KR20090004758A - Azo compound or its salt - Google Patents

Abstract

A novel azo compound or its salt is provided to improve the color density, thereby obtaining the dyed product having a good quality even with using a small amount of a dye and reducing the cost. An azo compound is represented by the formula I, wherein R1 to R4 are independently H, a C1-C10 saturated aliphatic hydrocarbon group or a carboxyl group; R5 to R12 are independently H, a halogen atom, a C1-C10 saturated aliphatic hydrocarbon group, a halogenated C1-C10 saturated aliphatic hydrocarbon group, a C1-C8 alkoxy group, a carboxyl group, a sulfonyl group, a sulfamoyl group or an N-substituted sulfamoyl group; and R13 and R14 are independently H, a cyano group, a carbamoyl group or an N-substituted carbamoyl group.

Description

Azo compound or its salt {AZO COMPOUND OR ITS SALT}

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

Conventionally, dyes, such as an azo compound, have been used for color display using reflected light or transmitted light in various fields (for example, a fiber material, a liquid crystal display device, etc.), For example, the azo compound which has a pyridone ring is also known. (Patent Documents 1 to 4, etc.). More specifically, Patent Documents 1 and 2 disclose pigments in which one biphenyl skeleton (biphenylene group) and two pyridone rings are linked to two azo groups, and Patent Document 3 discloses two phenyl groups, phenylene groups and pyridone rings. The dye connected with the azo group is disclosed, and patent document 4 has disclosed the pigment | dye with which the phenyl group and the pyridone ring were connected with the azo group. In these patent documents 1-3, it does not describe at all about the color density of these pigment | dyes. On the other hand, the structure of the pigment | dye currently disclosed by patent document 4 is completely different from the azo compound or its salt of this invention described in detail below.

Patent Document 1: German Patent Application Publication No. 3416327

Patent Document 2: US Patent No. 3979378

Patent Document 3: Japanese Patent Laid-Open No. 51-64536

Patent Document 4: Japanese Patent Publication Hei 7-88633

In recent years, the demand from the consumer about the color density and color of a dyestuff is becoming severe, especially the novel azo compound or its salt with high color density is calculated | required. It is therefore an object of the present invention to provide a novel azo compound or salt thereof which exhibits a high color density.

As a result of earnestly examining in order to further improve the color density of an azo compound or its salt, the present inventors discovered that the compound or its salt which the pyridone ring was connected through the azo group at both ends of a biphenyl skeleton shows high color density. From such knowledge, the azo compound or its salt of this invention which could achieve the said objective is represented by Formula (I). In addition, the azo compound represented by Formula (I) or its salt may be abbreviated as "azo compound (I)" below. The compound represented by another chemical formula or its salt may also be abbreviated similarly.

Equation (Ⅰ) of, R ¹ ~ R ⁴ represents a hydrogen atom, C _{1 -10} saturated aliphatic hydrocarbon group or a carboxyl group each independently.

R ⁵ ~ R ¹² each independently represent a hydrogen atom, a halogen atom, a C _{1 -10} aliphatic saturated hydrocarbon group, a halogenated C _{1 -10} saturated aliphatic hydrocarbon group, a C _{1 -8} alkoxy group, a carboxyl group, a sulfo group, a sulfamoyl group, Or an N-substituted sulfamoyl group.

R ¹³ and R ¹⁴ each independently represent a hydrogen atom, a cyano group, a carbamoyl group, or an N-substituted carbamoyl group.

In addition, in this invention, C _{a -b} means that carbon number is more than a and less than b.

In formula (I), Preferably R <^5> -R <^12> At least one is an N-substituted sulfamoyl group. At least one of R ⁵ to R ⁸ , and R ⁹ to R ¹² medium More preferably, at least one is an N-substituted sulfamoyl group, and R ⁵ and R ⁸ At least one of, and R ⁹ and R ¹² It is more preferable that at least one of them is an N-substituted sulfamoyl group. The N- substituted a sulfamoyl group -SO ₂ NHR ¹⁵ group (R ¹⁵ is C _{1 -10} saturated aliphatic hydrocarbon group, a C _{1 -8} alkoxy group a C _{1 -10} aliphatic saturated hydrocarbon group which is substituted, the number of carbon atoms is 6 to An aryl group having 20, an aralkyl group having 7 to 20 carbon atoms, or an acyl group having 2 to 10 carbon atoms) is preferable. By having an N-substituted sulfamoyl group, preferably -SO ₂ NHR ¹⁵ group, the azo compound or salt thereof of the present invention can have both water solubility and usefulness. In formula (I), Preferably it is R <^13> and R <^14>. At least one of them is a cyano group. The azo compound of the present invention having a cyano group or a salt thereof may exhibit a particularly high color density. In addition, R ¹³ and R ¹⁴ At least one of -CON (R ¹⁶⁾ R ¹⁷ group (wherein, R ¹⁶ and R ¹⁷ each independently represent a hydrogen atom, C _{1 -10} saturated aliphatic hydrocarbon groups, C _{1 -8} alkoxy group in C ₁ is substituted _-10 saturated aliphatic hydrocarbon groups, aryl groups having 6 to 20 carbon atoms, aralkyl groups having 7 to 20 carbon atoms, or acyl groups having 2 to 10 carbon atoms) are also preferred azo compounds or salts thereof of the present invention.

