JP2008129450A - Image forming method and image forming apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an image forming method capable of suppressing image slipping and outputting image quality without any faults. <P>SOLUTION: The image forming method is composed of; an electrifying process electrifying an image carrier surface, an exposure process exposing an image carrier and forming an electrostatic latent image, a developing process forming a toner image by having toner transit to the electrostatic latent image, a transfer process transferring the toner image to a recording medium, and a cleaning process cleaning the image carrier surface with a blade. Friction coefficient for the image carrier surface is 0.6 to 1.4, material for the blade fulfill formula (1):3.92≤M≤29.42 [M expresses 100% modulus (MPa)], formula (2): 0<α≤0.294 [α expresses äΔ stress/Δ amount of distortion=(stress at amount of distortion at 200% - stress at amount of distortion at 100%)/(200-100)}(MPa/%)], formula (3): S≥250[S expresses breaking elongation (%) ] and abrading agent is supplied to a contact part between the image carrier and the cleaning blade. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an image forming method that can be used in a copying machine or the like that forms an image by electrophotography, and an image forming apparatus using the image forming method.

  The electrophotographic image forming apparatus includes a mechanism for forming an image by directly transferring a toner image formed on an image holding member to paper by electrostatic attraction, or transferring the toner image to paper via an intermediate transfer member. . Most of the toner image developed on the image carrier in the process of image formation is transferred from the image carrier to the transfer member, but the toner remaining on the image carrier is removed by a cleaning blade located in the post-process of the cycle. It is removed from the image carrier by a cleaning member such as a brush. The image holding member and the transfer member are in contact with each other, and an electric field (hereinafter referred to as a transfer electric field) for transferring the toner is applied to the contact portion (nip portion) when the toner image is transferred. For forming the transfer electric field, a technique such as a transfer roll positioned opposite to the image holding member with the transfer member interposed therebetween is generally used.

Further, the image carrier has a process of being charged by, for example, a corona discharge or a charging means using a charging roll in order to form an electrostatic image necessary for image formation. Along with this charging step, discharge products such as nitrogen oxide (NO _x ) and ozone (O ₃ ) are generated. These discharge products are adsorbed with moisture and become nitrates and adhere to the surface of the image carrier. Since the discharge product and nitrate are conductive, the uniformity of the charge on the surface of the image carrier is impaired in the charging step, and image drift occurs in the image. The number of discharge products that cause image drift increases depending on the amount of charge, and it is inevitable that a certain amount adheres on the image carrier in order to secure the amount of charge necessary for image formation. In view of this, a cleaning means has been devised that removes the attached discharge product with a cleaning blade or brush that contacts the image carrier. In general, these cleaning means wear not only the transfer residual toner and discharge products but also the surface layer of the image carrier itself to prevent image drift. However, conventional rubber blades wear rapidly, and sufficient cleaning properties may not be obtained, and a method using a material with low friction and high hardness for the portion of the cleaning blade that contacts the image carrier (for example, Although a method using a material having a high modulus (high hardness) for a portion of the cleaning blade that contacts the image holding member (for example, see Patent Document 2) is known, the hardness of the cleaning blade is By simply raising it, the adhesion with the image carrier is impaired, and the discharge product cannot be sufficiently removed over the entire surface of the image carrier.
JP 2001-343874 A JP 2003-241599 A

  An object of the present invention is to solve the above problems. That is, an object of the present invention is to provide an image forming method capable of efficiently suppressing image drift and stably outputting image quality without defects, and an image forming apparatus using the method.

The above object is achieved by the present invention described below. That is, the image forming method of the present invention includes:
A charging step for charging the surface of the image carrier, an exposure step for exposing the image carrier to form an electrostatic latent image based on image data, and transferring toner to the electrostatic latent image to form an electrostatic latent image on the image carrier. A developing step for forming a toner image on the surface, a transfer step for transferring the toner image on the image carrier to a recording medium, and a cleaning step for cleaning the surface of the image carrier after the toner image is transferred with a cleaning blade; The friction coefficient of the surface of the image carrier is 0.6 to 1.4, and the material of the portion of the cleaning blade that contacts the surface of the image carrier is represented by the following formulas (1) to (3): An abrasive is supplied to a portion where the image carrier and the cleaning blade are in contact with each other.

Formula (1) 3.92 ≦ M ≦ 29.42
Formula (2) 0 <α ≦ 0.294
Formula (3) S ≧ 250

(In the formulas (1) to (3), M represents a 100% modulus (MPa), and α represents a strain amount change (Δ strain amount in a stress-strain curve in a range of 100% to 200% strain). ) Represents the ratio of stress change (Δstress) to Δ {stress / Δstrain amount = (stress at 200% strain−stress at 100% strain) / (200−100)} (MPa /%). (The elongation at break (%) measured based on JIS-K6251 (using dumbbell-shaped No. 3 test piece)).

The image forming apparatus according to the present invention includes:
An image carrier, a charging unit for charging the surface of the image carrier, an exposure unit for exposing the image carrier to form an electrostatic latent image based on image data, and transferring toner to the electrostatic latent image. Developing means for forming a toner image on the image carrier, transfer means for transferring the toner image on the image carrier to a recording medium, and transferring the toner image in contact with the surface of the image carrier. A cleaning blade for cleaning the surface of the image carrier later, and forming an image using the image forming method of the present invention, that is, the coefficient of friction of the surface of the image carrier is 0.6 to 1. 4, the material of the portion of the cleaning blade that contacts the surface of the image carrier satisfies the above formulas (1) to (3), and the abrasive is supplied to the portion of the cleaning blade that contacts the image carrier. And

  According to the present invention, it is possible to provide an image forming method capable of efficiently suppressing image drift and stably outputting image quality without defects, and an image forming apparatus using the method.

  The image forming method of the present invention comprises a charging step for charging the surface of an image carrier, an exposure step for exposing the image carrier to form an electrostatic latent image based on image data, and a toner on the electrostatic latent image. A developing step for forming a toner image on the image carrier by transfer, a transfer step for transferring the toner image on the image carrier to a recording medium, and a surface of the image carrier after the toner image is transferred. A cleaning step of cleaning with a cleaning blade, the coefficient of friction of the surface of the image carrier is 0.6 to 1.4, and the material of the portion of the cleaning blade that contacts the surface of the image carrier is (1) to (3) are satisfied, and an abrasive is supplied to a portion where the image carrier and the cleaning blade are in contact with each other.

Formula (1) 3.92 ≦ M ≦ 29.42
Formula (2) 0 <α ≦ 0.294
Formula (3) S ≧ 250

(In the formulas (1) to (3), M represents a 100% modulus (MPa), and α represents a strain amount change (Δ strain amount in a stress-strain curve in a range of 100% to 200% strain). ) Represents the ratio of stress change (Δstress) to Δ {stress / Δstrain amount = (stress at 200% strain−stress at 100% strain) / (200−100)} (MPa /%). (The elongation at break (%) measured based on JIS-K6251 (using dumbbell-shaped No. 3 test piece)).

  When the portion of the cleaning blade that contacts the surface of the image carrier (hereinafter sometimes simply referred to as “cleaning blade tip”) satisfies the above formulas (1) to (3), it exhibits high hardness and high elongation characteristics. Excellent wear resistance and chipping resistance.

Further, as shown in FIG. 1A, the cleaning blade 1 is in contact with the image carrier 2, and when the contact portion is enlarged, the cleaning blade 1 is attached to the image carrier 2 as shown in FIG. It stretches to follow, and a certain range is in close contact.
In the present invention, since the image carrier having a surface with high friction is used as the image carrier 2, the cleaning blade 1 may extend following the rotation of the image carrier 2 and adhere to the image carrier 2. The area becomes larger, and the space for holding the abrasive 4 becomes wider than the conventional combination of the cleaning blade 5 and the image carrier 6 shown in FIG. The abrasive 4 has an effect of removing discharge products adhering to the surface of the image carrier 2 by moving following the tip of the blade 1 while being deposited on the contact portion between the image carrier 2 and the blade 1. As the amount of the abrasive 4 retained as in the present invention increases, the discharge product can be removed very efficiently, and as a result, the image forming method in which the degree of image drift is remarkably reduced, and can do.

  In particular, in the past, the image carrier 6 to be used has been studied in the direction of reducing friction from the viewpoint of suppressing the wear of the blade 5, but in the present invention, the cleaning is very excellent in wear resistance and chipping resistance. Since the blade 1 is used, there is no need to worry about wear even if the image carrier 2 having a large friction is used. Therefore, the blade 1 of the present invention having excellent extensibility can follow the image carrier 2 well and can hold a large amount of the abrasive 4.

  Hereinafter, in describing the present invention in detail, an image carrier, a cleaning blade, and an abrasive, which are main constituent elements of the present invention, will be described in detail.

-Image carrier (photoreceptor)-
The image carrier used in the present invention is required to have a surface friction coefficient of 0.6 to 1.4. When the friction coefficient is less than the above lower limit, the cleaning blade does not follow well and the abrasive is not sufficiently retained, so that effective discharge product removal cannot be expected. On the other hand, when the above upper limit is exceeded, the occurrence of blade squeezing and squealing (blade vibration) becomes a problem. From the viewpoint of more effectively removing the discharge products, the surface friction coefficient is more preferably 0.8 to 1.2, and particularly preferably 0.8 to 1.0.

[Coefficient of friction]
Here, the friction coefficient represents a dynamic friction coefficient measured by the following method.
A cleaning blade was brought into contact with the image carrier, and the dynamic torque (F) was measured when the pressing pressure (N) was 2 gf / mm and 4 gf / mm, and the dynamic friction coefficient (μ) was determined from the following equation.
(Expression) ΔF = μ · ΔN
The dynamic torque (F) is measured by using a measuring device (trade name: Torque Deuter TD001, manufactured by Kubota Corporation), and setting the peripheral speed of the image holding resistance to 165 mm / sec as a measurement condition. Body axial torque was measured.

  Here, the coefficient of friction can be controlled by selecting a material constituting the surface of the image carrier, adjusting the surface roughness of the surface of the image carrier, or the like.

The surface roughness Rz measured based on JIS-B0601 (1994) of the image carrier in the present invention from the viewpoint of controlling the friction coefficient of the surface as described above, although it varies depending on the material constituting the surface. Is preferably 0.01 to 2 μm, more preferably 0.05 to 1 μm, and particularly preferably 0.1 to 1 μm.
Incidentally, as a method for controlling the surface roughness Rz within the above range, there may be mentioned, for example, surface polishing with a wrapping sheet or the like at an initial stage. The method of using etc. is mentioned.

  The image carrier used in the present invention is not limited as long as the surface friction coefficient satisfies the above range as described above, but a particularly preferred image carrier is (1) having a crosslinked structure. Examples thereof include an image carrier having a surface layer containing a resin, and (2) an image carrier having a surface layer in which inorganic particles are dispersed.

(1) Image carrier having a surface layer containing a resin having a crosslinked structure An image carrier having a surface layer containing a resin having a crosslinked structure is high in strength and has excellent mechanical durability on the surface of the image carrier. Is difficult to occur, but has the disadvantage that image flow is likely to occur. However, image flow can be effectively prevented by applying the image forming method of the present invention having the cleaning step using the cleaning blade and the abrasive to the image carrier having a high surface friction coefficient. .

As an image carrier having a surface layer containing a resin having a crosslinked structure, an organic photoreceptor having a configuration in which at least a photosensitive layer is provided on a conductive substrate can be suitably used. The photosensitive layer may be a function-separated type having a layer structure in which a charge generation layer and a charge transport layer are laminated in this order, and between the photosensitive layer and the conductive substrate, or between the photosensitive layer and the surface protective layer. An intermediate layer may be provided as necessary.
Here, the surface layer containing a resin having a crosslinked structure may function as a surface protective layer separately formed on the photosensitive layer, or functions as a layer constituting at least the outermost surface of the photosensitive layer. (In the following description, the surface layer is basically assumed to be separately formed on the photosensitive layer). Moreover, it is preferable that the resin having a crosslinked structure has charge transporting properties.
In the following description, the image carrier used in the present invention will be described in more detail on the assumption that the image carrier is a function-separated organic photoconductor. However, the layer structure of the image carrier used in the present invention is as follows. It is not limited to the following description.

  Conductive substrates include metal drums such as aluminum, copper, iron, stainless steel, zinc, nickel; aluminum, copper, gold, silver, platinum, palladium, titanium, nickel on a substrate such as sheet, paper, plastic, glass, etc. -Deposited metal such as chromium, stainless steel, copper-indium; Deposited conductive metal compound such as indium oxide and tin oxide on the substrate; Laminated metal foil on the substrate; Carbon black Indium oxide, tin oxide-antimony oxide powder, metal powder, copper iodide, and the like are dispersed in a binder resin and applied to the substrate to conduct a conductive treatment. The shape of the conductive substrate may be any of a drum shape, a sheet shape, and a plate shape.

When a metal pipe base is used as the conductive base, the surface of the metal pipe base may be a raw pipe, but the base surface may be roughened by surface treatment in advance. It is. Such roughening can prevent grain-like density unevenness due to interference light that can be generated inside the photosensitive member when a coherent light source such as a laser beam is used as the exposure light source. Examples of the surface treatment method include mirror cutting, etching, anodizing, rough cutting, centerless grinding, sand blasting, wet honing and the like.
In particular, in terms of improving adhesion to the photosensitive layer and improving film formability, for example, an anodized surface of the aluminum substrate is preferably used as the conductive substrate.

  The charge generation layer is formed by depositing a charge generation material by a vacuum deposition method or by applying a solution containing an organic solvent and a binder resin.

