JP2005141010A - Image forming apparatus and image forming unit - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a stable image forming apparatus which suppresses occurrence of vertical streaky density unevenness. <P>SOLUTION: The image forming apparatus comprises an electrophotographic photoreceptor comprising a conductive substrate and a photosensitive layer disposed on the substrate; a charging means for charging the electrophotographic photoreceptor; an exposure means for forming an electrostatic latent image on the electrophotographic photoreceptor; a developing means for forming a toner image by developing the electrostatic latent image formed on the electrophotographic photoreceptor with toner; and a transfer mean for transferring the toner image to a transfer body, wherein the exposure mean is a light emitting device array in which a plurality of self-scan type LEDs are arrayed and the photosensitive layer contains at least one charge generating material selected from the group consisting of hydroxy-gallium phthalocyanine, chloro-gallium phthalocyanine and a trisazo pigment. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to an image forming apparatus and an image forming unit.

  2. Description of the Related Art An LED print head (LPH: LED Print Head) using an LED as a light source is used as a print head for a printer, a copier, a facsimile, or the like. In recent years, a self-scanning LED (SLED: Self-scanning LED) is used for LPH. ) Has been proposed (see Patent Document 1).

  The SLED uses a thyristor structure as a part corresponding to a switch for selectively turning on and off the light emitting point, and by applying this thyristor structure, the switch part can be arranged on the same chip as the light emitting point. Light emitting source array.

Since this SLED can selectively emit light by using two signal lines at the on / off timing of the switch, the data line can be shared and the wiring can be simplified.
JP-A-2-263668

  However, since the SLED is a self-scanning type, the light emission time of each light emitting point per dot is characterized by being limited to one-fifth or less of the number of light emitting points per chip. For example, when 256 light emission points are formed on one chip and light is emitted sequentially by self-scanning, the light emission time is less than 1/256 compared to an LED that can emit light continuously. Thus, the SLED has a drawback that the amount of light emission per dot is small because the light emission time per dot is shorter than other LEDs. Therefore, in an electrophotographic image forming apparatus having a high process speed or an electrophotographic image forming apparatus having a high image resolution with respect to the traveling direction of the surface of the photoconductor, the potential after exposure of the photoconductor cannot be lowered sufficiently, and the amount of light is insufficient. There was a thing.

  Moreover, in LED, in order to suppress the generation | occurrence | production of the vertical stripe in the halftone by the light emission amount between light emitting elements or the difference in a profile, the light emission amount of each light emitting element is controlled by lighting time. However, when the usage environment changes, there is a problem that vertical stripes are generated particularly in a low temperature and low humidity environment.

  Accordingly, an object of the present invention is to use an SLED with a small amount of light emission without causing a shortage of light amount, and to generate vertical stripe-like density unevenness that occurs when the environment changes even after the light amount correction of each light emitting element (LED). An object of the present invention is to provide a stable image forming apparatus that suppresses the above. Another object of the present invention is to provide an image forming unit capable of such image formation.

  In order to solve the above-described object, the present invention provides an electrophotographic photosensitive member comprising a conductive support and a photosensitive layer disposed on the support, a charging means for charging the electrophotographic photosensitive member, and electrophotography. An exposure means for forming an electrostatic latent image on the photosensitive member, a developing means for developing the electrostatic latent image formed on the electrophotographic photosensitive member with toner, and a toner image, An image forming apparatus comprising: a transfer unit configured to transfer to a transfer target; wherein the exposure unit is a light emitting element array in which a plurality of self-scanning LEDs (SLEDs) are arranged, and the photosensitive layer includes a hydroxy group. Provided is an image forming apparatus containing at least one charge generation material selected from the group consisting of gallium phthalocyanine, chlorogallium phthalocyanine and trisazo pigment.

  The image forming apparatus of the present invention includes an SLED that scans a light beam in accordance with image data. Since the above-described compound is used as a charge generation material, the amount of light is insufficient even in an SLED that emits a small amount of light. It can be used without any problems, and even after the light quantity correction of each light emitting element (LED), the occurrence of vertical stripe-shaped density unevenness that occurs when the environment fluctuates is suppressed, and a stable image layer can be formed.

  In this image forming apparatus, the exposure unit may be a staggered arrangement of light emitting element units each including a plurality of self-scanning LEDs so that adjacent light emitting element units partially overlap. By arranging the light emitting element units in a staggered manner in this way, it is possible to prevent an adverse effect on the image of the joint between the light emitting element units.

  The hydroxygallium phthalocyanine used in the image forming apparatus has a diffraction peak at Bragg angles (2θ ± 0.2 °) of 7.6 ° and 28.2 ° in an X-ray diffraction spectrum using CuKα characteristic X-rays. Hydroxygallium phthalocyanine having is preferable.

Particularly preferable as the hydroxygallium phthalocyanine used in the image forming apparatus is hydroxygallium phthalocyanine having a maximum peak wavelength in the range of 810 to 839 nm in the spectral absorption spectrum in the wavelength region of 600 to 900 nm. It is preferable that at least one characteristic of (1) to (3) is further provided.
(1) The average particle size is 0.20 μm or less, and the BET specific surface area is 45 m ² / g or more.
(2) In an X-ray diffraction spectrum using CuKα characteristic X-ray, Bragg angles (2θ ± 0.2 °) 7.5 °, 9.9 °, 12.5 °, 16.3 °, 18.6 ° , 25.1 ° and 28.3 °.
(3) The thermal weight loss rate when the temperature is raised from 25 ° C. to 400 ° C. is 2.0 to 4.0%.

  Such hydroxygallium phthalocyanine has a Bragg angle (2θ ± 0.2 °) of 6.9 °, 13.2-14.2 °, 16.5 ° in an X-ray diffraction spectrum using CuKα characteristic X-rays, Hydroxygallium phthalocyanine having diffraction peaks at 26.0 ° and 26.4 °, or 7.0 °, 13.4 °, 16.6 °, 26.0 °, and 26.7 °, with an outer diameter of 0. Obtained by wet-grinding the gallium phthalocyanine to 1 part by weight with a pulverizer using spherical media of 1 to 3.0 mm so that the medium is 50 parts by weight or more and subjected to crystal conversion. Are preferred.

［式中、Ｒは水素原子、ハロゲン原子、アルキル基、アルコキシ基又はシアノ基を表し、Ａｒはカップラー残基を表す。］ As for chlorogallium phthalocyanine used in the image forming apparatus, Bragg angles (2θ ± 0.2 °) of 7.4 °, 16.6 °, 25.5 ° and X-ray diffraction spectrum using CuKα characteristic X-ray Chlorogallium phthalocyanine having a diffraction peak at 28.3 ° is preferable, and the trisazo pigment is preferably a trisazo pigment represented by any one of the following general formulas (1) to (4).

[Wherein, R represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group or a cyano group, and Ar represents a coupler residue. ]

  By using the above-mentioned hydroxygallium phthalocyanine, chlorogallium phthalocyanine and trisazo pigment, a shortage of light is not particularly likely to occur even in an SLED with a small amount of light emission, and vertical stripes that occur when the environment changes even after the light amount correction of each light emitting element (LED). Occurrence of the density unevenness is remarkably suppressed, and a very stable image layer can be formed. Further, in the embodiment in which the electrophotographic photosensitive member is rotated, the linear velocity of the photosensitive layer can be increased, and at the same time, an image can be formed with stable electrophotographic characteristics and few image defects.

  Since such characteristics can be exhibited more effectively, the photosensitive layer is composed of a charge generation layer formed on a conductive support and a charge transport layer formed on the charge generation layer. The layer may contain the charge generating material.

  The electrophotographic photosensitive member is formed by forming a photosensitive layer on the curved surface of a drum-shaped conductive support, and the electrophotographic photosensitive member is formed on the surface of the photosensitive layer with the drum-shaped central axis as a center. What rotates so that a linear velocity may be 100 mm / sec or more is preferable. When the linear velocity on the surface of the photosensitive layer is 100 mm / second or more, the exposure amount per unit area of the photoconductor is reduced, so that high-sensitivity electrophotographic photosensitivity is possible, and as a result, the image forming apparatus is accelerated. Will be able to.

  In the image forming apparatus, it is preferable that the image resolution of the photosensitive layer in the rotation direction of the electrophotographic photosensitive member is 1200 dots / inch or more. When the image resolution is 1200 dots / inch or more, the effective lighting time of the LED is reduced, and the exposure amount per unit area of the photoreceptor is reduced, so that high-sensitivity electrophotographic photosensitivity is possible. It becomes possible to achieve high resolution and high image quality of the apparatus.

  The present invention also provides an electrophotographic photosensitive member comprising a conductive support and a photosensitive layer disposed on the support, a charging means for charging the electrophotographic photosensitive member, and an electrostatic latent image on the electrophotographic photosensitive member. An exposure means for forming an image, a developing means for forming a toner image by developing the electrostatic latent image formed on the electrophotographic photosensitive member with toner, and a toner remaining on the electrophotographic photosensitive member are removed. And at least one selected from the group consisting of cleaning means, wherein the exposure means is a light emitting element array in which a plurality of self-scanning LEDs are arranged, and the photosensitive layer comprises: Provided is an image forming unit containing at least one charge generating material selected from the group consisting of hydroxygallium phthalocyanine, chlorogallium phthalocyanine and trisazo pigment .

  In this image forming unit, the light-emitting element array can be a light-emitting element array in which light-emitting element units including a plurality of self-scanning LEDs are arranged so that adjacent light-emitting element units partially overlap each other, and hydroxygallium phthalocyanine The chlorogallium phthalocyanine, the trisazo pigment, and the photosensitive layer may be of the same type or configuration as described above.

  SLED with a small amount of light emission can be used without causing a shortage of light amount, and stable image layer formation that suppresses the occurrence of vertical streak density unevenness that occurs when the environment changes even after the light amount correction of each light emitting element (LED). An apparatus and an image forming unit capable of such image formation are provided.

  Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings as the case may be. In the drawings, the same or corresponding parts are denoted by the same reference numerals, and redundant description is omitted.

  FIG. 1 is a schematic configuration diagram of an image forming apparatus according to an embodiment. An image forming apparatus 100 shown in FIG. 1 is covered with a casing 102, and an upper surface of the image forming apparatus 100 also serves as a discharge tray unit 104.

  A photosensitive drum (electrophotographic photosensitive member) 106 is disposed in the center of the casing 102. Around the photosensitive drum 106, a charging unit 108 for uniformly charging the surface of the photosensitive drum 106, counterclockwise from right above and slightly to the right, and an exposure unit 110 in which self-scanning LEDs (SLEDs) are arranged. The CMYK color toner tanks 112 are installed and rotated, and the respective color toner rolls 114 are sequentially wound around a rotary developing unit 116 and a plurality of rollers 120 that can be associated with the photosensitive drum 106. An intermediate transfer belt 122 and a cleaning unit 124 are disposed as a primary transfer member that is driven in the direction of arrow A in FIG.

  The photosensitive drum 106 is rotated in the direction of arrow B in FIG. 1, whereby the respective processes of the charging unit 108, the exposure unit 110, the rotary development unit 116, the intermediate transfer belt 122, and the cleaning unit 124 are performed. .

  The lower end portion of the intermediate transfer belt 122 is a part of the conveyance path of the image forming sheet 126, and the image forming sheet 126 is nipped and conveyed between the intermediate transfer belt 122 and the roller 118 at this lower end portion. It is like that.

  A plurality of rollers 118 are arranged in the conveyance path of the image forming sheet 126, and the uppermost image forming sheet 126 stacked on the sheet feeding tray 128 is taken out by the sheet feeding device 130, and the lower end portion of the intermediate transfer belt 122. The sheet is conveyed while being in contact with each other and is sent out to the discharge tray section 104 through the fixing section 132.

  A density sensor 134 is provided at a position facing a part of the conveyance path of the intermediate transfer belt 122 so as to detect the density of, for example, a test patch (color and density sample).

  FIG. 2 is a perspective view of the exposure unit. The exposure unit 110 shown in FIG. 2 is a light emitting element array configured by further arranging a plurality of light emitting element units 152 in which a plurality of SLEDs 150 are arranged in series along the axial direction of the photosensitive drum 106. The exposure unit 110 is controlled to be turned on by a drive circuit 156 (see FIG. 4) housed in the same casing 154.

  The exposure unit 110 may have a configuration different from that shown in FIG. For example, as in the exposure unit 110 shown in FIG. 3, light emitting element units including a plurality of SLEDs 150 may be a light emitting element array arranged in a staggered manner so that adjacent light emitting element units 152 partially overlap.

4 is a drive circuit diagram of a single SLED constituting the exposure unit 110, and FIG. 5 is a drive circuit diagram of the exposure unit 110. As shown in FIG. As shown in FIG. 4, when the thyristor 10 is off, when the trigger to the high level, the current Itr flows to the point P, the current Ib2 flows simultaneously from the point P to the base of the transistor _{Q 2} (Itr ≒ Ib2). Thus, the transistor Q ₂ is turned on, the collector current of the Torajisuta Q ₂ flows. That results in that the base current Ib1 of the transistor _{Q 1} is flowing, the transistor _{Q 1} is also turned on.

When the transistor _{Q 1} is turned on, the collector current Ic1 of the transistor _{Q 1} is the flow, increases the voltage at point P is, the current Itr does not flow. However, (current Ib2) for the collector current Ic1 of the transistor _{Q 1} is flows to the base of the transistor _{Q 2,} the transistor _{Q 2} is turned on is maintained.

Accordingly, the trigger is also at the low level, the transistors Q ₁ and transistor Q ₂ is kept on. In this state, the voltage _VEE is maintained, the LED can be turned on, and a predetermined light amount can be obtained by performing pulse width modulation.

Note that in order to turn off the thyristor 10, the transistor Q ₁ is also turned on, so as not to base current flows through the transistor Q _2. That is, when the self-holding state of the thyristor 10, when the voltage V _EE to 0V, and the voltage at point P becomes a high impedance, the charge accumulated in the parasitic capacitance is discharged through the high resistor 12, as a result the transistor Q ₁ and the transistor Q ₂ is off.

  Since the drive circuit 156 shown in FIG. 5 is basically a combination of the single drive circuits shown in FIG. 4, the detailed description of the thyristor 10 and the like is omitted here.

As a trigger for turning on the SLED, the voltage V _S is applied to the point P1 (the number following the point P indicates the order of the plurality of LEDs arranged) via the resistor 158. All the points P (1 to N (N is a positive integer)) including the point P1 are connected to the base line 161 via the resistor 160, respectively. The base line 161 maintains a predetermined voltage in the first stage, and is set to a potential (Φga) that decreases by a predetermined potential (Vf) as it goes to each stage.

  Further, the point P (1 to N) is connected to the anode side of the SLED 150. Note that the cathode side of the SLED 150 is connected to a gradation signal line 163 described later.

  Here, as shown in FIG. 6, Φga is driven at a constant current by receiving a light quantity instruction value from an APC (auto power control) 162 based on a detection signal from the density sensor 134 (see FIG. 6). Constant current drive circuit). That is, the light quantity instruction value is converted into an analog value by the DA converter 164 and connected to the negative side input terminal of the first comparator 168 via the resistor 166. The positive side input terminal of the first comparator 168 is grounded (GND). The output terminal of the first comparator 168 and the negative input terminal are connected via a resistor 170. As a result, the output of the first comparator 168 changes depending on the light quantity instruction value and becomes a predetermined voltage.

Here, connecting the output voltage to the positive input terminal of the second comparator 172, connected to a voltage source V _SS reference to the negative input terminal through a resistor 174, further, the output of the second comparator 172 By connecting the end to the MOS transistor 176, a constant current flows through the MOS transistor 176.

  In FIG. 6, the driving circuit of Φga is the constant current driving circuit 178, but it may be a constant voltage driving circuit 180 as shown in FIG. Since the circuit configuration may use the output of the first comparator 168 in FIG. 6, the same reference numerals are given and description of the configuration is omitted.

As shown in FIG. 5, the emitter of the odd-numbered transistor Q ₂ is connected to the first control line (V 1) 182, and the emitter of the even-numbered transistor Q ₂ is connected to the second control line (V 2) 184. Has been. The point P (1 to N) of each stage is connected to one end of the SLED 150, and the other end of the SLED is connected to a gradation signal line 163 that outputs a pulse wave that is a gradation signal of each stage. Yes. When the gradation signal line 163 is at a low level (L), if the point P (1 to N) is at a predetermined potential, the LED is lit.

  FIG. 8 is a circuit diagram for generating a pulse waveform sent to the gradation signal line 163. In the generation circuit 200 shown in FIG. 8, the image processing unit 202 (for example, converts various types of images sent from a recording medium, a communication line, etc. into a format corresponding to the image forming apparatus 100 of the present embodiment. ) Is output to the accumulator 204. Correction data (4 bits) held in the correction data holding unit 206 is also input to the accumulator 204, and unevenness of the light emission point of each SLED is corrected. The corrected gradation signal added with the correction data by the integrator is converted to an analog signal (density signal) by the DA converter 208 and input to the plus side input terminal of the comparator 210.

