JP2010001469A - Azo compound or salt thereof, and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an azo compound or a salt thereof capable of forming coating films excellent in heat resistance and light stability. <P>SOLUTION: The azo compound or its salt is expressed by formula (I), preferably by formula (II), wherein R<SP>1</SP>represents an organic group having an azo group; R<SP>2</SP>and R<SP>3</SP>represent each a 1-16C aliphatic hydrocarbon group, a 3-16C alicyclic hydrocarbon group, a 7-20C aralkyl group or a 6-14C aryl group; A represents a phenylene group or a naphthylene group; R<SP>4</SP>and R<SP>5</SP>represent each H, a 1-16C aliphatic hydrocarbon group, a 3-16C alicyclic hydrocarbon group, a 7-20C aralkyl group or a 6-14C aryl group; and R<SP>6</SP>represents H, a cyano group or a carbamoyl group. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

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

  Dyes are used as colorants for color filters used in display devices such as liquid crystal display panels, electroluminescence, and plasma display panels.

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

Japanese translation of PCT publication No. 2003-510398

  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.

As a result of studying an azo compound or a salt thereof capable of forming a coating film excellent in heat resistance and light resistance, the present inventors have found the present invention.
That is, the present invention provides the following.
1. An azo compound represented by the formula (I) or a salt thereof.

[In Formula (I), R ¹ represents an organic group having an azo group.
R ² and R ³ are each independently a C _1-16 aliphatic hydrocarbon group which may have a substituent, or a C _3-16 alicyclic hydrocarbon group which may have a substituent. Represents a C _7-20 aralkyl group which may have a substituent, or a C _6-14 aryl group which may have a substituent. ]

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

[In formula (II), R ² and R ³ represent the same meaning as in formula (I).
A is at least one 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 one or two groups, or at least one group selected from the group consisting of an N-substituted azo group, a sulfone group, a sulfamoyl group and an N-substituted sulfamoyl group. The naphthylene group which may have one piece is represented.
R ⁴ and R ⁵ are each independently a hydrogen atom, a C _1-16 aliphatic hydrocarbon group which may have a substituent, or a C _3-16 alicyclic group which may have a substituent. It represents a hydrocarbon group, an _optionally substituted C _7-20 aralkyl group, or an _optionally substituted C _6-14 aryl group.
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), comprising a step of reacting an azo compound represented by formula (III) with an acylating agent.

[In Formula (I) and Formula (III), R ¹ represents an organic group having an azo group.
R ² and R ³ are each independently a C _1-16 aliphatic hydrocarbon group which may have a substituent, or a C _3-16 alicyclic hydrocarbon group which may have a substituent. Represents a C _7-20 aralkyl group which may have a substituent, or a C _6-14 aryl group which may have a substituent. ]
4). 4. The method according to 3 above, wherein the acylating agent is acid chloride or acid anhydride.
5). A dimer of the azo compound or a salt thereof according to the preceding item 1.
6). A dimer of the azo compound or a salt thereof according to the preceding two items.

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

The present invention is a compound represented by formula (I) (hereinafter sometimes referred to as azo compound (I)).

[In Formula (I), R ¹ represents an organic group having an azo group.
R ² and R ³ are each independently a C _1-16 aliphatic hydrocarbon group which may have a substituent, or a C _3-16 alicyclic hydrocarbon group which may have a substituent. Represents a C _7-20 aralkyl group which may have a substituent, or a C _6-14 aryl group which may have a substituent.
The compound represented by the formula (I) may form a dimer or more multimer at an arbitrary position. ]
Hereinafter, the compound represented by formula (I) will be described in detail.

In formula (I), R ¹ is an organic group having an azo group, specifically, a group derived from a pyridone azo compound, a group derived from a pyrazolone azo compound, a group derived from a pyridine azo compound, or a pyrimidine azo compound. Examples include groups derived from oxindole azo compounds. In addition, the group derived from a compound means a group from which one hydrogen atom has been removed from the compound.

