JP2010032597A - Toner and image forming method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a toner and an image forming method strong in developing electric field intensity and without generating leaking spots due to dielectric breakdown even under a low atmospheric pressure condition in a high speed developing system. <P>SOLUTION: Concerning the toner used for the image forming method having an electrostatic latent image forming process for forming an electrostatic latent image on a charged static charge image carrier, and a developing process for transferring the toner carried on a toner carrier on the electrostatic latent image to be visualized, the static charge image carrier is a photoreceptor sequentially laminating a photoconducting layer and a surface layer formed of hydrogenation amorphous silicon carbide. The sum of atomic density of silicon atoms and atomic density of carbon atoms of the surface layer is 6.60×10<SP>22</SP>atoms/cm<SP>3</SP>or more. The toner has a binder resin, toner particles containing a coloring agent, and inorganic fine powder. The inorganic fine powder contains an inorganic fine powder (A) whose dielectric constant is 50-500 pF/m at 100 kHz and 40°C. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a toner used in an image forming method for visualizing an electrostatic charge image in electrophotography and an image forming method.

  Conventionally, a number of methods are known as electrophotographic methods. In general, a charging step for charging an electrostatic charge image carrier (hereinafter also referred to as “photosensitive member”) using a photoconductive substance, Forming an electrostatic latent image on the photosensitive member, a developing step of transferring the toner carried on the toner carrier onto the electrostatic latent image for visualization, and the developed image on a transfer material by a transfer unit. A target fixed matter is obtained through a transfer step of transferring and transferring, and a fixing step of heating and fixing the transferred image transferred onto the transfer material.

  In recent years, with the widespread use of image forming apparatuses such as copying machines and printers, the base has been expanded from personal use to professional use. In particular, it has begun to be used in earnest as a POD (print-on-demand; POD) application capable of high-mix low-volume printing. In the POD application, since the output image becomes a product as it is, high image quality and high definition are required.

  On the other hand, high durability and high reliability as well as high image quality are required at the same time, and the performance required for image forming systems and toners has become higher.

  Various studies have been made on the required performance from the toner and the image forming system.

  For example, with regard to high image quality, an attempt is made to develop a high tribotoner having high adhesion to the photoreceptor by increasing the development electric field strength (hereinafter also referred to as “electric field strength”) applied during development, thereby obtaining a high-definition image. Is being considered.

  On the other hand, with regard to high durability, amorphous silicon (hereinafter referred to as “a-Si”) photoconductor that can be used stably for a long period of time because it is excellent in wear resistance as a photoconductor and is suitable for high image quality. Are preferably used.

  However, when the electric field strength during development is increased, dielectric breakdown is likely to occur between the toner carrying member and the photosensitive member, and as a result, so-called “leak spots” are likely to occur. These phenomena are particularly prominent in low-pressure environments and high-speed development systems.

  In order to solve such problems, many improved methods have been proposed from toners and photoreceptors.

  For example, Patent Document 1 proposes a technique using imidazolium salts as a charge control agent for toner. Patent Document 2 proposes an image forming method characterized by using a magnetic one-component toner containing polyhedral magnetic powder having a specific volume resistivity in toner particles. Although these proposals are effective for preventing leak spots in the cleaning process, there is room for improvement in leak spots caused by development at low pressure.

  Patent Document 3 proposes a developing device in which specific carbon black is added as conductive fine particles to be added to the toner carrier. With respect to these technologies, a system using an organic photoconductor can obtain an effect of suppressing leakage spots regardless of the environment, but there is room for improvement in a system using an a-Si photoconductor.

  Patent Documents 4, 5 and 6 propose a technique for preventing dielectric breakdown by using a toner containing magnetic powder having a specific shape and electric resistance in a system using an a-Si photoreceptor. ing. Also in this regard, there is room for improvement in leak spots caused by development at low pressure.

  In Patent Document 7, in magnetic one-component toner to which magnetic powder is externally added, externally added magnetic powder having a specific shape and resistance value is used to prevent dielectric breakdown due to leakage to the photosensitive drum. Thus, a technique for ensuring the long-term stability of the toner thin layer formation on the toner carrier has been proposed. Also in this regard, there is room for improvement in leak spots caused by development at low pressure.

  Japanese Patent Application Laid-Open No. H10-228667 proposes a relationship between the dielectric constant of the toner and the dielectric constant of the metal oxide added to the toner particles. Although this proposal is effective in terms of density, fogging, and dot reproducibility, there is room for improvement in the leak spots caused by development at low pressures.

  In Patent Document 9, the atomic density of each atom constituting a surface layer (hereinafter also referred to as “a-SiC surface layer”) formed of hydrogenated amorphous silicon carbide is made smaller than a predetermined value, and a− Techniques have been proposed in which the SiC surface layer has a relatively rough film structure. Regarding this proposal, by making the a-SiC surface layer easy to scrape, the charged product and moisture adsorbed on the outermost surface together with the oxide layer on the outermost surface of the a-SiC surface layer can be removed, and the flow of high humidity can be suppressed. However, there is room for improvement in leak spots caused by development at low pressure.

  Patent Document 10 proposes a method of obtaining a photoconductor with less dangling bonds by forming a photoconductor layer by a method in which the plasma density is defined in the method of forming a photoconductor by plasma CVD. . With regard to this proposal, it is possible to produce an a-Si photoconductor having good electrical characteristics such as charging ability and sensitivity, and optical characteristics such as optical memory, image flow, and image defect. There is room for improvement in the leak pot.

JP 2002-365853 A JP-A-2005-227773 JP 2007-052350 A JP 2006-301306 A JP 2006-323124 A JP 2007-206530 A JP 2007-101745 A JP 2005-134751 A Japanese Patent No. 3124841 Japanese Patent Application Laid-Open No. 08-211641

  An object of the present invention is to provide a toner and an image forming method that solve the above-mentioned problems. That is, an object of the present invention is to provide a toner and an image forming method in which a developing electric field strength is strong and leakage spots due to dielectric breakdown do not occur even under a low-pressure condition in a high-speed developing system.

The present invention for solving the above problems includes at least a step of charging an electrostatic charge image carrier with a charging member, and an electrostatic latent image formation step of forming an electrostatic latent image on the charged electrostatic charge image carrier. A toner used in an image forming method having a developing step of transferring the toner carried on the toner carrying member to the electrostatic latent image for visualization;
The electrostatic image bearing member is a photoreceptor in which at least a photoconductive layer and a surface layer formed of hydrogenated amorphous silicon carbide are sequentially laminated, and the sum of the atomic density of silicon atoms and the atomic density of carbon atoms is 6.60 × 10 ²² atoms / cm ³ or more,
The toner is a toner having toner particles containing at least a binder resin and a colorant, and inorganic fine powder;
The inorganic fine powder relates to a toner characterized by containing at least an inorganic fine powder A having a dielectric constant of 50 pF / m or more and 500 pF / m or less at 100 kHz and 40 ° C., and an image forming method.

  According to the present invention, it is possible to provide a toner and an image forming method in which a developing electric field strength is strong and leakage spots due to dielectric breakdown do not occur even under a low-pressure condition in a high-speed developing system.

  The inventors of the present invention have found that a synergistic effect can be obtained by combining a specific a-Si photoconductor and a toner having an inorganic fine powder having a specific dielectric constant, thereby solving the above-described problems.

That is, the present invention includes at least a step of charging the electrostatic image carrier with a charging member, an electrostatic latent image forming step for forming an electrostatic latent image on the charged electrostatic image carrier, and a toner carrier. In a toner used in an image forming method having a development step of visualizing a transferred toner by transferring it to the electrostatic latent image,
The electrostatic image bearing member is a photoreceptor in which at least a photoconductive layer and a surface layer formed of hydrogenated amorphous silicon carbide are sequentially laminated, and the sum of the atomic density of silicon atoms and the atomic density of carbon atoms is 6.60 × 10 ²² atoms / cm ³ or more,
The toner is a toner having toner particles containing at least a binder resin and a colorant, and inorganic fine powder;
The inorganic fine powder relates to a toner characterized by containing at least an inorganic fine powder A having a dielectric constant of 50 pF / m or more and 500 pF / m or less at 100 kHz and 40 ° C., and an image forming method.

  First, an image forming process using an electrophotographic apparatus will be briefly described.

  FIG. 1 shows an example of a conventional typical electrophotographic image forming apparatus. As shown in the figure, the electrophotographic image forming apparatus has a drum-like electrophotographic photosensitive member (hereinafter also referred to as “photosensitive member”) 1003 that is a drum-like rotating member that is an electrostatic latent image carrier. The photoreceptor 1003 is charged by a primary charging device 1008, and an electrostatic latent image is formed by an exposure device 1009 such as a laser. The latent image is converted into a visible image (toner image) by the developing device 1001 using toner.

  Next, the toner image is transferred to a transfer material 1010 by a transfer device 1004. Thereafter, the transfer material is discharged by a charge eliminator 1005, and then separated from the photosensitive member 1003 by a separation device (not shown) and fixed. The apparatus 1011 converts the toner image into a fixed image.

  Among these, an amorphous silicon (a-Si) photoreceptor that is excellent in wear resistance and can be used stably for a long time is suitably used as the photoreceptor in order to meet the high durability required for POD applications. .

  As a basic configuration of the a-Si photosensitive member, a positive charging a-Si photosensitive member as shown in FIG. 2 is known. In the positively charged amorphous silicon (a-Si) photoreceptor, a photoreceptive layer 2002 made of a-Si is formed on a conductive substrate 2001, and a surface layer made of hydrogenated amorphous silicon carbide (a -SiC surface layer) 2005 is laminated.

  Next, the developing device will be described. By applying an AC bias on top of the DC developing bias, an electric field that causes toner to fly from the toner carrier 1002 to the photoconductor 1003, and an electric field that pulls excess toner once attached to the photoconductor 1003 back to the toner carrier 1002 again. The image quality is improved by alternately applying.

  As the AC bias waveform, a sine wave, a rectangular wave, a triangular wave, or the like can be used as appropriate. Further, the developing bias may be a pulse wave formed by periodically turning on / off a DC power source. Thus, as the developing bias, a bias whose voltage value periodically changes can be used.

In normal development, the maximum electric field strength during development is expressed by the following equation.
Maximum electric field strength (V / μm) = {1/2 Vpp + (VD−Vdc)} / (between SD)

  Here, Vpp is the peak-to-peak voltage of the AC voltage, VD is the dark potential of the photoreceptor, and Vdc is the potential of the DC voltage. In regular development, VD-Vdc corresponds to the development contrast Vcnt. Between SD, there is a gap (distance) between the toner carrier and the photoreceptor.

  When the ratio of the time of the electric field applied during development and the time of the electric field of pullback is different, the potential of the AC component during development is used instead of 1/2 Vpp. The case where the ratio of the electric field times is equal is illustrated.

  In order to achieve high image quality that can be used in POD applications, the strength of the electric field for flying the toner is increased, the pull-back electric field is weakened, and the high tribotoner is a developing method that has high adhesion to the electrostatic latent image and is faithful to the latent image. Selective development is required.

  However, if the magnitude of the electric field intensity exceeds the dielectric breakdown strength of air, abnormal discharge occurs in the SD gap, and the developing bias leaks to the photoconductor, causing damage to the photoconductor. As a result, it tends to appear as white spots (hereinafter also referred to as “leak spots”) on the solid black image. Furthermore, leakage due to this dielectric breakdown is likely to be promoted in a low-pressure environment.

  Therefore, the present inventors have conducted intensive studies on a system using an a-Si photoconductor, in which dielectric breakdown does not easily occur even under high electric field conditions. As a result, it has been found that the above problem can be solved by combining an a-Si photosensitive member having a specific atomic density and a toner containing inorganic fine powder having a specific dielectric constant.

That is, the present invention relates to an a-Si photosensitive member in which the sum of the atomic density of silicon atoms and the atomic density of carbon atoms is 6.60 × 10 ²² atoms / cm ³ or more, and a dielectric constant at 100 kHz and 40 ° C. is 50 pF / m. It is characterized by being combined with a toner containing inorganic fine powder A that is 500 pF / m or less.

