JPH0973182A - Electrophotographic photoreceptor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel electrophotographic photoreceptor having improved sensitivity, electrical characteristics and stability. SOLUTION: This photoreceptor is a single layer type photoreceptor contg. an electric charge transferring agent and an electric charge generating agent, and a mixture of metal-free phthalocyanine having diffraction peaks of its X-ray diffraction spectrum with CuK-αas a ray source at 7.5 deg., 9.1 deg., 16.7 deg., 17.9 deg., 22.3 deg. and 28.6 deg. Bragg angles (2θ±0.2 deg.) with titanyl phthalocyanine having diffraction peaks at 9.5 deg., 14.2 deg., 24.0 deg. and 27.2 deg. is used as the electric charge generating agent. The titanyl phthalocyanine content of the electric charge generating agent is >50wt.%.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrophotographic photosensitive member used in an image forming apparatus such as an electrostatic copying machine, a laser printer, a plain paper facsimile machine.

[0002]

2. Description of the Related Art The photoconductor in the above image forming apparatus is
Organic photoconductors are widely used because they are easier to manufacture than photoconductors using inorganic semiconductor materials and have a large degree of freedom in functional design due to the variety of constituent materials of the photoconductors. For the organic photoreceptor, a charge generating agent that generates a charge by light irradiation and a charge transporting agent that transports a charge generated by the charge generating agent are used. Of these, various pigments are used as the charge generating agent depending on the sensitivity region of the photoreceptor. For example, phthalocyanine-based pigments such as metal-free phthalocyanine and titanyl phthalocyanine are widely used as charge generating agents in photoreceptors that are sensitive to light such as semiconductor laser light having a wavelength in the infrared or near-infrared region and infrared LED light. ing.

The phthalocyanine pigments have various crystal types, but the wavelength region of absorbed light and the quantum yield are different depending on the crystal forms, and an electrophotographic photosensitive member using such a pigment as a charge generating agent. It is known to affect the sensitivity, electrical characteristics, stability, etc. 2. Description of the Related Art In recent years, electrophotographic photoreceptors having further improved sensitivity, electric characteristics, stability and the like have been demanded due to higher speed and higher image quality of image forming apparatuses or maintenance-free for a long period of time. Therefore, it is required to improve the characteristics of the phthalocyanine-based pigment, which is a charge generating agent, and various studies have been made on its crystal form.

[0004] For example, Japanese Patent Application Laid-Open No. 1-2221461 contains α-type titanyl phthalocyanine and metal-free phthalocyanine, and

[0005]

[Outside 2]

In an X-ray diffraction spectrum with a radiation source of, the Bragg angle (2θ ± 0.2 degrees) is 6.9 degrees and 9.
6 degrees, 15.6 degrees, 17.6 degrees, 21.9 degrees, 23.6 degrees
There are disclosed α-type titanyl phthalocyanine compositions exhibiting strong diffraction peaks at deg, 24.7 and 28.0 degrees. Further, in JP-A-2-272067, a crystal transition is carried out by adding titanyl phthalocyanine to X-type metal-free phthalocyanine, and the Bragg angle (2θ ± 0.2 degrees) in the above X-ray diffraction spectrum. Is 7.5
Disclosed are X-type metal-free phthalocyanine compositions that exhibit strong diffraction peaks at 9.1 degrees, 9.1 degrees, 16.7 degrees, and 17.3 degrees.

Further, in Japanese Patent Laid-Open No. 3-200790, in the above X-ray diffraction spectrum, strong Bragg angles (2θ ± 0.2 degrees) show strong diffraction peaks at 9.6 degrees and 27.2 degrees, and Peak intensity at 9.6 degrees is 2
A crystalline titanyl phthalocyanine having a peak intensity of 60% or more at 7.2 degrees is disclosed.

[0008]

DISCLOSURE OF THE INVENTION However, as a result of the study by the present inventors,
Both have improved characteristics as a charge generating agent compared to conventionally used metal-free phthalocyanine and titanyl phthalocyanine, etc., but the sensitivity of the photoconductor, the chargeability, residual potential, electrical characteristics such as dark decay, Alternatively, it became clear that there is room for further improvement in terms of the stability of the photoconductor.

For example, the titanyl phthalocyanine disclosed in the above-mentioned Japanese Patent Laid-Open No. 3-200790 has a high quantum yield η indicating the charge generation efficiency, but it has a wavelength in the above infrared or near infrared region (for example, 780 nm). ) Has a small extinction coefficient for light. For this reason, a photoreceptor using such titanyl phthalocyanine alone as a charge generating agent tends not to obtain high sensitivity. Further, in order to increase the sensitivity of the photoconductor to an effective level, the amount of the above-mentioned titanyl phthalocyanine in the photoconductive layer must be set to a large amount, which results in the stability of the photoconductor when the image formation is repeated. May decrease. Such problems of lowering of sensitivity and lowering of stability are particularly remarkable in the single-layer type photoreceptor.

On the other hand, metal-free phthalocyanine has a large absorption coefficient in the above-mentioned wavelength region, but has a low quantum yield η. For this reason, a photoreceptor using metal-free phthalocyanine alone as a charge generating agent also tends not to obtain high sensitivity. An object of the present invention is to provide a novel electrophotographic photosensitive member having improved sensitivity, electrical characteristics and stability.

[0011]

The electrophotographic photoreceptor of the present invention is a single-layer type photoreceptor containing a charge transporting agent and a charge generating agent in a photosensitive layer, wherein the charge generating agent is

[0012]

[Outside 3]

In an X-ray diffraction spectrum having a radiation source of (wavelength 1.541Å), the Bragg angle (2θ ± 0.2
Degree) is 7.5 degrees, 9.1 degrees, 16.7 degrees, 17.4 degrees,
Metal-free phthalocyanine showing diffraction peaks at 22.3 degrees and 28.6 degrees, and Bragg angles (2θ ± 0.2 degrees) at 9.5 degrees, 14.2 degrees, 24.0 degrees and 27.2 degrees. It is composed of a mixture with titanyl phthalocyanine showing a diffraction peak, and the content of the titanyl phthalocyanine in the total amount of the charge generating agent is more than 50% by weight.

According to the above structure, it is possible to exhibit a high absorbance for light such as semiconductor laser light having a wavelength in the infrared or near-infrared region and infrared LED light, and a high quantum yield. Therefore, it is possible to solve the above-mentioned problems and obtain an electrophotographic photoreceptor having high sensitivity and excellent electric characteristics and stability. In the electrophotographic photosensitive member of the present invention, either a hole transfer material or an electron transfer material is used as the charge transfer material. Further, the hole transport material and the electron transport material may be used in combination.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The metal-free phthalocyanine used in the present invention is a characteristic X-ray of copper.

[0016]

[Outside 4]

In the X-ray diffraction spectrum having a radiation source of (wavelength 1.541Å), as shown in FIG. 1, the Bragg angles (2θ ± 0.2 degrees) are 7.5 degrees, 9.1 degrees, 16. 7
It has a crystal structure showing strong diffraction peaks at degrees, 17.4 degrees, 22.3 degrees and 28.6 degrees. More specifically, the Bragg angle (2θ ± 0.2 degrees) is 7.5 degrees, 9.
1 degree, 16.7 degrees, 17.4 degrees, 22.3 degrees, 23.9 degrees
It has a crystal structure showing diffraction peaks at 27.2 and 28.6 degrees.

