JPH0480033B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a coupler that is useful as a raw material for azo dyes, and more specifically, it not only improves the light resistance of the resulting dye itself, but also the light resistance of the material to be colored that is colored by the dye. This invention relates to a coupler that can provide improved azo dyes, especially azo pigments. (Prior Art) Various azo dyes have been known in the past. Among these azo dyes, for example, an azo pigment called a naphthol azo pigment uses a naphthol compound as a coupler. , by coupling it with a diazonium salt or tetrazonium salt of an aromatic primary monoamino or diamine. (Problems to be Solved by the Invention) As the coupling component of the naphthol azo dye, the amino group of β-naphthol, β-oxynaphthoic acid, and aniline or aniline derivative is acylated with β-oxynaphthoic acid. Coupler etc. obtained by this method are known, and the characteristics of azo dyes obtained using these couplers, such as hue, clarity, light resistance, weather resistance,
Solvent resistance etc. are often primarily determined by the structure of the coupler and the structure of the aromatic primary amine coupled to the coupler. Therefore, couplers and/or aromatic primary amines with various structures have been proposed in order to improve various physical properties of the resulting azo dye. Many naphthol-based azo dyes are known. Although these azo dyes are generally characterized by having rich hues and clear tones, none of them are particularly satisfactory in terms of light resistance. Therefore, for example, when these azo dyes are used as colorants for plastics, printing inks, paints, etc., sufficient consideration must be given to the light resistance of the azo dyes used. For example, if an azo dye with insufficient light resistance is used, it will not only cause discoloration or fading of the colored product, but also
A problem has arisen in that the light resistance of the material to be colored itself, such as a coating of plastic, ink, or paint, is also reduced. The above-mentioned problems of discoloration and deterioration of the colored material are
This problem can be solved by using other pigments with excellent light resistance, such as polycyclic pigments, but these pigments with good light resistance are expensive and cannot be used economically for general purposes. In addition, the hue, sharpness, etc. are limited, so it cannot be used satisfactorily. Therefore, when coloring paints, printing inks, plastics, etc. with azo dyes, light stabilizers such as ultraviolet absorbers and deterioration inhibitors are also used, but these light stabilizers Because it is a relatively unstable and low molecular weight organic compound, it is known to cause various problems in resins and binders, and its applications are extremely limited.
It lacked versatility. Therefore, there is a need for the development of a technology that can easily and inexpensively provide azo dyes with excellent light resistance. (Means for Solving the Problems) In response to the above-mentioned demands of the prior art, the inventors of the present invention have conducted extensive research in order to provide an inexpensive azo dye with excellent light resistance. It has been found that the object of the present invention can be achieved by employing a coupler having a specific structure. That is, the present invention is a coupler represented by the following general formula (). However, R ₁ and R ₂ in the above formula are a hydrogen atom, an alkyl group, or an aryl group, but are not hydrogen atoms at the same time. (Preferred Embodiment) Next, to explain the present invention in more detail, the coupler of the above general formula (), which mainly characterizes the present invention, is a conventionally known 5-