  By combining both of these, the mechanism for eliminating leakage spots caused by dielectric breakdown even under low-pressure conditions in a high-speed development system is presumed as follows.

  First, the present inventors considered that it is necessary to control the dielectric behavior of the toner in an electric field in order to suppress leakage spots due to dielectric breakdown.

  That is, it is considered that the dielectric breakdown between S and D occurs through the toner present there, so if the electric field can be relaxed by dielectric polarization when the electric field is applied to the toner, the high tribo development is maintained. It is expected that dielectric breakdown can be suppressed in this state.

  Therefore, the present inventors pay attention to the dielectric properties of the inorganic fine powder existing between the toner particles, and by generating appropriate dielectric polarization between the toners via the inorganic fine powder A, even under conditions where the electric field strength is high. The possibility of suppressing the dielectric breakdown between SD was found.

  That is, the toner of the present invention is a toner having toner particles containing at least a binder resin and a colorant and an inorganic fine powder, and the inorganic fine powder has a dielectric constant of 50 pF / m or more at 100 kHz and 40 ° C. It contains at least inorganic fine powder A which is 500 pF / m or less.

  The inventors of the present invention need a photoconductor having an increased surface layer electron density in order to cause appropriate dielectric polarization between the toners through the inorganic fine powder A and to suppress leakage spots due to dielectric breakdown. I found out.

That is, the photoreceptor of the present invention is a photoreceptor in which at least a photoconductive layer and a surface layer formed of hydrogenated amorphous silicon carbide are sequentially laminated, and the sum of the atomic density of silicon atoms and the atomic density of carbon atoms. Is 6.60 × 10 ²² atoms / cm ³ or more.

  The mechanism by which the dielectric polarization of the toner is more effectively expressed by the photoconductor with the increased atomic density is presumed as follows. That is, by increasing the atomic density of silicon atoms and carbon atoms that form the skeleton of the film structure of the photoreceptor surface layer to a certain level or more, the electric field formed between S and D becomes dense, and the inorganic fine powder A is passed through. This is presumably because the dielectric polarization of the toner was expressed more effectively.

Furthermore, by improving the atomic density of silicon atoms and carbon atoms, the interatomic distance is shortened and the bonding force can be increased. As a result, a surface layer that can withstand dielectric breakdown is constructed, and the resistance to dielectric breakdown is enhanced. More preferably, when the sum of atomic densities is 6.81 × 10 ²² atoms / cm ³ or more, the bonding strength of the surface layer is further increased, and a stable strength is maintained even in a higher-speed development system. .

  The greatest feature of the present invention is that in order to generate appropriate dielectric polarization between toners through the inorganic fine powder A, it has been found that a photoconductor having an atomic density higher than a certain level is necessary. . As a result of the above, a synergistic effect between the two has been developed, and leakage due to dielectric breakdown can be suppressed even in a severe environment such as a low humidity / low pressure environment.

  Next, the toner of the present invention will be described more specifically.

  As the inorganic fine powder A satisfying the dielectric constant of the present invention, for example, an inorganic fine powder having a perovskite type crystal structure such as rutile type titanium oxide, anatase type titanium oxide, strontium titanate, barium titanate, magnesium titanate, etc. One or more selected from these, or two or more mixed crystals can be used.

  The inorganic fine powder A of the present invention preferably has a dielectric constant of 50 pF / m or more and 200 pF / m or less at 100 kHz and 40 ° C.

  When the dielectric constant is within the above range, dielectric breakdown can be stably suppressed even in a higher-speed development system, and toner performance is further improved.

  In addition, the inorganic fine powder A of the present invention is preferably titanium oxide. When electrically stable titanium oxide is used as the inorganic fine powder A, dielectric polarization is more stably generated, and dielectric breakdown can be suppressed and fogging can be suppressed. This is presumably because the use of titanium oxide stabilizes the chargeability of the toner, and the titanium oxide relaxes the concentration of the electric field between the toner particles, thereby applying a uniform electric field to the toner.

  Examples of the titanium oxide fine powder used in the present invention include oxidation methods obtained by low-temperature oxidation (thermal decomposition, hydrolysis) of sulfuric acid method, chlorine method, volatile titanium compounds such as titanium alkoxide, titanium halide, and titanium acetylacetonate. Titanium fine powder is used. As the crystal system, any of anatase type, rutile type, mixed crystal type thereof, and amorphous type can be used.

  Among the titanium oxide fine powders used in the present invention, methods for producing hydrophobized titanium oxide fine powders are exemplified below, but the present invention is not particularly limited to these methods.

  (A) A slurry-like metatitanic acid is produced by hydrolyzing a dispersion obtained by using ilmenite as a starting material and decomposing it with sulfuric acid. After adjusting the pH of this slurry of metatitanic acid, a hydrophobizing agent is added dropwise and reacted while being sufficiently dispersed in a hydrogen medium so that coalescence of metatitanic acid particles does not occur in the slurry. This is filtered, dried, and pulverized to produce hydrophobized titanium oxide fine powder.

  (B) Titanium tetraisopropoxide is used as a raw material, and the raw material is fed in small quantities with a chemical pump, using nitrogen gas as a carrier gas, and sent to a vaporizer glass wool heated to about 200 ° C. for evaporation. In the reactor, after instantaneous thermal decomposition at about 300 ° C., rapid cooling is performed to collect the product. This is further baked at about 300 ° C. for about 2 hours, and is further hydrophobized to produce hydrophobic titanium oxide fine powder.

  The inorganic fine powder A of the present invention is preferably rutile type titanium oxide. Among the titanium oxides, the use of rutile type titanium oxide makes the control of the dielectric constant more stable, and the use of rutile type titanium oxide that is more stable in terms of crystal structure improves the environmental stability of dielectric polarization. Therefore, it is preferable.

In addition, the inorganic fine powder A of the present invention has a specific surface area by nitrogen adsorption measured by BET method of 10 m ² / g or more and 180 m ² / g or less, preferably 40 m ² / g or more and 150 m ² / g or less. Give the result. Controlling the specific surface area of the inorganic fine powder A within the above range is preferable because the adhesion between the toner particles and the inorganic fine powder A is improved.

  Moreover, it is preferable that the inorganic fine powder A of the present invention has been subjected to a hydrophobic treatment. Examples of the hydrophobic treatment agent include a treatment agent such as a coupling agent, silicone oil, fatty acid metal salt, and fatty acid.

  By subjecting the surface of the inorganic fine powder A to a hydrophobization treatment, fluctuations in chargeability and cohesiveness due to the environment can be suppressed.

  Examples of coupling agents include titanate, aluminum, and silane coupling agents. Examples of fatty acid metal salts include zinc stearate, sodium stearate, calcium stearate, zinc laurate, aluminum stearate, and magnesium stearate. The same effect can be obtained with stearic acid, which is a fatty acid.

  The treatment method includes dissolving and dispersing a surface treatment agent or the like in a solvent, adding an inorganic fine powder therein, removing the solvent while stirring, a coupling method, and a fatty acid metal salt. Examples thereof include a dry method in which inorganic fine powder is directly mixed and treated with stirring.

  Further, regarding the surface treatment, it is not necessary to completely treat and coat the inorganic fine powder, and the inorganic fine powder may be exposed as long as the effect is obtained. That is, the surface treatment may be formed discontinuously.

  The content of the inorganic fine powder A in the toner is preferably 0.05 to 5.00 parts by mass with respect to 100 parts by mass of the toner particles.

  Examples of the binder resin used in the toner of the present invention include the following. Vinyl resin, styrene resin, styrene copolymer resin, polyester resin, polyol resin, polyvinyl chloride resin, phenol resin, natural modified phenol resin, natural resin modified maleic acid resin, acrylic resin, methacrylic resin, polyvinyl acetate, Silicone resin, polyurethane resin, polyamide resin, furan resin, epoxy resin, xylene resin, polyvinyl butyral, terpene resin, coumarone indene resin, petroleum resin. Among these, styrene copolymer resins, polyester resins, hybrid resins in which a polyester resin and a vinyl resin are mixed, or partially reacted are used as resins that are preferably used.

  The following compounds are mentioned as a polyester-type monomer which comprises the polyester resin used for the binder resin concerning this invention, or the polyester-type unit of the said hybrid resin.

  The following are mentioned as an alcohol component. Ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol 2-ethyl-1,3-hexanediol, bisphenol A hydride, bisphenol derivatives represented by the following formula (I-1) and diols represented by the following formula (I-2).

  Examples of the acid component include the following. Benzene dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid, and phthalic anhydride, or anhydrides thereof; alkyl dicarboxylic acids such as succinic acid, adipic acid, sebacic acid, azelaic acid, or anhydrides thereof; Succinic acid or anhydride thereof substituted with the following alkyl or alkenyl groups; unsaturated dicarboxylic acids such as fumaric acid, maleic acid, citraconic acid, itaconic acid or anhydrides thereof.

  The polyester resin or the polyester unit according to the present invention is preferably a polyester resin having a crosslinked structure of a trivalent or higher polyvalent carboxylic acid or anhydride thereof and / or a trivalent or higher polyhydric alcohol. Examples of the trivalent or higher polyvalent carboxylic acid or anhydride thereof include the following. 1,2,4-benzenetricarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, pyromellitic acid and acid anhydrides or lower alkyl esters thereof. Examples of the trihydric or higher polyhydric alcohol include the following. 1,2,3-propanetriol, trimethylolpropane, hexanetriol, pentaerythritol. In the binder resin of the present invention, an aromatic alcohol having high stability due to environmental fluctuation is particularly preferable, and examples thereof include 1,2,4-benzenetricarboxylic acid and anhydrides thereof.

  Examples of the vinyl monomer constituting the vinyl polymer unit of the vinyl resin or hybrid resin used in the binder resin according to the present invention include the following compounds.

  Styrene; o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, 3,4-dichlorostyrene, p-ethylstyrene, 2,4-dimethyl Styrene, pn-butyl styrene, p-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene Styrene and its derivatives such as: styrene unsaturated monoolefins such as ethylene, propylene, butylene and isobutylene; unsaturated polyenes such as butadiene and isoprene; halogenated such as vinyl chloride, vinylidene chloride, vinyl bromide and vinyl fluoride Vinyls: Vinyl acetate, vinyl propionate, vinyl benzoate Vinyl esters such as: methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, methacrylic acid Α-methylene aliphatic monocarboxylic acid esters such as phenyl, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate; methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, propyl acrylate, n-acrylate Acrylic esters such as octyl, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate; vinyl methyl ether Vinyl ethers such as vinyl ethyl ether and vinyl isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and methyl isopropenyl ketone; N-vinyl pyrrole, N-vinyl carbazole, N-vinyl indole, N-vinyl pyrrolidone N-vinyl compounds such as these; vinyl naphthalenes; acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile and acrylamide.

  Furthermore, the following are mentioned. Unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid, mesaconic acid; unsaturated such as maleic acid anhydride, citraconic acid anhydride, itaconic acid anhydride, alkenyl succinic acid anhydride Dibasic acid anhydride: maleic acid methyl half ester, maleic acid ethyl half ester, maleic acid butyl half ester, citraconic acid methyl half ester, citraconic acid ethyl half ester, citraconic acid butyl half ester, itaconic acid methyl half ester, alkenyl succinic acid Half-esters of unsaturated dibasic acids such as acid methyl half ester, fumaric acid methyl half ester and mesaconic acid methyl half ester; Unsaturated dibasic acid esters such as dimethylmaleic acid and dimethylfumaric acid; Acrylic acid, Methacrylic acid Α, β-unsaturated acids such as crotonic acid and cinnamic acid; α, β-unsaturated acid anhydrides such as crotonic acid anhydride and cinnamic anhydride, and anhydrides of the α, β-unsaturated acid and lower fatty acids A monomer having a carboxyl group such as alkenylmalonic acid, alkenylglutaric acid, alkenyladipic acid, acid anhydrides and monoesters thereof.

  Further, acrylic acid or methacrylic acid esters such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate; 4- (1-hydroxy-1-methylbutyl) styrene, 4- (1-hydroxy-1 -Methylhexyl) Monomers having a hydroxy group such as styrene.