  On the other hand, control signal lines V1 (Φ1) and V2 (Φ2) output from the timing generator 212 are connected to branch lines 182A and 184A, respectively, and these branch lines 182A and 184A are input to the OR circuit 186. For this reason, the output of the OR circuit 186 is active when either one of V1 and V2 is active (here, low level). In synchronization with this active time, the triangular wave generation circuit 188 generates a triangular wave and inputs it to the negative side input terminal of the comparator 210.

  This operation is shown in the timing chart of FIG. That is, a triangular wave is formed according to a signal obtained by ORing V1 (Φ1) and V2 (Φ2). At this time, a space a is generated between the triangular waves, and this becomes an interval for sequentially lighting one by one at the lighting timing of the odd-numbered LED and the even-numbered LED. By superimposing the density signal on this triangular wave, the range of the level higher than the density signal in the triangular wave becomes the actual lighting time, and a pulse waveform to be sent to the gradation signal line 163 can be generated.

  Next, a preferred embodiment of the electrophotographic photoreceptor will be described in detail.

  10 to 13 are schematic views showing cross sections of the electrophotographic photoreceptors according to the first to fourth embodiments, respectively. In the electrophotographic photosensitive member shown in FIG. 10, a charge generation layer 1 is provided on a conductive support 3, and a charge transport layer 2 is provided thereon. The electrophotographic photoreceptor shown in FIG. 11 has the same configuration as the electrophotographic photoreceptor of FIG. 10 except that an undercoat layer 4 is provided between the conductive support 3 and the charge generation layer 1. The electrophotographic photosensitive member shown in FIG. 12 has the same configuration as the electrophotographic photosensitive member in FIG. 10 except that the protective layer 5 is provided on the charge transport layer 2. The electrophotographic photoreceptor shown in FIG. 13 has the same configuration as the electrophotographic photoreceptor of FIG. 12 except that an undercoat layer 4 is provided between the conductive support 3 and the charge generation layer 1. Yes.

  In the first to fourth embodiments, the charge generation layer 1 and the charge transport layer 2 form a photosensitive layer. As in the first to fourth embodiments, the photosensitive layer can be formed as a so-called function-separated photosensitive layer by forming a layer containing a charge generating material and a layer containing a charge transporting material adjacent to each other. The so-called single-layer type photosensitive layer may be formed by including the charge generation material and the charge transport material in the same layer.

  Next, each element of the electrophotographic photosensitive member will be described in detail.

  As the conductive support 3, a metal drum such as aluminum, copper, iron, zinc, nickel; aluminum, copper, gold, silver, platinum, palladium, titanium, nickel—on a substrate such as sheet, paper, plastic, or glass Deposited metal such as chromium, stainless steel, copper-indium; Deposited conductive metal compound such as indium oxide and tin oxide on the base; Laminated metal foil on the base; Carbon black, Indium oxide, tin oxide-antimony oxide powder, metal powder, copper iodide and the like are dispersed in a binder resin and applied on the substrate to conduct a conductive treatment. The shape of the conductive support 3 may be a drum shape, a sheet shape, a plate shape, or the like.

  When a metal pipe base material is used as the conductive support 3, the surface of the base material may remain as a raw tube, and in advance, mirror cutting, etching, anodizing, rough cutting, centerless grinding, sandblasting, You may perform processes, such as wet honing and a coloring process. By roughening the surface of the base material, it is possible to prevent grain-like density spots caused by interference light in the photoconductor, which may occur when a coherent light source is used.

  The undercoat layer 4 prevents injection of charges from the conductive support 3 to the photosensitive layer when the photosensitive layer having a laminated structure is charged, and the photosensitive layer is integrated with the conductive support 3. It has an action as an adhesive layer for adhering and holding. Moreover, the undercoat layer 4 shows the antireflection effect of the light of the electroconductive support body 3, etc. depending on the case.

  Materials for the undercoat layer 4 include acetal resins such as polyvinyl butyral, polyvinyl alcohol resin, casein, polyamide resin, cellulose resin, gelatin, polyurethane resin, polyester resin, methacrylic resin, acrylic resin, polyvinyl chloride resin, and polyvinyl acetate resin. , Vinyl chloride-vinyl acetate-maleic anhydride resin, silicone resin, silicone-alkyd resin, phenol-formaldehyde resin, polymer resin compound such as melamine resin, zirconium chelate compound, titanium chelate compound, aluminum chelate compound, titanium alkoxide compound, An organic titanium compound, a silane coupling agent, etc. are mentioned. In addition, a charge transporting resin having a charge transporting group, a conductive resin such as polyaniline, or the like can be used. These compounds can be used alone or as a mixture or polycondensate of a plurality of compounds. Among them, a resin insoluble in a solvent contained in the coating solution for forming the upper layer (for example, the charge generation layer 1), particularly a phenol resin, a phenol-formaldehyde resin, a melamine resin, a urethane resin, an epoxy resin, or the like is preferably used. Furthermore, zirconium chelate compounds and silane coupling agents are excellent in performance, such as low residual potential, little potential change due to environment, and little potential change due to repeated use.

  As silane coupling agents, vinyltrimethoxysilane, γ-methacryloxypropyl-tris (β-methoxyethoxy) silane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxy Silane, vinyltriacetoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ -Aminopropylmethylmethoxysilane, N, N-bis (β-hydroxyethyl) -γ-aminopropyltriethoxysilane, γ-chloropropyltrimethoxysilane and the like. Among these, vinyltriethoxysilane, vinyltris (2-methoxyethoxysilane), 3-methacryloxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxy Silane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3- Examples of the silane coupling agent include aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, and 3-chloropropyltrimethoxysilane.

  Zirconium chelate compounds include: zirconium butoxide, zirconium zirconium acetoacetate, zirconium triethanolamine, acetylacetonate zirconium butoxide, ethyl acetoacetate butoxide, zirconium acetate, zirconium oxalate, zirconium lactate, zirconium phosphonate, zirconium octoate, naphthenic acid Zirconium, zirconium laurate, zirconium stearate, zirconium isostearate, methacrylate zirconium butoxide, stearate zirconium butoxide, isostearate zirconium butoxide and the like.

  Titanium chelate compounds include tetraisopropyl titanate, tetranormal butyl titanate, butyl titanate dimer, tetra (2-ethylhexyl) titanate, titanium acetylacetonate, polytitanium acetylacetonate, titanium octylene glycolate, titanium lactate ammonium salt, titanium Examples include lactate, titanium lactate ethyl ester, titanium triethanolamate, and polyhydroxytitanium stearate.

  Examples of the aluminum chelate compound include aluminum isopropylate, monobutoxy aluminum diisopropylate, aluminum butyrate, diethyl acetoacetate aluminum diisopropylate, and aluminum tris (ethyl acetoacetate).

  The undercoat layer 4 can contain a conductive substance for improving the photoreceptor characteristics. Examples of the conductive material include metal oxides such as titanium oxide, zinc oxide, and tin oxide, and any known material can be used as long as desired photoreceptor characteristics can be obtained.

  These metal oxides can be surface treated. By performing the surface treatment, resistance value control, dispersibility control, and improvement in photoreceptor characteristics can be achieved. As the surface treatment agent, known materials such as a zirconium chelate compound, a titanium chelate compound, an aluminum chelate compound, a titanium alkoxide compound, an organic titanium compound, and a silane coupling agent can be used. These compounds can be used alone or as a mixture or polycondensate of a plurality of compounds. Among them, the silane coupling agent is excellent in performance such as low residual potential, little potential change due to environment, little potential change due to repeated use, and excellent image quality characteristics.

  Examples of the silane coupling agent, the zirconium chelate compound, the titanium chelate compound, and the aluminum chelate compound include the same substances as those described above.

  As the surface treatment method, any known method can be used, but a dry method or a wet method can be used.

  When surface treatment is performed by a dry method, while stirring the metal oxide fine particles with a mixer having a large shearing force or the like, the silane coupling agent is dissolved directly or dissolved in an organic solvent, and the mixture is added to dry air or nitrogen gas. By spraying together, uniform surface treatment is performed. The dropping of the silane coupling agent and the spraying of the mixture are preferably performed at a temperature below the boiling point of the solvent. When the dropping or spraying is performed at a temperature equal to or higher than the boiling point of the solvent, the solvent evaporates before being uniformly stirred, and the silane coupling agent is locally aggregated to make uniform treatment difficult.

  The surface-treated metal oxide particles can be further baked at 100 ° C. or higher. Baking can be carried out in an arbitrary range as long as the temperature and time allow the desired electrophotographic characteristics to be obtained. As a wet method, the metal oxide fine particles are dispersed in a solvent using stirring, ultrasonic waves, a sand mill, an attritor, a ball mill, etc., and a silane coupling agent solution is added and stirred or dispersed, and then the solvent is removed. Uniformly processed. The solvent is preferably distilled off by distillation. The removal method by filtration is not preferable because unreacted silane coupling agent tends to flow out and it is difficult to control the amount of silane coupling agent for obtaining desired characteristics. After removing the solvent, baking can be performed at 100 ° C. or higher. Baking can be carried out in an arbitrary range as long as the temperature and time allow the desired electrophotographic characteristics to be obtained. In the wet method, as a method for removing the metal oxide fine particle-containing water, a method of removing with stirring and heating in a solvent used for surface treatment, or a method of azeotropically removing with a solvent can be used.

  The amount of the silane coupling agent relative to the metal oxide fine particles in the undercoat layer 4 can be any amount as long as desired electrophotographic characteristics can be obtained. Further, the ratio between the gold image oxide fine particles and the resin used in the undercoat layer 4 can be arbitrarily set as long as desired electrophotographic characteristics can be obtained.

  Various organic or inorganic fine powders can be mixed in the undercoat layer 4 for the purpose of improving light scattering properties. Preferred examples of such fine powder include white pigments such as titanium oxide, zinc oxide, zinc sulfide, lead white, and lithopone, inorganic pigments such as alumina, calcium carbonate, and barium sulfate, Teflon (registered trademark) resin particles, and benzoguanamine resin particles. And styrene resin particles. The particle size of these fine powders is preferably 0.01 to 2 μm. The fine powder is a component added as necessary, but the addition amount is preferably 10 to 80% by weight with respect to the solid content contained in the undercoat layer 4, and is preferably 30 to 70%. It is preferable that it is weight%.

  Various additives can be used in the coating liquid used for forming the undercoat layer 4 in order to improve electrical characteristics, environmental stability, and image quality. Additives include quinone compounds such as chloranil, bromoanil and anthraquinone, tetracyanoquinodimethane compounds, fluorenones such as 2,4,7-trinitrofluorenone and 2,4,5,7-tetranitro-9-fluorenone Compound, 2- (4-biphenyl) -5- (4-t-butylphenyl) -1,3,4-oxadiazole, 2,5-bis (4-naphthyl) -1,3,4-oxadi Azoles, oxadiazole compounds such as 2,5-bis (4-diethylaminophenyl) -1,3,4-oxadiazole, xanthone compounds, thiophene compounds, 3,3 ′, 5,5′-tetra- Examples thereof include electron transport materials such as diphenoquinone compounds such as t-butyldiphenoquinone, electron transport pigments such as polycyclic condensation systems and azo systems.

  When preparing the coating liquid for forming the undercoat layer, when mixing fine powders such as the above-mentioned conductive substances and light scattering substances, the fine powder is added to the solution in which the resin component is dissolved and the dispersion treatment is performed. It is preferable. As a method for dispersing the fine powder in the resin, methods such as a roll mill, a ball mill, a vibrating ball mill, an attritor, a sand mill, a colloid mill, and a paint shaker can be used.

  In addition, as a method for applying the coating liquid for forming the undercoat layer, conventional methods such as a blade coating method, a wire bar coating method, a spray coating method, a dip coating method, a bead coating method, an air knife coating method, and a curtain coating method can be used. Can be used.

  The film thickness of the undercoat layer 4 is preferably 0.01 to 50 μm, more preferably 0.05 to 30 μm.

The charge generation layer 1 includes a charge generation material and a binder resin. The charge generating material is at least one selected from hydroxygallium phthalocyanine, chlorogallium phthalocyanine, and trisazo pigment. By using these charge generating materials, the sensitivity of the electrophotographic photosensitive member and its environmental stability are sufficiently enhanced, so that even an SLED with a small amount of emitted light can be used without causing a shortage of light and each light emitting element (LED ), The occurrence of vertical stripe-like density unevenness that occurs when the environment changes is suppressed, and a stable image layer can be formed. Among these charge generation materials, it is preferable to use at least one selected from hydroxygallium phthalocyanine, chlorogallium phthalocyanine, and trisazo pigments, and it is particularly preferable to use the following charge generation materials.
(I) In an X-ray diffraction spectrum using CuKα characteristic X-rays, Bragg angles (2θ ± 0.2 °) 7.5 °, 9.9 °, 12.5 °, 16.3 °, 18.6 ° , Hydroxygallium phthalocyanine having diffraction peaks at 25.1 ° and 28.3 °,
(Ii) hydroxygallium phthalocyanine having diffraction peaks at positions of Bragg angles (2θ ± 0.2 °) of 7.6 ° and 28.2 ° in an X-ray diffraction spectrum using CuKα characteristic X-rays,
(Iii) a trisazo pigment represented by the general formula (1),
(Iv) a trisazo pigment represented by the general formula (2),
(V) a trisazo pigment represented by the general formula (3),
(Vi) A trisazo pigment represented by the general formula (4).

  In the formula, R represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group or a cyano group.

［上記式（５）中、Ｘ^１は−ＯＨ、−Ｎ（Ｒ^２）（Ｒ^３）又は−ＮＨＳＯ_２−Ｒ^４を表し（Ｒ^２及びＲ^３は水素原子、アシル基又は置換若しくは未置換のアルキル基を表し、Ｒ^４は置換若しくは未置換のアルキル基又は置換若しくは未置換のアリール基を表す）、Ｙ^１は水素原子、ハロゲン原子、置換若しくは未置換のアルキル基、アルコキシ基、カルボキシ基、スルホン基、ベンズイミダゾリル基、置換若しくは未置換のスルファモイル基、置換若しくは未置換のアロファノイル基又は−ＣＯＮ（Ｒ^５）（Ｙ^２）を表し（Ｒ^５は水素原子、アルキル基若しくはその置換対又はフェニル基若しくはその置換体を表し、Ｙ^２は炭化水素環基若しくはその置換体、複素環基若しくはその置換体又は−Ｎ＝Ｃ（Ｒ^６）（Ｒ^７）を表し（Ｒ^６は炭化水素環基若しくはその置換体、複素環基若しくはその置換体又はスチリル基若しくはその置換体を表し、Ｒ^７は水素原子、アルキル基若しくはその置換体又はフェニル基若しくはその置換体を表すか、あるいはＲ^６及びＲ^７はそれらに結合する炭素原子と共に環を形成してもよい）、Ｚは炭化水素環基若しくはその置換体又は複素環基若しくはその置換体を表す。］

［式中、Ｒ^８は置換又は未置換の炭化水素基を表す。］

［式中、Ｒ^９は置換又は未置換の炭化水素基を表す。］

［式中、Ｒ^１０はアルキル基、カルバモイル基、カルボキシル基又はそのエステルを表し、Ａｒ^２は置換又は未置換の芳香族炭化水素基を表す。］

［式中、Ｘ^２は２価の芳香族炭化水素基又は２価の複素環基を表す。］

［式中、Ｘ^３は２価の芳香族炭化水素基又は２価の複素環基を表す。］

［式中、Ｒ^１１及びＲ^１２は同一でも異なっていてもよく、それぞれ水素原子、ハロゲン原子、アルキル基又はアルコキシ基を表し、Ｒ^１３は水素原子又はハロゲン原子を表す。］ Ar represents a coupler residue. Preferable examples of the coupler residue include groups represented by the following general formulas (5) to (11).

[In the above formula (5), X ¹ represents —OH, —N (R ² ) (R ³ ) or —NHSO ₂ —R ⁴ (R ² and R ³ represent a hydrogen atom, an acyl group, or a substituted or unsubstituted group. R ⁴ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group), Y ¹ represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, an alkoxy group, or a carboxy group , A sulfone group, a benzimidazolyl group, a substituted or unsubstituted sulfamoyl group, a substituted or unsubstituted allophanoyl group, or —CON (R ⁵ ) (Y ² ) (R ⁵ represents a hydrogen atom, an alkyl group or a substituted pair thereof, or Y ² represents a hydrocarbon ring group or a substituent thereof, a heterocyclic group or a substituent thereof, or —N═C (R ⁶ ) (R ⁷ ). (R ⁶ represents a hydrocarbon ring group or a substituted product thereof, a heterocyclic group or a substituted product thereof, or a styryl group or a substituted product thereof, and R ⁷ represents a hydrogen atom, an alkyl group or a substituted product thereof, a phenyl group or a substituted product thereof. Or R ⁶ and R ⁷ may form a ring together with carbon atoms bonded to them), and Z represents a hydrocarbon ring group or a substituent thereof, or a heterocyclic group or a substituent thereof.

