JP2010049245A - Toner and image forming method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide toner and an image forming method by which a high-resolution and high-definition image are stably obtained independently of the environment over a long period of time. <P>SOLUTION: The toner is used in the image forming method including: an electrostatic latent image forming step where an electrostatic latent image is formed on a charged electrostatic charge image carrier; and a development step where the electrostatic latent image is visualized by transferring the toner carried on a toner carrier to the electrostatic latent image. The electrostatic charge image carrier is an electrophotographic photoreceptor in which a photoconductive layer and a surface layer formed of hydrogenated amorphous silicon carbide are laid in order, wherein the sum of the atomic density of silicon atoms and the atomic density of carbon atoms in the surface layer is ≥6.60×10<SP>22</SP>atoms/cm<SP>3</SP>. The toner includes toner particles including a binder resin and a colorant, and an inorganic fine powder, wherein the flow rate index FRI of the inorganic fine powder is 0.8-2.0. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a toner used in electrophotography, electrostatic recording, and magnetic recording, and an image forming method.

  Conventionally, many methods are known as electrophotographic methods. In general electrophotography, an electric latent image is formed on a charged image carrier (photosensitive member) by various methods using a photoconductive substance, and then toner is supplied to the latent image. To visualize the toner image. After transferring the toner image to a transfer material such as paper as necessary, the toner image is fixed on the transfer material by heat / pressure as necessary to obtain a copy, and the toner remaining on the photoreceptor after the transfer process There is known a method of cleaning the substrate with a cleaning member.

  Among these, since the cleaning process has a simple structure, a system in which a blade-like elastic member is brought into contact with the photosensitive member at a predetermined pressure or more and the remaining toner is physically scraped is often used.

  However, in this blade cleaning, if the contact pressure of the cleaning blade is low, the toner slips through between the photoreceptor and the blade, causing an adverse effect on the image. Conversely, if the blade contact pressure is high, the surface of the photoreceptor is worn and the cleaning blade is removed. It has been difficult to balance the cleaning property and the life of the electrophotographic member, for example, the chipping of the toner is promoted and a sufficient life cannot be obtained.

  In the photoreceptor field, a photoconductive layer and a surface protective layer containing amorphous silicon (hereinafter referred to as “a-Si”) are used for the purpose of pursuing high durability and high image quality and making maintenance-free. More and more photoreceptors are used. In particular, the a-Si photosensitive drum is excellent in wear resistance due to its hard surface layer, and has been suitably used in a usage environment where continuous printing is performed at a high speed over a long period of time.

  As a basic configuration of such an a-Si photosensitive member, a positive charging a-Si photosensitive member as shown in FIG. 1 is known. The positively charged a-Si photosensitive member is formed by forming a photoreceptive layer 102 made of a-Si on a conductive substrate 101 and further a surface layer made of hydrogenated amorphous silicon carbide (hereinafter referred to as “a-”). It is referred to as an “SiC surface layer.”) 105.

  In the field of a-Si photoreceptors, as shown in Japanese Patent Application Laid-Open No. H10-260707, ones having a higher photoreceptor surface hardness have been proposed for the purpose of further improving the abrasion resistance. Although the life of the body itself is extended, deterioration of peripheral members, particularly cleaning members, etc., is promoted, and it does not lead to an improvement in the life of the entire electrophotographic system.

  On the contrary, in Patent Document 2, the atomic density of silicon atoms, carbon atoms, hydrogen or fluorine atoms in the photoreceptor surface layer is made smaller than a predetermined value, and the a-SiC surface layer has a relatively rough film structure. Thus, there has been proposed a photoconductor that easily scrapes the surface of the photoconductor and reduces the load on the cleaning member. However, the wear of the photoconductor itself deteriorates, and it is not optimal as a whole.

  Also in the toner field, various proposals have been made to include fine inorganic powder as an abrasive and a lubricant in the toner for the purpose of improving the durability of these cleaning members. For example, Patent Documents 3 to 5 disclose that toner contains cerium oxide particles, magnetite particles, and calcium carbonate particles, respectively. However, in the improvement with the toner alone as described above, the movement within the cleaning of the inorganic fine powder is limited due to the minute roughness existing on the surface of the photoreceptor, and the surface of the photoreceptor is partially polished to cause unevenness. It sometimes worsened to scratches.

  In other words, in order to combine the high durability and cleaning properties of electrophotographic members such as the photoconductor and the cleaning blade in a well-balanced manner, it is necessary to improve the system, not the photoconductor, the toner, and the cleaning mechanism. Yes.

Japanese Patent No. 3728255 Japanese Patent No. 3124841 Japanese Patent No. 3874362 Japanese Patent No. 3290273 JP-A-8-190221

  An object of the present invention is to provide a toner and an image forming method which have solved the above problems. That is, an object of the present invention is to achieve a long life of the photosensitive member and the cleaning member without causing defective cleaning.

  In order to achieve the above object, the present inventors have prepared an electrophotographic photosensitive member having a special surface layer and a photosensitive member without causing a cleaning defect such as toner slipping by containing a special inorganic fine powder in the toner. It has been found that a long life can be achieved at a high level.

  That is, the present invention is as follows.

(1) charging the electrostatic charge image carrier with a charging member; forming an electrostatic latent image on the charged electrostatic charge carrier; and a toner carried on the toner carrier. Development process for transferring to the electrostatic latent image for visualization, transfer process for transferring the toner image formed on the electrostatic charge image carrier onto the recording medium, and cleaning the surface of the electrostatic charge image carrier after the transfer In a toner used in an image forming method having a cleaning step of cleaning with a member,
The electrostatic image bearing member is an electrophotographic photosensitive member in which at least a photoconductive layer and a surface layer formed of hydrogenated amorphous silicon carbide are sequentially stacked, and the atomic density of silicon atoms and carbon atoms in the surface layer The sum of the atomic densities of 6.60 × 10 ²² atoms / cm ³ or more,
The toner is a toner having at least toner particles containing a binder resin and a colorant and an inorganic fine powder, and the flow rate index FRI of the inorganic fine powder is from 0.8 to 2.0. toner.

  (2) The toner, wherein the inorganic fine powder is a particle having a number average particle size of primary particles of 30 nm to 800 nm and having an octahedral or hexahedral shape.

  (3) A toner wherein the inorganic fine powder is surface-treated with a fatty acid or a metal salt of a fatty acid.

  (4) The toner, wherein the inorganic fine powder is a metal carbonate.

(5) charging the electrostatic charge image carrier with a charging member; forming an electrostatic latent image on the charged electrostatic charge carrier; and a toner carried on the toner carrier. A developing process for transferring to the electrostatic latent image for visualization, a transferring process for transferring the toner image formed on the electrostatic image bearing member onto a recording medium, and a fixing process for fixing the toner image on the recording medium by heating. And a cleaning step of cleaning the surface of the electrostatic charge image carrier after transfer with a cleaning member,
The electrostatic image bearing member is an electrophotographic photosensitive member in which at least a photoconductive layer and a surface layer formed of hydrogenated amorphous silicon carbide are sequentially stacked, and the atomic density of silicon atoms and carbon atoms in the surface layer The sum of the atomic densities of 6.60 × 10 ²² atoms / cm ³ or more,
The toner is a toner having at least toner particles containing a binder resin and a colorant and an inorganic fine powder, and the flow rate index FRI of the inorganic fine powder is from 0.8 to 2.0. Image forming method.

  (6) The surface layer of the electrophotographic photosensitive member is characterized in that the ratio of the number of carbon atoms to the sum of the number of silicon atoms and the number of carbon atoms is 0.61 or more and 0.75 or less. Forming method.

(7) The image forming method, wherein the sum of the atomic density of silicon atoms and the atomic density of carbon atoms is 6.81 × 10 ²² atoms / cm ³ or more in the surface layer of the electrophotographic photosensitive member.

