JP6663236B2 - Electrophotographic photoreceptor, electrophotographic apparatus and process cartridge, modified hydroxygallium phthalocyanine crystal, and method for producing the same - Google Patents

Description

  The present invention relates to an electrophotographic photosensitive member, an electrophotographic apparatus, and a process cartridge. Further, the present invention relates to a modified hydroxygallium phthalocyanine crystal and a method for producing the same.

  In order to cope with higher image quality of an electrophotographic apparatus, further improvement in fine line reproducibility is required. Fine line reproducibility can be improved by making the surface of the photoreceptor a bright portion potential proportional to the amount of exposure. Therefore, a charge generation material capable of maintaining carrier generation even in a weak electric field (a weak electric field region) near a light portion potential is required. Patent Document 1 discloses a prior art in which fine particle reproducibility is improved by combining toner particle size control and phthalocyanine.

  As a modified gallium phthalocyanine crystal, a prior art has been disclosed in which the surface of a chlorogallium phthalocyanine crystal is modified with hydroxygallium phthalocyanine for the purpose of improving the dispersibility of the chlorogallium phthalocyanine crystal. Patent Document 2 describes a technique relating to a modified chlorogallium phthalocyanine crystal in which a hydroxygallium phthalocyanine film is formed on the crystal surface of a chlorogallium phthalocyanine crystal. Patent Document 3 discloses a method for producing a modified chlorogallium phthalocyanine crystal, which comprises transforming a chlorogallium phthalocyanine crystal by wet grinding in water, and modifying the crystal surface to hydroxygallium phthalocyanine. Technology is described.

JP 2014-63180 A JP-A-8-245900 JP-A-10-130521

  However, with further improvement in image quality in recent years, further improvement in fine line reproducibility, which was not sufficient even when gallium phthalocyanine crystal was used as a charge generation material, has been desired.

  An object of the present invention is to provide an electrophotographic photosensitive member, an electrophotographic apparatus, and a process cartridge which can maintain carrier generation even in a weak electric field region and have excellent fine line reproducibility. Still another object of the present invention is to provide a modified hydroxygallium phthalocyanine crystal having chlorogallium phthalocyanine on the surface of the hydroxygallium phthalocyanine crystal, and a method for producing the same.

The present invention is an electrophotographic photosensitive member having a support and a photosensitive layer in this order, wherein the photosensitive layer contains a modified hydroxygallium phthalocyanine crystal, and the modified hydroxygallium phthalocyanine crystal is a hydroxygallium phthalocyanine crystal. a surface crystal having a chlorogallium phthalocyanine, chlorination degree of the modified hydroxy gallium phthalocyanine crystals, at least 18%, an electrophotographic photoreceptor, characterized in der Rukoto less 76%.

  Further, the present invention provides a process cartridge which integrally supports the electrophotographic photoreceptor and at least one means selected from the group consisting of a charging means, a developing means, and a cleaning means, and is detachable from an electrophotographic apparatus main body. It is.

  Further, the present invention is an electrophotographic apparatus having the above electrophotographic photosensitive member, and a charging unit, an exposing unit, a developing unit and a transferring unit.

  Further, the present invention is a modified hydroxygallium phthalocyanine crystal having chlorogallium phthalocyanine on the surface of the hydroxygallium phthalocyanine crystal.

  Furthermore, the present invention is a method for producing the modified hydroxygallium phthalocyanine crystal, wherein the production method includes a step of mixing hydroxygallium phthalocyanine and an aqueous hydrochloric acid solution to obtain the modified hydroxygallium phthalocyanine crystal. This is a method for producing a modified hydroxygallium phthalocyanine crystal.

  According to the present invention, it is possible to provide an electrophotographic photosensitive member excellent in fine line reproducibility, a process cartridge having the electrophotographic photosensitive member, and an electrophotographic apparatus.

  Further, according to the present invention, it is possible to provide a modified hydroxygallium phthalocyanine crystal having chlorogallium phthalocyanine on the surface of the hydroxygallium phthalocyanine crystal, and a method for producing the same.

FIG. 2 is a diagram illustrating an example of a schematic configuration of an electrophotographic apparatus including a process cartridge having an electrophotographic photosensitive member. FIG. 2 is a diagram illustrating an example of a layer configuration of an electrophotographic photosensitive member.

  The present invention is characterized in that the photosensitive layer of the electrophotographic photosensitive member contains a modified hydroxygallium phthalocyanine crystal, and the modified hydroxygallium phthalocyanine crystal is a crystal having chlorogallium phthalocyanine on the surface of the hydroxygallium phthalocyanine crystal.

  The present inventors have found that, by modifying the surface of a hydroxygallium phthalocyanine crystal with chlorogallium phthalocyanine having a large polarity, recombination can be suppressed even in a weak electric field region and carrier generation can be maintained. The mechanism is presumed to be due to the fact that chlorogallium phthalocyanine having a large polarity extracts carriers generated near the hydroxygallium phthalocyanine crystal. As a result, the residual potential is also reduced.

  The content of chlorogallium phthalocyanine in the modified hydroxygallium phthalocyanine crystal is preferably from 10% by mass to 95% by mass, more preferably from 15% by mass to 30% by mass, or from 60% by mass to 90% by mass. More preferred. Within this range, the balance between carrier generation and carrier extraction is good.

