JPH10148953A - Electrophotographic photoreceptor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the laminated electrophotographic photoreceptor high in sensitivity and durability by forming a charge generating layer containing phthalocyanines as a charge generating material and a charge transfer layer containing a specified enamine compound as a charge transfer material. SOLUTION: The charge generating layer contains at least one of the phthalocyanines as a charge generating material and the charge transfer layer contains as a charge transfer material one of the enamine compounds represented by formulae I and II in which each of R1 , R2 , R7 , and R8 is an optionally substituted alkyl or aryl or heterocyclic group; each of R3 and R9 is an H or halogen atom or an optionally substituted alkyl or alkoxy group; each of (m) and (n) is 0 or 1; R6 is an optionally substituted alkyl or aralkyl or aryl group or the like; each of R4 , R5 , R11 , is an optionally substituted alkyl or alkenly group or the like; and R12 is an atomic group necessary to form a ring together with the N atom.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an electrophotographic photosensitive member using a phthalocyanine as a charge generating substance and an enamine compound as a charge transporting substance on a conductive support.

[0002]

2. Description of the Related Art In recent years, the use of electrophotography is not limited to the field of copying machines, but has spread to fields in which photographic technology was conventionally used, such as printing plates, slide films, and microfilms. Application to a high-speed printer using a light source is also being studied. Recently, the use of a photoconductive material for applications other than the electrophotographic photoreceptor, for example, an electrostatic recording element, a sensor material, an EL element, and the like has been studied. Accordingly, demands for photoconductive materials and electrophotographic photoreceptors using the same are becoming higher and wider. Heretofore, inorganic photoconductive materials such as selenium, cadmium sulfide, zinc oxide, and silicon have been known as electrophotographic photosensitive members, and have been widely studied and put to practical use. While these inorganic materials have many advantages, they also have various disadvantages. For example, selenium has drawbacks in that the production conditions are difficult and it is easy to crystallize due to heat and mechanical shock, and cadmium sulfide and zinc oxide have poor moisture resistance and durability. It has been pointed out that silicon is insufficient in chargeability and difficult to manufacture. Furthermore,
Selenium and cadmium sulfide also have toxicity problems.

On the other hand, organic photoconductive materials have good film-forming properties, excellent flexibility, are lightweight, have good transparency, and are sensitive to a wide wavelength range by an appropriate sensitization method. Due to its advantages such as easy design of the body, its practical use is gradually attracting attention.

Incidentally, the photoreceptor used in the electrophotographic technology is generally required to have the following basic properties. That is, (1) high chargeability against corona discharge in a dark place, (2) little leakage (dark decay) of the obtained charge in a dark place, and (3) charge charge by light irradiation. (4) The residual charge after light irradiation is small.

However, many studies have been made on photoconductive polymers such as polyvinyl carbazole as organic photoconductive substances to date, but these have not always had sufficient film-forming properties, flexibility and adhesiveness. Also, it is difficult to say that the above-mentioned basic properties of the photoreceptor are sufficiently provided.

On the other hand, as for the organic low-molecular-weight photoconductive compound, by selecting a binder or the like used for forming the photoreceptor, the photoreceptor having excellent mechanical strength such as film property, adhesiveness and flexibility can be obtained. Can be obtained, but it is difficult to find a compound suitable for maintaining high-sensitivity properties.

Various substances such as phthalocyanine pigments, squarium dyes, azo pigments, and perylene pigments have been studied as substances in charge of the charge generation function. Among them, azo pigments can have various molecular structures and have high molecular weight. Since charge generation efficiency can be expected, it has been widely studied and its practical use has been advanced. However, in this azo pigment, the relationship between the molecular structure and the charge generation efficiency has not been clarified yet. The fact is that we are searching for the optimal structure through extensive synthesis research, but it fully satisfies the basic properties and high durability demands of the photoconductors listed above. Things have not yet been obtained.

In recent years, laser beam printers, which use laser light as a light source instead of conventional white light and have advantages of high speed, high image quality, and non-impact, have become widespread in conjunction with the progress of information processing systems. At the same time, there is a demand for the development of a material that can withstand the demand. In particular, among laser beams, in recent years, applications to compact discs, optical discs, and the like have increased, and semiconductor lasers, which have undergone remarkable technological advances, have been actively applied in the field of printers as compact and highly reliable light source materials. In this case, since the wavelength of the light source is around 780 nm, there is a strong demand for the development of a photoreceptor having high sensitivity to long wavelength light around 780 nm. Among them, the development of photoreceptors using phthalocyanine, which has light absorption particularly in the near infrared region, has been actively conducted. However, nothing has yet been achieved.

[0009] On the other hand, the substances in charge of the charge transport function include a hole transport substance and an electron transport substance. Examples of the hole transport substance include hydrazone compounds and stilbene compounds. Among them, a description of a laminated electrophotographic photoreceptor using a titanyloxyphthalocyanine as a charge generation substance and a hydrazone compound as a charge transport substance is disclosed in JP-A-61-109056.
No., published in Japanese Unexamined Patent Publication No. However, none of the above-mentioned charge transport materials has a sufficiently satisfactory sensitivity.

[0010] Further, as the electron transporting substance, 2,4,7
Various kinds of substances such as -trinitro-9-fluorenone and diphenoquinone derivatives have been studied and put to practical use,
Here, too, is the fact that they are conducting extensive synthetic research to search for the optimal structure. In fact, many improvements have been made so far, but none of the above-mentioned photoconductors sufficiently satisfy the requirements such as the basic properties and high durability required for the photoconductors.

As described above, various improvements have been made in the production of an electrophotographic photosensitive member, but the basic characteristics and high durability required for the above-described photosensitive member have not been sufficiently satisfied. At present, there is no satisfactory product yet.

[0012]

SUMMARY OF THE INVENTION An object of the present invention is to provide an optimal laminated electrophotographic photoreceptor capable of exhibiting high sensitivity and stable performance even when used repeatedly.

[0013]

Means for Solving the Problems The present inventors have conducted studies to achieve the above-mentioned object, and have reached the present invention. That is, the present invention provides a laminate type electrophotographic photoreceptor in which a charge generating layer containing a charge generating substance and a charge transporting layer containing a charge transporting substance are separately formed on a conductive support, wherein the charge generating substance is a phthalocyanine, The transport substance is represented by the following general formula (1),
Or at least one of the enamine compounds represented by (2).

[0014]

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In the general formula (1) or (2), R
₁ , R ₂ , R ₇ , and R ₈ each represent an alkyl group, an aryl group, or a heterocyclic ring which may have a substituent, and R ₃ and R _{9 each} have a hydrogen atom, a halogen atom, or a substituent. Represents an alkyl group or an alkoxy group which may be substituted. m and n show the integer of 0-1. R ₆ represents an optionally substituted alkyl group, aralkyl group, aryl group, or heterocyclic ring. R ₄ , R ₅ , R
₁₀ and R ₁₁ each represent an optionally substituted alkyl group, alkenyl group, aralkyl group, aryl group, or heterocyclic ring. R ₁₂ represents an atom group necessary for forming a ring together with a nitrogen atom.

Specific examples of R ₁ , R ₂ , R ₇ and R ₈ include an alkyl group such as a methyl group and an ethyl group, an aryl group such as a phenyl group and a naphthyl group, a heterocycle such as a furyl group and a thienyl group. Can be mentioned. R ₁ , R ₂ , R ₇ ,
R ₈ may have a substituent, and specific examples thereof include the above-mentioned alkyl group, alkoxy group such as methoxy group and ethoxy group, and halogen atom such as fluorine atom and chlorine atom.

Specific examples of R ₃ and R ₉ include a halogen atom such as a hydrogen atom, a fluorine atom and a chlorine atom, an alkyl group such as a methyl group and an ethyl group, and an alkoxy group such as a methoxy group and an ethoxy group. be able to. Also, R
₃ , R ₉ may have a substituent, and specific examples thereof include the above-mentioned halogen atom, the above-mentioned alkyl group, and the above-mentioned alkoxy group.

