JP2000284513A - Electrophotographic photoreceptor and its manufacture - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrophotographic photoreceptor which is superior in electrophotographic characteristics, especially, potential holding rate and its manufacture capable of form a photosensitive layer, especially superior in the potential holding rate when forming the photosensitive layer from coating solution. SOLUTION: The electrophotographic photoreceptor formed on a conductive substrate is provided with the photosensitive layer containing as a photoconductive material a phthalocyanine compound containing a phthalocyanine dimer in an amount of 100 nmol to 300 mmol based on 1 mmol of the above phthalocyanine compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photoreceptor for electrophotography (hereinafter, also simply referred to as "photoreceptor") and a method for producing the same, and more particularly, to a photosensitive layer containing an organic material provided on a conductive substrate. Electrophotography-based printers, copiers,
The present invention relates to an electrophotographic photosensitive member used for a facsimile and the like, and a method for manufacturing the same.

[0002]

2. Description of the Related Art A photoreceptor for electrophotography is required to have a function of retaining surface charges in a dark place, a function of receiving light to generate charges, and a function of receiving light and transporting charges. A so-called single-layer type photoreceptor that combines these functions in one layer, and a layer that separates functions into a layer that mainly contributes to charge generation and a layer that contributes to charge retention and surface charge retention in a dark place and charge transfer during photoreception. Are laminated.

For example, the Carlson method is applied to image formation by electrophotography using these electrophotographic photosensitive members. Image formation in this method involves charging a photoreceptor by corona discharge in a dark place, forming an electrostatic latent image such as a character or picture of a document on the charged photoreceptor surface, and forming the formed electrostatic latent image. The image is developed with toner, and the developed toner image is transferred and fixed to a support such as paper.The photoreceptor after transfer of the toner image is reused after performing static elimination, removal of residual toner, light neutralization, etc. To be served.

Conventionally, as the photosensitive material of the above-described electrophotographic photosensitive member, in addition to a material in which an inorganic photoconductive substance such as selenium, a selenium alloy, zinc oxide or cadmium sulfide is dispersed in a resin binder, An organic photoconductive substance such as poly-N-vinylcarbazole, polyvinylanthracene, a phthalocyanine compound or a bisazo compound is dispersed in a resin binder, or a material obtained by vacuum evaporation is used.

On the other hand, among such organic photoconductive substances, various studies have been made on the purification of phthalocyanine compounds. Among them, μ-oxo dimer and μ-dimer of phthalocyanine (hereinafter abbreviated as “multi-oxide type element-containing phthalocyanine”) mainly having an element having an oxidation state of +3 or more are known. , PHTHAL
OCYANINES, C.I. C. Leznoff et al, 1989 (VCH Publishe
rs. Inc. ) Etc. are described.

Further, 29H, 31H-phthalocyanine titanyl complex is described in the following literature, Capobianchi, A .;
et al, Sens. Actuators, B (1998), B48 (1-3), 333-33
8, and Scrocco, Marisa et al, Inorg. Chem, (19
96), 35 (16), 4788-4790.

In addition, at least one carbon atom,
As a phthalocyanine dimer compound having a structure composed of two phthalocyanine rings linked via a nitrogen atom or an oxygen atom and a titanium atom, 7,12: 13,
58: 22,27; 28,38-tetrimino-15,
20: 30,5-Dinitrilo-12, 28:27, 13
-Bis (nitriloisoindole [3] ylidenenitrillometheno [1,2] benzono) tetrabenzo [c,
h, n, s] [1,6,12,17] tetraazacyclodocosin, titanium (+1) derivative, 7,12: 13,5
8: 22,27; 28,38-Tetrimino-15,2
0: 30,5-dinitrilo-12,28: 27,13-
Bis (nitriloisoindole [3] ylidenenitrilometheno [1,2] benzono) tetrabenzo [c, h,
n, s] [1,6,12,17] tetraazacyclodocosin and titanyl complex (hereinafter abbreviated as “tetraazacyclodocosin complex”) have been reported. Literature, Capobianchi, A. et al, Inor
g. Chem, (1993), 32 (21), 4605-11, Ercolani, Claud
io et al. Chem. Soc. , Dalton Trans. (1990),
(6), 1971-7, Baldini, F .; et al, Sens. Actuators,
B (1998), B51 (1-3), 176-180.

[0008]

As described above, it is known to use a phthalocyanine compound containing a multioxidative element as a photosensitive material for an electrophotographic photosensitive member, and various purifications have been studied. At present, among the impurities contained in the phthalocyanine compound containing a multi-oxidation element, substances related to the characteristics of the electrophotographic photoreceptor are not always clear. That is, various purification methods of the phthalocyanine compound containing the multioxidative element and various examination examples of the polymer of the phthalonitrile compound have been proposed. In particular, the relationship with the potential holding ratio was not always clear.

Therefore, an object of the present invention is to clarify such a relationship, and to form an electrophotographic photosensitive member having excellent electrophotographic characteristics, particularly, an electric potential holding ratio, and a photosensitive layer formed by a coating solution.
In particular, it is an object of the present invention to provide a method for producing an electrophotographic photosensitive member capable of forming a photosensitive layer having an excellent potential holding ratio.

[0010]

Means for Solving the Problems The inventors of the present invention have made intensive studies to solve the above problems, and as a result, a photosensitive layer on a conductive substrate specifically contains a phthalocyanine dimer compound together with phthalocyanine as a photoconductive material. It was found that when the content was within the range, the potential holding ratio of the photoreceptor was significantly increased, and the electrophotographic photoreceptor of the present invention was completed.

That is, the electrophotographic photoreceptor of the present invention comprises an electrophotographic photoreceptor having a photosensitive layer on a conductive substrate, wherein the photosensitive layer contains a phthalocyanine compound as a photoconductive material. The content of the phthalocyanine dimer compound in the layer having
0 mmol or less.

In producing the electrophotographic photoreceptor, the present inventors include a phthalocyanine compound and a phthalocyanine dimer compound in a coating solution containing a charge generating material, and adjust the content of the latter to the former. When it was within a specific range, it was found that the potential holding ratio of the photoreceptor using such a coating solution was significantly improved, and the method of the present invention was completed.

That is, the method for producing an electrophotographic photoreceptor of the present invention comprises the step of applying a coating solution containing a charge generating material on a conductive substrate to form a photosensitive layer. In the production method, the coating solution contains a phthalocyanine compound and a phthalocyanine dimer compound, and the content of the phthalocyanine dimer compound is set to 100 nmol or more and 300 mmol per 1 mol of the phthalocyanine compound.
1 or less.

Here, in the present invention, “dimer” refers to
It is intended to include "multimers" in which one or more phthalocyanines are further bound to the dimers.

The photosensitive layer in the electrophotographic photoreceptor of the present invention includes both a single layer type and a laminated type, and is not limited to either type. Further, the coating liquid in the production method of the present invention can be applied to various coating methods such as a dip coating method or a spray coating method, and is not limited to any one of the coating methods.

[0016]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The specific structure of the photoreceptor of the present invention will be described below with reference to the drawings. For electrophotographic photoreceptors,
There are a so-called negatively charged laminated photoreceptor, a positively charged laminated photoreceptor, and a positively charged single-layer photoreceptor. Hereinafter, the present invention will be specifically described by taking a negatively charged laminated photoreceptor as an example, but components and methods for forming or producing a photoreceptor other than the phthalocyanine compound according to the present invention are suitably suitable. Can be selected.

As shown in FIG. 1, the negatively charged laminated photoreceptor is formed by further laminating a photosensitive layer 5 on an undercoat layer 2 laminated on a conductive substrate 1. Such photosensitive layer 5
Has a charge transport layer 4 laminated on the charge generation layer 3,
It is a function-separated type in which the charge generation layer 3 and the charge transport layer 4 are separated. In any of the above types, the undercoat layer 2 is not always necessary.

The conductive substrate 1 functions not only as an electrode of the photoreceptor but also as a support for the other layers, and may be cylindrical, plate-like or film-like. Alternatively, a conductive material may be applied to a metal such as stainless steel, nickel or an alloy thereof, or glass or resin.

For the undercoat layer 2, an alcohol-soluble polyamide, a solvent-soluble aromatic polyamide, a thermosetting urethane resin, or the like can be used. As the alcohol-soluble polyamide, copolymer compounds such as nylon 6, nylon 8, nylon 12, nylon 66, nylon 610, and nylon 612, and N-alkyl-modified or N-alkoxyalkyl-modified nylon are preferable. These specific compounds include Amilan CM8000 (Toray Industries, Inc.)
6/66/610/12 copolymerized nylon), Elvamide 9061 (manufactured by Dupont Japan K.K., 6/6
6/612 copolymerized nylon), diamide T-170
(Nylon 12-based copolymer nylon manufactured by Daicel Huls Co., Ltd.) and the like. Further, the undercoat layer 2 may contain an inorganic fine powder such as titanium oxide (TiO ₂ ), SnO ₂ , alumina, calcium carbonate, silica or the like.

The charge generating layer 3 is formed by vacuum-depositing an organic photoconductive substance or applying a material in which particles of the organic photoconductive substance are dispersed in a resin binder, and receives light. Generate electric charge. It is important that the charge generation layer 3 has high charge generation efficiency and at the same time injectability of the generated charge into the charge transport layer 4, has little electric field dependence, and preferably has good injection even at a low electric field.

It is necessary that at least a phthalocyanine compound is contained as a charge-generating substance, but other charge-generating substances such as pigments and dyes such as various azo, quinone, indigo, cyanine, squarylium, and azurenium compounds are used in combination. Can also.

In the present invention, the content of the phthalocyanine dimer compound in the charge generation layer 3 is 100 nmol to 300 mm per 1 mol of the phthalocyanine compound.
ol or less, preferably 200 nmol or more and 200 mmol
It is as follows. As described above, by including a specific amount of the phthalocyanine dimer compound in the phthalocyanine compound, the potential retention rate is significantly increased. Although such an action mechanism is not always clear, it can be considered as follows.
That is, the content of the phthalocyanine dimer compound is 10
If it is less than 0 nmol, it can be considered that the phthalocyanine compound is too pure and the crystal grows too much, or the dispersibility is lowered to cause a decrease in the retention. 300
If the amount exceeds mmol, it can be considered that the crystal arrangement of the phthalocyanine compound is excessively disturbed, or that the retention of the phthalocyanine compound decreases due to the action of the phthalocyanine dimer compound itself. The phthalocyanine dimer compound included in the phthalocyanine compound is not limited to the phthalocyanine compound having the same central element as the phthalocyanine compound, and the same effect can be obtained even when a dimer having a different central element is included.

The method for synthesizing the phthalocyanine compound that can be used in the present invention is known, and is described, for example, in PHTHALOCYANINES C.
C. Leznoff et al., 1989 (VCH Publishers. Inc.) or THE PHTHALOCYANINES FH Moser. Et al., 1983
(CRC Press), Sens. Actuators, B (1998), B48 (1-3),
Compounds can be synthesized according to the methods disclosed in 333-338 and the like.

