JP6763213B2 - New azo compound - Google Patents

Description

The present invention relates to novel azo compounds.

Patent Document 1 discloses an azo compound having a certain structure. However, Patent Document 1 does not disclose the azo compound of the present invention represented by the following formula (I).

Japanese Unexamined Patent Publication No. 2012-215865

Conventionally, azo compounds have been used in various applications such as coloring compositions for color filters, coloring compositions for inkjets, paints, printing inks, colored plastics, and toners. In order to cope with such a wide range of applications and new applications arising from technological progress, there is a demand for the creation of compounds having excellent chromatic characteristics such as high brightness and vivid hue. Further, depending on the application, it is required to have excellent solvent resistance, weather resistance, heat resistance and the like. However, the search for new compounds that solve these problems relies on trial and error.

As a result of diligent studies, the present inventors have found that the compound represented by the following formula (I) can solve the above-mentioned problems, and have completed the present invention. That is, the present invention has the formula (I) :.

（式中、Ｘ^１、Ｘ^２、Ｘ^３、Ｘ^４及びＸ^５はそれぞれ独立に−Ｈ、−Ｆ、−Ｃｌ、−Ｂｒ、−Ｉ、−ＯＨ、−ＣＯＲ^１、−ＮＲ^２ＣＯＲ^３、−ＳＯ_２Ｒ^４、−ＮＯ_２又は−ＯＣＨ_３であって；
Ｘ^１、Ｘ^２、Ｘ^３、Ｘ^４、Ｘ^５のうち少なくとも１つが−Ｆ、−Ｂｒ、−Ｉ、−ＯＨ、−ＣＯＲ^１、−ＮＲ^２ＣＯＲ^３又は−ＳＯ_２Ｒ^４であるという条件を満たし；
前記Ｒ^１はＣ_１〜Ｃ_８アルキル基、又は、置換基を有してもよいアリール基であり；
前記Ｒ^２は−Ｈ又はＣ_１〜Ｃ_８アルキル基であり；
前記Ｒ^３はＣ_１〜Ｃ_８アルキル基であり；
前記Ｒ^４はＣ_１〜Ｃ_８アルキル基、−Ｒ^５Ｃ_６Ｈ_５、−Ｎ（Ｒ^６）_２、−ＮＨＲ^７又は−ＯＲ^８であり；
前記Ｒ^５はＣ_１〜Ｃ_８アルキル基であり；
前記Ｒ^６はＣ_１〜Ｃ_８アルキル基であり；
前記Ｒ^７はＣ_２〜Ｃ_８アルキル基又は−Ｃ_６Ｈ_５であり；
前記Ｒ^８はＣ_１〜Ｃ_８アルキル基又は−Ｃ_６Ｈ_５である）で表される化合物（以下、「本発明化合物」と表記する場合がある）に関する。

(In the formula, X ¹ , X ² , X ³ , X ⁴ and X ⁵ are independently -H, -F, -Cl, -Br, -I, -OH, -COR ¹ , -NR ² COR ³ , -SO ₂ R ⁴ , -NO ₂ or -OCH ₃ ;
The condition that at least one of X ¹ , X ² , X ³ , X ⁴ , and X ⁵ is -F, -Br, -I, -OH, -COR ¹ , -NR ² COR ³ or -SO ₂ R ^4. The filling;
The R ¹ is a C _{1 to} C ₈ alkyl group or an aryl group which may have a substituent;
The R ² is a -H or C _{1 to} C ₈ alkyl group;
The R ³ is a C _{1 to} C ₈ alkyl group;
The R ⁴ is a C _{1 to} C ₈ alkyl group, -R ⁵ C ₆ H ₅ , -N (R ⁶ ) ₂ , -NHR ⁷ or -OR ⁸ ;
The R ⁵ is a C _{1 to} C ₈ alkyl group;
The R ⁶ is a C _{1 to} C ₈ alkyl group;
The R ⁷ is a C _{2 to} C ₈ alkyl group or -C ₆ H ₅ ;
Wherein ^{R 8} is _C 1 -C ₈ alkyl group or _-C 6 _{H 5} a is) a compound represented by (hereinafter, relates may be referred to as "the present compound").