Specific examples of R ₆ include a methyl group,
Examples include an alkyl group such as an ethyl group, an aralkyl group such as a benzyl group and an α-naphthylmethyl group, an aryl group such as a phenyl group and a naphthyl group, and a heterocycle such as a furyl group and a thienyl group. R ₆ may have a substituent, and specific examples thereof include the above-described alkyl group, methoxy group, alkoxy group such as ethoxy group, fluorine atom,
Examples include a halogen atom such as a chlorine atom.

Specific examples of R ₄ , R ₅ , R ₁₀ and R ₁₁ include an alkyl group such as a methyl group and an ethyl group, an alkenyl group such as an allyl group and a methallyl group, a benzyl group,
Examples include an aralkyl group such as a naphthylmethyl group, an aryl group such as a phenyl group and a naphthyl group, and a heterocycle such as a furyl group and a thienyl group. R ₄ , R ₅ ,
R ₁₀ and R ₁₁ may have a substituent, and specific examples thereof include an alkoxy group such as a methoxy group and an ethoxy group;
Examples include a halogen atom such as a fluorine atom and a chlorine atom, the above-mentioned alkyl group, and the above-mentioned aryl group.

Further, specific examples of the ring formed together with R ₁₂ and the nitrogen atom include a carbazole ring, a phenoxazine ring, a phenothiazine ring, a tetrahydroquinoline ring and the like. The ring formed together with R ₁₂ and the nitrogen atom may have a substituent. Specific examples thereof include an alkyl group such as a methyl group and an ethyl group, an alkoxy group such as a methoxy group and an ethoxy group, and a fluorine atom. And halogen atoms such as chlorine.

[0021]

BEST MODE FOR CARRYING OUT THE INVENTION The general formula (1) according to the present invention,
Alternatively, specific examples of the charge transporting substance represented by (2) include, for example, those having the following structural formulas A-01 to A-57, but are not limited thereto.

[0022]

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[0023]

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[0024]

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[0025]

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[0026]

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[0027]

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[0028]

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[0029]

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[0030]

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[0031]

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As the phthalocyanines used in the present invention, any of the phthalocyanines known per se and derivatives thereof can be used. Specifically, metal-free phthalocyanines, titanyloxy phthalocyanines, copper phthalocyanines, aluminum phthalocyanines, Diphenoxygermanium phthalocyanines, germanium phthalocyanines, gallium phthalocyanines, chlorogallium phthalocyanines, bromogallium phthalocyanines, chloroindium phthalocyanines, bromoindium phthalocyanines, iodoindium phthalocyanines, magnesium phthalocyanines, chloroaluminum phthalocyanines, bromoaluminum Phthalocyanines, tin phthalocyanines, dichlorotin phthalocyanines, vanadi Oxyphthalocyanines, zinc phthalocyanines, cobalt phthalocyanines, nickel phthalocyanines, hydroxygallium phthalocyanines, dihydroxygallium phthalocyanines, barium phthalocyanines, beryllium phthalocyanines, cadmium phthalocyanines, chlorocobalt phthalocyanines, dichlorotitanyl phthalocyanines, iron phthalocyanines , Silicon phthalocyanines, lead phthalocyanines, platinum phthalocyanines, metal-free naphthalocyanines, aluminum naphthalocyanines, titanyloxynaphthalocyanines, ruthenium phthalocyanines, palladium phthalocyanines, and the like. In particular, among them, metal-free phthalocyanine, titanyloxyphthalocyanine, copper phthalocyanine, chloroaluminum phthalocyanine, chloroindium phthalocyanine, vanadyloxyphthalocyanine, diphenoxygermanium phthalocyanine, chlorogallium phthalocyanine, and hydroxygallium phthalocyanine are preferably used in the present invention.

Also, phthalocyanines are known as polymorphic compounds, and various types of phthalocyanines have been found. As a description of these crystal forms and production methods, metal-free phthalocyanine is described in JP-B-49-4338.
JP-A-58-182639, JP-A-58-182639
-19151, JP-A-62-47054,
JP-A-62-143058, JP-A-63-286
857, JP-A-1-138563, JP-A-1-230581, JP-A-2-233969, and Phys. Chem. 72 , 3230
(1968), titanyloxyphthalocyanine is disclosed in JP-A-61-217050 and JP-A-62-6709.
No. 4, JP-A-62-222953, JP-A-6-229253
3-364, JP-A-63-365, JP-A-63-366, JP-A-63-37163,
JP-A-63-80263, JP-A-63-1161
No. 58, JP-A-63-198067, JP-A-63-218768, JP-A-64-17066, JP-A-1-123868, JP-A-1-13
No. 8562, Japanese Unexamined Patent Publication No. 1-153775, Japanese Unexamined Patent Publication No. 1-172459, Japanese Unexamined Patent Publication No. 1-172462, Japanese Unexamined Patent Publication No. 1-189200, Japanese Unexamined Patent Publication No. 1-20
No. 4,969, JP-A-1-207755, JP-A-1-299874, JP-A-2-8256, JP-A-2-99969, JP-A-2-1312
No. 43, JP-A-2-165156 and JP-A-2
JP-A-165157, JP-A-2-215866, JP-A-2-267563, JP-A-2-297
560, JP-A-3-35064, JP-A-3
JP-A-54264, JP-A-3-84068, JP-A-3-94264, JP-A-3-100658, JP-A-100659, and JP-A-3-1233
No. 59, JP-A-3-199268, JP-A-3-1992
-200790, JP-A-3-269064, JP-A-4-145166, JP-A-4-145
167, JP-A-4-153273, JP-A-4-159373, JP-A-4-179964, JP-A-5-202309, JP-A-5-279
592, JP-A-5-289380, JP-A-6-336554, JP-A-7-82503, JP-A-7-82505, and further JP-A-8-1.
No. 10649, copper phthalocyanine is disclosed in
-1667, JP-A-51-108847,
JP-A-55-60958, and further, γ-type, π-type,
Types and ρ types are known. Chloroaluminum phthalocyanine is disclosed in JP-A-58-158649, JP-A-62-133462, and JP-A-62-16306.
No. 0, JP-A-63-43155 and JP-A-64-70762, and chloroindium phthalocyanine is disclosed in JP-A-59-44054 and JP-A-60-sho.
-59355, JP-A-61-45249,
Further, JP-A-7-13375 discloses that vanadyloxyphthalocyanine is disclosed in JP-A-63-18361, JP-A-1-204968, JP-A-268763, JP-A-3-269063, and furthermore, Kaihei 7-
No. 247442, diphenoxyphthalocyanine is described in JP-A-4-360150, chlorogallium phthalocyanine is described in JP-A-5-194523, further JP-A-7-102183, and hydroxygallium phthalocyanine is described in JP-A-Heisei 102102183. Examples thereof include those described in JP-A-5-263007 and JP-A-7-53892.

