JP4524212B2 - Azo compound and its tautomer, and dye composition - Google Patents

Description

  The present invention relates to a novel azo compound and a tautomer thereof, and a dye composition, and more particularly to a novel azo dye and a tautomer thereof having good fastness to hue and light, and a dye composition.

  Conventionally, since azo compounds often have various visible light absorptions, they have been used as dyes in various fields. For example, coloring of synthetic resins, printing inks, dyes for sublimation thermal transfer materials, inks for ink jet recording, and the like have recently been used in the field of electronics as functional dyes.

  One important performance required for azo compounds as dyes is an absorption spectrum. The hue of the pigment affects the color and texture of the object colored by the pigment and has a great visual appeal. Therefore, researches on the absorption spectrum of dyes have been extensively performed for a long time, and are described in several documents (for example, see Non-Patent Documents 1 and 2).

  In addition, the performance of dyes is diversified depending on the application. For example, when dyeing sheepskin or cowhide, a dye having a bright hue and good dyeability is desired, and in the case of clothing, a dye having a low water solubility and a bright hue so that it can be washed. In many situations, it is required that the dye has a plurality of functions depending on the application. In addition to the above, particularly when used as a printing ink, a dye for sublimation type thermal transfer material, and an ink for ink jet recording, the hue is vivid and strongly fast against light (light resistance) under various environmental conditions is strong. desired.

Various diazo compounds or couplers have been disclosed as solutions for improving the light resistance of dyes (see, for example, Patent Documents 1 and 2 and Non-Patent Document 2). Although these improvements have been made for the time being, they are still insufficient, and there is still room for further improvement in light resistance. Moreover, an azo dye containing a quaternary salt has been proposed as a means of achieving both vivid hue and light resistance (see, for example, Patent Documents 3 to 4). However, the improvement is limited to a slight level, and it has not yet been possible to ensure satisfactory light resistance.
JP-A-4-59287 JP-A-4-201483 Japanese Patent Laid-Open No. 2002-129047 DE 1980544 J. et al. Fabian and H.M. By Hartmann, "Light Absorption of Organic Colors", Springer-Verlag, Berlin, 1980 Mohr, J. et al. J. et al. Pract. Chem. 1909, 2, 47.

  As described above, pigments not only have good hue and color density and vividness as basic performance, but also have the ability to maintain vividness and density even when exposed to light for a long period of time. It is important to have an azo-based dye compound that has a hue color density and vividness but also has good light fastness, but the present state of technology has not yet been provided. .

  The present invention has been made in view of the above, a novel azo compound excellent in light fastness (hereinafter also referred to as light resistance) and a tautomer thereof having good hue and vividness, and It aims at providing the dye composition containing these, and makes it a subject to achieve this objective.

The present invention has been achieved on the basis of the knowledge that an azo compound having a specific dye structure exhibits a vivid hue with a high color density and exhibits a large molar extinction constant.
Specific means for achieving the above object are as follows.

<1> An azo compound represented by the following general formula (1) and a tautomer thereof.

In the general formula (1), R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom, alkyl group, aryl group, alkoxy group, aryloxy group, alkylsulfonyl group, arylsulfonyl group, alkylthio group. R ⁵ and R ⁶ each independently represents a hydrogen atom, an alkyl group, or an aryl group, and R ⁷ represents an alkyl group or an aryl group. m represents an integer of 1 or more. X represents a nitrogen atom or a sulfur atom, Y represents a carbon atom, Z represents a nitrogen atom when X represents a nitrogen atom, and represents a carbon atom when X represents a sulfur atom. The 5-membered ring containing X, Y, and Z may be condensed. A ⁻ represents a counter anion. In R ¹ to R ⁶ , when the alkyl moiety is substituted, the substituent is phenyl group, halogen atom, alkoxy group, aryloxy group, alkoxycarbonyl group, acyloxy group, acylamino group, carbamoyl group, cyano group, carvone Represents an acid group, a sulfonic acid group, or a heterocyclic group, and when the aryl moiety is substituted, the substituent is an alkyl group, a phenyl group, a halogen atom, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an acyloxy group, An acylamino group, a carbamoyl group, a cyano group, a carboxylic acid group, a sulfonic acid group, or a heterocyclic group is represented. In R ⁷ , when the alkyl moiety is substituted, the substituent represents a phenyl group, a halogen atom, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an acyloxy group, or a carboxylic acid group, and the aryl moiety is substituted. In this case, the substituent represents an alkyl group, a halogen atom, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an acyloxy group, or a carboxylic acid group.

<2> The azo compound and the tautomer thereof according to <1>, wherein in general formula (1), R ⁵ and R ⁶ are each independently an alkyl group or an aryl group.

<3> In the general formula (1), R ¹ is an alkoxy group, an aryloxy group, an alkylsulfonyl group, an arylsulfonyl group, an alkylthio group, or arylthio group, R ^2, R ^3, and R ⁴ Is an azo compound according to the above <1> or <2> and a tautomer thereof.

<4> The azo compound and the tautomer thereof according to any one of <1> to <3>, wherein R ¹ is an alkoxy group in the general formula (1).

<5> In the general formula (1), m is an azo compound according to <4> and a tautomer thereof, wherein m is an integer of 1 to 3 .

<6> An azo compound represented by the following general formula (2) and a tautomer thereof.

In the general formula (2), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁸ , and R ⁹ are each independently a hydrogen atom, alkyl group, aryl group, alkoxy group, aryl Oxy group, alkylsulfonyl group, arylsulfonyl group, alkylthio group, arylthio group, amino group, alkoxycarbonyl group, aryloxycarbonyl group, acyl group, acylamino group, sulfonylamino group, carbamoylamino group, alkoxycarbonylamino group, halogen atom , A cyano group, or a nitro group, R ⁷ and R ¹⁰ represent an aryl group, and A ⁻ represents a counter anion. R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ⁵ , R ⁵ and R ⁶ , R ⁷ and R ⁸ , R ⁸ and R ⁹ , R ⁹ and R ¹⁰ are respectively They may be connected to each other to form a ring.

<7> In the general formula (2), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁸ , and R ⁹ are each independently a hydrogen atom, an alkyl group, an aryl group, The azo compound according to <6> and a tautomer thereof, which is an alkoxy group, an aryloxy group, an alkylsulfonyl group, an arylsulfonyl group, an alkylthio group, or an arylthio group.

<8> In the general formula (2), R ¹ is an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylsulfonyl group, an arylsulfonyl group, an alkylthio group, or an arylthio group, and R ² , R ⁵ And the azo compound according to <6> or <7>, wherein R ⁶ is a hydrogen atom, and tautomers thereof.

<9> The azo compound and the tautomer thereof according to any one of <6> to <8>, wherein R ³ and R ⁴ in the general formula (2) are aryl groups.
<10> The azo compound and the tautomer thereof according to any one of <6> to <8>, wherein R ³ and R ⁴ in the general formula (2) are alkyl groups.

<11> An azo compound represented by the following general formula (3) and a tautomer thereof.

In the general formula (3), R ¹ , R ² , R ³ , R ⁴ , R ⁶ , and R ⁷ are each independently a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, or an alkylsulfonyl group. , Arylsulfonyl group, alkylthio group, arylthio group, amino group, alkoxycarbonyl group, aryloxycarbonyl group, acyl group, acylamino group, sulfonylamino group, carbamoylamino group, alkoxycarbonylamino group, halogen atom, cyano group, or nitro R ⁵ represents an aryl group, and R ⁸ represents a hydrogen atom, an alkyl group, or an aryl group. X represents —N (R ⁹ ) — or —O—, and R ⁹ represents an alkyl group or an aryl group. Y represents —O— or —S—, and A ⁻ represents a counter anion. R ¹ and R ² , R ³ and R ⁴ may be connected to each other to form a ring, and R ² and R ⁸ , R ³ and R ⁸ , R ⁵ and R ⁶ are connected to each other. May form a ring, or R ⁶ and R ⁷ may be linked to each other to form a ring.

<12> In the general formula (3), R ¹ , R ² , R ³ , and R ⁴ are each independently a hydrogen atom, alkyl group, aryl group, alkoxy group, aryloxy group, alkylsulfonyl group, arylsulfonyl The azo compound according to <11>, which is a group, an alkylthio group, or an arylthio group, and a tautomer thereof.
<13> The azo compound or the tautomer thereof according to <11> or <12>, wherein R ⁸ is an alkyl group or an aryl group in the general formula (3).

<14> The azo compound and the tautomer thereof according to any one of <11> to <13>, in which, in the general formula (3), X is —N (R ⁹ ) —.
<15> The azo compound and the tautomer thereof according to any one of <11> to <14>, wherein R ⁶ and R ⁷ in the general formula (3) are hydrogen atoms.
<16> A dye composition comprising at least one selected from the azo compounds according to any one of <1> to <15> and tautomers thereof.

  According to the present invention, it is possible to provide a novel azo compound and a tautomer thereof having good hue and vividness and excellent light fastness, and a dye composition containing these.

Hereinafter, the azo compound of the present invention and its tautomer will be described in detail.
The azo compound of the present invention is a compound represented by the following general formula (1) (including an azo dye), and is suitable as an azo dye having a good hue, vividness and excellent light fastness.

In the general formula (1), R ¹ , R ² , R ³ , and R ⁴ are each independently a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylsulfonyl group, an arylsulfonyl group, An alkylthio group or an arylthio group is represented.

The alkyl group represented by R ¹ , R ² , R ³ , or R ⁴ may be unsubstituted or substituted, and examples thereof include a methyl group, an ethyl group, a normal propyl group, an isopropyl group, and a normal group. Butyl, isobutyl, tertiary butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, heptyl, octyl, tertiary octyl, 2-ethylhexyl, decyl, dodecyl, octadecyl, etc. Preferably mentioned.

  As the substituent when the alkyl group further has a substituent, a phenyl group, a halogen atom, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an acyloxy group, an acylamino group, a carbamoyl group, a cyano group, a carboxylic acid group, A sulfonic acid group and a heterocyclic group are preferable, and a methyl group is more preferable.

The alkyl group represented by R ¹ , R ² , R ³ , or R ⁴ is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 15 carbon atoms, and 1 to 10 carbon atoms. Are more preferable, and a methyl group, a tertiary butyl group, and a heptyl group are particularly preferable.

The aryl group represented by R ¹ , R ² , R ³ , or R ⁴ may be unsubstituted or substituted, and is preferably an aryl group having 6 to 25 carbon atoms, preferably 6 to 10 carbon atoms. The aryl group is more preferably an unsubstituted or substituted phenyl group. Examples of the substituent when the aryl group has a substituent include an alkyl group, a phenyl group, a halogen atom, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an acyloxy group, an acylamino group, a carbamoyl group, a cyano group, Carboxylic acid groups, sulfonic acid groups, and heterocyclic groups are preferred.

As the aryl group represented by R ¹ , R ² , R ³ or R ⁴ , a phenyl group, a 4-chlorophenyl group, a 4-methylphenyl group, a 4-butoxyphenyl group, a 2-methoxyphenyl group, 2 A -hydroxyphenyl group, a 2-hydroxy-5-octylphenyl group, a 2,5-diheptyloxyphenyl group, or a 2-hydroxy-5-butoxyphenyl group is preferred.