The metal-free phthalocyanine in the present invention can be obtained by a conventionally known method. For example, o-phthalodinitrile and piperidine are usually added in the presence of a strong base catalyst in an alcohol solvent at 160 to 230 ° C. for 8 to 13 ° C.
Stir for about an hour to react. Next, the obtained reddish purple reaction product is treated with alcohols such as methanol, ethanol and isopropyl alcohol, ketones such as acetone and methyl ethyl ketone, tetrahydrofuran, 1,4-
It is obtained by washing with an electron-donating solvent such as ethers such as dioxane, N, N-dimethylformamide, N-methylpyrrolidone, pyridine and the like, and drying.

The titanyl phthalocyanine used in the present invention is a characteristic X-ray of copper.

[0020]

[Outside 5]

In an X-ray diffraction spectrum having a radiation source of (wavelength 1.541Å), as shown in FIG. 2, the Bragg angle (2θ ± 0.2 degrees) is 9.5 degrees, 14.2 degrees, 24.
It has a crystal structure showing strong diffraction peaks at 0 degree and 27.2 degrees. More specifically, the Bragg angle (2θ ± 2θ ±
0.2 degree) is 7.3 degrees, 9.5 degrees, 11.5 degrees, 14.
It has a crystal structure showing diffraction peaks at 2 degrees, 17.9 degrees, 24.0 degrees and 27.2 degrees.

The above-mentioned titanyl phthalocyanine of the present invention can also be obtained by a conventionally known method. For example, Japanese Unexamined Patent Application Publication No.
As described in Japanese Patent No. 00790, titanium tetrachloride and o-
The phthalodinitrile is usually reacted in a solvent such as α-chloronaphthalene or quinoline at 160 to 260 ° C. for about 2 to 7 hours. The reaction product is then hydrolyzed,
After being dissolved in sulfuric acid, it is precipitated in water to obtain amorphous titanyl phthalocyanine. Further, it can be obtained by treating with an organic solvent such as tetrahydrofuran or dichloroethane.

As described above, the charge generating agent in the electrophotographic photosensitive member of the present invention is a mixture of the metal-free phthalocyanine and titanyl phthalocyanine, and the content ratio of the titanyl phthalocyanine in the total amount of the charge generating agent is 50. Suitably it is greater than 50% by weight, preferably 50 to 99.5% by weight, more preferably 70 to 99% by weight. In the present invention, the mixture of metal-free phthalocyanine and titanyl phthalocyanine means a simple mixture of both phthalocyanines.

When the content ratio of titanyl phthalocyanine is less than the above range, the effect of increasing the quantum yield becomes insufficient, and the sensitivity, electric characteristics, stability and the like of the electrophotographic photoreceptor cannot be improved. On the other hand, when the content ratio of titanyl phthalocyanine exceeds the above range, the effect of increasing the absorption coefficient for light having a wavelength in the infrared or near-infrared region becomes insufficient, and as described above, the sensitivity of the photoreceptor,
It is not possible to improve electric characteristics and stability.

The above-mentioned mixture of metal-free phthalocyanine and titanyl phthalocyanine is obtained by mixing and stirring the above-mentioned both phthalocyanines by various conventionally known means such as a ball mill, a paint shaker, a sand mill, ultrasonic dispersion, a mixer and an attritor. Further, both phthalocyanines may be mixed and stirred together with components such as a binder resin constituting the electrophotographic photosensitive member.

In order to uniformly mix and stir the both phthalocyanines, it is preferable that the phthalocyanine has a small particle size. Usually, the average particle size of both phthalocyanines is 10 to 10.
The thickness is 1000 nm, preferably 20 to 300 nm. By mixing the phthalocyanine having an average particle diameter within the above range with stirring by the above-mentioned means, usually for about 1 minute to 72 hours, a uniformly mixed mixture of the metal-free phthalocyanine and titanyl phthalocyanine of the present invention can be obtained. .

Since the electrophotographic photoreceptor of the present invention contains a mixture of the metal-free phthalocyanine and the titanyl phthalocyanine in the photosensitive layer as a charge generating agent, as described above, it has a high quantum yield and a large absorption coefficient. It is possible to obtain a photoreceptor having both The reason for this is presumed as follows. In a mixed system of metal-free phthalocyanine and titanyl phthalocyanine, the metal-free phthalocyanine having a large absorption coefficient mainly absorbs light to be in an excited state. The metal-free phthalocyanine thus excited transfers energy to titanyl phthalocyanine, but since the quantum yield of this titanyl phthalocyanine is high, the energy obtained from the metal-free phthalocyanine can be efficiently converted to the generation of electric charges. It is considered possible.

The electrophotographic photoreceptor of the present invention comprises a conductive substrate and a single-layer type photosensitive layer containing a charge generating agent comprising the mixture of the metal-free phthalocyanine and titanyl phthalocyanine of the present invention. This photoreceptor can be applied to a laminated type, but the effect of using the charge generating agent is remarkably exhibited in a single-layer type photosensitive layer. As the charge transfer agent used in the electrophotographic photoreceptor of the present invention, as described above, either one of the hole transfer agent and the electron transfer agent is used, or the hole transfer agent and the electron transfer agent are combined. Used in combination. In particular, it is preferable to use a hole transporting agent and an electron transporting agent together, because the sensitivity, electrical characteristics, stability of the photoreceptor are more excellent.

It is desirable that the charge-transporting agent has good matching with the charge-generating agent and can efficiently transport the electrons or holes generated in the charge-generating agent. Although the photoconductor using both of the above-mentioned transfer agents can be applied to both the positive charging type and the negative charging type, both the transfer agents form a charge transfer complex to inhibit the charge transfer and reduce the sensitivity of the photoconductor. May cause In such a case, it is necessary to consider formation of a charge transfer complex by introducing a bulky substituent into the charge transfer agent.

Specific examples of the hole transfer material and the electron transfer material are shown below. <Hole Transfer Agent> Examples of the hole transfer agent usable in the present invention include compounds represented by the following general formulas (HT1) to (HT13).

[0031]

Embedded image

(In the formula, R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² and R ¹³ are the same or different and each represents a hydrogen atom, a halogen atom, an optionally substituted alkyl group or a substituent. 1 represents an alkoxy group which may have or an aryl group which may have a substituent, wherein a and b are the same or different and are 1 to 4
, And c, d, e and f are the same or different and each represents an integer of 1 to 5. When a, b, c, d, e or f is 2 or more, each of R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R
¹² and R ¹³ may be different. )

[0033]

Embedded image

(Wherein R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R
¹⁸ is the same or different and represents a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or an aryl group which may have a substituent. g, h, i and j are the same or different and are 1 to 5
Is shown, k shows the integer of 1-4. Note that g,
When h, i, j or k is 2 or more, each R ¹⁴ , R ¹⁵ , R
¹⁶ , R ¹⁷ and R ¹⁸ may be different. )

[0035]

Embedded image

(In the formula, R ¹⁹ , R ²⁰ , R ²¹ and R ²² are the same or different and each is a hydrogen atom, a halogen atom, an alkyl group which may have a substituent or an alkoxy which may have a substituent. A group or an aryl group which may have a substituent is shown.
R ²³ is a hydrogen atom, a halogen atom, a cyano group, a nitro group,
It represents an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or an aryl group which may have a substituent. m, n, o and p are the same or different and are 1
Represents an integer of from 5 to 5. q shows the integer of 1-6. In addition,
When m, n, o, p or q is 2 or more, each R ¹⁹ ,
R ²⁰ , R ²¹ , R ²² and R ²³ may be different. )

[0037]

Embedded image

(In the formula, R ²⁴ , R ²⁵ , R ²⁶ and R ²⁷ are the same or different and each is a hydrogen atom, a halogen atom, an alkyl group which may have a substituent or an alkoxy which may have a substituent. A group or an aryl group which may have a substituent is shown.
r, s, t and u are the same or different and each represents an integer of 1 to 5. When r, s, t or u is 2 or more,
Each R ²⁴ , R ²⁵ , R ²⁶ and R ²⁷ may be different. )

[0039]

Embedded image

(In the formula, R ²⁸ and R ²⁹ are the same or different and represent a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group. R ³⁰ , R ³¹ , R ³² and R ³³ are the same or different and are hydrogen. Indicates an atom, an alkyl group or an aryl group.)