  In the toner of the present invention, the vinyl resin or vinyl polymer unit used for the binder resin may have a crosslinked structure crosslinked with a crosslinking agent having two or more vinyl groups. The following are mentioned as a crosslinking agent used in this case. Aromatic divinyl compounds (divinylbenzene, divinylnaphthalene); diacrylate compounds linked by alkyl chains (ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5- Pentanediol acrylate, 1,6-hexanediol diacrylate, neopentylglycol diacrylate, and acrylates of the above compounds replaced with methacrylate); diacrylate compounds linked by an alkyl chain containing an ether bond (for example, , Diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 400 diacrylate, polyethylene glycol # 600 , Dipropylene glycol diacrylate, and acrylates of the above compounds replaced with methacrylate); diacrylate compounds entrapped with chains containing aromatic groups and ether bonds [polyoxyethylene (2) -2 , 2-bis (4hydroxyphenyl) propane diacrylate, polyoxyethylene (4) -2,2-bis (4hydroxyphenyl) propane diacrylate, and acrylates of the above compounds replaced with methacrylate]; polyester type Diacrylate compounds (“MANDA” manufactured by Nippon Kayaku Co., Ltd.).

  The following are mentioned as a polyfunctional crosslinking agent. Pentaerythritol triacrylate, trimethylol ethane triacrylate, trimethylol propane triacrylate, tetramethylol methane tetraacrylate, oligoester acrylate, and acrylates of the above compounds replaced with methacrylate; triallyl cyanurate, triallyl trimellitate .

  These crosslinking agents can be used in an amount of 0.01 to 10.00 parts by mass, and more preferably 0.03 to 5.00 parts by mass with respect to 100 parts by mass of other monomer components.

  Among these cross-linking agents, those which are preferably used in the binder resin from the viewpoint of fixability and offset resistance, are bonded with an aromatic divinyl compound (particularly divinylbenzene), a chain containing an aromatic group and an ether bond. Diacrylate compounds are mentioned.

  The following are mentioned as a polymerization initiator used for superposition | polymerization of the said vinyl-type resin or a vinyl-type polymer unit. 2,2′-azobisisobutyronitrile, 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2, 2'-azobis (2-methylbutyronitrile), dimethyl-2,2'-azobisisobutyrate, 1,1'-azobis (1-cyclohexanecarbonitrile), 2- (carbamoylazo) -isobutyronitrile 2,2′-azobis (2,4,4-trimethylpentane), 2-phenylazo-2,4-dimethyl-4-methoxyvaleronitrile, 2,2-azobis (2-methylpropane), methyl ethyl ketone peroxide, Ketone peroxides such as acetylacetone peroxide, cyclohexanone peroxide, 2,2-bis (tert-butyl) Peroxy) butane, tert-butyl hydroperoxide, cumene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, di-tert-butyl peroxide, tert-butylcumyl peroxide, dicumyl peroxide , Α, α'-bis (tert-butylperoxyisopropyl) benzene, isobutyl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, benzoyl peroxide M-trioyl peroxide, di-isopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di-2-e Xylethylperoxycarbonate, dimethoxyisopropylperoxydicarbonate, di (3-methyl-3-methoxybutyl) peroxycarbonate, acetylcyclohexylsulfonyl peroxide, tert-butylperoxyacetate, tert-butylperoxyisobutyrate, tert-butyl peroxyneodecanoate, tert-butyl peroxy 2-ethylhexanoate, tert-butyl peroxylaurate, tert-butyl peroxybenzoate, tert-butyl peroxyisopropyl carbonate, di-tert- Butyl peroxyisophthalate, tert-butyl peroxyallyl carbonate, tert-amyl peroxy 2-ethylhexanoate, di-tert-butyl perper Carboxymethyl hexahydro terephthalate, di -tert- butyl peroxy azelate.

  In the present invention, when the above-described hybrid resin is used as the binder resin, it is preferable that a monomer component capable of reacting with both resin components is contained in the vinyl resin and / or the polyester resin component. Examples of monomers that can react with the vinyl resin among the monomers constituting the polyester resin component include unsaturated dicarboxylic acids such as phthalic acid, maleic acid, citraconic acid, and itaconic acid, or anhydrides thereof. Among the monomers constituting the vinyl resin component, those capable of reacting with the polyester resin component include those having a carboxyl group or a hydroxy group, and acrylic acid or methacrylic acid esters.

  As a method for obtaining a reaction product of a vinyl resin and a polyester resin, a polymer containing a monomer component capable of reacting with each of the vinyl resin and the polyester resin listed above is present. A method obtained by polymerizing a resin is preferred.

  Examples of the colorant contained in the toner particles used in the present invention include carbon black, lamp black, iron black, ultramarine, nigrosine dye, aniline blue, phthalocyanine blue, phthalocyanine green, Hansa Yellow G, rhodamine 6G, calco oil blue, Conventionally known dyes such as chrome yellow, quinacridone, benzidine yellow, rose bengal, triarylmethane dyes, monoazo dyes, disazo dyes and the like can be used alone or in combination. The colorant of the present invention is preferably magnetic iron oxide.

  As the magnetic iron oxide, iron oxide such as magnetite, maghemite, and ferrite is used.

  In the present invention, a release agent (wax) can be used as necessary to give the toner releasability. As the wax, hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, microcrystalline wax, and paraffin wax are preferably used because of easy dispersion in toner particles and high releasability. If necessary, a small amount of one or two or more kinds of waxes may be used in combination. Examples include the following:

  Oxides of aliphatic hydrocarbon waxes such as oxidized polyethylene wax, or block copolymers thereof; waxes based on fatty acid esters such as carnauba wax, sazol wax, and montanate ester wax; deacidified carnauba Deoxidized part or all of fatty acid esters such as wax. Furthermore, the following are mentioned. Saturated linear fatty acids such as palmitic acid, stearic acid and montanic acid; unsaturated fatty acids such as brassic acid, eleostearic acid and valinalic acid; stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnauvyl alcohol, seryl alcohol, Saturated alcohols such as sil alcohols; long-chain alkyl alcohols; polyhydric alcohols such as sorbitol; fatty acid amides such as linoleic acid amide, oleic acid amide, lauric acid amide; methylene bis stearic acid amide, ethylene biscapric acid amide Saturated fatty acid bisamides such as ethylene bislauric acid amide and hexamethylene bis stearic acid amide; ethylene bisoleic acid amide, hexamethylene bisoleic acid amide, N, N′-dioleyl adipine Amides, unsaturated fatty acid amides such as N, N-dioleyl sebacic acid amide; m-xylene bisstearic acid amide, aromatic bisamides such as N, N-distearylisophthalic acid amide; calcium stearate, calcium laurate, Fatty acid metal salts such as zinc stearate and magnesium stearate (generally called metal soap); waxes grafted with aliphatic hydrocarbon waxes using vinyl monomers such as styrene and acrylic acid; behenine A partially esterified product of a fatty acid such as an acid monoglyceride and a polyhydric alcohol; a methyl ester compound having a hydroxyl group obtained by hydrogenation of a vegetable oil.

  Examples of waxes that are particularly preferably used in the present invention include aliphatic hydrocarbon waxes. Examples of such aliphatic hydrocarbon waxes include the following. Low molecular weight alkylene polymer obtained by radical polymerization of alkylene under high pressure or Ziegler catalyst under low pressure; alkylene polymer obtained by thermally decomposing high molecular weight alkylene polymer; synthesis containing carbon monoxide and hydrogen Synthetic hydrocarbon waxes obtained from the distillation residue of hydrocarbons obtained from the gas by the age method and synthetic hydrocarbon waxes obtained by hydrogenating them; press sweating method, solvent method, vacuum Wax separated by use of distillation or fractional crystallization.

  Examples of the hydrocarbon as the matrix of the aliphatic hydrocarbon wax include the following. Carbonization synthesized by the reaction of carbon monoxide and hydrogen using a metal oxide catalyst (often a multi-component system of two or more types) (for example, the Gintor method, Hydrocol method (using a fluidized catalyst bed)) Hydrogen compounds); hydrocarbons having up to about several hundred carbon atoms obtained by the age method (using an identified catalyst bed) in which a large amount of waxy hydrocarbons can be obtained; hydrocarbons obtained by polymerizing alkylene such as ethylene with a Ziegler catalyst. Among such hydrocarbons, in the present invention, it is preferable that the hydrocarbon is a linear hydrocarbon having a small number of branches and a long saturation, and particularly a hydrocarbon synthesized by a method not based on polymerization of alkylene has a molecular weight distribution. Is also preferable.

  Specific examples that can be used include the following. Biscol (registered trademark) 330-P, 550-P, 660-P, TS-200 (Sanyo Chemical Industry Co., Ltd.); High Wax 400P, 200P, 100P, 410P, 420P, 320P, 220P, 210P, 110P (Mitsui Chemicals) Sazol H1, H2, C80, C105, C77 (Sazol Corporation); HNP-1, HNP-3, HNP-9, HNP-10, HNP-11, HNP-12 (Nippon Seiwa Co., Ltd.), Unilin (registered trademark) 350, 425, 550, 700, Unicid (registered trademark) 350, 425, 550, 700 (Toyo Petrolite); wood wax, beeswax, rice wax, candelilla wax, carnauba wax (Co., Ltd.) Celerica NODA).

  The timing of adding the release agent (wax) may be added at the time of melt-kneading during the production of the toner particles or may be at the time of producing the binder resin, and is appropriately selected from existing methods. These release agents may be used alone or in combination.

  The release agent is preferably added in an amount of 1 part by weight to 20 parts by weight with respect to 100 parts by weight of the binder resin. When the amount is less than 1 part by mass, it is difficult to obtain the desired release effect. When the amount exceeds 20 parts by mass, the dispersion in the toner particles is poor, so that the toner adheres to the electrostatic image carrier, the developing member or the cleaning member. The surface of the member is likely to be contaminated, and the toner image is likely to deteriorate.

  In the toner of the present invention, a charge control agent can be used to stabilize the triboelectric chargeability. Although the charge control agent varies depending on the type and physical properties of other toner particle constituent materials, generally, the toner particles are contained in an amount of 0.1 to 10.0 parts by mass per 100 parts by mass of the binder resin. Preferably, it is contained in an amount of 0.1 to 5.0 parts by mass. As such charge control agents, there are known ones for controlling the toner to be negatively charged and those for controlling the toner to be positively charged. One or two kinds of various kinds of charge control agents are used depending on the kind and use of the toner. The above can be used.

  Examples of toners that are negatively charged include the following. Organometallic complexes (monoazo metal complexes; acetylacetone metal complexes); metal complexes or metal salts of aromatic hydroxycarboxylic acids or aromatic dicarboxylic acids. In addition, examples of toners that are negatively charged include aromatic mono- and polycarboxylic acids and metal salts and anhydrides thereof; phenol derivatives such as esters and bisphenol. Among these, in particular, a metal complex or metal salt of an aromatic hydroxycarboxylic acid capable of obtaining stable charging performance is preferably used.

  Examples of controlling the toner to be positively charged include the following. Modified products with nigrosine and fatty acid metal salts; quaternary ammonium salts such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate, tetrabutylammonium tetrafluoroborate, and the like; onium salts such as phosphonium salts and These lake pigments: triphenylmethane dyes and these lake pigments (as rake agents, phosphotungstic acid, phosphomolybdic acid, phosphotungsten molybdic acid, tannic acid, lauric acid, gallic acid, ferricyanic acid, ferrocyanic compound Etc.); metal salts of higher fatty acids. In the present invention, these can be used alone or in combination. Among them, charge control agents such as nigrosine compounds and quaternary ammonium salts are particularly preferably used for controlling the toner to be positively charged.

  Specific examples that can be used include the following. Spiron Black TRH, T-77, T-95, TN-105 (Hodogaya Chemical Co., Ltd.); BONTRON (registered trademark) S-34, S-44, E-84, E-88 (Orient Chemical Industry Co., Ltd.) ). Examples of positive charging include the following. TP-302, TP-415 (Hodogaya Chemical Co., Ltd.); BONTRON (registered trademark) N-01, N-04, N-07, P-51 (Orient Chemical Co., Ltd.); Copy Blue PR (Clariant) ).