The alkoxy group represented by R ¹ , R ² , R ³ , or R ⁴ may be unsubstituted or substituted, and examples thereof include a methoxy group, an ethoxy group, a normal propyloxy group, and an isopropyloxy group. Normal butyloxy group, isobutyloxy group, tertiary butyloxy group, pentyloxy group, cyclopentyloxy group, hexyloxy group, cyclohexyloxy group, heptyloxy group, octyloxy group, tertiary octyloxy group, 2-ethylhexyloxy Preferred examples include a group, a decyloxy group, a dodecyloxy group, an octadecyloxy group, a 1-ethylpropyloxy group, or a 2-methyl-4,4-dimethylpentyloxy group.

  Examples of the substituent when the alkoxy group further has a substituent include a phenyl group, a halogen atom, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an acyloxy group, an acylamino group, a carbamoyl group, a cyano group, and a carboxylic acid. Group, sulfonic acid group and heterocyclic group are preferred.

As the alkoxy group represented by R ¹ , R ² , R ³ , or R ⁴ , an alkoxy group having 1 to 20 carbon atoms is preferable, an alkoxy group having 1 to 15 carbon atoms is more preferable, and 1-ethylpropyloxy The group 2-methyl-4,4-dimethylpentyloxy is particularly preferred.

The aryloxy group represented by R ¹ , R ² , R ³ , or R ⁴ may be unsubstituted or substituted, and is preferably an aryloxy group having 6 to 25 carbon atoms, preferably 6 to 6 carbon atoms. 10 aryloxy groups are more preferable, and an unsubstituted or substituted phenoxy group is more preferable. Examples of the substituent when the aryloxy group further has a substituent include an alkyl group, a phenyl group, a halogen atom, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an acyloxy group, an acylamino group, a carbamoyl group, and a cyano group. Group, carboxylic acid group, sulfonic acid group and heterocyclic group are preferred.

The aryloxy group represented by R ¹ , R ² , R ³ , or R ⁴ is particularly a phenoxy group, 4-chlorophenyloxy group, 4-methylphenyloxy group, 4-butoxyphenyloxy group, 2-methoxy. A phenyloxy group, a 2-hydroxyphenyloxy group, a 2-hydroxy-5-octylphenyloxy group, a 2,5-diheptyloxyphenyloxy group, or a 2-hydroxy-5-butoxyphenyloxy group is preferred.

The alkylsulfonyl group represented by R ¹ , R ² , R ³ , or R ⁴ may be unsubstituted or substituted, and examples thereof include a methylsulfonyl group, an ethylsulfonyl group, a normal propylsulfonyl group, isopropyl Sulfonyl group, normal butylsulfonyl group, isobutylsulfonyl group, tertiary butylsulfonyl group, pentylsulfonyl group, cyclopentylsulfonyl group, hexylsulfonyl group, cyclohexylsulfonyl group, heptylsulfonyl group, octylsulfonyl group, tertiary octylsulfonyl group, 2- Preferable examples include an ethylhexylsulfonyl group, a decylsulfonyl group, a dodecylsulfonyl group, and an octadecylsulfonyl group.

  Examples of the substituent in the case where the alkylsulfonyl group further has a substituent include a phenyl group, a halogen atom, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an acyloxy group, an acylamino group, a carbamoyl group, a cyano group, and a carboxyl group. An acid group, a sulfonic acid group, and a heterocyclic group are preferable.

The alkylsulfonyl group represented by R ¹ , R ² , R ³ , or R ⁴ is preferably an alkylsulfonyl group having 1 to 20 carbon atoms, more preferably an alkylsulfonyl group having 1 to 15 carbon atoms, 1-10 alkylsulfonyl groups are more preferable, and a methylsulfonyl group and an ethylsulfonyl group are particularly preferable.

The arylsulfonyl group represented by R ¹ , R ² , R ³ , or R ⁴ may be unsubstituted or substituted, and is preferably an arylsulfonyl group having 6 to 25 carbon atoms. 10 to 10 arylsulfonyl groups are more preferable, and an unsubstituted or substituted phenylsulfonyl group is more preferable. Examples of the substituent when the arylsulfonyl group further has a substituent include an alkyl group, a phenyl group, a halogen atom, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an acyloxy group, an acylamino group, a carbamoyl group, and a cyano group. Group, carboxylic acid group, sulfonic acid group and heterocyclic group are preferred.

As the arylsulfonyl group represented by R ¹ , R ² , R ³ or R ⁴ , phenylsulfonyl group, 4-chlorophenylsulfonyl group, 4-methylphenylsulfonyl group, 4-butoxyphenylsulfonyl group, 2- A methoxyphenylsulfonyl group, 2-hydroxyphenylsulfonyl group, 2-hydroxy-5-octylphenylsulfonyl group, 2,5-diheptyloxyphenylsulfonyl group, or 2-hydroxy-5-butoxyphenylsulfonyl group is preferred.

The alkylthio group represented by R ¹ , R ² , R ³ , or R ⁴ may be unsubstituted or substituted, and examples thereof include a methylthio group, an ethylthio group, a normal propylthio group, and an isopropylthio group. , Normal butylthio group, isobutylthio group, tertiary butylthio group, pentylthio group, cyclopentylthio group, hexylthio group, cyclohexylthio group, heptylthio group, octylthio group, tertiary octylthio group, 2-ethylhexylthio group, decylthio group , Dodecylthio group, or octadecylthio group is preferable.

  Examples of the substituent when the alkylthio group further has a substituent include a phenyl group, a halogen atom, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an acyloxy group, an acylamino group, a carbamoyl group, a cyano group, and a carboxylic acid. Group, sulfonic acid group and heterocyclic group are preferred.

The alkylthio group represented by R ¹ , R ² , R ³ , or R ⁴ is preferably an alkylthio group having 1 to 20 carbon atoms, more preferably an alkylthio group having 1 to 15 carbon atoms, and 1 to 10 carbon atoms. Are more preferable, and a methylthio group, an ethylthio group, and a normal butylthio group are particularly preferable.

The arylthio group represented by R ¹ , R ² , R ³ , or R ⁴ may be unsubstituted or substituted, and is preferably an arylthio group having 6 to 25 carbon atoms, and 1 to 15 carbon atoms. The arylthio group is more preferably an unsubstituted or substituted phenylthio group. Examples of the substituent when the arylthio group further has a substituent include an alkyl group, a phenyl group, a halogen atom, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an acyloxy group, an acylamino group, a carbamoyl group, and a cyano group. , A carboxylic acid group, a sulfonic acid group, and a heterocyclic group are preferable.

As the arylthio group represented by R ¹ , R ² , R ³ , or R ⁴ , a phenylthio group, a 4-chlorophenylthio group, a 4-methylphenylthio group, a 4-butoxyphenylthio group, and 2-methoxyphenyl are particularly preferable. A thio group, 2-hydroxyphenylthio group, 2-hydroxy-5-octylphenylthio group, 2,5-diheptyloxyphenylthio group, or 2-hydroxy-5-butoxyphenylthio group is preferred.

In R ¹ , R ² , R ³ , and R ⁴ , R ¹ is an alkyl group, aryl group, alkoxy group, aryloxy group, alkylsulfonyl group, arylsulfonyl group, alkylthio group, or arylthio group, and R ² , R ³ , and R ⁴ are all preferably hydrogen atoms, and R ¹ is more preferably a 1-ethylpropyloxy group or a 2-methyl-4,4-dimethylpentyloxy group. .

In the general formula (1), R ⁵ and R ⁶ each independently represent a hydrogen atom, an alkyl group, or an aryl group.

The alkyl group represented by R ⁵ or R ⁶ may be unsubstituted or substituted, and examples thereof include a methyl group, an ethyl group, a normal propyl group, an isopropyl group, a normal butyl group, an isobutyl group, and a tar group. Preferable are butyl group, pentyl group, cyclopentyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, tertiary octyl group, 2-ethylhexyl group, decyl group, dodecyl group, octadecyl group, benzyl group, or allyl group. Can be mentioned.

  Examples of the substituent when the alkyl group further has a substituent include a phenyl group, a halogen atom, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an acyloxy group, an acylamino group, a carbamoyl group, a cyano group, and a carboxylic acid. Group, sulfonic acid group and heterocyclic group are preferred.

The alkyl group represented by R ⁵ or R ⁶ is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 15 carbon atoms, a methyl group, or a normal, iso, or tertiary butyl group. Is particularly preferred.

The aryl group represented by R ⁵ or R ⁶ may be unsubstituted or substituted, preferably an aryl group having 6 to 25 carbon atoms, more preferably an aryl group having 6 to 10 carbon atoms, Furthermore, an unsubstituted or substituted phenyl group is preferable. Examples of the substituent when the aryl group further has a substituent include an alkyl group, a phenyl group, a halogen atom, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an acyloxy group, an acylamino group, a carbamoyl group, and a cyano group. , A carboxylic acid group, a sulfonic acid group, and a heterocyclic group are preferable.

Among the above, the aryl group represented by R ⁵ or R ⁶ is particularly a phenyl group, a 4-chlorophenyl group, a 4-methylphenyl group, a 4-butoxyphenyl group, a 2-methoxyphenyl group, or 2-hydroxyphenyl. Group, 2-hydroxy-5-octylphenyl group, 2,5-diheptyloxyphenyl group, or 2-hydroxy-5-butoxyphenyl group is preferred.

Of the groups represented by R ⁵ or R ⁶ , each of R ⁵ and R ⁶ is preferably an alkyl group or an aryl group, more preferably a methyl group, or a normal, iso, or tertiary butyl group.

In the general formula (1), R ⁷ represents an alkyl group or an aryl group.
The alkyl group represented by R ⁷ may be unsubstituted or may have a substituent, may be branched, or may have an unsaturated bond in the chain. Specific examples include methyl group, ethyl group, normal propyl group, isopropyl group, normal butyl group, isobutyl group, tertiary butyl group, pentyl group, cyclopentyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, and tertiary. Preferable examples include octyl group, 2-ethylhexyl group, decyl group, dodecyl group, and octadecyl group.

When the alkyl group represented by R ⁷ has a substituent, examples of the substituent include an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkoxycarbonyl group, an acyloxy group, and an alkyloxycarbonyl. Group, aryloxycarbonyl group, carboxyl group, alkylsulfonyl group, arylsulfonyl group and halogen atom are preferred.

The alkyl group represented by R ⁷ is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, a methyl group, an ethyl group, a normal propyl group, a tertiary butyl group, A heptyl group, a pentyl group, a decyl group, a phenylethyl group, and a phenylmethyl group are particularly preferable.

The aryl group represented by R ⁷ may be unsubstituted or substituted, and examples thereof include a phenyl group, a 4-chlorophenyl group, a 4-dimethylaminophenyl group, a 4-cyanophenyl group, a naphthyl group, Or anthranyl group etc. are mentioned suitably.