  The modified hydroxygallium phthalocyanine crystal preferably contains an organic compound in the crystal. The organic compound in the crystal has an effect of promoting carrier extraction. Examples of the organic compound include formamide, N-methylformamide, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylacetamide, N-propylformamide, N-methylpropionamide, N-vinylformamide, and N-vinylformamide. Preferred are amide solvents such as -methyl-2-pyrrolidone, halogen solvents such as chloroform, ether solvents such as tetrahydrofuran, sulfoxide solvents such as dimethyl sulfoxide, and ketone solvents such as acetone. Among them, a compound having an amide group is preferable, and more preferably, any of formamide, N-methylformamide, N, N-dimethylformamide, N-propylformamide, and N-vinylformamide. These may be used alone or in combination of two or more.

  Further, the organic compound is preferably contained in an amount of 0.1% by mass or more and 1.5% by mass or less based on the modified hydroxygallium phthalocyanine crystal. If the content of the organic compound is less than 0.1% by mass, the carrier may not be easily extracted. If the content is more than 1.5% by mass, carriers may be trapped in the organic compound.

  The content of chlorogallium phthalocyanine in the modified hydroxygallium phthalocyanine crystal according to the present invention was determined by analyzing the chlorine atom weight by combustion ion chromatography. That is, a calibration curve was prepared from hydroxygallium phthalocyanine and chlorogallium phthalocyanine, and the content (chlorination rate) of chlorogallium phthalocyanine with respect to the modified hydroxygallium phthalocyanine crystal of the present invention was determined.

The analysis conditions are as follows.
<Combustion ion chromatography>
Combustion and absorption conditions System: AQF-100, GA-100 (Mitsubishi Chemical Analytech Co., Ltd.)
Electric furnace temperature: Inlet 900 ° C, Outlet 1000 ° C
Gas: Ar / O ₂ 200 mL / min, O ₂ 400 mL / min Absorbent: H ₂ O ₂ 30 ppm, internal standard P 1 ppm
Absorbing liquid volume: 10 mL
Ion chromatography and anion analysis conditions System: ICS2000 (manufactured by DIONEX)
Eluent: KOH aqueous solution (concentration: 22.4% by mass)
Flow rate: 1.0 mL / min
Detector: Electric conduction detector Injection volume: 20 μL
Column temperature: 35 ° C
Further, the content of the organic compound contained in the modified hydroxygallium phthalocyanine crystal according to the present invention was determined by analyzing the obtained modified hydroxygallium phthalocyanine crystal by ¹ H-NMR measurement and analyzing the data. The measurement was performed under the following conditions.
^<1 H-NMR measurement>
Measuring instrument used: manufactured by BRUKER, AVANCE III 500
Solvent: bisulfuric acid (D ₂ SO ₄ )
Number of accumulation: 2000

  The modified hydroxygallium phthalocyanine crystal according to the present invention is preferably a modified hydroxygallium phthalocyanine crystal obtained through a hydrochloric acid treatment step of mixing hydroxygallium phthalocyanine and an aqueous hydrochloric acid solution. The present inventors have found that the modified hydroxygallium phthalocyanine crystal obtained by this production method is excellent in carrier extraction in a weak electric field region.

  In the hydrochloric acid treatment step, the concentration of the aqueous hydrochloric acid solution mixed with hydroxygallium phthalocyanine is preferably 10% by mass or more, and more preferably 30% by mass or more from the viewpoint of reactivity. As a method of mixing the hydrochloric acid aqueous solution, a milling treatment or a stirring treatment can be used. The amount of the hydrochloric acid aqueous solution to be mixed is preferably 10 mol or more, more preferably 50 mol or more, of hydrochloric acid (HCl) in the hydrochloric acid aqueous solution with respect to 1 mol of hydroxygallium phthalocyanine. In this hydrochloric acid treatment step, hydroxygallium phthalocyanine reacts with an aqueous hydrochloric acid solution to obtain a modified hydroxygallium phthalocyanine crystal.

  Further, a modified hydroxygallium phthalocyanine crystal obtained by having the following synthesis step, the following acid pasting step, the above hydrochloric acid treatment step, and the following crystal conversion step in this order is more preferable. The synthesis step is a step of reacting a gallium compound and a compound forming a phthalocyanine ring in a chloroaromatic compound to synthesize chlorogallium phthalocyanine. The acid pasting step is a step of mixing chlorogallium phthalocyanine obtained in the above synthesis step with sulfuric acid to obtain hydroxygallium phthalocyanine. The crystal conversion step is a step of mixing the modified hydroxygallium phthalocyanine crystal obtained in the hydrochloric acid treatment step with an organic compound to convert the crystal form of the modified hydroxygallium phthalocyanine crystal.

  In the above synthesis step, the gallium compound is preferably gallium trichloride. Further, the compound forming the phthalocyanine ring is preferably orthophthalonitrile, and the chlorinated aromatic compound is preferably α-chloronaphthalene.

  The organic compound used in the crystal conversion step is the same as the organic compound contained in the modified hydroxygallium phthalocyanine crystal. In the crystal conversion step, the organic compound is incorporated into the modified hydroxygallium phthalocyanine crystal. The amount of the organic compound used in the crystal conversion step is preferably 5 to 30 times the modified hydroxygallium phthalocyanine crystal on a mass basis. Further, the crystal conversion step may be performed by mixing media such as glass beads. In that case, the amount of the medium is preferably 10 to 50 times the modified hydroxygallium phthalocyanine crystal on a mass basis. Examples of a device used in the crystal conversion step include a milling device such as a sand mill, a ball mill, and a paint shaker, a homogenizer, a magnetic stirrer, a stirring device using a stirring blade, and an ultrasonic disperser. The processing time of the crystal conversion step is preferably about 0.1 to 100 hours.