Examples of charge generation materials include amorphous selenium, crystalline selenium, selenium-tellurium alloy, selenium-arsenic alloy, and other selenium compounds; inorganic photoconductors such as selenium alloy, zinc oxide, and titanium oxide; Sensitized, various phthalocyanine compounds such as metal-free phthalocyanine, titanyl phthalocyanine, copper phthalocyanine, tin phthalocyanine, gallium phthalocyanine; Various organic pigments such as salts; or dyes are used.
In addition, these organic pigments generally have several types of crystals. In particular, phthalocyanine compounds have various crystal types including α type and β type. Any of these crystal forms can be used as long as it is a pigment capable of obtaining characteristics.

  Of the charge generation materials described above, phthalocyanine compounds are preferred. In this case, when the photosensitive layer is irradiated with light, the phthalocyanine compound contained in the photosensitive layer absorbs photons and generates carriers. At this time, since the phthalocyanine compound has a high quantum efficiency, the absorbed photons can be efficiently absorbed to generate carriers.

  Examples of the binder resin used for the charge generation layer include the following. That is, polycarbonate resin such as bisphenol A type or bisphenol Z type and copolymers thereof, polyarylate resin, polyester resin, methacrylic resin, acrylic resin, polyvinyl chloride resin, polystyrene resin, polyvinyl acetate resin, styrene-butadiene copolymer resin Vinylidene chloride-acrylonitrile copolymer resin, vinyl chloride-vinyl acetate-maleic anhydride resin, silicone resin, silicon-alkyd resin, phenol-formaldehyde resin, styrene-alkyd resin, poly-N-vinylcarbazole and the like.

  These binder resins can be used alone or in admixture of two or more. The mixing ratio of the charge generation material and the binder resin (charge generation material: binder resin) is preferably in the range of 10: 1 to 1:10 by mass ratio. The thickness of the charge generation layer is generally preferably in the range of 0.01 to 5 μm, and more preferably in the range of 0.05 to 2.0 μm.

The charge generation layer may contain at least one electron accepting substance for the purpose of improving sensitivity, reducing residual potential, reducing fatigue during repeated use, and the like. Examples of the electron accepting material used in the charge generation layer include succinic anhydride, maleic anhydride, dibromomaleic anhydride, phthalic anhydride, tetrabromophthalic anhydride, tetracyanoethylene, tetracyanoquinodimethane, and o-dinitrobenzene. M-dinitrobenzene, chloranil, dinitroanthraquinone, trinitrofluorenone, peak phosphoric acid, o-nitrobenzoic acid, p-nitrobenzoic acid, phthalic acid and the like. Of these, fluorenone-based, quinone-based, and benzene derivatives having electron-withdrawing substituents such as Cl, CN, NO ₂ are particularly preferable.

As a method for dispersing the charge generating material in the resin, methods such as a roll mill, a ball mill, a vibrating ball mill, an attritor, a dyno mill, a sand mill, and a colloid mill can be used.
Known organic solvents as coating solution solvents for forming the charge generation layer, for example, aromatic hydrocarbon solvents such as toluene and chlorobenzene, fats such as methanol, ethanol, n-propanol, iso-propanol, and n-butanol Aromatic alcohol solvents, ketone solvents such as acetone, cyclohexanone and 2-butanone, halogenated aliphatic hydrocarbon solvents such as methylene chloride, chloroform and ethylene chloride, cyclic or straight chain such as tetrahydrofuran, dioxane, ethylene glycol and diethyl ether And ether solvents such as methyl ether, methyl acetate, ethyl acetate, and n-butyl acetate.

As the charge transport layer, a layer formed by a known technique can be used. The charge transport layer may be formed using a charge transport material and a binder resin, or may be formed using a polymer charge transport material.
Examples of charge transport materials include quinone compounds such as p-benzoquinone, chloranil, bromanyl, anthraquinone, tetracyanoquinodimethane compounds, fluorenone compounds such as 2,4,7-trinitrofluorenone, xanthone compounds, benzophenone compounds Electron transporting compounds such as cyanovinyl compounds and ethylene compounds, triarylamine compounds, benzidine compounds, arylalkane compounds, aryl-substituted ethylene compounds, stilbene compounds, anthracene compounds, hydrazone compounds, etc. Examples thereof include pore-transporting compounds.
These charge transport materials may be used alone or in combination of two or more, but are not limited thereto. From the viewpoint of mobility, for example, it is preferable to use materials represented by the following structural formulas (1) to (3).

In the structural formula (1), R ¹⁴ represents a hydrogen atom or a methyl group. N means 1 or 2. Ar ₆ and Ar ₇ represent a substituted or unsubstituted aryl group, or —C (R ¹⁸ ) ═C (R ¹⁹ ) (R ²⁰ ), —CH═CH—CH═C (Ar) _2, and Represents a substituted amino group substituted with a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an alkyl group having 1 to 3 carbon atoms.

In the structural formula (2), R ¹⁵ and R ^{15 ′} may be the same or different and each represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms. R ¹⁶ , R ^{16 ′} , R ¹⁷ and R ^{17 ′} may be the same or different and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or 1 to 2 carbon atoms. An amino group substituted with an alkyl group, a substituted or unsubstituted aryl group, or —C (R ¹⁸ ) ═C (R ¹⁹ ) (R ²⁰ ), —CH═CH—CH═C (Ar) ₂ Represent. m and n are integers of 0-2.
In the substituents of the structural formulas (1) and (2), R ¹⁸ , R ¹⁹ and R ^{20 each} represent a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group.

In Structural Formula (3), R ₂₁ represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a substituted or unsubstituted aryl group, or —CH═CH—CH═C ( Ar) ₂ is represented.
R ₂₂ and R ₂₃ may be the same or different, and are an amino group substituted with a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an alkyl group having 1 to 2 carbon atoms. Represents a group, a substituted or unsubstituted aryl group.
In the substituents of structural formulas (1) to (3), Ar represents a substituted or unsubstituted aryl group.

  Further, the binder resin used for the charge transport layer is polycarbonate resin, polyester resin, methacrylic resin, acrylic resin, polyvinyl chloride resin, polyvinylidene chloride resin, polystyrene resin, polyvinyl acetate resin, styrene-butadiene copolymer, vinylidene chloride- Acrylonitrile copolymer, vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate-maleic anhydride copolymer, silicone resin, silicone-alkyd resin, phenol-formaldehyde resin, styrene-alkyd resin, poly-N- Vinyl carbazole, polysilane, and polymer charge transport materials such as polyester polymer charge transport materials disclosed in JP-A-8-176293 and JP-A-8-208820 can also be used. These binder resins can be used alone or in admixture of two or more. The blending ratio (mass ratio) between the charge transport material and the binder resin is preferably 10: 1 to 1: 5.

  A polymer charge transport material can also be used alone. As the polymer charge transporting material, known materials having charge transporting properties such as poly-N-vinylcarbazole and polysilane can be used. In particular, polyester polymer charge transport materials disclosed in JP-A-8-176293 and JP-A-8-208820 have a high charge transporting property and are particularly preferable. The polymer charge transport material can be used as a charge transport layer by itself, but may be mixed with the binder resin to form a charge transport layer.

  In general, the thickness of the charge transport layer is preferably 5 to 50 μm, and more preferably 10 to 30 μm. As a coating method, a normal method such as a blade coating method, a Meyer bar coating method, a spray coating method, a dip coating method, a bead coating method, an air knife coating method, or a curtain coating method can be used. Furthermore, as a solvent used when providing a charge transport layer, aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene, ketones such as acetone and 2-butanone, and halogenation such as methylene chloride, chloroform and ethylene chloride Ordinary organic solvents such as aliphatic hydrocarbons, cyclic ethers such as tetrahydrofuran and ethyl ether and linear ethers can be used alone or in admixture of two or more.

  In addition, additives such as antioxidants, light stabilizers, and heat stabilizers are added to the photosensitive layer for the purpose of preventing deterioration of the photoreceptor due to ozone, oxidizing gas, or light or heat generated in the image forming apparatus. Can be added. For example, examples of the antioxidant include hindered phenol, hindered amine, paraphenylenediamine, arylalkane, hydroquinone, spirochroman, spiroidanone and derivatives thereof, organic sulfur compounds, and organic phosphorus compounds. Examples of the light stabilizer include derivatives such as benzophenone, benzotriazole, dithiocarbamate, and tetramethylpiperidine.

Moreover, at least one kind of electron accepting substance can be contained for the purpose of improving sensitivity, reducing residual potential, reducing fatigue during repeated use, and the like. Examples of the electron-accepting substance that can be used for the photoreceptor used in the present invention include succinic anhydride, maleic anhydride, dibromomaleic anhydride, phthalic anhydride, tetrabromophthalic anhydride, tetracyanoethylene, tetracyanoquinodimethane. O-dinitrobenzene, m-dinitrobenzene, chloranil, dinitroanthraquinone, trinitrofluorenone, picric acid, o-nitrobenzoic acid, p-nitrobenzoic acid, phthalic acid, etc., and compounds represented by general formula (I) I can give you. Of these, benzene derivatives having electron-withdrawing substituents such as fluorenone, quinone and Cl, CN, NO ₂ are particularly preferred.

In (1) the image carrier having a surface layer containing a resin having a crosslinked structure, the surface layer contains at least a resin having a crosslinked structure. Examples of the resin having a crosslinked structure include phenolic resins, urethane resins, and siloxane resins having a crosslinked structure. Since these resins having a crosslinked structure have excellent wear resistance, even when used for a long period of time, it is possible to suppress the wear and scratches on the surface of the image carrier. In addition, it is preferable that resin which has a crosslinked structure is what has charge transportability.
Although various materials can be used as the resin having a crosslinked structure, phenolic resin, urethane resin, siloxane resin and the like are preferable in terms of characteristics, and those made of siloxane-based resin are more preferable. Of these, those having structures derived from compounds represented by the following general formulas (I) and (II) are particularly preferred because of their excellent strength and stability.

F- [D-Si (R ² ) _(3-a) Q _a ] _b (I)
In general formula (I), F is an organic group derived from a compound having a hole transport ability, D is a flexible subunit, R ² is hydrogen, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl. Group, Q represents a hydrolyzable group, a represents an integer of 1 to 3, and b represents an integer of 1 to 4.
The flexible subunit represented by D in the general formula (I) necessarily includes a — (CH ₂ ) _n — group, which includes —COO—, —O—, —CH═CH—, — It may be a divalent linear group in which a CH═N— group is combined. _{Incidentally, - (CH 2) n -} n group is an integer of 1-5. Moreover, as a hydrolysable group represented by Q, -OR group (however, R represents an alkyl group) is represented.

F-((X) _n (R ₁ ) ₁ -ZH) _m (II)
In general formula (II), F is an organic group derived from a compound having a hole transporting ability, R ¹ is an alkylene group, Z is —O—, —S—, —NH—, or —COO—, m shows the integer of 1-4. X represents -O- or -S-, and n and l represent 0 or 1.
More preferable examples of the compounds represented by the general formulas (I) and (II) include those in which the organic group F is particularly represented by the following general formula (III).

In general formula (III), Ar _{1 to} Ar ₄ each independently represents a substituted or unsubstituted aryl group, Ar ₅ represents a substituted or unsubstituted aryl group or an arylene group, and Ar _{1 to} Ar 1-4 of ₅ the general formula ^-D-Si in _{(I) (R 2) (} 3-a) Q a or formula (II) in the _{- (X) n (R 1} ) l - It preferably has a bond represented by ZH. K represents 0 or 1.

Ar _{1 to} Ar ₄ in the general formula (III) each independently represent a substituted or unsubstituted aryl group, and specifically, those shown in the following structural group 1 are preferable.

  In addition, Ar shown in the structure group 1 is preferably selected from the following structure group 2, and Z ′ is preferably selected from the following structure group 3.

In Structural Groups 1 to 3, R ⁶ is substituted with hydrogen, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. Selected from a substituted phenyl group, an unsubstituted phenyl group, and an aralkyl group having 7 to 10 carbon atoms.
R ^{7 to} R ¹³ are hydrogen, a phenyl group substituted with an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. Or an unsubstituted phenyl group, an aralkyl group having 7 to 10 carbon atoms, and a halogen.
m and s represent 0 or 1, q and r represent an integer of 1 to 10, and t represents an integer of 1 to 3. Here, X is the formula ^-D-Si _{(R 2)} shown in _{(I) (3-a)} Q a or formula (II) in the _{- (X) n (R 1} ) with l -ZH The group represented is shown.
Further, W shown in the structure group 3 is preferably that shown in the following structure group 4. In Structural Group 4, s ′ represents an integer of 0 to 3.

The specific structure of Ar ₅ in the general formula (III) is as follows. When k = 0, the structure of Ar _{1 to} Ar ₄ shown in the structural group 1 is m = 1, and when k = 1, , the structure of m = 0 of _Ar 1 to Ar ₄ shown in the structure group 1 and the like.

Specific examples of the compound corresponding to the general formula (I) among the compounds represented by the general formula (III) include the compounds (III-1) to (III-61) shown in the following Tables 1 to 7. However, the compound represented by the general formula (I) used in the present invention is not limited thereto.
In addition, in the structural formulas shown in the columns “Ar ₁ ” to “Ar ₅ ” in Tables 1 to 7, “—S” groups bonded to the benzene ring are listed in the “S” column in Tables 1 to 7. means a monovalent radical represented (general formula (I) in _{^{-D-Si (R 2) (}} 3-a) group corresponding to the structure represented by _{Q a).}

  Specific examples of the general formula (II) include the compounds shown in the following (II) -1 to (II) -26, but the present invention is not limited thereto.

In order to control various physical properties such as strength and film resistance, a compound represented by the following general formula (IV) can also be added.
Si (R ² ) _(4-c) Q _c (IV)
In general formula (IV), R ² represents hydrogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, Q represents a hydrolyzable group, and c represents an integer of 1 to 4.