The phthalocyanine compound forming the phthalocyanine dimer compound is particularly preferably titanyl oxo phthalocyanine. Further, in the present invention, the central element of the phthalocyanine compound is a transition metal, particularly titanium, vanadium, chromium, manganese, iron, cobalt, nickel, zirconium, niobium, molybdenum, rhodium, cerium, neodymium, samarium, europium and tungsten. Those selected from the group consisting of can also be suitably used. Furthermore, phthalocyanine whose central element is selected from the group consisting of indium, gallium, aluminum, germanium, tin, antimony, lead, bismuth, silicon, and phosphorus can also be suitably used. Further, the phthalocyanine compound has the following formula: (In the formula, M is a group Ia element (however, in this case, it may contain 2 atoms), or an element capable of being in an oxidation state of +2 or more, or an oxide, hydroxide, halide, or alcohol of the element. R ^{1 to} R ^{16 each} represent a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a cyano group, an ester group, an alkyl group, an alkenyl group, an alkoxyl group, an aryl group, or an aryloxy group which may be the same or different. Compounds having various functional groups introduced therein, such as the phthalocyanine compound represented by formula (1), can also be suitably used. In the present invention, it is also preferable to use a metal-free phthalocyanine as the phthalocyanine compound.

Incidentally, the dimer compound of the phthalocyanine compound takes various forms, for example, a μ-oxo metal phthalocyanine dimer, a μ metal phthalocyanine dimer, a μ metal phthalocyanine oligomer and the like. The 29H, 31H-phthalocyanine titanyl complex also falls under this category. Preferably, the phthalocyanine dimer compound is a mu oxo dimer compound, and more preferably the phthalocyanine dimer compound is Pc-MOMP
c-type structure (Pc is a phthalocyanine compound, M is an oxidation number +
Three or more elements, and O represents oxygen).
Similarly, preferably, the phthalocyanine dimer compound is μ
It is a dimer compound, and more preferably, the phthalocyanine dimer compound has a Pc-M-Pc type structure (Pc, M is the same as described above). Examples of such a phthalocyanine dimer compound having a Pc-M-Pc type structure include the 29H, 31H-phthalocyanine titanyl complex described above. Further, as another form of the dimer compound of the phthalocyanine compound, a dimer compound having a structure comprising two phthalocyanine rings bonded via at least one carbon atom, nitrogen atom or oxygen atom, and a titanium atom Are also mentioned. For example,
7,12: 13,58: 22,27; 28,38-tetrimino-15,20: 30,5-dinitrilo-12,
28: 27,13-bis (nitriloisoindole [3]
Ilylidenenitrilometheno [1,2] benzono) tetrabenzo [c, h, n, s] [1,6,12,17] tetraazacyclodocosin, titanium (+1) derivative, 7,
12: 13,58: 22,27; 28,38-tetrimino-15,20: 30,5-dinitrilo-12,2
8: 27,13-bis (nitriloisoindole [3] ylylidenenitrilometheno [1,2] benzono) tetrabenzo [c, h, n, s] [1,6,12,17] tetraazacyclodocosin , Titanyl complexes and the like.

As a method for detecting a phthalocyanine compound and a phthalocyanine dimer compound, matrix-assisted laser desorption ionization time-of-flight mass spectrometry (hereinafter referred to as M
ALDI-TOF-MS method or simply TOF-MS
, Field emission mass spectrometry, fast atom bombardment mass spectrometry, electron bombardment ionization mass spectrometry, and the like.

Since the phthalocyanine compound and the phthalocyanine dimer compound have a large absorption coefficient, MALDI-
When the TOF-MS method is used, a state of a fine powder having a particle diameter of less than 400 nm, a state in which only the fine powder having a diameter of less than 400 nm is dispersed or dissolved in an organic solvent and then dried by an appropriate method, and a fine powder having a diameter of less than 400 nm is used. For any sample form in which various resin binders are dispersed or dissolved in an organic solvent and then dried by an appropriate method, it is only possible to detect a phthalocyanine compound without adding a matrix compound. Instead, a mass spectrum reflecting the abundance ratio of the phthalocyanine compound can be obtained for any of the forms.

When the phthalocyanine compound is titanyl oxo phthalocyanine, when a TOF-MS analysis is performed on a crudely synthesized product, a peak may be generated not only in the titanyl oxo phthalocyanine ion having a mass number of 576 but also in the mass number 1136. One example of such a spectrum diagram is shown in FIG. Table 1 below shows a list of the detection intensities of the respective components. It should be noted that only the maximum isotope peak is shown.

[0029]

[Table 1] * Described for peaks with an area intensity ratio of 0.20% or more ** Calculated with the peak at M = 576 as 100%

Since the peak of mass number 1136 has the same mass number as that of the mu oxotitanyl phthalocyanine dimer, when the peak of mass number 1136 is detected,
The presence of the mu oxotitanyl phthalocyanine dimer compound is apparent.

The μ-oxotitanyl phthalocyanine dimer-containing titanyl oxo phthalocyanine was obtained from MA
LDI-TOF-MS analyzer (manufactured by Shimadzu Corporation)
When measured using Kompact MALDI IV), by optimizing the irradiation laser intensity,
200 per 1 mol of titanyl oxophthalocyanine
μmol or more of μoxotitanyl phthalocyanine dimer could be detected. In addition, when the abundance ratio of the μoxotitanyl phthalocyanine dimer exceeds 300 mmol per 1 mol of titanyl oxophthalocyanine, the area intensity of the peak of mass number 1136 with respect to the peak of mass number 576 exceeds 30%. Was.

Such components can be removed by a sublimation method. In the present invention, a phthalocyanine dimer compound by-produced during the synthesis can be used as it is.

Since the charge transport layer is laminated on the charge generating layer, its thickness is determined by the light absorption coefficient of the charge generating substance, and is generally 5 μm or less, preferably 1 μm or less.

The charge generation layer 3 can be mainly composed of a charge generation substance and added with a charge transport substance and the like. As the resin binder for the charge generation layer, polycarbonate, polyester, polyamide, polyurethane,
Epoxy, polyvinyl butyral, phenoxy, silicone, methacrylic acid ester polymers and copolymers,
And their halides, cyanoethyl compounds and the like can be used in appropriate combination. The amount of the charge generating substance used is 10 to 5000 parts by weight, preferably 50 to 10 parts by weight, based on 100 parts by weight of the resin binder.
00 parts by weight.

The charge transporting layer 4 is made of a material in which a charge transporting substance, for example, various hydrazone-based compounds, styryl-based compounds, amine-based compounds, and derivatives thereof, alone or in combination, are dispersed in a resin binder. It is a coating film and has a function of retaining charges of the photoreceptor as an insulator layer in a dark place and transporting charges injected from the charge generation layer when receiving light. As the resin binder for the charge transport layer, polycarbonate, polyester, polystyrene, polymers of methacrylic acid ester, mixed polymers and copolymers are used, but mechanical, chemical and electrical stability,
In addition to adhesion, compatibility with the charge transport material is important. The charge transporting substance is used in an amount of 20 to 500 parts by weight, preferably 30 to 300 parts by weight, per 100 parts by weight of the resin binder.
Parts by weight. In order to maintain a practically effective surface potential, the thickness of the charge transport layer is preferably in the range of 3 to 50 μm, and more preferably 15 to 40 μm.

[0036]

EXAMPLES Specific examples of the present invention will be described below, but the present invention is not limited to these examples.

Example 1 Formation of Undercoat Layer Polyamide resin (Amilan CM8000 manufactured by Toray Industries, Inc.)
70 parts by weight and methanol (manufactured by Wako Pure Chemical Industries, Ltd.) 9
The mixture was mixed with 30 parts by weight to prepare a coating liquid for an undercoat layer. The undercoat layer coating solution was applied onto an aluminum substrate by a dip coating method, and a dried undercoat layer having a thickness of 0.5 μm was formed.

Formation of Charge Generation Layer In a reaction vessel, 800 g of o-phthalonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) and quinoline (manufactured by Kanto Chemical Co., Ltd.)
1.8 liters were added and stirred. Under a nitrogen atmosphere, 297 g of titanium tetrachloride (manufactured by Kishida Chemical Co., Ltd.) was added dropwise,
Stirred. After the dropwise addition, the mixture was heated at 180 ° C. for 15 hours and further stirred.

The reaction solution was allowed to cool to 130 ° C., filtered, and washed with 3 liters of N-methyl-2-pyrrolidinone (Kanto Chemical Co., Ltd.). This wet cake was placed in a nitrogen atmosphere under N-methyl-2-pyrrolidinone.
The mixture was heated and stirred at 160 ° C. for 1 hour at 8 liters. This was allowed to cool, filtered, and washed sequentially with 3 liters of N-methyl-2-pyrrolidinone, 2 liters of acetone (manufactured by Kanto Kagaku), 2 liters of methanol (manufactured by Kanto Kagaku) and 4 liters of hot water. did.

The thus obtained titanyl oxophthalocyanine wet cake was further heated and stirred at 80 ° C. for 1 hour with 4 liters of water and 360 ml of 36% hydrochloric acid (manufactured by Kanto Chemical Co., Ltd.). . This was allowed to cool, filtered, washed with 4 liters of warm water and dried. This was purified by vacuum sublimation three times and then dried.

Next, 200 g of the above dried product was added to 4 kg of 96% sulfuric acid (manufactured by Kanto Chemical Co., Ltd.) at −5 ° C. while cooling and stirring so that the liquid temperature did not exceed −5 ° C.
And cooled for 1 hour and stirred. Further, this sulfuric acid solution was added to 35 liters of water and 5 kg of ice while cooling and stirring so that the liquid temperature did not exceed 10 ° C., followed by cooling for 1 hour and stirring. This was filtered and washed with 10 liters of warm water.

Further, 10 liters of water, 36%
The mixture was heated and stirred with 770 ml of dilute hydrochloric acid at 80 ° C. for 1 hour. Then, the mixture was allowed to cool, filtered, washed with 10 liters of warm water, and dried to obtain titanyloxophthalocyanine.

This titanyl oxo phthalocyanine has
Said document, PHTHALOCYANINES, C.I. C. Leznoff et al, 19
89 (VCH Publishers. Inc.), 100 nmol was added per 1 mol of titanyl oxophthalocyanine. 0.5 liter of water and 1.5 liter of o-dichlorobenzene (manufactured by Kanto Chemical Co., Ltd.)
6.6 kg of zirconia balls were placed in a ball mill and milled for 24 hours. Next, this was taken out with 1.5 liter of acetone and 1.5 liter of methanol, filtered, washed with 1.5 liter of water and dried.

10 parts by weight of the μ-oxo titanyl phthalocyanine dimer-containing titanyl oxo phthalocyanine,
Vinyl chloride resin (MR-110 manufactured by Zeon Corporation)
10 parts by weight, 686 parts by weight of dichloromethane and 1,
The mixture was mixed with 294 parts by weight of 2-dichloroethane and subjected to ultrasonic dispersion to prepare a coating solution for a charge generation layer. This coating solution for a charge generation layer was applied on the undercoat layer by dip coating to form a charge generation layer having a thickness of 0.2 μm after drying.

Formation of charge transport layer 4- (diphenylamino) benzaldehyde phenyl (2-thienylmethyl) hydrazone (Fuji Electric Co., Ltd.)
100 parts by weight), 100 parts by weight of a polycarbonate resin (Panlite K-1300 manufactured by Teijin Chemicals Limited), 800 parts by weight of dichloromethane, 1 part by weight of a silane coupling agent (KP-340 manufactured by Shin-Etsu Chemical Co., Ltd.) And 4 parts by weight of bis (2,4-di-tert-butylphenyl) phenylphosphonite (manufactured by Fuji Electric Co., Ltd.)
A coating solution for a charge transport layer was prepared. The coating solution for a charge transport layer was applied onto the charge generation layer by a dip coating method to form a charge transport layer having a thickness of 20 μm after drying, thereby producing an electrophotographic photoreceptor.

Example 2 The amount of the dioxomuth titanyl phthalocyanine dimer of Example 1 was changed to 10 per 1 mol of titanyl oxo phthalocyanine.
A photoconductor was prepared by the same way as that of Example 1 except that the composition was changed to μmol.