The azo compound or salt thereof of the present invention also includes tautomers thereof in addition to those represented by formula (I).

(Effects of the Invention)

The azo compound or its salt of this invention shows high color density, and is useful as a pigment | dye used for a fiber material, a liquid crystal display device, etc., for example.

The azo compound or its salt of this invention has a pyridone ring through an azo group at both ends of a biphenyl skeleton as represented by Formula (I), It is characterized by the above-mentioned. In addition, in addition to the enol type represented by Formula (I), a part of a pyridone ring contains a keto type. By such a structure, the azo compound or its salt of this invention shows high color density. Moreover, the azo compound or its salt of this invention is excellent also in the solubility (especially usefulness) as a solvent in the preferable form, and is also suitable for the color display using transmitted light. Moreover, in the said solvent, volatiles, such as hydroxycarboxylic acid esters (ethyl lactate etc.), hydroxy ketones (diacetone alcohol etc.), ethers (propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate etc.) This low water soluble solvent is selected.

Formula (I) is explained in full detail below. Equation (Ⅰ) of, R ¹ ~ R ⁴ represents a hydrogen atom, C _{1 -10} saturated aliphatic hydrocarbon group or a carboxyl group. The saturated aliphatic hydrocarbon group of R ¹ to R ⁴ may be linear, branched or cyclic. The carbon number of the saturated aliphatic hydrocarbon group does not include the carbon number of the substituent. The lower limit of the carbon number is usually 1, preferably 2, and the upper limit of the carbon number is usually 10, preferably 8, more preferably 6, still more preferably 3. The saturated aliphatic hydrocarbon group includes, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group and the like.

Equation (Ⅰ) of, R ⁵ ~ R ¹² each independently represent a hydrogen atom, a halogen atom (preferably a fluorine atom, a chlorine atom or a bromine atom), C _{1 -10} saturated aliphatic hydrocarbon group (a saturated aliphatic C _{1 -10} including that the halogen atom is bonded to a hydrocarbon), C _{1 -8} represents an alkoxyl group, a carboxyl group, a sulfo group, a sulfamoyl group, or N- substituted sulfamoyl group.

As in the case of R ¹ to R ⁴ , the saturated aliphatic hydrocarbon group of R ⁵ to R ¹² may be linear, branched or cyclic, and its carbon number is usually 1 to 10, preferably 2 to 8, and more. Preferably it is 3-6. Specific examples of the saturated aliphatic hydrocarbon group of R ⁵ to R ¹² are the same as those of R ¹ to R ⁴ . The saturated aliphatic hydrocarbon group of R ⁵ to R ¹² may be substituted with a halogen atom, preferably a fluorine atom. Specific examples of the halogenated saturated aliphatic hydrocarbon group include trifluoromethyl group and the like.

Carbon number of the alkoxyl group of R <^5> -R <^12> is 1-8 normally, Preferably it is 1-4. As this alkoxyl group, a methoxy group, an ethoxy group, isopropoxy group, n-propoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, etc. are mentioned, for example.

The N-substituted sulfamoyl group of R ⁵ to R ¹² is, for example, an N-1 substituted sulfamoyl group, and can be represented by the formula -SO ₂ NHR ¹⁵ . The R ¹⁵ is C _{1 -10} saturated aliphatic hydrocarbon group (a C _{1 -10} including that with a C _{1 -8} alkoxy group, saturated aliphatic hydrocarbon groups combined), an aryl group having 6 to 20 carbon atoms, aralkyl of 7 to 20 Or a acyl group having 2 to 10 carbon atoms.

The saturated aliphatic hydrocarbon group for R ¹⁵ may be linear, branched or cyclic. The carbon number of the saturated aliphatic hydrocarbon group does not include the carbon number of the substituent. The lower limit of the number of carbon atoms is usually 1, preferably 3, more preferably 6, and the upper limit is usually 10, preferably 8. Examples of the saturated aliphatic hydrocarbon group for R ¹⁵ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group and methylbutyl group (1,1 , 3,3-tetramethylbutyl group, etc.), methylhexyl group (1,5-dimethylhexyl group etc.), ethylhexyl group (2-ethylhexyl group etc.), cyclopentyl group, cyclohexyl group, methylcyclohexyl group (2-methylcyclohexyl group, etc.), a cyclohexyl alkyl group, etc. are contained. Saturated aliphatic hydrocarbon of R ¹⁵ is desired,, C _{1 -8} (preferably C _{1 -4)} may be substituted with a substituent such as an alkoxy group as described above. As this substituted saturated aliphatic hydrocarbon group, a propoxypropyl group (3- (isopropoxy) propyl group etc.) etc. can be illustrated.

The aryl group of R ¹⁵ may be unsubstituted or may have a substituent such as a saturated aliphatic hydrocarbon group or a hydroxyl group. Carbon number of the said aryl group is counted including carbon number of a substituent, and is 6-20 normally, Preferably it is 6-10. As these aryl groups, unsubstituted or substituted phenyl groups, such as a phenyl group, a hydroxyphenyl group (4-hydroxyphenyl group etc.), and a trifluoromethylphenyl group (4-trifluoromethylphenyl group etc.), etc. are mentioned, for example.

