JPH0571632B2 - - Google Patents

Description

[Detailed description of the invention]

[Object of the Invention] (Industrial Field of Application) The present invention relates to a method for producing an azo pigment that has high tinting power and excellent clarity, fluidity, and storage stability. (Prior Art) Conventionally, azo pigments, particularly monoazo lake pigments made of an aromatic amine having a soluble group and β-naphthol or β-oxynaphthoic acid, and disazo pigments made of dichlorobenzidine and acetoacetanilide, have been used in printing inks and pigments. It is widely used for coloring plastics, etc. Among them, CINo.21090,
21100, 21095, 15630:1, 15850:1, etc. are often used in process inks and are required to have high concentration, high transparency, and good fluidity.
In contrast, with conventional technology, 10 to 30% of rosin is added to the pigment.
If the diazo component or coupler component has a substituent such as a methyl group, halogen atom, or nitro group,
The solution has been to add 0.1 to 50 mol%. However, in the case of conventional addition of substituents, the dry cohesive force of the pigment is large, and dispersion into the vehicle takes a lot of time, and the resulting ink also has a high viscosity. Furthermore, when rosin is treated in an amount of 10 to 30% by weight, the dispersibility of the pigment in the vehicle and the transparency of the ink are improved, but the tinting power is reduced. Furthermore, the method of mixing pigments and pigment derivatives as seen in JP-A No. 56-166266 has a great effect of making the pigments fine and stabilizing them, and this dispersion has a low viscosity and is stable in storage. will also be good. Furthermore, when different types of pigments are mixed and used, it is possible to prevent color separation and sedimentation due to aggregation. However, in offset inks, gravure inks, etc., yellow and red colors are required to have excellent sharpness, transparency, and fluidity due to the printing process, and satisfactory quality cannot be obtained with this method. As a means to solve these problems, Japanese Patent Application Laid-Open No. 61-24620 reports an example in which an alkylamine such as tetramine or triamine is directly bonded to a dye. However, the anchoring effect of this dispersant on the adsorbed dye is still insufficient, resulting in problems such as color staining, poor dispersibility, gloss, density, viscosity, and stability over time, all of which are unsatisfactory. has not been obtained. (Problems to be Solved by the Invention) The object of the present invention is to provide a pigment having excellent clarity and fluidity and coloring power for use in printing inks and paints. (Means for solving the problem) That is, aromatic amines as diazo components used in the present invention are known, for example, 1-
amino-4-methylbenzene-2-sulfonic acid,
1-amino-4-methyl-5-chlorobenzene-
2-sulfonic acid, 1-aminonaphthalene-2-sulfonic acid, 1-amino-4-chloro-5-methylbenzene-2-sulfonic acid, 2-nitro-p-toluidine, 3,3'-dichlorobenzidine, etc. can be given. In addition, the Kappler components are also known compounds such as β-naphthol, β-oxynaphthoic acid, and naphthol AS.
and acetoacetanilide. The method for producing an azo pigment using the above-mentioned raw materials can be carried out according to a conventional method for producing an azo pigment. That is, the compound represented by the general formula () is added as a powder or dissolved in acetic acid or mineral acid to the diazo component or coupler component. Then, the two are coupled according to a conventional method, and if the pigment is a lake pigment, a lake forming agent is added thereto to form a lake. Lake forming may be performed simultaneously with coupling by adding a lake forming agent to the diazo component and coupler component in advance. Of course, the surface treatment of pigments can also be carried out by adding water-soluble resins, surfactants, and other additives to the diazo component, coupler component, dye, or pigment slurry. In the above, a compound of the following general formula () is used as a part of the diazo component or coupler component.

[Chemical formula] Here, Q is a diazo component residue of the following general formula (),

[Formula] Or a coupler component residue of the following general formulas () to ().

