JPH08134368A - Production of copper phthalocyanine pigment - Google Patents

Abstract

PURPOSE: To directly obtain a fine copper phthalocyanine pigment by drying and desolvating a solvent mixture of crude copper phthalocyanine pigment prepared by synthesis and simultaneously grinding without passing through a pigmenting process. CONSTITUTION: For example, 1mol of phthalic acid (anhydride) (derivative) is reacted with about 2-10mols of urea in the presence of copper (compound) and a catalyst such as antimony trioxide in a solvent such as dichlorobenzene at about 60-20 deg.C for about 3-10 hours. The prepared reaction mixture of crude copper phthalocyanine and the solvent is preferably mixed with a grinding auxiliary such as preferably salt and dried while vibrating and mechanical grinding to give the objective pigment. A method for throwing balls for a mill made of a metal or ceramic in a dryer rotatable like revolution of a drum may be cited as the grinding method.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a copper phthalocyanine pigment, and more specifically, it is possible to directly obtain fine pigments by carrying out grinding at the same time as desolvation without a pigmentation step. The present invention relates to a method for producing a phthalocyanine pigment.

[0002]

2. Description of the Related Art Conventionally, the most general method for producing copper phthalocyanine is a so-called urea method in which a phthalic anhydride, a nitrogen source such as urea, a copper source and a catalyst are heated in a high boiling organic solvent. First, crude copper phthalocyanine is produced using these raw materials in the synthesis step. The copper phthalocyanine obtained in the synthesis step is one in which coarse particles are aggregated, and since it is of low practical value as it is, it is made into fine particles in the next pigmentation step, and coloring power as a pigment, sharpness and other pigment suitability are reduced. It has been granted. In the pigmentation step, a chemical method called an acid paste method or an acid slurry method is used to dissolve or suspend coarse particles of copper phthalocyanine in concentrated sulfuric acid or the like, and then pour this into a large amount of water to recrystallize the fine particles. The particles are made into fine particles by a physical method such as crushing or mechanically grinding with a ball mill or the like.

[0003]

In the above-mentioned pigmenting step, since a large amount of concentrated sulfuric acid is used in the chemical method, the problem of treating the waste liquid and the countermeasure against the corrosion of the apparatus are major problems. . Further, since an organic solvent is used in the synthesis step and water is used in the pigmentation step, it is also a big problem to separate and recover the organic solvent. In the physical method, there are problems in that it takes a long time and a large amount of energy to make the particles fine, and the efficiency is low. In order to eliminate the above problems in the pigmentation step, a method has been proposed in which the reaction mixture is reacted while being mechanically ground in the synthesis step, and the pigmentation step is omitted, but satisfactory results have not yet been obtained. Not not. The present invention has been made against such a background, and an object of the present invention is to provide a method for producing a copper phthalocyanine pigment without a pigmenting step.

[0004]

That is, the present invention is characterized in that a reaction mixture containing a crude copper phthalocyanine obtained through a synthesis step and a solvent is dried while being subjected to vibration and mechanical milling force. It is a method for producing a pigment.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below with reference to preferred embodiments. Copper phthalocyanine is usually synthesized by the urea method as described above. In the present invention, the synthesis method of copper phthalocyanine is not limited at all, and conventionally known synthesis methods such as the urea method and an improved method thereof can be used.
As an example, the general urea method is shown below.

In the urea method, phthalic acid or phthalic anhydride or a derivative thereof is used in an amount of about 2 to about 2 mol of urea.
It is generally used in a proportion of 10 mol. Further, as the copper source, in addition to powdered metallic copper, various copper compounds such as copper chloride, copper oxide, copper sulfate, and copper acetate are used. Generally, copper is used in a ratio of about 1.0 to 2.0 mol. As the catalyst, antimony trioxide, ammonium molybdate, molybdic acid, ammonium vanadate, boric acid, arsenic pentoxide, zirconium chloride, titanium tetrachloride, etc. are used, and these catalysts are the above-mentioned phthalic acid or phthalic anhydride. It is generally used in a ratio of about 0.001 to 0.5 mol per mol. In the synthesis of copper phthalocyanine, the above raw materials are reacted in a solvent. As the reaction solvent, for example, dichlorobenzene, trichlorobenzene, nitrobenzene, chloronaphthalene, nitrotoluene, polyalkylbenzene having a high boiling point, etc. are used.
These solvents are used in an amount of 2 to 5 times the weight of the above-mentioned phthalic acid or the like. The reaction conditions are, for example, about 1 for temperature.
The reaction time is about 3 to 10 hours.

In the present invention, for example, a reaction mixture containing a crude copper phthalocyanine synthesized by the urea method as described above, a solvent and the like is used. The characteristic feature of the present invention is that the reaction mixture is directly dried without passing through the pigmentation step to remove the solvent, in which case the reaction mixture is vibrated and the reaction mixture is dried while being mechanically ground. Is. The method of vibrating the reaction mixture while drying is to install a mechanical vibration generator such as an electromagnetic vibration generator or a vibration motor in the dryer, or a stand that vibrates mechanically or electromagnetically with a vibration motor. Examples thereof include a method of installing a dryer on top, but the method is not limited to these. The vibration applied to the reaction mixture may be vibration of a strength such that the reaction mixture is sufficiently mixed in the drier, depending on the capacity of the drier, the charged amount of the reaction mixture, the solid content and the amount of the following crushing medium, etc. Although different, the frequency is not particularly limited.

