JPS636060A - Production of azo lake pigment - Google Patents

Abstract

PURPOSE:To obtain the title pigment having excellent clarity, coloring power and gloss, by coupling diazonium salt of a naphthaleneamine with beta- hydroxynaphthoic acid in the presence of a specified compd. and forming a lake. CONSTITUTION:A diazo component (A) composed of diazonium salt of a benzeneamine having carboxyl or sulfo group at the m- or p-position against amino group, is coupled with a coupling component (B) composed of beta- hydroxynaphthoic acid in an aq. medium to obtain a compd. A diazo component (C) composed of diazonium salt of a toluene- or naphthaleneamine having sulfo group at the o-position against amino group is coupled with the component B in the presence of 0.1-20wt% said compd. at 10 deg.C or lower. At the time of coupling or after coupling, a lake is formed.

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 lake pigment, and more particularly to a method for producing an azo lake pigment that provides printing inks with excellent clarity, color strength, and gloss. Regarding the law.

(Prior art) A diazonium salt of a toluene-based amine or a naphthalene-based amine having a sulfonic acid group at the position ortho to the amino group is added to the diazo component 9, such as C acid (3-chloro-6-amino-p-)toluenesulfonic acid. ), 2B acid (4-chloro-6
diazonium salts such as -amino-m-)luenesulfonic acid), 6B acid (p-toluidine-m=sulfonic acid), and Tobiasic acid (2-amino-1-naphthalenesulfonic acid), etc.
Pigment 1 obtained by coupling with β-oxynaphthoic acid (BON acid), which is a coupler component, and forming a lake.For example, C, 1, Pigment Red 52 series pigment, Carmino 6B series pigment, Watchan Resodo series pigment, Bordeaux series pigment. , used in the production of printing inks and paints. The crystal form of these pigments tends to change under the influence of reaction conditions such as heat and pH during synthesis. For this reason, sharpness 9 coloring power,
For example, C, 1, Pigment Red 52 dye has multiple transition points in the range of 15 to 50°C, and its crystal form is unstable. There is remarkable crystal growth due to heat. In addition, the pigment after being made into a lake undergoes significant changes in hue, transparency, etc. due to transition and crystal growth.

Even if various conditions were investigated for the coupling and lake formation of C acid and BON acid dyes, it was difficult to obtain a vivid deep red pigment, and as the primary particle size increased due to crystal growth, the sharpness decreased and the color became yellow. In terms of hue, gloss, transparency, sharpness, and coloring power were insufficient.

Traditional methods to solve this problem have been mixed coupling using different types of pastes and different couplers, and surface treatment methods for pigments using various resins and surfactants.
These methods have not always been able to sufficiently solve the above-mentioned drawbacks.

(Problems to be Solved by the Invention) A diazonium salt of a toluene-based amine or a naphthalene-based amine having a sulfonic acid group at the position ortho to the amino group is used as a diazo component, and β-oxynaphthoic acid is coupled as a cuff puller component, To provide a method for producing an azo lake pigment which is obtained by forming a lake from a dye obtained at the same time or after coupling, and which has excellent hue, sharpness, coloring power, and gloss, and has good stability over time.

[Structure of the invention]

(Means for Solving the Problems) As a result of extensive research in order to solve the above-mentioned drawbacks of the prior art, the present inventors have developed a carboxylic acid group or a sulfonic acid group at the meta or para position to the amino group. In the presence of a compound (I) obtained by coupling a diazonium salt of a benzene-based amine having the following as a diazo component and β-oxynaphthoic acid as a cuff puller component, a toluene-based compound having a sulfonic acid group at the ortho position to the amino group is prepared. β-
It has been found that the above drawbacks can be solved by a method for producing azo lake pigment (II) in which oxynaphthoic acid is coupled as a coupler component and laked simultaneously or after the coupling.

That is, a compound CI) obtained by cuff-pulling a diazonium salt of a benzene-based amine having a carboxylic acid group or a sulfonic acid group at the meta- or para-position with respect to the amino group as a diazo component and β-oxynaphthoic acid as a coupler component, At least before the coupling of the azo lake pigment (II), the resulting azo lake pigment (II) is added to the diazo component and/or the coupling component.
It has been found that (2) is a pigment that is excellent in hue, sharpness, coloring power, and gloss, and has good stability over time.

