JP2019211547A - Process cartridge - Google Patents

Abstract

To sufficiently improve wear resistance to prevent an increase in torque and an increase in temperature caused by rubbing between a cleaning blade and a photoreceptor associated with an increase in speed/elongation of a life.SOLUTION: In a process cartridge, a toner has a Martens hardness of 200 MPa or more and 1100 MPa or less when the toner is measured under a condition of a maximum load of 2.0×10N, and a protective layer of an electrophotographic photoreceptor has a Martens hardness of 200 MPa or more and 280 MPa or less.SELECTED DRAWING: None

Description

  The present invention relates to a toner for developing an electrostatic charge image (electrostatic latent image) used in an image forming method such as electrophotography and electrostatic printing, an electrophotographic photoreceptor, a process cartridge having the electrophotographic photoreceptor, and The present invention relates to an electrophotographic apparatus.

  In recent years, the electrophotographic apparatus is required to further improve the friction resistance of the toner to be mounted as the service life and the speed of the electrophotographic apparatus are greatly enhanced. As an example, a technique of toner particles having a surface layer containing an organosilicon polymer is disclosed (Patent Document 1). On the other hand, an electrophotographic photosensitive member mounted on an electrophotographic apparatus uses a radical polymerizable compound on the surface of the electrophotographic photosensitive member, and discloses a technique for greatly improving wear resistance (mechanical durability). (Patent Document 2).

  In addition, as the process cartridge speed increases, torque increases and temperature rises due to friction between the cleaning blade and the photosensitive member. In order to prevent these problems, downtime occurs to prevent temperature rise. In addition, in order to prevent cleaning failure and blade turning due to torque increase, toner is sent to the photoreceptor other than during printing, and the occurrence of problems is suppressed by ensuring lubricity by the toner and external additives.

JP 2014-130242 A JP 2000-66425 A

  According to the study by the present inventors, the toner having a surface layer containing an organosilicon polymer disclosed in Patent Document 1 is greatly improved in terms of developability accompanying durability deterioration. On the other hand, the combination with a general electrophotographic photosensitive member may not have a sufficient improvement effect on the increase in torque and temperature rise due to the friction between the cleaning blade and the photosensitive member due to high speed / long life. I understood.

  In addition, the high durability photoconductor configuration disclosed in Patent Document 2 has sufficiently improved wear resistance. However, the torque increases or increases due to the friction between the cleaning blade and the photoconductor due to high speed / long life. It has been found that the temperature may not be sufficient.

  Therefore, the object of the present invention is to suppress the temperature rise and the deterioration of the cleaning property accompanying the increase in the speed, and the downtime is generated in the toner having the frictional resistance in the developing portion significantly improved as compared with the conventional toner. It is an object of the present invention to provide a process cartridge and an electrophotographic apparatus with high productivity.

The above object is achieved by the present invention described below. That is, the process cartridge and the electrophotographic apparatus according to the present invention include an electrophotographic photosensitive member and a toner accommodated in a toner accommodating portion, and the electrostatic latent image formed on the electrophotographic photosensitive member is converted into the toner. A process cartridge or an electrophotographic apparatus having a developing means for developing using a toner and a cleaning means for removing a toner on the electrophotographic photosensitive member by bringing a blade into contact with the electrophotographic photosensitive member,
The toner has toner particles containing a binder resin and a colorant, and has a Martens hardness of 200 MPa or more and 1100 MPa or less when measured under a maximum load of 2.0 × 10 ⁻⁴ N.
The electrophotographic photoreceptor is a process cartridge and an electrophotographic apparatus having a support, a photosensitive layer, and a protective layer as a surface layer, and the protective layer has a Martens hardness of 200 MPa to 280 MPa. .

  According to the present invention, torque increase and temperature rise due to friction between the cleaning blade and the photosensitive member can be significantly reduced as compared with the conventional configuration even through high-speed and long-life durability. Furthermore, since the cleaning property can be sufficiently secured, even in a higher-speed machine, the downtime associated with the prevention of temperature rise and the securing of the cleaning property does not occur, and a highly productive process cartridge and electrophotographic apparatus can be provided.

It is the schematic of a grinding | polishing apparatus.

Hereinafter, the present invention will be described in detail with reference to preferred embodiments.
In order to solve the above technical problem, a feature is that a combination of a toner having a specific surface layer and a combination of an electrophotographic photosensitive member having a specific protective layer are used.

  In the present invention, the description of “XX or more and XX or less” or “XX to XX” representing a numerical range means a numerical range including a lower limit and an upper limit as endpoints unless otherwise specified.

  Conventional technical ideas for increasing the wear resistance of toner have been studied in the direction of allowing the toner to withstand a strong share. On the other hand, even when these techniques are used, the toner may not withstand depending on the process conditions. The reason is as follows.

  In addition to a strong share of toner in the developing machine, it also receives a weak share such as rubbing against hard materials such as metal members and external additives. At first glance, it was thought that such a weak share due to rubbing had no effect, but it was found that small scratches such as micro scratches would occur on the toner surface when scratched by a material harder than the toner. When the rotation speed of the developing roller and the developer stirring speed are increased, this is repeated again and again, and the change is eventually increased. In order to prevent the toner change due to these, it was found that it is necessary not only to design a toner that can withstand a strong share but also to prepare for a very small change due to a weak share.

The toner of the present invention is a toner having toner particles containing a binder resin and a colorant, and has a Martens hardness of 200 MPa to 1100 MPa when measured under a maximum load of 2.0 × 10 ⁻⁴ N. is there.

  Hardness is one of the mechanical properties at or near the surface of an object. It is difficult to deform or scratch an object when it is about to be deformed or scratched by a foreign object. Measurement methods and definitions exist. For example, the measurement method is properly used depending on the size of the measurement region. When the measurement region is 10 μm or more, the Vickers method is often used, and when it is 10 μm or less, the nanoindentation method is used. . For example, Brinell hardness and Vickers hardness are used as indentation hardness, Martens hardness is used as scratch hardness, and Shore hardness is used as rebound hardness.

  In the measurement of toner, since the general particle diameter is 3 μm to 10 μm, the nanoindentation method is a measurement method that is preferably used. According to the study by the inventors, Martens hardness representing scratch hardness was appropriate as the definition of hardness for expressing the effect of the present invention. This is thought to be because the scratch hardness represents the strength against which the toner is scratched by a hard substance such as a metal or an external additive in the developing machine.

In the present invention, by adjusting the Martens hardness when measured under the condition of the maximum load of the toner of 2.0 × 10 ⁻⁴ N to 200 MPa or more and 1100 MPa or less, the abrasion resistance of the toner in the developing portion is improved as compared with the conventional toner. It became possible to greatly improve.

  When the Martens hardness is lower than 200 MPa, the effects of the present invention cannot be obtained satisfactorily. On the other hand, if the Martens hardness is higher than 1100 MPa, it may cause damage to members such as a regulation blade and a developing roller depending on the case, so care must be taken.

The means for adjusting the Martens hardness when measuring under the condition of the maximum load of 2.0 × 10 ⁻⁴ N to 200 MPa to 1100 MPa is not particularly limited. However, since the hardness is significantly higher than the hardness of organic resins used in general toners, it is difficult to achieve it by means usually used to increase the hardness. For example, it is difficult to achieve by means of designing a resin with a high glass transition temperature, means for increasing the resin molecular weight, means for thermosetting, means for adding a filler to the surface layer, and the like.

The Martens hardness of an organic resin used in a general toner is about 50 MPa to 80 MPa when measured under a maximum load of 2.0 × 10 ⁻⁴ N. Furthermore, even when the hardness is increased by increasing the resin design or the molecular weight, it is about 120 MPa or less. Further, even when a filler such as a magnetic material or silica is filled in the vicinity of the surface layer and thermally cured, it is about 180 MPa or less, and the toner of the present invention is significantly harder than a general toner.

  As one means for adjusting to the above specific hardness range, for example, the surface layer of the toner is formed of a substance such as an inorganic substance having an appropriate hardness, and the chemical structure and the macro structure are controlled to have an appropriate hardness. The method of doing is mentioned.

  As a specific example, an organic silicon polymer can be cited as a substance having the above-mentioned specific hardness, and the number of carbon atoms directly bonded to the silicon atom of the organosilicon polymer, the carbon chain length, etc. as a material selection It is possible to adjust the hardness. The toner particles have a surface layer containing an organosilicon polymer, and the number of carbon atoms directly bonded to the silicon atom of the organosilicon polymer is 1 or more and 3 or less (preferably 1 or more and 2 or less) , More preferably 1) because it is easy to adjust to the specific hardness.

  As means for adjusting the Martens hardness by the chemical structure, it is possible to adjust the chemical structure such as cross-linking of the surface layer material or degree of polymerization. As a means for adjusting the Martens hardness by the macro structure, it is possible to adjust the surface layer unevenness and the network structure connecting the protrusions. When the organosilicon polymer is used as a surface layer, these adjustments can be made by adjusting the pH, concentration, temperature, time, etc. when pretreating the organosilicon polymer. Further, it can be adjusted by the timing, form, concentration, reaction temperature, etc. of the surface coating of the organosilicon polymer on the toner core particles.

  Particularly preferred in the present invention is the following method. First, toner core particles containing a binder resin and a colorant are produced and dispersed in an aqueous medium to obtain a core particle dispersion. The concentration at this time is preferably dispersed so that the solid content of the core particles is 10% by mass or more and 40% by mass or less with respect to the total amount of the core particle dispersion. The temperature of the core particle dispersion is preferably adjusted to 35 ° C. or higher. The pH of the core particle dispersion is preferably adjusted to a pH at which the condensation of the organosilicon compound does not proceed easily. Since the pH at which the condensation of the organosilicon polymer is difficult to proceed differs depending on the substance, it is preferably within ± 0.5, centering on the pH at which the reaction is most difficult to proceed.

  On the other hand, it is preferable to use an organosilicon compound that has been subjected to a hydrolysis treatment. For example, it is hydrolyzed in a separate container as a pretreatment of the organosilicon compound. The preparation concentration of hydrolysis is preferably 40 parts by mass or more and 500 parts by mass or less, more preferably 100 parts by mass of water from which ion content such as ion-exchanged water or RO water is removed when the amount of the organosilicon compound is 100 parts by mass. The amount is 400 parts by mass or less. The hydrolysis conditions are preferably a pH of 2 to 7, a temperature of 15 to 80 ° C., and a time of 30 to 600 minutes.

  By mixing the obtained hydrolyzate and the core particle dispersion and adjusting the pH to be suitable for condensation (preferably 6 to 12, or 1 to 3, more preferably 8 to 12), the organosilicon compound is adjusted. The surface layer can be applied to the surface of the toner core particles while being condensed. Condensation and surface layering are preferably performed at 35 ° C. or higher for 60 minutes or longer. In addition, it is possible to adjust the macro structure of the surface by adjusting the holding time at 35 ° C. or higher before adjusting to a pH suitable for condensation. However, if the time is too long, the toner having the Martens hardness of the present invention can be obtained. Since it is difficult, 3 minutes or more and 120 minutes or less are preferable.

