JPS58183756A - Preparation of azo pigment - Google Patents

Abstract

PURPOSE:To obtain an azo pigment having improved brightness of hue, gloss, bleed resistance and migration resistance in high yield, by pulverizing an alkaline aqueous suspension of a coupler under wet conditions, and reacting the resultant coupler solution with a diazo component. CONSTITUTION:A coupler component, e.g. Naphthol AS, is added to an alkaline aqueous solution in an amount of preferably 5-10 times of that of the coupler component to give a coupler solution in the suspension state, and the resultant coupler solution is then previously mixed preferably in a homomixer, etc. and pulverized in a wet pulverizer. The resultant coupler solution is then reacted with a diazo component to afford the aimed azo pigment.

Description

[Detailed description of the invention] The present invention relates to a new method for producing azo pigments.

Conventionally, insoluble azo pigments, especially naphthollend type forces of insoluble azo pigments, when preparing the puller component, for example, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metals such as sodium carbonate and potassium carbonate, etc. Kaede carbonate and basic compounds such as ammonia are dissolved in water or hot water (hereinafter abbreviated as aqueous alkaline solution), and 7-tall As is added thereto and dissolved by heating to high temperature (50 to 100°C)! A method is known in which a diazo component is subjected to a coupling reaction with a diazo component.

However, the conventional force and puller adjustment method requires force.

In order to dissolve the blur, it is necessary to heat it to a high temperature in an alkaline aqueous solution, which removes the force and causes hydrolysis of the plastic components. ,) produces large amounts of by-products, paints,
When used for coloring printing inks, plastic snacks, pigment textile printing, etc., this by-product often causes problems such as blurred hue, low F gloss, and bleeding or migration. In addition, due to the poor wetting ability of the aqueous alkaline solution, when the puller component is dissolved, a large amount of lumps that are not converted to alkali metal chloride or ammonium chloride are generated, and the coupling reaction in this part does not proceed, resulting in serious problems in terms of quality and yield. I failed.

In order to solve the above-mentioned drawbacks of the prior art, the present inventor has made intensive research and found that when adjusting the force and blur component of an insoluble azo pigment, especially the naphthol red type of an insoluble azo pigment, The coupler liquid, which is added to an alkaline aqueous solution at room temperature or near room temperature and is in a substantially suspended state, is ground using a wet grinder, and at the same time as the alkali or ammonium chloride of 7-L is ground, its fineness is ground down. It was discovered that a pigment obtained by a force-flinder reaction with a diazo component is a pigment that overcomes the above-mentioned drawbacks [7] The present invention has been accomplished.

That is, the present invention uses force, force in which the puller component is substantially suspended in an alkaline aqueous solution at room temperature or around room temperature, and fine force obtained by pulverizing the puller liquid with a wet grinder. , relates to a novel method for producing azo pigments in which a puller component is reacted with a diazo component.

The pigment produced in accordance with the present invention 1.' is a safthollenoid series of insoluble azo pigments, which is combined with #
Examples of the cassolar components include nuts A and S, such as 3-hydroxy-2-naphthoanilite, 4'-
Chloro-3-hydroquine-2-naphthoanilide, 3'
-chloro-3-hydroxy-2-naphthoanilide,
3-hydroxy/-3'-nitro-2-naphthoanilide, 3-hydroxy-4'-nitro-2-naphthoanilide, 3-hydroxy-2-nando-〇-)luidide,
3-Hydroquine-2-naphtho-P-)luidide, 4'
-Chloro-3-hydroxy-2-naphtho-0-toluidide, 5'-chloro-3-hydroxy-2-naphtho-0
-Toluidide, 3-hydroquine-2-naphtho-2,4
xylidide, 3-hydroxy-2-naphtho-0-anindite, 5'-chloro-3-hydroxy-2-nano1
．． -0-anisidide, 3-hydroxy-2-naphtho-
P-anindite, 3-hydroxy/-2'methyl-2-
Naphtho-p-anindite, 4'-chloro-3-hydroxy-5'-methyl-2-naphtho-0-anindite,
3-Hydroquine-2゛,5'-,;Memetokki/-2-
Naphthoanilide, 5''~riLJO-3-human(]]g-2,4'->:methoxy/-2-naphthoanilide, 4-chloro-3-vitroquine-2',5'-dime).
xy-2-natuaninide, 3-=hydroxy 2
-Capto-〇-Fuefute, Daito, 3-Hydroquine-2
-naphl--P-7 ezidide, 3-hydrogine-N-1-naphthyl-2-naphthamide, 3-hydroquine-N-2-naphthyl-2-naphthamide, and the like.