The modified hydroxygallium phthalocyanine crystal according to the present invention is a crystal having chlorogallium phthalocyanine on the surface of the hydroxygallium phthalocyanine crystal.
The modified hydroxygallium phthalocyanine crystal according to the present invention has excellent functions as a photoconductor, and can be applied to a solar cell, a sensor, a switching element, and the like in addition to an electrophotographic photosensitive member.

  Next, a case where the modified hydroxygallium phthalocyanine crystal according to the present invention is applied as a charge generating material in an electrophotographic photosensitive member will be described.

The electrophotographic photoreceptor of the present invention has a support and a photosensitive layer in this order.
The photosensitive layer is a single-layer type photosensitive layer containing a charge transporting substance and a charge generating substance in the same layer, a laminated type in which a charge generating layer containing a charge generating substance and a charge transporting layer containing a charge transporting substance are separated ( Function-separated type) photosensitive layer. From the viewpoint of electrophotographic characteristics, a laminated photosensitive layer having a charge generation layer and a charge transport layer formed on the charge generation layer is preferable.

  FIGS. 2A and 2B are diagrams illustrating an example of a layer configuration of the electrophotographic photosensitive member. FIG. 2A shows a single-layer type photosensitive layer, in which an undercoat layer 102 is formed on a support 101, and a photosensitive layer 103 is formed on the undercoat layer 102. FIG. 2B shows a laminated photosensitive layer, in which an undercoat layer 102 is formed on a support 101, a charge generation layer 104 is formed on the undercoat layer 102, and a charge transport layer is formed on the charge generation layer 104. 105 is formed.

(Support)
The support is preferably a conductive material (conductive support). For example, a support made of a metal such as aluminum or stainless steel or an alloy may be used. In addition, a metal, plastic, or paper support having a conductive film provided on the surface may be used.
Examples of the shape of the support include a cylindrical shape and a film shape.

  A conductive layer may be provided between the support and an undercoat layer described below for the purpose of hiding unevenness on the surface of the support and suppressing interference fringes. The conductive layer can be formed by forming a coating film of a coating solution for a conductive layer obtained by dispersing conductive particles, a binder resin, and a solvent, and drying / curing the coating film.

  Examples of the conductive particles include aluminum particles, titanium oxide particles, tin oxide particles, zinc oxide particles, carbon black, and silver particles. Examples of the binder resin include polyester, polycarbonate, polyvinyl butyral, acrylic resin, silicone resin, epoxy resin, melamine resin, urethane resin, phenol resin, and alkyd resin. Examples of the solvent for the conductive layer coating solution include ether solvents, alcohol solvents, ketone solvents, and aromatic hydrocarbon solvents.

  The thickness of the conductive layer is preferably 5 to 40 μm, more preferably 10 to 30 μm.

  An undercoat layer (also referred to as an intermediate layer) having a barrier function or an adhesive function can be provided between the support and the photosensitive layer. The undercoat layer can form a coating film of an undercoat layer coating solution prepared by mixing a binder resin and a solvent, and then dry the coating film to form an undercoat layer.

  Examples of the binder resin used for the undercoat layer include polyvinyl alcohol, polyethylene oxide, ethyl cellulose, methyl cellulose, casein, polyamide, glue, and gelatin. The thickness of the undercoat layer is preferably from 0.1 to 10 μm, more preferably from 0.3 to 5.0 μm.

(Photosensitive layer, charge generation layer)
When the photosensitive layer is a laminated photosensitive layer, the charge generation layer contains the modified hydroxygallium phthalocyanine crystal according to the present invention as a charge generation substance. For the charge generation layer, first, a modified hydroxygallium phthalocyanine crystal and a binder resin are mixed in a solvent to prepare a charge generation layer coating solution. And it can form by forming this coating film and drying this coating film. When the modified hydroxygallium phthalocyanine crystal is dispersed, the crystal form of the modified hydroxygallium phthalocyanine crystal does not change if a binder resin is added.
The thickness of the charge generation layer is preferably from 0.05 to 1 μm, and more preferably from 0.1 to 0.3 μm.

The content of the charge generation substance in the charge generation layer is preferably from 30 to 90% by mass, more preferably from 50 to 80% by mass, based on the total mass of the charge generation layer.
As the charge generating substance used in the charge generating layer, a substance other than the modified hydroxygallium phthalocyanine crystal according to the present invention may be used in combination. In that case, the content of the modified hydroxygallium phthalocyanine crystal according to the present invention is preferably 50% by mass or more based on the total mass of the charge generating substance.

  As the binder resin used for the charge generation layer, for example, polyester, acrylic resin, phenoxy resin, polycarbonate, polyvinyl butyral, polystyrene, polyvinyl acetate, polysulfone, polyarylate, vinyl chloride, vinylidene chloride, acrylonitrile copolymer, polyvinyl benzene Saar. Among these, polyvinyl butyral and polyvinyl benzal are preferred.

(Photosensitive layer, charge transport layer)
The charge transport layer can be formed by forming a coating film of a charge transport layer coating solution prepared by dissolving a charge transport material and a binder resin in a solvent, and drying the coating film.

  Examples of the charge transport material include a triarylamine compound, a hydrazone compound, a stilbene compound, a pyrazoline compound, an oxazole compound, a thiazole compound, and a triallylmethane compound. Among these, a triarylamine compound is preferred.

  Examples of the binder resin used for the charge transport layer include polyester, acrylic resin, phenoxy resin, polycarbonate, polystyrene, polyvinyl acetate, polysulfone, polyarylate, vinylidene chloride, and acrylonitrile copolymer. Among these, polycarbonate and polyarylate are preferred.