Example 3 The amount of the dioxomuth titanyl phthalocyanine of Example 1 was 1 m per 1 mol of titanyl oxo phthalocyanine.
A photoconductor was prepared by the same way as that of Example 1 except that mol was changed to mol.

Example 4 The amount of the dioxomuth titanyl phthalocyanine dimer of Example 1 was changed to 10 with respect to 1 mol of titanyl oxo phthalocyanine.
A photoconductor was prepared by the same way as that of Example 1 except that 0 mmol was used.

Example 5 The amount of the dioxo-oxo titanyl phthalocyanine of Example 1 was changed to 30 with respect to 1 mol of titanyl oxo phthalocyanine.
A photoconductor was prepared by the same way as that of Example 1 except that 0 mmol was used.

Example 6 The procedure of Example 1 was repeated except that the μ-oxotitanyl phthalocyanine dimer of Example 1 was added, acid-pasted with 96% sulfuric acid, washed with water, and dried. A photoreceptor was manufactured.

EXAMPLE 7 The amount of the dioxo-oxotitanyl phthalocyanine of Example 6 was changed to 10 per 1 mol of titanyl oxophthalocyanine.
A photoconductor was prepared by the same way as that of Example 6 except for changing to μmol.

Example 8 The amount of the μ-oxotitanyl phthalocyanine dimer of Example 6 was 1 m per 1 mol of titanyl oxo phthalocyanine.
A photoconductor was prepared by the same way as that of Example 6 except for changing to mol.

Example 9 The amount of the dioxo-oxo titanyl phthalocyanine of Example 6 was changed to 10 per 1 mol of titanyl oxo phthalocyanine.
A photoconductor was prepared by the same way as that of Example 6 except that 0 mmol was used.

Example 10 The amount of the dioxo-oxo titanyl phthalocyanine of Example 6 was changed to 30 with respect to 1 mol of titanyl oxo phthalocyanine.
A photoconductor was prepared by the same way as that of Example 6 except that 0 mmol was used.

[0055] The amount of Comparative Example 1 mu titanyl phthalocyanine dimer of Example 1 with respect to the titanyl oxo phthalocyanine 1 mol 50
A photoconductor was prepared by the same way as that of Example 1 except that the composition was changed to nmol.

Comparative Example 2 The amount of the dioxomuth titanyl phthalocyanine dimer of Example 1 was changed to 40 with respect to 1 mol of titanyl oxo phthalocyanine.
A photoconductor was prepared by the same way as that of Example 1 except that 0 mmol was used.

Comparative Example 3 The amount of the dioxo-oxo titanyl phthalocyanine of Example 6 was changed to 50 with respect to 1 mol of titanyl oxo phthalocyanine.
A photoconductor was prepared by the same way as that of Example 6 except for changing to nmol.

Comparative Example 4 The amount of the dioxo-oxotitanyl phthalocyanine dimer of Example 6 was changed to 40 with respect to 1 mol of titanyl oxophthalocyanine.
A photoconductor was prepared by the same way as that of Example 6 except that 0 mmol was used.

The electrical characteristics of the photoreceptor thus obtained were measured using an electrostatic recording paper tester (EPA-82 manufactured by Kawaguchi Electric Works).
00). The photoreceptor was charged to a surface potential of -600 V by a corotron in a dark place, allowed to stand in a dark portion for 5 seconds, and the potential retention rate (%) during that time was measured. The results obtained are shown in Table 2 below.

[0060]

[Table 2]

As is clear from Table 2, all the examples have a high retention and are good, but all the comparative examples have a low retention as compared with the examples.

Further, the titanyl oxophthalocyanine containing the μ-oxo titanyl phthalocyanine dimer used in Examples 3 to 5 and Examples 8 to 10 was analyzed using MALDI-TOF.
-MS analyzer (Kompact, manufactured by Shimadzu Corporation)
The measurement was carried out using MALDI IV), and both showed clear peaks at mass numbers 576 and 1136, and the mass number 576 could be identified as a titanyloxophthalocyanine molecular ion. At this time, the area intensity ratio of the peak with the mass number of 1136 was more than 10 ⁻⁵ % with respect to the peak with the mass number of 576.

Further, the photoreceptors for electrophotography prepared in Examples 3 to 5 and Examples 8 to 10 were subjected to extraction and removal of a charge generating material, an antioxidant, and a silane coupling material using an acetone ultrasonic bath. After dissolving and removing the charge transport layer resin by immersion in dichloromethane, a solution in which the charge generating material and the charge generating material resin are dispersed by immersion in dichloromethane under an ultrasonic bath is prepared, and the TOF-MS analyzer is used. As a result of the measurement, clear peaks were observed at both mass number 576 and mass number 1136, and mass number 576 could be identified as a titanyloxophthalocyanine molecular ion. At this time, the area intensity ratio of the peak with the mass number of 1136 was more than 10 ⁻⁵ % with respect to the peak with the mass number of 576.

Example 11 The μ-oxotitanyl phthalocyanine dimer of Example 1 was
A photoreceptor was produced in the same manner as in Example 1, except that the μ-oxomanganese phthalocyanine dimer synthesized according to a conventional method was used.

Example 12 The amount of the μoxomanganese phthalocyanine dimer of Example 11 was 1 to 1 mol of titanyloxophthalocyanine.
A photoconductor was prepared by the same way as that of Example 11 except that 0 μmol was used.

Example 13 The amount of the μ-oxomanganese phthalocyanine dimer of Example 11 was 1 to 1 mol of titanyl oxophthalocyanine.
A photoconductor was prepared by the same way as that of Example 11 except for changing to mmol.

Example 14 The amount of the dioxo manganese phthalocyanine dimer of Example 11 was 1 to 1 mol of titanyl oxo phthalocyanine.
A photoconductor was prepared by the same way as that of Example 11 except that it was changed to 00 mmol.

Example 15 The amount of the μoxomanganese phthalocyanine dimer of Example 11 was changed to 3 with respect to 1 mol of titanyloxophthalocyanine.
A photoconductor was prepared by the same way as that of Example 11 except that it was changed to 00 mmol.

Example 16 The procedure of Example 11 was repeated, except that the μ-oxomanganese phthalocyanine dimer of Example 11 was added, acid-pasted with 96% sulfuric acid, washed with water, and dried. A photoreceptor was manufactured.

Example 17 The amount of the μ-oxomanganese phthalocyanine dimer of Example 16 was 1 to 1 mol of titanyloxophthalocyanine.
A photoconductor was prepared by the same way as that of Example 16 except that it was changed to 0 μmol.

Example 18 The amount of the dioxo-oxo manganese phthalocyanine of Example 16 was changed to 1 with respect to 1 mol of titanyl oxo phthalocyanine.
A photoconductor was prepared by the same way as that of Example 16 except for changing to mmol.

Example 19 The amount of the μ-oxomanganese phthalocyanine dimer of Example 16 was changed to 1 with respect to 1 mol of titanyl oxophthalocyanine.
A photoconductor was prepared by the same way as that of Example 16 except that the content was changed to 00 mmol.

Example 20 The amount of the dioxo manganese phthalocyanine dimer of Example 16 was 3 to 1 mol of titanyl oxo phthalocyanine.
A photoconductor was prepared by the same way as that of Example 16 except that the content was changed to 00 mmol.

COMPARATIVE EXAMPLE 5 The amount of the μ-oxomanganese phthalocyanine dimer of Example 11 was calculated based on 1 mol of titanyl oxophthalocyanine.
A photoconductor was prepared by the same way as that of Example 11 except that 0 nmol was used.

COMPARATIVE EXAMPLE 6 The amount of the μoxomanganese phthalocyanine dimer of Example 11 was changed to 4 with respect to 1 mol of titanyloxophthalocyanine.
A photoconductor was prepared by the same way as that of Example 11 except that it was changed to 00 mmol.

COMPARATIVE EXAMPLE 7 The amount of the dioxo-manganese phthalocyanine dimer of Example 16 was 5 to 1 mol of titanyl oxophthalocyanine.
A photoconductor was prepared by the same way as that of Example 16 except that 0 nmol was used.

Comparative Example 8 The amount of the μ-oxomanganese phthalocyanine dimer of Example 16 was changed to 4 with respect to 1 mol of titanyloxophthalocyanine.
A photoconductor was prepared by the same way as that of Example 16 except that the content was changed to 00 mmol.

The electrical characteristics of the photoreceptor thus obtained were measured in the same manner as described above, and the retention (%) was determined.
The results obtained are shown in Table 3 below.

[0079]

[Table 3]

As is clear from Table 3, all the examples have high retention rates and are good, but all the comparative examples have low retention rates as compared with the examples.

Example 21 Example 1 was repeated except that the titanyl oxophthalocyanine of Example 1 was replaced with iron phthalocyanine synthesized according to a conventional method.
A photoreceptor was produced in the same manner as described above.

Example 22 A photoconductor was prepared by the same way as that of Example 21 except that the amount of .mu. Oxotitanyl phthalocyanine dimer in Example 21 was changed to 10 .mu.mol per 1 mol of iron phthalocyanine.

Example 23 A photoconductor was prepared by the same way as that of Example 21 except that the content of .mu. Oxotitanyl phthalocyanine dimer in Example 21 was changed to 1 mmol per 1 mol of iron phthalocyanine.

Example 24 The amount of the dioxo-oxotitanyl phthalocyanine of Example 21 was changed to 100 mmol per 1 mol of iron phthalocyanine.
A photoconductor was prepared by the same way as that of Example 21 except that the above was used.

Example 25 The amount of the dioxo-oxotitanyl phthalocyanine dimer of Example 21 was changed to 300 mmol per 1 mol of iron phthalocyanine.
A photoconductor was prepared by the same way as that of Example 21 except that the above was used.

Example 26 Photosensitization was performed in the same manner as in Example 21 except that the μ-oxotitanyl phthalocyanine dimer of Example 21 was added, acid-pasted with 96% sulfuric acid, washed with water, and dried. Body manufactured.

Example 27 A photoconductor was prepared by the same way as that of Example 26 except that the amount of μ-oxotitanyl phthalocyanine dimer was changed to 10 μmol per 1 mol of iron phthalocyanine.

Example 28 A photoconductor was prepared by the same way as that of Example 26 except that the amount of μ-oxotitanyl phthalocyanine dimer in Example 26 was changed to 1 mmol per 1 mol of iron phthalocyanine.

Example 29 The amount of the dioxo-oxotitanyl phthalocyanine of Example 26 was changed to 100 mmol per 1 mol of iron phthalocyanine.
A photoconductor was prepared by the same way as that of Example 26 except that the above was replaced with.

Example 30 The amount of the dioxomuth titanyl phthalocyanine of Example 26 was changed to 300 mmol per 1 mol of iron phthalocyanine.
A photoconductor was prepared by the same way as that of Example 26 except that the above was replaced with.

Comparative Example 9 A photoconductor was prepared by the same way as that of Example 21 except that the content of .mu. Oxotitanyl phthalocyanine dimer in Example 21 was changed to 50 nmol per 1 mol of iron phthalocyanine.

Comparative Example 10 The amount of the dioxomuth titanyl phthalocyanine dimer of Example 21 was changed to 400 mmol per 1 mol of iron phthalocyanine.
A photoconductor was prepared by the same way as that of Example 21 except that the above was used.

Comparative Example 11 A photoconductor was prepared by the same way as that of Example 26 except that the content of .mu. Oxotitanyl phthalocyanine dimer was changed to 50 nmol per 1 mol of iron phthalocyanine.