  According to the present invention, it is possible to stably obtain a high-resolution, high-definition image for a long period of time without depending on an environment and a print image without occurrence of cleaning failure.

It is a schematic diagram of the electrophotographic photosensitive member of the present invention. It is a schematic diagram of an example of the plasma CVD apparatus used for preparation of the electrophotographic photosensitive member of the present invention.

  The present invention includes a step of charging an electrostatic charge image carrier with a charging member, an electrostatic latent image forming step of forming an electrostatic latent image on the charged electrostatic charge carrier, and a toner carried on the toner carrier. A developing process for transferring the toner image to the electrostatic latent image for visualization, a transfer process for transferring the toner image formed on the electrostatic charge image carrier onto a recording medium, and a surface of the electrostatic charge image carrier after the transfer. It is based on an image forming method having a cleaning step of cleaning with a cleaning member.

A feature of the present invention is that the photosensitive drum has a structure in which at least a photoconductive layer and a surface layer formed of hydrogenated amorphous silicon carbide are sequentially laminated, and the surface layer has an atomic density of silicon atoms and carbon. The sum of the atomic densities of the atoms is 6.60 × 10 ²² atoms / cm ³ or more,
As a toner, it contains inorganic fine powder with a flow rate index FRI of 0.8 or more and 2.0 or less, so that the life of the photosensitive drum and the cleaning blade can be suppressed and long life can be achieved without causing defective cleaning. can do.

  That is, the inorganic fine powder with controlled flow rate index of the present invention is supplied to the cleaning as a residual toner and selectively stays in the vicinity of the contact portion between the photosensitive drum and the cleaning blade edge, thereby improving the lubricity between the photosensitive member and the cleaning blade. A blocking layer is formed to improve the toner and prevent the toner from slipping through. Furthermore, the photoconductor of the present invention controls the atomic density of silicon atoms and carbon atoms and is excellent in wear resistance, and has an atomic level surface smoothing activity. Therefore, the stay layer formed of the inorganic fine powder of the present invention is elongated. It is possible to stably hold in the direction without unevenness. Therefore, the contact pressure of the cleaning blade to the photosensitive drum is reduced, and even if the load on the photosensitive drum surface and the cleaning blade is reduced, it is possible to extend the life of the photosensitive member and cleaning blade without causing defective cleaning such as toner slipping. To.

  A feature of the present invention is that the toner has an inorganic fine powder having a flow rate index FRI of 0.8 or more and 2.0 or less. The flow rate index FRI is a numerical value measured by a powder rheometer (manufactured by Sysmec Co., Ltd.). A rotation generated by rotating a rotating blade spirally in packed particles and rotating at a low speed (10 rpm). The total torque Et (10) of torque and vertical load and the total torque Et (100) of rotational torque and vertical load generated during high speed (100 rpm) rotation are measured, and the ratio Et (10) / Et (100) is calculated. is there. As a result of studies, the present inventors have found that the flow velocity index FRI = ratio Et (10) / Et (100) has a correlation with the behavior of the inorganic fine powder in the vicinity of the cleaning blade edge portion.

  That is, when the flow velocity index FRI is less than 0.8, the slipping prevention layer at the edge of the cleaning blade is easily destroyed and slipping easily occurs when the rubbing speed between the photosensitive member and the cleaning blade is slow at the end of printing. Become.

  On the other hand, when the flow velocity index FRI exceeds 2.0, the slipping prevention layer is similarly easily broken and flows through in the longitudinal direction in the situation where the rubbing speed between the photosensitive member and the cleaning blade at the start of printing increases.

  In the present invention, the number average particle size of the primary particles of the inorganic fine powder is preferably 30 nm or more and 800 nm or less.

  When the number average particle diameter is less than 30 nm, the inorganic fine powder itself easily slips out of the cleaning blade, thereby causing a filming phenomenon on the photoreceptor.

  On the other hand, if it exceeds 800 nm, the photoconductor may be damaged in a streak pattern at the edge of the cleaning blade, which is liable to cause image problems such as a streak-like image in a halftone image.

  In the present invention, the inorganic fine powder is preferably particles having an octahedral or hexahedral shape.

  Since the inorganic fine powder has a vertex, the inorganic fine powder is easily caught near the nip of the photoconductor-cleaning blade and can stay near the edge for a long time. Thereby, it is possible to maintain the toner slip-in preventing effect and the lubricating effect over a long period of time.

  The inorganic fine powder is preferably subjected to a hydrophobic treatment. In particular, the surface treatment is preferably performed with a fatty acid or a metal salt of a fatty acid.

  By coating the surface of the inorganic fine powder with a hydrophobizing agent, the charging stability of the toner under a high humidity environment is improved and the inorganic near the edge of the cleaning blade in a low humidity-high humidity environment. It becomes possible to stabilize the fluidity of the fine powder.

  The hydrophobization treatment in the present invention indicates that the degree of hydrophobicity of the inorganic fine powder of the present invention is 70% or more. The method is not limited, but it is preferable to coat the surface of the inorganic fine powder of the present invention with a hydrophobizing agent.

  Examples of the hydrophobizing agent for the inorganic fine powder include silicone oils and titanate-based, aluminum-based, silane-based coupling agents, and fatty acid metal salts as coupling agents.

  Among these, surface treatment with a fatty acid having 8 to 35 carbon atoms or a metal salt of a fatty acid having 8 to 35 carbon atoms is preferable because it has an effect of improving the lubricity between the cleaning blade and the photoreceptor.

  When the number of carbon atoms exceeds 35, the adhesion between the surface of the inorganic fine powder and the fatty acid or metal salt thereof is lowered, peeled off from the surface of the inorganic fine powder due to long-term use, and the durability is lowered. Fatty acid metal salts are not preferred because they cause fogging.

  A preferable treatment amount of the fatty acid or the metal salt thereof with respect to the inorganic fine powder is 0.1 to 15.0 mass%, more preferably 0.5 to 12.0 mass% with respect to the inorganic fine powder matrix.

  The surface treatment agent to be treated is dissolved and dispersed in a solvent, the inorganic fine powder is added to the solution, the solvent is removed while stirring, the wet treatment method, the coupling agent, and the fatty acid metal salt. And a dry method in which the inorganic fine powder is directly mixed and treated with stirring.

  The inorganic fine powder is preferably a metal carbonate.

  The inorganic fine powder of the present invention comprises various metal oxides (iron oxide, aluminum oxide, titanium oxide, cerium oxide, magnesium oxide, chromium oxide, tin oxide, zinc oxide, etc.), metal acid salts (strontium titanate, calcium titanate). , Titanates such as magnesium titanate, aluminates and zirconates), nitrides (silicon nitride, etc.), carbides (silicon carbide, etc.), metal salts (calcium sulfate, barium sulfate, calcium carbonate, etc.), fatty acids Metal salts (zinc stearate, calcium stearate, etc.), carbon black, silica, etc. can be mentioned, but among calcium carbonates, calcium carbonate and magnesium carbonate have a small specific gravity of inorganic fine powder and give an extra load to the cleaning blade. It is preferable because there is no

  A preferable addition amount of these inorganic fine powders is 0.03 parts by mass or more and less than 5 parts by mass with respect to 100 parts by mass of the toner particles. When the added amount of the inorganic fine powder is less than 0.03 parts by mass, a sufficient cleaning stay layer forming effect cannot often be obtained. On the other hand, when the amount is 5 parts by mass or more, the fluidity of the toner is deteriorated and the developability and the like are easily adversely affected.

  As the binder resin for the toner particles contained in the toner of the present invention, a polyester resin, a vinyl copolymer resin, an epoxy resin, or a binder resin including a hybrid resin having a vinyl polymer unit and a polyester unit. Can be used.

