JP2001188372A - Electrophotographic photoreceptor, electrophotographic method, electrophotographic device and process cartridge for same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a highly durable photoreceptor which does not cause the lowering of its electrification performance, the increase of residual potential and film scraping even after repeated use and which gives a stable image free from image abnormalities, and to provide an electrophotographic method, an electrophotographic device and an electrophotographic process cartridge. SOLUTION: The photoreceptor comprises a layer containing an electric charge generating material and a layer containing an electric charge transferring material on an electrically conductive substrate. The electric charge generating material is titanyl phothalocyanine having the maximum peak at 27.2 deg. and peaks at 7.33 deg. and 26.3 deg. as diffraction peaks of Bragg angle 2 θ to characteristic X-rays of CuK α. The mobility of the electric charge transferring layer is >=110-5 (cm/Vsec) and the electric charge transferring material is styryl, benzidine, tertiary amine and triallylamine materials.

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 using a novel photoconductive material. See the specific X
The present invention relates to an electrophotographic photoreceptor comprising a charge generation layer using a phthalocyanine crystal that gives a line diffraction spectrum, and a charge transport layer having physical properties that make full use of its excellent photocarrier generation ability. In addition, the present invention relates to an electrophotographic method, an electrophotographic apparatus, and an electrophotographic process cartridge using the photoconductor. Furthermore, the present invention relates to an electrophotographic apparatus using a charging roller arranged in contact or close proximity and having less image defects, and a mechanically highly durable electrophotographic apparatus having improved abrasion resistance of a photoreceptor while maintaining the above characteristics. Related to the device.

[0002]

2. Description of the Related Art In recent years, the development of information processing systems using electrophotography has been remarkable. In particular, optical printers that convert information into digital signals and record information with light have significantly improved print quality and reliability. This digital recording technology is applied not only to printers but also to ordinary copying machines, and so-called digital copying machines have been developed. In addition, a copier equipped with the digital recording technology in a conventional analog copier is expected to be increasingly demanded in the future because various information processing functions are added.

At present, semiconductor lasers (LDs) and light-emitting diodes (LEDs) that are small, inexpensive and highly reliable have been widely used as light sources for optical printers. The emission wavelength of currently used LEDs is 660 nm, and L
The emission wavelength range of D is in the near infrared region. Therefore, development of an electrophotographic photosensitive member having high sensitivity from a visible light region to a near infrared light region is desired.

The photosensitive wavelength range of an electrophotographic photosensitive member is almost determined by the photosensitive wavelength range of a charge generating substance used in the photosensitive member. Therefore, many charge generation substances such as various azo pigments, polycyclic quinone pigments, trigonal selenium, various phthalocyanine pigments, etc. have been developed. Among them, JP-A-3-35064, JP-A-3-35245, JP-A-3-37669, and JP-A-3-2690
No. 64, JP-A-7-319179, etc., titanyl phthalocyanine (abbreviated as TiOPc) has high sensitivity to long-wavelength light of 600 to 800 nm, and thus the light source is an LED or LD. It is extremely important and useful as a photoconductor material for electrophotographic printers and digital copiers.

On the other hand, the conditions of the electrophotographic photosensitive member repeatedly used in the Carlson process and similar processes include sensitivity, accepting potential, potential holding property, potential stability,
It is required that the electrostatic characteristics represented by the residual potential and the spectral characteristics be excellent. In particular, for high-sensitivity photoreceptors, the chargeability decreases and the residual potential increases due to repeated use.
It is empirically known that many photoconductors govern the life characteristics of the photoconductor, and the above-mentioned titanyl phthalocyanine is no exception. Therefore, the stability of a photoreceptor using titanyl phthalocyanine by repeated use is not yet sufficient, and there has been an eager desire to complete the technology.

A charging roller system has been proposed from the viewpoint of reducing the amount of ozone / NOx generated during the electrophotographic process and saving energy during charging. In this case, the charging roller is used in a state where the charging roller is in contact with or close to the photoconductor. Certainly, compared with a non-contact charging device represented by a scorotron, a voltage applied to the charging device can be reduced, and the amount of the reactive gas generated can be reduced. However, a serious side effect is a problem of dielectric breakdown of the photoconductor. This is interpreted as that the charging of the photoreceptor by using the charging roller is performed by discharging in a minute gap, but the details are not known. Further, almost no effective means for preventing this dielectric breakdown has been proposed.

[0007]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a stable electrophotographic photoreceptor which does not cause a decrease in chargeability or an increase in residual potential even when repeatedly used without losing high sensitivity. . Another object of the present invention is to provide an electrophotographic photoreceptor with less film shaving even when used repeatedly. Another object is an electrophotographic method capable of obtaining a stable image with few abnormal images even by repeated use,
An object of the present invention is to provide an electrophotographic apparatus and an electrophotographic process cartridge. It is still another object of the present invention to provide an electrophotographic apparatus which can cope with high-speed printing and forms a stable image without causing dielectric breakdown of a photoreceptor by repeated use. Another object of the present invention is to provide a highly durable electrophotographic apparatus in which the abrasion resistance of the photoconductor is improved while maintaining the above characteristics.

[0008]

The basic structure of the titanyl phthalocyanine pigment used in the present invention is represented by the following general formula (1):
Is represented by

[0009]

Embedded image (In the formula, X ₁ , X ₂ , X ₃ , and X ₄ each independently represent various halogen atoms, and n, m, l, and k each independently represent a number from 0 to _4. )

Documents relating to the synthesis method and electrophotographic characteristics of TiOPc include, for example, JP-A-57-148745, JP-A-59-36254, and JP-A-59-44.
No. 054, JP-A-59-31965, JP-A-61-239248, and JP-A-62-67094. Various crystal systems are known for TiOPc.
JP-A-59-166959, JP-A-61-239
248, JP-A-62-67094, JP-A-63-366, JP-A-63-116158, JP-A-63-196067, and JP-A-64-1
No. 7066 discloses TiOPc having different crystal forms.

The present inventors have paid attention to the crystal form of TiOPc and made intensive studies on the electrostatic characteristics of the photoreceptor after repeated use in order to solve the above-mentioned problems, and have completed the present invention. Even when a photoreceptor using TiOPc exhibiting high sensitivity is repeatedly used in the Carlson process and similar processes, the chargeability decreases and the residual potential increases,
The life of the photoconductor has been limited. We have found that TiO
Focusing on the crystal form of Pc, and as a result of examining the electrostatic characteristics of the photoreceptor after repeated use in order to solve this problem, it was found that when the crystal having the specific X-ray diffraction spectrum described above was used, a favorable It was confirmed that a photoreceptor with a small decrease in chargeability during repeated use was obtained while maintaining light sensitivity.

Furthermore, even when a photoreceptor using TiOPc showing high sensitivity is repeatedly used in the Carlson process using a charging roller and similar processes, the occurrence of an image is recognized due to dielectric breakdown, and the life of the photoreceptor is determined. Was. The present inventors have paid attention to the crystal form of TiOPc and the mobility of the charge transport layer, and have studied the image characteristics after repeated use of the photoconductor in order to solve this problem. It has been confirmed that when crystals exhibiting a spectrum are used in combination with a charge transport layer having a specific mobility, the repetition characteristics of the above physical properties are excellent, and the present invention has been completed.

However, depending on the type of the charge transport layer (charge transport material), the high photocarrier generation ability of the titanyl phthalocyanine cannot be sufficiently functioned.
In some cases, the light sensitivity was reduced and the residual potential was increased upon repeated use. The present inventors have examined this point, and found that this phenomenon can be explained by the mobility of the charge transport layer.By having the specific mobility of the charge transport layer, the characteristics of the titanyl phthalocyanine can be maximized. This led to the completion of the present invention.

That is, according to the present invention, (1) “a charge generating layer containing at least a charge generating substance, a charge transporting layer containing a low molecular charge transporting substance and an inert polymer are provided on a conductive support. In the electrophotographic photoreceptor, the charge generation layer has a maximum diffraction peak at least at 27.2 ° as a diffraction peak (± 0.2 °) at a Bragg angle of 2θ with respect to CuKα characteristic X-ray (wavelength 1.514 °). And a peak at 7.3 ° as a diffraction peak on the lowest angle side, and 2
An electrophotographic photoreceptor containing a titanyl phthalocyanine having a peak at 6.3 °, wherein the peak intensity at 26.3 ° is 1 to 10% of the peak intensity at 27.2 °; Has a mobility of 1 × 10 ⁻⁵ (cm / V) in the electric field intensity at the time of writing image light in actual use.
sec) or more, and (2) “9.4 ° of the titanyl phthalocyanine.
(3) The electrophotographic photoreceptor according to the above (1), wherein the diffraction peak in the lower angle side region is 7.3 °.
(1) The electrophotographic photoreceptor according to the above (1), wherein the titanyl phthalocyanine has a peak at 28.6 ° at the same time. , The intensity is 27.2 ° of intensity 20
%, The electrophotographic photoreceptor according to any one of the above items (1) to (3) ", (5)
"The electrophotographic photoreceptor according to any one of the above items (1) to (4), wherein the titanyl phthalocyanine is synthesized without using a titanium halide", ( 6) The electrophotographic photosensitive member according to any one of the above items (1) to (5), wherein the charge transport material is a compound represented by the following general formula (I);

[0015]

Embedded image (Wherein R ₁ , R ₂ , R ₃ and R ₄ represent a hydrogen atom, a substituted or unsubstituted lower alkyl group, a substituted or unsubstituted aryl group, and Ar ₁ represents a substituted or unsubstituted aryl group. , Ar ₂ represents a substituted or unsubstituted arylene group, R ₁ and Ar ₁ may form a ring together, and k is an integer of 0 or 1.) ”, (7)“ The electrophotographic photoreceptor according to any one of the above (1) to (5), wherein the transport substance is a compound represented by the following general formula (II);

[0016]

Embedded image (Wherein, R ₅ represents a lower alkyl group, a lower alkoxy group or a halogen atom, 1 represents an integer of 0 to 4,
₆ , R ₇ may be the same or different and represent a hydrogen atom, a lower alkyl group, a lower alkoxy group or a halogen atom. )), (8) wherein the charge transporting material is represented by the following general formula (II)
The electrophotographic photoreceptor according to any one of the above (1) to (5), which is a compound represented by I);

[0017]

Embedded image (Wherein R ₈ , R ₉ and R ₁₀ represent a hydrogen atom, an amino group, an alkoxy group, a thioalkoxy group, an aryloxy group, a methylenedioxy group, a substituted or unsubstituted alkyl group,
Represents a halogen atom or a substituted or unsubstituted aryl group. m represents an integer of 1 to 3. )), (9), wherein the charge transporting substance is a compound represented by the following general formula (IV):
Electrophotographic photoreceptor according to the above item;

[0018]

Embedded image (In the formula, A ₁ and A ₂ represent a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, which may be the same or different. Ar ₃ represents a substituted or unsubstituted fused polycyclic carbon. (Represents hydrogen.) ", (10) The electrophotography according to any one of the above items (1) to (5), wherein the charge transporting material is a compound represented by the following general formula (V). Photoreceptor;

[0019]

Embedded image (Wherein, Ar ₄ represents an aromatic group, R ₁₁ represents a hydrogen atom, a substituted or unsubstituted alkyl group or an aryl group. P is 0 or 1, q is 1 or 2, and p = 0, q In the case of = 1, Ar ₄ and R ₁₁ may form a ring together. ”)
(11) The electrophotographic photoreceptor according to any one of the above items (1) to (5), wherein the charge transport material is a compound represented by the following general formula (VI);

[0020]

