JPH03181570A - Production of oxititanium phthalocyanine - Google Patents

Abstract

PURPOSE:To obtain low-crystalline M-type oxititanium phthalocyanine able to perform mass production by dissolving oxititanium phthalocyanine as a raw material in sulfuric acid and reprecipitating in mixed solution of methanol and water. CONSTITUTION:Oxititanium phthalocyanine as a raw material is added into concentrated sulfuric acid with stirring and dissolved. Next, methanol is mixed with water in a ratio of 10-90%, preferably 40-80% (amount of methanol is wt.%) to obtain a mixed solution, then the above-mentioned oxititanium phthalocyanine solution in sulfuric acid is dropped into the mixed solution, thus reprecipitation is generated to afford the aimed M-type oxititanium phthalocyanine exhibiting 7.2 deg., 14.2 deg., 24.0 deg. and 27.2 deg. diffraction angle (2theta+ or -0.2 deg.) by Cu-Kalpha characteristic X-ray.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing low-crystalline oxytitanium phthalocyanine. For more details, see the diffraction angle (2θ±0.2°) of CuKα characteristic X-rays described in Japanese Patent Application No. 1-189199.
The present invention relates to a method for producing low-crystalline M-type oxytitanium phthalocyanine whose angles are 7.2°, 14.2°, 24.0°, and 27.2°.

[Conventional technology]

Traditionally, phthalocyanine pigments have been used to color paints, inks, and resins, as well as catalysts, electrophotographic photoreceptors, solar cells,
It has attracted attention as an electronic material used in sensors, etc., and has come to be widely used.

Oxytitanium phthalocyanine can be obtained in various crystal forms depending on subtle differences in manufacturing conditions.

For example, Japanese Patent Application Laid-Open No. 59-49544 (USP 4.4
44,861), JP-A-59-166959, JP-A-61-239248 (USP 4,728,5)
92), Japanese Unexamined Patent Publication No. 62-67094 (USP 4,6
64,997) JP-A-63-366, JP-A-63-116158, JP-A-63-198067
Oxytitanium phthalocyanine having different crystal forms can be produced under various conditions as shown in Japanese Patent Application Laid-Open No. 64-17066.

Low-crystalline M-type oxytitanium phthalocyanine can be easily and stably produced in the laboratory by the production method described in Japanese Patent Application No. 1-189199. Dry crushing performed when producing titanium phthalocyanine requires strong crushing force, which can lead to equipment wear and metal powder contamination during mass production. Acid paging, another method for producing amorphous oxytitanium phthalocyanine, produces very fine crystals and is difficult to handle, as filtration is slow.

[Problem that the invention seeks to solve]

Therefore, an object of the present invention is to provide a method for producing low-crystalline M-type oxytitanium phthalocyanine that is suitable for industrialization and that can be mass-produced.

[Means to solve the problem]

The present inventors have conducted intensive studies to produce M-type oxytitanium phthalocyanine by a method suitable for industrialization. After dissolving it in concentrated sulfuric acid, the M-type oxytitanium phthalocyanine is produced by re-precipitating it in a mixed solution of methanol and water. It was discovered that oxytitanium phthalocyanine can be obtained, leading to the present invention.

[Detailed description of the invention]

The oxytitanium phthalocyanine obtained by the production method of the present invention is diffracted by CuKα characteristic X-rays, and the Black angle (2θ±0.2°) is 7.2° 14.2° 24.0°
A strong peak is observed at 27.2°.

Here, the structure of oxytitanium phthalocyanine is It is expressed as

However, x, , x, , x3. x4 is CI! or Br, n, m, I! , is an integer from O to 4.

The oxytitanium phthalocyanine used as a raw material for producing M-type oxytitanium phthalocyanine is
Since it is used after being dissolved in concentrated sulfuric acid, it may be any crystal or a mixture of various polymorphs. The amount of concentrated sulfuric acid used is 10 to 60 parts by weight, preferably 25 to 40 parts by weight, based on the weight of oxytitanium phthalocyanine.

The mixing ratio of the mixed solution of methanol and water required for reprecipitation is 1
0% to 90%, preferably 40 to 80% (methanol weight %).

[Example 1] Japanese Patent Application Laid-Open No. 61-239248 (USP 4.728,
592), 1.0 kg of B-type succititanium phthalocyanine obtained according to the production example disclosed in
The mixture was slowly added to 30.0 kg of concentrated sulfuric acid maintained at the following temperature while stirring, and dissolved. Next, 150 kg of methanol and 150 kg of ice water were mixed, cooled to -10°C, and the sulfuric acid solution of oxytitanium phthalocyanine was added to the methanol-ice water solution for 4 hours while cooling it to below 15°C. dripped.

The obtained blue crystals were separated by filtration, thoroughly washed with methanol and water, and dried. This oxytitanium phthalocyanine has an X-ray diffraction angle (2θ±0.2°) of 7.2° 14.
The angles were 0° 24, 2° 27.2°, and there was a shoulder at 11.6°, which was M-type oxytitanium phthalocyanine.

The X-ray diffraction diagram is shown in FIG.

[Example 2] Japanese Patent Application Laid-Open No. 62-67094 (USP 4,664.9)
1.0 kg of type A oxytitanium phthalocyanine obtained according to the production example disclosed in No. 97) was slowly added to and dissolved in 30.0 kg of concentrated sulfuric acid kept below 5° C. with stirring. Next, 240 kg of methanol and 60 kg of ice water were mixed, cooled to -10'C, and the sulfuric acid solution of oxytitanium phthalocyanine was added to the methanol-ice water solution for 6 hours while cooling it to below -15°C. It dripped. Filter the obtained blue crystals,
It was thoroughly washed with methanol and water and dried. This oxytitanium phthalonanine has an X-ray diffraction angle (2θ±
0.2°) is 7.2°14. , O' 24.2° 2
It was 7.2° and was M-type oxytitanium phthalocyanine.

The X-ray diffraction diagram is shown in FIG.

Comparative Example 1 2.0 kg of B-type oxytitanium phthalocyanine used in Example 1 was slowly added to 60 kg of concentrated sulfuric acid at 5° C. or lower to dissolve it, and the solution was added dropwise to 800 kg of water at 25° C. over 1 hour. The obtained pigment was separated by filtration, thoroughly washed with water, and then dried. The X-ray diffraction pattern of the obtained oxytitanium phthalocyanine is shown in FIG.

Comparative Example 2 20 kg of A-type oxytitanium phthalocyanine used in Example 2 was slowly added to and dissolved in 60 kg of concentrated sulfuric acid at 5° C. or lower, and then added dropwise to 600 kg of methanol at 5° C. over 6 hours. The obtained pigment was separated by filtration, thoroughly washed with water and methanol, and then dried.

The X-ray diffraction pattern of the obtained oxytitanium phthalocyanine is shown in FIG.

[Brief explanation of drawings]

Figures 1 and 2 are X-ray diffraction diagrams of low-crystalline M-type oxytitanium phthalocyanine obtained in Examples 1 and 2, respectively. Figure 5 is an X-ray diffraction diagram of type B oxytitanium phthalocyanine used in Examples and Comparative Examples. Figure 6 is an X-ray diffraction diagram of Type A oxytitanium phthalocyanine used in Examples and Comparative Examples. X of
It is a line diffraction diagram.

Claims (1)

[Claims] It is characterized by being dissolved in sulfuric acid and then reprecipitated in a mixed solution of methanol and water, with diffraction angles (2θ±0.2°) of CuKα characteristic X-rays of 7.2° and 14.2°, 2
4.0° and 27.2°. A method for producing low crystalline M-type oxytitanium phthalocyanine.