Specific examples of the compound represented by the general formula (IV) include the following silane coupling agents.
Tetrafunctional alkoxysilane such as tetramethoxysilane and tetraethoxysilane (c = 4); methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, methyltrimethoxyethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane , Phenyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltri Methoxysilane, γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, (tridecafluoro-1,1,2,2-tetrahydrooctyl) triethoxysilane, (3, 3,3-trifluoropropyl) trimethoxysilane, 3- (heptafluoroisopropoxy) propyltriethoxysilane, 1H, 1H, 2H, 2H-perfluoroalkyltriethoxysilane, 1H, 1H, 2H, 2H-par Trifunctional alkoxysilanes (c = 3) such as 1-fluorodecyltriethoxysilane, 1H, 1H, 2H, 2H-perfluorooctyltriethoxysilane; dimethyldimethoxysilane, diphenyldimethoxysilane, methylphenyldimethoxysilane and the like Examples thereof include functional alkoxysilane (c = 2); monofunctional alkoxysilane such as trimethylmethoxysilane (c = 1). Trifunctional and tetrafunctional alkoxysilanes are preferable for improving the strength of the film, and bifunctional and monofunctional alkoxysilanes are preferable for improving the flexibility and film-forming property.

  Moreover, a silicon-based hard coat agent produced mainly from these coupling materials can also be used. Commercially available hard coat agents include KP-85, X-40-9740, X-40-2239 (manufactured by Shin-Etsu Silicone), and AY42-440, AY42-441, AY49-208 (manufactured by Toray Dow Corning). Etc.) can be used.

In order to increase the strength, it is also preferable to use a compound having two or more silicon atoms represented by the general formula (V).
B- (Si (R ² ) _(3-a) Q _a ) ₂ (V)
In general formula (V), B represents a divalent organic group, R ² represents hydrogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, Q represents a hydrolyzable group, and a represents 1 to 3 Represents an integer.
Specifically, the materials shown in Table 8 below can be mentioned as preferable ones, but the present invention is not limited by these.

  Further, a resin soluble in an alcohol solvent or a ketone solvent may be added for controlling the film characteristics and extending the liquid life. As this resin, polyvinyl butyral resin, polyvinyl formal resin, polyvinyl acetal resin such as partially acetalized polyvinyl acetal resin in which a part of butyral is modified with formal, acetoacetal or the like (for example, Sleksui B or K manufactured by Sekisui Chemical Co., Ltd.) , Polyamide resin, cellulose resin, phenol resin and the like. In particular, polyvinyl acetal resin is preferable in terms of electrical characteristics.

Various resins can be added for the purpose of discharge gas resistance, mechanical strength, scratch resistance, particle dispersibility, viscosity control, torque reduction, wear amount control, pot life extension, and the like. Particularly in the case of a siloxane-based resin, it is preferable to add a resin that dissolves in alcohol.
Examples of resins soluble in alcohol solvents include polyvinyl butyral resins, polyvinyl formal resins, and polyvinyl acetal resins such as partially acetalized polyvinyl acetal resins in which a part of butyral is modified with formal or acetoacetal (for example, manufactured by Sekisui Chemical Co., Ltd.) ESREC B, K, etc.), polyamide resin, cellulose resin, phenol resin and the like. In particular, polyvinyl acetal resin is preferable in terms of electrical characteristics.

  The molecular weight of the resin is preferably 2000-100000, more preferably 5000-50000. If the molecular weight is less than 2000, the desired effect cannot be obtained. If the molecular weight is more than 100,000, the solubility becomes low and the addition amount is limited, or the film formation is poor at the time of coating. The addition amount is preferably 1 to 40% by mass, more preferably 1 to 30% by mass, and most preferably 5 to 20% by mass. When the amount is less than 1% by mass, it is difficult to obtain a desired effect. When the amount is more than 40% by mass, image blurring under high temperature and high humidity tends to occur. These resins may be used alone or in combination.

  Further, for the purpose of extending the pot life and controlling the film properties, a cyclic compound having a repeating structural unit represented by the following general formula (VI) or a derivative thereof can be contained.

In general formula (VI), A ¹ and A ² each independently represent a monovalent organic group.
Examples of the cyclic compound having the repeating structural unit represented by the general formula (VI) include a commercially available cyclic siloxane. Specifically, cyclic dimethylcyclosiloxanes such as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, 1,3,5-trimethyl-1,3,5- Triphenylcyclotrisiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetraphenylcyclotetrasiloxane, 1,3,5,7,9-pentamethyl-1,3,5,7 , 9-pentaphenylcyclopentasiloxane and other cyclic methylphenylcyclosiloxanes, hexaphenylcyclotrisiloxane and other cyclic phenylcyclosiloxanes, and 3- (3,3,3-trifluoropropyl) methylcyclotrisiloxane and other fluorine Contain cyclosiloxanes and methylhydrosiloxane Things, pentamethylcyclopentasiloxane include a phenyl hydrosilyl group-containing cyclosiloxanes such hydrocyclosiloxane, cyclic siloxanes and vinyl group-containing cyclosiloxanes, such as penta vinyl pentamethylcyclopentasiloxane like. These cyclic siloxane compounds may be used alone or as a mixture thereof.

  Furthermore, various particles can be added in order to improve the contamination resistance adhesion and lubricity on the surface of the photoreceptor. They can be used alone or in combination. An example of the particles may include silicon-containing particles. Silicon-containing particles are particles containing silicon as a constituent element, and specific examples include colloidal silica and silicone particles. The colloidal silica used as the silicon-containing particles is selected from acidic or alkaline aqueous dispersions having an average particle diameter of 1 to 100 nm, preferably 10 to 30 nm, or those dispersed in organic solvents such as alcohols, ketones and esters. A commercially available product can be used. The solid content of the colloidal silica in the surface layer is not particularly limited, but is in the range of 0.1 to 50% by mass in the total solid content of the surface layer in terms of film forming properties, electrical properties, and strength. Preferably, it is used in the range of 0.1 to 30% by mass.

  Silicone particles used as silicon-containing particles are spherical and have an average particle diameter of 1 to 500 nm, preferably 10 to 100 nm, and are selected from silicone resin particles, silicone rubber particles, and silicone surface-treated silica particles, and are generally commercially available. Can be used. Silicone particles are small particles that are chemically inert and have excellent dispersibility in the resin, and because the content required to obtain sufficient properties is low, photosensitivity can be achieved without hindering the crosslinking reaction. The surface properties of the body can be improved. In other words, it is possible to improve the lubricity and water repellency of the surface of the photoreceptor while being uniformly incorporated into a strong cross-linked structure, and to maintain good wear resistance and adherence to contaminants over a long period of time. . The content of the silicone particles in the surface layer in the photoreceptor of the present invention is in the range of 0.1 to 30% by mass, preferably in the range of 0.5 to 10% by mass, based on the total solid content of the surface layer. .

Other particles include fluorine-based particles such as ethylene tetrafluoride, ethylene trifluoride, propylene hexafluoride, vinyl fluoride, vinylidene fluoride, and the 8th Polymer Materials Forum Lecture Proceedings p89. Particles made of a resin obtained by copolymerizing the fluororesin and a monomer having a hydroxyl group, ZnO—Al ₂ O ₃ , SnO ₂ —Sb ₂ O ₃ , In ₂ O ₃ —SnO ₂ , ZnO—TiO ₂ , Examples thereof include semiconductive metal oxides such as ZnO—TiO ₂ , MgO—Al ₂ O ₃ , FeO—TiO ₂ , TiO ₂ , SnO ₂ , In ₂ O ₃ , ZnO, and MgO.
For the same purpose, an oil such as silicone oil can be added. Examples of the silicone oil include silicone oils such as dimethylpolysiloxane, diphenylpolysiloxane, and phenylmethylsiloxane, amino-modified polysiloxane, epoxy-modified polysiloxane, carboxyl-modified polysiloxane, carbinol-modified polysiloxane, methacryl-modified polysiloxane, and mercapto. Examples thereof include reactive silicone oils such as modified polysiloxanes and phenol-modified polysiloxanes.

  Moreover, it is preferable that the exposure rate to the surface layer surface of the said particle | grain is 40% or less. When the above range is exceeded, the influence of the particles alone becomes large, and image flow or the like due to low resistance tends to occur. A more preferable range within the above range is 30% or less, and the particles exposed on the surface are effectively refreshed by the cleaning blade, and over a long period of time, toner component filming on the surface of the photoreceptor is suppressed, discharge products are removed, torque The reduction in the wear of the cleaning blade due to the reduction of the above is maintained.

  In addition, additives such as plasticizers, surface modifiers, antioxidants, and photodegradation inhibitors can also be used. Examples of the plasticizer include biphenyl, biphenyl chloride, terphenyl, dibutyl phthalate, diethylene glycol phthalate, dioctyl phthalate, triphenyl phosphate, methyl naphthalene, benzophenone, chlorinated paraffin, polypropylene, polystyrene, and various fluorohydrocarbons.

  An antioxidant having a hindered phenol, hindered amine, thioether or phosphite partial structure can be added to the surface layer, which is effective in improving the potential stability and image quality when the environment changes. Antioxidants include the following compounds, for example, “Sumizer BHT-R”, “Sumizer MDP-S”, “Sumizer BBM-S”, “Sumizer WX-R”, “Sumizer NW”, “Sumizer” as hindered phenols. "BP-76", "Sumizer BP-101", "Sumizer GA-80", "Sumizer GM", "Sumizer GS" or more manufactured by Sumitomo Chemical Co., Ltd., "IRGANOX1010", "IRGANOX1035", "IRGANOX1076", "IRGANOX1098" “IRGANOX1135”, “IRGANOX1141”, “IRGANOX1222”, “IRGANOX1330”, “IRGANOX1425” L ”,“ IRGANOX1520L ”,“ IRGANOX245 ”,“ IRGANOX259 ”,“ IRGANOX3114 ”,“ IRGANOX3790 ”,“ IRGANOX5057 ”,“ IRGANOX565 ”or more, manufactured by Ciba Specialty Chemicals,“ Adekastab AO-20 ”,“ Adekastab AO-30 ” ”,“ ADK STAB AO-40 ”,“ ADK STAB AO-50 ”,“ ADK STAB AO-60 ”,“ ADK STAB AO-70 ”,“ ADK STAB AO-80 ”,“ ADK STAB AO-330 ”or more, manufactured by Asahi Denka, Hindert As amines, “Sanol LS2626”, “Sanol LS765”, “Sanol LS770”, “Sanol LS744”, “Tinuvin 144”, “Tinuvin 622LD”, “Mark LA57”, “Mar CL LA67 "," MARK LA62 "," MARK LA68 "," MARK LA63 "," SUMILIZER TPS "," SUMILIZER TP-D "as thioether," MARK 2112 "," MARK PEP-8 "as phosphite, “Mark PEP · 24G”, “Mark PEP · 36”, “Mark 329K”, “Mark HP · 10” can be mentioned, and hindered phenols and hindered amine antioxidants are particularly preferable. Further, they may be modified with a substituent such as an alkoxysilyl group capable of undergoing a crosslinking reaction with the material forming the crosslinked film.

It is preferable to add or use a catalyst at the time of forming the coating liquid used for forming the surface layer and the coating liquid. Catalysts used include inorganic acids such as hydrochloric acid, acetic acid, phosphoric acid and sulfuric acid, organic acids such as formic acid, propionic acid, oxalic acid, p-toluenesulfonic acid, benzoic acid, phthalic acid and maleic acid, potassium hydroxide and hydroxide Alkali catalysts such as sodium, calcium hydroxide, ammonia and triethylamine, and solid catalysts insoluble in the following systems can also be used.
For example, Amberlite 15, Amberlite 200C, Amberlist 15E (above, manufactured by Rohm and Haas); Dowex MWC-1-H, Dowex 88, Dowex HCR-W2 (above, Dow Chemical Co., Ltd.) ); Lebatit SPC-108, Lebatit SPC-118 (manufactured by Bayer); Diaion RCP-150H (Mitsubishi Kasei); Sumikaion KC-470, Duolite C26-C, Duolite C-433, Duolite -464 (manufactured by Sumitomo Chemical Co., Ltd.); cation exchange resins such as Nafion-H (manufactured by DuPont); Amberlite IRA-400, Amberlite IRA-45 (manufactured by Rohm and Haas) Anion exchange resin of Zr (O ₃ PCH ₂ CH ₂ SO ₃ H) ₂ , An inorganic solid in which a group containing a protonic acid group such as Th (O ₃ PCH ₂ CH ₂ COOH) ₂ is bonded to the surface; a polyorganosiloxane containing a protonic acid group such as a polyorganosiloxane having a sulfonic acid group; Heteropolyacids such as cobalt tungstic acid and phosphomolybdic acid; isopolyacids such as niobic acid, tantalum acid and molybdic acid; monometallic oxides such as silica gel, alumina, chromia, zirconia, CaO and MgO; silica-alumina, silica- Composite metal oxides such as magnesia, silica-zirconia, and zeolites; clay minerals such as acidic clay, activated clay, montmorillonite, and kaolinite; metal sulfates such as LiSO ₄ and MgSO ₄ ; zirconia phosphate, lanthanum phosphate, etc. Metal phosphate; LiNO ₃ , Mn (NO ₃ ) Metal nitrates such as ₂ ; inorganic solids having amino group-containing groups such as solids obtained by reacting aminopropyltriethoxysilane on silica gel; amino groups such as amino-modified silicone resins And polyorganosiloxane containing.