The alkyl portion of the aralkyl group of R ¹⁵ may be linear or branched. Carbon number of an aralkyl group is 7-20 normally, Preferably it is 7-10. As this aralkyl, phenylalkyl groups, such as a benzyl group and a phenylbutyl group (3-amino-1-phenylbutyl group, etc.), are typical.

Unsubstituted may be sufficient as the acyl group of R <^15> , and substituents, such as a saturated aliphatic hydrocarbon group and an alkoxyl group, may be couple | bonded. Carbon number of an acyl group is counted including carbon number of a substituent, The number is 2-10 normally, Preferably it is 6-10. The acyl group is, for example, an acetyl group, a benzoyl group, a methoxy benzoyl group (such as a p-methoxybenzoyl group) or the like.

R ¹³ and R ¹⁴ represent a hydrogen atom, a cyano group, a carbamoyl group, or an N-substituted carbamoyl group. The carbamoyl group is -CON (R ¹⁶⁾ R ¹⁷ Formula (wherein, R ¹⁶ and R ¹⁷ is is a hydrogen atom, C _{1 -10} saturated aliphatic hydrocarbon groups, C _{1 -8} alkoxy group substituted independently of C _{1 -10} saturated aliphatic hydrocarbon group, the carbon number can be represented by 6 to 20 aryl group, an aralkyl group, or represents a carbon number of 2-10 is acyl), a carbon number of 7-20. The description and the specific examples of the saturated aliphatic hydrocarbon group, aryl group, aralkyl group and acyl group of R ¹⁶ and R ¹⁷ are as described above for R ¹⁵ . However, as a specific example of an acyl group, the benzoyl group which further contains a halogen atom, for example, a bromobenzoyl group (p-bromobenzoyl group etc.) etc. are mentioned.

R ¹ to R ¹⁷ may be further limited from the viewpoint of increasing color density, water solubility, oil solubility, light resistance, and the like. For example, to increase color depth, R ¹ to R ⁴ It is recommended to select a saturated aliphatic hydrocarbon group (for example, methyl group, ethyl group, etc.) or a hydrogen atom having 5 or less (preferably 3 or less) carbon atoms in at least one of them (preferably all).

Also, to increase color depth, use R ¹⁶ and R ¹⁷ It is recommended to select a saturated aliphatic hydrocarbon group having a carbon number of 3 or less (e.g., a methyl group, especially a methyl group such as a methyl group) or a hydrogen atom in at least one of them (preferably both). Moreover, in order to improve solubility, it is preferable to select an acetyl group for at least 1 of R <^16> and R <^17> .

From the viewpoint of further increasing the color density and water solubility, one or two or more of R ⁵ to R ¹² (for example, one or more (especially one) in R ⁵ to R ⁸ and one or more in R ⁹ to R ¹² ( In particular, it is recommended to use a sulfo group for 1)), and to employ a hydrogen atom or a sulfo group for the remaining R ⁵ to R ¹² . By increasing water solubility, it can be widely used as a pigment in the medical field. As a pigment | dye of a medical field, 1 type of azo compound (I) may be used independently, and 2 or more types may be used together.

From the standpoint of increasing color depth and usability, one or two or more of R ⁵ to R ¹² (e.g., one or more (especially one) of R ⁵ to R ⁸ and one or more of R ⁹ to R ¹² ( In particular, it is recommended to employ a trifluoromethyl group and an N-substituted sulfamoyl group for 1)). Especially R ⁵ to R ¹² Azo compound (I) in which one of the N-substituted sulfamoyl groups is represented by R ⁵ to R ¹² Even if the other one is a hydrophilic sulfo group, it shows high utility. By increasing the usefulness, the usefulness as a pigment in the liquid crystal display field is increased. As a pigment | dye in the field of a liquid crystal display device, 1 type of azo compound (I) may be used independently, and 2 or more types may be used together.

When two or more types of azo compounds (I) are used in combination, the amount of dissolving (soluble) in an organic solvent is larger than that in the case of using one of them alone. Therefore, it is also a preferable aspect to use 2 or more types of combinations of an azo compound (I) as a pigment | dye of a liquid crystal display device from a usability viewpoint. Combination of azo compounds (disulfonamides) having two N-substituted sulfamoyl groups and azo compounds (monosulfonamides) having one N-substituted sulfamoyl group and one sulfo group Can be mentioned. Among these combinations, R ⁵ to R ⁸ One of and one of R ⁹ to R ¹² is an N-substituted sulfamoyl group and the other is a hydrogen atom, and one of R ⁵ to R ⁸ is an N-substituted sulfamoyl group, and R ⁹ to R ¹² Preferred is a combination of monosulfonamides in which one is a sulfo group and the other is a hydrogen atom. Monosulfonamide is more preferable than disulfonamide in terms of color density. This is because the molecular weight is low.