The aliphatic hydrocarbon group for R ² and R ³ may be either linear or branched. The carbon number of the aliphatic hydrocarbon group does not include the carbon number of the substituent, and the carbon number is 1 to 16, preferably 6 to 10. Examples of the aliphatic hydrocarbon group include 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, a methylbutyl group (1,1, 3,3-tetramethylbutyl group and the like), methylhexyl group (1,5-dimethylhexyl group and the like), and ethylhexyl group (2-ethylhexyl group and the like).
The aliphatic hydrocarbon group may be substituted with a substituent such as a C _1-8 alkoxy group or a carboxyl group. Examples of the aliphatic hydrocarbon group having a substituent include a propoxypropyl group (such as 3- (isopropoxy) propyl group), 2- (carboxy) ethyl group, 3- (carboxy) ethylpropyl group, and 4- (carboxy ) Butyl group and the like.
The carbon number of the alicyclic hydrocarbon group of R ² and R ³ does not include the carbon number of the substituent, and the carbon number is 3 to 16. Examples of the alicyclic hydrocarbon group include a cyclopentyl group, a cyclohexyl group, a methylcyclohexyl group (such as a 2-methylcyclohexyl group), and a cyclohexylalkyl group. Examples of the substituent of the alicyclic hydrocarbon group include the same groups as the substituent of the aliphatic hydrocarbon group.

The portion other than the aromatic ring of the aralkyl group of R ² and R ³ may be linear, branched or cyclic. The carbon number of the aralkyl group does not include the carbon number of the substituent, and the carbon number is 7 to 20, preferably 7 to 10. Examples of the aralkyl group include benzyl group, phenylethyl group (such as 2-phenylethyl group and 2- (4-hydroxyphenyl) ethyl group), phenylethylene group (such as 2-phenylethylene group), and phenylbutyl group (3- And phenylalkyl groups such as amino-1-phenylbutyl group). The aralkyl group may be substituted with a substituent such as a C _1-6 alkoxy group or a carboxyl group. Examples of the aralkyl group having a substituent include (methoxyphenyl) ethyl group (such as 2- (4-methoxyphenyl) ethyl group), (carboxyphenyl) ethyl group (such as 2- (4-carboxyphenyl) ethyl group) (carboxy Phenyl) propyl group (3- (2-carboxyphenyl) propyl group and the like) and the like.

The aryl group of R ² and R ³ may be unsubstituted or may have a substituent such as an aliphatic hydrocarbon group, a hydroxyl group, or a carboxyl group. Carbon number of the said aryl group is counted including carbon number of a substituent, is 6-14, Preferably it is 6-10. Examples of these aryl groups include phenyl group, hydroxylphenyl group (2-hydroxylphenyl group, 3,4,5-trihydroxylphenyl group, etc.), carboxyphenyl group (2-carboxyphenyl group, 2,4-dicarboxyl group). Phenyl group etc.), trifluoromethylphenyl group (4-trifluoromethylphenyl group etc.), unsubstituted or substituted phenyl groups such as methoxyphenyl group (4-methoxyphenyl group etc.) and the like.

The azo compound (I) is preferably a compound represented by the formula (II) (hereinafter sometimes referred to as azo compound (II)).
[In formula (II), R ² and R ³ represent the same meaning as in formula (I).
A is at least one 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 one or two groups, or at least one group selected from the group consisting of an N-substituted azo group, a sulfone group, a sulfamoyl group and an N-substituted sulfamoyl group. The naphthylene group which may have one piece is represented.
R ⁴ and R ⁵ are each independently a hydrogen atom, a C _1-16 aliphatic hydrocarbon group which may have a substituent, or a C _3-16 alicyclic group which may have a substituent. It represents a hydrocarbon group, an _optionally substituted C _7-20 aralkyl group, or an _optionally substituted C _6-14 aryl group.
R ⁶ represents a hydrogen atom, a cyano group, or a carbamoyl group.
The compound represented by the formula (II) may form a dimer or more multimer at an arbitrary position. ]

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 carboxyl group, an N-substituted azo group, a sulfone group, a sulfamoyl group, and an N-substituted sulfamoyl group. At least one selected from the group consisting of a phenylene group which may have one or two selected groups, or an N-substituted azo group, a sulfone group, a sulfamoyl group and an N-substituted sulfamoyl group. Represents a naphthylene group optionally having 1 to 3 groups. 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, so that it can be dissolved in water-soluble and organic solvents. It can have solubility. In order to improve the solubility in an organic solvent, in the 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 one group selected.

