocarbon group which may have a substituent, a C _7-20 aralkyl group which may have a substituent, or C _6-14 aryl group which may have a substituent.] The method of claim 3, wherein The manufacturing method of the azo compound whose acylating agent is an acid chloride or an acid anhydride. Dimer of the azo compound of Claim 1, or its salt. Dimer of the azo compound or its salt of Claim 2.