JP2871577B2 - Copper phthalocyanine crystal and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a solar cell, for example,
Charge generation materials such as electrophotographic photoreceptors, or ink,
The present invention relates to a copper phthalocyanine crystal used as a toner and a paint, and more particularly, to a copper phthalocyanine crystal having characteristics capable of efficiently absorbing light in a near-infrared region in order to improve utilization efficiency with respect to sunlight and the like. Things.

[0002]

2. Description of the Related Art Copper phthalocyanines include α-type, β-type and γ-type.
There are many crystal forms such as type, δ, ε, π, ρ, and χ. Among them, the ε-type is known as a copper phthalocyanine crystal having strong absorption in the near infrared region. Each crystal form is characterized by an absorption spectrum and an X-ray diffraction spectrum.

According to the article by Isao Kumano in the literature "Journal of the Electrophotographic Society, 22, 111 (1984)", the absorption spectrum of an ε-type crystal has absorption maximums at 616 nm and 778 nm. Also,
According to German Patent No. 1181248, the X-ray diffraction spectrum of the ε-type crystal has three main peaks at lattice spacings of 5.07, 9.55 and 12.0 °.

[0004] A number of methods have been proposed for producing the above-mentioned ε-type crystal, but the most practical method is to add a specific additive when synthesizing ε-type copper phthalocyanine from a precursor. The method of adding an agent is disclosed in
-39325 and JP-A-57-149358
No. 6,086,045.

[0005]

However, Japanese Patent Application Laid-Open Nos. 53-39325 and 57-39325 describe the above.
In the ε-type copper phthalocyanine produced by the method disclosed in JP-A-149358, the additive added during the production process still remains at the time when the final product is obtained. When used, there arises a problem that causes deterioration of functions such as optical characteristics and electrical characteristics, and solving this problem has been an issue.

[0006]

According to the present invention, as a specific means for solving the above-mentioned conventional problems, a copper phthalocyanine crystal is heated in a vessel adjusted to a constant pressure by an inert gas. A method for producing a copper phthalocyanine crystal, which comprises dispersing in benzene, performing benzene treatment after atomization by a gas evaporation method, and thereafter evaporating and removing the benzene. The object of the present invention is to solve the above-mentioned conventional problems by providing a copper phthalocyanine crystal having a characteristic of having a strong absorption in an infrared region.

[0007]

Next, the present invention will be described in detail based on an embodiment shown in the drawings. As described above, copper phthalocyanine has many crystal forms other than the typical α-type and β-type. Since each crystal form has a specific electrical property and optical property, a crystal form suitable for each application is used. Among them, crystal forms having strong absorption, especially on the long wavelength side, have high utility value as functional dyes,
Another object of the present invention is to obtain a copper phthalocyanine having the above characteristics.

Hereinafter, a method for producing copper phthalocyanine according to the present invention will be described. First, solid copper phthalocyanine is heated and evaporated in a container in an atmosphere of an inert gas adjusted to a certain pressure to generate fine particles. Generally, the method for producing such fine particles is as follows.
This method is called a gas evaporation method and is one of well-known typical production methods.

The raw material used for producing the fine particles may be copper phthalocyanine, which is generally commercially available. The conditions for generating the fine particles include the type and flow rate of the inert gas, the pressure of the atmosphere, and the like.
Heating method, etc., 100nm
There is no particular limitation as long as the following particle size can be obtained.

[0010] Here, a solvent treatment is known as one of the above-mentioned methods for crystallizing copper phthalocyanine. Normally, when copper phthalocyanine is treated with benzene and crystallized, β having no strong absorption in the near infrared region
It is known that the crystal transitions to the form.

However, the above-mentioned finely divided copper phthalocyanine is subjected to a solvent treatment with benzene, that is, a raw material to be treated is dispersed in benzene at a certain temperature, and after a certain time or more,
It has been found by the present inventors that an operation of evaporating and removing benzene yields a copper phthalocyanine crystal having strong absorption in the near infrared region.

That is, according to the results of experiments and studies conducted by the inventor, a simple benzene treatment is performed after finely dividing copper phthalocyanine by the above-described method to obtain an absorption spectrum which has not been expected at all. It has been confirmed that this is a production method for obtaining copper phthalocyanine crystals.

Example 1 A commercially available α-type copper phthalocyanine (P1005, manufactured by Tokyo Chemical Industry Co., Ltd.) was used as a raw material.
Fine particles are generated by an in-gas evaporation method under an atmosphere of a He gas pressure of 1 Torr. Observation of the generated fine particles with a scanning electron microscope revealed that the particle size was about 50 nm, and the absorption spectrum was measured. The result was an absorption spectrum characteristic AT as shown in FIG. No strong absorption is observed. At this time, the measurement was 0.1
% Triton X-100 aqueous solution was used as a dispersion medium.

As shown in FIG. 2, X is obtained by a powder method.
When the diffraction spectrum AS was measured by X-rays (CuKα ray, wavelength 1.542 °), the structure was similar to the α-type crystal. However, it is recognized that the half width of the diffraction peak intensity is much wider than that of a general α-type crystal.

