JPS59232148A - Disazo pigment composition - Google Patents

Abstract

PURPOSE:To provide the titled compsn. which is excellent in clarity and does not lose tinting power even when heated, by coupling a tetrazo compd. of 3.3'- dichlorobenzene with an acetoacetanilide compd. substituted with a specified compd. CONSTITUTION:A grounding soln. of each of the tetrazo compd. of 3.3'-dichlorobenzene and an acetoacetanilide compd. substituted with 0.5-20mol% of a compd. of the formula (wherein R1 is one or more H, methyl, ethyl, methoxy, nitro, halogen, ethoxy; R2, R3 are each H, methyl, ethyl; n is 1,2), such as 2- acetoacetaminophenylurea, is prepd. by a conventional method. Both solutions are mixed together by a conventional method to effect a coupling reaction, thus obtaining a disazo pigment compsn.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a disazo pigment composition, and an object of the present invention is to provide a novel disazo pigment composition useful for various uses, such as printing inks, paints, etc., and particularly as a pigment for paper gravure inks. do.

Conventionally, disazo pigments obtained from dichlorobenzidine and acetoacedoanilides have been widely used as pigments for gravure inks, but when printing on paper with gravure inks containing these pigments, the ink changes to the paper. It has the disadvantage that it soaks in heavily and the gloss and coloring power of the printed surface are poor, and this disadvantage becomes more pronounced as the paper used becomes lower grade. In addition, the above-mentioned disazo pigments are widely used in paints and other printing inks, but they have the disadvantage that, when used in printing inks such as offset inks, they lose their coloring power due to heating during flushing. .

In order to improve these shortcomings,
26, No. 47-50767, No. 53-35090, No. 55-10630, No. 55-49087, Japanese Patent Application Laid-Open No. 53-41322, etc., but these methods However, this does not provide any improvement as a pigment for gravure ink, and the improvement in heat resistance during flushing is also not satisfactory.

The present inventors have discovered that a disazo pigment composition substituted with a compound that solves the drawbacks of the prior art as described above is a highly improved pigment that can be used not only as a pigment for gravure inks but also for paints and other printing inks. The present invention was completed based on this knowledge.

In other words, the present invention provides a disazo pigment obtained by coupling a tetrazotized product of 3,3-dichlorobenzidine to an acetoacedoanilide compound, wherein the acetoacedoanilide compound contains about 0.5 to Disa characterized in that 20 moles are substituted with a compound represented by the following general formula (I) (wherein R1 is one or more hydrogen atoms, methyl group, ethyl group, methoxy group, nitro group, halogen atomic size, ethoxy group, R2 and R3 are hydrogen atoms, methyl groups, or ethyl groups, n is 1 or 2. Use 3
, 3'-dichlorobenzidine, and acetoacetoanilide compounds other than the compound of general formula (I) are known, for example, acetoacetoanilide, 0-chloroacetoacetoanilide, P-chloroacetoacetoanilide. Doanilide, 4-chloro-2,5-dimethoxyacetoacetanilide, 2,4-dimethoxyacetoacetanilide, 0
-acetoacetoanididite, 0-acetoacetotoluidide, 2.4-acetoacetoanilide, P-acetoacetoanidide, P-acetoacetotoluidide,
4-chloro-2-methyl-acetoacedoanilide, P
-ethoxyacetoacetanilide, 4-nitro-2-
Methylacetoacetoanilide, 4-acetoacetaminophthalimide, 5-acetoacetaminobenzimidacylone, 4-benzoylamino-2,5-diethoxyacetoacetanilide, 4-acetylamino-acetoacetoanilide etc. can be mentioned.

Examples of the compound represented by the general formula (■) for substituting part 0 of the above-mentioned known acetoacedoanilide compound include 2-13- or 4-acetoacetaminophenyl urea, 2-. Particularly preferred are 3-"t- or 4-acetoacetamino-P-, m-, 4- or 0-phenylene diurea and their methyl, ethyl, methoxy, nitro, nitrogen, and ethoxy substituted products. The most aggressive is 4-acetoacetaminophenyl urea.Such a compound contains about 0.5 to about 20 moles, preferably about 1.0 mole, of the aforementioned acetoacedoanilide compounds.
About 10 molar proportions are substituted.

The method for producing the disazo pigment composition of the present invention using the above raw materials can be carried out in accordance with conventionally known methods for producing disazo pigments. That is, 3.3'-dichlorobenzidine is tetrazotized according to a conventional method, and a subsoaking solution is prepared according to a conventional method using a mixture consisting of the compound of the above-mentioned general formula α) and an acetoacedoanilide compound,
By mixing and coupling the two in a conventional manner, a disazo pigment composition with improved heat resistance can be obtained by the method of the present invention. In addition, in the above method, the general formula (■
2 of the diacetoacedoanilide type compound by the compound of )
After carrying out a coupling reaction in the same manner with 0 mole or more substitution, a disazo pigment obtained without substituting the compound of general formula (I) is mixed therewith to adjust the usage ratio of the compound of general formula (I). 0.5 to 20 of acetoacedoanilide compounds
The same effect can be obtained even if the disazo pigment of the present invention is prepared by preparing a disazo pigment using only the compound of the general formula (D) in advance and mixing it with a general disazo pigment in a predetermined ratio. If such a post-mixing method is used, the pigments to be mixed are preferably in a pre-dried state.