[0041]

[Chemical 6]

(In the formula, R ³⁴ , R ³⁵ and R ³⁶ are the same or different and each represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group.)

[0043]

[Chemical 7]

(In the formula, R ³⁷ , R ³⁸ , R ³⁹ and R ⁴⁰ are the same or different and each represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group.)

[0045]

Embedded image

(Wherein R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ and R
⁴⁵ is the same or different and represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group. )

[0047]

Embedded image

(In the formula, R ⁴⁶ represents a hydrogen atom or an alkyl group, R ⁴⁷ , R ⁴⁸ and R ⁴⁹ are the same or different,
A hydrogen atom, a halogen atom, an alkyl group or an alkoxy group is shown. )

[0049]

Embedded image

(In the formula, R ⁵⁰ , R ⁵¹ and R ⁵² are the same or different and each represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group.)

[0051]

Embedded image

(In the formula, R ⁵³ and R ⁵⁴ are the same or different and each represents a hydrogen atom, a halogen atom, an alkyl group which may have a substituent or an alkoxy group which may have a substituent ^. And R ⁵⁶ is the same or different and represents a hydrogen atom, an alkyl group which may have a substituent or an aryl group which may have a substituent.)

[0053]

[Chemical 12]

(In the formula, R ⁵⁷ , R ⁵⁸ , R ⁵⁹ , R ⁶⁰ , R ⁶¹ and R ⁶² are the same or different and each has a hydrogen atom, an alkyl group which may have a substituent or a substituent. Is an alkoxy group or an aryl group which may have a substituent.
Represents an integer of 1 to 10, and v, w, x, y, z and β
Are the same or different and are 1 or 2. Note that v,
When w, x, y, z or β is 2, each R ⁵⁷ , R ⁵⁸ , R
⁵⁹ , R ⁶⁰ , R ⁶¹ and R ⁶² may be different. )

[0055]

Embedded image

(In the formula, R ⁶³ , R ⁶⁴ , R ⁶⁵ and R ⁶⁶ are the same or different and each represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group, and Ar is

[0057]

Embedded image

The groups (Ar1), (Ar2) or (Ar3) represented by are shown below. ) In the above-described hole transporting agent, the alkyl group is
For example, methyl, ethyl, n-propyl, isopropyl,
Examples thereof include groups having 1 to 6 carbon atoms such as n-butyl, isobutyl, s-butyl, t-butyl, pentyl and hexyl. Examples of the alkoxy group include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy,
Examples thereof include groups having 1 to 6 carbon atoms such as isobutoxy, s-butoxy, t-butoxy, pentyloxy and hexyloxy. Examples of the aryl group include groups such as phenyl, tolyl, xylyl, biphenylyl, o-terphenyl, naphthyl, anthryl, phenanthryl and the like. Examples of the halogen atom include fluorine, chlorine, bromine and iodine. Examples of the substituent that may be substituted on the above group include a halogen atom, an amino group, a hydroxyl group, an optionally esterified carboxyl group, a cyano group, an alkyl group having 1 to 6 carbon atoms, and a carbon atom having 1 to 6 carbon atoms. Examples thereof include an alkenyl group having 2 to 6 carbon atoms which may have an alkoxy group or an aryl group. Further, the substitution position of the substituent is not particularly limited.

In the present invention, in addition to the above examples, conventionally known hole transporting substances, that is, for example, 2,5-
Oxadiazole compounds such as di (4-methylaminophenyl) -1,3,4-oxadiazole, 9- (4-
Styryl compounds such as diethylaminostyryl) anthracene, carbazole compounds such as polyvinylcarbazole, organic polysilane compounds, 1-phenyl-3- (p
-Pyrazoline compounds such as dimethylaminophenyl) pyrazolin, hydrazone compounds, triphenylamine compounds, indole compounds, oxazole compounds,
Nitrogen-containing cyclic compounds such as isoxazole-based compounds, thiazole-based compounds, thiadiazole-based compounds, imidazole-based compounds, pyrazole-based compounds and triazole-based compounds, condensed polycyclic compounds and the like can be used.

Among the hole transfer agents exemplified above, among others, a benzidine derivative represented by the general formula (HT1), a general formula
A phenylenediamine derivative represented by (HT2), a general formula (H
T11) diphenylenediamine derivative and the stilbene derivative represented by the general formula (HT12) have good matching with metal-free phthalocyanine and titanyl phthalocyanine, and have an excellent hole-transporting ability, so that the hole-transporting agent in the present invention It is preferably used as an agent. <Electron Transfer Agent> Examples of the electron transfer agent usable in the present invention include compounds represented by the following general formulas (ET1) to (ET14).

[0061]

[Chemical 15]

(Wherein R^Three, R^Four, R^FiveAnd R⁶Is the same
One or differently, may have a hydrogen atom or a substituent
Alkyl group, optionally substituted alkoxy group, substituent
An aryl group which may have a substituent or an aryl group which may have a substituent
Alkyl group, optionally substituted cycloalkyl group, or
Represents an amino group which may have a substituent. Where R
^Three, R^Four, R^FiveAnd R⁶Two of them are the same group
You. )

[0063]

Embedded image

(In the formula, R ¹⁴² , R ¹⁴³ , R ¹⁴⁴ , R ¹⁴⁵
And R ¹⁴⁶ are the same or different and each have a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an aryl group which may have a substituent, and a substituent. Represents an optionally substituted aralkyl group, an optionally substituted phenoxy group or a halogen atom. )

[0065]

Embedded image

(Wherein R ¹⁴⁷ is an alkyl group, R ¹⁴⁸ is an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an aryl group which may have a substituent, a substituent Represents an aralkyl group which may have a group or a halogen atom, ω represents an integer of 0 to 4, and γ represents an integer of 0 to 5. When γ is 2 or more, each R ¹⁴⁸ is different from each other. It may be.)

[0067]

Embedded image

(In the formula, R ¹⁴⁹ and R ¹⁵⁰ are the same or different and each represents an alkyl group. Δ represents an integer of 1 to 4 and ε represents an integer of 0 to 4. δ and ε are 2 In the above case, each R ¹⁴⁹ and R ¹⁵⁰ may be different.)

[0069]

Embedded image

(In the formula, R ¹⁵¹ represents an alkyl group, an aryl group, an aralkyl group, an alkoxy group, a halogenated alkyl group or a halogen atom. Ζ is 0 to 4 and η is 0 to 5
Is an integer. When η is 2 or more, each R ¹⁵¹ may be different. )

[0071]

Embedded image

(In the formula, θ is an integer of 1 to 2.)