【formula】

【formula】

【formula】

【formula】

[Formula] (However, R ₄ and R ₅ in formulas () to () are each independently a hydrogen atom, an alkyl group, a methoxy group,
Indicates a halogen atom, a sulfone group, and a nitro group. ) can be given. R ₁ to _{R 2} in formula () are a hydrogen atom or a saturated or unsaturated alkyl group having 1 to 20 carbon atoms.
From the viewpoint of production and effectiveness, R ₁ , R ₂ , and R ₃ are all lower alkyl groups such as methyl, ethyl, propyl, butyl, or at least one of R ₁ and R ₂ is a lower alkyl group. It is a long chain alkyl. R ₁ and R ₂ may be a heterocycle containing a nitrogen atom, an oxygen atom, or a sulfur atom. Further, A is a divalent bonding group represented by -SO ₂ NR'- or -CONR'- (wherein R' represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms). The compound represented by formula () of the present invention can be produced by a known method. When Q in the formula is a residue of a diazo component, for example, it is a substituent that can react with an amino compound, such as nitrobenzoyl chloride or acetoacetylaminobenzenesulfonyl chloride, and it can be easily removed by reduction or hydrolysis. It is advantageous to use as a starting material a compound containing a substituent that can be converted into an aromatic amine.
That is, after reacting the starting material and an amino compound having two or more amino groups in water or an organic solvent by adding an alkaline compound such as potassium carbonate or sodium carbonate as necessary, palladium-
It can be easily obtained by a method in which a nitro group is converted into an amino group by catalytic reduction using a carbonic acid catalyst or the like or reduction with iron-acetic acid, and a method in which an acetylamino group is hydrolyzed with dilute hydrochloric acid or the like to be converted into an amino group. When Q in the formula is a residue of a coupler component, it can be easily obtained, for example, by reacting the above compound with diketene in water or an organic solvent. The amount of the compound represented by the general formula () according to the present invention added is preferably 0.1 to 30% by mole based on the diazo component or coupler component. If it is less than 0.1 mol%, the effect of the compound represented by the general formula () cannot be obtained, and even if it is used in an amount greater than 30 mol%, the effect of the compound used cannot be obtained. The azo pigment of the present invention has high coloring, sharpness, and transparency compared to conventional azo pigments. In addition to satisfying these effects, the fluidity is also good. In other words, mixed coupling in which a component having a substituent group is added to the diazo component or coupler component has the disadvantage of reduced fluidity, but the azo pigment of the present invention overcomes this problem. . Further, when conventional azo pigments treated with a large amount of rosin deteriorate printability when used in printing inks, the azo pigment of the present invention has good printability. The azo pigment of the present invention also has excellent thermal stability during flushing operations. In other words, with conventional azo pigments, crystal growth and aggregation of pigment particles occur during the heating operation during flushing, resulting in opaque ink and a significant decrease in coloring power, but the azo pigment of the present invention does not have these drawbacks. It is a thermally stable pigment that does not generate any color. In the examples, "part" and "%" indicate parts by weight and weight %. Example 1 17.7 parts of 1-amino-4-methylbenzene-2-sulfonic acid are dissolved at room temperature with 300 parts of water and 4 parts of sodium hydroxide. Add 25 parts of 35% hydrochloric acid for acidification, then add 200 parts of ice and cool to 0°C. Next, add the following diazo component (1) to 50 parts of 10% acetic acid in advance.