When the aryl group represented by R ⁷ has a substituent, examples of the substituent include an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkoxycarbonyl group, an acyloxy group, an alkyloxycarbonyl group, and an aryloxycarbonyl group. , A carboxyl group, an alkylsulfonyl group, an arylsulfonyl group and a halogen atom are preferable, and an alkoxy group and an aryloxy group are preferable.

The aryl group represented by R ⁷ is preferably an aryl group having 6 to 25 carbon atoms, more preferably an aryl group having 6 to 15 carbon atoms, a phenyl group, a 4-chlorophenyl group, a 4-dimethylaminophenyl group, A 4-cyanophenyl group is particularly preferred.

Both the alkyl group and aryl group represented by R ⁷ are preferably unsubstituted groups from the viewpoint of vividness of hue.

  In the said General formula (1), m represents an integer greater than or equal to 1, the integer of 1-10 is preferable, and the integer of 1-3 is more preferable.

In the general formula (1), X, Y, and Z is a carbon atom, a nitrogen atom, an oxygen atom, and represents an atom selected from the group consisting of a sulfur atom, but it may also be the same or different from each other. In the present invention , X represents a nitrogen atom or a sulfur atom, Y represents a carbon atom, Z represents a nitrogen atom when X represents a nitrogen atom, and represents a carbon atom when X represents a sulfur atom. . The 5-membered ring containing X, Y, and Z may be condensed.

  X, Y, and Z together with a nitrogen atom and a carbon atom form a 5-membered ring salt. Examples of the 5-membered ring salt include imidazolium salt, oxazolium salt, thiazolium salt, pyrazolium salt, isoxazol. Examples thereof include a lithium salt, an isothiazolium salt, a triazolium salt, an oxadiazolium salt, and a thiadiazolium salt. An imidazolium salt, a thiazolium salt, or a triazolium salt is preferable, and a salt of a diazole ring (especially an imidazolium salt) is more preferable.

  Each of X, Y, and Z may be unsubstituted or may have a substituent. Examples of the substituent in the case of having a substituent include an alkyl group, an aryl group, an alkylthio group, an arylthio group, and a substituted group. An amino group, a cyano group, a nitro group, a halogen group and the like are preferable.

  Among the above, as a combination of X, Y, and Z, an embodiment in which X is a nitrogen atom, Y is a nitrogen atom or a carbon atom, and Z is a carbon atom is preferable, and X is a nitrogen atom. An embodiment in which Y is a nitrogen atom and Z is a carbon atom is particularly preferable.

  When a 5-membered salt containing X, Y, and Z is condensed, it may be condensed by a ring such as a benzene ring. The ring may be a heterocycle. When the benzene ring is condensed, the 5-membered ring salt includes benzimidazolium salt, benzoxazolium salt, benzothiazolium salt, benzopyrazolium salt, benzoisoxazolium salt, benzoisothiol An azolium salt or the like is preferable, and a pyrazolotriazolium salt or an imidazolotriazolium salt is preferable as a 5-membered ring salt when the heterocyclic ring is condensed.

  Of the above, the salt formed by X, Y and Z together with the nitrogen atom is particularly preferably an imidazolium salt, thiazolium salt, triazolium salt or benzoimidazolium salt. From the viewpoint of light resistance, a salt of a diazole ring In particular, an imidazolium salt is preferable.

In the general formula (1), A ⁻ represents a counter anion. The counter anion represented by A ⁻ is not particularly limited as long as it can form a counter anion, and may be either a monoanion or a polyanion, or may be an inorganic anion or an organic anion. . Specifically, Cl ⁻ , Br ⁻ , I ⁻ , a sulfonate anion having 1 to 20 carbon atoms, a carboxylate anion having 2 to 21 carbon atoms, an alkyl sulfate ion, a hexafluorophosphate ion, a tetrafluoroboron ion, and perchlorine. Acid ions, carbonate ions and sulfate ions are preferable, and hexafluorophosphate ions are more preferable.

When R ⁷ has a substituent, the substituent may form a salt in place of the counter anion represented by A ⁻ , and in this case, the azo compound is constituted as an inner salt.

  The tautomer of the azo compound of the present invention is also a compound (including an azo dye) having a bright and good hue and excellent in light fastness, and can be suitably used as an azo dye. .

  Hereinafter, specific examples (exemplary compounds D-1 to D-34) of the azo compound represented by the general formula (1) are shown. However, the present invention is not limited to these.

Next, a method for synthesizing the azo compound of the present invention will be described.
For the synthesis method of the azo compound, see, for example, H.P. Zollinger, “Color Chemistry” 1991, Weinheim, p. 109 and the like have been reported variously. Among them, a method of synthesizing an azo compound by reacting a diazonium salt compound and a coupler compound is versatile and useful. The azo compound of the present invention can also be suitably synthesized by reacting a diazonium salt compound with a coupler compound.

  Specifically, as shown in the following scheme, by reacting the diazonium salt compound represented by the general formula (a) with the coupler compound represented by the general formula (b), The azo compound represented by the formula (1) can be suitably synthesized.

Here, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , m, X, Y, Z, and A ⁻ described in the scheme are each represented by the general formula ( It is synonymous with R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , m, X, Y, Z, and A ⁻ in 1). B ⁻ in the general formula (a) represents a counter anion, for example, Cl ⁻ , Br ⁻ , PF ₆ ⁻ , BF ₄ ^{− and the} like.

  Various solvents can be used for the above synthesis, and examples of the solvent include water, alcohol, ethyl acetate, ether, tetrahydrofuran (THF) and the like. Further, for the purpose of increasing the yield, an organic or inorganic base may coexist, and examples of these bases include sodium hydroxide, ammonia, triethylamine, pyridine, sodium bicarbonate, sodium methoxide and the like.

  The conditions for reacting the diazonium salt compound represented by the above general formula (a) with the coupler compound represented by the general formula (b) are 1.0 to 1 coupler compound per 1 mole equivalent of the diazonium salt. It is preferably added in the range of 1 equivalent, and the reaction temperature is preferably 0 ° C. to room temperature. Further, since the diazonium salt is decomposed by light, it is preferable to use a light-shielding container as a reaction container or to react in a dark room.

  Next, a different embodiment of the azo compound of the present invention is a compound (including an azo dye) represented by the following general formula (2), which has a good hue, vividness and excellent light fastness. Suitable as a dye.

In the general formula (2), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁸ , and R ⁹ are each independently a hydrogen atom, alkyl group, aryl group, alkoxy group, aryl Oxy group, alkylsulfonyl group, arylsulfonyl group, alkylthio group, arylthio group, amino group, alkoxycarbonyl group, aryloxycarbonyl group, acyl group, acylamino group, sulfonylamino group, carbamoylamino group, alkoxycarbonylamino group, halogen atom , A cyano group, or a nitro group, and R ⁷ and R ¹⁰ represent an aryl group.

In the general formula (2), the alkyl group represented by R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁸ , or R ⁹ is an alkyl group having 1 to 20 carbon atoms. Preferably, C1-C15 is more preferable and C1-C10 is especially preferable. Specific examples include methyl group, ethyl group, normal propyl group, isopropyl group, normal butyl group, isobutyl group, tertiary butyl group, pentyl group, cyclopentyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, Examples include a decyl group, a tertiary octyl group, a 2-ethylhexyl group, a decyl group, a dodecyl group, and an octadecyl group.

In the general formula (2), the aryl group represented by R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , or R ¹⁰ has 6 carbon atoms. -14 aryl groups are preferred, C6-10 aryl groups are more preferred, and C6 aryl groups are particularly preferred. Specific examples include a phenyl group, a naphthyl group, and an anthracenyl group.

In the general formula (2), the alkoxy group represented by R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁸ , or R ⁹ is an alkoxy group having 1 to 20 carbon atoms. Preferably, an alkoxy group having 1 to 15 carbon atoms is more preferable, and an alkoxy group having 1 to 10 carbon atoms is particularly preferable. Specific examples include methoxy, ethoxy, normal propyloxy, isopropyloxy, normal butyloxy, isobutyloxy, tertiary butyloxy, pentyloxy, cyclopentyloxy, hexyloxy, cyclohexyl Oxy group, heptyloxy group, octyloxy group, tertiary octyloxy group, 2-ethylhexyloxy group, decyloxy group, dodecyloxy group, octadecyloxy group, 1-ethylpropyl group, 2-methyl-4,4-dimethylpentyl Groups and the like.

In the general formula (2), the aryloxy group represented by R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁸ , or R ⁹ is an aryloxy group having 6 to 14 carbon atoms. Is preferable, an aryloxy group having 6 to 10 carbon atoms is more preferable, and an aryloxy group having 6 carbon atoms is particularly preferable. Specific examples include a phenyloxy group, a naphthyloxy group, an anthranyloxy group, and the like.

In the general formula (2), the alkylsulfonyl group represented by R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁸ , or R ⁹ is an alkylsulfonyl group having 1 to 20 carbon atoms. Group is preferable, more preferable is an alkylsulfonyl group having 1 to 15 carbon atoms, and particularly preferable is an alkylsulfonyl group having 1 to 10 carbon atoms. Specific examples include methylsulfonyl group, ethylsulfonyl group, normal propylsulfonyl group, isopropylsulfonyl group, normal butylsulfonyl group, isobutylsulfonyl group, tertiary butylsulfonyl group, pentylsulfonyl group, cyclopentylsulfonyl group, hexylsulfonyl group. Cyclohexylsulfonyl group, heptylsulfonyl group, octylsulfonyl group, tertiary octylsulfonyl group, 2-ethylhexylsulfonyl group, decylsulfonyl group, dodecylsulfonyl group, octadecylsulfonyl group and the like.

In the general formula (2), the arylsulfonyl group represented by R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁸ , or R ⁹ is an arylsulfonyl group having 6 to 14 carbon atoms. Group is preferable, an arylsulfonyl group having 6 to 10 carbon atoms is more preferable, and an arylsulfonyl group having 6 carbon atoms is particularly preferable. Specific examples include phenylsulfonyl group, naphthylsulfonyl group, anthracenylsulfonyl group and the like.

In the general formula (2), the alkylthio group represented by R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁸ , or R ⁹ is an alkylthio group having 1 to 20 carbon atoms. An alkylthio group having 1 to 15 carbon atoms is preferable, and an alkylthio group having 1 to 10 carbon atoms is particularly preferable. Specific examples include methylthio group, ethylthio group, normal propylthio group, isopropylthio group, normal butylthio group, isobutylthio group, tertiary butylthio group, pentylthio group, cyclopentylthio group, hexylthio group, and cyclohexylthio group. , Heptylthio group, octylthio group, tertiary octylthio group, 2-ethylhexylthio group, decylthio group, dodecylthio group, octadecylthio group and the like.

In the general formula (2), the arylthio group represented by R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁸ , or R ⁹ is an arylthio group having 6 to 14 carbon atoms. Preferably, an arylthio group having 6 to 10 carbon atoms is more preferable, and an arylthio group having 6 carbon atoms is particularly preferable. Specific examples include a phenylthio group, a naphthylthio group, an anthracenylthio group, and the like.