  By the means as described above, the reaction residue can be reduced, irregularities can be formed on the surface layer, and a network structure can be formed between the projections, so that it is easy to obtain a toner having the specific Martens hardness. .

[About surface layer]
When the toner particles have a surface layer, the surface layer is a layer that covers the toner core particles and exists on the outermost surface of the toner particles. The surface layer containing the organosilicon polymer is very hard compared to conventional toner particles. Therefore, it is also preferable to provide a portion where the surface layer is not formed on a part of the toner particle surface from the viewpoint of fixing property.

[Surface layer containing organosilicon polymer]
When the toner particle has a surface layer containing an organosilicon polymer, it preferably has a partial structure represented by the formula (1).
R-SiO _3/2 formula (1)
(In the formula, R represents a hydrocarbon group having 1 to 6 carbon atoms.)

In the organosilicon polymer having the structure of the formula (1), one of the four valences of Si atoms is bonded to R, and the remaining three are bonded to O atoms. O atoms constitute a state in which two valences are both bonded to Si, that is, a siloxane bond (Si—O—Si). Considering Si atoms and O atoms as an organosilicon polymer, two Si atoms and three O atoms are expressed as —SiO _3/2 . The —SiO _3/2 structure of this organosilicon polymer is considered to have properties similar to silica (SiO ₂ ) composed of a large number of siloxane bonds. Therefore, it is considered that the Martens hardness can be increased because of the structure closer to the inorganic material than the toner formed on the surface layer of the conventional organic resin.
The ratio of the peak area of the partial structure represented by the formula (1) is the kind and amount of the organosilicon compound used for forming the organosilicon polymer, and the hydrolysis, addition polymerization and condensation polymerization of the organosilicon polymer. It can be controlled by reaction temperature, reaction time, reaction solvent and pH.

  In the partial structure represented by the formula (1), R is preferably a hydrocarbon group having 1 to 6 carbon atoms. As a result, the charge amount tends to be stable. In particular, an aliphatic hydrocarbon group having 1 to 5 carbon atoms, which is excellent in environmental stability, or a phenyl group is preferable.

  In the present invention, it is more preferable for R to be an aliphatic hydrocarbon group having 1 to 3 carbon atoms in order to further improve chargeability and antifogging. When the charging property is good, the transfer property is good and the residual toner is small, so that the contamination of the drum, the charging member and the transfer member is improved.

  Preferred examples of the aliphatic hydrocarbon group having 1 to 3 carbon atoms include a methyl group, an ethyl group, a propyl group, and a vinyl group. From the viewpoints of environmental stability and storage stability, R is more preferably a methyl group.

  As an example of producing an organosilicon polymer, a sol-gel method is preferable. The sol-gel method is a method in which a liquid raw material is used as a starting material for hydrolysis and condensation polymerization and gelation is performed through a sol state, and is used for a method of synthesizing glass, ceramics, organic-inorganic hybrid, and nanocomposite. By using this production method, functional materials having various shapes such as surface layers, fibers, bulk bodies, and fine particles can be produced from a liquid phase at a low temperature.

  Specifically, the organosilicon polymer present in the surface layer of the toner particles is preferably produced by hydrolysis and condensation polymerization of a silicon compound represented by alkoxysilane.

  By providing the toner particles with a surface layer containing this organosilicon polymer, the environmental stability is improved, and the toner performance is less likely to deteriorate during long-term use, and a toner having excellent storage stability can be obtained. .

  Further, since the sol-gel method starts with a liquid and forms the material by gelling the liquid, various microstructures and shapes can be created. In particular, when the toner particles are produced in an aqueous medium, the toner particles are easily deposited on the surface of the toner particles due to the hydrophilicity of a hydrophilic group such as a silanol group of the organosilicon compound. The fine structure and shape can be adjusted by the reaction temperature, reaction time, reaction solvent, pH, type and amount of the organometallic compound, and the like.

（式（Ｚ）中、Ｒ^１は、炭素数１以上６以下の炭化水素基を表し、Ｒ^２、Ｒ^３及びＲ^４は、それぞれ独立して、ハロゲン原子、ヒドロキシ基、アセトキシ基、又は、アルコキシ基を表す。） The organosilicon polymer on the surface layer of the toner particles is preferably a polycondensation product of an organosilicon compound having a structure represented by the following formula (Z).

(In Formula (Z), R ¹ represents a hydrocarbon group having 1 to 6 carbon atoms, and R ² , R ^3, and R ⁴ are each independently a halogen atom, a hydroxy group, an acetoxy group, or Represents an alkoxy group.)

Hydrophobicity can be improved by the hydrocarbon group (preferably an alkyl group) of R ¹ , and toner particles having excellent environmental stability can be obtained. An aryl group that is an aromatic hydrocarbon group, such as a phenyl group, can also be used as the hydrocarbon group. When the hydrophobicity of R ¹ is large, the charge amount variation tends to increase in various environments. Therefore, in view of environmental stability, R ¹ is preferably a hydrocarbon group having 1 to 3 carbon atoms, More preferred is a methyl group.

R ² , R ³ and R ⁴ are each independently a halogen atom, a hydroxy group, an acetoxy group or an alkoxy group (hereinafter also referred to as a reactive group). These reactive groups are hydrolyzed, addition-polymerized and condensation-polymerized to form a crosslinked structure, and a toner having excellent resistance to member contamination and development durability can be obtained. The hydrolyzability is moderate at room temperature, and from the viewpoints of precipitation on the surface of toner particles and coverage, an alkoxy group having 1 to 3 carbon atoms is preferable, and a methoxy group or an ethoxy group is more preferable. . The hydrolysis, addition polymerization and condensation polymerization of R ² , R ³ and R ⁴ can be controlled by the reaction temperature, reaction time, reaction solvent and pH.

In order to obtain the organosilicon polymer used in the present invention, an organosilicon compound having ^three reactive groups (R ² , R ³ and R ⁴ ) in one molecule excluding R ¹ in the formula (Z) shown above (Hereinafter also referred to as trifunctional silane) may be used alone or in combination.

Examples of the formula (Z) include the following.
Methyltrimethoxysilane, methyltriethoxysilane, methyldiethoxymethoxysilane, methylethoxydimethoxysilane, methyltrichlorosilane, methylmethoxydichlorosilane, methylethoxydichlorosilane, methyldimethoxychlorosilane, methylmethoxyethoxychlorosilane, methyldiethoxychlorosilane, methyl Triacetoxysilane, methyldiacetoxymethoxysilane, methyldiacetoxyethoxysilane, methylacetoxydimethoxysilane, methylacetoxymethoxyethoxysilane, methylacetoxydiethoxysilane, methyltrihydroxysilane, methylmethoxydihydroxysilane, methylethoxydihydroxysilane, methyldimethoxy Hydroxysilane, methylethoxymethoxyhydroxysila , Methyl diethoxy hydroxy silane, trifunctional methylsilane like.
Ethyltrimethoxysilane, ethyltriethoxysilane, ethyltrichlorosilane, ethyltriacetoxysilane, ethyltrihydroxysilane, propyltrimethoxysilane, propyltriethoxysilane, propyltrichlorosilane, propyltriacetoxysilane, propyltrihydroxysilane, butyltri Trifunctional like methoxysilane, butyltriethoxysilane, butyltrichlorosilane, butyltriacetoxysilane, butyltrihydroxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, hexyltrichlorosilane, hexyltriacetoxysilane, hexyltrihydroxysilane Sex silane.
Trifunctional phenylsilanes such as phenyltrimethoxysilane, phenyltriethoxysilane, phenyltrichlorosilane, phenyltriacetoxysilane, and phenyltrihydroxysilane.

Moreover, you may use the organosilicon polymer obtained by using together the following with the organosilicon compound which has a structure represented by a formula (Z) to such an extent that the effect of this invention is not impaired. Organosilicon compound having four reactive groups in one molecule (tetrafunctional silane), organosilicon compound having two reactive groups in one molecule (bifunctional silane), or organosilicon compound having one reactive group ( Monofunctional silane). Examples include the following.
Dimethyldiethoxysilane, tetraethoxysilane, hexamethyldisilazane, 3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3- (2-aminoethyl) aminopropyltrimethoxysilane, 3- (2-amino Ethyl) aminopropyltriethoxysilane, vinyltriisocyanatesilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyldiethoxymethoxysilane, vinylethoxydimethoxysilane, vinylethoxydihydroxysilane, vinyldimethoxyhydroxysilane, vinylethoxymethoxyhydroxysilane, Trifunctional vinyl silanes such as vinyldiethoxyhydroxysilane.

  Further, the content of the organosilicon polymer in the toner particles is preferably 0.5% by mass or more and 10.5% by mass or less.

  When the content of the organosilicon polymer is 0.5% by mass or more, the surface free energy of the surface layer can be further reduced, the fluidity is improved, and the occurrence of member contamination and fogging can be suppressed. . When it is 10.5% by mass or less, it is possible to make charge-up less likely to occur. The content of the organosilicon polymer is controlled by the type and amount of the organosilicon compound used for forming the organosilicon polymer, the method of producing the toner particles during the formation of the organosilicon polymer, the reaction temperature, the reaction time, the reaction solvent and the pH. Can do.

  The surface layer containing the organosilicon polymer and the toner core particles are preferably in contact with each other without any gap. As a result, the occurrence of bleeding due to the resin component and the release agent inside the surface layer of the toner particles is suppressed, and a toner having excellent storage stability, environmental stability, and development durability can be obtained. In addition to the above organosilicon polymer, the surface layer may contain a resin such as styrene-acrylic copolymer resin, polyester resin, urethane resin, various additives, and the like.

[Binder resin]
The toner particles contain a binder resin. The binder resin is not particularly limited, and conventionally known resins can be used. Vinyl resin, polyester resin and the like are preferable. Examples of vinyl resins, polyester resins, and other binder resins include the following resins or polymers.

  Styrene, such as polystyrene and polyvinyltoluene, and substituted homopolymers thereof; styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene -Ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-dimethylaminoethyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-methacrylic acid Ethyl copolymer, styrene-butyl methacrylate copolymer, styrene-dimethylaminoethyl methacrylate copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer Coalescence, styrene Styrene copolymers such as diene copolymer, styrene-isoprene copolymer, styrene-maleic acid copolymer, styrene-maleic acid ester copolymer; polymethyl methacrylate, polybutyl methacrylate, polyvinyl acetate, polyethylene , Polypropylene, polyvinyl butyral, silicone resin, polyamide resin, epoxy resin, polyacrylic resin, rosin, modified rosin, terpene resin, phenol resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin. These binder resins can be used alone or in combination.

  As the polyester resin, those obtained by condensation polymerization of the following carboxylic acid component and alcohol component can be used. Examples of the carboxylic acid component include terephthalic acid, isophthalic acid, phthalic acid, fumaric acid, maleic acid, cyclohexanedicarboxylic acid, and trimellitic acid. Examples of the alcohol component include bisphenol A, hydrogenated bisphenol, bisphenol A ethylene oxide adduct, bisphenol A propylene oxide adduct, glycerin, trimethylolpropane, and pentaerythritol.

  Further, the polyester resin may be a polyester resin containing a urea group. As a polyester resin, it is preferable not to cap carboxyl groups such as terminals.

