JP5618785B2 - Electrophotographic equipment - Google Patents

Description

  The present invention relates to an electrophotographic apparatus (an image forming apparatus that forms an image using an electrophotographic process).

  In the market, in order to improve image quality, save energy, and save resources, there is a demand for longer life by lowering the surface of the electrophotographic photoreceptor. Furthermore, suppression of image flow that is likely to occur in an electrophotographic apparatus provided with an electrophotographic photosensitive member whose surface is reduced in wear is also demanded.

  2. Description of the Related Art Conventionally, a technique for suppressing the occurrence of image flow while maintaining an electrophotographic photosensitive member with low wear has been attempted. Patent Document 1 discloses a technique for removing a discharge product (charged product) that causes image flow using a non-woven fabric as a toner holding member while making the surface layer of an electrophotographic photosensitive member a crosslinked structure. ing. Patent Document 2 discloses a technique for protecting the surface of an electrophotographic photosensitive member with a fatty acid metal salt to protect it from discharge products that cause image blur. Patent Document 3 discloses a technique for defining the abrasion rate of the electrophotographic photosensitive member and supplying basic particles having a pH of 7 to 11 to the surface of the electrophotographic photosensitive member.

JP 2007-310117 A JP 2007-292866 A JP 2006-309141 A

  However, in the technique disclosed in Patent Document 1, since toner is held by a nonwoven fabric, toner filming may occur. If the pressing force of the nonwoven fabric to the electrophotographic photosensitive member is increased to suppress this problem, the cleaning blade may be worn out due to insufficient supply of toner.

  In addition, as in the technique disclosed in Patent Document 2, when a fatty acid metal salt is coated on the surface of an electrophotographic photosensitive member, the fatty acid metal salt, which is usually a lubricant, is a substance that increases friction after exposure to electric discharge. The wear of the cleaning blade may increase compared to the case where the fatty acid metal salt is not used.

  When the technique disclosed in Patent Document 3 is used, toner filming may occur in a low-humidity environment, or image flow may deteriorate when repeated image formation is performed under high-temperature and high-humidity conditions. These problems are particularly prominent when the surface of the electrophotographic photosensitive member is subjected to strong discharge exposure or when the electrophotographic apparatus is left for a long period of time.

  An object of the present invention is to provide an electrophotographic apparatus in which wear of an electrophotographic photosensitive member and a cleaning blade is suppressed, and image flow and toner filming are suppressed.

The present invention is an electrophotographic apparatus having an electrophotographic photosensitive member, a charging unit with discharge, an image exposing unit, a developing unit, a transferring unit, and a cleaning unit having a cleaning blade in contact with the surface of the electrophotographic photosensitive member. And
The surface layer of the electrophotographic photoreceptor contains a resin composed of a polymer of a charge transporting compound having two or more polymerizable functional groups, and a compound represented by the following general formula (1):
The electrophotographic apparatus further includes means for supplying basic particles having a number average particle size of 30 to 500 nm and having a pH of 11.0 or less to a portion where the surface of the electrophotographic photosensitive member is in contact with the cleaning blade. An electrophotographic apparatus.

The present invention also provides an electrophotographic apparatus comprising: an electrophotographic photosensitive member; a charging unit with discharge; an image exposing unit; a developing unit; a transferring unit; and a cleaning unit having a cleaning blade that contacts the surface of the electrophotographic photosensitive member. Because
The surface layer of the electrophotographic photoreceptor contains a resin composed of a polymer of a charge transporting compound having two or more polymerizable functional groups, and a compound represented by the following general formula (1):
The developing means is an electrophotographic apparatus having a developer containing basic particles having a number average particle diameter of 30 to 500 nm and having a pH of 11.0 or less.

(In General Formula (1), X represents an oxygen atom or a sulfur atom, R ¹ and R ² each independently represents an alkyl group having 1 to 3 carbon atoms, and Ar ¹ and Ar ² represent Each independently represents a substituted or unsubstituted aryl group, provided that the aryl group may have a carboxy group, a cyano group, a substituted or unsubstituted amino group, a hydroxy group, a substituted or unsubstituted group; A substituted alkoxy group, a substituted or unsubstituted alkyl group, a nitro group, or a halogen atom.)

  According to the present invention, it is possible to provide an electrophotographic apparatus in which wear of an electrophotographic photosensitive member and a cleaning blade is suppressed, and image flow and toner filming are suppressed.

FIG. 5 is a schematic view of the surface of the electrophotographic photosensitive member and the state of the contact portion of the cleaning blade as viewed in the traveling direction of the surface of the electrophotographic photosensitive member. It is a figure which shows the example of a layer structure of an electrophotographic photoreceptor. It is a figure which shows the example of a structure of the electrophotographic apparatus of this invention. FIG. 3 is a schematic cross-sectional view of the vicinity of a surface of an electrophotographic photosensitive member and a contact portion of a cleaning blade. It is a figure for demonstrating the amount of discharge current. It is a figure for demonstrating image flow recoverability. It is a figure which shows the evaluation result of image-flow recoverability. It is a figure which shows the evaluation result of image-flow recoverability. It is a figure of the image for an endurance test. It is a figure for demonstrating wear and tear of a cleaning blade.

  As in the present invention, when a resin (curable resin) obtained by polymerizing or crosslinking a compound having a polymerizable functional group and curing is used for the surface layer of the electrophotographic photoreceptor, the surface of the electrophotographic photoreceptor is While it is difficult to wear and the life of the electrophotographic photosensitive member is extended, the discharge products that cause the image flow are hardly removed, and the image flow is likely to occur.

  The basic particles having a number average particle size of 30 to 500 nm and having a pH of 11.0 or less (hereinafter also simply referred to as “basic particles”) used in the present invention are discharge products (nitric oxides produced from nitrogen oxides and nitrogen oxides). ) And the reaction or the adsorbed discharge product, thereby suppressing the image flow. In the present invention, the basic particles are brought into contact with the surface of the electrophotographic photosensitive member and the cleaning blade by means for supplying basic particles provided in the electrophotographic apparatus and / or a developer containing basic particles. Supplied.

  As a result of the study by the present inventors, it was found that the wear of the cleaning blade is caused by the reaction with the discharge product or the basic particles adsorbing the discharge product remaining on the surface of the electrophotographic photosensitive member. Then, by adding a compound having a specific structure ((thio) urea derivative) in addition to the curable resin to the surface layer of the electrophotographic photoreceptor, basic particles remaining on the surface of the electrophotographic photoreceptor (hereinafter referred to as “ It was also known that it is effective in removing “residual basic particles”.

  In the present invention, a cleaning blade provided in the cleaning means is used as a member for removing basic particles remaining on the surface of the electrophotographic photosensitive member.

  The removal of the basic particles may be non-uniform due to the distribution state of the basic particles in the longitudinal direction of the cleaning blade and the localization of the formed image. In addition, characteristics such as hardness of the cleaning blade may change depending on the environment such as temperature and humidity, and the removal of basic particles may be uneven or insufficient. Here, if the contact pressure of the cleaning blade against the surface of the electrophotographic photosensitive member is simply increased in order to improve the removal uniformity and removal ability of the basic particles, the wear (localized) of the electrophotographic photosensitive member and the cleaning blade will be increased. Scratches and uneven wear).

  Further, the basic particles (basic particles that react with the discharge product or adsorb the discharge product) to be removed in the present invention are the toner external additives known to cause toner filming. The size is equivalent (in the order of several tens of nm to several hundreds of nm). Toner filming occurs when fine particles such as external additives adhere to the surface of the electrophotographic photosensitive member, and the toner adheres thereon. That is, basic particles having a size equivalent to that of the external additive can also cause toner filming.

  The present inventors considered that the removal uniformity of basic particles and the removal ability could be improved by increasing the elasticity of the surface of the electrophotographic photosensitive member in a microscopic range. As a result of investigation based on this idea, as a result of containing a (thio) urea derivative having a specific structure (a compound represented by the general formula (1)) in the surface layer of the electrophotographic photosensitive member, It was found that can be solved. Further, when the content of the (thio) urea derivative in the surface layer of the electrophotographic photosensitive member is increased, the elastic deformation rate (We%) of the surface of the electrophotographic photosensitive member tends to increase, but the elastic deformation It has also been found that the above problem can be solved even if the content is such that the rate (We%) hardly changes. In addition, although the detail of the elastic deformation rate (We%) in this invention is mentioned later, it is a value by the method of measuring in the range of several micrometers square.

The inventors of the present invention have a special chemical structure in which the compound represented by the general formula (1) has an aryl group (Ar ¹ and Ar ² ) in the same molecule that is likely to face each other. For this reason, it is considered that the distance between these aryl groups is reduced to act as a kind of molecular level spring.

  By increasing the elasticity in the microscopic range of the surface of the electrophotographic photosensitive member, the basic particles that react with the discharge product or adsorb the discharge product are removed from the surface of the electrophotographic photosensitive member. It becomes easy to supply new basic particles to the surface. The present inventors consider the following as a reason why such replacement of basic particles is promoted.

  A cleaning blade used in an electrophotographic apparatus is usually a blade-like elastic member, and is made of, for example, urethane rubber. The cleaning blade is disposed in contact with the surface of the electrophotographic photosensitive member.

  FIG. 4 is a schematic cross-sectional view (cross section orthogonal to the contact portion) in the vicinity of a portion where the surface of the electrophotographic photosensitive member and the cleaning blade come into contact (hereinafter also referred to as “contact portion”). In FIG. 4, 101 is an electrophotographic photosensitive member, 107 is a cleaning blade, a is a small particle particle, b is a large particle particle, c is a deposit, and d is a toner particle. X is the traveling direction of the surface of the electrophotographic photosensitive member. The small particle size particles a and the large particle size particles b enter the wedge-shaped portion on the front side (left side in FIG. 4) of the contact portion between the electrophotographic photosensitive member 101 and the cleaning blade 107 to form a particle weir. . From the large wedge area (left side in FIG. 4) to the narrow area (right side in FIG. 4), the main particles for forming the weir gradually change from the large particle b to the small particle a.

  After the toner image is transferred from the surface of the electrophotographic photosensitive member to the transfer material, the toner (transfer residual toner) d remaining on the surface of the electrophotographic photosensitive member 101 is sufficiently larger than the small particle size particles a and the large particle size particles b. Largely cleaned by the cleaning blade 107 and the particle weir. The adhering substance c on the surface of the electrophotographic photosensitive member 101 such as the residual basic particles is rubbed with the small particle size particle a and the large particle size particle b forming the weir, and is scraped off by the cleaning blade 107. It is removed from the surface of the electrophotographic photosensitive member 101.

  FIG. 1 is a schematic view of the state of the surface of the electrophotographic photosensitive member 101 and the contact portion of the cleaning blade 107 as viewed in the traveling direction of the surface of the electrophotographic photosensitive member 101. The cleaning blade 107 tries to maintain the contact with the surface of the electrophotographic photosensitive member 101 by the deformation of the cleaning blade 107 due to the elasticity of the cleaning blade 107 against the trapping of foreign matters such as particles in the contact portion.

  As shown in FIG. 1A, when the surface elasticity of the electrophotographic photosensitive member 101 is small, the contact between the surface of the electrophotographic photosensitive member 101 and the cleaning blade 107 is not uniform due to the distribution of foreign matters such as particles. become. In order to eliminate this non-uniformity, if the contact pressure of the cleaning blade 107 is increased, or a material with a special range of hardness and rebound resilience is used for the cleaning blade, the cleaning performance is affected, and the electrophotographic photosensitive member Wear of the 101 and the cleaning blade 107 is likely to occur.