[0073]

[Chemical 21]

(In the formula, R ¹⁵² represents an alkyl group, and σ is an integer of 1 to 4. When σ is 2 or more, each R is R 2.
¹⁵² may be different. )

[0075]

Embedded image

(In the formula, R ¹⁵³ and R ¹⁵⁴ are the same or different and each represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an aralkyloxycarbonyl group, an alkoxy group, a hydroxyl group, a nitro group or a cyano group. Basis:
Indicates O, N-CN or C (CN) ₂ . )

[0077]

Embedded image

(In the formula, R ¹⁵⁵ represents a hydrogen atom, a halogen atom, an alkyl group or a phenyl group which may have a substituent, and R ¹⁵⁶ represents a hydrogen atom, a halogen atom or an alkyl group which may have a substituent, A phenyl group, an alkoxycarbonyl group, an N-alkylcarbamoyl group, a cyano group or a nitro group which may have a substituent is shown.
Is an integer of 1 to 3. When λ is 2 or more, each R
¹⁵⁶ may be different from each other. )

[0079]

Embedded image

(In the formula, R ¹⁵⁷ is a hydrogen atom, an alkyl group which may have a substituent, a phenyl group which may have a substituent, a halogen atom, an alkoxycarbonyl group, N
-Indicates an alkylcarbamoyl group, a cyano group or a nitro group. μ is an integer of 1 to 3. When μ is 2 or more, each R ¹⁵⁷ may be different from each other. )

[0081]

Embedded image

(In the formula, R ¹⁵⁸ and R ¹⁵⁹ are the same or different and each represents a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, a cyano group, a nitro group or an alkoxycarbonyl group. Ν and ξ are It is an integer of 1 to 3. When ν or ξ is 2 or more, each R ¹⁵⁸ and R ¹⁵⁹ may be different from each other.)

[0083]

[Chemical formula 26]

(In the formula, R ¹⁶⁰ and R ¹⁶¹ are the same or different and each represents a phenyl group, a polycyclic aromatic group or a heterocyclic group, and these groups may have a substituent.)

[0085]

Embedded image

(In the formula, R ¹⁶² represents an amino group, a dialkylamino group, an alkoxy group, an alkyl group or a phenyl group, and π is an integer of 1 to 2. When π is 2,
Each R ^{16 2} may be different from each other. )

[0087]

Embedded image

(In the formula, R ¹⁶³ represents a hydrogen atom, an alkyl group,
It represents an aryl group, an alkoxy group or an aralkyl group. ) And the like, and further malononitrile, thiopyran-based compound, tetracyanoethylene, 2,4,8-trinitrothioxanthone, dinitrobenzene, dinitroanthracene, dinitroacridine, nitroanthraquinone, dinitroanthraquinone, succinic anhydride, maleic anhydride, Examples include dibromomaleic anhydride.

In the electron transfer agent exemplified above, examples of the alkyl group, alkoxy group, aryl group and halogen atom include the same groups as described above. Examples of the aralkyl group include groups having 1 to 6 carbon atoms in the alkyl moiety such as benzyl, α-phenethyl, β-phenethyl, benzhydryl, styryl, cinnamyl and trityl.
Examples of the halogenated alkyl group include a chloromethyl group, a bromomethyl group, a fluoromethyl group, an iodomethyl group, a 2-chloroethyl group, a 1-fluoroethyl group, and a 3-
Chloropropyl group, 2-bromopropyl group, 1-chloropropyl group, 2-chloro-1-methylethyl group, 1-bromo-1-methylethyl group, 4-iodobutyl group, 3-
Fluorobutyl group, 3-chloro-2-methylpropyl group, 2-iodo-2-methylpropyl group, 1-fluoro-2-methylpropyl group, 2-chloro-1,1-dimethylethyl group, 2-bromo- 1,1-dimethylethyl group,
Examples thereof include halogenated alkyl groups in which the alkyl group portion such as 5-bromopentyl group and 4-chlorohexyl group has 1 to 6 carbon atoms. Examples of the cycloalkyl group include those having 3 to 3 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl.
And 8 groups.

Examples of the polycyclic aromatic group include naphthyl group, phenanthryl group and anthryl group. Examples of the heterocyclic group include thienyl group, pyrrolyl group, pyrrolidinyl group, oxazolyl group, isoxazolyl group, thiazolyl group, isothiazolyl group, imidazolyl group, 2H-imidazolyl group, pyrazolyl group, triazolyl group, tetrazolyl group, pyranyl group, pyridyl group. Group, piperidyl group, piperidino group, 3-morpholinyl group, morpholino group, thiazolyl group and the like. It may also be a heterocyclic group condensed with an aromatic ring.

Substituents that may be substituted on the above groups include
For example, a halogen atom, an amino group, a hydroxyl group, a carboxyl group which may be esterified, a cyano group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 2 to 2 carbon atoms. And the alkenyl group of 6 and the like. Among the electron transfer agents exemplified above, among others,
Diphenoquinone derivative represented by general formula (ET1), general formula
The 2,4,7-trinitrofluorenone imine derivative represented by (ET2) or the 2-alkylated nitrofluorenone imine derivative represented by the general formula (ET3) has good matching with metal-free phthalocyanine and titanyl phthalocyanine, Moreover, since it has an excellent electron transporting ability, it is suitably used as the electron transporting agent in the present invention.

Next, a method for manufacturing the electrophotographic photosensitive member of the present invention will be described. As described above, the electrophotographic photosensitive member of the present invention is one in which a single-layer type photosensitive layer containing a charge generating agent comprising a mixture of the metal-free phthalocyanine and titanyl phthalocyanine of the present invention is provided on a conductive substrate. is there. In this photosensitive layer, in addition to the charge generating agent, a charge transport agent and a binder resin are dissolved or dispersed in an appropriate solvent,
The obtained coating liquid may be applied onto the conductive substrate by a means such as coating and dried. Such a single-layer type photosensitive layer,
The layer structure is simple and excellent in productivity.

In the above-mentioned photoreceptor of the present invention, the charge generating agent is added in a proportion of 0.1 to 50 parts by weight, preferably 0.5 to 30 parts by weight, based on 100 parts by weight of the binder resin. When an electron transfer agent is used as the charge transfer agent, the compounding amount of the electron transfer agent is 5 to 1 with respect to 100 parts by weight of the binder resin.
The amount is 00 parts by weight, preferably 10 to 80 parts by weight. On the other hand, when a hole transport material is used as the charge transport material,
The compounding amount of the hole transport material is 5 to 500 parts by weight, preferably 25 to 200 parts by weight, based on 100 parts by weight of the binder resin. Further, when the hole transfer agent and the electron transfer agent are used in combination, the total amount of both transfer agents is 20 to 500 parts by weight, preferably 30 to 200 parts by weight, based on 100 parts by weight of the binder resin. Is. The thickness of the photosensitive layer is 5 to 1
The thickness is 00 μm, preferably 10 to 50 μm.

In the above-mentioned photoconductor, a barrier layer may be formed between the conductive substrate and the photoconductor layer within a range not impairing the characteristics of the photoconductor. Further, a protective layer may be formed on the surface of the photoconductor. Further, in the photosensitive layer, various additives known per se, for example, antioxidants, radical scavengers, singlet quenchers, deterioration inhibitors such as ultraviolet absorbers, etc., are used within a range that does not adversely affect electrophotographic properties. , A softener, a plasticizer, a surface modifier, a bulking agent, a thickener, a dispersion stabilizer, a wax, an acceptor, a donor and the like can be added. Further, in order to improve the sensitivity of the photosensitive layer, known sensitizers such as terphenyl, halonaphthoquinones and acenaphthylene may be used in combination with the charge generating agent.