  The toner particles contained in the toner of the present invention can be added as a release agent as necessary.

  Examples of release agents that can be used in the present invention include aliphatic hydrocarbon waxes and oxides thereof; block copolymers of the oxides; waxes based on fatty acid esters; Or what deoxidized all is mentioned. Among these release agents, one or more release agents may be contained in the toner particles as necessary.

  A preferable addition amount of the release agent is 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts by mass per 100 parts by mass of the binder resin.

  In addition, these release agents can usually be contained in the toner particles by dissolving the resin in a solvent, increasing the temperature of the resin solution, adding and mixing with stirring, or mixing at the time of kneading.

  In the toner of the present invention, a charge control agent can be used as necessary in order to further stabilize the chargeability. Examples of the negative charge control agent for controlling the toner to be negative charge include an organometallic complex or a chelate compound. Examples of positive charge control agents that control the toner to be positively charged include modified products of nigrosine and fatty acid metal salts, quaternary ammonium salt compounds, triphenylmethane dyes and their lake pigments, metal salts of higher fatty acids, etc. Is effective.

  A preferable content of the charge control agent is 0.5 to 10 parts by mass per 100 parts by mass of the binder resin. When the amount of the charge control agent is less than 0.5 parts by mass, sufficient charging characteristics may not be obtained, which is not preferable. When the amount exceeds 10 parts by mass, compatibility with other materials may be deteriorated, or charging may be excessive under low humidity, which is not preferable.

  The toner particles contained in the toner of the present invention are preferably made into a magnetic toner by adding a magnetic material as necessary. As the magnetic material, magnetic oxides such as magnetite, maghematite, ferrite and mixtures thereof are preferably used.

  Examples of the magnetic material include at least one element selected from the group consisting of magnesium, aluminum, silicon, phosphorus, titanium, zirconium, tin, calcium, manganese, cobalt, copper, nickel, strontium, and zinc. Magnetic iron oxide is included.

  The number average particle diameter of these magnetic materials is preferably 0.05 μm or more and less than 1.0 μm, more preferably 0.1 μm or more and less than 0.5 μm.

The BET specific surface area by nitrogen adsorption of the magnetic material is preferably 2 to 40 m ² / g, more preferably 4 to 20 m ² / g.

A preferable magnetic property of the magnetic material is that the saturation magnetization measured with a magnetic field of 795.8 kA / m is 10 to 200 Am ² / kg, and more preferably 70 to 100 Am ² / kg.

A preferable residual magnetization is 1 to 100 Am ² / kg, and more preferably 2 to 20 Am ² / kg.

  A preferable coercive force is 1 to 30 kA / m, and more preferably 2 to 15 kA / m.

  A preferable content of the magnetic material is 20 to 200 parts by mass with respect to 100 parts by mass of the binder resin.

  To the toner particles contained in the toner of the present invention, a colorant can be added as necessary. Any appropriate pigment or dye can be used as the colorant.

  Examples of the pigment include carbon black, aniline black, acetylene black, naphthol yellow, hansa yellow, rhodamine yellow, alizarin yellow, bengara, phthalocyanine blue and the like. A preferable addition amount of the pigment is 0.1 to 20 parts by mass, more preferably 0.2 to 10 parts by mass with respect to 100 parts by mass of the binder resin.

  Examples of the dye include azo dyes, anthraquinone dyes, xanthene dyes, methine dyes, and the like. A preferable addition amount of the dye is 0.1 to 20 parts by mass, more preferably 0.3 to 10 parts by mass with respect to 100 parts by mass of the binder resin.

  In the toner of the present invention, the binder resin and other additives are sufficiently mixed by a mixer such as a Henschel mixer and a ball mill and then melt-kneaded using a heat kneader such as a heating roll, a kneader, and an extruder. .

  Further, after cooling and solidification, pulverization and classification are performed, and further, the composite inorganic fine powder and, if necessary, desired additives are sufficiently mixed by a mixer such as a Henschel mixer.

  Examples of the mixer include a Henschel mixer (manufactured by Mitsui Mining); a super mixer (manufactured by Kawata); a ribocorn (manufactured by Okawara Seisakusho); a nauter mixer, a turbulizer, a cyclomix (manufactured by Hosokawa Micron); Pin mixer one (manufactured by Taiheiyo Kiko Co., Ltd.);

  Examples of the kneader include: KRC kneader (manufactured by Kurimoto Iron Works); bus co-kneader (manufactured by Buss); TEM type extruder (manufactured by Toshiba Machine); TEX twin-screw kneader (manufactured by Nippon Steel Works) PCM kneading machine (manufactured by Ikekai Tekkosho); three roll mill, mixing roll mill, kneader (manufactured by Inoue Seisakusho); kneedex (manufactured by Mitsui Mining Co., Ltd.); MS pressure kneader, Nider Ruder (Moriyama Seisakusho) Manufactured); Banbury mixer (manufactured by Kobe Steel).

  Examples of the pulverizer include counter jet mill, micron jet, inomizer (manufactured by Hosokawa Micron Co.); IDS type mill, PJM jet pulverizer (manufactured by Nippon Pneumatic Industry Co., Ltd.); cross jet mill (manufactured by Kurimoto Iron Works Co., Ltd.); ULMAX (manufactured by Nisso Engineering Co., Ltd.); SK Jet O Mill (manufactured by Seishin Enterprise Co., Ltd.); Kryptron (manufactured by Kawasaki Heavy Industries, Ltd.);

  Examples of the classifier include a class seal, a micron classifier, a speck classifier (manufactured by Seishin Enterprise Co., Ltd.); a turbo classifier (manufactured by Nissin Engineering Co., Ltd.); a micron separator, a turboplex (ATP), and a TSP separator (Hosokawa Micron). Elbow Jet (manufactured by Nippon Steel & Mining Co., Ltd.), dispersion separator (manufactured by Nippon Pneumatic Engineering Co., Ltd.); YM Microcut (manufactured by Yaskawa Shoji Co., Ltd.).

  Examples of sieving devices used for sieving coarse particles include Ultrasonic (manufactured by Sakae Sangyo Co., Ltd.); Resonator Sheave, Gyroshifter (Tokuju Kogakusha Co., Ltd.); Vibrasonic System (manufactured by Dalton Co., Ltd.); Shinto Kogyo Co., Ltd.); turbo screener (Turboe Co., Ltd.); micro shifter (Ogino Sangyo Co., Ltd.); circular vibrating screen, etc.

<Measurement method of flow velocity index>
Et100 (mJ) and Et10 (mJ) in the present invention are measured by using a “powder fluidity analyzer powder rheometer FT4” (manufactured by Freeman Technology, hereinafter sometimes abbreviated as FT4).

  Specifically, the measurement is performed by the following operation.

  In all operations, a 48 mm-diameter blade dedicated to FT4 (see FIG. 1, model number: C210, material: SUS, hereinafter may be abbreviated as “blade”) is used as the propeller blade. This propeller-type blade has a rotation axis in the normal direction at the center of a 48 mm × 10 mm blade plate, and the blade plate has an outermost edge portion (24 mm portion from the rotation shaft) of 70 ° and a portion 12 mm from the rotation shaft. It is smoothly twisted counterclockwise, such as 35 °.

  As the measurement container, a cylindrical split container dedicated to FT4 (model number: C203, material: glass, diameter 50 mm, volume 160 ml, height 82 mm from the bottom surface to the split part, hereinafter may be abbreviated as container) is used. .

  In addition, 100 g of inorganic fine powder left in an environment of a temperature of 23 ° C. and a humidity of 60% RH for 3 days or more is put in the measurement container to form a powder layer.