[Wherein R ⁸ represents a substituted or unsubstituted hydrocarbon group. ]

[Wherein R ⁹ represents a substituted or unsubstituted hydrocarbon group. ]

[Wherein, R ¹⁰ represents an alkyl group, a carbamoyl group, a carboxyl group or an ester thereof, and Ar ² represents a substituted or unsubstituted aromatic hydrocarbon group. ]

[Wherein, X ² represents a divalent aromatic hydrocarbon group or a divalent heterocyclic group. ]

[Wherein X ³ represents a divalent aromatic hydrocarbon group or a divalent heterocyclic group. ]

[Wherein, R ¹¹ and R ¹² may be the same or different and each represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group, and R ¹³ represents a hydrogen atom or a halogen atom. ]

  As a method for producing the charge generating material used in the present invention, pigment crystals produced by a known method are mechanically dry-pulverized with an automatic mortar, planetary mill, vibration mill, CF mill, roller mill, sand mill, kneader, or the like. Examples thereof include a method and a method of performing a wet pulverization treatment using a ball mill, a mortar, a sand mill, a kneader or the like together with a solvent after dry pulverization.

  Solvents used in the above treatment include aromatics (toluene, chlorobenzene, etc.), amides (dimethylformamide, N-methylpyrrolidone, etc.), aliphatic alcohols (methanol, ethanol, butanol, etc.), aliphatic poly Monohydric alcohols (ethylene glycol, glycerin, polyethylene glycol, etc.), aromatic alcohols (benzyl alcohol, phenethyl alcohol, etc.), esters (acetic ester, butyl acetate, etc.), ketones (acetone, methyl ethyl ketone, etc.), dimethyl sulfoxide, Examples thereof include ethers (diethyl ether, tetrahydrofuran, etc.), a mixed solvent of two or more of the above solvents, and a mixed solvent of the above solvent and water. The amount of the solvent used is preferably 1 to 200 parts by weight, more preferably 10 to 100 parts by weight with respect to 1 part by weight of the pigment crystals. The treatment temperature is preferably in the range of 0 ° C. to the boiling point of the solvent, more preferably in the range of 10 to 60 ° C.

  In addition, grinding aids such as sodium chloride and sodium nitrate can be used during grinding. The amount of the grinding aid used is preferably 0.5 to 20 times, more preferably 1 to 10 times in terms of the weight ratio to the pigment crystals.

  In addition, the pigment crystals produced by a known method can be controlled by combining acid pasting or acid pasting with dry pulverization or wet pulverization as described above. As the acid used for acid pasting, sulfuric acid is preferable, and one having a concentration of 70 to 100%, preferably 95 to 100% is used. The dissolution temperature is preferably -20 to 100 ° C, more preferably 0 to 60 ° C. The amount of sulfuric acid is preferably 1 to 100 times, more preferably 3 to 50 times, by weight ratio to the pigment crystals. Examples of the solvent for precipitating pigment crystals dissolved in sulfuric acid include water or a mixed solvent of water and an organic solvent. The amount of such solvent used is arbitrary. Moreover, there is no restriction | limiting in particular about the temperature which deposits a pigment crystal, However, In order to prevent heat_generation | fever, it is preferable to cool with ice etc.

  Particularly preferred as the charge generation material of the present invention is a hydroxygallium phthalocyanine (hereinafter sometimes referred to as “hydroxygallium phthalocyanine 1”) having a maximum peak wavelength in the range of 810 to 839 nm in the spectral absorption spectrum in the wavelength region of 600 to 900 nm. And is different from conventional V-type hydroxygallium phthalocyanine. Further, those having a maximum peak wavelength in the range of 810 to 835 nm are preferable because more excellent dispersibility can be obtained. In this way, by shifting the maximum peak wavelength of the spectral absorption spectrum to a shorter wavelength side than the conventional V-type hydroxygallium phthalocyanine, it becomes a fine hydroxygallium phthalocyanine in which the crystal arrangement of the pigment particles is suitably controlled. When used as a material for a photoconductor, excellent dispersibility, sufficient sensitivity, chargeability, and dark decay characteristics can be obtained.

Hydroxygallium phthalocyanine 1 preferably has an average particle size in a specific range and a BET specific surface area in a specific range. Specifically, the average particle size is preferably 0.20 μm or less, more preferably 0.01 to 0.15 μm, while the BET specific surface area is preferably 45 m ² / g or more, more preferably 50 m ² / g or more, and particularly preferably 55~120m ² / g.

When the average particle diameter is larger than 0.20 μm, or when the specific surface area value is less than 45 m ² / g, the pigment particles are coarsened or aggregates of the pigment particles are formed, and the electrophotographic photosensitive member When used as a material, there is a tendency that defects are likely to occur in characteristics such as dispersibility, sensitivity, chargeability, and dark decay characteristics, thereby tending to cause image quality defects.

  Hydroxygallium phthalocyanine 1 has a Bragg angle (2θ ± 0.2 °) of 7.5 °, 9.9 °, 12.5 °, 16.3 °, 18 in an X-ray diffraction spectrum using CuKα characteristic X-rays. It is preferable to have diffraction peaks at .6 °, 25.1 °, and 28.3 °.

  Furthermore, the hydroxygallium phthalocyanine 1 preferably has a thermogravimetric reduction rate of 2.0 to 4.0% when heated from 25 ° C to 400 ° C, and preferably 2.5 to 3.8%. More preferred. The thermal weight reduction rate can be measured with a thermobalance or the like.

  When the thermal weight reduction rate exceeds 4.0%, the impurities contained in hydroxygallium phthalocyanine 1 affect the electrophotographic photosensitive member, and the sensitivity characteristics, potential stability during repeated use, and image quality are degraded. Tend to occur. Further, if it is less than 2.0%, the sensitivity tends to be lowered. This is due to the fact that hydroxygallium phthalocyanine 1 exhibits a sensitizing action by interaction with a solvent molecule contained in a trace amount in the crystal.

  Hydroxygallium phthalocyanine 1 can be produced by the following production method. That is, in an X-ray diffraction spectrum using CuKα characteristic X-rays, Bragg angles (2θ ± 0.2 °) of 6.9 °, 13.2 to 14.2 °, 16.5 °, 26.0 ° and 26 Hydroxygallium which is crystal-converted by wet-grinding hydroxygallium phthalocyanine having diffraction peaks at .4 ° or 7.0 °, 13.4 °, 16.6 °, 26.0 ° and 26.7 ° A method for producing phthalocyanine. In this case, the wet pulverization treatment is performed by using a pulverizer using spherical media having an outer diameter of 0.1 to 3.0 mm so that the amount of media used is 50 parts by weight or more with respect to 1 part by weight of hydroxygallium phthalocyanine. The wet pulverization time is preferably determined by measuring the absorption wavelength of the hydroxygallium phthalocyanine in the pulverization process. In the wet pulverization treatment, the crystal conversion state is changed so that the hydroxygallium phthalocyanine after the wet pulverization treatment has a maximum peak wavelength in the range of 810 to 839 nm in the spectral absorption spectrum in the wavelength range of 600 to 900 nm. It is preferable to determine the wet grinding time while monitoring by measuring the absorption wavelength of the wet grinding liquid.

  In an X-ray diffraction spectrum using CuKα characteristic X-rays used as a raw material in such a production method, Bragg angles (2θ ± 0.2 °) of 6.9 °, 13.2 to 14.2 °, 16.5 Hydroxygallium phthalocyanine having diffraction peaks at °, 26.0 ° and 26.4 °, or 7.0 °, 13.4 °, 16.6 °, 26.0 ° and 26.7 ° (hereinafter referred to as “ "Type I hydroxygallium phthalocyanine") can be obtained by a conventionally known method. An example is shown below.

  First, a method in which o-phthalodinitrile or 1,3-diiminoisoindoline and gallium trichloride are reacted in a predetermined solvent (type I chlorogallium phthalocyanine method); o-phthalodinitrile, alkoxygallium and ethylene glycol Crude gallium phthalocyanine is produced by a method of synthesizing a phthalocyanine dimer (phthalocyanine dimer) by reacting with heating in a predetermined solvent (phthalocyanine dimer method). As the solvent in the above reaction, α-chloronaphthalene, β-chloronaphthalene, α-methylnaphthalene, methoxynaphthalene, dimethylaminoethanol, diphenylethane, ethylene glycol, dialkyl ether, quinoline, sulfolane, dichlorobenzene, dimethylformamide, dimethyl It is preferable to use an inert and high boiling point solvent such as sulfoxide or dimethylsulfamide.

  Next, the crude gallium phthalocyanine obtained in the above step is subjected to an acid pasting process, whereby the crude gallium phthalocyanine is made into fine particles and converted into I-type hydroxygallium phthalocyanine. Here, the acid pasting treatment, specifically, a solution obtained by dissolving crude gallium phthalocyanine in an acid such as sulfuric acid or an acid salt such as a sulfate, is poured into an aqueous alkaline solution, water or ice water, Recrystallized. As the acid used for the acid pasting treatment, sulfuric acid is preferable, and sulfuric acid having a concentration of 70 to 100% (particularly preferably 95 to 100%) is more preferable.

  In the method for producing hydroxygallium phthalocyanine 1, the I-type hydroxygallium phthalocyanine obtained by the acid pasting treatment is wet-pulverized with a solvent to convert the crystal.

  Here, the wet pulverization treatment is performed using a pulverizer using a spherical medium having an outer diameter of 0.1 to 3.0 mm, preferably a spherical medium having an outer diameter of 0.2 to 2.5 mm. Is done using. When the outer shape of the media is larger than 3.0 mm, the pulverization efficiency is lowered, so that the particle diameter does not become small and aggregates tend to be easily generated. Further, when the outer diameter of the medium is smaller than 0.1 mm, it tends to be difficult to separate the medium and the hydroxygallium phthalocyanine 1. In addition, when the media is not spherical, but in other shapes such as a columnar shape or an indefinite shape, the grinding efficiency is reduced, the media is easily worn by grinding, and the wear powder becomes an impurity, which deteriorates the characteristics of hydroxygallium phthalocyanine 1. There is a tendency to make it easy.

  The material of the media is not particularly limited, but it is preferable that it does not easily cause image quality defects when mixed in hydroxygallium phthalocyanine 1, and glass, zirconia, alumina, meno and the like are preferable.

  Further, the container for performing the wet pulverization treatment is preferably one that hardly causes image quality defects even when part of it is mixed in the hydroxygallium phthalocyanine 1, and is made of glass, zirconia, alumina, meno, polypropylene, Teflon (registered trademark). ), Polyphenylene sulfide and the like are preferable. Alternatively, the inner surface of a metal container such as iron or stainless steel may be lined with glass, polypropylene, Teflon (registered trademark), polyphenylene sulfide, or the like.

  The amount of the media used varies depending on the apparatus used, but is 50 parts by weight or more, preferably 55 to 100 parts by weight, based on 1 part by weight of the type I hydroxygallium phthalocyanine. Also, as the media outer diameter decreases, the media density in the device increases even with the same weight (use amount), and the viscosity of the mixed solution increases and the pulverization efficiency changes. It is desirable to perform wet processing at an optimal mixing ratio by controlling the amount of media used and the amount of solvent used.

  Moreover, the temperature of the wet pulverization treatment is preferably 0 to 100 ° C, more preferably 5 to 80 ° C, and particularly preferably 10 to 50 ° C. When the temperature is low, the rate of crystal transition tends to be slow, and when the temperature is too high, the solubility of hydroxygallium phthalocyanine tends to be high and crystal growth tends to be difficult. .

  Examples of the solvent used in the wet grinding treatment include amides such as N, N-dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone; esters such as ethyl acetate, n-butyl acetate, and iso-amyl acetate. In addition to ketones such as acetone, methyl ethyl ketone, methyl iso-butyl ketone, dimethyl sulfoxide and the like. The amount of these solvents used is usually 1 to 200 parts by weight, preferably 1 to 100 parts by weight, based on 1 part by weight of hydroxygallium phthalocyanine.

  As an apparatus used for the wet pulverization treatment, an apparatus using a media such as a vibration mill, an automatic mortar, a sand mill, a dyno mill, a coball mill, an attritor, a planetary ball mill, or a ball mill as a dispersion medium can be used.

  In the method for producing hydroxygallium phthalocyanine 1 described above, the progress speed of crystal conversion is greatly affected by the scale of the wet pulverization process, the stirring speed, the media material, and the like. The wet pulverization treatment time is determined while monitoring the crystal conversion state by measuring the absorption wavelength of the wet pulverization treatment liquid so as to have a maximum peak wavelength in the range of 810 to 839 nm in the spectral absorption spectrum in the wavelength region of 900 nm. It is preferable to continue until crystal conversion to gallium phthalocyanine 1. Here, as a method for monitoring the crystal conversion state by measuring the absorption wavelength of the wet pulverization treatment liquid, for example, a small amount of the pigment solution during the crystal conversion treatment is sampled from the wet pulverization treatment apparatus, and acetone, ethyl acetate, etc. The method of measuring the solution diluted with the solvent by the liquid cell method using a spectrophotometer is mentioned.

  The wet pulverization time thus determined is usually in the range of 5 to 500 hours, preferably in the range of 7 to 300 hours. When the treatment time is less than 5 hours, the crystal conversion is not completed, and the electrophotographic characteristics are deteriorated, and particularly, the sensitivity is apt to be insufficient. Further, when the processing time exceeds 500 hours, sensitivity tends to decrease due to the influence of pulverization stress, productivity decreases, and media wear powder tends to be mixed. By determining the wet pulverization time as described above, it is possible to complete the wet pulverization process in a state where the hydroxygallium phthalocyanine particles are uniformly finely divided. Therefore, it is possible to suppress the quality variation between lots.

  In the method for producing hydroxygallium phthalocyanine 1, it is preferable to perform washing with a solvent and / or heat drying after the wet pulverization treatment. The impurity concentration of hydroxygallium phthalocyanine can be controlled by such washing with a solvent or heat drying. In particular, the thermal weight loss rate when the temperature is raised from 25 ° C. to 400 ° C. is 2.0 to 4.0. % Hydroxygallium phthalocyanine can be obtained efficiently and reliably.

  When the impurity concentration is controlled by washing with a solvent, examples of the solvent used include water, ethanol, methanol, n-butanol, benzyl alcohol, methyl cellosolve, ethyl cellosolve, acetone, methyl ethyl ketone, cyclohexanone, methyl acetate, and ethyl acetate. Organic solvents such as n-butyl acetate, dioxane, tetrahydrofuran, methylene chloride, chloroform, benzene, toluene, xylene, chlorobenzene, dimethylformaldehyde, dimethylacetamide, N, N-dimethylformamide, dimethylsulfoxide, and mixed solvents thereof, And supercritical fluids such as carbon dioxide and nitrogen. As a cleaning method, a known method can be used without any particular limitation. From the viewpoint of cleaning efficiency, a ceramic filter, an ultrasonic cleaner, a Soxhlet extractor, a micromixer having a channel diameter of 10 to 1000 μm, or the like The cleaning method using the is effective.

  Moreover, when controlling an impurity density | concentration by heat drying, as temperature of heat drying, Preferably it is 50-200 degreeC, More preferably, it is 100-180 degreeC. If the heating temperature is less than 50 ° C., it tends to be difficult to completely remove impurities affecting various characteristics of hydroxygallium phthalocyanine. If the heating temperature exceeds 200 ° C., the sensitivity of hydroxygallium phthalocyanine is remarkably reduced. There is a tendency. Moreover, it is preferable that the heat drying treatment time is appropriately adjusted according to the weight of the hydroxygallium phthalocyanine to be treated.

  In order to efficiently remove impurities of hydroxygallium phthalocyanine by heat drying, it is preferable to heat and dry hydroxygallium phthalocyanine under reduced pressure. When performing heat drying under reduced pressure, there is an advantage that the temperature of heat drying can be made lower than when performing under normal pressure. The temperature of the heat drying at this time is preferably in the range of 50 ° C. to 200 ° C., although it depends on the degree of reduced pressure.

  Moreover, it is preferable to perform heat drying in presence of an inert gas. Examples of the inert gas include helium, neon, argon, and the like of group 0 of the periodic table, and these can be used alone or in admixture of two or more. By performing heat drying in the presence of these inert gases, there is an advantage that hydroxygallium phthalocyanine is prevented from being oxidized by oxygen in the air and heat drying at a high temperature is possible. Moreover, it is also preferable to perform heat drying in the state which interrupted light. Thereby, it is possible to prevent hydroxygallium phthalocyanine from being light-fatigued during heat drying.

