JPS5930862A - Azo pigment compound - Google Patents

Abstract

PURPOSE:To obtain titled composition with improved fluidity and flocculation- proof ability, useful for (non)aqueous printing inks, etc., by incorporating a -COOH-contg. compound in part of a diazo and/or coupling component before carring out a coupling. CONSTITUTION:A coupling is carried out between (A) a diazo component, i.e., a diazonium compound from benzene-based amine or from napthalene-based amine, or a tetrazo compound from benzidine-based amine, and (B) a coupling component, i.e., an acetic arylamide, with 0.5-20mol% of either or both of the components (A) and (B) havng -COOH, followed by converting the -COOH group in the product obtained above into a salt of alkaline earth metal, Al, Zn, or amine, thus obtaining the objective pigment composition. Alternatively, a product from coupling reaction which contains no -COOH group is incorporated with 0.5-20mol% of another product containing -COOH, followed by carrying out the same conversion as the above.

Description

[Detailed description of the invention] This invention relates to pigment compositions.

There is no known method for producing a large number of water-insoluble organic pigments by reacting a diazo component of a diazonium compound or a tetrazo compound of benzene-based amines, naphthalene-based amines, or benzidine-based amines with a coupling component consisting of acetoacetate arylamides. However, these pigments are widely used in printing inks and paints. For example, if pigment particles agglomerate during storage or during drying, the color tone may become unclear and discoloration may occur. This has caused serious problems in practical use, such as a decrease in strength, opacity, color separation when mixed with other pigments, and deterioration of fluidity.

Conventionally, methods to solve this problem have been proposed, such as adding an anti-agglomerating agent, treating the surface of the pigment with various resins or surfactants, etc. However, these methods have not been able to solve the above-mentioned drawbacks. It couldn't be.

Another solution, as seen in Japanese Patent Publication No. 11026/1983, is to solidify the alkaline earth metal or organic amine salt of the mixture containing the sulfonic acid group-containing component, thereby dispersing it in a low-viscosity non-aqueous vehicle. The body has been shown to have a low viscosity and prevent viscosity increase during storage. However, the above-mentioned method does not necessarily sufficiently solve the problem of decrease in coloring power and opacity during storage.

On the other hand, in Japanese Patent Publication No. 55-10630, it is described that the force containing a polar group and mixed coupling with a pulling component improves the recrystallization stability of a monoazo pigment in printing ink. Even with this method, the solvent resistance was insufficient.

As a result of studies to improve the shortcomings of conventional techniques, the present inventors have determined that a part of the corresponding diazonium compound or coupling component in the insoluble azo pigment is mixed with a compound containing a carboxyl group as a polar group. By that,
It has been found that the above-mentioned drawbacks can be overcome. Furthermore, the inventors have completed the present invention by discovering that the pigment thus obtained is a significantly improved pigment not only for non-aqueous but also for water-based printing inks and paints.

That is, the present invention couples a diazonium compound of a benzene-based amine, a diazonium compound of a naphthalene-based amine, or a diazo component of a tetrazotized benzidine-based amine to a coupling component of an acetoacetate arylamide, and in this case, at least one A diazo component and/or a coupling component is used, and 0.5 to 20 molar portions of the diazo component and/or coupling component contain carboxyl groups, and the carboxyl groups in the coupling product are subsequently converted to alkaline earth. carboxyl groups, pre-carboxyl-free coupling products as alkaline earth metal salts, aluminum salts, zinc salts or amine salts. After mixing the coupling products containing the groups in a 0.5 to 20 molar chiller or in the dry state, the carboxyl group can be converted into an azo-containing compound in the form of an alkaline earth metal salt, aluminum salt, zinc salt or amine salt. In the latter case, the pigment composition may be a mixture of a carboxyl-free force, a salt of a pulling product, and a carboxyl-containing force, a salt of a pulling product.

