JPH0480032B2 - - 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, azo pigments called anilide azo pigments combine acetoacetanilide compounds. It is obtained by coupling it with a diazonium salt or tetrazonium salt of an aromatic primary monoamine or diamine. (Problems to be Solved by the Invention) The coupling component of the anilide azo dye is obtained by acetoacetylating the amino group of aniline or an aniline derivative,
The properties of azo dyes obtained using these couplers, such as hue, sharpness, light resistance, weather resistance, and solvent resistance, depend on the structure of the coupler and the aromatic primary amine to which the coupler is coupled. In many cases, it is primarily determined by structure. 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 azo dyes are known. Although these azo dyes generally have rich hues and are characterized by clear tones,
In particular, there are no satisfactory results regarding 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 coloring material 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 multi-dry pigments, but these pigments with good light resistance are expensive and cannot be used economically for general purposes. In addition, since the hue, sharpness, etc. are limited, it cannot be fully supported. Therefore, when coloring paints, printing inks, plastics, etc. with azo chromaticity, 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 demands of the prior art as described above, the present inventor has 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 diketene or acetoacetate, etc., in the same manner as in the production method of conventionally known anilide couplers. The compound represented by the above general formula () is a conventionally known compound, and for example, preferred compounds include (a) 2-(3'-methyl-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-amyl-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′-
t-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'-
Examples include hydroxyphenyl)-5-aminobenzotriazole. Acetoacetylation of the 5-aminobenzotriazole compound of the above general formula () with diketene or acetoacetate, for example, can be carried out by adding the compound of the above general formula () in an inert organic solvent such as benzene, xylene, toluene, etc. This can be easily carried out by dissolving or dispersing the diketene or acetoacetate at an appropriate temperature, for example, room temperature to about 150°C, for several minutes to several hours. The coupler of the invention is obtained, 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-acetoacetylaminobenzotriazole, (2) 2-(3',5'-dimethyl-2'-hydroxyphenyl)-5-acetoacetylaminobenzotriazole, (3) 2-(3'-t- Butyl-5'-methyl-2'-hydroxyphenyl)-5-acetoacetylaminobenzotriazole, (4) 2-(3',5'-di-t-butyl-2'-hydroxyphenyl)-5 -acetoacetylaminobenzotriazole, (5) 2-(3',5'-di-t-amyl-2'-hydroxyphenyl)-5-acetoacetylaminobenzotriazole, (6) 2-(3', 5′-di-t-octyl-2′-hydroxyphenyl)-5-acetoacetylaminobenzotriazole, (7) 2-[3′,5′-di-(α,α-dimethylbenzyl)-2′ -hydroxyphenyl)-5-acetoacetylaminobenzotriazole, (8) 2-[3'(α,α-dimethylbenzyl)-5′-
Methyl-2'-hydroxyphenyl)-5-acetoacetylaminobenzotriazole, (9) 2-[3'(α,α-dimethylbenzyl)-5′-
t-Butyl-2'-hydroxyphenyl)-5-
Acetoacetylaminobenzotriazole, (10) 2-[3′(α,α-dimethylbenzyl)-5′-
t-octyl-2'-hydroxyphenyl)-5
-acetoacetylaminobenzotriazole, (11) 2-[3'-t-butyl-5'-(α,α-dimethylbenzyl)-2'-hydroxyphenyl)-5
-acetoacetylaminobenzotriazole, (12) 2-[3'-t-octyl-5'-(α,α-dimethylbenzyl)-2'-hydroxyphenyl)-
5-acetoacetylaminobenzotriazole, (13) 2-[3'-(methylbenzyl)-5'-t-octyl-2'-hydroxyphenyl)-5-acetoacetylaminobenzotriazole, (14) 2- [3'-benzyl-5'-t-butyl-2'-
hydroxyphenyl)-5-acetoacetylaminobenzotriazole, etc. (Function/Effect) The coupler of the present invention obtained as described above is useful as a coupler for azo pigments or azo dyes, and is used in the production of conventionally known azo pigments and azo dyes. By diazotizing or tetrazotizing and coupling such aromatic primary amines, azo pigments or azo dyes having excellent light resistance can be easily provided. For example, if an aromatic monoamine is used as an aromatic primary amine, a monoazo pigment or a monoazo dye cannot be obtained, but if an aromatic diamine is used as an aromatic primary amine, a disazo pigment or a disazo dye cannot be obtained. easily provided. The pigment or dye obtained using the coupler of the present invention is itself useful as a pigment or dye having excellent light resistance. Further, one preferable method for using the above coupler of the present invention is to prepare an azo pigment containing the coupler of the present invention in the same manner as a conventionally known method for producing an azo pigment, and then add this azo pigment to a conventionally known azo pigment. According to this method, by adding and mixing at a ratio of about 0.5 to 300 parts by weight per 100 parts by weight of a conventionally known azo pigment, the light resistance of the resulting azo pigment composition and the content of the azo pigment can be improved. The light resistance of the colored material is significantly improved. Another preferable usage method is to add and mix the coupler of the present invention in a conventionally known coupler to be used in a proportion accounting for 0.5 to about 50 mol% of the entire coupler when producing a conventionally known azo pigment. This is a method of preparing a mixed coupler, and then 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 containing the coupler of the invention is more uniformly distributed in the pigment composition, the light resistance improving effect of the azo pigment is more preferably exhibited. Next, the present invention will be explained in more detail by giving Examples, Usage Examples, Comparative Examples, etc. In addition, in the text, part or %