Aminobenzotriazole compounds (R ₁ and R ₂ in the formula are the same as defined above),
It can be obtained by acylation with 2-oxy-3-naphthoic acid or its derivatives in the same manner as the conventionally known method for producing naphthol couplers. The compound represented by the above general formula () is a conventionally known compound, and for example, preferred compounds include (a) 2-(3'-metal-2'-hydroxyphenyl)
-5-aminobenzotriazole, (b) 2-(3',5'-dimethyl-2'-hydroxyphenyl)-5-aminobenzotriazole, (c) 2-(3'-t-butyl-5'-Methyl-2'-hydroxyphenyl)-5-aminobenzotriazole, (d) 2-(3',5'-di-t-butyl-2'-hydroxyphenyl)-5-aminobenzotriazole, ( e) 2-(3',5'-di-t-aluminum-2'-hydroxyphenyl)-5-aminobenzotriazole, (f) 2-(3',5'-di-t-octyl-2 '-hydroxyphenyl)-5-aminobenzotriazole, (t)2-[3',5'-di-(α,α-dimethylbenzyl)-2'-hydroxyphenyl]-5-aminobenzotriazole, (H) 2-[3′-(α,α-dimethylbenzyl)-
5'-methyl-2'-hydroxyphenyl]-5-
Aminobenzotriazole, (li)2-[3'-(α,α-dimethylbenzyl)-
5'-butyl-2'-hydroxyphenyl]-5-
Aminobenzotriazole, (nu)2-[3'-(α,α-dimethylbenzyl)-
5'-t-octyl-2'-hydroxyphenyl]
-5-aminobenzotriazole, (ru)2-[3'-t-butyl-5'-(α,α-dimethylbenzyl)-2'-hydroxyphenyl]-5
-Aminobenzotriazole, (o)2-[3'-t-octyl-5'-(α,α-dimethylbenzyl)-2'-hydroxyphenyl]-5
-aminobenzotriazole, (w) 2-[3'-(αmethylbenzyl)-5'-t-octyl-2'-hydroxyphenyl]-5-aminobenzotriazole, (f) 2-[3'- Benzyl-5'-t-butyl-2'-
hydroxyphenyl]-5-aminobenzotriazole, (yo)2-[3'-N-phenylcarboxamide-5'-
t-butyl-2'-hydroxyphenyl]5-aminobenzotriazole, (ta)2-[3'-t-butyl-5'-methoxy-2'-
Examples include hydroxyphenyl]-5-aminobenzotriazole. Acylation of the 5-aminobenzotriazole compound of the general formula () with 2-hydroxy-3-naphthoic acid or a derivative thereof can be carried out, for example, in an inert organic solvent such as benzene, xylene, toluene, or other inert organic solvent. ) and 2-
Hydroxy-3-naphthoic acid or a derivative thereof is dissolved or dispersed and reacted at an appropriate temperature, for example, room temperature to about 150°C, in the presence of a condensing agent or catalyst as necessary for several minutes to several hours. The coupler of the present invention having the above general formula () can be easily obtained by the following method, and the manufacturing method itself may be based on any conventionally known method. Examples of preferred couplers of general formula () in the present invention are as follows. (1) 2-(3'-methyl-2'-hydroxyphenyl)
-5-(2″-hydroxy-3″-naphthoyl)aminobenzotriazole, (2) 2-(3′,5′-dimethyl-2′-hydroxyphenyl)-5-(2″-hydroxy-3″ -niphthoyl)aminobenzotriazole, (3) 2-(3'-t-butyl-5'-methyl-2'-hydroxyphenyl)-5-(2''-hydroxy-3''-
naphthoyl)aminobenzotriazole, (4) 2-(3′,5′-di-t-butyl-2′-hydroxyphenyl)-5-(2″-hydroxy-3″-naphthoyl)aminobenzotriazole, ( 5) 2-(3′,5′-di-t-amyl-2′-hydroxyphenyl)-5-(2″-hydroxy-3″-naphthoyl)aminobenzotriazole, (6) 2-(3′ ,5′-di-t-octyl-2′-hydroxyphenyl)-5-(2″-hydroxy-3″-naphthoyl)aminobenzotriazole, (7) 2-[3′,5′-di-( α,α-dimethylbenzyl)-2′-hydroxyphenyl]-5-(2″-hydroxy-3″-naphthoyl)aminobenzotriazole, (8) 2-[3′-(α,α-dimethylbenzyl) −
5′-methyl-2′-hydroxyphenyl]-5
(2″-hydroxy-3″-naphthoyl)aminobenzotriazole, (9) 2-[3′-(α,α-dimethylbenzol)-
5'-t-butyl-2'-hydroxyphenyl]-