In other words, a diazonium compound of a benzene-based amine or a diazonium compound of a naphthalene-based amine is an azo pigment formed by cutting the diazo component of a tetrazo compound of a benzidine-based amine with the power of an acetoacetate arylamide and a pulling component. (1) As a diazo component and/or a pulling component, 0.5 to 20 moles are coupled using a diazo component containing a carboxyl group and/or a pulling component (mixed coupling). , or (II) A product obtained by coupling a diazo component that does not contain a carboxyl group and a force or pulling component with a diazo component containing a carboxyl group and/or a force or pulling component. An azo pigment composition in which the product is mixed with 0.5 to 20 mol of azate9 (mixture), and the carboxyl group of the coupling product is converted into an alkaline earth metal salt, aluminum salt, zinc salt, or amine salt. It is a thing.

To explain the present invention in detail, the bare-cephalic amines, naphthalene-based amines and benzidine-based amines that do not have a carboxyl group and are used in the present invention are known, and examples of the benzene-based amines include aniline, 2-chloroaniline, , 3-rioo7niline, 2-nitroaniline, 3-nitroaniline, 4-nitroaniline, 5-7minor 1,3-bistrifluoromethylbenzene, 4-chloro-3-aminobenzotrifluoromethylbenzene,
2.5-dichloroaniline, 2-19-5-nitroaniline, 2-men-11-5-nitroaniline, 2-methyl-3-chloroaniline, 3-benzylsulfonyl-
6-methquinaniline, 2-amino-5-chlorobenzotrifluoride, 2-1tro-4-
ri oo Aniline, 2-nitro-4-methylaniline, 2-methyl-4-chloroaniline, 2-)-f-ru 5-10 loaniline, 2-methyl-4-nitroaniline, 2-methquin-5-chloro Aniline, 2-methoxy-
4-nitroaniline, 0-7=7dine-4-sulfone diethylamide, 2-nido 0-4-methoxyaniline,
0-aminoazotoluene, 2-methyl-4-amino-5
-methquinbenzanilide, 2,5-dimethoxy-4-
Examples include aminobenzanilide and 2,5-shedquino-4-aminobenzanilide, and examples of Natsuta 1/1-based amines include 1-naphthylamine, 2-naphthylamine, and 5-naphthylamine.
Nitro-1-su7thylamine, 8-nitro-1-naphthylamine, ■-amino-5-naphthol, 1-amino-
64-naphthol, 1-amino-7-naphthol, 1-
Amino-8-naphthol is mentioned, and benzidine-based amines include benzidine, 3.3'-dimethylbenzidine, 3.3'-dimethoxybenzidine, 3.3'-chlorobenzidine, 2.5.2', 5-tetra Examples include chlorobenzidine. Furthermore, acetoacetate arylamides having no carboxyl group are known, such as acetoacetylaminobenzene, 2-acetoacetylaminotoluene, 4-acetoacetylaminotoluene, 2-acetoacetylaminoanisole, 4-acetoacetylaminoanisole, 2-chloroacetoacetylaminobenzene, 4-chloroacetoacetylaminobenzene, ■-acetoacetylamino-2-ethylbenzene, ■-acetoacetylamino-2-ethoxybenzene, 1-acetylamino-2,4-dimethylbenzene, ■ -acetylamino-2,4-dimethoxybenzene, 1-acetylamino-2,5-dimethoxybenzene, 1-acetoacetylamino-4-ethquinbenzene, ■-acetoacetylamino/-2,5-dimethoxy-4-chlorobenzene, 1-acetoacetylamino-4-chloro-2=methylbenzene, 1-acetoacetylamino-5-chloro-2-methylbenzene, ■-acetoacetylamino-3-chloro-4
-Methylbenzene, 1-acetoacetylamino-2,5
-dichlorobenzene, 5-acetoacetylamine benzimidacylon, 4-acetoacetylaminoacetoacetanilide, 0-ditoluidite, 0-cyanididite and the like.