  Moreover, it is preferable to use a solid catalyst that is insoluble in a photofunctional compound, reaction product, water, solvent, or the like in the preparation of the coating liquid because the stability of the coating liquid tends to be improved. A solid catalyst that is insoluble in the system is particularly suitable if the catalyst component is insoluble in the compounds represented by the general formulas (I), (II), (III), (V), other additives, water, solvents, etc. It is not limited. Although the usage-amount of these solid catalysts is not restrict | limited in particular, 0.1-100 mass parts is preferable with respect to a total of 100 mass parts of the compound which has a hydrolysable group. Further, as described above, these solid catalysts are insoluble in raw material compounds, reaction products, solvents and the like, and therefore can be easily removed after the reaction according to a conventional method. The reaction temperature and reaction time are selected according to the type and amount of the raw material compound or solid catalyst, but the reaction temperature is usually 0 to 100 ° C., preferably 10 to 70 ° C., more preferably 15 to 50 ° C. The reaction time is preferably 10 minutes to 100 hours. If the reaction time exceeds the upper limit, gelation tends to occur.

  When a catalyst that is insoluble in the system is used in the coating liquid preparation step, it is preferable to use a catalyst that is further dissolved in the system for the purpose of improving strength, liquid storage stability and the like. Examples of the catalyst include aluminum triethylate, aluminum triisopropylate, aluminum tri (sec-butyrate), mono (sec-butoxy) aluminum diisopropylate, diisopropoxyaluminum (ethyl acetoacetate), Aluminum tris (ethyl acetoacetate), aluminum bis (ethyl acetoacetate) monoacetylacetonate, aluminum tris (acetylacetonate), aluminum diisopropoxy (acetylacetonate), aluminum isopropoxy-bis (acetylacetonate), aluminum Use organoaluminum compounds such as tris (trifluoroacetylacetonate) and aluminum tris (hexafluoroacetylacetonate) Door can be.

  Besides organic aluminum compounds, organic compounds such as dibutyltin dilaurate, dibutyltin dioctiate, and dibutyltin diacetate; titanium tetrakis (acetylacetonate), titanium bis (butoxy) bis (acetylacetonate), titanium bis Organic titanium compounds such as (isopropoxy) bis (acetylacetonate); zirconium tetrakis (acetylacetonate), zirconium bis (butoxy) bis (acetylacetonate), zirconium bis (isopropoxy) bis (acetylacetonate), etc. Zirconium compounds; etc. can also be used, but from the viewpoints of safety, low cost, and pot life length, it is preferable to use an organoaluminum compound, particularly an aluminum chelate compound. It is more preferable. Although the usage-amount in particular of these catalysts is not restrict | limited, 0.1-20 mass parts is preferable with respect to a total of 100 mass parts of the compound which has a hydrolysable group, and 0.3-10 mass parts is especially preferable.

  When an organometallic compound is used as a catalyst, it is preferable to add a multidentate ligand from the viewpoint of pot life and curing efficiency. Examples of the polydentate ligand include those shown below and those derived therefrom, but the present invention is not limited thereto.

Specifically, β-diketones such as acetylacetone, trifluoroacetylacetone, hexafluoroacetylacetone, and dipivaloylmethylacetone; acetoacetate esters such as methyl acetoacetate and ethyl acetoacetate; bipyridine and derivatives thereof; glycine and its Derivatives; ethylenediamine and derivatives thereof; 8-oxyquinoline and derivatives thereof; salicylaldehyde and derivatives thereof; catechol and derivatives thereof; bidentate ligands such as 2-oxyazo compounds; diethyltriamine and derivatives thereof; nitrilotriacetic acid and derivatives thereof And tridentate ligands such as ethylenediaminetetraacetic acid (EDTA) and derivatives thereof. In addition to the above organic ligands, inorganic ligands such as pyrophosphoric acid and triphosphoric acid can be used. As the multidentate ligand, a bidentate ligand is particularly preferable, and specific examples include a bidentate ligand represented by the following general formula (VII) in addition to the above. Among them, a bidentate ligand represented by the following general formula (VII) is more preferable, and R ⁵ and R ⁶ in the following general formula (VII) are particularly preferable. By making R ⁵ and R ^{6 the} same, the coordination power of the ligand at room temperature becomes stronger, and the coating liquid can be further stabilized.

In general formula (VII), R ⁵ and R ⁶ each independently represents an alkyl group having 1 to 10 carbon atoms, a fluorinated alkyl group, or an alkoxy group having 1 to 10 carbon atoms.
The compounding amount of the polydentate ligand can be arbitrarily set, but is 0.01 mol or more, preferably 0.1 mol or more, more preferably 1 mol or more, with respect to 1 mol of the organometallic compound used. It is preferable to do this.
The coating solution can be produced in the absence of a solvent, but if necessary, alcohols such as methanol, ethanol, propanol and butanol; ketones such as acetone and methyl ethyl ketone; tetrahydrofuran; ethers such as diethyl ether and dioxane Various other solvents can be used. As this solvent, those having a boiling point of 100 ° C. or less are preferable, and they can be arbitrarily mixed and used. The amount of the solvent can be arbitrarily set, but if it is too small, the organosilicon compound is likely to be precipitated, so that it is 0.5 to 30 parts by mass, preferably 1 to 20 parts by mass with respect to 1 part by mass of the organosilicon compound. preferable.

  The reaction temperature and reaction time for curing the coating solution are not particularly limited, but the reaction temperature is preferably 60 ° C. or higher, more preferably 80 to 200 from the viewpoint of mechanical strength and chemical stability of the resulting silicon resin. The reaction time is preferably 10 minutes to 5 hours. In addition, maintaining the surface layer obtained by curing the coating liquid in a high humidity state is effective in stabilizing the characteristics of the surface layer. Furthermore, the surface layer can be subjected to surface treatment using hexamethyldisilazane, trimethylchlorosilane, or the like depending on the application to make it hydrophobic.

  When a charge transporting material is added to a resin having a cross-linked structure or a charge transporting function is given, it has excellent mechanical strength and sufficient photoelectric properties. It can also be used as a charge transport layer. In that case, a usual method such as a blade coating method, a Meyer bar coating method, a spray coating method, a dip coating method, a bead coating method, an air knife coating method, or a curtain coating method can be used. However, when a required film thickness cannot be obtained by a single application, the necessary film thickness can be obtained by applying a plurality of times. When performing multiple times of repeated application, the heat treatment may be performed every time of application, or after multiple times of repeated application.

  In the case of a single-layer type photosensitive layer, it is formed containing the charge generation material and a binder resin. As the binder resin, the same resin as the binder resin used for the charge generation layer and the charge transport layer can be used. The content of the charge generating substance in the single-layer type photosensitive layer is 10 to 85% by mass, preferably 20 to 50% by mass. A charge transport material or a polymer charge transport material may be added to the single-layer type photosensitive layer for the purpose of improving photoelectric characteristics. The addition amount is preferably 5 to 50% by mass. Moreover, you may add the compound shown by general formula (I). The same solvent and coating method as those described above can be used. The film thickness is preferably about 5 to 50 μm, more preferably 10 to 40 μm.

(2) Image carrier having a surface layer in which inorganic particles are dispersed An image carrier having a surface layer in which inorganic particles are dispersed has excellent surface scratch resistance because the surface roughness can be maintained over a long period of time. Has the advantage. However, on the other hand, there is a drawback that image flow tends to occur. However, image flow can be effectively prevented by applying the image forming method of the present invention having the cleaning step using the cleaning blade and the abrasive to the image carrier having a high surface friction coefficient. .

As an image carrier having a surface layer in which inorganic particles are dispersed, an organic photoreceptor having a configuration in which at least a photosensitive layer is provided on a conductive substrate can be suitably used. The photosensitive layer may be a function-separated type having a layer structure in which a charge generation layer and a charge transport layer are laminated in this order, or an intermediate layer or a surface protective layer may be provided.
Here, the surface layer in which the inorganic particles are dispersed may function as a surface protective layer separately formed on the photosensitive layer, or function as a layer constituting at least the outermost surface of the photosensitive layer (for example, The charge transport layer may correspond to the “layer constituting the outermost surface” as long as it is an image carrier in which a charge generation layer and a charge transport layer are formed in this order on a conductive substrate.

Note that the conductive substrate, the charge generation layer, the charge transport layer, and the intermediate layer that constitute the image carrier having the surface layer in which the inorganic particles are dispersed (2) correspond to the layers constituting the outermost surface. Except for dispersing inorganic particles, the same configuration as each layer described in the section of (1) Image carrier having a surface layer containing a resin having a crosslinked structure can be applied.
In addition, a surface layer in which inorganic particles are further dispersed is separately formed on the photosensitive layer in the structure of the surface protective layer described in the section of the image carrier having the surface layer containing a resin having a crosslinked structure (1). It can also be set as an aspect.

Preferable examples of the inorganic particles dispersed in the surface layer include alumina and titania.
As a method for dispersing the inorganic particles, known methods such as a roll mill, a ball mill, a vibrating ball mill, an attritor, a dyno mill, a sand mill, and a colloid mill can be applied.
Moreover, as addition amount of the inorganic particle in the said surface layer, 0.2-1.0 mass% is preferable.

-Cleaning blade-
As described above, the cleaning blade used in the present invention is such that at least the material in contact with the surface of the image carrier satisfies the above formulas (1) to (3). Since the cleaning blade exhibits a high elongation characteristic, a wide abrasive holding space can be ensured by extending well following the image bearing member having the high friction surface. As described above, the abrasive that is retained in a large amount can remove discharge products very efficiently, and can significantly reduce the occurrence of image drift.

In this cleaning blade, the material at the tip of the blade that comes into contact with the surface of the image carrier satisfies the formula (1), so that it exhibits excellent cleaning properties and excellent wear resistance.
When the 100% modulus M is less than 3.92 MPa (40 kgf / cm ² ), the wear resistance is insufficient, and good cleaning properties cannot be maintained over a long period of time. Further, when the pressure exceeds 29.42 MPa (300 kgf / cm ² ), the cleaning blade tip material is too hard, so that the followability with respect to the surface of the image carrier is deteriorated, and a large amount of abrasive cannot be held. The product cannot be removed well. Also, good cleaning performance cannot be exhibited. In addition, the image carrier surface may be easily damaged.
The 100% modulus M is preferably in the range of 5 to 20 MPa, and more preferably in the range of 6.5 to 15 MPa.

Moreover, since the cleaning blade tip portion material satisfies the expressions (2) and (3), the chipping resistance is excellent.
When α shown in Expression (2) exceeds 0.294, the cleaning blade tip portion material lacks flexibility. Therefore, when a two-component developer is used as a developer, a part of the carrier is transferred to the surface of the image carrier by electrostatic attraction force when a BCO (Bead Carry Over; two-component developer is used. ), Foreign matter existing on the surface of the image carrier, such as foreign matter buried or fixed on the surface of the image carrier, in particular, contact between the image carrier surface and the cleaning blade. By repeatedly passing through the part, when a large stress is repeatedly applied to the tip of the cleaning blade, it cannot be deformed so that this stress can be dispersed efficiently, so that edge chipping occurs within a relatively short period of time. . Therefore, since chipping occurs early, good cleaning properties cannot be maintained over a long period of time. Further, since the followability with respect to the surface of the image carrier is deteriorated due to lack of flexibility, a large amount of abrasive cannot be held, and discharge products cannot be removed well.
Α is preferably 0.2 or less, more preferably 0.1 or less, and the closer to 0, which is the lower limit of physical properties, the better.

Further, when the breaking elongation S shown in the expression (3) is less than 250%, when the foreign matter on the surface of the image carrier and the tip of the cleaning blade collide with a strong force, the tip of the cleaning blade extends and follows. Since it cannot be deformed, edge chipping occurs within a relatively short period of time. Therefore, since chipping occurs early, good cleaning properties cannot be maintained over a long period of time.
The breaking elongation S is preferably 300% or more, more preferably 350% or more, and it is more preferable for the edge chipping. On the other hand, when the breaking elongation S is more than 500%, the surface of the image carrier. Followability (adhesiveness) with respect to the surface, and the frictional force with the surface of the image carrier increases, and as a result, edge wear tends to increase. Therefore, from the viewpoint of edge wear, the elongation at break S is preferably 500% or less, more preferably 450% or less, and still more preferably 400% or less.

  The temperature around the cleaning blade of the image forming apparatus, that is, the use environment temperature is generally in the range of 10 to 60 ° C. Therefore, when the glass transition temperature Tg of the material in contact with the surface of the image carrier exceeds the operating environment temperature, the rubber-like property disappears and the contact pressure of the cleaning blade may become unstable. Therefore, the glass transition temperature Tg of the material in contact with the surface of the image carrier is preferably not more than the lower limit (10 ° C.) of the use environment temperature.

On the other hand, the rebound resilience R of the material in contact with the surface of the image carrier tends to decrease as the glass transition temperature Tg of the material is 10 ° C. or lower. In particular, when the rebound resilience R is less than 10%, the sticking and slipping behavior of the tip of the cleaning blade becomes dull, and a portion that rubs in a deformed state in a certain contact posture is likely to occur.
When the contact posture is not released due to the stick-and-slip behavior, rubbing occurs with the posture of the tip of the cleaning blade maintained, and local plastic deformation is likely to occur. When this local plastic deformation occurs, the adhesion between the tip of the cleaning blade and the surface of the image carrier is lowered, and cleaning failure may easily occur. In order to suppress this local plastic deformation, it is preferable that the tip of the cleaning blade always has a stick-and-slip behavior. For this purpose, a temperature that is a practical lower limit of the use environment temperature is 10 ° C. or higher. In this environment, the rebound resilience R is preferably 10% or more, more preferably 15% or more, and still more preferably 20% or more.

The 100% modulus M shown in the formula (1) was measured at a tensile speed of 500 mm / min using a dumbbell-shaped No. 3 test piece in accordance with JIS-K6251 and obtained from the stress at 100% strain. . In addition, the measuring apparatus used the Toyo Seiki Co., Ltd. product and the strograph AE elastomer.
Further, α shown in the equation (2) is obtained from a stress-strain curve, and here, the stress and strain amount are obtained by the procedure and method described below. That is, in accordance with JIS-K6251, a dumbbell-shaped No. 3 test piece was used and measured at a tensile speed of 500 mm / min and obtained from the stress at 100% strain and the stress at 200% strain. In addition, the measuring apparatus used the Toyo Seiki Co., Ltd. product and the strograph AE elastomer.