  The thickness of the charge transport layer is preferably from 5 to 40 μm, more preferably from 10 to 25 μm. The content of the charge transporting substance in the charge transporting layer is preferably 20 to 80% by mass, more preferably 30 to 60% by mass, based on the total mass of the charge transporting layer.

  When the photosensitive layer is a single-layer type photosensitive layer, it can be formed by forming a coating film of a coating solution for a single-layer type photosensitive layer and drying the coating film. The single-layer type photosensitive layer coating solution can be prepared by mixing the modified hydroxygallium phthalocyanine crystal according to the present invention, the charge transporting substance, and the binder resin as a charge generating substance in a solvent.

A protective layer may be provided on the photosensitive layer for the purpose of protecting the photosensitive layer.
The protective layer can be formed by dissolving a binder resin in a solvent to form a coating film of a coating liquid for a protective layer prepared and drying the coating film. Examples of the binder resin used for the protective layer include polyvinyl butyral, polyester, polycarbonate, nylon, polyimide, polyarylate, polyurethane, styrene-butadiene copolymer, styrene-acrylic acid copolymer, and styrene-acrylonitrile copolymer.

Further, in order to give the protective layer a charge transporting ability, the protective layer may be formed by curing a monomer having a charge transporting ability (hole transporting ability) using various polymerization reactions and crosslinking reactions. Specifically, it is preferable to form a protective layer by polymerizing or crosslinking a charge transporting compound having a chain polymerizable functional group (hole transporting compound) and curing the compound.
The thickness of the protective layer is preferably 0.05 to 20 μm.

  Examples of the method of applying the coating solution for each layer include a dip coating method (dipping method), a spray coating method, a spinner coating method, a bead coating method, a blade coating method, and a beam coating method.

  The surface layer of the electrophotographic photoreceptor may contain lubricating particles such as conductive particles, an ultraviolet absorber, and fluorine atom-containing resin particles. Examples of the conductive particles include metal oxide particles such as tin oxide particles.

FIG. 1 is a diagram illustrating an example of a schematic configuration of an electrophotographic apparatus including a process cartridge having an electrophotographic photosensitive member.
The cylindrical (drum-shaped) electrophotographic photosensitive member 1 is driven to rotate around a shaft 2 in a direction indicated by an arrow at a predetermined peripheral speed (process speed).
The surface (peripheral surface) of the electrophotographic photoreceptor 1 is charged to a predetermined positive or negative potential by a charging unit (primary charging unit) 3 during the rotation process. Next, the surface of the electrophotographic photosensitive member 1 is irradiated with exposure light (image exposure light) 4 from an exposure unit (image exposure unit) (not shown), and an electrostatic latent image corresponding to target image information is electrophotographically formed. It is formed on the surface of the photoconductor 1. The exposure light 4 is light that is intensity-modulated in accordance with a time-series electric digital image signal of target image information output from exposure means such as slit exposure or laser beam scanning exposure.

  The electrostatic latent image formed on the surface of the electrophotographic photosensitive member 1 is developed (regular development or reversal development) with a developer (toner) stored in a developing unit 5, and the surface of the electrophotographic photosensitive member 1 A toner image is formed. The toner image formed on the surface of the electrophotographic photosensitive member 1 is transferred to the transfer material P by the transfer unit 6. At this time, a voltage (transfer bias) having a polarity opposite to the charge retained in the toner is applied to the transfer unit 6 from a bias power supply (not shown). The transfer material P is taken out from a transfer material supply unit (not shown) in synchronization with the rotation of the electrophotographic photosensitive member 1, and is fed between the electrophotographic photosensitive member 1 and the transfer unit 6.

  The transfer material P to which the toner image has been transferred is separated from the surface of the electrophotographic photoreceptor 1, conveyed to a fixing unit 8, subjected to a fixing process of the toner image, and subjected to electrophotography as an image formation (print, copy) Printed out of the device.

  After the toner image has been transferred to the transfer material P, the surface of the electrophotographic photoreceptor 1 is cleaned by a cleaning unit 7 by removing extraneous matters such as untransferred developer (transfer residual toner). Further, the transfer residual toner can be collected by a developing unit or the like without using a cleaning unit (cleanerless system).

  Further, the surface of the electrophotographic photoreceptor 1 is irradiated with pre-exposure light (not shown) from a pre-exposure unit (not shown), and after being subjected to a charge elimination process, is repeatedly used for image formation. In addition, as shown in FIG. 1, when the charging unit 3 is a contact charging unit using a charging roller or the like, the pre-exposure unit is not necessarily required.

  Of the components such as the electrophotographic photosensitive member 1, the charging unit 3, the developing unit 5, and the cleaning unit 7, a plurality of components may be contained in a container and integrally supported to form a process cartridge. This process cartridge can be configured to be detachable from the main body of the electrophotographic apparatus. For example, at least one unit selected from the charging unit 3, the developing unit 5, and the cleaning unit 7 is integrally supported with the electrophotographic photosensitive member 1 to form a cartridge. The process cartridge 9 can be detachably attached to the main body of the electrophotographic apparatus by using the guide means 10 such as a rail of the main body of the electrophotographic apparatus.

  When the electrophotographic apparatus is a copying machine or a printer, the exposure light 4 may be reflected light or transmitted light from a document. Alternatively, the light may be light emitted by reading a document with a sensor, converting the signal into a signal, scanning a laser beam performed in accordance with the signal, driving an LED array, driving a liquid crystal shutter array, or the like.