In the present invention, CuKα1.5
The next Bragg angle (2θ ±) for the X-ray of 41 angstroms
0.2 °) is particularly preferably used. Metal-free phthalocyanine: 7.6 °, 9.2 °, 16.8
°, 17.4 °, 20.4 °, 20.9 °, a metal-free phthalocyanine having an X-ray diffraction spectrum showing main peaks (τ-type metal-free phthalocyanine), 7.5 °, 9.1
°, 16.8 °, 17.3 °, 20.3 °, 20.8
Metal-free phthalocyanine (τ′-) having an X-ray diffraction spectrum showing major peaks at °, 21.4 ° and 27.4 °.
Metal-free phthalocyanine), 7.6 °, 9.2 °, 16.
8. °, 17.4 °, 28.5 ° or 7.6 °, 9.
Metal-free phthalocyanine (η-type metal-free phthalocyanine) having an X-ray diffraction spectrum showing major peaks at 2 °, 16.8 °, 17.4 °, and 21.5 °, 7.5 °, 9.
1 °, 16.8 °, 17.3 °, 20.3 °, 20.8
°, 21.4 °, 27.4 ° or 7.5 °, 9.
1 °, 16.8 °, 17.3 °, 20.3 °, 20.8
°, 21.4 °, 22.1 °, 27.4 °, 28.5 °
A metal-free phthalocyanine (η′-type metal-free phthalocyanine) having an X-ray diffraction spectrum showing a main peak at
7.7 °, 9.3 °, 16.9 °, 22.4 °, 28.
Metal-free phthalocyanine having an X-ray diffraction spectrum showing a main peak at 8 °, metal-free phthalocyanine having an X-ray diffraction spectrum showing a main peak at 6.7 °, 1
Metal-free phthalocyanine having an X-ray diffraction spectrum showing a shoulder at 13.5 ° centered at 5.2 °, 26.8
Metal-free phthalocyanine having an X-ray diffraction spectrum showing a shoulder at 24.8 ° around 6.7 °, 6.7 °, 8.
7 °, 15.1 °, 17.7 °, 23.8 °, 26.1
Metal-free phthalocyanine having an X-ray diffraction spectrum showing major peaks at °, 27.4 ° and 30.0 °, 6.7
°, 7.2 °, 13.4 °, 14.5 °, 15.2 °,
16.0 °, 20.2 °, 21.7 °, 24.0 °, 2
A metal-free phthalocyanine having an X-ray diffraction spectrum showing major peaks at 4.8 °, 26.6 °, 27.3 °,
6.6 °, 13.4 °, 14.5 °, 20.2 °, 2
A metal-free phthalocyanine having an X-ray diffraction spectrum showing major peaks at 4.8 °, 26.6 °, 27.2 °,
6.7 °, 7.3 °, 13.5 °, 14.9 °, 15.
Metal-free phthalocyanine having an X-ray diffraction spectrum showing major peaks at 9 °, 16.7 °, 24.7 °, 26.1 °, or 7.4 °, 9.0 °, 16.5 °, 17.2 °.
2 °, 22.1 °, 23.8 °, 27.0 °, 28.4
Metal-free phthalocyanine having an X-ray diffraction spectrum showing a major peak at °.

Titanyloxyphthalocyanine: 7.5
°, 12.3 °, 16.3 °, 25.3 °, 28.7 °
Titanyloxyphthalocyanine (α-type titanyloxyphthalocyanine) having an X-ray diffraction spectrum showing major peaks at 9.3 °, 10.6 °, 13.2 °, 1
5.1 °, 15.7 °, 16.1 °, 20.8 °, 2
Titanyloxyphthalocyanine (β-type titanyloxyphthalocyanine) having an X-ray diffraction spectrum showing major peaks at 3.3 °, 26.3 ° and 27.1 °, 7.0
°, 15.6 °, 23.4 °, 25.5 °, titanyloxyphthalocyanine having an X-ray diffraction spectrum showing main peaks (C-type titanyloxyphthalocyanine),
Titanyloxyphthalocyanine (m-type titanyloxyphthalocyanine) having an X-ray diffraction spectrum showing major peaks at 6.9 °, 15.5 ° and 23.4 °, 9.5
°, 9.7 °, 11.7 °, 15.0 °, 23.5 °,
Titanyloxyphthalocyanine having an X-ray diffraction spectrum showing major peaks at 24.1 ° and 27.3 ° (Y-type titanyloxyphthalocyanine), 7.3 ° and 17.
Titanyloxyphthalocyanine (γ-type titanyloxyphthalocyanine) having an X-ray diffraction spectrum showing major peaks at 7 °, 24.0 °, 27.2 °, 28.6 °, 9.0 °, 14.2 °, 23.9 °, 27.1 °
Titanyloxyphthalocyanine (X-ray titanyloxyphthalocyanine type I) having an X-ray diffraction spectrum showing major peaks at 7.4 °, 10.1 °, 12.4 °, 2
Titanyloxyphthalocyanine (ω-type titanyloxyphthalocyanine) having an X-ray diffraction spectrum showing major peaks at 4.1 °, 25.2 ° and 28.5 °, 7.4
°, 11.0 °, 17.9 °, 20.1 °, 26.5
°, 29.0 °, titanyloxyphthalocyanine (X-type titanyloxyphthalocyanine E) having an X-ray diffraction spectrum showing main peaks, 7.5 °, 22.4 °, 2
4.4 °, 25.4 °, 26.2 °, 27.2 °, 2
12. Titanyloxyphthalocyanine having an X-ray diffraction spectrum showing a major peak at 8.6 °, 9.2 °, 13.
Titanyloxyphthalocyanine having an X-ray diffraction spectrum showing major peaks at 1 °, 20.7 °, 26.2 °, 27.1 °, major at 7.3 °, 22.9 °, 27.4 ° Titanyloxyphthalocyanine having an X-ray diffraction spectrum showing peaks, 7.6 °, 10.5 °, 1
2.5 °, 15.6 °, 16.4 °, 17.7 °, 2
Titanyloxyphthalocyanine having an X-ray diffraction spectrum showing main peaks at 6.3 °, 28.9 °, 30.5 °, 32.0 °, and an X-ray diffraction spectrum showing main peaks at 26.2 °. Titanyloxyphthalocyanine having an X-ray diffraction spectrum showing major peaks at 7.3 °, 15.2 °, 26.2 °, 13.1 °, 20.6 °, 26.1 °,
Titanyloxyphthalocyanine having an X-ray diffraction spectrum showing a major peak at 27.0 °, 6.7 °, 7.
4 °, 10.2 °, 12.6 °, 15.2 °, 16.0
°, 17.1 °, 18.2 °, 22.4 °, 23.2
°, 24.2 °, 25.2 °, 28.5 °, titanyloxyphthalocyanine having an X-ray diffraction spectrum showing major peaks, 27.3 °, titanyloxy having an X-ray diffraction spectrum showing a major peak at 27.3 ° Phthalocyanine,
6. titanyloxyphthalocyanine having an X-ray diffraction spectrum showing major peaks at 6.8 ° and 27.3 °;
4 °, 11.0 °, 17.9 °, 20.1 °, 26.4
°, titanyloxyphthalocyanine having an X-ray diffraction spectrum showing a main peak at 29.0 °, 6.8 °,
8. Titanyloxyphthalocyanine having an X-ray diffraction spectrum showing major peaks at 9.7 ° and 15.4 °,
2 °, 11.6 °, 13.0 °, 24.1 °, 26.2
°, titanyloxyphthalocyanine having an X-ray diffraction spectrum showing a major peak at 27.2 °, 9.1 °,
Titanyloxyphthalocyanine having an X-ray diffraction spectrum showing major peaks at 12.2 °, 16.3 °, and 26.9 °, 7.4 °, 9.2 °, 10.4 °, 11.6
°, 13.0 °, 14.3 °, 15.0 °, 15.5
°, 23.4 °, 24.1 °, 26.2 °, 27.2 °
Titanyloxyphthalocyanine having an X-ray diffraction spectrum showing major peaks at 9.5 °, 24.1 °, 2
13. titanyloxyphthalocyanine having an X-ray diffraction spectrum showing a major peak at 7.2 °, 7.2 °, 14.
X showing major peaks at 2 °, 24.0 ° and 27.2 °
Titanyloxyphthalocyanine having an X-ray diffraction spectrum having main peaks at 4.8 °, 9.6 ° and 26.2 °, 6.5 °, 14.5 °, 23 Titanyloxyphthalocyanine having an X-ray diffraction spectrum showing a major peak at 0.8 °, 7.0 °, 9.1 °, 14.1 °,
Titanyloxyphthalocyanine having an X-ray diffraction spectrum showing a major peak at 26.2 °, 6.8 °, 1
Titanyloxyphthalocyanine having an X-ray diffraction spectrum showing major peaks at 4.9 °, 24.8 ° and 26.2 °, X showing major peaks at 7.5 ° and 27.3 °
Titanyloxyphthalocyanine with X-ray diffraction spectrum, 21.6 °, titanyloxyphthalocyanine with major X-ray diffraction spectrum at 28.0 °, 9.6 °,
Titanyloxyphthalocyanine having a major X-ray diffraction spectrum at 27.2 °, 7.3 °, 19.4 °, 2
Titanyloxyphthalocyanine having an X-ray diffraction spectrum showing major peaks at 1.5 ° and 23.8 °, 1
Titanyloxyphthalocyanine having an X-ray diffraction spectrum showing major peaks at 0.5 °, 12.6 °, 15.0 °, 26.6 °, 8.5 °, 13.6 °, 17.1
Titanyloxyphthalocyanine having an X-ray diffraction spectrum showing major peaks at °, 18.0 °, 23.9 °, 27.4 °, major peaks at 8.9 °, 11.4 °, 27.2 ° Titanyloxyphthalocyanine having an X-ray diffraction spectrum of 7.5 °, 22.5 °, 28.6
Titanyloxyphthalocyanine having an X-ray diffraction spectrum with a major peak at °, 6.8 °, 26.1
°, titanyloxyphthalocyanine having an X-ray diffraction spectrum showing a main peak at 27.1 °, titanyloxyphthalocyanine having an X-ray diffraction spectrum showing a main peak at 8.4 °, 7.6 °, 10 0.3 °, 1
2.7 °, 16.3 °, 22.7 °, 24.3 °, 2
5. titanyloxyphthalocyanine having an X-ray diffraction spectrum showing major peaks at 5.5 ° and 28.6 °,
8 °, 7.4 °, 15.0 °, 24.7 °, 26.2
Titanyloxyphthalocyanine having an X-ray diffraction spectrum showing main peaks at ° and 27.2 °, or amorphous titanyloxyphthalocyanine having no distinct peak.