From the standpoint to increase the availability R ⁵ ~ R greater than or equal to 1 or 2 of the ¹² (for example, R ⁵ ~ at least one from R ⁸ (in particular one) and, R ⁹ ~ at least one in R ¹² (especially 1 )) Or a relatively bulky group in the above example, or one or two or more of R ⁵ to R ¹² (for example, one or more (especially one in R ⁵ to R ⁸ ) and R ⁹ to It is also recommended that at least one (particularly one) substitution position in R ^{12 be} a meta position or an ortho position relative to the azo group. By selecting a bulky group or setting the substitution position to the meta position relative to the azo group, stacking of the biphenyl moiety can be reduced, and the usefulness can be improved. In addition, by selecting a bulky group or changing the substitution position to the ortho position relative to the azo group, the azo group can be protected and the light resistance can be improved. Examples of the bulky R ⁵ to R ¹² include halogen atoms of two or more (particularly three or more) such as branched saturated aliphatic hydrocarbon groups (particularly tertiary saturated aliphatic hydrocarbon groups) such as tert-butyl groups and trifluoromethyl groups. The saturated saturated aliphatic hydrocarbon group, N-substituted sulfamoyl group, etc. can be illustrated.

In addition, the R ¹⁵ degree of the N-substituted sulfamoyl group may be further limited from the viewpoint of further increasing the color density, usability, and the like. Such R ¹⁵ includes, for example, a methylbutyl group (1,1,3,3-tetramethylbutyl group, etc.), a methylhexyl group (1,5-dimethylhexyl group, etc.), an ethylhexyl group (2-ethylhexyl) And a branched saturated aliphatic hydrocarbon group such as a methyl group, a methylcyclohexyl group (such as 2-methylcyclohexyl group), and a phenylbutyl group (3-amino-1-phenylbutyl group), or an aralkyl group.

Particularly preferred azo compounds (I) include at least one of R ⁵ to R ¹² , preferably at least two (for example, at least one of R ⁵ to R ⁸ (particularly one), and at R ⁹ to R ¹²⁾ . At least one (particularly one) is an N-substituted sulfamoyl group.

Preferred examples of formula (I) include formulas (I-1) to (I-11).

Moreover, among azo compounds (I), as represented by Formula (II), R <^5> -R <^8>. At least one of (in particular any one of R ⁵ and R ⁸ ), and R ⁹ to R ¹² At least one of them, especially R ⁹ and R ¹² Preferred are compounds in which any one) is a -SO ₂ NHR ¹⁵ group and the remainder are hydrogen atoms. And even more preferred an azo compound (Ⅰ) as equation (Ⅰ) of R ¹ ~ R ⁴ are each independently C _{1 -3} alkyl, the R ⁵ and R ⁹ -SO ₂ NHR ¹⁵ group, and, R ¹⁵ is C _{1 - 10} is an alkyl group (especially _-10 C ₆ alkyl group), and, R ~ ⁶ R ⁷ and R ¹⁰ ~ R ¹² is a hydrogen atom, R ¹³ and R ¹⁴ are each independently a cyano group, or -CON (R ¹⁶⁾ R ^17, R ¹⁶ and R ¹⁷ may be mentioned those wherein each independently represent a hydrogen atom or C _{1 -10} alkyl group (particularly a hydrogen atom).

Preferred examples of formula (II) are formulas (II-1) to (II-8).

This invention is not limited to the compound represented by Formula (I), It also includes the salt. As a salt, the sulfonate salt when R <^5> -R <^12> is a sulfo group, and the carboxylate salt when R <^5> -R <^12> is a carboxyl group is mentioned. In addition, the cation forming these salts is not particularly limited, but considering the solubility in a solvent, alkali metal salts such as lithium salts, sodium salts and potassium salts; 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, organic amine salt is useful when it contains in a resin curable compound, and also is useful also in the field where insulation is important because it is a nonmetal salt.

The azo compounds of the present invention can be prepared by coupling diazonium salts and pyridones, as is well known in the dyeing art. For example, the compound of formula (b) obtained by diazotizing the benzidine compound (diazo component) represented by formula (a) with nitrous acid, nitrite, or nitrite ester can be used as the diazonium salt (formula (a) And (b) R ⁵ to R ¹² represent the same meaning as above).

And an azo compound (I) can be manufactured by making a diazonium salt (b) and the pyridones (coupling component) represented by Formula (c) react at 20-60 degreeC in an aqueous solvent normally (in formula (c) R ¹⁸ represents the same as R ¹ or R ³ , R ¹⁹ represents the same as R ² or R ^4, and R ²⁰ represents the same as R ¹³ or R ¹⁴ ).

R ⁵ to R ¹² in formula (I) Although the target compound whose at least 1 is a sulfamoyl group or N-substituted sulfamoyl group can also be manufactured using compound (a) which has a sulfamoyl group or N-substituted sulfamoyl group, the compound (a) which has a sulfo group It is sure to produce by sulfonamide after carrying out a coupling reaction using a. For example, in formula (I), at least 1 of R <^5> -R <^12> is a sulfo group (henceforth "azosulfonic acid (I)") is synthesize | combined, and a sulfo group (- The sulfo group can be sulfonated by reacting SO ₃ H) with a sulfon halide (-SO ₂ X; X is a halogen atom) and then reacting with an amine.

Preferred examples of azosulfonic acid (I) include formulas (I-1) to (I-7), (I-9) and (I-10), and in particular, formulas (I-1) to (I-3). , (I-9) and (I-10) are mentioned. As a halogenated thionyl compound, thionyl fluoride, thionyl chloride, thionyl bromide, thionyl iodide, etc., Preferably thionyl chloride, thionyl bromide, etc. can be illustrated especially. The use amount of thionyl halide is about 1-10 mol with respect to 1 mol of azosulfonic acid (I), for example. In addition, when water is introduced into the reaction system, it is preferable to use an excess of a halogenated thionyl compound.

