JP2007232926A - Process cartridge and electrophotographic apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a process cartridge and an electrophotographic apparatus in which the toner or the external additives used for the toner are less likely to stick to the surface of an electrifying member, even in long-term repeated use, so that stable charging and image output are attained for a long period of time, even if the cartridge is used for a DC contact charging system. <P>SOLUTION: The process cartridge and the electrophotographic apparatus includes the charging member, the surface layer of which contains polysiloxane having an oxyalkylene group and a toner which comprises dry toner particles containing a binder resin, a colorant and a wax component, and inorganic particles, wherein the toner is such that the toner particles have a circle-equivalent number average diameter D1 of 2 to 8 μm, and an average circularity of 0.960 to 0.995 in an equivalent circle diameter-circularity scattergram, measured by a flow type particle image measuring device of the toner particles; the toner particles contain coarse particles, having a circular equivalent diameter that exceeds 10 μm by 0.02 to 3 number%; the coarse particles have average circularity of 0.930 to 0.975; and the inorganic particles contain polysiloxane. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a process cartridge and an electrophotographic apparatus having a charging member.

  At present, a contact charging method has been put into practical use as one of methods for charging the surface of an electrophotographic photosensitive member.

  In the contact charging method, a voltage is applied to a charging member disposed in contact with the electrophotographic photosensitive member, and a slight discharge is caused in the vicinity of a contact portion between the charging member and the electrophotographic photosensitive member, thereby causing the electron In this method, the surface of the photographic photosensitive member is charged.

  As a charging member for charging the surface of the electrophotographic photosensitive member, from the viewpoint of sufficiently securing a contact nip between the electrophotographic photosensitive member and the charging member, a supporting member and an elastic layer provided on the supporting member ( A material having a conductive elastic layer) is generally used.

  In addition, since the elastic layer (conductive elastic layer) often contains a relatively large amount of low molecular weight components, this low molecular weight component is prevented from bleeding out and contaminating the surface of the electrophotographic photosensitive member. On the conductive elastic layer, another surface layer having a smaller elastic modulus than the conductive elastic layer is often provided.

  In addition, the shape of the charging member is generally a roller shape. Hereinafter, the roller-shaped charging member is also referred to as a “charging roller”.

  In addition, a widely used method among contact charging methods is a method in which a voltage obtained by superimposing an AC voltage on a DC voltage is applied to a charging member (hereinafter also referred to as “AC + DC contact charging method”). In the case of the AC + DC contact charging method, a voltage having a peak-to-peak voltage that is twice or more the charging start voltage is used as the AC voltage.

  The AC + DC contact charging system is a system that can perform stable charging with high charging uniformity by using an AC voltage, but a system that applies only a DC voltage to the charging member (hereinafter referred to as an AC voltage source). Compared to “DC contact charging method”), the charging device and the electrophotographic apparatus are increased in size and cost.

  That is, the DC contact charging method is superior to the AC + DC contact charging method in terms of downsizing and cost reduction of the charging device and the electrophotographic apparatus.

  However, since the DC contact charging method does not have an effect of improving the charging uniformity due to an AC voltage, the surface of the charging member (such as toner or an external additive used for the toner) or the electric resistance of the charging member itself is not uniform. Tends to appear in the output image.

  In particular, in the case of the DC contact charging method, if a toner or an external additive used for the toner adheres non-uniformly and strongly to the surface of the charging member due to repeated use (fixed), the fixed portion is generated when a halftone image is output. May cause overcharging and poor charging (toner contamination).

  On the other hand, demands for higher image quality of electrophotographic apparatuses are increasing day by day, and Patent Documents 1 to 6 and the like have proposed small particle size toners exhibiting a specific particle size distribution.

  However, the toner having such a small particle diameter has a larger adhesion force (mirror image force, van der Waals force, etc.) of the toner particles to the photoconductor than the Coulomb force applied to the toner particles during transfer. As a result, there is a problem in that the untransferred toner increases, and further, toner contamination of the charging member appears in the image.

Japanese Patent Laid-Open No. 1-112253 JP-A-1-191156 JP-A-2-214156 JP-A-2-284158 Japanese Patent Laid-Open No. 3-181952 JP-A-4-162048

  The object of the present invention is to prevent toner and external additives used in the toner from sticking to the surface of the charging member even after repeated use over a long period of time. It is an object of the present invention to provide a process cartridge and an electrophotographic apparatus that can perform the above-described process.

The present invention provides at least a photosensitive member, a charging unit that charges the photosensitive member with a charging member, and supplies toner to the photosensitive member on which an electrostatic latent image is formed so that a toner image corresponding to the electrostatic latent image is obtained. In the process cartridge that integrally supports the developing means formed on the top and is configured to be detachable from the image forming apparatus,
The charging member includes a conductive support, a conductive elastic layer formed on the support, and a surface layer formed on the conductive elastic layer, wherein the surface layer is an oxyalkylene It is a charging member characterized by containing a polysiloxane having a group,
The toner contains dry toner particles and inorganic particles containing a binder resin, a colorant, and a wax component;
In the number-based equivalent circle diameter-circularity scattergram measured by the flow particle image measuring device for the toner particles, the equivalent circle number average diameter D1 of the toner particles is 2 to 8 μm, and the average circularity is 0.960 to 0.995,
The toner contains 0.02 to 3% by number of coarse particles having a circle-equivalent diameter exceeding 10 μm, and the average circularity of the coarse particles is 0.930 to 0.975.
A process cartridge and an electrophotographic apparatus, wherein the inorganic particles are inorganic particles containing polysiloxane.

  Polysiloxane is a compound that can maintain a very high hardness, and is a compound that is very effective in suppressing bleeding. Further, the siloxane bond has good heat resistance, and by using this compound, the temperature rise on the surface of the charging member can be suppressed. When the temperature of the charging member surface is high, the above-described transfer residual toner becomes softer, which causes a problem that it easily adheres to the charging member.

  However, as a result of intensive studies by the present inventors, in the case of polysiloxane alone, the surface layer as a charging member becomes too hard, and the above-described toner contamination of the charging member appears remarkably. This is presumably due to the phenomenon that the transfer residual toner is crushed by the charging member having high hardness and rubbed against the charging member.

  Thus, as a result of further studies by the present inventors, it has become clear that by allowing the oxyalkylene group to be present in the polysiloxane, it is possible to express moderate flexibility in the charging member surface layer. It was.

  By the way, the oxyalkylene group is a divalent group having a structure represented by —O—R— (R: alkylene group) (sometimes referred to as “alkylene ether group”). As this R (alkylene group), a C1-C6 alkylene group is preferable.

  Since this alkylene group causes hydrogen bonding with the elastic layer components, it has the effect of improving the adhesion between the elastic layer and the surface layer. Even when a material having a large expansion coefficient due to heat or moisture is used for the elastic layer, The effect of suppressing wrinkles and cracks on the surface due to expansion and contraction of the charging member can be further exhibited.

  Further, as a result of intensive studies by the present inventors, it has been clarified that, even when the bleed is suppressed, the suppression effect is further exhibited by containing an oxyalkylene group rather than a polysiloxane alone.

  It is expected that the effect is exhibited by mixing the inorganic compound structure of polysiloxane and the organic compound structure of oxyalkylene in one compound. Both compounds such as salts, which are representative substances of bleed, and even organic substances are considered to be able to exert bleed suppression effect by repelling or mixing materials with affinity in the film. be able to.

  Usually, in order to prevent bleeding of low molecular components from the elastic layer, the charging member is often provided with a surface layer of about several μm to 1000 μm. However, the thickness of the surface layer of the charging member of the present invention is 0. It can be as thin as 1 to 1.0 μm. A particularly preferable range is 0.2 to 0.6 μm.

  Thus, by controlling the surface layer thickness, the electrostatic capacity, which is the electrical property of the charging member, can be made extremely large. In addition, by using a mixed material of an organic compound and an inorganic compound called polysiloxane having an oxyalkylene group as a material, it has become possible to maintain a capacitance that is not found in conventional resin materials. is there.

Specifically, the electrostatic capacity (C) of the surface layer of the charging member of the present invention is preferably 5.0 × 10 ⁻⁹ F or more and 1.0 × 10 ⁻⁶ F or less.

  As described above, since the electrostatic capacity of the charging member can be made extremely large, charges can be accumulated on the surface of the charging member when a voltage is applied. As a result, even if the transfer residual toner once adheres to the surface of the charging member, the toner can be sufficiently charged, and the electric repulsion can suppress the toner from adhering to the surface of the charging member. I was able to find out.

  In order to find out further high durability as a process cartridge and an electrophotographic apparatus, the present inventors have conducted intensive studies from the viewpoint of toner.

  As described above, when the particle size of the toner is reduced, the van der Waals force between the toners becomes dominant, so that the toner particles are easily aggregated or the adhesion to the charging member is increased.

  The present inventors have found that this problem can be solved by precisely controlling the shape distribution of toner particles. That is, in the number-based circle equivalent diameter-circularity scattergram measured by the flow particle image measuring apparatus for toner particles, the circle equivalent number average diameter D1 of the toner particles is 2 to 8 μm and the average circularity is 0.960. The toner particles contain 0.02 to 3% by number of coarse particles having a circle-equivalent diameter exceeding 10 μm, and the average circularity of the coarse particles is 0.930 to 0.975. To control. As described above, although the toner particles are reduced in size as a whole, the adhesion between the toner particles can be suppressed by containing a small amount of toner particles of 10 μm or more. In addition, by defining the circularity, it is possible to more uniformly charge the toner particles from the charging member. It has also been found that the adhesion to the charging member can be further suppressed by improving the circularity of toner particles other than coarse particles.

  The toner is preferably composed of toner particles and inorganic particles containing polysiloxane. By adhering inorganic particles to the toner particle surface, the fluidity of the toner can be improved, and the adhesion force to the charging member can be reduced. In addition, the inclusion of inorganic particles containing polysiloxane constituting the surface layer of the charging member has the effect of suppressing adhesion between the toner and the charging member due to the chemical repulsive force with the surface of the charging member. It became clear by examination of inventors.

  Further, the toner that does not adhere to the charging member is collected by the developing means. Since it becomes difficult to receive external pressure due to the charging member, it is clear that it is possible to suppress deterioration such as deformation of the toner through the durability test, and it is possible to dramatically improve the durability of the toner. became.

  According to the present invention, contamination of the charging member due to toner or the like can be suppressed and deterioration of the toner can be suppressed even by repeated use over a long period of time. Accordingly, it is possible to provide a process cartridge and an electrophotographic apparatus that can stably charge and output an image for a long period of time even when the DC contact charging method is used.

(1) Charging member First, the configuration of the charging member of the present invention will be described.

  The charging member of the present invention has a support, a conductive elastic layer formed on the support, and a surface layer formed on the conductive elastic layer. The “surface layer” means a layer located on the outermost surface of the charging member among the layers of the charging member.

  The simplest configuration of the charging member of the present invention is a configuration in which two layers of a conductive elastic layer and a surface layer are provided on the support, but between the support and the conductive elastic layer or between the conductive elastic layer. One or more other layers may be provided between the surface layer and the surface layer.

  In addition, the conductive elastic layer and the surface layer may be layers formed using a material for the conductive elastic layer and a material for the surface layer, respectively (hereinafter also referred to as “lamination form 1”). Alternatively, after forming a layer using the material for the conductive elastic layer, the surface region (surface and its vicinity) of the layer is modified, and the modified region is used as the surface layer, thereby conducting the conductive elasticity. It is good also as a laminated structure with a layer and a surface layer (henceforth "lamination form 2").

  FIG. 1 shows an example of the configuration of the charging member of the present invention. In FIG. 1, 101 is a support, 102 is a conductive elastic layer, and 103 is a surface layer.

  As a support for the charging member, it is only necessary to have conductivity (conductive support). For example, a support made of metal (made of alloy) such as iron, copper, stainless steel, aluminum, aluminum alloy, or nickel is used. Can be used. In addition, for the purpose of imparting scratch resistance to these surfaces, surface treatment such as plating treatment may be performed within a range not impairing conductivity.

  As the conductive elastic layer, one type or two or more types of elastic bodies such as rubber and thermoplastic elastomer used in the conventional elastic layer (conductive elastic layer) of the charging member can be used.

  Examples of the rubber include urethane rubber, silicone rubber, butadiene rubber, isoprene rubber, chloroprene rubber, styrene-butadiene rubber, ethylene-propylene rubber, polynorbornene rubber, styrene-butadiene-styrene rubber, acrylonitrile rubber, epichlorohydrin rubber, and alkyl ether. For example, rubber.

  Examples of the thermoplastic elastomer include styrene elastomers and olefin elastomers. Examples of commercially available styrene elastomers include “Lavalon” manufactured by Mitsubishi Chemical Corporation and “Septon Compound” manufactured by Kuraray Co., Ltd. Examples of commercially available olefin elastomers include “Thermorun” manufactured by Mitsubishi Chemical Corporation, “Miralastomer” manufactured by Mitsui Petrochemical Co., Ltd., “Sumitomo TPE” manufactured by Sumitomo Chemical Co., Ltd. and Examples include "Santplane" manufactured by Advanced Elastomer Systems.

