JPH0441186B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an azo pigment composition that provides printing inks and paints for various uses, particularly excellent fluidity and non-agglomeration properties. Naphthol-based azo pigments are widely used in the production of printing inks, paints, etc. However, during storage of printing inks, for example, physicochemical interactions between the pigment and the solvents and binders present in the ink can lead to undesirable crystal growth and agglomeration of the pigment particles, resulting in increased viscosity and gelation of the ink. This has caused serious problems in practical use, such as deterioration of rheological properties, opacity, and color separation when mixed with other pigments. Conventionally, methods for solving this problem have included adding anti-aggregation agents and treating the surface of pigments with various resins and surfactants, but these methods have not been able to solve the above-mentioned drawbacks. Other solutions include carboxylic acid compounds obtained by phthalimidomethylation of naphthol AS and its hydrolysis, or sulfonic acids obtained by reaction with sulfuric acid, as seen in Japanese Patent Publication No. 44-18588. It has been shown that the use of compounds or their alkaline earth metal salts or organic amine salts can reduce the viscosity of printing inks and paints and prevent viscosity increases during storage.
It is not possible to significantly inhibit the crystal growth and agglomeration of pigment particles, and as a result, problems such as deterioration of rheological properties and blurring of color tone have not yet been satisfactorily solved. On the other hand, Japanese Patent Publication No. 55-10630 describes a method for improving the recrystallization stability of monoazo pigments in printing inks by combining them with a coupling component having an acidic group. It is difficult to say that sufficient improvements have been made. As a result of extensive research in order to solve the above-mentioned drawbacks of the conventional technology, the present inventors have developed a naphthol-based azo lake pigment () having a carboxylic acid group or a sulfonic acid group at the meta or para position relative to the amino group. The above drawbacks are solved by creating an azo pigment composition consisting of a metal salt or organic amine salt of a compound formed by coupling a diazonium salt of a benzene-based amine as a diazo component and β-oxynaphthoic acid as a coupler component. I have discovered what is possible. That is, an amino group has a carboxylic acid group or a sulfonic acid group at the meta or para position, and its benzene nuclear hydrogen atom is substituted with a substituent such as a halogen atom, hydroxyl group, nitro group, methyl group, or methoxy group. A metal salt or an organic amine salt () of a compound formed by coupling a diazonium salt of a benzene-based amine, which may be used as a diazo component, and β-oxynaphthoic acid as a coupler component, is used as Lake Red C (CI15585) or Brilliant Carmine 6B (CI15850). It has been found that the above drawbacks can be solved by mixing usually 0.5 to 20 mol %, preferably 1 to 10 mol %, with at least one azo lake pigment () selected from ) and Watch Young Gread (CI15865). . Note that when the carboxylic acid group or sulfonic acid group was located at the ortho position, no effect was observed at all. The reason for this is not clear, but it is presumed that the carboxylic acid group or sulfonic acid group loses its effect due to interactions such as hydrogen bonding with the adjacent azo group. To explain the present invention in more detail, the benzene-based amine having a carboxylic acid group or sulfonic acid group at the meta or para position used in the present invention is a known one, and examples of those having a carboxylic acid group include 4-aminobenzoic acid. acid, 3-aminobenzoic acid, 2-hydroxy-3-aminobenzoic acid, 2-
Hydroxy-5-aminobenzoic acid, 3-amino-
4-Hydroxybenzoic acid, 3-amino-4-methoxybenzoic acid, 3-amino-4-chlorobenzoic acid, 3-chloro-4-aminobenzoic acid, 2-chloro-4-aminobenzoic acid, 3-amino- 4-methylbenzoic acid, 2-nitro-4-aminobenzoic acid,
2-nitro-5-aminobenzoic acid, 3-amino-
Examples include 4-acetylaminobenzoic acid. On the other hand, as having a sulfonic acid group, 3-
Aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4-chlorobenzenesulfonic acid, 2-chloro-5-aminobenzenesulfonic acid, 2,5-dichloro-4-aminobenzenesulfonic acid, 3-amino- 4-hydroxybenzenesulfonic acid, 2-hydroxy-5-aminobenzenesulfonic acid, 2-hydroxy-4-aminobenzenesulfonic acid, 2-hydroxy-3-amino-5-chlorobenzenesulfonic acid, 3-methyl-