Examples of the binder resin include styrene polymers, styrene-butadiene copolymers, styrene-acrylonitrile copolymers, styrene-maleic acid copolymers,
Acrylic polymer, styrene-acrylic copolymer, polyethylene, ethylene-vinyl acetate copolymer, chlorinated polyethylene, polyvinyl chloride, polypropylene, vinyl chloride-vinyl acetate copolymer, polyester, alkyd resin, polyamide, polyurethane , Polycarbonate,
Thermoplastic resin such as polyarylate, polysulfone, diallyl phthalate resin, ketone resin, polyvinyl butyral resin, polyether resin, silicone resin, epoxy resin, phenol resin, urea resin, melamine resin and other crosslinkable thermosetting resin, epoxy Examples thereof include photo-curable resins such as acrylate and urethane-acrylate. These binder resins can be used alone or in combination of two or more.

In addition to the above components, various additives such as a sensitizer, a fluorene compound, an ultraviolet absorber, a plasticizer, an interfacial slip agent, and a leveling agent may be added to the photosensitive layer. . Further, in order to improve the sensitivity of the photoreceptor, a sensitizer such as terphenyl, halonaphthoquinones, and acenaphthylene may be used in combination with the charge generating agent. Further, in order to adjust the sensitivity region of the photoconductor, the effect of the present invention by using the mixture of the metal-free phthalocyanine and titanyl phthalocyanine in the present invention described above is not impaired, and does not adversely affect the electrophotographic characteristics. Other charge generating agents may be used in combination within the range. Other charge generating agents are not particularly limited, for example, selenium, selenium-tellurium, selenium-arsenic, cadmium sulfide, powder of an inorganic photoconductive material such as α-silicon, or the following general formula (CG1) ~ (C
G10) compound, further ansanthuron-based pigment,
Examples thereof include triphenylmethane pigments, threnic pigments, toluidine pigments, pyrazoline pigments, quinacridone pigments and the like. (CG1) Perylene pigment

[0097]

[Chemical 29]

(In the formula, R ⁷⁰ and R ⁷¹ are the same or different and each represents a substituted or unsubstituted alkyl group, cycloalkyl group, aryl group, alkanoyl group or aralkyl group having 18 or less carbon atoms.) (CG2 ) Bisazo pigment

[0099]

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[Wherein, A ¹ and A ² are the same or different and each represents a coupler residue, and X is

[0101]

[Chemical 31]

(In the formula, R ⁷² represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and the alkyl group, the aryl group or the heterocyclic group may have a substituent n.
Represents 0 or 1. )

[0103]

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[0104]

[Chemical 33]

(In the formula, R ⁷³ and R ⁷⁴ are the same or different and each represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom, an alkoxy group, an aryl group or an aralkyl group.)

[0106]

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[0107]

Embedded image

[0108]

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(In the formula, R ⁷⁵ represents a hydrogen atom, an ethyl group, a chloroethyl group or a hydroxyethyl group.)

[0110]

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Or

[0112]

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(Wherein R ⁷⁶ , R ⁷⁷ and R ⁷⁸ are the same or different and each represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom, an alkoxy group, an aryl group or an aralkyl group). . ] (CG3) Dithioketopyrrolopyrrole pigment

[0114]

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(In the formula, R ⁷⁹ and R ⁸⁰ are the same or different and represent a hydrogen atom, an alkyl group, an alkoxy group or a halogen atom, and R ⁸¹ and R ⁸² are the same or different and are a hydrogen atom, an alkyl group or an aryl group. (CG4) Metal-free naphthalocyanine pigment

[0116]

[Chemical 40]

(In the formula, R ⁸³ , R ⁸⁴ , R ⁸⁵ and R ⁸⁶ are the same or different and each represents a hydrogen atom, an alkyl group, an alkoxy group or a halogen atom.) (CG5) Metal naphthalocyanine pigment

[0118]

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(In the formula, R ⁸⁷ , R ⁸⁸ , R ⁸⁹ and R ⁹⁰ are the same or different and each represents a hydrogen atom, an alkyl group, an alkoxy group or a halogen atom, and M represents Ti or V.) (CG6) Squaraine pigment

[0120]

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(In the formula, R ⁹¹ and R ⁹² are the same or different and each represents a hydrogen atom, an alkyl group, an alkoxy group or a halogen atom.) (CG7) Trisazo pigment

[0122]

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(In the formula, Cp ₁ , Cp ₂ and Cp ₃ are the same or different and represent a coupler residue.) (CG8) Indigo pigment

[0124]

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(In the formula, R ⁹³ and R ⁹⁴ are the same or different and each represents a hydrogen atom, an alkyl group or an aryl group,
Z represents an oxygen atom or a sulfur atom. ) (CG9) Azurenium pigment

[0126]

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(In the formula, R ⁹⁵ and R ⁹⁶ are the same or different and each represents a hydrogen atom, an alkyl group or an aryl group.) (CG10) Cyanine pigment

[0128]

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(Wherein R ⁹⁷ and R ⁹⁸ are the same or different and represent a hydrogen atom, an alkyl group, an alkoxy group or a halogen atom, and R ⁹⁹ and R ¹⁰⁰ are the same or different and are a hydrogen atom, an alkyl group or an aryl group. In the above-mentioned charge generating agent, the alkyl group is
The same groups as described above can be mentioned. The alkyl group having 1 to 5 carbon atoms is the above-mentioned alkyl group having 1 to 6 carbon atoms with hexyl removed. The substituted or unsubstituted alkyl group having 18 or less carbon atoms is a group containing octyl, nonyl, decyl, dodecyl, tridecyl, pentadecyl, octadecyl and the like in addition to the above-mentioned alkyl group having 1 to 6 carbon atoms. Examples of the alkanoyl group include a formyl group, an acetyl group, a propionyl group, a butyryl group, a pentanoyl group and a hexanoyl group. Examples of the alkoxy group, aryl group, aralkyl group, cycloalkyl group and heterocyclic group include the same groups as described above. As the substituent which may be substituted on the above group, for example, a halogen atom,
Amino group, hydroxyl group, carboxyl group which may be esterified, cyano group, alkyl group having 1 to 6 carbon atoms, 1 carbon atom
Examples include an alkoxy group having 6 to 6 and an alkenyl group having 2 to 6 carbon atoms, which may have an aryl group.

A ¹ , A ² and Cp ₁ , Cp ₂ , Cp ₃
The coupler residue represented by, for example, the following general formula
Examples thereof include groups shown in (21) to (29).

[0131]

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[0132]

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In each formula, R ¹²⁰ represents a carbamoyl group, a sulfamoyl group, an allofanoyl group, an oxamoyl group, an anthraniloyl group, a carbazoyl group, a glycyl group, a hydantoyl group, a phthalamoyl group or a succinamoyl group. These groups, a halogen atom, a phenyl group which may have a substituent, a naphthyl group which may have a substituent, a nitro group, a cyano group, an alkyl group, an alkenyl group,
It may have a substituent such as a carbonyl group or a carboxyl group.

R ¹²¹ represents an atomic group necessary for being condensed with a benzene ring to form an aromatic ring, a polycyclic hydrocarbon or a heterocycle, and these rings have a substituent similar to the above. May be. R ¹²² represents an oxygen atom, a sulfur atom or an imino group. R ¹²³ represents a divalent chain hydrocarbon group or an aromatic hydrocarbon group, and these groups may have the same substituents as described above.

