JPH07207171A - Production of chlorogallium-ohthalocyanine - Google Patents

Abstract

PURPOSE:To provide a production method for stably producing chloro-gallium- phthalocyanine excellent in electrophotographic characteristics in a constant quality. CONSTITUTION:In reacting gallium trichloride with 1,3-diiminoisoindolin in an aromatic solvent, the reaction is carried out at 150-200 deg.C solvent temperature and, in case of elevating a solvent temperature to >=150 deg.C, a temperature increasing rate is controlled in <=0.5 deg.C/min. from 150 deg.C to the last end temperature to produce chlorogallium-phthalocyanine.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing chlorogallium phthalocyanine.

[0002]

BACKGROUND OF THE INVENTION Phthalocyanine compounds are useful materials as pigments, printing inks, catalysts or materials for electronic parts, and in recent years, they have been extensively studied as materials for electrophotographic photoreceptors, optical recording materials and photoelectric conversion materials. Has been done. In general, phthalocyanine compounds are known to show a large number of crystal forms due to differences in production method and treatment method, and it is known that the difference in crystal forms has a great influence on photoelectric conversion characteristics of phthalocyanine compounds. There is. Also,
It is known that these crystal forms can be mutually transformed by mechanical strain, sulfuric acid treatment, organic solvent treatment, heat treatment and the like (for example, US Pat. Nos. 2,770,629, 3,160,635 and 3,708,292). Issue and No. 33
57989 specification etc.). As a material for an electrophotographic photoreceptor, various crystal types of metal-free phthalocyanine, oxytitanium phthalocyanine, hydroxygallium phthalocyanine, copper phthalocyanine, chloroaluminum phthalocyanine, chloroindium phthalocyanine, etc. have been proposed.

The present inventors have conducted investigations from the viewpoint of the crystal form and electrophotographic characteristics of various phthalocyanine compounds, and found in JP-A-5-98181 three new crystal forms of chlorogallium phthalocyanine. ,
It has been disclosed that these are excellent as electrophotographic photoreceptors. Regarding the synthesis method of chlorogallium phthalocyanine, (1) a method of reacting gallium trichloride and 1,3-diiminoisoindoline in the absence of a solvent (DCR Ac
ad. Sci. , 1956, 242, 1026),
(2) A method of reacting gallium trichloride and phthalonitrile in the absence of a solvent (Japanese Patent Publication No. 3-30854), (3)
Method for reacting gallium trichloride and phthalonitrile in butyl cellosolve using 1,8-diazabicyclo [5.4.0] -7-undecene (DBU) as a catalyst (Japanese Patent Publication No. 1-2221459), (4) Method of reacting gallium trichloride and phthalonitrile in quinoline (Inor
g. Chem. 1980, 19, 3131) and the like are known.

[0004]

By the way, when chlorogallium phthalocyanine is synthesized under solventless conditions as disclosed in Japanese Patent Publication No. 330854/1993,
Chlorination occurs on the phthalocyanine ring, resulting in a mixture of various substitution products, and it is difficult to obtain a preferred crystal form.
When the reaction is carried out using a solvent, the electrophotographic characteristics of the obtained chlorogallium phthalocyanine are strongly influenced by the solvent and the manufacturing conditions. The present inventor et al.
According to the method of reacting gallium trichloride and 1,3-diiminoisoindoline in quinoline disclosed in Japanese Patent No. 8181, it is possible to obtain chlorogallium phthalocyanine excellent in electrophotographic characteristics with high yield. However, in this method, the reaction solution is heated to 200 ° C. or higher and reacted for 3 hours, and the reaction conditions are quite severe,
There was a problem that the purity and sensitivity of the chlorogallium phthalocyanine produced varied depending on the synthesis lot, and chlorogallium phthalocyanine of constant quality could not be obtained. The present invention has been made to solve the above problems, and an object of the present invention is to provide a manufacturing method for stably manufacturing chlorogallium phthalocyanine excellent in electrophotographic characteristics with constant quality. To provide.

[0005]

Means for Solving the Problems The inventors of the present invention have conducted earnest research on a method for producing chlorogallium phthalocyanine, and as a result, when gallium trichloride and 1,3-diiminoisoindoline are reacted in an aromatic solvent, 200 It has been found that the reaction can be carried out even at a low reaction temperature of not higher than 0 ° C., in which case the above object can be achieved by carrying out the reaction at an extremely slow reaction rate, and the present invention has been completed. That is, the method for producing chlorogallium phthalocyanine of the present invention, when reacting potassium trichloride and 1,3-diiminoisoindoline in an aromatic solvent,
When the reaction is carried out at a solvent temperature in the range of 150 ° C. to 200 ° C. and the solvent temperature is made higher than 150 ° C., the temperature is raised from 150 ° C. to the final reached temperature at a heating rate of 0.5 ° C./min or less. It is characterized by

In the practice of the present invention, the aromatic solvent may be quinoline, α-chloronaphthalene, β-chloronaphthalene, α-methylnaphthalene, methoxynaphthalene, diphenylethane, dichlorobenzene or dichlorotoluene. Inert high boiling point solvents can be used.