Copper phthalocyanine: 7.0 °, 9.2 °,
12.5 °, 16.8 °, 18.6 °, 21.3 °, 2
Copper phthalocyanine (β-type copper phthalocyanine) having an X-ray diffraction spectrum showing main peaks at 3.8 °, 26.2 °, 28.0 °, and 30.5 °, 7.6 °, 9.1
°, 14.2 °, 17.4 °, 20.4 °, 21.2
°, 23.0 °, 26.5 °, 27.2 °, 29.5 °
A copper phthalocyanine (ε-type copper phthalocyanine) having an X-ray diffraction spectrum showing a main peak at 7.0 °;
9.8 °, 15.8 °, 24.9 °, 26.7 °, 2
6. Copper phthalocyanine having an X-ray diffraction spectrum showing a main peak at 7.3 ° (α-type copper phthalocyanine);
Copper phthalocyanine having an X-ray diffraction spectrum showing main peaks at 0 °, 7.7 °, and 9.2 °.

Chloroaluminum phthalocyanine: 7.
10. Chloroaluminum phthalocyanine with X-ray diffraction spectrum showing a major peak at 0 °, 6.7 °, 11.
X showing major peaks at 2 °, 16.7 ° and 25.6 °
Chloroaluminum phthalocyanine having an X-ray diffraction spectrum showing a main peak at 25.5 ° or 6.5 °, 11.1 °, 13.7 °, 17.0 °,
Chloroaluminum phthalocyanine having an X-ray diffraction spectrum showing major peaks at 22.0 °, 23.0 °, 24.1 °, and 25.7 °.

Chloroindium phthalocyanine: 7.4
Chloroindium phthalocyanine having an X-ray diffraction spectrum showing major peaks at °, 16.7 ° and 27.8 °.

Vanadyl oxyphthalocyanine: 9.3
°, 10.7 °, 13.1 °, 15.1 °, 15.7
°, 16.1 °, 20.7 °, 23.3 °, 26.2
°, vanadyloxyphthalocyanine having an X-ray diffraction spectrum showing a major peak at 27.1 °, 7.5 °,
Vanadyloxyphthalocyanine having an X-ray diffraction spectrum showing major peaks at 24.2 °, 27.7 °, 28.6 °, 14.3 °, 18.0 °, 24.1 °, 2
Vanadyloxyphthalocyanine having an X-ray diffraction spectrum showing a major peak at 7.3 °, 7.4 °, 10.
3 °, 12.6 °, 16.3 °, 17.8 °, 18.5
°, 22.4 °, 24.2 °, 25.4 °, 27.2
Vanadyloxyphthalocyanine having an X-ray diffraction spectrum showing main peaks at 0 ° and 28.6 °, or vanadyloxyphthalocyanine which is an amorphous type having no clear peak.

Chlorogallium phthalocyanine: 7.4
Chlorogallium phthalocyanine having an X-ray diffraction spectrum showing major peaks at °, 16.6 °, 25.5 ° and 28.3 °, major peaks at 11.0 °, 13.5 ° and 27.1 ° Chlorogallium phthalocyanine having an X-ray diffraction spectrum of 6.8 °, 17.3 °, 2
Chlorogallium phthalocyanine having an X-ray diffraction spectrum showing major peaks at 3.6 ° and 26.9 °, or 8.7 to 9.2 °, 17.6 °, 27.4 °, 28.
A chlorogallium phthalocyanine having an X-ray diffraction spectrum showing a major peak at 8 °.

Hydroxygallium phthalocyanine: 7.
5 °, 9.9 °, 12.5 °, 16.3 °, 18.6
Hydroxygallium phthalocyanine with X-ray diffraction spectra showing major peaks at °, 25.1 °, 28.3 °, 7.7 °, 16.5 °, 25.1 °, 26.6 °
Hydroxygallium phthalocyanine having an X-ray diffraction spectrum showing a major peak at 7.9 °, 16.5
Hydroxygallium phthalocyanine having an X-ray diffraction spectrum showing major peaks at °, 24.4 °, 27.6 °, 7.0 °, 7.5 °, 10.5 °, 11.7 °,
12.7 °, 17.3 °, 18.1 °, 24.5 °, 2
Hydroxygallium phthalocyanine having an X-ray diffraction spectrum showing major peaks at 6.2 ° and 27.1 °,
Hydroxygallium phthalocyanine having an X-ray diffraction spectrum showing major peaks at 6.8 °, 12.8 °, 15.8 °, 26.0 °, or 7.4 °, 9.9 °,
Hydroxygallium phthalocyanine having an X-ray diffraction spectrum showing major peaks at 25.0 °, 26.2 °, and 28.2 °.

Diphenoxygermanium phthalocyanine: 9.0 °, 11.2 °, 17.1 °, 18.1 °,
Diphenoxygermanium phthalocyanine having an X-ray diffraction spectrum showing major peaks at 20.9 °, 22.7 °, 25.8 ° and 29.3 °.

Generally, phthalocyanine is produced by a phthalodinitrile method in which phthalodinitrile and a metal chloride or an alkoxy metal are melted by heating or heated in the presence of an organic solvent, and phthalic anhydride is converted into urea and a metal chloride. And the Wiler method of heating and melting or heating in the presence of an organic solvent
A method of reacting cyanobenzamide with a metal salt at a high temperature, a method of reacting dilithium phthalocyanine with a metal salt, and the like are not limited thereto. As the organic solvent used in the reaction, α-chloronaphthalene, β-chloronaphthalene, α-methylnaphthalene, methoxynaphthalene, diphenylnaphthalene,
Ethylene glycol, dialkyl ether, quinoline,
A reaction-inactive high-boiling solvent such as sulfolane, dichlorobenzene, N-methyl-2-pyrrolidone, and dichlorotoluene is desirable.