R ¹²⁴ represents an alkyl group, an aralkyl group, an aryl group or a heterocyclic group, and these groups may have the same substituents as described above. R ¹²⁵ is a divalent chain hydrocarbon group, an aromatic hydrocarbon group or the above general formulas (25) to (28)
In the following formula:

[0136]

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It represents an atomic group necessary for forming a heterocycle together with the moiety represented by, and these rings may have the same substituents as described above. R ¹²⁶ represents a hydrogen atom, an alkyl group, an amino group, a carbamoyl group, a sulfamoyl group, an allofanoyl group, a carboxyl group, an alkoxycarbonyl group, an aryl group or a cyano group, and groups other than the hydrogen atom have the same substituents as described above. You may have.

R ¹²⁷ represents an alkyl group or an aryl group, and these groups may have the same substituents as described above. Examples of the alkenyl group include vinyl, allyl, 2-butenyl, 3-butenyl, 1-methylallyl, 2-pentenyl and 2-hexenyl alkenyl groups having 2 to 6 carbon atoms. .

Examples of the atomic group necessary for forming an aromatic ring by condensing with the benzene ring in the above R ¹²¹ include alkylene groups such as methylene group, ethylene group, propylene group and butylene group. Examples of the aromatic ring formed by the condensation of R ¹²¹ and the benzene ring include naphthalene ring, anthracene ring, phenanthrene ring, pyrene ring, chrysene ring, and naphthacene ring.

In R ¹²¹ , the atomic group necessary for condensation with the benzene ring to form a polycyclic hydrocarbon is, for example, a methylene group, an ethylene group, a propylene group or a butylene group having 1 to 4 carbon atoms. The alkylene group of Examples of the atomic group necessary for forming a polycyclic hydrocarbon by condensing with the benzene ring in R ¹²¹ include a carbazole ring, a benzocarbazole ring, a dibenzofuran ring, and the like.

Further, in R ¹²¹ , the atomic group necessary for condensing with the benzene ring to form a heterocycle is, for example, a benzofuranyl group, a benzothiophenyl group, an indolyl group, a 1H-indolyl group, a benzoxazolyl group. Group, benzothiazolyl group, 1H-indaryl group, benzimidazolyl group, chromenyl group, chromanyl group, isochromanyl group, quinolinyl group, isoquinolinyl group, cinnolinyl group, phthalazinyl group, quinazonilyl group, quinoxalinyl group, dibenzofuranyl group, carbazolyl group, xanthenyl group , An acridinyl group, a phenanthridinyl group, a phenazinyl group, a phenoxazinyl group and a thianthrenyl group.

Examples of the aromatic heterocyclic group formed by condensation of the above R ¹²¹ and a benzene ring include, for example, thienyl group, furyl group, pyrrolyl group, oxazolyl group, isoxazolyl group, thiazolyl group, isothiazolyl group, imidazolyl group, Examples thereof include a pyrazolyl group, a triazolyl group, a tetrazolyl group, a pyridyl group and a thiazolyl group. Also,
Further, it may be a heterocyclic group condensed with another aromatic ring (for example, a benzofuranyl group, a benzimidazolyl group, a benzoxazolyl group, a benzothiazolyl group, a quinolyl group, etc.).

In the above R ¹²³ and R ¹²⁵ , examples of the divalent chain hydrocarbon include ethylene group, propylene group and butylene group, and examples of the divalent aromatic hydrocarbon include phenylene group, naphthylene group, Examples thereof include a phenanthrylene group. ^Examples of the heterocyclic group for R ¹²⁴ include a pyridyl group, a pyrazyl group, a thienyl group, a pyranyl group and an indolyl group.

In R ¹²⁵ , the atomic group necessary to form a heterocycle with the moieties represented by the formulas (30) and (31) is, for example, a phenylene group, a naphthylene group, a phenanthrylene group, an ethylene group, Examples thereof include a propylene group and a butylene group. Examples of the aromatic heterocyclic group formed by R ¹²⁵ and the moieties represented by the formulas (30) and (31) include a benzimidazole group, a benzo [f] benzimidazole group, a dibenzo [e, g] Benzimidazole group, benzopyrimidine group and the like. These groups may have the same substituents as described above.

Examples of the alkoxycarbonyl group for R ¹²⁶ include methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, butoxycarbonyl group and the like. The content of the other charge generating agent is 30 with respect to 100 parts by weight of the mixture of the metal-free phthalocyanine and titanyl phthalocyanine in the present invention.
It is preferably not more than 10 parts by weight, especially not more than 10 parts by weight.

As the conductive substrate forming each of the above layers,
Various conductive materials can be used, for example, metals such as iron, aluminum, copper, tin, platinum, silver, vanadium, molybdenum, chromium, cadmium, titanium, nickel, palladium, indium, stainless steel, brass, etc. Alternatively, a plastic material obtained by vapor deposition or lamination of the above metal, glass coated with aluminum iodide, tin oxide, indium oxide, or the like can be given.

The conductive substrate may be in the form of a sheet, a drum or the like, depending on the structure of the image forming apparatus used. The substrate itself may be conductive, or the surface of the substrate may be conductive. In addition, the conductive substrate preferably has sufficient mechanical strength when used. When each layer constituting the photoreceptor is formed by a coating method, the charge generating agent, charge transporting agent,
The binder resin and the like are mixed with a suitable solvent by a known method, for example, using a roll mill, a ball mill, an attritor, a paint shaker or an ultrasonic disperser to prepare a coating solution, which is prepared by a known means. It may be applied and dried.

As the solvent for preparing the coating solution, various organic solvents can be used, for example, alcohols such as methanol, ethanol, isopropanol, butanol, etc.
Aliphatic hydrocarbons such as n-hexane, octane and cyclohexane, aromatic hydrocarbons such as benzene, toluene and xylene, halogenated hydrocarbons such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride and chlorobenzene, dimethyl ether, diethyl ether, Examples thereof include ethers such as tetrahydrofuran, ethylene glycol dimethyl ether and diethylene glycol dimethyl ether, ketones such as acetone, methyl ethyl ketone and cyclohexanone, esters such as ethyl acetate and methyl acetate, dimethylformaldehyde, dimethylformamide and dimethyl sulfoxide. These solvents can be used alone or in combination of two or more.

Further, in order to improve the dispersibility of the charge transporting agent or the charge generating agent and the smoothness of the surface of the photosensitive layer, a surfactant, a leveling agent or the like may be added to the coating liquid.

[0150]

The present invention will be described below with reference to examples and comparative examples. Preparation of Charge Generating Reference Example 1 (Preparation of Metal-Free Phthalocyanine) Metal-free phthalocyanine was prepared according to a known method using o-phthalodinitrile and piperidine as starting materials.

The X-ray diffraction spectrum and infrared absorption spectrum of the obtained metal-free phthalocyanine are shown in FIG. 1 and FIG. 2, respectively. Reference Example 2 (Preparation of titanyl phthalocyanine) Using titanium tetrachloride and phthalodinitrile as starting materials, a titanyl phthalocyanine was prepared according to Synthesis Example 4 described in JP-A-3-200790.

The X-ray diffraction spectrum and infrared absorption spectrum of the obtained titanyl phthalocyanine are shown in FIG. 3 and FIG. 4, respectively. Preparation of Single-Layer Photosensitive Member I Examples 1 and 2 and Comparative Example 1 2 parts by weight of charge generating agent, 100 parts by weight of hole transferring material and 100 parts by weight of polycarbonate as a binder resin were placed in a ball mill together with 800 parts by weight of tetrahydrofuran. 50
After mixing and dispersing for a time, a coating liquid for a single-layer type photosensitive layer was obtained.