In the general formula (2), the amino group represented by R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁸ , or R ⁹ is preferably an amino group having 1 to 20 carbon atoms. A C1-C10 amino group is more preferable, and a 1-8 amino group is particularly preferable. Specific examples of the mono-substituted product include, for example, a methylamino group, an ethylamino group, a butylamino group, a hexylamino group, a benzylamino group, and a phenylamino group. Preferred examples include amino group, diethylamino group, dibutylamino group, dihexylamino group, dibenzylamino group, diphenylamino group, phenylmethylamino group and the like.

In the general formula (2), the alkoxycarbonyl group or aryloxycarbonyl group represented by R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁸ , or R ⁹ has 2 carbon atoms. An alkoxycarbonyl group having 20 to 20 carbon atoms and an aryloxycarbonyl group having 7 to 25 carbon atoms are preferable, an alkoxycarbonyl group having 2 to 15 carbon atoms and an aryloxycarbonyl group having 7 to 15 carbon atoms are more preferable, and an alkyloxy group having 2 to 10 carbon atoms. An alkoxycarbonyl group and an aryloxycarbonyl group having 7 to 10 carbon atoms are particularly preferable.

  Specific examples of the alkoxycarbonyl group include a methyloxycarbonyl group, an ethyloxycarbonyl group, a normalpropyloxycarbonyl group, an isopropyloxycarbonyl group, a normal butyloxycarbonyl group, an isobutyloxycarbonyl group, and a tertiary butyloxycarbonyl group. Pentyloxycarbonyl group, cyclopentyloxycarbonyl group, hexyloxycarbonyl group, cyclohexyloxycarbonyl group, heptyloxycarbonyl group, octyloxycarbonyl group, tertiary octyloxycarbonyl group, 2-ethylhexyloxycarbonyl group, decyloxycarbonyl group, A dodecyloxycarbonyl group, an octadecyloxycarbonyl group, etc. are mentioned. Examples of the aryloxycarbonyl group include a phenyloxycarbonyl group, a naphthyloxycarbonyl group, and an anthracenyloxycarbonyl group.

In the general formula (2), the acyl group represented by R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁸ , or R ⁹ is an acyl group having 2 to 20 carbon atoms. Preferably, an acyl group having 2 to 10 carbon atoms is more preferable, and an acyl group having 2 to 5 carbon atoms is more preferable. Specific examples include methylcarbonyl group, ethylcarbonyl group, normal propylcarbonyl group, isopropylcarbonyl group, normal butylcarbonyl group, isobutylcarbonyl group, tertiary butylcarbonyl group, pentylcarbonyl group, cyclopentylcarbonyl group, hexylcarbonyl group. Cyclohexylcarbonyl group, heptylcarbonyl group, octylcarbonyl group, tertiary octylcarbonyl group, 2-ethylhexylcarbonyl group, decylcarbonyl group, dodecylcarbonyl group, octadecylcarbonyl group, benzoyl group and the like.

In the general formula (2), the acylamino group represented by R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁸ , or R ⁹ is an acylamino group having 1 to 20 carbon atoms. Preferably, an acylamino group having 1 to 15 carbon atoms is more preferable, and an acylamino group having 1 to 10 carbon atoms is particularly preferable. Specific examples include methylcarbonylamino group, ethylcarbonylamino group, normal propylcarbonylamino group, isopropylcarbonylamino group, normal butylcarbonylamino group, isobutylcarbonylamino group, tertiary butylcarbonylamino group, pentylcarbonylamino group. , Cyclopentylcarbonylamino group, hexylcarbonylamino group, cyclohexylcarbonylamino group, heptylcarbonylamino group, octylcarbonylamino group, tertiary octylcarbonylamino group, 2-ethylhexylcarbonylamino group, decylcarbonylamino group, dodecylcarbonylamino group, Examples include an octadecylcarbonylamino group and a benzoylamino group.

In the general formula (2), the sulfonylamino group represented by R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁸ , or R ⁹ is a sulfonylamino group having 1 to 20 carbon atoms. Group is preferable, a sulfonylamino group having 1 to 15 carbon atoms is more preferable, and a sulfonylamino group having 1 to 10 carbon atoms is particularly preferable. Specific examples include methylsulfonylamino group, ethylsulfonylamino group, normal propylsulfonylamino group, isopropylsulfonylamino group, normal butylsulfonylamino group, isobutylsulfonylamino group, tertiary butylsulfonylamino group, pentylsulfonylamino group. , Cyclopentylsulfonylamino group, hexylsulfonylamino group, cyclohexylsulfonylamino group, heptylsulfonylamino group, octylsulfonylamino group, tertiary octylsulfonylamino group, 2-ethylhexylsulfonylamino group, decylsulfonylamino group, dodecylsulfonylamino group, An octadecylsulfonylamino group, a phenylsulfonylamino group, etc. are mentioned.

In the general formula ^{(2), R 1, R} 2, R 3, R 4, R 5, R 6, R 8, or a carbamoylamino group represented by R ⁹ is carbamoylamino having 1 to 20 carbon atoms Group is preferable, a carbamoylamino group having 1 to 15 carbon atoms is more preferable, and a carbamoylamino group having 1 to 10 carbon atoms is particularly preferable. Specific examples include a methylcarbamoylamino group, an ethylcarbamoylamino group, a normalpropylcarbamoylamino group, an isopropylcarbamoylamino group, a normalbutylcarbamoylamino group, an isobutylcarbamoylamino group, a tertiary butylcarbamoylamino group, and a pentylcarbamoylamino group. , Cyclopentylocarbamoylamino group, hexylcarbamoylamino group, cyclohexylcarbamoylamino group, heptylcarbamoylamino group, octylcarbamoylamino group, tertiary octylcarbamoylamino group, 2-ethylhexylcarbamoylamino group, decylcarbamoylamino group, dodecylcarbamoylamino group , Octadecylcarbamoylamino group, phenylcarbamoylamino group, etc.

In the general formula (2), the alkoxycarbonylamino group represented by R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁸ , or R ⁹ is an alkoxy having 2 to 20 carbon atoms. A carbonylamino group is preferable, an alkoxycarbonylamino group having 2 to 15 carbon atoms is preferable, and an alkoxycarbonylamino group having 2 to 10 carbon atoms is particularly preferable. Specific examples include methoxycarbonylamino group, ethoxycarbonylamino group, normal propyloxycarbonylamino group, isopropyloxycarbonylamino group, normal butyloxycarbonylamino group, isobutyloxycarbonylamino group, tertiary butyloxycarbonylamino group. Pentyloxycarbonylamino group, cyclopentyloxycarbonylamino group, hexyloxycarbonylamino group, cyclohexyloxycarbonylamino group, heptyloxycarbonylamino group, octyloxycarbonylamino group, tertiary octyloxycarbonylamino group, 2-ethylhexyloxycarbonyl Amino group, decyloxycarbonylamino group, dodecyloxycarbonylamino group, octadecyloxy Ruboniruamino group, and a phenyloxycarbonylamino group.

In the general formula (2), the halogen atom represented by R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁸ , or R ⁹ is preferably F, Cl, Br, or I. , Cl, Br, and I are more preferable, and Cl and Br are particularly preferable.

In the general formula (2), the group represented by R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁸ , R ⁹ , or R ¹⁰ further has a substituent. For example, an alkyl group, aryl group, alkoxy group, aryloxy group, alkylsulfonyl group, arylsulfonyl group, alkylthio group, arylthio group, amino group, alkoxycarbonyl group, aryloxycarbonyl group, acyl group, acylamino group, Examples include a sulfonylamino group, a carbamoylamino group, an alkoxycarbonylamino group, a halogen atom, a cyano group, a nitro group, and a hydroxy group. Specific examples of these substituents are the same as those already described.

Among the above, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , and R ^{10 in the} general formula (2) are represented by R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁸ and R ⁹ are each independently a hydrogen atom, alkyl group, aryl group, alkoxy group, aryloxy group, alkylsulfonyl group, arylsulfonyl group, alkylthio group. Or an arylthio group is preferred, and R ¹ is an alkyl group, aryl group, alkoxy group, aryloxy group, alkylsulfonyl group, arylsulfonyl group, alkylthio group, or arylthio group, and R ² , R ^5, and more preferably embodiment R ⁶ is a hydrogen atom, R ¹ is a methyl group, a methoxy group, a butoxy group, tert-butoxy group, a 2-ethylhexyl group, a pentyloxy group, Mechiruchi A group, or an ethylthio group, R ^2, R ^5, and aspects R ⁶ is a hydrogen atom is particularly preferred. An embodiment in which R ³ and R ⁴ are an alkyl group or an aryl group is preferable, and a methyl group, a butyl group, a methoxycarbonylpropyl group, a dibutylaminocarbonylmethyl group, or a phenyl group is most preferable. Further, when R ³ and R ⁴ are linked to form a ring, a carbazole group is most preferable. R ⁷ and R ¹⁰ are most preferably a phenyl group, 2,4,6-trimethoxyphenyl, or 2,6-diisopropylphenyl group, and R ⁸ and R ⁹ are most preferably a hydrogen atom. From the viewpoint of purification by crystallization during synthesis, it is desirable that R ⁷ and R ¹⁰ are the same group.

In the general formula (2), A ⁻ represents a counter anion.
The counter anion represented by A ⁻ may be any as long as it can form a counter anion, and may be a monoanion or a polyanion, and may be an inorganic anion or an organic anion. Specifically, Cl ⁻ , Br ⁻ , I ⁻ , sulfonate anion having 1 to 20 carbon atoms, carboxylate anion having 2 to 21 carbon atoms, alkyl sulfate ion, hexafluorophosphate ion, tetrafluoroboron ion, perchlorine Acid ions, carbonate ions and sulfate ions are preferable, Cl ⁻ , Br ⁻ , tetrafluoroboron ions and hexafluorophosphate ions are more preferable, and hexafluorophosphate ions are particularly preferable.

In the general formula (2), R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ⁵ , R ⁵ and R ⁶ , R ⁷ and R ⁸ , R ⁸ and R ⁹ , R ⁹ and R ¹⁰ may be connected to each other to form a ring.

When R ¹ and R ² , R ⁵ and R ⁶ are connected to each other to form a ring, it is preferable to form a saturated or unsaturated 5- to 7-membered ring, and a saturated or unsaturated 5- to 6-membered ring Is more preferable, and a benzene ring is particularly preferable. When R ³ and R ⁴ are connected to each other to form a ring, it is preferable to form a saturated 5- to 7-membered ring, more preferably a saturated 5- to 6-membered ring, particularly preferably a saturated 5-membered ring, In the case where R ³ and R ⁴ form a ring, it is particularly preferable that benzene or the like is condensed to the ring.

  Hereinafter, specific examples (exemplary compounds D-35 to D-66) of the azo compound represented by the general formula (2) are shown. However, the present invention is not limited to these.

  As shown in the following scheme, the azo compound represented by the general formula (2) includes a diazonium salt represented by the following general formula (a) and a coupler compound represented by the following general formula (b). It can be synthesized by reacting.