  Any of the charge generation materials described above can be subjected to a surface treatment to improve the stability of electrical characteristics and prevent image quality defects. As the surface treatment agent, a coupling agent, an organic zirconium compound, an organic titanium compound, an organic aluminum compound, or the like can be used.

  As coupling agents, vinyltrimethoxysilane, γ-methacryloxypropyl-tris (β-methoxyethoxy) silane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane , Vinyltriacetoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ- Examples include silane coupling agents such as aminopropylmethylmethoxysilane, N, N-bis (β-hydroxyethyl) -γ-aminopropyltriethoxysilane, and γ-chloropropyltrimethoxysilane. Among these, silane coupling agents particularly preferably used include vinyltriethoxysilane, vinyltris (2-methoxyethoxysilane), 3-methacryloxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 2- ( 3,4-epoxycyclohexyl) ethyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-aminopropyl Examples include silane coupling agents such as triethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, and 3-chloropropyltrimethoxysilane.

  Examples of the organic zirconium compound include zirconium butoxide, zirconium zirconium acetoacetate, zirconium triethanolamine, acetylacetonate zirconium butoxide, ethyl acetoacetate butoxide, zirconium acetate, zirconium oxalate, zirconium lactate, zirconium phosphonate, zirconium octoate, Organic zirconium compounds such as zirconium naphthenate, zirconium laurate, zirconium stearate, zirconium isostearate, methacrylate zirconium butoxide, stearate zirconium butoxide, isostearate zirconium butoxide can also be used.

  In addition, as the organic titanium compound, tetraisopropyl titanate, tetranormal butyl titanate, butyl titanate dimer, tetra (2-ethylhexyl) titanate, titanium acetylacetonate, polytitanium acetylacetonate, titanium octylene glycolate, titanium lactate ammonium salt , Titanium lactate, titanium lactate ethyl ester, titanium triethanolamate, polyhydroxy titanium stearate and the like.

  Examples of the organoaluminum compound include aluminum isopropylate, monobutoxyaluminum diisopropylate, aluminum butyrate, diethyl acetoacetate aluminum diisopropylate, and aluminum tris (ethyl acetoacetate).

  The binder resin used for the charge generation layer 1 can be selected from a wide range of insulating resins. It can also be selected from organic photoconductive polymers such as poly-N-vinylcarbazole, polyvinylanthracene, polyvinylpyrene, and polysilane. Preferred binder resins include polyvinyl acetal resin, polyarylate resin (polycondensate of bisphenol A and phthalic acid, etc.), polycarbonate resin, polyester resin, phenoxy resin, vinyl chloride-vinyl acetate copolymer, polyamide resin, acrylic resin Examples thereof include, but are not limited to, resins, polyacrylamide resins, polyvinyl pyridine resins, cellulose resins, urethane resins, epoxy resins, caseins, polyvinyl alcohol resins, and polyvinyl pyrrolidone resins. These binder resins can be used alone or in combination of two or more. Of these, polyvinyl acetal resin is particularly preferably used. The blending ratio (weight ratio) between the charge generating substance and the binder resin is preferably in the range of 10: 1 to 1:10.

  The charge generation layer 1 is formed using, for example, a coating liquid in which the specific charge generation material and the binder resin are added to a predetermined solvent. In preparing the charge generation layer coating solution, a dispersion method such as a ball mill dispersion method, an attritor dispersion method, or a sand mill dispersion method can be used. In this dispersion, it is effective that the average particle size of the charge generating material is preferably 0.5 μm or less, more preferably 0.3 μm or less, and still more preferably 0.15 μm or less.

Further, in order to remove foreign matters mixed at the time of dispersion after dispersion, coarse particles having poor dispersion, etc., and obtain a good electrophotographic photosensitive member, a centrifugal separation process or a filtering process can be performed.
Centrifugation and filtering can be performed under any conditions that provide the desired electrophotographic photoreceptor characteristics, but care must be taken not to remove the necessary charge generating material. .
Furthermore, as a coating method used when providing this charge generation layer, a normal method such as a blade coating method, a wire bar coating method, a spray coating method, a dip coating method, a bead coating method, an air knife coating method, or a curtain coating method is used. Can be used.

  Furthermore, various additives can be added to the coating solution for forming the charge generation layer in order to improve the electrical characteristics of the charge generation layer and the image quality. Additives include quinone compounds such as chloranil, bromoanil and anthraquinone, tetracyanoquinodimethane compounds, fluorenones such as 2,4,7-trinitrofluorenone and 2,4,5,7-tetranitro-9-fluorenone Compound, 2- (4-biphenyl) -5- (4-t-butylphenyl) -1,3,4-oxadiazole, 2,5-bis (4-naphthyl) -1,3,4-oxadi Azoles, oxadiazole compounds such as 2,5-bis (4-diethylaminophenyl) -1,3,4-oxadiazole, xanthone compounds, thiophene compounds, 3,3 ′, 5,5′-tetra- Electron transport materials such as diphenoquinone compounds such as t-butyldiphenoquinone, electron transport pigments such as polycyclic condensation systems and azo systems, zirconium chelate compounds Titanium chelate compounds, aluminum chelate compounds, titanium alkoxide compounds, organic titanium compounds, there can be used a known material such as a silane coupling agent.

  As silane coupling agents, vinyltrimethoxysilane, γ-methacryloxypropyl-tris (β-methoxyethoxy) silane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxy Silane, vinyltriacetoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ -Aminopropylmethylmethoxysilane, N, N-bis (β-hydroxyethyl) -γ-aminopropyltriethoxysilane, γ-chloropropyltrimethoxysilane and the like.

  Zirconium chelate compounds include: zirconium butoxide, zirconium zirconium acetoacetate, zirconium triethanolamine, acetylacetonate zirconium butoxide, ethyl acetoacetate butoxide, zirconium acetate, zirconium oxalate, zirconium lactate, zirconium phosphonate, zirconium octoate, naphthenic acid Zirconium, zirconium laurate, zirconium stearate, zirconium isostearate, methacrylate zirconium butoxide, stearate zirconium butoxide, isostearate zirconium butoxide and the like.

  Titanium chelate compounds include tetraisopropyl titanate, tetranormal butyl titanate, butyl titanate dimer, tetra (2-ethylhexyl) titanate, titanium acetylacetonate, polytitanium acetylacetonate, titanium octylene glycolate, titanium lactate ammonium salt, titanium Examples include lactate, titanium lactate ethyl ester, titanium triethanolamate, and polyhydroxytitanium stearate.

  Examples of the aluminum chelate compound include aluminum isopropylate, monobutoxy aluminum diisopropylate, aluminum butyrate, diethyl acetoacetate aluminum diisopropylate, and aluminum tris (ethyl acetoacetate).

  These compounds can be used alone or as a mixture or polycondensate of a plurality of compounds.

  The charge transport layer 2 includes, for example, a charge transport material and a binder resin. Examples of the charge transport material used for the charge transport layer include oxadiazole derivatives such as 2,5-bis (p-diethylaminophenyl) -1,3,4-oxadiazole, and 1,3,5-triphenyl. Pyrazoline, pyrazoline derivatives such as 1- [pyridyl- (2)]-3- (p-diethylaminostyryl) -5- (p-diethylaminostyryl) pyrazoline, triphenylamine, tri (p-methylphenyl) amine, N , N′-bis (3,4-dimethylphenyl) biphenyl-4-amine, dibenzylaniline, 9,9-dimethyl-N, N′-di (p-tolyl) fluorenon-2-amine Tertiary amino compounds, N, N′-diphenyl-N, N′-bis (3-methylphenyl)-[1,1-biphenyl] -4,4′-diamine, etc. Aromatic tertiary diamino compounds, 1,2, such as 3- (4,4′-dimethylaminophenyl) -5,6-di- (4,4′-methoxyphenyl) -1,2,4-triazine Hydrazone derivatives such as 4-triazine derivatives, 4-diethylaminobenzaldehyde-1,1-diphenylhydrazone, 4-diphenylaminobenzaldehyde-1,1-diphenylhydrazone, [p- (diethylamino) phenyl]-(1-naphthyl) phenylhydrazone Quinazoline derivatives such as 2-phenyl-4-styrylquinazoline, benzofuran derivatives such as 6-hydroxy-2,3-di (p-methoxyphenyl) -benzofuran, p- (2,2-diphenylvinyl) -N, N Α-stilbene derivatives such as' -diphenylaniline, enamine derivatives, N-ethyl Hole transport materials such as carbazole derivatives such as carbazole, poly-N-vinylcarbazole and derivatives thereof; quinone compounds such as chloranil, bromoanil and anthraquinone, tetracyanoquinodimethane compounds, 2,4,7-trinitrofluorenone Fluorenone compounds such as 2,4,5,7-tetranitro-9-fluorenone, 2- (4-biphenyl) -5- (4-t-butylphenyl) -1,3,4-oxadiazole, 2, Oxadiazole compounds such as 5-bis (4-naphthyl) -1,3,4-oxadiazole, 2,5-bis (4-diethylaminophenyl) -1,3,4-oxadiazole, xanthone Compounds, thiophene compounds, diphenoquinone compounds such as 3,3 ′, 5,5′-tetra-t-butyldiphenoquinone, etc. Electron transport material; or the like polymers and the like having a group having a structure similar to the above compound in the main chain or side chain. These charge transport materials can be used alone or in combination of two or more.

  The binder resin used for the charge transport layer 2 is not particularly limited, but a resin that exhibits electrical insulation and can form a film is preferable. Examples of such binder resins include polycarbonate resin, polyester resin, methacrylic resin, acrylic resin, polyvinyl chloride resin, polyvinylidene chloride resin, polystyrene resin, polyvinyl acetate resin, styrene-butadiene copolymer, and vinylidene chloride. Acrylonitrile copolymer, vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate-maleic anhydride copolymer, silicone resin, silicone-alkyd resin, phenol-formaldehyde resin, styrene-alkyd resin, poly-N-carbazole , Polyvinyl butyral, polyvinyl formal, polysulfone, casein, gelatin, polyvinyl alcohol, ethyl cellulose, phenol resin, polyamide, carboxymethyl cellulose, vinylidene chloride Polymer waxes, polyurethanes, and the like. Among these, a polycarbonate resin, a polyester resin, a methacrylic resin, and an acrylic resin are preferable because they are excellent in compatibility with a charge transport material, solubility in a solvent, and strength. These binder resins can be used alone or in combination of two or more. The mixing ratio (weight ratio) between the binder resin and the charge transport material can be arbitrarily set, but is preferably 70:30 to 40:60.

  The charge transport layer 2 can be formed by applying a coating liquid obtained by adding a charge transport material and a binder resin to a predetermined solvent on the charge generation layer 1 and drying it. As a coating method, a normal method such as a blade coating method, a wire bar coating method, a spray coating method, a dip coating method, a bead coating method, an air knife coating method, or a curtain coating method can be used. As the solvent used in the coating solution, a common organic solvent such as dioxane, tetrahydrofuran, methylene chloride, chloroform, chlorobenzene, toluene and the like can be used alone or in admixture of two or more.

  The film thickness of the charge transport layer 2 is preferably 5 to 50 μm, and more preferably 10 to 35 μm, from the viewpoint of suppressing deterioration of electrical characteristics and film strength.

The charge mobility of the charge transport layer 2 is preferably faster from the viewpoint of use at high speed and suppression of streak density unevenness, preferably 1.0 × 10 ⁻⁶ cm ² / V · s or more, more preferably 5 0.0 × 10 ⁻⁶ cm ² / V · s or more, more preferably 1.0 × 10 ⁻⁵ cm ² / V · s or more.

  Further, the electrophotographic photosensitive member of the present invention includes an antioxidant and a light stabilizer in the photosensitive layer for the purpose of preventing deterioration of the photosensitive member due to ozone, oxidizing gas, or light / heat generated in the electrophotographic apparatus. -Additives such as heat stabilizers can be added.

  Examples of the antioxidant include hindered phenol, hindered amine, paraphenylenediamine, arylalkane, hydroquinone, spirochroman, spiroidanone and derivatives thereof, organic sulfur compounds, and organic phosphorus compounds.

  Examples of phenolic antioxidants include 2,6-di-t-butyl-4-methylphenol, styrenated phenol, n-octadecyl-3- (3 ′, 5′-di-t-butyl-4′-hydroxy Phenyl) -propionate, 2,2′-methylene-bis- (4-methyl-6-tert-butylphenol), 2-t-butyl-6- (3′-tert-butyl-5′-methyl-2′-) Hydroxybenzyl) -4-methylphenyl acrylate, 4,4′-butylidene-bis (3-methyl-6-tert-butylphenol), 4,4′-thio-bis (3-methyl-6-tert-butylphenol), 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, tetrakis [methylene-3- (3 ′, 5 ′,-di-t-butyl-4 ′ Hydroxyphenyl) propionate] -methane, 3,9-bis [2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl] -2,4 , 8,10-tetraoxaspiro [5,5] undecane and the like.

  Examples of hindered amine compounds include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, 1- [2- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl] -4- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy]- 2,2,6,6-tetramethylpiperidine, 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, dimethyl-1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine succinate Condensate, poly [{6- (1,1,3,3-tetramethylbutyl) imino-1,3,5-triazine-2,4-diimyl} {(2,2,6,6-tetramethyl- 4-piperidyl) imino} hexamethylene {(2,3,6,6-tetramethyl-4-piperidyl) imino}], 2- (3,5-di-t-butyl-4-hydroxybenzyl) -2- n-Butylmalonate bis (1,2,2,6,6-pentamethyl-4-piperidyl), N, N′-bis (3-aminopropyl) ethylenediamine-2,4-bis [N-butyl-N— (1,2,2,6,6-pentamethyl-4-piperidyl) amino] -6-chloro-1,3,5-triazine condensate and the like.

  Examples of organic sulfur-based antioxidants include dilauryl-3,3′-thiodipropionate, dimyristyl-3,3′-thiodipropionate, distearyl-3,3′-thiodipropionate, pentaerythritol-tetrakis. (Β-lauryl thiopropionate), ditridecyl-3,3′-thiodipropionate, 2-mercaptobenzimidazole and the like.

  Examples of the organophosphorus antioxidant include trisnonylphenyl phosfte, triphenyl phosfeft, and tris (2,4-di-t-butylphenyl) phosphite.

  Organic sulfur-based and organic phosphorus-based antioxidants are said to be secondary antioxidants, and when used in combination with primary antioxidants such as phenol-based antioxidants and amine-based antioxidants, a synergistic effect can be obtained. .

  Examples of the light stabilizer include benzophenone, benzotriazole, dithiocarbamate, and tetramethylpiperidine derivatives.

  Examples of the benzophenone light stabilizer include 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 2,2'-dihydroxy-4-methoxybenzophenone.

  Examples of the benzotriazole-based light stabilizer include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- [2′-hydroxy-3′-3 ″, 4 ″, 5 ″, 6 ″ -tetrahydro. Phthalimidomethyl) -5′-methylphenyl] benzotriazole, 2- (2′-hydroxy-3′-tert-butyl-5′-methylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3) '-T-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3', 5'-di-t-butylphenyl) benzotriazole, 2- (2'-hydroxy -5'-t-octylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-amylphenyl) -benzotriazole, and the like. It is.

  Other compounds include 2,4-di-t-butylphenyl-3 ', 5'-di-t-butyl-4'-hydroxybenzoate, nickel dibutyldithiocarbamate, and the like.

Further, at least one kind of electron accepting substance can be included for the purpose of improving sensitivity, reducing residual potential, reducing fatigue during repeated use, and the like. Examples of the electron accepting substance that can be used in the electrophotographic photoreceptor of the present invention include succinic anhydride, maleic anhydride, dibromomaleic anhydride, phthalic anhydride, tetrabromophthalic anhydride, tetracyanoethylene, tetracyanoquinodimethane. O-dinitrobenzene, m-dinitrobenzene, chloranil, dinitroanthraquinone, trinitrofluorenone, picric acid, o-nitrobenzoic acid, p-nitrobenzoic acid, phthalic acid and the like. Of these, fluorenone-based, quinone-based, and benzene derivatives having electron-withdrawing substituents such as Cl, CN, and NO ₂ are particularly preferable.

  A small amount of silicone oil can be added to the coating solution as a leveling agent for improving the smoothness of the coating film.

  The electrophotographic photosensitive member of the present invention can be provided with a protective layer 5 as necessary. By providing the protective layer 5, in the electrophotographic photosensitive member having a laminated structure, chemical change of the charge transport layer 2 during charging can be prevented, and the mechanical strength of the photosensitive layer can be further improved. The protective layer 5 is constituted by containing a conductive material in an appropriate binder resin, for example.