As the charge generating agent, a mixture of the metal-free phthalocyanine obtained in Reference Example 1 and the titanyl phthalocyanine obtained in Reference Example 2 was used. The metal-free phthalocyanine and titanyl phthalocyanine were mixed by adding both phthalocyanines to a ball mill and stirring and mixing for 24 hours. The content ratio of titanyl phthalocyanine in the total amount of both phthalocyanines is as shown in Table 1 below.

The hole transporting agent is represented by the formula (HT1-1) belonging to the benzidine derivative represented by the general formula (HT1):

[0155]

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Was used. Next, the above coating solution is applied onto an aluminum base tube which is a conductive substrate by a dip coating method, and dried with hot air at 110 ° C. for 30 minutes to give a film thickness of 25.
An electrophotographic photosensitive member having a single-layer type photosensitive layer of μm was produced. Comparative Example 2 According to Example 1 described in JP-A-2-272067, 10 parts by weight of α-type metal-free phthalocyanine and 1 part by weight of X-type metal-free phthalocyanine were stirred to transfer the crystal form to X-type. Then, 1 part by weight of titanyl phthalocyanine and 200 parts by weight of tetrahydrofuran were added and further stirred for 5 hours to prepare an X-type metal-free phthalocyanine composition.

The infrared absorption spectrum of the obtained X-type metal-free phthalocyanine composition is shown in FIG. In FIG. 5, the peak attributed to the absorption of titanyl phthalocyanine [892 cm
^-1 (Arrow 1), 970cm ^-1 (Arrow 2), 1070cm
^-1 (arrow 3)], but no such peak is seen in the infrared absorption spectrum (FIG. 2) of the metal-free phthalocyanine obtained in Reference Example 1.

An X-type metal-free phthalocyanine composition,
Mixing with the titanyl phthalocyanine produced according to Raw Material Production Example 5 described in JP-A-2-272067,
A charge generating agent for a single-layer type photoconductor was prepared. The content ratio of titanyl phthalocyanine in the total amount of the charge generating agent, that is, in the total amount of the mixture of the X-type metal-free phthalocyanine composition and the titanyl phthalocyanine was 70% by weight. The X-type metal-free phthalocyanine composition and titanyl phthalocyanine were mixed in the same manner as in Example 1.

In addition to 2 parts by weight of the above-mentioned charge generating agent, 100 parts by weight of a hole transporting agent (the benzidine derivative of the above formula (HT1-1)) and a formal resin (# 20 manufactured by Denka Co.) as a binder resin.
100 parts by weight of 0) and 800 parts by weight of tetrahydrofuran were kneaded in a ball mill for 50 hours, mixed and dispersed to prepare a coating solution for a single-layer type photosensitive layer. Then, an electrophotographic photosensitive member having a single-layer type photosensitive layer was prepared in the same manner as in Examples 1 and 2 and Comparative Example 1 using the coating liquid for a single-layer type photosensitive layer. Examples 3 and 4 and Comparative Example 3 As the hole transfer agent, a compound (HT1-2) belonging to the benzidine derivative represented by the general formula (HT1):

[0160]

[Chemical 51]

Electrophotographic photoreceptors having a single-layer type photosensitive layer were prepared in the same manner as in Examples 1 and 2 and Comparative Example 1 except that the compound represented by the formula (1) was used. Comparative Example 4 An electrophotographic photosensitive member having a single-layer type photosensitive layer was prepared in the same manner as in Comparative Example 2 except that the benzidine derivative of the above formula (HT1-2) was used as the hole transferring material. Examples 5 and 6 and Comparative Example 5 As a hole transporting agent, a formula (HT2-1) belonging to the phenylenediamine derivative represented by the general formula (HT2):

[0162]

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Electrophotographic photoreceptors having a single-layer type photosensitive layer were prepared in the same manner as in Examples 1 and 2 and Comparative Example 1 except that the compound represented by the formula (1) was used. Comparative Example 6 An electrophotographic photosensitive member having a single-layer type photosensitive layer was prepared in the same manner as in Comparative Example 2 except that the phenylenediamine derivative represented by the above formula (HT2-1) was used as the hole transferring material.

In Examples 3 to 6 and Comparative Examples 3 and 5, the content ratio of titanyl phthalocyanine in the total amount of metal-free phthalocyanine and titanyl phthalocyanine is as shown in Table 1 below. Examples 7 and 8 and Comparative Example 7 As a hole transporting agent, a formula (HT2-2) belonging to the phenylenediamine derivative represented by the general formula (HT2):

[0165]

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Electrophotographic photoreceptors having a single-layer type photosensitive layer were prepared in the same manner as in Examples 1 and 2 and Comparative Example 1 except that the compound represented by the formula (1) was used. Comparative Example 8 An electrophotographic photosensitive member having a single-layer type photosensitive layer was prepared in the same manner as in Comparative Example 2 except that the phenylenediamine derivative represented by the above formula (HT2-2) was used as the hole transferring material. Examples 9 and 10 and Comparative Example 9 As a hole-transporting agent, a formula (HT12-1) belonging to the diphenylenediamine derivative represented by the general formula (HT12):

[0167]

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Electrophotographic photoreceptors having a single-layer type photosensitive layer were prepared in the same manner as in Examples 1 and 2 and Comparative Example 1 except that the compound represented by the formula (1) was used. Comparative Example 10 An electrophotographic photosensitive member having a single-layer type photosensitive layer was prepared in the same manner as in Comparative Example 2 except that the diphenylenediamine derivative represented by the above formula (HT12-1) was used as the hole transferring material. Examples 11 and 12 and Comparative Example 11 As a hole-transporting agent, a formula (HT11-1) belonging to the stilbene derivative represented by the general formula (HT11):

[0169]

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An electrophotographic photosensitive member having a single-layer type photosensitive layer was prepared in the same manner as in Examples 1 and 2 and Comparative Example 1 except that the compound represented by the formula (1) was used. Comparative Example 12 An electrophotographic photosensitive member having a single-layer type photosensitive layer was prepared in the same manner as in Comparative Example 2 except that the stilbene derivative represented by the above formula (HT11-1) was used as the hole transferring material.

Examples 7 to 12 and Comparative Examples 7 and 9,
In Table 11, the content ratio of titanyl phthalocyanine in the total amount of metal-free phthalocyanine and titanyl phthalocyanine is as shown in Table 2 below. With respect to the electrophotographic photoconductors of Examples 1 to 12 and Comparative Examples 1 to 12, an initial electrical characteristic test and an electrical characteristic test after repeated exposure described below were performed to evaluate the characteristics. Initial electrical characteristic test Using a drum sensitivity tester manufactured by GENTEC, an applied voltage was applied to the surface of the electrophotographic photoreceptors of Examples and Comparative Examples, and the surface was charged to + 700 ± 20V. The surface potential V ₀ (V) was measured. Then, the wavelength of 780 nm (half-value width 2) extracted from the white light of the halogen lamp as the exposure light source using a bandpass filter.
(0 nm) and a light intensity of 10 μJ / cm ² on the surface of the photosensitive member (irradiation time 1.5 seconds), and the time required for the surface potential to become 1/2 is measured, and half exposure is performed. Quantity E
_1/2 (μJ / cm ² ) was calculated. In addition, the surface potential at the time when 0.5 seconds has elapsed from the start of exposure is the residual potential
_r (V). Electrical property test after repeated exposure After the electrophotographic photoreceptors of Examples and Comparative Examples were used in a laser beam printer (model TC-650 manufactured by Mita Kogyo Co., Ltd.), image formation was performed 10,000 times. In the same manner as above, the surface potential V ₀ (V) and the residual potential V _r (V) were measured using the above-mentioned drum sensitivity tester, and the difference ΔV ₀ (V) and their respective initial values from each other were measured. ΔV _r (V) was calculated.