Further, the method of mechanically grinding the reaction mixture is carried out by introducing a grinding medium such as a milling ball such as a metal ball or a ceramic ball into the above-mentioned dryer, and grinding by vibrating the dryer. Examples of the method include a method of exhibiting the effect or a method of causing the dryer to rotate like a drum so as to induce the effect by vibration and rotation. However, the method is not limited to these. At the time of milling, the milling effect can be enhanced by using a conventionally known milling aid such as salt or mirabilite as the milling aid. Drying is usually performed under reduced pressure by heating with a heating source (circulation of a heating medium such as steam) installed in a dryer. Drying can be performed by a batch system or a continuous system. Examples of the dryer having the above-mentioned function that can be used in the present invention include a commercial product called a vibration fluidized dryer, a vibration mill having a heating device and a decompression device, and the like. As described above, the reaction mixture containing the copper phthalocyanine obtained through the synthesis step, the reaction solvent and the like is directly dried without passing through the pigmentation step to produce a finely divided copper phthalocyanine pigment.

If necessary, the obtained copper phthalocyanine pigment can be treated with sodium hydroxide and sulfuric acid to remove impurities contained therein. Furthermore, when a higher pigment is desired, the obtained pigment can be subjected to salt milling or solvent finish in a kneader. Even if such an additional treatment is carried out, the method of the present invention can obtain a high-quality pigment having a clear and large concentration in a shorter time than in the case where the conventional pigmentation step is carried out.

[0010]

EXAMPLES The present invention will be described in more detail with reference to the following examples. In the text, parts and% are based on weight unless otherwise specified. Synthetic example Phthalic anhydride 3000
Parts, 4500 parts of urea, 530 parts of cuprous chloride, 10 parts of ammonium molybdate and 8000 parts of Hisol P (alkylbenzene produced by Nippon Oil Co., Ltd.) were placed in a 30 liter glass-lined reaction vessel and heated to 170 to 200 ° C. with stirring. The mixture was warmed and reacted for 4 to 7 hours to obtain a slurry of crude copper phthalocyanine (solid content: 26.5%).

Example 1 Crude copper obtained in the synthesis example in a vibrating fluid dryer made of SUS316 (VHS30 type made by Chuo Kakoki Co., Ltd.) filled with 70% of the inner volume of steel balls having a diameter of 3/8 inch as a crushing medium The phthalocyanine slurry was dried by continuous operation while supplying a fixed amount of a slurry with a pump. Removal of the solvent was completed after about 2 hours of operation. The obtained disintegrated copper phthalocyanine was heated (90 to 10 to 10 times) with 20 to 30 times the amount of 2% sodium hydroxide aqueous solution and 2% sulfuric acid aqueous solution, respectively.
Impurities (unreacted substances, by-products, etc.) were removed by treatment at 0 ° C.), washed with water and dried to obtain a clear copper phthalocyanine pigment having a particle size of 30 to 60 μm.

EXAMPLE 2 In Example 1, salt was further added as a grinding aid.
The solid content of Drying was performed using 50%. Less than
As in Example 1, a clear copper foil having a particle size of 10 to 30 mμ was used.
A tarocyanine pigment was obtained.

Example 3 In the synthesis example, phthalic anhydride was replaced with tetrabromophthalic acid.
And replace the tetrachlorophthalic acid with cyanine green
Synthesized and dried in the same manner as in Example 1 to obtain a particle size. 10-20
A clear cyanine green pigment of mμ was obtained.

[0014]

As described above, according to the present invention, in the production of copper phthalocyanine, the reaction mixture containing the crude copper phthalocyanine obtained through the synthesis step is subjected to vibration and mechanical milling by omitting the pigmentation step. By applying a force and drying, a finely divided clear copper phthalocyanine pigment is obtained. Since the pigmentation step is not necessary, the problems of equipment corrosion countermeasures and waste sulfuric acid treatment are reduced, the process can be simplified, and the manufacturing time is significantly shortened, so the economic effect is extremely large.

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Ryo Mori 1-7-6 Nihonbashi Bakurocho, Chuo-ku, Tokyo Within Dainichi Seika Kogyo Co., Ltd. (72) Inori Natonaka Takami 1-7 Nihonbashi Bakuro-cho, Chuo-ku, Tokyo 6 Dainichi Seika Kogyo Co., Ltd. (72) Inventor Yoshio Abe 1-7-6 Nihonbashi Bakurocho, Chuo-ku, Tokyo Inside Dainichi Seika Kogyo Co., Ltd. (72) Shojiro Horiguchi 1-chome, Nihonbashi Bakurocho, Chuo-ku, Tokyo 7-6 Dainichi Seika Kogyo Co., Ltd.

Claims (1)

[Claims] 1. A method for producing a copper phthalocyanine pigment, which comprises drying a reaction mixture containing a crude copper phthalocyanine obtained through a synthesis step and a solvent while applying vibration and mechanical milling force.