The following are important criteria unless otherwise specified. Example 1 2-[3',5'-di(α,α-dimethylbenzyl)
46.2 parts of -2'-hydroxyphenyl]-5-aminobenzotriazole (the above exemplified compound),
Dispersed in 670 parts of xylene, the temperature of the dispersion was adjusted to 50 to 55°C, and 10 parts of diketene was added to 30
The mixture was added dropwise over a period of minutes, and after further stirring for 60 minutes, the temperature was raised to 80° C., and the reaction was completed over a further 3 hours to obtain a white product with a slight yellowish brown color. This product was purified by recrystallization from a mixed solvent of ethanol and ethyl acetate (weight ratio 1:1), and the melting point was 285.
36.5 parts of the coupler of the present invention (Coupler 7), which is a white crystal with a temperature of ~287°C, was obtained. Example 2 In place of the 5-aminobenztriazole compound (g) in Example 1, the above exemplary compounds I to
The above-mentioned coupler was obtained in the same manner as in Example 1 except for using the following. The properties and melting point were as follows. Katsupular (1) White crystals Melting point 147-149℃ Katsupular (2) White crystals Melting point 159-161℃ Katsupular (3) White crystals Melting point 180-182℃ Katsupular (4) White crystals Melting point 195-197℃ Katsupular (5) White crystals Melting point 206-209℃ Katsupla (6) White crystal Melting point 211-213℃ Katsupla (8) White crystal Melting point 256-258℃ Katsupla (9) White crystal Melting point 265-267℃ Katsupla (10) White crystal Melting point 269-271℃ Katsupla (11) White crystals Melting point 262-264℃ Kuplar (12) White crystals Melting point 274-276℃ Kuplar (13) White crystals Melting point 250-252℃ Kuplar (14) White crystals Melting point 246-248℃ Usage example 1 In Example 1 5.5 parts of the obtained coupler (7) of the present invention and 45.5 parts of acetoaceto-2,5-dimethoxy-4-chloroanilide are dissolved in 1000 parts of water containing 18.4 parts of caustic soda. After adding 9.5 parts of sodium acetate, adjust the temperature to 20℃ and add 40% acetic acid aqueous solution.
70 parts of the solution was added dropwise over 30 minutes to precipitate both coupler components at the same time to form a subsoaking solution. Separately, 3,3'-dichlorbendine hydrochloride 25.7
A tetrazonium salt consisting of: Stirring was continued at 20°C for 60 minutes and then at 40°C for 60 minutes to complete the reaction. After the reaction was completed, an emulsion consisting of xylene-polyoxyethylene alkyl ether was added and pigmentation was performed at 90°C for 60 minutes to form a yellow azo pigment. A composition was obtained. Usage example 2 12.9 parts of 3,3'-dichlorbendine hydrochloride in 60
of glacial acetic acid, add 26.1 parts of concentrated hydrochloric acid with vigorous stirring, and continue stirring for an additional 60 minutes. 0
After cooling to .degree. C., 17.8 parts of a 40% aqueous nitrous acid solution was added to obtain a tetrazonium salt of 3,3'-dichlorobenzidine. Separately, 54.6 parts of the coupler (7) of Example 1 was dissolved in 800 parts of methanol containing 9.2 parts of caustic soda,
After adding 7.3 parts of sodium acetate, 15.3 parts of 90% acetic acid is added dropwise to prepare a subsoaking solution. After cooling this subsoaking liquid to 0℃ or less, 0 to 5℃
After 30 minutes, the tetrazonium salt of 3,3'-dichlorobendine prepared earlier was added dropwise. After the dropwise addition, the reaction is further carried out at 0 to 5°C for 1 hour to complete coupling, and then heated to raise the temperature to the boiling point. After aging at boiling point for 1 hour, filter, wash, dry,
Pulverization was performed to obtain a powder of a disazo pigment into which a substituted benzotriazole group was introduced. 7 parts of this disazo pigment into which a substituted benzotriazole group has been introduced;
CI Pigment Yellow (PY)-83 (93 parts) was uniformly mixed to obtain an azo pigment composition. Comparative Example 1 10 parts each of CIPY-83 and the azo pigment compositions of Usage Examples 1 and 2 were added to an alkyd resin varnish (N.
V.60%) 26.4 parts, melamine resin varnish (NV50
%) 13.6 parts and xylene/n-butanol = 8/
The mixture was placed in a mayonnaise bottle with 20 parts of thinner consisting of 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=(weight ratio solid content 7/3)] to prepare a deep-colored 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 thus created was treated with thinner (xylene/n-butanol = 8/
2) to a spraying viscosity, apply it on a tin plate using an air spray gun, and spray at 120°C x 30°C.
Bake for a minute. The prepared coated plates were subjected to a Sunshine Weather-Ometer to examine their weather resistance. The results are shown in Table 1 below.