The compound (I) of the present invention has a carboxylic acid group or a sulfonic acid group at the meta or para position to the amino group, and the benzene nuclear hydrogen atom is a substituent of a halogen atom, hydroxyl group, nitro group, or methoxy group. A diazonium salt of a benzene-based amine which may be substituted with is used as a diazo component,
This is a compound formed by coupling β-oxynaphthoic acid as a cuff puller component. Compound (I) may be formed into a lake depending on the case. Compound (I) is
C, 1, Pigment Red52. Brilliant Carmine 6B (C, 1, 15850).

Watch Young Red (C, 1, 15865).

9 applicable to β-oxynaphthoic acid type azo pigment represented by Bordeaux 10B (C, 1, 15880).

To explain the present invention in more detail, the benzene-based amine having a carboxylic acid group at the meta or para position used in the present invention is a known one.

4-aminobenzoic 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-
Examples include chloro-4-aminobenzoic acid, 3-amino-4-methylbenzoic acid, 2-nitro-4-aminobenzoic acid, 2-nitro-4-aminobenzoic acid, 2-nitro-5-aminobenzoic acid, etc. It will be done.

On the other hand, as those having a sulfonic acid group, 3-aminebenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid,
-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-aminol 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-aminebenzenesulfonic 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-5-7minobenzenesulfonic acid, 3-amino-4-methoxybenzenesulfonic acid, 2
-Methoxyl 5-aminobenzenesulfonic acid, 3-methoxy-4-aminobenzenesulfonic acid, 2-methyl-4
-Amino-5-methoxybenzenesulfonic acid.

Examples include 2-hydroxy-3-amino-5-methoxybenzenesulfonic acid, 3-acetylamino-5-aminobenzenesulfonic acid, and 3-acetylamino-5-amino-6-hydroxybenzenesulfonic acid.

The carboxylic acid group or sulfonic acid group of compound (I) is preferably a free acidic group. If necessary, metal salts can be used, and metal salts include aluminum, zinc, manganese, etc., but preferably alkaline earth metals such as calcium, barium, strontium, and magnesium. The metal 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 at the meta or para position is dissolved in water together with an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, or an alkali metal carbonate such as sodium carbonate or potassium carbonate.

Alternatively, it is dissolved in water by salt formation with an acid, then acidified with an acid such as hydrochloric acid, formic acid, or acetic acid. After cooling to 5° C. or lower, sodium nitrite is added to complete diazotization.

- On the other hand, a solution of BON acid and an alkali metal hydroxide or alkali metal carbonate in water is used as a coupler component, and the aforementioned diazo component is gradually added to the coupler component to terminate the coupling reaction. Alternatively, the coupling reaction can be similarly terminated by gradually adding this coupler component to the diazo component.

Free compounds can be separated from the reaction solution by acidifying the force amplifier solution or by salting out. In addition, in order to improve the filterability of the generated compounds,
The coupling liquid may be heat treated. In addition, in this coupling reaction, various resins may be present in the diazo component, in the Kafbler component, during coupling, or after the coupling is completed.

Surfactants or other additives may be added.

Compound (I) thus obtained is an azo lake pigment (II
) is added to the diazo component, coupler component, or both.

Compound (I) is 0.0% relative to Azo Lake pigment (II).
It is blended in an amount of 1 to 20% by weight, preferably 0.5 to 5% by weight. If it is less than 0.1% by weight, the effect is small (.

If it exceeds 20% by weight, not only will it be impossible to obtain an ink with a desired hue, but problems such as bleeding will likely occur. In addition, in the production process, it is preferable to produce compound (I) by previously adding excess BON acid, and then adding to the system a toluene-based amine or a naphthalene-based amine having a sulfonic acid group at the ortho position to the amino group. This is one example.

The azo lake pigment produced by the above method is a compound (
Compared to those produced in the absence of I), the disadvantages of reduced tinting strength, poor sharpness, reduced gloss, and opacity problems that occur when used in printing inks are significantly improved.

For example, C I formed by coupling a diazonium salt of 3-chloro-6-amino-p-toluenesulfonic acid as a diazo component and BON acid as a coupler component.
The crystals of Pigment Red 52 dye are extremely unstable and have several crystal transition points below 50°C. Usually, coupling is carried out at a relatively stable temperature of 10'C or below, and lacing is carried out at the same temperature (I0 ºC or below), or lacing is carried out by adding a laked metal to the diazonium salt in advance. . The pigment thus obtained is also unstable to heat like dyes, and when heated, crystals grow and the color changes significantly from deep red to orange. However, by carrying out the coupling and lake formation in the presence of the compound (I) of the present invention.