  For the purpose of improving the viscosity change of the toner at high temperature, the binder resin may have a polymerizable functional group. Examples of the polymerizable functional group include a vinyl group, an isocyanate group, an epoxy group, an amino group, a carboxy group, and a hydroxy group.

[About cross-linking agent]
In order to control the molecular weight of the binder resin, a crosslinking agent may be added during the polymerization of the polymerizable monomer.

  For example, ethylene glycol dimethacrylate, ethylene glycol diacrylate, diethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, triethylene glycol diacrylate, neopentyl glycol dimethacrylate, neopentyl glycol diacrylate, divinylbenzene, bis (4 -Acryloxypolyethoxyphenyl) propane, ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, Neopentyl glycol diacrylate, diethylene glycol diacrylate, triethylene glycol Diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 200, # 400, # 600 diacrylate, dipropylene glycol diacrylate, polypropylene glycol diacrylate, polyester type diacrylate (MANDA Nippon Kayaku), and above acrylates Is changed to methacrylate.

  The addition amount of the crosslinking agent is preferably 0.001 part by mass or more and 15.000 parts by mass or less with respect to 100 parts by mass of the polymerizable monomer.

[About mold release agent]
The toner particles preferably contain a release agent. As the release agent usable for the toner particles, paraffin wax, microcrystalline wax, petroleum wax such as petrolatum and derivatives thereof, montan wax and derivatives thereof, hydrocarbon wax and derivatives thereof by Fischer-Tropsch method, polyethylene, Polyolefin wax such as polypropylene and derivatives thereof, natural wax such as carnauba wax and candelilla wax and derivatives thereof, fatty acids such as higher aliphatic alcohol, stearic acid and palmitic acid, or compounds thereof, acid amide wax, ester wax , Ketones, hydrogenated castor oil and derivatives thereof, plant waxes, animal waxes, and silicone resins. Derivatives include oxides, block copolymers with vinyl monomers, and graft modified products.

  The content of the release agent is preferably 5.0 parts by mass or more and 20.0 parts by mass or less with respect to 100.0 parts by mass of the binder resin or polymerizable monomer.

[About colorants]
The toner particles contain a colorant. The colorant is not particularly limited, and for example, the following known ones can be used.

Examples of yellow pigments include yellow iron oxide, navel yellow, naphthol yellow S, hansa yellow G, hansa yellow 10G, benzidine yellow G, benzidine yellow GR, quinoline yellow lake, permanent yellow NCG, and tartrazine lake. Isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds are used. Specific examples include the following.
C. I. Pigment Yellow 12, 13, 14, 15, 17, 62, 74, 83, 93, 94, 95, 109, 110, 111, 128, 129, 147, 155, 168, 180.

Examples of the orange pigment include the following.
Permanent orange GTR, pyrazolone orange, Vulcan orange, benzidine orange G, indanthrene brilliant orange RK, indanthrene brilliant orange GK.

Red pigments include Bengala, Permanent Red 4R, Resol Red, Pyrazolone Red, Watching Red Calcium Salt, Lake Red C, Lake D, Brilliant Carmine 6B, Brilliant Carmine 3B, Eoxin Lake, Rhodamine Lake B, Alizarin Lake, etc. Examples include azo compounds, diketopyrrolopyrrole compounds, anthraquinone compounds, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds. Specific examples include the following.
C. I. Pigment Red 2, 3, 5, 6, 7, 23, 48: 2, 48: 3, 48: 4, 57: 1, 81: 1, 122, 144, 146, 166, 169, 177, 184, 185, 202, 206, 220, 221, 254.

Blue pigments include alkali blue lake, Victoria blue lake, phthalocyanine blue, metal-free phthalocyanine blue, phthalocyanine blue partial chloride, first sky blue, indanthrene blue BG and other copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, basic dye lakes Compounds and the like. Specific examples include the following.
C. I. Pigment Blue 1, 7, 15, 15: 1, 15: 2, 15: 3, 15: 4, 60, 62, 66.

Examples of purple pigments include fast violet B and methyl violet lake.
Examples of the green pigment include Pigment Green B, Malachite Green Lake, and Final Yellow Green G.
Examples of white pigments include zinc white, titanium oxide, antimony white, and zinc sulfide.
Examples of the black pigment include carbon black, aniline black, non-magnetic ferrite, magnetite, the above-described yellow colorant, red colorant, and blue colorant, and those that are toned in black. These colorants can be used alone or in combination and further in the form of a solid solution.
If necessary, the colorant may be surface-treated with a substance that does not inhibit polymerization.

  In addition, it is preferable that content of a coloring agent is 3.0 to 15.0 mass parts with respect to 100.0 mass parts of binder resins or polymerizable monomers.

[Charge control agent]
The toner particles may contain a charge control agent. A well-known thing can be used as a charge control agent. In particular, a charge control agent that has a high charging speed and can stably maintain a constant charge amount is preferable. Further, when the toner particles are produced by a direct polymerization method, a charge control agent having a low polymerization inhibition property and substantially free from a solubilized product in an aqueous medium is particularly preferable.

Examples of the charge control agent that control the toner particles to be negatively charged include the following.
As an organic metal compound and a chelate compound, a monoazo metal compound, an acetylacetone metal compound, an aromatic oxycarboxylic acid, an aromatic dicarboxylic acid, an oxycarboxylic acid, and a dicarboxylic acid-based metal compound. Other examples include aromatic oxycarboxylic acids, aromatic mono- and polycarboxylic acids and their metal salts, anhydrides or esters, and phenol derivatives such as bisphenol. Furthermore, urea derivatives, metal-containing salicylic acid compounds, metal-containing naphthoic acid compounds, boron compounds, quaternary ammonium salts, and calixarene can be mentioned.

On the other hand, examples of the charge control agent for controlling the toner particles to be positively charged include the following.
Nigrosine modified products such as nigrosine and fatty acid metal salts; guanidine compounds; imidazole compounds; quaternary ammonium salts such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate, tetrabutylammonium tetrafluoroborate, and these Onium salts such as phosphonium salts and their lake pigments; triphenylmethane dyes and their lake pigments (including phosphotungstic acid, phosphomolybdic acid, phosphotungsten molybdic acid, tannic acid, Lauric acid, gallic acid, ferricyanide, ferrocyanide, etc.); metal salts of higher fatty acids; resin charge control agents.

  These charge control agents can be contained alone or in combination of two or more. The addition amount of these charge control agents is preferably 0.01 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the binder resin.

[External additives]
The toner particles according to the present invention can be used as a toner without external addition, but in order to improve fluidity, chargeability, cleaning properties, etc., so-called external additives such as a fluidizing agent, a cleaning aid, etc. May be added as a toner.

  Examples of the external additive include inorganic oxide fine particles composed of silica fine particles, alumina fine particles, titanium oxide fine particles, inorganic stearate compound fine particles such as aluminum stearate fine particles and zinc stearate fine particles, strontium titanate, titanium, and the like. Inorganic titanic acid compound fine particles such as zinc acid are listed. These can be used alone or in combination of two or more.

These inorganic fine particles are preferably subjected to a gloss treatment with a silane coupling agent, a titanium coupling agent, a higher fatty acid, a silicone oil or the like in order to improve heat-resistant storage stability and environmental stability. The BET specific surface area of the external additive is preferably 10 m ² / g or more and 450 m ² / g or less.

The BET specific surface area can be determined by a low temperature gas adsorption method based on a dynamic constant pressure method according to a BET method (preferably a BET multipoint method). For example, by using a specific surface area measuring apparatus (trade name: Gemini 2375 Ver. 5.0, manufactured by Shimadzu Corporation), nitrogen gas is adsorbed on the sample surface, and measurement is performed using the BET multipoint method. The BET specific surface area (m ² / g) can be calculated.

  The total addition amount of these various external additives is preferably 0.05 parts by mass or more and 5 parts by mass or less, more preferably 0.1 parts by mass or more and 3 parts by mass with respect to 100 parts by mass of the toner particles. It is as follows. In addition, various external additives may be used in combination.

[About developer]
The toner of the present invention can be used as a magnetic or nonmagnetic one-component developer, but may be mixed with a carrier and used as a two-component developer.

  As the carrier, for example, magnetic particles made of a known material such as a metal such as iron, ferrite, and magnetite, and an alloy of such metal and a metal such as aluminum or lead can be used. Among these, it is preferable to use ferrite particles. As the carrier, a coated carrier in which the surface of magnetic particles is coated with a coating agent such as a resin, a resin-dispersed carrier in which a magnetic fine powder is dispersed in a binder resin, or the like may be used.

  The carrier preferably has a volume average particle size of 15 μm to 100 μm, more preferably 25 μm to 80 μm.

[Toner particle production method]
A known method can be used for the production method of the toner particles, and a kneading and pulverizing method or a wet production method can be used. From the viewpoint of uniform particle size and shape controllability, a wet production method can be preferably used. Furthermore, examples of the wet production method include a suspension polymerization method, a dissolution suspension method, an emulsion polymerization aggregation method, and an emulsion aggregation method.

  Here, the suspension polymerization method will be described. In the suspension polymerization method, first, a polymerizable monomer for producing a binder resin, a colorant, and other additives as necessary are mixed using a dispersing machine such as a ball mill or an ultrasonic dispersing machine. A polymerizable monomer composition that is uniformly dissolved or dispersed is prepared (preparation step of polymerizable monomer composition). At this time, a polyfunctional monomer, a chain transfer agent, a wax as a release agent, a charge control agent, a plasticizer, and the like can be added as necessary. Preferred examples of the polymerizable monomer in the suspension polymerization method include the following vinyl polymerizable monomers.

  Styrene; α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert-butylstyrene, p- Styrene derivatives such as n-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene, p-phenyl styrene; methyl acrylate , Ethyl acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, n-amyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, Acrylic polymerizable monomers such as n-nonyl acrylate, cyclohexyl acrylate, benzyl acrylate, dimethyl phosphate ethyl acrylate, diethyl phosphate ethyl acrylate, dibutyl phosphate ethyl acrylate, 2-benzoyloxyethyl acrylate; methyl methacrylate, ethyl Methacrylate, n-propyl methacrylate, iso-propyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, tert-butyl methacrylate, n-amyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, n-nonyl Methacrylate, diethyl phosphate ethyl methacrylate, dibutyl phosphate Methacrylic polymerizable monomers such as toethyl methacrylate; methylene aliphatic monocarboxylic esters; vinyl esters such as vinyl acetate, vinyl propionate, vinyl benzoate, vinyl butyrate, vinyl benzoate, vinyl formate; vinyl Vinyl ethers such as methyl ether, vinyl ethyl ether, vinyl isobutyl ether; vinyl methyl ketone, vinyl hexyl ketone, vinyl isopropyl ketone.

  Next, the polymerizable monomer composition is put into an aqueous medium prepared in advance, and droplets made of the polymerizable monomer composition are desired using a stirrer or a disperser having high shearing force. To the size of the toner particles (granulation step).