The compound represented by the above formula (I) has excellent brightness. Therefore, it can be used as a colorant for a wide range of applications such as printing inks, paints, colored plastics, toners, inkjet inks, and color filters.

In the above formula (I), the alkyl of the "C _{1 to} C ₈ alkyl group" of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁸ may be linear or branched. Often, specific examples thereof include methyl, ethyl, normal propyl, isopropyl, normal butyl, isobutyl, secondary butyl, tertiary butyl, normal pentyl, isopentyl, neopentyl, tertiary pentyl, normal hexyl, isohexyl, normal heptyl, normal octyl Something like.
In the above formula (I), alkyl of "C ₂ -C ₈ alkyl group" of R ⁷ may be linear or branched, and specific examples thereof include ethyl, n-propyl, isopropyl, n-butyl, Examples include isobutyl, secondary butyl, tertiary butyl, normal pentyl, isopentyl, neopentyl, tertiary pentyl, normal hexyl, isohexyl, normal heptyl, normal octyl and the like.

In the above formula (I), the "aryl group" of the "aryl group which may have a substituent" is not particularly limited, but is a phenyl group, an o-biphenyl group, an m-biphenyl group, a p-biphenyl group, and naphthyl. Something like a group. The aryl group may have a substituent.
Examples of the "substituent" contained in the aryl group include halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl, cyano and nitro. Among these, C _{1 to} C ₆ alkyl and halogen are preferable. The number of substitutions of these "substituents" may be 1 or 2 or more, and when 2 or more, each substituent may be the same or different. Further, the substitution position of each substituent may be any position. Here, as the halogen as a substituent in this paragraph, each atom of fluorine, chlorine, bromine or iodine can be mentioned. The number of halogens as the substituent may be 1 or 2 or more, and when 2 or more, each halogen may be the same or different. Further, the halogen replacement position may be any position.

In the above formula (I), X ¹ , X ² , X ³ , X ⁴ and X ⁵ are independently -H, -F, -Cl, -Br, -I, -OH, -COR ¹ , -NR ^2. COR ³ , -SO ₂ R ⁴ , -NO ₂ or -OCH ₃ , but in addition, at least one of X ¹ , X ² , X ³ , X ⁴ , X ⁵ is -F, -Br, -I, It is important to satisfy the condition of -OH, -COR ¹ , -NR ² COR ³ or -SO ₂ R ⁴ (hereinafter, may be referred to as condition A). Specific groups of -F, -Br, -I, -OH, -COR ¹ , -NR ² COR ³ or -SO ₂ R ⁴ in any of X ¹ , X ² , X ³ , X ⁴ and X ^5. Contributes to the excellent brightness of the compound of the present invention.

All of the compounds of the present invention are excellent in that they have a vivid hue and lightness. Among these, if the characteristics are examined in more detail, in the above formula (I), preferably, an azo compound in which X ³ is -NR ² COR ³ is used. , X ¹ is -COR ¹ or X ⁴ is -SO ₂ R ⁴ azo compounds contribute to excellent saturation.
When a yellowish red color is sought, it is preferable that at least one of X ¹ , X ² , X ³ , X ⁴ , and X ⁵ is −F.
On the other hand, when a bluish red color is required, it is preferable that at least one of X ¹ , X ² , X ³ , X ⁴ , and X ⁵ is −OCH ₃ after satisfying the condition A.
The R ⁷ is a C _{2 to} C ₈ alkyl group or −C ₆ H ₅ , but from the viewpoint of compatibility, R ⁷ is more preferably − C ₆ H ₅ .

The compound represented by the above formula (I) may have a crystal structure of α, β, γ type or the like depending on the production method, but these are also included in the present invention and are the same regardless of the crystal type. The effect of is demonstrated.