Here, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , A are R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , and A have the same meanings. B represents a counter anion, for example, Cl ⁻ , Br ⁻ , PF ₆ ⁻ , BF ₄ ^{− and the} like. Various solvents can be used as the solvent used at this time, and examples thereof include water, alcohol, ethyl acetate, ether, and THF. For the purpose of increasing the yield, an organic base or an inorganic base may coexist. Examples of such a base include sodium hydroxide, ammonia, triethylamine, pyridine, sodium hydrogen carbonate, sodium methoxide, diazabicycloundecene. (DBU).

  Next, another embodiment of the azo compound of the present invention is a compound (including an azo dye) represented by the following general formula (3), which has a good hue and vividness, and is also light fast. Suitable as an excellent azo dye.

In the general formula (3), R ¹ , R ² , R ³ , R ⁴ , R ⁶ , and R ⁷ are each independently a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, or an alkylsulfonyl. Group, arylsulfonyl group, alkylthio group, arylthio group, amino group, alkoxycarbonyl group, aryloxycarbonyl group, acyl group, acylamino group, sulfonylamino group, carbamoylamino group, alkoxycarbonylamino group, halogen atom, cyano group, or Represents a nitro group, R ⁵ represents an aryl group, and R ⁸ represents a hydrogen atom, an alkyl group, or an aryl group. X represents —N (R ⁹ ) — or —O—, and R ⁹ represents an alkyl group or an aryl group.

In the general formula (3), the alkyl group represented by R ¹ , R ² , R ³ , R ⁴ , R ⁶ , R ⁷ , R ⁸ , or R ⁹ is an alkyl group having 1 to 20 carbon atoms. Preferably, an alkyl group having 1 to 15 carbon atoms is more preferable, and an alkyl group having 1 to 10 carbon atoms is particularly preferable. Specific examples include methyl group, ethyl group, normal propyl group, isopropyl group, normal butyl group, isobutyl group, tertiary butyl group, pentyl group, cyclopentyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, Examples include a decyl group, a tertiary octyl group, a 2-ethylhexyl group, a decyl group, a dodecyl group, and an octadecyl group.

In the general formula (3), the aryl group represented by R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , or R ⁹ has 6 to 14 carbon atoms. An aryl group is preferable, an aryl group having 6 to 10 carbon atoms is more preferable, and an aryl group having 6 carbon atoms is particularly preferable. Specific examples include a phenyl group, a naphthyl group, and an anthranyl group.

In the general formula (3), the alkoxyl group represented by R ¹ , R ² , R ³ , R ⁴ , R ⁶ , or R ⁷ is preferably an alkoxy group having 1 to 20 carbon atoms, 15 alkoxy groups are more preferable, and alkoxy groups having 1 to 10 carbon atoms are particularly preferable. Specific examples include methoxy, ethoxy, normal propyloxy, isopropyloxy, normal butyloxy, isobutyloxy, tertiary butyloxy, pentyloxy, cyclopentyloxy, hexyloxy, cyclohexyl Oxy group, heptyloxy group, octyloxy group, tertiary octyloxy group, 2-ethylhexyloxy group, decyloxy group, dodecyloxy group, octadecyloxy group, 1-ethylpropyl group, 2-methyl-4,4-dimethylpentyl Groups and the like.

In the general formula (3), the aryloxy group represented by R ¹ , R ² , R ³ , R ⁴ , R ⁶ , or R ⁷ is preferably an aryloxy group having 6 to 14 carbon atoms, A 6-10 aryloxy group is more preferable, and an aryloxy group having 6 carbon atoms is particularly preferable. Specific examples include a phenyloxy group, a naphthyloxy group, an anthracenyloxy group, and the like.

In the general formula (3), the alkylsulfonyl group represented by R ¹ , R ² , R ³ , R ⁴ , R ⁶ , or R ⁷ is preferably an alkylsulfonyl group having 1 to 20 carbon atoms. An alkylsulfonyl group having 1 to 15 carbon atoms is more preferable, and an alkylsulfonyl group having 1 to 10 carbon atoms is particularly preferable. Specific examples include methylsulfonyl group, ethylsulfonyl group, normal propylsulfonyl group, isopropylsulfonyl group, normal butylsulfonyl group, isobutylsulfonyl group, tertiary butylsulfonyl group, pentylsulfonyl group, cyclopentylsulfonyl group, hexylsulfonyl group. Cyclohexylsulfonyl group, heptylsulfonyl group, octylsulfonyl group, tertiary octylsulfonyl group, 2-ethylhexylsulfonyl group, decylsulfonyl group, dodecylsulfonyl group, octadecylsulfonyl group and the like.

In the general formula (3), the arylsulfonyl group represented by R ¹ , R ² , R ³ , R ⁴ , R ⁶ , or R ⁷ is preferably an arylsulfonyl group having 6 to 14 carbon atoms. Specific examples of 6 to 10 arylsulfonyl groups are more preferable, and arylsulfonyl groups having 6 carbon atoms are particularly preferable, such as a phenylsulfonyl group, a naphthylsulfonyl group, and an anthranylsulfonyl group.

In the general formula (3), the alkylthio group represented by R ¹ , R ² , R ³ , R ⁴ , R ⁶ , or R ⁷ is preferably an alkylthio group having 1 to 20 carbon atoms, 15 alkylthio groups are preferable, and an alkylthio group having 1 to 10 carbon atoms is particularly preferable. Specific examples include methylthio group, ethylthio group, normal propylthio group, isopropylthio group, normal butylthio group, isobutylthio group, tertiary butylthio group, pentylthio group, cyclopentylthio group, hexylthio group, and cyclohexylthio group. , Heptylthio group, octylthio group, tertiary octylthio group, 2-ethylhexylthio group, decylthio group, dodecylthio group, octadecylthio group and the like.

In the general formula (3), the arylthio group represented by R ¹ , R ² , R ³ , R ⁴ , R ⁶ , or R ⁷ is preferably an arylthio group having 6 to 14 carbon atoms, 10 arylthio groups are more preferable, and arylthio groups having 6 carbon atoms are particularly preferable. Specific examples include a phenylthio group, a naphthylthio group, and an anthranylthio group.

In the general formula (3), the amino group represented by R ¹ , R ² , R ³ , R ⁴ , R ⁶ , or R ⁷ is preferably an amino group having 1 to 20 carbon atoms, 10 amino groups are more preferred, and 1-8 amino groups are particularly preferred. Specific examples include a mono-substituted product such as a methylamino group, an ethylamino group, a butylamino group, a hexylamino group, a benzylamino group, and a phenylamino group, and a disubstituted product such as a dimethylamino group, Examples thereof include a diethylamino group, a dibutylamino group, a dihexylamino group, a dibenzylamino group, a diphenylamino group, and a phenylmethylamino group.

In the general formula (3), the alkoxycarbonyl group or aryloxycarbonyl group represented by R ¹ , R ² , R ³ , R ⁴ , R ⁶ , or R ⁷ is an alkoxycarbonyl group having 2 to 20 carbon atoms. , An aryloxycarbonyl group having 7 to 25 carbon atoms is preferable, an alkoxycarbonyl group having 2 to 15 carbon atoms, an aryloxycarbonyl group having 7 to 15 carbon atoms is more preferable, an alkoxycarbonyl group having 2 to 10 carbon atoms, and a carbon number 7-10 aryloxycarbonyl groups are particularly preferred.

  Specific examples of the alkoxycarbonyl group include a methyloxycarbonyl group, an ethyloxycarbonyl group, a normalpropyloxycarbonyl group, an isopropyloxycarbonyl group, a normal butyloxycarbonyl group, an isobutyloxycarbonyl group, and a tertiary butyloxycarbonyl group. Pentyloxycarbonyl group, cyclopentyloxycarbonyl group, hexyloxycarbonyl group, cyclohexyloxycarbonyl group, heptyloxycarbonyl group, octyloxycarbonyl group, tertiary octyloxycarbonyl group, 2-ethylhexyloxycarbonyl group, decyloxycarbonyl group, And dodecyloxycarbonyl group, octadecyloxycarbonyl group, etc. Le oxycarbonyl group, naphthyloxycarbonyl group, and anthranyl oxycarbonyl group.

In the general formula (3), the acyl group represented by R ¹ , R ² , R ³ , R ⁴ , R ⁶ , or R ⁷ is preferably an acyl group having 2 to 20 carbon atoms, An acyl group having 10 carbon atoms is more preferable, and an acyl group having 2 to 5 carbon atoms is more preferable. Specific examples include methylcarbonyl group, ethylcarbonyl group, normal propylcarbonyl group, isopropylcarbonyl group, normal butylcarbonyl group, isobutylcarbonyl group, tertiary butylcarbonyl group, pentylcarbonyl group, cyclopentylcarbonyl group, hexylcarbonyl group. Cyclohexylcarbonyl group, heptylcarbonyl group, octylcarbonyl group, tertiary octylcarbonyl group, 2-ethylhexylcarbonyl group, decylcarbonyl group, dodecylcarbonyl group, octadecylcarbonyl group, benzoyl group and the like.

In Formula (3), the acylamino group represented by ^{R 1, R 2, R 3} , R 4, R 6, R 7, preferably an acylamino group having 1 to 20 carbon atoms, 1 to 15 carbon atoms Are more preferable, and an acylamino group having 1 to 10 carbon atoms is particularly preferable. Specific examples include methylcarbonylamino group, ethylcarbonylamino group, normal propylcarbonylamino group, isopropylcarbonylamino group, normal butylcarbonylamino group, isobutylcarbonylamino group, tertiary butylcarbonylamino group, pentylcarbonylamino group. , Cyclopentylcarbonylamino group, hexylcarbonylamino group, cyclohexylcarbonylamino group, heptylcarbonylamino group, octylcarbonylamino group, tertiary octylcarbonylamino group, 2-ethylhexylcarbonylamino group, decylcarbonylamino group, dodecylcarbonylamino group, Examples include an octadecylcarbonylamino group and a benzoylamino group.

In the general formula (3), the sulfonylamino group represented by R ¹ , R ² , R ³ , R ⁴ , R ⁶ , or R ⁷ is preferably a sulfonylamino group having 1 to 20 carbon atoms. A sulfonylamino group having 1 to 15 carbon atoms is more preferable, and a sulfonylamino group having 1 to 10 carbon atoms is particularly preferable. Specific examples include methylsulfonylamino group, ethylsulfonylamino group, normal propylsulfonylamino group, isopropylsulfonylamino group, normal butylsulfonylamino group, isobutylsulfonylamino group, tertiary butylsulfonylamino group, pentylsulfonylamino group. , Cyclopentylsulfonylamino group, hexylsulfonylamino group, cyclohexylsulfonylamino group, heptylsulfonylamino group, octylsulfonylamino group, tertiary octylsulfonylamino group, 2-ethylhexylsulfonylamino group, decylsulfonylamino group, dodecylsulfonylamino group, An octadecylsulfonylamino group, a phenylsulfonylamino group, etc. are mentioned.