Embedded image (Wherein R ₁₂ and R ₁₃ represent a hydrogen atom, a halogen atom, a nitro group, a cyano group, a substituted or unsubstituted alkyl group, etc.
₁₄ and R ₁₅ represent a hydrogen atom, a cyano group, an alkoxycarbonyl group, a substituted or unsubstituted alkyl group, and R ₁₆ represents a hydrogen atom, a lower alkyl group or an alkoxy group. W is a hydrogen atom, a substituted or unsubstituted alkyl group or the like;
An integer of 5, s is an integer of 1 to 4, t is an integer of 0 to 2, u is an integer of 1 to 3, and v is an integer of 1 to 2. ) ", (1
2) “the electrophotographic photoreceptor according to any one of the above items (1) to (11), wherein the inert polymer is a polycarbonate”; (14) The electrophotographic photoreceptor according to any one of (1) to (12), wherein the charge transport material concentration is 45 wt% or less. In an electrophotographic photoreceptor provided with a charge generating layer containing a charge generating substance and a charge transporting layer containing a polymer charge transporting substance, the charge generating layer has a characteristic X of CuKα.
A maximum diffraction peak at at least 27.2 ° as a diffraction peak (± 0.2 °) at a Bragg angle of 2θ with respect to a line (wavelength 1.514 °), and a diffraction peak at 7.3 ° as the lowest diffraction peak. A peak at 26.3 °, and the peak intensity at 26.3 ° is 27.2 °.
And the mobility of the charge transporting layer in the electric field intensity at the time of writing image light when the electrophotographic photosensitive member is actually used is 1 × 10 ^{−. 5} (cm / Vsec) or more, "(15)" the polymer charge transport material is a polycarbonate containing at least a triarylamine structure in a main chain and / or a side chain. (16) The electrophotographic photoreceptor according to the above (14), wherein the polymer charge transport material is a compound represented by the following general formula (VII). The electrophotographic photoreceptor according to item (15);

[0021]

Embedded imageWhere R₁, R_Two, R_ThreeAre each independently substituted or
Unsubstituted alkyl group or halogen atom, R_FourIs a hydrogen atom
Or a substituted or unsubstituted alkyl group, R_Five, R ₆Is replaced
Or an unsubstituted aryl group, o, p and q are each independently
An integer of 0 to 4, k and j represent compositions, and 0.1 ≦
k ≦ 1, 0 ≦ j ≦ 0.9, and n is the number of repeating units.
It is an integer of 5 to 5000. X is aliphatic divalent
Group, a cyclic aliphatic divalent group, or represented by the following general formula
Represents a divalent group.

[0022]

Embedded image In the formula, R ₁₀₁ and R ₁₀₂ each independently represent a substituted or unsubstituted alkyl group, aryl group or halogen atom. l and m are integers of 0 to 4; Y is a single bond;
~ 12 linear, branched or cyclic alkylene groups,
-O -, - S -, - SO -, - SO 2 -, - CO -, -
CO—O—Z—O—CO— (wherein, Z represents an aliphatic divalent group) or

[0023]

Embedded image (In the formula, a represents an integer of 1 to 20, b represents an integer of 1 to 2000, and R ₁₀₃ and R ₁₀₄ represent a substituted or unsubstituted alkyl group or aryl group.) Here, R _{10 1} and R
₁₀₂ , R ₁₀₃ and R ₁₀₄ may be the same or different. (17) The electrophotographic photoreceptor according to the above (15), wherein the polymer charge transporting substance is a compound represented by the following general formula (VIII):

[0024]

Embedded image In the formula, R ₇ and R ₈ represent a substituted or unsubstituted aryl group, A
r ₁ , Ar ₂ and Ar ₃ represent the same or different arylene groups. X, k, j and n are the same as in the case of the formula (VII). (18) The electrophotographic photoreceptor according to the above (15), wherein the polymer charge transporting substance is a compound represented by the following general formula (IX);

[0025]

Embedded image In the formula, R ₉ and R ₁₀ are a substituted or unsubstituted aryl group,
Ar ₄ , Ar ₅ and Ar ₆ represent the same or different arylene groups. X, k, j and n are the same as in the case of the formula (VII). (19) The electrophotographic photoreceptor according to the above (15), wherein the polymer charge transport material is a compound represented by the following general formula (X):

[0026]

Embedded image In the formula, R ₁₁ and R ₁₂ are a substituted or unsubstituted aryl group,
Ar ₇ , Ar ₈ and Ar ₉ are the same or different arylene groups, p
Represents an integer of 1 to 5. X, k, j and n are (V
II) Same as equation. (20) "The electrophotographic photoreceptor according to the above (15), wherein the polymer charge transporting substance is a compound represented by the following general formula (XI):

[0027]

Embedded imageWhere R₁₃, R₁₄Is a substituted or unsubstituted aryl group,
Ar_Ten, Ar₁₁, Ar ₁₂Are the same or different arylene groups,
X₁, X_TwoIs a substituted or unsubstituted ethylene group, or
Alternatively, it represents an unsubstituted vinylene group. X, k, j and
And n are the same as in the case of the formula (VII). ”, (21)
"The polymer charge transport material is represented by the following general formula (XII).
(15).
Electrophotographic photoreceptor according to the above item;

[0028]

Embedded image In the formula, R ₁₅ , R ₁₆ , R ₁₇ and R ₁₈ are a substituted or unsubstituted aryl group, Ar ₁₃ , Ar ₁₄ , Ar ₁₅ and Ar ₁₆ are the same or different arylene groups, and Y ₁ , Y ₂ and Y ₃ are A single bond, a substituted or unsubstituted alkylene group, a substituted or unsubstituted cycloalkylene group, a substituted or unsubstituted alkylene ether group, an oxygen atom, a sulfur atom, and a vinylene group may be the same or different. X, k, j and n are
This is the same as the case of the equation (VII). (22) the electrophotographic photoreceptor according to the above (15), wherein the polymer charge transporting substance is a compound represented by the following general formula (XIII);

[0029]

Embedded imageWhere R₁₉, R₂₀Is a hydrogen atom, a substituted or unsubstituted
Represents a reel group, R ₁₉And R₂₀May form a ring
No. Ar₁₇, Ar₁₈, Ar₁₉Are the same or different allylenes
Represents a group. X, k, j and n are in the case of the formula (VII)
Is the same as , (23) "the charge transport polymer material"
Is a compound represented by the following general formula (XIV)
(15) The electrophotographic photosensitive member according to the above (15),
body;

[0030]

Embedded image In the formula, R ₂₁ represents a substituted or unsubstituted aryl group, and Ar ₂₀ , Ar ₂₁ , Ar ₂₂ , and Ar ₂₃ represent the same or different arylene groups. X, k, j and n are (VII)
Same as for expressions. (24) the electrophotographic photoreceptor according to the above (15), wherein the polymer charge transporting substance is a compound represented by the following general formula (XV);

[0031]

Embedded image In the formula, R ₂₂ , R ₂₃ , R ₂₄ , and R ₂₅ are a substituted or unsubstituted aryl group, Ar ₂₄ , Ar ₂₅ , Ar ₂₆ , Ar ₂₇ , Ar ₂₈
Represents the same or different arylene groups. X, k, j and n are the same as in the case of the formula (VII). ”, (25)
"The polymer charge transport material is a compound represented by the following general formula (XVI),
The electrophotographic photosensitive member according to the item 5);

[0032]

Embedded imageWhere R₂₆, R₂₇Is a substituted or unsubstituted aryl group,
Ar₂₉, Ar₃₀, Ar ₃₁Represents the same or different arylene groups
Express. X, k, j and n are the same as in the case of the formula (VII).
The same. Is provided.

According to the present invention, there is also provided (26) an electrophotographic method in which at least charging, image exposure, development, and transfer are repeatedly performed on the electrophotographic photosensitive member, wherein the electrophotographic photosensitive member is as described in the above item (1). To an electrophotographic photoreceptor according to any one of (25) to (25). "

According to the present invention, there is also provided (27) an electrophotographic apparatus comprising at least a charging means, an image exposing means, a developing means, a transferring means and an electrophotographic photosensitive member, Are the above (1) to (25)
13. An electrophotographic apparatus, which is the electrophotographic photosensitive member according to any one of the above items. (28) "The charging means is
(29) The electrophotographic apparatus according to (27), wherein the charging member is in contact with or close to the photosensitive member. And the photoreceptor is charged by superimposing the photoreceptor on the electrophotographic apparatus described in (28).

According to the present invention, there is also provided (30) "a process cartridge for an electrophotographic apparatus comprising at least an electrophotographic photosensitive member, wherein the electrophotographic photosensitive member is any of the above items (1) to ( (25) The process cartridge for an electrophotographic apparatus, which is the electrophotographic photosensitive member according to any one of (25) and (31), wherein the charging unit is a charging member that is in contact with or close to the photosensitive member. (30) The process cartridge for an electrophotographic apparatus according to the above (30), (32), wherein in the electrophotographic apparatus, an alternating current component is superimposed on a direct current component on a charging member to charge the photoreceptor. A process cartridge for an electrophotographic apparatus according to the above mode (31), is provided.

Hereinafter, the present invention will be described in detail. Methods for obtaining the desired crystal form of titanyl phthalocyanine include a method similar to a known synthesis process, a method of changing crystals in a washing / purifying process, and a method of providing a special crystal conversion step. Further, among the methods for providing a crystal conversion step, a solvent, a general conversion method using mechanical load, and
A sulfuric acid pasting method in which titanyl phthalocyanine is dissolved in sulfuric acid and the above-mentioned conversion is carried out through an amorphous crystal obtained by pouring the solution into water is mentioned.

Among them, a method of obtaining a desired crystal form by crystal transformation by contacting with an organic solvent in the presence of water after passing through amorphous crystals is preferably used. In particular, it is preferable to use an amorphous crystal having a maximum diffraction peak at 7.0 ° and more preferably to use an amorphous crystal having a peak half width of 1 ° or more at 7.0 °.

As the organic solvent used for the crystal conversion, any organic solvent can be used as long as it can obtain a predetermined crystal form. In particular, tetrahydrofuran, cyclohexanone, toluene, methylene chloride, carbon disulfide, orthodichlorobenzene, It is desirable to include one selected from 1,1,2-trichloroethane. Note that two or more organic solvents may be used as a mixture.

Furthermore, the properties of the photoreceptor using the titanyl phthalocyanine described above also differ greatly depending on the synthesis process. Although several routes for synthesizing titanyl phthalocyanine are known, a method using a titanium halide is known. It has been found that a photoreceptor using titanyl phthalocyanine produced by this method shows a remarkable decrease in chargeability after repeated use. In order to avoid this, it is desirable to produce by a method of synthesizing without using a titanium halide (for example, using organic titanium as a raw material).

The X-ray diffraction spectrum of TiOPc in the present invention can be measured by using a commercially available X-ray diffraction spectrum measuring device for a TiOPc crystal produced through synthesis, purification, crystal conversion steps and the like.

2θ in TiOP in the present invention =
The peak intensity at 7.3 °, 26.3 °, 27.2 ° and 28.6 ° will be described. The value obtained by calculating the peak intensity after performing baseline correction in a general X-ray diffraction spectrum is the peak intensity ratio referred to in the present invention.

The mobility of the charge transport layer can be measured by a time-of-flight method or a xerographic method. The time-of-flight method is an effective means and is generally used when performing a wide range measurement on the electric field strength. Generally, the charge transport layer to be measured is sandwiched between electrodes (one side is at least translucent)
A sample having the structure described above is prepared, and a charge carrier is directly excited by using a short-wavelength excitation light source such as a nitrogen laser to generate photocarriers, and the mobility is measured.

[0043]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, an electrophotographic photosensitive member according to the present invention will be described with reference to the drawings. FIG. 1 is a cross-sectional view showing an electrophotographic photoreceptor of the present invention.
A charge generation layer (35) mainly composed of a charge generation material and a charge transport layer (37) mainly composed of a charge transport material are stacked. FIG. 2 is a cross-sectional view illustrating another configuration example of the electrophotographic photoreceptor of the present invention, in which a charge generation layer (35) is laminated on a charge transport layer (37).