Such a compound of the present invention is not particularly limited and can be produced by appropriately using a conventionally known method. Hereinafter, a preferred embodiment of the method for producing the compound of the present invention will be described. However, the present invention is not limited thereto.

(In the formula, X ¹ , X ² , X ³ , X ⁴ and X ⁵ are as described above.)
As described in the above reaction scheme, the base compound (i) can be a commercially available product, but it can also be appropriately synthesized by using a reaction that can be generally performed such as a nucleophilic substitution reaction and used. ..

The compound of the present invention can be produced by a coupling reaction between a diazonium compound obtained by diazotizing the base (i) (also referred to as a diazo component) and a coupler component in which the coupler (ii) is dissolved in a solvent.

<Preparation of diazo component>
The diazotization reaction can be carried out by reacting the base (i) with a nitrosonium ion source in an acidic solvent such as hydrochloric acid, sulfuric acid, phosphoric acid or acetic acid.
Specific examples of the nitrosonium ion source include nitrite esters, nitrites, nitrosylsulfuric acid and the like. Among them, sodium nitrite, potassium nitrite, isoamyl nitrite, nitrosylsulfuric acid and the like are preferable, and in particular, the diazo component can be stably and efficiently obtained by using sodium nitrite.
The nitrosonium ion source is preferably 1.0 to 1.3 equivalents relative to the base.
The acidic solvent is preferably 3.0 to 8.0 equivalents with respect to the base.
The reaction temperature can be carried out at −10 to 30 ° C., preferably −5 to 5 ° C.
The reaction time can be carried out by reacting for about 10 minutes to 6 hours.
Here, in order to remove the excess nitrosonium ion source remaining in the obtained solution containing the diazo component, an operation of adding an aqueous solution such as sulfamic acid may be performed. This makes it possible to suppress the formation of impurities due to an excessive amount of nitrosonium ion source.

<Preparation of coupler components>
The coupler (ii) is sodium = 2-N- (2,3-dihydro-2-oxo-1H-benzimidazol-5-yl) -carboxyamino-3-naphtholate dihydrate, which reacts as an aqueous solution. Use. This aqueous solution is preferably used as an alkaline aqueous solution.
Here, when it is dissolved in water, the water temperature is preferably 40 to 70 ° C. When dissolved in water, it is preferable to add an aqueous sodium hydroxide solution in order to maintain an appropriate reaction rate.
Moreover, you may use an organic solvent. The organic solvent that can be used may be any solvent as long as it is inert to the reaction, and examples thereof include alcohol solvents, ketone solvents, and polar aprotic solvents. As an example of the alcohol solvent, methanol, ethanol, isopropanol, ethylene glycol, diethylene glycol and the like are preferable. As an example of the ketone solvent, acetone, methyl ethyl ketone, cyclohexanone and the like are preferable. Examples of polar aprotic solvents include acetone and methyl ethyl ketone exemplified as ketone solvents, as well as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, and tetramethylurea. , Acetone and the like are preferable.

<Coupling reaction>
The coupling reaction can be carried out by reacting the diazo component obtained by the above method with the coupler component. Further, the compound of the present invention can be obtained by filtering, washing and drying the obtained reaction product by a usual method.

Both the diazo component and the coupler component may be an aqueous solution or an aqueous dispersion.

The azo compound in the present invention is a diazonium salt and a coupler component sodium = 2-N- (2,3-dihydro-2-oxo-1H-benzimidazol-5-yl) -carboxyamino-3-naphtholate dihydration. The product is subjected to a coupling reaction according to a known and commonly used coupling method. It is also possible to heat and age an aqueous slurry containing this and water at a predetermined temperature and a predetermined pH.