5-(2″-hydroxy-3″-naphthoyl)aminobenzotriazole, (10) 2-[3′-(α,α-dimethylbenzyl)-
5'-t-octyl-2'-hydroxyphenyl]
-5-(2″-hydroxy-3″-naphthoyl)aminobenzotriazole, (11) 2-[3′-t-butyl-5′(α,α-dimethylbenzyl)-2′-hydroxyphenyl]- 5-
(2″-hydroxy-3″naphthoyl)aminobenzotriazole, (12) 2-[3′-t-octyl-5′-(α,α-dimethylbenzyl)-2′-hydroxyphenyl]-
5-(2″-hydroxy-3″-naphthoyl)aminobenzotriazole, (13) 2-[3′-(α-methylbenzyl)-5′-t-
octyl-2'-hydroxyphenyl]-5-
(2″-hydroxy-3″-naphthoyl)aminobenzotriazole, (14) 2-(3′-benzyl-5′-t-butyl-2′-
hydroxyphenyl)-5-(2″-hydroxy-
3″-naphthoyl)aminobenzotriazole, (15) 2-(3′-N-phenylcarboxamide-5′-
t-Butyl-2'-hydroxyphenyl)-5-
(2″-hydroxy-3″-naphthoyl)aminobenzotriazole, (16) 2-3′-t-butyl-5′-methoxy-2′-hydroxyphenyl)-5-(2″-hydroxy-
3″-naphthoyl)aminobenzotriazole, etc. (Function/Effect) The coupler of the present invention obtained as described above is useful as a coupler for an azo pigment or azo dye, and the coupler can be used as a coupler for a conventionally known azo pigment. By diazotizing or tetrazoting and coupling aromatic primary amines such as those used in the production of aromatic and azo dyes, azo pigments or azo dyes with excellent light resistance can be easily provided. If an aromatic monoamine is used as the group primary amine, a monoazo pigment or a monoazo dye can be obtained, and by using an aromatic diamine as the aromatic primary amine, a disazo pigment or a disazo pigment can be easily provided. The pigment or dye obtained using the coupler of the present invention is itself useful as a pigment or dye with excellent light resistance.One preferable method for using the coupler of the present invention is to use a conventionally known azo dye. This is a method in which an azo pigment containing the coupler of the present invention is prepared in the same manner as the pigment manufacturing method, and this azo pigment is mixed with a conventionally known azo pigment. According to this method, 100 parts by weight of a conventionally known azo pigment is mixed. By adding and mixing at a ratio of about 0.5 to 300 parts by weight, the light resistance of the resulting azo pigment composition and the light resistance of the colored material containing the azo pigment are significantly improved. A preferred method of use is to add and mix the coupler of the present invention into a conventionally known coupler to be used in a proportion accounting for 0.5 to about 50 mol% of the entire coupler to form a mixed coupler. The following is a method of carrying out a coupling reaction according to a conventional method to obtain a pigment composition of an azo pigment containing the coupler of the present invention and an azo pigment not containing the coupler of the present invention. Since the azo pigment contained in the pigment composition is more uniformly distributed in the pigment composition, the effect of improving the light resistance of the azo pigment is even more preferably exhibited. Explain specifically.In addition, in the text, parts or %
Unless otherwise specified, data are based on weight. Example 1 20.6 parts of β-oxynaphthoic acid are dispersed in 300 parts of O-dichlorobenzene and salified using soda carbonate in a conventional manner. After sufficiently removing water, 7.6 parts of phosphorus trichloride is added to convert the mixture into acid chloride. After removing the generated hydrogen chloride gas, 450
2-[3′,
A slurry of 46.2 parts of 5'-di(α,α-dimethylbentyl)-2'-hydroxyphenyl]-5-aminobenzotriazole (the above exemplified compound) was heated at 80°C.