As the N-substituted sulfamoyl group, a —SO ₂ NHR ² group (R ² represents the above-described substituent) or a —SO ₂ NHR ² (COR ³ ) group (R ² and R ³ are the above-described substituents). Represents a group). The azo compound or a salt thereof of the present invention can have both water solubility and solubility in an organic solvent by having an N-substituted sulfamoyl group.

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

The part 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 . The carbon number of the aralkyl group does not include the carbon number of the substituent, and the carbon number is 7 to 20, preferably 7 to 10. Specific examples of the aralkyl group for R ⁴ and R ⁵ are the same as those for R ² and R ³ . The aralkyl group may be substituted with a substituent such as a C _1-6 alkoxy group or a carboxyl group.

As in the case of R ² and R ³ , the aryl group of R ⁴ and R ⁵ may be unsubstituted or may have a substituent such as an aliphatic hydrocarbon group, a hydroxyl group or a carboxyl group. Good. The carbon number is counted including the carbon number of a substituent, and is 6-14, Preferably it is 6-10. Specific examples of the aralkyl group for R ⁴ and R ⁵ are the same as those for R ² and R ³ .

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

In order to increase the color density, 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.). Preferably there is. In order to improve the solubility in an organic solvent, R ² is preferably an aliphatic hydrocarbon group having 6 to 12 carbon atoms.

In order to increase the color density, R ⁵ is preferably an aliphatic hydrocarbon group having 3 or less carbon atoms (eg, a methyl group, an ethyl group, etc., particularly a methyl group). In order to increase the solubility in an organic solvent, R ⁴ is preferably an aliphatic hydrocarbon group having 2 to 12 carbon atoms.

  In order to further increase the color density, A is preferably a para-substituted phenylene group or a meta-substituted phenylene group. Para-substitution here means that the azo group and sulfamoyl group in the formula (II) are in a para positional relationship on the phenylene group.

When two or more azo compounds (I) are used in combination, the amount dissolved in an organic solvent tends to be larger than when one of them is used alone. As a dye for a liquid crystal display device, azo compound (I) It is also preferable to use a combination of two or more. As an example of a combination that improves the solubility in an organic solvent, an azo compound having two N-substituted sulfamoyl groups (disulfonamide) and an azo compound having one N-substituted sulfamoyl group and one sulfone group (monosulfone) A combination with amide).
Monosulfonamide is particularly preferred from the viewpoint of color density because of its low molecular weight.

In order to increase the solubility in an organic solvent, R ^{2 to} R ⁵ are preferably a branched aliphatic hydrocarbon group and an aliphatic hydrocarbon group to which two or more halogen atoms are bonded, such as a tert-butyl group. Particularly preferred are aliphatic hydrocarbon groups to which 3 or more halogen atoms are bonded, such as tertiary aliphatic hydrocarbon groups and trifluoromethyl groups. By selecting a bulky group, stacking of azo dyes can be reduced and solubility in organic solvents can be increased. Further, by selecting a bulky group, the azo group can be protected and the light resistance can be improved.

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

  Of the azo compounds (I), more preferable in terms of chromaticity are pyridone azo compounds such as the compound represented by the formula (II).

  The present invention includes not only the compounds represented by formula (I) and formula (II) but also salts thereof. Examples of the salt include a sulfonate salt having a sulfone group in the molecule and a carboxylate salt having a carboxyl group. The cations forming these salts are not particularly limited, but considering solubility in solvents, alkali metal salts such as lithium salts, sodium salts and potassium salts; ammonium salts; and ethanolamine salts and alkylamine salts. Organic amine salts and the like are preferred. In particular, an alkali metal salt (preferably a sodium salt) is useful when contained in a polarizing film substrate. Further, the organic amine salt is useful when it is contained in the curable resin composition, and is also useful in a field where insulation is important because it is a non-metallic salt.

