JP2589705B2 - Optical semiconductor material and electrophotographic photosensitive member using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Object of the Invention] (Industrial application field) The present invention is useful for an electrophotographic photosensitive member or the like using a phthalocyanine-based compound having a metal having a valence of three or more in the center. The present invention relates to an optical semiconductor material, and more particularly, to an electrophotographic photoreceptor using a non-crystalline phthalocyanine-based compound having excellent dispersibility and coatability as a charge generating agent in addition to excellent exposure sensitivity characteristics and wavelength characteristics.

(Prior Art) Conventionally, as an electrophotographic photoconductor, a photoconductor using an inorganic photoconductor such as selenium, a selenium alloy, zinc oxide, cadmium sulfide, and titanium oxide has been mainly used. In recent years, the development of semiconductor lasers has been remarkable, and small and stable laser oscillators have become available at low cost, and have begun to be used as light sources for electrophotography. However, the use of a semiconductor laser that oscillates short-wavelength light in these devices has many problems in view of life and output. Therefore, materials that have been used in the short wavelength region, which have been used in the past, are not suitable for use in semiconductor lasers, and there is a need to study materials that have high sensitivity in the long wavelength region (780 nm or more). Was. In recent years, studies on organic photoconductors in which organic materials, particularly phthalocyanine, which is expected to have a sensitivity in a long wavelength region, are laminated and laminated with these materials have been actively conducted. For example, as a divalent metal phthalocyanine,
ε-type copper phthalocyanine (ε-CuPc) and τ-type metal-free phthalocyanine (τ-H2Pc) have sensitivity in the long wavelength region, and as trivalent and tetravalent metal phthalocyanines, chloroaluminum phthalocyanine (AlPcCl), chloroaluminum A method in which phthalocyanine chloride (ClAlPcCl), titanyl phthalocyanine (TiOPc), or chloroindium phthalocyanine (InPcCl) is vapor-deposited and then contacted with a soluble solvent vapor to increase the wavelength and sensitivity (Japanese Patent Laid-Open No. 57-39)
No. 484, JP-A-59-166959).
A method in which phthalocyanine containing i, Sn and Pb is subjected to long-wavelength treatment using various substituents, derivatives or shifting agents such as crown ethers (Japanese Patent Application Nos. 59-36254 and 59-204045) ).

LEDs are also in practical use as digital light sources for printers. LEDs in the visible light range are also used, but those that have been put to practical use generally have an oscillation wavelength of 650 nm or more, typically 670 nm. Azo compounds, perylene compounds,
Selenium, zinc oxide and the like cannot be said to have sufficient photosensitivity at around 650 nm, but phthalocyanine compounds have an absorption peak at around 650 nm, so they can be expected as effective materials for LED.

A phthalocyanine compound having a central atom with a valence of three or more is a material that satisfies the above applications. However, the compounds reported so far are often in the form of strongly agglomerated agglomerated particles. The charge generator is
Due to the large amount of impurities contained between the agglomerated particles and the inevitable crystal growth during crystallization, and the large pigment particle size, the charge generation layer deposited and dispersed using these particles must be dispersed. It lacked stability and caused a decrease in coatability. Therefore, it was difficult to obtain a uniform generation layer, and it was difficult to obtain a beautiful image.

In some cases, they are ground using a ball mill, etc.
Even in that case, the grinding effect was not sufficient.

Therefore, in the case of these crystalline phthalocyanines, the light absorption efficiency is not sufficient, and the carrier generation efficiency of the charge generation layer is reduced, the injection efficiency of the carrier into the charge transfer layer is reduced, and furthermore, the deterioration resistance during repeated use over a long period of time. There is a drawback that the electrophotographic characteristics such as characteristics, printing durability and image stability are not sufficiently satisfied.

(Problems to be Solved by the Invention) An object of the present invention is to obtain a uniform charge generating layer having excellent dispersibility and having no defects in a coating film by using an amorphous phthalocyanine compound. An object of the present invention is to obtain excellent exposure sensitivity characteristics and wavelength characteristics, and to obtain deterioration resistance characteristics, printing durability, and image stability when used repeatedly over a long period of time.

The present invention relates to a phthalocyanine compound represented by the following general formula [I], wherein the phthalocyanine does not show a strong X-ray diffraction peak. An electrophotographic photosensitive member using a charge generating agent and a charge transfer agent, wherein the charge generating agent is the phthalocyanine-based compound.