  Furthermore, in the present invention, the glass transition temperature of the material in contact with the surface of the image carrier and the glass transition temperature of the soft segment material and hard segment material described later are measured by measuring the temperature dispersion with a viscoelasticity measuring device, and tan δ ( Loss tangent) peak temperature.

Here, the tan δ value is derived from the storage and loss elastic modulus described below.
When a sinusoidal distortion is applied to a linear elastic body in a steady vibration manner, the stress is expressed by the following equation (4). | E * | is called the complex elastic modulus. From the theory of rheology, the elastic body component is represented by the following formula (5), and the viscous body component is represented by the following formula (6). Here, E ′ is called storage elastic modulus, and E ″ is called loss elastic modulus. δ represents a phase difference angle between stress and strain, and is called “mechanical loss angle”.
The tan δ value is expressed by E ″ / E ′ as in the following formula (7), and is called “loss sine”. The larger the value, the more the linear elastic body has rubber elasticity. Become.
Formula (4) σ = | E * | γ cos (ωt)
Formula (5) E ′ = | E * | cos δ
Formula (6) E ″ = | E * | sin δ
Formula (7) tan δ = E ″ / E ′
The tan δ value was measured by LeoPectra-DVE-V4 (manufactured by Rheology Co., Ltd.) with a static strain of 5% and a 10 Hz sine wave tensile vibration in a temperature range of −60 to 100 ° C.

As described above, the cleaning blade used in the present invention is excellent in both wear resistance and chipping resistance, and can maintain good cleaning performance over a long period of time.
For this reason, in order to cope with foreign matter existing on the surface of the image carrier, particularly foreign matter buried or stuck on the surface, such as foreign matter buried or stuck on the surface of the image carrier, as BCO occurs, In addition, since it is not necessary to newly provide a device for improving wear resistance and chipping resistance in the image forming apparatus, it is possible to prevent an increase in size and cost of the apparatus.

  In addition, since the life of the cleaning blade is prolonged, it is easy to extend the life of the process cartridge equipped with the cleaning blade used in the present invention, the cleaning device, and the image forming apparatus, and to reduce the maintenance cost. In addition to this, in the present invention, since the image carrier having improved surface wear resistance is used in combination, the above-mentioned merit can be further enjoyed.

In the cleaning blade used in the present invention, at least the cleaning blade tip material is made of a material satisfying the formulas (1) to (3), but not only the cleaning blade tip but other parts are represented by the formula (1). You may be comprised from the material which satisfy | fills (3).
In addition, the material satisfying the formulas (1) to (3) is not particularly limited as long as it is an elastomer material, but an elastomer material including a hard segment and a soft segment is particularly preferable. When the elastomer material contains both the hard segment and the soft segment, it becomes easy to satisfy the physical properties shown in the formulas (1) to (3), and both the wear resistance and chipping resistance are increased to a higher level. This is because both can be achieved.
The “hard segment” and the “soft segment” are the materials that make up the former in the elastomer material and are relatively harder than the materials that make up the latter. Means a segment made of a material relatively softer than the material constituting the former.

Here, the glass transition temperature of the elastomer material including the hard segment and the soft segment is preferably in the range of −50 to 30 ° C., and preferably in the range of −30 to 10 ° C. When the glass transition temperature exceeds 30 ° C., embrittlement may occur in a practical temperature range where the cleaning blade is used. If the glass transition temperature is less than −50 ° C., sufficient hardness and stress may not be obtained in the actual use region.
Therefore, in order to realize the glass transition temperature described above, the glass transition temperature of the material constituting the hard segment of the elastomer material (hereinafter sometimes referred to as “hard segment material”) is in the range of 30 to 100 ° C. Preferably, the glass transition temperature of the material constituting the soft segment (hereinafter sometimes referred to as “soft segment material”) is −100 to −50 ° C. It is preferable that it exists in the range of -90--60 degreeC, and it is more preferable.

When using the hard segment material and soft segment material having the glass transition temperature described above, the mass ratio of the material constituting the hard segment to the total amount of the hard segment material and soft segment material (hereinafter referred to as “hard segment material ratio”) Is preferably in the range of 46 to 96% by mass, more preferably in the range of 50 to 90% by mass, and still more preferably in the range of 60 to 85% by mass.
When the hard segment material ratio is less than 46% by mass, the wear resistance at the tip of the cleaning blade becomes insufficient, and wear occurs early, so that good cleaning properties cannot be maintained over a long period of time. There is. In addition, when the hard segment material ratio exceeds 96% by mass, the tip of the cleaning blade becomes too hard, the flexibility and extensibility become insufficient, and chipping occurs early, which is good for a long time. Cleanability may not be maintained.

The combination of the hard segment material and the soft segment material is not particularly limited, and is selected from known resin materials so that one is relatively hard with respect to the other and the other is relatively soft with respect to the other. However, in the present invention, the following combinations are suitable.
That is, it is preferable to use a polyurethane resin as the hard segment material. In this case, the weight average molecular weight of the polyurethane resin is preferably in the range of 1000 to 4000, and more preferably in the range of 1500 to 3500.
When the weight average molecular weight is less than 1000, when the cleaning blade is used in a low temperature environment, the elasticity of the polyurethane resin constituting the hard segment is lost, which may cause cleaning failure. Further, when the weight average molecular weight exceeds 4000, the permanent deformation of the polyurethane resin constituting the hard segment becomes large, and the tip of the cleaning blade cannot maintain the contact force with respect to the surface of the image carrier. Defects may occur.
In addition, as a polyurethane resin used as a hard segment material mentioned above, Daicel Chemical Industries make, Plaxel 205, Plaxel 240, etc. are mentioned, for example.

Moreover, as a soft segment material when using a polyurethane resin as a hard segment material, it is preferable to use (i) a resin having a functional group capable of reacting with an isocyanate group. The physical properties of this resin are (ii) a glass transition temperature of 0 ° C. or lower, (iii) a viscosity at 25 ° C. in the range of 600 to 35000 mPa · s, and (iv) a weight average molecular weight in the range of 700 to 3000. It is preferable. If these physical properties are not satisfied, the moldability when producing the cleaning blade may be insufficient, or the characteristics of the cleaning blade itself may be insufficient.
The physical properties are more preferably that the glass transition temperature is −10 ° C. or lower, the viscosity at 25 ° C. is in the range of 1000 to 3000 mPa · s, and the weight average molecular weight is in the range of 900 to 2800. Moreover, when producing a cleaning blade using centrifugal molding, it is preferable that the viscosity in 25 degreeC exists in the range of 600-3500 mPa * s.

The soft segment material satisfying the structure and physical properties shown in the above items (i) to (iv) can be selected from known resins, but has at least a terminal having a functional group capable of reacting with an isocyanate group. It is preferable that it is resin with. The resin is preferably an aliphatic resin having a linear structure from the viewpoint of flexibility. As a specific example, it is preferable to use an acrylic resin containing two or more hydroxyl groups, a polybutadiene resin containing two or more hydroxyl groups, or an epoxy resin having two or more epoxy groups.
As an acrylic resin containing two or more hydroxyl groups, for example, Actflow (grade: UMB-2005B, UMB-2005P, UMB-2005, UME-2005, etc.) manufactured by Soken Chemical Co., Ltd. can be exemplified. As polybutadiene resin containing the above hydroxyl group, Idemitsu Kosan make, R-45HT etc. can be mentioned, for example.

Moreover, as an epoxy resin which has two or more epoxy groups, it is not what has a hard and brittle property like the conventional general epoxy resin, and what is flexible toughness rather than the conventional epoxy resin is preferable.
As this epoxy resin, for example, in terms of molecular structure, those having a structure (flexible skeleton) that can increase the mobility of the main chain in the main chain structure are suitable. Examples include a skeleton, a cycloalkane skeleton, and a polyoxyalkylene skeleton, and a polyoxyalkylene skeleton is particularly preferable.
In terms of physical properties, an epoxy resin having a lower viscosity than the molecular weight of the conventional epoxy resin is preferable. Specifically, the weight average molecular weight is approximately in the range of 900 ± 100, the viscosity at 25 ° C. is preferably in the range of 15000 ± 5000 mPa · s, and is preferably in the range of 15000 ± 3000 mPa · s. More preferred. As an epoxy resin which has this characteristic, Dainippon Ink and Chemicals make, EPLICON EXA-4850-150 etc. can be mentioned, for example.

  The cleaning blade used in the present invention is not particularly limited as long as at least the tip portion of the cleaning blade is made of a material satisfying the formulas (1) to (3) as described above, but the whole is made of this material. It may be. Further, when the cleaning blade is formed by laminating two or more layers, it is necessary that the layer in contact with the surface of the image carrier is made of a material satisfying the expressions (1) to (3).

  As the method for producing the cleaning blade used in the present invention, a conventionally known method can be used according to the raw material used for producing the cleaning blade. For example, a sheet is formed using centrifugal molding, extrusion molding, or the like. The cleaning blade can be manufactured by cutting into a shape of 2 or by bonding two or more sheets.

  By using the cleaning blade according to the present invention, the toner, external additives, discharge products, talc, paper dust and other deposits adhering to the above-mentioned various image carrier surfaces can be stably cleaned over a long period of time. be able to. Further, when a two-component developer is used, it is possible to suppress the occurrence of chipping due to foreign matters such as carrier pieces buried or fixed on the surface of the image carrier due to the generation of BCO.

From the viewpoint of more reliably suppressing the occurrence of image flow, the Young's modulus E per mm in the axial direction of the cleaning blade used in the present invention is preferably 60 to 200 (gf / mm ² ), and preferably 80 to 180 (gf / mm ² ) is more preferable, and 90 to 150 (gf / mm ² ) is particularly preferable.
Here, the Young's modulus E can be calculated according to JIS-K6254 (1993) by obtaining a stress when the elongation rate is 25% using a strip-shaped No. 1 test piece.

  Further, from the viewpoint of more reliably removing the discharge products and more effectively suppressing the occurrence of image flow, the cleaning blade is preferably used for the image carrier as follows.

・ Pressure force NF (Normal Force)
If the force NF for pressing the cleaning blade against the image carrier (force in the vertical direction) is too large, there is a concern that the tip of the blade will be chipped or the blade will be unevenly worn. From the viewpoint of not only insufficient retention of the chipped abrasive but also insufficient cleaning performance, which is the original function, 2.0 to 5.0 gf / mm is preferable. It is more preferably 0 to 4.0 (gf / mm).

・ Eating length d
Drip amount d of the cleaning blade tip into the image carrier (as shown in FIG. 2, the blade tip position when the cleaning blade 101 is pressed against the image carrier 102, and the blade tip when released from the pressing. If the displacement is too large, there is a concern that the amount of deformation (deformation amount) will increase and the amount of sag (permanent deformation) will increase. On the other hand, if it is too small, the adhesiveness will decrease, resulting in poor cleaning. Since there is a possibility of occurrence, it is preferably 0.4 to 1.6 (mm), more preferably 0.6 to 1.4 (mm), and 0.8 to 1.2 (mm). Is particularly preferred.

・ Angle W / A (Working Angle)
Angle W / A at the contact portion between the cleaning blade and the image carrier (as shown in FIG. 2, the surface of the image carrier 102 and the image held by the cleaning blade 101 when the cleaning blade 101 is pressed against the image carrier 102. If the angle θ between the surface facing the body and the surface facing the body is too large, there is a risk of blade squeezing or squealing (blade vibration). It is preferably 0 to 18.0 (°), more preferably 8.0 to 16.0 (°), and particularly preferably 10.0 to 14.0 (°).

-Abrasive-
The method of supplying the abrasive supplied to the portion where the cleaning blade and the image carrier are in contact with each other is not particularly limited. For example, a method of adding the developer to the developer, which will be described later, is disposed on the surface of the image carrier. There is a method of supplying to the contact portion between the cleaning blade and the image carrier using the abrasive supply means.
As a method of using the abrasive supply means, for example, as shown in FIG. 3, a solid abrasive 19 is applied to the image carrier 17 via a medium (brush in FIG. 3) 18 and finally cleaned. It is supplied to the contact portion with the blade 16.

  As an abrasive that can be added to the developer or supplied to the contact portion by a method such as using an abrasive supply means, a known abrasive for toner can be used. For example, cerium oxide, strontium titanate, magnesium oxide , Alumina, silicon carbide, zinc oxide, silica, titanium oxide, boron nitride, calcium pyrophosphate, zirconia, barium titanate, calcium titanate, calcium carbonate, and the like, and a composite material thereof may be used. Of these, at least cerium oxide is preferably used in the present invention. Moreover, you may use a polishing agent in combination of 2 or more types as needed.

The volume average primary particle size of the abrasive when supplied to the contact portion between the cleaning blade and the image carrier (hereinafter sometimes abbreviated as “particle size”) is not particularly limited, but is 1 nm. Within the range of ˜1000 nm is preferable, and within the range of 50 nm to 800 nm is more preferable. If the particle size is too small, the effect of polishing and removing deposits such as discharge products adhering to the surface of the image carrier cannot be sufficiently obtained, and the effect of preventing image drift may not be obtained. On the other hand, if the particle size is too large, the surface of the image carrier is likely to be damaged, and the life of the image carrier may be shortened.
The volume average primary particle size of external additives such as abrasives can be measured using a multisizer (manufactured by Nikka Kisha Co., Ltd.) and an aperture diameter of 100 μm.

  When the abrasive is added to the developer, the abrasive having the above particle diameter may be added directly to the developer. When a solid abrasive is used as in the abrasive supply means, the abrasive is used. What is necessary is just to set so that the abrasive | polishing agent shaved so that it may become the said particle size by a supply means may be supplied to the said contact part.