Moreover, the electroconductivity can be set to a predetermined value by appropriately using a conductive agent in the conductive elastic layer. The electrical resistance of the conductive elastic layer can be adjusted by appropriately selecting the type and amount of the conductive agent, and the preferred range of the electrical resistance is 10 ² to 10 ⁸ Ω, and the more preferred range is 10 ³ to 10 ⁶ Ω.

  Examples of the conductive agent used in the conductive elastic layer include a cationic surfactant, an anionic surfactant, an amphoteric surfactant, an antistatic agent, and an electrolyte.

  Examples of the cationic surfactant include lauryltrimethylammonium, stearyltrimethylammonium, octadodecyltrimethylammonium, dodecyltrimethylammonium, hexadecyltrimethylammonium, and quaternary ammonium salts such as modified fatty acid and dimethylethylammonium. Specific examples of the quaternary ammonium salt include perchlorate, chlorate, borofluoride, ethosulphate salt, benzyl halide salt (benzyl bromide salt, benzyl chloride salt, etc.) and the like. .

  Examples of the anionic surfactant include aliphatic sulfonate, higher alcohol sulfate ester salt, higher alcohol ethylene oxide addition sulfate ester salt, higher alcohol phosphate ester salt and higher alcohol ethylene oxide addition phosphate ester salt.

  Examples of the antistatic agent include nonionic antistatic agents such as higher alcohol ethylene oxide, polyethylene glycol fatty acid ester and polyhydric alcohol fatty acid ester.

Examples of the electrolyte include salts (such as quaternary ammonium salts) of metals (Li, Na, K, etc.) belonging to Group 1 of the periodic table. Specific examples of the metal salt of Group 1 of the periodic table include LiCF ₃ SO ₃ , NaClO ₄ , LiAsF ₆ , LiBF ₄ , NaSCN, KSCN, and NaCl.

In addition, as a conductive agent for the conductive elastic layer, a salt of a Group 2 metal (Ca, Ba, etc.) (Ca (ClO ₄ ) _2, etc.) and an antistatic agent derived therefrom are isocyanate (primary). It is also possible to use one having at least one group having an active hydrogen capable of reacting with an amino group or a secondary amino group (such as a hydroxyl group or a carboxyl group). Also, complexes of these with polyhydric alcohols (1,4-butanediol, ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, etc.) or derivatives thereof, and monools (ethylene glycol monomethyl ether, ethylene glycol monoethyl) An ion conductive conductive agent such as a complex with ether or the like) can also be used.

  In addition, as a conductive agent for the conductive elastic layer, conductive carbon such as ketjen black EC, acetylene black, carbon for rubber, carbon for color (ink) subjected to oxidation treatment, and pyrolytic carbon should be used. You can also. Specific examples of carbon for rubber include Super Abrasion Furnace (SAF: Super Abrasion Resistance), Intermediate Super Abrasion Furnace (ISAF: Quasi Super Abrasion Resistance), High Ablation Furnace (HAF: Fast Abrasion E), Furnace (FEF: good extrudability), General Purpose Furnace (GPF: versatility), Semi Rein Forcing Furnace (SRF: medium reinforcement), Fine Thermal (FT: fine particle thermal decomposition) and Medium Thermal decomposition (Medium Thermal decomposition) ) And the like.

  Further, graphite such as natural graphite and artificial graphite can also be used as a conductive agent for the conductive elastic layer.

  Further, as a conductive agent for the conductive elastic layer, metal oxides such as tin oxide, titanium oxide and zinc oxide, and metals such as nickel, copper, silver and germanium can be used.

  In addition, conductive polymers such as polyaniline, polypyrrole, and polyacetylene can be used as the conductive agent for the conductive elastic layer.

  In addition, an inorganic or organic filler or a crosslinking agent may be added to the conductive elastic layer. Examples of the filler include silica (white carbon), calcium carbonate, magnesium carbonate, clay, talc, zeolite, alumina, barium sulfate, and aluminum sulfate. Examples of the crosslinking agent include sulfur, peroxide, crosslinking aid, crosslinking accelerator, crosslinking acceleration aid, crosslinking retarder and the like.

  The hardness of the conductive elastic layer is preferably 70 degrees or more with Asker C from the viewpoint of suppressing the deformation of the charging member when the charging member and the electrophotographic photosensitive member as the member to be charged are brought into contact with each other. In particular, it is more preferably 73 degrees or more.

  In the present invention, the Asker C hardness was measured under the condition of a load of 1000 g by bringing a pusher of an Asker C type hardness meter (manufactured by Kobunshi Keiki Co., Ltd.) into contact with the surface of the object to be measured.

  Further, from the viewpoint of sufficiently exerting the function of the conductive elastic layer provided in order to ensure a sufficient contact nip with the electrophotographic photosensitive member, the elastic modulus of the surface layer of the charging member is preferably 2000 MPa or less. . On the other hand, in general, as the elastic modulus of the layer decreases, the crosslinking density tends to decrease. Therefore, from the viewpoint of suppressing contamination of the surface of the electrophotographic photosensitive member by the low molecular weight component bleed out on the surface of the charging member, The elastic modulus of the surface layer of the member is preferably 100 MPa or more.

  Further, from the viewpoint of suppressing the adhesion of the toner and the external additive to the surface of the charging member, the roughness (Rz) of the surface of the charging member (= surface of the surface layer) is preferably 10 μm or less according to JIS94, 7 μm Or less, more preferably 5 μm or less.

  Subsequently, the charging member of the present invention will be described in more detail.

  As described above, the charging member of the present invention includes a support, a conductive elastic layer formed on the support, and a surface layer formed on the conductive elastic layer. Contains a polysiloxane having an oxyalkylene group. Furthermore, the charging member is characterized by containing a fluorinated alkyl group.

  The oxyalkylene group is a divalent group having a structure represented by —O—R— (R: alkylene group) (sometimes referred to as “alkylene ether group”). As this R (alkylene group), a C1-C6 alkylene group is preferable.

  The content of the oxyalkylene group in the polysiloxane is preferably 5.0 to 70.0% by mass with respect to the total mass of the polysiloxane, and the siloxane moiety (—Si—O—Si—O— in the polysiloxane is included. The content of the portion having a structure represented by... Is preferably 20.0 to 90.0% by mass with respect to the total mass of the polysiloxane.

  Examples of the fluorinated alkyl group include those in which part or all of the hydrogen atoms of a linear or branched alkyl group are substituted with fluorine atoms. Among these, a linear perfluoroalkyl group having 6 to 31 carbon atoms is preferable. The content of the fluorinated alkyl group in the polysiloxane is preferably 5.0 to 50.0 mass% with respect to the total mass of the polysiloxane.

  The polysiloxane further preferably has an alkyl group and a phenyl group. The alkyl group is preferably a linear or branched alkyl group having 1 to 21 carbon atoms, and more preferably a methyl group, an ethyl group, an n-propyl group, a hexyl group, or a decyl group.

  When the polysiloxane further has an alkyl group and a phenyl group, the content of the fluorinated alkyl group in the polysiloxane is preferably 5.0 to 50.0% by mass with respect to the total mass of the polysiloxane, The content of the oxyalkylene group in the polysiloxane is preferably 5.0 to 30.0% by mass with respect to the total mass of the polysiloxane, and the content of the alkyl group in the polysiloxane is based on the total mass of the polysiloxane. The content of the phenyl group in the polysiloxane is preferably 5.0 to 30.0% by mass with respect to the total mass of the polysiloxane, The content of the siloxane moiety in the polysiloxane is preferably 20.0 to 80.0 mass% with respect to the total mass of the polysiloxane.

  The polysiloxane is a functional group that generates an oxyalkylene group by cleavage, for example, a hydrolyzable silane compound having a cationically polymerizable group such as a cyclic ether group such as an epoxy group or an oxetane group, and a vinyl ether group. It can be obtained by cleaving and crosslinking the aforementioned cationically polymerizable group.

  As the hydrolyzable silane compound having a group capable of cationic polymerization, a hydrolyzable silane compound having a structure represented by the following formula (2) is preferable.

上記式（２）中、Ｒ²¹は、飽和もしくは不飽和の１価の炭化水素基を示す。Ｒ²²は、飽和もしくは不飽和の１価の炭化水素基を示す。Ｚ²¹は、２価の有機基を示す。Ｒｃ²¹は、カチオン重合可能な基を示す。ｄは０〜２の整数であり、ｅは１〜３の整数であり、ｄ＋ｅ＝３である。

In the above formula (2), R ²¹ represents a saturated or unsaturated monovalent hydrocarbon group. R ²² represents a saturated or unsaturated monovalent hydrocarbon group. Z ²¹ represents a divalent organic group. Rc ²¹ represents a group capable of cationic polymerization. d is an integer of 0 to 2, e is an integer of 1 to 3, and d + e = 3.

The cationically polymerizable group Rc ²¹ in the formula (2), means a cationic polymerizable organic group which forms an oxyalkylene group by cleavage, for example, cyclic ether groups such as an epoxy group and an oxetane group, and And vinyl ether groups. Among these, an epoxy group is preferable from the viewpoint of availability and reaction control.

Examples of the saturated or unsaturated monovalent hydrocarbon group of R ²¹ and R ^{22 in} the above formula (2) include an alkyl group, an alkenyl group, and an aryl group. Among these, a linear or branched alkyl group having 1 to 3 carbon atoms is preferable, and a methyl group and an ethyl group are more preferable.

Examples of the divalent organic group of Z ^{21 in} the above formula (2) include an alkylene group and an arylene group. Among these, an alkylene group having 1 to 6 carbon atoms is preferable, and an ethylene group is more preferable.

  E in the above formula (2) is preferably 3.

When d in the above formula (2) is 2, two R ²¹ may be the same or different.

When e in the above formula (2) is 2 or 3, two or three R ²² may be the same or different.

  Specific examples of the hydrolyzable silane compound having the structure represented by the above formula (2) are shown below.

(2-1): Glycidoxypropyltrimethoxysilane (2-2): Glycidoxypropyltriethoxysilane (2-3): Epoxycyclohexylethyltrimethoxysilane (2-4): Epoxycyclohexylethyltriethoxysilane

  Moreover, as a hydrolysable silane compound which has the said fluorinated alkyl group, the hydrolysable silane compound which has a structure shown by following formula (3) is suitable.

  The polysiloxane in this case is obtained by condensing the hydrolyzable silane compound having a cationic polymerizable group and the hydrolyzable silane compound having a fluorinated alkyl group by hydrolysis to obtain a hydrolyzable condensate. It can then be obtained by crosslinking the hydrolyzable condensate by cleaving the cationically polymerizable group.

上記式（３）中、Ｒ³¹は、飽和もしくは不飽和の１価の炭化水素基を示す。Ｒ³²は、飽和もしくは不飽和の１価の炭化水素基を示す。Ｚ³¹は、２価の有機基を示す。Ｒｆ³¹は、炭素数１〜３１の直鎖状のパーフルオロアルキル基を示す。ｆは０〜２の整数であり、ｇは１〜３の整数であり、ｆ＋ｇ＝３である。

In the above formula (3), R ³¹ represents a saturated or unsaturated monovalent hydrocarbon group. R ³² represents a saturated or unsaturated monovalent hydrocarbon group. Z ³¹ represents a divalent organic group. Rf ³¹ represents a linear perfluoroalkyl group having 1 to ³¹ carbon atoms. f is an integer of 0 to 2, g is an integer of 1 to 3, and f + g = 3.

Examples of the saturated or unsaturated monovalent hydrocarbon group of R ³¹ and R ^{32 in} the above formula (3) include an alkyl group, an alkenyl group, and an aryl group. Among these, a linear or branched alkyl group having 1 to 3 carbon atoms is preferable, and a methyl group and an ethyl group are more preferable.

Examples of the divalent organic group for Z ^{31 in} the above formula (3) include an alkylene group and an arylene group. Among these, an alkylene group having 1 to 6 carbon atoms is preferable, and an ethylene group is more preferable.

The linear perfluoroalkyl group having 1 to ³¹ carbon atoms of Rf ^{31 in} the above formula (3) is particularly preferably a linear perfluoroalkyl group having 6 to ³¹ carbon atoms from the viewpoint of processability. .

G in the above formula (3) is preferably 3. When f in the above formula (3) is 2, two R ³¹ may be the same or different. When g in the above formula (3) is 2 or 3, two or three R ³² may be the same or different.

  Specific examples of the hydrolyzable silane compound having the structure represented by the above formula (3) are shown below.