4-aminobenzenesulfonic acid, 3-amino-4
-Methylbenzenesulfonic acid, 2-methyl-4-
Aminobenzenesulfonic acid, 2-methyl-5-aminobenzenesulfonic acid, 2,4-dimethyl-5
-aminobenzenesulfonic acid, 2-methyl-3-
Chloro-5-aminobenzenesulfonic acid, 2-methyl-4-amino-5-hydroxybenzenesulfonic acid, 3-nitro-4-aminobenzenesulfonic acid, 2-nitro-4-aminobenzenesulfonic acid, 3-amino- 4-Hydroxy-5-nitrobenzenesulfonic acid, 2-hydroxy-3-nitro-5-aminobenzenesulfonic acid, 3-amino-
4-Methoxybenzenesulfonic acid, 2-methoxy-5-aminobenzenesulfonic acid, 3-methoxy-4-aminobenzenesulfonic acid, 2-methyl-
4-amino-5-methoxybenzenesulfonic acid,
2-Hydroxy-3-amino-5-methoxybenzenesulfonic acid, 3-acetylamino-5-aminobenzenesulfonic acid, 3-acetylamino-5
-Amino-6-hydroxybenzenesulfonic acid and the like can be mentioned. The carboxylic acid group and sulfonic acid group used in the present invention are preferably used after being insolubilized as a metal salt or an organic amine salt. Examples of metal salts include aluminum, zinc, manganese, etc., but alkaline earth metals such as calcium, barium, styrontium, and magnesium are preferred. The organic amine is not particularly limited, but is preferably an aliphatic primary amine represented by R- _NH2 (wherein R is an alkyl group having 8 to 24 carbon atoms). Specific examples include caprylamine, octylamine, laurylamine, and stearylamine. These metals or organic amines can be used in a stoichiometric ratio with respect to the acidic group, but may be used in excess or in excess. The method for producing the above () according to the present invention is carried out in an aqueous medium by a known method. That is, the benzene-based amine having a carboxylic acid group or sulfonic acid group at the meta or para position is converted into an equimolar amount of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, or an alkali metal carbonate such as sodium carbonate or potassium carbonate. After dissolving in water, acidify with more than twice the molar amount of acid such as hydrochloric acid, formic acid, acetic acid, etc., and heat at 5℃.
After cooling, the equivalent mole of sodium nitrite is added to complete the diazotization. On the other hand, β-oxynaphthoic acid was
The above-mentioned diazo component is gradually added to the coupler component, which is dissolved in water together with a mole or more of alkali metal hydroxide or alkali metal carbonate, and the coupling reaction is terminated. In particular, when the acidic group of the benzene-based amine is a carboxylic acid group, the compound is precipitated by acidifying the coupling liquid, so that its removal becomes easy. If the acidic group is a sulfonic acid group, it will precipitate by acidification, depending on the position of the sulfonic acid group and the type of substituent on the benzene amine. However, some compounds are in a dissolved state, so if the reaction solution is made alkaline. After that, it is desirable to make it insolubilized as a metal or organic amine salt. Of course, in the case of a carboxylic acid group, it is also possible to use a metal salt or an organic amine salt. Further, the coupling liquid may be heat-treated to improve the filterability of the produced compound or to promote conversion to metal salts or organic amines. Further, in this coupling reaction, various resins, surfactants and other additives can be added to the diazo component, to the coupler component, during coupling, and after coupling is completed. The compound () thus obtained is mixed with the naphthol azo lake pigment in a slurry state or in a dry state. According to this method, it is possible to arbitrarily mix the compound () according to the present invention with various pigments () according to a wide variety of printing inks and paints, so it is a general-purpose type, and unlike the mixing coupling method described below, it is not suitable for industrial use. This method is extremely suitable for producing pigments. The azo pigment composition of the present invention can also be produced by a method called mixed coupling. That is, the diazo component of the compound () is converted into a pigment ()
It is used in the coupling reaction with the diazo component. In addition, the composition of the present invention is not only a simple mixture, but also a mixture.
It also includes forms such as mixed crystals. The compound () is usually 0.5 to 20 mol%, preferably 1% to the naphthol azo lake pigment ().