[Table] Usage example 2 ○ ○ ○ △
○ ○ △ ×
CIPY−83 ○ ○ △ ×
○ △ × ×
The evaluation criteria in the table above are as follows: ◯ indicates no discoloration or fading, △ indicates discoloration or fading, and × indicates significant discoloration. In addition, coated plates prepared in the same manner were exposed outdoors (Iwata City, Shizuoka Prefecture, facing south, at a 60° angle), and the ΔE value and condition of the coating film were measured. The results shown in Table 2 below were obtained.

【table】

[Table] Usage example 2 ○ ○ ○ △
CIPY−83 ○ △ △ ×
Judgments were made by visually observing the state of deterioration such as gloss, darkening, yoking, and cracking, and were graded into three levels: ◯: almost no deterioration, △: deterioration observed, and ×: severe deterioration. Usage example 3 Instead of the coupler (7) in Example 1, use the coupler (2)
1.7 parts and acetoacetic acid-0-chloroanilide
12.1 parts are dissolved in 400 parts of water containing 6.5 parts of caustic soda. Next, 17.6 parts of sodium acetate was added and dissolved, the temperature was adjusted to 20°C, and 25 parts of a 40% acetic acid aqueous solution was added.
The solution was added dropwise over 30 minutes to prepare a dipping solution. Separately, a diazonium salt containing 17.3 parts of 2-nitro-4-chloroaniline was prepared in a conventional manner and added dropwise to the above-mentioned submerging solution over a period of 30 minutes. 60 at 20℃
After stirring was continued for 60 minutes at 40°C to complete the reaction, an emulsion consisting of xylene-polyoxyethylene alkyl ether was added, and stirring was continued for 60 minutes at 85°C.
Pigmentation was performed for a minute to obtain a greenish-yellow azo pigment composition. Comparative Example 2 10 parts each of the azo pigment compositions of CIPY-3 and Usage Example 3 were added to an air-dry alkyd resin varnish (NV50%).
Add 40 parts and 20 parts of turpentine to a mayonnaise jar, add glass beads and mix in a paint shaker.
Dispersed for 60 minutes. After dispersion, dry alkyd varnish
It was diluted with 160 parts to create a dark enamel. The obtained dark-colored enamel was diluted to a spraying viscosity using a turben, 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 were made by measuring the state of deterioration such as gloss, tarnishing, yoking, and fading of the paint film, and were made in three stages: ◯: almost no deterioration, △: deterioration observed, ×: severe deterioration.