The phthalocyanine compound obtained by the above-mentioned method is converted into an acid, an alkali, acetone, methanol, ethanol, methyl ethyl ketone, tetrahydrofuran, pyridine, quinoline, sulfolane, α-chloronaphthalene,
By purifying with toluene, xylene, dioxane, chloroform, dichloroethane, N, N'-dimethylformamide, N-methyl-2-pyrrolidone, etc., a high-purity phthalocyanine compound usable for electrophotography can be obtained.
Examples of the purification method include a washing method, a recrystallization method, an extraction method such as Soxhlet, a hot suspension method, and a sublimation method. The purification method is not limited to these, and any method may be used as long as it removes unreacted substances and reaction by-products.

Next, the synthesis examples of the compounds according to the present invention will be described in more detail, but the present invention is not limited thereto.

[0046]

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Synthesis Example 1 Synthesis of Exemplified Compound A-18 3.01 g of the amine compound (3) shown above, 2.94 g of diphenylacetaldehyde and 0.03 g of p-toluenesulfonic acid monohydrate were dissolved in 60 ml of toluene. The mixture was heated to reflux while removing the generated water. After 9.5 hours, the reaction solution was cooled and the solvent was distilled off under reduced pressure. The obtained oily substance was purified by silica gel column chromatography to obtain 2.8 g of Exemplified Compound A-18. Melting point 1
20 ° C.

[0048]

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Synthesis Example 2 Synthesis of Exemplified Compound A-37 1.60 g of the hydrazone compound (4) shown above was added to N, N
-Dissolved in 5 ml of dimethylformamide (DMF), and 0.67 g of potassium t-butoxide was slowly added at room temperature with stirring. After continuing stirring at the same temperature for 45 minutes, the reaction solution was poured into 500 ml of ice water to precipitate crystals. 1N
After neutralization with hydrochloric acid, the organic component was extracted with ethyl acetate.
After drying over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure.
The obtained crystals were recrystallized from acetonitrile to obtain 1.15 g of Exemplified Compound A-37. Melting point 108.5 ° C.

There are various types of photoreceptors of a laminated type, and any of them can be used. For example, on a conductive support, a charge-generating layer composed of a charge-generating substance and a binder resin, and a laminated photoconductor provided with a charge-transporting layer composed of a charge-transporting substance and a binder resin, Either of the charge generation layer and the charge transport layer may be an upper layer. If necessary, an undercoat layer may be provided between the conductive support and the photosensitive layer, an overcoat layer may be provided on the surface of the photosensitive member, and an intermediate layer may be provided between the charge generation layer and the charge transport layer. As a support for producing a photoreceptor by using the compound of the present invention, a metal drum, a metal plate, a sheet-like or drum-like or belt-like support of paper or plastic film subjected to conductive processing, and the like are used. You.

As the film-forming binder resin used for forming the photosensitive layer on the support, various resins can be used depending on the field of use. For example, for photoreceptors for copying, polystyrene resin, polyvinyl acetal resin, polysulfone resin, polycarbonate resin, vinyl acetate
Crotonic acid copolymer resin, polyester resin, polyphenylene oxide resin, polyarylate resin, alkyd resin, acrylic resin, methacrylic resin, phenoxy resin and the like. Among them, polystyrene resin, polyvinyl acetal resin, polycarbonate resin, polyester resin, polyarylate resin, and the like have excellent potential characteristics as a photoconductor. These resins can be used alone or as a mixture of one or more of them as a copolymer. The amount of the binder resin to be added to the photoconductive compound is 20 to 1000% by weight.
Is preferable, and 50 to 500% by weight is more preferable.

In the case of a laminate type photoreceptor, these resins contained in the charge generation layer are 10 to 50 with respect to the charge generation substance.
0% by weight is preferable, and 50 to 150% by weight is more preferable. If the ratio of the resin is too high, the charge generation efficiency is lowered, and if the ratio of the resin is too low, there is a problem in film formability. Further, the content of these resins contained in the charge transport layer is preferably from 20 to 1,000% by weight, more preferably from 50 to 500% by weight, based on the charge transport material. If the ratio of the resin is too high, the sensitivity is lowered, and if the ratio of the resin is too low, the repetition characteristics may be deteriorated or the coating film may be damaged.

Among these resins, there are tension, bending,
Some have weak mechanical strength such as compression. To improve this property, substances which impart plasticity can be added. Specifically, phthalic acid esters (eg, DOP, DOP
BP), phosphoric acid esters (eg, TCP, TOP, etc.), sebacic acid esters, adipic acid esters, nitrile rubber, chlorinated hydrocarbons and the like. If these substances are added unnecessarily, they adversely affect the electrophotographic properties. Therefore, the ratio is preferably 20% by weight or less based on the binder resin.

Other additives such as an antioxidant and an anti-curl agent may be added to the photoreceptor as needed to improve coating properties.

The enamine compound represented by the general formula (1) or (2) can be used in combination with another charge transporting substance. The charge transport materials include a hole transport material and an electron transport material. An example of the former is, for example,
Oxadiazoles disclosed in JP-B-4-5466, triphenylmethanes disclosed in JP-B-45-555, pyrazolines described in JP-B-52-4188, and the like; Japanese Patent Publication 55-42380
Hydrazones disclosed in Japanese Patent Application Laid-Open No.
Oxadiazoles and the like described in JP-A-123544 and the like can be mentioned. On the other hand, examples of the electron transporting substance include chloranil, tetracyanoethylene, tetracyanoquinodimethane, 2,4,7-trinitro-9
-Fluorenone, 2,4,5,7-tetranitro-9-
Fluorenone, 2,4,5,7-tetranitroxanthone, 2,4,8-trinitrothioxanthone, 1,3
Examples include 7-trinitrodibenzothiophene and 1,3,7-trinitrodibenzothiophene-5,5-dioxide. These charge transport materials can be used alone or in combination of two or more.

A certain electron-withdrawing compound is added as a sensitizer that forms a charge transfer complex with the enamine compound represented by the general formula (1) or (2) and further increases the sensitizing effect. You can also. Examples of the electron-withdrawing compound include quinones such as 2,3-dichloro-1,4-naphthoquinone, 1-nitroanthraquinone, 1-chloro-5-nitroanthraquinone, 2-chloroanthraquinone, and phenanthrenequinone; Aldehydes such as benzaldehyde, ketones such as 9-benzoylanthracene, indandione, 3,5-dinitrobenzophenone, 3,3 ', 5,5'-tetranitrobenzophenone, phthalic anhydride, 4-chloronaphthalic anhydride and the like Acid anhydride, terephthalalmalononitrile,
Cyano compounds such as 9-anthrylmethylidenemalononitrile, 4-nitrobenzalmalonenitrile, 4- (p-nitrobenzoyloxy) benzalmalonenitrile,
Phthalides such as 3-benzalphthalide, 3- (α-cyano-p-nitrobenzal) phthalide, 3- (α-cyano-p-nitrobenzal) -4,5,6,7-tetrachlorophthalide and the like can be mentioned. it can.

The phthalocyanine and the enamine compound represented by the general formula (1) or (2) are dissolved or dispersed in a suitable solvent together with various additives as necessary.
The coating solution is applied onto the above-described conductive support and dried to produce a photoreceptor.

Examples of the coating solvent include halogenated hydrocarbons such as chloroform, dichloroethane, dichloromethane, trichloroethane, trichloroethylene, chlorobenzene and dichlorobenzene, aromatic hydrocarbons such as benzene, toluene and xylene, dioxane, tetrahydrofuran, methyl cellosolve, ethyl cellosolve, and the like. Ether solvents such as ethylene glycol dimethyl ether, ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, methyl isopropyl ketone and cyclohexanone, ester solvents such as ethyl acetate, methyl formate, methyl cellosolve acetate, N, N-dimethylformamide, acetonitrile; N-methylpyrrolidone, aprotic polar solvents such as dimethyl sulfoxide and alcohol-based solvents and the like It is possible. These solvents can be used as one kind or a mixture of two or more kinds.