In the general formula (3), the carbamoylamino group represented by R ¹ , R ² , R ³ , R ⁴ , R ⁶ , or R ⁷ is preferably a carbamoylamino group having 1 to 20 carbon atoms. A carbamoylamino group having 1 to 15 carbon atoms is more preferable, and a carbamoylamino group having 1 to 10 carbon atoms is particularly preferable. Specific examples include a methylcarbamoylamino group, an ethylcarbamoylamino group, a normalpropylcarbamoylamino group, an isopropylcarbamoylamino group, a normalbutylcarbamoylamino group, an isobutylcarbamoylamino group, a tertiary butylcarbamoylamino group, and a pentylcarbamoylamino group. , Cyclopentylocarbamoylamino group, hexylcarbamoylamino group, cyclohexylcarbamoylamino group, heptylcarbamoylamino group, octylcarbamoylamino group, tertiary octylcarbamoylamino group, 2-ethylhexylcarbamoylamino group, decylcarbamoylamino group, dodecylcarbamoylamino group , Octadecylcarbamoylamino group, phenylcarbamoylamino group, etc.

In the general formula (3), the alkoxycarbonylamino group represented by R ¹ , R ² , R ³ , R ⁴ , R ⁶ , or R ⁷ is preferably an alkoxycarbonylamino group having 2 to 20 carbon atoms, An alkoxycarbonylamino group having 2 to 15 carbon atoms is preferable, and an alkoxycarbonylamino group having 2 to 10 carbon atoms is particularly preferable. Specific examples include methoxycarbonylamino group, ethoxycarbonylamino group, normal propyloxycarbonylamino group, isopropyloxycarbonylamino group, normal butyloxycarbonylamino group, isobutyloxycarbonylamino group, tertiary butyloxycarbonylamino group. Pentyloxycarbonylamino group, cyclopentyloxycarbonylamino group, hexyloxycarbonylamino group, cyclohexyloxycarbonylamino group, heptyloxycarbonylamino group, octyloxycarbonylamino group, tertiary octyloxycarbonylamino group, 2-ethylhexyloxycarbonyl Amino group, decyloxycarbonylamino group, dodecyloxycarbonylamino group, octadecyloxy Ruboniruamino group, and a phenyloxycarbonylamino group.

In the general formula (3), the halogen atom represented by R ¹ , R ² , R ³ , R ⁴ , R ⁶ , or R ⁷ is preferably F, Cl, Br, I, and Cl, Br, I Is more preferable, and Cl and Br are particularly preferable.

In the general formula (1), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , and R ⁹ may further have a substituent. Group, aryl group, alkoxy group, aryloxy group, alkylsulfonyl group, arylsulfonyl group, alkylthio group, arylthio group, amino group, alkoxycarbonyl group, aryloxycarbonyl group, acyl group, acylamino group, sulfonylamino group, carbamoylamino A group, an alkoxycarbonylamino group, a halogen atom, a cyano group, a nitro group, and a hydroxy group. Specific examples of these groups are the same as those already described.

Among the above, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ^{9 in the} general formula (3) are R ¹ , R ² , R ³ , And R ⁴ are each independently a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylsulfonyl group, an arylsulfonyl group, an alkylthio group, or an arylthio group. Group, octyl group, methoxy group, butoxy group, tertiary butoxy group, pentyloxy group, methylthio group, and ethylthio group are most preferable, and as R ⁵ , phenyl group, 2,4,6-trimethoxyphenyl, 2, A 6-diisopropylphenyl group is most preferable, and R ⁶ and R ⁷ are most preferably a hydrogen atom. Moreover, as R < ⁸ >, the aspect which is an alkyl group or an aryl group is preferable, and a methyl group, an octyl group, and a tolyl group are the most preferable. R ⁹ is most preferably a methyl group or a tolyl group.
An embodiment in which R ⁵ and R ⁹ are the same group is preferable from the viewpoint of purification by crystallization during synthesis.

In the general formula (3), X represents —N (R ⁹ ) — or —O—, and —N (R ⁹ ) — is particularly preferable. Examples of the 5-membered salt composed of X, a nitrogen atom and three carbon atoms in the general formula (3) include imidazolium salts and oxazolium salts.

In the general formula (3), A ⁻ represents a counter anion. The counter anion represented by A ⁻ may be any as long as it can form a counter anion, and may be a monoanion or a polyanion, and may be an inorganic anion or an organic anion. Specifically, Cl ⁻ , Br ⁻ , I ⁻ , sulfonate anion having 1 to 20 carbon atoms, carboxylate anion having 2 to 21 carbon atoms, alkyl sulfate ion, hexafluorophosphate ion, tetrafluoroboron ion, perchloric acid Ions, carbonate ions and sulfate ions are preferable, Cl ⁻ , Br ⁻ , tetrafluoroboron ions and hexafluorophosphate ions are more preferable, and hexafluorophosphate ions are particularly preferable.

In the general formula (3), R ¹ and R ² , R ³ and R ⁴ may be connected to each other to form a ring, and R ² and R ⁸ , R ³ and R ⁸ , R ⁵ and R ⁶ may be linked to each other to form a ring, or R ⁶ and R ⁷ may be linked to each other to form a ring.

When R ¹ and R ² , R ³ and R ⁴ are connected to each other to form a ring, it is preferable to form a saturated or unsaturated 5- to 7-membered ring, more preferably a saturated or unsaturated 5- to 6-membered ring. Saturated or unsaturated 6-membered rings are preferred. When R ⁶ and R ⁷ are connected to each other to form a ring, it is preferably a saturated or unsaturated 5- to 7-membered ring, more preferably a saturated or unsaturated 5- to 6-membered ring, saturated or An unsaturated 6-membered ring is particularly preferred. When R ² and R ⁸ , R ³ and R ⁸ , R ⁵ and R ⁶ are connected to each other, it is preferable to form a saturated or unsaturated 5- to 7-membered ring, and saturated 5 to 6-membered A ring is more preferable, and a saturated 6-membered ring is particularly preferable.

  Hereinafter, specific examples (exemplary compounds D-67 to D-81) of the azo compound represented by the general formula (3) are shown. However, the present invention is not limited to these.

  The azo compound represented by the general formula (3) can be synthesized by reacting a diazonium salt represented by the following general formula (a) with a coupler compound represented by the following general formula (b). it can.

Here, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , X, Y, A are R ¹ , R ² , R ^{3 in the} general formula (3). , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , X, Y, and A have the same meanings. B represents a counter anion, for example, Cl ⁻ , Br ⁻ , PF ₆ ⁻ , BF ₄ ^{− and the} like. Various solvents can be used as the solvent used at this time, and examples thereof include water, alcohol, ethyl acetate, ether, and THF. For the purpose of increasing the yield, an organic base or an inorganic base may coexist. Examples of such a base include sodium hydroxide, ammonia, triethylamine, pyridine, sodium hydrogen carbonate, sodium methoxide, diazabicyclone. Examples include decene (DBU).

  The azo compound of the present invention contains an azo dye, and the azo dye contains an azo dye. This azo dye has a good absorption spectrum, a good hue and vividness, as well as light fastness. It is an excellent pigment. For example, it can be suitably used as an azo dye having a good hue, vividness and excellent light fastness.

  The dye composition of the present invention comprises one or more selected from the azo compounds of the present invention described above and tautomers thereof, and other components are used in combination according to the purpose and application. It can be configured. This dye composition is also a coloring material having a good hue and vividness and excellent light fastness.

  The azo compounds (including azo dyes) and the dye composition of the present invention are used for, for example, synthetic resin coloring dyes, sublimation thermal transfer materials, inks used for printing or ink jet recording, and further electronics. It is suitable as a functional dye in the field.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist thereof.

Example 1
As shown below, 1.8 g of the following coupler (b) was dissolved in 50 ml of methanol, and 3.0 g of diazonium salt (a) was added. Further, 1.0 g of sodium methoxide was added thereto, followed by stirring at room temperature for 1 hour. To this reaction solution, 200 ml of water and 200 ml of ethyl acetate were added, and extraction operation was performed. And after concentrating an organic layer, it refine | purified by column chromatography and synthesize | combined the said exemplary compound D-1 which is an azo compound of this invention.

The ¹ H NMR data of the obtained azo compound D-1 is shown below.
¹ H NMR (300 MHz, CDCl ₃ ) δ 0.83 (m, 3H), 0.90 (s, 9H), 1.10 (d, 3H), 1.21-1.41 (m, 15H), 1 .65 to 1.87 (m, 6H), 1.90 to 2.08 (m, 4), 2.51 (t, 4H), 3.58 (t, 4H), 3.68 (s, 6H) ), 4.01 (s, 3H), 4.21 to 4.44 (m, 4H), 6.60 (s, 1H), 6.64 (s, 1H), 7.18 (d, 1H) 7.24 (d, 1H), 7.86 (d, 1H)

(Example 2)
In Example 1, Exemplified Compound D-2, which is the azo compound of the present invention, was prepared in the same manner as in Example 1 except that 1.8 g of coupler (b) was replaced with 1.9 g of the following coupler (c). Synthesized.

The ¹ H NMR data of the obtained azo compound D-2 is shown below.
¹ H NMR (300 MHz, CDCl ₃ ) δ 0.83 to 1.01 (m, 12H), 1.13 (d, 3H), 1.19 to 1.40 (m.11H), 1.67 to 1. 81 (m, 2H), 1.83 to 1.91 (m, 2H), 2.09 (t, 4H), 2.54 (t, 4H), 3.63 to 3.81 (bs, 10H) 4.01 (s, 3H), 4.21 to 4.50 (m, 4H), 6.71 (s, 1H), 6.95 (d, 1H), 7.99 (d, 1H)

(Example 3)
In Example 1, 1.8 g of coupler (b) was replaced with 1.7 g of the following coupler (d), and 1.0 g of triethylamine was used as a base, and the same procedure as in Example 1 was followed. The exemplified compound D-5, which is an azo compound, was synthesized.

The ¹ H NMR data of the obtained azo compound D-5 is shown below.
¹ H NMR (300 MHz, CDCl ₃ ) δ 0.81 (t, 3H), 0.91 (s, 9H), 1.05 (d, 3H), 1.20 to 1.40 (m, 7H), 1 .41 to 1.58 (m, 6H), 1.80 to 2.10 (m, 6H), 2.54 (t, 4H), 3.60 to 3.79 (bs, 10H), 4.31 To 4.50 (m, 4H), 6.65 (s, 1H), 6.69 (d, 1H), 7.01 (s, 1), 7.34 (s, 1H), 8.01 ( d, 2H)

Example 4
In Example 1, 1.8 g of coupler (b) was replaced with 2.1 g of the following coupler (e), and 1.0 g of triethylamine was further used as a base, and the same procedure as in Example 1 was followed. The exemplified compound D-7, which is an azo compound, was synthesized.