To explain in detail one example of the power of the present invention and the puller adjustment method, 1 mole of the coupler component such as naphthol AS as mentioned above (
(On the other hand, in a tank equipped with a stirrer, 1.
5 to 4 moles, preferably 2 to 3 moles by 11°, of alkali metal hydroxide, alkali metal carbonate or ammonia are dissolved.

At this time, the temperature of the liquid will rise with some heat generation, but after cooling to room temperature or around room temperature, gradually add the Kagura ingredient while stirring to make it uniform □! vl Shu l night (
slurry liquid). In addition, the naphile A used for this
The cuffler component such as S type is usually a powder, but it may also be a powder containing water or the like. Alternatively, the coupler component and the f/I potash aqueous solution may be simply mixed. - Leave it as -. Next, in order to use the force generated in the above operation to break up the lumps of the puller components and at the same time make them fine, they are ground using a powerful wet grinder such as a super mill, sand mill, attritor, ball mill, or high-speed stone mill.
A coupler liquid finely divided to 25 μm or less is obtained. This power.

Fuller's solution may be used as is for the next camping reaction, but the quality of the resulting pigment is better if it is diluted with water to a concentration of preferably 2 to 7% by weight and then reacted. .

The above-mentioned preparation (the Kaglar component is subjected to a campling reaction with the diazo component in accordance with the conventionally known manufacturing method of insoluble ano pigments, and the yield is higher than that of the pigment obtained by the conventional force and buller heating method. High-quality pigments can be obtained at low yields.

Of course, this force, in the diazo component in the pulling reaction,
Various resins, surfactants, and other additives may be added to the fuller component, during coupling, and after cuffing.

The pigments obtained by the method of the present invention as described above can be used in paints such as amino alkyd resin baking paints, alkyd resin air-dry paints, acrylic resin paints, nitrocellulose lacquer paints, gravure inks such as publishing gravure and packaging gravure, and off-cent inks. It is suitable for coloring plastics such as , polyvinyl chloride, various polyethylenes, and poly-10-pyreno, and for coloring pigment printing. When used in these applications, compared to pigments produced using conventional methods, it exhibits excellent hue clarity, gloss, and coloring power, and is particularly suitable for 7" in bleed resistance and migration resistance. Heat resistance, weather resistance, chemical resistance, etc. (r1 Equivalent to pigments obtained by conventional methods, no problems at all.

As described above, according to the method of the present invention, the target pigment can be obtained in a very high yield, and the hue sharpness, which is a drawback of the conventional method, can be improved.
Since gloss, bleed resistance, and migration resistance are improved, this method is suitable as an industrial method for producing azo pigments.

The present invention will be specifically explained below with reference to Examples, but the present invention is not limited by the Examples. In addition, in the text “
"Parts" and "%" refer to parts by weight and 1 inch by weight.

Example 1 1800 parts of water is placed in a tank equipped with a stirrer, and 100 parts of sodium hydroxide is dissolved therein. After cooling, 357 parts of 5'-chloro-3-hydroxy-2',4'-dimethoxy/-2-naphthoanilide was gradually added and stirred for 30 minutes to obtain a homogeneous coupler liquid. Next, this coupler liquid was passed through a small sand mill to obtain finely divided 5'-chloro-3
The sodium salt of -hydroxy/-2',4'-dimethoxy-2-naphthoanilide is obtained. Add 5,600 parts of water to this to adjust to a 5% solution. On the other hand, 0-Aninji-2・-4-
35% hydrochloric acid 28% to 258 parts of sulfone diethylamide
After stirring and dissolving with 0 parts and 5000 parts of ice water, an aqueous solution of 70 parts of sodium nitrite dissolved in 400 parts of water was added to diano.

The Kuffler solution was added dropwise to the Ich solution, and the reaction was completed at 7°1. The mixture was heated at 80° C., filtered, washed with water, and dried to obtain 623 parts of the pigment of the present invention (yield: 99.5 qb).

Comparative Example 1 A Kuffler solution was prepared in the same manner as in Example 1 by dissolving 5-chloro-3-hydroquine-214'-dimethoxy-2-naphthoanilide in the same aqueous alkali solution as in Example 1 heated to 90 to 95°. A force and bling reaction was performed with the diazo component to obtain 608 parts of a comparative pigment (yield 97%).