Add with The temperature is then raised to 130°C and condensation is carried out for 15 hours. After cooling to 90°C and neutralizing with an aqueous solution containing 7 parts of sodium carbonate, the solvent is removed by steam distillation, followed by filtration and washing at 80°C. The obtained product is dissolved in 1000 parts of methanol containing 6.5 parts of caustic soda, impurities are removed using activated carbon, and the purified product is slowly precipitated using 10 parts of glacial acetic acid. Kuplar (Kuplar 7) of the present invention, which is a green-yellow powder with a melting point of 271-273°C 48.6
I got the department. Example 2 In place of the 5-aminobenztriazole compound (g) in Example 1, the above-mentioned exemplified compounds A to F and C to A were used, and the other exemplary couplers were obtained in the same manner as in Example 1. . The properties and melting point were as follows. Katsupular (1) Green-yellow powder, melting point 153-155℃ Katsupular (2) Green-yellow powder, melting point 160-162℃ Katsupular (3) Green-yellow powder, melting point 178-180℃ Katsupular (4) Green-yellow powder, melting point 185-187°C Katsupular (5) Green-yellow powder Melting point 190-192℃ Katsupular (6) Green-yellow powder Melting point 195-197℃ Katsupular (8) Green-yellow powder Melting point 253-255°C Katsupular (9) Green-yellow powder Melting point 261-263°C Katsupular (10) Green-yellow powder Melting point 264-266°C Katsupular (11) Green-yellow powder Melting point 262-264℃ Katsupular (12) Green-yellow powder Melting point 267-269℃ Katsupular (13) Green-yellow powder Melting point 249-251°C Katsupular (14) Green-yellow powder Melting point 243-245°C Katsupular (15) Green-yellow powder Melting point 198-200℃ Katsupular (16) Green-yellow powder Melting point 173-175℃ Usage example 1 3.2 parts of Katsupular (7) of the present invention obtained in Example 1 and 34 parts of naphthol AS-ITR are mixed with 1000 parts of methanol containing 9.2 parts of caustic soda. dissolve. Separately, 25.8 parts of ITR base was diazotized in 500 parts of methanol,
At 0 to 5°C, the previously prepared submerging solution is added dropwise. After the addition was completed, stirring was continued for 1 hour at 0 to 5°C.
Crystallization was carried out for 1 hour by raising the temperature to the boiling point,
A bluish red azo pigment composition was obtained. Usage example 2 4.6 parts of 31.6 parts of coupler (7) obtained in Example 1
Dissolve in 800 parts of methanol containing 1 part of caustic soda. This prepared submerging solution was added dropwise to a methanol solution of diazonium salt obtained from 12.9 parts of ITR base at 0 to 5°C in the same manner as in Use Example 1 for coupling, and then aged to produce a deep bluish red color. I got the pigment. 10 parts of the obtained pigment and 90 parts of CIPR (Pigment Red)-5 were mixed to obtain an azo pigment composition. Comparative Example 1 10 parts each of CIPR-5 and the azo pigment compositions of Usage Examples 1 and 2 were mixed with 26.4 parts of alkyd resin varnish (NV60%), melamine resin varnish (N.
V.50%) 13.6 parts and xylene/n-butanol =
The mixture was placed in a mayonnaise bottle with 20 parts of thinner of 8/2 (weight ratio), glass beads were added, and the mixture was dispersed in a paint shaker for 60 minutes. After dispersion, the mixture was further diluted with 48.3 parts of the above-mentioned mixed varnish of alkyd and melamine [alkyd/melamine = 7/3 (solid content by weight)] to prepare a dark enamel. Further, the obtained dark-colored enamel was mixed with white enamel so that pig/TiO ₂ =1/20 to prepare a light-colored enamel. Each dark-colored and light-colored enamel created in this way was coated with thinner (xylene/n-butanol =
8/2 (weight ratio)) to the spraying viscosity,
It was applied onto a tin plate using an air spray gun and baked at 120°C for 30 minutes. Exposing the created painted plate outdoors (Iwata City, Shizuoka Prefecture, facing south, 60° angle)
The condition of each coating film was then measured. The results shown in Table 1 below were obtained.