  Examples of the conductive material used for the protective layer 5 include metallocene compounds such as N, N′-dimethylferrocene, N, N′-diphenyl-N, N′-bis (3-methylphenyl)-[1,1′-biphenyl, ] Aromatic amine compounds such as -4,4'-diamine, molybdenum oxide, tungsten oxide, antimony oxide, tin oxide, titanium oxide, indium oxide, solid solution carrier of tin oxide and antimony oxide or antimony oxide, or a mixture thereof. Or what mixed these metal oxides in single particle, or what coat | covered is mentioned, However, It is not limited to these.

  The binder resin used for the protective layer 5 is polyamide resin, polyvinyl acetal resin, polyurethane resin, polyester resin, epoxy resin, polyketone resin, polycarbonate resin, polyvinyl ketone resin, polystyrene resin, polyacrylamide resin, polyimide resin, polyamideimide resin. These can be used, and these can be used after crosslinking. Furthermore, a siloxane-based resin having a charge transporting property and having a crosslinked structure can also be used as a protective layer. In the case of a cured siloxane resin film containing a charge transporting compound, any known material can be used as the charge transporting compound. For example, JP-A-10-95787, JP-A-10-251277, Examples thereof include, but are not limited to, compounds disclosed in JP-A-11-32716, JP-A-11-38656, and JP-A-11-236391. A specific example of the cured siloxane resin film containing a charge transporting compound can be represented by the general formula (I).

F- [D-SiR ¹⁴ _3-a (OR ¹⁵ ) _a ] _b (I)
[In General Formula (I), F represents an organic group derived from a photofunctional compound, D represents a divalent group, R ¹⁴ represents a hydrogen atom, an alkyl group, or a substituted or unsubstituted aryl group. , R ¹⁵ represents a hydrogen atom, an alkyl group, or a substituted or unsubstituted aryl group, a represents an integer of 1 to 3, and b represents an integer of 1 to 4. ]

  In general formula (I), F is an organic group having photoelectric characteristics, more specifically, photocarrier transport characteristics, and the structure of a photofunctional compound conventionally known as a charge transport material can be used as it is. it can. Specific examples of the organic group represented by F include triarylamine compounds, benzidine compounds, arylalkane compounds, aryl-substituted ethylene compounds, stilbene compounds, anthracene compounds, hydrazone compounds, and the like. Examples include a compound skeleton having a hole transport property, and a compound skeleton having an electron transport property such as a quinone compound, a fluorenone compound, a xanthone compound, a benzophenone compound, a cyanovinyl compound, and an ethylene compound.

In the general formula (I), a group represented by —SiR ¹⁴ _3-a (OR ¹⁵ ) _a forms a three-dimensional Si—O—Si bond, that is, an inorganic glassy network by cross-linking reaction with each other. Is to do.

In the general formula (I), the divalent group represented by D is for directly binding F for imparting charge transporting properties to a three-dimensional inorganic glassy network. In addition, the inorganic glassy network, which has firmness but is brittle, is imparted with appropriate flexibility and has an effect of improving the strength as a film. _{Specifically, -C n H 2n -, -} C n H 2n-2 -, - C n H 2n-4 - 2 divalent hydrocarbon group represented by (n is preferably 2 to 15) _{, -COO -, - S -,} - O -, - CH 2 -C 6 H 4 -, - N = H -, - C 6 H 4 -C 6 H 4 -, and introducing these combinations and substituents And the like.

Preferable examples of the organic group represented by F include groups represented by the following general formula (II). When F is a group represented by the general formula (II), particularly excellent photoelectric characteristics and mechanical characteristics are exhibited.

[In General Formula (II), Ar ^{3 to} Ar ⁶ each independently represents a substituted or unsubstituted aryl group, Ar ⁷ represents a substituted or unsubstituted aryl group or an arylene group, and k represents 0 or 1 And b of Ar ^{3 to} Ar ⁷ have a bond bonded to a group represented by —D—SiR ¹⁴ _3-a (OR ¹⁵ ) _a . ]

−Ａｒ−Ｚ’_ｓ−Ａｒ−Ｘ_ｍ （ＩＩ−７）
［式中、Ｒ^１６は水素原子、炭素数１〜４のアルキル基、炭素数１〜４のアルキル基若しくは炭素数１〜４のアルコキシ基で置換されたフェニル基、又は未置換のフェニル基、炭素数７〜１０のアラルキル基からなる群より選ばれる１種を表し、Ｒ^１７〜Ｒ^１９はそれぞれ水素原子、炭素数１〜４のアルキル基、炭素数１〜４のアルキル基若しくは炭素数１〜４のアルコキシ基で置換されたフェニル基、又は未置換のフェニル基、炭素数７〜１０のアラルキル基、ハロゲン原子からなる群より選ばれる１種を表し、Ａｒは置換又は未置換のアリーレン基を表し、Ｘは一般式（Ｉ）中の−Ｄ−ＳｉＲ^１４ _３−ａ（ＯＲ^１５）_ａを表し、ｔは１〜３の整数を表す。］ Ar ^{3 to} Ar ⁶ in the general formula (II) are preferably any of the following formulas (II-1) to (II-7).

_{-Ar-Z 's -Ar-X} m (II-7)
[Wherein, R ¹⁶ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group substituted with an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, or an unsubstituted phenyl group, It represents one selected from the group consisting of an aralkyl group having 7 to 10 carbon ^atoms, each of R 17 ^{to R 19} a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkyl group or a carbon of 1 to 4 carbon atoms 1 Represents one selected from the group consisting of a phenyl group substituted by an alkoxy group of ˜4 or an unsubstituted phenyl group, an aralkyl group having 7 to 10 carbon atoms, and a halogen atom, and Ar represents a substituted or unsubstituted arylene group X represents -D-SiR ¹⁴ _3-a (OR ¹⁵ ) _a in general formula (I), and t represents an integer of 1 to 3. ]

［式中、Ｒ^２０及びＲ^２１はそれぞれ水素原子、炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基若しくは炭素数１〜４のアルコキシ基で置換されたフェニル基又は未置換のフェニル基、炭素数７〜１０のアラルキル基、ハロゲン原子からなる群より選ばれる１種を表し、ｔは１〜３の整数を表す。］ Here, as Ar in Formula (II-7), what is represented by following formula (II-8) or (II-9) is preferable.

[Wherein R ²⁰ and R ²¹ are each a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a phenyl group substituted with an alkoxy group having 1 to 4 carbon atoms, or an unsubstituted group. 1 type selected from the group which consists of a phenyl group, a C7-10 aralkyl group, and a halogen atom is represented, and t represents the integer of 1-3. ]

［式中、Ｒ^２２及びＲ^２３はそれぞれ水素原子、炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基若しくは炭素数１〜４のアルコキシ基で置換されたフェニル基又は未置換のフェニル基、炭素数７〜１０のアラルキル基、ハロゲン原子からなる群より選ばれる１種を表し、Ｗは２価の基を表し、ｑ及びｒはそれぞれ１〜１０の整数を表し、ｔはそれぞれ１〜３の整数を表す。］ Moreover, as Z 'in Formula (II-7), what is represented by either of following formula (II-10)-(II-17) is preferable.
_{- (CH 2) q - (} II-10)
_{- (CH 2 CH 2 O)} r - (II-11)

[Wherein R ²² and R ²³ are each a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a phenyl group substituted with an alkoxy group having 1 to 4 carbon atoms, or an unsubstituted group. 1 type chosen from the group which consists of a phenyl group, a C7-10 aralkyl group, and a halogen atom, W represents a bivalent group, q and r represent the integer of 1-10, respectively, t represents Represents an integer of 1 to 3; ]

  W in the above formulas (II-16) and (II-17) is preferably any one of divalent groups represented by the following (II-18) to (II-26).

—CH ₂ — (II-18)

_{-C (CH 3) 2 - (} II-19)

  -O- (II-20)

  -S- (II-21)

_{-C (CF 3) 2 - (} II-22)

［式中、ｕは０〜３の整数を表す。］ —Si (CH ₃ ) ₂ — (II-23)

[Wherein u represents an integer of 0 to 3. ]

In general formula (II), Ar ⁵ is an aryl group exemplified in the description of Ar ^{1 to} Ar ⁴ when k is 0, and when k is 1, a predetermined hydrogen atom is taken from the aryl group. Excluded arylene group.

In the general formula (I), the divalent group represented by D plays a role of linking F that imparts photoelectric characteristics and A that is directly bonded to a three-dimensional inorganic glassy network, On the other hand, it plays a role of imparting appropriate flexibility to an inorganic glassy network having brittleness and improving toughness as a film. Examples of the divalent group represented by D, and _{specifically, -C n H 2n -, -} C n H 2n-2 -, - C n H 2n-4 - 2 divalent hydrocarbon group represented by (n represents an integer of 1~15), - COO -, - S -, - O -, - CH 2 -C 6 H 4 -, - n = CH -, - C 6 H 4 -C 6 H 4 -, A combination of these, or a substituent introduced.

  In general formula (I), b is preferably 2 or more. When b is 2 or more, the photofunctional organosilicon compound represented by the general formula (I) has two or more Si atoms, which facilitates formation of an inorganic glassy network and improves mechanical strength. Tend to.

  The compound represented by general formula (I) may be used individually by 1 type, and may be used in combination of 2 or more type.

  A compound represented by the following general formula (III) may be used in combination with the compound represented by the general formula (I) for the purpose of further improving the mechanical strength of the cured film.

B (—SiR ¹⁴ _3-a (OR ¹⁵ ) _a ) _n (III)
[In the formula ^(III), it represents an ^{R 14,} R ^15, a is ^{R 14, R 15,} a same definitions and in the general formula (I). B represents an n-valent group composed of one or a combination of two or more selected from an n-valent hydrocarbon group and —NH—, and n represents an integer of 2 or more. ]

  B in the general formula (III) represents an n-valent group composed of a group selected from an n-valent hydrocarbon group and —NH— or a combination of two or more thereof, as described above. When B is an n-valent hydrocarbon group or includes the hydrocarbon group, the hydrocarbon group may be any of an alkyl group, an aryl group, an alkylaryl group, and an arylalkyl group. . Further, the alkyl group of the hydrocarbon group may be either linear or branched. Further, the hydrocarbon group may have a substituent.

The compound represented by the general formula (III) is a compound having a substituted silicon group having a hydrolyzable group represented by -SiR ¹⁴ _3-a (OR ¹⁵ ) _a . The compound represented by the general formula (III) forms a Si—O—Si bond by the reaction with the compound represented by the general formula (I) or the reaction between the compounds represented by the general formula (III). To give a three-dimensional crosslinked cured film. When the compound represented by the general formula (III) and the compound represented by the general formula (I) are used in combination, the crosslinked structure of the cured film tends to be three-dimensional, and the cured film has an appropriate flexibility. Therefore, stronger mechanical strength can be obtained. Preferred examples of the compound represented by the general formula (III) are shown in Table 1.

  The compound represented by the general formula (I) may be used alone, or for the purpose of adjusting the film formability and flexibility of the film, the compound represented by the general formula (III) and other cups You may mix and use a ring agent and a fluorine compound. As such a compound, various silane coupling agents and commercially available silicone hard coat agents can be used.

  As silane coupling agents, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxy Silane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, tetramethoxysilane, methyltrimethoxysilane, Dimethyldimethoxysilane and the like can be used. Commercially available hard coat agents include KP-85, X-40-9740, X-40-2239 (above, manufactured by Shin-Etsu Silicone), AY42-440, AY42-441, AY49-208 (above, Toray Dow Corning) Etc.) can be used. In addition, (tridecafluoro-1,1,2,2-tetrahydrooctyl) triethoxysilane, (3,3,3-trifluoropropyl) trimethoxysilane, 3- ( Heptafluoroisopropoxy) propyltriethoxysilane, 1H, 1H, 2H, 2H-perfluoroalkyltriethoxysilane, 1H, 1H, 2H, 2H-perfluorodecyltriethoxysilane, 1H, 1H, 2H, 2H-perfluoro A fluorine-containing compound such as octyltriethoxysilane may be added. The silane coupling agent can be used in any amount, but the amount of the fluorine-containing compound is desirably 0.25 or less by weight with respect to the compound not containing fluorine. Beyond this, there may be a problem with the film formability of the crosslinked film.

  These coating solutions are prepared without solvent or, if necessary, alcohols such as methanol, ethanol, propanol and butanol; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran, diethyl ether and dioxane. Although it can be used, it preferably has a boiling point of 100 ° C. or less, and can be used by arbitrarily mixing. The amount of the solvent can be arbitrarily set, but if it is too small, the compound represented by the general formula (I) is likely to be precipitated, so 0.5 to 30 parts by weight with respect to 1 part by weight of the compound represented by the general formula (I). Preferably, it is used at 1 to 20 parts by weight. The reaction temperature and time vary depending on the type of raw material, but it is usually 0-100 ° C, preferably 10-70 ° C, particularly preferably 10-50 ° C. Although there is no restriction | limiting in particular in reaction time, Since it will become easy to produce gelation when reaction time becomes long, it is preferable to carry out in 10 minutes-100 hours.

In order to adjust the coating solution, the following catalyst can be used as a solid catalyst insoluble in the system, and hydrolysis can be performed in advance.
Cation exchange resin: Amberlite 15, Amberlite 200C, Amberlist 15 (above, manufactured by Rohm and Haas); Dowex MWC-1-H, Dowex 88, Dowex HCR-W2 (above, Dow Chemical Company); Lebatit SPC-108, Lebatit SPC-118 (above, Bayer); Diaion RCP-150H (Mitsubishi Kasei); Sumikaion KC-470, Duolite C26-C, Duolite C-433 Duolite-464 (above, manufactured by Sumitomo Chemical Co., Ltd.); Anion exchange resin such as Nafion-H (produced by DuPont): Amberlite IRA-400, Amberlite IRA-45 (above, manufactured by Rohm and Haas Co., Ltd.) Inorganic solid in which a group containing a protonic acid group or the like is bonded to the surface: Z _{(O 3 PCH 2 CH 2 SO} 3 H) 2, Th (O 3 PCH 2 CH 2 COOH) polyorganosiloxanes containing ₂ such protonic acid group: polyorganosiloxane such as a heteropoly acid having a sulfonic acid group: cobalt tungstate Isopolyacids such as phosphomolybdic acid: Monometallic oxides such as niobic acid, tantalum acid, and molybdic acid: Composite metal oxides such as silica gel, alumina, chromia, zirconia, CaO, and MgO: silica-alumina, silica-magnesia, silica - zirconia, zeolites such as clay minerals: acid clay, activated clay, montmorillonite, etc. kaolinite metal sulfates: LiSO _4, MgSO _4, metal phosphates: phosphate zirconia, etc. lanthanum phosphate metal nitrate: LiNO _3, Mn (NO _{3) 2} a group containing an amino group such as tables Inorganic solids are coupled to: aminopropyltriethoxysilane on silica gel reacted containing an amino group such as a solid obtained polyorganosiloxane: such as amino-modified silicone resin.

  Of these catalysts, at least one kind is used to cause the hydrolysis condensation reaction. These catalysts can be installed in a fixed bed and the reaction can be carried out in a flow system or batchwise. Although the usage-amount of a catalyst is not specifically limited, 0.1-20 weight% is preferable with respect to the total amount of the material containing a hydrolysable silicon substituent.

  The amount of water added during the hydrolytic condensation is not particularly limited. However, since it affects the storage stability of the product and further the suppression of gelation when subjected to polymerization, it is preferable to add water of the compound represented by the general formula (I). It is preferable to use it in a proportion of 30 to 500%, more preferably 50 to 300%, based on the theoretical amount necessary for hydrolyzing all the degradable groups. When the amount of water is more than 500%, the storage stability of the product is deteriorated or the product is easily precipitated. On the other hand, when the amount of water is less than 30%, unreacted compounds are increased and phase separation is likely to occur during application and curing of the coating solution, and strength is likely to decrease.

  Further, as curing catalysts, proton acids such as hydrochloric acid, acetic acid, phosphoric acid and sulfuric acid, bases such as ammonia and triethylamine, organic tin compounds such as dibutyltin diacetate, dibutyltin dioctoate and stannous oxalate, tetra-n -Organic titanium compounds such as butyl titanate and tetraisopropyl titanate, organoaluminum compounds such as aluminum tributoxide and aluminum triacetylacetonate, iron salts of organic carboxylic acids, manganese salts, cobalt salts, zinc salts, zirconium salts, etc. . Among these, a metal compound is preferable from the viewpoint of storage stability, and further, metal acetylacetonate or acetylacetate is preferable, and aluminum triacetylacetonate is particularly preferable. The amount of the curing catalyst used can be arbitrarily set, but is preferably 0.1 to 20% by weight with respect to the total amount of materials containing hydrolyzable silicon substituents in terms of storage stability, characteristics, strength, etc. More preferably, it is 3 to 10% by weight. The curing temperature can be arbitrarily set, but is set to 60 ° C. or higher, more preferably 80 ° C. or higher in order to obtain a desired strength. Although hardening time can be arbitrarily set as needed, 10 minutes-5 hours are preferable. It is also effective to stabilize the characteristics after the curing reaction by maintaining a high humidity state. Furthermore, depending on the application, it can be hydrophobized by surface treatment with hexamethyldisilazane, trimethylchlorosilane, or the like.