Benzene amines, naphthalene amines and benzidine amines containing at least one carboxyl group that can be used in combination with the above carboxyl group-free benzene amines, naphthalene amines and/or benzidine amines, or used alone. are known, such as 2-aminobenzoic acid, 3-aminobenzoic acid,
4-aminobenzoic acid, 3-amino-4-methoxybenzoic acid 1,3-amino-4-chlorobenzoic acid, 2-amino-
4-Nitrobenzoic acid, 2-amino-5-acetylamide 7
Benzoic acid, 3-amine salicylic acid, 5-amine salicylic acid, 3-aminophthalic acid, 4-aminophthalic acid, 5
-aminoterephthalic acid, 2-aminoterephthalic acid,
2-amino-3-naphthoic acid, benzidine-3,3'-
Examples include dicarboxylic acids.

Also used in combination with carboxyl group-free acetoacetate arylamides in the production of the pigment composition according to the present invention, and/
Examples of carboxyl group-containing acetoacetate arylamides suitable for use alone include the following. 2-acetoacetylaminobenzoic acid,
These are 3-acetoacetylaminobenzoic acid, 4-acetoacetylaminobenzoic acid, 3-acetoacetylamino-4-methquinbenzoic acid, and 3-acetoacetylamino-4-chlorobenzoic acid.

The force/pulling reaction is carried out by a known method, and in some cases, it is useful to add various water-soluble resins, surfactants, and other additives during or after the force/pulling.

In addition, mixed coupling (1) or mixed coupling (II)
In vc, 0.5 to 20 moles of a diazo component and/or a coupling component or a coupling product containing all carboxyl groups are used, but 0.5
If the molar ratio is less than 20 molar, the effect will be small, and if it exceeds 20 molar, problems such as bleeding will easily occur when used as printing ink. Further, in the mixing of (II), it is preferable to mix in a thriller form, but dry mixing may also be used.

Lake formation of carboxyl groups contained in a pigment composition with an alkaline earth metal, aluminum or zinc involves first forming an ammonium salt or an alkali metal salt with the carboxyl groups contained, and then forming a lake with an alkaline earth metal, aluminum or zinc. Make it into a rake.

The formation of amine salts can be done in the same way as metal salts, or
Alternatively, add the diazo component or the pulling component in advance, and after pulling, make the pigment mixture weakly alkaline with an alkaline aqueous solution, or add to the pigment mixture and make the pigment mixture suspension weakly alkaline with an alkaline aqueous solution It can be processed by

The amine used in the present invention is not particularly limited, but may be represented by the following formula (A) (wherein R1 is a hydrogen atom, an alkyl group having 8 to 24 carbon atoms, a substituted alkyl group, or a hetero It is a ring.R2 and R3 are monoamino with 1 to 14 carbon atoms (D is an alkyl group of H or a hydrogen atom, or have the following formula (
B) R4NHR5NH2) (wherein R4 is the same as R1 in the above formula (1), and R5 is an alkylene group having 1 to 4 carbon atoms). Specific examples of the general formulas (A) and ('I3) include the following: caprylamine,
Octylamine, laurylamine, dimethyloctylamine, dimethyllaurylamine, dimethylmyristylamine, triglylamine, methyldistearylamine, methyldilaurylamine, dimethylbenzylamine,
Tetramethylpropylene diamine, stearylpropylene diamine, laurylpropylene diamine, myristylpropylene diamine, octylpropylene diamine, oleylpropylene diamine, diethylpropylene diamine.

During the precursor step, it is desirable that the ammonium salt or alkali metal salt of the carboxyl group is completely laked, but it may be partially present as an unlaked portion as an ammonium salt, an alkali metal salt, or a free carboxyl group.

The azo pigment composition produced by the above method has the same sharpness, etc. as the insoluble azo pigment produced by the conventional method, and the conventional insoluble azo pigment can be used as printing ink or paint. The disadvantages of reduced tinting power, blurring of color tone, opacity, and poor flowability that occur during storage, as well as gelation that occurs during long-term storage, have been improved.