(1) Conditioning operation (a) The propeller blade is rotated clockwise with respect to the powder layer surface so that the peripheral speed of the outermost edge of the blade is 60 mm / sec (the powder layer is loosened by the rotation of the blade). Direction). The surface of the powder layer at an approach speed at which the angle between the locus drawn by the outermost edge of the moving blade and the surface of the powder layer (hereinafter sometimes referred to as the angle formed) is 5 °. To 10 mm from the bottom of the powder layer in the vertical direction. Thereafter, the toner powder layer is rotated while rotating clockwise with respect to the surface of the powder layer so that the peripheral speed of the outermost edge of the blade is 60 mm / sec. The blade is advanced to a position of 1 mm from the bottom surface. Furthermore, while rotating clockwise with respect to the powder layer surface so that the formed angle is 5 ° and the peripheral speed of the outermost edge of the blade is 60 mm / sec, 100 mm from the bottom surface of the powder layer. Move the blade to the position and remove it. When the extraction is completed, the blade is rotated clockwise and counterclockwise alternately, and the inorganic fine powder adhering to the blade is wiped off.
(B) The operations of (1)-(a) are repeated five times to remove air taken in the powder layer.

(2) Split operation The powder layer is ground at the split portion of the above-mentioned FT4 container, and the inorganic fine powder on the upper part of the powder layer is removed. By this operation, the volume of the powder layer can be made the same for each measurement.

(3) Measurement operation (i) Et100 measurement (a) Conditioning operation similar to (1)-(a) is performed once.
(B) Rotate the propeller blade counterclockwise with respect to the powder layer surface (direction in which the powder layer is pushed in by rotation of the blade) so that the peripheral speed of the outermost edge of the blade is 100 mm / sec. To do. The blade is advanced in the vertical direction from the powder layer surface to a position 10 mm from the bottom surface of the toner powder layer at an approach speed of 5 °. Thereafter, the blade rotates clockwise with respect to the surface of the powder layer so that the peripheral speed of the outermost edge of the blade is 60 mm / sec, and the angle forming the vertical entry speed to the powder layer becomes 2 °. It is made to approach to the position of 1 mm from the bottom face of the powder layer at the approach speed. Further, the blade is moved to a position of 100 mm from the bottom surface of the powder layer at a speed of 5 °, and is extracted. When the extraction is completed, the blade is rotated clockwise and counterclockwise alternately, and the inorganic fine powder adhering to the blade is wiped off.
(C) The operations of (3)-(i)-(b) are further repeated 6 times, and the rotation obtained when the blade enters the position from 100 mm to 10 mm from the bottom of the toner powder layer at the sixth time. The total Et of the torque and the vertical load is Et100.

(Ii) Measurement of Et10 (a) Using the toner powder layer for which the measurement of Et100 has been completed, a conditioning operation similar to the above (1)-(a) is performed once.
(B) The same operation as (3)-(i)-(b) is performed once.
(C) The same operation as (3)-(i)-(b) is performed once except that the peripheral speed of the outermost edge of the blade is changed to 70 mm / sec.
(D) The same operation as (3)-(i)-(b) is performed once except that the peripheral speed of the outermost edge of the blade is changed to 40 mm / sec.
(E) The same operation as (3)-(i)-(b) is performed once except that the peripheral speed of the outermost edge portion of the blade is changed to 10 mm / sec. At this time, Et10 is the total Et of rotational torque and vertical load obtained when the blade is moved from the position of 100 mm to the position of 10 mm from the bottom surface of the toner powder layer.

<Method for measuring particle size of inorganic fine powder>
About the number average particle diameter of the inorganic fine powder in the present invention, 100 average particle diameters were measured from photographs taken at a magnification of 50,000 times with an electron microscope, and the average was determined.

<Measurement method of melting point of wax>
The peak temperature of the maximum endothermic peak of the wax and toner is measured according to ASTM D3418-82 using a differential scanning calorimeter “Q1000” (manufactured by TA Instruments).

  The temperature correction of the device detection unit uses the melting points of indium and zinc, and the correction of heat uses the heat of fusion of indium.

  Specifically, about 10 mg of toner is precisely weighed, put in an aluminum pan, and an empty aluminum pan is used as a reference. Measurement is performed at ° C / min. In the measurement, the temperature is once raised to 200 ° C., subsequently lowered to 30 ° C., and then the temperature is raised again. The maximum endothermic peak of the DSC curve in the temperature range of 30 to 200 ° C. in the second temperature raising process is defined as the maximum endothermic peak of the endothermic curve in the DSC measurement of the toner of the present invention.

<Measurement method of molecular weight distribution of resin>
The molecular weight distribution of the THF soluble part of the toner is measured by gel permeation chromatography (GPC) as follows.

First, the toner is dissolved in tetrahydrofuran (THF) at room temperature over 24 hours. The obtained solution is filtered through a solvent-resistant membrane filter “Maescho Disc” (manufactured by Tosoh Corporation) having a pore diameter of 0.2 μm to obtain a sample solution. The sample solution is adjusted so that the concentration of the component soluble in THF is about 0.8% by mass. Using this sample solution, measurement is performed under the following conditions.
Apparatus: HLC8120 GPC (detector: RI) (manufactured by Tosoh Corporation)
Column: Seven series of Shodex KF-801, 802, 803, 804, 805, 806, 807 (manufactured by Showa Denko KK)
Eluent: Tetrahydrofuran (THF)
Flow rate: 1.0 ml / min
Oven temperature: 40.0 ° C
Sample injection volume: 0.10 ml

  In calculating the molecular weight of the sample, standard polystyrene resin (for example, trade name “TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F— 10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500 ", manufactured by Tosoh Corporation) are used.

  The photosensitive drum of the present invention will be described below.

One of the features of the present invention is that the sum of the atomic density of silicon atoms and the atomic density of carbon atoms in the a-SiC surface layer is 6.60 × 10 ²² atoms / cm ³ or more. Thereby, a big effect is acquired in abrasion resistance improvement and maintenance of surface smoothness.

  In the electrophotographic process, it is considered that oxidation and desorption of carbon atoms occur due to the reaction between ionic species generated in the charging step and carbon atoms. Oxidation and elimination of the carbon atom breaks the bond between the silicon atom and the carbon atom, and the oxidized material reacts with the dangling bond of the newly generated silicon atom, thereby deteriorating the wear resistance.

  Therefore, in order to suppress these, by increasing the atomic density of silicon atoms and carbon atoms constituting the a-SiC surface layer, the distance between each atom can be shortened and the space ratio can be reduced. Increases the binding force of and suppresses the formation of polar groups on the outermost surface. As a result, a surface layer having a high hardness can be obtained. As a result, the wear resistance can also be improved, and the surface of the photoreceptor can be prevented from being roughened by the wear.

Therefore, it is more preferable that the sum of the atomic density of silicon atoms and the atomic density of carbon atoms in the a-SiC surface layer is higher. Further, by setting the sum to 6.81 × 10 ²² atoms / cm ³ or more, the wear resistance is further increased. A great effect is obtained in improving the above. In a-SiC, since the SiC crystal having the above composition range is in the highest density state, the upper limit of the sum of the atomic density of silicon atoms and the atomic density of carbon atoms is 13.0 × 10 ²² atoms / cm 3. ³ or less.

  In the present invention, the sum of the atomic density of silicon atoms and the atomic density of carbon atoms is in the above range, and the number of carbon atoms relative to the sum of the number of silicon atoms and the number of carbon atoms in the a-SiC surface layer The number ratio is preferably in the range of 0.61 to 0.75 in order to obtain excellent electrophotographic photoreceptor characteristics.

  When the ratio of the number of carbon atoms to the sum of the number of silicon atoms and the number of carbon atoms in the a-SiC surface layer is smaller than 0.61, particularly when a-SiC having a high atomic density is produced. The resistance of a-SiC may decrease. In such a case, the carrier tends to cause a lateral flow in the surface layer when forming the electrostatic latent image. As a result, the isolated dots are reduced as an electrostatic latent image. As a result, in the output image, in particular, the image density on the low printing side is lowered, and the gradation may be deteriorated.