As a method for producing the azo compound (I), for example, a method described in JP-B-7-88633 represented by the formula (VI), an azo compound represented by the formula (III) (hereinafter referred to as an azo compound (III) And a method of reacting an acylating agent with each other, and a method of reacting an azo compound (III) with an acylating agent is preferred.

  As the azo compound (III), an azo compound described in Japanese Patent Publication No. 7-88633 or the like is preferably used in addition to a commonly distributed dye (such as CI Solvent Yellow 162 manufactured by BASF). Can do.

As the acylating agent, known substances such as acid anhydrides and acid chlorides can be used, and acid anhydrides are more preferable from the viewpoint of reactivity.
Preferred examples of the acid chloride include acetic acid chloride, propionic acid chloride, butyric acid chloride, and benzoyl chloride.

  As the acid anhydride, an aliphatic carboxylic acid or an aromatic carboxylic acid anhydride can be used, and a linear or cyclic anhydride may be used. Specifically, acetic anhydride, propionic anhydride, maleic anhydride Butyric anhydride, succinic anhydride, hymic anhydride, phthalic anhydride and the like are preferably used. There is no restriction | limiting in particular in the kind of acylating agent to be used, You may use together 2 or more types of acylating agents. The amount of the acylating agent used is preferably about 1 to 3 moles relative to 1 mole of the azo compound (III). When water is brought into the reaction system, it is preferable to use an acid anhydride in excess of the 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, and 4-pyrrole Examples include dinopyridine. From the viewpoint of improving the reaction rate, 4-dimethylaminopyridine and 4-pyrrolidinopyridine are particularly preferable. The usage-amount of an 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 2 or more types of organic amine.

The reaction between the azo compound (III) and the acylating agent is preferably performed in an organic solvent. Examples of the solvent include ethers such as 1,4-dioxane (particularly cyclic ethers);
Halogenated hydrocarbons such as chloroform, methylene chloride, carbon tetrachloride, 1,2-dichloroethane, dichloroethylene, trichloroethylene, perchloroethylene, dichloropropane, amyl chloride, 1,2-dibromoethane;
Ketones such as acetone, methyl isobutyl ketone, cyclohexanone;
Examples thereof include carbon-based aromatics such as benzene, toluene and xylene, and two or more kinds of solvents may be used in combination. The amount of the solvent used is, for example, about 1 part by mass (preferably 5 parts by mass or more) and 20 parts by mass or less (preferably 10 parts by mass or less) with respect to 1 part by mass of the azo compound (III).

The reaction between the azo compound (III) and the acylating agent is performed in a nitrogen atmosphere or an argon atmosphere, but the reaction proceeds even in air dried with calcium chloride or the like.
The reaction temperature is, for example, 0 ° C. or higher (preferably 10 ° C. or higher) and 70 ° C. or lower (preferably 60 ° C. or lower). 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 the acid anhydride is preferably added (dropped) to the reaction solution composed of the azo compound (III), the organic amine, and the organic solvent.

  The method for obtaining the target compound azo compound (I) from the reaction mixture is not particularly limited, and various known techniques can be employed. For example, a method of purifying the reaction mixture by extraction with an organic solvent, specifically, The reaction mixture, an organic solvent and water are mixed, the azo compound (I) is eluted into the organic phase, and the organic phase separated by a separating funnel is distilled off to remove the azo compound (I). The method of obtaining is mentioned. The extraction temperature is preferably 10 ° C. or higher (preferably 20 ° C. or higher) and 50 ° C. or lower (preferably 30 ° C. or lower). The extraction is preferably stirred at the same temperature for about 0.5 to 4 hours. The azo compound (I) after extraction is usually washed with alcohol or the like and then dried. Moreover, you may refine | purify further by well-known methods, such as recrystallization, as needed.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited by these Examples. In the examples, “%” and “part” representing the content and the amount used are mass% and part by mass unless otherwise specified.