It has also been found that the product of the present invention can be used as a pigment for water-based printing inks and water-based coatings and has improved fluidity and less increase in needle viscosity over time.

Next, an example will be explained. "bu" or "chi" in a sentence
Unless otherwise specified, values are based on multiple weights.

Example 1 a) 14.5 parts of 2-nitro-4-methylayu 9F, a diazo component containing no carboxyl group, are stirred with 100 parts by volume of water and 26 parts of 35-dihydrochloric acid at room temperature for several hours. Next, 150 parts by volume of water was added to the resulting paste-like Shioshun salt, and after the mixture was heated to 0 to 3° C., 34.5 parts of a 20% aqueous sodium nitrite solution was added thereto while stirring to diazotize the mixture. Thereafter, stirring was continued for 1 hour at 0 to 5°C, and the resulting diazonium aqueous solution was clarified with activated carbon, and a sufficient amount of amidosulfonic acid was added to remove excess nitrite ions.

b) Diazo component containing a carboxyl group 0.69 parts of 2-aminobenzoic acid was dissolved in 20 parts of a 1% aqueous sodium hydroxide solution, and then 1.5 parts of 35-thihydrochloric acid was added to make the solution sufficiently acidic. To this material was added 1.75 parts of a 20% sodium nitrite aqueous solution at 0 to 3°C to diazotize it. This was mixed with the diazonium solution prepared in a).

The molar ratio of both components is 95:5.

C) Coupling 17.7 parts of acetoacetylaminobenzene are added to an aqueous solution of 250 parts by volume of water and 10 parts of caustic soda and completely dissolved. After diluting with 1000 volumes of water, add 90% to this aqueous solution.
Add 17.7 parts of acetic acid diluted with 250 parts of water, and add p
Adjust the H value to 5.5 to 60. Then, the diazonium component was added dropwise to complete the coupling reaction, and a pigment composition was obtained. After stirring for about 1 hour, it was filtered, the precipitate was redispersed in 3000 parts by volume of water, the pH was adjusted to 9.0 to 9.5 by adding 1 t aqueous solution of caustic soda, and then the pH was adjusted to 10%.
After adding 16 parts of gold chloride aqueous solution and heating to 80℃,
It was filtered and washed with water to obtain calcium lake. Drying was carried out overnight at 80±10° C. in a hot air circulation type open chamber, and then pulverized to obtain a yellow pigment powder.

Comparative Pigment 1a Comparative pigment 1a was prepared in the same manner as in Example 1. However, only 15.2 parts of 2-nitro-4-methylaniline is used.

Comparative Pigment 1b Comparative Pigment 1b is prepared in the same manner as in Example I. However, in place of 2-aminoben 7Ω aromatic acid,
A calcium lake was prepared using 0.94 parts of sulfonic acid.

Pigment 1a prepared according to the present invention and comparative pigment 1b″f
:Nitrocellulose vehicle (solid content 20%)
) when dispersed in a ball mill (pigment content: 10 cm), the two comparative pigments had poor coloring power and were unclear, whereas the product of the present invention had high coloring power and its viscosity was as follows. The product of the present invention is compared with other comparative pigments 2f! I! It has a significantly lower viscosity than similar products. The viscosity of this pigment dispersion after being stored for 3 months shows almost no change from the initial viscosity.

Example 2 The same effect as in Example 1 was obtained when a pigment composition prepared in the same manner as in Example 1 was used as a barium salt instead of a calcium salt as the laked metal.

Example 3 a) Preparation of pigment containing no carboxyl group 2-=to0-4
-Chloroaniline16. s parts are stirred with 600 parts by volume of water and 30 parts of 35% hydrochloric acid at room temperature for several hours. After adding 200 parts of ice water to this paste and bringing it to 0 to 3℃,
Add 34 parts of 20% sodium nitrite aqueous solution to diazotize.