Comparative Example 12 The amount of the dioxo-oxotitanyl phthalocyanine dimer of Example 26 was changed to 400 mmol per 1 mol of iron phthalocyanine.
A photoconductor was prepared by the same way as that of Example 26 except that the above was replaced with.

The electrical characteristics of the thus-obtained photoreceptor were measured in the same manner as described above, and the retention (%) was determined.
The results obtained are shown in Table 4 below.

[0096]

[Table 4]

As is clear from Table 4, all the examples have a high retention and are good, but all the comparative examples have a low retention as compared with the examples.

Example 31 A photoconductor was prepared by the same way as that of Example 21 except that the μ-oxotitanyl phthalocyanine dimer of Example 21 was changed to μ-oxo-iron phthalocyanine dimer synthesized according to a conventional method.

Example 32 A photoconductor was prepared by the same way as that of Example 31 except that the amount of μ-oxo iron phthalocyanine dimer was changed to 10 μmol per 1 mol of iron phthalocyanine.

Example 33 A photoconductor was prepared by the same way as that of Example 31 except that the amount of μoxo-iron phthalocyanine dimer was changed to 1 mmol per 1 mol of iron phthalocyanine.

Example 34 A photoconductor was prepared by the same way as that of Example 31 except that the amount of μoxo-iron phthalocyanine dimer was changed to 100 mmol per 1 mol of iron phthalocyanine.

Example 35 A photoconductor was prepared by the same way as that of Example 31 except that the content of μoxo-iron phthalocyanine dimer was changed to 300 mmol per 1 mol of iron phthalocyanine.

Example 36 Photosensitization was carried out in the same manner as in Example 31 except that the μ-oxoiron phthalocyanine dimer of Example 31 was added, acid-pasted with 96% sulfuric acid, washed with water, and dried. Body manufactured.

Example 37 A photoconductor was prepared by the same way as that of Example 36 except that the content of μoxo-iron phthalocyanine dimer was changed to 10 μmol per 1 mol of iron phthalocyanine.

Example 38 A photoconductor was prepared by the same way as that of Example 36 except that the amount of μoxo-iron phthalocyanine dimer was changed to 1 mmol per 1 mol of iron phthalocyanine.

Example 39 A photoconductor was prepared by the same way as that of Example 36 except that the amount of μoxo-iron phthalocyanine dimer was changed to 100 mmol per 1 mol of iron phthalocyanine.

Example 40 A photoconductor was prepared by the same way as that of Example 36 except that the amount of μoxo-iron phthalocyanine dimer was changed to 300 mmol per 1 mol of iron phthalocyanine.

Comparative Example 13 A photoconductor was prepared by the same way as that of Example 31 except that the amount of μoxo-iron phthalocyanine dimer was changed to 50 nmol per 1 mol of iron phthalocyanine.

Comparative Example 14 A photoconductor was prepared by the same way as that of Example 31 except that the amount of μoxo-iron phthalocyanine dimer was changed to 400 mmol per 1 mol of iron phthalocyanine.

Comparative Example 15 A photoconductor was prepared by the same way as that of Example 36 except that the amount of μoxo-iron phthalocyanine dimer was changed to 50 nmol per 1 mol of iron phthalocyanine.

Comparative Example 16 A photoconductor was prepared by the same way as that of Example 36 except that the amount of μoxo-iron phthalocyanine dimer was changed to 400 mmol per 1 mol of iron phthalocyanine.

The electrical characteristics of the photoreceptor thus obtained were measured in the same manner as described above, and the retention (%) was determined.
The results obtained are shown in Table 5 below.

[0113]

[Table 5]

As is evident from Table 5, all of the examples have high retention rates and are good, but all of the comparative examples have low retention rates as compared with the examples.

Example 41 The iron phthalocyanine of Example 31 was synthesized according to a conventional method to obtain iron (II) 1,2,3,4,8,9,10,11,15,
16, 17, 18, 22, 23, 24, 25-hexadecafluoro-29H, 31H-phthalocyanine (hereinafter, referred to as “16,
A photoconductor was prepared by the same way as that of Example 31 except that fluoroiron phthalocyanine was used).

Example 42 The amount of the dioxo-oxo-iron phthalocyanine of Example 41 was changed to 10 μmol per 1 mol of fluoro-iron phthalocyanine.
A photoconductor was prepared by the same way as that of Example 41 except that the above-mentioned was used.

Example 43 A photoconductor was prepared by the same way as that of Example 41 except that the amount of μoxo-iron phthalocyanine dimer was changed to 1 mmol per 1 mol of fluoroiron phthalocyanine.

Example 44 The amount of the dioxo-oxo-iron phthalocyanine of Example 41 was changed to 100 mmol per 1 mol of fluoro-iron phthalocyanine.
A photoconductor was prepared by the same way as that of Example 41 except that 1 was changed.

Example 45 The amount of the μoxo-iron phthalocyanine dimer of Example 41 was changed to 300 mmol per 1 mol of fluoroiron phthalocyanine.
A photoconductor was prepared by the same way as that of Example 41 except that 1 was changed.

Example 46 A photosensitizer was prepared in the same manner as in Example 41 except that the dioxo-iron phthalocyanine dimer of Example 41 was added, acid-pasted with 96% sulfuric acid, washed with water, and dried. Body manufactured.

Example 47 The amount of the dioxo-iron phthalocyanine dimer of Example 46 was changed to 10 μmol per 1 mol of fluoroiron phthalocyanine.
A photoconductor was prepared by the same way as that of Example 46 except that the above-mentioned was used.

Example 48 A photoconductor was prepared by the same way as that of Example 46 except that the amount of μoxo-iron phthalocyanine dimer was changed to 1 mmol per 1 mol of fluoroiron phthalocyanine.

Example 49 The amount of the dioxo-oxo-iron phthalocyanine of Example 46 was set to 100 mmol per 1 mol of fluoro-iron phthalocyanine.
A photoconductor was prepared by the same way as that of Example 46 except that 1 was changed.

Example 50 The amount of the dioxo-oxo-iron phthalocyanine of Example 46 was changed to 300 mmol per 1 mol of fluoro-iron phthalocyanine.
A photoconductor was prepared by the same way as that of Example 46 except that 1 was changed.

Comparative Example 17 The amount of the μoxoiron phthalocyanine dimer of Example 41 was changed to 50 nmol per 1 mol of fluoroiron phthalocyanine.
A photoconductor was prepared by the same way as that of Example 41 except that the above-mentioned was used.

Comparative Example 18 The amount of the μoxoiron phthalocyanine dimer of Example 41 was 400 mmol per 1 mol of fluoroiron phthalocyanine.
A photoconductor was prepared by the same way as that of Example 41 except that 1 was changed.

Comparative Example 19 The amount of the μ-oxo iron phthalocyanine dimer of Example 46 was changed to 50 nmol per 1 mol of fluoroiron phthalocyanine.
A photoconductor was prepared by the same way as that of Example 46 except that the above-mentioned was used.

Comparative Example 20 The amount of the μoxoiron phthalocyanine dimer of Example 46 was changed to 400 mmol per 1 mol of fluoroiron phthalocyanine.
A photoconductor was prepared by the same way as that of Example 46 except that 1 was changed.

The electrical characteristics of the photoreceptor thus obtained were measured in the same manner as described above, and the retention (%) was determined.
The results obtained are shown in Table 6 below.

[0130]

[Table 6]

As is evident from Table 6, all of the examples have a high retention and are good, but all of the comparative examples have a low retention as compared with the examples.

Example 51 Example 2 was repeated except that the iron phthalocyanine of Example 21 was replaced with zirconium phthalocyanine synthesized according to a conventional method.
In the same manner as in Example 1, a photoconductor was manufactured.

Example 52 The amount of the dioxomuth titanyl phthalocyanine of Example 51 was changed to 10 per 1 mol of zirconium phthalocyanine.
A photoconductor was prepared by the same way as that of Example 51 except that the composition was changed to μmol.

Example 53 The amount of the μ-oxotitanyl phthalocyanine dimer of Example 51 was 1 m per 1 mol of zirconium phthalocyanine.
A photoconductor was prepared by the same way as that of Example 51 except for changing to mol.

Example 54 The amount of the dioxo-oxotitanyl phthalocyanine dimer of Example 51 was changed to 10 with respect to 1 mol of zirconium phthalocyanine.
A photoconductor was prepared by the same way as that of Example 51 except that 0 mmol was used.

Example 55 The amount of the dioxomuth titanyl phthalocyanine dimer of Example 51 was 30 per 1 mol of zirconium phthalocyanine.
A photoconductor was prepared by the same way as that of Example 51 except that 0 mmol was used.

Example 56 Photosensitization was carried out in the same manner as in Example 51 except that the μ-oxotitanyl phthalocyanine dimer of Example 51 was added, acid-pasted with 96% sulfuric acid, washed with water and dried. Body manufactured.

Example 57 The amount of the dioxo-oxotitanyl phthalocyanine dimer of Example 56 was changed to 10 per 1 mol of zirconium phthalocyanine.
A photoconductor was prepared by the same way as that of Example 56 except that μmol was changed.

Example 58 The amount of the dioxo-oxotitanyl phthalocyanine dimer of Example 56 was 1 m per 1 mol of zirconium phthalocyanine.
A photoconductor was prepared by the same way as that of Example 56 except for changing to mol.

Example 59 The amount of the dioxomuth titanyl phthalocyanine dimer of Example 56 was changed to 10 per mol of zirconium phthalocyanine.
A photoconductor was prepared by the same way as that of Example 56 except that the content was changed to 0 mmol.

Example 60 The amount of the dioxomuth titanyl phthalocyanine dimer of Example 56 was changed to 30 with respect to 1 mol of zirconium phthalocyanine.
A photoconductor was prepared by the same way as that of Example 56 except that the content was changed to 0 mmol.

Comparative Example 21 The amount of the dioxo-oxotitanyl phthalocyanine dimer of Example 51 was adjusted to 50 with respect to 1 mol of zirconium phthalocyanine.
A photoconductor was prepared by the same way as that of Example 51 except that it was changed to nmol.

Comparative Example 22 The amount of the dioxo-oxotitanyl phthalocyanine of Example 51 was changed to 40 with respect to 1 mol of zirconium phthalocyanine.
A photoconductor was prepared by the same way as that of Example 51 except that 0 mmol was used.

Comparative Example 23 The amount of the dioxomuth titanyl phthalocyanine dimer of Example 56 was adjusted to 50 with respect to 1 mol of zirconium phthalocyanine.
A photoconductor was prepared by the same way as that of Example 56 except that nmol was used.

Comparative Example 24 The amount of the dioxo-oxotitanyl phthalocyanine of Example 56 was changed to 40 with respect to 1 mol of zirconium phthalocyanine.
A photoconductor was prepared by the same way as that of Example 56 except that the content was changed to 0 mmol.

The electrical characteristics of the photoreceptor thus obtained were measured in the same manner as described above, and the retention (%) was determined.
The results obtained are shown in Table 7 below.

[0147]

[Table 7]

As is clear from Table 7, all of the examples have a high retention and are good, and all the comparative examples have a low retention as compared with the examples.

Example 61 Example 31 was repeated except that the iron phthalocyanine of Example 31 was replaced with vanadium phthalocyanine synthesized according to a conventional method.
A photoreceptor was produced in the same manner as described above.

Example 62 The amount of the dioxo-iron phthalocyanine dimer of Example 61 was changed to 10 μmol per 1 mol of vanadium phthalocyanine.
A photoreceptor was manufactured in the same manner as in Example 61 except that the above was replaced with

Example 63 A photoconductor was prepared by the same way as that of Example 61 except that the amount of μoxo-iron phthalocyanine dimer was changed to 1 mmol per 1 mol of vanadium phthalocyanine.