  Further, when the ratio of the number of carbon atoms to the sum of the number of silicon atoms and the number of carbon atoms is greater than 0.75, particularly when a-SiC having a high atomic density is produced, the a-SiC surface layer In some cases, the light absorption at the abruptly increases. In such a case, a large amount of image exposure light is required when forming the electrostatic latent image, and the sensitivity may deteriorate. Further, since the sensitivity to abrasion of the a-SiC surface layer is increased, image density unevenness may occur when the electrophotographic photosensitive member is shaved and uneven.

  In the present invention, the ratio of the number of hydrogen atoms to the sum of the number of silicon atoms, the number of carbon atoms, and the number of hydrogen atoms is preferably 0.30 to 0.45. As a result, an electrophotographic photosensitive member having excellent electrophotographic photosensitive member characteristics and further excellent high-humidity flow suppression and wear resistance can be obtained.

  When the atomic density ratio of hydrogen atoms is less than 0.30, in an a-SiC surface layer having a high atomic density, the optical band gap becomes narrow, and the sensitivity may deteriorate due to increased light absorption.

  On the other hand, when the ratio of the number of hydrogen atoms is more than 0.45, there is a tendency that the number of terminal groups having many hydrogen atoms such as methyl groups increases in the surface layer. These may form a large space in the structure of a-SiC and cause distortion in the bonds between the atoms existing around. Such a weak part in structure may become a weak part with respect to oxidation.

  Next, a production apparatus and a production method for producing the electrophotographic photosensitive member of the present invention will be shown by specific examples.

  FIG. 2 is a view schematically showing an example of an apparatus for depositing a photoconductor by an RF plasma CVD method using a high frequency power source for producing the a-Si type photoconductor of the present invention.

  This apparatus is roughly composed of a deposition apparatus 1100 having a reaction vessel 1110, a raw material gas supply apparatus 1200, and an exhaust device (not shown) for depressurizing the inside of the reaction container 1110.

  A conductive substrate 1112, a conductive substrate heating heater 1113, and a source gas introduction pipe 1114 connected to the ground are installed in the reaction vessel 3110 in the deposition apparatus 1100. Further, a high frequency power source 1120 is connected to the cathode electrode 1111 via a high frequency matching box 1115.

The source gas supply device 1200 includes source gas cylinders 1221 to 1225 such as SiH ₄ , H ₂ , CH ₄ , NO, and B ₂ H ₆ , valves 1231 to 1235, pressure regulators 1261 to 1265, inflow valves 1241 to 1245, and outflow valves. 1251 to 1255 and mass flow controllers 1211 to 1215. A gas cylinder filled with each source gas is connected to a source gas introduction pipe 1114 in the reaction vessel 1110 via an auxiliary valve 1260.

  Next, a method for forming a deposited film using this apparatus will be described. First, the conductive substrate 1112 that has been degreased and washed in advance is placed in the reaction vessel 1110 via a cradle 1123. Next, an exhaust device (not shown) is operated to exhaust the reaction vessel 1110. While viewing the display on the vacuum gauge 1119, when the pressure in the reaction vessel 1110 reaches a predetermined pressure of, for example, 1 Pa or less, power is supplied to the substrate heating heater 1113, and the conductive substrate 1112 is moved to, for example, 50 ° C. to 350 ° C. To the desired temperature. At this time, an inert gas such as Ar or He can be supplied from the gas supply apparatus 1200 to the reaction vessel 1110 and heated in an inert gas atmosphere.

  Next, a gas used to form a deposited film is supplied from the gas supply device 1200 to the reaction vessel 1110. That is, if necessary, the valves 1231 to 1235, the inflow valves 1241 to 1245, and the outflow valves 1251 to 1255 are opened, and the flow rate is set in the mass flow controllers 1211 to 1215. When the flow rate of each mass flow controller is stabilized, the main valve 1118 is operated while viewing the display of the vacuum gauge 1119 to adjust the pressure in the reaction vessel 1110 to a desired pressure. When a desired pressure is obtained, high-frequency power is applied from the high-frequency power source 3120 and simultaneously the high-frequency matching box 1115 is operated to generate plasma discharge in the reaction vessel 1110. Thereafter, the high frequency power is quickly adjusted to a desired power, and a deposited film is formed.

  When the formation of the predetermined deposited film is finished, the application of the high-frequency power is stopped, the valves 1231 to 1235, the inflow valves 1241 to 1245, the outflow valves 1251 to 1255, and the auxiliary valve 1260 are closed, and the supply of the source gas is finished. At the same time, the main valve 1118 is fully opened, and the reaction vessel 1110 is evacuated to a pressure of 1 Pa or less.

  The formation of the deposited layers is completed as described above. When a plurality of deposited layers are formed, the above procedure is repeated again to form each layer. The bonding region can also be formed by changing the raw material gas flow rate, pressure, and the like to the conditions for forming the photoconductive layer in a certain time.

  After all the deposited films are formed, the main valve 1118 is closed, an inert gas is introduced into the reaction vessel 1110 to return to atmospheric pressure, and then the conductive substrate 1112 is taken out.

  The electrophotographic photosensitive member of the present invention has a film structure having a high atomic density by increasing the atomic density of silicon atoms and carbon atoms constituting a-SiC as compared with the surface layer of a conventionally known electrophotographic photosensitive member. Forming a layer. As described above, when producing an a-SiC surface layer having a high atomic density according to the present invention, generally, the amount of gas supplied to the reaction vessel is smaller, although it depends on the conditions at the time of creating the surface layer. The high frequency power is better, the pressure in the reaction vessel is better, and the temperature of the conductive substrate is better.

First, the gas decomposition can be promoted by reducing the amount of gas supplied into the reaction vessel and increasing the high-frequency power. Thereby, a carbon atom supply source (for example, CH ₄ ) that is harder to decompose than a silicon atom supply source (for example, SiH ₄ ) can be efficiently decomposed. As a result, active species having a small number of hydrogen atoms are generated, and the number of hydrogen atoms in the film deposited on the substrate is reduced, so that an a-SiC surface layer having a high atomic density can be formed.

  In addition, by increasing the pressure in the reaction vessel, the residence time of the raw material gas supplied into the reaction vessel becomes longer, and a weakly bonded hydrogen abstraction reaction occurs due to hydrogen atoms generated by the decomposition of the raw material gas. This is because the networking of silicon and carbon atoms has been promoted.

  Furthermore, by raising the temperature of the conductive substrate, the surface movement distance of the active species that has reached the conductive substrate is increased, and a more stable bond can be created. As a result, it is considered that each atom is bonded to a more structurally stable arrangement as the a-SiC surface layer.

(Measurement of Si + C atomic density and hydrogen atom (H) ratio of atomic density of hydrogen atom (Si) and atomic density of carbon atom (C) First, only the charge injection blocking layer and the photoconductive layer of Table 1 were laminated. A reference sample was prepared by cutting out a longitudinal central portion of the reference electrophotographic photosensitive member in an arbitrary circumferential direction with 15 mm □, and then an electrophotographic photosensitive member in which a charge injection blocking layer, a photoconductive layer, and a surface layer were laminated. The reference sample and the measurement sample were measured by spectroscopic ellipsometry (manufactured by JA Woollam: high-speed spectroscopic ellipsometry M-2000) to determine the film thickness of the surface layer. It was.

  Specific measurement conditions are incident angles: 60 °, 65 °, 70 °, measurement wavelength: 195 nm to 700 nm, analysis software: WVASE 32, beam diameter: 1 mm × 2 mm. As the calculation model, the outermost roughness layer was calculated as surface layer: air layer = 8: 2.