Such changes due to crystal transition, crystal growth, etc. are alleviated, and extremely excellent clarity, color strength, and gloss are achieved.

An azo lake pigment with good stability was obtained.

The above two azo lake pigments of the present invention are extremely effective azo lake pigments that can produce high quality printing inks and the like.

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 one example is based on weight.

Example 1 2.4 parts of 5-aminosalicylic acid are stirred with 100 parts of water and 5 parts of 35% hydrochloric acid at room temperature for 15 minutes to completely dissolve. Add 50 parts of ice and cool to 0 to 5°C. After adding 1.5 parts of sodium nitrite and stirring for 30 minutes at 8°C or lower, 3 parts of soda ash dissolved in 10 parts of water was gradually added to the solution, which was cleaved to pH 6-7. ). - direction.

155 parts of β-oxynaphthoic acid (BON acid) and 350 parts of water
0 parts of sodium hydroxide, 70 parts of sodium hydroxide, and 26 parts of rosin were stirred at 30°C for 20 minutes to completely dissolve them, and this was used as a cuff puller component. The above diazo component (i) was added dropwise to this coupler component over a period of 5 minutes, and stirring was continued for an additional 30 minutes to obtain compound (I). Note that this coupling liquid contains at least compound (I) and BON acid.

Further, 173 parts of 3-chloro-6-amino-p-toluenesulfonic acid (C acid), 2500 parts of water, and 34 parts of sodium hydroxide are heated to 90'C and stirred for 30 minutes to completely dissolve. After adding 185 parts of 35% hydrochloric acid for acid precipitation, 3500 parts of ice was added and the mixture was cooled to 0°C. 55 parts of sodium nitrite was dissolved in 200 parts of water, added all at once to the suspension, and stirred for 1 hour. Diazo component (ii) is prepared by gradually adding 10 parts of soda ash dissolved in 100 parts of water to adjust the pH to 6 to 7. This diazo component (ii)
, a coupling solution containing compound (I).

It takes 20 minutes to add the dye to 8-10'C.

Stir for 1 hour at pH 10-11. Calcium chloride 10
0 part was dissolved in 300 parts of water and added to -qi to form a lake. After stirring for 3 hours, heat to 80°C.

Calcium salt was obtained by filtration and washing with water. It was dried overnight at 80° C. in a hot air circulating oven to obtain 380 parts of a red compound.

Comparative example (by conventional method.
A comparison with the red compound prepared with BON acid and BON acid is shown in the table below.

The test method was to create an oil-based gravure or flexo ink using a nitrocellulose (NC), nitrocellulose and polyamide (NC+PA), nitrocellulose (flexo), or cyclized rubber binder, and then measure the viscosity, coloring power, and gloss. compared.

The viscosity is the reading value (25° C., cps) of a B-type rotational viscometer at a rotor rotational speed of 6.6 Orpm when taken out immediately after making 9 and after 1 month of aging. Coloring strength was measured using a color machine. The gloss was measured using a Suga Test Instruments digital variable angle gloss meter UGU-5D. (The coloring strength and gloss were measured at the time of removal.) Example 2 In Example 1, 1 to 5-aminosalicylic acid was replaced with
Compound using hydroxy-5-aminosulfonic acid (
I), and an azo lake pigment was obtained in accordance with Example 1 except for the following. Almost the same as in Example 1, it showed better results than the conventional product.

Example 3 An azo lake pigment was obtained in the same manner as in Example 1 except that part of the calcium salt was replaced with a strontium salt. Almost the same as in Example 1, it showed better results than the conventional product.