[0059]

EXAMPLES Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

Example 1 1 part by weight of τ-type metal-free phthalocyanine and 1 part by weight of a polyester resin (Vylon 220 manufactured by Toyobo) were mixed with 1 part of dioxane.
And mixed with glass beads in a paint conditioner for 3 hours. The dispersion thus obtained was applied on an aluminum-evaporated polyester using an applicator and dried to form a charge generation layer having a thickness of about 0.2 μm. Next, an enamine compound (exemplified compound A-01) is
Polyarylate resin (U-polymer manufactured by Unitika) and 1:
1 by weight, and 10 parts by weight of dichloroethane as a solvent.
A solution of about 20% by weight was prepared and applied on the above-mentioned charge generating layer with an applicator to form a charge transporting layer having a thickness of about 20 μm.

The electrophotographic characteristics of the laminated photoreceptor thus manufactured were evaluated using an electrostatic recording tester (SP-428, manufactured by Kawaguchi Electric). Measurement conditions: applied voltage -6 kV, static No. 3 (turntable rotation speed mode: 10 m / min)
). As a result, the charged potential (V0) was -805 V, and the half-life exposure amount (E1 / 2) was 1.4 lux / sec, which was a high sensitivity value.

Further, the same apparatus was used to evaluate the characteristics with respect to repeated use in which one cycle of charging-discharging (discharging light: irradiation with white light at 400 lux × 1 second) was performed. 5000
The change in the charged potential due to the repetition of
The 5000th charging potential (V0) was -785V compared to the charging potential (V0) of -805V at the time, and showed stable characteristics with almost no decrease in potential due to repetition. The first half-exposure dose (E1 / 2) is 1.4 lux / sec, whereas the 5000th half-exposure dose (E1 / 2) is 1.4.
It showed excellent characteristics without change in looks and seconds.

Examples 2 to 37 The τ-type metal-free phthalocyanine of Example 1, Exemplified Compound A-
A photoconductor was prepared in the same manner as in Example 1 except that phthalocyanines and enamine compounds shown in Tables 2 and 3 were used instead of 01, respectively, and the characteristics were evaluated. The results are shown in Tables 2 and 3. Table 1 shows the crystal forms of each phthalocyanine used in Examples 1 to 37.

[0064]

[Table 1]

[0065]

[Table 2]

[0066]

[Table 3]

[0067]

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Comparative Example 1 A photoconductor was prepared in the same manner as in Example 1, except that the comparative compound (5) shown above was used in place of the exemplary compound A-01 as a charge transporting substance, and the characteristics were evaluated. As a result, 1
The second charging potential is (V0) -760V, and the half-exposure amount (E1
/ 2) was 4.8 lux / sec, which was insufficient sensitivity.

[0069]

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Comparative Example 2 An m-type titanyloxyphthalocyanine was used in place of the τ-type metal-free phthalocyanine as the charge generating substance, and the comparative compound (6) shown above was used in place of the exemplary compound A-01 as the charge transporting substance. A photoreceptor was prepared in the same manner as in Example 1, and its characteristics were evaluated. As a result, the first charging potential (V0) was -605 V, and the half-life exposure (E1 / 2) was 3.2 lux / sec, which was insufficient sensitivity.

[0071]

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Comparative Example 3 Example 1 was repeated except that the comparative compound (7) shown above was used instead of the τ-type metal-free phthalocyanine as the charge generating substance.
A photoreceptor was prepared in the same manner as described above, and its characteristics were evaluated. As a result, the charging potential (V0) was -740 V, and the half-exposure amount (E1
/ 2) was 3.7 lux-seconds, which was insufficient sensitivity.

[0073]

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Comparative Example 4 A photoconductor was prepared in the same manner as in Example 1 except that the comparative compound (8) was used instead of the τ-type metal-free phthalocyanine as a charge generating substance, and the characteristics were evaluated. As a result, the first charging potential (V0) was -670 V, and the half-exposure amount (E1 / 2)
Was 3.5 lux / sec, which was insufficient sensitivity.

From these results, when the phthalocyanine is used as the charge generating substance and the enamine compound represented by the general formula (1) or (2) is used as the charge transporting substance, the sensitivity is higher than that of the hydrazone compound described above. It has been found that a highly durable electrophotographic photosensitive member can be obtained.

[0076]

As is apparent from the above description, a laminated electrophotographic photosensitive member having high sensitivity and high durability can be provided by using a combination of a phthalocyanine and an enamine compound in the present invention.

Claims (11)