  On the other hand, when the elasticity of the surface of the electrophotographic photosensitive member 101 is large as shown in FIG. 1B, the surface of the electrophotographic photosensitive member 101 and the cleaning blade 107 are located at a location where a large amount of foreign matters such as particles are present. When attempting to contact, the surface of the electrophotographic photosensitive member 101 is also deformed by its elasticity. As a result, the cleaning blade 107 can easily come into contact with the surface of the electrophotographic photosensitive member 101 even if there is a distribution of foreign matter such as particles. Thereby, it is considered that the basic particles can be easily and uniformly removed while suppressing an increase in the contact pressure of the cleaning blade against the surface of the electrophotographic photosensitive member.

  Moreover, the deterioration of the electrical characteristics of the electrophotographic photosensitive member due to the surface layer containing the compound having the specific structure ((thio) urea derivative) was not observed. This is considered to be because deterioration of electrical characteristics is suppressed because the facing aryl groups also act as conductive paths having anisotropy.

-Electrophotographic photoreceptor An electrophotographic photoreceptor generally has a support and a photosensitive layer formed on the support.

  The photosensitive layer of the electrophotographic photosensitive member used in the electrophotographic apparatus of the present invention may be a single layer type photosensitive layer containing a charge transport material and a charge generation material in the same layer, or contains a charge generation material. It may be a laminated photosensitive layer separated into a charge generation layer and a charge transport layer containing a charge transport material. From the viewpoint of electrophotographic characteristics, a laminated photosensitive layer is preferable. In addition, between the support and the photosensitive layer, a conductive layer for the purpose of suppressing interference fringes, covering defects on the surface of the support, ensuring adhesion to the support, and preventing electrical breakdown of the photosensitive layer. An undercoat layer (also referred to as an intermediate layer or a barrier layer) may be provided for the purpose of protection, improvement of charge injection property to the photosensitive layer, or the like.

  FIG. 2 is a diagram showing an example of the layer structure of the electrophotographic photosensitive member used in the electrophotographic apparatus of the present invention. In the electrophotographic photosensitive member 101 shown in FIG. 2A, a conductive layer 101b, an undercoat layer 101c, a charge generation layer 101d, and a charge transport layer 101e are provided in this order on a support 101a. In the electrophotographic photoreceptor 101 shown in FIG. 2B, a conductive layer 101b, an undercoat layer 101c, a charge generation layer 101d, a charge transport layer 101e, and a protective layer 101f are provided in this order on a support 101a. ing. In the case of the electrophotographic photoreceptor shown in FIG. 2A, the surface layer of the electrophotographic photoreceptor is the charge transport layer 101e, and in the case of the electrophotographic photoreceptor shown in FIG. 2B, the surface layer of the electrophotographic photoreceptor is This is the protective layer 101f. The thickness of the charge transport layer 101e is preferably 5 to 40 μm. The thickness of the protective layer 101f is preferably 0.5 to 20 μm.

  For the layers other than the support and surface layer of the electrophotographic photosensitive member used in the electrophotographic apparatus of the present invention, known materials and known forming methods can be used.

  As described above, the surface layer of the electrophotographic photoreceptor used in the electrophotographic apparatus of the present invention is cured by polymerizing or crosslinking a compound having a polymerizable functional group (a compound having at least one polymerizable functional group). Contains the resulting resin (curable resin). When polymerizing a compound having a polymerizable functional group, a polymerization initiator may be used as necessary. The polymerization of the compound having a polymerizable functional group can be performed using heat, light (such as ultraviolet rays) or radiation (such as an electron beam). Among these, it is not always necessary to use a polymerization initiator, polymerization using radiation is preferable, and polymerization using an electron beam is more preferable. In addition, when a compound having a polymerizable functional group is polymerized using an electron beam, it may be heated in an inert gas atmosphere after irradiating the electron beam in an inert gas atmosphere for the purpose of removing the polymerization inhibiting action due to oxygen. preferable. Examples of the inert gas include nitrogen and argon.

  The surface layer of the electrophotographic photosensitive member used in the electrophotographic apparatus of the present invention further contains a compound ((thio) urea derivative) represented by the following general formula (1).

  X in the general formula (1) represents an oxygen atom or a sulfur atom.

Moreover, R < ¹ > and R < ² > in the said General formula (1) shows a C1-C3 alkyl group each independently. Examples of the alkyl group having 1 to 3 carbon atoms include a methyl group, an ethyl group, and a propyl group (n-propyl group, isopropyl group). When R ¹ and R ² are hydrogen atoms, the effect of the present invention cannot be obtained. Further, when the carbon number of the alkyl group of R ¹ and R ² is 4 or more, it acts as a factor that inhibits the densification of the structure (three-dimensional network structure) of the curable resin that forms the surface layer, and a sufficient surface The film strength of the layer cannot be obtained.

Ar ¹ and Ar ² in the general formula (1) each independently represent a substituted or unsubstituted aryl group. Examples of the aryl group include a phenyl group, a naphthyl group, a fluorenyl group, and the like. The substituent that the aryl group may have includes a carboxy group, a cyano group, a substituted or unsubstituted amino group, a hydroxy group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkyl group, a nitro group, Or it is a halogen atom. Examples of the substituted amino group include alkyl group-substituted amino groups such as dimethylamino group and diethylamino group. Examples of the alkoxy group include a methoxy group and an ethoxy group. Examples of the unsubstituted alkyl group include a methyl group, an ethyl group, a propyl group (n-propyl group, isopropyl group), and the like. Examples of the substituted alkyl group include a trifluoromethyl group. Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.

In addition, the compound represented by the general formula (1) is a group in which R ¹ and R ² in the general formula (1) are the same, because the aryl groups in the molecule are easily arranged to face each other. and, Ar ¹ and Ar ² are identical groups preferably has a structure symmetrical.

  In the present invention, the surface layer of the electrophotographic photoreceptor preferably contains 0.5 to 25% by mass of the compound represented by the general formula (1) with respect to the total mass of the surface layer. When there is too little content, the effect of this invention may become small. If the content is too large, densification of the structure (three-dimensional network structure) of the curable resin that forms the surface layer is suppressed, and the film strength of the surface layer is reduced, or the surface layer is reduced to the above general formula (1 ) May be easily precipitated.

  The compound represented by the general formula (1) may contain only one type or two or more types in the surface layer of the electrophotographic photosensitive member.

The compound represented by the general formula (1) can be synthesized, for example, using a synthesis method described in the following literature.
-Photochem. Photobiol. Sci. , 2002, 1, 30-37
・ Transactions of the Faraday Society, 34, 1938, 783-786
Tetrahedron Letters 39 (1998) 6267-6270
Bulletin of the chemical society of Japan, vol. 47 (4), 1974, 935-937.

  Specific examples (exemplary compounds) of the compound represented by the general formula (1) are listed below, but the present invention is not limited thereto.

  Among the above compounds, the compound represented by the above formula (U-1), the compound represented by the above formula (U-2), the compound represented by the above formula (U-3), and the above formula (U-10). Are more preferred. Hereinafter, the compounds represented by the formulas (U-1) to (U-24) are also referred to as exemplary compounds (U-1) to (U-24), respectively.

  Exemplified compounds (U-1) to (U-24) are specific examples of urea derivatives among the compounds represented by the above general formula (1), but among the compounds represented by the above general formula (1) Specific examples of the thiourea derivative include those in which the oxygen atom corresponding to X in the general formula (1) in the exemplary compounds (U-1) to (U-24) is replaced with a sulfur atom.

  The compound having a polymerizable functional group used in the present invention is a compound that can form a curable resin by polymerization. Specifically, for example, an olefin compound (a compound having only one double bond C = C) or a halogenated olefin compound (having only one double bond C = C, a halogen X (X is F , Cl, Br or I)), diene compounds (compounds having two or more double bonds C = C), acetylene compounds (compounds having one or more triple bonds C≡C), and the like. , A styrene compound (C = C-Ar (a compound having a structure of an aromatic ring or an aromatic heterocycle)), a vinyl compound (a compound having a vinyl group C = C-), an acrylic acid compound (C = C—CO—Z (where Z is O, S or N) or a compound having a C═C—CN structure), a cyclic ether compound (a cyclic compound having an —O— bond in the ring), a lactone compound (ring -CO-O- bond A cyclic compound.), A lactam compound (a cyclic compound having a —NH—CO— bond in the ring), a cyclic amine compound (a cyclic compound having a —NH— bond in the ring), a cyclic sulfide compound (S in the ring). A cyclic compound having an atom.), A cyclic carbonate compound (a cyclic compound having a —O—CO—O— bond in the ring), a cyclic acid anhydride (a cyclic compound having a —CO—O—CO— bond in the ring) ), A cyclic imino ether compound (a cyclic compound having a —N═C—O— bond in the ring), and an amino acid-N-carboxylic acid anhydride (—O—CO—N═C—CO— bond in the ring). And cyclic imide compounds (cyclic compounds having a —CO—NH—CO— bond, —NH—CO—O— bond or —NH—CO—NH— bond in the ring), Phosphorus compounds (having P atoms in the ring Cyclic compounds, cyclic silicon-containing compounds (cyclic compounds having a Si atom in the ring), cyclic olefin compounds (cyclic compounds in which the ring is composed of carbon or carbon multiple bonds), phenolic compounds (aromatic hydroxyl structure). ), Melamine / urea compounds (melamines or urea derivatives), diamine compounds (including diamine derivatives and polyamines), dicarboxylic acid compounds (dicarboxylic acid (ester) derivatives), oxycarbons Acid compounds (oxycarboxylic acid (ester) derivatives), aminocarboxylic acid compounds (aminocarboxylic acid (ester) derivatives), diol compounds (polyols having two or more free OH groups), diisocyanate compounds (Iso (thio) cyanate derivatives) and sulfur-containing compounds (sulfur-containing (S ) Monomers. ), Phosphorus-containing compounds (phosphorus-containing (P) monomers), aromatic ether compounds (compounds in which aromatic hydrocarbon groups are bonded with oxygen), dihalogen compounds (carbon-halogens other than acid halides) A compound having a plurality of bonds), an aldehyde compound (a compound having an aldehyde group), a diketone compound, a carbonic acid derivative compound, an aniline derivative compound, a silicon compound, and the like.

  The compound having a polymerizable functional group is preferably a charge transporting compound having a charge transporting structure in the molecule from the viewpoint of electrical characteristics. Examples of the charge transporting structure include structures such as triarylamine, hydrazone, pyrazoline, and carbazole.

The polymerizable functional group is an acrylic group (acryloyloxy group: CH ₂ ═CHCOO—) or a methacryl group (methacryloyloxy group: CH ₂ ═C (CH ₃ ) COO—) from the viewpoint of polymerization efficiency. Is preferred.

  Furthermore, from the viewpoint of forming a sufficient three-dimensional network structure on the surface layer of the electrophotographic photoreceptor, the compound having a polymerizable functional group is a charge transporting compound having two or more polymerizable functional groups. Is preferred.

  Furthermore, the compound having a polymerizable functional group is preferably a compound represented by the following general formula (4). The compound represented by the following general formula (4) has a monoamine structure with good polymerization efficiency, and has a structure in which the number of excessive polymerizable functional groups that can easily increase the internal stress of the surface layer and easily cause scratches is suppressed. It is.

In the general formula (4), R ³ and R ⁴ each independently represent a hydrogen atom or a methyl group, and Ar ³ represents a substituted or unsubstituted aryl group. m and n are each independently an integer of 0 to 5. Examples of the substituted or unsubstituted aryl group include a phenyl group, a naphthyl group, a fluorenyl group, and a 9,9-dimethylfluorenyl group. Further, m and n in the general formula (4) preferably satisfy 3 ≦ m + n ≦ 10.

Furthermore, from the viewpoint of increasing the density of the three-dimensional network structure of the surface layer of the electrophotographic photosensitive member, Ar ³ in the general formula (4) is preferably a substituted or unsubstituted phenyl group.

  Although the specific example (exemplary compound) of the compound shown by the said General formula (4) below is given, this invention is not necessarily limited to these.

  In the above formulas (J-1) and (J-2), y and z are each independently an integer of 0 to 5.