The copper phthalocyanine fine particles having the above characteristics are dispersed in benzene at a room temperature (concentration: 1 g / liter), and after 12 hours, the benzene is evaporated off. FIG. 3 shows the absorption spectrum characteristic BT of the crystal obtained by the benzene treatment, and the absorption spectrum characteristic BT has an absorption maximum at wavelengths of 614 nm and 774 nm.

According to FIG. 3 described above, the spectral characteristic BT of the absorption spectrum of the copper phthalocyanine of the present invention has an absorption maximum on the long wavelength side similarly to the copper phthalocyanine of the ε-type crystal of the conventional example, and the light It is clear that the absorption range is wider than that of copper phthalocyanine of the α-type crystal.

In addition, FIG. 4 shows a diffraction spectrum BS of the copper phthalocyanine of the present invention by X-rays, which is shown in FIG.
5.07, 8.86, 11.4 and 15.1Å, 5.07, 9.55 and 1
Not only is it clearly different from the copper phthalocyanine of the ε-type crystal of 2.0 °, but it does not match the spectrum of any known crystal system. That is, the copper phthalocyanine crystal produced by the method of the present invention is a crystal showing a novel X-ray diffraction spectrum.

Example 2 A commercially available α-type copper phthalocyanine (P1005, manufactured by Tokyo Chemical Industry Co., Ltd.) was used as a raw material.
Under an atmosphere of He gas at a pressure of 0.1 Torr, fine particles having a particle size of about 50 nm are generated by a gas evaporation method. The absorption spectrum of the crystal after subjecting the fine particles to benzene treatment at room temperature for 12 hours has an absorption maximum at wavelengths of 614 nm and 774 nm, and the absorption spectrum characteristic B shown in FIG.
A product almost identical to T was obtained.

Example 3 A commercially available β-type copper phthalocyanine (P1006, manufactured by Tokyo Chemical Industry Co., Ltd.) was used as a raw material.
Fine particles having a particle size of about 50 nm are generated by an in-gas evaporation method under an atmosphere of a He gas pressure of 1 Torr. The absorption spectrum of the crystal obtained after subjecting the fine particles to benzene treatment at room temperature for 12 hours has an absorption maximum at wavelengths of 612 nm and 769 nm, and almost coincides with the absorption spectrum characteristic BT shown in FIG. was gotten.

[0020]

As described above, according to the present invention, prior to the benzene treatment step, a step of micronizing copper phthalocyanine by an in-gas evaporation method is carried out, so that the benzene treatment is a very simple step. This makes it possible to produce a copper phthalocyanine crystal having a strong absorption in the infrared region, and is extremely effective in simplifying the process and reducing the cost.

In the production process, no additives other than benzene are used, and the benzene is completely removed by evaporation, so that the product does not contain any impurities and high-purity crystals can be obtained. It will be something that can be done. Therefore, when the copper phthalocyanine crystal of the present invention is used as a functional dye, the optical properties and the electrical properties are not deteriorated due to the mixing of impurities, and the effect of improving the quality is extremely excellent. It is.

[Brief description of the drawings]

FIG. 1 is a graph showing an absorption spectrum characteristic in a micronization step in a method for producing a copper phthalocyanine crystal according to the present invention.

FIG. 2 is a graph showing a diffraction spectrum by X-rays during a micronization step in the method for producing a copper phthalocyanine crystal according to the present invention.

FIG. 3 is a graph showing absorption spectrum characteristics in a completed state after benzene treatment in the method for producing a copper phthalocyanine crystal according to the present invention.

FIG. 4 is a graph showing a diffraction spectrum by X-rays in a completed state after benzene treatment in the method for producing a copper phthalocyanine crystal according to the present invention.

[Explanation of symbols]

 AT: Absorption spectrum characteristics during micronization process AS: X-ray diffraction spectrum during micronization process BT: Absorption spectrum characteristics upon product completion BS: X-ray diffraction spectrum upon product completion

──────────────────────────────────────────────────続 き Continuation of the front page (51) Int.Cl. ⁶ identification code FI G03G 9/08 G03G 9/08 365 (58) Field surveyed (Int.Cl. ⁶ , DB name) C09B 67/12 C09B 67 / 50 C07D 487/22 G03G 5/06 G03G 9/08

Claims (3)

(57) [Claims] Claims 1. A copper phthalocyanine crystal is finely divided by a gas evaporation method in which a copper phthalocyanine crystal is heated in a vessel adjusted to a constant pressure by an inert gas, and then dispersed in benzene to perform benzene treatment. A method for producing a copper phthalocyanine crystal, comprising removing benzene by evaporation. 2. In the spectrum measurement by powder X-ray diffraction, the lattice spacing between main peaks is 5.07, 8.8.
A copper phthalocyanine crystal which is located at positions of 6, 11.4, and 15.1 ° and has an absorption maximum in the vicinity of wavelengths 614 nm and 774 nm in absorption spectrum characteristics. 3. A copper phthalocyanine crystal is finely divided by a gas evaporation method in which the copper phthalocyanine crystal is heated in a vessel adjusted to a constant pressure with an inert gas, and then dispersed in benzene to perform benzene treatment. 3. The copper phthalocyanine crystal according to claim 2, wherein the phthalocyanine crystal has strong absorption in the near infrared region by removing benzene by evaporation.