The coupling component is 1000 parts by volume of water and 10 parts by volume of caustic soda.
20.7 parts of 2-chloroacetoacetylamine benzene was added and dissolved, and then 1 part of 90% acetic acid was added.
Dilute 7.7 parts with 200 volume parts of water and add to pH 5.5.
A diazonium solution was added dropwise to the adjustment solution to obtain an insoluble azo pigment.

b) Preparation of carboxyl group-containing dye 0.41 part of 2-aminobenzoic acid is dissolved in 12 parts of 1% aqueous sodium hydroxide solution, and then 35-thihydrochloric acid is added to 19 parts of O to make it sufficiently acidic and cooled. When the temperature reached 0 to 3°C, 1.05 parts of a 20% sodium nitrite aqueous solution was added to diazotize the mixture. The coupling component was 0.65 parts of 2-chloroacetoacetylaminobenzene, 37.8 parts of a 1% caustic soda solution added to 30 parts of water, and after completely dissolving 1c, 60 parts of a 1% acetic acid aqueous solution was added, pH 5.5
Adjust to 6.0 to 6.0.

A diazonium solution was added dropwise to this prepared solution to obtain a carboxyl group-containing dye.

This product was mixed in slurry form with the carboxyl group-free pigment prepared in step a), and then stearylamine acetate 2
100 parts by volume of water was added, and the pH was further adjusted to 8.5 to 90 with caustic soda to form a lake, heated at 80°C, filtered, washed with water, and dried to give a yellow color. A powder was obtained. The molar ratio of both components is 97:3. A pigment containing no carboxyl group is obtained as Comparative Pigment 2a, and a pigment whose carboxyl group is not laked with an organic amine is obtained as Comparative Pigment 2b.

When the pigment thus obtained was dispersed in a lime rosin-toluene vehicle and developed using a paint conditioner, Comparative Pigment 2a and Comparative Pigment 2b had an unclear tone, poor tinting power, and a high viscosity, whereas the present invention The product was clear and had high tinting strength, and the viscosity immediately after adjustment was extremely low, and almost no change was observed in the viscosity over time after 3 months.

An example carried out in the same manner as Example 3 will be shown below.

The obtained pigment showed the same excellent properties as the pigment obtained in Example 3.

Example 8 32.4 parts of 3.3-dichlorobenzidine hydrochloride was added to 20 parts of water.
0 part by volume, and then 63 parts of 35% hydrochloric acid and stirred at room temperature for several hours. After adding 1000 parts by volume of the obtained paste to ice water and bringing the temperature below 0° C., 142 parts of a 20% aqueous sodium nitrite solution was added all at once to form a tetrazotized paste. After adding 2 parts of activated carbon to decolorize, purify and filter, amidosulfonic acid is added to eliminate excess nitrite ions and a tetrazo solution is obtained.

The strength and pulling ingredients are 1000 parts by volume of water and 20 parts of caustic soda.
3 parts of acetoacetylaminobenzene in an aqueous solution containing 3 parts of acetoacetylaminobenzene.
4 parts of 2-acetoacetylaminobenzoic acid and 1.77 parts of 2-acetoacetylaminobenzoic acid were added to completely dissolve the mixture, and then 345 parts of 90-thiacetic acid was diluted in 200 parts of water to adjust the pH to 5.5 to 6.0. Both coupling components are in a molar ratio of 96:4.

The coupling component is maintained at 20°C, and the tetrazo solution is added to this solution while adjusting the amount so that it flows from below the liquid surface.
Complete the coupling. After stirring for about 1 hour, it was filtered, the precipitate was redispersed in 5000 parts by volume of water, the pH was adjusted to 9.0 to 9.5 with a 1% aqueous solution of caustic soda, 8 parts of aluminum sulfate was added, and the mixture was heated at 80°C. After heating, filtration,
It was washed with water and made into an aluminum lake. It was dried at 80±10°C and ground to obtain a yellow powder.