(Where M is a metal atom other than titanium having a valence of 3 or more, R
₁ represents a halogen atom, an oxygen atom or an alkoxy group,
R ₂ , R ₃ , R ₄ and R ₅ are a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group,
A nitro group, a cyano group, a hydroxyl group, a benzyloxy group or an amino group; j is an integer of 1 or 2; k, l, m and n are integers of 0 to 4; Further, it is a fine primary particle having a particle diameter of 0.2 μ or less, and is an amorphous phthalocyanine compound.

Phthalocyanine In general, phthalodinitrile method in which phthalodinitrile and metal chloride are heated and melted or heated in the presence of an organic solvent, phthalic anhydride is heated in urea and metal chloride in the form of heat melting or heated in the presence of an organic solvent The method includes, but is not limited to, the Weyler method, a method of reacting cyanobenzamide with a metal salt at a high temperature, and a method of reacting dilithium phthalocyanine with a metal salt. Examples of the organic solvent include α-chloronaphthalene, β-chloronaphthalene, α-methylnaphthalene, methoxynaphthalene, diphenylethane, ethylene glycol, dialkyl ether, quinoline, sulfolane, and dichlorobenzene. desirable. Further, it can be synthesized by a solid phase reaction without using a solvent.

The phthalocyanine used in the present invention is a "phthalocyanine compound" of Moser and Thomas (Moser and Th.
omas "Phthaloeyamine Compounds") and those obtained by the appropriate methods described above, and synthesizing the acid, alkali, acetone, methyl ethyl ketone,
Tetrahydrofuran, pyridine, quinoline, sulfolane, α-chloronaphthalene, toluene, dioxane, xylene, chloroform, carbon tetrachloride, dichloromethane,
It is obtained by washing with dichloroethane, triclopropane, N, N'-dimethylformamide. Furthermore, sublimation purification is also possible. In the phthalocyanine compound synthesized by the above method, the particles are strongly aggregated and crystallized, and
Micron and large particles form secondary particles of 10 micron or more.

In an electrophotographic photoreceptor containing crystalline coarse secondary particles in a charge generation layer, the number of generated carriers is reduced due to a decrease in light absorption efficiency, and the photosensitivity is reduced. In addition, since the charge generation layer is not uniform, the efficiency of carrier injection into the charge transfer layer also decreases,
As a result, with respect to the electrostatic characteristics, undesired phenomena such as an induction phenomenon, a decrease in surface potential, and inferior potential stability during repeated use occur in the sensitivity of the photoconductor. In addition, the image lacks homogeneity and causes minute defects. Particle size 0.2 composed of fine primary particles of the present invention
The charge generation layer using an amorphous phthalocyanine compound of μ or less is a uniform layer with high light absorption efficiency, has few voids between particles in the charge generation layer,
It is possible to obtain an electrophotographic photosensitive member that satisfies many requirements such as characteristics of an electrophotographic photosensitive member such as potential stability and prevention of a rise in a bright portion potential, and reduction of image defects and printing durability.

Although the phthalocyanine compound of the present invention can be obtained by a single chemical method or mechanical method, it is more preferable to use various methods for producing a substance having a low cohesive force and then finely grinding them by each method. Can be obtained by a combination of

For example, very fine primary particles can be obtained by weakening the cohesion between particles by a method such as acid pasting method or acid slurry method and then grinding by a mechanical treatment method. The equipment used during grinding is
Kneader, Banbury mixer, Attritor, Edge runner mill, Roll mill, Ball mill, Sand mill SP
Examples include, but are not limited to, EX mills, homomixers, dispersers, agitators, jaw crushers, stamp mills, cutter mills, micronizers, and the like. The acid pasting method, which is well known as a chemical treatment method, is a method in which a pigment is dissolved or sulfated in 95% or more sulfuric acid and poured into water or ice water to reprecipitate. Is maintained at 5 ° C. or lower, and sulfuric acid is slowly injected into water stirred at a high speed, whereby fine particles can be obtained with better conditions.

Other methods include grinding the crystalline particles directly for a very long time with a mechanical treatment device, and grinding the particles obtained by the acid pasting method after treating them with the solvent, etc., and immediately after the acid pasting. It is also possible to obtain very little amorphous primary particles.