Example 64 The amount of the dioxo-oxo-iron phthalocyanine dimer of Example 61 was changed to 100 mmol per 1 mol of vanadium phthalocyanine.
A photoconductor was prepared by the same way as that of Example 61 except that 1 was changed.

Example 65 The amount of the dioxo-oxo-iron phthalocyanine of Example 61 was changed to 300 mmol per 1 mol of vanadium phthalocyanine.
A photoconductor was prepared by the same way as that of Example 61 except that 1 was changed.

Example 66 Photosensitization was performed in the same manner as in Example 61 except that the dioxo-iron phthalocyanine dimer of Example 61 was added, acid-pasted with 96% sulfuric acid, washed with water, and dried. Body manufactured.

Example 67 The amount of the dioxo-iron phthalocyanine dimer of Example 66 was changed to 10 μmol per 1 mol of vanadium phthalocyanine.
A photoconductor was manufactured by the same way as that of Example 66 except that the above was replaced with.

Example 68 A photoconductor was prepared by the same way as that of Example 66 except that the amount of μoxo-iron phthalocyanine dimer was changed to 1 mmol per 1 mol of vanadium phthalocyanine.

Example 69 The amount of the dioxo-oxo-iron phthalocyanine dimer of Example 66 was changed to 100 mmol per 1 mol of vanadium phthalocyanine.
A photoconductor was prepared by the same way as that of Example 66 except that 1 was changed.

Example 70 The amount of the dioxo-oxo-iron phthalocyanine dimer of Example 66 was changed to 300 mmol per 1 mol of vanadium phthalocyanine.
A photoconductor was prepared by the same way as that of Example 66 except that 1 was changed.

Comparative Example 25 The quantity of the dioxo-oxo-iron phthalocyanine dimer of Example 61 was changed to 50 nmol per 1 mol of vanadium phthalocyanine.
A photoreceptor was manufactured in the same manner as in Example 61 except that the above was replaced with

Comparative Example 26 The amount of the μoxoiron phthalocyanine dimer of Example 61 was changed to 400 mmol per 1 mol of vanadium phthalocyanine.
A photoconductor was prepared by the same way as that of Example 61 except that 1 was changed.

Comparative Example 27 The amount of the dioxo-oxo-iron phthalocyanine dimer of Example 66 was changed to 50 nmol per 1 mol of vanadium phthalocyanine.
A photoconductor was manufactured by the same way as that of Example 66 except that the above was replaced with.

Comparative Example 28 The amount of the dioxo-μ iron phthalocyanine dimer of Example 66 was set to 400 mmol per 1 mol of vanadium phthalocyanine.
A photoconductor was prepared by the same way as that of Example 66 except that 1 was changed.

The electrical characteristics of the photoreceptor thus obtained were measured in the same manner as described above, and the retention (%) was determined.
The results obtained are shown in Table 8 below.

[0164]

[Table 8]

As is clear from Table 8, all of the examples have high retention rates and are good, but all of the comparative examples have low retention rates as compared with the examples.

Example 71 A photoconductor was prepared by the same way as that of Example 31 except that the iron phthalocyanine of Example 31 was replaced with niobium phthalocyanine synthesized according to a conventional method.

Example 72 A photoconductor was prepared by the same way as that of Example 71 except that the amount of μoxo-iron phthalocyanine dimer was changed to 10 μmol per 1 mol of niobium phthalocyanine.

Example 73 A photoconductor was prepared by the same way as that of Example 71 except that the amount of μoxo-iron phthalocyanine dimer was changed to 1 mmol per 1 mol of niobium phthalocyanine.

Example 74 A photoconductor was prepared by the same way as that of Example 71 except that the amount of μoxo-iron phthalocyanine dimer was changed to 100 mmol per 1 mol of niobium phthalocyanine.

Example 75 A photoconductor was prepared by the same way as that of Example 71 except that the amount of μoxo-iron phthalocyanine dimer was changed to 300 mmol per 1 mol of niobium phthalocyanine.

Example 76 Photosensitization was carried out in the same manner as in Example 71 except that the μ-oxo iron phthalocyanine dimer of Example 71 was added, acid-pasted with 96% sulfuric acid, washed with water, and dried. Body manufactured.

Example 77 A photoconductor was prepared by the same way as that of Example 76 except that the amount of μoxo-iron phthalocyanine dimer was changed to 10 μmol per 1 mol of niobium phthalocyanine.

Example 78 A photoconductor was prepared by the same way as that of Example 76 except that the amount of μoxo-iron phthalocyanine dimer was changed to 1 mmol per 1 mol of niobium phthalocyanine.

Example 79 A photoconductor was prepared by the same way as that of Example 76 except that the amount of μoxo-iron phthalocyanine dimer was changed to 100 mmol per 1 mol of niobium phthalocyanine.

Example 80 A photoconductor was prepared by the same way as that of Example 76 except that the amount of μoxo-iron phthalocyanine dimer was changed to 300 mmol per 1 mol of niobium phthalocyanine.

Comparative Example 29 A photoconductor was prepared by the same way as that of Example 71 except that the amount of μoxo-iron phthalocyanine dimer was changed to 50 nmol per 1 mol of niobium phthalocyanine.

Comparative Example 30 A photoconductor was prepared by the same way as that of Example 71 except that the amount of μoxo-iron phthalocyanine dimer was changed to 400 mmol per 1 mol of niobium phthalocyanine.

Comparative Example 31 A photoconductor was prepared by the same way as that of Example 76 except that the amount of μoxo-iron phthalocyanine dimer was changed to 50 nmol per 1 mol of niobium phthalocyanine.

Comparative Example 32 A photoconductor was prepared by the same way as that of Example 76 except that the amount of μoxo-iron phthalocyanine dimer was changed to 400 mmol per 1 mol of niobium phthalocyanine.

The electrical characteristics of the photoreceptor thus obtained were measured in the same manner as described above, and the retention (%) was determined.
The results obtained are shown in Table 9 below.

[0181]

[Table 9]

As is clear from Table 9, all of the examples have high retention rates and are good, but all of the comparative examples have low retention rates as compared with the examples.

Example 81 Example 31 was repeated except that the iron phthalocyanine of Example 31 was replaced with indium phthalocyanine synthesized according to a conventional method.
A photoreceptor was produced in the same manner as described above.

Example 82 The amount of the dioxo-iron phthalocyanine dimer of Example 81 was changed to 10 μmol per 1 mol of indium phthalocyanine.
A photoconductor was prepared by the same way as that of Example 81 except that the above was used.

Example 83 A photoconductor was prepared by the same way as that of Example 81 except that the amount of μoxo-iron phthalocyanine dimer was changed to 1 mmol per 1 mol of indium phthalocyanine.

Example 84 The amount of the dioxomuth iron phthalocyanine dimer of Example 81 was changed to 100 mmol per 1 mol of indium phthalocyanine.
A photoconductor was prepared by the same way as that of Example 81 except that 1 was used.

Example 85 The amount of the dioxo-iron phthalocyanine dimer of Example 81 was set at 300 mmol per 1 mol of indium phthalocyanine.
A photoconductor was prepared by the same way as that of Example 81 except that 1 was used.

Example 86 A photosensitizer was prepared in the same manner as in Example 81 except that the μ-oxo iron phthalocyanine dimer of Example 81 was added, acid-pasted with 96% sulfuric acid, washed with water, and dried. Body manufactured.

Example 87 The amount of the dioxo-oxo-iron phthalocyanine of Example 86 was changed to 10 μmol per 1 mol of indium phthalocyanine.
A photoconductor was manufactured by the same way as that of Example 86 except that the above-mentioned was used.

Example 88 A photoconductor was prepared by the same way as that of Example 86 except that the amount of μoxo-iron phthalocyanine dimer was changed to 1 mmol per 1 mol of indium phthalocyanine.

Example 89 The amount of the dioxo-oxo-iron phthalocyanine dimer of Example 86 was changed to 100 mmol per 1 mol of indium phthalocyanine.
A photoconductor was prepared by the same way as that of Example 86 except that 1 was used.

Example 90 The amount of the dioxo-oxo-iron phthalocyanine of Example 86 was set at 300 mmol per 1 mol of indium phthalocyanine.
A photoconductor was prepared by the same way as that of Example 86 except that 1 was used.

Comparative Example 33 The amount of the dioxo-iron phthalocyanine dimer of Example 81 was changed to 50 nmol per 1 mol of indium phthalocyanine.
A photoconductor was prepared by the same way as that of Example 81 except that the above was used.

Comparative Example 34 The amount of the μoxo-iron phthalocyanine dimer of Example 81 was changed to 400 mmol per 1 mol of indium phthalocyanine.
A photoconductor was prepared by the same way as that of Example 81 except that 1 was used.

Comparative Example 35 The amount of the dioxomuth iron phthalocyanine dimer of Example 86 was changed to 50 nmol per 1 mol of indium phthalocyanine.
A photoconductor was manufactured by the same way as that of Example 86 except that the above-mentioned was used.

Comparative Example 36 The amount of the μoxo-iron phthalocyanine dimer of Example 86 was changed to 400 mmol per 1 mol of indium phthalocyanine.
A photoconductor was prepared by the same way as that of Example 86 except that 1 was used.

The electrical characteristics of the photoreceptor thus obtained were measured in the same manner as described above, and the retention (%) was determined.
The results obtained are shown in Table 10 below.

[0198]

[Table 10]

As is clear from Table 10, all the examples have a high retention and are good, but all the comparative examples have a low retention as compared with the examples.

Example 91 A photoconductor was prepared by the same way as that of Example 31 except that gallium phthalocyanine synthesized according to a conventional method was used instead of iron phthalocyanine.

Example 92 A photoconductor was prepared by the same way as that of Example 91 except that the amount of μoxo-iron phthalocyanine dimer was changed to 10 μmol per 1 mol of gallium phthalocyanine.

Example 93 A photoconductor was prepared by the same way as that of Example 91 except that the amount of μoxo-iron phthalocyanine dimer was changed to 1 mmol per 1 mol of gallium phthalocyanine.

Example 94 The amount of the dioxo-iron phthalocyanine dimer of Example 91 was changed to 100 mmol per 1 mol of gallium phthalocyanine.
A photoconductor was manufactured by the same way as that of Example 91 except that the above was replaced with.

Example 95 The amount of the dioxo-iron phthalocyanine dimer of Example 91 was changed to 300 mmol per 1 mol of gallium phthalocyanine.
A photoconductor was manufactured by the same way as that of Example 91 except that the above was replaced with.

Example 96 A photosensitizer was prepared in the same manner as in Example 91 except that the dioxo-iron phthalocyanine dimer of Example 91 was added, acid-pasted with 96% sulfuric acid, washed with water, and dried. Body manufactured.

Example 97 A photoconductor was prepared by the same way as that of Example 96 except that the amount of μ-oxo iron phthalocyanine dimer was changed to 10 μmol per 1 mol of gallium phthalocyanine.

Example 98 A photoconductor was prepared by the same way as that of Example 96 except that the amount of μoxo-iron phthalocyanine dimer was changed to 1 mmol per 1 mol of gallium phthalocyanine.

Example 99 The amount of the μoxoiron phthalocyanine dimer of Example 96 was changed to 100 mmol per 1 mol of gallium phthalocyanine.
A photoconductor was prepared by the same way as that of Example 96 except that the above-mentioned was used.

Example 100 The amount of the dioxo-oxo-iron phthalocyanine dimer of Example 96 was set to 300 mmol per 1 mol of gallium phthalocyanine.
A photoconductor was prepared by the same way as that of Example 96 except that the above-mentioned was used.