As the conductive support (31), those exhibiting conductivity of 10 ¹⁰ Ω · cm or less, for example, aluminum, nickel, chromium, nichrome, copper, gold, silver,
Metals such as platinum, tin oxide, metal oxides such as indium oxide, coated on film or cylindrical plastic or paper by evaporation or sputtering,
Alternatively, a plate made of aluminum, an aluminum alloy, nickel, stainless steel, or the like, or a tube formed by extruding, drawing, or the like, and then surface-treated such as cutting, superfinishing, or polishing can be used. Further, an endless nickel belt and an endless stainless belt disclosed in JP-A-52-36016 can also be used as the conductive support (31).

In addition to the above, a support obtained by dispersing a conductive powder on a suitable binder resin on the above support and applying the same can also be used as the conductive support (31) of the present invention. This conductive powder includes carbon black, acetylene black, aluminum, nickel, iron, nichrome, copper,
Metal powder such as zinc and silver, conductive tin oxide, IT
And metal oxide powders such as O. The binder resins used simultaneously include polystyrene and styrene-
Acrylonitrile copolymer, styrene-butadiene copolymer, styrene-maleic anhydride copolymer, polyester, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyvinylidene chloride, polyarylate resin, phenoxy resin , Polycarbonate, cellulose acetate resin, ethyl cellulose resin, polyvinyl butyral, polyvinyl formal, polyvinyl toluene,
Thermoplasticity such as poly-N-vinyl carbazole, acrylic resin, silicone resin, epoxy resin, melamine resin, urethane resin, phenol resin, alkyd resin,
A thermosetting resin or a photocurable resin is used. Such a conductive layer can be provided by dispersing the conductive powder and the binder resin in an appropriate solvent, for example, tetrahydrofuran, dichloromethane, methyl ethyl ketone, toluene, or the like, and applying the dispersion.

Further, heat shrinkage of a material such as polyvinyl chloride, polypropylene, polyester, polystyrene, polyvinylidene chloride, polyethylene, chlorinated rubber, Teflon (registered trademark) or the like containing the above-mentioned conductive powder on a suitable cylindrical substrate. Also those that have a conductive layer provided by a tube,
It can be favorably used as the conductive support (31) of the present invention.

Next, the photosensitive layer will be described. The photosensitive layer has a laminated structure of a charge generation layer (35) and a charge transport layer (37). The charge generation layer (35) is a layer mainly composed of TiOPc exhibiting the above-mentioned specific X-ray diffraction spectrum as a charge generation material. The charge generation layer (35)
The iOPc is formed by dispersing iOPc in a suitable solvent together with a binder resin, if necessary, using a ball mill, an attritor, a sand mill, ultrasonic waves, or the like, coating this on a conductive support, and drying.

If necessary, the binder resin used for the charge generation layer (35) may be polyamide, polyurethane, epoxy resin, polyketone, polycarbonate, silicon resin, acrylic resin, polyvinyl butyral, polyvinyl formal, polyvinyl ketone, polystyrene, polystyrene, Polysulfone, poly-N-vinylcarbazole, polyacrylamide, polyvinyl benzal, polyester, phenoxy resin, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyphenylene oxide, polyamide, polyvinyl pyridine, cellulose resin, casein, polyvinyl alcohol And polyvinylpyrrolidone. Above all, polyvinyl acetal represented by polyvinyl butyral is used favorably, and in particular, polyvinyl acetal having a degree of acetylation of 4 mol% or more (butyral).
Is used well. The amount of the binder resin is the charge generation material 1
0 to 500 parts by weight, preferably 10 to 100 parts by weight
300 parts by weight are suitable.

In the charge generation layer (35), it is possible to use other charge generation materials in addition to the above-mentioned TiOPc giving the specific X-ray diffraction spectrum, and typical examples thereof include monoazo pigments, disazo pigments, Trisazo pigments,
Perylene pigments, perinone pigments, quinacridone pigments, quinone condensed polycyclic compounds, squaric acid dyes,
Other phthalocyanine pigments, naphthalocyanine pigments,
Azurenium salt dyes and the like are used.

The solvents used herein include isopropanol, acetone, methyl ethyl ketone, cyclohexanone, tetrahydrofuran, dioxane, ethyl cellosolve, ethyl acetate, methyl acetate, dichloromethane, dichloroethane, monochlorobenzene, cyclohexane,
Toluene, xylene, ligroin and the like can be mentioned. Particularly, ketone solvents, ester solvents and ether solvents are preferably used. As a method of applying the coating solution, a method such as a dip coating method, a spray coat, a bead coat, a nozzle coat, a spinner coat, and a ring coat can be used. The thickness of the charge generation layer (35) is 0.01 to 5 μm.
The degree is appropriate, and preferably 0.1 to 2 μm.

The charge transport layer (37) is a layer containing a low-molecular charge transport substance and an inert polymer. The mobility measured in the state of the charge transport layer has an electric field strength of 5 × 10 ⁵ (Vcm
^-1 ), it is 1 × 10 ⁻⁵ (cmV ⁻¹ sec ⁻¹ ) or more. The charge transport layer (37) can be formed by dissolving or dispersing a low-molecular charge transport substance and an inert polymer in a suitable solvent, coating and drying. If necessary, a plasticizer, a leveling agent, an antioxidant and the like can be added. As the low-molecular charge transport material that can be used, any material can be used as long as it can satisfy the above physical properties when the charge transport layer is formed using the charge transport material.
In particular, the compounds represented by the general formulas (I) to (VI) can be effectively used.

These charge transporting substances may be used alone, but may be used in combination of two or more kinds with other charge transporting substances. Other miscible charge transport materials include hole transport materials and electron transport materials. Examples of the charge transport material include chloranil, bromanil, tetracyanoethylene, tetracyanoquinodimethane, 2,4,7-
Trinitro-9-fluorenone, 2,4,5,7-tetranitro-9-fluorenone, 2,4,5,7-tetranitroxanthone, 2,4,8-trinitrothioxanthone, 2,6,8-trinitro- 4H-indeno [1,
2-b] thiophen-4-one, 1,3,7-trinitrodibenzothiophene-5,5-dioxide, an electron accepting substance such as a benzoquinone derivative.

Examples of the hole transport material include poly-N-vinylcarbazole and its derivatives, poly-γ-carbazolylethylglutamate and its derivatives, pyrene-formaldehyde condensate and its derivatives, polyvinylpyrene, polyvinylphenanthrene, polysilane, Oxazole derivatives, oxadiazole derivatives, imidazole derivatives, monoarylamine derivatives, diarylamine derivatives, triarylamine derivatives, stilbene derivatives,
α-phenylstilbene derivative, benzidine derivative,
Diarylmethane derivatives, triarylmethane derivatives,
9-styrylanthracene derivatives, pyrazoline derivatives,
Other known materials such as a divinylbenzene derivative, a hydrazone derivative, an indene derivative, a butadiene derivative, a pyrene derivative, a bisstilbene derivative, an enamine derivative and the like can be used.

The following are examples of the charge transport materials represented by the general formulas (I) to (VI). Examples of the charge transport material represented by the general formula (I) include those shown in Table 1.

[0055]

[Table 1-1]

[0056]

[Table 1-2] Examples of the charge transport material represented by the general formula (II) include Table 2
Are shown.

[0057]

[Table 2-1]

[0058]

[Table 2-2] Examples of the charge transport material represented by the general formula (III) include those shown in Table 3.

[0059]

[Table 3-1]

[0060]

[Table 3-2] Examples of the charge transporting material represented by the general formula (IV) include those shown in Table 4.

[0061]

[Table 4-1]

[0062]

[Table 4-2]

[0063]

[Table 4-3] As the charge transporting material represented by the general formula (V), Table 5
Are shown.

[0064]

[Table 5-1]

[0065]

[Table 5-2] Examples of the charge transport material represented by the general formula (VI) include those shown in Table 6.

[0066]

[Table 6-1]

[0067]

[Table 6-2]

[0068]

[Table 6-3]

[0069]

[Table 6-4]

As the inert polymer, polystyrene, styrene-acrylonitrile copolymer, styrene-
Butadiene copolymer, styrene-maleic anhydride copolymer, polyester, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyvinylidene chloride, polyalate, phenoxy resin, polycarbonate, cellulose acetate resin, ethyl cellulose resin , Polyvinyl butyral, polyvinyl formal, polyvinyl toluene, poly-N-vinyl carbazole, acrylic resin, silicone resin, epoxy resin, melamine resin, urethane resin, phenol resin, thermoplastic or thermosetting resin such as alkyd resin, Among them, polycarbonate is preferably used in terms of transparency and abrasion resistance.

The amount of the low-molecular charge transporting substance is suitably 20 to 300 parts by weight, preferably 40 to 150 parts by weight, per 100 parts by weight of the inert polymer. In particular, from the viewpoint of abrasion resistance, it is preferable that the weight of the low molecular weight charge transporting substance in all the materials constituting the charge transporting layer is 45 wt% or less.

The charge transport layer (37) according to the present invention.
In place of the layer containing the low-molecular charge transport material and the inert polymer, a layer containing a high-molecular charge transport material as a main component can be used. In this case, the charge transport layer (37) can be formed by dissolving or dispersing the polymer charge transport substance in an appropriate solvent, coating and drying. If necessary, a plasticizer, a leveling agent, an antioxidant and the like can be added. As the polymer charge transporting material that can be used, a known polymer charge transporting material can be used. However, when a charge transporting layer is formed using the material, those that can satisfy the above physical properties (mobility) are more preferably used. Can be used.

In particular, polycarbonates containing a triarylamine structure in the main chain and / or side chain are preferably used. Among them, polymeric charge transport materials represented by the formulas (VII) to (XVI) are preferably used, and these are exemplified below and specific examples are shown.

[0074]

Embedded imageWhere R₁, R_Two, R_ThreeAre each independently substituted or
Unsubstituted alkyl group or halogen atom, R_FourIs a hydrogen atom
Or a substituted or unsubstituted alkyl group, R_Five, R ₆Is replaced
Or an unsubstituted aryl group, o, p and q are each independently
An integer of 0 to 4, k and j represent compositions, and 0.1 ≦
k ≦ 1, 0 ≦ j ≦ 0.9, and n is the number of repeating units.
It is an integer of 5 to 5000. X is aliphatic divalent
Group, a cyclic aliphatic divalent group, or represented by the following general formula
Represents a divalent group.

[0075]

Embedded image In the formula, R ₁₀₁ and R ₁₀₂ each independently represent a substituted or unsubstituted alkyl group, aryl group or halogen atom. l and m are integers of 0 to 4; Y is a single bond;
~ 12 linear, branched or cyclic alkylene groups,
-O -, - S -, - SO -, - SO 2 -, - CO -, -
CO—O—Z—O—CO— (wherein, Z represents an aliphatic divalent group) or

[0076]

Embedded image (In the formula, a represents an integer of 1 to 20, b represents an integer of 1 to 2000, and R ₁₀₃ and R ₁₀₄ represent a substituted or unsubstituted alkyl group or aryl group.) Here, R _{10 1} and R
₁₀₂ , R ₁₀₃ and R ₁₀₄ may be the same or different.

[0077]

Embedded image In the formula, R ₇ and R ₈ represent a substituted or unsubstituted aryl group, A
r ₁ , Ar ₂ and Ar ₃ represent the same or different arylene groups. X, k, j and n are the same as in the case of the formula (VII).

[0078]

Embedded image In the formula, R ₉ and R ₁₀ are a substituted or unsubstituted aryl group,
Ar ₄ , Ar ₅ and Ar ₆ represent the same or different arylene groups. X, k, j and n are the same as in the case of the formula (VII).

[0079]

Embedded image In the formula, R ₁₁ and R ₁₂ are a substituted or unsubstituted aryl group,
Ar ₇ , Ar ₈ and Ar ₉ are the same or different arylene groups, p
Represents an integer of 1 to 5. X, k, j and n are (V
II) Same as equation.