  Moreover, charge control resin can also be used and can also be used together with the above-mentioned charge control agent.

  In the toner of the present invention, in addition to the inorganic fine powder A, silica fine powder is preferably externally added to the toner particles in order to improve charging stability, developability, fluidity and durability.

The silica fine powder used in the present invention has good results when the specific surface area by the BET method by nitrogen adsorption is in the range of 30 m ² / g or more (particularly 50 m ² / g or more and 400 m ² / g or less). Silica fine powder is used in an amount of 0.01 to 8.00 parts by weight, preferably 0.10 to 5.00 parts by weight, based on 100 parts by weight of the toner. The BET specific surface area of the silica fine powder is silica using, for example, a specific surface area measuring device Autosorb 1 (manufactured by Yuasa Ionics), GEMINI 2360/2375 (manufactured by Micrometric), or Tristar 3000 (manufactured by Micrometric). Nitrogen gas is adsorbed on the surface of the fine powder, and calculation can be performed using the BET multipoint method.

  In addition, the silica fine powder used in the present invention is optionally modified with an unmodified silicone varnish, various modified silicone varnishes, unmodified silicone oil, various modified silicone oils, silane cups for the purpose of hydrophobization and tribocharging control. It is also preferable to treat with a treating agent such as a ring agent, a silane compound having a functional group, or another organosilicon compound, or in combination with various treating agents.

  Furthermore, you may add another external additive to the toner of this invention as needed. Examples of such external additives include charging aids, conductivity-imparting agents, fluidity-imparting agents, anti-caking agents, release agents at the time of heat roller fixing, lubricants, abrasives, etc. An inorganic fine powder is mentioned.

  For example, examples of the lubricant include polyfluorinated ethylene powder, zinc stearate powder, and polyvinylidene fluoride powder.

  Examples of the abrasive include cerium oxide powder, silicon carbide powder, and strontium titanate powder. Of these, strontium titanate powder is preferable.

  In order to produce the toner of the present invention, a binder resin, a colorant, and other additives are sufficiently mixed by a mixer such as a Henschel mixer or a ball mill, and then a heat kneader such as a heating roll, a kneader, and an extruder. The mixture is melt-kneaded, cooled and solidified, and then pulverized and classified to obtain toner particles. Further, inorganic fine powder A, silica fine powder, etc. are added to the toner particles externally and mixed thoroughly by a mixer such as a Henschel mixer. The toner of the invention can be obtained.

  The following are mentioned as a mixer. Henschel mixer (made by Mitsui Mining); Super mixer (made by Kawata); Ribocorn (made by Okawara Seisakusho); Nauta mixer, turbulizer, cyclomix (made by Hosokawa Micron); Spiral pin mixer (made by Taiheiyo Kiko) A Ladige mixer (manufactured by Matsubo). Examples of the kneader include the following. 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); Steel mill); three roll mill, mixing roll mill, kneader (Inoue Seisakusho); kneedex (Mitsui Mining Co.); MS pressure kneader, Nider Ruder (Moriyama Seisakusho); Banbury mixer (Kobe Steel) (Made by the company). Examples of the pulverizer include the following. Counter jet mill, micron jet, inomizer (manufactured by Hosokawa Micron); IDS type mill, PJM jet crusher (manufactured by Nippon Pneumatic Industrial Co., Ltd.); cross jet mill (manufactured by Kurimoto Iron Works); Urmax (manufactured by Nisso Engineering Co., Ltd.) SK; jet mill (manufactured by Seishin Enterprise Co., Ltd.); kryptron (manufactured by Kawasaki Heavy Industries, Ltd.); turbo mill (manufactured by Turboe Industry Co., Ltd.); super rotor (manufactured by Nissin Engineering Co., Ltd.). Examples of the classifier include the following. Classifier, Micron Classifier, Spedick Classifier (manufactured by Seishin Enterprise); Turbo Classifier (manufactured by Nissin Engineering); Micron Separator, Turboplex (ATP), TSP Separator (manufactured by Hosokawa Micron); Elbow Jet (Japan) Iron Mining Co., Ltd.), Dispersion Separator (manufactured by Nippon Pneumatic Engineering Co., Ltd.); YM Micro Cut (manufactured by Yaskawa Shoji Co., Ltd.). Examples of the sieving apparatus used for sieving coarse particles include the following. Ultrasonic (manufactured by Sakae Sangyo Co., Ltd.); Resonator Sheave, Gyroshifter (Tokuju Kosakusha Co., Ltd.); Vibrasonic System (manufactured by Dalton Co.); Soniclean (manufactured by Shinto Kogyo Co., Ltd.); Micro shifter (manufactured by Hadano Sangyo Co., Ltd.); circular vibrating sieve.

  Next, the photoreceptor will be described in more detail.

  As described above, a positive charging a-Si photosensitive member as shown in FIG. 2 is known as a basic configuration of the a-Si photosensitive member. This is referred to as positive charging a-Si. The photoreceptor has a structure in which a photoreceptive layer 2002 made of a-Si is formed on a conductive substrate 2001, and a surface layer (a-SiC surface layer) 2005 made of hydrogenated amorphous silicon carbide is laminated. It has become.

FIG. 3 is a diagram 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 divided into a deposition apparatus 3100 having a reaction vessel 3110, a source gas supply device 3200, and an exhaust device (not shown) for reducing the pressure inside the reaction vessel 3110. In a reaction vessel 3110 in the deposition apparatus 3100, a conductive substrate 3112, a conductive substrate heating heater 3113, and a source gas introduction pipe 3114 connected to the ground are installed. Further, a high frequency power source 3120 is connected to the cathode electrode 3111 via a high frequency matching box 3115. The source gas supply device 3200 includes source gas cylinders 3221 to 3225 such as SiH ₄ , H ₂ , CH ₄ , NO, and B ₂ H ₆ , valves 3231 to 3235, pressure regulators 3261 to 3265, inflow valves 3241 to 3245, and outflow valves. 3251 to 3255 and mass flow controllers 3211 to 3215. A gas cylinder filled with each source gas is connected to a source gas introduction pipe 3114 in the reaction vessel 3110 via an auxiliary valve 3260.

  Next, a method for forming a deposited film using this apparatus will be described. First, a conductive substrate 3112 that has been degreased and washed in advance is placed in the reaction vessel 3110 via a cradle 3123. Next, an exhaust device (not shown) is operated to exhaust the reaction vessel 3110. While viewing the display of the vacuum gauge 3119, when the pressure in the reaction vessel 3110 reaches a predetermined pressure of, for example, 1 Pa or less, power is supplied to the substrate heating heater 3113, and the conductive substrate 3112 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 device 3200 to the reaction vessel 3110 and heated in an inert gas atmosphere. Next, a gas used to form a deposited film is supplied from the gas supply device 3200 to the reaction vessel 3110. That is, if necessary, the valves 3231 to 3235, the inflow valves 3241 to 3245, and the outflow valves 3251 to 3255 are opened, and the flow rate is set in the mass flow controllers 3211 to 3215. When the flow rate of each mass flow controller is stabilized, the main valve 3118 is operated while viewing the display of the vacuum gauge 3119 to adjust the pressure in the reaction vessel 3110 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 3115 is operated to generate plasma discharge in the reaction vessel 3110. 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 3231 to 3235, the inflow valves 3241 to 3245, the outflow valves 3251 to 3255, and the auxiliary valve 3260 are closed, and the supply of the source gas is finished. At the same time, the main valve 3118 is fully opened, and the reaction vessel 3110 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 3118 is closed, an inert gas is introduced into the reaction vessel 3110 to return to atmospheric pressure, and then the conductive substrate 3112 is taken out.

  The photoreceptor of the present invention forms a surface layer having a film structure with 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 photoreceptor. ing.

  As described above, when an a-SiC surface layer having a high atomic density according to the present invention is manufactured, the balance between the amount of gas and high-frequency power is generally important, although it depends on conditions at the time of surface layer preparation. The smaller the amount of gas supplied to the reaction vessel, the better the high frequency power. Moreover, the one where the pressure in a reaction container is high is good, and the one where the temperature of an electroconductive board | substrate is high is also good.

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.

  In the photoreceptor of the present invention, the ratio of the atomic density of carbon atoms to the sum of the atomic density of silicon atoms and the atomic density of carbon atoms in the surface layer is preferably from 0.61 to 0.75. By controlling the ratio of the atomic density of carbon atoms to the sum of the atomic densities within the above range, the sensitivity of the photoreceptor is stabilized and the developability is further improved.

  When the ratio of the atomic density of the carbon atom to the sum of the atomic density of the silicon atom and the atomic density of the carbon atom is larger than 0.75, particularly when a-SiC having a high atomic density is produced, Light absorption may increase rapidly. In such a case, the amount of image exposure necessary for forming the electrostatic latent image increases, and the sensitivity deteriorates, so that an appropriate image density cannot be obtained.

  On the other hand, when the value is smaller than 0.61, particularly when a-SiC having a high atomic density is produced, the resistance of the a-SiC may decrease. In such a case, the image density on the low density side tends to decrease, which is not preferable.

  In the present invention, the ratio of the atomic density of hydrogen atoms to the sum of the atomic density of silicon atoms, the atomic density of carbon atoms and the atomic density of hydrogen atoms is preferably 0.30 or more and 0.45 or less. By controlling to the above range, the uniformity of sensitivity is improved and, for example, the density unevenness of the halftone image is improved.

  If the number of hydrogen atoms is less than 0.30 in the a-SiC surface layer, the sensitivity is deteriorated and concentration unevenness tends to occur, which is not preferable.

  On the other hand, when hydrogen atoms are contained in the a-SiC surface layer in an amount of more than 0.45, the a-SiC surface layer tends to increase termination groups having many hydrogen atoms such as methyl groups. When a terminal group having a plurality of hydrogen atoms such as a methyl group is present in the a-SiC surface layer, a large space is formed in the structure of the a-SiC, and a bond between adjacent atoms is distorted. Therefore, uneven density tends to occur, which is not preferable.

  A method for measuring physical properties of the toner of the present invention is as follows. Examples described later are also based on this method.

<Measurement of dielectric constant of inorganic fine powder A>
1 g of inorganic fine powder is weighed and molded into a disk-shaped measurement sample having a diameter of 25 mm and a thickness of 1 mm or less (preferably 0.5 to 0.9 mm) over a period of 2 minutes under a load of 19600 kPa (200 kg / cm ² ). . This measurement sample is mounted on ARES (manufactured by Rheometric Scientific F.E.) equipped with a dielectric constant measuring jig (electrode) having a diameter of 25 mm, and the temperature is fixed at 40 ° C. to 1.47 N (150 g). ) Was applied, and the dielectric constant of the inorganic fine powder at a frequency of 100 KHz was determined.

<Measurement of crystal system of titanium oxide (X-ray diffraction)>
Measuring instrument used: Rigaku Corporation / Sample horizontal strong X-ray diffractometer (RINT TTRII)
Tube: Cu
Parallel beam optical system voltage: 50 kV
Current: 300mA
Starting angle: 3 °
End angle: 60 °
Sampling width: 0.02 °
Scan speed: 4.00 ° / min
Divergent slit: Open divergence longitudinal slit: 10 mm
Scattering slit: Open light receiving slit: 1.0 mm

  The obtained X-ray diffraction peak was analyzed using analysis software “Jade 6” manufactured by Rigaku Corporation to confirm the crystal system.

<Measurement of specific surface area of inorganic fine powder A>
The BET specific surface area of the inorganic fine powder A is measured according to JIS Z8830 (2001). A specific measurement method is as follows.

  As a measuring device, an “automatic specific surface area / pore distribution measuring device TriStar 3000 (manufactured by Shimadzu Corporation)” which employs a gas adsorption method by a constant volume method as a measuring method is used. Setting of measurement conditions and analysis of measurement data are performed using dedicated software “TriStar3000 Version 4.00” attached to the apparatus, and a vacuum pump, a nitrogen gas pipe, and a helium gas pipe are connected to the apparatus. The value calculated by the BET multipoint method using nitrogen gas as the adsorption gas is defined as the BET specific surface area in the present invention.

