JPH02294366A - Manufacturing method of disazo pigment - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for producing a disazo pigment, and more particularly to a method for producing a disazo pigment useful for various uses, particularly for coloring rubber and printing inks. (Prior art and its problems) Conventionally, disazo pigments obtained from 3.3°-dichlorobenzidine and various acetoacetanilide compounds are:
It is widely used for coloring rubber, vinyl chloride resin, paint, printing ink, etc. However, when used for coloring rubber, for example, the coloring power decreases significantly during vulcanization of the rubber, and the color tone becomes unclear. I have it. 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, the
No. 53-35090, No. 55-10630, No. 55-49087, and No. 59-19150, etc. have been proposed, but these methods do not improve heat resistance during coloring of rubber. The improvement in heat resistance during flushing is also not satisfactory.

Therefore, an object of the present invention is to solve the problems of the prior art described above and to provide a disazo pigment that has excellent performance when used for rubber or printing ink.

(Means for solving problems) The above objects are achieved by the present invention as described below.

That is, the present invention provides a method for producing a disazo pigment, which comprises coupling a tetrazotized product of 3,3°-dichlorobenzidine to an acetoacetanilide compound, in which 0.5 to 0.5 to 5
This is a method for producing a disazo pigment, characterized in that 0 mol% of the disazo pigment is substituted with a compound represented by the following general formula (I).

(However, R in the formula represents a carboxyl group, a sulfonic acid group, a carboxamide group, or a sulfamide group.) (Function) When coupling the base agent component and the tetrazo component in the production of disazo pigments, A disazo pigment having excellent performance when used for rubber or printing ink can be provided by substituting a part of the agent component with the compound of the above general formula N) to prepare a mixed pigment.

(Preferred Embodiments) Next, the present invention will be explained in more detail by citing preferred embodiments.

The 3,3'-dichlorobenzidine used in the present invention and the acetoacetanilide compounds that are used as priming agents and do not have a carboxyl group, sulfonic acid group, or hydroxyl group are known, such as , acetoacetanilide, 0-chloroacetoacetanilide, p-chloroacetoacetanilide, 4-chloro-25-dimethoxyacetoacetanilide, 2,4-dimethoxyacetoacetanilide, 0-acetoacetanisidide , 0-acetoacetotoluidide, 2,4-acetoacetoxylidide, p-acetoacetanisidide, p-acetoacetotoluidide, 4-chloro-2-methyl-acetoacetanilide, p-ethoxyacetoacetanilide , 4-nitro-2
-Methylacetoacetanilide, 4-acetoacetaminophthalimide, 5-acetoacetaminobenzimidazolone, 4-penzoyl-2,5
-diethoxyacetoacetanilide, 4-acetylaminoacetoacetanilide, and the like.

The compound represented by the general formula (1) used in combination with the above-mentioned known acetoacetanilide-based compound is about 0.5 to 50 mol% of the above-mentioned acetoacetanilide-based compound,
Preferably, 1.0 to 30 mol % of << is used as a substitute.

If the usage ratio is less than the above range, the desired effect of the present invention will be low, while if it is used in an amount exceeding the above range, the original excellent properties of the disazo pigment will deteriorate, which is not preferred.

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 subsoaking solution is prepared according to a conventional method using a mixture consisting of a predetermined amount of the compound of the general formula (1) and an acetoacetanilide compound. A disazo pigment with improved heat resistance can be obtained by the method of the present invention by mixing and coupling the two according to a conventional method.

Of course, during or after coupling, various aliphatic amines, various water-soluble resins, surfactants, and other additives and processing agents may be added to an extent that does not interfere with the purpose of the present invention. Pigment treatment can also be performed. (Effect) The disazo pigment obtained by the method of the present invention as described above is
It has the same clarity, etc. as compared to conventional disazo pigments of the same type, and does not cause a significant decrease in coloring power and dullness of color when coloring rubber with conventional disazo pigments and disazo pigments prepared by the method described in the cited publication. On the other hand, the disazo pigment according to the present invention overcomes these drawbacks.

The disazo pigments according to the invention are also greatly improved for use in paints and printing inks. That is, 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 method, but with conventional disazo pigments, pigment particle growth occurs during this flushing operation. , a significant decrease in tinting strength occurred. However, the disazo pigment according to the present invention does not suffer from such drawbacks even if the operating temperature increases during flushing. can be done. (Example) Next, the present invention will be described in more detail with reference to Examples. It should be noted that unless otherwise specified, the terms in the text or % are based on weight.

Example 1 17.6 parts of 3,3°-dichlorobenzidine is tetrazotized according to a conventional method to obtain a tetrazonium salt solution. Separately, a submerging solution is prepared from 27.0 parts of 0-acetoacetotoluidide and 1.3 parts of 4,4°-bisacetoacetylamino-3.3′-dicarboxybiphenyl according to a conventional method. Both liquids were mixed and coupled, and the resulting pigment was filtered, washed with water, dried and ground to obtain 45.0 parts of the disazo pigment of the present invention.