[0080]

Embedded imageWhere R₁₃, R₁₄Is a substituted or unsubstituted aryl group,
Ar_Ten, Ar₁₁, Ar ₁₂Are the same or different arylene groups,
X₁, X_TwoIs a substituted or unsubstituted ethylene group, or
Alternatively, it represents an unsubstituted vinylene group. X, k, j and
And n are the same as in the case of the formula (VII).

[0081]

Embedded image In the formula, R ₁₅ , R ₁₆ , R ₁₇ and R ₁₈ are a substituted or unsubstituted aryl group, Ar ₁₃ , Ar ₁₄ , Ar ₁₅ and Ar ₁₆ are the same or different arylene groups, and Y ₁ , Y ₂ and Y ₃ are A single bond, a substituted or unsubstituted alkylene group, a substituted or unsubstituted cycloalkylene group, a substituted or unsubstituted alkylene ether group, an oxygen atom, a sulfur atom, and a vinylene group may be the same or different. X, k, j and n are
This is the same as the case of the equation (VII).

[0082]

Embedded imageWhere R₁₉, R₂₀Is a hydrogen atom, a substituted or unsubstituted
Represents a reel group, R ₁₉And R₂₀May form a ring
No. Ar₁₇, Ar₁₈, Ar₁₉Are the same or different allylenes
Represents a group. X, k, j and n are in the case of the formula (VII)
Is the same as

[0083]

Embedded image In the formula, R ₂₁ represents a substituted or unsubstituted aryl group, and Ar ₂₀ , Ar ₂₁ , Ar ₂₂ , and Ar ₂₃ represent the same or different arylene groups. X, k, j and n are (VII)
Same as for expressions.

[0084]

Embedded image In the formula, R ₂₂ , R ₂₃ , R ₂₄ , and R ₂₅ are a substituted or unsubstituted aryl group, Ar ₂₄ , Ar ₂₅ , Ar ₂₆ , Ar ₂₇ , Ar ₂₈
Represents the same or different arylene groups. X, k, j and n are the same as in the case of the formula (VII).

[0085]

Embedded imageWhere R₂₆, R₂₇Is a substituted or unsubstituted aryl group,
Ar₂₉, Ar₃₀, Ar ₃₁Represents the same or different arylene groups
Express. X, k, j and n are the same as in the case of the formula (VII).
The same.

These polymer charge transporting substances may be used alone, but may be used as a mixture of two or more kinds with other polymer charge transporting substances. It is also possible to use a low molecular charge transport material in combination.

The low-molecular-weight charge transporting materials that can be used in combination include a hole-transporting material and an electron-transporting material as in the case of the layer containing the low-molecular-weight charge-transporting material and the inert polymer. The electron transport material is the same as that of the electron transport layer containing the low molecular charge transport material and the inert polymer.

Further, if necessary, an inert polymer may be used in combination. Examples of the inert polymer that can be used include polystyrene, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, styrene-maleic anhydride copolymer, polyester, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, and polystyrene. Vinyl acetate, polyvinylidene chloride, polyalate, phenoxy resin, polycarbonate, cellulose acetate resin, ethyl cellulose resin, polyvinyl butyral, polyvinyl formal, polyvinyl toluene, poly-N-vinyl carbazole, acrylic resin, silicone resin, epoxy resin, melamine resin,
Thermoplastic or thermosetting resins such as urethane resins, phenolic resins, and alkyd resins.

In the present invention, the thickness of the charge transport layer is preferably about 5 to 100 μm both when using a low molecular charge transport substance and when using a high molecular charge transport substance. As the solvent used here, tetrahydrofuran, dioxane, toluene, dichloromethane, monochlorobenzene, dichloroethane, cyclohexanone, methyl ethyl ketone, acetone and the like are used.

In the photoreceptor of the present invention, the charge transport layer (3
In 7), a plasticizer or a leveling agent may be added. As the plasticizer, those used as general plasticizers for general resins, such as dibutyl phthalate and dioctyl phthalate, can be used as they are.
About 30% by weight is appropriate. Examples of the leveling agent include silicone oils such as dimethyl silicone oil and methylphenyl silicone oil, and polymers or oligomers having a perfluoroalkyl group in a side chain. 1
% By weight is appropriate.

In the photosensitive member of the present invention, an undercoat layer can be provided between the conductive support (31) and the photosensitive layer (charge transport layer or charge generation layer). The undercoat layer generally contains a resin as a main component. However, considering that the photosensitive layer is coated thereon with a solvent, these resins are resins having high solvent resistance to general organic solvents. desirable. Examples of such a resin include water-soluble resins such as polyvinyl alcohol, casein and sodium polyacrylate, alcohol-soluble resins such as copolymerized nylon and methoxymethylated nylon, polyurethane, melamine resin, phenol resin, alkyd-melamine resin, and epoxy resin. Curable resins that form a three-dimensional network structure, such as resins, are exemplified. In addition, in order to prevent moire and reduce residual potential, the undercoating layer includes titanium oxide, silica, alumina, zirconium oxide,
Fine powder pigments of metal oxides, such as tin oxide and indium oxide, may be added.

These undercoat layers can be formed by using a suitable solvent and a coating method as in the above-mentioned photosensitive layer. Further, a silane coupling agent, a titanium coupling agent, a chromium coupling agent or the like can be used as the undercoat layer in the present invention. In addition, the undercoat layer according to the present invention may be provided with Al ₂ O ₃ provided by anodic oxidation,
Organic substances such as polyparaxylylene (parylene) and Si
Those provided with an inorganic substance such as O ₂ , SnO ₂ , TiO ₂ , ITO, CeO ₂ by a vacuum thin film forming method can also be used favorably. In addition, known materials can be used. The thickness of the undercoat layer is suitably from 0 to 5 μm.

In the photoreceptor of the present invention, a protective layer may be provided on the photosensitive layer (charge transport layer or charge generation layer) for the purpose of protecting the photosensitive layer. Materials used for the protective layer include ABS resin, ACS resin, olefin-vinyl monomer copolymer, chlorinated polyether, allyl resin, phenol resin, polyacetal, polyamide, polyamideimide, polyacrylate, polyallyl sulfone, polybutylene, Polybutylene terephthalate, polycarbonate, polyether sulfone, polyethylene,
Examples of resins include polyethylene terephthalate, polyimide, acrylic resin, polymethylpentene, polypropylene, polyphenylene oxide, polysulfone, polystyrene, AS resin, butadiene-styrene copolymer, polyurethane, polyvinyl chloride, polyvinylidene chloride, and epoxy resin. . In addition to the protective layer, a fluorine resin such as polytetrafluoroethylene, a silicone resin, and a titanium oxide,
A dispersion of an inorganic material such as tin oxide or potassium titanate can be added. As a method for forming the protective layer, a normal coating method is employed. The thickness of the protective layer is 0.1 to
About 10 μm is appropriate. In addition to the above, known materials such as aC and a-SiC formed by a vacuum thin film forming method can be used as the protective layer.

In the photoreceptor of the present invention, an intermediate layer can be provided between the photosensitive layer (charge transport layer or charge generation layer) and the protective layer. The intermediate layer generally uses a binder resin as a main component. Examples of these resins include polyamide, alcohol-soluble nylon, water-soluble polyvinyl butyral, polyvinyl butyral, and polyvinyl alcohol. As a method for forming the intermediate layer, a normal coating method is employed as described above. The thickness of the intermediate layer is suitably about 0.05 to 2 μm.

In the present invention, antioxidants, plasticizers, lubricants, ultraviolet absorbers, low molecular weight compounds are added to each layer for the purpose of improving environmental resistance, especially for preventing a decrease in sensitivity and a rise in residual potential. Charge transport materials and leveling agents can be added. Representative materials of these compounds are described below. As an antioxidant that can be added to each layer, for example,
The following are mentioned, but are not limited to these.

(A) Phenol compound 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-4-ethylphenol, n-octadecyl-3- ( 4'-hydroxy-3 ', 5'-di-t-butylphenol),
2,2'-methylene-bis- (4-methyl-6-t-butylphenol), 2,2'-methylene-bis- (4-
Ethyl-6-t-butylphenol), 4,4′-thiobis- (3-methyl-6-t-butylphenol),
4,4′-butylidenebis- (3-methyl-6-t-butylphenol), 1,1,3-tris- (2-methyl-4-hydroxy-5-t-butylphenyl) butane,
1,3,5-trimethyl-2,4,6-tris (3,5
-Di-t-butyl-4-hydroxybenzyl) benzene, tetrakis- [methylene-3- (3 ', 5'-di-
[t-butyl-4'-hydroxyphenyl) propionate] methane, bis [3,3'-bis (4'-hydroxy-3'-t-butylphenyl) butyric acid] glycol ester, tocopherols and the like.

(B) Paraphenylenediamines N-phenyl-N'-isopropyl-p-phenylenediamine, N, N'-di-sec-butyl-p-phenylenediamine, N-phenyl-N-sec-butyl- p-
Phenylenediamine, N, N'-di-isopropyl-p
-Phenylenediamine, N, N'-dimethyl-N, N '
-Di-t-butyl-p-phenylenediamine and the like.

(C) Hydroquinones 2,5-di-t-octylhydroquinone, 2,6-didodecylhydroquinone, 2-dodecylhydroquinone, 2-dodecyl-5-chlorohydroquinone, 2-t
-Octyl-5-methylhydroquinone, 2- (2-octadecenyl) -5-methylhydroquinone and the like.

(D) Organic sulfur compounds Dilauryl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate, ditetradecyl-3,3'-thiodipropionate and the like.

(E) Organic phosphorus compounds Triphenylphosphine, tri (nonylphenyl) phosphine, tri (dinonylphenyl) phosphine, tricresylphosphine, tri (2,4-dibutylphenoxy) phosphine and the like.

Examples of the plasticizer that can be added to each layer include the following, but are not limited thereto. (A) Phosphate ester plasticizer triphenyl phosphate, tricresyl phosphate, trioctyl phosphate, octyl diphenyl phosphate, trichloroethyl phosphate, cresyl diphenyl phosphate, tributyl phosphate, tri-2-ethylhexyl phosphate, Triphenyl phosphate and the like.

(B) Phthalate ester plasticizer Dimethyl phthalate, diethyl phthalate, diisobutyl phthalate, dibutyl phthalate, diheptyl phthalate, di-2-ethylhexyl phthalate, diisooctyl phthalate, di-n-phthalate Octyl, dinonyl phthalate, diisononyl phthalate, diisodecyl phthalate, diundecyl phthalate, ditridecyl phthalate, dicyclohexyl phthalate, butyl benzyl phthalate, butyl lauryl phthalate, methyl oleyl phthalate, octyl decyl phthalate, dibutyl fumarate, Dioctyl fumarate and the like.

(C) Aromatic carboxylic acid ester plasticizers Trioctyl trimellitate, Tri-n trimellitate
-Octyl, octyl oxybenzoate and the like.

(D) Fatty acid dibasic ester plasticizer dibutyl adipate, di-n-hexyl adipate, di-2-ethylhexyl adipate, di-n-adipate
Octyl, n-octyl-n-octyl-n-decyl adipate, diisodecyl adipate, dicapryl adipate, di-2-ethylhexyl azelate, dimethyl sebacate,
Diethyl sebacate, dibutyl sebacate, di-n-octyl sebacate, di-2-ethylhexyl sebacate, di-2-ethoxyethyl sebacate, dioctyl succinate, diisodecyl succinate, dioctyl tetrahydrophthalate, dihydrotetrahydrophthalate -N-octyl and the like.

(E) Fatty acid ester derivatives butyl oleate, glycerin monooleate, methyl acetyl ricinoleate, pentaerythritol ester, dipentaerythritol hexaester,
Triacetin, tributyrin and the like.

(F) Oxyacid ester plasticizers Methyl acetyl ricinoleate, butyl acetyl ricinoleate, butyl phthalyl butyl glycolate, tributyl acetyl citrate and the like.