Comparative Example 37 A photoconductor was prepared by the same way as that of Example 91 except that the amount of μoxo-iron phthalocyanine dimer was changed to 50 nmol per 1 mol of gallium phthalocyanine.

Comparative Example 38 The amount of the μ-oxo iron phthalocyanine dimer of Example 91 was changed to 400 mmol per 1 mol of gallium phthalocyanine.
A photoconductor was manufactured by the same way as that of Example 91 except that the above was replaced with.

Comparative Example 39 A photoconductor was prepared by the same way as that of Example 96 except that the amount of μoxo-iron phthalocyanine dimer was changed to 50 nmol per 1 mol of gallium phthalocyanine.

Comparative Example 40 The amount of the μ-oxo iron phthalocyanine dimer of Example 96 was changed to 400 mmol per 1 mol of gallium phthalocyanine.
A photoconductor was prepared by the same way as that of Example 96 except that the above-mentioned was used.

The electrical characteristics of the photoreceptor thus obtained were measured in the same manner as described above, and the retention (%) was determined.
The results obtained are shown in Table 11 below.

[0215]

[Table 11]

As is clear from Table 11, all the examples have high retention rates and are good, but all the comparative examples have low retention rates as compared with the examples.

Example 101 Example 3 was repeated except that the iron phthalocyanine of Example 31 was replaced with germanium phthalocyanine synthesized according to a conventional method.
In the same manner as in Example 1, a photoconductor was manufactured.

Example 102 The amount of the dioxo-oxo-iron phthalocyanine dimer of Example 101 was 10 μm per 1 mol of germanium phthalocyanine.
A photoconductor was manufactured by the same way as that of Example 101 except that ol was used.

Example 103 The amount of the dioxo-oxo-iron phthalocyanine dimer of Example 101 was 1 mmol per 1 mol of germanium phthalocyanine.
A photoconductor was prepared by the same way as that of Example 101 except that 1 was changed.

Example 104 The amount of the dioxo-iron phthalocyanine dimer of Example 101 was set to 100 m with respect to 1 mol of germanium phthalocyanine.
A photoconductor was prepared by the same way as that of Example 101 except that the mol was changed to mol.

Example 105 The amount of the dioxo-oxo-iron phthalocyanine dimer of Example 101 was 300 m per 1 mol of germanium phthalocyanine.
A photoconductor was prepared by the same way as that of Example 101 except that the mol was changed to mol.

Example 106 After the addition of the μ-oxo iron phthalocyanine dimer of Example 101, acid pasting treatment with 96% sulfuric acid was carried out.
A photoconductor was prepared by the same way as that of Example 101 except that it was washed with water and dried.

Example 107 The amount of the dioxo-oxo-iron phthalocyanine dimer of Example 106 was 10 μm per 1 mol of germanium phthalocyanine.
A photoconductor was prepared by the same way as that of Example 106 except that ol was used.

Example 108 The amount of the dioxomuth iron phthalocyanine dimer of Example 106 was 1 mmol per 1 mol of germanium phthalocyanine.
A photoconductor was prepared by the same way as that of Example 106 except that 1 was changed.

Example 109 The amount of the μoxoiron phthalocyanine dimer of Example 106 was set to 100 m with respect to 1 mol of germanium phthalocyanine.
A photoconductor was prepared by the same way as that of Example 106 except that the mol was changed to mol.

Example 110 The amount of the dioxo-oxo-iron phthalocyanine dimer of Example 106 was 300 m per 1 mol of germanium phthalocyanine.
A photoconductor was prepared by the same way as that of Example 106 except for changing to mol.

Comparative Example 41 The amount of the μ-oxo iron phthalocyanine dimer of Example 101 was changed to 50 nm with respect to 1 mol of germanium phthalocyanine.
A photoconductor was manufactured by the same way as that of Example 101 except that ol was used.

Comparative Example 42 The amount of the μ-oxo iron phthalocyanine dimer of Example 101 was 400 m per 1 mol of germanium phthalocyanine.
A photoconductor was prepared by the same way as that of Example 101 except that the mol was changed to mol.

Comparative Example 43 The amount of the dioxo-oxo-iron phthalocyanine of Example 106 was changed to 50 nm with respect to 1 mol of germanium phthalocyanine.
A photoconductor was prepared by the same way as that of Example 106 except that ol was used.

Comparative Example 44 The amount of the dioxo-iron phthalocyanine dimer of Example 106 was 400 m per 1 mol of germanium phthalocyanine.
A photoconductor was prepared by the same way as that of Example 106 except that the mol was changed to mol.

The electrical characteristics of the photoreceptor thus obtained were measured in the same manner as described above, and the retention (%) was determined.
The results obtained are shown in Table 12 below.

[0232]

[Table 12]

As is clear from Table 12, all the examples have high retention and are good, but all the comparative examples have low retention as compared with the examples.

Example 111 A photoconductor was prepared by the same way as that of Example 31 except that the iron phthalocyanine of Example 31 was replaced with tin phthalocyanine synthesized according to a conventional method.

Example 112 A photoconductor was prepared by the same way as that of Example 111 except that the amount of μoxo-iron phthalocyanine dimer was changed to 10 μmol per 1 mol of tin phthalocyanine.

Example 113 A photoconductor was prepared by the same way as that of Example 111 except that the amount of μoxo-iron phthalocyanine dimer was changed to 1 mmol per 1 mol of tin phthalocyanine.

Example 114 A photoconductor was prepared by the same way as that of Example 111 except that the amount of μoxo-iron phthalocyanine dimer was changed to 100 mmol per 1 mol of tin phthalocyanine.

Example 115 A photoconductor was prepared by the same way as that of Example 111 except that the amount of μoxo-iron phthalocyanine dimer was changed to 300 mmol per 1 mol of tin phthalocyanine.

Example 116 After the addition of the μoxoiron phthalocyanine dimer of Example 111, acid pasting treatment with 96% sulfuric acid was carried out.
A photoconductor was prepared by the same way as that of Example 111 except that it was washed with water and dried.

Example 117 A photoconductor was prepared by the same way as that of Example 116 except that the amount of μoxo-iron phthalocyanine dimer was changed to 10 μmol per 1 mol of tin phthalocyanine.

Example 118 A photoconductor was prepared by the same way as that of Example 116 except that the amount of μ-oxo iron phthalocyanine dimer was changed to 1 mmol per 1 mol of tin phthalocyanine.

Example 119 A photoconductor was prepared by the same way as that of Example 116 except that the amount of μoxo-iron phthalocyanine dimer was changed to 100 mmol per 1 mol of tin phthalocyanine.

Example 120 A photoconductor was prepared by the same way as that of Example 116 except that the amount of μoxo-iron phthalocyanine dimer was changed to 300 mmol per 1 mol of tin phthalocyanine.

Comparative Example 45 A photoconductor was prepared by the same way as that of Example 111 except that the amount of μoxo-iron phthalocyanine dimer was changed to 50 nmol per 1 mol of tin phthalocyanine.

Comparative Example 46 A photoconductor was prepared by the same way as that of Example 111 except that the amount of μoxo-iron phthalocyanine dimer was changed to 400 mmol per 1 mol of tin phthalocyanine.

Comparative Example 47 A photoconductor was prepared by the same way as that of Example 116 except that the amount of μ-oxo iron phthalocyanine dimer was changed to 50 nmol per 1 mol of tin phthalocyanine.

Comparative Example 48 A photoconductor was prepared by the same way as that of Example 116 except that the amount of μoxo-iron phthalocyanine dimer was changed to 400 mmol per 1 mol of tin phthalocyanine.

The electrical characteristics of the photoreceptor thus obtained were measured in the same manner as described above, and the retention (%) was determined.
The results obtained are shown in Table 13 below.

[0249]

[Table 13]

As is clear from Table 13, all the examples have high retention rates and are good, but all the comparative examples have low retention rates as compared with the examples.

Example 121 A titanyl oxo phthalocyanine of Example 11 was replaced with a manganese phthalocyanine synthesized according to a conventional method.
A photoconductor was manufactured in the same manner as in Example 11.

Example 122 The amount of the dioxo manganese phthalocyanine dimer of Example 121 was 10 μm per 1 mol of manganese phthalocyanine.
A photoconductor was prepared by the same way as that of Example 121 except that the mol was changed to mol.

Example 123 The amount of the μoxomanganese phthalocyanine dimer of Example 121 was 1 mm per 1 mol of manganese phthalocyanine.
A photoconductor was prepared by the same way as that of Example 121 except that ol was used.

Example 124 The amount of the μoxomanganese phthalocyanine dimer of Example 121 was changed to 100 with respect to 1 mol of manganese phthalocyanine.
A photoconductor was prepared by the same way as that of Example 121 except for changing to mmol.

Example 125 The amount of the dioxo-manganese phthalocyanine dimer of Example 121 was set to 300 based on 1 mol of manganese phthalocyanine.
A photoconductor was prepared by the same way as that of Example 121 except for changing to mmol.

Example 126 A photosensitizer was prepared in the same manner as in Example 121, except that the μ-oxomanganese phthalocyanine dimer of Example 121 was added, acid-pasted with 96% sulfuric acid, washed with water, and dried. Body manufactured.

Example 127 The amount of the dioxo manganese phthalocyanine dimer of Example 126 was changed to 10 μm per 1 mol of manganese phthalocyanine.
A photoconductor was prepared by the same way as that of Example 126 except for changing to mol.

Example 128 The amount of the dioxo manganese phthalocyanine dimer of Example 126 was 1 mm per 1 mol of manganese phthalocyanine.
A photoconductor was prepared by the same way as that of Example 126 except that ol was used.

Example 129 The amount of the μ-oxomanganese phthalocyanine dimer of Example 126 was changed to 100 with respect to 1 mol of manganese phthalocyanine.
A photoconductor was prepared by the same way as that of Example 126 except changing to mmol.

Example 130 The amount of the dioxo manganese phthalocyanine dimer of Example 126 was changed to 300 with respect to 1 mol of manganese phthalocyanine.
A photoconductor was prepared by the same way as that of Example 126 except changing to mmol.

Comparative Example 49 The amount of the dioxo manganese phthalocyanine dimer of Example 121 was changed to 50 n with respect to 1 mol of manganese phthalocyanine.
A photoconductor was prepared by the same way as that of Example 121 except that the mol was changed to mol.

Comparative Example 50 The amount of the dioxo-manganese phthalocyanine dimer of Example 121 was set to 400 with respect to 1 mol of manganese phthalocyanine.
A photoconductor was prepared by the same way as that of Example 121 except for changing to mmol.

Comparative Example 51 The amount of the dioxo-manganese phthalocyanine dimer of Example 126 was set to 50 nm with respect to 1 mol of manganese phthalocyanine.
A photoconductor was prepared by the same way as that of Example 126 except that ol was used.

Comparative Example 52 The amount of the dimer of μoxomanganese phthalocyanine in Example 126 was 400 m per 1 mol of manganese phthalocyanine.
A photoconductor was prepared by the same way as that of Example 126 except that mol was used.

The electrical characteristics of the photoreceptor thus obtained were measured in the same manner as described above, and the retention (%) was determined.
The results obtained are shown in Table 14 below.

[0266]

[Table 14]

As is clear from Table 14, all the examples have a high retention and are good, but all the comparative examples have a low retention as compared with the examples.

Example 131 The μ-oxotitanyl phthalocyanine dimer of Example 1 was
A photoreceptor was produced in the same manner as in Example 1, except that the μ-dysprosium phthalocyanine dimer synthesized according to a conventional method was used.

