JP2932932B2 - Method for producing gallium phthalocyanine compound - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to a method for producing a gallium phthalocyanine compound.

[0002]

2. Description of the Related Art Phthalocyanine compounds are useful as paints, printing inks, catalysts or electronic materials. In particular, in recent years, they have been extensively studied as electrophotographic photoreceptor materials, optical recording materials and photoelectric conversion materials. I have. In general, phthalocyanine compounds are known to exhibit a large number of crystal forms depending on the production method and treatment method, and it is known that this difference in crystal type greatly affects the photoelectric conversion characteristics of phthalocyanine. Also, these crystal forms
It is known that mutual transformation is possible by mechanical strain, sulfuric acid treatment, organic solvent treatment, heat treatment and the like. (For example, U.S. Pat. Nos. 2,770,629 and 3,160,635)
No. 3,708,292 and No. 3,357,899). As a material for an electrophotographic photoreceptor, various crystal-type materials such as metal-free phthalocyanine, oxytitanium phthalocyanine, hydroxygallium phthalocyanine, copper phthalocyanine, chloroaluminum phthalocyanine, and chloroindium phthalocyanine have been proposed. Further, JP-A-5-98181 discloses that three types of chlorogallium phthalocyanine are excellent as electrophotographic photoreceptors.

A method for synthesizing chlorogallium phthalocyanine is described in (1) a method in which gallium trichloride is reacted with 1,3-diiminoisoindoline in the absence of a solvent (D.C.
R. Acad. Sci. , 1956, 242, 102
6), (2) a method of reacting gallium trichloride with phthalonitrile in the absence of a solvent (JP-B-3-30854).
(3) gallium trichloride and phthalonitrile in butyl cellosolve in 1,8-diazabicyclo [5.4.0] -7-
Method for reacting using undecene as a catalyst (Japanese Unexamined Patent Publication No.
No. 2,221,459), (4) A method of reacting gallium trichloride with phthalonitrile in quinoline (Inorg. C)
hem. 1980, 19, 3131).
Also, for other metal phthalocyanine compounds, for example, oxytitanium phthalocyanine, a reaction in α-chloronaphthalene, and for oxyvanadium phthalocyanine, a reaction in ethylene glycol are known.

[0004]

In the case of synthesizing a phthalocyanine compound, if the reaction is carried out under solvent-free conditions, the product is undesirably a mixture of various substances due to side reactions. For example, in the case of chlorogallium phthalocyanine, chlorination occurs on the phthalocyanine ring under a solvent-free condition as described in JP-B-3-30854, resulting in a mixture of various halogen-substituted products, and a preferable crystal form is obtained. It is hard to be. In addition, even when the reaction is performed using a solvent, the electrical characteristics of the obtained metal phthalocyanine compound are strongly affected by the solvent and the synthesis conditions. For example, when oxytitanium phthalocyanine is produced in α-chloronaphthalene, it is necessary to control the reaction temperature to obtain a desired product. Further, Japanese Patent Application Laid-Open No. 5-98
No. 181 discloses gallium trichloride and 1,3-
In the case of a method in which diiminoisoindoline is reacted in quinoline, chlorogallium phthalocyanine having excellent electrophotographic properties can be obtained in a relatively high yield. However,
During the reaction, the raw material 1,3-diiminoisoindoline, a complex formation intermediate thereof with gallium ions, the resulting chlorogallium phthalocyanine and by-products have a relatively low solubility in quinoline. The system is liable to be in an inhomogeneous state, and as a result, there is a problem that the purity of the produced chlorogallium phthalocyanine is low and the physical properties vary depending on the synthesis lot. Therefore, it is necessary to produce a metal phthalocyanine compound such as chlorogallium phthalocyanine having high purity and excellent quality stability, and development of a production method thereof is strongly desired.
The present invention has been made in view of the above-mentioned circumstances in the prior art, and it is an object of the present invention to provide a gully film having high purity, excellent quality stability, and excellent electrophotographic characteristics.
An object of the present invention is to provide a method for producing an umphthalocyanine compound.

[0005]

Means for Solving the Problems The present inventors have conducted intensive studies on a method for synthesizing a metal phthalocyanine compound. As a result, when dimethyl sulfoxide was used as a solvent, quinoline or the like was used as a reaction solvent. It has been found that a uniform reaction can be carried out at a lower reaction temperature than when used, and that a metal phthalocyanine compound having high purity and low quality variation can be synthesized, and in particular, chlorogallium phthalocyanine synthesized by this method has an electron-emitting property. They discovered that they had excellent photographic properties, and completed the present invention.