-Developer (toner)-
The toner used in the present invention is not particularly limited as long as it is a known toner, but it is particularly preferable that at least an abrasive is externally added as an external additive.
Further, the toner shape factor SF1 is preferably less than 140. When the shape factor SF is 140 or more, it is difficult to obtain good transferability and the like, and it may be difficult to improve the image quality of the obtained image.
The shape factor SF1 is a value defined by the following equation (8).
Formula (8) SF1 = ML ² / (4A / π)
Here, ML represents the maximum toner length (μm), and A represents the toner projected area (μm ² ).

The shape factor SF1 can be measured as follows using a Luzex image analyzer (manufactured by Nireco Corporation, FT).
First, an optical microscope image of the toner spread on the slide glass is taken into a Luzex image analyzer through a video camera, and the maximum length (ML) and the projected area (A) are measured for 50 or more toners. Next, the square of the maximum length / (4 × projected area / π), that is, ML ² / (4A / π) was calculated for each toner, and an average value of these values was obtained as the shape factor SF.

On the other hand, the toner used in the present invention preferably has a volume average particle diameter of 2 to 8 μm in order to obtain high image quality.
The toner used in the present invention contains a binder resin and a colorant, and contains a release agent and other additives as necessary. As the binder resin, a binder resin conventionally used for toner can be used and is not particularly limited.

Specific examples of the binder resin include styrenes such as styrene, parachlorostyrene, and α-methylstyrene; methyl acrylate, ethyl acrylate, n-propyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate, and the like. Acrylic monomers such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, lauryl methacrylate, 2-ethylhexyl methacrylate, etc .; acrylic acid, methacrylic acid, sodium styrenesulfonate, etc. Ethylenically unsaturated acid monomers; vinyl nitriles such as acrylonitrile and methacrylonitrile; vinyl ethers such as vinyl methyl ether and vinyl isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl ethyl ketone and vinyl isopropenyl ketone; Ren, propylene, homopolymer consisting of a monomer such as olefins such as butadiene, copolymers combinations thereof monomers of two or more, or the like mixtures thereof.
Furthermore, to these homopolymers, copolymers or mixtures, epoxy resins, polyester resins, polyurethane resins, polyamide resins, cellulose resins, polyether resins, etc., non-vinyl condensation resins, or those and the vinyl resins And a graft polymer obtained by polymerizing a vinyl monomer in the presence of these.

  A conventionally known colorant can be used as the colorant, and is not particularly limited. For example, carbon black, chrome yellow, hansa yellow, benzidine yellow, selenium yellow, quinoline yellow, permanent orange GTR, pyrazolone orange, vulcan orange, watch young red, permanent red, brilliantamine 3B, brilliantamine 6B, dupont oil red, pyrazolone Various pigments such as red, resol red, rhodamine B lake, lake red C, rose bengal, aniline blue, ultramarine blue, chalcoil blue, methylene blue chloride, phthalocyanine blue, phthalocyanine green, malachite green oxalelate, acridine series, Xanthene, azo, benzoquinone, azine, anthraquinone, thioindico, dioxazine Various dyes such as thiazine, azomethine, indico, phthalocyanine, aniline black, polymethine, triphenylmethane, diphenylmethane, and thiazole can be used singly or in combination. .

  Release agents that can be added to the toner used in the present invention as needed include low molecular weight polyolefins such as polyethylene, polypropylene, and polybutene; silicones, oleic acid amide, erucic acid amide, ricinoleic acid amide, stearic acid amide, and the like. Fatty acid amides; plant waxes such as carnauba wax, rice wax, candelilla wax, tree wax, jojoba oil; animal waxes such as beeswax; montan wax, ozokerite, ceresin, paraffin wax, microcrystalline wax, Fischer-Tropsch Examples thereof include mineral-based or petroleum-based waxes such as waxes, and modified products thereof. At least one of these may be contained in the toner particles.

  In addition to the above components, the toner can contain various components in order to control various characteristics. For example, when used as a magnetic toner, a magnetic powder (for example, ferrite or magnetite), a metal such as reduced iron, cobalt, nickel, or manganese, an alloy, or a compound containing these metals may be included. Furthermore, if necessary, a charge control agent that is usually used, such as a quaternary ammonium salt, a nigrosine compound, or a triphenylmethane pigment, may be selected and contained.

  Furthermore, known external additives such as abrasives, lubricants, and transfer aids can be externally added to the toner as necessary. In the case where the abrasive supply means for supplying the abrasive directly to the surface of the image carrier is not disposed, the abrasive is applied to the contact portion between the cleaning blade and the image carrier by externally adding the abrasive to the toner. It is preferable to supply.

  The addition amount of the abrasive is preferably in the range of 0.1 to 2.0% by mass with respect to the toner particles and all additives externally added to the surface, and is preferably 0.3 to 1.0. More preferably, it is in the range of mass%. When the addition amount is less than 0.1% by mass, the effect of polishing and removing the deposit is insufficient, and the removal of the discharge product adhering to the image carrier may be insufficient. . On the other hand, when it is larger than 2.0% by mass, toner cloud may be easily generated.

In addition, a lubricant can be added to the toner, but if it is added too much, the high friction property on the surface of the image carrier is impaired.
Lubricating particles can also be used as the lubricant externally added to the toner. These lubricating particles have a fatty acid metal salt such as zinc stearate, solid lubricants such as graphite, molybdenum disulfide, talc and fatty acids, low molecular weight polyolefins such as polypropylene, polyethylene and polybutene, and a softening point upon heating. Aliphatic amides such as silicones, oleic acid amide, erucic acid amide, ricinoleic acid amide, stearic acid amide, plant waxes such as carnauba wax, rice wax, candelilla wax, tree wax, jojoba oil, beeswax animals Mineral wax, montan wax, ozokerite, ceresin, paraffin wax, microcrystalline wax, Fischer-Tropsch wax and other minerals, petroleum wax, and modified products thereof can be used, and these listed materials may be used alone or in combination. Among these, in the present invention, it is preferable to use zinc stearate.

  The volume average primary particle size of the slippery particles is preferably in the range of 0.1 to 10 μm, and more preferably in the range of 0.2 to 8 μm. In addition, by pulverizing the slipping particles, the particle size distribution may be reduced and the particle sizes may be made uniform. The addition amount of the lubricious particles is preferably in the range of 0.05 to 2.0% by mass, preferably 0.1 to 1.5% by mass with respect to the toner particles and all additives externally added to the surface. Within the range is more preferable.

The method for producing the toner used in the present invention is not particularly limited. For example, a normal pulverization method, a wet melt spheronization method prepared in a dispersion medium, suspension polymerization, dispersion polymerization, emulsification A toner production method by a known polymerization method such as a polymerization aggregation method can be used.
In addition to the above-described abrasives and lubricants, the toner used in the present invention includes various external additives such as silica and titania having an average particle diameter of about 10 to 300 nm. It can be attached.

-Developer (carrier)-
The carrier that can be used in the two-component developer is not particularly limited, and a known carrier can be used. In particular, magnetic metals such as iron oxide, nickel, and cobalt, magnetic oxides such as ferrite and magnetite, and the like can be used. It is preferable to use a polymerized carrier and a filled carrier obtained by solidifying a core material (core) with a resin. The filled carrier is a carrier in which a core material having a gap is filled with a resin by a pressure kneader manufacturing method, and the polymerized carrier is a carrier obtained by coating a core produced by a polymerization manufacturing method with a resin by a pressure kneader manufacturing method.

The polymerized carrier and the filled carrier are charged by being stirred together with the toner and the external additive in the developing device. Since the surface of the polymerized carrier and the filled carrier is covered with a resin, the damage due to the mechanical rubbing force is small, and the polymer carrier and the filled carrier are very rarely crushed to generate fine powder.
In the conventional carrier in which the generation of fine powder or the like is remarkable, the fine powder or the like may be pressed against the image holding body in the transfer portion where the transfer process is performed, and the image holding body may be damaged or stabbed. Fine powder once stabbed is difficult to come off and enters the cleaning blade for a long period of time. The toner leaks from the portion where the blade tip is missing, and the toner enters an image in a later process, resulting in an image quality defect. However, the above-mentioned polymerized carrier and filled carrier generate very little fine powder, and these problems are remarkably improved.

As shown in FIG. 4A, in the present invention, a space for holding a large amount of abrasive is provided at the contact portion between the cleaning blade 11 and the image carrier 12, and this space is provided with a carrier. The accumulation of fine powder 13 and the like also increases. Accumulated fine powder 13 and the like cause chipping at the tip of the blade 11 at the contact portion.
However, as shown in FIG. 4B, since the generation of fine powder and the like is extremely small in the polymerization carrier (or filled carrier) 14, both the image carrier 12 and the cleaning blade 11 are hardly damaged even when entering the space. It is possible to effectively prevent image quality defects accompanying damage.

As the resin used for the polymerization carrier and the filled carrier, known resins can be used as long as they are used as a resin layer material for carriers, and two or more kinds of resins may be blended and used. The resin constituting the resin layer is roughly classified into a charge imparting resin for imparting chargeability to the toner and a resin having a low surface energy used for preventing the toner component from being transferred to the carrier.
Here, examples of the charge imparting resin for imparting negative chargeability to the toner include amino resins such as urea-formaldehyde resin, melamine resin, benzoguanamine resin, urea resin, polyamide resin, and epoxy resin. Further, polystyrene resins such as polyvinyl and polyvinylidene resins, acrylic resins, polymethyl methacrylate resins, styrene acrylic copolymer resins, polyacrylonitrile resins, polyvinyl acetate resins, polyvinyl acetate resins, polyvinyl alcohol resins, polyvinyl butyral resins, ethyl cellulose resins And the like.
Examples of the charge imparting resin for imparting positive chargeability to the toner include polystyrene resins, halogenated olefin resins such as polyvinyl chloride, polyester resins such as polyethylene terephthalate resins and polybutylene terephthalate resins, and polycarbonate resins. Can be mentioned.
Examples of the resin having a low surface energy used for preventing the transfer of the toner component to the carrier include polyethylene resin, polyvinyl fluoride resin, polyvinylidene fluoride resin, polytrifluoroethylene resin, polyhexafluoropropylene resin, fluororesin. Fluoroterpolymers such as copolymers of vinylidene fluoride and acrylic monomers, copolymers of vinylidene fluoride and vinyl fluoride, terpolymers of tetrafluoroethylene, vinylidene fluoride and non-fluorinated monomers, And silicone resin.

  Moreover, you may add electroconductive particle to a resin layer for the purpose of resistance adjustment. Examples of the conductive particles include metal powder, carbon black, titanium oxide, tin oxide, and zinc oxide. These conductive powders preferably have an average particle size of 1 μm or less. Furthermore, a plurality of conductive resins and the like can be used in combination as necessary.

The resin layer may contain resin particles for the purpose of charge control. As the resin constituting the resin particles, a thermoplastic resin or a thermosetting resin can be used.
In the case of thermoplastic resins, polyolefin resins, such as polyethylene, polypropylene; polyvinyl and polyvinylidene resins, such as polystyrene, acrylic resin, polyacrylonitrile, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, polyvinyl chloride, polyvinyl carbazole, polyvinyl Ether and polyvinyl ketone; vinyl chloride-vinyl acetate copolymer; styrene-acrylic acid copolymer; straight silicone resin composed of an organosiloxane bond or a modified product thereof; fluororesin such as polytetrafluoroethylene, polyvinyl fluoride, polyfluoride And vinylidene chloride, polychlorotrifluoroethylene; polyester; polycarbonate and the like.

  Examples of thermosetting resins include phenol resins; amino resins such as urea-formaldehyde resins, melamine resins, benzoguanamine resins, urea resins, polyamide resins; epoxy resins and the like.

  Examples of the core material for the polymerized carrier and the filled carrier include magnetic metals such as iron, nickel and cobalt, and magnetic oxides such as ferrite and magnetite. The volume average particle diameter of the core material is generally 10 to 500 μm, preferably 30 to 100 μm.

In addition, when the core material of the polymerization carrier and the filling carrier is made of a polycrystalline material, it is preferable to use a polycrystalline material made of crystal grains having an average particle size of 2.0 μm or less.
If the average particle size of the polycrystalline material constituting the core material is as small as the above-mentioned range, even if the carrier is destroyed, the core material tends to be small and cracked. It becomes difficult to generate fine powder. For this reason, it is possible to further suppress the occurrence of damage to the surface of the image carrier and the cleaning blade.
In addition to this, since the individual crystal grains constituting the polycrystalline material are small, when stress is applied to the carrier, even if stress is concentrated on a part of the core material, the stress concentrated on a part of the whole core material is applied. It is possible to uniformly disperse and absorb the carrier, the carrier is not easily destroyed, and it is possible to suppress the generation amount of the fragments due to the carrier destruction.

If the average grain size of the crystal grains contained in the polycrystalline material exceeds 2.0 μm, the core material tends to be largely and roughly cracked when the carrier is destroyed, so that sharply broken pieces are likely to occur. Become. In addition, since the individual crystal grains constituting the polycrystalline material are large, when stress is applied to the carrier, the stress can be evenly distributed even if stress is concentrated on a part of the core material. Since it is not possible, the carrier is easily destroyed.
Therefore, from this viewpoint, the average grain size of the crystal grains contained in the polycrystalline material is more preferably 1.5 μm or less. However, if the average particle size is too small, the crystallinity of the polycrystalline material is lowered, the mechanical strength of the core material itself is lowered, and as a result, the carrier may be easily broken. The average particle size of is preferably 1.0 μm or more.