Comparative Pigment 8a For separate comparison, a pigment containing no carboxyl group was prepared in the same manner as in Example 8 by force and bling using only acetoacetylaminobenzene and a tetrazo solution.

Comparative Pigment 8b Made according to the method of Example 8, but without aluminum salt after force and pulling.

The product of the present invention (Example 8) was compared with Comparative Pigment 8a and Comparative Pigment 8.
When printing ink using three rolls of B and a commercially available offset printing face is printed using a simple printing machine, the print of the present invention is very transparent and clear, and has excellent coloring power, whereas the print made from the comparative pigment is Ink was unclear, opaque, and had poor coloring power.

Example 9 5 parts of stearylamine acetate was added to an aqueous solution of the mixed coupling product prepared by the method of Example 8, and the pH was adjusted to 8.5 to 9.0 with a 10% aqueous sodium hydroxide solution, followed by filtration and washing with water ( After drying and grinding, a yellow powder is obtained, which exhibits the same excellent properties as Example 8.

An example carried out in the same manner as Example 8 will be shown below.

The resulting pigment exhibited excellent properties similar to those of the pigment of Example 8.

58.7 parts of 3,3'-dichlorobenzidine hydrochloride was added to 400 parts by volume of water, followed by 85 parts of 35-dihydrochloric acid, and the mixture was stirred for several hours. After adding 2,000 parts by volume of ice water to the paste-like contents to bring the temperature below 0° C., 130 parts of a 20% sodium nitrite solution was added all at once to form a tetrazotate. Add 5 parts of activated carbon to decolorize the mixture, filter it, and eliminate excess nitrite ions with amidosulfonic acid to obtain a tetrazotized solution (1).

Separately, 6.82 parts of benzidine-3-3'-dicarboxylic acid was added to a solution of 150 parts by volume of water and 2.1 parts of caustic soda and completely dissolved. Next, add 11 parts of 35% hydrochloric acid to make it sufficiently acidic, add 200 parts of ice water by volume, and
After cooling to below ℃, 20% sodium nitrite aqueous solution 17.7
Add all parts at once to form tetrazotization. Excess nitrite ions are eliminated with amitosulfonic acid to obtain a tetrazotized solution (II).

Separately, dissolve 48 parts of caustic soda in 2,000 parts by volume of water.To this, dissolve 80 parts of 2-acetoacetylamine Toluev, and add 84 parts of 90-thiacetic acid diluted with 1000 parts of water.
Adjust to H5, 5 to 6.0.

After adjusting the liquid temperature to 20°C, the above tetrazotized liquid (n) is then added dropwise to the tetrazotized liquid (+1 so as to flow below the liquid surface, respectively) to perform coupling.The resulting pigment mixture Add 25 parts of stearylamine acetate as an aqueous solution to a chiller, then adjust the pH to 8.5 to 9.0 with a 10% aqueous solution of caustic soda, form a lake, and heat at 80°C. Filter, wash with water, dry and grind to obtain a yellow powder.

The molar ratio of the caprylic acid-free component to the caprylic acid-containing component in the pigment composition is 88:12.

Separately, as a comparative pigment, a pigment containing no carboxyl group was prepared in the same manner as above, except that only 2-acetoacetylaminotoluene and the tetrazotized liquid (1) were coupled.

When both pigments prepared in this way were dispersed in a nitrocellulose vehicle (solid content 20%) using a ball mill and developed, the comparative pigments had poor coloring power, unclear color tone, and were opaque. On the other hand, the present invention has significantly higher tinting strength, sharpness, and transparency. In addition, the viscosity immediately after dispersion is extremely low, and the viscosity shows almost no change from the initial viscosity when stored for 3 months. The measurement results of viscosity are shown below.

