JP3395949B2 - Metal phthalocyanine crystal and method for producing the same - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a metal phthalocyanine crystal used as a charge generating substance for a solar cell, an electrophotographic photoreceptor, a gas molecule adsorbing substance for a gas sensor, and the like. The object is to provide a film-capable metal phthalocyanine crystal.

[0002]

2. Description of the Related Art Needle crystals or amorphous crystals are known as solid metal phthalocyanine crystals. For example, in the case of a copper phthalocyanine crystal, a needle crystal 90 as shown in FIG. 6 can be produced by the sublimation method, and an amorphous crystal 91 as shown in FIG. 7 can be produced by the acid pasting method using concentrated sulfuric acid.

The size of the crystals can be controlled to some extent by changing the conditions for producing the crystals or by performing a process such as crushing after the production. Also,
When the crystals or powders of the above forms are used in the form of a film, prepare a liquid in which the crystals and powders are dispersed in a binder resin together with an organic solvent, and apply the liquid.
A film is formed by a cloth method , a dip method, a spin coating method, or the like.

[0004]

However, as the use of the metal phthalocyanine crystal, a binder resin such as a charge generating substance for a solar cell, a charge generating substance for an electrophotographic photoreceptor, or a gas molecule adsorbing substance for a gas sensor is used. In many cases, a film formed without the film is required. However, the above-mentioned needle-like crystals and powdery metal phthalocyanine cannot be prepared as a solution because the metal phthalocyanine is substantially insoluble in any organic solvent.

Accordingly, for applications as described above, the vacuum chamber, without the need for film deposition by vacuum evaporation method which requires a large apparatus relatively such exhaust system becomes that does not become the coating The simple film-forming method such as the coating method , the dipping method, and the spin coating method cannot be adopted, and as a result, there arises a problem that the cost of the entire product such as the solar cell or the electrophotographic photosensitive member is increased. It has become one.

[0006]

As a concrete means for solving the above-mentioned conventional problems, the present invention makes zinc phthalocyanine or cobalt phthalocyanine having no axial ligand a constant pressure by an inert gas. Zinc phthalocyanine characterized by obtaining a metastable thread-like zinc phthalocyanine crystal or cobalt phthalocyanine crystal by immersing in benzene and subjecting it to crystal transition treatment after atomizing by a gas evaporation method heating in a prepared container By providing a method for producing a crystal or cobalt phthalocyanine crystal, and zinc phthalocyanine or cobalt phthalocyanine having a thread-like crystal structure obtained by the above-mentioned production method, it is possible to form a film by a simple means such as coating without using a binder resin. Is to solve the problem.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Next, a method for producing a metal phthalocyanine crystal according to the present invention will be described in detail. The present invention is a method for producing a filamentous crystal targeting a metal phthalocyanine having no axial ligand. First, an inert gas is introduced into a container whose pressure is reduced by an exhaust device to adjust the pressure within a predetermined pressure range. To do.

Solid metal phthalocyanine in this container,
For example, by heating and evaporating copper phthalocyanine, fine particles of metal phthalocyanine are generated. In general,
The method of producing fine particles by such means is one of the typical methods called the in-gas evaporation method.

At this time, the type of the inert gas, the flow rate, the pressure of the atmosphere, and the conditions for producing the above-mentioned fine particles, and
Conditions such as a heating method are not particularly limited in the present invention as long as fine particles having a size of 100 nm or less can be obtained, and any conditions can be freely used.

Here, the inventor of the present invention treats the metal phthalocyanine atomized by the above-mentioned gas evaporation method with benzene, that is, performs a crystal transition treatment in which the raw material for treatment is immersed in benzene at a constant temperature for a certain time or more. As a result, it was found that thread-like metastable metal phthalocyanine crystals were obtained. It should be noted that, here, a crystal that does not cause crystal transition by heat treatment is called a stable type, and a crystal that causes crystal transition by heat treatment is called a metastable type.

Generally, solvent treatment is known as one of the methods for crystal transition of metal phthalocyanine. However, when treated with an appropriate organic solvent, metastable metal phthalocyanine crystals are generally strip-shaped. Since it is said that the crystals are changed to stable crystals, the production method of the present invention in which a thread-like metastable metal phthalocyanine crystal is obtained by subjecting the metal phthalocyanine to benzene treatment has a novel result that has never been obtained. The reason why such a result is obtained is that the production method peculiar to the present invention is that the fine particles generated by the gas evaporation method are treated with benzene.

[0012]

【Example】

Example 1: A commercially available copper phthalocyanine (manufactured by Tokyo Chemical Industry Co., Ltd., P1005) was used as a raw material, and the above raw material was heated by resistance heating under an atmosphere of He (helium) gas and a pressure of 1 Torr to produce fine particles. When the produced fine particles were observed with a scanning electron microscope, they were amorphous particles having a size of about 50 nm.

The copper phthalocyanine fine particles thus produced were dispersed in benzene (concentration 1 g / liter) at room temperature to obtain 12
The width 50 as shown in FIG. 1 and FIG.
Filamentous crystal 1 having a size of 100 nm was obtained. The absorption spectrum of the filamentous crystal 1 in the visible to near infrared region has a wavelength of 614 nm.
The spectra have absorption maximums at and 774 nm. However, the dispersion medium is polyoxyethylene (10) with a concentration of 0.1%.
It is an aqueous solution of Octylphenyl Ether (abbreviation: Triton X-100).

By coating the glass substrate with the benzene dispersion of the filamentous crystals 1, a film made of filamentous crystals of copper phthalocyanine could be produced. As shown in FIG. 3, the X-ray diffraction spectrum BS of the filamentous crystal film measured by the X-ray powder method shows that the diffraction angles 2θ of the main peaks are 5.8, 7.8, 10.0,
It was 17.5 degree and was a metastable crystal. At this time, CuKα rays and a wavelength of 1.542 Å were used as X-rays.