Example 1
The following reaction was performed in a nitrogen atmosphere. After adding 0.6 parts of 4-dimethylaminopyridine, 20 parts of triethylamine, and 200 parts of chloroform to 32 parts of Solvent Yellow162 (manufactured by BASF) represented by the formula (A-1), the reaction solution is stirred for 30 minutes. Prepared. Under ice cooling, 9 parts of acetic anhydride was added dropwise over 30 minutes while stirring the reaction solution. After completion of dropping, the mixture was stirred for 12 hours while returning to room temperature. The reaction solution was poured into 2 liters of water, 1 liter of ethyl acetate was added, and the mixture was stirred for 2 hours. The organic phase was separated using a separatory funnel and then washed with 2 liters of water. The separated organic phase was evaporated 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 an azo compound represented by the 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. ECA-500 (manufactured by JASCO Corporation) was used as the NMR apparatus, and JMS-700 (manufactured by JEOL Ltd.) was used as the mass spectrometer. :
¹ H-NMR (500 MHz, δ value (ppm, TMS standard), DMSO); 0.86-0.92 (9H, m), 1.23-1.36 (10H, 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, br.d, J = 8.4 Hz), 14.9 (1H, s)
¹³ C-NMR (125 MHz, δ value (ppm, TMS standard), 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 a volume of 250 cm ³ , 2 cm ^{3 of} which was diluted with ethyl lactate to a volume of 100 cm ³ (concentration: 0.028 g / L ), And the absorption spectrum was measured using a spectrophotometer [quartz cell, cell length is 1 cm]. This compound showed an absorbance of 2.48 (arbitrary unit) at λmax = 423 nm.

Example 2
The following reaction was performed in a nitrogen atmosphere. After adding 0.2 parts of 4-dimethylaminopyridine, 6.1 parts of triethylamine, and 62 parts of chloroform to 10.0 parts of Solvent Yellow162 (manufactured by BASF) represented by the formula (A-1), the mixture was stirred for 30 minutes. A reaction solution was prepared. Under ice-cooling, 2.2 parts of succinic anhydride was added while stirring the reaction solution. After completion of dropping, the mixture was stirred for 12 hours while returning to room temperature. The reaction solution was poured into 2 liters of water, 0.5 liters of ethyl acetate was added, and the mixture was stirred for 2 hours. The organic phase was separated using a separatory funnel and then washed with 1 liter of water. The separated organic phase was distilled off to obtain 8.5 parts of a crude product. The crude product was washed with 0.2 liters of methanol to obtain 7.6 parts of an azo compound represented by the 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. ECA-500 (manufactured by JASCO Corporation) was used as the NMR apparatus, and JMS-700 (manufactured by JEOL Ltd.) was used as the mass spectrometer. :
¹ H-NMR (500 MHz, δ value (ppm, TMS standard), DMSO); 0.88-0.94 (9H, m), 1.23-1.37 (11H, m), 1.54 (2H , Qq, J = 6.8, 6.9 Hz), 1.73 (1H, m), 2.62 (3H, 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 (2H, br.d, J = 8.4 Hz), 14.9 (1H, s)
¹³ C-NMR (125 MHz, δ value (ppm, TMS standard), 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 a volume of 250 cm ³ , 2 cm ^{3 of} which was diluted with ethyl lactate to a volume of 100 cm ³ (concentration: 0.028 g / L ), And the absorption spectrum was measured using a spectrophotometer [quartz cell, cell length is 1 cm]. This compound showed an absorbance of 2.46 (arbitrary unit) at λmax = 426 nm.

Example 3
After adding 150 parts of water to 25.0 parts of 3-methylaniline-4-sulfonic acid represented by the formula (B-1), the pH was adjusted to 7 to 8 with a 30% aqueous sodium hydroxide solution under ice cooling. The following operations were performed under ice cooling. 27.6 parts of sodium nitrite was added and stirred for 30 minutes. After adding 97.4 parts of 35% hydrochloric acid little by little to make a brown solution, the mixture was stirred for 2 hours. An aqueous solution obtained by dissolving 25.1 parts of amidosulfuric acid in 250 parts of water was added to the reaction solution and stirred to obtain a suspension containing a diazonium salt.

  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 30% under ice cooling. The pH was adjusted to 8-9 with an aqueous sodium hydroxide solution.