In the above test results, the lower the residual potential V _r (V) and the smaller the half-exposure amount E _{1/2, the} higher the sensitivity of the photoreceptor before repeated exposure, and It means that the smaller ΔV ₀ (V) and ΔV _r (V), the more stable the photosensitive member is. The results of each of the above tests are shown in Tables 1 and 2.

[0173]

[Table 1]

[0174]

[Table 2]

In Tables 1 and 2, "TiOPc content ratio" means the content ratio of titanyl phthalocyanine in the total amount of the charge generating agent (that is, in the total amount of the mixture of metal-free phthalocyanine and titanyl phthalocyanine here). Show. Further, "*" in the "TiOPc content ratio" column indicates that the content ratio of titanyl phthalocyanine in the total amount of the mixture of the X-type metal-free phthalocyanine composition obtained in Comparative Example 2 and titanyl phthalocyanine. .

As is clear from Tables 1 and 2, the photosensitive materials of Examples 1 to 12 using the mixture of the metal-free phthalocyanine obtained in Reference Example 1 and the titanyl phthalocyanine obtained in Reference Example 2 as the charge generating agent. The bodies are Comparative Examples 2, 4, 6, 8, and 10 using the mixture of the X-type metal-free phthalocyanine composition obtained in Comparative Example 2 and titanyl phthalocyanine.
And excellent in electrical characteristics and repeatability as compared with the photoreceptors of Nos. 12 and 12. Further, even when the mixture of the metal-free phthalocyanine and titanyl phthalocyanine in the present invention is used as the charge generating agent, the content ratio of titanyl phthalocyanine is below the preferable range described above in Comparative Examples 1, 3, 5, and 7. , 9 and 11 have insufficient sensitivity, electrical characteristics and stability. Preparation of Single Layer Type Photoreceptor II Examples 13 to 18 In addition to the charge generating agent, the hole transferring material and the binder resin (polycarbonate), the above general formula (ET1) was used as an electron transferring material.
Of the formula (ET1-1) belonging to the diphenoquinone derivative of:

[0177]

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Electrophotographic photoreceptors having a single-layer type photosensitive layer were prepared in the same manner as in Examples 2, 4, 6, 8, 10 and 12, except that 10 parts by weight of the compound represented by the formula (1) was used.
The content ratio of titanyl phthalocyanine in the total amount of the charge generating agent (mixture of metal-free phthalocyanine and titanyl phthalocyanine in the present invention) is 95% by weight. Examples 19 to 24 As the electron transfer agent, the formula (ET1-2) belonging to the diphenoquinone derivative represented by the general formula (ET1):

[0179]

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An electrophotographic photosensitive member having a single-layer type photosensitive layer was prepared in the same manner as in Examples 13 to 18 except that 30 parts by weight of the compound represented by the above was used. Examples 25 to 30 Formulas (ET2-1) belonging to the 2,4,7-trinitrofluorenone imine derivative represented by the general formula (ET2) are used as electron transfer agents.
:

[0181]

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An electrophotographic photosensitive member having a single-layer type photosensitive layer was prepared in the same manner as in Examples 13 to 18 except that 30 parts by weight of the compound represented by the above was used. Examples 31 to 35 Formulas (ET3-1) belonging to the ethylated nitrofluorenone imine derivative represented by the general formula (ET3) as electron transfer agents:

[0183]

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Electrophotographic photoreceptors having a single-layer type photosensitive layer were prepared in the same manner as in Examples 13 to 18 except that 30 parts by weight of the compound represented by the formula (1) was used. Examples 13-35 above
With respect to the electrophotographic photosensitive member (1), the initial electrical characteristic test and the electrical characteristic test after repeated exposure were conducted to evaluate the characteristics. The results are shown in Table 3 together with the types of the hole transfer agent and the electron transfer agent used in each example.

[0185]

[Table 3]

As is apparent from Table 3, the photoconductors 13 to 35 in which the hole transfer material and the electron transfer material were used in combination as the charge transfer material were the same as those in Example 2 in which only the hole transfer material was used as the charge transfer material. It can be seen that the electrical characteristics and the repeating characteristics are more excellent than those of 4, 6, 8, 10, and 12.

[0187]

As described above in detail, the electrophotographic photosensitive member of the present invention has sensitivity, electric characteristics, stability, etc. by using the mixture of the metal-free phthalocyanine and titanyl phthalocyanine of the present invention as the charge generating agent. Excellent in.
Further, by using the hole transfer material and the electron transfer material in combination, it is possible to obtain a photoreceptor having further excellent sensitivity, electrical specification and stability.

[Brief description of drawings]

FIG. 1 is an X-ray diffraction spectrum of metal-free phthalocyanine in the present invention.

FIG. 2 is an infrared absorption spectrum of the metal-free phthalocyanine in the present invention.

FIG. 3 is an X-ray diffraction spectrum of titanyl phthalocyanine in the present invention.

FIG. 4 is an infrared absorption spectrum of titanyl phthalocyanine in the present invention.

5 is an infrared absorption spectrum of the X-type metal-free phthalocyanine composition obtained in Comparative Example 1. FIG.

Front Page Continuation (72) Inventor Kazuya Hamasaki 1-22 Tamatsukuri Chuo-ku, Osaka City, Osaka Prefecture Mita Industry Co., Ltd.

Claims (3)

[Claims] 1. A single-layer type photoreceptor containing a charge transporting agent and a charge generating agent in a photosensitive layer, wherein the charge generating agent comprises: In the X-ray diffraction spectrum with the X-ray as the radiation source, the Bragg angles (2θ ± 0.2 degrees) are 7.5 degrees, 9.1 degrees, and 16.7.
, Metal-free phthalocyanine showing diffraction peaks at 17.4 degrees, 17.4 degrees, 22.3 degrees and 28.6 degrees, and Bragg angle (2
θ ± 0.2 degrees) is a mixture with titanyl phthalocyanine showing diffraction peaks at 9.5 degrees, 14.2 degrees, 24.0 degrees and 27.2 degrees, and the titanyl phthalocyanine is contained in the total amount of the charge generating agent. The electrophotographic photosensitive member is characterized in that the content ratio of is greater than 50% by weight. 2. The diffraction peak of the metal-free phthalocyanine has a Bragg angle (2θ ± 0.2 degrees) of 7.5 degrees and 9.
1 degree, 16.7 degrees, 17.4 degrees, 22.3 degrees, 23.9 degrees
, 27.2 degrees and 28.6 degrees, and the diffraction peak of the titanyl phthalocyanine has a Bragg angle (2θ ± 0.2 degrees) of 7.3 degrees, 9.5 degrees, and 11.
5 degrees, 14.2 degrees, 17.9 degrees, 24.0 degrees and 2 degrees
The electrophotographic photoconductor according to claim 1, wherein the electrophotographic photoconductor is 7.2 degrees. 3. The electrophotographic photosensitive member according to claim 1, wherein the charge transfer material is a hole transfer material and / or an electron transfer material.