  The aqueous medium in the granulation step preferably contains a dispersion stabilizer in order to control the particle size of the toner particles, sharpen the particle size distribution, and suppress coalescence of the toner particles in the production process. Dispersion stabilizers are generally roughly classified into polymers that develop a repulsive force due to steric hindrance and poorly water-soluble inorganic compounds that achieve dispersion stabilization with an electrostatic repulsive force. The fine particles of the hardly water-soluble inorganic compound are preferably used because they are dissolved by an acid or an alkali and can be easily removed by washing with an acid or an alkali after polymerization.

  As the dispersion stabilizer for the hardly water-soluble inorganic compound, those containing any of magnesium, calcium, barium, zinc, aluminum and phosphorus are preferably used. More preferably, any of magnesium, calcium, aluminum, and phosphorus is desired. Specific examples include the following.

  Magnesium phosphate, tricalcium phosphate, aluminum phosphate, zinc phosphate, magnesium carbonate, calcium carbonate, magnesium hydroxide, calcium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate, hydroxyapatide.

  An organic compound such as polyvinyl alcohol, gelatin, methylcellulose, methylhydroxypropylcellulose, ethylcellulose, sodium salt of carboxymethylcellulose, or starch may be used in combination with the dispersion stabilizer. These dispersion stabilizers are preferably used in an amount of 0.01 to 2.00 parts by mass with respect to 100 parts by mass of the polymerizable monomer.

  Furthermore, in order to refine these dispersion stabilizers, 0.001 part by mass or more and 0.1 part by mass or less of a surfactant may be used in combination with 100 parts by mass of the polymerizable monomer. Specifically, commercially available nonionic, anionic and cationic surfactants can be used. For example, sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate, potassium stearate, and calcium oleate are preferably used.

  After the granulation step or while performing the granulation step, the temperature is preferably set to 50 ° C. or higher and 90 ° C. or lower to polymerize the polymerizable monomer contained in the polymerizable monomer composition, and A particle dispersion is obtained (polymerization step).

  In the polymerization step, it is preferable to perform a stirring operation so that the temperature distribution in the container is uniform. When adding a polymerization initiator, it can carry out at arbitrary timing and required time. In addition, the temperature may be raised in the latter half of the polymerization reaction for the purpose of obtaining a desired molecular weight distribution, and in order to remove unreacted polymerizable monomers and by-products from the system, the latter half of the reaction, or the completion of the reaction. Later, part of the aqueous medium may be distilled off by distillation. The distillation operation can be performed under normal pressure or reduced pressure.

As the polymerization initiator used in the suspension polymerization method, an oil-soluble initiator is generally used. For example, the following are mentioned.
2,2′-azobisisobutyronitrile, 2,2′-azobis-2,4-dimethylvaleronitrile, 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2′-azobis-4 -Azo compounds such as methoxy-2,4-dimethylvaleronitrile; acetylcyclohexylsulfonyl peroxide, diisopropylperoxycarbonate, decanonyl peroxide, lauroyl peroxide, stearoyl peroxide, propionyl peroxide, acetyl peroxide, tert- Butylperoxy-2-ethylhexanoate, benzoyl peroxide, tert-butylperoxyisobutyrate, cyclohexanone peroxide, methyl ethyl ketone peroxide, dicumyl peroxide, tert- Peroxide-based initiators such as butyl hydroperoxide, di-tert-butyl peroxide, tert-butyl peroxypivalate, cumene hydroperoxide.

As the polymerization initiator, a water-soluble initiator may be used in combination as necessary, and the following may be mentioned.
Ammonium persulfate, potassium persulfate, 2,2'-azobis (N, N'-dimethyleneisobutyroamidine) hydrochloride, 2,2'-azobis (2-aminodinopropane) hydrochloride, azobis (isobutylamidine) Hydrochloride, sodium 2,2′-azobisisobutyronitrile sulfonate, ferrous sulfate or hydrogen peroxide.

  These polymerization initiators can be used singly or in combination, and a chain transfer agent, a polymerization inhibitor and the like can be further added and used in order to control the degree of polymerization of the polymerizable monomer.

  The toner particles preferably have a weight average particle size of 3.0 μm or more and 10.0 μm or less from the viewpoint of obtaining a high-definition and high-resolution image. The weight average particle diameter of the toner can be measured by a pore electrical resistance method. For example, it can be measured using “Coulter Counter Multisizer 3” (manufactured by Beckman Coulter, Inc.). The toner particle dispersion thus obtained is sent to a filtration step for solid-liquid separation of the toner particles and the aqueous medium.

  Solid-liquid separation for obtaining toner particles from the obtained toner particle dispersion can be carried out by a general filtration method. Thereafter, in order to remove foreign substances that could not be removed from the toner particle surface, reslurry or washing water is used. It is preferable to perform further washing, such as by overwashing. After sufficient washing, solid-liquid separation is performed again to obtain a toner cake. Thereafter, it is dried by a known drying means, and if necessary, a particle group having a particle diameter outside the predetermined range is separated by classification to obtain toner particles. The separated particles having a particle size outside the predetermined range may be reused to improve the final yield.

  In the case of forming a surface layer having an organosilicon polymer, when forming toner particles in an aqueous medium, a hydrolyzing solution of an organosilicon compound is added as described above while performing a polymerization step in the aqueous medium. The surface layer can be formed. The surface layer may be formed by adding a hydrolyzed liquid of an organosilicon compound using a dispersion of toner particles after polymerization as a core particle dispersion. Further, in the case of other than an aqueous medium such as a kneading pulverization method, the obtained toner particles are dispersed in an aqueous medium and used as a core particle dispersion, and an organic silicon compound hydrolyzed solution is added as described above, and the surface layer is added. Can be formed.

[Combination with protective layer]
The reason why the combination of the toner having the organosilicon polymer of the present invention as a surface layer and the electrophotographic photosensitive member having a protective layer contributes to a reduction in torque of the process cartridge and an improvement in the cleaning property by a synergistic effect will be described.

  The electrophotographic photoreceptor having the protective layer of the present invention has a Martens hardness of 200 MPa to 280 MPa, preferably 245 MPa to 280 MPa. This is because when the Martens hardness is within the above-mentioned range, the hard surface toner and the hard protective layer photoreceptor each have point contact due to the high surface hardness due to the external pressure, and exhibit the effect of reducing torque. It is inferred. Further, since it becomes point contact, it is presumed that the friction frequency between the toner surface layer and the protective layer of the photosensitive member is reduced, the friction resistance is improved, and the effect of improving the cleaning property is exhibited.

  In order to make the protective layer within the above-mentioned range of physical properties, it can be achieved by having a partial structure described later, optimizing the polymerization conditions of the photosensitive member in a timely manner, and the like.

  The surface layer as the protective layer of the electrophotographic photosensitive member has a ten-point average roughness Rzjis = 0.4 μm to 0.6 μm and an average length Rsm of the roughness curve element = 00.005 mm to 0.020 mm. It is more preferable to have the shape of When the roughness of the protective layer is within this range, it is possible to increase the chance of point contact between the cleaning blade and the surface of the photosensitive member while ensuring sufficient cleaning performance, and from the viewpoint of reducing torque. A higher effect can be expressed. If the roughness of the photoconductor satisfies the above range, the effect is effectively exhibited. However, the shape of the groove on the peripheral surface of the photoconductor is preferably the groove shape. As an example of the roughening means of the protective layer, polishing using a polishing sheet can be mentioned. The abrasive sheet is a sheet-like abrasive member in which a layer in which abrasive grains are dispersed in a binder resin is provided on a sheet base material. The surface of the protective layer having a groove shape can be roughened by pressing the abrasive sheet and the surface of the protective layer and feeding the sheet. A detailed roughening method will be described later.

  As described above, the effects of the present invention can be achieved by the effects of the constitutions of the toner having the organosilicon polymer in the surface layer and the electrophotographic photoreceptor having the specific structure and physical properties in the protective layer. It becomes possible.

[Electrophotographic photoconductor]
The electrophotographic photosensitive member according to an aspect of the present invention includes a support, and a photosensitive layer and a protective layer on the support.

  Examples of the method for producing the electrophotographic photoreceptor of the present invention include a method in which a coating solution for each layer described later is prepared, applied in the order of desired layers, and dried. At this time, examples of the coating method of the coating liquid include dip coating, spray coating, inkjet coating, roll coating, die coating, blade coating, curtain coating, wire bar coating, and ring coating. Among these, dip coating is preferable from the viewpoints of efficiency and productivity.

Hereinafter, each layer will be described.
<Support>
In the present invention, the support is preferably a conductive support having conductivity. Moreover, examples of the shape of the support include a cylindrical shape, a belt shape, and a sheet shape. Among these, a cylindrical support is preferable. Further, the surface of the support may be subjected to electrochemical treatment such as anodic oxidation, blast treatment, cutting treatment or the like.
As the material for the support, metal, resin, glass and the like are preferable.
Examples of the metal include aluminum, iron, nickel, copper, gold, stainless steel, and alloys thereof. Among these, an aluminum support using aluminum is preferable.
In addition, the resin or glass may be imparted with conductivity by a treatment such as mixing or coating with a conductive material.

<Conductive layer>
In the present invention, a conductive layer may be provided on the support. By providing the conductive layer, it is possible to conceal scratches and irregularities on the surface of the support and to control light reflection on the surface of the support.
The conductive layer preferably contains conductive particles and a resin.

Examples of the material of the conductive particles include metal oxide, metal, carbon black and the like.
Examples of the metal oxide include zinc oxide, aluminum oxide, indium oxide, silicon oxide, zirconium oxide, tin oxide, titanium oxide, magnesium oxide, antimony oxide, and bismuth oxide. Examples of the metal include aluminum, nickel, iron, nichrome, copper, zinc, silver and the like.
Among these, it is preferable to use a metal oxide as the conductive particles, and it is particularly preferable to use titanium oxide, tin oxide, or zinc oxide.
When a metal oxide is used as the conductive particles, the surface of the metal oxide may be treated with a silane coupling agent or the like, or an element such as phosphorus or aluminum or an oxide thereof may be doped into the metal oxide.
Further, the conductive particles may have a laminated structure including core material particles and a coating layer that covers the particles. Examples of the core material particles include titanium oxide, barium sulfate, and zinc oxide. Examples of the coating layer include metal oxides such as tin oxide.
Moreover, when using a metal oxide as electroconductive particle, it is preferable that the volume average particle diameters are 1 nm or more and 500 nm or less, and it is more preferable that they are 3 nm or more and 400 nm or less.

Examples of the resin include polyester resin, polycarbonate resin, polyvinyl acetal resin, acrylic resin, silicone resin, epoxy resin, melamine resin, polyurethane resin, phenol resin, alkyd resin, and the like.
The conductive layer may further contain a masking agent such as silicone oil, resin particles, and titanium oxide.

  The average film thickness of the conductive layer is preferably 1 μm or more and 50 μm or less, and particularly preferably 3 μm or more and 40 μm or less.

  The conductive layer can be formed by preparing a coating liquid for a conductive layer containing each of the above materials and solvent, forming this coating film, and drying it. Examples of the solvent used for the coating solution include alcohol solvents, sulfoxide solvents, ketone solvents, ether solvents, ester solvents, and aromatic hydrocarbon solvents. Examples of the dispersion method for dispersing the conductive particles in the coating liquid for the conductive layer include a method using a paint shaker, a sand mill, a ball mill, and a liquid collision type high-speed disperser.