The pigment composition of the present invention as described above is subjected to pigment treatment by adding various aliphatic amines, various water-soluble resins, surfactants, and other additives according to known methods during or after coupling. You can also do this. In particular, during or after the coupling, about 1 to 25 parts by weight per 100 parts of pigment of long-chain aliphatic amines, such as tallow alkylamines, tallow alkylpropylene diamines,
By performing pigment treatment by adding alkylhydroxypropylene diamine, dialkyl diethylene triamine, etc., various performances of the pigment composition obtained in the present invention in inks, paints, and other media are improved.

The disazo pigment composition obtained by the method of the present invention as described above has a sharpness equivalent to that of the conventional disazo pigment, and the conventional disazo pigment and the disazo pigment prepared by the method described in the cited publication are more suitable for gravure. The disazo pigment composition according to the present invention overcomes the above-mentioned drawbacks when used in inks. The disazo pigments according to the present invention are also greatly improved for use in paints and printing inks such as offset inks.

In other words, when disazo pigments are used in paints and printing inks, the pigment is transferred from an aqueous pigment paste to an organic phase by a flushing method, but with conventional disazo pigments, pigment particles grow during this flushing operation, resulting in coloring. However, the disazo pigment composition according to the present invention does not suffer from such a drawback at all even when the operating temperature increases during flushing, and the disazo pigment composition according to the present invention exhibits a significant decrease in strength compared to the disazo pigment prepared by the method described in the cited publication. This invention provides excellent printing inks and paints. Next, the present invention will be specifically explained with reference to Examples.

Note that the text in the middle of the text or ``chi'' is based on weight unless otherwise specified.

Example 1 3.30 parts of 3'-dichlorobenzidine is tetrazotized according to a conventional method to obtain a tetrazonium salt solution.

On the other hand, a submerging solution is prepared from 42.2 parts of acetoacedoanilide and 3.0 parts of 4-acetoacetaminophenyl urea according to a conventional method. Mix and couple both liquids,
The obtained pigment was filtered, washed with water, dried and ground to obtain 75.3 parts of the disazo pigment composition of the present invention. 114 parts of the face f was added to 86 parts of lime rosin varnish (solid content: 40 parts) and dispersed using a paint conditioner.
A gravure ink was obtained. When gravure printing was performed on paper using this ink, printed matter was obtained which had a clearer hue and significantly improved gloss and tinting power compared to when conventional disazo pigments were used.

Example 2 5.3 parts of commercially available tallow alkylpropylene diamine were mixed with the coupling mixture in Example 1, and the pigment composition of the present invention was obtained in the same manner. The pigment composition had further improved various performances than the pigment composition of the present invention obtained in Example 1.

Example 3 In place of acetoacedoanilide in Example 1, 46.7 parts of acetoaceto-p-toluidide and 1.8 parts of P-acetoacetaminophenyl urea were used, and the other conditions were the same as in Example 1. A disazo pigment composition of the present invention was obtained. The pigment composition, like that of Example 1, was excellent in various performances.

Example 4 A disazo pigment composition similar to that in Example 1 was prepared using an equimolar amount of acetoaceto-0-toluidide instead of acetoacedoanilide in Example 1, and in the same manner as in Example 1. Obtained.

Example 5 An offset ink was prepared using the pigment of the present invention in Example 1, and compared with an offset ink using a conventionally known pigment of the same type, the results shown in Table 1 below were obtained.

Pigment of Example 1 100 No change 27
．． 5 Known pigments 2 90 Changes to slightly opaque 26
．． 5 Known pigments 3 90 // 25
．． 3. Known Pigment 1 in Table 1 above is untreated Pigment Yellow 12, and Known Pigment 2 is 2-acetoacetaminobenzoic acid 1,6 instead of 4-acetoacetaminophenyl urea in Example 1. The pigment was obtained in the same manner as in Example 1 (for example, Japanese Patent Publication No. 55-49087), and the known pigment 3 was acetoacedoanilide in place of the above-mentioned 2-acetoacetaminobenzoic acid. 1.8 parts of -2-methoxy-5-carboxamide was used (see Japanese Patent Application Laid-Open No. 53-41322).

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°C for 60 seconds to observe changes in color tone, tinting strength, and transparency to evaluate heat resistance. The flow value was measured using a spread meter (manufactured by Toyo Seiki Co., Ltd., load (acrylic): 115 f, sample volume: 0.5 cc) using the ink, and the coloring power was determined by diluting each ink above with titanium white ink. The dilution ratio is as follows.

The ink according to Example 1 was diluted with 14 parts of white ink, and the ink with known pigment 1 was diluted with 10 parts of white ink, known pigment 2.
．． The ink according to 3 is diluted with 13 parts of white ink Patent applicant Dainichiseika Kagyo Co., Ltd.

Claims (1)

[Claims] 3. In a disazo pigment formed by coupling a tetrazotized product of 3'-dichlorobenzidine to an acetoacedoanilide compound, about 0.5 to 20 mol of the acetoacedoanilide compound has the following general formula ( A disazo pigment group characterized by being substituted with a compound represented by I+ (wherein R1 in the above formula is one or more hydrogen atoms, methyl group, ethyl group, methoxy group, nitro group, halogen atom) or ethoxy group, 11, R2o and R3 are hydrogen atoms, methyl groups or ethyl groups, n
is 1 or 2. )