(3-1): CF ₃ — (CH ₂ ) ₂ —Si— (OR) ₃
(3-2): F (CF ₂ ) ₂ — (CH ₂ ) ₂ —Si— (OR) ₃
(3-3): F (CF ₂ ) ₄ — (CH ₂ ) ₂ —Si— (OR) _{3
(3-4): F (CF 2} ) 6 - (CH 2) 2 -Si- (OR) 3
(3-5): F (CF ₂ ) ₈ — (CH ₂ ) ₂ —Si— (OR) ₃
(3-6): F (CF ₂ ) ₁₀ — (CH ₂ ) ₂ —Si— (OR) ₃
R in the above (3-1) to (3-6) represents a methyl group or an ethyl group. Among the above (3-1) to (3-6), (3-4) to (3-6) are preferable.

  The hydrolyzable silane compound having a cationically polymerizable group and the hydrolyzable silane compound having a fluorinated alkyl group may be used alone or in combination of two or more.

In particular, when a hydrolyzable silane compound having a structure represented by the above formula (3) is used as the hydrolyzable silane compound having a fluorinated alkyl group, the carbon number n _{A of} Rf ³¹ (n _A is 6 to ³¹ ). And a compound having n _B (n _B is an integer of 6 to 31 and n _B ≠ n _A ), and the resulting polysiloxane has perfluoroalkyl groups having different carbon numbers. It will be. Since the perfluoroalkyl group tends to be oriented toward the surface of the charging member, if the polysiloxane contained in the surface layer of the charging member has perfluoroalkyl groups having different carbon numbers, the charging member Perfluoroalkyl groups having different lengths are oriented toward the surface. In this case, the concentration of fluorine atoms in the vicinity of the surface of the charging member is higher and the surface free energy of the charging member is lower than when a single length of perfluoroalkyl group is oriented toward the surface of the charging member. For this reason, it is possible to further suppress sticking of toner, external additives, and the like to the surface of the charging member when repeatedly used for a long period of time.

  When using 2 or more types of hydrolyzable silane compounds which have a structure shown by said Formula (3), it is preferable to select 2 or more types from said (3-4)-(3-6).

  As described above, the polysiloxane used in the first charging member of the present invention condenses a hydrolyzable silane compound having a cationically polymerizable group and a hydrolyzable silane compound having a fluorinated alkyl group by hydrolysis. Can be obtained by crosslinking the hydrolyzable condensate by cleaving the cationically polymerizable group and then controlling the surface properties of the charging member. From the viewpoint, when obtaining a hydrolyzable condensate, in addition to the hydrolyzable silane compound having a cationically polymerizable group and the hydrolyzable silane compound having a fluorinated alkyl group, the following formula (1) It is preferable to use a hydrolyzable silane compound having the structure shown in combination.

上記式（１）中、Ｒ¹¹は、フェニル基置換のアルキル基もしくは無置換のアルキル基、または、アルキル基置換のアリール基もしくは無置換のアリール基を示す。Ｒ¹²は、飽和もしくは不飽和の１価の炭化水素基を示す。ａは０〜３の整数であり、ｂは１〜４の整数であり、ａ＋ｂ＝４である。

In the above formula (1), R ¹¹ represents a phenyl group-substituted alkyl group or an unsubstituted alkyl group, or an alkyl group-substituted aryl group or an unsubstituted aryl group. R ¹² represents a saturated or unsaturated monovalent hydrocarbon group. a is an integer of 0 to 3, b is an integer of 1 to 4, and a + b = 4.

As the alkyl group of the phenyl group-substituted alkyl group or unsubstituted alkyl group represented by R ^{11 in} the above formula (1), a linear alkyl group having 1 to 21 carbon atoms is preferable. As the aryl group of the alkyl group-substituted aryl group or unsubstituted aryl group of R ^{11 in} the above formula (1), a phenyl group is preferable.

  A in the formula (1) is preferably an integer of 1 to 3, and more preferably 1. In the above formula (1), b is preferably an integer of 1 to 3, and more preferably 3.

Examples of the saturated or unsaturated monovalent hydrocarbon group represented by R ^{12 in} the above formula (1) include an alkyl group, an alkenyl group, and an aryl group. Among these, a linear or branched alkyl group having 1 to 3 carbon atoms is preferable, and a methyl group, an ethyl group, and an n-propyl group are more preferable.

When a in formula (1) is 2 or 3, two or three R ¹¹ may be the same or different. When b in the above formula (1) is 2, 3 or 4, 2, 3 or 4 R ¹² may be the same or different.

  Specific examples of the hydrolyzable silane compound having the structure represented by the above formula (1) are shown below.

(1-1): Tetramethoxysilane (1-2): Tetraethoxysilane (1-3): Tetrapropoxysilane (1-4): Methyltrimethoxysilane (1-5): Methyltriethoxysilane (1- 6): methyltripropoxysilane (1-7): ethyltrimethoxysilane (1-8): ethyltriethoxysilane (1-9): ethyltripropoxysilane (1-10): propyltrimethoxysilane (1- 11): Propyltriethoxysilane (1-12): Propyltripropoxysilane (1-13): Hexyltrimethoxysilane (1-14): Hexyltriethoxysilane (1-15): Hexyltripropoxysilane (1- 16): Decyltrimethoxysilane (1-17): Decyltriethoxysilane (1-18): Decyl Rutripropoxysilane (1-19): Phenyltrimethoxysilane (1-20): Phenyltriethoxysilane (1-21): Phenyltripropoxysilane (1-22): Diphenyldimethoxysilane (1-23): Diphenyldi Ethoxysilane When a hydrolyzable silane compound having a structure represented by the above formula (1) and a hydrolyzable silane compound having a structure represented by the above formula (3) are used in combination, a in the above formula (1) is 1 Is preferably an integer of ˜3, b is preferably an integer of 1 to 3, and one R ¹¹ out of a R ¹¹ is a linear alkyl group having 1 to 21 carbon atoms. Preferably, the carbon number of the linear alkyl group having ₁ to 21 carbon atoms is n ₁ (n ₁ is an integer of ₁ to 21), and the carbon number of Rf ³¹ in the above formula (3) the n ₂ ( _{When 2} was 1 to 31 integer), it is preferable that _{n 2 -1 ≦ n 1 ≦ n} 2 +1.

The linear alkyl group having 1 to 21 carbon atoms has a tendency to be oriented toward the surface of the charging member, like the perfluoroalkyl group, but when n ₁ <n ₂ +2, the above formula (3) In some cases, the effect of the perfluoroalkyl group of the hydrolyzable silane compound having a structure represented by On the other hand, if n ₁ > n ₂ -2, the details of the reason are unknown, but it affects the discharge during charging, and when a halftone image is output, the previous character or black figure slightly appears. An afterimage phenomenon (ghost phenomenon) is likely to occur.

Only 1 type of hydrolysable silane compound which has a structure shown by the said Formula (1) may be used, and may be used 2 or more types. When using 2 or more types, it is preferable to use together that whose R < ¹¹ > in said Formula (1) is an alkyl group, and whose R < ¹¹ > in said Formula (1) is a phenyl group. This is because the alkyl group is preferable from the viewpoint of controlling the surface properties of the charging member, and the phenyl group is preferable from the viewpoint of suppressing the ghost phenomenon.

  Hereinafter, a specific method for producing the charging member of the present invention (a specific method for forming the surface layer containing the polysiloxane) will be described.

  First, a hydrolyzable silane compound having a cationically polymerizable group and a hydrolyzable silane compound having a fluorinated alkyl group, and if necessary, hydrolyzing the other hydrolyzable silane compound in the presence of water. A hydrolyzable condensate is obtained by reacting.

  During the hydrolysis reaction, a hydrolyzable condensate having a desired degree of condensation can be obtained by controlling temperature, pH and the like.

  In the hydrolysis reaction, the degree of condensation may be controlled by using a metal alkoxide or the like as a catalyst for the hydrolysis reaction. Examples of the metal alkoxide include aluminum alkoxide, titanium alkoxide, zirconia alkoxide, and the like, and complexes thereof (acetylacetone complex and the like).

  In addition, when the hydrolyzable condensate is obtained, the blending ratio of the hydrolyzable silane compound having a cationically polymerizable group and the hydrolyzable silane compound having a fluorinated alkyl group has a cationically polymerizable group. The blending ratio of the hydrolyzable silane compound, the hydrolyzable silane compound having a fluorinated alkyl group, and the hydrolyzable silane compound having the structure represented by the above formula (1) is the ratio of the fluorinated alkyl group in the resulting polysiloxane. The content of the oxyalkylene group is 5.0 to 70.0% by mass with respect to the total mass of the polysiloxane so that the content is 5.0 to 50.0% by mass with respect to the total mass of the polysiloxane. Further, the content of the siloxane portion is preferably 20.0 to 90.0 mass% with respect to the total mass of the polysiloxane.

  Specifically, the hydrolyzable silane compound having a fluorinated alkyl group is preferably blended so as to be in the range of 0.5 to 20.0 mol% with respect to the total hydrolyzable silane compound, and in particular, 1 It is more preferable to mix | blend so that it may become the range of 0.0-10.0 mol%.

Further, when used in combination hydrolyzable silane compound having the structure represented by the formula (1) is further hydrolysable silane compound having a cationically polymerizable group (M _C) and the above formula (1) It is preferable that the molar ratio (M _C : M ₁ ) with the hydrolyzable silane compound (M ₁ ) having the structure shown is in the range of 10: 1 to 1:10.

  Next, a coating solution for the surface layer containing the obtained hydrolyzable condensate is prepared, and a member having a support and a conductive elastic layer formed on the support (hereinafter also referred to as “conductive elastic member”). .) Apply the prepared surface layer coating solution on top.

  When preparing the coating solution for the surface layer, an appropriate solvent may be used in addition to the hydrolyzable condensate in order to improve the coating property. Suitable solvents include, for example, alcohols such as ethanol and 2-butanol, ethyl acetate, methyl ethyl ketone, or a mixture thereof. Moreover, when applying the surface layer coating liquid onto the conductive elastic member, coating using a roll coater, dip coating, ring coating, or the like can be employed.

  Next, the surface layer coating liquid applied on the conductive elastic member is irradiated with an active energy ray. Then, the cationically polymerizable group in the hydrolyzable condensate contained in the coating solution for the surface layer is cleaved, whereby the hydrolyzable condensate can be crosslinked. The hydrolyzable condensate is cured by crosslinking. As the active energy ray, ultraviolet rays are preferable.

  When the conductive elastic layer of the conductive elastic member expands due to the heat generated during the irradiation of the active energy and then contracts due to cooling, the surface layer has many wrinkles and cracks if the surface layer does not sufficiently follow the expansion / contraction. However, when ultraviolet rays are used for the crosslinking reaction, the hydrolyzable condensate can be crosslinked in a short time (within 15 minutes) and the generation of heat is small. Less likely to wrinkle or crack.

  Also, when the charging member is placed in an environment where the temperature and humidity change is abrupt, the surface layer will not wrinkle or wrinkle unless the surface layer sufficiently follows the expansion and contraction of the conductive elastic layer due to the change in temperature and humidity. Cracks may occur, but if the cross-linking reaction is carried out with ultraviolet rays that generate little heat, the adhesion between the conductive elastic layer and the surface layer is increased, and the surface layer is sufficient for expansion and contraction of the conductive elastic layer. Since it can follow, wrinkles and cracks in the surface layer due to changes in environmental temperature and humidity can be suppressed.

  In addition, if the crosslinking reaction is performed using ultraviolet rays, it is possible to suppress deterioration of the conductive elastic layer due to thermal history, and thus it is possible to suppress a decrease in electrical characteristics of the conductive elastic layer.

  For irradiation with ultraviolet rays, a high-pressure mercury lamp, a metal halide lamp, a low-pressure mercury lamp, an excimer UV lamp, or the like can be used. Among these, an ultraviolet ray source having abundant light with an ultraviolet wavelength of 150 to 480 nm is used.

The integrated light quantity of ultraviolet rays is defined as follows.
UV integrated light quantity [mJ / cm ² ] = UV intensity [mW / cm ² ] × irradiation time [s]

  The adjustment of the integrated amount of ultraviolet light can be performed by the irradiation time, lamp output, distance between the lamp and the irradiated object, and the like. Moreover, you may give a gradient to integrated light quantity within irradiation time.

  In the case of using a low-pressure mercury lamp, the integrated light amount of ultraviolet light can be measured using an ultraviolet integrated light meter UIT-150-A or UVD-S254 manufactured by USHIO INC., And in the case of using an excimer UV lamp, Can be measured using an ultraviolet integrated light meter UIT-150-A or VUV-S172 manufactured by USHIO INC.

  In the crosslinking reaction, it is preferable that a cationic polymerization catalyst (polymerization initiator) is allowed to coexist from the viewpoint of improving the crosslinking efficiency. For example, since an epoxy group exhibits high reactivity with respect to an onium salt of a Lewis acid activated by an active energy ray, the above cationic polymerizable group is an epoxy group. It is preferable to use an onium salt of an acid.

  Examples of other cationic polymerization catalysts include borate salts, compounds having an imide structure, compounds having a triazine structure, azo compounds, and peroxides.