(G) Epoxy plasticizer Epoxidized soybean oil, epoxidized linseed oil, butyl epoxy stearate, decyl epoxy stearate, octyl epoxy stearate, benzyl epoxy stearate, dioctyl epoxy hexahydrophthalate, epoxy hexahydrophthalate Didecyl acid and the like.

(H) Dihydric alcohol ester plasticizers Diethylene glycol dibenzoate, triethylene glycol di-2-ethyl butyrate and the like.

(I) Chlorinated plasticizers Chlorinated paraffin, chlorinated diphenyl, chlorinated fatty acid methyl, methoxy chlorinated fatty acid methyl and the like.

(J) Polyester plasticizers Polypropylene adipate, polypropylene sepate, polyester, acetylated polyester and the like.

(K) Sulfonic acid derivatives p-toluenesulfonamide, o-toluenesulfonamide, p-toluenesulfonethylamide, o-toluenesulfonethylamide, toluenesulfone-N-ethylamide, p-toluenesulfon-N-cyclohexyl Amides and the like.

(L) Citric acid derivatives Triethyl citrate, triethyl acetyl citrate, tributyl citrate, tributyl acetyl citrate, tri-2-ethylhexyl acetyl citrate, n-octyldecyl acetyl citrate and the like.

(M) Others terphenyl, partially hydrogenated terphenyl, camphor, 2
-Nitrodiphenyl, dinonylnaphthalene, methyl abietic acid and the like.

Examples of the lubricant that can be added to each layer include the following, but are not limited thereto. (A) Hydrocarbon compounds Liquid paraffin, paraffin wax, microwax, low-polymerized polyethylene and the like. (B) Fatty acid compounds Lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid and the like. (C) Fatty acid amide compounds stearylamide, palmitylamide, oleinamide, methylenebisstearamide, ethylenebisstearamide and the like. (D) Ester-based compounds Lower alcohol esters of fatty acids, polyhydric alcohol esters of fatty acids, polyglycol esters of fatty acids, and the like. (E) Alcohol compounds Cetyl alcohol, stearyl alcohol, ethylene glycol, polyethylene glycol, polyglycerol and the like. (F) Metal soaps Lead stearate, cadmium stearate, barium stearate, calcium stearate, zinc stearate, magnesium stearate and the like. (G) Natural wax Carnauba wax, candelilla wax, beeswax, whale wax, Ibota wax, montan wax and the like. (H) Others Silicone compounds, fluorine compounds and the like.

The ultraviolet absorber which can be added to each layer includes
For example, the following may be mentioned, but it is not limited to them. (A) Benzophenone 2-hydroxybenzophenone, 2,4-dihydroxybenzophenone, 2,2 ′, 4-trihydroxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2,2′-dihydroxy-4 -Methoxybenzophenone and the like. (B) salicylate phenyl salicylate, 2,4-di-t-butylphenyl 3,5-di-t-butyl-4-hydroxybenzoate and the like. (C) benzotriazole-based (2′-hydroxyphenyl) benzotriazole,
(2′-hydroxy-5′-methylphenyl) benzotriazole, (2′-hydroxy-5′-ethylphenyl) benzotriazole, (2′-hydroxy-3′-
Tert-butyl-5'-methylphenyl) 5-chlorobenzotriazole and the like. (D) cyanoacrylate-based ethyl-2-cyano-3,3-diphenylacrylate, methyl-2-carbomethoxy-3- (paramethoxy) acrylate and the like. (E) Quencher (metal complex salt) Nickel (2,2′-thiobis (4-t-octyl) phenolate) normal butylamine, nickel dibutyldithiocarbamate, cobalt dicyclohexyldithiophosphate and the like. (F) HALS (hindered amine) bis (2,2,6,6-tetramethyl-4-piperidyl) separate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) separate, 1- [2 − ｛3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionyloxy {ethyl} -4- {3- (3,5-
Di-tert-butyl-4-hydroxyphenyl) propionyloxy {-2,2,6,6-tetramethylpyridine;
8-benzyl-7,7,9,9-tetramethyl-3-octyl-1,3,8-triazaspiro [4,5] undecane-2,4-dione, 4-benzoyloxy-2,
2,6,6-tetramethylpiperidine and the like.

Next, the electrophotographic method and the electrophotographic apparatus of the present invention will be described in detail with reference to the drawings. FIG. 3 is a schematic view for explaining the electrophotographic process and the electrophotographic apparatus of the present invention. Around the photosensitive member (1), a static elimination lamp (2), a charging charger (3), and an eraser ( 4), image exposure section (5), developing unit (6), pre-transfer charger (7), transfer charger (10), separation charger (11), separation claw (12), pre-cleaning charger (13), fur brush (14) Each unit such as a cleaning brush (15) is arranged. A toner image is transferred at a transfer position to the transfer paper (9) supplied to the photoconductor (1) by the registration roller (8). The following modified examples also belong to the category of the present invention.

In FIG. 3, the photoreceptor (1) is formed by laminating a charge generating layer containing titanyl phthalocyanine giving a specific X-ray diffraction spectrum and a charge transporting layer having a mobility satisfying the above-mentioned values on a conductive support. It is composed of a photosensitive layer. The photoreceptor (1) has a drum shape,
It may be in the form of a sheet or an endless belt.
Charger (3), pre-transfer charger (7), transfer charger (10), separation charger (11), and pre-cleaning charger (13) include corotron, scorotron, solid state charger (solid state charger), and charging A known means such as a roller is used. As the transfer means, generally, the above-mentioned charger can be used, but as shown in the figure, a combination of a transfer charger and a separation charger is effective.

Light sources such as an image exposure section (5) and a neutralizing lamp (2) include a fluorescent lamp, a tungsten lamp, a halogen lamp, a mercury lamp, a sodium lamp, a light emitting diode (LED), a semiconductor laser (LD), and an electro-optical device. A general light-emitting material such as luminescence (EL) can be used. To irradiate only light in a desired wavelength range, various filters such as a sharp cut filter, a band pass filter, a near infrared cut filter, a dichroic filter, an interference filter, and a color temperature conversion filter can be used. Such a light source and the like include, in addition to the steps shown in FIG.
The photoreceptor is irradiated with light by providing a step such as a charge removal step, a cleaning step, or a pre-exposure.

The toner developed on the photoreceptor (1) by the developing unit (6) is transferred to the transfer paper (9), but not all of the toner is transferred.
Some toner remains on the top. Such toner is removed from the photoreceptor by the fur brush (14) and the blade (15). Cleaning may be performed only with a cleaning brush, and a known brush such as a fur brush or a mag fur brush is used as the cleaning brush. When a positive (negative) charge is applied to the electrophotographic photosensitive member and image exposure is performed, a positive (negative) electrostatic latent image is formed on the surface of the photosensitive member. If this is developed with negative (positive) polarity toner (electrostatic fine particles), a positive image can be obtained,
If the toner is developed with positive (negative) polarity toner, a negative image can be obtained. A known method can be applied to such a developing unit, and a known method is also used for the charge removing unit.

FIG. 4 shows another example of the electrophotographic process according to the present invention. The photoreceptor (21) comprises a photosensitive layer in which a charge generation layer containing titanyl phthalocyanine giving a specific X-ray diffraction spectrum on a conductive support and a charge transport layer having a mobility satisfying the above value are laminated. And driven by the driving rollers (22a) and (22b), charging by the charger (23), image exposure by the light source (24), development (not shown), transfer using the charger (25), and light source ( Exposure before cleaning by 26), cleaning by brush (27), and static elimination by light source (28) are repeatedly performed. In FIG. 4, the photosensitive member (21) (of course, in this case, the support is translucent) is irradiated with light for pre-cleaning exposure from the support side.

FIGS. 6 and 7 illustrate an electrophotographic apparatus and a process cartridge using a charging roller in the present invention in detail. A charging member (38) is placed in contact with or close to the photoconductor. If necessary, the pre-transfer charger (7), the transfer belt, and the pre-cleaning charger (1)
3) is disposed, and known means such as a corotron, a scorotron, a solid state charger (solid state charger), and a charging roller are used. When charging the photoreceptor by the charging member, charging the photoreceptor by an electric field in which an AC component is superposed on a DC component on the charging member is effective in reducing charging unevenness. Further, in consideration of the adhesion of the uncleaned toner on the photoconductor to the charging member, the charging member is more excellent in the non-contact proximity arrangement than in contact with the photoconductor.

The above-described electrophotographic process is an example of the embodiment of the present invention, and other embodiments are of course possible. For example, in FIG. 4, the pre-cleaning exposure is performed from the support side, but this may be performed from the photosensitive layer side, or the image exposure and the irradiation of the charge removing light may be performed from the support side.

On the other hand, the light irradiation step includes image exposure, pre-cleaning exposure, and charge removal exposure. However, in addition to this, a pre-transfer exposure, a pre-exposure of image exposure, and other known light irradiation steps are provided to provide a light irradiation step. Light irradiation can also be performed on the body.

The image forming means of the present invention as described above may be fixedly incorporated in a copying apparatus, a facsimile, or a printer, or may be incorporated in the apparatus in the form of a process cartridge. The process cartridge is one device (part) that includes a photoconductor and further includes a charging unit, an exposure unit, a developing unit, a transfer unit, a cleaning unit, and a charge removing unit. There are many shapes and the like of the process cartridge, but as a general example,
One shown in FIG. In this example, the photoreceptor (16) was formed by laminating a charge generation layer containing titanyl phthalocyanine giving a specific X-ray diffraction spectrum and a charge transport layer having a mobility satisfying the above-mentioned values on a conductive support. It consists of a photosensitive layer.

[0125]

The present invention will be described below with reference to examples.
The present invention is not limited by the embodiments. All parts are parts by weight. [Synthesis of titanyl phthalocyanine] First, a specific synthesis example of titanyl phthalocyanine in the present invention will be described.

[Synthesis Examples 1 to 6, and Comparative Synthesis Examples 1 and 2]
29.2 g of 1,3-diiminoisoindoline and 200 ml of sulfolane are mixed, and 20.4 g of titanium tetrabutoxide is added dropwise under a nitrogen stream. After completion of the dropwise addition, the temperature was gradually raised to 180 ° C, and the reaction was carried out by stirring for 5 hours while maintaining the reaction temperature between 170 ° C and 180 ° C. After the reaction, the precipitate was filtered after standing to cool, washed with chloroform until the powder turned blue, washed with methanol several times, further washed with hot water at 80 ° C. several times, and dried. Crude titanyl phthalocyanine was obtained. The crude titanyl phthalocyanine was dissolved in 20 times the volume of concentrated sulfuric acid, added dropwise to 100 volumes of the ice water with stirring, and the precipitated crystals were filtered, and then repeatedly washed with water until the washing solution became neutral. I got 2 g of the obtained wet cake was added to 20 g of the organic solvent shown in Table 7, and stirred for 4 hours. 100 g of methanol was added thereto, and the mixture was stirred for 1 hour, filtered, and dried to obtain a titanyl phthalocyanine powder of the present invention.

[0127] The obtained titanyl phthalocyanine powder was
The X-ray diffraction spectrum was measured under the following conditions. X-ray tube: Cu, voltage: 50 kV, current: 30 mA, scanning speed: 2 ° / min, scanning range: 3 ° to 40 °, time constant:
2 seconds

From the X-ray diffraction spectrum, the peak position on the lowest angle side and the peak intensities at 26.3 ° and 28.6 ° were the same.
The ratio to the peak intensity at 7.2 ° was determined as follows. First, the spectrum is subjected to baseline correction, and 2
Determine peak intensities at 6.3 °, 27.2 ° and 28.6 °. This was simply compared to determine the percentage as a percentage. Table 7 also shows the results. The X-ray diffraction spectra of the dried wet cake and the pigments prepared in Synthesis Examples 1 to 6 and Comparative Synthesis Examples 1 and 2 are shown in FIG.
To FIG. Since the spectra of Synthesis Examples 1 to 6 are almost the same, an X-ray diffraction spectrum of the pigment prepared in Synthesis Example 4 is shown in FIG. 7 as a representative example.