  Thereafter, the number of atoms of silicon atoms and carbon atoms was measured for the above measurement sample by RBS (Rutherford backscattering method) (manufactured by Nisshin High Voltage Co., Ltd .: backscattering measurement device AN-2500). In addition, the number of hydrogen atoms was measured by HFS (hydrogen forward scattering method) (manufactured by Nisshin High Voltage Co., Ltd .: backscattering measuring device AN-2500).

  Specific measurement conditions are incident ion: 4He +, incident energy: 2.3 MeV, incident angle: 75 °, sample current: 35 nA, incident beam length: 1 mm, and an RBS detector has a scattering angle of 160 °, Aperture diameter: 8 mm, HFS detector has recoil angle: 30 °, aperture diameter: 8 mm + Slit.

  As described above, from the film thickness obtained by spectroscopic ellipsometry, the number of silicon atoms, the number of carbon atoms and the number of hydrogen atoms obtained by RBS and HFS, the sum of the atomic density of hydrogen atoms and the atomic density of carbon atoms, hydrogen Atomic ratio was calculated.

(Measurement of the ratio C / (Si + C) of the number of carbon atoms to the sum of the number of silicon atoms and the number of carbon atoms)
C / (Si + C) is an XPS device (X-ray photoelectron spectroscope) (manufactured by ULVAC-PHI Co., Ltd .: QUANTUM2000) obtained by cutting a central portion of the electrophotographic photosensitive member in the longitudinal direction in an arbitrary circumferential direction with 10 mm □. Calculated by SCANNING ESCA MICROPROBE).

  Specifically, the depth profiles of silicon atoms (Si), carbon atoms (C), and oxygen atoms (O) from the outermost surface of the electrophotographic photosensitive member to the photoconductive layer were measured. From the obtained results, the ratio of Si and C at a position where O was no longer detected was calculated, and the value was defined as C / (Si + C).

  The analyzed orbits of Si, C, and O are Si2p, C1s, and O1s, and the measurement conditions are spot diameter 100 μm, X-ray intensity = 25 W−15 kV, Pass energy = 23.5 eV, Step size = 0.1 eV, SWEEP. Number = 10. As sputtering conditions, sputtering was performed in an area of 2 mm □ using Ar ions at an acceleration voltage of 4 kV for 1 minute. Sputtering and measurement were performed alternately to create Si, C, and O depth profiles.

  The present invention will be described more specifically with reference to the following examples.

(Inorganic fine powder production example 1)
Using slaked lime powder obtained by dehydrating quicklime, the concentration was adjusted to 120 g / L. Carbonation reaction was performed by blowing CO ₂ gas into lime milk while stirring. In the carbonation reaction, a CO ₂ -containing gas is blown until the carbonation rate reaches 6.0% at a feed rate of 20 m ³ / m ² · hr as the first stage, and then the feed rate is set to 1.2 m ³ / Reduce to m ² · hr and blow in CO ₂ -containing gas until the carbonation rate reaches 13.0%. Further, as the third stage, increase the feed rate to 18 m ³ / m ² · hr and increase the carbonation rate to 45.0%. The reaction was carried out by blowing a gas containing CO ₂ until the reaction product was obtained.

1 mol of a calcium hydroxide aqueous suspension having a viscosity of 2500 cp at 25 ° C. and a concentration of 400 g / L was mixed with 1 mol of the obtained reaction product. The obtained mixture was blown with a CO ₂ -containing gas at a reaction start temperature of 25 ° C. at a supply rate of 8.0 m ³ / m ² · hr to be carbonated to a carbonation rate of 50.5%. Aqueous suspension A was prepared by coarsening to a thickness of 0.4 μm at 8 μm. On the other hand, an aqueous calcium hydroxide suspension having a viscosity of 2500 cp at 25 ° C. and a concentration of 400 g / L is prepared to a concentration of 50 g / L, and a CO ₂ -containing gas is supplied at a reaction start temperature of 13 ° C. at a feed rate of 10.0 m ³ / m ^2. Aqueous suspension B was prepared by blowing until hr to a carbonation rate of 32.3%. Next, liquid A and liquid B are mixed so that the molar ratio of the Ca-based compound in liquid A and the Ca-based compound in liquid B is 100: 8, and then the CO ₂ gas supply rate at a reaction start temperature of 15 ° C. The mixture was blown at 15 m ³ / m ² · hr and reacted to obtain uniform cubic calcium carbonate having a number average particle size of 150 nm.

  After washing the suspension containing calcium carbonate, it was adjusted to a slurry having a solid content of 10% by mass. While the slurry was stirred with a disperser at 65 ° C., a sodium stearate content of 20% by mass was added and stirred, followed by press dehydration. The obtained filter cake was dried with a box-type dryer and then crushed to obtain inorganic fine powder 1 which is calcium carbonate particles treated with stearic acid. Table 3 shows the physical property values of the obtained inorganic fine powder 1.

(Inorganic fine powder production example 2)
To a reaction vessel containing 20 L of 3.0 mol / L sodium hydroxide aqueous solution, 20 L of ferrous sulfate aqueous solution with Fe ²⁺ of 1.5 mol / L is added, and the temperature is set to 95 ° C. A ferrous salt suspension containing was produced. The mixture was stirred for 90 minutes while aeration of 100 L / min air was conducted to obtain a ferrous suspension containing magnetite. A 6.0 mol / L aqueous sodium hydroxide solution was added thereto to adjust the pH to 10.0. Further, the mixture was stirred for 60 minutes while ventilating 100 L / min of air to generate magnetite particles. After stirring sufficiently, the magnetite was filtered off. The magnetite was washed with water; dried and then crushed to obtain octahedral magnetite particles.

  An inorganic fine powder 4 which is octahedral magnetite particles having a number average particle diameter of 250 nm was obtained. Table 3 shows the physical properties of the obtained inorganic fine powder.

(Inorganic fine powder production example 3)
In Production Example 2 of inorganic fine powder, the suspension containing magnetite particles was washed and then adjusted to a slurry with a solid content of 10% by mass. While stirring the slurry with a disperser at 65 ° C., 15% by mass of sodium stearate content was added and stirred, followed by press dehydration. The obtained filter cake was dried with a box-type dryer and then pulverized to obtain inorganic fine powder 3 which is magnetite particles treated with stearic acid. The physical properties of the obtained inorganic fine powder 3 are shown in Table 3.

(Inorganic fine powder production example 4)
Into a reaction vessel containing 20 L of 3.0 mol / L sodium hydroxide aqueous solution, 20 L of ferrous sulfate aqueous solution with Fe ²⁺ of 1.5 mol / L is added, the temperature is set to 95 ° C., and ferrous hydroxide colloid A ferrous salt suspension containing was produced. The mixture was stirred for 90 minutes while aeration of 100 L / min air was conducted to obtain a ferrous suspension containing magnetite. A 6.0 mol / L aqueous sodium hydroxide solution was added thereto to adjust the pH to 10.0. Furthermore, it stirred for 60 minutes, ventilating 100 L / min air, and the magnetite particle | grains were produced | generated. After stirring sufficiently, the magnetite was filtered off. The magnetite was washed with water; dried, and then crushed to obtain octahedral magnetite particles.

  The inorganic fine powder 4 which is hexagonal magnetite particles having a number average particle diameter of 250 nm was obtained. Table 3 shows the physical properties of the obtained inorganic fine powder.