  It is preferable to add an antioxidant to the protective layer 5 of the electrophotographic photosensitive member for the purpose of preventing deterioration due to an oxidizing gas such as ozone generated by a charger. When the mechanical strength of the surface of the electrophotographic photosensitive member is increased to extend its life, the electrophotographic photosensitive member is brought into contact with the oxidizing gas for a long time, so that stronger oxidation resistance than before is required. Antioxidants are preferably hindered phenols or hindered amines, organic sulfur antioxidants, phosphite antioxidants, dithiocarbamate antioxidants, thiourea antioxidants, benzimidazole antioxidants. , Etc., may be used. The addition amount of the antioxidant is preferably 20% by weight or less, and more preferably 10% by weight or less.

  Examples of the hindered phenol antioxidant include 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-butylhydroquinone, N, N′-hexamethylene bis (3,5-di). -T-butyl-4-hydroxyhydrocinnamide, 3,5-di-t-butyl-4-hydroxybenzylphosphonate diethyl ester, 2,4-bis [(octylthio) methyl] -o-cresol, 2, 6-di-t-butyl-4-ethylphenol, 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2,2'-methylenebis (4-ethyl-6-t-butylphenol), 4 , 4'-butylidenebis (3-methyl-6-t-butylphenol), 2,5-di-t-amylhydroquinone, 2-t-butyl-6- (3-butyl-2-hydride) Roxy-5-methylbenzyl) -4-methylphenyl acrylate, 4,4'-butylidenebis (3-methyl-6-t-butylphenol) and the like.

  Also, a resin that dissolves in alcohol can be added for the purposes of discharge gas resistance, mechanical strength, scratch resistance, particle dispersibility, viscosity control, torque reduction, wear amount control, pot life extension, and the like. Examples of resins soluble in alcohol solvents include polyvinyl acetal resins such as polyvinyl butyral resin, polyvinyl formal resin, and partially acetalized polyvinyl acetal resin in which a part of butyral is modified with formal, acetoacetal, etc. (for example, manufactured by Sekisui Chemical Co., Ltd.) ESREC B, K, etc.), polyamide resin, cellulose resin, phenol resin and the like. In particular, polyvinyl acetal resin is preferable in terms of electrical characteristics. The average molecular weight of the resin is preferably 2,000 to 100,000, more preferably 5,000 to 50,000. When the average molecular weight is less than 2,000, a desired effect tends to be hardly obtained. On the other hand, if the average molecular weight exceeds 100,000, the solubility becomes low and the addition amount is limited, or the film formation may be poor at the time of coating. The amount of the resin added is preferably 1 to 40% by weight, more preferably 1 to 30% by weight, and particularly preferably 5 to 20% by weight. If the amount of resin added is less than 1% by weight, the desired effect tends to be difficult to obtain, and if it exceeds 40% by weight, image blurring tends to occur under high temperature and high humidity.

  Various fine particles can also be added in order to improve the antifouling substance adhesion and lubricity on the surface of the electrophotographic photosensitive member. The fine particles may be used alone or in combination of two or more. Examples of the fine particles include silicon-containing fine particles. Silicon-containing fine particles are fine particles containing silicon as a constituent element, and specific examples include colloidal silica and silicone fine particles. The colloidal silica used as the silicon-containing fine particles is selected from acidic or alkaline aqueous dispersions having an average particle diameter of 1 to 100 nm, preferably 10 to 30 nm, or those dispersed in organic solvents such as alcohols, ketones and esters. A commercially available product can be used. The solid content of colloidal silica in the outermost surface layer is not particularly limited, but is 0.1 to 50 based on the total solid content of the outermost surface layer in terms of film forming properties, electrical characteristics, and strength. It is used in the range of wt%, preferably 0.1-30 wt%.

  Silicone fine particles used as silicon-containing fine particles are spherical and have an average particle diameter of 1 to 500 nm, preferably 10 to 100 nm, and are selected from silicone resin particles, silicone rubber particles, and silicone surface-treated silica particles, and are generally commercially available. Can be used. Silicone fine particles are small particles that are chemically inert and excellent in dispersibility in resin, and since the content required to obtain sufficient characteristics is low, the electron does not hinder the crosslinking reaction, The surface properties of the photographic photoreceptor can be improved. In other words, it is possible to improve the lubricity and water repellency of the surface of the electrophotographic photosensitive member while being uniformly incorporated into a strong cross-linked structure, and to maintain good wear resistance and adherence to contaminants over a long period of time. it can. The content of the silicone fine particles in the outermost surface layer in the electrophotographic photoreceptor of the present invention is in the range of 0.1 to 30% by weight, preferably in the range of 0.5 to 10% by weight, based on the total solid content of the outermost surface layer. .

Other fine particles include fluorine-based fine particles such as ethylene tetrafluoride, ethylene trifluoride, propylene hexafluoride, vinyl fluoride, vinylidene fluoride, and “8th Polymer Materials Forum Lecture Proceedings p89”. Fine particles made of a resin obtained by copolymerizing a fluororesin and a monomer having a hydroxyl group, ZnO—Al ₂ O ₃ , SnO ₂ —Sb ₂ O ₃ , In ₂ O ₃ —SnO ₂ , ZnO—TiO ₂ , Examples thereof include semiconductive metal oxides such as ZnO—TiO ₂ , MgO—Al ₂ O ₃ , FeO—TiO ₂ , TiO ₂ , SnO ₂ , In ₂ O ₃ , ZnO, and MgO. For the same purpose, an oil such as silicone oil can be added. Silicone oils include silicone oils such as dimethylpolysiloxane, diphenylpolysiloxane, and phenylmethylsiloxane, amino-modified polysiloxane, epoxy-modified polysiloxane, carboxyl-modified polysiloxane, carbinol-modified polysiloxane, methacryl-modified polysiloxane, and mercapto-modified polysiloxane. Reactive silicone oils such as siloxane and phenol-modified polysiloxane, cyclic dimethylcyclosiloxanes such as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, 1,3,5- Trimethyl-1,3,5-triphenylcyclotrisiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetraphenylcyclo Cyclosiloxane, cyclic methylphenylcyclosiloxanes such as 1,3,5,7,9-pentamethyl-1,3,5,7,9-pentaphenylcyclopentasiloxane, and cyclic phenylcyclosiloxanes such as hexaphenylcyclotrisiloxane , Fluorine-containing cyclosiloxanes such as 3- (3,3,3-trifluoropropyl) methylcyclotrisiloxane, hydrosilyl group-containing cyclosiloxanes such as methylhydrosiloxane mixtures, pentamethylcyclopentasiloxane, and phenylhydrocyclosiloxanes And cyclic siloxanes such as vinyl group-containing cyclosiloxanes such as pentavinylpentamethylcyclopentasiloxane.

  In addition, additives such as plasticizers, surface modifiers, antioxidants, and photodegradation inhibitors can also be used. Examples of the plasticizer include biphenyl, biphenyl chloride, terphenyl, dibutyl phthalate, diethylene glycol phthalate, dioctyl phthalate, triphenyl phosphate, methyl naphthalene, benzophenone, chlorinated paraffin, polypropylene, polystyrene, and various fluorohydrocarbons.

  A siloxane-based resin having a charge transporting property and having a cross-linked structure has excellent mechanical strength and sufficient photoelectric characteristics. Therefore, it can be used as it is as a charge transport layer of a multilayer photoreceptor. In that case, a usual method such as a blade coating method, a Meyer bar coating method, a spray coating method, a dip coating method, a bead coating method, an air knife coating method, or a curtain coating method can be used. However, when a required film thickness cannot be obtained by a single application, the necessary film thickness can be obtained by applying a plurality of times. When performing multiple times of repeated application, the heat treatment may be performed each time the application is performed or after multiple times of repeated application.

  The single-layer type photosensitive layer includes a charge generation material, a charge transport material, and a binder resin. As the binder resin, the same binder resins as those used for the charge generation layer and the charge transport layer can be used. The content of the charge generating material in the single-layer type photosensitive layer is preferably 10 to 85% by weight, more preferably 20 to 50% by weight. A charge transport material or a polymer charge transport material may be added to the single-layer type photosensitive layer 8 for the purpose of improving photoelectric characteristics. The addition amount is preferably 5 to 50% by weight. Moreover, you may add the compound shown by general formula (I). The solvent and coating method used for coating can be the same as described above. The film thickness is preferably about 5 to 50 μm, more preferably 10 to 40 μm.

  Next, the image forming unit (process cartridge) of the present invention will be described.

  FIG. 14 is a cross-sectional view schematically showing a basic configuration of a preferred embodiment of the image forming unit of the present invention. The image forming unit 300 includes, together with the electrophotographic photosensitive member 307, a charging device 308, a developing device 311, an intermediate transfer member 320 (intermediate transfer device), a cleaning device 313, an opening 318 for exposure, and a discharge exposure. The opening 317 is combined and integrated using a mounting rail 316. In addition, the image forming unit 300 has a configuration in which the transfer method of the transfer device 312 employs an intermediate transfer method in which a toner image is transferred to the transfer medium 500 via the intermediate transfer member 320. The electrophotographic photoreceptor 307 has the above-described configuration of the electrophotographic photoreceptor.

  The image forming unit 300 is detachable from an image forming apparatus main body including a transfer device 312, a fixing device 315, and other components not shown, and forms an image together with the image forming apparatus main body. It constitutes a device.

  In the image forming unit of the present invention, the charging device 308 (charging member) can employ a contact charging method using a charging roll, a charging brush, a charging film, a charging tube, or the like. In the contact charging method, the surface of the photosensitive member is charged by applying a voltage to a conductive member brought into contact with the surface of the photosensitive member. The shape of the conductive member may be any of a brush shape, a blade shape, a pin electrode shape, a roller shape, and the like, but a roller-like member is particularly preferable. Usually, the roller-shaped member is composed of a resistance layer, an elastic layer supporting them, and a core material from the outside. Furthermore, a protective layer can be provided outside the resistance layer as necessary.

  The developing device 311 used in the above-described image forming unit of the present invention will be specifically described. The developing device 311 can be appropriately selected according to the purpose. For example, a one-component developer or a two-component developer. Examples include a known developing device that develops a developer based on contact or non-contact with a brush or roller. The toner is made by mechanical grinding or chemical polymerization. Examples of the shape of the toner include an irregular shape and a spherical shape.

  The intermediate transfer device 320 used in the image forming unit will be described in detail. As the intermediate transfer device 320, for example, a contact type transfer charger using a belt, a roller, a film, a rubber blade or the like, a corona discharge is used. A transfer charger known per se such as a scorotron transfer charger and a corotron transfer charger can be used. Among these, a contact type transfer charger is preferable in that it has excellent transfer charge compensation capability. In the present invention, in addition to the transfer charger, a peeling charger can be used in combination.

  The cleaning device 313 used in the image forming unit will be specifically described. The cleaning device 313 is not particularly limited, and a known cleaning device or the like may be used. Examples thereof include a urethane blade and a cleaning brush.

  A specific description will be given of a static eliminator (photo static eliminator) used in the image forming unit. Examples of the photo static eliminator include tungsten lamps and LEDs. Examples of the light quality used in the photo static eliminator include: White light such as a tungsten lamp, red light such as LED light, and the like. The irradiation light intensity in the photostatic process is usually set to output several times to about 30 times the amount of light indicating the half exposure sensitivity of the electrophotographic photosensitive member. In the present embodiment, the light from such a light neutralizing device is taken in through the opening 317 to neutralize the photosensitive member.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example at all.

(Example 1)
The outer peripheral surface of the aluminum substrate of the ED tube was subjected to a liquid honing treatment using spherical alumina fine powder having a D50 of 30 μm to obtain a 30 mmφ conductive substrate having a center line average roughness Ra of 0.18 μm.

  Next, to 170 parts by weight of n-butyl alcohol in which 4 parts by weight of polyvinyl butyral resin (ESREC BM-S, manufactured by Sekisui Chemical Co., Ltd.) was dissolved, 30 parts by weight of an organic zirconium compound (acetylacetone zirconium butyrate) and an organic silane compound ( 3 parts by weight of (γ-aminopropyltrimethoxysilane) was added, mixed and stirred to obtain a coating solution for forming an undercoat layer. The obtained coating solution was applied to the outer peripheral surface of the substrate using a dip coating apparatus and air-dried at room temperature for 5 minutes, and then the support was heated to 50 ° C. in 10 minutes, and 50 ° C. and 85%. It was placed in a constant temperature and humidity chamber of RH (dew point 47 ° C.), and a humidification hardening acceleration treatment was performed for 20 minutes. Then, it put into the hot air dryer and dried for 10 minutes at 170 degreeC, and formed the undercoat layer of the film thickness of 1.0 micron.

Next, it is represented by the following formula (12) and has diffraction peaks at positions of at least 7.6 ° and 28.2 ° in the Bragg angle (2θ ± 0.2 °) of the X-ray diffraction spectrum using the CuKα tip. A mixture of 4 parts by weight of hydroxygallium phthalocyanine, 1 part by weight of a binder resin (vinyl chloride-vinyl acetate copolymer resin (VMCH, manufactured by Nihon Unicar)) and 120 parts by weight of n-butyl acetate is dispersed in a sand mill for 4 hours. Thus, a charge generation layer coating solution was obtained. The obtained coating solution was dip-coated on the undercoat layer and dried to form a charge generation layer having a thickness of 0.2 μm.

  Next, 5 parts by weight of N, N′-diphenyl-N, N′-bis (3-methylphenyl)-[1,1 ′] biphenyl-4,4′-diamine as a charge transport material, bisphenol Z-type polycarbonate resin (Viscosity average molecular weight 40,000) 5 parts by weight, tetrahydrofuran 80 parts by weight, 2,6-di-t-butyl-4-methylphenol 0.2 parts by weight were mixed to obtain a charge transport layer forming coating solution. . This coating solution was applied onto the charge generation layer and dried at 120 ° C. for 40 minutes to form a charge transport layer having a thickness of 28 μm, thereby obtaining the intended electrophotographic photosensitive member.

  Using the electrophotographic photoreceptor thus obtained, an image forming apparatus having the structure shown in FIG. 1 was produced. Note that an exposure apparatus having an emission wavelength of 780 nm and a scanning line number of 1200 dpi was used.

(Example 2)
As a charge generation material, instead of hydroxygallium phthalocyanine in Example 1, it is represented by the following formula (13), and at least 7.4 in the Bragg angle (2θ ± 0.2 °) of the X-ray diffraction spectrum using CuKα rays. An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that chlorogallium phthalocyanine having diffraction peaks at positions of 16.6 °, 25.5 °, and 28.3 ° was used. A forming apparatus was produced.

(Example 3)
An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that a trisazo pigment represented by the following formula (14) was used as the charge generation material instead of hydroxygallium phthalocyanine in Example 1. Further, an image forming apparatus was produced.

Example 4
An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that a trisazo pigment represented by the following formula (15) was used as the charge generation material instead of hydroxygallium phthalocyanine in Example 1. Further, an image forming apparatus was produced.

(Comparative Example 1)
Oxytitanium phthalocyanine having a diffraction peak at a position of at least 27.3 ° in the Bragg angle (2θ ± 0.2 °) of the X-ray diffraction spectrum using CuKα rays instead of hydroxygallium phthalocyanine in Example 1 as the charge generation material An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that was used, and an image forming apparatus was further produced.

(Comparative Example 2)
An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that x-type metal-free phthalocyanine was used in place of hydroxygallium phthalocyanine in Example 1 as the charge generation material, and an image forming apparatus was further produced.

(Example 5)
First, an aluminum substrate having a diameter of 30 mm, a length of 340 mm, and a thickness of 1 mm was prepared. Next, a mixture of 100 parts by weight of zinc oxide (average particle diameter 70 nm, prototype manufactured by Teika) and 500 parts by weight of toluene is stirred, and 1.5 parts by weight of a silane coupling agent (KBM603, manufactured by Shin-Etsu Chemical Co., Ltd.) is added. The mixture was further stirred for 2 hours. Thereafter, toluene was distilled off under reduced pressure and baked at 150 ° C. for 2 hours.

  In this way, 60 parts by weight of the surface-treated zinc oxide was mixed with 15 parts by weight of a curing agent (blocked isocyanate sumijoule 3175, manufactured by Sumitomo Bayern Urethane Co., Ltd.) and butyral resin (BM-1, manufactured by Sekisui Chemical Co., Ltd.) A solution was prepared by dissolving in 85 parts by weight of methyl ethyl ketone together with parts by weight. 38 parts by weight of this solution was mixed with 25 parts by weight of methyl ethyl ketone, and dispersion treatment was performed for 2 hours with a sand mill using 1 mmφ glass beads to obtain a dispersion. As a catalyst, 0.005 part by weight of dioctyltin dilaurate and 3.5 parts by weight of a silicone resin ball having an average particle diameter of 4.5 μm (manufactured by GE Toshiba Silicone Co., Ltd., Tospearl 145) are added to the resulting dispersion. Was added and stirred to obtain a coating solution for forming an undercoat layer. This coating solution was applied onto the substrate by a dip coating method and dried and cured at 160 ° C. for 100 minutes to obtain an undercoat layer having a thickness of 20 μm.