  The BET specific surface area is calculated as follows.

First, nitrogen gas is adsorbed onto the inorganic fine powder A, and the equilibrium pressure P (Pa) in the sample cell and the nitrogen adsorption amount Va (mol · g−1) of the inorganic fine powder A at that time are measured. The relative pressure Pr, which is a value obtained by dividing the equilibrium pressure P (Pa) in the sample cell by the saturated vapor pressure Po (Pa) of nitrogen, is plotted on the horizontal axis, and the nitrogen adsorption amount Va (mol · g−1) is plotted on the vertical axis. The adsorption isotherm is obtained. Next, a monomolecular layer adsorption amount Vm (mol · g−1), which is an adsorption amount necessary for forming a monomolecular layer on the surface of the inorganic fine powder A, is obtained by applying the following BET equation.
Pr / Va (1-Pr) = 1 / (Vm * C) + (C-1) * Pr / (Vm * C)
(Here, C is a BET parameter, which is a variable that varies depending on the measurement sample type, adsorbed gas type, and adsorption temperature.)

The BET equation is interpreted as a straight line with an inclination of (C-1) / (Vm × C) and an intercept of 1 / (Vm × C), where Pr is X axis and Pr / Va (1-Pr) is Y axis. Yes (this line is called a BET plot).
Straight line slope = (C-1) / (Vm × C)
Straight line intercept = 1 / (Vm × C)

  When the measured value of Pr and the measured value of Pr / Va (1-Pr) are plotted on a graph and a straight line is drawn by the least square method, the slope and intercept value of the straight line can be calculated. Vm and C can be calculated by solving the above slope and intercept simultaneous equations using these values.

Further, the BET specific surface area S (m ² · g−1) of the inorganic fine powder A is calculated from the calculated Vm and the molecular occupation cross-sectional area (0.162 nm ² ) of the nitrogen molecule based on the following formula. .
S = Vm × N × 0.162 × 10−18
(N is Avogadro's number (mol-1).)

  The measurement using this apparatus follows the “TriStar 3000 Instruction Manual V4.0” attached to the apparatus, and specifically, the measurement is performed according to the following procedure.

  Thoroughly weigh the tare of a dedicated glass sample cell (stem diameter 3/8 inch, volume about 5 ml) that has been thoroughly cleaned and dried. Then, about 1.5 g of inorganic fine powder A is put into this sample cell using a funnel.

  The sample cell containing the inorganic fine powder A is set in a “pretreatment device Bacuprep 061 (manufactured by Shimadzu Corporation)” connected with a vacuum pump and a nitrogen gas pipe, and vacuum degassing is continued at 23 ° C. for about 10 hours. To do. In vacuum degassing, the inorganic fine powder A is gradually degassed while adjusting the valve so that the inorganic fine powder A is not sucked into the vacuum pump. The pressure in the cell gradually decreases with deaeration and finally becomes about 0.4 Pa (about 3 mTorr). After completion of vacuum degassing, nitrogen gas is gradually injected to return the inside of the sample cell to atmospheric pressure, and the sample cell is removed from the pretreatment device. And the mass of this sample cell is precisely weighed, and the exact mass of the inorganic fine powder A is calculated from the difference from the tare. At this time, the sample cell is covered with a rubber stopper during weighing so that the inorganic fine powder A in the sample cell is not contaminated by moisture in the atmosphere.

  Next, a dedicated “isothermal jacket” is attached to the stem portion of the sample cell containing the inorganic fine powder A. Then, a dedicated filler rod is inserted into the sample cell, and the sample cell is set in the analysis port of the apparatus. The isothermal jacket is a cylindrical member having an inner surface made of a porous material and an outer surface made of an impermeable material capable of sucking liquid nitrogen to a certain level by capillary action.

  Subsequently, the free space of the sample cell including the connection tool is measured. Free space is measured by measuring the volume of the sample cell with helium gas at 23 ° C., and then measuring the volume of the sample cell after cooling the sample cell with liquid nitrogen in the same manner using helium gas. Calculated from the difference in volume. Further, the saturated vapor pressure Po (Pa) of nitrogen is automatically measured separately using a Po tube built in the apparatus.

  Next, after performing vacuum deaeration in the sample cell, the sample cell is cooled with liquid nitrogen while continuing the vacuum deaeration. Thereafter, nitrogen gas is gradually introduced into the sample cell to adsorb nitrogen molecules on the inorganic fine powder A. At this time, the adsorption isotherm is obtained by measuring the equilibrium pressure P (Pa) as needed, and the adsorption isotherm is converted into a BET plot. Note that the points of the relative pressure Pr for collecting data are set to a total of 6 points of 0.05, 0.10, 0.15, 0.20, 0.25, and 0.30. A straight line is drawn from the obtained measurement data by the least square method, and Vm is calculated from the slope and intercept of the straight line. Further, using the value of Vm, the BET specific surface area of the inorganic fine powder A is calculated as described above.

<Measurement of glass transition temperature of binder resin>
Using a differential scanning calorimeter (DSC), MDSC-2920 (manufactured by TA Instruments), measurement is performed under normal temperature and humidity according to ASTM D3418-82.

  As the measurement sample, a precisely weighed sample of 2 mg to 10 mg, preferably about 3 mg is used. This is put in an aluminum pan and an empty aluminum pan is used as a reference. The measurement temperature range is 30 ° C. or more and 200 ° C. or less, once the temperature is increased from 30 ° C. to 200 ° C. at a temperature increase rate of 10 ° C./min, then the temperature is decreased from 200 ° C. to 30 ° C. at a temperature decrease rate of 10 ° C./min. The temperature is raised to 200 ° C. at a temperature rising rate of 10 ° C./min. In the DSC curve obtained in the second temperature raising process, the intersection between the baseline intermediate line before and after the specific heat change and the differential heat curve is defined as the glass transition temperature Tg of the binder resin.

<Measurement of softening point of binder resin>
The softening point of the binder resin is measured using a constant-load extrusion type capillary rheometer “Flow Characteristic Evaluation Device Flow Tester CFT-500D” (manufactured by Shimadzu Corporation) according to the manual attached to the device. In this device, while applying a constant load from the top of the measurement sample with the piston, the measurement sample filled in the cylinder is heated and melted, and the molten measurement sample is pushed out from the die at the bottom of the cylinder, and the piston drop amount at this time A flow curve showing the relationship between temperature and temperature can be obtained.

  In the present invention, the “melting temperature in the 1/2 method” described in the manual attached to the “flow characteristic evaluation apparatus Flow Tester CFT-500D” is the softening point. The melting temperature in the 1/2 method is calculated as follows. First, ½ of the difference between the piston lowering amount Smax at the time when the outflow ends and the piston lowering amount Smin at the time when the outflow starts is obtained (this is X. X = (Smax−Smin) / 2). And the temperature of the flow curve when the amount of descending piston is the sum of X and Smin in the flow curve is the melting temperature in the 1/2 method.

  As a measurement sample, about 1.0 g of a sample is compression-molded at about 10 MPa using a tablet molding compressor (for example, NT-100H, manufactured by NPA System) in an environment of 25 ° C. for about 60 seconds. A cylindrical shape having a diameter of about 8 mm is used.

The measurement conditions of CFT-500D are as follows.
Test mode: Temperature rising start temperature: 50 ° C
Achieving temperature: 200 ° C
Measurement interval: 1.0 ° C
Temperature increase rate: 4.0 ° C./min
Piston cross-sectional area: 1.000 cm ²
Test load (piston load): 10.0 kgf (0.9807 MPa)
Preheating time: 300 seconds Die hole diameter: 1.0 mm
Die length: 1.0mm

<Measurement of molecular weight distribution of wax>
The molecular weight distribution of the wax is measured by gel permeation chromatography (GPC) as follows.

To o-dichlorobenzene for gel chromatography, special grade 2,6-di-t-butyl-4-methylphenol (BHT) is added so that the concentration becomes 0.10 wt / vol%, and dissolved at room temperature. The wax and o-dichlorobenzene to which the above BHT is added are put into a sample bottle and heated on a hot plate set at 150 ° C. to dissolve the wax. Once the wax has melted, place it in a preheated filter unit and place it on the body. The sample that has passed through the filter unit is used as a GPC sample. The sample solution is adjusted so that the concentration is about 0.15% by mass. Using this sample solution, measurement is performed under the following conditions.
Apparatus: HLC-8121GPC / HT (manufactured by Tosoh Corporation)
Detector: RI for high temperature
Column: TSKgel GMHHR-H HT 2 series (manufactured by Tosoh Corporation)
Temperature: 135.0 ° C
Solvent: o-dichlorobenzene for gel chromatography (BHT added at 0.10 wt / vol%)
Flow rate: 1.0 ml / min
Injection volume: 0.4ml

  In calculating the molecular weight of the wax, a 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.

<Measurement of maximum endothermic peak of wax>
The peak temperature of the maximum endothermic peak of the wax 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 3 mg of wax is precisely weighed, placed 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 ° C. to 200 ° C. in the second temperature rising process is defined as the maximum endothermic peak of the endothermic curve in the DSC measurement of the toner of the present invention.

<Measurement of average primary particle diameter of magnetic iron oxide particles>
The average primary particle diameter is obtained by observing magnetic iron oxide particles with a scanning electron microscope (magnification 40000 times), measuring the ferret diameter of 200 particles, and determining the number average particle diameter. In this example, S-4700 (manufactured by Hitachi, Ltd.) was used as the scanning electron microscope.

<Measurement of magnetic properties of magnetic iron oxide particles>
Using a vibrating sample magnetometer VSM-P7 manufactured by Toei Industry Co., Ltd., measurement was performed at a sample temperature of 25 ° C. and an external magnetic field of 795.8 kA / m.

<Measurement of weight average particle diameter (D4) of toner particles>
The weight average particle diameter (D4) of the toner particles is calculated as follows. As a measuring device, a precise particle size distribution measuring device “Coulter Counter Multisizer 3” (registered trademark, manufactured by Beckman Coulter, Inc.) using a pore electrical resistance method equipped with a 100 μm aperture tube is used. For setting the measurement conditions and analyzing the measurement data, the attached dedicated software “Beckman Coulter Multisizer 3 Version 3.51” (manufactured by Beckman Coulter, Inc.) is used. Note that the measurement is performed with 25,000 effective measurement channels.

  As the electrolytic aqueous solution used for the measurement, special grade sodium chloride is dissolved in ion-exchanged water so as to have a concentration of about 1% by mass, for example, “ISOTON II” (manufactured by Beckman Coulter, Inc.) can be used.

  Prior to measurement and analysis, the dedicated software was set as follows.

  On the “Change Standard Measurement Method (SOM)” screen of the dedicated software, set the total count in the control mode to 50,000 particles, set the number of measurements once, and set the Kd value to “standard particles 10.0 μm” (Beckman Coulter Set the value obtained using By pressing the “Threshold / Noise Level Measurement Button”, the threshold and noise level are automatically set. In addition, the current is set to 1600 μA, the gain is set to 2, the electrolyte is set to ISOTON II, and the “aperture tube flush after measurement” is checked.

  In the “Pulse to particle size conversion setting” screen of the dedicated software, the bin interval is set to logarithmic particle size, the particle size bin is set to 256 particle size bin, and the particle size range is set to 2 μm to 60 μm.

  The specific measurement method is as follows.

  (1) About 200 ml of the electrolytic aqueous solution is put in a glass 250 ml round bottom beaker exclusively for Multisizer 3, set on a sample stand, and the stirrer rod is stirred counterclockwise at 24 rotations / second. Then, the dirt and bubbles in the aperture tube are removed by the “aperture flush” function of the dedicated software.