  Among the above compounds, from the viewpoint of achieving both electrical properties and film strength (abrasion resistance, scratch resistance), y and z in the above formula (J-1) are represented by the above formula (J-1). Compounds in which both are 3 are more preferred.

  The compound having a polymerizable functional group may be used alone or in combination of two or more when forming a surface layer containing a curable resin.

  The surface layer of the electrophotographic photosensitive member used in the electrophotographic apparatus of the present invention may contain conductive particles, an ultraviolet absorber and the like. Examples of the conductive particles include metal oxides such as tin oxide particles.

  The surface layer of the electrophotographic photosensitive member used in the electrophotographic apparatus of the present invention may contain a lubricity imparting agent that enhances the lubricity of the surface of the electrophotographic photosensitive member. As a result, it is possible to suppress changes in the lubricity of the surface of the electrophotographic photosensitive member due to wear of the surface layer and chemical deterioration due to charging, development, transfer, etc. during repeated use. The body contact state is easily maintained. Further, toner particles and other particles in the vicinity of the surface of the electrophotographic photosensitive member and the contact portion of the cleaning blade move in a direction orthogonal to the traveling direction of the surface of the electrophotographic photosensitive member (hereinafter also referred to as “longitudinal direction”). And the influence of localization of the image ratio can be suppressed.

  Examples of the lubricity-imparting agent include fluorine atom-containing resin particles, carbon fluoride particles, and polyolefin resin particles.

  In the present invention, the elastic deformation rate (We%) and universal hardness value (HU) of the surface of the electrophotographic photosensitive member were measured as follows.

  The elastic deformation rate (We%) is a value of the degree of shape recovery of the surface of the electrophotographic photosensitive member that has been deformed by an external force. A large value indicates that the elasticity is large, and a reversible deformation capacity with respect to the external force. It is an indicator. The universal hardness value (HU) is a value of the mechanical strength of the surface of the electrophotographic photosensitive member, and is an index of the amount of dents on the surface of the electrophotographic photosensitive member that is deformed by an external force.

  In the present invention, these values were measured using a microhardness measuring device (trade name: Fischerscope H100VP-HCU) manufactured by Fischer in accordance with ISO / FDIS14577 in an environment of 25 ° C./50% RH. Value. The measurement conditions were that a load was applied to a diamond pyramid indenter with a face-to-face angle of 136 °, the diamond indenter was pushed into the surface layer of the electrophotographic photosensitive member, and the load was reduced until the load became zero. The indentation depth and load were measured to calculate the elastic deformation rate (We%). More specifically, the measurement was performed according to the method described in [0037] to [0043] of JP-A-2007-086524.

  Moreover, the universal hardness value (HU) was calculated from the ratio (the following mathematical formula) divided by the indentation depth when a load was applied and the surface area calculated from the shape of the diamond indenter.

In the above formula, F _f is the load at the time of measurement, S _f is the surface area of the portion where the diamond indenter is pushed in, and h _f is the depth of the diamond indenter. In the present invention, the load was increased at a predetermined speed (273 points with a holding time of 0.1 seconds for each point) until the load reached 6 mN at the maximum. However, 1 μm was set as the limit of the indentation depth. Note that the rightmost side of the above formula is when the load reaches 6 mN.

The surface of the electrophotographic photoreceptor is moderately deformed to reduce the local load on the particles and the cleaning blade, and to equalize the load, while suppressing excessive penetration of particles into the surface of the electrophotographic photoreceptor The surface universal hardness value (HU) of the electrophotographic photosensitive member is preferably 150 to 220 N / mm ² . More preferably, it is 170-220 N / mm < ² >. Within this range, it is difficult for the basic particles to be crushed or spread near the surface of the electrophotographic photosensitive member and the contact portion of the cleaning blade, and the basic particles are effectively removed. In addition, the movement of the basic particles in the longitudinal direction of the electrophotographic photosensitive member is promoted. Further, the wear of the electrophotographic photosensitive member and the cleaning blade due to the dragging of the basic particles can be further suppressed.

  Further, if the elastic deformation ratio (We%) of the surface of the electrophotographic photosensitive member is 40% or more, it is several μm level in the longitudinal direction of the electrophotographic photosensitive member due to variations in the edge shape of the cleaning blade or toner particles. This is preferable because followability with respect to non-uniformity is improved. As a result, image flow is further suppressed, and filming is further suppressed because the cleaning blade's scraping ability is less likely to change even in a portion where the load on the cleaning blade such as the edge of the image changes extremely. . In addition, since the wear and scratches of the electrophotographic photosensitive member are suppressed, a change in shape near the surface of the electrophotographic photosensitive member and the contact portion of the cleaning blade during repeated use can be suppressed.

  In the present invention, the film thickness of the electrophotographic photosensitive member was measured by using an eddy current type film thickness meter (trade name: Fischer scope GROUNDEINHEIT MMS 3AM) manufactured by Fischer.

Basic Particles In the electrophotographic apparatus of the present invention, in order to suppress the occurrence of image flow, the basicity of the surface of the electrophotographic photosensitive member and the contact portion of the cleaning blade with a number average particle size of 30 to 500 nm and pH of 11.0 or less. While supplying the particles, it is important to remove residual basic particles that have reacted with the discharge products or adsorbed the discharge products from the surface of the electrophotographic photoreceptor.

  Since the basic particles used in the present invention are basic, their pH is higher than 7.0. Furthermore, the basic particles used in the present invention have a pH of 11.0 or less. Preferably, pH is 7.5 or more and 10.5 or less. If the pH is 7.0 or less, that is, if it is not basic, the effect of suppressing the occurrence of image blur cannot be obtained. On the other hand, when the particles have a pH exceeding 11.0 (strongly basic particles), the hydrophilicity becomes high, or the resulting salt becomes strongly basic, and the ionization property becomes strong.

  In the present invention, the pH value of the basic particles means the pH value of the dispersion adjusted using ion-exchanged water whose pH is adjusted to 7.0, and the measurement is performed according to JIS K5101-17-2 ( According to the room temperature method), it was carried out at room temperature (23 ± 2 ° C.).

  The basic particles used in the present invention have a number average particle size of 30 to 500 nm. If the number average particle diameter is too small, it will be difficult to remove from the surface of the electrophotographic photoreceptor. If the number average particle size is too large, the effect of suppressing image flow is reduced.

  The basic particles used in the present invention preferably have a Mohs hardness of 3 or more, more preferably 5 or more. If the Mohs hardness is too small, the surface of the electrophotographic photosensitive member and the contact portion of the cleaning blade are crushed and easily formed into a film, so that it is difficult to remove from the surface of the electrophotographic photosensitive member. The Mohs hardness in the present invention is a 15-step Mohs hardness.

  The basic particles used in the present invention are preferably transparent or white.

In addition, the volume resistivity of the basic particles used in the present invention is preferably 1 × 10 ¹² Ωcm or more because a reduction in charging uniformity due to abnormal discharge in the charging means can be suppressed.

  The basic particles used in the present invention may be basic organic compound particles or basic inorganic compound particles. Examples of the basic inorganic compound particles include magnesium carbonate particles and calcium carbonate particles. Among these, calcium carbonate particles are preferable because they are excellent in lubricity, can suppress an increase in friction in the cleaning process, and can suppress wear of the electrophotographic photosensitive member and the cleaning blade.

  Further, the hydrophobicity of the basic particles can be adjusted as necessary. The lower the degree of hydrophobicity, the higher the surface activity and the higher the efficiency of action on acids and moisture. On the other hand, when the degree of hydrophobicity is too low, durability and environmental stability tend to decrease. Specifically, it is preferable that the methanol concentration (hereinafter also simply referred to as “hydrophobization degree”) at which the light transmittance according to the measurement of methanol hydrophobization degree starts to decrease is 40 to 80%.

  In the present invention, the number average particle size and the degree of hydrophobicity of the basic particles were measured as follows.

  First, the number average particle diameter of the basic particles was observed with a scanning electron microscope (SEM), and the equivalent circle diameter of the same area as the observed basic particles was defined as the particle diameter of the basic particles. The number average particle diameter is an average value of the particle diameters of the basic particles randomly selected in the range of 100 to 1000 particles.

  The hydrophobicity of the basic particles was determined as follows using a powder wettability tester (trade name: WET-100P) manufactured by Reska Co., Ltd. First, 70 ml of pure water from which bubbles have been removed is placed in a flask, and 0.50 g of the basic particles to be measured are precisely weighed and added thereto to prepare a measurement sample solution. Next, while stirring the sample liquid for measurement at a speed of 6.67 m / sec, methanol is continuously added at a dropping rate of 1.3 ml / min, and the transmittance becomes 90% with light having a wavelength of 780 nm. Measure the methanol concentration. As the flask, a glass having a circular shape with a diameter of 5 cm and a thickness of 1.75 mm is used. As the magnetic stirrer, a spindle having a length of 25 mm and a maximum diameter of 8 mm and having a fluororesin coating is used. Using.

Inorganic particles In the present invention, the surface of the electrophotographic photosensitive member and the contact portion of the cleaning blade have a Mohs hardness of 5 or more and a number average particle size larger than the basic particles and 1000 nm or less (1 μm or less) ) Inorganic particles are preferably present. In the present invention, the number average particle size of the inorganic particles was measured in the same manner as the number average particle size of the basic particles.

  Since inorganic particles have a higher hardness than organic materials, they are loaded with a cleaning blade and rub against the remaining basic particles on the surface of the electrophotographic photosensitive member to improve the scraping property of the cleaning blade. be able to. In addition, the above particle size moves the basic particles in the longitudinal direction of the surface of the electrophotographic photosensitive member in the vicinity of the contact portion between the electrophotographic photosensitive member and the cleaning blade, thereby suppressing the influence of localization of the image ratio. be able to. Therefore, wear of the electrophotographic photosensitive member and the cleaning blade can be suppressed.

  The inorganic particles are preferably transparent or white.

  Examples of inorganic particles include alumina particles, titanium oxide particles, and strontium titanate particles. Among these, alumina particles have a high Mohs hardness of 12 and are preferable.

Electrophotographic apparatus FIG. 3 is a diagram showing an example of the configuration of the electrophotographic apparatus of the present invention.

  FIG. 3A shows the overall configuration of the electrophotographic apparatus. The electrophotographic photosensitive member 101 is a rotatable cylindrical (drum type) electrophotographic photosensitive member, and is rotationally driven in a direction indicated by an arrow X at a predetermined speed by a driving mechanism (not shown). The shape of the electrophotographic photosensitive member 101 may be a belt shape or the like in addition to a cylindrical shape. Around the electrophotographic photosensitive member 101, there are arranged a charging means 102 with discharge, an image exposure means (not shown) for irradiating the image exposure light 103, a developing means 104, a transfer means 105, and a cleaning means 106. Examples of the charging unit 102 that accompanies discharge include a corona charging type or roller charging type charging unit.

  An electrostatic latent image is formed on the surface of the electrophotographic photosensitive member 101 charged by the charging unit 102 by irradiation with image exposure light 103. In Examples described later, the charging roller was brought into contact with the surface of the electrophotographic photosensitive member, and a voltage obtained by superimposing a sine wave alternating current (AC) voltage on a direct current (DC) voltage was applied to the charging roller. The image exposure by the image exposure unit is an image exposure method, and the light portion potential Vl becomes −100 V so that the dark portion potential Vd on the surface of the electrophotographic photosensitive member becomes −600 V at the position facing the developing unit. Set to.

  A toner image corresponding to the formed electrostatic latent image is formed on the surface of the electrophotographic photosensitive member 101 by the developing unit 104, and then the toner image is transferred to the transfer material P by the transfer unit 105. Residues such as transfer residual toner and paper dust are removed from the surface of the electrophotographic photosensitive member 101 that has undergone the transfer process by the transfer unit 105 by the cleaning blade of the cleaning unit 106, and is subjected to the next image forming process.