  Next, it has a diffraction peak at a position of at least 7.6 ° and 28.2 ° in the Bragg angle (2θ ± 0.2 °) of the X-ray diffraction spectrum represented by the above formula (12) and using the CuKα tip. A mixture of 4 parts by weight of hydroxygallium phthalocyanine, 1 part by weight of a binder resin (vinyl chloride-vinyl acetate copolymer resin (VMCH, manufactured by Nihon Unicar)) and 120 parts by weight of n-butyl acetate is dispersed in a sand mill for 4 hours. Thus, a charge generation layer coating solution was obtained. The obtained coating solution was dip-coated on the undercoat layer and dried to form a charge generation layer having a thickness of 0.2 μm.

  Next, 5 parts by weight of N, N′-diphenyl-N, N′-bis (3-methylphenyl)-[1,1 ′] biphenyl-4,4′-diamine as a charge transport material, bisphenol Z-type polycarbonate resin (Viscosity average molecular weight 40,000) 5 parts by weight, tetrahydrofuran 80 parts by weight, 2,6-di-t-butyl-4-methylphenol 0.2 parts by weight were mixed to obtain a charge transport layer forming coating solution. . This coating solution was applied onto the charge generation layer and dried at 120 ° C. for 40 minutes to form a charge transport layer having a thickness of 28 μm, thereby obtaining the intended electrophotographic photosensitive member.

(Example 6)
As a charge generation material, instead of hydroxygallium phthalocyanine in Example 5, at least 7.4 in the Bragg angle (2θ ± 0.2 °) of the X-ray diffraction spectrum represented by the above formula (13) using CuKα rays. An electrophotographic photosensitive member was produced in the same manner as in Example 5 except that chlorogallium phthalocyanine having diffraction peaks at positions of 16.6 °, 25.5 °, and 28.3 ° was used. A forming apparatus was produced.

(Example 7)
An electrophotographic photosensitive member was produced in the same manner as in Example 5 except that the trisazo pigment represented by the above formula (14) was used as the charge generation material instead of hydroxygallium phthalocyanine in Example 5. Further, an image forming apparatus was produced.

(Example 8)
An electrophotographic photosensitive member was produced in the same manner as in Example 5 except that a trisazo pigment represented by the following formula (15) was used as the charge generation material instead of hydroxygallium phthalocyanine in Example 5. Further, an image forming apparatus was produced.

[Comparative Example 3]
Oxytitanium phthalocyanine having a diffraction peak at a position of at least 27.3 ° in the Bragg angle (2θ ± 0.2 °) of the X-ray diffraction spectrum using CuKα rays instead of hydroxygallium phthalocyanine in Example 1 as the charge generation material An electrophotographic photosensitive member was produced in the same manner as in Example 5 except that was used, and an image forming apparatus was further produced.

[Comparative Example 4]
An electrophotographic photosensitive member was produced in the same manner as in Example 5 except that x-type metal-free phthalocyanine was used in place of hydroxygallium phthalocyanine in Example 5 as the charge generation material, and an image forming apparatus was further produced.

(Evaluation of image quality)
For each of the image forming apparatuses of Examples 1 to 8 and Comparative Examples 1 to 4, the light emitting points of the SLEDs are set so as not to cause streak density unevenness that occurs in the rotation direction of the photosensitive member under the conditions of 22 ° C. and 50% RH. The exposure amount was adjusted. Next, a print test was performed at 10 ° C. and 15% RH to examine whether or not streak density unevenness occurred. The obtained results are shown in Table 2. In Table 2, A means that there is no or very slight occurrence of streak density unevenness, B means that streak density unevenness is slight, and C means that streak density unevenness is remarkable.

[Examples using hydroxygallium phthalocyanine 1]
(Synthesis Example 1)
30 parts by weight of 1,3-diiminoisoindoline and 9.1 parts by weight of gallium trichloride were added to 230 parts by weight of dimethyl sulfoxide and reacted at 160 ° C. with stirring for 6 hours to obtain reddish purple crystals. The obtained crystal was washed with dimethyl sulfoxide, then washed with ion-exchanged water, and dried to obtain 28 parts by weight of crude crystals of type I chlorogallium phthalocyanine.

  Next, a solution obtained by sufficiently dissolving 10 parts by weight of the obtained crude crystals of type I chlorogallium phthalocyanine in 300 parts of sulfuric acid (concentration 97%) heated to 60 ° C. was ion-exchanged with 600 parts by weight of 25% aqueous ammonia. A hydroxygallium phthalocyanine crystal was precipitated by dropping into a mixed solution with 200 parts by weight of water. The crystals were collected by filtration, washed with ion exchange water, and then dried to obtain 8 parts by weight of type I hydroxygallium phthalocyanine.

The X-ray diffraction spectrum of the I-type hydroxygallium phthalocyanine thus obtained was measured. The result is shown in FIG. In addition, the measurement of the X-ray diffraction spectrum in a present Example was performed on condition of the following using the CuK (alpha) characteristic X ray by the powder method.
Measuring instrument: X-ray diffractometer Miniflex manufactured by Rigaku Corporation
X-ray tube: Cu
Tube current: 15 mA
Scan speed: 5.0 deg. / Min
Sampling interval: 0.02 deg.
Start angle (2θ): 5 deg.
Stop angle (2θ): 35 deg.
Step angle (2θ): 0.02 deg.

(Production Example 1)
Using a glass ball mill, 6 parts by weight of the type I hydroxygallium phthalocyanine obtained in Synthesis Example 1 is used together with 90 parts by weight of N, N-dimethylformamide and 350 parts by weight of a spherical glass medium having an outer diameter of 0.9 mm. Wet grinding was performed at 25 ° C. for 48 hours. At this time, the progress of crystal conversion is monitored by measuring the absorption wavelength of the wet pulverization treatment liquid, and the maximum peak wavelength (λ _MAX ) in the spectral absorption spectrum of hydroxygallium phthalocyanine after wet pulverization treatment in the wavelength region of 600 to 900 nm is obtained. It was confirmed to be 827 nm.

  Next, the obtained crystal was washed with acetone, dried, and Bragg angles (2θ ± 0.2 °) 7.5 °, 9.9 ° in an X-ray diffraction spectrum using CuKα characteristic X-rays. 5.5 parts by weight of hydroxygallium phthalocyanine having diffraction peaks at 12.5 °, 16.3 °, 18.6 °, 25.1 ° and 28.3 ° were obtained. FIG. 16 shows an X-ray diffraction spectrum of the obtained hydroxygallium phthalocyanine, FIG. 21 shows a spectral absorption spectrum, and FIG. 28 shows a transmission electron micrograph.

  The spectral absorption spectrum was measured by using a U-2000 spectrophotometer manufactured by Hitachi, Ltd., and the measurement liquid was prepared by dispersing 0.6 g of hydroxygallium phthalocyanine in 8 mL of n-butyl acetate at room temperature. Moreover, the particle shape state of the obtained hydroxygallium phthalocyanine was observed using a transmission electron microscope (H-9000, manufactured by Hitachi, Ltd.).

(Production Example 2)
Except that the wet pulverization time was changed from 48 hours to 96 hours, 5.5 parts by weight of hydroxygallium phthalocyanine satisfying the diffraction peak conditions in the same X-ray diffraction spectrum as in Production Example 1 was obtained in the same manner as in Production Example 1. It was. In addition, the maximum peak wavelength (λ _MAX ) in the spectral absorption spectrum in the wavelength region of 600 to 900 nm of hydroxygallium phthalocyanine after the wet pulverization treatment when the progress of crystal conversion in the wet pulverization treatment was monitored was 825 nm. . FIG. 17 shows the X-ray diffraction spectrum of the obtained hydroxygallium phthalocyanine, FIG. 22 shows the spectral absorption spectrum, and FIG. 29 shows the transmission electron micrograph.

(Production Example 3)
Except that the wet pulverization time was changed from 48 hours to 192 hours, 5.5 parts by weight of hydroxygallium phthalocyanine satisfying the diffraction peak condition in the X-ray diffraction spectrum as in Production Example 1 was obtained in the same manner as in Production Example 1. It was. In addition, the maximum peak wavelength (λ _MAX ) in the spectral absorption spectrum in the wavelength region of 600 to 900 nm of hydroxygallium phthalocyanine after the wet pulverization treatment when the degree of progress of crystal conversion was monitored in the wet pulverization treatment was 819. . FIG. 18 shows the X-ray diffraction spectrum of the obtained hydroxygallium phthalocyanine, FIG. 23 shows the spectral absorption spectrum, and FIG. 30 shows the transmission electron micrograph.

(Production Example 4)
Similar to Production Example 1 except that 350 parts by weight of glass spherical media having an outer diameter of 2.0 mm were used instead of 350 parts by weight of glass spherical media having an outer diameter of 0.9 mm. As a result, 5.5 parts by weight of hydroxygallium phthalocyanine satisfying the condition of the diffraction peak in the X-ray diffraction spectrum was obtained. In addition, the maximum peak wavelength (λ _MAX ) in the spectral absorption spectrum in the wavelength region of 600 to 900 nm of hydroxygallium phthalocyanine after the wet pulverization treatment when the progress of crystal conversion in the wet pulverization treatment was monitored was 827 nm. . The X-ray diffraction spectrum and the spectral absorption spectrum of the obtained hydroxygallium phthalocyanine showed almost the same spectrum as in Production Example 1, respectively.

(Production Example 5)
Instead of 350 parts by weight of glass spherical media having an outer diameter of 0.9 mm, 400 parts by weight of glass spherical media having an outer diameter of 0.3 mm was used, and the amount of N, N-dimethylformamide used was 90 to 120 parts by weight. In the same manner as in Production Example 1 except that the part was replaced with 5.5 parts by weight, 5.5 parts by weight of hydroxygallium phthalocyanine satisfying the diffraction peak condition in the X-ray diffraction spectrum as in Production Example 1 was obtained. In addition, the maximum peak wavelength (λ _MAX ) in the spectral absorption spectrum in the wavelength region of 600 to 900 nm of hydroxygallium phthalocyanine after the wet pulverization treatment when the progress of crystal conversion in the wet pulverization treatment was monitored was 826 nm. . The X-ray diffraction spectrum and the spectral absorption spectrum of the obtained hydroxygallium phthalocyanine showed almost the same spectrum as in Production Example 1, respectively.

(Production Example 6)
The wet pulverization treatment was performed in the same manner as in Production Example 1, and then the obtained crystal was washed with 300 parts by weight of acetone on a ceramic filter having a pore size of 1.0 μm (UF winding ceramic filter, manufactured by NGK). . Next, after drying for 24 hours at 80 ° C. using a dryer (DFB type, manufactured by Irie Trading Co., Ltd.) that blocks light, using a vacuum dryer (DP61 type, manufactured by Yamato Scientific Co., Ltd.) that blocks light. And dried at 110 ° C. under a reduced pressure of 0.01 mmHg for 2 hours to obtain 5.5 parts by weight of hydroxygallium phthalocyanine satisfying the diffraction peak conditions in the X-ray diffraction spectrum as in Production Example 1. In addition, the maximum peak wavelength (λ _MAX ) in the spectral absorption spectrum in the wavelength region of 600 to 900 nm of hydroxygallium phthalocyanine after the wet pulverization treatment when the progress of crystal conversion in the wet pulverization treatment was monitored was 823 nm. . The X-ray diffraction spectrum and the spectral absorption spectrum of the obtained hydroxygallium phthalocyanine showed almost the same spectrum as in Production Example 1, respectively.

(Production Example 7)
After performing wet pulverization in the same manner as in Production Example 1 except that 350 parts by weight of glass spherical media with an outer diameter of 1.0 mm were used instead of 350 parts by weight of glass spherical media with an outer diameter of 0.9 mm The obtained crystals were washed with 300 parts by weight of acetone on a ceramic filter having a pore size of 1.0 μm. Next, after drying for 24 hours at 80 ° C. using a dryer (DFB type, manufactured by Irie Trading Co., Ltd.) that blocks light, using a vacuum dryer (DP61 type, manufactured by Yamato Scientific Co., Ltd.) that blocks light. And dried at 110 ° C. under a reduced pressure of −0.98 kPa for 2 hours to obtain 5.5 parts by weight of hydroxygallium phthalocyanine satisfying the diffraction peak conditions in the X-ray diffraction spectrum as in Production Example 1. In addition, the maximum peak wavelength (λ _MAX ) in the spectral absorption spectrum in the wavelength region of 600 to 900 nm of hydroxygallium phthalocyanine after the wet pulverization treatment when the progress of crystal conversion in the wet pulverization treatment was monitored was 818 nm. . The spectral absorption spectrum of the resulting hydroxygallium phthalocyanine is shown in FIG. In addition, the X-ray diffraction spectrum of the obtained hydroxygallium phthalocyanine was almost the same as in Production Example 1.

(Production Example 8)
Hydroxygallium that satisfies the conditions of the diffraction peak in the X-ray diffraction spectrum as in Production Example 1 in the same manner as in Production Example 7 except that the temperature of heat drying by a vacuum dryer with light blocked is changed from 110 ° C. to 150 ° C. 5.5 parts by weight of phthalocyanine was obtained. The maximum peak wavelength (λ _MAX ) in the spectral absorption spectrum in the wavelength region of 600 to 900 nm of hydroxygallium phthalocyanine after the wet pulverization treatment when the progress of crystal conversion in the wet pulverization treatment was monitored was 821 nm. . The X-ray diffraction spectrum and the spectral absorption spectrum of the obtained hydroxygallium phthalocyanine showed almost the same spectrum as in Production Example 1, respectively.

(Production Example 9)
Similar to Production Example 7, except that 350 parts by weight of glass spherical media having an outer diameter of 3.0 mm were used instead of 350 parts by weight of glass spherical media having an outer diameter of 1.0 mm. As a result, 5.5 parts by weight of hydroxygallium phthalocyanine satisfying the condition of the diffraction peak in the X-ray diffraction spectrum was obtained. In addition, the maximum peak wavelength (λ _MAX ) in the spectral absorption spectrum in the wavelength region of 600 to 900 nm of the hydroxygallium phthalocyanine after the wet pulverization treatment when the progress of the crystal conversion in the wet pulverization treatment was monitored was 835 nm. . The X-ray diffraction spectrum and the spectral absorption spectrum of the obtained hydroxygallium phthalocyanine showed almost the same spectrum as in Production Example 1, respectively.

(Production Example 10)
Hydroxygallium that satisfies the conditions of the diffraction peak in the X-ray diffraction spectrum as in Production Example 1 in the same manner as in Production Example 7, except that the temperature of heat drying by a vacuum dryer with light blocked is changed from 110 ° C. to 220 ° C. 5.5 parts by weight of phthalocyanine was obtained. In addition, the maximum peak wavelength (λ _MAX ) in the spectral absorption spectrum in the wavelength region of 600 to 900 nm of hydroxygallium phthalocyanine after the wet pulverization treatment when the progress of crystal conversion in the wet pulverization treatment was monitored was 823 nm. . The X-ray diffraction spectrum and the spectral absorption spectrum of the obtained hydroxygallium phthalocyanine showed almost the same spectrum as in Production Example 1, respectively.

(Production Example 11)
30 parts by weight of 1,3-diiminoisoindoline and 9.1 parts by weight of gallium trichloride were added to 230 parts by weight of quinoline and reacted at 200 ° C. for 3 hours, and then the product was filtered off. Next, this product was washed with acetone and methanol, and the obtained wet cake was dried to obtain 28 parts by weight of chlorogallium phthalocyanine crystals. A solution prepared by dissolving 3 parts by weight of this chlorogallium phthalocyanine crystal in 60 parts by weight of concentrated sulfuric acid (concentration 97%) at 0 ° C. was dropped into 450 parts by weight of distilled water at 5 ° C. to precipitate hydroxygallium phthalocyanine crystals. . The crystals were washed with distilled water and dilute ammonia water and then dried to obtain 2.5 parts by weight of hydroxygallium phthalocyanine crystals. The obtained hydroxygallium phthalocyanine crystal was pulverized in an automatic mortar for 5.5 hours to obtain amorphous hydroxygallium phthalocyanine.