However, after the chemical treatment of the crystalline particles, the fine particles obtained by the mechanical treatment are refined with the solvent used for washing the above-mentioned compound, and then subjected to the chemical treatment again. Needless to say, it is desired to improve the degree of purification and reduce the particle size by repeating the appropriate treatment many times. However, since phthalocyanine may be hydrolyzed by the acid pasting method, a method in which grinding is performed for a long time only by a mechanical method may be selected depending on the material.

The phthalocyanine compound according to the present invention is non-crystalline particles having no clear plane spacing from which the diffraction angle cannot be read. Amorphous particles can also be obtained by sublimation. For example, it can be obtained by heating the phthalocyanine as a raw material obtained by various methods under vacuum to 500 ° C. to 600 ° C. to sublimate it, and immediately depositing it on the substrate. The resulting phthalocyanine is in an amorphous state and becomes fine particles depending on the precipitation conditions. More preferably, the particles are further finely divided by mechanical grinding. The absorption peak of the film obtained by sublimation by this treatment is around 750 nm, whereas the absorption peak after mechanical treatment is 830 nm.
nm, which makes the characteristics suitable for semiconductor lasers. In addition, although the X-ray diffraction measurement mainly uses CuKα radiation, even if another source is used, there is no strong X-ray diffraction peak, and it can be seen that it is in an amorphous state.

The photoreceptor has an undercoat layer, a charge generation layer,
It is preferable that the charge transfer layer is laminated in this order. However, the undercoat layer, the charge transfer layer, and the charge generation layer are laminated in this order, and the charge generation agent and the charge transfer agent are dispersed on the undercoat layer with an appropriate resin. Coated one may be used. By coating one or more of these phthalocyanine-based compounds on a substrate with a suitable binder as a charge generating agent, a charge generating layer having extremely good dispersibility and extremely high light absorption efficiency can be obtained. Although it is known that the charge generation layer is obtained by vapor deposition, the material obtained according to the present invention can be very efficiently vapor-deposited because the material obtained in the present invention is atomized and impurities present between the particles are removed. It is also effective as an application material.

The coating of the photoreceptor is performed by spin coater, applicator,
Spray coater, bar coater, immersion coater, doctor blade, roller coater, curtain coater,
Drying is preferably performed by heating and drying at 40 to 200 ° C. for 10 minutes to 6 hours under static or blowing conditions. After drying, the film is coated to have a thickness of 0.01 to 5 microns, preferably 0.05 to 1 micron.

The binder that can be used when forming the charge generation layer by coating can be selected from a wide range of insulating resins, and can be selected from organic photoconductive polymers such as poly-N-vinylcarbazole, polyvinylanthracene, and polyvinylpyrene. Preferably, polyvinyl butyral, polyarylate (polycondensate of bisphenol A and phthalic acid, etc.), polycarbonate, polyester, phenoxy resin, polyvinyl acetate, acrylic resin, polyacrylamide resin, polyamide resin, polyvinylpyridine, cellulose resin, urethane Resin, ethoxy resin, silicone resin, polystyrene, polyketone resin, polyvinyl chloride,
Insulating resins such as polyvinyl chloride copolymer, polyvinyl acetal, polyacrylonitrile, phenolic resin, melamine resin, casein, polyvinyl alcohol, and polyvinylpyrrolidone can be exemplified. The resin contained in the charge generation layer is suitably at most 100% by weight, preferably at most 40% by weight. These resins may be used alone or in combination of two or more. The solvent for dissolving these resins differs depending on the type of the resin, and it is preferable to select a charge generation layer or an undercoat layer, which will be described later, from those that do not affect the coating. Specifically, benzene, xylene, ligroin,
Aromatic hydrocarbons such as monochlorobenzene and dichlorobenzene, ketones such as acetone, methyl ethyl ketone and cyclohexanone, alcohols such as methanol, ethanol and isopropanol, esters such as ethyl acetate and methyl cellosolve, carbon tetrachloride, chloroform, Aliphatic halogenated hydrocarbons such as dichloromethane, dichloroethane, and trichloroethylene; ethers such as tetrahydrofuran, dioxane, ethylene glycol mono and methyl ether; amides such as N, N-dimethylformamide and N, N-dimethylacetamide; and Sulfoxides such as dimethyl sulfoxide are used.