~10 mol% is blended. Less than 1 mol%, especially less than 0.5 mol%, is less effective, 10 mol%, especially 20 mol%
If it exceeds this value, in applications such as printing ink, not only will it not be possible to obtain ink of a desired hue, but problems such as bleeding will likely occur. Note that the naphthol azo pigment () and the compound () may be blended in the manufacturing process of printing inks, paints, etc., depending on the case. Compared to azo pigments that are not mixed, azo pigment compositions produced by the above method suffer from decreased tinting power, changes in color tone, opacity, poor fluidity, and especially for long periods of time when used in printing inks and paints. The drawbacks of thickening and gelling problems that occur during storage are significantly improved. It has also been found that the pigment has improved fluidity as a pigment for water-based printing inks and water-based paints, and exhibits little increase in viscosity over time. As described above, the azo pigment composition of the present invention is an extremely useful azo pigment composition that can produce high-quality printing inks, paints, and the like. EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited by the Examples. Note that "part" or "%" in the text is based on weight. However, "mol%" is excluded. Example 1 3-methyl-4-aminobenzenesulfonic acid
18.7 parts are stirred with 400 parts of water and 4 parts of sodium hydroxide at room temperature for 30 minutes to completely dissolve. 35
After acidifying by adding 23 parts of % hydrochloric acid, 200 parts of ice was added,
Cool to 0-3°C. Add 7 parts of sodium nitrite dissolved in 50 parts of water and continue stirring at 5°C or lower for 1 hour to obtain the diazo component. Meanwhile, 19 parts of β-oxynaphthoic acid was added to 1000 parts of water and 8.5 parts of sodium hydroxide.
1 part, and 4 parts of sodium carbonate, stirred at room temperature for 20 minutes until completely dissolved, and this is used as the coupler component. After the diazo component was added dropwise to the coupler component over a period of 30 minutes, stirring was continued for an additional hour to complete the coupling reaction. The pH of the coupling liquid was 8.5. Next, 60 parts of a 10% calcium chloride aqueous solution was added, heated to 80°C, filtered, and washed with water to obtain a calcium salt. 80℃ in hot air circulation oven
The mixture was dried overnight to obtain 44 parts of red pigment. Example 2 In Example 1, manganese salt was used instead of calcium salt. Example 3 In Example 1, 33 parts of stearylamine acetate dissolved in water was added in place of the calcium salt to obtain an organic amine salt. Comparative Example 1 A coupling reaction was carried out in the same manner as in Example 1 using 3-methyl-6-aminobenzenesulfonic acid and β-oxynaphthoic acid to obtain a pigment made into a strontium salt. A pigment composition of the present invention in which 5 mol% of the pigments prepared in Examples 1 to 3 was mixed with Brilliant Carmine 6B,
Conventional pigments not mixed (Comparative Example 2) and Comparative Example 1
The pigment composition was dispersed in a polyamide vehicle for 20 hours in a ball mill. The pigment content of the dispersion at this time was 10%. When the obtained dispersion was aged for one month, the pigment composition of the present invention was significantly superior to those of the comparative example in terms of coloring strength, change in color tone, and transparency. Furthermore, as shown in Table 1, the pigment composition of the present invention had very good initial viscosity and viscosity after one month.

[Table] Example 4 16.7 parts of 3-amino-4-methoxybenzoic acid was added to water.
400 parts of sodium hydroxide and 4 parts of sodium hydroxide. Heat to 50° C. with stirring to completely dissolve. Add 23 parts of 35% hydrochloric acid to make it acidic, then add 200 parts of ice to make it zero.
Cool to -3°C. Add 7 parts of sodium sulfite dissolved in 50 parts of water and continue stirring at 5°C or below for 1 hour to obtain the diazo component. On the other hand, 19 parts of β-oxynaphthoic acid was added to 1000 parts of water,
Stir with 9.5 parts of sodium hydroxide at room temperature for 20 minutes until completely dissolved, and use this as the coupler component. Add 20% of the above diazo component to this coupler component.
After the dropwise addition, stirring was continued for an additional hour to complete the coupler reaction. In addition, the PH of the reaction solution is
It was 9.0. Then add 31 parts of barium chloride,
It was heated to 80°C to obtain a slurry containing 51 parts of pigment. Example 5 In Example 4, strontium salt was used instead of barium salt. The pigments prepared in Examples 4 and 5 were used as Lake Red C.