The grain size distribution of the crystal grains contained in the polycrystalline material preferably satisfies the following formula (9): Formula (9) D85 / D50 <1.5
Here, in formula (9), D50 represents a particle size that accumulates from the smaller diameter side of the grain size distribution of the crystal grains to 50 number%, and D85 represents an accumulation of 85 number% from the smaller diameter side of the grain size distribution of the crystal grains. Represents the particle size.
When the particle size distribution becomes wide, even if the average particle size is small, there are coarse grains in each crystal grain, so when the carrier is broken, when the core material breaks, This is because there is a high possibility of cracking depending on the size, and it becomes easy to generate fragments with sharp corners. In addition, when coarse crystal particles are present, not only the effect of dispersing external stress is reduced, but also the core material itself may have a relatively large empty envelope, which weakens the strength of the core material itself. May end up.
From this viewpoint, D85 / D50 is preferably 1.3 or less, more preferably closer to monodispersion.
The average particle size and particle size distribution of the crystal grains constituting the polycrystalline material used for the core material can be easily controlled by adjusting the firing temperature or the like according to the material used. Specifically, the average particle size can be reduced and the particle size distribution can be narrowed by lowering the firing temperature.

The average particle size and particle size distribution of the polycrystalline material contained in the core material were measured as follows.
For the average particle size and particle size distribution, a sample was deposited with platinum using a focused ion beam processing observation device (FB-2100, manufactured by Hitachi High-Technologies Corporation), and the sample was cut under the conditions of an applied potential of 40 kV and 150 nA, and the cutting energy was adjusted by the current value. A cross-section of the core material was prepared and observed.
The core cross-section image was taken at an acceleration voltage of 5 kv and 5000 times. Next, the major axis of each crystal grain observed in the captured image was measured with a ruler, and this was converted to the actual size. Measurement and image processing were performed on the cross-sections of 15 core materials.

Here, the average particle size was determined as the particle size (D50) of 50% by number of particles from the small diameter side of the particle size distribution by measuring the long diameter of each crystal grain as described above. D85 / D50 represents a ratio of the particle size (D85) of 85% by number to the average particle size (D50) from the smaller diameter side of the particle size distribution.
In addition, since individual crystal grains observed in the cross section of the core material do not necessarily appear as a cross section at the center, the particle size distribution obtained by binarization processing of the cross-sectional image (hereinafter, “raw particle size distribution”) ")" Also includes measurement results resulting from the cross-section of the end portion other than the center portion of the crystal grains.
For this reason, the above-mentioned values of D50 and D85 are obtained from the small diameter side of the raw particle size distribution up to 50% by number in order to approximately exclude the measurement result due to the cross section of the end portion of the crystal grain from the raw particle size distribution. It calculated | required using the particle size distribution obtained except the value.

As the magnetic material dispersion type carrier, a known magnetic material powder dispersion type carrier can be used as long as it has a configuration including a resin matrix and a magnetic material powder dispersed in the resin matrix. It is preferable to use those having a structure in which a core layer containing magnetic powder dispersed in a matrix is provided with a resin layer coated with a resin. In addition, as a resin composition which coat | covers a core particle, the same thing as the above can be utilized.
In this magnetic powder-dispersed carrier, a magnetic component having a hardness sufficient to damage the surface of the image carrier is dispersed in the carrier as a magnetic powder having a relatively small size. For this reason, even if the magnetic powder-dispersed carrier is destroyed, the fragments made of the magnetic powder are generated in comparison with the fragments made of the magnetic material that are generated when the general polymerization carrier and the filled carrier or the non-coated carrier are broken. The occurrence of chipping of the cleaning blade due to small pieces can be suppressed.

As the material constituting the magnetic powder dispersed in the resin matrix, the same materials as those for the core material used for the above-described polymerization carrier and filled carrier can be used.
Further, the size of the magnetic powder is preferably in the range of 0.02 to 5 μm in terms of the number average particle diameter although it depends on the particle diameter of the carrier. Two or more kinds of magnetic powders may be dispersed in the resin matrix. The number average particle size of the magnetic powder can be determined as follows. That is, using a photographic image magnified 5000 to 20000 times with a transmission electron microscope, 300 or more particles having a particle size of 0.01 μm or more were extracted at random, and an image processing analysis apparatus (manufactured by Nireco Corporation, Luxex III). ) Is measured as the metal oxide particle diameter with the horizontal ferret diameter and averaged to calculate the number average particle diameter.

  Examples of matrix resins for dispersing magnetic powder include vinyl resins; polyester resins, epoxy resins, phenol resins, urea resins, polyurethane resins, polyimide resins, cellulose resins, polyether resins, and other non-vinyl condensation resins; A mixture with a resin can be used.

  Examples of vinyl monomers for forming the vinyl resin include styrene; o-methylstyrene, m-methylstyrene, p-methylstyrene, p-phenylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, p- Styrene derivatives such as n-butylstyrene and p-tert-butylstyrene; ethylene and unsaturated monoolefins such as ethylene, propylene, butylene and isobutylene; unsaturated diolefins such as butadiene and isoprene; vinyl chloride, vinylidene chloride and odor Vinyl halides such as vinyl fluoride and vinyl fluoride; vinyl esters such as vinyl acetate and vinyl propionate; methacrylic acid; methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, Methacrylic acid n- Α-methylene aliphatic monocarboxylic acid esters such as octyl, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate; acrylic acid; methyl acrylate, ethyl acrylate, n-butyl acrylate, Acrylic esters such as isobutyl acrylate, propyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, and phenyl acrylate; maleic acid, half maleate Esters; Vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, and vinyl isobutyl ether; Vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone, and methyl isopropenyl ketone; N-vinyl pillow N-vinyl compounds such as benzene, N-vinylcarbazole, N-vinylindole and N-vinylpyrrolidone; vinyl naphthalenes; acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile and acrylamide; and acroleins. A vinyl resin polymerized by using one or more of these is used.

  As a method for producing core particles containing magnetic powder and matrix resin in which the magnetic powder is dispersed, a vinyl or non-vinyl thermoplastic resin, a magnetic metal oxide, and other additives such as a curing agent are mixed. Then, after sufficiently mixing, the mixture is melted and kneaded using a kneader such as a heating roll, a kneader, or an extruder, cooled, ground, and classified to obtain core particles. At this time, it is preferable to spheroidize the obtained core particles thermally or mechanically.

  As another method for producing the core particles, in addition to the method in which the resin and the magnetic metal oxide described above are melt-kneaded and pulverized to form core particles, the monomer and the metal oxide are mixed and the monomer is polymerized. There is also a method for obtaining core particles. At this time, as monomers used for the polymerization, in addition to the vinyl monomers described above, bisphenols and epichlorohydrin for forming an epoxy resin; phenols and aldehydes for forming a phenol resin; for forming a urea resin Urea and aldehydes, melamine and aldehydes are used. For example, as a method for producing a carrier core using a curable phenol resin, a phenol and an aldehyde are placed in an aqueous medium in the presence of a basic catalyst and the above-described metal oxide and dispersion stabilizer are added, and suspension polymerization is performed. Obtain core particles.

  As a particularly preferable method for producing core particles, it is preferable to use a crosslinked binder resin in order to increase the strength of the core particles or to better coat the coating resin. For example, a method of adding a crosslinking component at the time of melt-kneading and crosslinking at the time of kneading; a method of using a monomer for forming a curable resin and polymerizing the monomer in the presence of a metal oxide to obtain a core; A method of polymerizing the charged monomer composition in the presence of a metal oxide can be mentioned.

  In addition, as for content of the magnetic body powder contained in a magnetic body dispersion type carrier, 50 mass%-99 mass% are preferable. When the amount of the metal oxide is less than 50% by mass, the chargeability may be unstable, and when it exceeds 99% by mass, the strength of the carrier particles may be reduced and the carrier particles may be easily destroyed. is there.

  In the two-component developer using the carrier described above, the mixing ratio (mass ratio) of the toner and the carrier is in the range of toner: carrier = 1: 100 to 30: 100, and 3: 100 to 20: 100. A range of the degree is more preferable.

-Specific examples of image forming apparatus and cleaning apparatus-
Next, specific examples of the image forming apparatus and the cleaning apparatus using the cleaning blade in the present invention will be described in more detail with reference to the drawings.
FIG. 5 is a schematic diagram showing an example of the image forming apparatus of the present invention, and shows a so-called tandem type image forming apparatus.
In FIG. 5, 21 is a main body housing, 22 and 22a to 22d are image forming engines, 23 is a belt module, 24 is a recording medium supply cassette, 25 is a recording medium conveyance path, 30 is each photosensitive unit, and 31 is a photosensitive drum. (Image holder), 32 is a charging device, 33 is each developing unit, 34 is a cleaning device, 35 and 35a to 35d are toner cartridges, 40 is an exposure unit, 41 is a unit case, 42 is a polygon mirror, and 51 is a primary. Transfer device 52 is a secondary transfer device, 53 is a belt cleaning device, 61 is a feed roll, 62 is a take away roll, 63 is a registration roll, 66 is a fixing device, 67 is a discharge roller, 68 is a discharge unit, and 71 is a manual feed Feeder 72, feed roll 73, duplex recording unit 74, guide roll 74, transport path 76, transport Roll, 230 is an intermediate transfer belt, 231 and 232 tension roller, 521 is a secondary transfer roll, 531 represents a cleaning blade.

  The tandem type image forming apparatus shown in FIG. 5 has an image forming engine 22 (specifically, 22a to 22d) of four colors (in this embodiment, black, yellow, magenta, cyan) in the main body housing 21 in the horizontal direction. A belt module 23 including an intermediate transfer belt 230 that is circulated and conveyed along the direction in which the image forming engines 22 are arranged is arranged above the image forming engine 22. A recording medium supply cassette 24 in which a medium (not shown) is accommodated is disposed, and a recording medium conveyance path 25 serving as a conveyance path for the recording medium from the recording medium supply cassette 24 is disposed in the vertical direction. .

In the present embodiment, the image forming engines 22 (22a to 22d) are, for example, for black, yellow, magenta, and cyan in order from the upstream side in the circulation direction of the intermediate transfer belt 230. (Not limited) toner image, each photosensitive unit 30, each developing unit 33, and one common exposure unit 40.
Here, the photosensitive unit 30 includes, for example, a photosensitive drum 31, a charging device 32 that precharges the photosensitive drum 31, and a cleaning device 34 that removes residual toner on the photosensitive drum 31. It is a cartridge.

The developing unit 33 develops the electrostatic latent image exposed and formed by the exposure unit 40 on the charged photosensitive drum 31 with a corresponding color toner (for example, negative polarity in the present embodiment). For example, a process cartridge (so-called CRU: Customer Replaceable Unit) is configured by being integrated with a sub-cartridge including the photosensitive unit 30.
Of course, the photoconductor unit 30 may be separated from the developing unit 33 to form a single CRU. In FIG. 5, reference numeral 35 (35a to 35d) denotes a toner cartridge for supplying each color component toner to each developing unit 33 (a toner supply path is not shown).

  On the other hand, the exposure unit 40 includes, for example, four semiconductor lasers (not shown), one polygon mirror 42, an imaging lens (not shown), and respective mirrors (corresponding to the respective photoreceptor units 30) in a unit case 41. (Not shown), the light from the semiconductor laser for each color component is deflected and scanned by the polygon mirror 42, and the light image is guided to the exposure point on the corresponding photosensitive drum 31 through the imaging lens and mirror. It is a thing.

  Further, in the present embodiment, the belt module 23 is obtained by, for example, spanning the intermediate transfer belt 230 between a pair of stretching rolls (one of which is a drive roll) 231 and 232, and the photoreceptor of each photoreceptor unit 30. A primary transfer device (primary transfer roll in this example) 51 is disposed on the back surface of the intermediate transfer belt 230 corresponding to the drum 31, and a voltage having a polarity opposite to the toner charging polarity is applied to the primary transfer device 51. The toner image on the photosensitive drum 31 is electrostatically transferred to the intermediate transfer belt 230 side. Further, a secondary transfer device 52 is disposed at a portion corresponding to the tension roll 232 on the downstream side of the most downstream image forming engine 22d of the intermediate transfer belt 230, and the primary transfer image on the intermediate transfer belt 230 is recorded. Secondary transfer (collective transfer) is performed on the medium.

In the present embodiment, the secondary transfer device 52 includes a secondary transfer roll 521 arranged in pressure contact with the toner image holding surface side of the intermediate transfer belt 230, and a secondary transfer roll disposed on the back side of the intermediate transfer belt 230. A backup roll (in this example, also serving as a stretching roll 232) is provided. For example, the secondary transfer roll 521 is grounded, and a bias having the same polarity as the charging polarity of the toner is applied to the backup roll (stretching roll 232).
Furthermore, a belt cleaning device 53 is disposed on the upstream side of the most upstream image forming engine 22a of the intermediate transfer belt 230 so as to remove residual toner on the intermediate transfer belt 230.

  The recording medium supply cassette 24 is provided with a feed roll 61 for picking up the recording medium. A takeaway roll 62 for feeding the recording medium is disposed immediately after the feed roll 61, and a secondary transfer site is also provided. A registration roll (registration roll) 63 for supplying the recording medium to the secondary transfer portion at a predetermined timing is disposed in the recording medium conveyance path 25 positioned immediately before. On the other hand, a fixing device 66 is provided in the recording medium conveyance path 25 located on the downstream side of the secondary transfer site, and a discharge roll 67 for discharging the recording medium is provided on the downstream side of the fixing device 66. A discharge recording medium is accommodated in a discharge portion 68 formed in the upper portion of the housing 21.

Further, in the present embodiment, a manual feeding device (MSI) 71 is provided on the side of the main body housing 21, and the recording medium on the manual feeding device 71 is recorded by the feed roll 72 and the takeaway roll 62. It is sent out toward the medium conveyance path 25.
Furthermore, the main body housing 21 is provided with a double-sided recording unit 73. The double-sided recording unit 73 discharges the recording medium on which single-side recording has been performed when the double-sided mode in which image recording is performed on both sides of the recording medium is selected. 67 is reversed and taken in by the guide roll 74 in front of the entrance, the recording medium is conveyed along the recording medium return conveyance path 76 by an appropriate number of conveyance rolls 77, and again toward the registration roll 63 side. And supply.