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

  The following reaction was performed in a nitrogen atmosphere. Into a flask equipped with a condenser and a stirrer, 30 parts of an azo compound (D-1), 300 parts of chloroform and 11.9 parts of N, N-dimethylformamide were added, while maintaining at 20 ° C. or lower with stirring, 16.6 parts of thionyl chloride was added dropwise. After completion of the dropwise addition, the temperature was raised to 50 ° C., the reaction was continued for 5 hours at the same temperature, and then cooled to 20 ° C. While maintaining the reaction solution after cooling at 20 ° C. or lower with stirring, a mixed solution of 47.9 parts of 2-ethylhexylamine and 90.1 parts of triethylamine was added dropwise. Then, it was made to react by stirring at the same temperature for 5 hours. Next, after the solvent of the obtained reaction mixture was distilled off with a rotary evaporator, a small amount of methanol was added and stirred vigorously. This mixture was added to a mixed solution of 60 parts of acetic acid and 600 parts of ion-exchanged water with stirring to precipitate crystals. The precipitated crystals were separated by filtration, washed well with ion exchange water, and dried under reduced pressure at 60 ° C. to obtain 27.0 parts (yield 71%) of the azo compound represented by the formula (A-2).

  The following reaction was performed in a nitrogen atmosphere. After adding 0.1 part of 4-dimethylaminopyridine, 2.0 parts of triethylamine and 26.9 parts of chloroform to the azo compound part represented by the formula (A-2), the reaction solution is prepared by stirring for 30 minutes. did. Under ice cooling, 1.1 parts of acetic anhydride was added dropwise over 30 minutes while stirring the reaction solution. After completion of dropping, the mixture was stirred for 12 hours while returning to room temperature. The reaction solution was poured into 2 liters of water, 0.5 liters of ethyl acetate was added, and the mixture was stirred for 2 hours. The organic phase was separated using a separatory funnel and then washed with 1 liter of water. The separated organic phase was distilled off to obtain 4.0 parts of a crude product. The crude product was washed with 1 liter of methanol to obtain 3.7 parts of an azo compound represented by the 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. ECA-500 (manufactured by JASCO Corporation) was used as the NMR apparatus, and JMS-700 (manufactured by JEOL Ltd.) was used as the mass spectrometer. :
¹ H-NMR (500 MHz, δ value (ppm, TMS standard), DMSO); 0.90-0.97 (9H, m), 1.26-1.48 (10H, m), 1.60 (2H) , Qq, J = 6.8, 6.8 Hz), 1.81 (1H, m), 2.23 (3H, 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, br.d) , J = 8.7 Hz), 8.03 (1H, br.d, J = 8.7 Hz), 14.8 (1H, s)
¹³ C-NMR (125 MHz, δ value (ppm, TMS standard), 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 a volume of 250 cm ³ , 2 cm ^{3 of} which was diluted with ethyl lactate to a volume of 100 cm ³ (concentration: 0.028 g / L ), And the absorption spectrum was measured using a spectrophotometer [quartz cell, cell length is 1 cm]. This compound showed an absorbance of 2.41 (arbitrary unit) at λmax = 425 nm.

Example 4
The following reaction is performed in a nitrogen atmosphere. After adding 0.9 parts of 4-dimethylaminopyridine, 20.0 parts of triethylamine, and 200 parts of chloroform to 35.0 parts of Solvent Yellow162 (manufactured by BASF) represented by the formula (A-1), the reaction is conducted with stirring. Prepare the solution. Under ice cooling, 6.0 parts of acetic acid chloride is 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. The organic phase is separated using a separatory funnel and then washed with 2 liters of water. The separated organic phase is evaporated to obtain 24.9 parts of a crude product. The crude product is washed with 1 liter of methanol to obtain an azo compound represented by the formula (II-1).

Comparative Example 1
400 parts of water was added to 40.0 parts of sulfanilic acid represented by the formula (B-2), and then adjusted to pH 7 to 8 with a 30% aqueous sodium hydroxide solution under ice cooling. The following operations were performed under ice cooling. 19.1 parts of sodium nitrite was added and stirred for 30 minutes. After adding 72.2 parts of 35% hydrochloric acid little by little to give a brown solution, the mixture was stirred for 2 hours. An aqueous solution obtained by dissolving 4.4 parts of amidosulfuric acid in 30 parts of water was added to the reaction solution and stirred to obtain a suspension containing a diazonium salt.