Sulfonation is usually carried out in a solvent. As a solvent, For example, ethers, 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, 1,2-dibromoethane and the like can be used. The usage-amount of a solvent is about 3 mass parts or more (preferably 5 mass parts or more), and about 10 mass parts or less (preferably 8 mass parts or less) with respect to 1 mass part of azo compound (I).

In addition, it is recommended to use N, N-dialkylformamide (for example, N, N-dimethylformamide, N, N-diethylformamide, etc.) together in sulfonation halide. When using N, N-dialkylformamide, the usage-amount is about 0.05-1 mol with respect to 1 mol of thionyl halides, for example. After azosulfonic acid (I) and N, N-dialkylformamide are mixed in advance in a solvent, the addition of thionyl halide can suppress the exotherm.

Reaction temperature is 0 degreeC or more (preferably 30 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 8 hours or less (preferably 5 hours or less).

The sulfone halide compound prepared as described above may be isolated and then reacted with an amine, or may be reacted with an amine in a reaction mixture without being isolated. In the case of isolating, for example, the reaction mixture may be mixed with water, and the precipitated crystals may be collected by filtration. The crystal of the obtained sulfon halide compound may be washed with water and dried as necessary before the reaction with the amine.

There may be mentioned for example, a primary amine as the amine, the primary amine is represented by the formula H ₂ NR ¹⁵ (R ¹⁵ is as above). Specific examples of H ₂ NR ¹⁵ include n-propylamine, n-butylamine, n-hexylamine, dimethylhexylamine (such as 1,5-dimethylhexylamine), tetramethylbutylamine (1,1,3,3 -Tetramethylbutylamine etc.), ethylhexylamine (2-ethylhexylamine etc.), aminophenylbutane (3-amino-1-phenylbutane etc.), isopropoxypropylamine, etc. are included. The use amount of the amine is usually about 3 moles or more and about 10 moles or less (preferably 7 moles or less) with respect to 1 mole of the sulfone halide compound. In addition, in this specification, in order to distinguish this amine from the basic catalyst mentioned later, it may be called reactive amine below.

Although the addition order of a sulfon halide compound and an amine is not specifically limited, In many cases, an amine is added (dropped) to a sulfon halide compound. Moreover, reaction of a sulfon halide compound and an amine is normally performed in a solvent. As a solvent, the same solvent as that used when preparing a sulfon halide compound can be used.

In addition, the reaction of the sulfon halide and the reactive amine is preferably carried out in the presence of a basic catalyst. Examples of basic catalysts include tertiary amines (particularly aliphatic tertiary amines such as triethylamine and triethanolamine), pyridine bases such as pyridine and methylpyridine. Among these, aliphatic tertiary amines, such as tertiary amine, especially triethylamine, are preferable. The amount of the basic catalyst to be used is usually about 1.1 moles or more and about 6 moles or less (preferably 5 moles or less) with respect to the reactive amine (the amine reacted with the sulfon halide).

When adding a reactive amine and a basic catalyst to a sulfone halide compound, addition timing of a basic catalyst is not specifically limited, Either before and after addition of a reactive amine may be sufficient, and may be added at the same timing as a reactive amine. Moreover, you may add, after mixing previously with a reactive amine, and you may add separately from a reactive amine.

The reaction temperature of the sulfon halide and the reactive amine is, for example, 0 ° C or more and 50 ° C or less (preferably 30 ° C or less). Moreover, reaction time is about 1 to 5 hours normally.

The method for obtaining the sulfonamide as the target compound from the reaction mixture is not particularly limited, and various known methods can be employed. For example, the reaction mixture is mixed with an acid (acetic acid) and water to filter out the precipitated crystals. You may also The acid and water are often used after preparing an aqueous solution of an acid in advance, and the reaction mixture is often added to the aqueous solution of this acid. The addition temperature of a reaction mixture is 10 degreeC or more (preferably 20 degreeC or more) and 50 degrees C or less (preferably 30 degrees C or less). Moreover, after addition, it is common to stir at the same temperature for 0.5 to 2 hours. The crystals collected by filtration are usually washed with water or the like and then dried. Moreover, you may refine | purify further by well-known methods, such as recrystallization as needed.

EXAMPLE

Hereinafter, although an Example is given and this invention is demonstrated more concretely, this invention is not limited by the following example, Of course, it is also possible to add suitably and implement in the range which may be suitable for the said and following meaning. And they are all included in the technical scope of this invention. In addition, unless otherwise indicated, "%" and "part" in an Example and a comparative example are mass% and a mass part.

(Example 1)

100 parts of water was added to 10 parts of 2,2'-benzidine disulfonic acids (30% of water) represented by Formula (a-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. 5.6 parts of sodium nitrite were added, and it stirred for 30 minutes. A small amount of 14.8 parts of 35% hydrochloric acid was added to give a brown solution, followed by stirring for 2 hours. An aqueous solution in which 3.8 parts of amic sulfate was dissolved in 38.3 parts of water was added to the reaction solution, followed by stirring to obtain a suspension containing a diazonium salt.

After adding 47.9 parts of water to 9.6 parts of 1-ethyl-3-carbamoyl-4-methyl-6-hydroxypyrido-2-one represented by formula (c-1), 30% sodium hydroxide aqueous solution under ice-cooling PH was adjusted to 8-9.