[Table] Judgment is made by visually observing the state of deterioration such as gloss, darkening, chalking, cracking, and change in hue of the paint film. ○: Almost no deterioration, △: Some deterioration is observed, ×: Severe deterioration. It was done in three stages. Usage example 3 In place of the coupler (7) in Example 1, use a coupler
(2) 4.2 parts and 32 parts of naphthol AS-ITR are hot-dissolved in 1000 parts of an aqueous solution containing 9.2 parts of caustic soda, then cooled and used as a submerging solution. Separately, a diazonium salt obtained by diazotizing 25.8 parts of ITR base using hydrochloric acid and sodium nitrite in the usual manner was placed in a submerging solution at 20°C for 1 hour while adjusting the pH with calcium carbonate so that the pH did not go below 7. Drip into. After completion of the dropwise addition, stirring was continued for 1 hour at 20°C and 1 hour at 40°C to eliminate the diazonium salt. Next, an emulsion consisting of xylol-polyoxyethylene alkyl ether was added, the temperature was raised to 90°C, and crystallization was performed at 90°C for 1 hour to obtain a bluish-red azo pigment composition. Usage example 4 Katsupura (12) 6.3 parts, naphthol AS-
A bluish red azo pigment composition was obtained in the same manner as in Use Example 2 using 32 parts of ITR and 25.8 parts of ITR base. Comparative Example 2 10 parts each of the azo pigment compositions of CIPR-5, Usage Example 3 and Usage Example 4 were placed in a mayonnaise bottle along with 40 parts of air-dry alkyd resin varnish (NV50%) and 20 parts of turpentine, and glass beads were added. and dispersed in a paint shaker for 60 minutes. After dispersion, the mixture was further diluted with 160 parts of air-dry alkyd varnish to create a deep-colored enamel. Pig the resulting dark enamel:
A light-colored enamel was prepared by mixing TiO ₂ with white enamel at a ratio of 1:20. Each dark-colored enamel and light-colored enamel was diluted with a turpentine to a spraying viscosity and a dryer was added, and then applied onto a tin plate using an air spray gun, and the coating film was cured. The obtained coated plate was exposed outdoors (Iwata City, Shizuoka Prefecture, facing south, at a 60° angle), and the condition of the coating film was visually judged, and the results shown in Table 4 below were obtained. Judgments are made by measuring the state of deterioration such as gloss, darkening, yoking, and fading of the paint film, and are graded into three stages: ○: Almost no deterioration, △: Some deterioration is observed, ×: Severe deterioration. Ivy.

[Table] Usage example 5 1,4-di-(2'-hydroxynaphthalene-
43.4 parts of 3'-carbamoyl)-2-chlorobenzene and 12.5 parts of the coupler (12) used in Application Example 4 were added.
Dissolve in 2500 parts of methanol containing 18.4 parts of caustic soda and cool. Separately, 34 parts of Scarlet GG base was diazotized in 150 parts of concentrated sulfuric acid in a conventional manner and neutralized with a buffer to prepare a diazonium salt solution. This diazonium salt solution was placed in a submerging solution cooled to below 0°C.
The mixture was added dropwise over 1 hour, and further stirred at 0 to 5°C for 1 hour to eliminate the diazonium salt. This slurry was heated to the boiling point and aged for 1 hour at the boiling point to obtain a dull bluish red crude pigment. The obtained aqueous press cake of the crude pigment was dispersed in 1700 parts of nitrobenzene and crystallized at 200°C for 2 hours to obtain a bluish-red azo pigment composition. Comparative Example 3 CIPR-144 and the azo pigment composition of Use Example 5 are each mixed with zinc stearate in a weight ratio of pig:Zn-St=6:4 to prepare a dark dry color.
Also, pig this dark dry color: TiO ₂ = 1:5
Mix it with white dry color to create light dry color. The obtained dark and light dry colors were mixed with polyethylene resin so that the dark color was 0.1 PHR and the light color was 0.5 PHR, formed into pellets using an extruder, and then plates were made using an injection molding machine. Put the resulting plate through a fade meter,
The ΔE value of each was measured and the results shown in Table 3 below were obtained.