  (2) About 30 ml of the electrolytic aqueous solution is put into a glass 100 ml flat bottom beaker. In this, "Contaminone N" (nonionic surfactant, anionic surfactant, 10% by weight aqueous solution of neutral detergent for pH7 precision measuring instrument cleaning, made by organic builder, manufactured by Wako Pure Chemical Industries, Ltd. About 0.3 ml of a diluted solution obtained by diluting 3) with ion-exchanged water is added.

  (3) Two oscillators with an oscillation frequency of 50 kHz are incorporated with the phase shifted by 180 degrees, and an ultrasonic disperser “Ultrasonic Dissipation System Tetora 150” (manufactured by Nikki Bios Co., Ltd.) having an electrical output of 120 W is prepared. About 3.3 l of ion-exchanged water is placed in the water tank of the ultrasonic disperser, and about 2 ml of Contaminone N is added to the water tank.

  (4) The beaker of (2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. And the height position of a beaker is adjusted so that the resonance state of the liquid level of the electrolyte solution in a beaker may become the maximum.

  (5) In a state where the electrolytic aqueous solution in the beaker of (4) is irradiated with ultrasonic waves, about 10 mg of toner particles are added to the electrolytic aqueous solution little by little and dispersed. Then, the ultrasonic dispersion process is continued for another 60 seconds. In the ultrasonic dispersion, the temperature of the water tank is appropriately adjusted so as to be 10 ° C. or higher and 40 ° C. or lower.

  (6) To the round bottom beaker of (1) installed in the sample stand, the electrolyte solution of (5) in which the toner is dispersed is dropped using a pipette, and the measurement concentration is adjusted to about 5%. . The measurement is performed until the number of measured particles reaches 50,000.

  (7) The measurement data is analyzed with the dedicated software attached to the apparatus, and the weight average particle diameter (D4) is calculated. The “average diameter” on the “analysis / volume statistics (arithmetic average)” screen when the graph / volume% is set by the dedicated software is the weight average particle diameter (D4).

  Next, a method for measuring physical properties according to the photoreceptor of the present invention will be described below.

<Measurement of C / (Si + C), Si + C atom density, and H atom ratio>
First, a reference electrophotographic photosensitive member in which only the charge injection blocking layer and the photoconductive layer shown in Table 2 were laminated was prepared, and a central portion in the longitudinal direction in an arbitrary circumferential direction was cut out in a 15 mm square to prepare a reference sample. Next, an electrophotographic photosensitive member in which the charge injection blocking layer, the photoconductive layer, and the surface layer were laminated was similarly cut out to prepare a measurement sample. 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.

  Specific measurement conditions of spectroscopic ellipsometry are incident angles: 60 °, 65 °, 70 °, measurement wavelengths: 195 nm to 700 nm, and beam diameter: 1 mm × 2 mm.

  First, the relationship between the wavelength, the amplitude ratio Ψ, and the phase difference Δ was determined for each reference angle of the reference sample by spectroscopic ellipsometry.

  Next, using the measurement result of the reference sample as a reference, the relationship between the wavelength, the amplitude ratio Ψ, and the phase difference Δ was determined at each incident angle by spectroscopic ellipsometry, similarly to the reference sample.

  Furthermore, a charge injection blocking layer, a photoconductive layer, and a surface layer are sequentially laminated, and a layer structure having a roughness layer in which the surface layer and the air layer coexist on the outermost surface is used as a calculation model. By changing the volume ratio of the surface layer to the air layer, the relationship between the wavelength at each incident angle and Ψ and Δ was calculated. Then, a calculation model was selected when the mean square error of the relationship between the wavelength, Ψ and Δ obtained by measuring the measurement sample and the relationship between the wavelength obtained by the above calculation at each incident angle and Ψ and Δ was minimized. . The film thickness of the surface layer was calculated using the selected calculation model, and the obtained value was taken as the film thickness of the surface layer. The analysis software is J.I. A. Woolase WVASE32 was used. The volume ratio of the surface layer to the air layer in the roughness layer was calculated by changing the ratio of the air layer in the roughness layer by 1 from 10: 0 to 1: 9 in the surface layer: air layer. In the positively charged a-Si photoconductor produced according to each film forming condition in this example, the wavelength, Ψ, and The mean square error of the relationship between Δ and the wavelength obtained by measurement and the relationship between Ψ and Δ was minimized.

  After the measurement by spectroscopic ellipsometry is completed, the sample for measurement is subjected to RBS (Rutherford backscattering method) (manufactured by Nisshin High Voltage Co., Ltd .: backscattering measuring device AN-2500) in the surface layer in the RBS measurement area. The number of silicon atoms and carbon atoms was measured.

  The ratio of the number of carbon atoms to the sum of the measured number of silicon atoms and carbon atoms (hereinafter referred to as “C / (Si + C)”) was determined.

  Next, with respect to the number of silicon atoms and carbon atoms obtained from the RBS measurement area, the atomic density of silicon atoms (hereinafter referred to as “Si atom density”) is determined using the surface layer thickness obtained by spectroscopic ellipsometry. ), The atomic density of carbon atoms (hereinafter referred to as “C atom density”), and the sum of the atomic densities of silicon atoms and carbon atoms (hereinafter referred to as “Si + C atom density”).

  Simultaneously with the RBS, the number of hydrogen atoms in the surface layer in the HFS measurement area was measured using the HFS (hydrogen forward scattering method) (manufactured by Nisshin High Voltage Co., Ltd .: backscattering measurement device AN-2500). Was measured. Based on the number of hydrogen atoms determined by HFS and the number of silicon atoms and carbon atoms determined by RBS, the sum of the number of silicon atoms, the number of carbon atoms and the number of hydrogen atoms is The ratio of the number of hydrogen atoms (hereinafter referred to as “H atomic ratio”) was determined.

  Next, with respect to the number of hydrogen atoms determined from the HFS measurement area, the atomic density of hydrogen atoms (hereinafter referred to as “H atomic density”) was determined using the thickness of the surface layer determined by spectroscopic ellipsometry.

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

  Although the basic configuration and features of the present invention have been described above, the present invention will be specifically described below based on examples. However, this does not limit the embodiment of the present invention.

<Method for producing inorganic fine powder A (A-1)>
Ilmenite ore containing 50% by mass of TiO ₂ equivalent was used as a starting material. The raw material was dried at 150 ° C. for 2 hours, and sulfuric acid was added and dissolved to obtain an aqueous TiOSO ₄ solution. This was concentrated, and after adding 4.5 parts by mass of a titania sol having rutile crystals as a seed, hydrolysis was performed at 125 ° C. to obtain a slurry of TiO (OH) ₂ containing impurities. This slurry was repeatedly washed with water at pH 5 to 6 to sufficiently remove sulfuric acid, FeSO ₄ , and impurities. Then, a slurry of high purity metatitanic acid [TiO (OH) ₂ ] was obtained. This slurry was filtered, baked at 170 ° C. for 2 hours, and then repeatedly pulverized by a jet mill until fine powder aggregates disappeared to obtain fine titanium oxide powder.

1 part by mass of titanium oxide fine powder is added to 100 parts by mass of an aqueous medium composed of water and sufficiently stirred, and a silane coupling agent (C ₈ H ₁₇ Si (OC ₂ H ₅ ) ₃ ) is added to 100 parts by mass of titanium oxide. 17 parts by mass with respect to the aqueous medium. And it stirred sufficiently so that a titanium oxide fine powder might not unite, it filtered after agitation, dried, and pulverized lightly, and obtained inorganic fine powder A-1 which is a titanium oxide fine powder. This inorganic fine powder A-1 had a BET specific surface area of 75 m ² / g and a dielectric constant of 115 pF / m. Further, as a result of X-ray diffraction measurement of the inorganic fine powder A-1, a peak attributed to rutile titanium oxide was observed.

<Method for producing inorganic fine powder A (A-2)>
Inorganic fine powder A-1 is a titanium oxide fine powder in the same manner as the inorganic fine powder A-1, except that hydrolysis is performed at 120 ° C. and baking is performed at 165 ° C. for 2 hours. Fine powder A-2 was obtained. This inorganic fine powder A-2 had a BET specific surface area of 95 m ² / g and a dielectric constant of 105 pF / m. Further, as a result of X-ray diffraction measurement of the inorganic fine powder A-2, a peak attributed to rutile titanium oxide was observed.

<Method for producing inorganic fine powder A (A-3)>
In the production method of the inorganic fine powder A-1, hydrolysis is performed at 160 ° C., and a silane coupling agent (i-C ₄ H ₉ Si (OCH ₃ ) ₃ is used as a hydrophobizing agent with respect to 100 parts by mass of titanium oxide. ) Was added in the same manner as the inorganic fine powder A-1 except that 7 parts by mass of the solid content was added to obtain an inorganic fine powder A-3 that was a fine titanium oxide powder. This inorganic fine powder A-3 had a BET specific surface area of 165 m ² / g and a dielectric constant of 147 pF / m. Further, as a result of X-ray diffraction measurement of the inorganic fine powder A-3, a peak attributed to rutile titanium oxide was observed.

<Method for producing inorganic fine powder A (A-4)>
In the manufacturing method of inorganic fine powder A-1, it hydrolyzes at 130 degreeC, is baked at 200 degreeC for 2 hours, and is the same as the manufacturing method of inorganic fine powder A-1, except not performing surface hydrophobization treatment. An inorganic fine powder A-4, which is a fine titanium oxide powder, was obtained. This inorganic fine powder A-4 had a BET specific surface area of 62 m ² / g and a dielectric constant of 85 pF / m. Further, as a result of X-ray diffraction measurement of the inorganic fine powder A-4, a peak attributed to rutile titanium oxide was observed.

<Method for producing inorganic fine powder A (A-5)>
Ilmenite ore containing 50% by mass of TiO ₂ equivalent was used as a starting material. The raw material was dried at 150 ° C. for 2 hours, and sulfuric acid was added and dissolved to obtain an aqueous TiOSO ₄ solution. This was concentrated, and 6.0 parts by mass of titania sol having anatase crystals as a seed was added, followed by hydrolysis at 130 ° C. to obtain a slurry of TiO (OH) ₂ containing impurities. This slurry was repeatedly washed with water at pH 5 to 6 to sufficiently remove sulfuric acid, FeSO ₄ , and impurities. Then, a slurry of high purity metatitanic acid [TiO (OH) ₂ ] was obtained.

The pH of the metatitanic acid slurry was adjusted to 8 to 9, and the metatitanic acid was sufficiently pulverized with a ball mill. Thereafter, the temperature of the slurry was adjusted to 30 ° C. and the pH to about 2 with sufficient stirring. Metatitanic acid was contained in the slurry in an amount of about 6% by mass. For 100 parts by mass of metatitanic acid in the slurry, 35 parts by mass of silane coupling agent (i-C ₄ H ₉ Si (OCH ₃ ) ₃ ) as a hydrophobizing agent in solid content, and coalescence of particles occurs. The mixture was dropped and mixed with sufficient stirring so that there was no reaction. Further, the pH of the slurry was adjusted to 6.5 with sufficient stirring.

This is filtered and dried, then heat-treated at 140 ° C. for 2 hours to produce hydrophobic titanium oxide fine powder, and then repeatedly pulverized by a jet mill until there are no aggregates of hydrophobic titanium oxide fine powder. To obtain inorganic fine powder A-5 which is a fine powder of titanium oxide. This inorganic fine powder A-5 had a BET specific surface area of 148 m ² / g and a dielectric constant of 53 pF / m. Moreover, as a result of performing X-ray-diffraction measurement about inorganic fine powder A-5, the peak attributed to anatase type titanium oxide was observed.

<Method for producing inorganic fine powder A (A-6)>
A hydrous titanium oxide slurry obtained by hydrolyzing a titanyl sulfate aqueous solution was washed with an alkaline aqueous solution. Next, hydrochloric acid was added to the hydrous titanium oxide slurry to adjust the pH to 0.7 to obtain a titania sol dispersion. NaOH was added to the titania sol dispersion, the pH of the dispersion was adjusted to 5.0, and washing was repeated until the electrical conductivity of the supernatant liquid reached 50 μS / cm.