The following operation was performed under ice cooling. After stirring the alkali aqueous solution of the said pyridones to make it a colorless solution, the suspension containing a diazonium salt was dripped by the pump, adjusting to pH 8-9 with 30% sodium hydroxide aqueous solution. After completion of the dropwise addition, the mixture was stirred for 3 hours to obtain a yellow suspension. The yellow solid obtained by filtration was dried at 60 degreeC under reduced pressure, and 15.7 parts of azo compounds represented by Formula (I-1) were obtained.

The structure of the azo compound (I-1) was determined by ¹ H-NMR and ¹³ C-NMR analysis. The analyzer used ECA-500 (made by Nippon Denshi Co., Ltd.).

¹ H-NMR (500 MHz, δ value in ppm, TMS), DMSO); 1.15 (6H, t, J = 6.9 Hz), 2.25 (6H, s), 3.91 (4H, q, J = 6.9 Hz), 7.37 (2H, d, J = 8.5 Hz), 7.46 (2H, dd, J = 8.5, 2.3 kV), 7.51 (2H, br.d, J = 1.9 kV), 7.71 (2H, br.d, J = 1.9 kV), 8.03 (2H, d, J = 2.3 kV), 14.44 (2H , s)

¹³ C-NMR (125 MHz, δ value in ppm, TMS), DMSO); 12.9, 14.1, 33.8, 114.9, 115.1, 123.1, 125.4, 133.9, 135.0, 139.6, 143.8, 146.2, 160.6, 160.7, 166.4

0.35 g of the obtained azo compound (I-1) was dissolved in N, N-dimethylformamide to a volume of 250 cm 3, of which 2 cm 3 was diluted with water to a volume of 100 cm 3 (concentration: 0.028 g / L). Absorption spectrum was measured using the spectrophotometer [The quartz cell and the length of the cell are 1 cm]. The obtained absorption spectrum is shown in FIG. This compound showed an absorbance of 2.86 (arbitrary unit) at λ max = 450 nm.

(Example 2)

156 parts of ethanol and 52 parts of water were added to 10.4 parts of 2,2'-bis (trifluoromethyl) benzidines represented by formula (a-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. 6.7 parts of sodium nitrite were added, and it stirred for 30 minutes. A small amount of 30.4 parts of 35% hydrochloric acid was added to give a brown suspension, followed by stirring for 2 hours. An aqueous solution in which 3.1 parts of amic sulfuric acid was dissolved in 31 parts of water was added to the reaction solution, followed by stirring to obtain a suspension containing a diazonium salt.

15 parts of ethanol and 221 parts of water were added to 14.7 parts of 1-ethyl-3-carbamoyl-4-methyl-6-hydroxypyrido-2-one represented by formula (c-1), and then ice-cooled 30 It was adjusted to pH 8-9 with% aqueous sodium hydroxide solution.

The following operation was performed under ice cooling. After stirring the alkali aqueous solution of the said pyridones to make a brown solution, the suspension containing diazonium salt was dripped by the pump, adjusting to pH 8-9 with 30% sodium hydroxide aqueous solution. After completion of the dropwise addition, the mixture was stirred for 3 hours to obtain a yellow suspension. The yellow solid obtained by filtration was dried at 60 degreeC under reduced pressure, and 19.2 parts of azo compounds represented by a formula (I-8) were obtained.

0.35 g of the obtained azo compound (I-8) was dissolved in ethyl lactate to make a volume of 250 cm 3, of which 2 cm 3 was diluted with ethyl lactate to make a volume of 100 cm 3 (concentration: 0.028 g / L). The absorption spectrum was measured using a quartz cell and a cell length of 1 cm]. The obtained absorption spectrum is shown in FIG. This compound had an absorbance of 2.42 (arbitrary unit) at λ max = 430 nm.

(Example 3)

After 1000 parts of water was added to 100 parts of 2,2'-benzidine disulfonic acid (containing 30% of water) represented by the formula (a-1), the mixture was adjusted to pH 7 to 8 with 30% sodium hydroxide aqueous solution under ice cooling. The following operation was performed under ice cooling. 56.1 parts of sodium nitrite were added and stirred for 30 minutes. A small amount of 148 parts of 35% hydrochloric acid was added to give a brown solution, followed by stirring for 2 hours. An aqueous solution in which 38.3 parts of amid sulfate was dissolved in 383 parts of water was added to the reaction solution, followed by stirring to obtain a suspension containing a diazonium salt.

761 parts of water was added to 76.1 parts of 1-ethyl-3-cyano-4-methyl-6-hydroxypyrido-2-one represented by formula (c-2), and then ice-cooled to 30% aqueous sodium hydroxide solution. pH was adjusted to 8-9.

The following operation was performed under ice cooling. After stirring the alkali aqueous solution of the said pyridones to make it a colorless solution, the suspension containing a diazonium salt was dripped by the pump, adjusting to pH 8-9 with 30% sodium hydroxide aqueous solution. After completion of the dropwise addition, the mixture was stirred for 3 hours to obtain a yellow suspension. The yellow solid obtained by filtration was dried at 60 degreeC under reduced pressure, and 157 parts of azo compounds represented by Formula (I-9) were obtained.