[Table] Usage example 4 In place of coupler (7) in Example 1, 10.8 parts of coupler (12) and 27.4 parts of 1,4-di-acetoacetylamino-2,5-di-methylbenzene were added with 24 parts of caustic soda. Dissolved in 800 parts of methanol containing
Furthermore, after adding 44 parts of sodium acetate, 100 parts of methanol containing 38 parts of glacial acetic acid was added dropwise at 20°C to obtain a subsoaking solution. Separately, 3-amino-4 prepared by the usual sulfuric acid method
- A solution of diazonium salt containing 60 parts of chloro-2'-methyl-5'-chlorobenzanilide was added dropwise to the submerging liquid at below 0°C over 60 minutes, and then at below 0°C until no diazonium salt was observed. Continue stirring. Then, after filtering and washing the pigment obtained, the cake water paste is mixed with water containing 30 parts of caustic soda.
The mixture was peptized in 2,000 parts, and an emulsion of nitrobenzene-bolyoxyethylene sorbitanate was added thereto, followed by crystallization at 85 to 90°C for 4 hours to obtain a reddish-yellow azo pigment composition. Comparative Example 3 CIPY-95 and the azo pigment composition of Use Example 4 are each mixed with zinc stearate to create a dark dry color. Further, each pigment is mixed with rutile type titanium oxide in a ratio of pig:Tio ₂ =1:5, and zinc stearate is further added to prepare a pale dry color. Each of the dark and light dry colors was mixed with polyethylene resin to give a dark color of 0.1 PHR and a light color of 0.5 PHR, and after forming into pellets using an extruder, plates were made using an injection molding machine. Put the resulting plate through a fade meter,
Each ΔE value was measured and the results shown in Table 5 below were obtained.

[Table] Use example 5 A submerging solution of 5-acetoacetylaminobenzimidazolone containing 10% of Coupler (7) of use example 1 was
An orange azo pigment composition was obtained by coupling with a diazonium salt of diazotized 2-nitro-4-chloroaniline and performing a pigmentation treatment using a conventional method. Comparative Example 4 CI Pigment Orange (PO)-36 and the azo pigment composition synthesized in Usage Example 5 were made into a paint according to the method of Comparative Example 1, and the coated plates obtained in the same manner were exposed outdoors to determine the color of each coating film. The situation was measured. Judgment was made by visually observing the state of deterioration such as gloss, darkening, yoking, and discoloration of the coating film, and the evaluation was performed in three stages: ◯: almost no deterioration, △: deterioration observed, ×: severe deterioration. The results shown in Table 6 below were obtained.

[Table] Usage example 5 ○ ○ ○ ○
CIPO−36 ○ ○ △ △
Usage Example 6 Using a submerging solution of 1-phenyl-3-carboxyethyl-5-pyrazolone containing 5% of Katsuplar (2) and a tetrazonium salt of 3,3'-dichlorobenzidine prepared by a conventional method, The two were coupled and pigmented using xylene emulsion to obtain a yellowish red azo pigment composition. Comparative example 5 CI Pigment Red (PR)-38 and usage example 6
Each air-drying alkyd paint was prepared using the azo pigment composition obtained in Comparative Example 2, and the coated plates obtained in the same manner as above were exposed outdoors to visually observe the condition of the paint film. It was determined that Judgment is made by visually observing the state of deterioration such as gloss of the paint film, tarnishing, yoking, and fading of hue. ○: Almost no deterioration, △: Deterioration observed.
×: Judgment was made on a 3-level scale of severe deterioration. The results shown in Table 7 below were obtained.

[Table] Usage example 7 CI Pigment Violet (PV) -09 50
1 part was mixed with 50 parts of the azo pigment composition synthesized in Use Example 5 to prepare a mixed pigment. Usage Example 8 In the same manner as Usage Example 7, 50 parts of CIPR-5 was mixed with 50 parts of the azo pigment composition synthesized in Usage Example 5 to prepare a mixed pigment. Usage Example 9 A mixed pigment was prepared by mixing 50 parts of CIPY-110, 45 parts of the azo pigment composition synthesized in Usage Example 1, and 5 parts of the azo pigment synthesized in Usage Example 2 into which a substituted benzotriazole group was introduced. Usage Example 10 A mixed pigment was prepared by mixing 30 parts of CIPY-110, 40 parts of CIPY-110, and 30 parts of the azo pigment synthesized in Usage Example 2 into which a substituted benzotriazole group was introduced. Comparative Example 6 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 8 below. did.

[Table] Melamine-alkyd baking paints were prepared using the mixed pigments of Usage Examples 7 to 10 and Comparative Example 6 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 measuring deterioration such as gloss, darkening, chalking, and color change of the paint film. Judgment was made visually and in three stages: ◯: Almost no deterioration, △: Deterioration observed, ×: Severe deterioration.
The results shown in Table 9 below were obtained.

【table】

[Table] Usage Example 11 Various pigment compositions were prepared in the same manner as in Usage Example 1, except that the coupler shown in Table 10 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 10 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.)