The charge transfer layer is formed by dissolving and dispersing the charge transfer agent alone or in a binder resin. The charge transfer material includes an electron transfer material and a hole transfer material. Examples of the electron transfer material include chloranil, bromoanil, tetracyanoethylene, tetracyanoquinodimethane, 2.4.7-trinitro-9.
Electron-withdrawing substances such as fluorenone, 2.4.5.7-tetranitro-9-fluorenone, 2.4.7-trinitro-9-dicyanomethylenefluorenone, 2.4.5.7-tetranitroxanthone, 2.4.8-trinitrothioxanthone There is a highly differentiated substance.

Examples of the hole transfer material include pyrene, N-ethylcarbazole, N-isopropylcarbazole, N-methyl-N-phenylhydrazino-3-methylidene-9-ethylcarbazole, N, N-diphenylhydrazino-3. -Methylidene-
9-ethylcarbazole, N, N-diphenylhydrazino-
3-methylidene-10-ethylphenothiazine, N, N-diphenylhydrazino-3-methylidene-10-ethylphenoxazine, P-diethylaminobenzaldehyde-N, N-
Diphenylhydrazone, P-diethylaminobenzaldehyde-N-α-naphthyl-N-phenylhydrazone, P-
Pyrrolidinobenzaldehyde-N, N-diphenylhydrazone, 2-methyl-4-dibenzylaminobenzaldehyde-1′-ethyl-1′-benzothiazolylhydrazone, 2-methyl-4-dibenzylaminobenzaldehyde 1'-propyl-1'-benzothiazolylhydrazone, 2-methyl-4-dibenzylaminobenzaldavido-1 ', 1'-diphenylhydrazone, 9-ethylcarbazole-3-carboxaldehyde-1-methyl -1'-phenylhydrazone, 1-phenyl-1.2.3.4-tetrahydroquinoline-6-carboxaldehyde-1 ', 1'-diphenylhydrazone, 1.3.3-trimethylindolenine-
hydrazones such as ω-aldehyde-N, N-diphenylhydrazone, P-diethylbenzaldehyde-3-methylbenzthiazolinone-2-hydrazone, 2.5-bis (P-diethylaminophenyl) -1.3.4-oxadi Azole, 1
-Phenyl-3- (P-diethylaminostyryl) -5
-(P-diethylaminophenyl) pyrazolin, 1- [quinolyl (2)]-3- (P-diethylaminostynyl)
-5- (P-diethylaminophenyl) pyrazolin, 1-
[Pyridyl (2)]-3- (P-diethylaminostyryl) -5- (P-diethylaminophenyl) pyrazolin, 1- [6-methoxy-pyridyl (2)]-3- (P-
Diethylaminostyryl) -5- (P-diethylaminophenyl) pyrazoline, 1- [pyridyl (3)]-3-
(P-diethylaminostyryl) -5- (P-diethylaminosphenyl) pyrazolin, 1- [levidyl (2)]
-3- (P-diethylaminostyryl) -5- (P-diethylaminophenyl) pyrazolin, 1- [pyridyl (2)]-3- (P-diethylaminostyryl) -4-
Methyl-5- (P-diethylaminophenyl) pyrazoline, 1- [pyridyl (2)]-3- (α-methyl-P-diethylaminostyryl) -5- (P-diethylaminophenyl) pyrazoline, 1-phenyl- 3- (P-diethylaminostyryl) -4-methyl-5- (P-diethylaminophenyl) pyrazoline, 1-phenyl-3- (α-benzyl-P-diethylaminostyryl) -5- (P-diethylaminophenyl) Pyrazolines such as -6-pyrazolin and spiropyrazolin, 2- (P-diethylaminostyryl) -6-diethylaminobenzoxazole, 2-
Oxazole compounds such as (P-diethylaminophenyl) -4- (P-diethylaminophenyl) -5- (2-chlorophenyl) oxazole, α-phenyl-4-
A stilbene compound such as N, N-diphenyl-amino-stilbene, a thiazole compound such as 2- (P-diethylaminostyryl) -6-diethylaminobenzothisol,
Triarylmethane compounds such as bis (4-diethylamino-2-methylphenyl) -phenylmethane, 1.1-bis (4-N, N-diethylamino-2-methylphenyl)
Polyarylalkanes such as heptane, 1.1.2.2-tetrakis (4-N, N-dimethylamino-2-methylphenyl) ethane, triphenylamine, poly-N-vinylcarbazole, polyvinylpyrene, polyvinylanthracene, polyvinylacridine, poly -9-vinylphenylanthracene, pyrene-formaldehyde resin, ethylcarbazole formaldehyde resin and the like.