(Inorganic fine powder production example 5)
A ferrous sulfate solution containing 0.95 equivalents of sodium hydroxide aqueous solution was mixed with Fe ^{2+ in a} ferrous sulfate solution, and then a ferrous salt aqueous solution containing Fe (OH) ₂ was produced. Next, air was passed through the aqueous ferrous salt solution containing Fe (OH) ₂ at a temperature of 90 ° C. to cause an oxidation reaction under the condition of pH 7. Further, 1.05 equivalent of an aqueous sodium hydroxide solution was added to this suspension with respect to the remaining Fe ²⁺ , and the mixture was further oxidized at a temperature of 8 to 11.5 while being heated at 90 ° C. To produce magnetite. The produced magnetite was washed, filtered, dried, and crushed by a conventional method to obtain an inorganic fine powder 5 that is spherical magnetite particles having a number average particle diameter of 40 nm. Table 3 shows the physical properties of the obtained inorganic fine powder 5.

(Inorganic fine powder production example 6)
Cerium oxalate was molded at a pressure of 1200 kg / cm ² and sintered at a temperature of 2200 ° C. for 5 hours. Thereafter, the mixture was mechanically pulverized to obtain inorganic fine powder 6 which is cerium oxide particles having an average particle diameter of 750 nm. Table 3 shows the physical properties of the obtained inorganic fine powder 6.

(Inorganic fine powder production example 7)
In Production Example 6 of inorganic fine powder, the conditions for mechanical grinding were adjusted to obtain inorganic fine powder 7 which is cerium oxide particles having an average particle diameter of 1100 nm. Table 3 shows the physical properties of the inorganic fine powder 7 obtained.

(Inorganic fine powder production example 8)
Aluminum hydroxide was molded at a pressure of 1000 kg / cm ² and sintered at a temperature of 1600 ° C. for 2 hours. Thereafter, the mixture was mechanically pulverized to obtain inorganic fine powder 8 which is aluminum oxide particles having a number average particle diameter of 25 nm. The physical properties of the obtained inorganic fine powder 8 are shown in Table 3.

(Inorganic fine powder production example 9)
A mixed gas having a volume ratio of argon and oxygen of 3: 1 is introduced into the reaction vessel to replace the atmosphere. Oxygen gas is supplied into the reaction vessel at 40 m ³ / hr and hydrogen gas is supplied at 20 m ³ / hr, and a combustion flame composed of oxygen-hydrogen is formed using an ignition device. Next, a metal silicon powder as a raw material is charged into the combustion flame with a hydrogen carrier gas having a pressure of 5 kg / cm ² to form a dust cloud. This dust cloud is ignited by a combustion flame and causes an oxidation reaction by dust explosion. After the oxidation reaction, the inside of the reaction vessel was cooled at a rate of 3 ° C./min to obtain inorganic fine powder 9 of silica having an irregular shape with a number average particle diameter of 1100 nm. Table 3 shows the physical properties of the inorganic fine powder 9 obtained.

(Inorganic fine powder production example 10)
40 parts by mass of silica fine powder (specific surface area 110 m ² / g) synthesized by a wet method is treated with 60 parts by mass of dimethyl silicone oil (12,500 cSt), and is an inorganic oil-treated silica having a number average particle size of 2500 nm. A fine powder 10 was obtained. Table 3 shows the physical properties of the obtained inorganic fine powder 10.

[Example 1]
(Toner Production Example 1)
Styrene-n-butylacrylic copolymer (copolymerization mass ratio = 78: 22, weight average molecular weight = 380,000) 100 parts by mass Low molecular weight ethylene-propylene copolymer (melting point 102 ° C.) 6 parts by mass Charge control Agent (Azo-based iron complex compound) 2 parts by mass / 90 parts by mass of magnetic iron oxide (average particle size 0.25 μm, coercive force 11.2 kA / m, remanent magnetization 8.8 Am ² / kg, saturation magnetization 80.3 Am ² / kg)
The above mixture was melt-kneaded with a twin-screw kneader heated to 130 ° C., and the cooled mixture was coarsely pulverized with a hammer mill. Further, the mixture was finely pulverized by a collision type pulverizer, and the obtained finely pulverized product was classified by an air classifier to obtain toner particles having a weight average particle diameter of 7.6 μm, 10.1 μm or more of 6.8 vol% .

To 100 parts by mass of the toner particles, 1.0 part by mass of hydrophobic dry silica (BET specific surface area: 300 m ² / g) and 1.0 part by mass of inorganic fine powder 1 were added, and a Henschel mixer FM500 (Mitsui Miike Co., Ltd.) was added. The toner 1 of the present invention was obtained by rotating and stirring for 3 minutes at a stirring blade rotation speed of 1100 rpm to disperse and adhere to the toner surface.

(Photoconductor Production Examples 1 to 9)
Using a plasma processing apparatus using a high frequency power source in the RF band as shown in FIG. 2, on a cylindrical substrate (cylindrical aluminum substrate having a diameter of 80 mm, a length of 358 mm, and a thickness of 3 mm). The charge injection blocking layer, the photoconductive layer, and the surface layer are formed in this order under the conditions shown in Table 1 below, and the high frequency power, SiH ₄ flow rate, and CH ₄ flow rate during the surface layer preparation are shown in Table 2 below. A positively charged a-Si photosensitive member was prepared as follows, and photosensitive members 1 to 9 were prepared.

  Two electrophotographic photoreceptors were produced under each film forming condition.

  Using the produced electrophotographic photosensitive member, the sum of the atomic density of silicon atoms and the atomic density of carbon atoms (hereinafter referred to as “Si + C atomic density”), the atomic density of silicon atoms and the atomic density of carbon atoms, Ratio of atomic density of hydrogen atom to sum of atomic density of hydrogen atom (hereinafter referred to as “H atomic ratio”), ratio of atomic density of carbon atom to sum of atomic density of silicon atom and atomic density of carbon atom (hereinafter referred to as “H atomic ratio”) , C / (Si + C)). Then, another machine test, wear resistance, and evaluation were performed under the conditions described later using another electrophotographic photosensitive member. The evaluation results are shown in Tables 3 and 4.

<Image evaluation test>
The photosensitive drum of a commercially available copying machine imageRUNNER iR5075N (manufactured by Canon Inc.) is replaced with the photosensitive drum 1 of the present invention, the cleaning roller of the cleaning unit is eliminated, and the contact pressure between the cleaning blade and the photosensitive member is set to a linear pressure of 12 0.0 gf / cm is changed to 9.0 gf / cm, and each of toner 1 is used in a low temperature and low humidity environment (7.5 ° C./5% RH) and a high temperature and high humidity environment (40 ° C./90% RH). In Example 1, 100,0000 copies were made in a 5/30 sec intermittent mode using a test chart with a printing ratio of 20%, and image density, fog, and dot reproducibility were evaluated as shown below. The results are shown in Table 4.

  Using the toner 1, the following evaluation was performed.

1) Image Density With a “Macbeth reflection densitometer” (manufactured by Macbeth Co., Ltd.), an SPI filter was used to measure the reflection density of an image having a 5 mm diameter circle, and the average value was evaluated.
Rank 5: Reflection density 1.45 or more Rank 4: Reflection density 1.40 or more and 1.44 or less Rank 3: Reflection density 1.35 or more and 1.39 or less Rank 2: Reflection density 1.30 or more and 1.34 or less Rank 1 : Reflection density less than 1.29

2) Fog Using a reflection densitometer (reflectometer model TC-6DS manufactured by Tokyo Denshoku), the reflection density (Dr) of the transfer paper before image formation and the reflection density after copying the solid white image The worst value was measured as (Ds), and the difference (Ds−Dr) was evaluated as the fog value.
Rank 5: Fog less than 0.1 Rank 4: Fog 0.1 to less than 0.5 Rank 3: Fog 0.5 to less than 1.5 Rank 2: Fog 1.5 to less than 2.0 Rank 1: Fog 2. 0 or more

3) CLN slip-through evaluation After a copy test of 100,000 0000 sheets, the transfer device was removed, the paper was set to be out, and the developed toner was directly supplied to the cleaning via the photoconductor, and a solid black image was printed on A3 paper 3 Developed for one sheet.