<Underlayer>
In the present invention, an undercoat layer may be provided on the support or the conductive layer. By providing the undercoat layer, the adhesion function between the layers can be enhanced, and a charge injection blocking function can be provided.

  The undercoat layer preferably contains a resin. Moreover, you may form an undercoat layer as a cured film by superposing | polymerizing the composition containing the monomer which has a polymerizable functional group.

  Polyester resin, polycarbonate resin, polyvinyl acetal resin, acrylic resin, epoxy resin, melamine resin, polyurethane resin, phenol resin, polyvinyl phenol resin, alkyd resin, polyvinyl alcohol resin, polyethylene oxide resin, polypropylene oxide resin, polyamide resin , Polyamic acid resin, polyimide resin, polyamideimide resin, cellulose resin and the like.

  As the polymerizable functional group that the monomer having a polymerizable functional group has, an isocyanate group, a blocked isocyanate group, a methylol group, an alkylated methylol group, an epoxy group, a metal alkoxide group, a hydroxyl group, an amino group, a carboxyl group, a thiol group, Examples thereof include a carboxylic acid anhydride group and a carbon-carbon double bond group.

The undercoat layer may further contain an electron transport material, a metal oxide, a metal, a conductive polymer, and the like for the purpose of improving electrical characteristics. Among these, it is preferable to use an electron transport material and a metal oxide.
Examples of the electron transport material include quinone compounds, imide compounds, benzimidazole compounds, cyclopentadienylidene compounds, fluorenone compounds, xanthone compounds, benzophenone compounds, cyanovinyl compounds, halogenated aryl compounds, silole compounds, and boron-containing compounds. . An undercoat layer may be formed as a cured film by using an electron transport material having a polymerizable functional group as the electron transport material and copolymerizing with the monomer having the polymerizable functional group described above.
Examples of the metal oxide include indium tin oxide, tin oxide, indium oxide, titanium oxide, zinc oxide, aluminum oxide, and silicon dioxide. Examples of the metal include gold, silver, and aluminum.
The undercoat layer may further contain an additive.

  The average thickness of the undercoat layer is preferably from 0.1 μm to 50 μm, more preferably from 0.2 μm to 40 μm, and particularly preferably from 0.3 μm to 30 μm.

  The undercoat layer can be formed by preparing a coating solution for the undercoat layer containing the above-described materials and solvent, forming this coating film, and drying and / or curing it. Examples of the solvent used for the coating solution include alcohol solvents, ketone solvents, ether solvents, ester solvents, and aromatic hydrocarbon solvents.

<Photosensitive layer>
The photosensitive layer of the electrophotographic photoreceptor is mainly classified into (1) a multilayer type photosensitive layer and (2) a single layer type photosensitive layer. (1) The laminated photosensitive layer has a charge generation layer containing a charge generation material and a charge transport layer containing a charge transport material. (2) The single-layer type photosensitive layer has a photosensitive layer containing both a charge generation material and a charge transport material.

(1) Laminated Photosensitive Layer The laminated photosensitive layer has a charge generation layer and a charge transport layer.

(1-1) Charge Generation Layer The charge generation layer preferably contains a charge generation material and a resin.

  Examples of the charge generation material include azo pigments, perylene pigments, polycyclic quinone pigments, indigo pigments, and phthalocyanine pigments. Among these, azo pigments and phthalocyanine pigments are preferable. Among the phthalocyanine pigments, oxytitanium phthalocyanine pigments, chlorogallium phthalocyanine pigments, and hydroxygallium phthalocyanine pigments are preferable.

  The content of the charge generation material in the charge generation layer is preferably 40% by mass to 85% by mass and more preferably 60% by mass to 80% by mass with respect to the total mass of the charge generation layer. preferable.

  The resin includes polyester resin, polycarbonate resin, polyvinyl acetal resin, polyvinyl butyral resin, acrylic resin, silicone resin, epoxy resin, melamine resin, polyurethane resin, phenol resin, polyvinyl alcohol resin, cellulose resin, polystyrene resin, polyvinyl acetate resin. And polyvinyl chloride resin. Among these, polyvinyl butyral resin is more preferable.

  The charge generation layer may further contain additives such as an antioxidant and an ultraviolet absorber. Specific examples include hindered phenol compounds, hindered amine compounds, sulfur compounds, phosphorus compounds, and benzophenone compounds.

  The average film thickness of the charge generation layer is preferably from 0.1 μm to 1 μm, and more preferably from 0.15 μm to 0.4 μm.

  The charge generation layer can be formed by preparing a coating solution for a charge generation layer containing the above-described materials and solvent, forming this coating film, and drying it. Examples of the solvent used for the coating solution include alcohol solvents, sulfoxide solvents, ketone solvents, ether solvents, ester solvents, and aromatic hydrocarbon solvents.

(1-2) Charge Transport Layer The charge transport layer preferably contains a charge transport material and a resin.

Examples of the charge transport material include polycyclic aromatic compounds, heterocyclic compounds, hydrazone compounds, styryl compounds, enamine compounds, benzidine compounds, triarylamine compounds, and resins having groups derived from these materials. It is done. Among these, a triarylamine compound and a benzidine compound are preferable.
The content of the charge transport material in the charge transport layer is preferably 25% by mass to 70% by mass and more preferably 30% by mass to 55% by mass with respect to the total mass of the charge transport layer. preferable.

Examples of the resin include polyester resin, polycarbonate resin, acrylic resin, and polystyrene resin. Among these, polycarbonate resin and polyester resin are preferable. As the polyester resin, polyarylate resin is particularly preferable.
The content ratio (mass ratio) between the charge transport material and the resin is preferably 4:10 to 20:10, and more preferably 5:10 to 12:10.

  Further, the charge transport layer may contain additives such as an antioxidant, an ultraviolet absorber, a plasticizer, a leveling agent, a slipperiness imparting agent, and an abrasion resistance improving agent. Specifically, hindered phenol compounds, hindered amine compounds, sulfur compounds, phosphorus compounds, benzophenone compounds, siloxane-modified resins, silicone oil, fluorine resin particles, polystyrene resin particles, polyethylene resin particles, silica particles, alumina particles, boron nitride particles Etc.

  The average film thickness of the charge transport layer is preferably 5 μm or more and 50 μm or less, more preferably 8 μm or more and 40 μm or less, and particularly preferably 10 μm or more and 30 μm or less.

  The charge transport layer can be formed by preparing a coating solution for a charge transport layer containing the above-mentioned materials and solvent, forming this coating film, and drying it. Examples of the solvent used for the coating solution include alcohol solvents, ketone solvents, ether solvents, ester solvents, and aromatic hydrocarbon solvents. Among these solvents, ether solvents or aromatic hydrocarbon solvents are preferable.

(2) Single-layer type photosensitive layer A single-layer type photosensitive layer is formed by preparing a coating solution for a photosensitive layer containing a charge generating substance, a charge transporting substance, a resin and a solvent, forming this coating film, and drying it. can do. Examples of the charge generating substance, the charge transporting substance, and the resin are the same as those exemplified in the above-mentioned “(1) Multilayer type photosensitive layer”.

<Protective layer>
In the present invention, the electrophotographic photosensitive member is provided with a protective layer on the photosensitive layer. As described above, the protective layer as the surface layer has a Martens hardness of 200 MPa to 280 MPa, preferably 245 MPa to 280 MPa.

  The protective layer may be formed as a cured film by polymerizing a composition containing a monomer having a polymerizable functional group. Examples of the reaction at that time include a thermal polymerization reaction, a photopolymerization reaction, and a radiation polymerization reaction. Examples of the polymerizable functional group possessed by the monomer having a polymerizable functional group include an acryl group and a methacryl group. As the monomer having a polymerizable functional group, a material having a charge transporting ability may be used.

Examples of the monomer having a polymerizable functional group having charge transporting ability include the following compounds.

  The protective layer may contain additives such as an antioxidant, an ultraviolet absorber, a plasticizer, a leveling agent, a slipperiness imparting agent, and an abrasion resistance improver. Specifically, hindered phenol compounds, hindered amine compounds, sulfur compounds, phosphorus compounds, benzophenone compounds, siloxane-modified resins, silicone oil, fluorine resin particles, polystyrene resin particles, polyethylene resin particles, silica particles, alumina particles, boron nitride particles Etc.

The protective layer may contain conductive particles and / or a charge transport material and a resin.
Examples of the conductive particles include metal oxide particles such as titanium oxide, zinc oxide, tin oxide, and indium oxide.
Examples of the charge transport material include polycyclic aromatic compounds, heterocyclic compounds, hydrazone compounds, styryl compounds, enamine compounds, benzidine compounds, triarylamine compounds, and resins having groups derived from these materials. Among these, a triarylamine compound and a benzidine compound are preferable.
Examples of the resin include polyester resin, acrylic resin, phenoxy resin, polycarbonate resin, polystyrene resin, phenol resin, melamine resin, and epoxy resin. Among these, polycarbonate resin, polyester resin, and acrylic resin are preferable.

  The average film thickness of the protective layer is preferably 0.5 μm or more and 10 μm or less, and preferably 1 μm or more and 7 μm or less.

  The protective layer can be formed by preparing a coating liquid for the protective layer containing each of the above materials and solvent, forming this coating film, and drying and / or curing it. Examples of the solvent used for the coating solution include alcohol solvents, ketone solvents, ether solvents, sulfoxide solvents, ester solvents, and aromatic hydrocarbon solvents.

[Measurement method of toner properties]
<Measurement of Martens hardness of toner>
The method for measuring the Martens hardness of the toner by the nano-indentation method is calculated from the obtained load-displacement curve in accordance with the procedure of the indentation test specified in ISO 14577-1 using a commercially available apparatus conforming to ISO 14577-1. be able to. In the present invention, an ultra-fine indentation hardness tester “ENT-1100b” (manufactured by Elionix Co., Ltd.) was used as an apparatus conforming to the ISO standard. The measurement method is described in the “ENT1100 operation manual” attached to the apparatus. The specific measurement method is as follows.

  The measurement environment was maintained at 30.0 ° C. inside the shield case with the attached temperature control device. Keeping the ambient temperature constant is effective in reducing variations in measurement data due to thermal expansion and drift. The set temperature was set at 30.0 ° C. assuming a temperature in the vicinity of the developing machine where the toner is rubbed. The sample stage used was a standard sample stage attached to the apparatus. After applying the toner, weak air was blown so that the toner was dispersed, and the sample stage was set on the apparatus and held for 1 hour or more, and then the measurement was performed. .

The indenter was measured using a flat indenter (titanium indenter, tip made of diamond) having a 20 μm square tip attached to the apparatus. A flat indenter is used for a small-diameter and spherical object such as a toner, an object to which an external additive is attached, or an object having irregularities on the surface, because the use of a sharp indenter greatly affects the measurement accuracy. The maximum load of the test is set to 2.0 × 10 ⁻⁴ N. By setting this test load, it is possible to measure the hardness without destroying the surface layer of the toner under the condition corresponding to the stress applied to one toner particle in the developing portion. In the present invention, since friction resistance is important, it is important to measure hardness while maintaining the surface layer without breaking.