The ¹ H NMR data of the obtained azo compound D-7 is shown below.
¹ H NMR (300 MHz, CDCl ₃ ) δ 0.92 (s, 9H), 1.02 (d, 3H), 1.20 to 1.63 (m, 5H), 1.84 to 2.03 (m, 4H), 2.53 (t, 4H), 2.71 (s, 3H), 3.60 to 3.75 (bs, 10H), 3.89 to 4.20 (m, 2H), 6.45. (S, 1H), 6.80 (d, 2H), 7.35-7.42 (m, 2H), 7.44-7.65 (m, 6H), 7.75 (d, 1H), 7.83 (d, 2H)

(Example 5)
In Example 1, 1.8 g of coupler (b) was replaced with 2.2 g of the following coupler (f), and 1.0 g of triethylamine was further used as a base, and the same procedure as in Example 1 was followed. The exemplified compound D-10, which is an azo compound, was synthesized.

The ¹ H NMR data of the obtained azo compound D-10 is shown below.
¹ H NMR (300 MHz, CDCl ₃ ) δ 0.95 (s, 9H), 1.01 (d, 3H), 1.10 to 1.35 (m, 2H), 1.40 to 1.71 (m, 3H), 1.90 to 2.03 (m, 4H), 2.43 to 2.61 (m, 4H), 3.60 to 3.85 (bs, 10H), 4.00 to 4.21 ( m, 2H), 6.51 (s, 1H), 6.80 (d, 1H), 7.31-7.40 (m, 6H), 7.42-7.60 (m, 7H), 7 .71 (d, 1H), 7.84 (d, 2H)

(Example 6)
In Example 1, 1.8 g of the coupler (b) was replaced with 1.9 g of the following coupler (g), and 1.0 g of triethylamine was used as a base, and the same procedure as in Example 1 was followed. The exemplified compound D-13, which is an azo compound, was synthesized.

The ¹ H NMR data of the obtained azo compound D-13 is shown below.
¹ H NMR (300 MHz, CDCl ₃ ) δ 0.82 (s, 9H), 0.98 (d, 3H), 1.05 to 1.25 (m, 3H), 1.60 to 1.85 (m, 2H), 2.00 to 2.18 (m, 4H), 2.59 (t, 4H), 2.61 (s, 3H), 2.65 (s, 3H), 3.65 to 3.81. (Bs, 10H), 4.27 to 4.42 (m, 2H), 6.09 (d, 2H), 6.77 (s, 1H), 6.91 (d, 1H), 7.20 ( s, 1H), 7.35-7.41 (m, 3H), 7.49-7.60 (m, 2H), 8.21 (d, 1H)

(Comparative Examples 1-4)
As comparative pigment compounds, the following comparative compounds (1) to (4) were prepared, and these were used as targets for evaluation described later.

(Evaluation 1)
About each of the azo compound of the present invention and the comparative compounds (1) to (4) obtained from the above, color development hue (λ _max ), half width, color development density (molar extinction constant ε), and light resistance are measured and evaluated. did. The evaluation results are shown in Table 1 below.

1. Absorption spectrum Using the azo compound of the present invention and the comparative compounds (1) to (4), each chloroform / methanol (= 1/1) solution (2.0 × 10 ⁻⁵ mol / l) was prepared. Taking a 1 cm square quartz cell, an ultraviolet-visible absorption spectrum was measured using an absorbance measuring device MPS-2400 (manufactured by Shimadzu Corporation). The absorption maximum wavelength (λ _max ) was measured from the obtained absorption spectrum, and the molar absorption constant (ε) was calculated from the absorbance at that wavelength. Also, the absorption spectrum is normalized, and Abs. The wavelength width (half-value width) at which = 0.5 was measured. The hue increases in vividness as the half-value width of absorption becomes narrower.

2. Light resistance Using the azo compound of the present invention and the comparative compounds (1) to (4), each butyl acetate solution (2.0 × 10 ⁻⁵ mol / l) was prepared, and this was placed in a 1 cm square quartz cell. Using a merry-go-round type light resistance tester (Eagle Engineering Co., Ltd.) equipped with a xenon light 500W lamp, irradiate xenon light for 5 hours, and obtain the dye residual rate (%) after irradiation with xenon light from the change in the UV-visible absorption spectrum. It was.

(Example 7)
As shown below, 2.26 g of the following coupler (b2) was dissolved in 50 ml of tetrahydrofuran (THF), and 1.4 g of the following diazonium salt (a2) was added thereto. Further, 0.7 g of 1,8-diazabicyclo [5.4.0] -7-undecene (DBU) was added thereto, followed by stirring in an ice bath for 1 hour. To the reaction solution, 200 ml of water and 200 ml of ethyl acetate were added, and extraction operation was performed. Then, after concentrating an organic layer, it refine | purified by column chromatography and synthesize | combined the said exemplary compound D-35 which is an azo compound of this invention.

The ¹ H NMR data of the obtained azo compound D-35 is shown below.
¹ H NMR (300 MHz, CDCl ₃ ) δ 0.90 (s, 9H), 1.04 (d, 3H), 1.15 to 1.31 (m, 3H), 1.51 to 1.70 (m, 2H), 2.09 (s, 12H), 2.38-2.48 (m, 10H), 3.49 (t, 4H), 3.64 (s, 6H), 3.90-4.10. (M, 2H), 6.33 (d, 1H), 6.42 (dd, 1H), 6.99 (s, 4H), 7.18 (s, 2H), 7.38 (d, 1H)

(Example 8)
In Example 7, Exemplified Compound D-37, which is an azo compound of the present invention, was prepared in the same manner as in Example 7 except that 2.26 g of coupler (b2) was replaced with 2.5 g of the following coupler (c2). Synthesized.

The ¹ H NMR data of the obtained azo compound D-37 is shown below.
¹ H NMR (300 MHz, CDCl ₃ ) δ 0.91 (s, 9H), 1.01 (d, 3H), 1.10 to 1.30 (m, 2H), 1.39 to 1.63 (m, 3H), 1.91 (bs, 4H), 2.43 (t, 4H), 3.56 (t, 4H), 3.65 (s, 6H), 3.90 to 4.09 (m, 2H) ), 6.40 (d, 1H), 6.52 (dd, 1H), 7.41 (s, 2H), 7.44-7.60 (m, 11H)

Example 9
In Example 7, Exemplified Compound D-40, which is an azo compound of the present invention, was prepared in the same manner as in Example 7 except that 2.26 g of coupler (b2) was replaced with 2.5 g of the following coupler (d2). Synthesized.

The ¹ H NMR data of the obtained azo compound D-40 is shown below.
¹ H NMR (300 MHz, CDCl ₃ ) δ 0.92 (s, 9H), 1.03 (d, 3H), 1.17 to 1.38 (m, 3H), 1.52 to 1.70 (m, 2H), 1.91 (bs, 4H), 2.44 (t, 4H), 3.54 t, 4H), 3.69 (s, 6H), 3.92 to 4.17 (m, 2H) , 6.41 (d, 1H), 6.57 (dd, 1H), 7.38 (s, 2H), 7.46 (bs, 4H), 7.57 (d, 2H)

(Example 10)
In Example 7, except that 1.4 g of diazonium salt (a2) was replaced with 2.5 g of diazonium salt (e2) below, Exemplified Compound D- which is the azo compound of the present invention was prepared in the same manner as in Example 7. 44 was synthesized.

The ¹ H NMR data of the obtained azo compound D-44 is shown below.
¹ H NMR (300 MHz, CDCl ₃ ) δ 0.85 (t, 6H), 1.20 to 1.41 (m, 20H), 1.62 (bs, 4H), 2.06 (s, 12H), 2 .39 (s, 6H), 3.40 (t, 4H), 3.49 (s, 6H), 5.58 (s, 2H), 7.02 (s, 4H), 7.18 (s, 2H)

(Example 11)
In Example 7, except that 1.4 g of diazonium salt (a2) was replaced with 2.5 g of diazonium salt (f2) below, Exemplified Compound D- which is the azo compound of the present invention was prepared in the same manner as in Example 7. 45 was synthesized.

The ¹ H NMR data of the obtained azo compound D-45 is shown below.
¹ H NMR (300 MHz, CDCl ₃ ) δ 0.77 (t, 6H), 0.96 (t, 6H), 1.24 to 1.40 (m, 4H), 1.42 to 1.53 (m , 4H), 2.08 (s, 12H), 2.37 (s, 6H), 3.39 (t, 4H), 4.08 (m, 1H), 5.81 (d, 1H), 6 .22 (dd, 1H), 6.98 (s, 4H), 7.21 (s, 2H), 7.35 (bs, 1H)

(Example 12)
In Example 7, except that 1.4 g of diazonium salt (a2) was replaced with 2.5 g of the following diazonium salt (g2), the Exemplified Compound D- which is the azo compound of the present invention was prepared in the same manner as in Example 7. 46 was synthesized.

The ¹ H NMR data of the obtained azo compound D-46 is shown below.
¹ H NMR (300 MHz, CDCl ₃ ) δ 0.92 t, 3H), 1.67 (m, 2H), 2.04 s, 12H), 2.38 (s, 6H), 3.51 (s, 3H) ), 3.72 (t, 2H), 5.85 (d, 1H), 6.06 (dd, 1H), 6.99 (s, 4H), 7.15 (d, 2H), 7.21 (D, 1H), 7.28 (s, 2H), 7.38-7.48 (m, 3H)

(Example 13)
In Example 7, Exemplified Compound D- which is the azo compound of the present invention was prepared in the same manner as in Example 7 except that 1.4 g of diazonium salt (a2) was replaced with 2.5 g of diazonium salt (h2) shown below. 47 was synthesized.

The ¹ H NMR data of the obtained azo compound D-47 is shown below.
¹ H NMR (300 MHz, CDCl ₃ ) δ 0.64 (t, 6H), 0.92 (t, 3H), 1.27 to 1.46 (m, 4H), 1.58 to 1.67 (m, 2H), 2.03 (s, 12H), 2.18 (s, 6H), 3.24 (t, 2H), 3.95 to 4.02 (m, 1H), 5.21 (s, 2H) ), 6.71 (s, 1H), 6.97 (s, 4H), 7.22-7.37 (m, 6H), 7.46 (s, 2H)

(Example 14)
In Example 7, except that 1.4 g of diazonium salt (a2) was replaced with 2.5 g of diazonium salt (i2) below, Exemplified Compound D- which is the azo compound of the present invention was prepared in the same manner as in Example 7. 53 was synthesized.

The ¹ H NMR data of the obtained azo compound D-53 is shown below.
¹ H NMR (300 MHz, CDCl ₃ ) δ 2.04 (s, 12H), 2.38 (s, 6H), 3.41 (s, 3H), 6.11 (d, 1H), 6.27 (dd , 1H), 7.00 (s, 4H), 7.19 (d, 4H), 7.24-7.32 (m, 3H), 7.37-7.43 (m, 6H)

(Example 15)
In Example 7, Exemplified Compound D- which is the azo compound of the present invention was prepared in the same manner as in Example 7 except that 1.4 g of diazonium salt (a2) was replaced with 2.5 g of diazonium salt (j2) shown below. 54 was synthesized.