  After the main body power is turned off during the third development and the photoconductor rotation is forcibly stopped, an adhesive material such as cello tape (registered trademark) is applied to the surface of the photoconductor at the downstream of the photoconductor cleaning. An adhesive material was pasted on the transfer material. The reflection density due to residual toner or the like adhering to the adhesive was measured using a reflection densitometer in the same manner as the evaluation of the fog. Let this average value be Dt. On the other hand, with the surface of the photoconductor wiped dry or with alcohol and the toner remaining on the surface was removed, an adhesive was applied to the same position, and the reflection density of the residual toner was evaluated. This value is Dn. The cleaning failure was determined by the difference between the two; Dt−Dn.

In addition to the evaluation criteria similar to the above-mentioned fogging, when Dt-Dn is 2.0% or more, or black streaks due to toner are generated in the direction of rotation of the photosensitive member on the image, it is determined that the cleaning is defective.
Rank 5: Very good black streak, no black spots, and Dt-Dn is less than 1.0% Rank 4: Good black streak, no black spots, and Dt-Dn is 1.0 or more and 1 Less than 3% Rank 3: Cleaning defects are slightly good black streaks, black spots are within 1.5 mm and within three places, and Dt-Dn is 1.3 or more and less than 1.7%. No black streaks in practical use, black spots are within 2.0 mm and within 5 locations, and Dt-Dn is 1.7 or more and less than 2.0%. Slightly problematic in practical use, black streaks, black spots exceeding the above range, or Dt-Dn was 2.0% or more.

4) Drum wear (Abrasion resistance evaluation)
The abrasion resistance evaluation method was performed by calculating the difference in film thickness of the surface layer before and after the 100,000 000 copy test.

  The method for measuring the film thickness of the surface layer is to irradiate the surface of the electrophotographic photoreceptor perpendicularly with a spot diameter of 2 mm, and perform spectroscopic measurement of reflected light using a spectrometer (manufactured by Otsuka Electronics: MCPD-2000). The surface layer thickness was calculated based on the obtained reflection waveform. At this time, the wavelength range was 500 nm to 750 nm, the refractive index of the photoconductive layer was 3.30, and the refractive index of the surface layer was a value obtained from the spectroscopic ellipsometry measurement performed during the Si + C atom density measurement described above. . The film pressure of the surface layer is 9 points in the longitudinal direction in any circumferential direction of the electrophotographic photosensitive member (0 mm, ± 50 mm, ± 90 mm, ± 130 mm, ± 150 mm with respect to the longitudinal center of the electrophotographic photosensitive member) 9 points in the longitudinal direction at a position rotated 180 ° from an arbitrary circumferential direction, a total of 18 points, were measured, and the average value of the 18 points was calculated.

And the ratio of the difference of the average film thickness of the surface layer of each electrophotographic photosensitive member to the difference of the average film thickness of the surface layer obtained before and after the continuous paper passing test of the photoconductor 8 produced in Photoconductor Production Example 8 Relative evaluation was performed.
Rank 5: Particularly excellent abrasion resistance when the ratio of the difference in the average film thickness of the surface layer of the electrophotographic photosensitive member produced under each film forming condition to the difference in the average film thickness of the surface layer of the photosensitive drum 8 is 60% or less. Has wear.
Rank 4... Excellent wear resistance when the ratio of the difference in the average film thickness of the surface layer of the photosensitive drum 8 is greater than 60% and less than 70%.
Rank 3: The ratio of the difference in the average film thickness of the surface layer to the difference in the average film thickness of the surface layer of the photosensitive drum 8 is excellent when it is greater than 70% and 80% or less.
Rank 2: The ratio of the difference in the average film thickness of the surface layer to the difference in the average film thickness of the surface layer of the photosensitive drum 8 is excellent when it is greater than 80% and 90% or less.
Rank 1: The ratio of the difference in the average film thickness of the surface layer to the difference in the average film thickness of the surface layer of the photosensitive drum 8 is greater than 90%.

[Examples 2 to 15 and Comparative Examples 1 to 4]
In Example 1, as shown in Table 3, the evaluation was performed in the same manner as in Example 1 except that the inorganic fine powder added to the toner and the photoreceptor were changed. The evaluation results are shown in Table 4.

  100 electrophotographic photoreceptor for positive charging, 101 conductive substrate, 102 photoreceptive layer, 103 lower charge injection blocking layer, 104 photoconductive layer, 105 surface layer, 1100 deposition apparatus, 1110 reaction vessel, 1111 cathode electrode, 1112 conductivity Substrate, 1113 Substrate heating heater, 1114 gas introduction pipe, 1115 high-frequency matching box, 1116 gas piping, 1117 leak valve, 1118 main valve, 1119 vacuum gauge, 1120 high-frequency power supply, 1121 insulating material, 1123 cradle, 1200 gas supply device 1211-1215 Mass flow controller, 1221-1225 cylinder, 1231-1235 valve, 1241-1245 Inflow valve, 1251-1255 Outflow valve, 1260 Auxiliary valve, 1261-1265 Pressure regulator

Claims (7)

A step of charging the electrostatic image carrier with a charging member, an electrostatic latent image forming step of forming an electrostatic latent image on the charged electrostatic image carrier, and a toner carried on the toner carrier. Development process for transferring to a latent image for visualization, transfer process for transferring a toner image formed on the electrostatic charge image carrier onto a recording medium, and cleaning the surface of the electrostatic charge image carrier after transfer with a cleaning member In a toner used for an image forming method having a cleaning step,
The electrostatic image bearing member is an electrophotographic photosensitive member in which at least a photoconductive layer and a surface layer formed of hydrogenated amorphous silicon carbide are sequentially stacked, and the atomic density of silicon atoms and carbon atoms in the surface layer The sum of the atomic densities of 6.60 × 10 ²² atoms / cm ³ or more,
The toner is a toner having at least toner particles containing a binder resin and a colorant and an inorganic fine powder, and the flow rate index FRI of the inorganic fine powder is from 0.8 to 2.0. toner.   2. The toner according to claim 1, wherein the inorganic fine powder is a particle having a primary particle number average particle size of 30 nm to 800 nm and having an octahedral or hexahedral shape.   The toner according to claim 1, wherein the inorganic fine powder is surface-treated with a fatty acid or a metal salt of a fatty acid.   The toner according to claim 1, wherein the inorganic fine powder is a metal carbonate. A step of charging the electrostatic image carrier with a charging member, an electrostatic latent image forming step of forming an electrostatic latent image on the charged electrostatic image carrier, and a toner carried on the toner carrier. A developing process for transferring to a latent image and visualizing; a transferring process for transferring a toner image formed on the electrostatic charge image bearing member onto a recording medium; a fixing process for fixing the toner image on a recording medium by heating; and a transfer process In the image forming method having a cleaning step of cleaning the surface of the subsequent electrostatic image carrier with a cleaning member,
The electrostatic image bearing member is an electrophotographic photosensitive member in which at least a photoconductive layer and a surface layer formed of hydrogenated amorphous silicon carbide are sequentially stacked, and the atomic density of silicon atoms and carbon atoms in the surface layer The sum of the atomic densities of 6.60 × 10 ²² atoms / cm ³ or more,
The toner is a toner having at least toner particles containing a binder resin and a colorant and an inorganic fine powder, and the flow rate index FRI of the inorganic fine powder is from 0.8 to 2.0. Image forming method.   6. The surface layer of the electrophotographic photoreceptor is characterized in that the ratio of the atomic density of carbon atoms to the sum of the number of silicon atoms and the number of carbon atoms is 0.61 or more and 0.75 or less. The image forming method described in 1. 7. The surface layer of the electrophotographic photoreceptor, wherein the sum of the atomic density of silicon atoms and the atomic density of carbon atoms is 6.81 × 10 ²² atoms / cm ³ or more. Image forming method.

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