Cleaning means The cleaning means used in the electrophotographic apparatus of the present invention is of a blade cleaning type having a cleaning blade that comes into contact with the surface of the electrophotographic photosensitive member. In FIG. 3, the cleaning means 106 has a cleaning blade 107. The cleaning blade is preferably made of rubber. In the examples described later, a polyurethane rubber cleaning blade was used.

  FIG. 3B shows the cleaning blade 107 of the electrophotographic apparatus and its installation state. The cleaning blade 107 is held by the holding means 107B and is brought into contact with the surface of the electrophotographic photosensitive member 101 with a predetermined contact pressure (or intrusion amount) and a set angle θ. In order to make the contact pressure constant, the urging means 107S may be provided.

  When the ratio T / L of the cleaning blade thickness T to the free length L is 0.2 or more, the cleaning blade is prevented from being bent, and the cleaning blade edge is brought into stable contact with the surface of the electrophotographic photosensitive member. Can be preferred.

  Further, from the viewpoint of the life of the system, it is more preferable to use the rubber properties of the cleaning blade 107 that are defined with 100% modulus and elongation at break.

When a rubber cleaning blade is used, the rubber properties are preferably in the range of 2940 ≦ 100% modulus ≦ 5880 kN / m ² and elongation at break ≧ 300%. By setting it within this range, the wear of the cleaning blade can be suppressed.

-Particle supply means In the present invention, the method for supplying the basic particles and the inorganic particles to the surface of the electrophotographic photosensitive member and the contact portion of the cleaning blade is not particularly limited. A dedicated particle supply unit may be used, or the particles may be supplied via a transfer unit, a charging unit, or the like.

The supply amount of the basic particles is preferably 1 × 10 ⁻¹⁰ g / mm ² or more per unit area of the electrophotographic photoreceptor from the viewpoint of uniformity of particle supply. Moreover, if it is 5 * 10 < ^-6 > g / mm < ² > or less, the load of supply does not become excess and it can prolong the lifetime of basic particles, and is preferable.

  As the basic particle supply means, for example, as shown in FIG. 3A, a particle source 109 formed by forming particles as a supply into a block shape and a supply member 110 such as a brush roller can be used. In FIG. 3A, the supply source 110 is provided with a particle source 109 in contact therewith. In addition, a means (not shown) for leveling supplied particles on the surface of the electrophotographic photosensitive member 101, a flicker (not shown), or the like may be added.

In FIG. 3A, the supply member 110 is driven with a difference in relative speed (surface speed) from the electrophotographic photosensitive member 101 to apply basic particles to the surface of the electrophotographic photosensitive member 101. Examples of the material of the brush fibers of the brush roller of the supply member 110 include nylon, acrylic, and polyester. Further, the brush fibers may be provided with conductivity by including carbon or metal powder. The brush fibers preferably have a density of 1500 to 80000 pieces / cm ² and a thickness of 3.33 Tex or less so that the brush fibers can be uniformly contacted with the particle source 109. The fiber length of the brush fibers may be appropriately adjusted according to various setting conditions such as thickness, density, and driving speed.

  The amount of penetration when the brush roller of the supply member 110 is brought into contact with the surface of the electrophotographic photosensitive member 101 is preferably 3 mm or less from the viewpoint of suppressing wear of the brush fibers.

  The driving speed of the brush roller of the supply member 110 is preferably 5 to 50% of the difference in relative speed (surface speed) with respect to the electrophotographic photosensitive member supplied with particles relative to the electrophotographic photosensitive member 101. If the difference in relative speed is too small, the supply of the particle source 109 tends to be uneven. When the difference in relative speed is too large, the supply member 110 and the electrophotographic photosensitive member 101 are easily worn out.

  Further, the supply member 110 is preferably disposed after the transfer unit 105 (downstream side) and before the charging unit 101 (upstream side) in the traveling direction of the surface of the electrophotographic photosensitive member 101.

  Further, the supply member 110 can supply the basic particles and inorganic particles to the surface of the electrophotographic photosensitive member 101 in a non-contact manner with the electrophotographic photosensitive member 101.

  In addition, by supplying a basic particle in the developer without providing a dedicated particle supplying means or in combination with the dedicated particle supplying means, the surface is supplied to the surface of the electrophotographic photosensitive member and the contact portion of the cleaning blade. You can also do it. A method in which basic particles are contained in a developer and supplied from the developing means is preferable because the basic particles are also promoted to diffuse and the uniformity in the longitudinal direction of the surface of the electrophotographic photosensitive member is improved. Further, since it is not always necessary to provide a dedicated particle supply means, it is advantageous for miniaturization of the electrophotographic apparatus. As a developing method in which basic particles are contained in the developer, a known developing method can be applied. However, if the contact developing method is used, the basic particles are applied to the surface of the electrophotographic photosensitive member regardless of the image ratio or the like. Since it can supply, it is preferable. This method can also be used as a method for supplying inorganic particles.

  When the basic particles and inorganic particles are contained in the developer, the basic particles and inorganic particles are preferably externally added to the toner particles in an amount that does not adversely affect the developer characteristics such as development efficiency and transfer characteristics. The external addition amount is preferably 0.2 to 3.5 parts in total of basic particles and inorganic particles with respect to 100 parts of toner particles. As a method of externally adding basic particles and inorganic particles to toner particles, a known external addition method can be used.

・ Discharge current amount Idis
In an embodiment described later, a voltage (charging voltage) obtained by superimposing an AC voltage on a DC voltage is applied to a charging roller that is a charging unit 102 that accompanies discharge. When no discharge from the charging roller to the electrophotographic photosensitive member 101 occurs, according to the impedance between the charging roller and the electrophotographic photosensitive member 101, between the applied AC voltage Vac (amplitude: Vpp) and the AC current amount Iac. Has a linear relationship.

  On the other hand, when discharge from the charging roller to the electrophotographic photosensitive member 101 occurs, Iac ≧ Iz (Iz is a broken line portion in the discharge region in FIG. 5). The difference Idis between Iac and Iz is defined as the discharge current amount.

  It is difficult to theoretically obtain the discharge current amount Idis because an electrical transient phenomenon is included when the discharge is occurring. Furthermore, the discharge current amount Idis is easily influenced by temperature and humidity, contact conditions of the charging roller to the electrophotographic photosensitive member, physical properties, dirt due to a developer, and the like, and is not always constant. Therefore, the discharge current amount Idis needs to be obtained for each image forming operation or for every predetermined time.

  In the examples described later, the evaluation is performed by controlling the discharge current amount Idis to be constant. Hereinafter, this control method will be described.

  An electrophotographic apparatus according to an embodiment to be described later includes a controller (not shown) and current detection means (not shown). With these and a power source (not shown), at the time of non-image formation, an alternating voltage is applied at one point or more in the undischarged region and two or more points in the discharging region, and the total alternating current amount Iac at that time is measured. The controller performs an approximation process from the above measured value and the point of AC voltage 0 (the amplitude Vpp = 0, Iac and Idis are both 0), calculates the applied voltage corresponding to the desired discharge current amount Idis, and the calculated application A voltage is applied from the power source to the charging roller. In the case of the current control method, the AC current amount Iac corresponding to the desired discharge current amount Idis is applied as described above by applying the AC current amount Iac of the undischarged region and the discharge region as voltage detecting means instead of the current detecting means. May be obtained and applied to the charging roller.

  When image formation is performed continuously, the above operation can be performed between image formations.

Toner In the present invention, as the toner, a toner containing normal toner particles and an external additive can be used.

  The toner particles usually contain a binder resin, a colorant, a wax, a charge control agent, and the like. Examples of the toner particle production method include a pulverization method, a suspension granulation method, a suspension polymerization method, a dispersion polymerization method, an emulsion polymerization method, and an emulsion aggregation method. The mass average particle diameter (D4) of the toner particles is preferably 3 to 12 μm from the viewpoints of high image quality and cleanability. Further, particles such as a fluidity improver and a release agent can be externally added to the toner particles as necessary. Known types can be used for the type, amount, and external addition method of particles to be externally added (also referred to as “external additive”). Examples of a method for externally adding an external additive to toner particles include a method using a mixer such as a Henschel mixer (manufactured by Mitsui Miike Chemical Co., Ltd.).

  When the above basic particles and inorganic particles are externally added to the toner particles, they can be externally added in the same manner as the above external additives.

  When the developer is a two-component developer obtained by mixing a toner and a carrier (magnetic carrier), the amount of toner in the two-component developer is 2 to 35% by mass with respect to the total mass of the carrier. Is preferred. By setting the amount to 2 to 35% by mass, the balance between the developing property such as the charge imparting property to the toner and the reduction of the scattering of the toner can be obtained, and the contact between the developer ear and the electrophotographic photosensitive member is stabilized. When the developer contains basic particles and inorganic particles, their supply to the surface of the electrophotographic photoreceptor is stabilized.

  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”.

[Production example of basic particles]
<Production example of calcium carbonate particles>
The calcium carbonate particles can be produced by pulverization of naturally occurring limestone or the like, or synthesis by a known chemical reaction. When calcium carbonate particles are obtained by synthesis, it is easy to control the particle size (number average particle size) and particle size distribution. In this example, synthetic calcium carbonate particles having a calcite-type crystal structure were produced.

<Production example of zinc carbonate particles>
Zinc carbonate particles can be produced by synthesis by a known chemical reaction. In this example, carbon dioxide gas was introduced into a water slurry containing the raw material zinc oxide particles to produce basic zinc carbonate, and zinc carbonate particles were produced through a pulverization step.

<Production example of magnesium carbonate particles>
Magnesium carbonate particles can be produced by synthesis by a known chemical reaction. In this example, carbon dioxide gas was introduced into a water slurry containing magnesium oxide particles as a raw material to produce basic magnesium carbonate, and magnesium carbonate particles were produced through a pulverization step.

<Production example of magnesium oxide particles>
Magnesium carbonate particles can be produced by synthesis by a known chemical reaction such as hydrolysis or pyrolysis of carbonate or nitrate. In this example, magnesium oxide particles were produced by hydrolysis.

  The above basic particles were subjected to wet fatty acid treatment on the surface in order to control the degree of hydrophobicity. In addition, in this example, although the wet process was performed with the fatty acid, a dry process can also be used.

  Table 1 shows the number average particle size and pH of the obtained basic particles. Although (E01) in Table 1 is described in the column of “basic particles” for convenience, it is not basic particles because the pH is not 7. Hereinafter, it is also referred to as “particle (E01)”. In addition, although (E11) and (E12) are basic particles, they do not hit the basic particles used in the present invention because the pH exceeds 11.0. Further, although (E13) and (E19) are basic particles, the number average particle size deviates from the range of 30 to 500 nm, and therefore does not fall under the basic particles used in the present invention.

[Inorganic particle production example]
As inorganic particles, high-purity α-alumina (Al ₂ O ₃ ) particles obtained by a sintering method, apatite (Ca ₅ F (PO ₄ ) ₃ ) particles, garnet ((Mg, Ca, Fe) ₃ (Al, Cr, Fe) ₂ (SiO ₄ ) ₃ ) particles and silicon carbide (SiC) particles were produced.

  Table 2 shows the Mohs hardness and number average particle diameter of the obtained inorganic particles.

[Example of toner production]
100 parts of toner particles are mixed with 1.5 parts of hydrophobic silica particles (external additive) having a number average particle diameter of 20 nm, and a Henschel mixer (trade name: FM-75 type, manufactured by Mitsui Miike Chemical Co., Ltd.) is used. Then, the toner was obtained by externally adding hydrophobic silica particles to the toner particles. The processing conditions of the Henschel mixer were set at 30 s ^-1 for 10 minutes. Hereinafter, this is referred to as a standard toner.

  Further, 0.5 part of particles (E01) was mixed with 100 parts of standard toner, and external addition treatment was performed in the same manner as above to produce a basic particle externally added toner.

  Further, in the same manner as described above, basic toner particles were added using the standard toner and basic particles (E02) to (E19).