The structure of the azo compound (I-9) was determined by ¹ H-NMR and ¹³ C-NMR analysis. The analyzer used ECA-500 (made by Nippon Denshi Co., Ltd.).

¹ H-NMR (500 MHz, δ value in ppm, TMS), DMSO); 1.14 (6H, t, J = 7.1 μs), 2.53 (6H, s), 3.89 (4H, br.q, J = 7.1 μs), 7.37 (2H, d, J = 8.5 μs), 7.59 (2H, dd , J = 8.5, 2.3 μs), 8.15 (2H, br.d, J = 2.3 μs), 14.73 (2H, br.s)

¹³ C-NMR (125 MHz, δ value in ppm, TMS), DMSO); 12.8, 16.4, 34.5, 100.0, 115.3, 116.3, 116.5, 123.1, 133.9, 136.5, 139.3, 146.1, 158.9, 159.9, 160.2

0.35 g of the obtained azo compound (I-9) was measured under the same conditions as in Example 1. The obtained absorption spectrum is shown in FIG. This compound showed an absorbance of 3.31 (arbitrary unit) at λ max = 463 nm.

(Example 4)

5 parts of azo compound (I-1), 50 parts of chloroform, and 2.1 parts of N, N-dimethylformamide were added to a flask equipped with a cooling tube and a stirring device, and 6 parts of thionyl chloride were added dropwise while maintaining the temperature at 20 ° C. or lower while stirring. Was added. 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 1,5-dimethylhexylamine and 14 parts of triethylamine was added dropwise while maintaining the reaction solution after cooling at 20 ° C. or lower under stirring. Thereafter, the reaction was stirred overnight at the same temperature. Subsequently, the obtained reaction mixture was distilled off the solvent in a rotary evaporator, and a small amount of methanol was added thereto, followed by vigorous stirring. This mixture was added to the mixture of 29 parts of acetic acid and 300 parts of ion-exchanged water with stirring to precipitate crystals. The precipitated crystals were filtered out, washed well with ion exchanged water, and dried under reduced pressure at 60 ° C to obtain 3.6 parts (yield 56%) of azo compound represented by formula (II-1).

The absorption spectrum of the azo compound (II-1) was measured under the same conditions as in Example 2. The obtained absorption spectrum is shown in FIG. This compound showed an absorbance of 2.64 (arbitrary unit) at λ max = 451 nm.

(Example 5)

5 parts of azo compound (I-9), 50 parts of chloroform, and 2.1 parts of N, N-dimethylformamide were charged into a flask equipped with a cooling tube and a stirring device, and 3 parts of thionyl chloride were added dropwise while maintaining the temperature at 20 ° C. or lower while stirring. Was added. 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 1,5-dimethylhexylamine and 14 parts of triethylamine was added dropwise while maintaining the reaction solution after cooling at 20 ° C. or lower under stirring. Thereafter, the reaction was stirred overnight at the same temperature. Subsequently, the obtained reaction mixture was distilled off the solvent by the rotary concentrator, and a small amount of methanol was added thereto, followed by vigorous stirring. This mixture was added to the mixture of 29 parts of acetic acid and 300 parts of ion-exchanged water with stirring to precipitate crystals. The precipitated crystals were filtered out, washed well with ion-exchanged water, and dried under reduced pressure at 60 ° C to obtain 5.6 parts of azo compound.

The structural analysis by LC-MS analysis was performed about the obtained azo compound. The analytical instrument uses Agilent 1100 (manufactured by Agilent Technology), the column uses Sumipax ODS (manufactured by Sumika Bunseki Center Co., Ltd.), and the elution solvent is 0.1% trifluoromethylacetic acid in a water-acetonitrile mixed solvent. The added solvent system was used. As a result, the obtained azo compound has the azo compound represented by Formula (II-6) (disulfonamide, precise mass 944) in 58.3 mass% in total solid content, and the azo compound represented by Formula (I-11) ( Monosulfonamide, a precision mass 833) was a mixture present at 30.1 mass% in the total solid.

The absorption spectrum of the azo compound (II-6) was measured under the same conditions as in Example 2. The obtained absorption spectrum is shown in FIG. This compound had an absorbance of 3.47 (arbitrary unit) at λ max = 452 nm.

(Comparative Example 1)

The absorption spectrum of the azo compound represented by Formula (III-1) ("Neptun Yellow 075" by BASF Corporation) was measured on the conditions similar to Example 2. The obtained absorption spectrum is shown in FIG. This compound showed an absorbance of 2.46 (arbitrary unit) at λ max = 428 nm.

The azo compounds (II-1) and (II-6) of Examples 4 and 5 and the azo compound (III-1) of Comparative Example 1 have almost the same number (molar number) of azo groups, phenyl groups, and pyridone rings per gram. However, the absorbance (concentration: 0.028 g / L) of the azo compound (II-1) is 0.18 larger than that of the azo compound (III-1) at the same concentration. In the azo compound (II-6), the absorbance at the same concentration is 1.01 larger than that of the azo compound (III-1). These results show that the azo compound or salt thereof of the present invention having a pyridone ring at both ends of the biphenyl skeleton has a high color density.

(Example 6)

The availability (solubility in propylene glycol monomethyl ether) of the azo compound (I-1) having a sulfo group and the azo compound (II-1) having an N-substituted sulfamoyl group was determined as follows.