As shown in FIG. 7, each of the pigments produced in Synthesis Examples 1 to 6 showed the lowest angle peak at 7.3 °, and
No peak is shown between 4 ° and 9.4 °. Also,
The intensity of the 26.3 ° peak relative to the 27.2 ° peak is 1
0% or less, and the intensity of the 28.6 ° peak relative to the 27.2 ° peak was less than 20%.

[0130]

[Table 7]

[Comparative Synthesis Example 3] JP-A-1-299874
A pigment was prepared according to the method described in Japanese Patent Application Laid-Open Publication No. H11-146,036. That is, the wet cake prepared in Synthesis Example 1 was dried, 1 g of the dried product was added to 50 g of polyethylene glycol,
A sand mill was performed with g glass beads. After the crystallization, the pigment was washed with dilute sulfuric acid and an aqueous solution of ammonium hydroxide in that order and dried to obtain a pigment.

[Comparative Synthesis Example 4] JP-A-3-269064
A pigment was prepared according to the method described in Japanese Patent Application Laid-Open Publication No. H11-146,036. That is, the wet cake prepared in Synthesis Example 1 was dried, and 1 g of the dried product was replaced with 10 g of ion-exchanged water and 1 g of monochlorobenzene.
After stirring for 1 hour (50 ° C.) in a mixed solvent of the above, the mixture was washed with methanol and ion-exchanged water and dried to obtain a pigment.

Comparative Synthesis Example 5 A pigment was produced according to the method described in JP-A-2-8256. That is, 9.8 g of phthalodinitrile and 75 m of 1-chloronaphthalene
and 2.2 ml of titanium tetrachloride in a nitrogen stream.
Is dropped. After the completion of dropping, the temperature is gradually raised to 200 ° C.
The reaction was carried out with stirring for 3 hours while maintaining the reaction temperature between 200 ° C and 220 ° C. After the reaction is completed, allow to cool to 130 ° C
When it became hot, it was filtered while hot, then washed with 1-chloronaphthalene until the powder turned blue, then washed with methanol several times, further washed with hot water of 80 ° C. several times, and dried, A pigment was obtained.

[Comparative Synthesis Example 6] JP-A-64-17066
A pigment was prepared according to the method described in Japanese Patent Application Laid-Open Publication No. H11-146,036. That is, 5 parts of α-type TiOPc was added to a 100 g of a sand grinder together with 10 g of salt and 5 g of polyethylene glycol.
A crystal conversion treatment was performed at 10 ° C. for 10 hours. This is washed with ion-exchanged water and methanol, purified with a dilute sulfuric acid aqueous solution,
After washing with ion-exchanged water until the acid content disappeared, it was dried to obtain a pigment.

The X-ray diffraction spectra of the pigments prepared in Comparative Synthesis Examples 3 to 6 were measured in the same manner as described above, and it was confirmed that the spectra were the same as those described in the respective publications. Table 8 shows the results.

[0136]

[Table 8]

[Synthesis Examples 7 and 8] Pigments were synthesized by changing the conditions of the tetrahydrofuran treatment in Synthesis Example 3. Each diffraction spectrum was similar to FIG. Table 9 shows the relationship between the respective peak intensities.

[0138]

[Table 9]

[Examples in which the charge transport layer contains a low molecular charge transport material and an inert polymer] [Examples 1 to 8 and Comparative Examples 1 and 2] An undercoat layer having the following composition on an electroformed nickel belt Coating liquid, charge generation layer coating liquid,
And a charge transport layer coating solution are sequentially applied and dried, and
, A 0.3 μm charge generation layer and a 25 μm charge transport layer.

Undercoat layer coating liquid Titanium dioxide powder 15 parts Polyvinyl butyral 6 parts 2-butanone 150 parts

Coating solution for charge generation layer Pigment synthesized in Synthesis Examples 1 to 8 and Comparative Synthesis Examples 1 and 15 15 parts polyvinyl butyral 10 parts 600 parts methyl ethyl ketone Polyvinyl butyral was dissolved in methyl ethyl ketone,
Next, the synthesized pigments were added and dispersed by bead milling.

Coating solution for charge transport layer A type polycarbonate 10 parts Methylene chloride 80 parts Charge transport material of the following structural formula 7 parts

[0143]

Embedded image

Example 9 An electrophotographic photosensitive member was produced in the same manner as in Example 2, except that the charge transporting material in the coating liquid for the charge transporting layer in Example 2 was changed to the following.

[0145]

Embedded image

Example 10 An electrophotographic photoreceptor was produced in the same manner as in Example 2, except that the charge transport material in the coating liquid for the charge transport layer in Example 2 was changed to the following.

[0147]

Embedded image

Example 11 An electrophotographic photoreceptor was produced in the same manner as in Example 2, except that the charge transport material in the coating liquid for the charge transport layer in Example 2 was changed to the following.

[0149]

Embedded image

Example 12 An electrophotographic photoreceptor was produced in the same manner as in Example 2, except that the charge transport material in the coating liquid for the charge transport layer in Example 2 was changed to the following.

[0151]

Embedded image

Example 13 An electrophotographic photoreceptor was produced in the same manner as in Example 2 except that the charge transporting material in the coating solution for the charge transporting layer in Example 2 was changed to the following.

[0153]

Embedded image

[Comparative Examples 3 to 8] Electrophotographic photosensitive members were prepared in the same manner as in Examples 1 to 6, except that the charge transport material in the charge transport layer coating solution in Examples 1 to 6 was changed to the following. did.

[0155]

Embedded image

The electrophotographic photosensitive members produced in Examples 1 to 13 and Comparative Examples 1 to 8 were mounted in the electrophotographic process shown in FIG. 4 (however, there was no pre-cleaning exposure), and the image exposure light source was a 780 nm semiconductor laser ( In order to measure the surface potential of the photoconductor immediately before development, a probe of a surface voltmeter was inserted. Printing was continuously performed on 10,000 sheets, and the surface potentials of the image-exposed portion and the non-image-exposed portion at that time were measured initially and after 10,000 sheets. Table 10 shows the results. In addition, a sample for mobility measurement having the same composition as the charge transport layer used for each photoconductor was prepared,
Mobility at the electric field strength corresponding to the image non-exposed area (cm
² / Vsec). The results are also shown in Table 10.

[0157]

[Table 10]

Table 10 shows that the electrophotographic photosensitive members of Examples 1 to 13 maintain a stable surface potential even after repeated use. However, in the electrophotographic photoreceptors of Examples 7 and 8, the surface potential of the exposed portion was reduced in Examples 1 to 6 and Example 10.
It can be seen that this is slightly higher than that of No.-13.

[Example 14 and Comparative Examples 9 and 10] An undercoat layer coating solution, a charge generation layer coating solution, and a charge transport layer coating solution having the following compositions were sequentially coated and dried on an aluminum cylinder. 0.5 μm intermediate layer, 0.2 μm charge generation layer,
An electrophotographic photosensitive member comprising a 28 μm charge transport layer was formed.

Coating solution for undercoat layer Titanium dioxide powder 400 parts Melamine resin 65 parts Alkyd resin 120 parts 2-butanone 400 parts

Coating solution for charge generation layer Pigment synthesized in Synthesis Example 2 and Comparative Synthesis Examples 3 and 4 15 parts Polyvinyl butyral 10 parts 600 parts n-propyl acetate Polyvinyl butyral was dissolved in n-propyl acetate and then synthesized. The pigment was added and dispersed by bead milling.

Coating solution for charge transport layer Z-type polycarbonate 10 parts Methylene chloride 80 parts Charge transport material of the following structural formula 7 parts

[0163]

Embedded image

Example 15 An electrophotographic photosensitive member was produced in the same manner as in Example 14, except that the coating solution for the charge transport layer in Example 14 was changed to the one having the following composition.

Coating solution for charge transport layer Z-type polycarbonate 10 parts Methylene chloride 80 parts Charge transport material of the following structural formula 8 parts

[0166]

Embedded image

Example 16 An electrophotographic photosensitive member was produced in the same manner as in Example 14, except that the coating solution for the charge transport layer in Example 14 was changed to the one having the following composition.

Coating solution for charge transport layer Z-type polycarbonate 10 parts Methylene chloride 80 parts Charge transport material of the following structural formula 10 parts

[0169]

Embedded image

The above Examples 14 to 16 and Comparative Examples 9 and 1
Each electrophotographic photosensitive member of No. 0 was mounted in the electrophotographic process shown in FIG. 3 (however, the image exposure light source was an LD emitting at 780 nm), and 12,000 sheets were printed continuously, and the image at that time was printed. Evaluation was made at the initial stage and after 12,000 sheets. Table 11 shows the results.

[0171]

[Table 11]

Table 11 shows that the electrophotographic photosensitive members of Examples 14 and 15 maintain good images even after repeated use. Although the photoconductor of Example 16 is within a range that does not cause any particular problem, it can be seen that the image after repeated use is slightly inferior to the photoconductors of Examples 14 and 15.

Example 17 After the surface of an aluminum cylinder was anodized, a sealing treatment was performed. The following charge generation layer coating solution and charge transport layer coating solution were sequentially applied and dried to form a 0.2 μm charge generation layer and a 20 μm charge transport layer, respectively. Produced.

Coating solution for the charge generation layer 15 parts of the pigment synthesized in Synthesis Example 6 10 parts of polyvinyl butyral 10 parts 600 parts of n-butyl acetate Polyvinyl butyral was dissolved in n-butyl acetate, and then the synthesized pigment was added, and the mixture was mixed by beads milling Dispersion was performed.

Charge transport layer coating solution Polycarbonate 10 parts Methylene chloride 80 parts Charge transport material of the following structural formula 7 parts

[0176]

Embedded image

Example 18 An electrophotographic photosensitive member was prepared in the same manner as in Example 17, except that the coating solution for the charge transport layer in Example 17 was changed to the following.

Charge transport layer coating solution Polycarbonate 10 parts Methylene chloride 80 parts Charge transport material of the following structural formula 7 parts

[0179]

Embedded image

Example 19 An electrophotographic photosensitive member was prepared in the same manner as in Example 17, except that the coating solution for the charge transport layer in Example 17 was changed to the following.

Coating solution for charge transport layer Polycarbonate 10 parts Methylene chloride 80 parts Charge transport material of the following structural formula 7 parts

[0182]

Embedded image

Example 20 An electrophotographic photosensitive member was produced in the same manner as in Example 17, except that the coating liquid for the charge transport layer in Example 17 was changed to the following.

Charge transport layer coating solution Polycarbonate 10 parts Methylene chloride 80 parts Charge transport material of the following structural formula 7 parts

[0185]

Embedded image

Example 21 An electrophotographic photosensitive member was prepared in the same manner as in Example 17, except that the coating solution for the charge transport layer in Example 17 was changed to the following.

Charge transport layer coating liquid Polycarbonate 10 parts Methylene chloride 80 parts Charge transport material of the following structural formula 7 parts

[0188]

Embedded image

Example 22 An electrophotographic photosensitive member was prepared in the same manner as in Example 17, except that the coating solution for the charge transport layer in Example 17 was changed to the following.

Charge transport layer coating liquid Polycarbonate 10 parts Methylene chloride 80 parts Charge transport material of the following structural formula 7 parts

[0191]

Embedded image

Comparative Example 11 An electrophotographic photosensitive member was produced in the same manner as in Example 17, except that the charge generation layer in Example 17 was changed to the following.

Coating solution for charge generation layer 15 parts of pigment synthesized in Comparative Synthesis Example 5 10 parts of polyvinyl butyral 10 parts 600 parts of n-butyl acetate Polyvinyl butyral was dissolved in n-butyl acetate, and then the respective synthesized pigments were added, followed by bead milling. Was carried out.