  In addition, when adding inorganic particle | grains, after adding 1.0 part of inorganic particles further to the above, the external addition process was performed.

  The toner particles used in this example are manufactured as follows.

<Production example of low softening point resin>
As a vinyl copolymer material, 5 parts of styrene, 2.5 parts of 2-ethylhexyl acrylate, 1 part of fumaric acid, 2.5 parts of dimer of α-methylstyrene, and dicumyl peroxide are added to a dropping funnel. I put it in. Also, 30 parts of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, 20 parts of polyoxyethylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, Ten parts of terephthalic acid, 5 parts of trimellitic anhydride, 24 parts of fumaric acid, and dibutyltin oxide were placed in a 4-liter four-necked flask made of glass. A thermometer, a stir bar, a condenser and a nitrogen inlet tube were attached to a four-necked flask, and this four-necked flask was placed in a mantle heater. Next, after the inside of the four-necked flask was replaced with nitrogen gas, the temperature was gradually increased while stirring, and the monomer of the vinyl copolymer and the crosslinking agent were added from the previous dropping funnel while stirring at 130 ° C. And the polymerization initiator was dripped over 4 hours. Next, the temperature was raised to 180 ° C. and the reaction was allowed to proceed for 2.5 hours to obtain a low softening point resin (L-1) (hybrid resin).

<Production example of high softening point resin>
As a vinyl copolymer material, 10 parts of styrene, 5 parts of 2-ethylhexyl acrylate, 2 parts of fumaric acid, 5 parts of a dimer of α-methylstyrene, and dicumyl peroxide were placed in a dropping funnel. Also, 25 parts of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, 15 parts of polyoxyethylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, Ten parts of terephthalic acid, 5 parts of trimellitic anhydride, 23 parts of fumaric acid, and dibutyltin oxide were placed in a 4-liter four-necked flask made of glass. A thermometer, a stir bar, a condenser and a nitrogen inlet tube were attached to a four-necked flask, and this four-necked flask was placed in a mantle heater. Next, after the inside of the four-necked flask was replaced with nitrogen gas, the temperature was gradually increased while stirring, and the monomer of the vinyl copolymer and the crosslinking agent were added from the previous dropping funnel while stirring at 130 ° C. And the polymerization initiator was dripped over 4 hours. Next, the temperature was raised to 190 ° C., and the reaction was further advanced for 7 hours to obtain a high softening point resin (H-1).

<Production example of medium softening point resin>
In the production example of the low softening point resin, a medium softening point resin (M-1) was synthesized in the same manner as in the production example of the low softening point resin except that the reaction time was changed to 4.5 hours.

<Example of master batch production>
A master batch (P-1) was prepared using the following materials and manufacturing method.
Medium softening point resin (M-1) 60 parts C.I. I. Pigment Blue 15: 3 40 parts After the above materials were mixed with a Henschel mixer (FM-75 type, manufactured by Mitsui Miike Chemical Co., Ltd.), a twin screw extruder (trade name: PCM-30) set at 120 ° C. And kneaded with a mold, manufactured by Ikegai Seisakusho. The obtained kneaded material was cooled and coarsely pulverized to 1 mm or less with a hammer mill to obtain a master batch (P-1).

<Production example of toner particles>
Toner particles were prepared using the following materials and manufacturing method.
Low softening point resin (L-1) 50 parts High softening point resin (H-1) 50 parts Masterbatch (P-1) 16.5 parts Normal paraffin wax (W-1: maximum endothermic peak temperature: 75 ° C.) 5 .5 parts 3,5-di-t-butylsalicylic acid aluminum compound (C-1) 1.3 parts After the above materials were premixed using a Henschel mixer, the temperature of the kneaded product was 130 using a twin-screw extrusion kneader. It was melt-kneaded so that it might become ° C. The obtained kneaded material was cooled and coarsely pulverized to about 1 to 2 mm with a hammer mill. The obtained coarsely pulverized product is again coarsely pulverized to about 0.3 mm with a hammer mill with fine mesh, and then pulverized to about 6 μm using a turbo mill (trade name: RSS rotor / SNNB liner, manufactured by Turbo Kogyo). And made a medium pulverized product. The obtained medium pulverized product was again pulverized to about 5 μm using a turbo mill (RSS rotor / SNNB liner, manufactured by Turbo Kogyo Co., Ltd.) to produce a finely pulverized product. Next, the obtained finely pulverized product was classified using a factory manufactured by Hosokawa Micron Corporation to obtain toner particles.

[Developer production example]
8 parts of the toner was added to 92 parts of a magnetic carrier and shaken for 10 minutes with a V-type mixer to prepare a two-component developer.

  The magnetic carrier used in this example is manufactured as follows.

<Manufacturing example of magnetic fine particle dispersed resin core>
Magnetite fine particles with a number average particle size of 0.30 μm [magnetization strength 75 Am ² / kg under a magnetic field of 10,000 / 4π (kA / m), specific resistance 5 × 10 ⁷ (Ω · cm)], and number average particle size 3.5% by mass and 2.0% by mass of a silane coupling agent (3- (2-aminoethylamino) with respect to 0.30 μm hematite fine particles [specific resistance 3 × 10 ⁸ (Ω · cm)], respectively. Propyl) trimethoxysilane) was added, and the mixture was stirred and mixed at 120 ° C. or higher in a container to make each fine particle lipophilic.
Phenol 10 parts Formaldehyde solution (formaldehyde 37% by weight aqueous solution) 6 parts The above treated magnetite fine particles 74 parts The above treated hematite fine particles 10 parts The above materials, 5 parts 28% by weight ammonia water and 10 parts water are placed in a flask. While stirring and mixing, the temperature was raised and maintained up to 85 ° C. over 60 minutes, and the phenol resin produced by polymerization reaction at 85 ° C. for 3 hours was cured. Thereafter, the cured phenol resin was cooled to 30 ° C., water was further added, the supernatant was removed, the precipitate was washed with water, and then air-dried. Next, this was dried under reduced pressure (5 hPa or less) at a temperature of 60 ° C. to obtain a magnetic fine particle dispersed resin core (A) in which magnetic fine particles were dispersed. The obtained magnetic fine particle dispersed resin core (A) had a number average particle diameter of 34 μm and a BET specific surface area of 0.07 (m ² / g).

<Examples of magnetic carrier production>
The magnetic fine particle dispersed resin core (A) was put into a coater (trade name: Spira coater, manufactured by Okada Seiko Co., Ltd.), and humidified nitrogen was introduced to adjust the moisture content to 0.3 mass%. Thereafter, the core surface was treated with 3% by mass of γ-aminopropyltrimethoxysilane diluted with a toluene solvent while continuously applying a shear stress. While volatilizing the solvent under a dry nitrogen stream, a mixture of 0.5% by mass of straight silicone resin in which all substituents are methyl groups and 0.020% by mass of γ-aminopropyltrimethoxysilane was used with toluene as a solvent. Covered. Further, this resin-coated magnetic fine particle-dispersed resin core is baked at 120 ° C., and agglomerated coarse particles are cut with a 100 mesh sieve, and then fine particles and coarse particles are removed with a multi-division wind classifier. The distribution was adjusted. Thereafter, the carrier was conditioned for 100 hours in a hopper maintained at 23 ° C. and 60% RH to obtain a magnetic carrier.

[Production example of particle source]
Particles (E01) were compression molded into a rectangular parallelepiped shape to produce a particle source. For the basic particles (E02) to (E19), a particle source was produced in the same manner.

  In addition, as what further contains inorganic particle | grains (K01)-(K07), after mixing basic particle | grains and an inorganic particle by mass ratio of 1: 2, it compression-molded in the shape of a rectangular parallelepiped, and manufactured the particle source.

[Example of production of electrophotographic photosensitive member]
<Preparation example of base electrophotographic photoreceptor>
An aluminum cylinder having a diameter of 30 mm and a length of 357.5 mm was used as a support (cylindrical support).

  Next, 60 parts of barium sulfate particles (trade name: Pastoran PC1, manufactured by Mitsui Mining & Smelting Co., Ltd.) having a tin oxide coating layer, 15 parts of titanium oxide particles (trade name: TITANIX JR, manufactured by Teika Co., Ltd.), Resole type phenolic resin (trade name: Phenolite J-325, manufactured by Dainippon Ink & Chemicals, Inc., solid content 70%) 43 parts, silicone oil (trade name: SH28PA, manufactured by Toray Silicone Co., Ltd.) 0.015 Parts, silicone resin particles (trade name: Tospearl 120, manufactured by Toshiba Silicone Co., Ltd.), 3.6 parts, 2-methoxy-1-propanol 50 parts, and methanol 50 parts in a ball mill and dispersed for 20 hours By processing, the coating liquid for conductive layers was prepared. The conductive layer coating solution was dip-coated on a support, and the resulting coating film was heated and cured in an oven at 140 ° C. for 1 hour to form a conductive layer having a thickness of 15 μm.

  Next, 10 parts of copolymer nylon resin (trade name: Amilan CM8000, manufactured by Toray Industries, Inc.) and 30 parts of methoxymethylated 6 nylon resin (trade name: Toresin EF-30T, manufactured by Teikoku Chemical Co., Ltd.) An undercoat layer coating solution was prepared by dissolving in a mixed solvent of methanol 400 parts / n-butanol 200 parts. The undercoat layer coating solution was applied onto the conductive layer by dip coating, and the resulting coating film was dried in an oven at 100 ° C. for 30 minutes to form an undercoat layer having a thickness of 0.60 μm. .

  Next, 20 parts of a crystalline hydroxygallium phthalocyanine crystal (charge generating material) having strong peaks at 7.3 ° and 28.1 ° of the Bragg angle (2θ ± 0.2 °) in CuKα characteristic X-ray diffraction, polyvinyl 10 parts of butyral (trade name: ESREC BX-1, manufactured by Sekisui Chemical Co., Ltd.), 600 parts of cyclohexanone, and 0.2 part of calixarene compound represented by the following structural formula

Was dispersed in a sand mill using glass beads having a diameter of 1 mm for 4 hours. Thereafter, 700 parts of ethyl acetate was added to prepare a charge generation layer coating solution. This charge generation layer coating solution is dip coated on the undercoat layer, and the resulting coating film is dried in an oven at 80 ° C. for 15 minutes to form a charge generation layer having a thickness of 0.17 μm. did.

  Next, 70 parts of a compound represented by the following structural formula (charge transporting substance (hole transporting compound)),

Further, 100 parts of polycarbonate (trade name: Iupilon Z400, manufactured by Mitsubishi Engineering Plastics Co., Ltd.) is dissolved in a mixed solvent of 600 parts of monochlorobenzene / 200 parts of dimethoxymethane (methylal) to thereby apply a coating solution for a charge transport layer. Was prepared. The charge transport layer coating solution was dip-coated on the charge generation layer, and the resulting coating film was heated and dried in an oven at 90 ° C. for 50 minutes to form a charge transport layer having a thickness of 19 μm.

  In this way, a base electrophotographic photosensitive member was produced.

<Example 1 of production of electrophotographic photoreceptor (electrophotographic photoreceptor (P01))>
A protective layer was provided on the charge transport layer of the above-described underlying electrophotographic photoreceptor by the following method.

First, the following materials were prepared as raw materials for the protective layer coating solution.
35 parts of the compound represented by the above formula (J-1) (wherein y and z are 3) Illustrative compound (U-2) (Tokyo Chemical Industry Co., Ltd., GC purity> 98%) 5 parts Polytetrafluoroethylene particles (Product name: Lubron L2, manufactured by Daikin Corporation, average particle size: 0.18 μm) 10 parts

  These raw materials and 30 parts of n-propanol are mixed, and further 30 parts of 1,1,2,2,3,3,4-heptafluorocyclopentane (trade name: Zeolora H, manufactured by Nippon Zeon Co., Ltd.) are mixed. Then, a dispersion treatment was performed to prepare a protective layer coating solution.