  Hereinafter, the present invention will be described in more detail with reference to specific examples. However, the present invention is not limited to these. “Parts” shown below means “parts by mass”. The film thickness of each layer of the electrophotographic photoreceptors of the examples and comparative examples was determined from eddy current film thickness meter (FISCHERSCOPE, manufactured by Fisher Instruments) or from the weight per unit area in terms of specific gravity.

<Production Example 1>
36.7 parts of orthophthalonitrile, 25 parts of gallium trichloride, and 300 parts of α-chloronaphthalene were mixed. This was reacted at 200 ° C. for 5.5 hours in a nitrogen atmosphere, and then the product was filtered at 130 ° C. The obtained product was dispersed and washed with N, N-dimethylformamide at 140 ° C. for 2 hours, then filtered, and the collected matter was washed with methanol and dried to obtain 46 parts of chlorogallium phthalocyanine. This chlorogallium phthalocyanine was a crystal having peaks at Bragg angles 2θ of 7.4 °, 16.6 °, 25.5 ° and 28.3 ° in CuKα characteristic X-ray diffraction.

<Production Example 2>
24 parts of chlorogallium phthalocyanine obtained in Production Example 1 was dissolved in 750 parts of concentrated sulfuric acid at a temperature of 5 ° C., and reprecipitated by dropping into 2500 parts of ice water with stirring. This was filtered under reduced pressure. At this time, as a filter, 5C (manufactured by Advantech) was used. Thereafter, dispersion washing was performed with 2% aqueous ammonia for 30 minutes, and then dispersion washing was performed four times with ion-exchanged water. Finally, freeze-drying (freeze-drying) was performed to obtain hydroxygallium phthalocyanine at a yield of 97%.

<Comparative Production Example 1>
0.5 parts of chlorogallium phthalocyanine obtained in Production Example 1 and 15 parts of glass beads having a diameter of 0.9 mm were milled at room temperature (23 ° C.) with a paint shaker for 24 hours to obtain finely divided chlorogallium phthalocyanine. Obtained.

<Comparative Production Example 2>
30 parts of 1,3-diiminoisoindoline, 9.1 parts of gallium trichloride, and 230 parts of dimethyl sulfoxide were mixed. This was reacted at 150 ° C. for 4 hours in a nitrogen atmosphere, and then the product was filtered at 130 ° C. The obtained product was washed with ion-exchanged water and filtered to obtain 28 parts of chlorogallium phthalocyanine. This chlorogallium phthalocyanine was a crystal having a peak at a Bragg angle 2θ of 27.1 ° in CuKα characteristic X-ray diffraction.

[Example 1-1]
10 parts of the hydroxygallium phthalocyanine obtained in Production Example 2 and 100 parts of a hydrochloric acid aqueous solution having a concentration of 35% by mass and a temperature of 23 ° C. were mixed, and stirred with a magnetic stirrer for 90 minutes. The amount of the hydrochloric acid aqueous solution mixed was 59 mol of hydrochloric acid based on 1 mol of hydroxygallium phthalocyanine. After stirring, the mixture was dropped into 1000 parts of ion-exchanged water cooled with ice water, and stirred for 30 minutes. This was filtered under reduced pressure. At this time, as a filter, 5C (manufactured by Advantech) was used. Thereafter, dispersion washing was performed four times with ion-exchanged water at a temperature of 23 ° C. Thus, 9 parts of a modified hydroxygallium phthalocyanine crystal was obtained.

[Example 1-2]
A modified hydroxygallium phthalocyanine crystal was obtained in the same manner as in Example 1-1, except that the stirring time of the magnetic stirrer was changed from 90 minutes to 60 minutes in Example 1-1.

[Example 1-3]
A modified hydroxygallium phthalocyanine crystal was obtained in the same manner as in Example 1-1, except that the stirring time of the magnetic stirrer was changed from 90 minutes to 30 minutes in Example 1-1.

[Example 1-4]
A modified hydroxygallium phthalocyanine crystal was obtained in the same manner as in Example 1-1, except that the stirring time of the magnetic stirrer was changed from 90 minutes to 6 minutes.

[Example 1-5]
A modified hydroxygallium phthalocyanine crystal was obtained in the same manner as in Example 1-1, except that the stirring time of the magnetic stirrer was changed from 90 minutes to 24 hours.

[Example 1-6]
A modified hydroxygallium phthalocyanine crystal was obtained in the same manner as in Example 1-1, except that the aqueous hydrochloric acid solution having a concentration of 35% by mass was changed to the aqueous hydrochloric acid solution having a concentration of 10% by mass.

[Example 2-1]
0.5 part of the modified hydroxygallium phthalocyanine crystal obtained in Example 1-1 and 10 parts of N, N-dimethylformamide were subjected to a crystal conversion treatment at room temperature (23 ° C.) with a stirring blade (750 rpm) for 16 hours. . This dispersion was filtered, and the filter was thoroughly washed with tetrahydrofuran. The filtrate was dried under vacuum to obtain 0.47 parts of a modified hydroxygallium phthalocyanine crystal.
As a result of measurement by combustion ion chromatography, the chlorination ratio of the modified hydroxygallium phthalocyanine crystal was 76%. ^{From 1} H-NMR measurement, it was confirmed that 0.7% by mass of N, N-dimethylformamide was contained in the phthalocyanine in the modified hydroxygallium phthalocyanine crystal, as calculated from the proton ratio.