[Comparative Example 12] An electrophotographic photosensitive member was produced in the same manner as in Example 17, except that the charge generation layer in Example 17 was changed to the following.

Coating Solution for Charge Generating Layer 15 parts of pigment synthesized in Comparative Synthesis Example 6 10 parts of polyvinyl butyral 10 parts 600 parts of n-butyl acetate Polyvinyl butyral was dissolved in n-butyl acetate, and then the respective synthesized pigments were added, followed by bead milling. Was carried out.

Comparative Example 13 An electrophotographic photosensitive member was produced in the same manner as in Example 17, except that the coating solution for the charge transport layer in Example 17 was changed to the following.

Charge transport layer coating liquid Polycarbonate 10 parts Methylene chloride 80 parts Charge transport material of the following structural formula 7 parts

[0198]

Embedded image

Comparative Example 14 An electrophotographic photosensitive member was prepared in the same manner as in Example 17, except that the coating solution for the charge transport layer in Example 17 was changed to the following.

Charge transport layer coating solution Polycarbonate 10 parts Methylene chloride 80 parts Charge transport material of the following structural formula 7 parts

[0201]

Embedded image The electrophotographic photosensitive members produced in Examples 17 to 22 and Comparative Examples 11 to 14 were mounted on an electrophotographic process cartridge shown in FIG. 5, and then mounted on an image forming apparatus. However, the image exposure light source is a 780 nm semiconductor laser (polygon
For image writing with a mirror), a probe of a surface voltmeter was inserted so that the surface potential of the photoconductor immediately before development could be measured. Printing was continuously performed on 15,000 sheets, and the surface potentials of the image-exposed portion and the non-image-exposed portion at that time were initially set to 1
It was measured after 5,000 sheets. Further, as in the case of Example 1, the mobility of the charge transport layer was measured. Table 12 shows the results.

[0202]

[Table 12]

From Table 12, it can be seen that the electrophotographic photosensitive members of Examples 17 to 22 maintain a stable surface potential even after repeated use.

[Examples in which the charge transport layer contains a polymer charge transport material] [Examples 23 to 30 and Comparative Examples 15 and 16] Undercoat layer coating solution having the following composition on electroformed nickel belt, charge generation The layer coating solution and the charge transport layer coating solution are sequentially applied and dried, and a 4 μm intermediate layer, a 0.3 μm charge generation layer, and a 25 μm
An electrophotographic photoreceptor comprising a m. m of the charge transport layer was formed.

Undercoat layer coating liquid Titanium dioxide powder 15 parts Polyvinyl butyral 6 parts 2-butanone 150 parts

Coating Solution for Charge Generating Layer Pigment synthesized in Synthesis Examples 1 to 8 and Comparative Synthesis Examples 1 and 2 15 parts Polyvinyl butyral 10 parts Methyl ethyl ketone 600 parts Polyvinyl butyral was dissolved in methyl ethyl ketone,
Next, the synthesized pigments were added and dispersed by bead milling.

Coating solution for charge transport layer 100 parts of methylene chloride 10 parts of polymer charge transport material having the following structural formula

[0208]

Embedded image

Example 31 An electrophotographic photosensitive member was produced in the same manner as in Example 25, except that the polymer charge transport material in the charge transport layer coating solution in Example 25 was changed to the following.

[0210]

Embedded image

Example 32 An electrophotographic photosensitive member was produced in the same manner as in Example 23 except that the polymer charge transporting material in the coating solution for the charge transporting layer in Example 23 was changed to the following.

[0212]

Embedded image

[Comparative Examples 15 and 16] The same procedures as in Example 23 were carried out except that the polymer charge transport material in the charge transport layer coating liquid in Example 23 was changed to that of Comparative Synthesis Example 1 and Comparative Synthesis Example 2. Similarly, an electrophotographic photosensitive member was produced.

The electrophotographic photosensitive members produced in Examples 23 to 32 and Comparative Examples 15 and 16 were mounted in the electrophotographic process shown in FIG. 4 (however, there was no pre-cleaning exposure), and the image exposure light source was a 780 nm semiconductor laser ( In order to measure the surface potential of the photoconductor immediately before development, a probe of a surface voltmeter was inserted. Printing was continuously performed on 25,000 sheets, and the surface potentials of the image-exposed portion and the non-image-exposed portion at that time were set to the initial and 25
It was measured after 000 sheets. Table 13 shows the results. A sample for mobility measurement having the same composition as the charge transport layer used for each photoconductor was prepared, and the mobility (cm ² / Vsec) at an electric field intensity of 5 × 10 ⁵ (V / cm) was measured. . Table 13 also shows the results.

[0215]

[Table 13]

Table 13 shows that the electrophotographic photosensitive members of Examples 23 to 32 maintain a stable surface potential even after repeated use. Further, the electrophotographic photoreceptors of Examples 29 and 30 correspond to Examples 23 to 28 and Examples 31 and 3, respectively.
It can be seen that the potential of the exposed portion is slightly higher than that of the electrophotographic photosensitive member of No. 2.

Example 33 and Comparative Examples 17 and 18 An undercoat layer coating solution, a charge generation layer coating solution, and a charge transport layer coating solution having the following compositions were sequentially applied onto an aluminum cylinder.
After drying, an electrophotographic photosensitive member comprising a 3.5 μm intermediate layer, a 0.2 μm charge generation layer, and a 28 μm charge transport layer was formed.

Undercoat layer coating liquid Titanium dioxide powder 400 parts Melamine resin 65 parts Alkyd resin 120 parts 2-butanone 400 parts

Coating Solution for Charge Generating Layer Pigment synthesized in Synthesis Example 5 and Comparative Synthesis Examples 3 and 4 15 parts polyvinyl butyral 10 parts 600 parts n-propyl acetate Polyvinyl butyral was dissolved in n-propyl acetate and then synthesized. The pigment was added and dispersed by bead milling.

Coating solution for charge transport layer 100 parts of methylene chloride 10 parts of polymer charge transport material having the following structural formula

[0221]

Embedded image

Example 34 An electrophotographic photosensitive member was produced in the same manner as in Example 33, except that the polymer charge transporting substance in the coating liquid for the charge transporting layer in Example 33 was changed to the following.

[0223]

Embedded image

Comparative Example 19 An electrophotographic photosensitive member was produced in the same manner as in Example 33, except that the coating liquid for the charge transport layer in Example 33 was changed to the one having the following composition.

Coating solution for charge transport layer A type polycarbonate 10 parts Methylene chloride 80 parts Charge transport material of the following structural formula 10 parts

[0226]

Embedded image

The above Examples 33 and 34 and Comparative Examples 17 to
Each of the 19 electrophotographic photosensitive members was mounted on the electrophotographic process shown in FIG. 4 (however, an image exposure light source was an LD emitting at 780 nm), and 50,000 sheets were continuously printed, and the image at that time was printed. Was evaluated at the initial stage and after 40,000 sheets. Table 1 shows the results
It is shown in FIG.

[0228]

[Table 14]

From Table 14, it can be seen that the electrophotographic photosensitive members of Examples 32 and 33 maintain good images even after repeated use. Further, the change in the thickness of the charge transport layer of the photoconductors of Example 32 and Comparative Example 19 due to printing of 80,000 sheets was also examined. The photoconductor of Comparative Example 19 was about twice as large as the photoconductor of Example 32. The degree of wear was large.

Example 34 After the surface of an aluminum cylinder was anodized, a sealing treatment was performed. The following charge generation layer coating solution and charge transport layer coating solution were sequentially applied and dried to form a 0.2 μm charge generation layer and a 20 μm charge transport layer, respectively. Produced.

Coating solution for charge generation layer 15 parts of pigment synthesized in Synthesis Example 2 10 parts of polyvinyl butyral 10 parts 600 parts of n-butyl acetate Polyvinyl butyral was dissolved in n-butyl acetate, and then the synthesized pigments were added, followed by bead milling. Dispersion was performed.

Coating solution for charge transport layer 100 parts of methylene chloride 10 parts of polymer charge transport material having the following structural formula

[0233]

Embedded image

Example 35 An electrophotographic photoreceptor was produced in the same manner as in Example 34, except that the polymer charge transporting material in the coating liquid for the charge transporting layer in Example 34 was changed to the following.

[0235]

Embedded image

Example 36 An electrophotographic photoreceptor was produced in the same manner as in Example 34, except that the polymer charge transport material in the coating liquid for the charge transport layer in Example 34 was changed to the following.

[0237]

Embedded image

Comparative Example 20 An electrophotographic photosensitive member was produced in the same manner as in Example 34 except that the charge generation layer in Example 34 was changed to the following.

Coating solution for charge generation layer 15 parts of pigment synthesized in Comparative Synthesis Example 5 10 parts of polyvinyl butyral 10 parts 600 parts of n-butyl acetate Polyvinyl butyral was dissolved in n-butyl acetate, and then the respective synthesized pigments were added, followed by bead milling. Was carried out.

[Comparative Example 21] An electrophotographic photosensitive member was produced in the same manner as in Example 34 except that the charge generation layer in Example 34 was changed to the following.

Coating solution for charge generation layer 15 parts of pigment synthesized in Comparative Synthesis Example 6 10 parts of polyvinyl butyral 10 parts 600 parts of n-butyl acetate Polyvinyl butyral was dissolved in n-butyl acetate, and then the respective synthesized pigments were added, followed by bead milling. Was carried out.

The electrophotographic photosensitive members produced in Examples 34 to 36 and Comparative Examples 20 and 21 were mounted on an electrophotographic process cartridge shown in FIG. 5, and then mounted on an image forming apparatus. A 780 nm semiconductor laser (image writing by a polygon mirror) was used as an image exposure light source, and a probe of a surface voltmeter was inserted so that the surface potential of the photoconductor immediately before development could be measured. Printing was continuously performed on 25,000 sheets, and the surface potentials of the image exposed portion and the image non-exposed portion at that time were measured at the initial stage and after 25,000 sheets. In addition, a sample for mobility measurement having the same composition as the charge transport layer used for each photoconductor was prepared, and the mobility (cm ² / Vsec) at an electric field intensity corresponding to the image non-exposed area was measured. The results are shown in Table 15.

[0243]

[Table 15]

From Table 15, it can be seen that the electrophotographic photosensitive members of Examples 34 to 36 maintain a stable surface potential even after repeated use.

Example 37 The electrophotographic photosensitive member produced in Example 14 was mounted on the apparatus shown in FIG. 10 and charged under the following conditions, and an image exposure light source was a 780 nm semiconductor laser (image writing using a polygon mirror). ), 10,000 sheets were continuously printed in the same manner as in Example 14, and the image was evaluated. The charging member is in contact with the photoconductor.

Charging conditions: DC bias: -900 V AC bias: 1.8 kV (peak to peak) Frequency 2 kHz The images at the initial stage and after 10,000 sheets were all good. Further, the ozone odor was small and good as compared with the test of Example 14.

Example 38 Evaluation was performed in the same manner as in Example 37, except that the charging member was arranged in proximity to the photoreceptor surface at a distance of 100 μm. The images at the initial stage and after 10,000 copies were all good.
In addition, the charging roller was less contaminated than in the case of Example 37. For this reason, in Example 38, an abnormal image based on the contamination of the charging roller, which was slightly recognized after 10,000 sheets of Example 37, was not recognized at all, and the image was further excellent.

[Embodiment 39] Evaluation was made in the same manner as in the embodiment 38, except that the conditions for applying the AC bias were not changed. As a result, a good image was obtained without any problem in the initial image.However, when a halftone image was output after 10,000 sheets, there was no problem in practical use, but slight image density unevenness was recognized. Was done.

Example 40 The electrophotographic photosensitive member prepared in Example 17 was mounted on an image forming apparatus by mounting a process cartridge for an electrophotographic apparatus shown in FIG. 11, and charging was performed under the following conditions. Was used as a 780 nm semiconductor laser (image writing with a polygon mirror), and 10,000 sheets were continuously printed in the same manner as in Example 17 to evaluate the image. The charging member is in contact with the photoconductor.