This coupling reaction is carried out with the diazonium salt aqueous solution and sodium = 2-N- (2,3-dihydro-2-oxo-1H-benzimidazol-5-yl) -carboxyamino-3-naphtholate dihydrate aqueous solution. It is also possible to carry out a coupling reaction by adding the other aqueous solution to one aqueous solution by the combination of. Then, it is also possible to obtain an azo compound by simultaneously dropping both of these aqueous solutions into water and causing a coupling reaction, and heat-ripen the aqueous slurry containing this and water at a predetermined temperature and a predetermined pH. Specifically, in this coupling reaction, the aqueous solution of the diazonium component and the aqueous solution of the coupler component are simultaneously added dropwise to water. The temperature and pH of water at this time are not particularly limited, but are preferably in the range of 0 to 30 ° C. and pH 4 to 9.

The dropping time of the aqueous solution of the diazonium salt and the aqueous solution of the coupler component into water is not particularly limited, but it is preferably adjusted so that the solution is completed in 15 minutes to 12 hours, particularly 30 minutes to 7 hours.

In the present invention, mol% of sodium = 2-N- (2,3-dihydro-2-oxo-1H-benzimidazol-5-yl) -carboxyamino-3-naphtholate dihydrate per 1 mol of diazonium salt. Is not particularly limited. These theoretical molar ratios are 1: 1 and preferably sodium = 2-N- (2,3-dihydro-2-oxo-1H-benzimidazol-5-yl) -carboxy per mole of the diazonium salt. The number of moles of amino-3-naphtholate dihydrate is preferably 0.995 to 1.150.

It is also possible to have a pH buffer for keeping the pH constant in the water in which the diazonium salt aqueous solution and the coupler component aqueous solution are dropped at the same time. The pH buffer used here can be appropriately selected depending on the pH at the time of the coupling reaction, and the type thereof is not particularly limited, but for example, acetic acid-sodium acetate, citric acid-disodium hydrogen phosphate, etc. are used as the buffer. Can be used.

It is preferable that a surfactant is present in the water in which the aqueous solution of the diazonium salt and the aqueous solution of the coupler component are dropped at the same time. By doing so, a coupling product containing a surfactant can be obtained. When a surfactant is used, it becomes easier to control the crystal type and particle shape of the azo compound.

In addition, various polar surfactants can be used. Specifically, anionic surfactants (synonymous with anionic surfactants), cationic surfactants (synonymous with cationic surfactants), and nonionic surfactants (synonymous with nonionic surfactants). ), Amphoteric surfactants, silicone surfactants, fluorosurfactants and the like.

Examples of anionic surfactants include carboxylates, sulfonates, sulfates and phosphates, and cationic surfactants include, for example, fatty acid amine salts, aliphatic quaternary ammonium salts and aromatic quaternary surfactants. A quaternary ammonium salt, a heterocyclic quaternary ammonium salt and the like are used as nonionic surfactants, for example, ether type, ether ester type, ester type, nitrogen-containing type and the like, and as an amphoteric surfactant, for example, carboxybetaine, etc. Examples thereof include sulfobetaines, aminocarboxylates, and imidazoline derivatives.

Among the surfactants, nonionic surfactants or cationic surfactants are preferable. Among them, a nonionic surfactant containing a polyoxyethylene chain or a cationic surfactant having one or more hydrocarbon chains having 12 to 18 carbon atoms (hereinafter, referred to as long-chain alkyl for convenience) shows a remarkable effect. Is particularly preferable.

Examples of such nonionic surfactants include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene-polyoxypropylene condensate, and polyoxyethylene sorbitan oleyl ester. On the other hand, examples of such a cationic surfactant include long-chain alkyltrimethylammonium chloride and di-long-chain alkyldimethylammonium chloride.

In the synthesis of the azo compound of the present invention, the amount of the surfactant used is preferably 0.1 to 50% equivalent with respect to the monoazo pigment or its theoretical yield in terms of mass, particularly preferably 1 to 30%. The amount equivalent to 10% is most preferable.

In the azo compound of the present invention, additives such as a surface treatment agent and an aromatic carboxylic acid can be further used in combination. As the surface treatment agent, for example, various rosins and polymer dispersants can be used. When a surface treatment agent is used, it is effective in improving transparency and preventing pigment aggregation.