Add to this a solution of one part of [chemical formula]. Add 7 parts of sodium sulfite dissolved in 25 parts of water and heat at below 5℃.
The mixture was stirred for 30 minutes and used as the diazo component. On the other hand, 19 parts of β-oxynaphthoic acid was mixed with 1 part of natural rosin, 1000 parts of water, and 10 parts of sodium hydroxide at 15%
Dissolve at ℃ and use this as a coupler component. The above diazo component was added dropwise to the coupler component over 30 minutes, and stirring was continued for an additional hour to complete the coupling reaction. The coupling liquid has a pH of 9.
It was ~9.5. Next, 60 parts of 35% calcium chloride aqueous solution was added and stirred for 2 hours to complete the lake formation reaction. After heating to 70°C, the mixture was filtered, washed with water, dried and ground to obtain 43 parts of red pigment. Comparative Example 1 Pigment (Carmine 6B) synthesized without adding diazo component (1) in Example 1, and diazo component (1) in place of 1-amino-4-methylbenzene-2-sulfonic acid in Example 1 The following pigment derivative synthesized using only 27 parts

Prepare a mixture of 95 parts and 5 parts of [C]. The offset ink prepared from the pigment obtained in Example 1 and the rosin-modified phenolic resin was significantly clearer and clearer than the ink prepared from the pigment to which the diazo component (1) was not added and the pigment obtained in Comparative Example 1. It had great coloring power. In addition, the coloring power is based on the pigment that does not contain the diazo component (1).
When it was set as 100, it was 102 in Comparative Example 1 and 110 in Example 1. Example 2 A red pigment was prepared in the same manner as in Example 1 except that the following diazo component (2) was used in place of the diazo component (1) in Example 1. The offset ink prepared from the obtained pigment was clearer, more vivid, and had better coloring power than the ink prepared from one without the addition of diazo component (2).

EXAMPLE 3 22.4 parts of 2-aminonaphthalene-1-sulfonic acid are dissolved with 300 parts of water and 5 parts of sodium hydroxide. After adding 30 parts of barium chloride dihydrate to form a barium salt, acidify by adding 25 parts of 35% hydrochloric acid, add 200 parts of ice, and cool to 0°C. Add 7 parts of sodium sulfite dissolved in 25 parts of vinegar and heat at 0 to 3℃ for 30 minutes.
The diazo component was stirred for several minutes. Separately, 13.4 parts of β-naphthol was dissolved at 40°C with 5 parts of sodium hydroxide and 500 parts of water, and the following coupler component (3) was added to 50 parts of 10% acetic acid in advance.

Add 1 part of [chemical formula] to make a solution and use it as a coupler component. Add the coupler component to the above diazo component, continue stirring for 1 hour, and perform the coupling reaction.
Complete the rake reaction. After heating to 90°C, the mixture was filtered, washed with water, dried and ground to obtain 40 parts of red pigment. The publishing gravure ink prepared from the above pigment was clearer and had higher coloring power than the ink prepared from the pigment without the addition of the coupler component (3), and had a lower viscosity and good stability over time. [Test method] Pigment 10 parts Lime rosin 80 parts Toluene 10 parts 3 mm diameter glass beads 100 parts Total 200 parts Shake with paint conditioner for 2 hours and thicken. Colored ink. In addition, a light color ink was prepared by kneading 1 part of the dark color ink and 10 parts of the white ink, and the coloring strength was determined. Coloring strength is approximately 10% compared to ink prepared from pigments without Katsupla component (3) added.
It was big and warm. Further, the viscosity measurement results are shown in Table 1. It can be seen that the material according to the present invention has excellent fluidity and good stability over time.

[Table] Example 4 G base (5-nitro-o-toluidine) 19.2
1 part is dissolved at 60°C with 300 parts of water and 48 parts of 35% hydrochloric acid. Add 240 parts of ice to bring the temperature to 0°C. Add 8.8 parts of sodium sulfite dissolved in 25 parts of water,
The mixture was stirred for 30 minutes at 5°C or below and used as the diazo component. On the other hand, 33 parts of naphthol AS is dissolved together with 500 parts of water and 10 parts of sodium hydroxide at 90°C. Next, add the following coupler component (4) to 30 parts of 10% acetic acid in advance.