In addition to these organic charge transfer materials, selenium, selenium
Inorganic materials such as tellurium, amorphous silicon, and cadmium sulfide can also be used.

These charge transfer materials can be used alone or in combination of two or more. The resin used for the charge transfer layer is silicone resin, ketone resin, polymethyl methacrylate, polyvinyl chloride, acrylic resin, polyarylate, polyester, polycarbonate, polystyrene,
Acrylonitrile-styrene copolymer, acrylonitrile-butadiene copolymer, polyvinyl butyral,
Insulating resins such as polyvinyl formal, polysulfone, polyacrylamide, polyamide, chlorinated rubber, poly-N-vinyl carbazole, polyvinyl anthracene,
There is a photoconductive substance such as polyvinylpyrene.

The coating method is performed using a spin coater, an applicator, a spray coater, a bar coater, an immersion coater, a doctor blade, a roller coater, a curtain coater, and a bead coater.
Micron, preferably 10 to 20 micron is good. In addition to these layers, an undercoat layer can be provided on the conductive substrate for the purpose of improving chargeability and adhesion. As an undercoat layer, alcohol-soluble polyamides such as nylon 6, nylon 66, nylon 11, nylon 610, copolymerized nylon, alkoxymethylated nylon, casein, polyvinyl alcohol, nitrocellulose, ethylene-acrylic acid copolymer, gelatin, polyurethane, polyvinyl Metal oxides such as butyral and aluminum oxide are used. Also,
It is also possible to adjust the conductivity by incorporating conductive particles such as metal oxides and carbon black into the resin.

The material of the present invention has an absorption peak at a wavelength of 800 mm or more, and is suitable not only as an electrophotographic photosensitive member for copying machines and printers, but also as an absorbing material for solar cells, photoelectric conversion elements, and optical disks.

Hereinafter, embodiments of the present invention will be specifically described. Parts in the examples indicate parts by weight.

Example 1 50 parts of phthalodinitrile and 25.4 parts of tin tetrachloride were converted to quinoline.
After heating and reaction at 200 ° C for 2 hours in 300 parts, the solvent was removed by steam distillation, purified with a 2% hydrochloric acid aqueous solution, washed with acetone, dried, and dichlorotin phthalocyanine (SnPcCl ₂ ) 2
4.5 copies were obtained. 2 parts of this dichlorotin phthalocyanine is dissolved little by little in 40 parts of 98% sulfuric acid at 5 ° C., and the mixture is stirred for about 1 hour while maintaining the temperature at 5 ° C. or less. Subsequently, the sulfuric acid solution is slowly poured into 400 parts of ice water with high-speed stirring, and the precipitated crystals are filtered. The crystals are washed with distilled water until no acid remains and purified with acetone.
Drying yielded 1.8 parts. The mixture was further ground in a pole mill for 100 hours. The SnPcCl ₂ thus obtained is composed of fine primary particles of 0.2 μm or less, and has no diffraction peak as shown in the X-ray diffraction diagram of FIG.

9.7 parts of polyvinyl alcohol (86-89% saponification degree) was mixed on a 75μ thick aluminum aluminum terephthalate film (PET)
And a coating solution dispersed in a ball mill for 3 hours was applied with a wire bar and dried by heating to obtain a sheet having a 0.5 μm-thick undercoat layer.

2 parts of SnPcCl ₂ obtained by the above method was added to a solution of 1 part of a polyester resin (Vylon 200 manufactured by Toyobo) in 97 parts of dioxane, and dispersed in a ball mill for 2 hours. This dispersion is applied on the undercoat layer and dried, to form a 0.2 μm charge generation layer. Then, 1-phenyl-1,2,3,4-
Tetrahydroquinoline-6-carboxaldehyde-1,
A solution prepared by dissolving 10 parts of 1-diphenylhydrazone and 10 parts of a polyester resin (Vylon 200 manufactured by Toyobo) in 100 parts by weight of methylene chloride is applied on the charge generation layer, and dried to form a 15 μm charge transfer layer. The body was obtained and its properties were measured.