As the aromatic carboxylic acid at this time, for example, aromatic polybasic acids such as trimellitic anhydride, trimellitic acid, pyromellitic anhydride and pyromellitic acid or derivatives thereof can be used. When a small amount of aromatic carboxylic acid is used in combination, the effect of improving the soaring property of the gravure printing ink is further imparted to the obtained pigment. For example, a surfactant and a surface treatment agent, a surfactant and an aromatic carboxylic acid, and a surface treatment agent and an aromatic carboxylic acid can be used in combination. All of these various additives can be used in combination with a monoazo pigment or an amount equivalent to 0.1 to 50% of the theoretical yield in terms of mass.

In a general method for producing an azo compound, the reaction solution subjected to the coupling reaction (hereinafter referred to as the coupling reaction solution) is subjected to a conventional heat treatment for pigmentation. Conventional heat treatment involves filtering the coupling reaction solution to remove the liquid medium, and then redispersing the product in a large excess liquid medium having the same or different composition as the liquid medium at 70 to 150 ° C. Means heating in 1 to 10 hours. Examples of the liquid medium at this time include water, methanol, dimethylformamide and the like.

In the method for producing an azo compound of the present invention, the crystal type and / or average aspect ratio is controlled by pigmenting the coupling product in an aqueous medium, instead of performing the conventional heat treatment. It can also be pigmented as an azo compound of a quality that can withstand use as a colorant. Specifically, this pigmentation is carried out by heating and aging an aqueous slurry containing a coupling product and water in a specific temperature range and a specific pH range. A coupling reaction solution containing an aqueous medium corresponds to an aqueous slurry containing the coupling product and water.

Here, the aqueous medium means a medium containing only water or a mixture of water and an organic solvent and containing 60% or more of water in terms of mass. The smaller the amount of organic solvent in the aqueous medium, the better, in that the environmental load and safety measures become lighter or unnecessary. Therefore, it is preferable to use water containing no organic solvent as the aqueous medium. That is, it is most preferable that the liquid medium in the aqueous slurry is only water. Here, in order to adjust the pH of the aqueous slurry for heat aging at 100 to 150 ° C. to a pH exceeding 12.0, a necessary amount of a basic substance is added to the aqueous slurry as necessary. The amount of the basic substance added may be appropriately adjusted while checking the pH of the aqueous slurry with a pH meter, test paper, or the like. The type of this basic substance is not particularly limited, but a water-soluble metal hydroxide, preferably sodium hydroxide, potassium hydroxide, or the like can be used. If the aqueous slurry has a pH exceeding 12.0, the coupling reaction solution is once filtered to be aqueous even if the coupling reaction solution is treated as an aqueous slurry without filtering and treated in the temperature range and the suitable time range. Even if the aqueous slurry obtained by redispersing in the medium is treated in the temperature range and the suitable time range, the same effect can be obtained in any case.

In addition, the coupling reaction can be carried out in the presence of a solvent, if necessary. The solvent may be any solvent inert to the reaction, for example, ketones such as acetone, ethyl methyl ketone and diethyl ketone; halogenated hydrocarbons such as methylene chloride, chloroform, dichloroethane and trichloroethane. Classes; aromatic hydrocarbons such as benzene, toluene, xylene, nitrobenzene; esters such as methyl acetate, ethyl acetate, propyl acetate; acetonitrile, N, N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), Aprotonic polar solvents such as dimethylacetamide (DMA), hexamethylphosphate triamide (HMPA), sulfolane; ethers such as diethyl ether, dioxane, tetrahydrofuran (THF), dimethoxyethane and the like. As the solvent, one or more of these can be appropriately selected.

The above reaction can be carried out in the presence of an acid, if necessary, and one or more of these may be appropriately selected and mixed at 0.01 to 100 equivalents with respect to the base (i). can do.

The compound of the present invention is considered to be applicable to various uses. For example, it can be used as a colorant for a wide range of applications such as printing inks, paints, colored plastics, toners, inkjet inks, color filters, and seed coloring.