Example 4 1.2 parts of 5-aminosalicylic acid is stirred with 50 parts of water and 3 parts of 35% hydrochloric acid at room temperature for 15 minutes to completely dissolve. Add 30 parts of ice and cool to 0-5°C. After adding 1 part of sodium nitrite and stirring for 30 minutes at 8°C or below, a solution of 2 parts of soda ash dissolved in 5 parts of water was gradually added to adjust the pH.
The diazo component (i>) prepared in 6 to 7 was prepared by stirring 155 parts of BON acid with 4000 parts of water, 80 parts of sodium hydroxide, and 25 parts of rosin at 30°C for 20 minutes to completely melt it. This is used as a coupler component.The above diazo component (i) was added dropwise to this coupler component over a period of 5 minutes, and stirring was continued for an additional 30 minutes to obtain compound (I). Contains at least compound (I) and BON acid.

In addition, p-toluidine-m-sulfonic acid (6B acid) 15
0 parts, 3000 parts of water and 34 parts of sodium hydroxide in 5 parts.
Heat to 0°C and stir for 30 minutes.

Dissolve completely. Add 190 parts of 35% hydrochloric acid.

After acid precipitation, 2000 parts of ice is added and the mixture is cooled to 0 to 5°C. 55 parts of sodium nitrite was dissolved in 200 parts of water, added all at once to the suspension, and stirred for 1 hour to dissolve the diazo component (ii).
). Compound (I) is added to this diazo component (ii).
The coupling solution containing the dye was added over a period of 20 minutes, and the resulting dye was stirred at 10-15° C. and pH 10.5-11.5 for 1 hour. Dissolve 200 parts of calcium chloride in 300 parts of water and add to it to form a lake. After stirring for 1 hour, 80”
Heat to C.

Calcium salt was obtained by filtration and washing with water. The mixture was dried overnight at 80° C. in a hot air circulation type open air system to obtain 360 parts of a red compound. Almost the same as in Example 1, it showed better results than the conventional product.

Example 5 In Example 1, 4-chloro-
An azo lake pigment was obtained according to Example 1 except that 195 parts of sodium 6-amino-m-toluenesulfonate (sodium 2B acid) was used. Almost the same as in Example 1, it showed better results than the conventional product.

Example 6 An azo lake pigment was obtained in accordance with Example 1 except that Tobias' acid (2-amino-1-naphthalenesulfonic acid) was used in place of C acid. Almost the same as in Example 1, it showed better results than the conventional product.

Example 7 4.8 parts of 5-aminebenzenesulfonic acid and 200 parts of water,
Stir with 10 parts of 35% hydrochloric acid at room temperature for 15 minutes to ensure complete dissolution. Add 100 parts of ice and cool to 0-5°C. After adding 3.0 parts of sodium nitrite and stirring at 8°C or lower for 30 minutes, 6 parts of soda ash dissolved in 20 parts of water was gradually added to adjust the pH to 6-7. ). - 155 parts of BON acid to 3500 parts of water
Department.

30°C with 70 parts of sodium hydroxide and 26 parts of rosin
, stirred for 20 minutes to completely dissolve, and use as a coupler component. The above diazo component (I) is added to this coupler component.
After dripping for 5 minutes.

Stirring was continued for an additional 30 minutes to obtain Compound (I). Note that this coupling liquid contains at least compound (I) and BON acid.

Further, 195 parts of 2B acid soda and 3000 parts of water were heated to 90°C and stirred for 30 minutes to completely melt them. After adding 185 parts of 35% hydrochloric acid for acid precipitation.

Add 3000 parts of ice and 200 parts of calcium chloride and cool to 0°C. A suspension of 55 parts of sodium nitrite dissolved in 200 parts of water was added all at once and stirred for 1 hour. This 2
The mixture was stirred for 1 hour at 20-25"C1p H9-10 for 0 minutes. Thereafter, it was heated to 80°C, filtered, and washed with water to obtain a calcium salt.

The mixture was dried overnight at 80°C in a hot air circulation oven to obtain 380 parts of a red compound. Almost the same as in Example 1, it showed better results than the conventional product.

Claims (1)

[Scope of Claims] 1. 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, and β-oxynaphthoic acid is coupled as a coupler component. Compound (I)
A diazonium salt of a toluene-based amine or a naphthalene-based amine having a sulfonic acid group at the position ortho to the amino group is used as a diazo component, and β-oxynaphthoic acid is coupled as a coupler component, and simultaneously or simultaneously with the coupling. A method for producing an azo lake pigment, which is characterized in that it is later made into a lake. 2. Compound (I) is 0.1
A method for producing an azo lake pigment according to claim 1, wherein the azo lake pigment is present in a proportion of up to 20% by weight.