The pigment composition of the present invention mixed in dry or slurry form at 7 mol % and the unmixed conventional pigment (Comparative Example 3) were each dispersed in a nitrocellulose example vehicle using a ball mill. The pigment content of the dispersion at this time was 10%. When the obtained dispersion was aged for one month, the pigment composition of the present invention was superior to conventional pigments in terms of coloring strength, change in color tone, and transparency. Furthermore, as shown in Table 2, the pigment composition of the present invention had good initial viscosity and viscosity after one month.

[Table] Examples carried out in the same manner as Examples 1 to 5 are shown in Table 3 below. All of the obtained pigment compositions showed almost the same excellent properties even when combined with a naphthol-based azo pigment and in various vehicles.

【table】

[Table] Example 16 17.8 parts (95 mol%) of 2-amino-4-chloro-5-methylbenzenesulfonic acid, 2-methyl-5
- 0.9 part (5 mol%) of methylbenzenesulfonic acid,
with 400 parts of water and 4 parts of sodium hydroxide
Stir at 40°C for 30 minutes to completely dissolve. 35% hydrochloric acid
After adding 23 parts to make it acidic, add 200 parts of ice and make it 0.
Cool to -3°C. Add 7 parts of sodium sulfite dissolved in 50 parts of water and continue stirring at 5°C or below for 1 hour to obtain the diazo component. On the other hand, 19 parts of β-oxynaphthoic acid was added to 1000 parts of water,
The coupler component is obtained by stirring and dissolving the mixture with 8.5 parts of sodium hydroxide and 4 parts of sodium carbonate at room temperature for 20 minutes. The diazo component was added dropwise to the coupler component over a period of 30 minutes, and stirring was continued for an additional hour to complete the coupling reaction. then 10%
60 parts of calcium chloride aqueous solution was added, heated to 60°C, filtered, washed with water, and dried to obtain 44 parts of red pigment. Comparative Example 4 A comparative pigment is produced by the same method as in Example 16, except that the diazo component contains 2-amino-4-chloro-
18.7 parts of 5-methylbenzenesulfonic acid alone was used. Comparative Example 5 A comparative pigment is produced by the same method as in Example 16, except that the diazo component contains 2-amino-4-chloro-
18.7 parts of 5-methylbenzenesulfonic acid alone, 17.8 parts (95 mol%) of β-oxynaphthoic acid and 1 part (5 mol%) of 2-naphthol-3,6-disulfonic acid were used as coupling components. The pigments prepared in Example 16 and Comparative Examples 4 and 5 were dispersed in Santocemil in a styrene-acrylic acid copolymer aqueous solution resin varnish. The pigment content of the dispersion at that time was 15%. When the obtained dispersion was aged for one month, the water-based flexo ink using the pigment produced in Example 16 showed no change in coloring strength, color tone, Transparency was outstanding. In addition, the initial viscosity and the viscosity after one month were also extremely excellent.

Claims (1)

[Claims] 1 Lake Red C, Brilliant Carmine 6B,
A diazonium salt of a benzene-based amine having a carboxylic acid group or a sulfonic acid group at the meta- or para-position relative to the amino group is used as a diazo component for at least one naphthol-based azo lake pigment () selected from watch young pigments. , aluminum, zinc, manganese, calcium, barium, strontium, which is a compound formed by coupling β-oxynaphthoic acid as a coupler component,
0.5 to 20 mol% of at least one metal salt or organic amine salt selected from magnesium
An azo pigment composition. 2 For naphthol-based azo lake pigment (),
The azo pigment composition according to claim 1, which contains 1 to 10 mol% of the above (). 3. Any one of claims 1 to 2 in which the benzene nuclear hydrogen atom of the benzene-based amine is substituted with at least one substituent selected from a halogen atom, a hydroxyl group, a nitro group, a methyl group, and a methoxy group. The azo pigment composition according to. 4. The azo pigment composition according to claims 1 to 3, wherein the metal salt in () above is an alkaline earth metal. 5. The azo pigment composition according to any one of claims 1 to 3, wherein the organic amine salt in () above is an aliphatic primary amine. 6. The azo pigment composition according to claims 1 to 5, wherein the naphthol azo pigment () is a β-oxynaphthoic acid azo lake pigment.