The compounds of the present invention may be used alone or in combination of two or more in accordance with these wide-ranging uses.

The compound of the present invention exhibits properties as an organic pigment, and may be more preferably used by making the pigment particles finer by a salt milling treatment or the like. Such processing may be performed by a known and commonly used method.

The compound of the present invention may be used in combination with a coloring material such as an organic pigment, an organic dye, or an organic pigment derivative other than the compound of the present invention for the purpose of toning or the like. For example, C.I. I. Anthraquinone-based red pigments such as Pigment Red 177, C.I. I. Pigment Violet 19, C.I. I. Pigment Red 122, C.I. I. Pigment Red 202, C.I. I. A quinacridone-based red pigment such as Pigment Red 209, C.I. I. Examples thereof include xanthene-based red dyes such as Acid Red 289 and cyanine-based red dyes. Further, if necessary, a yellow organic pigment or a yellow organic pigment derivative may be used in combination for the purpose of toning or the like. For example, C.I. I. Isoindoline-based yellow pigments such as Pigment Yellow 139, C.I. I. Pigment Yellow 151, 154, Benzmidazolone-based yellow pigments, C.I. I. Examples thereof include nickel-azo yellow pigments such as Pigment Yellow 150.

As the pigment derivative, an organic pigment, a β-naphthol compound, an acridone compound or a triazine compound described in JP2012-215865 has a basic substituent, an acidic substituent or a substituent. Examples thereof include compounds having a good phthalimide methyl group introduced therein. In addition, C.I. I. Pigment Red 2 Sulfonized, C.I. I. Examples thereof include a sulfonate of Pigment Red 208 and a sulfonate of Pigment Red 242.

Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. Unless otherwise specified in Examples and Comparative Examples, "parts" and "%" are based on mass. The following Examples 1, 9 and 10 are outside the scope of the present invention, but are described for reference only. The measurement method used in this example is shown below.
<Molecular weight measurement>
A solution was prepared by dispersing about 5 mg of a sample in 1 ml of THF, and the solution was prepared using GC / TOFMS JMS-T100GC, manufactured by JEOL Ltd.

[Synthesis Example 1]
While stirring 13.7 parts of 3-amino-N, N-diethyl-4-methoxybenzenesulfonamide in 120.0 parts of water, add 22.1 parts of 35% hydrochloric acid and 120.0 parts of ice. The temperature was adjusted to -2 to 5 ° C., and 9.6 parts of a 40% aqueous sodium nitrite solution was added to carry out a diazotization reaction. After stirring for 1 hour, 2.6 parts of a 10% sulfamic acid aqueous solution was added to remove excess nitrite, 1.2 parts of activated carbon was further added, and the mixture was stirred for 10 minutes to prepare a diazonium salt solution.
On the other hand, 38.9 parts of a 25% sodium hydroxide aqueous solution was added to 250.0 parts of hot water at 60 ° C., and after stirring, sodium = 2-N- (2,3-dihydro-2-oxo-1H-benzimidazole-5). -Il) -carboxyamino-3-naphtholate dihydrate 22.4 parts was added and dissolved to obtain a coupler component. The diazo component and the coupler component were prepared by adding water and ice to adjust the liquid temperature and volume to 0 to 5 ° C., 500 parts and 15 ° C., 630 parts, respectively.
The diazonium solution was added to the coupler component at a constant rate for 30 minutes, and the mixture was stirred for 30 minutes after the addition was completed. Then, a 15% hydrochloric acid solution was added to adjust the pH to 7.0, the temperature was raised to 50 ° C. to confirm that the pH was 7.0, the temperature was raised to 85 ° C, and the mixture was stirred at 85 ° C for 2 hours. Then, it was filtered and washed with water, dried at 90 ° C. for 17 hours, and then pulverized to obtain 30.7 parts of the target product (Compound a).
・ M / z = 588