Example 132 A photoconductor was prepared by the same way as that of Example 131 except that the amount of μ-dysprosium phthalocyanine dimer was changed to 10 μmol per 1 mol of titanyloxophthalocyanine.

Example 133 A photoconductor was prepared by the same way as that of Example 131 except that the amount of μ-dysprosium phthalocyanine dimer was changed to 1 mmol per 1 mol of titanyloxophthalocyanine.

Example 134 A photoconductor was prepared by the same way as that of Example 131 except that the amount of μ-dysprosium phthalocyanine dimer in Example 131 was changed to 100 mmol per 1 mol of titanyloxophthalocyanine.

Example 135 A photoconductor was prepared by the same way as that of Example 131 except that the amount of μ-dysprosium phthalocyanine dimer was changed to 300 mmol per 1 mol of titanyloxophthalocyanine.

Example 136 A photoconductor was prepared by the same way as that of Example 131 except that the μ-dysprosium phthalocyanine dimer of Example 131 was added, the composition was acid-pasted with 96% sulfuric acid, washed with water, and dried. Was manufactured.

Example 137 A photoconductor was prepared by the same way as that of Example 136 except that the amount of μ-dysprosium phthalocyanine dimer was changed to 10 μmol per 1 mol of titanyloxophthalocyanine.

Example 138 A photoconductor was prepared by the same way as that of Example 136 except that the amount of μ-dysprosium phthalocyanine dimer was changed to 1 mmol per 1 mol of titanyloxophthalocyanine.

Example 139 A photoconductor was prepared by the same way as that of Example 136 except that the amount of μ-dysprosium phthalocyanine dimer was changed to 100 mmol per 1 mol of titanyloxophthalocyanine.

Example 140 A photoconductor was prepared by the same way as that of Example 136 except that the amount of μ-dysprosium phthalocyanine dimer was changed to 300 mmol per 1 mol of titanyloxophthalocyanine.

Comparative Example 53 A photoconductor was prepared by the same way as that of Example 131 except that the amount of μ-dysprosium phthalocyanine dimer of Example 131 was changed to 50 nmol per 1 mol of titanyloxophthalocyanine.

Comparative Example 54 A photoconductor was prepared by the same way as that of Example 131 except that the amount of μ-dysprosium phthalocyanine dimer of Example 131 was changed to 400 mmol per 1 mol of titanyloxophthalocyanine.

Comparative Example 55 A photoconductor was prepared by the same way as that of Example 136 except that the amount of μ-dysprosium phthalocyanine dimer in Example 136 was changed to 50 nmol per 1 mol of titanyloxophthalocyanine.

Comparative Example 56 A photoconductor was prepared by the same way as that of Example 136 except that the amount of μ-dysprosium phthalocyanine dimer was changed to 400 mmol per 1 mol of titanyloxophthalocyanine.

The electrical characteristics of the thus-obtained photoreceptor were measured in the same manner as described above, and the retention (%) was determined.
The results obtained are shown in Table 15 below.

[0283]

[Table 15]

As is clear from Table 15, all of the examples have high retention rates and are good, but all of the comparative examples have low retention rates as compared with the examples.

Example 141 A photoconductor was prepared by the same way as that of Example 31 except that the metal phthalocyanine synthesized according to a conventional method was used in place of the iron phthalocyanine of Example 31.

Example 142 A photoconductor was prepared by the same way as that of Example 141 except that the amount of μoxo-iron phthalocyanine dimer was changed to 10 μmol per 1 mol of nonmetal phthalocyanine.

Example 143 A photoconductor was prepared by the same way as that of Example 141 except that the amount of μoxo-iron phthalocyanine dimer in Example 141 was changed to 1 mmol per 1 mol of non-metallic phthalocyanine.

Example 144 The amount of the dioxomuth iron phthalocyanine dimer of Example 141 was changed to 100 mmol per 1 mol of metal-free phthalocyanine.
A photoconductor was manufactured by the same way as that of Example 141 except that the above was used.

Example 145 The amount of the μoxoiron phthalocyanine dimer of Example 141 was changed to 300 mmol per 1 mol of metal-free phthalocyanine.
A photoconductor was manufactured by the same way as that of Example 141 except that the above was used.

Example 146 After the addition of the μoxoiron phthalocyanine dimer of Example 141, acid pasting treatment with 96% sulfuric acid was carried out.
A photoconductor was prepared by the same way as that of Example 141 except that it was washed with water and dried.

Example 147 A photoconductor was prepared by the same way as that of Example 146 except that the amount of μoxo-iron phthalocyanine dimer in Example 146 was changed to 10 μmol per 1 mol of non-metallic phthalocyanine.

Example 148 A photoconductor was prepared by the same way as that of Example 146 except that the amount of μoxo-iron phthalocyanine dimer was changed to 1 mmol per 1 mol of nonmetal phthalocyanine.

Example 149 The amount of the μoxoiron phthalocyanine dimer of Example 146 was changed to 100 mmol per 1 mol of metal-free phthalocyanine.
A photoconductor was prepared by the same way as that of Example 146 except that the above was replaced.

Example 150 The amount of the dioxomuth iron phthalocyanine of Example 146 was changed to 300 mmol per 1 mol of metal-free phthalocyanine.
A photoconductor was prepared by the same way as that of Example 146 except that the above was replaced.

Comparative Example 57 A photoconductor was prepared by the same way as that of Example 141 except that the amount of μoxo-iron phthalocyanine dimer was changed to 50 nmol per 1 mol of non-metallic phthalocyanine.

Comparative Example 58 The amount of the μoxo-iron phthalocyanine dimer of Example 141 was changed to 400 mmol per 1 mol of metal-free phthalocyanine.
A photoconductor was manufactured by the same way as that of Example 141 except that the above was used.

Comparative Example 59 A photoconductor was prepared by the same way as that of Example 146 except that the amount of μoxo-iron phthalocyanine dimer was changed to 50 nmol per 1 mol of non-metallic phthalocyanine.

Comparative Example 60 The amount of the dioxomuth iron phthalocyanine of Example 146 was changed to 400 mmol per 1 mol of metal-free phthalocyanine.
A photoconductor was prepared by the same way as that of Example 146 except that the above was replaced.

The electrical characteristics of the thus-obtained photoreceptor were measured in the same manner as described above, and the retention (%) was determined.
The results obtained are shown in Table 16 below.

[0300]

[Table 16]

As is clear from Table 16, all of the examples have a high retention and are good, but all of the comparative examples have a low retention as compared with the examples.

Example 151 The titanyl oxo phthalocyanine obtained in the step of forming the charge generation layer in Example 1 was replaced with the above-mentioned document, Sens. Ac
29H, 31H-phthalocyanine titanyl complex synthesized according to Tuators, B (1998), B48 (1-3), 333-338, was added, and a coating solution containing the resulting 29H, 31H-phthalocyanine titanyl complex-containing titanyl oxophthalocyanine was added. A photoreceptor was manufactured in the same manner as in Example 1 except that a charge generation layer was formed by using the same.

Example 152 A photoconductor was prepared by the same way as that of Example 151 except that the amount of 29H, 31H-phthalocyanine titanyl complex was changed to 10 μmol per 1 mol of titanyloxophthalocyanine.

Example 153 A photoconductor was prepared by the same way as that of Example 151 except that the amount of 29H, 31H-phthalocyanine titanyl complex was changed to 1 mmol per 1 mol of titanyloxophthalocyanine.

Example 154 A photoconductor was prepared by the same way as that of Example 151 except that the amount of 29H, 31H-phthalocyanine titanyl complex was changed to 100 mmol per 1 mol of titanyloxophthalocyanine.

Example 155 A photoconductor was prepared by the same way as that of Example 151 except that the amount of 29H, 31H-phthalocyanine titanyl complex was changed to 300 mmol per 1 mol of titanyloxophthalocyanine.

Example 156 The procedure of Example 1 was repeated, except that the 29H, 31H-phthalocyanine titanyl complex of Example 151 was added, acid-pasted with 96% sulfuric acid, washed with water, and dried.
A photosensitive member was produced in the same manner as in Example 51.

Example 157 A photoconductor was prepared by the same way as that of Example 156 except that the amount of 29H, 31H-phthalocyanine titanyl complex was changed to 10 μmol per 1 mol of titanyloxophthalocyanine.

Example 158 A photoconductor was prepared by the same way as that of Example 156 except that the amount of 29H, 31H-phthalocyanine titanyl complex was changed to 1 mmol per 1 mol of titanyloxophthalocyanine.

Example 159 A photoconductor was prepared by the same way as that of Example 156 except that the amount of 29H, 31H-phthalocyanine titanyl complex was changed to 100 mmol per 1 mol of titanyloxophthalocyanine.

Example 160 A photoconductor was prepared by the same way as that of Example 156 except that the amount of 29H, 31H-phthalocyanine titanyl complex was changed to 300 mmol per 1 mol of titanyloxophthalocyanine.

Comparative Example 61 A photoconductor was prepared by the same way as that of Example 151 except that the content of 29H, 31H-phthalocyanine titanyl complex was changed to 50 nmol per 1 mol of titanyloxophthalocyanine.

Comparative Example 62 A photoconductor was prepared by the same way as that of Example 151 except that the content of 29H, 31H-phthalocyanine titanyl complex was changed to 400 mmol per 1 mol of titanyloxophthalocyanine.

Comparative Example 63 A photoconductor was prepared by the same way as that of Example 156 except that the amount of 29H, 31H-phthalocyanine titanyl complex was changed to 50 nmol per 1 mol of titanyloxophthalocyanine.

Comparative Example 64 A photoconductor was prepared by the same way as that of Example 156 except that the amount of 29H, 31H-phthalocyanine titanyl complex was changed to 400 mmol per 1 mol of titanyloxophthalocyanine.

The electrical characteristics of the photoreceptor thus obtained were evaluated by using an electrostatic recording paper tester (EPA-82 manufactured by Kawaguchi Electric Works).
00). The photoreceptor was charged to a surface potential of -600 V by a corotron in a dark place, allowed to stand in a dark portion for 5 seconds, and the potential retention rate (%) during that time was measured. The results obtained are shown in Table 17 below.

[0317]

[Table 17]

As is evident from Table 17, all the examples have high retention rates and are good, but all the comparative examples have low retention rates as compared with the examples.

Example 161 A photoconductor was prepared by the same way as that of Example 151 except that titanyl oxophthalocyanine of Example 151 was replaced with indium phthalocyanine synthesized according to a conventional method.

Example 162 A photoconductor was prepared by the same way as that of Example 161 except that the amount of 29H, 31H-phthalocyanine titanyl complex was changed to 10 μmol per 1 mol of indium phthalocyanine.

Example 163 A photoconductor was prepared by the same way as that of Example 161 except that the amount of 29H, 31H-phthalocyanine titanyl complex was changed to 1 mmol per 1 mol of indium phthalocyanine.

Example 164 A photoconductor was prepared by the same way as that of Example 161 except that the amount of 29H, 31H-phthalocyanine titanyl complex was changed to 100 mmol per 1 mol of indium phthalocyanine.

Example 165 A photoconductor was prepared by the same way as that of Example 161 except that the amount of 29H, 31H-phthalocyanine titanyl complex was changed to 300 mmol per 1 mol of indium phthalocyanine.

Example 166 Example 1 was repeated except that the 29H, 31H-phthalocyanine titanyl complex of Example 161 was added, followed by acid pasting treatment with 96% sulfuric acid, washing with water and drying.
A photosensitive member was produced in the same manner as in Example 61.