Example 25 A pigment composition was obtained in the same manner as in Example 24, except that 114 parts of 1-acetoacetylamino-2,5-dimethoxy-4-chlorobenzene was replaced with 2-acetoacetylaminotoluene. In order to compare with a comparative pigment containing no carboxyl group, this pigment was dispersed in an alkyd resin container and a paint conditioner at 50 to 6 degrees Celsius, respectively.

When this dispersion was applied to a glass plate J:, the comparative material M was extremely opaque, had poor tinting power, and color separation occurred when mixed with white edumel, whereas the invented product was extremely transparent.
There was no change in tinting strength, and color separation frequently occurred when mixed with white enamel. -! While the comparative pigments gelled during long-term storage, the products of the present invention showed almost no change in viscosity.

Example 26 In a similar manner to Example 24, but with benzidine-3,3-
A pigment composition was obtained using 95 parts of 2-amino-3-naphthoic acid as the carboxylic acid. The molar ratio of both components is 88:12. For comparison, a pigment containing no 2-amino-3-naphthoic acid was prepared and added to a water-based printing ink vehicle (solid content 30
%l) to obtain a dispersion with a pigment content of 10%.The product of the present invention was significantly glossier than the comparative pigment, and the viscosity immediately after dispersion was low and stable.
The viscosity remained stable with almost no change during storage at ℃ for one month, and no sedimentation occurred in the ink.

Example 27 Add 250 parts by volume of water, 25 parts of 2,2',5.5'-tetrachloro-benzidine and 45 parts of 35% hydrochloric acid, and stir for several hours to form a paste. Add 1,000 parts of ice water to this mixture, cool it to below 0°C, and add 54 parts of an aqueous solution of 20% sodium nitrite at once to form a tetrazotized mixture. After adding 5 parts of activated carbon for decolorization and filtration, excess nitrite ions are eliminated with amidosulfonic acid to obtain a tetrazotized solution (1).

Separately, 80 parts of 1% aqueous sodium hydroxide solution Q was added to 100 parts by volume of water, and then 273 parts of benzidine-3,3'-dicarboxylic acid was added thereto and completely dissolved. 3 for this thing
After making it sufficiently acidic by adding 5 parts of 5% hydrochloric acid, 400 parts by volume of ice water was added to cool it to below 0°C, and then 7 parts of a 20% sodium nitrite aqueous solution was added all at once to form a tetrazotate. Excess nitrite ions are eliminated with amidosulfonic acid and the tetrazotization solution (
ll). Separately, 300 parts by volume of water and 17 parts of caustic soda.
Then, 36 parts of 1-acetoacetylamino-2,4-methylbenzene was added and completely dissolved. 55.2 parts of 90% acetic acid are diluted with 200 parts by volume of water, and the diluted solution is added to the solution of the coupling component to make it sufficiently acidic. Add 1,000 parts by volume of ice water and adjust the temperature to 5°C.
) flows below the liquid surface of the bling component to cause a force and pull. 10 parts of stearylamine acetate was dissolved in 500 parts by volume of water, added to a pigment thriller, made weakly alkaline to pH 8.5 to 9.0 with a 10% aqueous sodium hydroxide solution to form a lake, and then heated to 90°C. It was filtered, washed with water, dried and ground to obtain a yellow powder. The molar ratio of both components is 88:11.5.

For comparison, a comparative pigment was prepared using the tetrazotized liquid (1) and l-acetoacetylamino-2,4-dimethylbenzene in the same manner.

When both pigments were dispersed in a water-based paint vehicle using a ball mill to create a dispersion, the comparison pigment had low tinting power and high viscosity immediately after dispersion, whereas the product of the present invention had high tinting power and The viscosity immediately after dispersion was also improved.

Further, when acceleration was carried out at 50° C. for one month, the viscosity of the comparative pigment increased significantly, whereas the viscosity change of the product of the present invention was small.