[Synthesis Example 2]
In Example 1, 13.7 parts of 3-amino-N, N-diethyl-4-methoxybenzenesulfonamide was changed to 8.0 parts of p-aminoacetanilide, and the same procedure as in Example 1 was carried out. 24.8 parts of (Compound b) was obtained.
・ M / z = 480

[Synthesis Example 3]
Except for changing 13.7 parts of 3-amino-N, N-diethyl-4-methoxybenzenesulfonamide to 10.2 parts of 4-amino- (N-methyl-N-acetyl) -aniline in Example 1. Was carried out in the same manner as in Example 1 to obtain 25.0 parts of the target product (compound c).
・ M / z = 494

[Synthesis Example 4] In Example 1, 13.7 parts of 3-amino-N, N-diethyl-4-methoxybenzenesulfonamide was changed to 14.8 parts of 2-methoxy-5-phenylmethylsulfonyl-aniline. Except for the above, the same procedure as in Example 1 was carried out to obtain 30.0 parts of the target product (compound d).
・ M / z = 607

[Synthesis Example 5]
In Example 1, 13.7 parts of 3-amino-N, N-diethyl-4-methoxybenzenesulfonamide was changed to 11.7 parts of 2-amino-5-nitrophenylmethyl sulfone, but the same as in Example 1. The same procedure was carried out to obtain 28.2 parts of the target product (compound e).
・ M / z = 546

[Synthesis Example 6]
In Example 1, 13.7 parts of 3-amino-N, N-diethyl-4-methoxybenzenesulfonamide was changed to 16.4 parts of 4-amino-3-fluorophenol in the same manner as in Example 1. This was carried out to obtain 23.6 parts of the target product (compound f).
・ M / z = 457

[Synthesis Example 7]
Example 1 except that 13.7 parts of 3-amino-N, N-diethyl-4-methoxybenzenesulfonamide was changed to 11.5 parts of 2-amino-4'-fluorobenzophenone methanesulfonate in Example 1. In the same manner as above, 19.6 parts of the target product (compound g) was obtained.
・ M / z = 545

[Synthesis Example 8]
In Example 1, 13.7 parts of 3-amino-N, N-diethyl-4-methoxybenzenesulfonamide was changed to 13.5 parts of phenyl 2-aminobenzenesulfonate, and the same procedure as in Example 1 was carried out. , 27.8 parts of the target product (compound h) was obtained.
・ M / z = 579

[Synthesis Example 9]
Except that in Example 1, 13.7 parts of 3-amino-N, N-diethyl-4-methoxybenzenesulfonamide was changed to 16.7 parts of 4-amino-2,5-dimethoxy-N-phenylsulfonamide. Was carried out in the same manner as in Example 1 to obtain 32.6 parts of the target product (Compound i).
・ M / z = 638

[Synthesis Example 10]
In Example 1, 13.7 parts of 3-amino-N, N-diethyl-4-methoxybenzenesulfonamide was added to 12.5 parts of 3-amino-4-methoxy-N, N-dimethyl-benzenesulfonamide. The same procedure as in Example 1 was carried out except for the change, and 28.4 parts of the target product (compound j) was obtained.
・ M / z = 560

[Synthesis Example 11]
In Example 1, 13.7 parts of 3-amino-N, N-diethyl-4-methoxybenzenesulfonamide was changed to 11.7 parts of 4-amino-3-hydroxy-N, N-dimethylbenzenesulfonamide. The same procedure as in Example 1 was carried out except that 19.9 parts of the target product (compound k) was obtained.
・ M / z = 546

[Example 1]
<Baking paint exhibition color test>
4 parts by mass of the compound (Compound a) obtained in Synthesis Example 1, 70% of an alkyd resin for baking paint (“Beckol J-524-IM-60” manufactured by DIC Corporation), and a melamine resin (“Super” manufactured by DIC Corporation). 10 parts by mass of the mixed resin with 30% of Beccamin G-821-60 "), 7 parts by mass of xylene and 3 parts by mass of n-butanol were dispersed in a paint conditioner for 2 hours using glass beads as a medium. Then, 50 parts by mass of the mixed resin was added, and the mixture was further mixed with a paint conditioner for 5 minutes. The obtained red paint composition was applied to a polyester film using an applicator and baked at 130 ° C. for 30 minutes. The obtained coating film was a glossy red color.