Charging conditions: DC bias: -850 V AC bias: 2.0 kV (peak to peak) Frequency 2 kHz The images at the initial stage and after 10,000 copies were all good. In addition, the ozone odor was small and good when the test of Example 17 was performed.

Example 41 Evaluation was performed in the same manner as in Example 40, except that the charging member was arranged close to the surface of the photoreceptor at a distance of 100 μm. The images at the initial stage and after 10,000 copies were all good.
In addition, the charging roller was less contaminated than in the case of Example 40. For this reason, in Example 41, an abnormal image based on the contamination of the charging roller, which was slightly recognized after 10,000 sheets of Example 40, was not recognized at all, and the image was further excellent.

Example 42 Evaluation was made in the same manner as in Example 41, except that the conditions for charging were changed so that no AC bias was applied. As a result, a good image was obtained without any problem in the initial image.However, when a halftone image was output after 10,000 sheets, there was no problem in practical use, but slight image density unevenness was recognized. Was done.

[0253]

As has been apparent from the detailed and concrete description, according to the present invention, a charge generation layer containing titanyl phthalocyanine giving a specific X-ray diffraction spectrum, and a polymer charge transport material are provided. By using the contained charge transport layer, an electrophotographic photoreceptor that is stable and has high abrasion resistance, which does not lose high sensitivity and does not cause a decrease in chargeability and an increase in residual potential even when repeatedly used, is provided. Further, by using the above-mentioned photoreceptor, there is provided a stable electrophotographic method which does not cause a decrease in chargeability and an increase in residual potential even when repeatedly used without losing high sensitivity. Further, in an electrophotographic apparatus in which a charging means is placed in contact with or close to a photoreceptor, an electron having a charge transport layer having a specific mobility using titanyl phthalocyanine giving a specific X-ray diffraction spectrum as a charge generating substance. By using a photographic photoreceptor, an electrophotographic apparatus capable of obtaining a stable image with less dielectric breakdown even after repeated use without losing high sensitivity is provided, and the photoreceptor is maintained while maintaining the above characteristics. And a highly durable electrophotographic apparatus having improved abrasion resistance. Furthermore, there is provided a stable electrophotographic apparatus and a process cartridge for the electrophotographic apparatus which do not cause a decrease in chargeability and an increase in residual potential even when repeatedly used without losing high sensitivity.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view illustrating a configuration example of an electrophotographic photosensitive member of the present invention.

FIG. 2 is a cross-sectional view showing another example of the configuration of the electrophotographic photosensitive member of the present invention.

FIG. 3 is a schematic view for explaining an electrophotographic process and an electrophotographic apparatus of the present invention.

FIG. 4 is a schematic view showing another example of the electrophotographic process according to the present invention.

FIG. 5 is a view showing a process cartridge of the present invention.

FIG. 6 is another schematic diagram for explaining the electrophotographic process and the electrophotographic apparatus of the present invention.

FIG. 7 is another view showing the process cartridge of the present invention.

FIG. 8 is a view showing an X-ray diffraction spectrum of a dried wet cake.

FIG. 9 is a view showing an X-ray diffraction spectrum of the pigment produced in Synthesis Example 4.

FIG. 10 is a view showing an X-ray diffraction spectrum of the pigment produced in Comparative Synthesis Example 1.

FIG. 11 is a view showing an X-ray diffraction spectrum of the pigment produced in Comparative Synthesis Example 2.

[Explanation of symbols]

 REFERENCE SIGNS LIST 1 photoconductor 2 static elimination lamp 3 charging charger 4 eraser 5 image exposure unit 6 developing unit 7 pre-transfer charger 8 registration roller 9 transfer paper 10 transfer charger 11 separation charger 12 separation claw 13 pre-cleaning charger 14 fur brush 15 cleaning brush 16 photoconductor 17 Charging Charger 18 Cleaning Brush 19 Image Exposure Unit 20 Developing Roller 21 Photoconductor 22a Driving Roller 22b Driving Roller 23 Charging Charger 24 Image Exposure Source 25 Transfer Charger 26 Pre-Cleaning Exposure 27 Cleaning Brush 28 Discharge Light Source 31 Conductive Support 35 Charge Generation Layer 37 Charge transport layer 38 Charging member 39 Transfer belt 40 Charging member 41 Transfer roller

 ──────────────────────────────────────────────────の Continuing on the front page (72) Inventor Rokutanen 1-3-6 Nakamagome, Ota-ku, Tokyo F-term in Ricoh Co., Ltd. (Reference) 2H068 AA19 AA20 AA28 BA12 BA13 BA14 BA39 FA01 FB07 FB08

Claims (22)

[Claims] 1. An electrophotographic photoreceptor comprising a conductive support and a charge generating layer containing at least a charge generating substance and a charge transporting layer containing a low molecular charge transporting substance and an inert polymer. The layer is CuKα characteristic X-rays (wavelength 1.
514 °) and a diffraction peak at a Bragg angle 2θ (±
0.2 °) and has a maximum diffraction peak at least at 27.2 °, and 7.3 as the lowest angle diffraction peak.
With a peak at 26.3 ° and a peak at 26.3 °,
The electric field at the time of image light writing containing titanyl phthalocyanine whose peak intensity at 26.3 ° is 1 to 10% with respect to the peak intensity at 27.2 ° at the time of actual use of the electrophotographic photosensitive member An electrophotographic photoreceptor, wherein the mobility of the charge transport layer in the strength is 1 × 10 ⁻⁵ (cm / Vsec) or more. 2. 9.4 ° of the titanyl phthalocyanine
The electrophotographic photoreceptor according to claim 1, wherein a diffraction peak in a lower angle side region is 7.3 °. 3. The method according to claim 2, wherein the titanyl phthalocyanine is 7.4.
2. The electrophotographic photoreceptor according to claim 1, wherein the electrophotographic photoreceptor has no peak in the range of -9.4 [deg.]. 4. The method according to claim 1, wherein the titanyl phthalocyanine is 28.
When a peak is simultaneously present at 6 °, the intensity is 27.
The electrophotographic photoreceptor according to any one of claims 1 to 3, wherein the intensity is less than 20% of the intensity at 2 °. 5. The electrophotographic photosensitive member according to claim 1, wherein the titanyl phthalocyanine is synthesized without using a titanium halide. 6. The electrophotographic photosensitive member according to claim 1, wherein the charge transporting material is a compound represented by the following general formula (I). Embedded image (Wherein R ₁ , R ₂ , R ₃ and R ₄ represent a hydrogen atom, a substituted or unsubstituted lower alkyl group, a substituted or unsubstituted aryl group, and Ar ₁ represents a substituted or unsubstituted aryl group. , Ar ₂ represents a substituted or unsubstituted arylene group, R ₁ and Ar ₁ may together form a ring, and k is an integer of 0 or 1.) 7. The electrophotographic photosensitive member according to claim 1, wherein the charge transporting material is a compound represented by the following general formula (II). Embedded image (Wherein, R ₅ represents a lower alkyl group, a lower alkoxy group or a halogen atom, 1 represents an integer of 0 to 4,
₆ , R ₇ may be the same or different and represent a hydrogen atom, a lower alkyl group, a lower alkoxy group or a halogen atom. ) 8. The charge transport material according to the following general formula (III)
The electrophotographic photoreceptor according to any one of claims 1 to 5, which is a compound represented by the following formula: Embedded image (Wherein R ₈ , R ₉ and R ₁₀ represent a hydrogen atom, an amino group, an alkoxy group, a thioalkoxy group, an aryloxy group, a methylenedioxy group, a substituted or unsubstituted alkyl group,
Represents a halogen atom or a substituted or unsubstituted aryl group. m represents an integer of 1 to 3. ) 9. The charge transport material according to the following general formula (IV)
The electrophotographic photoreceptor according to any one of claims 1 to 5, which is a compound represented by the following formula: Embedded image (In the formula, A ₁ and A ₂ represent a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, which may be the same or different. Ar ₃ represents a substituted or unsubstituted fused polycyclic carbon. Represents hydrogen.) 10. The charge transport material according to the following general formula (V)
The electrophotographic photoreceptor according to any one of claims 1 to 5, which is a compound represented by the following formula: Embedded image (Wherein, Ar ₄ represents an aromatic group, R ₁₁ represents a hydrogen atom, a substituted or unsubstituted alkyl group or an aryl group. P is 0 or 1, q is 1 or 2, and p = 0, q When = 1, Ar ₄ and R ₁₁ may together form a ring.) 11. The charge transport material according to the following general formula (V)
The electrophotographic photoreceptor according to any one of claims 1 to 5, which is a compound represented by I). Embedded image (Wherein R ₁₂ and R ₁₃ represent a hydrogen atom, a halogen atom, a nitro group, a cyano group, a substituted or unsubstituted alkyl group, etc.
₁₄ and R ₁₅ represent a hydrogen atom, a cyano group, an alkoxycarbonyl group, a substituted or unsubstituted alkyl group, and R ₁₆ represents a hydrogen atom, a lower alkyl group or an alkoxy group. W is a hydrogen atom, a substituted or unsubstituted alkyl group or the like;
An integer of 5, s is an integer of 1 to 4, t is an integer of 0 to 2, u is an integer of 1 to 3, and v is an integer of 1 to 2. ) 12. The electrophotographic photosensitive member according to claim 1, wherein the inert polymer is polycarbonate. 13. The charge transport material according to claim 1, wherein the charge transport layer has a charge transport material concentration of 45 wt% or less.
13. The electrophotographic photosensitive member according to any one of items 1 to 12. 14. An electrophotographic photoreceptor having a charge generating layer containing at least a charge generating substance and a charge transporting layer containing a polymer charge transporting substance on a conductive support, wherein the charge generating layer has a characteristic of CuKα. It has a maximum diffraction peak at least at 27.2 ° as a diffraction peak (± 0.2 °) at a Bragg angle of 2θ with respect to X-rays (wavelength 1.514 °), and 7.3 ° as a diffraction peak at the lowest angle side. And a peak also at 26.3 °, wherein the peak intensity at 26.3 ° is 1 to the peak intensity at 27.2 °.
-10% of titanyl phthalocyanine, and the mobility of the charge transport layer in the electric field intensity at the time of writing image light when the electrophotographic photosensitive member is actually used is 1 × 10
^-5 (cm / Vsec) or more. 15. The electrophotographic photoconductor according to claim 14, wherein the polymer charge transporting material is a polycarbonate containing at least a triarylamine structure in a main chain and / or a side chain. 16. An electrophotographic photosensitive member having at least a charge,
An electrophotographic method in which image exposure, development, and transfer are repeatedly performed, wherein the electrophotographic photosensitive member is the electrophotographic photosensitive member according to any one of claims 1 to 15. 17. At least charging means, image exposure means,
An electrophotographic apparatus comprising a developing unit, a transfer unit, and an electrophotographic photosensitive member, wherein the electrophotographic photosensitive member is provided.
16. An electrophotographic apparatus, which is the electrophotographic photosensitive member according to any one of claims 15 to 15. 18. An electrophotographic apparatus according to claim 17, wherein said charging means is a charging member which is in contact with or close to a photosensitive member. 19. The electrophotographic apparatus according to claim 18, wherein in the electrophotographic apparatus, an alternating current component is superimposed on a direct current component on the charging member to charge the photosensitive member. 20. A process cartridge for an electrophotographic apparatus comprising at least an electrophotographic photosensitive member, wherein the electrophotographic photosensitive member is the electrophotographic photosensitive member according to claim 1. A process cartridge for an electrophotographic apparatus. 21. The process cartridge for an electrophotographic apparatus according to claim 20, wherein said charging means is a charging member which is in contact with or close to a photosensitive member. 22. The process cartridge for an electrophotographic apparatus according to claim 21, wherein in the electrophotographic apparatus, an alternating current component is superimposed on a direct current component on the charging member to charge the photosensitive member.