Taking into consideration purity, decomposition during the reaction, etc., 1,3-diiminoisoindoline is preferably used in an amount of about 4 times equivalent, for example, 4 to 5 times equivalent to gallium trichloride. The aromatic solvent is preferably used in an amount of 2 to 6 times the weight of 1,3-diiminoisoindoline.

The reaction is carried out at a solvent temperature of 150 ° C to 200 ° C.
The reaction is carried out in the range of, but the range of 150 to 180 ° C. is particularly preferable. When the solvent temperature is lower than 150 ° C., the reaction mixture in a slurry state is caked to give a poor electrophotographic property, and when the solvent temperature is higher than 200 ° C. It is possible to obtain photographic characteristics with variations. The reaction mixture is heated in a relatively short time until the solvent temperature reaches 150 ° C. When the solvent temperature reaches 150 ° C, chlorogallium phthalocyanine begins to precipitate, so the reaction may be carried out while maintaining that temperature. However, when the temperature is further raised, the heating rate is 0.5 ° C / min or less. The temperature is raised to the final reaction temperature while controlling to, and the reaction is completed as it is. 200 ° C when the temperature rise is 0.5 ° C / min or less
Even in the high temperature region around, the obtained chlorogallium phthalocyanine has good purity and sensitivity, and does not have a constant quality that does not vary depending on the synthesis lot. After the reaction is complete, the reaction mixture is filtered and washed. The obtained chlorogallium phthalocyanine is further dry-ground,
Crystal conversion and pigmentation can be performed by wet pulverization or the like.

[0009]

When the reaction between potassium trichloride and 1,3-diiminoisoindoline is carried out at a reaction temperature of about 200 ° C. or higher, the electrophotographic characteristics will vary, but this will result in impurities in the product. Probably because it was mixed. However, in the present invention, the solvent temperature is set to 150 ° C.
To 200 ° C., and when the solvent temperature is increased above 150 ° C., the temperature rising rate is set to a slow rate of 0.5 ° C./minute or less, so that the reaction is carried out at a relatively low temperature,
The effect of suppressing the thermal decomposition of 1,3-diiminoisoindoline and other side reactions occurs, and also when the reaction is carried out by raising the reaction temperature to a high temperature region around 200 ° C, the formation of chlorogallium phthalocyanine is generated. The reaction rate and the crystallization rate of the crystal are controlled, and it becomes possible to obtain a large crystal having a uniform crystal form and containing no impurities. Therefore, according to the present invention, it becomes possible to obtain chlorogallium phthalocyanine having no variation in electrophotographic characteristics.

[0010]

EXAMPLES The present invention will be described below with reference to examples. In the examples and comparative examples, "part" means "part by weight".
Means Examples 1 to 6 17 parts of 1,3-diiminoisoindoline and 5 parts of gallium trichloride were put in 70 parts of quinoline, and the temperature was raised to 150 ° C in 1 hour. It was heated to the final reaction temperature at the rate of temperature rise shown in Table 1 as it was, and the reaction was continued at that temperature.
After cooling, the product was separated by filtration, washed with dimethyl sulfoxide and pure water, and dried to obtain 14 parts of chlorogallium phthalocyanine crystal. A typical powder X-ray diffraction diagram of the obtained chlorogallium phthalocyanine crystal is shown in FIG.
The elemental analysis values are shown in Table 2.

Examples 7 to 12 5 parts of the chlorogallium phthalocyanine crystals obtained in Examples 1 to 6 were mixed with a planetary ball mill (P-5, manufactured by Futsch Ltd.).
Type) and dry pulverization was carried out for 13 hours together with 200 parts of 20 mmφ menoball. A typical powder X-ray diffraction diagram at this point is shown in FIG. After milling 0.5 parts of this chlorogallium phthalocyanine crystal with 30 parts of glass beads (1 mmφ) in 20 parts of benzyl alcohol at room temperature for 24 hours, the glass beads were filtered off, washed with methanol and dried. , Chlorogallium phthalocyanine crystals were obtained. A typical powder X-ray diffraction diagram of the obtained chlorogallium phthalocyanine crystal is shown in FIG.