The resulting hydroxygallium phthalocyanine (5.0 parts by weight) was milled together with 150 parts by weight of dimethylformamide and 300 parts by weight of glass beads having a diameter of 1 mm, and the progress of crystal conversion was monitored by measuring the absorption wavelength of the wet pulverized liquid. The time course of the maximum peak wavelength (λ _MAX ) in the spectral absorption spectrum of gallium phthalocyanine in the wavelength range of 600 to 900 nm was followed up to 250 hours. The result is shown in FIG. From the graph shown in FIG. 33, it was confirmed that the maximum peak wavelength (λ _MAX ) shows the minimum value (824 nm) when the processing time is 150 hours. In addition, hydroxygallium phthalocyanine at a treatment time of 150 hours was washed with methanol and dried to obtain a target hydroxygallium phthalocyanine satisfying the diffraction peak conditions in the X-ray diffraction spectrum as in Production Example 1.

(Production Example 12)
5 parts by weight of the type I hydroxygallium phthalocyanine obtained in Synthesis Example 1 was stirred at 25 ° C. for 48 hours using 80 parts by weight of N, N-dimethylformamide using a glass stirring tank having a stirring device. The maximum peak wavelength (λ _MAX ) in the spectral absorption spectrum of hydroxygallium phthalocyanine after stirring in the wavelength region of 600 to 900 nm was 846 nm.

  Next, the obtained crystal was washed with acetone, dried, and Bragg angles (2θ ± 0.2 °) 7.5 °, 9.9 ° in an X-ray diffraction spectrum using CuKα characteristic X-rays. 5.5 parts by weight of hydroxygallium phthalocyanine having diffraction peaks at 12.5 °, 16.3 °, 18.6 °, 25.1 ° and 28.3 ° were obtained. FIG. 19 shows the X-ray diffraction spectrum of the obtained hydroxygallium phthalocyanine, FIG. 25 shows the spectral absorption spectrum, and FIG. 31 shows the transmission electron micrograph.

(Production Example 13)
Similar to Production Example 1 except that 350 parts by weight of glass spherical media having an outer diameter of 5.0 mm were used instead of 350 parts by weight of glass spherical media having an outer diameter of 0.9 mm. As a result, 5.5 parts by weight of hydroxygallium phthalocyanine satisfying the condition of the diffraction peak in the X-ray diffraction spectrum was obtained. In addition, the maximum peak wavelength (λ _MAX ) in the spectral absorption spectrum in the wavelength region of 600 to 900 nm of hydroxygallium phthalocyanine after the wet pulverization treatment when the progress of the crystal conversion was monitored in the wet pulverization treatment was 845 nm. . The X-ray diffraction spectrum of the obtained hydroxygallium phthalocyanine is shown in FIG. 20, the spectral absorption spectrum is shown in FIG. 26, and the transmission electron micrograph is shown in FIG.

(Production Example 14)
After performing wet pulverization in the same manner as in Production Example 1 except that 350 parts by weight of glass spherical media having an outer diameter of 5.0 mm was used instead of 350 parts by weight of glass spherical media having an outer diameter of 0.9 mm. The obtained crystals were washed with 300 parts by weight of acetone on a ceramic filter having a pore size of 1.0 μm. Next, using a drier (DFB type, manufactured by Irie Trading Co., Ltd.) that shields light, it was heated and dried at 60 ° C. for 24 hours, and the hydroxygallium phthalocyanine satisfying the diffraction peak conditions in the X-ray diffraction spectrum as in Production Example 1 was satisfied. 5.5 parts by weight were obtained. In addition, the maximum peak wavelength (λ _MAX ) in the spectral absorption spectrum in the wavelength region of 600 to 900 nm of hydroxygallium phthalocyanine after the wet pulverization treatment when the progress of crystal conversion in the wet pulverization treatment was monitored was 842 nm. . The X-ray diffraction spectrum and spectral absorption spectrum of the obtained hydroxygallium phthalocyanine showed almost the same spectrum as in Production Example 13, respectively.

(Production Example 15)
Crystals were obtained by stirring 5 parts by weight of type I hydroxygallium phthalocyanine obtained in Synthesis Example 1 together with 80 parts by weight of N, N-dimethylformamide at 25 ° C. for 48 hours using a glass stirring tank having a stirring device. Obtained. Next, the obtained crystal was washed with acetone and dried by heating at 80 ° C. for 24 hours using a dryer that shielded light, and the diffraction peak conditions in the same X-ray diffraction spectrum as in Production Example 1 were set. 5.5 parts by weight of hydroxygallium phthalocyanine to be filled was obtained. The maximum peak wavelength (λ _MAX ) in the spectral absorption spectrum of the obtained hydroxygallium phthalocyanine in the wavelength region of 600 to 900 nm was 858 nm. The spectral absorption spectrum of the obtained hydroxygallium phthalocyanine is shown in FIG. Further, the X-ray diffraction spectrum of the obtained hydroxygallium phthalocyanine showed a spectrum almost similar to that of Production Example 13.

(Production Example 16)
Crystal transformation treatment was carried out for 24 hours under the same conditions as in Production Example 11, and then washed with methanol and dried, and the target hydroxygallium phthalocyanine 0. 0 satisfying the diffraction peak conditions in the X-ray diffraction spectrum as in Production Example 1. 4 parts by weight were obtained.

(Production Example 17)
The crystal conversion treatment was performed for 48 hours under the same conditions as in Production Example 11, then washed with methanol, dried, and the target hydroxygallium phthalocyanine 0. 0 satisfying the diffraction peak conditions in the X-ray diffraction spectrum as in Production Example 1. 4 parts by weight were obtained.

The maximum peak wavelength (λ _MAX ) in the spectral absorption spectrum of the hydroxygallium phthalocyanine obtained in Production Examples 1 to 17, and the BET ratio measured using a BET specific surface area meter (Flow Soap II 2300, manufactured by Shimadzu Corporation) Table 3 shows the surface area and the average particle diameter measured by a laser diffraction / scattering particle size distribution analyzer (LA-700, manufactured by Horiba, Ltd.).

  Furthermore, the weight reduction rate when the temperature of the hydroxygallium phthalocyanine obtained in Production Examples 6 to 10 and Production Examples 14 to 15 was raised from 25 ° C. to 400 ° C. was measured using a thermobalance (stand-alone thermogravimetry apparatus TGA-50, Shimadzu). Table 3 shows the results measured by Seisakusho Co., Ltd.

(Examples 9 to 25)
An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the hydroxygallium phthalocyanine obtained in Production Examples 1 to 17 was used in place of the hydroxygallium phthalocyanine in Example 1 as the charge generation material. Further, an image forming apparatus was produced. In addition, what used the hydroxygallium phthalocyanine obtained in manufacture examples 1-17 corresponds to Examples 9-25, respectively.

(Evaluation of image quality)
In each of the image forming apparatuses of Examples 9 to 25, the exposure amount of each light emitting point of the SLED is adjusted so as not to cause streak density unevenness that occurs in the rotation direction of the photosensitive member under the conditions of 22 ° C. and 50% RH. went. Next, a print test was performed at 10 ° C. and 15% RH to examine whether or not streak density unevenness occurred. As a result, in all of Examples 9 to 25, there was no or very slight occurrence of streak density unevenness. However, an electrophotographic photosensitive member using hydroxygallium phthalocyanine having a spectral absorption spectrum having an absorption maximum at 810 to 839 nm has excellent electrophotographic characteristics, good dispersibility, thick and thin lines, fogging, etc. Whereas good image quality was obtained without causing the above phenomenon, electrophotographic photoreceptors using hydroxygallium phthalocyanine having an absorption maximum at 840 nm or more have problems with electrical characteristics such as dark decay and chargeability. In addition, the dispersibility of the charge generation material in the charge generation layer tends to be insufficient, and as a result, fog is likely to occur in the electrophotographic image forming apparatus.

1 is a schematic configuration diagram of an image forming apparatus according to an embodiment. It is a perspective view of the exposure part which concerns on embodiment. It is a perspective view of the exposure part which concerns on other embodiment. It is a drive circuit diagram in SLED single-piece | unit. It is a drive circuit diagram of an exposure unit. It is a constant current drive circuit diagram. It is a constant voltage drive circuit. It is a generation circuit diagram of a pulse waveform. It is a timing chart of FIG. It is a schematic diagram which shows the cross section of the electrophotographic photoreceptor which concerns on 1st Embodiment. It is a schematic diagram which shows the cross section of the electrophotographic photoreceptor which concerns on 2nd Embodiment. It is a schematic diagram which shows the cross section of the electrophotographic photoreceptor which concerns on 3rd Embodiment. It is a schematic diagram which shows the cross section of the electrophotographic photoreceptor which concerns on 4th Embodiment. It is sectional drawing of the image forming unit which concerns on embodiment. It is a powder X-ray diffraction pattern of the type I hydroxygallium phthalocyanine synthesized in the synthesis example. 2 is a powder X-ray diffraction pattern of hydroxygallium phthalocyanine produced in Production Example 1. FIG. 3 is a powder X-ray diffraction pattern of hydroxygallium phthalocyanine produced in Production Example 2. FIG. 6 is a powder X-ray diffraction pattern of hydroxygallium phthalocyanine produced in Production Example 3. FIG. 14 is a powder X-ray diffraction pattern of hydroxygallium phthalocyanine produced in Production Example 12. FIG. 14 is a powder X-ray diffraction pattern of hydroxygallium phthalocyanine produced in Production Example 13. FIG. 2 is a spectral absorption spectrum of hydroxygallium phthalocyanine produced in Production Example 1. 3 is a spectral absorption spectrum of hydroxygallium phthalocyanine produced in Production Example 2. 4 is a spectral absorption spectrum of hydroxygallium phthalocyanine produced in Production Example 3. 7 is a spectral absorption spectrum of hydroxygallium phthalocyanine produced in Production Example 7. 14 is a spectral absorption spectrum of hydroxygallium phthalocyanine produced in Production Example 12. 14 is a spectral absorption spectrum of hydroxygallium phthalocyanine produced in Production Example 13. 18 is a spectral absorption spectrum of hydroxygallium phthalocyanine produced in Production Example 15. 2 is a transmission electron micrograph of hydroxygallium phthalocyanine produced in Production Example 1. FIG. 3 is a transmission electron micrograph of hydroxygallium phthalocyanine produced in Production Example 2. FIG. 4 is a transmission electron micrograph of hydroxygallium phthalocyanine produced in Production Example 3. FIG. 4 is a transmission electron micrograph of hydroxygallium phthalocyanine produced in Production Example 12. FIG. 14 is a transmission electron micrograph of hydroxygallium phthalocyanine produced in Production Example 13. FIG. 12 is a graph showing the change with time of the maximum peak wavelength λ _MAX during the crystal conversion of hydroxygallium phthalocyanine in Production Example 11.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1 ... Charge generating layer, 2 ... Charge transport layer, 3 ... Conductive support body, 4 ... Undercoat layer 4, 5 ... Protective layer, 10 ... Thyristor, 100 ... Image forming apparatus 102, 154 ... casing, 104 ... discharge tray section, 106 ... photosensitive drum, 108 ... charging section, 110 ... exposure section, 112 ... toner tank, 114: Toner roll, 116: Rotary developing unit, 118, 120 ... Roller, 122 ... Intermediate transfer belt, 124 ... Cleaning unit, 126 ... Image forming paper, 128 ... Paper feed tray, 130 ... sheet-fed device, 132 ... fixing unit, 134 ... density sensor, 150 ... SLED, 152 ... light emitting element unit, 162 ... APC, 163 ... Gradation signal line, 164, 208 ... DA Barter, 166, 174 ... resistor, 168 ... first comparator, 172 ... second comparator, 176 ... MOS transistor, 178 ... constant current drive circuit, 180 ... constant Voltage drive circuit, 182 ... first control line, 184 ... second control line, 186 ... OR circuit, 188 ... triangular wave generation circuit, 200 ... generation circuit, 202 ... Image processing unit 204... Accumulator 206 206 Correction data holding unit 210 Comparator 300 Image forming unit 307 Electrophotographic photosensitive member 308 Charging device 311 ... Developing device, 312 ... Transfer device, 313 ... Cleaning device, 317 ... Opening for static elimination exposure, 318 ... Opening for exposure, 320 ... Intermediate transfer Body, 500 - the transfer body.

Claims (14)

An electrophotographic photosensitive member having a conductive support and a photosensitive layer disposed on the support, a charging means for charging the electrophotographic photosensitive member, and forming an electrostatic latent image on the electrophotographic photosensitive member Exposure means for developing, developing means for developing the electrostatic latent image formed on the electrophotographic photosensitive member with toner to form a toner image, and transferring the toner image to a transfer target An image forming apparatus comprising transfer means,
The exposure means is a light emitting element array in which a plurality of self-scanning LEDs are arranged,
The image forming apparatus, wherein the photosensitive layer contains at least one charge generating material selected from the group consisting of hydroxygallium phthalocyanine, chlorogallium phthalocyanine and trisazo pigment.   The image forming apparatus according to claim 1, wherein the exposure unit is a light emitting element array in which light emitting element units including a plurality of self-scanning LEDs are arranged so that adjacent light emitting element units partially overlap.   The hydroxygallium phthalocyanine is a hydroxygallium phthalocyanine having diffraction peaks at positions of Bragg angles (2θ ± 0.2 °) of 7.6 ° and 28.2 ° in an X-ray diffraction spectrum using CuKα characteristic X-rays. The image forming apparatus according to claim 1 or 2.   The image forming apparatus according to claim 1, wherein the hydroxygallium phthalocyanine is hydroxygallium phthalocyanine having a maximum peak wavelength in a range of 810 to 839 nm in a spectral absorption spectrum in a wavelength region of 600 to 900 nm. The image forming apparatus according to claim 4, wherein the hydroxygallium phthalocyanine is hydroxygallium phthalocyanine having an average particle diameter of 0.20 μm or less and a BET specific surface area of 45 m ² / g or more.   The hydroxygallium phthalocyanine has a Bragg angle (2θ ± 0.2 °) of 7.5 °, 9.9 °, 12.5 °, 16.3 °, 18 in an X-ray diffraction spectrum using CuKα characteristic X-ray. The image forming apparatus according to claim 4, wherein the image forming apparatus is hydroxygallium phthalocyanine having diffraction peaks at .6 °, 25.1 °, and 28.3 °.   The said hydroxygallium phthalocyanine is a hydroxygallium phthalocyanine whose thermal weight loss rate when it heats up from 25 degreeC to 400 degreeC is 2.0 to 4.0%, It is any one of Claims 4-6 Image forming apparatus. The hydroxygallium phthalocyanine is
In an X-ray diffraction spectrum using CuKα characteristic X-rays, Bragg angles (2θ ± 0.2 °) of 6.9 °, 13.2 to 14.2 °, 16.5 °, 26.0 ° and 26.4 Or a spherical shape of hydroxygallium phthalocyanine having diffraction peaks at 7.0 °, 13.4 °, 16.6 °, 26.0 ° and 26.7 ° with an outer diameter of 0.1 to 3.0 mm It is a hydroxygallium phthalocyanine obtained by crystal conversion by wet milling so that the media is 50 parts by weight or more with respect to 1 part by weight of the hydroxygallium phthalocyanine using a grinding apparatus using The image forming apparatus according to claim 4.   The chlorogallium phthalocyanine is diffracted to Bragg angles (2θ ± 0.2 °) of 7.4 °, 16.6 °, 25.5 ° and 28.3 ° in an X-ray diffraction spectrum using CuKα characteristic X-rays. The image forming apparatus according to claim 1, which is a chlorogallium phthalocyanine having a peak. The image forming apparatus according to claim 1, wherein the trisazo pigment is a trisazo pigment represented by any one of the following general formulas (1) to (4).

[Wherein, R represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group or a cyano group, and Ar represents a coupler residue. ]   The photosensitive layer includes a charge generation layer formed on the conductive support and a charge transport layer formed on the charge generation layer, and the charge generation layer contains the charge generation material. The image forming apparatus according to any one of 1 to 10.   The electrophotographic photosensitive member is formed by forming the photosensitive layer on a curved surface of the drum-shaped conductive support, and the electrophotographic photosensitive member has the photosensitive member centered on a central axis of the drum shape. The image forming apparatus according to claim 1, wherein the image forming apparatus rotates so that the linear velocity of the layer surface is 100 mm / second or more.   13. The image forming apparatus according to claim 12, wherein the image resolution of the photosensitive layer in the rotation direction of the electrophotographic photosensitive member is 1200 dots / inch or more. An electrophotographic photosensitive member comprising a conductive support and a photosensitive layer disposed on the support;
A charging unit for charging the electrophotographic photosensitive member, an exposure unit for forming an electrostatic latent image on the electrophotographic photosensitive member, and developing the electrostatic latent image formed on the electrophotographic photosensitive member with toner And at least one selected from the group consisting of a developing means for forming a toner image and a cleaning means for removing the toner remaining on the electrophotographic photosensitive member,
An image forming unit comprising:
The exposure means is a light emitting element array in which a plurality of self-scanning LEDs are arranged,
The image forming unit, wherein the photosensitive layer contains at least one charge generating material selected from the group consisting of hydroxygallium phthalocyanine, chlorogallium phthalocyanine and trisazo pigment.

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