Example 2 After reacting 23.3 parts of phthalodinitrile and 15 parts of aluminum trichloride in 150 parts of quinoline by heating at 200 ° C for 2 hours, removing the solvent by steam distillation, purifying with a 2% hydrochloric acid aqueous solution, and washing with acetone. And dried to obtain 26.0 parts of monochrome aluminum phthalocyanine (AlPcCl).

This AlPcCl was ground in a ball mill for 150 hours. The AlPcCl thus obtained consisted of fine primary particles of less than 0.2μ, and no X-ray diffraction peak was observed. An electrophotographic photosensitive member was prepared in the same manner as in Example 1 except that this AlPcCl was used as a charge generating agent, and its characteristics were measured.

Example 3 10 parts of AlPcCl synthesized in Example 2 was heated and sublimated to 550 ° C. under a vacuum condition of 10 ⁻⁵ Torr and deposited on a cooled substrate. This precipitate was taken out and ground in a ball mill for 100 hours. Example 2 was repeated except that AlPcCl, which had no diffraction peak on the X-ray diffraction diagram consisting of 7.6 parts of fine primary particles, was used as a charge generating agent. An electrophotographic photoreceptor was prepared in the same manner as in Example 1, and its characteristics were measured.

Example 4 12.8 parts of phthalodinitrile and 5.5 parts of indium trichloride were heated and reacted in 100 parts of quinoline at 220 ° C. for 3 hours, then the solvent was removed by steam distillation, purified with a 2% aqueous hydrochloric acid solution, and washed with acetone. And dried to obtain monochrome indium phthalocyanine (InPcCl). 5 parts of this InPcCl, 200 parts of diethylene glycol and 50 parts of a salt as a grinding aid are added to a kneader and ground for 5 hours. Purify this milled material to 4.6
Of InPcCl was obtained.

The thus obtained InPcCl consisted of fine primary particles of less than 0.2μ, and no diffraction peak was observed on the X-ray diffraction diagram. The InPcCl2 part obtained by the above method was placed in a crucible for vacuum evaporation, and deposited at a temperature of 500 ° C on a 75μ thick sheet of aluminum deposited on PET to form an average thick 0.1μ charge generation layer. did.

Then, an electrophotographic photosensitive member was manufactured in the same manner as in Example 1, and the characteristics were measured.

Example 5 An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that InPcCl produced in Example 4 was used, and its characteristics were measured.

Example 6 In a ball mill, 1 part of InPcCl2 prepared in Example 4 and 1-phenyl-1,2,3,4-tetrahydroquinoline-6-carboxyaldebit-1,1-diphenylhydrazone were used as a charge transfer agent for 2 minutes. Then, 16 parts of polyester resin (Toyobo Byron 200) and 80 parts of methylene chloride were added and dispersed for 6 hours. Then, it was coated on a 75 μm thick sheet of aluminum vapor-deposited on PET and dried to produce a single-layer electrophotographic photoreceptor having a thickness of 15 μm, and its characteristics were measured.

Comparative Example 1 An electrophotographic photoreceptor was prepared and characteristics were measured in the same manner as in Example 1, except that crystalline SnPcCl ₂ synthesized and purified only in the same manner as in Example 1 was used.

Comparative Example 2 An electrophotographic photoreceptor was prepared and characteristics were measured in the same manner as in Example 1, except that crystalline AlPcCl synthesized and purified only in the same manner as in Example 2 was used.

Comparative Example 3 Crystalline Al Only Sublimated by Heating in the Same Method as Example 3
An electrophotographic photosensitive member was prepared in the same manner as in Example 1 except that PcCl was used, and the characteristics were measured.

Comparative Example 4 A charge generation layer was formed by vapor deposition in the same manner as in Example 4, except that crystalline InPcCl synthesized and purified only in the same manner as in Example 4 was used, and a charge transfer layer was formed thereon. A coated electrophotographic photoreceptor was prepared and its characteristics were measured.

Comparative Example 5 Example 1 except that InPcCl prepared in Comparative Example 4 was used.
An electrophotographic photoreceptor was prepared in the same manner as described above, and characteristics were measured.