1 part of the above azo pigment, 0.9 part of rubber, 0.1 stearic acid
and 100 parts of a compound having the following composition are kneaded 10 times using an 8-inch mixing roll with a roll surface temperature of 20 to 50'C and a roll spacing of 1.0 mm (the product thus obtained is called a dark crepe). ．． Add 5 parts of this dark crepe and 50 parts of the following compound to 1 part in the same manner as above.
Knead o times to make a light colored crepe. This light-colored crepe was heated at 160℃±1℃, 200Kg/cnf, and thickness 1.
When vulcanization was carried out for 20 minutes under the conditions of 1.5 mm, a vulcanized rubber sheet with a clear and deep color was obtained. For comparison, Bifment Yellow 14 (a disazo pigment synthesized from 3,3-dichlorobenzidine and 0-acetoacetotoluidide) and the disazo pigment disclosed in Japanese Patent Publication No. 55-49087 were replaced with the pigment according to the present invention. When a similar test was carried out, in this case, the tinting strength was significantly lowered, and a rubber sheet with a dull color tone was obtained.

Example 2 27.0 parts of p-acetoacetotoluidide was used instead of 0-acetoacetotoluidide in Example 1,
The rest was the same as in Example 1, and a disazo pigment with good heat resistance as in Example 1 was obtained. Example 3 In place of 4.4°-bisacetoacetylamino-3,3°-dicarboxybiphenyl in Example 1, 4,
A disazo pigment having good heat resistance as in Example 1 was obtained in the same manner as in Example 1 except that 1.5 parts of 4°-bisacetoacetylamino-3.3°-disulfobiphenyl was used. Ta. Example 4 44.0 parts of 3.3°-dichlorobenzidine is tetrazotized according to a conventional method to obtain a tetrazonium salt solution. On the other hand, 62.0 parts of acetoacetanilide and 4.4 parts of 4,4°-bisacetoacetylamino-3,3°-dicarboxybiphenyl. A subsoaking solution is prepared from 0 parts according to a conventional method. Both liquids were mixed and coupled, and the resulting pigment was filtered and washed with water to obtain a water-containing breath cake with a solid content of 108.0 parts.

The coloring strength and heat resistance of the offset ink prepared from the above pigment were compared with those using conventionally known pigments of the same type, and the results shown in Table 1 below were obtained. Known pigment 1 in Table 1 above is Pigment Yellow 12 (a disazo pigment synthesized from 3,3°-dichlorobenzidine and acetoacetanilide), and known pigment 2 is Pigment Yellow 12 of Example 4. -bisacetoacetylamino-2- instead of 3,3゜-dicarboxybiphenyl
A pigment obtained in the same manner as in Example 4 except that 4.0 parts of acetoacetaminobenzoic acid was used (for example,
No. 087), and the known pigment 3 uses 4.5 parts of 2-methoxy-5-carpoamide acetoacetanilide in place of the above-mentioned 2-acetoacetaminobenzoic acid (Japanese Patent Publication No. 19150/1987). (See official bulletin! IQ).

In addition, for performance evaluation, 100 parts of each pigment (in pure quantity) of water-containing breath cake was added to 300 parts of offset ink face,
Flushing is performed in a flasher while mixing wires at a temperature of 60℃ or less, and after removing separated moisture,
The ink was spread on black art paper and heated at 200°C for 60 seconds to observe changes in color tone and transparency to evaluate heat resistance. Each of the above inks was diluted with titanium white ink, and the degree of ink of Example 4 was determined as 100. The dilution ratio is as follows. Ink of Example 4: 1 diluted with 4 parts white ink, known pigment 1
Ink = diluted with 10 parts of white ink Ink of known pigments 2 and 3 = diluted with 13 parts of white ink Example 5 4.4-Bisacetoacetylamino-3,3°-dicarboxybiphenyl in Example 4 Instead of 4.
4.0 parts of 4'-bisacetoacetylamino-3,3'-dicarboamide biphenyl was used, and the other conditions were the same as in Example 4. A pigment was obtained.

Applicant: Dainichiseika Industrial Co., Ltd. Agent: Patent Attorney Katsuhiro Yoshida

Claims (1)

[Scope of Claims] A method for producing a disazo pigment, which comprises coupling a tetrazotized product of 3,3'-dichloropenzidine to an acetoacetanilide compound, wherein 0.5 to A method for producing a disazo pigment, characterized in that 50 mol% of the pigment is substituted with a compound represented by the following general formula (I). ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) (However, R in the formula represents a carboxyl group, a sulfonic acid group, a carboxamide group, or a sulfamide group.)