[Table] Usage example 7 6.3 parts of the coupler (7) used in usage example 1 and 5-
(2′-hydroxynaphthalene-3′-carbamoyl)
Dissolve 28.7 parts of benzimidazolone in 1,000 ml of water containing 9.2 parts of caustic soda to prepare a submerging solution. Separately, 16.2 parts of Scarlet GG base was diazotized using hydrochloric acid and sodium nitrite in a conventional manner. The previously prepared subsoaking solution was added dropwise into the obtained diazonium salt solution over a period of 30 minutes without running out of ice, and the reaction was continued for another hour while correcting the pH with calcium carbonate. Complete. Thereafter, the temperature was raised to 80°C and immediately filtered to obtain a blackish brown crude pigment. The obtained crude pigment was dispersed in a 1% aqueous solution of caustic soda, and an emulsion of O-dichlorobenzene-polyoxyethylene sorbitanate was added to the mixture.
The temperature was raised to 85 to 90°C, and crystallization was performed at 85 to 90°C to obtain a dark brown azo pigment composition. Comparative Example 4 CIPBr (Pigment Brown)-25 and the azo pigment composition synthesized in Usage Example 6 were made into a paint using melamine-alkyd resin varnish according to the method of Comparative Example 1, and the coated plate obtained in the same manner was exposed outdoors. The condition of each coating film was measured. Judgment is based on the gloss of the paint film,
The state of deterioration, such as darkening, yoking, and fading of hue, was visually observed and ranked into three stages: ◯: almost no deterioration, △: some deterioration observed, ×: severe deterioration. The results shown in Table 4 below were obtained.

[Table] Usage example 6 ○ ○ ○ ○
CIPBr−25 ○ ○ ○ △
Usage Example 7 50 parts of CIPV (Pigment Violet)-19 was mixed with 50 parts of the azo pigment composition of Usage Example 1 to prepare a mixed pigment. Usage Example 8 50 parts of CIPR-170 and 50 parts of the azo pigment composition of Usage Example 1 were mixed to prepare a mixed pigment. Usage Example 9 A mixed pigment was prepared by mixing 50 parts of CIPR-170, 45 parts of CIPR-5, and 5 parts of the azo pigment composition of Usage Example 2. Usage Example 10 A mixed pigment was prepared by mixing 50 parts of CIPO (Pigment Orange)-36 and 50 parts of the azo pigment composition of Usage Example 1. Comparative Example 5 In order to compare the effects of the mixed pigments of Usage Examples 7 to 10, the existing azo pigments that do not contain the coupler component of the present invention and the corresponding existing pigments were mixed to create the mixed pigments shown in Table 5 below. did.

[Table] Melamine alkyd baking paints were prepared using the mixed pigments of Usage Examples 7 to 10 and Comparative Example 5 according to the method of Comparative Example 1, and the coated plates obtained in the same manner as above were exposed outdoors. The effects were compared by exposing the coatings and measuring deterioration such as gloss, darkening, yoking, and color change. Judgment was made visually, and was graded into three levels: ◯: almost no deterioration, △: some degree of deterioration observed, ×: severe deterioration. The results shown in Table 6 below were obtained.

[Table] Usage Example 11 Various pigment compositions were prepared in the same manner as Usage Example 1, except that the coupler shown in Table 7 below was used in place of the coupler (7) in Usage Example 1, and comparisons were made. Comparisons were made in the same manner as in Example 1, and the results shown in Table 7 below were obtained.

【table】 Note that the evaluation criteria are the same as in Comparative Example 1.

Claims (1)

[Scope of Claims] 1. A coupler represented by the following general formula (). (However, R ₁ and R ₂ in the above formula are hydrogen atoms, alkyl groups, or aryl groups, but are not hydrogen atoms at the same time.)