The method for producing a gallium phthalocyanine compound of the present invention comprises the steps of: preparing 1,3-diiminoisoindoline and trichloride
Gallium is reacted in dimethyl sulfoxide.

[0007]

[0008] Dimethyl sulfoxy used in the present invention
Sid is a polar aprotic solvent, polar rather high,
Ru Oh <br/> in Solvent having no hydrogen suitable for the formation of strong hydrogen bonds.

[0009] At the reaction, Taken together purity, the dispersion or the like in the reaction, 1,3-diiminoisoindoline 3 salt
It is preferable to use about 4 to 5 equivalents to gallium iodide, and to use 2 to 6 parts by weight of dimethyl sulfoxide based on 1,3-diiminoisoindoline. The reaction temperature is 1
40 ° C. to the boiling point of dimethyl sulfoxide, preferably but is set to the boiling point of 0.99 ° C. or dimethyl sulfoxide, the reaction temperature is too low, it takes time to generate gallium lid <br/> Roshianin compound, on the other hand,
If the temperature is too high, the purity of the resulting gallium phthalocyanine compound such as chlorogallium phthalocyanine decreases, and the quality stability deteriorates.

[0010] Gallium phthaloyl <br/> cyanine compound obtained as described above, then, have rows dry grinding process, further benzyl alcohol, isopropyl alcohol, dimethylformamide, dimethyl sulfoxide, cyclohexanone, toluene, butyl acetate It is preferable to perform the crystal conversion by performing a solvent treatment using the above solvent. As described above, a gallium phthalocyanine compound having high purity and excellent electrophotographic characteristics with little quality variation can be synthesized.

[0011]

The advantages of using dimethyl sulfoxide in the present invention are, firstly, that dimethyl sulfoxide has a much higher solubility than quinoline. Main raw material
The high solubility of gallium trichloride and 1,3-diiminoisoindoline in a solvent enables a reaction in a solution state, not in a slurry state as in the case of a quinoline solvent. As a result, a uniform reaction can be performed, and since the reaction is a liquid-liquid reaction, the time can be reduced by increasing the reaction rate. Secondly, it is conceivable to promote the reaction by the solvent effect of dimethyl sulfoxide. It is presumed that the formation of gallium phthalocyanine compound accompanied by the condensation of 1,3-diiminoisoindoline is promoted by the high proton-accepting ability and the promoting effect of the nucleophilic reaction, which are characteristic properties of dimethyl sulfoxide. In fact, a quinoline solvent which had been reacted at 200 ° C., but using dimethyl sulfoxide enables the reaction to be performed without extending the reaction time even if the reaction temperature was lowered by about 50 ° C. Third, since the resulting gallium phthalocyanine compound has relatively high solubility, the crystallization rate can be controlled more easily than the quinoline solvent, and a gallium phthalocyanine compound having a large particle size and high purity can be obtained. Can be Fourthly, the high solubility of the decomposition products and by-products of the raw materials in dimethyl sulfoxide prevents the product from being contaminated, and in this respect also acts to obtain highly pure crystals.

[0012]

The present invention will be described below by way of examples. In Examples, Comparative Examples and Application Examples, “parts” means “parts by weight”. Example 1 17 parts of 1,3-diiminoisoindoline and 5 parts of gallium trichloride were placed in 70 parts of dimethyl sulfoxide, and
After reacting at 0 ° C. for 2 hours, the product was separated by filtration, washed with dimethyl sulfoxide and pure water, and dried to obtain 14 parts of chlorogallium phthalocyanine crystals. FIG. 1 shows an X-ray powder diffraction pattern of the obtained chlorogallium phthalocyanine crystal. Table 1 shows the elemental analysis values.

Example 2 Five parts of the chlorogallium phthalocyanine crystal obtained in Example 1 were used in a planetary ball mill (Futsch: P-5 type).
And dry pulverization together with 200 parts of 20 mm φ menor ball for 13 hours. FIG. 2 shows the powder X-ray diffraction pattern at this time.
After 0.5 part of the chlorogallium phthalocyanine crystal was milled in 20 parts of benzyl alcohol at room temperature for 24 hours at room temperature together with 30 parts of glass beads (1 mmφ), the glass beads were filtered off, washed with methanol, and dried. ,
A chlorogallium phthalocyanine crystal was obtained. FIG. 3 shows a powder X-ray diffraction diagram of the obtained chlorogallium phthalocyanine crystal.