  This protective layer coating solution was dip coated on the charge transport layer of the underlying electrophotographic photoreceptor, and the resulting coating film was heat treated at 50 ° C. for 5 minutes. Thereafter, the coating film was irradiated with an electron beam for 1.5 seconds under conditions of 85 kV and 20000 Gy in a nitrogen atmosphere. Subsequently, the coating film was heat-treated for 50 seconds under the condition that the coating film temperature was 125 ° C. The oxygen concentration from electron beam irradiation to heat treatment was 10 ppm. Next, the coating film was heat-treated at 110 ° C. for 40 minutes in the atmosphere to form a protective layer having a thickness of 4.8 μm.

  In this way, an electrophotographic photoreceptor having a protective layer as a surface layer was produced. This electrophotographic photosensitive member is referred to as an electrophotographic photosensitive member (P01).

<Production Example 2 of Electrophotographic Photoreceptor (Electrophotographic Photoreceptor (P02))>
An electrophotographic photosensitive member was produced in the same manner as the electrophotographic photosensitive member (P01) except that the raw material for the coating solution for the protective layer was changed to the following and no dispersion treatment was performed. This electrophotographic photosensitive member is referred to as an electrophotographic photosensitive member (P02).
42.5 parts of the compound represented by the above formula (J-1) (where y and z are 6) Illustrative compound (U-1) (Tokyo Chemical Industry Co., Ltd., GC purity> 97%) 7.5 parts

<Production Example 3 of Electrophotographic Photoreceptor (Electrophotographic Photoreceptor (P03))>
An electrophotographic photosensitive member was produced in the same manner as the electrophotographic photosensitive member (P01) except that the raw material for the coating solution for the protective layer was changed to the following and no dispersion treatment was performed. This electrophotographic photosensitive member is referred to as an electrophotographic photosensitive member (P03).
42.5 parts of a compound represented by the above formula (J-1) (wherein y and z are 6) 7.5 parts of exemplary compound (U-3)

<Production Example 4 of Electrophotographic Photoreceptor (Electrophotographic Photoreceptor (P04))>
An electrophotographic photosensitive member was produced in the same manner as the electrophotographic photosensitive member (P01) except that the raw material for the coating solution for the protective layer was changed to the following and no dispersion treatment was performed. This electrophotographic photosensitive member is referred to as an electrophotographic photosensitive member (P04).
42.5 parts of a compound represented by the above formula (J-1) (where y and z are 6) 7.5 parts of exemplary compound (U-10)

<Production Example 5 of Electrophotographic Photoreceptor (Electrophotographic Photoreceptor (P05))>
An electrophotographic photosensitive member was produced in the same manner as the electrophotographic photosensitive member (P01) except that the raw material for the coating solution for the protective layer was changed to the following and no dispersion treatment was performed. This electrophotographic photosensitive member is referred to as an electrophotographic photosensitive member (P05).
42.5 parts of the compound represented by the above formula (J-1) (where y and z are 6) Illustrative compound (U-2) (Tokyo Chemical Industry Co., Ltd., GC purity> 98%) 7.5 parts

<Example 6 of production of electrophotographic photosensitive member (electrophotographic photosensitive member (P06))>
An electrophotographic photosensitive member was produced in the same manner as the electrophotographic photosensitive member (P01) except that the raw material for the coating liquid for the protective layer was changed to the following. This electrophotographic photosensitive member is referred to as an electrophotographic photosensitive member (P06).
32.5 parts of the compound represented by the above formula (J-1) (where y and z are 0) Exemplified compound (U-2) (manufactured by Tokyo Chemical Industry Co., Ltd., GC purity> 98%) 7.5 parts Poly 10 parts of tetrafluoroethylene particles (trade name: Lubron L2, manufactured by Daikin Co., Ltd., average particle size: 0.18 μm)

<Production Example 7 of Electrophotographic Photoreceptor (Electrophotographic Photoreceptor (P07)>)
An electrophotographic photosensitive member was produced in the same manner as the electrophotographic photosensitive member (P01) except that the raw material for the coating liquid for the protective layer was changed to the following. This electrophotographic photosensitive member is referred to as an electrophotographic photosensitive member (P07).
32.5 parts of the compound represented by the above formula (J-1) (wherein y and z are 1) Exemplary Compound (U-2) (Tokyo Chemical Industry Co., Ltd., GC purity> 98%) 7.5 parts Poly 10 parts of tetrafluoroethylene particles (trade name: Lubron L2, manufactured by Daikin Co., Ltd., average particle size: 0.18 μm)

<Production Example 8 of Electrophotographic Photoreceptor (Electrophotographic Photoreceptor (P08)>)
An electrophotographic photosensitive member was produced in the same manner as the electrophotographic photosensitive member (P01) except that the raw material for the coating liquid for the protective layer was changed to the following. This electrophotographic photosensitive member is referred to as an electrophotographic photosensitive member (P08).
32.5 parts of the compound represented by the above formula (J-1) (where y and z are 2) Exemplified compound (U-2) (Tokyo Chemical Industry Co., Ltd., GC purity> 98%) 7.5 parts Poly 10 parts of tetrafluoroethylene particles (trade name: Lubron L2, manufactured by Daikin Co., Ltd., average particle size: 0.18 μm)

<Production Example 9 of Electrophotographic Photoreceptor (Electrophotographic Photoreceptor (P09)>)
An electrophotographic photosensitive member was produced in the same manner as the electrophotographic photosensitive member (P01) except that the raw material for the coating liquid for the protective layer was changed to the following. This electrophotographic photosensitive member is referred to as an electrophotographic photosensitive member (P09).
32.5 parts of the compound represented by the above formula (J-1) (wherein y and z are 4) Illustrative compound (U-2) (Tokyo Chemical Industry Co., Ltd., GC purity> 98%) 7.5 parts Poly 10 parts of tetrafluoroethylene particles (trade name: Lubron L2, manufactured by Daikin Co., Ltd., average particle size: 0.18 μm)

<Example 10 of production of electrophotographic photosensitive member (electrophotographic photosensitive member (P10)>)
An electrophotographic photosensitive member was produced in the same manner as the electrophotographic photosensitive member (P01) except that the raw material for the coating liquid for the protective layer was changed to the following. This electrophotographic photosensitive member is referred to as an electrophotographic photosensitive member (P10).
32.5 parts of the compound represented by the above formula (J-1) (y and z are 5) Exemplified Compound (U-2) (Tokyo Chemical Industry Co., Ltd., GC purity> 98%) 7.5 parts Poly 10 parts of tetrafluoroethylene particles (trade name: Lubron L2, manufactured by Daikin Co., Ltd., average particle size: 0.18 μm)

<Production Example 11 of Electrophotographic Photoreceptor (Electrophotographic Photoreceptor (P11)>)
An electrophotographic photosensitive member was produced in the same manner as the electrophotographic photosensitive member (P01) except that the raw material for the coating liquid for the protective layer was changed to the following. This electrophotographic photosensitive member is referred to as an electrophotographic photosensitive member (P11).
32.5 parts of the compound represented by the above formula (J-1) (where y is 1 and z is 2) Exemplified compound (U-2) (manufactured by Tokyo Chemical Industry Co., Ltd., GC purity> 98%) 7.5 Part 10 parts of polytetrafluoroethylene particles (trade name: Lubron L2, manufactured by Daikin Co., Ltd., average particle size: 0.18 μm)

<Example 12 of electrophotographic photosensitive member (electrophotographic photosensitive member (P12))>
An electrophotographic photosensitive member was produced in the same manner as the electrophotographic photosensitive member (P01) except that the raw material for the coating solution for the protective layer was changed to the following and no dispersion treatment was performed. This electrophotographic photosensitive member is referred to as an electrophotographic photosensitive member (P12).
45 parts of the compound represented by the above formula (J-3) 10 parts of the exemplified compound (U-3)

<Production Example 13 of Electrophotographic Photoreceptor (Electrophotographic Photoreceptor (P13))>
An electrophotographic photosensitive member was produced in the same manner as the electrophotographic photosensitive member (P01) except that the raw material for the coating solution for the protective layer was changed to the following and no dispersion treatment was performed. This electrophotographic photosensitive member is referred to as an electrophotographic photosensitive member (P13).
45 parts of the compound represented by the above formula (J-1) (wherein y and z are 3) 10 parts of the exemplified compound (U-3)

<Example 14 of Electrophotographic Photoreceptor (Electrophotographic Photoreceptor (P14))>
An electrophotographic photosensitive member was produced in the same manner as the electrophotographic photosensitive member (P01) except that the raw material for the coating solution for the protective layer was changed to the following and no dispersion treatment was performed. This electrophotographic photosensitive member is referred to as an electrophotographic photosensitive member (P14).
45 parts of the compound represented by the above formula (J-4) 10 parts of the exemplified compound (U-3)

<Comparative Example 1 of Electrophotographic Photoreceptor (Electrophotographic Photoreceptor (PX01))>
An electrophotographic photosensitive member was produced in the same manner as the electrophotographic photosensitive member (P01) except that the raw material for the coating solution for the protective layer was changed to the following and no dispersion treatment was performed. This electrophotographic photosensitive member is referred to as an electrophotographic photosensitive member (PX01).
50 parts of the compound represented by the above formula (J-1) (wherein y and z are 6) 7.5 parts of the compound represented by the following formula (U-N1)

<Comparative electrophotographic photoreceptors production examples 2 to 9 (electrophotographic photoreceptors (PX02) to (PX09))>
The compounds represented by the following formula (U-N1) used as the raw material for the coating liquid for the protective layer are represented by the following formulas (U-N2), (U-N3), (U-N4), (U-N5), ( An electrophotographic photosensitive member is produced in the same manner as the electrophotographic photosensitive member (PX01) except that the compounds are changed to the compounds represented by U-N6), (U-N7), (U-N8), and (U-N9). did. These electrophotographic photosensitive members are sequentially referred to as electrophotographic photosensitive members (PX02), (PX03), (PX04), (PX05), (PX06), (PX07), (PX08), and (PX09).

<Comparative Example 10 of Electrophotographic Photoreceptor (Electrophotographic Photoreceptor (PX10))>
An electrophotographic photosensitive member was produced in the same manner as the electrophotographic photosensitive member (P01) except that the raw material for the coating solution for the protective layer was changed to the following and no dispersion treatment was performed. This electrophotographic photosensitive member is referred to as an electrophotographic photosensitive member (PX10).
50 parts of the compound represented by the above formula (J-1) (y and z are 6) (Exemplary compound (U-2) and polytetrafluoroethylene particles are not used.)

<Comparative Example 11 of Electrophotographic Photoreceptor (Electrophotographic Photoreceptor (PX11))>
Compound represented by the following formula

50 parts of antimony-doped tin oxide particles subjected to surface treatment (treatment amount: 8%) and 150 parts of ethanol were placed in a sand mill and subjected to a dispersion treatment for 60 hours. Then, after further adding 10 parts of polytetrafluoroethylene particles (trade name: Lubron L2, manufactured by Daikin Co., Ltd., average particle size 0.18 μm) for 2 hours, a resol type phenol resin (product) Name: PL-48044, manufactured by Gunei Chemical Co., Ltd.) 35 parts was dissolved. 7.5 parts of the exemplified compound (U-10) was added to this liquid to prepare a coating solution for a protective layer.

  This protective layer coating solution is dip-coated on the charge transport layer of the underlying electrophotographic photoreceptor, and the resulting coating film is heated at 150 ° C. for 60 minutes to form a protective layer having a thickness of 4.9 μm. did.

  In this way, an electrophotographic photoreceptor having a protective layer as a surface layer was produced. This electrophotographic photosensitive member is referred to as an electrophotographic photosensitive member (PX11).