Example 167 A photoconductor was prepared by the same way as that of Example 166 except that the amount of 29H, 31H-phthalocyanine titanyl complex was changed to 10 μmol per 1 mol of indium phthalocyanine.

Example 168 A photoconductor was prepared by the same way as that of Example 166 except that the amount of 29H, 31H-phthalocyanine titanyl complex was changed to 1 mmol per 1 mol of indium phthalocyanine.

Example 169 A photoconductor was prepared by the same way as that of Example 166 except that the amount of 29H, 31H-phthalocyanine titanyl complex was changed to 100 mmol per 1 mol of indium phthalocyanine.

Example 170 A photoconductor was prepared by the same way as that of Example 166 except that the amount of 29H, 31H-phthalocyanine titanyl complex was changed to 300 mmol per 1 mol of indium phthalocyanine.

Comparative Example 65 A photoconductor was prepared by the same way as that of Example 161 except that the amount of 29H, 31H-phthalocyanine titanyl complex was changed to 50 nmol per 1 mol of indium phthalocyanine.

Comparative Example 66 A photoconductor was prepared by the same way as that of Example 161 except that the amount of 29H, 31H-phthalocyanine titanyl complex was changed to 400 mmol per 1 mol of indium phthalocyanine.

Comparative Example 67 A photoconductor was prepared by the same way as that of Example 166 except that the amount of 29H, 31H-phthalocyanine titanyl complex was changed to 50 nmol per 1 mol of indium phthalocyanine.

Comparative Example 68 A photoconductor was prepared by the same way as that of Example 166 except that the amount of 29H, 31H-phthalocyanine titanyl complex was changed to 400 mmol per 1 mol of indium phthalocyanine.

[0333] The electrical characteristics of the photoreceptor thus obtained were evaluated by using an electrostatic recording paper tester (EPA-82 manufactured by Kawaguchi Electric Works).
00). The photoreceptor was charged to a surface potential of -600 V by a corotron in a dark place, allowed to stand in a dark portion for 5 seconds, and the potential retention rate (%) during that time was measured. The results obtained are shown in Table 18 below.

[0334]

[Table 18]

As is clear from Table 18, all the examples have high retention rates and are good, but all the comparative examples have low retention rates as compared with the examples.

Example 171 The 29H, 31H-phthalocyanine titanyl complex of Example 151 was prepared using the method described in the literature (Capobianchi, A. et al, Inorg. C).
Chem. (1993), 32 (21), 4605-11), except that the tetraazacyclodocosin complex was used instead of the tetraazacyclodocosin complex, to produce a photoconductor in the same manner as in Example 151.

Example 172 The amount of the tetraazacyclodocosin complex of Example 171 was adjusted to 10 μm with respect to 1 mol of titanyloxophthalocyanine.
A photoconductor was prepared by the same way as that of Example 171 except that ol was used.

Example 173 The amount of the tetraazacyclodocosin complex of Example 171 was changed to 1 mmol per 1 mol of titanyloxophthalocyanine.
A photoconductor was prepared by the same way as that of Example 171 except that l was changed.

Example 174 The amount of the tetraazacyclodocosin complex of Example 171 was adjusted to 100 m with respect to 1 mol of titanyloxophthalocyanine.
A photoconductor was prepared by the same way as that of Example 171 except that mol was used.

Example 175 The amount of the tetraazacyclodocosin complex of Example 171 was set to 300 m with respect to 1 mol of titanyloxophthalocyanine.
A photoconductor was prepared by the same way as that of Example 171 except that mol was used.

Example 176 After the addition of the tetraazacyclodocosin complex of Example 171, acid pasting treatment with 96% sulfuric acid was carried out.
A photoconductor was prepared by the same way as that of Example 171 except that it was washed with water and dried.

Example 177 The amount of the tetraazacyclodocosin complex of Example 176 was adjusted to 10 μm with respect to 1 mol of titanyloxophthalocyanine.
A photoconductor was prepared by the same way as that of Example 176 except that ol was used.

Example 178 The amount of the tetraazacyclodocosin complex of Example 176 was changed to 1 mmol per 1 mol of titanyloxophthalocyanine.
A photoconductor was prepared by the same way as that of Example 176 except that 1 was used.

Example 179 The amount of the tetraazacyclodocosin complex of Example 176 was changed to 100 m per 1 mol of titanyloxophthalocyanine.
A photoconductor was prepared by the same way as that of Example 176 except for changing to mol.

Example 180 The amount of the tetraazacyclodocosin complex of Example 176 was adjusted to 300 m with respect to 1 mol of titanyloxophthalocyanine.
A photoconductor was prepared by the same way as that of Example 176 except for changing to mol.

Comparative Example 69 The amount of the tetraazacyclodocosin complex of Example 171 was set to 50 nm with respect to 1 mol of titanyloxophthalocyanine.
A photoconductor was prepared by the same way as that of Example 171 except that ol was used.

Comparative Example 70 The amount of the tetraazacyclodocosin complex of Example 171 was set to 400 m with respect to 1 mol of titanyloxophthalocyanine.
A photoconductor was prepared by the same way as that of Example 171 except that mol was used.

Comparative Example 71 The amount of the tetraazacyclodocosin complex of Example 176 was set to 50 nm with respect to 1 mol of titanyloxophthalocyanine.
A photoconductor was prepared by the same way as that of Example 176 except that ol was used.

Comparative Example 72 The amount of the tetraazacyclodocosin complex of Example 176 was set to 400 m with respect to 1 mol of titanyloxophthalocyanine.
A photoconductor was prepared by the same way as that of Example 176 except for changing to mol.

The electrical characteristics of the photoreceptor thus obtained were evaluated by using an electrostatic recording paper tester (EPA-82 manufactured by Kawaguchi Electric Works).
00). The photoreceptor was charged to a surface potential of -600 V by a corotron in a dark place, allowed to stand in a dark portion for 5 seconds, and the potential retention rate (%) during that time was measured. The results obtained are shown in Table 19 below.

[0351]

[Table 19]

As is clear from Table 19, all of the examples have a high retention and are good, but all of the comparative examples have a low retention as compared with the examples.

[0353]

According to the present invention, at least a phthalocyanine compound is contained as a photoconductive material in a photosensitive layer of a conductive substrate, and a phthalocyanine dimer compound is added in an amount of 100 nmol or more to 1 mol of the phthalocyanine compound.
When the content is less than 00 mmol, an electrophotographic photoreceptor having an excellent potential holding ratio can be obtained.

According to the present invention, the phthalocyanine compound and the phthalocyanine dimer compound are contained in the coating solution for forming the photosensitive layer on the conductive substrate, and the content of the phthalocyanine dimer compound is based on 1 mol of the phthalocyanine. Ten
When the amount is 0 nmol or more and 300 mmol, it is possible to provide a method for producing an electrophotographic photosensitive member having an excellent potential holding ratio.

[Brief description of the drawings]

FIG. 1 is a schematic cross-sectional view of an example of a negatively charged laminated electrophotographic photoreceptor of the present invention.

FIG. 2 is a MALDI of titanyl oxo phthalocyanine containing a μ oxo titanyl phthalocyanine dimer according to the present invention.
FIG. 4 is a spectrum diagram showing an example of a -TOF-MS spectrum.

[Explanation of symbols]

 REFERENCE SIGNS LIST 1 conductive substrate 2 undercoat layer 3 charge generation layer 4 charge transport layer 5 photosensitive layer

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Shinjiro Suzuki 4-181-1, Chikuma, Matsumoto-shi, Nagano Fuji Electric Imaging Devices Co., Ltd. (72) Yoichi Nakamura 4-1-1, Chikuma, Matsumoto-shi, Nagano No. Fuji Electric Imaging Devices Co., Ltd. (72) Inventor Hideki Kina 4-181-1, Chikuma, Matsumoto City, Nagano Prefecture Fuji Electric Imaging Devices Co., Ltd.

Claims (15)

[Claims] 1. An electrophotographic photoreceptor having a photosensitive layer on a conductive substrate, wherein the photosensitive layer contains a phthalocyanine compound as a photoconductive material, wherein the phthalocyanine dimer compound in the layer having the phthalocyanine compound is The content is 100 nmol or more and 300 mmol based on 1 mol of the phthalocyanine compound.
A photoconductor for electrophotography, comprising: 2. The electrophotographic photoconductor according to claim 1, wherein the phthalocyanine compound forming the phthalocyanine dimer compound is titanyl oxo phthalocyanine. 3. The electrophotographic photoconductor according to claim 1, wherein the phthalocyanine compound is a metal-free phthalocyanine. 4. In a matrix-assisted laser desorption ionization time-of-flight mass spectrometry, peaks are generated at mass numbers 576 and 1136, and the peak area intensity at mass number 1136 is smaller than the peak area intensity at mass number 576. 10 ^-5
The electrophotographic photoreceptor according to claim 2, wherein the content is from 30% to 30%. 5. The electrophotographic photoconductor according to claim 1, wherein a central element of the phthalocyanine compound forming the phthalocyanine dimer compound is a transition metal. 6. The method of claim 5, wherein said transition metal is selected from the group consisting of titanium, vanadium, chromium, manganese, iron, cobalt, nickel, zirconium, niobium, molybdenum, rhodium, cerium, neodymium, samarium, europium and tungsten. Electrophotographic photoreceptor. 7. The method according to claim 1, wherein the central element of the phthalocyanine compound forming the phthalocyanine dimer compound is selected from the group consisting of indium, gallium, aluminum, germanium, tin, antimony, lead, bismuth, silicon and phosphorus. Photoconductor for electrophotography. 8. The phthalocyanine compound forming the phthalocyanine compound and the phthalocyanine dimer compound is represented by the following formula: (In the formula, M is an element of the group Ia (however, in this case, it may contain 2 atoms), or an element capable of taking an oxidation state of +2 or more, or an oxide, hydroxide, halide, or alcohol of the element R ^{1 to} R ^{16 each} represent a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a cyano group, an ester group, an alkyl group, an alkenyl group, an alkoxyl group, an aryl group, or an aryloxy group which may be the same or different. The electrophotographic photoconductor according to any one of claims 1 to 7, which is a phthalocyanine compound represented by the formula: 9. The electrophotographic photoconductor according to claim 1, wherein the phthalocyanine dimer compound has a structure of a μoxo dimer compound. 10. The phthalocyanine dimer compound is P
The electrophotographic photoreceptor according to claim 9, having a cMOMO-Pc type structure (Pc is a phthalocyanine compound, M is an element having an oxidation number of 3 or more, and O is an oxygen atom). 11. The method according to claim 11, wherein the phthalocyanine dimer compound is μ
The electrophotographic photoconductor according to claim 1, which has a dimer compound structure. 12. The method according to claim 12, wherein the phthalocyanine dimer compound is P
c-M-Pc type structure (Pc is a phthalocyanine compound, M
Is an element having an oxidation number of +3 or more). 13. The phthalocyanine dimer compound,
The electrophotographic photoconductor according to claim 12, which is a 29H, 31H-phthalocyanine titanyl complex compound. 14. The phthalocyanine dimer compound,
2. The electrophotographic photoreceptor according to claim 1, which has a structure comprising a titanium atom and two phthalocyanine rings linked via at least one carbon atom, nitrogen atom or oxygen atom. 15. The method for producing a photoreceptor for electrophotography according to claim 1, further comprising a step of forming a photosensitive layer by applying a coating solution containing a charge generating material on a conductive substrate. Including the compound and the phthalocyanine dimer compound, the content of the phthalocyanine dimer compound is set to 10 to 1 mol of the phthalocyanine compound.
A method for producing a photoreceptor for electrophotography, comprising 0 nmol to 300 mmol.