  As the particles to be measured, particles having a toner alone on a measurement screen (field size: 160 μm width, 120 μm width) with a microscope attached to the apparatus are selected. However, in order to eliminate the displacement error as much as possible, the particle diameter (D) is in the range of ± 0.5 μm of the number average particle diameter (D1) (D1−0.5 μm ≦ D ≦ D1 + 0.5 μm). . The particle size of the particles to be measured was measured by measuring the major axis and minor axis of the toner using software attached to the apparatus, and [(major axis + minor axis) / 2] was defined as the particle diameter D (μm). The number average particle diameter is measured by “Coulter Counter Multisizer 3” (manufactured by Beckman Coulter, Inc.) by the method described later.

In measurement, 100 arbitrary toner particles whose particle diameter D (μm) satisfies the above conditions are selected and measured. The conditions input at the time of measurement are as follows.
Test mode: Load-unloading test Test load: 20.000 mgf (= 2.0 × 10 ⁻⁴ N)
Number of divisions: 1000 steps
Step interval: 10msec
When measurement is performed by selecting “Data Analysis (ISO)” from the analysis menu, the Martens hardness is analyzed and output by the software attached to the apparatus after the measurement. The above measurement was performed on 100 toner particles, and the arithmetic average value was defined as the Martens hardness in the present invention.

<Measurement of content of organosilicon polymer in toner particles>
The content of the organosilicon polymer is measured using a wavelength dispersive X-ray fluorescence analyzer “Axios” (manufactured by PANalytical) and attached dedicated software “SuperQ ver.4. 0F "(manufactured by PANalytical) is used. Note that Rh is used as the anode of the X-ray tube, the measurement atmosphere is vacuum, the measurement diameter (collimator mask diameter) is 27 mm, and the measurement time is 10 seconds. Further, when measuring a light element, it is detected by a proportional counter (PC), and when measuring a heavy element, it is detected by a scintillation counter (SC).

  As a measurement sample, 4 g of toner particles were put in a dedicated aluminum ring for press and leveled, and a tablet molding compressor “BRE-32” (manufactured by Maekawa Test Instruments Co., Ltd.) was used. Pellets that have been pressed for 2 seconds and formed into a thickness of 2 mm and a diameter of 39 mm are used.

Silica (SiO ₂ ) fine powder is added to 0.5 parts by mass with respect to 100 parts by mass of toner particles not containing an organosilicon polymer, and sufficiently mixed using a coffee mill. Similarly, the silica fine powder is mixed with the toner particles so as to be 5.0 parts by mass and 10.0 parts by mass, respectively, and these are used as samples for the calibration curve.

For each sample, a pellet for a calibration curve was prepared as described above using a tablet molding compressor, and the diffraction angle (2θ) was observed at 109.08 ° when PET was used as a spectroscopic crystal. The counting rate (unit: cps) of Si-Kα rays is measured. At this time, the acceleration voltage and current value of the X-ray generator are 24 kV and 100 mA, respectively. A calibration curve of a linear function is obtained with the X-ray count rate obtained on the vertical axis and the added amount of SiO ₂ in each calibration curve sample on the horizontal axis.

  Next, the toner to be analyzed is pelletized as described above using a tablet molding compressor, and the Si-Kα ray count rate is measured. Then, the organosilicon polymer content in the toner is determined from the above calibration curve.

<Method for preparing THF-insoluble matter in toner particles for NMR measurement>
The tetrahydrofuran (THF) insoluble matter in the toner particles was prepared as follows.
10.0 g of toner particles are weighed, put into a cylindrical filter paper (No. 86R, manufactured by Toyo Filter Paper), and passed through a Soxhlet extractor. Extraction was carried out for 20 hours using 200 mL of THF as a solvent, and the residue obtained by vacuum drying the filtrate in the cylindrical filter paper at 40 ° C. for several hours was defined as the THF-insoluble content of the toner particles for NMR measurement.

If the surface of the toner particles is treated with an external additive or the like, the external additive is removed by the following method to obtain toner particles.
160 g of sucrose (manufactured by Kishida Chemical Co., Ltd.) is added to 100 mL of ion-exchanged water, and dissolved with a water bath to prepare a sucrose concentrate. 31g of the above sucrose concentrate in a centrifuge tube (capacity: 50mL) and 10 of neutral detergent for cleaning precision instruments with pH 7 consisting of Contaminone N (nonionic surfactant, anionic surfactant, organic builder) 6 mL of a mass% aqueous solution (manufactured by Wako Pure Chemical Industries, Ltd.) is added to prepare a dispersion. To this dispersion, 1.0 g of toner is added, and the mass of toner is loosened with a spatula or the like.
The centrifuge tube is shaken with a shaker at 350 spm (strokes per min) for 20 minutes. After shaking, the solution is replaced with a glass tube for swing rotor (capacity 50 mL), and separated with a centrifuge (H-9R manufactured by Kokusan Co., Ltd.) at 3500 rpm for 30 minutes. By this operation, the toner particles are separated from the detached external additive. It is visually confirmed that the toner and the aqueous solution are sufficiently separated, and the toner separated in the uppermost layer is collected with a spatula or the like. The collected toner is filtered with a vacuum filter and then dried with a dryer for 1 hour or longer to obtain toner particles. Perform this operation multiple times to ensure the required amount.

<The confirmation method of the partial structure represented by Formula (1)>
The following method is used to confirm the partial structure represented by the formula (1) in the organosilicon polymer contained in the toner particles.
The hydrocarbon group represented by R in the formula (1) was confirmed by ¹³ C-NMR.
(Measurement conditions for ¹³ C-NMR (solid))
Apparatus: JNM-ECX500II manufactured by JEOL RESONANCE
Sample tube: 3.2 mmφ
Sample: 150 mg of tetrahydrofuran insoluble in toner particles for NMR measurement
Measurement temperature: Room temperature Pulse mode: CP / MAS
Measurement nuclear frequency: 123.25 MHz ( ¹³ C)
Reference substance: adamantane (external standard: 29.5 ppm)
Sample rotation speed: 20 kHz
Contact time: 2ms
Delay time: 2s
Integration count: 1024 times

In this method, a methyl group (Si—CH ₃ ), an ethyl group (Si—C ₂ H ₅ ), a propyl group (Si—C ₃ H ₇ ), a butyl group (Si—C ₄ ) bonded to a silicon atom. H ₉ ), pentyl group (Si—C ₅ H ₁₁ ), hexyl group (Si—C ₆ H ₁₃ ) or phenyl group (Si—C ₆ H ₅ —) The hydrocarbon group represented by R was confirmed.
In addition, when it is necessary to confirm the partial structure represented by the formula (1) in more detail, it may be identified by the measurement result of ¹ H-NMR together with the measurement result of ¹³ C-NMR.

<Measurement of toner particle size>
A precision particle size distribution measuring apparatus (trade name: Coulter Counter Multisizer 3) by a pore electrical resistance method and dedicated software (trade name: Beckman Coulter Multisizer 3 Version 3.51, manufactured by Beckman Coulter, Inc.) are used. The aperture diameter is 100 μm, the number of effective measurement channels is 25,000, the measurement data is analyzed and calculated. 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 (trade name) manufactured by Beckman Coulter, Inc. can be used. Prior to measurement and analysis, the dedicated software is set as follows.

In the “standard measurement method (SOM) change screen” of the dedicated software, set the total count in the control mode to 50000 particles, the measurement count is 1 time, and the Kd value is (standard particle 10.0 μm, Beckman Coulter, Inc. Set the value obtained using The threshold and noise level are automatically set by pressing the threshold / noise level measurement button. Also, the current is set to 1600 μA, the gain is set to 2, the electrolyte is set to ISOTON II (trade name), and the aperture tube flash 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 or more and 60 μm or less.

The specific measurement method is as follows.
(1) About 200 mL of the electrolytic solution is placed in a glass 250 mL round-bottom beaker dedicated to Multisizer 3, set on a sample stand, and the stirrer rod is stirred counterclockwise at 24 rpm. Then, dirt and bubbles in the aperture tube are removed by the “aperture flush” function of the analysis software.
(2) About 30 mL of the electrolytic solution is placed in a glass 100 mL flat bottom beaker. Here, a diluted solution obtained by diluting Contaminone N (trade name) (10% by weight aqueous solution of a neutral detergent for precision measuring instrument washing, manufactured by Wako Pure Chemical Industries, Ltd.) 3 times by weight with ion-exchanged water was about 0.00. Add 3 mL.
(3) Two oscillators with an oscillation frequency of 50 kHz are incorporated in a state where the phase is shifted by 180 degrees, and an ultrasonic disperser having an electric output of 120 W (trade name: Ultrasonic Dispersion System Tetora 150, manufactured by Nikka Bios Co., Ltd.)
A predetermined amount of ion-exchanged water and about 2 mL of Contaminone N (trade name) are added to
(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) About 10 mg of toner (particles) is added to the electrolytic aqueous solution little by little in a state where the electrolytic aqueous solution in the beaker of (4) is irradiated with ultrasonic waves, and dispersed. Then, the ultrasonic dispersion process is continued for another 60 seconds. In 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) The electrolytic solution (5) in which the toner (particles) is dispersed with a pipette is dropped into the round bottom beaker (1) installed in the sample stand so that the measured concentration becomes about 5%. Adjust to. 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 with the dedicated software is the weight average particle diameter (D4). When the graph / number% is set in the dedicated software, the “average diameter” on the “analysis / number statistics (arithmetic average)” screen is the number average particle diameter (D1).

[Method for measuring physical properties of electrophotographic photosensitive member]
<Measurement of electrophotographic photoreceptor hardness>
The electrophotographic photoreceptor hardness was measured in a 25 ° C./50% RH environment using a microhardness measuring device Fischerscope H100V (Fischer).
The measurement conditions were measured using a Fischer hardness meter (trade name: H100VP-HCU, manufactured by Fischer) in an environment of a temperature of 23 ° C. and a humidity of 50% RH. Using a Vickers square pyramid diamond indenter with a face angle of 136 ° as the indenter, press the diamond indenter into the surface of the protective layer to be measured, apply a load to 2 mN over 7 seconds, and then gradually decrease it over 7 seconds. The indentation depth until the load reached 0 mN was continuously measured. From the result, Martens hardness was determined.

<Measurement of electrophotographic photoreceptor roughness>
The surface roughness of the protective layer of the electrophotographic photosensitive member after polishing was measured under the following conditions using a surface roughness measuring machine (trade name: SE700, SMB-9, manufactured by Kosaka Laboratory Ltd.). .
Measured in the longitudinal direction of the electrophotographic photosensitive member at a position of 30, 70, 150, 210 mm from the upper end of the coating. Measured in position. Furthermore, after rotating 120 degrees forward, the same measurement was performed, and a total of 12 points were measured. The average value was a ten-point average roughness measured by sweeping in the circumferential direction according to JIS B 0601-2001 standard. The average interval (RSm) measured by sweeping in the circumferential direction (Rzjis) was obtained. The measurement conditions were as follows: measurement length: 2.5 mm, cut-off value: 0.8 mm, feed rate: 0.1 mm / s, filter characteristics: 2CR, leveling: straight line (whole area).