Application Example 1 10 parts of a zirconium compound (trade name: Olgaixus ZC540, manufactured by Matsumoto Pharmaceutical Co., Ltd.) and 1 part of a silane compound (trade name: manufactured by Nippon Unicar Co., Ltd.) and 2-
A solution consisting of 40 parts of propanol and 20 parts of butanol was applied by a dip coating method.
By heating and drying for 0 minutes, an undercoat layer having a thickness of 0.5 μm was formed. Next, 0.1 part of the chlorogallium phthalocyanine crystal obtained in Example 2 was mixed with 0.1 part of a polyvinyl butyral resin (trade name: Esrec BM-S, manufactured by Sekisui Chemical Co., Ltd.) and n-butyl acetate 10, After treating with a glass shaker for 1 hour and dispersing with a paint shaker, the obtained coating solution was coated on the undercoat layer with a wire bar No. 5 and dried by heating at 100 ° C. for 10 minutes to form a charge generation layer having a thickness of about 0.15 μm. Further, it was confirmed by X-ray diffraction that the crystal form of the chlorogallium phthalocyanine crystal after dispersion did not change as compared with the crystal form before dispersion. Next, 2 parts of the compound represented by the following structural formula (I) and polycarbonate resin 3 represented by the following structural formula (II)
Was dissolved in 20 parts of monochlorobenzene, and the obtained coating solution was applied by dip coating on an aluminum substrate on which a charge generation layer was formed, and was dried by heating at 120 ° C. for 1 hour to give a film having a thickness of 20 μm. A charge transport layer was formed.

Embedded image The electrophotographic characteristics of the electrophotographic photoreceptor thus obtained were evaluated using a flat plate scanner under an environment of normal temperature and normal humidity (20 ° C., 40% RH). -2.
A corona discharge of 5 μA is performed, and charged to V ₀ (V).
V _DDP (V) is measured after standing for 2 seconds, and the dark decay rate DDR
[DDR = (V ₀ −V _DDP ) / V ₀ × 100 (%)] was calculated. Thereafter, the light of the tungsten lamp is converted into monochromatic light of 780 nm using a monochromator, adjusted to 0.25 μW / cm ² on the surface of the photoreceptor, and irradiated, and the initial sensitivity (dV / dE) (Vcm ² / erg) was measured. Table 2 shows the results.

COMPARATIVE EXAMPLE 1 17 parts of 1,3-diiminoisoindoline and 5 parts of gallium trichloride were placed in 70 parts of quinoline and reacted at 200 ° C. for 2 hours. -Washed with dimethylformamide and methanol, and dried to obtain 14 parts of chlorogallium phthalocyanine crystals. FIG. 4 shows a powder X-ray diffraction pattern of the obtained chlorogallium phthalocyanine crystal. Table 1 shows the elemental analysis values.

[0016]

[Table 1] As is clear from the above comparison, the case of Example 1 has higher purity than that of Comparative Example 1.

Comparative Example 2 The chlorogallium phthalocyanine crystal obtained in Comparative Example 1 was subjected to crystal conversion in the same manner as in Example 2. FIG. 5 shows an X-ray powder diffraction pattern after the dry pulverization, and FIG. 6 shows an X-ray powder diffraction pattern after the solvent treatment. Reference Example 1 An electrophotographic photoreceptor was produced using the chlorogallium phthalocyanine crystal obtained in Comparative Example 2 in the same manner as in Application Example 1, and was similarly evaluated using a flat plate scanner. Table 2 shows the results.

[0018]

[Table 2]

[0019]

According to the production method of the present invention, since the reaction is carried out using dimethyl sulfoxide as described above, as is clear from the results described in the above Examples, a high quality gallium phthalocyanine compound having high photosensitivity is obtained. Can be manufactured stably.

[Brief description of the drawings]

FIG. 1 is a powder X-ray diffraction diagram of a chlorogallium phthalocyanine crystal of Example 1.

FIG. 2 is a powder X-ray diffraction diagram of chlorogallium phthalocyanine crystal after dry pulverization in Example 2.

FIG. 3 is a powder X-ray diffraction diagram of a chlorogallium phthalocyanine crystal after a solvent treatment in Example 2.

FIG. 4 is a powder X-ray diffraction diagram of a chlorogallium phthalocyanine crystal of Comparative Example 1.

FIG. 5 is a powder X-ray diffraction chart of chlorogallium phthalocyanine crystal after dry grinding in Comparative Example 2.

6 is a powder X-ray diffraction diagram of a chlorogallium phthalocyanine crystal after a solvent treatment in Comparative Example 2. FIG.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-5-98181 (JP, A) JP-B-52-41288 (JP, B1) (58) Fields investigated (Int. Cl. ⁶ , DB name) C09B 47/073 G03G 5/06 371

Claims (1)

(57) [Claims] 1. A 1,3-diiminoisoindoline and 3 salt
A method for producing a gallium phthalocyanine compound, comprising reacting gallium halide in dimethyl sulfoxide.