Example 28 6.9 parts of 2-aminobenzoic acid was added to 1 tb of caustic soda aqueous solution
The mixture was dissolved in 2 parts of 0.02 parts, and then 15 parts of 35 dihydrochloric acid was added to make it sufficiently acidic. 0 to 3 by adding 300 parts by volume of ice water
℃, and 17.5 parts of a 20% aqueous sodium nitrite solution was added to diazotize the mixture. After completion of diazotization, excess nitrite ions are eliminated with amidosulfonic acid and diazonium solution is removed.

Separately, 9 parts of acetoacetylaminobenzene was added to an aqueous solution of 200 parts by volume of water and 5 parts of caustic soda to completely dissolve it, and then 8.9 parts of 9-thiacetic acid was diluted in 100 parts by volume of water and the pH value was adjusted. Adjust to 5.5 to 6.0.

A diazonium solution was added dropwise to the adjusted aqueous solution to complete the cuffling reaction, and a carboxyl group-containing component was obtained. After stirring for about 1 hour, it was filtered, and the precipitate was redispersed in 1,500 parts by volume of water, and the pH was adjusted to 9.0 to 9.5 with a 1 t aqueous solution of caustic soda.
After adding 5 parts to form a lake, heated to 80℃, filtered,
After washing with water, drying and grinding, a yellow powder is obtained.

This product was mixed with Comparative Pigment 1a of Example 1 at a molar ratio of carboxyl group-free component to carboxyl group-containing component of 9:1, and placed in a nitrocellulose vehicle (solid content 20%) together with Comparative Pigment 1a. Viscosity of the dispersion (pigment content 10%) when dispersed in a ball mill (BM type rotational viscometer, 25
C) has a significantly lower viscosity than Comparative Pigment 1a as shown below, and the viscosity when stored for 3 months is almost the same as the initial viscosity.

Patent Applicant: Toyo Ink Manufacturing Co., Ltd. Procedural Amendment (voluntary) September 1980/<//, Commissioner of the Japan Patent Office1, Indication of the case: Patent Application No. 138380 of 19802, Name of the invention: Azo pigment composition 3. Relationship with the case of the person making the amendment Patent applicant address: 2-3-13 Kyobashi, Chuo-ku, Tokyo Name:
Column 5 of Detailed Description of the Invention BAj of the Toyo Ink Manufacturing Co., Ltd. Specification: Contents of the Amendment Contents of the Amendment (1) In the 18th line from the second purchase of the specification, ``particles'' is corrected to ``particles''.

(2) In the 4th to 14th lines of the specification, "mono" is corrected to "compound."

(3) Correct "slurry" in lines 6 and 7 from the fifth purchase of the statement to "slurry."

(4) In the 11th to 14th line of the statement, change “slurry” to “
"Slurry" corrected.

(5) In the 5th line from the 12th purchase of the specification, "pigment mixture suspension" is corrected to "l!1 pigment mixture suspension".

(6) In line 19 from purchase to 12 of the specification, ``Development'' is corrected to ``Development''.

(7) From line 6 to line 7 from the 25th purchase of the specification, "slurry" is corrected to "slurry."

(8) Lines 18 to 19 from the 29th purchase in the specification: ``Correct slurry J to ``slurry''.

(9) On the 3rd line from the 31st purchase of the statement, change "Solubility" to "
Dissolve and correct to J.

Claims (1)

[Scope of Claims] ■ An azo pigment obtained by coupling a diazo component of a diazonium compound of a benzene-based amine, a diazonium compound of a naphthalene-based amine, or a tetrazo compound of a benzidine-based amine with the force of an acetoacetate allylamide or a bling component. , (+) As a diazo component and/or a coupling component, 05 to 20 mole ratio is a diazo component containing a carboxyl group and/or a coupling component is used to force or pull, or, (■) A product formed by coupling a diazo component containing a carboxyl group and a coupling component with a diazo component containing a carboxyl group and/or a bling component using 0.0. An azo pigment composition, characterized in that the carboxyl group of the coupling product is an alkaline earth metal salt, an aluminum salt, a zinc salt or an amine salt.