JPS58147458A - Preparation of azo dye - Google Patents

Abstract

PURPOSE:To prepare an azo dye having high coloring power and clear color tone, and useful for the coloring of rubber, by coupling a tetrazotized 3,3'-dichlorobenzidine with a specific acetoacetanilide compound. CONSTITUTION:Tetrazotized 3,3'-dichlorobenzidine is coupled with an acetoacetanilide compound (e.g. acetoaceto-o-toluidide) 1-50mol% of which is substituted with the compound of formula (R is H, methyl, ethyl, etc.) (e.g. 4-acetoacetaminophthalimide).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing disazo pigments useful for various uses, particularly for coloring rubber materials.

K rice, λ31-. Diazo pigments obtained from dichloroben, zidine, and various acetoacedoanilide compounds are
It is widely used for coloring rubber, paints, printing inks, etc. However, when used for coloring rubber, for example, it has the disadvantage that the coloring power decreases significantly when the rubber is vulcanized, and the color tone becomes unclear. There is.

Furthermore, when used in printing ink, it has the disadvantage that it loses its coloring power due to heating during flushing.

In order to improve these shortcomings,
No. 26, No. 47-50767, 1453-35090
No. 55-10630, No. 55-49087, and Japanese Unexamined Patent Publication No. 53-AIS2Z, etc. have been proposed.
Furthermore, the improvement in heat resistance during flushing is not satisfactory.

As a result of intensive research in order to solve the above-mentioned drawbacks of the prior art, the present inventors have discovered that if an acetoacedoanilide compound containing a specific compound is used as a coupling component when producing a disazo pigment, it is possible to obtain We have discovered that the disazo pigment obtained in this way is a pigment that has solved the above-mentioned drawbacks, and that the pigment thus obtained is also a very improved pigment for paints and stamp inks. The invention is complete.

That is, the present invention provides a method for producing an azo pigment, which comprises coupling a tetrazotized product of 3,3-dichlorobenzidine to an acetoacedoanilide compound,
This is a method for producing a disazo pigment, characterized in that about 1 to 50 moles of the acetoacedoanilide compound is substituted with a compound represented by the following general formula (I).

(However, the lice in the formula are a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, and a phenyl group which may have a substituent.) To explain the present invention in detail, in the present invention The 3-dichlorobenzidine and the acetoacedoanilide compound having no carboxyl group, sulfonic acid group or hydroxyl group to be used are known.For example, as the acetoacedoanilide compound, acetoacedoanilide, O-chloroacetoacedoanilide, P-chloroacetoacedoanilide, 4-chloro-2,5-dimethoxyacetoacedoanilide, 2,4-dimethoxyacetoacedoanilide, O-acetoacedoanilide Dite, 0-acetoacetotoluidide, 2,4-a7toacetoxylidide, P-acetoacetoanidide), P-acetoacetotoluidide, 4-chloro-2-methyl-acetoacetoanilide , P-ethoxyacetoacedoanilide, 4
-Nitro-2-methylacetoacedoanilide, 4-acetoacetaminophthalimide, 5-acetoacetaminobenzimidacylone, 4-benzoylamino-2,5
-diethoxyacetoacedoanilide, 4-acetylaminoacetoacedoanilide, etc. are used.

The compound represented by the general formula (I) to be used in combination with the above-mentioned known acetoacedoanilide compounds is, for example, a compound known from Japanese Patent Publication No. 41-2190 published by the applicant of the present application. The compound is about 0.0.1 mol per mole of the acetoacedoanilide compound described above. O1 mol~
It is used in a ratio of about i, o mole, preferably about 0.03 mole.

A method for producing a disazo pigment using the above raw materials can be carried out in accordance with a conventionally known method for producing a disazo pigment. That is, 3,3'-dichlorobenzidine is tetrazotized according to a conventional method, and a submerged liquid is prepared according to a conventional method using a mixture consisting of the compound of the above-mentioned general formula (1) and an acetoacedoanilide compound. However, by mixing and coupling the two in accordance with a conventional method, a disazo pigment with improved heat resistance can be obtained by the present feathering method. Of course, pigment treatment can be carried out by adding various water-soluble resins, surfactants, and other additives during or after coupling.

The disazo pigment obtained by the method of the present invention as described above is
Compared to conventional disazo pigments, it has a clearer appearance, etc.
In addition, while conventional disazo pigments and disazo pigments prepared by the method described in the cited publication suffer from a significant decrease in coloring power and dullness of color when coloring rubber, the disazo pigment according to the present invention overcomes these drawbacks. . Also,
The disazo pigments according to the invention are also highly improved for use in paints and printing inks. In other words, when disazo pigments are used in paints or printing inks, the pigment is transferred from an aqueous pigment paste to an organic phase by a flushing process, but with conventional disazo pigments, pigment particles grow during this flushing process. Although a significant decrease in coloring power occurred, the disazo pigment according to the present invention does not exhibit any defects such as pitting even when the operating temperature increases during flushing, and is superior to the disazo pigment produced by the method described in the cited publication. It provides printing ink and paint.

Next, the present invention will be specifically explained with reference to Examples.

Note that "Fi-" in the middle of the text is based on the @ part weight unless otherwise specified.

Example 1 17.6 parts of 3.31-dichlorobenzidine is tetrazotized according to a conventional method to obtain a tetrazonium salt solution.