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

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

  A flask equipped with a condenser and a stirrer was charged with 5 parts of an azo compound (D-2), 50 parts of chloroform and 2.1 parts of N, N-dimethylformamide, and while maintaining the temperature at 20 ° C. or lower with stirring, 6 parts of thionyl chloride was added dropwise. After completion of the dropwise addition, the temperature was raised to 50 ° C., the reaction was continued for 5 hours at the same temperature, and then cooled to 20 ° C. While maintaining the reaction solution after cooling at 20 ° C. or lower with stirring, a mixed solution of 4 parts of 3-isopropoxypropylamine and 14 parts of triethylamine was added dropwise. Then, it was made to react by stirring at the same temperature for 5 hours. Next, after the solvent of the obtained reaction mixture was distilled off with a rotary evaporator, a small amount of methanol was added and stirred vigorously. This mixture was added to a mixed solution of 29 parts of acetic acid and 300 parts of ion-exchanged water with stirring to precipitate crystals. The precipitated crystals were separated by filtration, washed well with ion-exchanged water, and dried under reduced pressure at 60 ° C. to obtain 3.5 parts (yield 56%) of the azo compound represented by the formula (A-3).

0.35 g of the obtained azo compound (A-3) was dissolved in ethyl lactate to 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), an absorption spectrum was measured using a spectrophotometer (quartz cell, optical path length: 1 cm). This compound showed an absorbance of 2.77 (arbitrary unit) at λmax = 430 nm.

Comparative Example 2
The following azo compound was synthesized by the method described in JP-B-7-88633. Azo compound (A-4) 0.35 g was dissolved in ethyl lactate to 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), The absorption spectrum was measured using a spectrophotometer (quartz cell, optical path length: 1 cm). This compound showed an absorbance of 2.6 (arbitrary unit) at λmax = 425 nm.

The components used in the following examples are as follows, and may be abbreviated 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 Taoka Chemical Co., Ltd.) )
(G-1) Solvent: N, N-dimethylformamide

Example 5
[Preparation of colored composition 1]
(II-1) 0.51 part by mass (F-1) 1.19 parts by mass (G-1) 8.30 parts by mass were mixed to obtain a colored composition 1.

Next, on the glass (# 1737; Corning), the colored composition 1 obtained above was applied by spin coating, and then the volatile components were volatilized at 100 ° C. for 3 minutes to form a coating film of the colored composition 1. .
In the coating film, the spectrum was measured using a colorimeter (OSP-SP-200; manufactured by Olympus Corporation), and the xy chromaticity coordinates in the XYZ color system of the CIE using the color matching function of the C light source ( Bx, By) and brightness were measured.

[Evaluation 1] Heat resistance evaluation method The obtained coating film was heated at 230 ° C. for 120 minutes, the chromaticity after heating was measured in the same manner as described above, and the color difference (ΔEab *) before and after heating was determined.
As an evaluation standard for color difference, if ΔEab * is 6 or less, almost no change in hue is observed, showing good characteristics as a color filter, and if ΔEab * is more than 6 and less than 10, slight hue change is recognized. However, if the color filter has a practically no problem level and ΔEab * is 10 or more, a clear hue change can be confirmed, which is a problematic level for the color filter.

[Evaluation 2] Light resistance evaluation method An ultraviolet cut filter (COLORED OPTICAL GLASS L38; manufactured by Hoya Co., Ltd.) is layered on the obtained coating film, and a light resistance tester (SUNTEST CPS +: manufactured by Toyo Seiki Seisakusho Co., Ltd.). ) Was irradiated with xenon lamp light for 48 hours.
Next, the chromaticity after the light resistance test was measured, and the color difference (ΔEab *) before and after the light resistance test was determined.

[Evaluation of coating film]
As a result of evaluating the obtained coating film in the same manner as described above, the color difference (ΔEab *) in the heat resistance evaluation was 4.0, and the color difference (ΔEab *) in the light resistance evaluation was 0.5. It was.