A part of [Chemical formula] is dissolved and added to this to form a coupler component. The diazo component is added to the coupler component over 30 minutes, followed by stirring for an additional hour to complete the coupling. After heating at 80°C for 30 minutes, the mixture was filtered, washed with water, dried, and crushed to obtain 50 parts of red pigment. The offset ink prepared from the obtained pigment was significantly clearer, more vivid, and had better coloring power than the ink prepared from the pigment without the coupler component (4). Example 5 20.5 parts of 3,3'-dichlorobenzine hydrochloride was added to water.
Dissolve at room temperature with 250 parts and 19 parts of 35% hydrochloric acid. Add 230 parts of ice and cool to 0°C. Dissolve 9.7 parts of sodium sulfite in 35 parts of water, and add this solution to obtain a diazo component. Meanwhile, 22.4 parts of acetoacetanilide, 250 parts of water,
It is dissolved at room temperature along with 13 parts of atrium hydroxide, and 205 parts of a 10% acetic acid solution is added dropwise thereto for acid precipitation. 2 parts of the following Katsupular ingredient (5)

Add [chemical formula] dissolved in 50 parts of 10% acetic acid solution to form a coupler component. Furthermore, the previously prepared diazo component was added over a period of 2 hours, and the mixture was stirred for an additional 10 minutes to complete the coupling reaction. The pH of the coupling liquid was 4.0.
Add sodium hydroxide to adjust the pH to 10.5, add 1.3 parts of natural rosin dissolved by heating with 10 parts of water and 0.3 parts of sodium hydroxide, and stir for 30 minutes.
Add 4 parts of zinc nitrate hexahydrate to precipitate rosin. After stirring for 30 minutes, the mixture was filtered, washed with water, dried, and ground to obtain 44 parts of yellow pigment. The offset ink prepared using the obtained pigment and the rosin-modified phenolic resin was significantly transparent, clear, and had excellent coloring power compared to the ink prepared from the pigment to which the coupler component (5) was not added. Example 6 A pigment was prepared in the same manner as in Example 5 except that 26 parts of acetoaceto-2,4-xylide was used in place of the coupler component acetanilide. The offset ink prepared from the obtained pigment was significantly clearer, more vivid, and had better coloring power than the ink prepared from the pigment to which the coupler component (5) was not added. Example 7 22 parts of 3-methyl-1-phenylpyrazolone was used instead of acetoacetanilide in Example 5, and the following coupler component (6) 2 was used instead of coupler component (5).
A yellow pigment was obtained in the same manner as in Example 5.

[Formula] A paint was prepared from the obtained pigment. [Test method] Pour the following composition into a 200 c.c. mayonnaise bottle and shake with a paint conditioner for 1 hour. Pigment: 9 parts Phthalamic varnish 66 parts Mineral spirits 25 parts 3 mm diameter glass beads 100 parts Total 200 parts The extracted enamel is made into dark enamel, and 1 part of dark enamel is mixed with 10 parts of blue enamel to make light color. Made with enamel. The dark enamel was applied onto a painted plate using a 6 mm applicator, and the hue and sharpness were evaluated. The light colored enamel was spread on a painted plate with a 4 mil applicator and the tinting strength was determined. The coloring power was approximately 9% higher than that of a paint prepared from a pigment without the addition of Kappler component (6). Further, the viscosity measurement results are shown in Table 2.

Table Example 8 20.5 parts of 3,3'-dichlorobenzidine hydrochloride are dissolved with 250 parts of water and 19.1 parts of 35% hydrochloric acid at room temperature. Add 230 parts of ice and cool to 0°C. water 35
9.7 parts of sodium nitrite is dissolved in 9.7 parts of sodium nitrite, and this solution is added to obtain a diazo component. Separately, 13 parts of sodium hydroxide and 24.1 parts of acetoaceto-o-toluidide are dissolved in 250 parts of water at room temperature, and 205 parts of a 10% acetic acid solution is added dropwise thereto for acid precipitation. Add 3.8 parts of the following Katsupular ingredient (7) in advance.