  Among various cationic polymerization catalysts, aromatic sulfonium salts and aromatic iodonium salts are preferable from the viewpoints of sensitivity, stability and reactivity, and in particular, bis (4-tert-butylphenyl) iodonium salt and the following formula (Trade name: Adekaoptoma-SP150, manufactured by Asahi Denka Kogyo Co., Ltd.)

  A compound having a structure represented by the following formula (trade name: Irgacure 261, manufactured by Ciba Specialty Chemicals)

が好ましい。

Is preferred.

  It is preferable that the usage-amount of a cationic polymerization catalyst is 1-3 mass% with respect to a hydrolyzable condensate.

  Subsequently, the capacitance (C) of the surface layer of the charging member will be described.

The electrostatic capacity (C) of the surface layer of the charging member of the present invention is preferably 5.0 × 10 ⁻⁹ F or more and 1.0 × 10 ⁻⁶ F or less.

  In the present invention, the capacitance of the surface layer of the charging member was measured as follows.

  First, the charging member to be measured was left in a 30 ° C./80% RH environment for 24 hours. Next, a charging member was attached to the measuring apparatus having the configuration shown in FIG. 2, and the dielectric constant was measured under the conditions of an applied voltage of 3 V and a measurement frequency of 0.1 Hz to 1 MHz. As a result of the measurement, for example, an impedance characteristic as shown in FIG. 3 is obtained.

  Next, as shown in FIG. 4, assuming that the charging member is an RC parallel equivalent circuit at the interface between the conductive elastic layer / surface layer / surface layer and the cylindrical electrode, the resistance of the conductive elastic layer is R1, electrostatic The value of C2 was calculated by setting the capacitance as C1, the resistance of the surface layer as R2, the capacitance as C2, the resistance at the interface between the surface layer and the cylindrical electrode as R3, and the capacitance as C3.

  In FIG. 2, 401 is a charging member, 402 is a cylindrical electrode (metal roller), 403 is a dielectric constant measurement system (in combination with Solartron's 1296 type dielectric constant measurement interface and 1260 type impedance analyzer). is there.

(2) Toner The circle equivalent number average diameter of the toner is preferably 2 to 8 μm, preferably 2 to 6 μm, and a good image can be obtained. In particular, by reducing the circle-equivalent number average diameter to 2 to 5 μm, the reproducibility in the development of the contour portion of an image, particularly a character image or a line pattern is improved. However, conventionally, when the toner particle size is reduced, the presence rate of the toner having a small particle size is inevitably increased, so that it becomes difficult to uniformly charge the toner, and not only image fogging occurs, but also the toner surface Since it becomes easy to receive deterioration, it was easy to produce a problem in durability or environmental stability. Also, matching with the image forming apparatus was not sufficient.

  However, the toner of the present invention contains 0.02 to 5% by number of particles having an equivalent circle diameter exceeding 10 μm in the equivalent circle diameter-circularity scattergram, and the average circularity of the coarse particles is 0.900. By setting it to ˜0.990, problems relating to the developability and durability of the toner, as well as the environmental stability can be significantly improved. The reason for this is that the presence of coarse particles having a specific shape in the toner allows the regulating force of the toner layer thickness regulating member to be normally increased when a thin layer of toner is formed on the toner carrier in the development process. Even if it is stronger than this, it is possible to minimize the deterioration of the toner surface caused by pressing the regulating member strongly while maintaining a sufficient toner coat amount. Further, since the charge amount of the toner can be made higher than usual, the image scattering and dot reproducibility are improved and improved even under high temperature and high humidity where deterioration of developability tends to appear as image defects. Further, even if the average particle diameter equivalent to the circle of the toner is reduced to 2 to 5 μm, the average circularity of the toner is set to 0.960 to 0.995, and coarse particles having an equivalent circle diameter of more than 10 μm are set to 0. By adding 02 to 3% by number and setting the average circularity of the coarse particles to 0.930 to 0.975, not only the balance between developability and transferability is improved, but also the chargeability of the toner becomes uniform. High-resolution and high-definition image reproduction is possible.

  When the content of coarse particles having an equivalent circle diameter exceeding 10 μm is less than 0.02% by number, the toner surface is remarkably deteriorated and the above-described improvement effect cannot be expected. Further, if the content of coarse particles exceeds 5% by number, selectivity is generated between particles having an average particle size and coarse particles during development, and the coarse particles are easily consumed without being consumed. Etc. are likely to occur. Further, such coarse particles often have different mechanical strength and thermal characteristics as compared with those having an average particle size, and are likely to cause a problem in matching with an image forming apparatus.

  The average circularity of the coarse particles should be 0.900 to 0.990. When the average circularity is less than 0.900, the shape of the toner surface becomes non-uniform, which adversely affects the chargeability of the entire toner or causes a problem in matching with the image forming apparatus. On the other hand, when the average circularity exceeds 0.990, the deterioration of the coarse particles themselves is promoted, causing problems such as deterioration in image quality.

  Since the above-mentioned problems become apparent as the toner particle size is reduced, the average circularity of the toner coarse powder particles is 0.930-0. 975 is preferable.

The equivalent circle diameter, circularity, and frequency distribution of the toner in the present invention are used as a simple method for quantitatively expressing the toner shape. In the present invention, the flow type particle image measuring device FPIA is used. -1000 type (manufactured by Toa Medical Electronics Co., Ltd.) was used for measurement, and calculation was performed using the following formula.
Equivalent circle diameter = (particle projected area / π) ^1/2 × 2

  Here, the “particle projected area” is the area of the binarized toner image, and the “peripheral length of the particle projected image” is defined as the length of the contour line obtained by connecting the edge points of the toner image. .

  In the present invention, the circularity is an index indicating the degree of unevenness of the toner, and is 1.00 when the toner is a perfect sphere. The more complicated the surface shape, the smaller the circularity.

  In the present invention, the circle-equivalent number average diameter D1, which means the average value of the particle number frequency distribution on the basis of the number of toners, is expressed as follows when the particle diameter (center value) at the division point i of the particle size distribution is di and the frequency is fi. Calculated from the formula.

  The average circularity C, which means the average value of the circularity frequency distribution, is calculated from the following equation, where the circularity (center value) at the dividing point i of the particle size distribution is ci and the frequency is fci.

  As a specific measurement method, 10 ml of ion-exchanged water from which impure solids have been removed in advance is prepared in a container, and a surfactant, preferably an alkylbenzene sulfonate, is added as a dispersant therein, and then further measurement is performed. Add 0.02 g of sample and disperse uniformly. As a means for dispersion, an ultrasonic dispersion UH-50 type (manufactured by SMT Corporation) equipped with a 5φ titanium alloy chip as a vibrator is used, and a dispersion treatment is performed for 5 minutes to obtain a dispersion for measurement. In that case, it cools suitably so that the temperature of this dispersion may not be 40 degreeC or more.

  To measure the shape of the toner, the flow type particle image measuring device is used, the concentration of the dispersion is readjusted so that the toner concentration at the time of measurement is 3000 to 10,000 / μl, and 1000 or more toner particles are measured. To do. After the measurement, a binary frequency distribution diagram (scattergram) of the equivalent circle diameter and circularity of the toner is obtained using this data.

  Examples of the binder resin used in the toner of the present invention include commonly used styrene- (meth) acrylic copolymers, polyester resins, epoxy resins, and styrene-butadiene copolymers. In a method for directly obtaining toner particles by a polymerization method, a monomer for forming them is used. Specifically, styrene; styrenic monomers such as o (m-, p-)-methylstyrene, m (p-)-ethylstyrene; methyl (meth) acrylate, ethyl (meth) acrylate, (meth ) Propyl acrylate, butyl (meth) acrylate, octyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, behenyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ( (Meth) acrylic acid ester monomers such as dimethylaminoethyl acrylate, diethylaminoethyl (meth) acrylate; ene monomers such as butadiene, isoprene, cyclohexene, (meth) acrylonitrile, acrylamide Preferably used. These may be used alone or in general so that the theoretical glass transition temperature (Tg) described in the publication Polymer Handbook 2nd edition III-P139-192 (John Wiley & Sons) is 40-50 ° C. It is used by appropriately mixing the monomer. When the theoretical glass transition temperature is less than 40 ° C., problems are likely to occur from the viewpoint of storage stability and durability stability of the toner, whereas when it exceeds 75 ° C., the fixing point of the toner is increased. In particular, in the case of a color toner for forming a full-color image, the color mixing property at the time of fixing each color toner is lowered, the color reproducibility is poor, and the transparency of the OHP image is further lowered.

  The molecular weight of the binder resin is measured by gel permeation chromatography (GPC). In the case of a toner having a core-shell structure, as a specific GPC measurement method, the toner is extracted beforehand with a toluene solvent using a Soxhlet extractor for 20 hours, and then the toluene is distilled off with a rotary evaporator. Further, an organic solvent (for example, chloroform) that dissolves the low softening point substance but not the outer shell resin is added to the extract and washed thoroughly, and then the residue is dissolved in tetrahydrofuran (THF). A sample (THF solution) filtered through a solvent-resistant membrane filter having a diameter of 0.3 μm is measured using 150C manufactured by Waters. The column structure can connect A-801, 802, 803, 804, 805, 806, 807 manufactured by Showa Denko and measure the molecular weight distribution using a standard polystyrene resin calibration curve. The main peak molecular weight of the binder resin according to the present invention is 5,000 to 1,000,000, and the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is 2 to 100. preferable.

  Examples of the colorant used in the present invention include the following yellow colorant, magenta colorant, and cyan colorant. As the black colorant, carbon black, magnetic substance, or yellow colorant / magenta colorant / cyan color shown below. What was mixed with the agent and was toned to black is used.

  As the yellow colorant, compounds typified by condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds are used. Specifically, C.I. I. Pigment Yellow 12, 13, 14, 15, 17, 62, 74, 83, 93, 94, 95, 109, 110, 111, 128, 129, 147, 168, 180, etc. are preferably used.

  As the magenta colorant, condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds are used. Specifically, C.I. I. Pigment Red 2, 3, 5, 6, 7, 23, 48; 2, 48; 3, 48; 4, 57; 1, 81; 1, 144, 146, 166, 169, 177, 184, 185, 202, 206, 220, 221, 254 are particularly preferred.

  As the cyan colorant, copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, basic dye lake compounds, and the like can be used. Specifically, C.I. I. Pigment Blue 1, 7, 15, 15; 1, 15; 2, 15; 3, 15; 4, 60, 62, 66 and the like can be used particularly preferably.

  These colorants can be used alone or mixed and further used in the form of a solid solution. The colorant is selected from the viewpoints of hue, saturation, lightness, weather resistance, OHP transparency, and dispersibility in the toner particles. The addition amount of the colorant is preferably 1 to 20 parts by mass with respect to 100 parts by mass of the resin component.

  When a magnetic material is used as the black colorant, it is preferable to use 40 to 150 parts by mass with respect to 100 parts by mass of the resin, unlike other colorants.

  Examples of the wax component according to the present invention include petroleum waxes such as paraffin wax, microcrystalline wax, petrolactam and derivatives thereof, montan wax and derivatives thereof, hydrocarbon waxes and derivatives thereof by Fischer-Tropsch method, and polyolefins represented by polyethylene Wax and its derivatives, carnauba wax, candelilla wax, natural wax and their derivatives, etc. The derivatives include oxides, block copolymers with vinyl monomers, graft modified products, and higher aliphatic alcohols. Alcohols such as stearic acid, palmitic acid and the like or compounds thereof; acid amides, esters, ketones, hydrogenated castor oil and derivatives thereof, vegetable waxes, animal waxes, etc., having a melting temperature of 40-80 ° C. in styrene monomers It can be used anywhere as long as it.

  Of these, polyolefin, Fischer-Tropsch hydrocarbon wax, petroleum wax, higher alcohol, or higher ester further enhances the developability and transferability.

  The wax component described above is preferably used in an amount of 1 to 30 parts by mass with respect to 100 parts by mass of the binder resin.

  In addition, an antioxidant may be added to the wax component as long as it does not affect the chargeability of the toner.

  The wax component according to the present invention is substantially spherical and / or spindle-shaped and island-shaped in a state where the wax component is not compatible with the binder resin in the tomographic observation of the toner using a transmission electron microscope (TEM). Is distributed.

  In the present invention, a specific method for observing the tomographic plane of the toner particles was obtained by sufficiently dispersing the toner particles in a room temperature curable epoxy resin and then curing the toner particles at an ambient temperature of 40 ° C. for 2 days. After the cured product is dyed with ruthenium tetroxide and, if necessary, osmium tetroxide, a flaky sample is cut out using a microtome with diamond teeth, and the tomographic morphology of toner particles using a transmission electron microscope (TEM) Measure. In the present invention, it is preferable to use a ruthenium tetroxide dyeing method in order to provide a contrast between materials by utilizing a slight difference in crystallinity between the wax component to be used and the resin constituting the outer shell. A typical example is shown in FIG. In the toner particles obtained in Examples described later, it was observed that the wax component was encapsulated with the outer shell resin.