[Image forming apparatus]
An image forming apparatus according to an aspect of the present invention develops an electrostatic latent image formed on an electrophotographic photosensitive member using toner stored in a toner storage unit, and forms a toner image. A transfer means for transferring the toner image on the photographic photosensitive member to a transfer material; and a cleaning means for removing the toner on the electrophotographic photosensitive member by bringing a blade into contact with the electrophotographic photosensitive member after the transfer step. And
The toner has toner particles containing a binder resin and a colorant, and has a Martens hardness of 200 MPa to 1100 MPa when measured under a maximum load of 2.0 × 10 ⁻⁴ N. The photoreceptor has a support, a photosensitive layer, and a protective layer as a surface layer, and the protective layer has a Martens hardness of 200 MPa to 280 MPa.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In the examples and comparative examples, “part” and “%” of each material are all based on mass unless otherwise specified.

[Production of Toner 1]
(Preparation process of aqueous medium 1)
To 1000.0 parts of ion-exchanged water in the reaction vessel, 14.0 parts of sodium phosphate (Rasa Industrial Co., Ltd., 12 hydrate) was added and kept at 65 ° C. for 1.0 hour while purging with nitrogen.
T.A. K. Using a homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), while stirring at 12,000 rpm, collect an aqueous solution of calcium chloride in which 9.2 parts of calcium chloride (dihydrate) is dissolved in 10.0 parts of ion-exchanged water. The aqueous medium containing the dispersion stabilizer was prepared. Furthermore, 10% by mass hydrochloric acid was added to the aqueous medium, and the pH was adjusted to 5.0, whereby an aqueous medium 1 was obtained.

(Hydrolysis process of organosilicon compound for surface layer)
In a reaction vessel equipped with a stirrer and a thermometer, 60.0 parts of ion-exchanged water was weighed and the pH was adjusted to 3.0 using 10% by mass hydrochloric acid. This was heated with stirring to bring the temperature to 70 ° C. Thereafter, 40.0 parts of methyltriethoxysilane, which is an organosilicon compound for the surface layer, was added and stirred for 2 hours or longer to conduct hydrolysis. The end point of hydrolysis was confirmed by visual observation that the oil and water were not separated and became one layer, and cooled to obtain a hydrolyzed liquid of the organosilicon compound for the surface layer.

(Preparation process of polymerizable monomer composition)
-Styrene: 60.0 parts-C.I. I. Pigment Blue 15: 3: 6.5 parts The above material was put into an attritor (manufactured by Mitsui Miike Chemical Co., Ltd.), and further dispersed using a zirconia particle having a diameter of 1.7 mm at 220 rpm for 5.0 hours. A dispersion was prepared. The following materials were added to the pigment dispersion.
Styrene: 20.0 parts n-Butyl acrylate: 20.0 parts Crosslinking agent (divinylbenzene): 0.3 parts Saturated polyester resin: 5.0 parts (Propylene oxide modified bisphenol A (2 mol adduct) And terephthalic acid polycondensate (molar ratio 10:12), glass transition temperature Tg = 68 ° C., weight average molecular weight Mw = 10000, molecular weight distribution Mw / Mn = 5.12)
Fischer-Tropsch wax (melting point: 78 ° C.): 7.0 parts Keep this at 65 ° C. K. Using a homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), the solution was uniformly dissolved and dispersed at 500 rpm to prepare a polymerizable monomer composition.

(Granulation process)
The temperature of the aqueous medium 1 is 70 ° C. K. While maintaining the rotation speed of the homomixer at 12000 rpm, the polymerizable monomer composition was charged into the aqueous medium 1, and 9.0 parts of t-butyl peroxypivalate as a polymerization initiator was added. The mixture was granulated for 10 minutes while maintaining 12000 rpm with the stirring device.

(Polymerization process)
After the granulation step, the stirrer is replaced with a propeller stirring blade and polymerization is carried out for 5.0 hours while maintaining at 70 ° C. while stirring at 150 rpm, and then heated to 85 ° C. and heated for 2.0 hours. To obtain core particles. When the pH of the slurry was measured after cooling to 55 ° C., the pH was 5.0. With the stirring continued at 55 ° C., 20.0 parts of a hydrolyzed liquid of the organosilicon compound for the surface layer was added to start the toner surface layer formation. After maintaining for 30 minutes, the slurry was adjusted to pH = 9.0 for completion of condensation using an aqueous sodium hydroxide solution and further maintained for 300 minutes to form a surface layer.

(Washing and drying process)
After completion of the polymerization process, the toner particle slurry is cooled, hydrochloric acid is added to the toner particle slurry, the pH is adjusted to 1.5 or lower, and the mixture is left to stir for 1 hour, and then solid-liquid separated with a pressure filter, and the toner cake Got. This was reslurried with ion-exchanged water to obtain a dispersion again, followed by solid-liquid separation with the aforementioned filter. Reslurry and solid-liquid separation were repeated until the electric conductivity of the filtrate was 5.0 μS / cm or less, and finally solid-liquid separation was performed to obtain a toner cake.
The obtained toner cake was dried with an air-flow dryer, a flash jet dryer (manufactured by Seishin Enterprise Co., Ltd.), and fine particles were cut using a multi-division classifier utilizing the Coanda effect to obtain toner particles 1. The drying conditions were adjusted such that the blowing temperature was 90 ° C., the dryer outlet temperature was 40 ° C., and the toner cake feed rate was adjusted so that the outlet temperature did not deviate from 40 ° C. according to the moisture content of the toner cake.
The obtained toner particles 1 were used as toner 1 as they were without external addition. The physical properties of Toner 1 are shown in Table 1.

[Production of Toners 2 to 4]
A toner was prepared in the same manner as in Example 1 except that the conditions for adding the hydrolyzed liquid in (polymerization step) and the retention time after the addition were changed as shown in Table 1. The pH of the slurry was adjusted with hydrochloric acid and sodium hydroxide aqueous solution. Table 1 shows the physical properties of the obtained toner.

[Production of Toners 5 to 9]
A toner was prepared in the same manner as in Example 1, except that the surface-layer organosilicon compound used in the (surface-layer organosilicon compound hydrolysis step) was changed as shown in Table 1. Table 1 shows the physical properties of the obtained toner.

[Production of Toner 10]
Toner 10 was prepared by externally adding toner particles 1. In the external addition method, 0.2 part of the external additive DHT-4A (manufactured by Kyowa Chemical Industry Co., Ltd.) is added to SUPERMIXER PICCOLO SMP-2 (manufactured by Kawata Co., Ltd.) with respect to 100 parts of the toner particles, and 3000 rpm. And mixed for 10 minutes. Table 1 shows the physical properties of the obtained toner.

[Production of Comparative Toners 1 and 2]
A toner was prepared in the same manner as in Example 1 except that the conditions for adding the hydrolyzed liquid in (polymerization step) and the retention time after the addition were changed as shown in Table 1. Table 1 shows the physical properties of the obtained toner.

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

(Formation of conductive layer)
Next, 214 parts of titanium oxide (TiO ₂ ) particles (average primary particle size of 230 nm) coated with oxygen-deficient tin oxide (SnO 2) as metal oxide particles, and phenol resin (of phenol resin) as a binder material Monomer / oligomer) (trade name: Priorofen J-325, manufactured by Dainippon Ink & Chemicals, Inc., resin solid content: 60% by mass), 132 parts, and 98 parts of 1-methoxy-2-propanol as a solvent , Put in a sand mill using 450 parts of glass beads with a diameter of 0.8 mm, perform dispersion treatment under the conditions of rotation speed: 2000 rpm, dispersion treatment time: 4.5 hours, cooling water set temperature: 18 ° C. Obtained. Glass beads were removed from this dispersion with a mesh (aperture: 150 μm).
Silicone resin particles (trade name: Tospearl 120, as a surface roughening agent) so as to be 10% by mass with respect to the total mass of the metal oxide particles and the binder material in the dispersion after removing the glass beads. Momentive Performance Materials Co., Ltd., average particle size of 2 μm) is added to the dispersion, and 0.01% by mass with respect to the total mass of the metal oxide particles and the binder in the dispersion. As described above, silicone oil as a leveling agent (trade name: SH28PA, manufactured by Toray Dow Corning Co., Ltd.) was added to the dispersion. Next, methanol is added so that the total mass of the metal oxide particles, the binder material, and the surface roughening agent in the dispersion (that is, the mass of the solid content) is 67% by mass with respect to the mass of the dispersion. A mixed solvent of 1-methoxy-2-propanol (mass ratio 1: 1) was added to the dispersion and stirred to prepare a coating solution for a conductive layer. This conductive layer coating solution was dip-coated on a support and heated at 150 ° C. for 30 minutes to form a conductive layer having a thickness of 30.0 μm.

(Formation of undercoat layer)
4 parts of an electron transport material (E), 5.5 parts of blocked isocyanate (trade name: Duranate SBN-70D, manufactured by Asahi Kasei Chemicals Corporation), polyvinyl butyral resin (ESREC KS-5Z, manufactured by Sekisui Chemical Co., Ltd.) 0 .3 parts, and 0.05 part of zinc hexanoate (II) (manufactured by Mitsuwa Chemical Co., Ltd.) as a catalyst were dissolved in a mixed solvent of 50 parts of tetrahydrofuran and 50 parts of 1-methoxy-2-propanol. An undercoat layer coating solution was prepared. This undercoat layer coating solution was dip-coated on the conductive layer, and this was heated at 170 ° C. for 30 minutes to form an undercoat layer having a thickness of 0.7 μm.

(Formation of charge generation layer)
Next, in a chart obtained from CuKα characteristic X-ray diffraction, 10 parts of a crystalline hydroxygallium phthalocyanine having a peak at positions of 7.5 ° and 28.4 ° and a polyvinyl butyral resin (trade name: ESREC BX-1, 5 parts of Sekisui Chemical Co., Ltd.) is added to 200 parts of cyclohexanone, and dispersed for 6 hours in a sand mill using glass beads having a diameter of 0.9 mm, and further diluted with 150 parts of cyclohexanone and 350 parts of ethyl acetate. Thus, a coating solution for charge generation layer was obtained. The obtained coating solution was dip-coated on the undercoat layer and dried at 95 ° C. for 10 minutes to form a charge generation layer having a thickness of 0.20 μm. The X-ray diffraction measurement was performed under the following conditions.

[Powder X-ray diffraction measurement]
Measuring instrument used: Rigaku Denki Co., Ltd., X-ray diffractometer RINT-TTRII
X-ray tube: Cu
Tube voltage: 50KV
Tube current: 300mA
Scanning method: 2θ / θ scan Scanning speed: 4.0 ° / min
Sampling interval: 0.02 °
Start angle (2θ): 5.0 °
Stop angle (2θ): 40.0 °
Attachment: Standard specimen holder Filter: Not used Incident monochrome: Used Counter monochrometer: Not used Divergence slit: Open Divergence vertical limit slit: 10.00mm
Scattering slit: Open Light receiving slit: Open Flat monochromator: Used Counter: Scintillation counter.