The ¹ H NMR data of the obtained azo compound D-54 is shown below.
¹ H NMR (300 MHz, CDCl ₃ ) δ 0.91 (t, 3H), 1.17 to 1.40 (m, 6H), 1.48 (t, 2H), 2.07 (s, 12H), 2 .36 (s, 6H), 3.59 (t, 2H), 6.90 (d, 1H), 6.24 (dd, 1H), 6.97 (s, 4H), 7.16-7. 21 (m, 4H), 7.24-7.32 (m, 2H), 7.34-7.43 (m, 5H)

(Example 16)
In Example 7, except that 1.4 g of diazonium salt (a2) was replaced with 2.5 g of diazonium salt (k2) below, Exemplified Compound D- which is the azo compound of the present invention was prepared in the same manner as in Example 7. 55 was synthesized.

The ¹ H NMR data of the obtained azo compound D-55 is shown below.
¹ H NMR (300 MHz, CDCl ₃ ) δ 0.73 (t, 3H), 0.84 (t, 3H), 1.04 to 1.36 (m, 9H), 2.08 (s, 12H), 2 .38 (s, 6H), 3.47 (d, 2H), 6.10 (d, 1H), 6.27 (dd, 1H), 6.98 (s, 4H), 7.18-7. 20 (m, 4H), 7.23 to 7.36 (m, 2H), 7.35 to 7.45 (m, 5H)

(Example 17)
In Example 7, except that 1.4 g of the diazonium salt (a2) was replaced with 2.5 g of the following diazonium salt (l2), the Example Compound D- 57 was synthesized.

The ¹ H NMR data of the obtained azo compound D-57 is shown below.
¹ H NMR (300 MHz, CDCl ₃ ) δ 1.57 (s, 3H), 2.05 (s, 12H), 2.37 (s, 6H), 6.54 (m, 2H), 7.03 (s , 4H), 7.17 (d, 4H), 7.21 to 7.31 (m, 3H), 7.39 (t, 4H), 7.54 (s, 2H)

(Example 18)
In Example 7, except that 1.4 g of diazonium salt (a2) was replaced with 2.5 g of the following diazonium salt (m2), the Exemplified Compound D- which is the azo compound of the present invention was prepared in the same manner as in Example 7. 58 was synthesized.

The ¹ H NMR data of the obtained azo compound D-58 is shown below.
¹ H NMR (300 MHz, CDCl ₃ ) δ 2.04 (s, 12H), 2.39 (s, 6H), 6.76 (d, 2H), 7.01 (s, 4H), 7.09 to 7.19 (m, 6H), 7.27 (t, 2H), 7.37 (t, 4H), 7.60 (s, 2H)

(Example 19)
In Example 7, Exemplified Compound D- which is the azo compound of the present invention was prepared in the same manner as in Example 7 except that 1.4 g of diazonium salt (a2) was replaced with 2.5 g of diazonium salt (n2) shown below. 59 was synthesized.

The ¹ H NMR data of the obtained azo compound D-59 is shown below.
¹ H NMR (300 MHz, CDCl ₃ ) δ 2.09 (s, 12H), 2.43 (s, 6H), 7.10 (s, 4H), 7.30-7.43 (m, 4H), 7 .51 (d, 2H), 7.59 (d, 2H), 7.75 (d, 2H), 7.88 (s, 2H), 8.14 (d, 2H)

(Example 20)
In Example 7, except that 1.4 g of diazonium salt (a2) was replaced with 2.5 g of diazonium salt (o2) below, Exemplified Compound D- which is the azo compound of the present invention was prepared in the same manner as in Example 7. 60 was synthesized.

The ¹ H NMR data of the obtained azo compound D-60 is shown below.
¹ H NMR (300 MHz, CDCl ₃ ) δ 2.10 (s, 12H), 2.41 (s, 6H), 3.74 (s, 3H), 7.09 (s, 4H), 7.11 7.20 (m, 2H), 7.30-7.54 (m, 7H), 7.68 (s, 2H), 8.11 (d, 2H)

(Comparative Examples 5-7)
As comparative pigment compounds, the following comparative compounds (5) to (7) were prepared, and these were used as targets for evaluation described later.

(Evaluation 2)
For each of the azo compound of the present invention and the comparative compounds (5) to (7) obtained above, the same method as the evaluation (Evaluation 1) performed in Examples 1 to 6 and Comparative Examples 1 to 4 above ( However, the color hue (λ _max ), the half-value width, and the light resistance were measured and evaluated according to “2. Light resistance” where the irradiation time of xenon light was 24 hours. The evaluation results are shown in Table 2 below.

(Example 21)
As shown below, 2.26 g of the following coupler (b3) was dissolved in 50 ml of tetrahydrofuran (THF), and 1.4 g of diazonium salt (a3) was added thereto. Further, 0.7 g of 1,8-diazabicyclo [5.4.0] -7-undecene (DBU) was added thereto, followed by stirring in an ice bath for 1 hour. To the reaction solution, 200 ml of water and 200 ml of ethyl acetate were added, and extraction operation was performed. Then, after concentrating an organic layer, it refine | purified by column chromatography and the said exemplary compound D-67 which is an azo compound of this invention was synthesize | combined.

The ¹ H NMR data and absorption maximum wavelength (chloroform: methanol = 1: 1 solution, 2 × 10 ⁻⁵ mol / l) of the obtained azo compound D-67 are shown below.
¹ H NMR (300 MHz, CDCl ₃ ) δ 2.08 (s, 12H), 2.281 (s, 6H), 3.88 (s, 3H), 6.81 (d, 2H), 7.07 (s , 4H), 7.436 (d, 2H), 7.74 (s2H)
λ _max (nm) = 514.5 nm

(Example 22)
In Example 21, except that 1.4 g of diazonium salt (a3) was replaced with 2.5 g of diazonium salt (c3) shown below, Exemplified Compound D- which is the azo compound of the present invention was prepared in the same manner as in Example 21. 68 was synthesized.

The ¹ H NMR data and absorption maximum wavelength (chloroform: methanol = 1: 1 solution, 2 × 10 ⁻⁵ mol / l) of the obtained exemplary compound D-68 are shown below.
¹ H NMR (300 MHz, CDCl ₃ ) δ 0.82 to 0.96 (m, 6H), 1.21 to 1.51 (m, 20H), 1.63 (t, 2H), 1.78 (t, 2H), 2.68 (s, 12H), 2.20 (s, 6H), 3.90 t, 2H), 4.09 (t, 2H), 4.04 (t, 2H), 6.30. (S, 1H), 6.38d, 1H), 7.02 (s, 4H), 7.29 (s, 1H), 7.58 (s, 2H)
λ _max (nm) = 453.0 nm

(Example 23)
In Example 21, except that 1.4 g of the diazonium salt (a3) was replaced with 2.6 g of the following diazonium salt (d3), the Exemplified Compound D- which is the azo compound of the present invention was prepared in the same manner as in Example 21. 69 was synthesized.

The ¹ H NMR data and absorption maximum wavelength (chloroform: methanol = 1: 1 solution, 2 × 10 ⁻⁵ mol / l) of the obtained exemplary compound D-69 are shown below.
¹ H NMR (300 MHz, CDCl ₃ ) δ 0.84 (t, 3H), 0.92 (t, 3H), 1.14 (q, 2H), 1.32 (q, 2H), 1.43 (q , 2H), 1.72 (q, 2H), 2.08 (s, 12H), 2.36 (s, 6H), 2.42 (s, 3), 3.45 (t, 2H), 3 .76 (t, 2H), 5.98 (s, 1H), 6.57 (s, 1H), 6.99 (s, 4H), 7.28 (d, 2H), 7.39 (d, 2H), 7.60 (s, 2H)
λ _max (nm) = 547.4 nm

(Comparative Examples 8-9)
As comparative pigment compounds, the following comparative compounds (8) to (9) were prepared, and these were used as evaluation targets described later.

(Evaluation 3)
For each of the azo compound of the present invention and the comparative compounds (8) to (9) obtained above, the same method as the evaluation (Evaluation 1) performed in Examples 1 to 6 and Comparative Examples 1 to 4 above ( However, the color hue (λ _max ), the half-value width, and the light resistance were measured and evaluated according to “2. Light resistance” where the irradiation time of xenon light was 24 hours. The evaluation results are shown in Table 3 below.

As shown in Table 1, the azo compound of the present invention exhibits a good hue as a dye in comparison with the dye compound used for comparison, has a large molar absorption constant, is bright, and has good light resistance. Excellent light fastness.
Further, as shown in Table 2, the azo compound of the present invention was excellent in light fastness. Further, in the general formula (2), a dye whose amino group substituent is an alkyl group is superior in terms of vividness.
Further, as shown in Table 3, the azo compound of the present invention was excellent in light fastness.

  In addition to the azo compounds of the present invention used in the above examples, other exemplary compounds of the azo compounds of the present invention described above have the same functions as the azo compounds of the present invention used in the examples. Therefore, it is possible to obtain the same hue and light fastness as described above.

Claims (6)

An azo compound represented by the following general formula (1) and a tautomer thereof.

[In General Formula (1), R ¹ , R ² , R ³ , and R ⁴ are each independently a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylsulfonyl group, an arylsulfonyl group, or an alkylthio group. A group or an arylthio group, R ⁵ and R ⁶ each independently represent a hydrogen atom, an alkyl group, or an aryl group, and R ⁷ represents an alkyl group or an aryl group. m represents an integer of 1 or more. X represents a nitrogen atom or a sulfur atom, Y represents a carbon atom, Z represents a nitrogen atom when X represents a nitrogen atom, and represents a carbon atom when X represents a sulfur atom. The 5-membered ring containing X, Y, and Z may be condensed. A ⁻ represents a counter anion. In R ¹ to R ⁶ , when the alkyl moiety is substituted, the substituent is phenyl group, halogen atom, alkoxy group, aryloxy group, alkoxycarbonyl group, acyloxy group, acylamino group, carbamoyl group, cyano group, carvone Represents an acid group, a sulfonic acid group, or a heterocyclic group, and when the aryl moiety is substituted, the substituent is an alkyl group, a phenyl group, a halogen atom, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an acyloxy group, An acylamino group, a carbamoyl group, a cyano group, a carboxylic acid group, a sulfonic acid group, or a heterocyclic group is represented. In R ⁷ , when the alkyl moiety is substituted, the substituent represents a phenyl group, a halogen atom, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an acyloxy group, or a carboxylic acid group, and the aryl moiety is substituted. In this case, the substituent represents an alkyl group, a halogen atom, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an acyloxy group, or a carboxylic acid group. ] The azo compound and tautomer thereof according to claim 1, wherein, in the general formula (1), R ⁵ and R ⁶ are each independently an alkyl group or an aryl group. In the general formula (1), R ¹ is an alkoxy group, an aryloxy group, an alkylsulfonyl group, an arylsulfonyl group, an alkylthio group, or an arylthio group, and all of R ² , R ³ , and R ⁴ are hydrogen. The azo compound according to claim 1 or 2 which is an atom, and a tautomer thereof. In Formula (1), an azo compound according to any one of claims 1 to 3 R ¹ is an alkoxy group and tautomers thereof.   In the said General formula (1), m is an integer of 1-3, The azo compound of Claim 4, and its tautomer.   A dye composition comprising at least one selected from the azo compounds according to any one of claims 1 to 5 and tautomers thereof.