  As the charge control agent used in the present invention, a known charge control agent can be used, but a charge control agent that has a high charging speed and can stably maintain a constant charge amount is preferable. Further, when a direct polymerization method is used for toner particles, a charge control agent having no polymerization inhibitory property and having no solubilized product in an aqueous dispersion medium is particularly preferable. Specific compounds include metal compounds of aromatic carboxylic acids such as salicylic acid, naphthoic acid and dicarboxylic acid as negative charge control agents; polymer compounds having a sulfonic acid or carboxylic acid group in the side chain; boron compounds; urea Compound; silicon compound; calixarene and the like. Examples of the positive charge control agent include quaternary ammonium salts; polymer type compounds having the quaternary ammonium salt in the side chain; guanidine compounds; imidazole compounds. The charge control agent is preferably used in an amount of 0.5 to 10 parts by mass with respect to 100 parts by mass of the resin. However, in the present invention, it is not essential to add a charge control agent. When a two-component development method is used, friction charging with a carrier is used, and when a non-magnetic one-component blade coating development method is used, It is not always necessary to include a charge control agent in the toner particles by actively utilizing frictional charging with the blade member or the sleeve member.

Adding an inorganic fine powder to the toner of the present invention is a preferred embodiment for improving developability, transferability, charging stability, fluidity, and durability. As the inorganic fine powder, known ones can be used, and it is particularly preferred to be selected from silica, alumina, titania or a double oxide thereof. Further, silica is more preferable. For example, the silica can be either a so-called dry method produced by vapor phase oxidation of silicon halide or alkoxide, or dry silica called fumed silica and so-called wet silica produced from alkoxide, water glass, etc. However, dry silica having less silanol groups on the surface and inside the silica fine powder and less production residue such as Na ₂ O, SO ₃ ²⁻ is more preferable. In dry silica, it is also possible to obtain composite fine powders of silica and other metal oxides by using other metal halogen compounds such as aluminum chloride and titanium chloride together with silicon halogen compounds in the production process. Is also included.

Inorganic fine powder used in the present invention is the specific surface area by nitrogen adsorption measured by BET method 30 m ² / g or more, especially given the 50 to 400 m ² / g good results in the range of, relative to 100 mass parts of the toner The silica fine powder is particularly preferably used in an amount of 0.1 to 8 parts by mass, preferably 0.5 to 5 parts by mass, and more preferably 1.0 to 3.0 parts by mass.

  In addition, the inorganic fine powder used in the present invention has a silicone varnish, various modified silicone varnishes, silicone oil, various modified silicone oils, a silane coupling agent, and a functional group as necessary for the purpose of hydrophobization and chargeability control. It is possible and preferable to treat with a treating agent such as a silane coupling agent, an organic silicon compound, an organic titanium compound, etc. or in combination with various treating agents.

  In accordance with the BET method, the specific surface area was determined by adsorbing nitrogen gas on the sample surface using a specific surface area measuring device Auto Soap 1 (manufactured by Yuasa Ionics) and calculating the specific surface area using the BET multipoint method.

  In order to maintain a high charge amount and achieve a low consumption and a high transfer rate, the inorganic fine powder is more preferably treated with at least silicone oil.

  In the toner of the present invention, other additives, such as a lubricant powder such as a polyfluorinated ethylene powder, a zinc stearate powder, and a polyvinylidene fluoride powder; a cerium oxide powder, a silicon carbide powder, within a range that does not substantially adversely affect the toner. A polishing agent such as strontium titanate powder; a fluidity imparting agent such as titanium oxide powder or aluminum oxide powder; an anti-caking agent or a conductivity imparting agent such as carbon black powder, zinc oxide powder or tin oxide powder; A small amount of organic fine particles and inorganic fine particles having opposite polarities can also be used as a developability improver.

  As a method for producing the toner of the present invention, a resin, a release agent composed of a low softening point substance, a colorant, a charge control agent, and the like are uniformly dispersed using a pressure kneader, an extruder, or a media dispersing machine, After colliding with the target under mechanical or jet airflow, and finely pulverizing to the desired toner particle size (adding toner particle smoothing and spheronization if necessary), the particle size distribution through the classification process In addition to a method for producing a toner by a pulverization method that sharpens and squeezes toner, a method of obtaining a spherical toner by atomizing a molten mixture in air using a disk or a multi-fluid nozzle described in JP-B-56-13945, etc. Direct toner production using the suspension polymerization method described in JP-B 36-10231, JP-A 59-53856, and JP-A 59-61842 Or a dispersion polymerization method that directly produces toner using a water-based organic solvent that is soluble in the monomer and insoluble in the polymer, or a soap that produces toner by direct polymerization in the presence of a water-soluble polar polymerization initiator. The toner can be produced using an emulsion polymerization method typified by a free polymerization method.

  In the method of producing toner using the pulverization method, it is difficult to keep the shape of the toner within the desired circularity frequency distribution range, and in the melt spray method, a certain degree of circularity can be obtained. There is a tendency that the particle size distribution of the obtained toner tends to be wide, and it is difficult to control the surface state of the toner. On the other hand, in the dispersion polymerization method, the obtained toner shows a very sharp particle size distribution, but the production equipment is used from the viewpoint of the processing of the waste solvent and the flammability of the solvent due to the narrow selection of materials to be used and the use of organic solvents. Complicated and complicated. The emulsion polymerization method represented by soap-free polymerization is effective because the particle size distribution of the toner is relatively uniform. However, when the used emulsifier or polymerization initiator terminal is present on the toner particle surface, it tends to deteriorate environmental characteristics.

  In the present invention, the circularity frequency distribution of the toner can be controlled, and an emulsifier polymerization method or a suspension polymerization method under normal pressure, or under pressure at which a toner with a reduced particle size can be obtained relatively easily, The pre-obtained polymer is shaped using media, the polymer is directly collided against the pressure impingement plate, the obtained polymer is frozen in an aqueous system, salt folding, or opposite surface charge An agglomeration method in which particles having a particle size are coalesced by considering conditions such as pH, and agglomeration and coalescence are particularly preferred. Furthermore, a seed polymerization method in which a monomer is further adsorbed to the obtained polymer particles and then polymerized using a polymerization initiator can be suitably used in the present invention.

  When the direct polymerization method is used as a toner production method, the control of the toner circularity frequency distribution and particle size distribution can be achieved by changing the type and amount of the hardly water-soluble inorganic salt and the dispersing agent acting as a protective colloid. The predetermined toner particles can be obtained by controlling the general apparatus conditions (for example, the rotor speed, the number of baths, the stirring conditions such as the shape of the stirring blades and the container shape), or the solid content concentration in the aqueous solution.

  When the toner is produced by the direct polymerization method, examples of the polymerization initiator used include 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, 1,1. Azo or diazo polymerization initiators such as' -azobis (cyclohexane-1-carbonitrile), 2,2'-azobis-4-methoxy-2,4-dimethylvaleronitrile, azobisisobutyronitrile; benzoyl peroxide Peroxide-based polymerization initiators such as methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, cumene hydroperoxide, 2,4-dichlorobenzoyl peroxide, lauroyl peroxide are used. The amount of the polymerization initiator used varies depending on the desired degree of polymerization, but is generally 0.5 to 20% by weight based on the polymerizable monomer. The kind of the polymerization initiator is slightly different depending on the polymerization method, but is used alone or in combination with reference to the 10-hour half-life temperature.

  In order to control the degree of polymerization, a known crosslinking agent, chain transfer agent, polymerization inhibitor and the like may be further added and used.

  When a suspension polymerization method using a dispersion stabilizer is used as a toner production method, the dispersion stabilizer used is an inorganic compound such as tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, calcium carbonate, Examples thereof include magnesium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate, bentonite, silica, and alumina. Examples of the organic compound include polyvinyl alcohol, gelatin, methyl cellulose, methyl hydroxypropyl cellulose, ethyl cellulose, carboxymethyl cellulose sodium salt, polyacrylic acid and its salt, starch and the like. These can be used by dispersing in an aqueous phase. These dispersion stabilizers are preferably used in an amount of 0.2 to 20 parts by mass with respect to 100 parts by mass of the polymerizable monomer.

  When an inorganic compound is used as the dispersion stabilizer, a commercially available one may be used as it is, but in order to obtain fine particles, fine particles of the inorganic compound may be generated in a dispersion medium. For example, in the case of tricalcium phosphate, a sodium phosphate aqueous solution and a calcium chloride aqueous solution may be mixed under high-speed stirring.

  For fine dispersion of these dispersion stabilizers, 0.001 to 0.1 parts by mass of a surfactant may be used in combination. This is for accelerating the intended action of the dispersion stabilizer, for example, sodium dodecylbenzene sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate, Examples include potassium stearate and calcium oleate.

  When the direct polymerization method is used as a method for producing the toner used in the present invention, the following production method is possible.

  A wax component consisting of a low softening point substance, a colorant, a charge control agent, a polymerization initiator and other additives are added to the polymerizable monomer, and the monomer is uniformly dissolved or dispersed by a homogenizer, an ultrasonic disperser, or the like. The meter composition is dispersed in an aqueous phase containing a dispersion stabilizer by a usual stirrer, homomixer, homogenizer or the like. Preferably, granulation is performed by adjusting the stirring speed and stirring time so that the droplets of the monomer composition have the desired toner particle size. Thereafter, stirring may be performed to such an extent that the particle state is maintained and the sedimentation of the particles is prevented by the action of the dispersion stabilizer. The polymerization is preferably carried out at a polymerization temperature of 40 ° C. or higher, generally 50 to 90 ° C. The temperature may be raised in the latter half of the polymerization reaction, and for the purpose of improving durability in the image forming method of the present invention, in order to remove unreacted polymerizable monomers and by-products, the latter half of the reaction, Alternatively, part of the aqueous medium may be distilled off from the reaction system after completion of the reaction. After completion of the reaction, the produced toner particles are recovered by washing and filtration and dried. In the suspension polymerization method, it is usually preferable to use 300 to 3000 parts by mass of water as a dispersion medium with respect to 100 parts by mass of the monomer composition.

  On the other hand, in order to obtain a desired toner shape distribution, it is one of preferred embodiments of the present invention to apply treatment to the shape and surface of toner particles by an impact type powder processing apparatus using a rotating blade.

  As an impact type powder processing apparatus using a rotating blade, Y.K. Takayama, Y .; Kikuchi and K.K. Ono: ZAIRYO GIJUTSU Vol. 8, no. 8, 10 (1990), known manufacturing devices such as a powder processing device, a hybridization system manufactured by Nara Machinery Co., Ltd., and an impact pulverizer manufactured by Turbo Industry Co., can be used. It is preferable to use the powder processing apparatus shown in FIGS. 6 to 8 in order to precisely perform the processing, precisely control the desired shape distribution, and achieve high productivity.

  An impact type powder processing apparatus using a rotating blade suitable for the present invention will be specifically described with reference to the drawings.

  6 is an example of a powder shape processing apparatus system incorporating a powder processing apparatus A suitable for the present invention, FIG. 7 is a partial sectional view of the powder processing apparatus A, and FIG. It is a perspective view of the rotational drive shaft which has a step.

  In the powder processing apparatus A shown in FIG. 7, first to fourth cylindrical processing chambers 79 a to 79 d are connected and provided in a cylindrical casing 51, and a rotary rotor 52 a having 10 blades each. ˜52d are included in a state of being fixed to the rotary drive shaft 53. The rotation drive shaft 53 is supported by bearings 61 and 62, and the rotation of the electric motor 84 is transmitted by the belt hung on the pulley 54 at the lower end, and rotates at high speed in the direction of the arrow.

  The toner particles in the quantitative supply device 66 shown in FIG. 6 are provided in the center of the front wall 83 of the first cylindrical processing chamber 79a through the vibration feeder 65, through the hopper 82 and the powder supply pipe 81. The air is introduced into the first cylindrical processing chamber 79 a together with air from the powder supply port 80 by the suction force of the suction pro 74. The toner particles introduced into the first cylindrical processing chamber 79a are side walls of the first cylindrical processing chamber due to an air flow from the central direction to the side wall 57a generated with the rotation of the rotary rotor 52a having ten blades. 57a, surface treatment is performed while convection in the space of the first cylindrical processing chamber 79a, and sequentially passes through the gap between the side wall 57a and the blade 59a, and the back surface of the rotary rotor 52a and the first rear wall 58a. It passes through a gap with the guide plate or the second front wall, and is discharged from a first powder discharge port 60a provided at the center of the first rear wall 58a. In the processing apparatus A, the first powder discharge port 60a also serves as the powder supply port of the second cylindrical processing chamber 79b, and the toner particles pass through the first powder discharge port 60a and are second. It is introduced into the central part of the cylindrical processing chamber 79b. In the second cylindrical processing chamber 79b, the toner particles subjected to the surface treatment in the first cylindrical processing chamber 79a are similar to the first cylindrical processing chamber 79a in the rotating rotor 52b having ten blades. Further surface treatment by rotation. Further, the toner particles surface-treated in the second cylindrical processing chamber 79b are subsequently surface-treated in the third cylindrical processing chamber 79c and the fourth cylindrical processing chamber 79d.