Comparative Example 1 An experiment was conducted in the same manner as in Example 1. However, 150 ° C
In the subsequent heating, the temperature was raised to 200 ° C. at a heating rate of 0.56 ° C./minute, and then the reaction was performed for 2 hours. The powder X-ray diffraction diagram of the obtained chlorogallium phthalocyanine crystal was the same as in FIG. The synthesis conditions are shown in Table 1 and the elemental analysis values are shown in Table 2. Comparative Example 2 The chlorogallium phthalocyanine crystal obtained in Comparative Example 1 was dry-pulverized and wet-pulverized in the same manner as in Example 7. The powder X-ray diffraction patterns of the obtained chlorogallium phthalocyanine crystal were the same as those in FIGS. 2 and 3, respectively.

[0013]

[Table 1]

[0014]

[Table 2]

Application Example 1 On an aluminum substrate, 10 parts of a zirconium compound (Organix ZC540, manufactured by Matsumoto Pharmaceutical Co., Ltd.) and 1 part of a silane compound (A1110, manufactured by Nippon Unicar Co.), 40 parts of 2-propanol and 20 parts of butanol were used. The solution is applied by the dip coating method, and at 150 ° C, 10
After heat-drying for a minute, an undercoat layer having a film thickness of 0.5 μm was formed. Next, 0.1 part of the chlorogallium phthalocyanine crystal obtained in Example 7 was added with 0.1 part of polyvinyl butyral resin (S-REC BM-S, Sekisui Chemical Co., Ltd.) and n-acetic acid.
-Butyl 10 and mixed with glass beads by a paint shaker for 1 hour to disperse, and the resulting coating liquid was applied to the above-mentioned pulling layer with a wire bar No. Apply with 5,
Heat-dry at 100 ° C for 10 minutes to obtain a film thickness of about 0.1
A 5 μm charge generation layer was formed. It was also confirmed that the crystal form of the chlorogallium phthalocyanine crystal after dispersion was not changed by X-ray diffraction as compared with the crystal form before dispersion. Next, 2 parts of the compound represented by the following formula (I) and 3 parts of a polycarbonate resin comprising a repeating structural unit represented by the following formula (II) were dissolved in 20 parts of monochlorobenzene, and the resulting coating solution was subjected to charge generation. It is applied by dip coating method on the aluminum substrate on which the layer is formed, and at 120 ° C.
Was dried by heating for 1 hour to form a charge transport layer having a film thickness of 20 μm.

[Chemical 1]

The electrophotographic characteristics of the electrophotographic photoreceptor thus obtained were evaluated using a flat plate scanner in an environment of normal temperature and normal humidity (20 ° C., 40% RH). A corona discharge of −2.5 μA is performed, the voltage is charged to V0 (V), left for 1 second, and VDDP (V) is measured, and the dark decay rate DDR [DDR = (V0 −VDDP / V0) × 100.
(%)] Was calculated. After that, the light of the tungsten lamp is converted into monochromatic light of 780 nm using a monochromator,
The initial sensitivity (dV / dE, Vcm ² / er) was adjusted by irradiating the surface of the photoconductor so that it was 0.25 μW / cm ^2.
g) was measured. The results are shown in Table 3.

Application Examples 2 to 6 An electrophotographic photosensitive member was formed in the same manner as in Application Example 1 except that the chlorogallium phthalocyanines of Examples 8 to 12 were used, and the same evaluation was performed. The results are shown in Table 3. Reference Example 1 (Comparative Example) Using the chlorogallium phthalocyanine crystal obtained in Comparative Example 2, an electrophotographic photosensitive member was produced in the same manner as in Application Example 1, and its electrophotographic characteristics were evaluated. The results are shown in Table 3.

[0018]

[Table 3]

[0019]

Since the present invention has the above-mentioned structure, it is possible to produce high-quality chlorogallium phthalocyanine having excellent electrophotographic characteristics without causing variations, as is apparent from the results of the above-mentioned examples. It will be possible. In addition, the chlorogallium phthalocyanine obtained by the present invention has large crystals and a uniform particle size, and thus is easy to process and handle after the reaction. Further, the electrophotographic photosensitive member produced using the chlorogallium phthalocyanine obtained by the present invention has excellent electrophotographic characteristics.

[Brief description of drawings]

1 shows a powder X-ray diffraction diagram of chlorogallium phthalocyanine crystals obtained in Examples 1 to 6. FIG.

FIG. 2 shows a powder X-ray diffraction diagram of chlorogallium phthalocyanine crystals after dry pulverization in Examples 7 to 12.

FIG. 3 shows a powder X-ray diffraction diagram of the chlorogallium phthalocyanine crystals obtained in Examples 7 to 12.

Claims (1)

[Claims] 1. When reacting potassium trichloride and 1,3-diiminoisoindoline in an aromatic solvent at a solvent temperature of 150 ° C. to 200 ° C. and a solvent temperature higher than 150 ° C. The method for producing chlorogallium phthalocyanine is characterized in that the temperature is raised from 150 ° C. to the final reached temperature at a heating rate of 0.5 ° C./min or less.