1 g of azo compound and 9 g of propylene glycol monomethyl ether were added to a vial bottle, stirred for one day, and the dissolved and remaining solids were removed by filtration (if the azo compound was completely dissolved, the filtrate concentration was 10% by mass). The absorption spectrum of the filtrate thus obtained was measured in the same manner as in Example 1 except that 3.5 g of the filtrate was used, and the absorbance (Int (a)) at lambda max of each azo compound was obtained. Moreover, absorbance (Int (r)) in (lambda) max of each azo compound was calculated like Example 1 using 0.35 g of each azo compound. And the following formula:

Solubility (mass%) = (Int (a) × 10) / Int (r)

The solubility of each azo compound was calculated from the equation. The results are shown in Table 1.

Azo compounds (I-1) (II-1) Solubility 0.05 mass% 9.54 mass%

The results of Table 1 show that the usefulness of the azo compound of the present invention is improved by introducing an N-substituted sulfamoyl group.

The azo compounds or salts thereof of the present invention exhibit very high color concentrations. Therefore, even a small amount of use can be obtained from the azo compound of the present invention or a salt thereof in the same quality as in the prior art, which is advantageous in terms of cost. Moreover, when using the azo compound of this invention or its salt in curable resin composition for manufacturing a liquid crystal display component, since the usage-amount is at least, a component excellent in performance, such as solvent resistance and heat resistance, can be manufactured. In addition, the azo compound or its salt of this invention may be used independently as an excellent pigment | dye, and may be used in combination with another pigment | dye as a coloring pigment | dye. Thus, the azo compound or its salt of this invention with high color density can be utilized for various uses other than manufacturing a dyeing material or a liquid crystal display component.

BRIEF DESCRIPTION OF THE DRAWINGS It is a figure which shows the absorption spectrum of the azo compound (Example 1) represented by Formula (I-1).

It is a figure which shows the absorption spectrum of the azo compound (Example 2) represented by Formula (I-8).

It is a figure which shows the absorption spectrum of the azo compound (Example 3) represented by Formula (I-9).

It is a figure which shows the absorption spectrum of the azo compound (Example 4) represented by Formula (II-1).

It is a figure which shows the absorption spectrum of the azo compound (Example 5) represented by Formula (II-6).

It is a figure which shows the absorption spectrum of the azo compound (comparative example 1) represented by Formula (III-1).

Claims (8)

The azo compound or its salt represented by Formula (I).

[Formula (Ⅰ) of, R ¹ ~ R ⁴ represents a hydrogen atom, C _{1 -10} saturated aliphatic hydrocarbon group or a carboxyl group each independently. R ⁵ ~ R ¹² each independently represent a hydrogen atom, a halogen atom, a C _{1 -10} aliphatic saturated hydrocarbon group, a halogenated C _{1 -10} saturated aliphatic hydrocarbon group, a C _{1 -8} alkoxy group, a carboxyl group, a sulfo group, a sulfamoyl group, Or an N-substituted sulfamoyl group. R ¹³ and R ¹⁴ each independently represent a hydrogen atom, a cyano group, a carbamoyl group, or an N-substituted carbamoyl group.] According to claim 1, wherein the R ⁵ ~ R ¹² At least one of the azo compound or a salt thereof, characterized in that the N- substituted sulfamoyl group. According to claim 2, wherein R ⁵ ~ R ⁸ At least one of, and R ⁹ to R ¹² At least one of the azo compound or a salt thereof, characterized in that the N- substituted sulfamoyl group. According to claim 3, wherein R ⁵ and R ⁸ At least one of and the R ⁹ and R ¹² At least one of the azo compound or a salt thereof, characterized in that the N- substituted sulfamoyl group. The method of claim 1, wherein the N- substituted sulfamoyl group is an -SO ₂ NHR ¹⁵ group, R ¹⁵ is C _{1 -10} saturated aliphatic hydrocarbon groups, C _{1 -8} alkoxy C _{1 -10} saturated aliphatic group which is substituted An azo compound or its salt characterized by showing a hydrocarbon group, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or an acyl group having 2 to 10 carbon atoms. According to claim 1, wherein R ⁵ and R ⁸ At least one of, and R ⁹ and R ¹² More than one is -SO ₂ NHR ¹⁵ group of a, R ¹⁵ is a C _{1 -10} aliphatic saturated hydrocarbon group, a C _{1 -8} alkoxy C _1-10 saturated aliphatic hydrocarbon group which is optionally substituted group, the carbon number is 6 to 20 An azo compound or its salt characterized by showing an aryl group, an aralkyl group having 7 to 20 carbon atoms, or an acyl group having 2 to 10 carbon atoms. The compound according to any one of claims 1 to 6, wherein R ¹³ and R ¹⁴ At least one of the azo compound or a salt thereof, characterized in that the cyano group. The compound according to any one of claims 1 to 6, wherein R ¹³ and R ¹⁴ At least one of is -CON (R ¹⁶⁾ R ¹⁷ group where, R ¹⁶ and R ¹⁷ is C ₁ which is a hydrogen atom, C _{1 -10} saturated aliphatic hydrocarbon groups, C _{1 -8} alkoxy group substituted independently _- An azo compound or its salt which shows a _10- saturated aliphatic hydrocarbon group, a C6-C20 aryl group, a C7-C20 aralkyl group, or a C2-C10 acyl group.

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