Comparative Example 6 Example 6 was performed except that the InPcCl prepared in Comparative Example 4 was used.
An electrophotographic photoreceptor was prepared in the same manner as described above, and characteristics were measured.

The electrostatic properties of the photoreceptor were measured using Kawaguchi Electric SP-428 tester. After the photoreceptor is corona-charged at −5.4 KV, it is irradiated with 800 μm light of 1 μW / cm ² at a surface potential (V
From o) and the time required for the surface potential after irradiation to decrease by half, the half-exposure dose sensitivity (E1 / 2) was determined. The results are shown in Table 1.

When Examples 1 to 6 and Comparative Examples 1 to 6 are compared with each other, the non-crystalline phthalocyanine that does not show a strong peak on the X-ray diffraction diagram has a higher surface potential (Vo),
The half-exposure sensitivity (E1 / 2) was also found to be good.

Further, the photoconductors produced in this example and the comparative example were
It was affixed to the drum of an electrophotographic copying machine having a corona charger, an exposure section, a development section, a transfer charging section, a charge removal exposure section, and a cleaner. The dark part potential of this copier was set to -650 V, and the light part potential was set to -150 V. After repeating the durability test of 10,000 sheets, the images were compared.

The photoreceptors of Examples 1 to 6 had extremely clear images even after the 10,000-sheet repetitive durability test. The photoconductors of Comparative Examples 1 to 6 were inferior in the initial image, but the images after the test of 10,000 sheets were also inferior in resolution and image clarity as compared with the photoconductors of Examples 1 to 6.

〔The invention's effect〕

By using the phthalocyanine-based compound having a metal having a valence of 3 or more at the center in the charge generation layer of the electrophotographic photoreceptor, it is possible to obtain excellent exposure sensitivity, electrostatic characteristics, and wavelength characteristics. As a result, an electrophotographic photosensitive member having extremely excellent dispersibility and coatability was obtained. The printed matter printed using the photoreceptor was extremely clear and had high resolution.

[Brief description of the drawings]

FIG. 1 is an X-ray diffraction diagram of the amorphous dichlorotin phthalocyanine of Example 1 by CuKα radiation.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification number Agency reference number FI Technical display location C09B 47/22 C09B 47/22

Claims (5)

(57) [Claims] 1. An optical semiconductor material which is a phthalocyanine compound represented by the following general formula [I], and wherein the phthalocyanine is non-crystalline and does not show a strong X-plug diffraction peak. General formula [I] (Wherein, M is a metal atom other than titanium having a valence of 3 or more, other than titanium, R ₁ is a halogen atom, an oxygen atom or an alkoxy group, and R ₂ , R ₃ , R ₄ and R ₅ are a hydrogen atom, a halogen atom , An alkyl group, an alkoxy group, an aryl group, an aryloxy group, a nitro group, a cyano group, a hydroxyl group, a benzyloxy group or an amino group, j is an integer of 1 or 2, k, l,
m and n represent the integer of 0-4. ) 2. The optical semiconductor material according to claim 1, wherein the primary particle system is a phthalocyanine compound having a particle size of 0.2 μm or less. 3. An electrophotographic photosensitive member using a charge generating agent and a charge transfer agent on a conductive support, wherein the charge generating agent is a phthalocyanine compound represented by the following general formula [I]; An electrophotographic photoreceptor, wherein the phthalocyanine is non-crystalline and does not show a strong X-ray peak. General formula [I] (Wherein, M is a metal atom other than titanium having a valence of 3 or more, other than titanium, R ₁ is a halogen atom, an oxygen atom or an alkoxy group, and R ₂ , R ₃ , R ₄ and R ₅ are a hydrogen atom, a halogen atom , An alkyl group, an alkoxy group, an aryl group, an aryloxy group, a nitro group, a cyano group, a hydroxyl group, a benzyloxy group or an amino group, j is an integer of 1 or 2, k, l,
m and n represent the integer of 0-4. ) 4. The electrophotographic photoreceptor according to claim 3, which is a phthalocyanine compound having a primary particle size of 0.2 μm or less. 5. The electrophotographic photoreceptor according to claim 3, wherein an inorganic or organic subbing layer is provided on the conductive support.