Example 6
[Preparation of Coloring Composition 2]
A colored composition 2 was obtained by mixing in the same manner as in Example 5 except that the colorant (II-1) in Example 5 was changed to the colorant (II-4).

[Formation and evaluation of coating film]
A coating film was prepared and evaluated in the same manner as in Example 5. As a result, the color difference (ΔEab *) in heat resistance evaluation was 4.9, and the color difference (ΔEab *) in light resistance evaluation was 0.6. Met.

Example 7
[Preparation of colored composition 3]
A colored composition 3 was obtained by mixing in the same manner as in Example 5 except that the colorant (II-1) in Example 5 was changed to the colorant (II-43).

[Formation and evaluation of coating film]
A coating film was prepared and evaluated in the same manner as in Example 5. 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. Met.

Comparative Example 3
[Preparation of Colored Composition 4]
A colored composition 4 was obtained by mixing in the same manner as in Example 5 except that the colorant (II-1) in Example 5 was changed to the colorant (A-1).

[Formation and evaluation of coating film]
A coating film was prepared and evaluated in the same manner as in Example 5. As a result, 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. Met.

Comparative Example 4
[Preparation of colored composition 5]
A colored composition 5 was obtained by mixing in the same manner as in Example 5 except that the colorant (II-1) in Example 5 was changed to the colorant (A-3).

[Formation and evaluation of coating film]
A coating film was prepared and evaluated in the same manner as in Example 5. As a result, 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. Met.

Comparative Example 5
[Preparation of colored composition 6]
A colored composition 6 was obtained by mixing in the same manner as in Example 5 except that the colorant (II-1) in Example 5 was changed to the colorant (A-4).

[Formation and evaluation of coating film]
A coating film was prepared and evaluated in the same manner as in Example 5. As a result, 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. Met.

  From the above results, it is understood that the azo compound of the present invention has improved heat resistance and light resistance as compared with the conventional azo compound.

Since the azo compound of the present invention or a salt thereof can form a coating film having excellent heat resistance and light resistance, coloring of color filters used in display devices such as liquid crystal display panels, electroluminescence, and plasma display panels. It can be suitably used as an agent.

Claims (6)

An azo compound represented by the formula (I) or a salt thereof.


[In Formula (I), R ¹ represents an organic group having an azo group.
R ² and R ³ are each independently a C _1-16 aliphatic hydrocarbon group which may have a substituent, or a C _3-16 alicyclic hydrocarbon group which may have a substituent. Represents a C _7-20 aralkyl group which may have a substituent, or a C _6-14 aryl group which may have a substituent. ] The azo compound or a salt thereof according to claim 1, wherein the azo compound or a salt thereof represented by the formula (I) is an azo compound or a salt thereof represented by the formula (II).


[In formula (II), R ² and R ³ represent the same meaning as in formula (I).
A is at least one 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 one or two groups, or at least one group selected from the group consisting of an N-substituted azo group, a sulfone group, a sulfamoyl group and an N-substituted sulfamoyl group. The naphthylene group which may have one piece is represented.
R ⁴ and R ⁵ are each independently a hydrogen atom, a C _1-16 aliphatic hydrocarbon group which may have a substituent, or a C _3-16 alicyclic group which may have a substituent. It represents a hydrocarbon group, an _optionally substituted C _7-20 aralkyl group, or an _optionally substituted C _6-14 aryl group.
R ⁶ represents a hydrogen atom, a cyano group, or a carbamoyl group. ] A method for producing an azo compound represented by formula (I), comprising a step of reacting an azo compound represented by formula (III) with an acylating agent.


[In Formula (I) and Formula (III), R ¹ represents an organic group having an azo group.
R ² and R ³ are each independently a C _1-16 aliphatic hydrocarbon group which may have a substituent, or a C _3-16 alicyclic hydrocarbon group which may have a substituent. Represents a C _7-20 aralkyl group which may have a substituent, or a C _6-14 aryl group which may have a substituent. ]   The process according to claim 3, wherein the acylating agent is an acid chloride or an acid anhydride.   A dimer of the azo compound or a salt thereof according to claim 1.   A dimer of the azo compound or a salt thereof according to claim 2.