Example 2: Using commercially available zinc phthalocyanine (P0767 manufactured by Tokyo Chemical Industry Co., Ltd.) as a raw material, the above raw material was heated by resistance heating under an atmosphere of He gas and a pressure of 1 Torr to produce fine particles. When the produced fine particles were observed with a scanning electron microscope, they were amorphous particles having a size of about 50 nm.

The zinc phthalocyanine fine particles thus produced were dispersed in benzene (concentration: 1 g / liter), and then 40 ° C.
As shown in Fig. 4, by leaving it in the constant temperature bath for 4 hours, the same width of 50 nm as in the case of the above copper phthalocyanine is obtained.
From which a filamentous crystal 2 of 100 nm was obtained.

The visible to near-infrared absorption spectrum of the filamentous crystal 2 is a spectrum having a characteristic absorption maximum at wavelengths of 619 nm and 786 nm, and the benzene dispersion of the filamentous crystal 2 is coated on a glass substrate. As a result, a film composed of the zinc phthalocyanine filamentous crystals 2 could be produced. When the X-ray diffraction spectrum of the filamentous crystal 2 was measured by the powder method, the spectrum was almost the same as in FIG. 3, and it was a metastable crystal.

Example 3 Using commercially available cobalt phthalocyanine (P0887 manufactured by Tokyo Chemical Industry Co., Ltd.) as a raw material,
Fine particles were generated by heating the above raw materials by resistance heating under an atmosphere of He gas and a pressure of 1 Torr, and the generated fine particles were observed with a scanning electron microscope.
The particles were irregularly sized particles.

The cobalt phthalocyanine fine particles thus produced were dispersed in benzene (concentration: 1 g / liter), and then 4
By leaving it in a constant temperature bath at 0 ° C. for 5 hours, a filamentous crystal 3 with a width of 50 nm to 100 nm is obtained as shown in FIG. 5, and the absorption spectrum of this filamentous crystal 3 in the visible to near infrared region has a wavelength of 620 nm. The spectrum has absorption maximums at and 750 nm.

By coating the glass substrate with this benzene dispersion of filamentous crystals 2, a film composed of filamentous crystals 3 of cobalt phthalocyanine could be produced. The X-ray diffraction spectrum of the filamentous crystal 3 was measured by the powder method.
The spectrum was almost the same, and it was a metastable crystal.

As described above, according to the present invention, zinc phthalocyanine or cobalt phthalocyanine having no axial ligand is atomized by the vaporization method in a gas, which is heated in a container adjusted to a constant pressure by an inert gas. After that, it was immersed in benzene and subjected to a crystal transition treatment to obtain a metastable thread-like zinc phthalocyanine crystal or cobalt phthalocyanine crystal. When a film of these phthalocyanines that does not use a binder is required, the film must be formed by, for example, a vacuum evaporation method that requires a relatively large-scale device, and a solar cell that uses this film. , The entire product such as the electrophotographic photoreceptor or the gas sensor The had become shall be up,
Since it can be formed as a filamentous crystal, it is possible to form a film by an extremely simple means such as coating, which is extremely effective in reducing the cost of the entire product such as a solar cell, an electrophotographic photoreceptor or a gas sensor. Is.

[Brief description of drawings]

FIG. 1 is an explanatory view showing an enlarged shape of a copper phthalocyanine crystal which is a first example of a metal phthalocyanine crystal according to the present invention.

FIG. 2 is an explanatory view showing the shape of the copper phthalocyanine crystal of the first embodiment in a further enlarged manner.

FIG. 3 is a graph showing an X-ray diffraction spectrum of a copper phthalocyanine crystal that is a first example of the metal phthalocyanine crystal according to the present invention.

FIG. 4 is an explanatory diagram showing an enlarged shape of a zinc phthalocyanine crystal which is a second example of the metal phthalocyanine crystal according to the present invention.

FIG. 5 is an explanatory view showing an enlarged shape of a cobalt phthalocyanine crystal which is a third example of the metal phthalocyanine crystal according to the present invention.

FIG. 6 is an explanatory view showing an enlarged shape of a needle-like crystal which is a shape of a metal phthalocyanine crystal of a conventional example.

FIG. 7 is an explanatory diagram showing an enlarged shape of an amorphous crystal which is a shape of a conventional metal phthalocyanine crystal.

[Explanation of symbols]

1 ... Filamentous crystal of copper phthalocyanine 2 ... Filamentous crystal of zinc phthalocyanine 3 ... Filamentous crystal of cobalt phthalocyanine BS: X-ray diffraction spectrum

Front page continuation (58) Fields surveyed (Int.Cl. ⁷ , DB name) C07D 487/22 C09B 47/04 C09B 67/50 CA (STN) REGISTRY (STN)

Claims (2)

(57) [Claims] 1. Zinc phthalocyanine or cobalt phthalocyanine having no axial ligand is atomized by a gas evaporation method in which it is heated in a vessel adjusted to a constant pressure by an inert gas, and then crystallized by immersing in benzene. A method for producing a zinc phthalocyanine crystal or a cobalt phthalocyanine crystal, which comprises obtaining a metastable thread-like zinc phthalocyanine crystal or a cobalt phthalocyanine crystal by performing a treatment. 2. Zinc phthalocyanine or cobalt phthalocyanine having no axial ligand is atomized by a gas evaporation method in which it is heated in a container adjusted to a constant pressure by an inert gas, and then crystallized by immersion in benzene. A zinc phthalocyanine crystal or a cobalt phthalocyanine crystal, which is formed into a metastable thread-like shape by treatment.