[Example 2-2]
A modified hydroxygallium phthalocyanine crystal was obtained in the same manner as in Example 2-1, except that 10 parts of N, N-dimethylformamide was changed to 10 parts of N-methylformamide in Example 2-1.
As a result of measurement by combustion ion chromatography, the chlorination ratio of the modified hydroxygallium phthalocyanine crystal was 76%. ^{By 1} H-NMR measurement, it was confirmed from the proton ratio that N-methylformamide was contained in an amount of 0.4% by mass based on the phthalocyanine in the modified hydroxygallium phthalocyanine crystal.

[Example 2-3]
In Example 2-1, except that 0.5 parts of the modified hydroxygallium phthalocyanine crystal obtained in Example 1-1 was changed to 0.5 part of the modified hydroxygallium phthalocyanine crystal obtained in Example 1-2, A modified hydroxygallium phthalocyanine crystal was obtained in the same manner as in Example 2-1.
As a result of measurement by combustion ion chromatography, the chlorination ratio of the modified hydroxygallium phthalocyanine crystal was 73%. ^{By 1} H-NMR measurement, it was confirmed that N, N-dimethylformamide was contained at 0.8% by mass based on the phthalocyanine in the modified hydroxygallium phthalocyanine crystal, calculated from the proton ratio.

[Example 2-4]
In Example 2-1, except that 0.5 parts of the modified hydroxygallium phthalocyanine crystal obtained in Example 1-1 was changed to 0.5 part of the modified hydroxygallium phthalocyanine crystal obtained in Example 1-3, A modified hydroxygallium phthalocyanine crystal was obtained in the same manner as in Example 2-1.
As a result of measurement by combustion ion chromatography, the chlorination ratio of the modified hydroxygallium phthalocyanine crystal was 61%. ^{By 1} H-NMR measurement, it was confirmed that N, N-dimethylformamide was contained at 0.8% by mass based on the phthalocyanine in the modified hydroxygallium phthalocyanine crystal, calculated from the proton ratio.

[Example 2-5]
In Example 2-1, except that 0.5 parts of the modified hydroxygallium phthalocyanine crystal obtained in Example 1-1 was changed to 0.5 part of the modified hydroxygallium phthalocyanine crystal obtained in Example 1-4, A modified hydroxygallium phthalocyanine crystal was obtained in the same manner as in Example 2-1.
As a result of measurement by combustion ion chromatography, the chlorination ratio of the modified hydroxygallium phthalocyanine crystal was 51%. ^{By 1} H-NMR measurement, it was confirmed that N, N-dimethylformamide was contained at 0.8% by mass based on the phthalocyanine in the modified hydroxygallium phthalocyanine crystal, calculated from the proton ratio.

[Example 2-6]
In Example 2-1, except that 0.5 parts of the modified hydroxygallium phthalocyanine crystal obtained in Example 1-1 was changed to 0.5 part of the modified hydroxygallium phthalocyanine crystal obtained in Example 1-5, A modified hydroxygallium phthalocyanine crystal was obtained in the same manner as in Example 2-1.
As a result of measurement by combustion ion chromatography, the chlorination ratio of the modified hydroxygallium phthalocyanine crystal was 89%. ^{By 1} H-NMR measurement, it was confirmed that N, N-dimethylformamide was contained at 0.8% by mass based on the phthalocyanine in the modified hydroxygallium phthalocyanine crystal, calculated from the proton ratio.

[Example 2-7]
A modified hydroxygallium phthalocyanine crystal was obtained in the same manner as in Example 1-1, except that 10 parts of N, N-dimethylformamide was changed to 10 parts of dimethylsulfoxide in Example 2-1.
As a result of measurement by combustion ion chromatography, the chlorination ratio of the modified hydroxygallium phthalocyanine crystal was 76%. ¹ H-NMR measurement confirmed that dimethyl sulfoxide was contained in an amount of 0.6% by mass, based on the phthalocyanine in the modified hydroxygallium phthalocyanine crystal, calculated from the proton ratio.

[Example 2-8]
In Example 2-1, except that 0.5 parts of the modified hydroxygallium phthalocyanine crystal obtained in Example 1-1 was changed to 0.5 part of the modified hydroxygallium phthalocyanine crystal obtained in Example 1-6, A modified hydroxygallium phthalocyanine crystal was obtained in the same manner as in Example 2-1.
As a result of measurement by combustion ion chromatography, the chlorination ratio of the modified hydroxygallium phthalocyanine crystal was 18%. ¹ H-NMR measurement confirmed that N, N-dimethylformamide was contained at 1.6% by mass based on the phthalocyanine in the modified hydroxygallium phthalocyanine crystal, calculated from the proton ratio.

[Comparative Example 2-1]
The chlorogallium phthalocyanine obtained in Comparative Production Example 1 and an aqueous sodium hydroxide solution (concentration: 0.5% by mass) were mixed and wet-pulverized at room temperature for 24 hours in a ball mill. Thereafter, this was washed with water and filtered to obtain a modified chlorogallium phthalocyanine crystal whose crystal surface was changed to hydroxygallium phthalocyanine.
As a result of measurement by combustion ion chromatography, the chlorination ratio of the modified chlorogallium phthalocyanine crystal was 84%.

[Comparative Example 2-2]
0.5 part of chlorogallium phthalocyanine obtained in Comparative Production Example 2, 1 part of ion-exchanged water and 25 parts of glass beads having a diameter of 0.9 mm were subjected to a milling treatment with a paint shaker at room temperature (23 ° C.) for 96 hours to be denatured. 0.4 parts of chlorogallium phthalocyanine crystals were obtained. As a result of measurement by combustion ion chromatography, the chlorination ratio of the modified chlorogallium phthalocyanine crystal was 93%.