[Claims] 1. A laminated electrophotographic photosensitive member in which a charge generating layer containing a charge generating substance and a charge transporting layer containing a charge transporting substance are separately formed on a conductive support, wherein the charge generating substance is a phthalocyanine, a charge An electrophotographic photoreceptor, wherein the transport substance is at least one of the enamine compounds represented by the following general formula (1) or (2). Embedded image (In the general formula (1) or (2), R ₁ , R ₂ , R
₇ and R ₈ each represent an optionally substituted alkyl group, an aryl group, or a heterocyclic ring; R ₃ and R _{9 each} represent a hydrogen atom;
A halogen atom, an alkyl group which may have a substituent,
Shows an alkoxy group. m and n show the integer of 0-1. R
₆ represents an alkyl group which may have a substituent, an aralkyl group, an aryl group, and a heterocyclic ring. R ₄ , R ₅ , R ₁₀ , R ₁₁
Represents an alkyl group, an alkenyl group, an aralkyl group, an aryl group, or a heterocyclic ring which may have a substituent.
R ₁₂ represents an atom group necessary for forming a ring together with a nitrogen atom. ) 2. The phthalocyanine according to claim 1, wherein the phthalocyanine is a metal-free phthalocyanine, a titanyloxyphthalocyanine,
An electrophotographic photosensitive member comprising at least one selected from copper phthalocyanine, chloroaluminum phthalocyanine, chloroindium phthalocyanine, vanadyloxyphthalocyanine, chlorogallium phthalocyanine, hydroxygallium phthalocyanine, and diphenoxygermanium phthalocyanine. 3. The phthalocyanine according to claim 2, wherein the metal-free phthalocyanine has a Bragg angle (2θ ± 0.2 °) of 7.6 ° with respect to X-rays of CuKα1.541 angstroms. 2 °, 16.
8. Metal-free phthalocyanine (τ-type metal-free phthalocyanine) having an X-ray diffraction spectrum showing major peaks at 8 °, 17.4 °, 20.4 °, and 20.9 °, 7.5 °, 9.
1 °, 16.8 °, 17.3 °, 20.3 °, 20.8
Metal-free phthalocyanine (τ′-) having an X-ray diffraction spectrum showing major peaks at °, 21.4 ° and 27.4 °.
Metal-free phthalocyanine), 7.6 °, 9.2 °, 16.
8. °, 17.4 °, 28.5 ° or 7.6 °, 9.
Metal-free phthalocyanine (η-type metal-free phthalocyanine) having an X-ray diffraction spectrum showing major peaks at 2 °, 16.8 °, 17.4 °, and 21.5 °, 7.5 °, 9.
1 °, 16.8 °, 17.3 °, 20.3 °, 20.8
°, 21.4 °, 27.4 ° or 7.5 °, 9.
1 °, 16.8 °, 17.3 °, 20.3 °, 20.8
°, 21.4 °, 22.1 °, 27.4 °, 28.5 °
A metal-free phthalocyanine (η′-type metal-free phthalocyanine) having an X-ray diffraction spectrum showing a main peak at
7.7 °, 9.3 °, 16.9 °, 22.4 °, 28.
Metal-free phthalocyanine having an X-ray diffraction spectrum showing a main peak at 8 °, metal-free phthalocyanine having an X-ray diffraction spectrum showing a main peak at 6.7 °, 1
Metal-free phthalocyanine having an X-ray diffraction spectrum showing a shoulder at 13.5 ° centered at 5.2 °, 26.8
Metal-free phthalocyanine having an X-ray diffraction spectrum showing a shoulder at 24.8 ° around 6.7 °, 6.7 °, 8.
7 °, 15.1 °, 17.7 °, 23.8 °, 26.1
Metal-free phthalocyanine having an X-ray diffraction spectrum showing major peaks at °, 27.4 ° and 30.0 °, 6.7
°, 7.2 °, 13.4 °, 14.5 °, 15.2 °,
16.0 °, 20.2 °, 21.7 °, 24.0 °, 2
A metal-free phthalocyanine having an X-ray diffraction spectrum showing major peaks at 4.8 °, 26.6 °, 27.3 °,
6.6 °, 13.4 °, 14.5 °, 20.2 °, 2
A metal-free phthalocyanine having an X-ray diffraction spectrum showing major peaks at 4.8 °, 26.6 °, 27.2 °,
6.7 °, 7.3 °, 13.5 °, 14.9 °, 15.
Metal-free phthalocyanine having an X-ray diffraction spectrum showing major peaks at 9 °, 16.7 °, 24.7 °, 26.1 °, or 7.4 °, 9.0 °, 16.5 °, 17.2 °.
2 °, 22.1 °, 23.8 °, 27.0 °, 28.4
An electrophotographic photosensitive member, which is a metal-free phthalocyanine having an X-ray diffraction spectrum showing a main peak at °. 4. The phthalocyanine according to claim 2, wherein the phthalocyanine is titanyloxyphthalocyanine, and the titanyloxyphthalocyanine has CuKα1.541 angstroms of X.
The Bragg angle (2θ ± 0.2 °) with respect to the line is 7.5
°, 12.3 °, 16.3 °, 25.3 °, 28.7 °
Titanyloxyphthalocyanine (α-type titanyloxyphthalocyanine) having an X-ray diffraction spectrum showing major peaks at 9.3 °, 10.6 °, 13.2 °, 1
5.1 °, 15.7 °, 16.1 °, 20.8 °, 2
Titanyloxyphthalocyanine (β-type titanyloxyphthalocyanine) having an X-ray diffraction spectrum showing major peaks at 3.3 °, 26.3 ° and 27.1 °, 7.0
°, 15.6 °, 23.4 °, 25.5 °, titanyloxyphthalocyanine having an X-ray diffraction spectrum showing main peaks (C-type titanyloxyphthalocyanine),
Titanyloxyphthalocyanine (m-type titanyloxyphthalocyanine) having an X-ray diffraction spectrum showing major peaks at 6.9 °, 15.5 ° and 23.4 °, 9.5
°, 9.7 °, 11.7 °, 15.0 °, 23.5 °,
Titanyloxyphthalocyanine having an X-ray diffraction spectrum showing major peaks at 24.1 ° and 27.3 ° (Y-type titanyloxyphthalocyanine), 7.3 ° and 17.
Titanyloxyphthalocyanine (γ-type titanyloxyphthalocyanine) having an X-ray diffraction spectrum showing major peaks at 7 °, 24.0 °, 27.2 °, 28.6 °, 9.0 °, 14.2 °, 23.9 °, 27.1 °
Titanyloxyphthalocyanine (X-ray titanyloxyphthalocyanine type I) having an X-ray diffraction spectrum showing major peaks at 7.4 °, 10.1 °, 12.4 °, 2
Titanyloxyphthalocyanine (ω-type titanyloxyphthalocyanine) having an X-ray diffraction spectrum showing major peaks at 4.1 °, 25.2 ° and 28.5 °, 7.4
°, 11.0 °, 17.9 °, 20.1 °, 26.5
°, 29.0 °, titanyloxyphthalocyanine (X-type titanyloxyphthalocyanine E) having an X-ray diffraction spectrum showing main peaks, 7.5 °, 22.4 °, 2
4.4 °, 25.4 °, 26.2 °, 27.2 °, 2
12. Titanyloxyphthalocyanine having an X-ray diffraction spectrum showing a major peak at 8.6 °, 9.2 °, 13.
Titanyloxyphthalocyanine having an X-ray diffraction spectrum showing major peaks at 1 °, 20.7 °, 26.2 °, 27.1 °, major at 7.3 °, 22.9 °, 27.4 ° Titanyloxyphthalocyanine having an X-ray diffraction spectrum showing peaks, 7.6 °, 10.5 °, 1
2.5 °, 15.6 °, 16.4 °, 17.7 °, 2
Titanyloxyphthalocyanine having an X-ray diffraction spectrum showing main peaks at 6.3 °, 28.9 °, 30.5 °, 32.0 °, and an X-ray diffraction spectrum showing main peaks at 26.2 °. Titanyloxyphthalocyanine having an X-ray diffraction spectrum showing major peaks at 7.3 °, 15.2 °, 26.2 °, 13.1 °, 20.6 °, 26.1 °,
Titanyloxyphthalocyanine having an X-ray diffraction spectrum showing a major peak at 27.0 °, 6.7 °, 7.
4 °, 10.2 °, 12.6 °, 15.2 °, 16.0
°, 17.1 °, 18.2 °, 22.4 °, 23.2
°, 24.2 °, 25.2 °, 28.5 °, titanyloxyphthalocyanine having an X-ray diffraction spectrum showing major peaks, 27.3 °, titanyloxy having an X-ray diffraction spectrum showing a major peak at 27.3 ° Phthalocyanine,
6. titanyloxyphthalocyanine having an X-ray diffraction spectrum showing major peaks at 6.8 ° and 27.3 °;
4 °, 11.0 °, 17.9 °, 20.1 °, 26.4
°, titanyloxyphthalocyanine having an X-ray diffraction spectrum showing a main peak at 29.0 °, 6.8 °,
8. Titanyloxyphthalocyanine having an X-ray diffraction spectrum showing major peaks at 9.7 ° and 15.4 °,
2 °, 11.6 °, 13.0 °, 24.1 °, 26.2
°, titanyloxyphthalocyanine having an X-ray diffraction spectrum showing a major peak at 27.2 °, 9.1 °,