0.98-fold molar amount of Sr (OH) ₂ .8H ₂ O was added to the hydrous titanium oxide, and the mixture was placed in a SUS reaction vessel and purged with nitrogen gas. Further, distilled water was added so as to be 0.5 mol / liter in terms of SrTiO ₃ . The slurry was heated to 80 ° C. at 7 ° C./hour in a nitrogen atmosphere, and reacted for 5 hours after reaching 80 ° C. After the reaction, the reaction solution was cooled to room temperature, and the supernatant was removed. Then, the washing was repeated with pure water, and then filtered with Nutsche. The obtained cake was dried to obtain strontium titanate inorganic fine powder A-6 having a BET specific surface area of 45 m ² / g and a dielectric constant of 195 pF / m.

<Method for producing inorganic fine powder A (A-7)>
A hydrous titanium oxide slurry obtained by hydrolyzing a titanyl sulfate aqueous solution was washed with an alkaline aqueous solution. Next, hydrochloric acid was added to the hydrous titanium oxide slurry to adjust the pH to 0.7 to obtain a titania sol dispersion. NaOH was added to the titania sol dispersion, the pH of the dispersion was adjusted to 5.3, and washing was repeated until the electrical conductivity of the supernatant reached 70 μS / cm.

0.93 times the molar amount of Sr (OH) ₂ .8H ₂ O was added to the hydrous titanium oxide, and the mixture was placed in a SUS reaction vessel and purged with nitrogen gas. Further, distilled water was added so as to be 0.7 mol / liter in terms of SrTiO ₃ .

  The slurry was heated to 70 ° C. at 8.5 ° C./hour in a nitrogen atmosphere, and reacted for 5 hours after reaching 70 ° C. After the reaction, the mixture was cooled to room temperature, the supernatant was removed, and washing was repeated with pure water.

  Furthermore, in a nitrogen atmosphere, the slurry is placed in an aqueous solution in which 5% by mass of sodium stearate is dissolved with respect to the solid content of the slurry, and while stirring, an aqueous calcium sulfate solution is dropped to stir the strontium titanate fine powder surface. Calcium phosphate was precipitated.

The slurry was repeatedly washed with pure water and then filtered with Nutsche, and the resulting cake was dried to obtain inorganic fine powder A-7, which was a fine strontium titanate powder. This inorganic fine powder A-7 had a BET specific surface area of 8 m ² / g and a dielectric constant of 300 pF / m.

<Method for producing inorganic fine powder A (A-8)>
After mixing barium titanate and strontium titanate at a ratio of 70/30 by weight and sintering at 500 ° C., the mixture is repeatedly crushed by a jet mill until no aggregates are left, and barium titanate / titanate Inorganic fine powder A-8 which is a fine powder of strontium mixed crystal was obtained. This inorganic fine powder A-8 had a BET specific surface area of 6 m ² / g and a dielectric constant of 495 pF / m.

<Method for producing inorganic fine powder A (A-9)>
Zinc hydroxide was molded at a pressure of 100 kg / cm ² and sintered at a temperature of 500 ° C. for 5 hours. Thereafter, mechanical pulverization and air classification were performed to obtain an inorganic fine powder A-9 which is a zinc oxide fine powder. This inorganic fine powder A-9 had a BET specific surface area of 11 m ² / g and a dielectric constant of ² pF / m.

<Method for producing inorganic fine powder A (A-10)>
A 0.15N NaOH aqueous solution was maintained at about 90 ° C. and heated to 45 ° C., and a TiCl ₄ aqueous solution (TiCl ₄ concentration 0.472 mol / l) was previously removed from the undissolved portion at about 95 ° C.
A BaCl ₂ / NaOH aqueous solution (BaCl ₂ concentration of 0.258 mol / liter, NaOH concentration of 2.73 mol / liter) was continuously supplied into the reaction vessel. The temperature of the mixed aqueous solution was kept constant at about 90 ° C. and stirred for 2 minutes to form particulate barium titanate. After aging, decantation was performed to separate and wash the supernatant and the precipitate, and the solid reaction product was recovered. The recovered solid reaction product was dried by heating at 150 ° C. in an air atmosphere. Furthermore, it heated at 1000 degreeC for 40 minutes, and obtained the inorganic fine powder A-10 which is a barium titanate fine powder. This inorganic fine powder A-10 had a BET specific surface area of 6 m ² / g and a dielectric constant of 1210 pF / m.

  Table 1 shows the physical property values of the inorganic fine powders A-1 to A-10.

<Method for Producing Photoreceptor B-1>
Using a plasma processing apparatus using a high-frequency power source in the RF band as shown in FIG. 3, on a cylindrical substrate (cylindrical aluminum substrate having a diameter of 80 mm, a length of 358 mm, and a thickness of 3 mm). A positively charged a-Si photoreceptor B-1 was produced under the conditions shown in Table 2 below. At that time, the charge injection blocking layer, the photoconductive layer, and the surface layer are formed in this order, and the SiH ₄ flow rate (X), CH ₄ flow rate (Y), and high frequency power (Z) at the time of surface layer preparation are shown in Table 3 below. The conditions shown in FIG. Two electrophotographic photoreceptors were produced under each film forming condition.

  For each of the two electrophotographic photoreceptors produced under the respective film forming conditions, C / (Si + C), Si atom density, C atom density, Si + C atom density, H atom ratio, H atom are obtained using one electrophotographic photoreceptor. Density measurements were taken. The results are shown in Table 6.

  Then, the electrophotographic characteristics described later were evaluated using another photoconductor.

<Method for producing photoconductors B-2 to B-8>
In the production method of the photoconductor B-1, the photoconductors B-2 to B-8 are manufactured in the same manner as the photoconductor B-1 except that the conditions for creating the surface layer are as shown in Table 3. Obtained. For Photoreceptors B-2 to B-8, C / (Si + C), Si atom density, C atom density, Si + C atom density, H atom ratio, and H atom density are measured in the same manner as the method for producing photoreceptor B-1. Went. The results are shown in Table 6.

<Method for Producing Photoreceptor B-9>
A positively charged a-Si photosensitive member B-9 was produced on a cylindrical substrate under the conditions shown in Table 4 below using a plasma processing apparatus using a high frequency power source in the RF band as the frequency shown in FIG. At that time, the charge injection blocking layer, the photoconductive layer, and the surface layer were formed in this order. For Photoreceptor B-9, C / (Si + C), Si atom density, C atom density, Si + C atom density, H atom ratio, and H atom density were measured in the same manner as in the method for producing photoreceptor B-1. The results are shown in Table 6.

<Method for Producing Photoreceptor B-10>
A positively charged a-Si photosensitive member B-10 was produced on a cylindrical substrate under the conditions shown in Table 5 below using a plasma processing apparatus using a high frequency power source in the RF band as the frequency shown in FIG. At that time, the charge injection blocking layer, the photoconductive layer, and the surface layer were formed in this order. For Photoreceptor B-10, C / (Si + C), Si atom density, C atom density, Si + C atom density, H atom ratio, and H atom density were measured in the same manner as in the method for producing photoreceptor B-1. The results are shown in Table 6.

<Example of production of binder resin C-1>
Propoxylated bisphenol A (2.2 mol adduct): 46.8 mol%
Terephthalic acid: 34.8 mol%
Trimellitic anhydride: 11.8 mol%
Isophthalic acid: 5.6 mol%
Phenol novolac EO adduct: 1.0 mol%

Charge the above monomers together with an esterification catalyst into a 5 liter autoclave and attach a reflux condenser, moisture separator, N ₂ gas inlet tube, thermometer and stirrer at 230 ° C. while introducing N ₂ gas into the autoclave. A polycondensation reaction was performed. After completion of the reaction, the reaction product was taken out from the container, cooled and pulverized to obtain a binder resin C-1.

  The binder resin C-1 had a Tg of 59.5 ° C. and a softening point of 151.3 ° C.

<Example of production of binder resin C-2>
Propoxylated bisphenol A (2.2 mol adduct): 47.1 mol%
Terephthalic acid: 49.9 mol%
Trimellitic anhydride: 3.0 mol%

Charge the above monomers together with an esterification catalyst into a 5 liter autoclave and attach a reflux condenser, moisture separator, N ₂ gas inlet tube, thermometer and stirrer at 230 ° C. while introducing N ₂ gas into the autoclave. A polycondensation reaction was performed. After completion of the reaction, the reaction product was taken out from the container, cooled and pulverized to obtain a binder resin C-2.

  The binder resin C-2 had a Tg of 59.4 ° C. and a softening point of 92.5 ° C.

<Example of production of binder resin C-3>
Into a four-necked flask, 250 parts by mass of degassed water and 50 parts by mass of a 1% by weight aqueous solution of polyvinyl alcohol were added, and then 83 parts by mass of styrene, 17 parts by mass of n-butyl acrylate, and 0.001 part by mass of divinylbenzene. Then, a mixed solution of 0.1 part by mass of 2,2-bis (4,4-di-tert-butylperoxycyclohexyl) propane was added and stirred to obtain a suspension.

  After the inside of the four-necked flask was placed in a nitrogen atmosphere, the temperature was raised to 85 ° C. to initiate polymerization. After maintaining at the same temperature for 20 hours, 0.1 part by mass of benzoyl peroxide was further added, and further maintained for 8 hours to complete the polymerization. Next, the polymer particles were separated by filtration, sufficiently washed with water, and dried to obtain a binder resin C-3.

  The binder resin C-3 had a Tg of 61.2 ° C. and a softening point of 143.5 ° C.

<Example of production of binder resin C-4>
Into a four-necked flask, 300 parts by mass of xylene was added, and the inside of the container was sufficiently replaced with nitrogen while stirring, and then heated to reflux.

  Under this reflux, a mixed solution of 83 parts by mass of styrene, 17 parts by mass of acrylic acid-n-butyl and 2 parts by mass of di-tert-butyl peroxide was dropped over 4 hours, and the polymerization was carried out by maintaining for 2 hours. Upon completion, a low molecular weight polymer solution was obtained. This polymer solution was dried under reduced pressure to obtain a binder resin C-4.

  The binder resin C-4 had a Tg of 60.0 ° C. and a softening point of 97.3 ° C.

<Example of production of binder resin D-1>
50 parts by mass of binder resin C-1 and 50 parts by mass of binder resin C-2 were mixed with a Henschel mixer to obtain binder resin D-1.

<Example of production of binder resin D-2>
A binder resin D-2 was prepared by mixing 60 parts by mass of the binder resin C-3 and 40 parts by mass of the binder resin C-4 with a Henschel mixer.

<Production Example of Toner Particle E-1>
Binder resin D-1 100 parts by mass Magnetic iron oxide particles 90 parts by mass (average particle size 0.15 μm, Hc = 11.5 kA / m, σs = 90 Am ² / kg, σr = 1 6 Am ² / kg)
Fischer-Tropsch wax b shown in Table 7 2 parts by weight Paraffin wax a shown in Table 7 2 parts by weight Charge control agent c shown below 2 parts by weight After the above materials were premixed with a Henschel mixer, they were melted by a twin-screw kneading extruder. Kneaded. At this time, the residence time was controlled so that the temperature of the kneaded resin was 150 ° C.

  The obtained kneaded product is cooled, coarsely pulverized with a hammer mill, then finely pulverized using a fine pulverizer using a jet stream, and the obtained finely pulverized powder is used using a multi-division classifier utilizing the Coanda effect. Thus, negatively triboelectrically charged toner particles E-1 having a weight average particle diameter (D4) of 6.9 μm were obtained.

<Production Example of Toner Particle E-2>
Binder resin D-2 100 parts by mass Magnetic iron oxide particles 90 parts by mass (average particle size 0.15 μm, Hc = 11.5 kA / m, σs = 90 Am ² / kg, σr = 1 6 Am ² / kg)
Fischer-Tropsch wax b shown in Table 7 3 parts by mass Charge control agent b shown below 2 parts by mass The above materials were premixed with a Henschel mixer and then melt-kneaded with a twin-screw kneading extruder. At this time, the residence time was controlled so that the temperature of the kneaded resin was 150 ° C.