<Comparative Example 12 of Electrophotographic Photoreceptor (Electrophotographic Photoreceptor (PX12))>
In the production example of the base electrophotographic photosensitive member, except that 7.5 parts of the exemplified compound (U-10) was added to the coating solution for the charge transport layer and the thickness of the charge transport layer to be formed was increased to 5 μm, the base electrophotography An electrophotographic photoreceptor was produced in the same manner as the photoreceptor. This electrophotographic photosensitive member is referred to as an electrophotographic photosensitive member (PX12). In the electrophotographic photoreceptor (PX12), no protective layer is formed on the charge transport layer.

<Comparative Example 13 of Electrophotographic Photoreceptor (Electrophotographic Photoreceptor (PX13))>
An electrophotographic photosensitive member was produced in the same manner as the electrophotographic photosensitive member (P13) except that the raw material for the protective layer coating solution was changed to the following. This electrophotographic photosensitive member is referred to as an electrophotographic photosensitive member (PX13).
45 parts of the compound represented by the above formula (J-1) (wherein y and z are 3) (Exemplary compound (U-3) is not used.)

[Measurement of Elastic Deformation Rate (We%) and Universal Hardness Value (HU)]
After the electrophotographic photosensitive members (P01) to (P14) and (PX01) to (PX13) are left in an environment of 25 ° C./50% RH for 24 hours, the elastic deformation rate (We%) of the surface of each electrophotographic photosensitive member is measured. ) And universal hardness values (HU). The results are shown in Table 3.

[Evaluation]
<Evaluation machine 1>
As an electrophotographic apparatus for evaluation, a digital color composite machine image RUNNER ADVANCE C5051 (tandem machine having a charging means with a discharge using a charging roller) manufactured by Canon Inc. whose schematic configuration is shown in FIG. 3 is used for black. A unit modified as follows was prepared as an evaluation machine 1.

  The rotational driving speed of the electrophotographic photosensitive member was variable. The speed of each means such as paper feeding, paper discharge, development, transfer, fixing, and exposure, the frequency of the AC bias to be applied, and the light intensity were synchronized with the rotational driving speed of the electrophotographic photosensitive member. The conditions for the yellow, magenta and cyan units were also tuned to the black unit.

  In addition, the power supply for the charging means was changed so that the frequency, applied DC voltage, and discharge current were variable. The means for heating the electrophotographic photosensitive member such as an environmental heater was turned off.

The cleaning blade 107 was made of urethane rubber having a rubber hardness of 70 °, a 100% modulus of 3450 kN / m ² , and an elongation at break of 320%. A plate-shaped cleaning blade having a thickness T = 2 mm, a free length L of 8 mm, a spring 107S, and a contact pressure = 29.4 N / m (30 g / cm) against the electrophotographic photosensitive member 101, a set angle θ = 24 Abutted at °.

  Further, a brush roller as a supply member 110 and a particle source 109 were installed in the vicinity of the cleaning blade as particle supply means. Further, a flicker (not shown) for removing transfer residual toner and the like was installed.

As the brush roller, a conductive roller woven into a base fabric and wound around a core metal having a diameter of 6 mm to form a roll brush having a diameter of 16 mm was used. As conductive fibers, acrylic conductive threads with a thickness of 0.67Tex (6 denier) were used, and the fibers were planted in a base fabric with a W weave so that the fiber density was 25000 / cm ² and formed into a sheet. The wire was wound so as to ensure conductivity with the cored bar. The resistance of the brush was 6 × 10 ² Ω · cm. The intrusion amount with respect to the electrophotographic photosensitive member is brought into contact with 0.5 mm, and the relative speed of 130% in the same direction as the electrophotographic photosensitive member is synchronized with the rotation of the electrophotographic photosensitive member in the opposite direction to the electrophotographic photosensitive member. It was made to drive with.

Further, a particle source 109 formed by compression molding basic particles or a mixture of basic particles and inorganic particles is brought into pressure contact with a brush roller so that a predetermined amount can be applied and supplied to the surface of the electrophotographic photosensitive member. did. The supply amount was adjusted by controlling the hardness according to the molding conditions of the particle source 109 and the contact pressure. The supply amount of basic particles was 1 × 10 ⁻⁸ g / mm ² per unit area of the surface of the electrophotographic photosensitive member. When basic particles and inorganic particles were used in combination, the amount of basic particles was made equal (the total supply amount of particles was 3 × 10 ⁻⁸ g / mm ² ).

  For the units for yellow, magenta and cyan, the developing means and cleaning means were removed.

<Evaluation machine 2>
An evaluator 2 was prepared in the same manner as the evaluator 1 except that the supply member (brush roller) 109 and the particle source 110 as the particle supply means were not installed.

  In both of the evaluation machines 1 and 2, the voltage applied to the charging roller was adjusted so that the absolute value of the dark portion potential Vd at the position facing the developing unit was 600V. The amount of image exposure light was adjusted so that the absolute value of the bright portion potential Vl was 100V.

  The electrophotographic photosensitive member was driven to rotate at a surface speed of 300 mm / s, and the developing bias and the transfer bias were appropriately adjusted according to the speed of the electrophotographic photosensitive member and the type of developer.

<Image for durability test>
As an image for the durability test, as shown in FIG. 9, an image was prepared in which the duty was varied in three levels of 1% / 5% / 10% in the longitudinal direction of the surface of the electrophotographic photosensitive member. In each duty area, a white background (duty = 0%) portion having a length of 1 cm was provided.

<Evaluation items and criteria>
<Evaluation of image recovery>
Using the evaluation machine 2, the electrophotographic photosensitive member to be evaluated, and the standard toner, the above-mentioned durability test image is continuously printed on A4 paper with a discharge current amount Idis of 200 μA in a 30 ° C./80% RH environment (HH environment). An endurance test (endurance test A) for outputting 20,000 sheets was performed. Immediately after the endurance test, images of 5 dots and 30 spaces (5D30S) were continuously formed, and then the power supply of the evaluation machine 2 was turned off and left for 2 days.

  After leaving for two days, the power is turned on, and the electrophotographic photosensitive member to be evaluated and the toner and / or particle source to be evaluated are set in the evaluation machine 2 and the discharge current amount Idis is set. Was set to 100 μA, and 5D30S image formation was continuously performed.

As an image flow index, a 5D30S image immediately after the durability test and after being left for two days was read with a 1200 dpi scanner in a range corresponding to one round of the electrophotographic photosensitive member. From the number of pixels, pixel recovery rate = 100 × (number of pixels of 5D30S image after being left for 2 days−number of pixels of 5D30S first image after being left for 2 days) / (5D30S before being left for 2 days immediately after the durability test) The number of pixels of the image—the number of pixels of the first image of 5D30S after being left for 2 days) was determined. When the pixel recovery rates are arranged for each number of image formations, the recovery is performed as shown in FIG. The slope in FIG. 6 is defined as a pixel recovery index. This recovery index was evaluated as the image flow recoverability in the following four grades A to D.
A: Recovery index is 38 or more: Image flow is recovered within 2 sheets of image formation.
B: Recovery index is 30 or more and less than 38: Recovery is within 3 sheets.
C: Recovery index of 20 or more and less than 30: 3 to 5 sheets recovered.
D: Recovery index is less than 20: Recovery is at 5 or more.

<Evaluation of image flow>
The electrophotographic photosensitive member to be evaluated, the toner to be evaluated and / or the particle source are set in the evaluation machine to be evaluated, and the above-mentioned durability test image is A4 under the HH environment with the discharge current amount Idis being 70 μA. An endurance test (endurance test B) for continuous output of 20000 sheets of paper was performed. Immediately after the durability test, 5D30S, ruled line image, fine line image, character image, 17 gradation image and uniform image of each density were formed, and then the power supply of the evaluation machine was turned off and left for 3 days.

  After standing for 3 days, the power was turned on, and the same image as that immediately after the durability test was formed. Thereafter, the above operation was repeated in the order of performing the durability test on the image for the durability test until the number of durability tests reached 200,000.

  The same durability test evaluation was also performed under a 15 ° C./10% RH environment (LL environment).

As an image flow index, a 5D30S image was read by a scanner immediately after the durability test and after being left for 3 days. From the number of pixels, the rate of change in the dot area of the image [%] = 100 × (number of pixels in the image before leaving for 3 days immediately after the durability test−number of pixels in the image after being left for 3 days) / (left for 3 days immediately after the durability test) The number of pixels of the previous image) was obtained. The image flow was evaluated in the following four grades A to D by the change rate [%] of the dot area of the image.
A: Change rate is 7% or less: No image flow is observed.
B: Rate of change is greater than 7% and 15% or less: The highlight portion may be uneven.
C: The rate of change is greater than 15% and 40% or less: Some of the ruled lines and fine lines may be thin.
D: Rate of change is greater than 40%: characters may be blurred.

<Evaluation of filming>
After the initial stage of the durability test (endurance test B) in the HH environment and the LL environment and after image evaluation, visual observation and optical microscope observation of the surface of the electrophotographic photosensitive member were performed. Filming was evaluated in the following four stages A to D based on the observation results of the image and the surface of the electrophotographic photosensitive member.
A: No filming.
B: Filming outside the image forming area on the surface of the electrophotographic photosensitive member. It does not occur in the image.
C: Filming is present in the image forming area on the surface of the electrophotographic photosensitive member. It does not occur in the image.
D: The effect of filming on the surface of the electrophotographic photosensitive member occurs in the image.

<Evaluation of wear of cleaning blade>
The initial stage of the durability test (endurance test B) under the HH environment and the LL environment described above and after the image evaluation, the cleaning blade wear was evaluated. When a portion corresponding to the contact portion with the electrophotographic photosensitive member in the cleaning blade is observed in the longitudinal direction, and there is a chip or a gap, the depth D [μm] and the width W [ μm] was measured. Specifically, the profile was measured with a laser microscope (VK-8510, manufactured by Keyence Co., Ltd.) with a magnification of the objective lens of 50 and observed in 0.02 μm steps, and then under simple ± 2 smoothing conditions.

The maximum value of D × W [μm ² ], which is the product of the depth D [μm] and the width W [μm], was used as an index of cleaning blade wear and evaluated in the following four stages A to D.
A: D × W ≦ 40 μm ² : No cleaning blade wear.
B: 40 μm ² <D × W ≦ 100 μm ² : Although there is wear on the cleaning blade, there is no problem in cleaning properties.
C: 100 μm ² <D × W ≦ 200 μm ² : There are many omissions of particles such as basic particles and inorganic particles. It does not occur in the image.
D: 200 μm ² <D × W: A cleaning failure may occur.

<Evaluation of electrophotographic photoreceptor wear>
After the initial stage of the durability test (endurance test B) in the HH environment and the LL environment and after image evaluation, the film thickness of the surface layer (protective layer) of the electrophotographic photosensitive member is measured, and the amount of wear per 100,000 rotations. [Μm / 100 krot] was calculated. Also, the presence / absence of scratches and the size of the scratches were measured at a total of 60 locations including 10 locations in the longitudinal direction of the surface of the electrophotographic photosensitive member including 6 locations in the circumferential direction including the position corresponding to the white background portion of the image for durability test. did. The observation and measurement conditions are the same as in the evaluation of cleaning blade wear.

The abrasion amount per 100,000 rotations of the surface layer (protective layer) of the electrophotographic photosensitive member and the scratches on the surface of the electrophotographic photosensitive member were evaluated in the following four grades A to D as an index of wear of the electrophotographic photosensitive member. .
A: Abrasion amount ≦ 5 × 10 ⁻² [μm / 100 krot]. No scratches with a depth of 0.5 μm or more.
B: 5 × 10 ⁻² [μm / 100 krot] <wear amount ≦ 30 × 10 ⁻² [μm / 100 krot]. No scratches with a depth of 0.5 μm or more.
C: 30 × 10 ⁻² [μm / 100 krot] <wear amount ≦ 50 × 10 ⁻² [μm / 100 krot]. No scratches with a depth of 1.0 μm or more.
D: 50 × 10 ⁻² [μm / 100 krot] <Amount of wear or scratches with a depth of 1.0 μm or more.