Titanyloxyphthalocyanine having an X-ray diffraction spectrum showing major peaks at 12.2 °, 16.3 °, and 26.9 °, 7.4 °, 9.2 °, 10.4 °, 11.6
°, 13.0 °, 14.3 °, 15.0 °, 15.5
°, 23.4 °, 24.1 °, 26.2 °, 27.2 °
Titanyloxyphthalocyanine having an X-ray diffraction spectrum showing major peaks at 9.5 °, 24.1 °, 2
13. titanyloxyphthalocyanine having an X-ray diffraction spectrum showing a major peak at 7.2 °, 7.2 °, 14.
X showing major peaks at 2 °, 24.0 ° and 27.2 °
Titanyloxyphthalocyanine having an X-ray diffraction spectrum having main peaks at 4.8 °, 9.6 ° and 26.2 °, 6.5 °, 14.5 °, 23 Titanyloxyphthalocyanine having an X-ray diffraction spectrum showing a major peak at 0.8 °, 7.0 °, 9.1 °, 14.1 °,
Titanyloxyphthalocyanine having an X-ray diffraction spectrum showing a major peak at 26.2 °, 6.8 °, 1
Titanyloxyphthalocyanine having an X-ray diffraction spectrum showing major peaks at 4.9 °, 24.8 ° and 26.2 °, X showing major peaks at 7.5 ° and 27.3 °
Titanyloxyphthalocyanine with X-ray diffraction spectrum, 21.6 °, titanyloxyphthalocyanine with major X-ray diffraction spectrum at 28.0 °, 9.6 °,
Titanyloxyphthalocyanine having a major X-ray diffraction spectrum at 27.2 °, 7.3 °, 19.4 °, 2
Titanyloxyphthalocyanine having an X-ray diffraction spectrum showing major peaks at 1.5 ° and 23.8 °, 1
Titanyloxyphthalocyanine having an X-ray diffraction spectrum showing major peaks at 0.5 °, 12.6 °, 15.0 °, 26.6 °, 8.5 °, 13.6 °, 17.1
Titanyloxyphthalocyanine having an X-ray diffraction spectrum showing major peaks at °, 18.0 °, 23.9 °, 27.4 °, major peaks at 8.9 °, 11.4 °, 27.2 ° Titanyloxyphthalocyanine having an X-ray diffraction spectrum of 7.5 °, 22.5 °, 28.6
Titanyloxyphthalocyanine having an X-ray diffraction spectrum with a major peak at °, 6.8 °, 26.1
°, titanyloxyphthalocyanine having an X-ray diffraction spectrum showing a main peak at 27.1 °, titanyloxyphthalocyanine having an X-ray diffraction spectrum showing a main peak at 8.4 °, 7.6 °, 10 0.3 °, 1
2.7 °, 16.3 °, 22.7 °, 24.3 °, 2
5. titanyloxyphthalocyanine having an X-ray diffraction spectrum showing major peaks at 5.5 ° and 28.6 °,
8 °, 7.4 °, 15.0 °, 24.7 °, 26.2
An electrophotographic photoreceptor comprising titanyloxyphthalocyanine having an X-ray diffraction spectrum showing main peaks at 0 ° and 27.2 °, or amorphous titanyloxyphthalocyanine having no clear peak. 5. The phthalocyanine according to claim 2, wherein the phthalocyanine is copper phthalocyanine.
Bragg angle for X-ray of α1.541 angstroms (2
θ ± 0.2 °) is 7.0 °, 9.2 °, 12.5 °,
16.8 °, 18.6 °, 21.3 °, 23.8 °, 2
Copper phthalocyanine (β-type copper phthalocyanine) having an X-ray diffraction spectrum showing main peaks at 6.2 °, 28.0 °, and 30.5 °, 7.6 °, 9.1 °, 14.2
°, 17.4 °, 20.4 °, 21.2 °, 23.0
Copper phthalocyanine (ε-type copper phthalocyanine) having an X-ray diffraction spectrum showing main peaks at °, 26.5 °, 27.2 ° and 29.5 °, 7.0 °, 9.8 °, 1
Copper phthalocyanine (α-type copper phthalocyanine) having an X-ray diffraction spectrum showing main peaks at 5.8 °, 24.9 °, 26.7 °, and 27.3 °, 7.0 °, 7.7
An electrophotographic photoreceptor comprising copper phthalocyanine having an X-ray diffraction spectrum showing main peaks at ° and 9.2 °. 6. The phthalocyanine in claim 2 is a chloroaluminum phthalocyanine, and the chloroaluminum phthalocyanine has a Bragg angle (2θ ± 0.2 °) with respect to X-rays of CuKα1.541 angstroms.
Chloroaluminum phthalocyanine having an X-ray diffraction spectrum showing a major peak at 7.0 °, 6.7 °, 1
A chloroaluminum phthalocyanine having an X-ray diffraction spectrum showing major peaks at 1.2 °, 16.7 °, 25.6 °, a chloroaluminum phthalocyanine having an X-ray diffraction spectrum showing major peaks at 25.5 °, or 6.5 °, 11.1 °, 13.7 °, 17.0
°, 22.0 °, 23.0 °, 24.1 °, 25.7 °
An electrophotographic photoreceptor comprising chloroaluminum phthalocyanine having an X-ray diffraction spectrum showing a main peak. 7. The phthalocyanine in claim 2 is chloroindium phthalocyanine, and the chloroindium phthalocyanine has a Bragg angle (2θ ± 0.2 °) of X-ray of CuKα1.541 angstroms of 7.4.
An electrophotographic photosensitive member comprising chloroindium phthalocyanine having an X-ray diffraction spectrum showing main peaks at °, 16.7 °, and 27.8 °. 8. The phthalocyanine according to claim 2, wherein the vanadyloxyphthalocyanine has a Bragg angle (2θ ± 0.2 °) with respect to X-rays of CuKα1.541 angstroms of 9.3 °,
10.7 °, 13.1 °, 15.1 °, 15.7 °, 1
6.1 °, 20.7 °, 23.3 °, 26.2 °, 2
Vanadyloxyphthalocyanine having an X-ray diffraction spectrum showing a major peak at 7.1 °, 7.5 °, 24.
X showing major peaks at 2 °, 27.7 ° and 28.6 °
Vanadyl oxyphthalocyanine with line diffraction spectrum, 14.3 °, 18.0 °, 24.1 °, 27.3 °
Vanadyloxyphthalocyanine having an X-ray diffraction spectrum showing major peaks at 7.4 °, 10.3 °, 1
2.6 °, 16.3 °, 17.8 °, 18.5 °, 2
2.4 °, 24.2 °, 25.4 °, 27.2 °, 2
An electrophotographic photoreceptor comprising vanadyloxyphthalocyanine having an X-ray diffraction spectrum showing a main peak at 8.6 ° or amorphous vanadyloxyphthalocyanine having no clear peak. 9. The phthalocyanine according to claim 2, wherein the phthalocyanine is chlorogallium phthalocyanine, and the chlorogallium phthalocyanine has a CuKα of 1.541 angstroms.
The Bragg angle (2θ ± 0.2 °) with respect to the line is 7.4
Chlorogallium phthalocyanine having an X-ray diffraction spectrum showing major peaks at °, 16.6 °, 25.5 ° and 28.3 °, major peaks at 11.0 °, 13.5 ° and 27.1 ° Chlorogallium phthalocyanine having an X-ray diffraction spectrum of 6.8 °, 17.3 °, 2
Chlorogallium phthalocyanine having an X-ray diffraction spectrum showing major peaks at 3.6 ° and 26.9 °, or 8.7 to 9.2 °, 17.6 °, 27.4 °, 28.
An electrophotographic photoreceptor comprising chlorogallium phthalocyanine having an X-ray diffraction spectrum showing a main peak at 8 °. 10. The phthalocyanine in claim 2 is hydroxygallium phthalocyanine, and the hydroxygallium phthalocyanine has a Bragg angle (2θ ± 0.2 °) with respect to X-rays of CuKα1.541 angstroms.
7.5 °, 9.9 °, 12.5 °, 16.3 °, 18.
X showing major peaks at 6 °, 25.1 °, 28.3 °
Hydroxygallium phthalocyanine with line diffraction spectrum, 7.7 °, 16.5 °, 25.1 °, 26.6
Hydroxygallium phthalocyanine having an X-ray diffraction spectrum showing a major peak at °, 7.9 °, 16.5
Hydroxygallium phthalocyanine having an X-ray diffraction spectrum showing major peaks at °, 24.4 °, 27.6 °, 7.0 °, 7.5 °, 10.5 °, 11.7 °,
12.7 °, 17.3 °, 18.1 °, 24.5 °, 2
Hydroxygallium phthalocyanine having an X-ray diffraction spectrum showing major peaks at 6.2 ° and 27.1 °,
Hydroxygallium phthalocyanine having an X-ray diffraction spectrum showing major peaks at 6.8 °, 12.8 °, 15.8 °, 26.0 °, or 7.4 °, 9.9 °,
An electrophotographic photosensitive member comprising hydroxygallium phthalocyanine having an X-ray diffraction spectrum showing main peaks at 25.0 °, 26.2 °, and 28.2 °. 11. The phthalocyanine according to claim 2, wherein the phthalocyanine is diphenoxygermanium phthalocyanine, and the diphenoxygermanium phthalocyanine CuKα1.
541 angstroms of X-ray Bragg angle (2θ ±
0.2 °), 9.0 °, 11.2 °, 17.1 °, 1
8.1 °, 20.9 °, 22.7 °, 25.8 °, 2
9. An electrophotographic photoreceptor comprising diphenoxygermanium phthalocyanine having an X-ray diffraction spectrum showing a main peak at 9.3 °.