  The toner particles surface-treated in the fourth cylindrical processing chamber 79d pass through the fourth powder discharge port 60d provided at the center of the guide plate 58d, and are discharged in the tangential direction of the cylindrical casing 51. It is stored in the cyclone 70 through the connection pipe 67 via the discharge port 63 a of the pipe 63. The surface-treated toner particles stored in the cyclone 70 are appropriately taken out from the valve 71.

  The shape distribution of the toner is not limited to the shape of the cylindrical processing chamber of the powder processing apparatus, the shape and number of blades fixed to the rotary rotor, the fixed position, the rotational speed of the rotary rotor, and the toner particles in the cylindrical processing chamber. The residence time, particle concentration, atmospheric temperature during processing, etc. can be appropriately adjusted.

(3) Process Cartridge and Electrophotographic Apparatus FIG. 9 shows an example of a schematic configuration of an electrophotographic apparatus provided with a process cartridge having a charging member of the present invention.

  In FIG. 9, reference numeral 1 denotes a cylindrical electrophotographic photosensitive member, which is driven to rotate at a predetermined peripheral speed in the direction of the arrow about the shaft 2. As an electrophotographic photosensitive member, those having a support and an inorganic photosensitive layer or an organic photosensitive layer formed on the support are generally used. In addition, the electrophotographic photosensitive member may have a charge injection layer as a surface layer.

  The surface of the electrophotographic photosensitive member 1 that is driven to rotate is uniformly charged to a predetermined positive or negative potential by the charging member 3 (roller-shaped charging member in FIG. 9) of the present invention, and then subjected to slit exposure or laser. Exposure light (image exposure light) 4 output from exposure means (not shown) such as beam scanning exposure is received. In this way, electrostatic latent images corresponding to the target image are sequentially formed on the surface of the electrophotographic photosensitive member 1.

  When the surface of the electrophotographic photosensitive member 1 is charged by the charging member 3, a voltage of only a DC voltage or a voltage obtained by superimposing an AC voltage on the DC voltage is applied to the charging member 3 from a voltage applying unit (not shown). In the examples described later, a voltage (-1200 V) of only DC voltage was applied to the charging member. In the examples described later, the dark portion potential was −600 V and the light portion potential was −350 V.

  The electrostatic latent image formed on the surface of the electrophotographic photosensitive member 1 is developed (reverse development or normal development) with toner contained in the developer of the developing unit 5 to become a toner image. Next, the toner image formed and supported on the surface of the electrophotographic photoreceptor 1 is transferred from a transfer material supply means (not shown) to the electrophotographic photoreceptor 1 and the transfer means by a transfer bias from a transfer means (transfer roller or the like) 6. 6 (contact portion) is sequentially transferred onto a transfer material (paper or the like) P taken out and fed in synchronization with the rotation of the electrophotographic photosensitive member 1.

  Examples of the developing means include a jumping developing means, a contact developing means, and a magnetic brush means. From the viewpoint of improving toner scattering properties, a contact developing means is preferable. Adopted.

  Moreover, as a transfer roller, what coat | covers the elastic resin layer adjusted to medium resistance on a support body is illustrated.

  The transfer material P that has received the transfer of the toner image is separated from the surface of the electrophotographic photosensitive member 1 and introduced into the fixing means 8 to receive the image fixing, and is printed out as an image formed product (print, copy). Is done. In the case of the double-sided image forming mode or the multiple image forming mode, the image formed product is introduced into a recirculation conveyance mechanism (not shown) and reintroduced into the transfer unit.

  The surface of the electrophotographic photosensitive member 1 after the transfer of the toner image is cleaned by a cleaning means (cleaning blade or the like) 7 to remove the developer (toner) remaining after transfer, and further from a pre-exposure means (not shown). After being subjected to charge removal processing by pre-exposure light (not shown), it is repeatedly used for image formation. When the charging unit is a contact charging unit, pre-exposure is not always necessary.

  Among the above-described components such as the electrophotographic photosensitive member 1, the charging member 3, the developing unit 5, the transfer unit 6, and the cleaning unit 7, a plurality of components are housed in a container and integrally combined as a process cartridge. The process cartridge may be configured to be detachable from an electrophotographic apparatus main body such as a copying machine or a laser beam printer. In FIG. 9, the electrophotographic photosensitive member 1, the charging member 3, the developing means 5, and the cleaning means 7 are integrally supported to form a cartridge, and the electrophotographic apparatus main body is guided using a guide means 10 such as a rail of the electrophotographic apparatus main body. The process cartridge 9 is detachable.

  Hereinafter, the present invention will be described in more detail with reference to specific examples. However, the present invention is not limited to these. In the examples, “part” means “part by mass”.

  First, charging member manufacturing examples will be described.

<Charging member production example 1>
100 parts of epichlorohydrin rubber (trade name: Epichromer CG102, manufactured by Daiso Corporation), 35 parts of MT carbon (trade name: HTC # 20, manufactured by Shin Nikka Carbon Co., Ltd.) as a filler, bentonite (trade name: Bengel) SH, manufactured by Hojun Co., Ltd.), 5 parts of zinc oxide, and 1 part of stearic acid were kneaded with an open roll for 30 minutes. To this kneaded mixture for 30 minutes, 1 part of di-2-benzothiazolyl disulfide (trade name: Noxeller DM-P, manufactured by Ouchi Shinsei Chemical Co., Ltd.) as a vulcanization accelerator, 1 part of tetramethylthiuram monosulfide (trade name: Noxeller TS, manufactured by Ouchi Shinsei Chemical Co., Ltd.) and 1.2 parts of sulfur as a vulcanizing agent are added, and the mixture is further kneaded with an open roll for 15 minutes. I was obtained.

  Next, the kneaded material I was extruded into a cylindrical shape having an outer diameter of 9.5 mm and an inner diameter of 5.4 mm with a rubber extruder, cut into a length of 250 mm, and primary for 30 minutes with steam at 160 ° C. with a vulcanizing can. By vulcanization, a primary vulcanization tube I for conductive elastic layer was obtained.

  On the other hand, a region up to 115.5 mm on both sides across the center in the axial direction of the cylindrical surface of a cylindrical steel support (surface plated with nickel) having a diameter of 6 mm and a length of 256 mm (along with an axial width of 231 mm) After applying a thermosetting adhesive containing metal and rubber (trade name: METALOC U-20, manufactured by Toyo Chemical Laboratories Co., Ltd.) to the region), drying it at 80 ° C. for 30 minutes, and then adding 1 Dry at 120 ° C. for hours.

  A support obtained by applying a thermosetting adhesive to the cylindrical surface and drying it is inserted into the primary vulcanization tube I for the conductive elastic layer, and then the primary vulcanization tube I for the conductive elastic layer is attached. Heated at 160 ° C. for 1 hour. By this heating, the primary vulcanization tube I for the conductive elastic layer was secondarily vulcanized, and the thermosetting adhesive was cured. In this way, a conductive elastic roller I before surface polishing was obtained.

  Next, both ends of the conductive elastic layer portion (rubber portion) of the conductive elastic roller I before surface polishing are cut so that the axial width of the conductive elastic layer portion is 231 mm, and then the surface of the conductive elastic layer portion Is polished with a rotating grindstone, and has a crown shape with an end diameter of 8.2 mm and a central diameter of 8.5 mm. The surface ten-point average roughness (Rz) is 4.9 μm and the runout is 22 μm. A roller (conductive elastic roller after surface polishing) I was obtained.

  Ten-point average roughness (Rz) was measured according to JISB6101.

  The shake was measured using a high-precision laser measuring machine LSM-430v manufactured by Mitutoyo Corporation. Specifically, the outer diameter is measured using the measuring device, and the difference between the maximum outer diameter value and the minimum outer diameter value is defined as the outer diameter difference run. This measurement is performed at five points, and the average of the five outer diameter difference shakes is measured. The value was the runout of the object to be measured.

  The hardness of the obtained conductive elastic roller (conductive elastic roller after surface polishing) I was 74 degrees (Asker C).

  Next, 27.84 g (0.1 mol) of glycidoxypropyltriethoxysilane (GPTES) as a hydrolyzable silane compound, 17.83 g (0.1 mol) of methyltriethoxysilane (MTES), and tridecafluoro-1 , 1,2,2-tetrahydrooctyltriethoxysilane (FTS, carbon number 6 of perfluoroalkyl group) 7.68 g (0.0151 mol (equivalent to 7 mol% with respect to the total amount of hydrolyzable silane compound)), water 17 .43 g and 37.88 g of ethanol were mixed and then stirred at room temperature, followed by heating under reflux for 24 hours to obtain a hydrolyzable silane compound condensate I.

  This condensate I was added to a mixed solvent of 2-butanol / ethanol to prepare a condensate-containing alcohol solution I having a solid content of 7% by mass.

  0.35 g of an aromatic sulfonium salt (trade name: Adekaoptomer SP-150, manufactured by Asahi Denka Kogyo Co., Ltd.) as a photocationic polymerization initiator was added to 100 g of this condensate-containing alcohol solution I. By adding to the solution I, a surface layer coating solution I was prepared.

Next, the surface layer coating liquid I is ring-coated on the conductive elastic layer of the conductive elastic roller (conductive elastic roller after surface polishing) I, and ultraviolet light with a wavelength of 254 nm is applied to this with an integrated light quantity of 9000 mJ / cm. ^The surface layer was formed by irradiating the coating solution I for surface layer ² and curing (curing by crosslinking reaction) and drying. A low-pressure mercury lamp manufactured by Harrison Toshiba Lighting Co., Ltd. was used for ultraviolet irradiation.

  It is considered that the glycidoxy group of glycidoxypropyltriethoxysilane was cleaved by irradiation with ultraviolet rays, and the crosslinking reaction of condensate I occurred.

As described above, the support, the conductive elastic layer formed on the support, and the surface layer (polysiloxane formed using the surface layer coating liquid I) formed on the conductive elastic layer. A charging roller having a layer containing This charging roller is referred to as a charging roller I. The electrostatic capacity (C) of the surface layer of the charging roller I was 1.43 × 10 ⁻⁸ F. Other physical properties are shown in Table 2.

-Composition analysis of the surface layer of the charging roller The composition analysis of the surface layer of the charging roller I was performed as follows.

  A sample of about 1 mg was collected from the surface layer of the charging roller I produced in the same manner as described above using a three-dimensional coarse / fine movement micromanipulator (manufactured by Narishige Co., Ltd.) placed under an optical microscope of 10 to 1000 times. did.

  The collected sample was traced as a function of temperature simultaneously with the weight change by the TG-MS method (the MS device was directly connected to the TG device) at the same time as the weight change. Table 1 shows the measurement conditions.

  According to the TG-DTG (Derivative thrombometry) curve obtained by the measurement under the above conditions, a mass decrease was observed from around room temperature, and a remarkable mass in two stages from around 400 to 500 ° C. and around 500 to 650 ° C. A decrease was observed.

  Here, the oxyalkylene group (derived from the glycidoxy group of glycidoxypropyltriethoxysilane) having a mass number (m / z) 31, 43, 58, 59 can be confirmed for the gas generated at 400 ° C to 500 ° C. From the weight reduction rate, it was found that the content of the oxyalkylene group in the polysiloxane was 38.20% by mass with respect to the total mass of the polysiloxane.

  Further, for gases generated at 500 ° C. to 600 ° C., fluorinated alkyl groups (tridecafluoro-1,1,2,2-tetrahydrooctyltriethoxysilane) having mass numbers (m / z) 51, 69, 119, and 131 are used. From the mass reduction rate, the content of the fluorinated alkyl group in the polysiloxane was found to be 18.36% by mass relative to the total mass of the polysiloxane.

  The residue is considered to be a siloxane part in the polysiloxane, and therefore the content of the siloxane part in the polysiloxane is 100.00− (37.36 + 19.20) = 43.44% by mass with respect to the total mass of the polysiloxane. It is.

  Table 3 shows the composition analysis results.

<Charging member production example 2>
A charging member was produced in the same manner as in Charging Member Production Example 1 except that tridecafluoro-1,1,2,2-tetrahydrooctyltriethoxysilane was removed from the surface layer coating solution I.

  Table 2 shows the physical properties of the manufactured charging roller, and Table 3 shows the results of composition analysis.

<Charging member production example 3>
A charging roller was produced in the same manner as in Example 1 except that the surface layer coating solution I was changed to the following surface layer coating solution II. This charging roller is referred to as a charging roller II.

  The surface layer coating solution II was prepared as follows.

  That is, glycidoxypropyltriethoxysilane (GPTES) 27.84 g (0.1 mol), methyltriethoxysilane (MTES) 17.83 g (0.1 mol) as a hydrolyzable silane compound, and tridecafluoro-1, 1,34,4-tetrahydrooctyltriethoxysilane (FTS, carbon number of perfluoroalkyl group: 10) 3.34 g (0.0047 mol (equivalent to 2.3 mol% with respect to the total amount of hydrolyzable silane compound)), water After mixing 16.6 g and 31.7 g of ethanol, the mixture was stirred at room temperature and then heated to reflux for 24 hours to obtain a hydrolyzable silane compound condensate II.