[Chemical] Add the solution dissolved in 64 parts of 10% acetic acid solution to make the coupler component. The previously prepared diazo component was added over a period of about 2 hours, and the mixture was stirred for an additional 10 minutes to complete the coupling reaction. Thereafter, it was filtered, washed with water, dried, and crushed to obtain 48 parts of yellow pigment. The gravure ink prepared from the above pigment had higher gloss, higher coloring power, and better fluidity than the ink prepared from the pigment without the addition of coupler component (7). [Test method] The following composition was placed in a 200 c.c. mayonnaise bottle and tested in the same manner as in Example 3. Nitrocellulose resin 60 parts Ethyl acetate 30 parts Pigment 10 parts 3 mm diameter glass beads 100 parts Total 200 parts

[Table] Example 9 The coupler component in Example 8 was replaced with acetoaceto-o-toluidide by 22.9 parts of acetoacetanilide, and the coupler component (7) was replaced by 5.5 parts of the following coupler component (8).

[C] Coupling is performed using each solution dissolved in 90 parts of 10% acetic acid solution. Thereafter, this slurry was adjusted to pH 10 to 11, heated to 90°C, filtered, washed with water, dried, and ground to obtain a yellow pigment. Comparative Example 2 Acetoacetanilide as a cutupler component
Coupling is carried out as in Example 8 using only 22.9 parts. Add a dilute acetic acid solution containing 4.5 parts of stearylpropylene diamine to this pigment slurry, and
11, heated to 90℃, filtered, washed with water,
It was dried and ground to obtain a yellow pigment. Comparative Example 3 Acetoacetanilide as a cutupler component
A yellow pigment was synthesized in the same manner as in Example 8 using only 22.9 parts, and the following pigment derivatives were synthesized in the same manner using only 68.4 parts of the coupler component (8).

[C] Then, prepare a pigment in which the former and the latter are mixed in a ratio of 17 parts to 3 parts, respectively. Comparative Example 4 A yellow pigment was synthesized in the same manner as in Example 9 using 5.5 parts of the following coupler component (10) in place of the coupler component (8) in Example 9. CH ₃ COCH ₂ CONH (CH ₂ ) ₃ NH (CH ₂ ) ₃ NHC ₁₈ H ₃₇
(10) The gravure ink prepared from the pigment obtained in Example 9 was clearer than the gravure ink prepared from the pigment synthesized without adding the coupler component (8) and the pigment obtained from Comparative Examples 2 to 4. big sex,
It had high tinting strength, high gloss, and low viscosity, and was particularly excellent in stability over time. Table 4 shows the results. [Test method] The same method as in Example 3 was conducted. In addition, discoloration over time occurs immediately after ink formation and when accelerated over time (50
After 96 hours at ℃, coat the ink with a bar coater (film thickness 20μ
m), and after drying, differences in hue were observed with the naked eye.

[Table] *Katsupura (8) not added

Claims (1)

[Scope of Claims] 1. Performing a coupling reaction using a diazo component or a coupler component containing 0.1 to 30 mol % of a compound represented by the following general formula () based on the component in the diazo component or coupler component. A method for producing an azo pigment characterized by the following. General formula () [Chemical formula] (wherein Q: the residue of the diazo component represented by the following general formula () or the residue of the coupler component represented by the following general formulas () to ()) A: -SO ₂ NR ′− or −CONR′− (however,
R' represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. ) R ₁ .R ₂ : Each independently hydrogen atom, carbon number 1~
20 saturated or unsaturated alkyl groups, aryl groups or R ₁ .R ₂ represent a heterocycle containing nitrogen, oxygen or sulfur atoms. n: An integer from 1 to 4 l: An integer from 0 to ₇ [C] [C] [C] [C] [C] [C _] [C] independently a hydrogen atom, an alkyl group, a methoxy group,
Indicates a halogen atom, a sulfone group, and a nitro group. ))