[Comparative Example 2-3]
In Example 2-1, 0.5 part of modified hydroxygallium phthalocyanine and 10 parts of N, N-dimethylformamide were changed to 0.5 part of hydroxygallium phthalocyanine obtained in Production Example 2 and 10 parts of dimethylsulfoxide. Except for the above, a hydroxygallium phthalocyanine crystal was obtained in the same manner as in Example 2-1.
¹ H-NMR measurement confirmed that 2.5 mass% of dimethyl sulfoxide was contained with respect to the phthalocyanine in the hydroxygallium phthalocyanine crystal in terms of the proton ratio.

[Comparative Example 2-4]
Comparative Example 2-3 was the same as Comparative Example 2-3 except that hydroxygallium phthalocyanine 0.5 part obtained in Production Example 2 was changed to 0.5 part of chlorogallium phthalocyanine obtained in Comparative Production Example 1. Similarly, chlorogallium phthalocyanine crystals were obtained.
As a result of measurement by combustion ion chromatography, the chlorination ratio of the surface was 100%. ¹ H-NMR measurement confirmed that dimethylsulfoxide was contained in an amount of 1.2% by mass with respect to the phthalocyanine in the chlorogallium phthalocyanine crystal, as calculated from the proton ratio.

[Example 3-1]
An aluminum cylinder (JIS-A3003, aluminum alloy) having a diameter of 24 mm and a length of 257.5 mm was used as a support (conductive support).

  First, 60 parts of barium sulfate particles (trade name: Pastran PC1, manufactured by Mitsui Mining & Smelting Co., Ltd.) coated with tin oxide, 15 parts of titanium oxide particles (trade name: TITANIXJR, manufactured by Teica Co., Ltd.), resole phenol 43 parts of resin (trade name: Phenolite J-325, manufactured by Dainippon Ink and Chemicals, Inc., solid content: 70% by mass), 0.015 part of silicone oil (trade name: SH28PA, manufactured by Toray Silicone Co., Ltd.), 3.6 parts of silicone resin particles (trade name: Tospearl 120, manufactured by Toshiba Silicone Co., Ltd.), 50 parts of 2-methoxy-1-propanol, and 50 parts of methanol are placed in a ball mill, and dispersed for 20 hours. A coating solution for a conductive layer was prepared. This conductive layer coating solution was applied onto a support by dip coating to form a coating film, and the obtained coating film was heated and cured at 140 ° C. for 1 hour to form a 15 μm-thick conductive layer. .

  Next, 10 parts of copolymerized nylon (trade name: Amilan CM8000, manufactured by Toray Industries, Inc.) and 30 parts of methoxymethylated 6 nylon (trade name: Toresin EF-30T, manufactured by Teikoku Chemical Co., Ltd.) were mixed with methanol. By dissolving in a mixed solvent of 400 parts / 200 parts of N-butanol, a coating liquid for an undercoat layer was prepared. This undercoat layer coating liquid is applied onto the conductive layer by dip coating to form a coating film, and the obtained coating film is dried at 80 ° C. for 6 minutes to form a 0.42 μm-thick undercoat layer. did.

  Next, 2 parts of the modified hydroxygallium phthalocyanine crystal (charge generating substance) obtained in Example 2-1, 1 part of polyvinyl butyral (trade name: Eslek BX-1, manufactured by Sekisui Chemical Co., Ltd.), and cyclohexanone 52 The portion was placed in a sand mill using glass beads having a diameter of 0.9 mm and subjected to a dispersion treatment for 4 hours. Thereafter, 75 parts of ethyl acetate was added to prepare a charge generating layer coating solution. The number-average particle size of the modified hydroxygallium phthalocyanine crystal in this coating solution was 189 nm (measured with a particle size measuring device Zetasizer Nano manufactured by Sysmex Corporation using cyclohexanone as a dispersion medium). This coating liquid for a charge generation layer is dip-coated on the undercoat layer to form a coating film, and the obtained coating film is dried at 100 ° C. for 10 minutes to form a charge generation layer having a thickness of 0.20 μm. Formed.

下記式（Ｃ−２）で示される化合物（電荷輸送物質（正孔輸送性化合物））４部、

および、ポリカーボネート（商品名：ユーピロンＺ２００、三菱エンジニアリングプラスチックス（株）製）４０部を、モノクロロベンゼン２００部／ジメトキシメタン５０部の混合溶剤に溶解させることによって電荷輸送層用塗布液を調製した。この電荷輸送層用塗布液を電荷発生層上に浸漬塗布して塗膜を形成し、塗膜を３０分間１２０℃で乾燥させることによって、膜厚が３０μｍの電荷輸送層を形成した。 Next, 28 parts of a compound represented by the following formula (C-1) (charge transport material (hole transport compound)):

4 parts of a compound represented by the following formula (C-2) (charge transporting substance (hole transporting compound)):

Also, 40 parts of polycarbonate (trade name: Iupilon Z200, manufactured by Mitsubishi Engineering-Plastics Corporation) was dissolved in a mixed solvent of 200 parts of monochlorobenzene / 50 parts of dimethoxymethane to prepare a coating solution for a charge transport layer. This coating solution for a charge transport layer was applied onto the charge generation layer by dip coating to form a coating film, and the coating film was dried at 120 ° C. for 30 minutes to form a charge transport layer having a thickness of 30 μm.

  Thus, a cylindrical (drum-shaped) electrophotographic photosensitive member of Example 3-1 was produced.