On the other hand, 27.0 parts of acetoaceto-〇-toluidide,
Prepare a subsoaking solution using 1.5 parts of 4-unit acetoacetaminophthalimide according to a conventional method. Both solutions were mixed and coupled, and the resulting pigment was subjected to V-filtration, water washing, drying, and pulverization.
41.0 parts of the disazo pigment of the invention were obtained.

1 part of the above pigment, 0.9 part of rubber, 0.1 part of stearic acid, and 100 parts of the following compound were added at a roll surface temperature of 20 parts.
Kneaded 10 times on 8-inch mixing rolls with a roll spacing of 1.0° C. at ~50° C. (The product thus obtained is referred to as a dark crepe). Five parts of this dark-colored crepe and 50 parts of the following compound were kneaded through 109 J in the same manner as above to prepare a light-colored crepe. 160 parts of this light-colored crepe were heated at 1°C, 200 cm - 1 thickness, and 20
After vulcanization for a minute, a vulcanized rubber sheet with a clear and deep color was obtained. Pigment Yellow 1 for comparison
4 (Kame s'-dicoolopenzidine and acetoacetate-o
When the disazo pigment synthesized from -4 luidide) and the disazo pigment according to Japanese Patent Publication No. 55-49087 were similarly tested in place of the pigment according to the present invention, in this case, the coloring strength was significantly reduced, and the color was dull. A colored rubber sheet was obtained.

Note 8BR $1507 31. Q part zinc service
1.0 parts stearic acid 04 parts light calcium carbonate 31.0 parts 10G titanium
4.0 parts vulcanization accelerator
1.2 parts sulfur 1.0 parts Example 2 27.0 parts of acetoaceto-P-)luidide was used in place of acetoaceto-0-)luidide in Example 1, and the rest was the same as in Example 1. As in Example 1, a disazo pigment with good heat resistance was obtained.

Example 3 17.6 parts of 3.3-dichlorobenzidine was tetrazotized according to a conventional method to obtain a tetrazonium salt solution.

On the other hand, ace) 1 vomit) -o-toluidide 27.0
After adjusting the pH to 0 to 6.0 with acetic acid in accordance with a conventional method, 1.5 parts of 4-acetoacetaminophthalimide is added to prepare a submerging solution. Hereinafter, similarly to Example 1, [7
As in Example 1, a disazo pigment with good heat resistance was obtained.

Example 4 17.6 parts of 3.3'-dicoubenzidine is tetrazotized according to a conventional method to obtain a tetrazonium salt solution.

On the other hand, from 24.7 parts of acetoacetoanilide and 4-acetoacetoacetate (7), prepare the solution using the usual method. The pigment was washed with water, and a solid content of 4 was obtained.

Comparing the color power, heat resistance and two-values of ζO arrogance-ktlA family, ζO 餉family, and ζO 錉family with the known opiiss family, ζRO following No. illowi Zhu is lI9 .

Iris 1111 Coloring strength Heat resistance 2 1 Example 40 pigment RO 1 No change jl
Li known face II) 3... changes to 中中ふ逓＠ 11 known pigment S --- I is lazy
Known Pigment 1 in Table 1 above is Mitsuruho's Vidament A 1), and Known Pigment 1 is Example 404-Acetoacetate Nofuruid ζ and is replaced with Acetoacetacetane Fluid 111L. There is a II meeting layer and the rest is Example 4 and ti.
141 and Tokumaru Noodle Department (for example, Tokuko Sho 55-49087
Publication No. 3), and the known pigment 3 is acetoacedoanilide L-2 in place of the above-mentioned 2-acetoacetaminobenzoic acid.
- using 1.8 parts of methoxy-5-carboxamide (
%).

In addition, for performance evaluation, a water-containing press cake containing 44.2 parts of each pigment was added to 300 parts of an offset ink face, and flushing was performed while mixing at a temperature of 60°C or less in a flasher to remove separated water. This ink was spread on black art paper and heat-treated at 200℃ for 60 seconds to observe changes in color tone, tinting strength, transparency, etc. to evaluate heat resistance. Flow values were created using a spread meter (manufactured by Toyo Seiki, load (acrylic) 11!F, sample volume 0.5 cc) using the inks, and the coloring strength was determined by diluting each ink above with titanium white ink. It was determined that The dilution ratio for the four companies is as follows.

The ink according to Example 4 was diluted with 14 parts of white ink and the ink with Known Pigment 1 was diluted with 10 parts of white ink and Known Pigment 2.
．． Diluted with 1 part of white ink according to Example 5. Diluted with 1 part of white ink according to Example 5. Diluted with 1 part of white ink. Similarly to Example 4, a disazo pigment with good tinting strength and heat resistance was obtained.

Example 6 In place of 4-acetoacetaminophthalimide in Example 4, 0.2 part of 4-acetoacetamino-N-ethylphthalimide was used, and in the same manner as in Example 4 of another company,
As in Example 4, a disazo pigment with good tinting strength and heat resistance was obtained.

Patent applicant: Dainichiseika Chemical Industry Co., Ltd.

Claims (1)

[Claims] 3. A method for producing an azo pigment comprising coupling a tetrazotized product of 31-dichlorobenzidine to an acetoacedoanilide compound, wherein about 1 to 50% of the acetoacedoanilide compound is Molch is the following general 2°
(Method for producing a disazo pigment characterized in that it is substituted with a compound represented by )