[Examples 2 to 11]
Example 1 above, except that the compound (Compound b) obtained in Synthesis Example 2 to the compound (Compound k) obtained in Synthesis Example 11 are used instead of the compound (Compound a) obtained in Synthesis Example 1. The same operation as in the above was carried out to obtain a red coating film.

[Comparative Example 1]
Instead of the compound of Synthesis Example 1 (Compound a), C.I. I. The same operation as in Example 1 was carried out except that an azo compound (SYMULER Fast Red 4586 manufactured by DIC Corporation), which is Pigment Red 185, was used to obtain a red coating film.

The ultraviolet-visible spectroscopic spectrum of the coating film obtained above was measured using a spectrophotometer (U-3900 manufactured by Hitachi High-Tech Science Co., Ltd.), and the chromaticity in the C light source 2 degree field was calculated from the results. The results of the chromaticity of the coating film are shown in Table 1.

<Explanation of the table>
In the table, "L *" indicates the brightness, and the larger the value, the better. “A *” and “b *” indicate chromaticity indicating hue and saturation. The larger the value of “a *” in the + (plus) direction, the more reddish, and the larger the value in the- (minus) direction, the greener. The larger the value of "b *" in the + (plus) direction, the more yellowish the taste, and the larger the value in the- (minus) direction, the more bluish. “C * ab” indicates saturation, and the larger the value, the better. “H” indicates a hue angle. In red, a large value is yellowish when the value is 0 to 90, and 340 to 360 is bluish when the value is small.

As is clear from these results, C.I. used as a comparison. I. Compared with the azo compound "R185" which is Pigment Red 185, all the azo compounds of the present invention had excellent L * (brightness).
In particular, in formula (I), at least one of X ¹ , X ² , X ³ , X ⁴ , and X ⁵ is -SO ₂ R ⁴ (R ⁴ is a C _{1 to} C ₈ alkyl group, -R ⁵ C ₆ H. ₅ , -OR ⁸ ; said R ⁵ is a C _{1 to} C ₈ alkyl group, and said R ⁸ is a C _{1 to} C ₈ alkyl group or -C ₆ H ₅ ), which makes it brighter and brighter. It can be said that it is a useful compound in applications that require a high compound. Further, the azo compounds of Examples 3, 4 and 7 had excellent C * ab (saturation) in addition to the above-mentioned excellent brightness. As the hue (h) suitable for the color filter, the value of h is preferably 1 to 100, preferably 10 to 60.

Claims (3)

Equation (I):

(I)
(In the formula, X ¹ , X ² , X ³ , X ⁴ and X ⁵ are independently -H, -F , -OH, -COR ¹ , -NR ² COR ³ , -SO ₂ R ⁴ , -NO ₂ Or -OCH ₃ ;
The condition that at least one of X ¹ , X ² , X ³ , X ⁴ , and X ⁵ is -OH, -COR ¹ , -NR ² COR ³ or -SO ₂ R ⁴ is satisfied;
The R ¹ is a C _{1 to} C ₈ alkyl group or an aryl group which may have a substituent;
The R ² is a -H or C _{1 to} C ₈ alkyl group;
The R ³ is a C _{1 to} C ₈ alkyl group;
Wherein ^{R 4} is _C 1 -C ₈ alkyl ^group, -R ₅ C 6 _{H ^5,} or be a -OR ^8;
The R ⁵ is a C _{1 to} C ₈ alkyl group;
R ⁸ is a compound represented by a C _{1 to} C ₈ alkyl group or -C ₆ H ₅ ). A colorant containing the compound according to claim 1. A colorant composition containing at least the colorant according to claim 2.