  By adding this condensate II to a mixed solvent of 2-butanol / ethanol, a condensate-containing alcohol solution II having a solid content of 7% by mass was prepared.

  0.35 g of an aromatic sulfonium salt (trade name: Adekaoptomer SP-150, manufactured by Asahi Denka Kogyo Co., Ltd.) as a photocationic polymerization initiator for 100 g of this condensate-containing alcohol solution II was used. By adding to the solution II, a surface layer coating solution II was prepared.

  Table 2 and Table 3 show the physical properties of the manufactured charging roller II.

<Charging member production example 4>
A charging roller was produced in the same manner as in Example 1 except that the surface layer coating liquid I in the charging member production example 1 was changed to the following surface layer coating liquid III. This charging roller is referred to as a charging roller III.

  The surface layer coating solution III was prepared as follows.

  That is, 27.84 g (0.1 mol) of glycidoxypropyltriethoxysilane (GPTES) as a hydrolyzable silane compound, 24.04 g (0.1 mol) of phenyltriethoxysilane (PhTES), and tridecafluoro-1, 17.68 g (0.0151 mol (equivalent to 7 mol% with respect to the total amount of hydrolyzable silane compound)) of 1,2,2-tetrahydrooctyltriethoxysilane (FTS, carbon number 6 of perfluoroalkyl group) and water 17. After mixing 43 g and 53.82 g of ethanol, the mixture was stirred at room temperature and then heated to reflux for 24 hours to obtain a hydrolyzable silane compound condensate III.

  By adding this condensate III to a mixed solvent of 2-butanol / ethanol, a condensate-containing alcohol solution III having a solid content of 7% by mass was prepared.

  0.35 g of an aromatic sulfonium salt (trade name: Adekaoptomer SP-150, manufactured by Asahi Denka Kogyo Co., Ltd.) as a photocationic polymerization initiator for 100 g of this condensate-containing alcohol solution III was converted into a condensate-containing alcohol. By adding to the solution III, a surface layer coating solution III was prepared.

  Table 2 shows the physical properties of the manufactured charging roller, and Table 3 shows the results of composition analysis.

  In addition, about the gas generate | occur | produced at 400 to 500 degreeC, phenyl groups, such as benzene of mass number (m / z) 78, and mass number (m / z) 91 (toluene), can be confirmed, From this, about the said phenyl group, Mass% was calculated.

<Charging member production example 5>
In the charging member production example 1, a charging roller was produced in the same manner as in Example 1 except that the surface layer coating liquid I was changed to the following surface layer coating liquid IV. This charging roller is referred to as a charging roller IV.

  The surface layer coating solution IV was prepared as follows.

  That is, 41.43 g (0.149 mol) of glycidoxypropyltriethoxysilane (GPTS) as a hydrolyzable silane compound, 30.71 g (0.149 mol) of hexyltrimethoxysilane (HeTMS), and tridecafluoro-1, 1.42 g of 1,2,2-tetrahydrooctyltriethoxysilane (FTS, carbon number 6 of perfluoroalkyl group) (0.0224 mol (equivalent to 7 mol% with respect to the total amount of hydrolyzable silane compound)) and water 25. After mixing 93 g and ethanol 83.14 g, the mixture was stirred at room temperature and then heated to reflux for 24 hours to obtain a hydrolyzable silane compound condensate IV.

  By adding this condensate IV to a mixed solvent of 2-butanol / ethanol, a condensate-containing alcohol solution IV having a solid content of 7% by mass was prepared.

  0.35 g of an aromatic sulfonium salt (trade name: Adekaoptomer SP-150, manufactured by Asahi Denka Kogyo Co., Ltd.) as a photocationic polymerization initiator for 100 g of this condensate-containing alcohol solution IV was used as a condensate-containing alcohol. By adding to the solution IV, a surface layer coating solution IV was prepared.

  Table 2 shows the physical properties of the manufactured charging roller, and Table 3 shows the results of composition analysis.

  In addition, about the gas generate | occur | produced at 400 to 500 degreeC, alkyl groups, such as mass number (m / z) 16, 41, can also be confirmed, and mass% regarding the said alkyl group was computed from this.

<Charging member production example 6>
A charging roller was produced in the same manner as in Example 1 except that the surface layer coating solution I was changed to the following surface layer coating solution V in the charging member production example 1. This charging roller is referred to as a charging roller V.

  The surface layer coating solution V was prepared as follows.

  That is, 32.52 g (0.117 mol) of glycidoxypropyltriethoxysilane (GPTES) as a hydrolyzable silane compound, 28.08 g (0.117 mol) of phenyltriethoxysilane (PhTES), hexyltrimethoxysilane (HeTMS) 13.21 g (0.064 mol) and tridecafluoro-1,1,2,2-tetrahydrooctyltriethoxysilane (FTS, carbon number 6 of perfluoroalkyl group) 11.42 g (0.022 mol (hydrolyzable) The total amount of the silane compound is equivalent to 7 mol%), 25.93 g of water and 77.12 g of ethanol, and then stirred at room temperature and then heated to reflux for 24 hours to condense the hydrolyzable silane compound. Product V was obtained.

  By adding this condensate V to a mixed solvent of 2-butanol / ethanol, a condensate-containing alcohol solution V having a solid content of 7% by mass was prepared.

  0.35 g of an aromatic sulfonium salt (trade name: Adekaoptomer SP-150, manufactured by Asahi Denka Kogyo Co., Ltd.) as a photocationic polymerization initiator for 100 g of this condensate-containing alcohol solution V was used as a condensate-containing alcohol. By adding to the solution V, the surface layer coating solution V was prepared.

  Table 2 shows the physical properties of the manufactured charging roller, and Table 3 shows the results of composition analysis.

<Charging member comparative production example 1>
Polyester polyol for elastomer (trade name: Nipponporan 4042 (hydroxyl value 56 KOHmg / g), manufactured by Nippon Polyurethane Industry Co., Ltd.) and conductive carbon (trade name: Toka Black # 3845, manufactured by Tokai Carbon Co., Ltd.) 1 part Was kneaded with three rolls to obtain a kneaded product CI.

  Next, the kneaded product CI was heated to 100 ° C. and dehydrated for 3 hours under a reduced pressure of 3 mmHg.

  Next, 2,6-tolylene diisocyanate (trade name: Cosmonate T-80, manufactured by Mitsui Chemicals) 19 so that the NCO / OH ratio is 1.05 in the kneaded product CI after the dehydration treatment. 0.1 g was added and these were mixed vigorously for 2 to 3 minutes to obtain a composition for a conductive elastic layer.

  By pouring this conductive elastic layer composition into a mold that has been heated to 150 ° C. in advance (the inner mold is a support similar to the support used in Example 1) and leaving it for 60 minutes, The composition for conductive elastic layer was cured, then demolded, and the composition for conductive elastic layer was further cured at 110 ° C. for 24 hours. In this way, a conductive elastic roller CI was obtained.

  Next, 100 parts of urethane resin (trade name: Resamine ME44-ELP, manufactured by Dainichi Seika Kogyo Co., Ltd.), fluorine-based modifier (trade name: Dialomer FF-101 (D), Dainichi Seika Kogyo Co., Ltd.) (Manufactured) 1.3 parts and leveling resin (trade name: GS-30, manufactured by Toagosei Co., Ltd.) 0.05 parts in a mixed solvent of methyl ethyl ketone 177 parts / dimethylformamide 98 parts, for the surface layer A coating solution CI was prepared.

  The surface layer coating liquid CI was dip-coated on the conductive elastic layer of the conductive elastic roller CI and dried at 100 ° C. for 30 minutes to form a surface layer having a layer thickness of 15 μm.

  Thus, a charging roller having a support, a conductive elastic layer formed on the support, and a surface layer formed on the conductive elastic layer was produced. This charging roller is a charging roller CI.

  Table 2 shows the physical properties of the manufactured charging roller, and Table 3 shows the results of composition analysis.

<Charging member comparative production example 2>
A conductive elastic roller (conductive elastic roller after surface polishing) CII was obtained in the same manner as in the charging member production example 1 except that the kneaded material I was changed to the following kneaded material CII.

  The kneaded material CII was obtained as follows.

  That is, 100 parts of epichlorohydrin rubber (trade name: Epichromer CG102, manufactured by Daiso Co., Ltd.), 5 parts of MT carbon (trade name: HTC # 20, manufactured by Shin-Nippon Carbon Co., Ltd.) as filler, 5 parts of zinc oxide , 1 part of stearic acid, 5 parts of bis (2-ethylhexyl) adipate as a plasticizer (trade name: DOA, manufactured by J. Plus) and 1 part of perchloric acid quaternary ammonium salt as an ionic conductive agent Was kneaded with an open roll for 30 minutes. To this kneaded mixture for 30 minutes, 1 part of di-2-benzothiazolyl disulfide (trade name: Noxeller DM-P, manufactured by Ouchi Shinsei Chemical Co., Ltd.) as a vulcanization accelerator, By adding 1.0 part of tetramethylthiuram monosulfide (trade name: Noxeller TS, manufactured by Ouchi Shinsei Chemical Co., Ltd.) and 1.2 parts of sulfur as a vulcanizing agent, kneading with an open roll for another 15 minutes, A kneaded product CII was obtained.

  The ten-point average roughness (Rz) of the surface of the obtained conductive elastic roller (conductive elastic roller after surface polishing) CII is 5.6 μm, the deflection is 28 μm, and the hardness is 70 degrees (Asker C). Met.

  Next, 42.9 parts of a lactone-modified acrylic polyol (trade name: Plaxel DC2016 (hydroxyl value 80 KOHmg / g), manufactured by Daicel Chemical Industries, Ltd.) is dissolved in 557.1 parts of methyl isobutyl ketone (MIBK) to obtain a solid. The solution was 5.0% by mass. 200 parts of this solution was mixed with 10.7 parts of an isophorone diisocyanate block type isocyanurate-type trimer (IPDI) (trade name: Bestanat B1370, manufactured by Degussa Huls), and these were stirred for 1 hour in a ball mill. After stirring, the solution was filtered through a 200 mesh screen to prepare a surface layer coating solution CII.

  Next, the surface layer coating liquid CII is ring-coated on the conductive elastic layer of the conductive elastic roller (conductive elastic roller after surface polishing) CII, and this is heated in an oven at 160 ° C. for 1 hour to form a surface layer. A surface layer was formed by curing (thermosetting) and drying the coating liquid CII. Thus, a charging roller having a support, a conductive elastic layer formed on the support, and a surface layer formed on the conductive elastic layer was produced. This charging roller is referred to as a charging roller CII.

  Table 2 shows the physical properties of the manufactured charging roller, and Table 3 shows the results of composition analysis.

<Charging member comparative production example 3>
A charging roller was produced in the same manner as in the charging member production example 1 except that the surface layer coating liquid I was changed to the following surface layer coating liquid CIV. This charging roller is referred to as a charging roller CIV.

  The surface layer coating solution CIV was prepared as follows.

  That is, 56.16 g (0.234 mol) of phenyltriethoxysilane (PhTES) as a hydrolyzable silane compound, 13.21 g (0.064 mol) of hexyltrimethoxysilane (HeTMS), and tridecafluoro-1,1,2 , 2-tetrahydrooctyltriethoxysilane (FTS, carbon number 6 of perfluoroalkyl group) 11.42 g (0.022 mol (corresponding to 7 mol% with respect to the total amount of hydrolyzable silane compound)), water 25.93 g and ethanol After mixing with 61.50 g, the mixture was stirred at room temperature and then heated to reflux for 24 hours to obtain a hydrolyzable silane compound condensate CIV.

  By adding this condensate CIV to a mixed solvent of 2-butanol / ethanol, a condensate-containing alcohol solution CIV having a solid content of 7% by mass was prepared.

  0.35 g of an aromatic sulfonium salt (trade name: Adekaoptomer SP-150, manufactured by Asahi Denka Kogyo Co., Ltd.) as a photocationic polymerization initiator for 100 g of this condensate-containing alcohol solution CIV was converted into a condensate-containing alcohol. By adding to the solution CIV, a surface layer coating solution CIV was prepared.

  Table 2 shows the physical properties of the manufactured charging roller, and Table 3 shows the results of composition analysis.

  Subsequently, toner production examples of the present invention and comparative production examples will be described.

<Toner Production Example 1>
650 g of ion-exchanged water and 500 g of 0.1 mol / l-Na ₃ PO ₄ aqueous solution are put into a 2 liter four-necked flask equipped with a high-speed stirring device TK type homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). Was adjusted to 13000 rpm and heated to 70 ° C. To this, 70 parts of a 1 mol / l-CaCl ₂ aqueous solution was gradually added to prepare an aqueous dispersion medium containing a minute hardly water-soluble dispersion stabilizer Ca ₃ (PO ₄ ) ₂ .