  The obtained kneaded product is cooled, coarsely pulverized with a hammer mill, then finely pulverized using a fine pulverizer using a jet stream, and the obtained finely pulverized powder is used using a multi-division classifier utilizing the Coanda effect. Thus, negatively triboelectrically chargeable toner particles E-2 having a weight average particle diameter (D4) of 7.0 μm were obtained.

<Production Example of Toner Particle E-3>
Binder resin D-2 100 parts by mass Magnetic iron oxide particles 90 parts by mass (average particle size 0.15 μm, Hc = 11.5 kA / m, σs = 90 Am ² / kg, σr = 16 Am ² / kg)
Fischer-Tropsch wax b shown in Table 7 2 parts by mass Charge control agent a shown below 2 parts by mass The above materials were premixed with a Henschel mixer and then melt-kneaded with a biaxial kneading extruder. At this time, the residence time was controlled so that the temperature of the kneaded resin was 150 ° C.

  The obtained kneaded product is cooled, coarsely pulverized with a hammer mill, then finely pulverized using a fine pulverizer using a jet stream, and the obtained finely pulverized powder is used using a multi-division classifier utilizing the Coanda effect. Thus, negatively triboelectrically chargeable toner particles E-3 having a weight average particle diameter (D4) of 7.2 μm were obtained.

<Production Example of Toner F-1>
Toner particles E-1 100 parts by weight Inorganic fine powder A-1 0.2 parts by weight Hydrophobic silica fine powder 0.8 parts by weight (BET 140 m ² / g, hexamethyldisilazane (HMDS) 30 parts by weight and dimethyl silicone oil 10 Hydrophobic treatment of 100 parts by mass of silica fine powder in parts by mass)
The above materials were externally mixed with a Henschel mixer and sieved with a mesh having a mesh size of 150 μm to obtain negatively triboelectrically charged toner F-1.

<Production Example of Toners F-2 to F-10>
Except for the formulation shown in Table 8, toners F-2 to F-10 were obtained in the same manner as in the production example of the toner F-1.

[Example 1]
As a machine used for evaluation in this example, a commercially available digital copying machine iR5075N (a-Si photosensitive drum mounted, magnetic one-component jumping development method adopted, manufactured by Canon Inc.) was used. In this evaluation machine, the following modifications / changes were made.
-The photoconductor is changed to the photoconductor B-1 manufactured in the present embodiment.-The development electric field strength is modified to be variable between two levels of 3.0 x 10 ⁶ V / m and 5.0 x 10 ⁶ V / m. Remodeling and changing the toner to the toner D-1 manufactured in this embodiment so that the process speed of the machine body (= the peripheral speed of the photosensitive drum) can be varied between two levels of 400 mm / sec and 600 mm / sec.

  Using this evaluation machine, 100,000 sheets were endured using a test chart with a printing ratio of 5% under the conditions shown in Table 9, and the following evaluations were performed. The results are shown in Table 10.

<Leak Poti>
The evaluation of the leak spot was obtained by outputting A3 solid black images after enduring 100,000 sheets in each test environment, and measuring the number of generated white spots (leak spots due to dielectric breakdown) for the images. From the obtained values, A to D were evaluated according to the following criteria.
A (very good): no white spots occur B (good): 1-3 white spots occur in a solid black image C (normal): 4-9 white spots occur in a solid black image D (Poor): 10 or more white spots occur in a solid black image

<Fog>
The fog is measured using a reflection densitometer (reflectometer model TC-6DS manufactured by Tokyo Denshoku Co., Ltd.). The worst white background reflection density after image formation is Ds, and the average reflection density of the transfer material before image formation is calculated. The fog was evaluated with Dr as D and Ds-Dr as the fog amount. Therefore, the smaller the value, the better the fog suppression. This evaluation was performed after the endurance of 100,000 sheets in each test environment and evaluated according to the following criteria.
A (very good): fog is less than 1 B (good): fog is 1 or more and less than 3 C (normal): fog is 3 or more and less than 5.
D (bad): fog is 5 or more.

<Image density>
The image density was determined by measuring the image density of the initial 100th and 100,000th test charts in each test environment. The image density was measured by measuring the reflection density of a 5 mm round solid black image using an SPI filter with a Macbeth densitometer (Macbeth Co.) which is a reflection densitometer. The evaluation standard of image density is shown below.

As a result of calculating a reduction rate of reflection density after endurance of 100,000 sheets with respect to the 100th sheet,
A (very good): The reduction rate is less than 3%.
B (good): The reduction rate is 3% or more and less than 6%.
C (Normal): The decrease rate is 6% or more and less than 10%.
D (poor): The reduction rate is 10% or more.

<Halftone density unevenness>
The evaluation of the image density unevenness was performed by visual evaluation after outputting an A3 halftone image after enduring 100,000 sheets. The evaluation criteria for image density unevenness are shown below.
A (very good): Halftone density unevenness cannot be visually confirmed.
B (good): Halftone density unevenness is hardly discernable visually.
C (Normal): Halftone density unevenness can be slightly discerned, but there is no practical problem.
D (bad): Halftone density unevenness is clear.

  As for Example 1, good results were obtained in any evaluation.

[Examples 2 to 15]
Evaluations were carried out in the same manner as in Example 1 for the combinations of the photoreceptors and toners shown in Table 10. Table 10 shows the evaluation results.

  As for Example 2, the same results as in Example 1 were obtained in any evaluation.

  Regarding Example 5, since the dielectric constant of the inorganic fine powder A was the lower limit value of Claim 1, the evaluation of leak potency was B rank in condition 3 and C rank in condition 4. Further, since the titanium oxide is anatase type, the evaluation of fog was B rank in conditions 2 and 3, and C rank in condition 4.

  Regarding Example 6, the dielectric constant of the inorganic fine powder A was the upper limit value of claim 2, and the evaluation of the leak potion was B rank under condition 4. Further, since the inorganic fine powder A was strontium titanate, the fog evaluation was B rank in conditions 1 and 2, and C rank in conditions 3 and 4.

  Regarding Example 8, since the dielectric constant of the inorganic fine powder A is the upper limit of claim 1, the evaluation of the leak potion was B rank in the conditions 2 and 3, and C rank in the condition 4. Moreover, since the inorganic fine powder A is a mixed crystal of strontium titanate and barium titanate, the evaluation of fog was B rank in condition 1 and C rank in conditions 2, 3 and 4.

  Regarding Example 9, since the Si + C atom density is the lower limit value of the preferred range of claim 1, the leak spot evaluation was ranked B under Condition 4.

  Regarding Example 11, since C / (Si + C) is less than or equal to the lower limit of claim 5, the image density was evaluated as B rank under conditions 2 and 4.

  Regarding Example 12, since the Si + C atom density was the lower limit of Claim 1, the evaluation of the leak spot was B rank under conditions 2 and 4. Further, since the H atomic ratio is equal to or higher than the upper limit of claim 6, the evaluation of the halftone density unevenness was ranked B in conditions 2 and 4.

  Regarding Example 14, since C / (Si + C) is equal to or higher than the upper limit of claim 5, the evaluation of the image density was ranked B under conditions 2 and 4. Further, since the H atomic ratio is less than or equal to the lower limit of claim 6, the evaluation of the halftone density unevenness was ranked B in Conditions 2 and 4.

  Regarding Example 15, since the dielectric constant of the inorganic fine powder A is the upper limit value of Claim 1, the evaluation of the leak potion was B rank in the conditions 2 and 3, and C rank in the condition 4.

  Moreover, since the inorganic fine powder A is a mixed crystal of strontium titanate and barium titanate, the evaluation of fog was B rank in condition 1 and C rank in conditions 2, 3 and 4.

  Further, since C / (Si + C) is equal to or higher than the upper limit of the fifth aspect, the evaluation of the image density is B rank in the conditions 2 and 4.

  Further, since the H atomic ratio is less than or equal to the lower limit of claim 6, the evaluation of the halftone density unevenness was ranked B in Conditions 2 and 4.

[Comparative Examples 1 to 5]
Evaluations were carried out in the same manner as in Example 1 for the combinations of the photoreceptors and toners shown in Table 10. Table 10 shows the evaluation results.

  Regarding Comparative Example 1 and Comparative Example 2, since the Si + C atom density was not more than the lower limit of Claim 1, the evaluation of the leakage spot was C rank in conditions 1 and 3, and D rank in conditions 2 and 4.

  For Comparative Example 3, the dielectric constant of the inorganic fine powder A is less than the lower limit of claim 1, and for Comparative Example 4, the dielectric constant of the inorganic fine powder A is greater than or equal to the upper limit of Claim 1. In all conditions, the D rank was obtained.

  Regarding Comparative Example 5, since the dielectric constant of the inorganic fine powder A is not more than the lower limit of claim 1 and the Si + C atom density is not more than the lower limit of claim 1, the evaluation of leak potency is D rank under any condition. It became.

1 is a configuration diagram of an example of an image forming apparatus. It is a typical schematic sectional drawing regarding the layer structure of the a-Si photoreceptor for positive charging. 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.

Explanation of symbols

1001 Developing device 1002 Toner carrier (developing sleeve)
1003 Electrostatic latent image carrier (photoconductor)
1004 Transfer device 1005 Static eliminator 1006 Cleaning device 1007 Pre-exposure device 1008 Primary charging device 1009 Exposure device 1010 Transfer material 1011 Fixing device 2000 Positive charging electrophotographic photosensitive member 2001 Conductive substrate 2002 Photoreceptive layer 2003 Lower charge injection blocking layer 2004 Light Conductive layer 2005 Surface layer 3100 Deposition apparatus 3110 Reaction vessel 3111 Cathode electrode 3112 Conductive substrate 3113 Heater 3114 for heating the substrate Gas introduction tube 3115 High-frequency matching box 3116 Gas piping 3117 Leak valve 3118 Main valve 3119 Vacuum gauge 3120 High-frequency power source 3121 Insulating material 3123 Receiving base 3200 Gas supply device 3211 to 3215 Mass flow controller 3221 to 3225 Cylinder 3231 to 3235 Valve 3241 245 inlet valves 3251-3255 outflow valves 3260 auxiliary valve 3261 to 3265 pressure regulators

Claims (7)

At least a step of charging the 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 image carrier, and a toner carried on the toner carrier. In a toner used in an image forming method having a development step of transferring to a latent image and visualizing the latent image,
The electrostatic charge image bearing member is a photoreceptor in which at least a photoconductive layer and a surface layer formed of hydrogenated amorphous silicon carbide are sequentially laminated, and the atomic density of silicon atoms and the number of carbon atoms in the surface layer The sum of the densities is 6.60 × 10 ²² atoms / cm ³ or more,
The toner is a toner having toner particles containing at least a binder resin and a colorant, and inorganic fine powder,
The inorganic fine powder contains at least an inorganic fine powder A having a dielectric constant of 50 pF / m or more and 500 pF / m or less at 100 kHz and 40 ° C.   2. The toner according to claim 1, wherein the inorganic fine powder A has a dielectric constant of 50 pF / m to 200 pF / m at 100 kHz and 40 ° C. 3.   The toner according to claim 1, wherein the inorganic fine powder A is titanium oxide.   4. The toner according to claim 1, wherein the inorganic fine powder A is rutile type titanium oxide. At least a step of charging the 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 image carrier, and a toner carried on the toner carrier. An image forming method including a development step of visualizing the image by transferring to the electrostatic latent image,
The electrostatic charge image bearing member is a photoreceptor in which at least a photoconductive layer and a surface layer formed of hydrogenated amorphous silicon carbide are sequentially laminated, and the atomic density of silicon atoms and the number of carbon atoms in the surface layer The sum of the densities is 6.60 × 10 ²² atoms / cm ³ or more, and the toner is a toner having toner particles containing at least a binder resin and a colorant, and inorganic fine powder, and the inorganic fine powder The body contains at least inorganic fine powder A having a dielectric constant of 50 pF / m or more and 500 pF / m or less at 100 kHz and 40 ° C.   6. The image according to claim 5, wherein 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 surface layer of the photoreceptor is 0.61 or more and 0.75 or less. Forming method.   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 in the surface layer of the photoreceptor is 0.30 or more and 0.45 or less. The image forming method according to claim 5 or 6.

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