[Examples 3-2 to 3-8 and Comparative Examples 3-1 to 3-4]
In Example 3-1, 2 parts of the modified hydroxygallium phthalocyanine crystal obtained in Example 2-1 was replaced with gallium phthalocyanine obtained in Examples 2-2 to 2-8 and Comparative examples 2-1 to 2-4. An electrophotographic photoreceptor was manufactured in the same manner as in Example 3-1 except that the crystal was changed to 2 parts.
The number average particle size of the hydroxygallium phthalocyanine crystals in the coating solution of Comparative Example 2-3 was 192 nm (measured using a particle size measuring apparatus Zetasizer Nano manufactured by Sysmex Corporation with cyclohexanone as a dispersion medium).

[Comparative Example 3-5]
In Example 3-1, 2 parts of the modified hydroxygallium phthalocyanine crystal obtained in Example 2-1 was obtained by mixing 1.4 parts of the hydroxygallium phthalocyanine crystal obtained in Comparative Example 2-3 with Comparative Example 2-4. An electrophotographic photosensitive member of Comparative Example 3-5 was produced in the same manner as in Example 3-1 except that the mixture was changed to a mixture of 0.6 parts of chlorogallium phthalocyanine crystal.

[Evaluation of Examples 3-1 to 3-8 and Comparative Examples 3-1 to 3-5]
・ Image evaluation method (evaluation method of fine line reproducibility)
An image was output using a modified machine of a laser beam printer (trade name: LaserJet Pro400Color M451dn) manufactured by Hewlett-Packard Company. As a modification, the amount of exposure light (image exposure light) was made variable. For image output, the electrophotographic photosensitive member manufactured was mounted on a black process cartridge, the developing cartridge was extracted from the apparatus, and a potential measuring device was inserted therein. This was mounted on the station of the black process cartridge of the printer, and the amount of exposure light was set so that the bright portion potential (Vl) became -120V. The potential measuring device is configured by disposing a potential measuring probe (trade name: model 6000B-8, manufactured by Trek Japan Co., Ltd.) at the developing position of the developing cartridge. The position was the center in the drum axis direction. Then, the potential at the center of the electrophotographic photosensitive member is measured using a surface electrometer (trade name: model 344, manufactured by Trek Japan Co., Ltd.).

Thereafter, the potential measuring device was removed, the developing cartridge was returned to the original state, and a test chart was output. The test chart was a black line with an output resolution of 1200 dpi and a line width of 2 points. Next, the output image was read at a resolution of 1200 dpi using a scanner (CanoScan 9900F manufactured by Canon Inc.), binarized into white and black, and compared with the original data of the test chart. The number of pixels where the output image is white within the black line of the test chart is A, and the number of pixels where the output image is black outside the black line of the test chart is B. And evaluated. Table 1 shows the results. For use, this numerical value is preferably 0.75 or more.
Evaluation formula: 1− (A + B) / N (where N is the total number of pixels in the test chart)

-Measuring method of residual potential The image exposure light source was adjusted so that the amount of light was maximized and irradiated with image exposure, and the surface potential of the electrophotographic photosensitive member was measured at the developing position to determine the residual potential.

Reference Signs List 1 electrophotographic photosensitive member 2 axis 3 charging means (primary charging means)
4 Exposure light (image exposure light)
Reference Signs List 5 developing means 6 transfer means 7 cleaning means 8 fixing means 9 process cartridge 10 guide means P transfer material

Claims (8)

In an electrophotographic photosensitive member having a support and a photosensitive layer in this order,
The photosensitive layer contains a modified hydroxygallium phthalocyanine crystal,
The modified hydroxygallium phthalocyanine crystal is a crystal having chlorogallium phthalocyanine on the surface of the hydroxygallium phthalocyanine crystal,
An electrophotographic photoreceptor, wherein the modified hydroxygallium phthalocyanine crystal has a chlorination rate of 18% or more and 76% or less . The modified hydroxygallium phthalocyanine crystals containing an organic compound in the crystal, an electrophotographic photosensitive member according to compound der Ru請 Motomeko 1 organic compound having an amide group. Compounds having an amide group is at least formamide, N- methylformamide, N, N- dimethylformamide, N- propyl formamide, electrophotographic photosensitive member according to 請 Motomeko 2 Ru der either N- vinylformamide. Said organic compound, an electrophotographic photosensitive member according to 請 Motomeko 2 you containing 1.5 mass% or less than 0.1 wt% with respect to phthalocyanine the modified hydroxygallium phthalocyanine crystal. An electrophotographic photosensitive member according to any one of claims 1-4, charging means, developing means, and integrally supports at least one means selected from the group consisting of cleaning means, the electrophotographic apparatus body A process cartridge that can be attached to and detached from. An electrophotographic photosensitive member according to any one of claims 1-4, a charging means, an exposure means,
An electrophotographic apparatus having an image unit and a transfer unit. A modified hydroxygallium phthalocyanine crystal having chlorogallium phthalocyanine on the surface of a hydroxygallium phthalocyanine crystal ,
A modified hydroxygallium phthalocyanine crystal, wherein the chlorination rate of the modified hydroxygallium phthalocyanine crystal is 18% or more and 76% or less . A method for producing a modified hydroxygallium phthalocyanine crystal according to claim 7 ,
Mixing a hydroxycarboxylic phthalocyanine and aqueous hydrochloric acid, stirred to have a step of obtaining the modified hydroxygallium phthalocyanine crystals,
In the step, a method for producing a modified hydroxygallium phthalocyanine crystal , wherein the aqueous hydrochloric acid solution is mixed such that the amount of hydrochloric acid in the aqueous hydrochloric acid solution is 10 mol or more and 59 mol or less per 1 mol of the hydroxygallium phthalocyanine.

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