Example 2 In a tank equipped with a stirrer, 1000 parts of water are charged and 50 parts of potassium hydroxide are dissolved therein. After cooling, 1315 parts of 3-hydroxy-2-naphthohydride was stirred for 20 minutes to form a slurry solution with uniform force. Next, it was passed through a high-speed stone mill to form a finely divided 3-hydroxy - Obtain the potassium salt of 2-naphthoanilide. Add 1,630 parts of water to this to make a 5% solution. Meanwhile, 76 parts of 2-methyl-5-nitroaniline are stirred with 200 parts of 35% salt powder and 4,000 parts of ice water. After dissolving, 35 parts of sodium nitrite dissolved in 200 parts of water is added to a bath for diazotization. The above diazotized solution is added dropwise to complete the canogling reaction. After heating to 85°C, filtration and washing with water are carried out. , and dried to obtain 216 parts of the pigment of the present invention (yield: 99%).

Comparative Example 2 3-
A coupler in which hydroxy-2-naphthoanilide was dissolved and 2-, methyl-5-nitroaniline were prepared by a conventional method and mixed with fc and diazo components to obtain Comparative Pigment 2.
13 parts are obtained (975% yield).

Example 3 In a tank equipped with a stirrer, 1300 parts of water was charged and 60 parts of sodium carbonate was dissolved therein. After cooling, 3-hydroquine-2
-131 parts of naphtho-P-phenetidide was gradually added and stirred for 40 minutes to obtain a homogeneous coupler liquid. Next, the finely divided 3-hydroxy-2-
Obtain the sodium salt of naphtho-P-phenetidide.

Add 3000 parts of water to dilute this to make a 3% solution. On the other hand, 109 parts of 5-benzamido-aninodine was added to 35%
After stirring and dissolving with 135 parts of hydrochloric acid and 5,000 parts of ice water, an aqueous solution of 315 parts of sodium nitrite dissolved in 180 parts of water was added to diazotize. This diazotized liquid is dropped into the coupler to complete the coupling reaction. 90℃
After heating at t, filtering, washing with water, and drying, the pigment of the present invention
5 parts are obtained (yield 99 g).

Comparative Example 3 3-
Hydroxy/-2-naphtho-P-phenotidide is bath-dissolved and 7-hikatsufura and 5-benzamido-0-anisidine are canonolated with a diazo component prepared by a conventional method to obtain 246 parts of a comparative pigment (yield 98%). .

The pigments obtained in Examples 1 to 3 and the pigments of Comparative Examples 1 to 3 were comparatively tested by the following method.

Head Amino alkyd baking paint test Enamelled primary color paint was adjusted to spray viscosity with a solvent, applied to a tin plate, and after baking, hue clarity and gloss were compared. In addition, a part of the coated plate was overcoated with an amino alkyd white paint whose viscosity was adjusted to spray, and after baking, the degree of bleeding into the overcoated area was observed. Next, the ratio of the red pigment in the primary color enamel to the white (TiO2) pigment in the white coating material is 1.
Enamels were mixed in a ratio of 10 to 10, and the tinting power of each was compared.

(2) Publication gravure ink test Primary color inks made with publication gravure varnish were diluted with a solvent to printing viscosity and printed on Ace paper to compare hue clarity and gloss. The above-mentioned printed matter was placed in close contact with the gelled soap, a load was applied, and the printed matter was kept at 50° C. for 3 days, and the degree of brining of the ink onto the soap gel was observed. Next, the inks were mixed so that the ratio of the red pigment in the primary color ink to the white pigment in the white ink was 1:10, and the coloring power of each was compared.

■ Polyvinyl chloride test Color kneaded with softener, 150 ~ on two rolls
After kneading into a polyvinyl chloride compound gelled at 155°C and taking it out, it was kneaded at a temperature of 160-165°C for 15
A dark tone was created by applying a load of 9/ffl to 0, and the hues were compared.

The shredded density sort was placed in close contact with a white sheet, and a load was applied to it and held at 70°C for 24 hours, and color transfer to the white sheet was observed. Next, a color and a white patch color were kneaded into a polyvinyl chloride compound so that the ratio of red pigment to white pigment was 1:1O, and a light colored sheet was prepared using the above method and the tinting power was compared.

The test results are shown in Table-1. Judgment is in 3 stages (3 characters represent the test results of the pigment of the comparative example.

1

Claims (2)

[Claims] (1) Production of an insoluble azo pigment characterized by pulverizing a suspension of a coupler component in an alkaline aqueous solution and a puller solution using a wet grinder, and reacting the resulting coupler solution with a diazo component. Method. (2) The method for producing an insoluble azo pigment according to claim 1, wherein the coupler component is naphthol AS.