[Example 1]
An electrophotographic photosensitive member (P01) and a standard toner were prepared. Further, a particle source composed of basic particles (E15) and inorganic particles (K02) was prepared, and these were set in the evaluation machine 1. Three evaluation machines 1 were prepared, and one of the evaluation machines 1 was evaluated for image flow recoverability. The remaining two aircraft were used for the durability test under HH environment (endurance test B) and the endurance test under LL environment (endurance test B), respectively, for image flow evaluation, filming evaluation, cleaning blade wear evaluation and The electrophotographic photosensitive member was evaluated for wear.

  Table 4 shows the evaluation conditions and the evaluation results.

[Example 2]
A toner composed of toner particles obtained by externally adding an electrophotographic photosensitive member (P01), basic particles (E15), and inorganic particles (K02) was prepared, and these were set in the evaluation machine 2. Three evaluation machines 2 were prepared, and each evaluation was performed in the same manner as in Example 1.

  Table 4 shows the evaluation conditions and the evaluation results.

  The “supply method” in the table is a method for supplying basic particles and inorganic particles. When the evaluation machine 1 is used, it is expressed as “member”, and when it is added to the developer (externally added to the toner particles) and the evaluation machine 2 is used, it is expressed as “external addition”.

  An electrophotographic photosensitive member was produced in which the amount of the exemplified compound (U-2) used in the electrophotographic photosensitive member (P01) was changed from 5 parts to 0.5 parts, 5.0 parts, 15 parts, and 25 parts. When the same evaluation was performed, the same good results as in Examples 1 and 2 were obtained.

[Examples 3 to 11 and Comparative Examples 1 to 4]
Each evaluation was performed in the same manner as in Example 1 except that the electrophotographic photosensitive member, basic particles, inorganic particles, and supply method as evaluation conditions were as shown in Table 5. Table 5 shows the evaluation conditions and the evaluation results. FIG. 7 also shows the evaluation result of the image flow recoverability. In Comparative Example 1, no particle source was installed.

  From FIG. 7, when using basic particles having a pH of 11.0 or less, the pixel recovery index was 20 or more compared to Comparative Example 1 (Δ in FIG. 7) that did not use basic particles. In particular, when basic particles having a pH of 7.5 or more and 10.5 or less were used, very good image flow recovery was observed. On the other hand, Comparative Examples 2 to 4 using particles that are not basic (pH is 7.0 or less) or basic particles having a pH of more than 11.0 did not have good image flow recoverability. By using basic particles having a pH higher than 7.0, it is considered that they act on the discharge product and contribute to the recovery of image flow. On the other hand, when basic particles having a pH of greater than 11.0 are used, the basic particles themselves are highly hydrophilic, are strongly ionic, or the formed salt is strongly ionized. For this reason, a sufficient effect was not obtained.

  In Examples 6 to 7 using calcium carbonate excellent in lubricity as basic particles, the wear of the cleaning blade is further suppressed as compared with Examples 3 to 5 and Examples 8 to 11.

  Further, in Example 11 using the electrophotographic photosensitive member (P05) having a surface elastic deformation rate (We%) of 40% or more, filming is further suppressed as compared with Examples 3 to 10.

[Examples 12 to 19 and Comparative Examples 5 to 6]
Except that the electrophotographic photosensitive member, basic particles, inorganic particles and supply method as the evaluation conditions are as shown in Table 6, Examples 12 to 16 and Comparative Examples 5 to 6 were the same as Example 1, Each of Examples 17 to 19 was evaluated in the same manner as Example 2. Table 6 shows the evaluation conditions and the evaluation results. The evaluation result of the image flow recoverability is also shown in FIG.

  From FIG. 8, when the number average particle diameter of the basic particles is 30 nm or more and 500 nm or less, the image flow recoverability is high and very good. On the other hand, in Comparative Example 5 in which the number average particle diameter of the basic particles is less than 30 nm and in Comparative Example 6 in which the number average particle diameter exceeds 500 nm, the image flow recoverability is not sufficient.

  In Examples 12 to 19 using the electrophotographic photosensitive member (P05) having a surface elastic deformation rate (We%) of 40% or more, filming is suppressed as in Example 11.

  In Comparative Example 5, the image flow was not sufficiently suppressed. The superiority and inferiority of Comparative Example 5 and Comparative Example 6 are reversed in the image flow recovery property and the image flow by the durability test. In Comparative Example 5, since the basic particle size is small, the immediate effect of suppressing the image flow is high, but it tends to remain on the surface of the electrophotographic photosensitive member, which is a factor of the image flow. Conceivable.

  In Examples 17 to 19 in which basic particles having a number average particle size of 30 to 500 nm and having a pH of 11.0 or less were contained in the developer, the same results as in Examples 12, 13 and 16 were obtained.

[Examples 20 to 28]
Each evaluation was performed in the same manner as in Example 1 except that the electrophotographic photosensitive member, basic particles, inorganic particles, and supply method as evaluation conditions were as shown in Table 7. Table 7 shows the evaluation conditions and the evaluation results.

  In Examples 22 to 28 in which the compound represented by the above general formula (4) and satisfying 3 ≦ m + n ≦ 10 was used as the compound having a polymerizable functional group, the image flow was lower than that in Examples 20 to 21. More suppressed.

[Examples 29 to 39]
Examples 29 to 36 are the same as Example 1 except that the electrophotographic photosensitive member, basic particles, inorganic particles, and supply method as evaluation conditions are shown in Table 8. Examples 37 to 39 Were evaluated in the same manner as in Example 2. Table 8 shows the evaluation conditions and the evaluation results.

  In Examples 29 to 39 using inorganic particles having a Mohs hardness of 5 or more, the wear of the electrophotographic photosensitive member is further suppressed as compared with Examples 3 to 28. By using inorganic particles having a Mohs hardness of 5 or more, it is considered that the load at the contact portion between the electrophotographic photosensitive member and the cleaning blade and the variation in the load are reduced. It is considered that inorganic particles having a Mohs hardness of 5 or more contribute to scraping of the basic particles.

  In Examples 29 to 33 and Examples 35 to 39 using inorganic particles having a number average particle size larger than the basic particles and 1000 nm or less, the cleaning blade wear is further suppressed as compared with Example 34. .

  In order to make scraping of the basic particles more efficient, the inorganic particles are introduced to the wedge part of the contact portion between the cleaning blade and the electrophotographic photosensitive member to some extent, but to the deeper side of the wedge portion than the basic particles. From the viewpoint, it is preferable that the number average particle diameter of the inorganic particles is larger than the basic particles and 1000 nm or less.

  In the toners used in Examples and Comparative Examples, hydrophobized silica particles having a number average particle diameter of 20 nm are used as an external additive, and the Mohs hardness is 6, but the small particle diameter (basic particles) is used. It is considered that the contribution to scraping of the basic particles does not appear particularly.

[Comparative Examples 7 to 19]
Each evaluation was performed in the same manner as in Example 1 except that the electrophotographic photosensitive member, basic particles, inorganic particles, and supply method as evaluation conditions were as shown in Table 9. Table 9 shows the evaluation conditions and the evaluation results.

  The compounds represented by the above formulas (U-N2) to (U-N9) used in Comparative Examples 7 to 16 with respect to the compound represented by the above general formula (1) used in the present invention are an aryl group. The filming was not sufficiently suppressed because the structure was too long, it was difficult to have a structure in which aryl groups face each other, or there was no aryl group facing each other.

  Further, since the resol type phenolic resin used in Comparative Example 17 is hard to be cured by polymerization or crosslinking, filming can be sufficiently suppressed in spite of the use of the compound represented by the general formula (1). There wasn't.

  In Comparative Example 19 in which the compound represented by the general formula (1) was not used, the elastic deformation rate (We%) of the surface of the electrophotographic photosensitive member was close to that of the electrophotographic photosensitive members of Examples 26 to 27. Nevertheless, filming was not sufficiently suppressed.

DESCRIPTION OF SYMBOLS 101 Electrophotographic photoreceptor 101a Support body 101b Conductive layer 101c Undercoat layer 101d Charge generation layer 101e Charge transport layer 101f Protective layer 102 Charging means with discharge 103 Image exposure light 104 Developing means 105 Transfer means 106 Cleaning means 107 Cleaning blade 107S With Force means 108 Waste toner conveying means 109 Particle source 110 Supply member X Traveling direction of surface of electrophotographic photosensitive member θ Setting angle of cleaning blade L Free length of cleaning blade (length of unfixed portion)
T Thickness of cleaning blade a Small particles b Large particles c Deposits d Toner (transfer residual toner)
Idis Discharge current amount Vac AC voltage Vpp Amplitude of AC voltage Iac AC current amount W Defect or chipping width of the cleaning blade D Depth of chipping or squashing of the cleaning blade

Claims (8)

An electrophotographic apparatus comprising: an electrophotographic photosensitive member; a charging unit with discharge; an image exposing unit; a developing unit; a transferring unit; and a cleaning unit having a cleaning blade in contact with the surface of the electrophotographic photosensitive member.
The surface layer of the electrophotographic photoreceptor contains a resin composed of a polymer of a charge transporting compound having two or more polymerizable functional groups, and a compound represented by the following general formula (1):
The electrophotographic apparatus further includes means for supplying basic particles having a number average particle size of 30 to 500 nm and a pH of 11.0 or less to a portion where the surface of the electrophotographic photosensitive member is in contact with the cleaning blade. An electrophotographic apparatus.
(In General Formula (1), X represents an oxygen atom or a sulfur atom, R ¹ and R ² each independently represents an alkyl group having 1 to 3 carbon atoms, and Ar ¹ and Ar ² represent Each independently represents a substituted or unsubstituted aryl group, provided that the aryl group may have a carboxy group, a cyano group, a substituted or unsubstituted amino group, a hydroxy group, a substituted or unsubstituted group; A substituted alkoxy group, a substituted or unsubstituted alkyl group, a nitro group, or a halogen atom.) An electrophotographic apparatus comprising: an electrophotographic photosensitive member; a charging unit with discharge; an image exposing unit; a developing unit; a transferring unit; and a cleaning unit having a cleaning blade in contact with the surface of the electrophotographic photosensitive member.
The surface layer of the electrophotographic photoreceptor contains a resin composed of a polymer of a charge transporting compound having two or more polymerizable functional groups, and a compound represented by the following general formula (1):
The electrophotographic apparatus is characterized in that the developing means has a developer containing basic particles having a number average particle diameter of 30 to 500 nm and a pH of 11.0 or less .
(In General Formula (1), X represents an oxygen atom or a sulfur atom, R ¹ and R ² each independently represents an alkyl group having 1 to 3 carbon atoms, and Ar ¹ and Ar ² represent Each independently represents a substituted or unsubstituted aryl group, provided that the aryl group may have a carboxy group, a cyano group, a substituted or unsubstituted amino group, a hydroxy group, a substituted or unsubstituted group; A substituted alkoxy group, a substituted or unsubstituted alkyl group, a nitro group, or a halogen atom.) The electrophotographic apparatus according to claim 1, wherein R ¹ and R ² in the general formula (1) are the same group, and Ar ¹ and Ar ² are the same group. The electrophotographic apparatus according to claim 1, wherein the charge transporting compound is a compound represented by the following general formula (4).
(In General Formula (4), R ³ and R ⁴ each independently represent a hydrogen atom or a methyl group, Ar ³ represents a substituted or unsubstituted aryl group. M and n are each independently And an integer of 0 to 5.)   The electrophotographic apparatus according to claim 1, wherein an elastic deformation rate (We%) of the surface of the electrophotographic photosensitive member is 40% or more. The electrophotographic apparatus according to claim 1, wherein the basic particles have a pH of 7.5 to 10.5. The electrophotographic apparatus according to any one of claims 1 to 6, wherein the basic particles are calcium carbonate particles. The electrophotographic apparatus according to any one of claims 1 to 7 , wherein alumina particles are interposed in a portion where the surface of the electrophotographic photosensitive member and the cleaning blade come into contact with each other.