On the other hand, as dispersoid,
・ Styrene 78 parts ・ 2-ethylhexyl acrylate 22 parts ・ Divinylbenzene 0.2 part ・ Carbon black (BET specific surface area = 125 m ² / g) 5 parts ・ Polyester resin (peak molecular weight = 8100, Tg = 65 ° C.) 3 parts Negative charge control agent (salicylic acid-based iron complex) 2 parts / ester wax (melting point = 69 ° C.) 4 parts The above mixture was dispersed for 4 hours using an attritor (manufactured by Mitsui Kinzoku Co., Ltd.), and then 2,2′-azobis 5 parts by mass of (2,4-dimethylvaleronitrile) was added to prepare a polymerizable monomer composition.

Next, the polymerizable monomer composition is charged into the aqueous dispersion medium, and stirred for 15 minutes while maintaining the rotational speed of the high-speed stirrer at 13000 rpm in an N ₂ atmosphere at an internal temperature of 70 ° C. The polymerizable monomer composition was granulated. Thereafter, the stirrer was changed to a propeller stirring blade, and the polymerization was completed by maintaining at the same temperature for 12 hours while stirring at 55 rpm.

  After completion of the polymerization, the suspension was cooled, and then diluted hydrochloric acid was added to remove the dispersion stabilizer. Further, after washing with water several times and drying, the polymer particles are subjected to surface treatment using a powder processing apparatus system having four stages of rotating rotors having 10 blades as shown in FIG. It was. At this time, the rotational speed of the rotary rotor of the powder processing apparatus system is 7900 rpm (the peripheral speed of the outermost edge: 100 m / sec), the processing amount of the polymer particles is 10 kg / hr, and the atmospheric temperature during the processing is 35 ° C. It was.

  The obtained polymer particles (A) had an equivalent number average diameter of 4.93 μm, an average circularity of 0.990, and the content of coarse particles having an equivalent circle diameter of more than 10 μm was 1.65% by number. The average circularity of the coarse particles was 0.964, the peak molecular weight by GPC was 16,000, and Mw / Mn was 35.

The toner (A) of the present invention was prepared by dry-mixing 100 parts of the polymer particles (A) and 2 parts by mass of hydrophobic oil-treated silica fine powder (BET; 300 m ² / g) with a Henschel mixer.

  The obtained toner (A) retained the same particle size distribution and shape distribution as the polymer particles (A).

<Toner Production Examples 2 to 4>
The particle size and shape of the polymer particles were controlled by adjusting the preparation conditions of the aqueous dispersion medium, the rotational speed of the rotating rotor of the powder processing apparatus system, the amount of polymer particles treated, and the atmospheric temperature during the treatment. Except for the above, polymer particles (B) to (D) were obtained in the same manner as in Toner Production Example 1, and then toners (B) to (D) were prepared.

<Toner Comparative Production Example 1>
Styrene-2-ethylhexyl acrylate-divinylbenzene terpolymer (peak molecular weight = 19000, Mw / Mn = 39, Tg = 50 ° C.) 100 parts Carbon black used in toner production example 1 5 parts -3 parts of polyester resin used in toner production example 1-2 parts of negative charge control agent used in toner production example 1-7 parts of ester wax used in toner production example 1 The above mixture was mixed with a biaxial extruder. Melted and kneaded, the cooled kneaded product was coarsely pulverized with a hammer mill, the coarsely pulverized product was finely pulverized with a jet mill, and the obtained finely pulverized product and commercially available calcium phosphate fine powder were mixed with a Henschel mixer and obtained. The mixed powder was put into a container containing water, further dispersed in water using a homomixer, and the temperature of the water was gradually raised, followed by heat treatment at a temperature of 60 ° C. for 3 hours. Thereafter, dilute hydrochloric acid was added to the container to sufficiently dissolve the calcium phosphate on the surface of the finely pulverized particles. This was filtered, washed and dried, then aggregated through a 400-mesh sieve, and classified to obtain a classified powder (a). A comparative toner (a) was prepared using the classified powder (a) in the same manner as in Example 1.

<Toner Comparative Production Example 2>
After obtaining classified powder (b) in the same manner as Comparative toner production example 1 except that the particle size and shape of the classified powder were controlled by changing the conditions of fine pulverization and the powder processing system, the comparison was made. Toner (b) was prepared.

<Toner Production Example 5>
In the same manner as in the toner production example 1 except that modified polypropylene wax (melting point = 105 ° C) was used instead of the ester wax and the stirring conditions during granulation and the processing conditions of the powder processing system were adjusted. After obtaining coalesced particles (E), toner (E) was prepared.

<Toner Comparative Production Example 3>
Except for not using the powder processing apparatus system, polymer particles (c) were obtained in the same manner as in Toner Production Example 5 above, and used as they were as comparative toner (c).

  Table 4 shows various properties of the toners (A) to (E) and the comparative toners (a) to (c) obtained above.

[Example 1]
● Evaluation 1
Using the charging roller I of Production Example 1, the following bleedout test and evaluation were performed.

  First, the produced charging roller I and the electrophotographic photosensitive member were incorporated into a process cartridge that integrally supports them, and this process cartridge was left in a high-temperature and high-humidity bath at 40 ° C./95% RH for one week.

  The electrophotographic photosensitive member incorporated in the process cartridge together with the charging roller I is an organic electrophotographic photosensitive member in which an organic photosensitive layer having a layer thickness of 14 μm is formed on a support. The organic photosensitive layer is a laminated photosensitive layer formed by laminating a charge generation layer and a charge transport layer containing a modified polycarbonate (binder resin) from the support side. The charge transport layer is an electrophotographic photoreceptor. It is a surface layer.

  After leaving for one week, the charging roller I and the electrophotographic photosensitive member are taken out from the process cartridge, the contact portion between the charging roller I and the electrophotographic photosensitive member is observed with an optical microscope, and bleed out from the charging roller I (bleed material) ) Was attached to the contact portion.

The evaluation criteria are as follows.
A: Bleed material is not attached.
C: Bleed material is adhered.

● Evaluation 2
Using the charging roller I produced in the same manner as described above, the following output image evaluation was performed.

  The produced charging roller I and the electrophotographic photosensitive member were assembled in a process cartridge that integrally supports them, and this process cartridge was mounted on a laser beam printer for vertical output of A4 paper. The developing method of this laser beam printer is a reversal developing method, the output speed of the transfer material is 47 mm / s, and the image resolution is 600 dpi.

  The electrophotographic photoreceptor incorporated in the process cartridge together with the charging roller I is the same as described above. Toner (A) was used as the toner.

  Image output is performed in an environment of 30 ° C./80% RH (H / H), and a halftone image is drawn on A4 paper (horizontal line with a width of 1 dot and an interval of 2 dots in the direction perpendicular to the rotation direction of the electrophotographic photosensitive member) Image) was formed, and 10,000 sheets were output at a process speed of 47 mm / s.

  The output image was evaluated by visually observing the output image every 2500 sheets.

The evaluation criteria are as follows.
AA: Uneven charging on the surface of the charging roller cannot be confirmed due to toner or external additives adhering to the surface of the charging roller.
A: Charging unevenness due to toner and external additives adhering to the surface of the charging roller can hardly be confirmed on the output image.
B: Uneven charging due to toner and external additives adhering to the surface of the charging roller can be confirmed on the output image.
C: Charging unevenness due to toner and external additives adhering to the surface of the charging roller can be confirmed on the output image, and the degree of the charging unevenness is large. Specifically, white vertical stripes of uneven charging.

  The above evaluation results are shown in Table 5.

[Examples 2 to 10 and Comparative Examples 1 to 8]
Evaluation was performed in the same manner as in Example 1. Table 5 shows the charging member and toner used. In addition, regarding the evaluation 1, the charging member is not duplicated.

  As described above, according to the present invention, the toner and the external additive used for the toner are not easily fixed to the surface of the charging member even after repeated use over a long period of time. A process cartridge and an electrophotographic apparatus capable of charging and outputting an image can be provided.

It is a figure which shows an example of a structure of the charging member of this invention. It is a figure which shows the structure of the measuring apparatus for measuring an electrostatic capacitance. It is a figure which shows an impedance characteristic. It is an assumption figure of the equivalent circuit of RC parallel in the interface / surface layer of a conductive elastic layer / conductive elastic layer and a surface layer. FIG. 4 is a schematic diagram illustrating an example of a cross section of toner particles encapsulating a wax component. 1 is a schematic external view of a powder processing apparatus system suitable for the present invention. It is a fragmentary sectional view of the principal part of the powder processing apparatus suitable for this invention. It is a perspective view of the rotary rotor of the powder processing apparatus suitable for this invention. 1 is a diagram illustrating an example of a schematic configuration of an electrophotographic apparatus including a process cartridge having a charging member of the present invention.

Explanation of symbols

101 Support 102 Conductive Elastic Layer 103 Surface Layer 401 Charging Member 402 Cylindrical Electrode 403 Dielectric Constant Measurement System R1 Conductive Elastic Layer Resistance C1 Conductive Elastic Layer Capacitance R2 Interface Resistance C2 Interface Capacitance R3 Surface Layer resistance C3 Capacitance 1 Electrophotographic photosensitive member 2 Axis 3 Charging member 4 Exposure light 5 Developing means 6 Transfer means 7 Cleaning means 8 Fixing means 9 Process cartridge 10 Guide means P Transfer material

Claims (9)

At least a photosensitive member, a charging unit that charges the photosensitive member with a charging member, and toner is supplied to the photosensitive member on which the electrostatic latent image is formed, and a toner image corresponding to the electrostatic latent image is formed on the photosensitive member In the process cartridge that integrally supports the developing unit and is configured to be detachable from the image forming apparatus,
The charging member includes a conductive support, a conductive elastic layer formed on the support, and a surface layer formed on the conductive elastic layer, wherein the surface layer is an oxyalkylene It is a charging member characterized by containing a polysiloxane having a group,
The toner contains dry toner particles and inorganic particles containing a binder resin, a colorant, and a wax component;
In the number-based equivalent circle diameter-circularity scattergram measured by the flow particle image measuring device for the toner particles, the equivalent circle number average diameter D1 of the toner particles is 2 to 8 μm, and the average circularity is 0.960 to 0.995,
The toner contains 0.02 to 3% by number of coarse particles having a circle-equivalent diameter exceeding 10 μm, and the average circularity of the coarse particles is 0.930 to 0.975.
A process cartridge, wherein the inorganic particles are inorganic particles containing polysiloxane.   The process cartridge according to claim 1, wherein the polysiloxane on the surface layer of the charging member further has an alkyl fluoride group.   The process cartridge according to claim 1, wherein the toner particles include a wax component.   The content of the fluorinated alkyl group in the polysiloxane of the surface layer of the charging member is 5.0 to 50.0% by mass with respect to the total mass of the polysiloxane, and the content of the oxyalkylene group in the polysiloxane is The process cartridge according to any one of claims 1 to 3, wherein the content is 5.0 to 70.0 mass% with respect to the total mass of the polysiloxane.   The polysiloxane of the charging member surface layer further has an alkyl group and a phenyl group, and the content of the fluorinated alkyl group in the polysiloxane is 5.0 to 50.0% by mass with respect to the total mass of the polysiloxane. Yes, the content of oxyalkylene groups in the polysiloxane is 5.0 to 30.0% by mass with respect to the total mass of the polysiloxane, and the content of alkyl groups in the polysiloxane is the total mass of the polysiloxane. The content of phenyl groups in the polysiloxane is 5.0 to 30.0 mass% with respect to the total mass of the polysiloxane. A process cartridge according to any one of the above.   The process cartridge according to claim 1, wherein the photosensitive member and the charging member are arranged in contact with each other. At least a photosensitive member, a charging unit that charges the photosensitive member with a charging member, and toner is supplied to the photosensitive member on which the electrostatic latent image is formed, and a toner image corresponding to the electrostatic latent image is formed on the photosensitive member In the electrophotographic apparatus that integrally supports the developing unit and is configured to be detachable from the image forming apparatus,
The charging member includes a conductive support, a conductive elastic layer formed on the support, and a surface layer formed on the conductive elastic layer, wherein the surface layer is an oxyalkylene It is a charging member characterized by containing a polysiloxane having a group,
The toner contains dry toner particles and inorganic particles containing a binder resin, a colorant, and a wax component;
In the number-based equivalent circle diameter-circularity scattergram measured by the flow particle image measuring device for the toner particles, the equivalent circle number average diameter D1 of the toner particles is 2 to 8 μm, and the average circularity is 0.960 to 0.995,
The toner contains 0.02 to 3% by number of coarse particles having a circle-equivalent diameter exceeding 10 μm, and the average circularity of the coarse particles is 0.930 to 0.975.
An electrophotographic apparatus, wherein the inorganic particles are inorganic particles containing polysiloxane.   The electrophotographic apparatus according to claim 7, wherein the photosensitive member and the charging member are disposed in contact with each other.   The electrophotographic apparatus according to claim 7, further comprising a voltage applying unit that applies a voltage of only a direct current voltage to the charging member.

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