(Formation of charge transport layer)
Next, 6 parts of a compound represented by the following formula (C-1) (charge transporting material (hole transporting compound)), a compound represented by the following formula (C-2) (charge transporting material (hole transporting compound) )) 3 parts, 1 part of a compound represented by the following formula (C-3) (charge transporting material (hole transporting compound)), 10 parts of polycarbonate (trade name: Iupilon Z400, manufactured by Mitsubishi Engineering Plastics) And 0.02 part of polycarbonate resin having a copolymer unit of (C-4) and (C-5) (x / y = 9/1: Mw = 20000), 25 parts of o-xylene / methyl benzoate 25 A coating solution for charge transport layer was prepared by dissolving in a mixed solvent of parts / dimethoxymethane (25 parts). The charge transport layer coating solution was dip coated on the charge generation layer to form a coating film, and the coating film was dried at 120 ° C. for 30 minutes to form a charge transport layer having a thickness of 12 μm.

(Formation of protective layer)
Next, 10 parts of a compound represented by the following formula (O-1) and 10 parts of a compound represented by the following formula (O-2) are mixed with 50 parts of 1-propanol, 1,1,2,2,3,3, 25 parts of 4-heptafluorocyclopentane (trade name: Zeolora H, manufactured by Nippon Zeon Co., Ltd.) were mixed and stirred. Thereafter, this solution was filtered with a polyflon filter (trade name: PF-020, manufactured by Advantech Toyo Co., Ltd.) to prepare a coating solution for a protective layer.

  This protective layer coating solution was dip coated on the charge transport layer to form a coating film, and the resulting coating film was dried at 50 ° C. for 6 minutes. Thereafter, the coating film was irradiated with an electron beam for 5.0 seconds under a nitrogen atmosphere while rotating the support (object to be irradiated) at a speed of 200 rpm under the conditions of an acceleration voltage of 70 kV and a beam current of 5.0 mA. In addition, when the absorbed dose of the electron beam at this time was measured, it was 15 kGy. Then, it heated up over 30 seconds until the temperature of the coating film became 25 degreeC to 117 degreeC in nitrogen atmosphere, and the coating film was heated. The oxygen concentration from the electron beam irradiation to the subsequent heat treatment was 15 ppm or less. Next, in the atmosphere, the coating film was naturally cooled until the temperature of the coating film reached 25 ° C., and heat treatment was performed for 30 minutes under the condition that the temperature of the coating film reached 105 ° C., thereby forming a protective layer having a thickness of 3 μm. Thus, an electrophotographic photosensitive member having a protective layer was produced. Thus, a cylindrical (drum-shaped) electrophotographic photoreceptor 1 having a support, an undercoat layer, a charge generation layer, a charge transport layer, and a protective layer in this order was produced. The physical properties of the electrophotographic photoreceptor 1 are shown in Table 3.

[Production of electrophotographic photoreceptors 2 to 5]
In forming the protective layer of the electrophotographic photosensitive member, the accelerating voltage, the beam current, and the electron beam irradiation time were changed, and an electrophotographic photosensitive member having the conditions shown in Table 2 was produced. Table 3 shows the physical properties of the obtained electrophotosensitive material.

[Manufacture of electrophotographic photoreceptors 6 to 12]
After the formation of the electrophotographic photosensitive member having the protective layer, the surface of the electrophotographic photosensitive member was polished using a polishing apparatus shown in FIG. The polishing sheet 18 is wound in the direction of the arrow by a winding mechanism (not shown). The electrophotographic photosensitive member 19 rotates in the direction of the arrow. The backup roller 20 rotates in the direction of the arrow. As polishing conditions, a polishing sheet manufactured by Riken Corundum Co., Ltd. (trade name: GC # 3000, base sheet thickness: 75 μm) was used as the polishing sheet 18, and a urethane roller (outer diameter: 50 mm) having a hardness of 20 ° was used as the backup roller 20. Was used, the intrusion amount was 2.5 mm, the sheet feed amount was 400 mm / s, and the polishing sheet was polished for the polishing time shown in Table 2 with the same feeding direction of the polishing sheet and the rotation direction of the electrophotographic photosensitive member. Table 3 shows the physical properties of the obtained electrophotosensitive material.

[Production of Comparative Electrophotographic Photosensitive Member 1]
In the formation of the protective layer of the electrophotographic photosensitive member 1, it is prepared in the same manner as the electrophotographic photosensitive member 1 except that the acceleration voltage, the beam current, and the electron beam irradiation time are changed, and is further polished when polishing using a polishing apparatus. The comparative electrophotographic photosensitive member 1 having the conditions shown in Table 2 was produced by changing the time. Table 3 shows the physical properties of the obtained electrophotosensitive material.

[Production of Comparative Electrophotographic Photoreceptor 2]
In forming the protective layer of the electrophotographic photosensitive member 1, (O-1) and (O-2) are not used, the following formula (O-3) is 10 parts, and the following formula (O-4) is 10 parts. Further, except that 50 parts of 1-propanol and 40 parts of 1,1,2,2,3,3,4-heptafluorocyclopentane are placed in an ultrahigh pressure disperser and dispersed and mixed to adjust the protective layer coating liquid. Was produced in the same manner as the electrophotographic photoreceptor 1 to obtain a comparative electrophotographic photoreceptor 2. Table 3 shows the physical properties of the obtained electrophotosensitive material.

<Example 1>
<Evaluation of toner developability with LBP>
A modified machine of a commercially available Canon laser beam printer LBP7600C was used. The remodeling point was set so that the rotation speed of the developing roller was rotated at a peripheral speed of 1.8 times by changing the evaluation machine main body and the software. Specifically, the rotation speed of the developing roller before remodeling is a peripheral speed of 200 mm / sec, and the rotation speed after remodeling is 360 mm / sec.
60 g of electrophotographic photosensitive member 1 and toner 1 were loaded into a toner cartridge of LBP7600C. The toner cartridge was allowed to stand for 24 hours in an environment of normal temperature and humidity NN (25 ° C./50% RH). The toner cartridge was left in the environment for 24 hours and then attached to the LBP7600C.
In the evaluation of charging rise, D-roller Si amount, transferability and retransferability, a print rate image of 1.0% was printed up to 5,000 sheets of A4 paper in the NN environment, and 5,000. Evaluation was performed after the sheet was output. The results are shown in Table 4.

<Evaluation of process cartridge torque>
After the initial 10 sheets and 5,000 sheets have passed, the cyan process cartridge after 60 seconds is rotated in the counter direction with respect to the C blade at 300 mm / sec with the developing machine separated in the evaluation apparatus. Torque measurement was performed. The results are shown in Table 4.

<Evaluation of development lines>
A halftone image (toner loading: 0.2 mg / cm ² ) was printed on LETTER size XEROX 4200 paper (manufactured by XEROX, 75 g / m ² ), and development streaks were evaluated. The results are shown in Table 4.
(Evaluation criteria)
A: No vertical streak in the paper discharge direction is seen on the developing roller or the image.
B: Five or less fine stripes in the circumferential direction are seen at both ends of the developing roller. Or there are only a few vertical streaks in the paper discharge direction on the image. However, it can be erased by image processing.
C: 6 or more and 20 or less fine stripes in the circumferential direction are seen at both ends of the developing roller. Or a few fine lines can be seen on the image. It cannot be erased even with image processing.
D: 21 or more streaks are observed on the developing roller. Alternatively, one or more noticeable lines or a large number of fine lines are seen on the image. It cannot be erased even with image processing.

<Evaluation of cleaning properties>
Five halftone images with a toner loading of 0.2 mg / cm ² were printed and evaluated. The results are shown in Table 4.
A: No defective cleaning image, no charging roller contamination.
B: No poor cleaning image and charging roller contamination.
C: A little cleaning defect can be confirmed on the halftone image.
D: A cleaning defect is conspicuous on the halftone image.

<Examples 2 to 21 and Comparative Examples 1 to 4>
The same evaluation as in Example 1 was performed using the toner and the electrophotographic photosensitive member shown in Table 4. The results are shown in Table 4.

Claims (7)

Electrophotographic photoreceptor,
Development means for developing an electrostatic latent image formed on the electrophotographic photosensitive member with the toner contained in the toner containing portion using the toner, and a blade in contact with the electrophotographic photosensitive member Cleaning means for removing toner on the electrophotographic photosensitive member,
A process cartridge having
The toner has toner particles containing a binder resin and a colorant, and has a Martens hardness of 200 MPa or more and 1100 MPa or less when measured under a maximum load of 2.0 × 10 ⁻⁴ N.
The electrophotographic photosensitive member has a support, a photosensitive layer, and a protective layer that is a surface layer, and the Martens hardness of the protective layer is 200 MPa or more and 280 MPa or less.
A process cartridge characterized by that. The process cartridge according to claim 1, wherein the toner particles have a surface layer containing an organosilicon polymer, and the organosilicon polymer has a partial structure represented by the formula (1).
R-SiO _3/2 formula (1)
(R in the formula represents a hydrocarbon group having 1 to 6 carbon atoms.)   The process cartridge according to claim 2, wherein R in the formula (1) is a hydrocarbon group having 1 to 3 carbon atoms.   The process cartridge according to any one of claims 1 to 3, wherein the protective layer has a Martens hardness of 245 MPa or more and 280 MPa or less.   The ten-point average roughness Rzjis of the protective layer is 0.4 μm or more and 0.6 μm or less, and the average length Rsm of the roughness curve element is in the range of 0.005 mm or more and 0.020 mm or less. 5. The process cartridge according to any one of items 1 to 4. Developing means for developing the electrostatic latent image formed on the electrophotographic photosensitive member with toner to form a toner image;
Transfer means for transferring the toner image on the electrophotographic photosensitive member to a transfer material, and cleaning means for removing the toner on the electrophotographic photosensitive member by bringing a blade into contact with the electrophotographic photosensitive member after the transfer step;
An image forming apparatus having
The toner has toner particles containing a binder resin and a colorant, and has a Martens hardness of 200 MPa or more and 1100 MPa or less when measured under a maximum load of 2.0 × 10 ⁻⁴ N.
The electrophotographic photoreceptor has a support, a photosensitive layer, and a protective layer as a surface layer, and the Martens hardness of the protective layer is 200 MPa or more and 280 MPa or less.
An image forming apparatus. A developing step of developing the electrostatic latent image formed on the electrophotographic photosensitive member with toner to form a toner image;
A transfer step of transferring the toner image on the electrophotographic photosensitive member to a transfer material, and a cleaning step of removing a toner on the electrophotographic photosensitive member by bringing a blade into contact with the electrophotographic photosensitive member after the transfer step;
An image forming method comprising:
The toner has toner particles containing a binder resin and a colorant, and has a Martens hardness of 200 MPa or more and 1100 MPa or less when measured under a maximum load of 2.0 × 10 ⁻⁴ N.
The electrophotographic photoreceptor has a support, a photosensitive layer, and a protective layer as a surface layer, and the Martens hardness of the protective layer of the electrophotographic photoreceptor is 200 MPa or more and 280 MPa or less.
An image forming method.

Images