Next, the cleaning device 34 disposed in the tandem image forming apparatus shown in FIG. 5 will be described in detail.
FIG. 6 is a schematic sectional view showing an example of the cleaning device used in the present invention. The photosensitive drum 31, the charging roll 32, and the developing unit 33 which are sub-cartridges together with the cleaning device 34 shown in FIG. FIG.
In FIG. 6, 32 is a charging roll (charging device), 331 is a unit case, 332 is a developing roll, 333 is a transport auger, 334 is a transport paddle, 335 is a trimming member, 341 is a cleaning case, 342 is a cleaning blade, 344 is A film seal 345 represents a transport auger.

  The cleaning device 34 has a cleaning case 341 that contains residual toner and opens to face the photosensitive drum 31, and a cleaning blade 342 that is disposed in contact with the photosensitive drum 31 at the lower edge of the opening of the cleaning case 341. Is attached via a bracket (not shown), and a film seal 344 is attached to the upper edge of the opening of the cleaning case 341 so that the space between the cleaning drum 341 and the photosensitive drum 31 is kept airtight. Reference numeral 345 denotes a transport auger that guides waste toner accommodated in the cleaning case 341 to a side waste toner container. As the material for at least the cleaning blade tip of the cleaning blade 342, a material satisfying the above formulas (1) to (3) is used. As the photosensitive drum 31, the above-described image carrier in the present invention is used. It is done.

Next, the cleaning blade provided in the cleaning device 34 will be described in detail with reference to the drawings.
FIG. 7 is a schematic cross-sectional view showing an example of the cleaning blade used in the present invention, and shows the cleaning blade 342 shown in FIG. 6 together with the photosensitive drum 31 in contact therewith. Here, in FIG. 7, 342a represents a layer on the cleaning edge side, and 342b represents a layer on the back side.
The cleaning blade 342 shown in FIG. 7 includes a cleaning edge side layer 342a that is in contact with the photosensitive drum 31, and a back surface provided on the surface opposite to the surface on which the photosensitive drum 31 of the cleaning edge side layer 342a is provided. It consists of two layers with the side layer 342b and is made of an elastic material made of polyurethane rubber.
Examples of the polyurethane material constituting the back layer 342b include ester polyurethane and ether polyurethane, but ester polyurethane is preferred.

In producing an ester-based urethane rubber, polyester polyol and polyisocyanate can be used.
Here, as polyisocyanate, 2,6-toluene diisocyanate (TDI), 4,4′-diphenylmethane diisocyanate (MDI), paraphenylene diisocyanate (PPDI), 1,5-naphthalene diisocyanate (NDI), 3,3- Examples thereof include dimethyldiphenyl-4,4′-diisocyanate (TODI). In particular, MDI is preferable in terms of performance and cost.
Moreover, in order to manufacture urethane rubber using the polyester polyol described above, polyisocyanate is blended and reacted with the polyester polyol and the short-chain polyol as the chain extender. For the reaction, a general method for producing polyurethane such as a prepolymer method or a one-shot method can be used.

In addition to the material used for forming the back side layer 342b, the cleaning edge side layer 342a includes an acrylic resin containing two or more hydroxyl groups, a polybutadiene resin containing two or more hydroxyl groups, or 2 It can be produced using a soft segment material that satisfies the conditions described in the above items (i) to (iv), such as an epoxy resin having two or more epoxy groups.
Here, the cleaning edge side layer 342a is adjusted to a thickness of 0.5 mm, and the back side layer 342b is adjusted to a thickness of 1.5 mm. Note that the cleaning blade 342 can be manufactured by, for example, pasting a cleaning edge side layer 342a and a back side layer 342b, which have been prepared in a sheet shape, by bonding materials of each layer using an adhesive, a double-sided tape, or the like. . Moreover, when producing using centrifugal molding, when inject | pouring the raw material of each layer into a molding machine, it can also produce by providing sequentially, providing a time difference.

  In this embodiment, the cleaning blade used in the present invention is used as the cleaning blade 342 in all the cleaning devices 34 of the image forming engines 22 (22a to 22d), and the belt cleaning device 53 is used. The cleaning blade 531 used may also be the cleaning blade used in the present invention.

Further, the developing unit (developing device) 33 used in the present embodiment has a unit case 331 that contains a developer and opens to face the photosensitive drum 31 as shown in FIG. 6, for example. . Here, a developing roll 332 is disposed at a position facing the opening of the unit case 331, and a transport auger 333 for stirring and transporting the developer is disposed in the unit case 331. Further, a transport paddle 334 can be disposed between the developing roll 332 and the transport auger 333 as necessary.
At the time of development, after supplying the developer to the developing roll 332, the developer is conveyed to a developing region facing the photosensitive drum 31 in a state where the thickness of the developer is regulated by the trimming member 335, for example.
In the present embodiment, as the developing unit 33, for example, a two-component developer composed of toner and carrier is used, but a one-component developer composed only of toner may be used.

Next, the operation of the image forming apparatus according to the present embodiment will be described. First, when the image forming engines 22 (22a to 22d) form single color toner images corresponding to the respective colors, the single color toner images of the respective colors are sequentially superimposed on the surface of the intermediate transfer belt 230 so as to coincide with the original document information. Primary transcription. Subsequently, the color toner image transferred to the surface of the intermediate transfer belt 230 is transferred to the surface of the recording medium by the secondary transfer device 52, and the recording medium to which the color toner image has been transferred undergoes fixing processing by the fixing device 66. , And discharged to the discharge unit 68.
On the other hand, in each image forming engine 22 (22a to 22d), residual toner on the photosensitive drum 31 is cleaned by the cleaning device 34, and residual toner on the intermediate transfer belt 230 is cleaned by the belt cleaning device 53. The
In this image forming process, each residual toner is cleaned by the cleaning device 34 (or the belt cleaning device 53).

The cleaning blade 342 may be fixed via a spring material instead of being directly fixed to the frame member in the cleaning device 34 as shown in FIG.
FIG. 8 is a schematic diagram showing an example of a method for fixing the cleaning blade used in the present invention, in which 342 indicates a cleaning blade, 342c indicates a spring material, and 342d indicates a holder. As shown in FIG. 6, the cleaning blade 342 has one surface (the surface not in contact with the photoreceptor) joined and fixed to a plate-shaped spring material 342c, and the cleaning blade of the spring material 342c is fixed. The portion opposite to the side is attached to the holder 342d. As the spring material 342c, a metal member such as SUS, which is less susceptible to plastic deformation and has a low Young's modulus temperature dependency, can be used.
As shown in FIG. 8, when the cleaning blade is fixed to the frame member of the cleaning device via a spring material or a holder, the spring material is responsible for pressurization of the cleaning blade. Compared with the case where the cleaning blade is fixed, it is possible to suppress the sag of the cleaning blade and reduce the environmental dependency of the contact pressure. Therefore, the contact pressure of the cleaning blade with respect to the photosensitive member is stable over a long period of time, and excellent cleaning performance can be maintained.

The image forming apparatus of the present invention may be in the following modes.
[Toner holding member]
The image forming apparatus of the present invention may have a toner holding member 83 shown in FIG. 9 from the viewpoint of more reliably removing the discharge products.
Transfer residual toner (or toner developed intentionally in a predetermined mode) 84 attached to the image carrier 82 is carried downstream in the process as the image carrier 82 operates. Most of the toner 84 that has entered the toner holding member 83 is blocked by the toner holding member 83. By adjusting the material and pressing force of the toner holding member 83 and holding the toner 84 on the toner holding member 83, the toner 84 adsorbed on the holding member 83 is always held while the image holding body 82 is operating. In order to rub the surface of the body 82, the toner 84 adsorbs the discharge product adhering to the image holding body 82. The discharge product is also removed by the toner holding member 83 itself. However, when the discharge product is adsorbed by the toner 84, the contact surface between the toner holding member 83 and the image holding member 82 is successively supplied by the toner 84 supplied one after another. Is moved downstream by the frictional force with the image carrier 82 and finally collected by the cleaning blade 81. Therefore, the toner 84 held by the toner holding member 83 is always replaced, and the efficiency of removing the discharge product by the toner 84 does not decrease.

  Further, the toner holding member 83 can be vibrated in parallel or perpendicular to the operation direction of the image holding body 82. When the toner holding member 83 is vibrated, the toner 84 adsorbed on the holding member 83 obtains kinetic energy due to the vibration and rubs the surface of the image holding member 82, so that the discharge product can be further removed. As power for vibrating the toner holding member 83, an external power source such as a motor may be used, or driving force of the image holding body 82 or other image forming apparatus may be transmitted via a gear. The period of vibration is preferably 0.1 to 5 seconds, and it is not desirable that the toner 84 is separated from the holding member 83 due to the period becoming too small or too large.

As a material of the toner holding member, for example, a nonwoven fabric or a brush can be used, and a cloth made of other fibers may be used. When using a non-woven fabric, it is preferable to use a sponge attached to the lower part of the non-woven fabric and then fix the sponge to SUS or a metal shaft. The length in the axial direction of both the nonwoven fabric and the brush is preferably about the same as the axial length of the image carrier.
The place where the toner holding member is installed is upstream of the process of the cleaning blade 81 as shown in FIG. 9 and is not shown in the figure, but is preferably downstream of the transfer portion located further upstream. . The toner holding member to be installed is pressed against the image holding body by a predetermined pressure. When using a non-woven fabric, the image holding body is rubbed without moving following the image holding body, whereas when using a brush Rotates following the image carrier. However, when the toner holding member is a roll of nonwoven fabric, the member may follow the operation of the image holding member. It is desirable that the member used as the toner holding member contacts the image holding member uniformly and the contact pressure does not vary.

[Toner reservoir]
Further, the image forming apparatus of the present invention may be an embodiment in which the toner reservoir shown in FIG. 9 is formed from the viewpoint of more reliably removing discharge products.
In this embodiment, the cleaning blade 81 is directed upward with respect to the direction in which gravity is applied, and a tape 85 made of a resin such as polyester is uniformly applied to the sheet metal of the cleaning blade 81 in the axial direction as shown in FIG. As a result, the toner 84 removed by the cleaning blade 81 accumulates in an area partitioned by the tape 85, and when a certain amount or more of the toner 84 accumulates, a toner reservoir that contacts the image carrier 82 is formed. The toner 84 in contact with the image carrier 82 adsorbs the discharge product on the surface of the image carrier 82, and as a result, image drift due to the discharge product can be more effectively prevented.

  It is also possible to adjust the amount of toner 84 held in the toner pool by changing the material, length, or thickness of the tape 85. It is also possible to improve the scraping property of the discharge product by providing a hole through which the toner 84 is removed in the tape 85 to circulate the toner 84 in the toner pool and forming the toner pool with the newly entered toner 84 as needed. .

Further, when the toner reservoir and the toner holding member are used in combination, since the discharge product scraping property due to the toner reservoir is present, the pressing force of the toner holding member 83 to the image holding body 82 is reduced to reduce the toner holding member. The discharge product may be removed by a predetermined amount by 83 and the toner reservoir.
In the case where the toner reservoir and the toner holding member are used in combination, when the toner 84 is to be accumulated in the toner reservoir, during a machine operation other than the process of forming the image by transferring the developed image to the recording medium. Then, a toner image of a certain amount or more is formed on the image holding member 82, and most of the toner 84 enters the toner holding member 83 without transferring the toner image (for example, with the transfer bias turned off). . When the amount of toner that enters the holding member 83 increases, the toner 84 that has entered the contact portion between the toner holding member 83 and the image holding member 82 is pushed out by the toner 84 supplied from the upstream of the process, so that the cleaning blade 81 is finally used. The toner 84 accumulates between the blade 81 and the tape 85, and a toner reservoir is formed in which part of the toner 84 comes into contact with the image carrier 82.

[Control of charging means]
In addition, the image forming apparatus of the present invention detects the temperature, the humidity, the film thickness of the image carrier, etc. from the viewpoint of minimizing the generation of the discharge product itself, and based on the detection result, the AC of the charging unit is detected. A mechanism for controlling current may be provided.
The image forming apparatus of the present invention uses discharge by a charging member using a charging roll or the like to uniformly charge an electrostatic charge on the surface of the image carrier, but the amount of discharge required for charging to a predetermined potential is as follows: It varies depending on the film thickness of the image carrier and the temperature and humidity around the apparatus. Regarding the film thickness of the image carrier, the smaller the amount of discharge, the smaller the amount of discharge for obtaining a specific charged potential. Therefore, the amount of discharge product generated is required by adjusting the amount of discharge according to the film thickness. It can be minimized. Also, the higher the temperature and the higher the humidity, the smaller the amount of discharge for obtaining a specific charged potential. Therefore, the amount of discharge products generated can be minimized by adjusting the amount of discharge according to temperature and / or humidity. It is possible to limit to the limit.
The amount of discharge is regulated by the alternating current (Iac) in the scorotron, charging roll, etc., so the film thickness and temperature / humidity of the image carrier are detected by some means, and the minimum required discharge based on the result. By defining the amount, the amount of discharge products can be suppressed, and as a result, the image blur that is the subject of the present invention can be further reduced.

[Magnetic carrier recovery member]
Furthermore, when the image forming apparatus of the present invention uses a carrier containing a magnetic material as a developer, the purpose is to collect the carrier transferred onto the image carrier or the fine powder generated when the carrier is destroyed. Thus, a magnetic carrier recovery member may be provided. The magnetic carrier recovery member adsorbs the carrier adhering to the moving image holding member well, so that the number of carriers (particularly fine powder) entering the cleaning blade can be reduced and the damage to the blade can be effectively suppressed. .

As the magnetic carrier recovery member, a magnet blade 93A, which is a magnetic body having a flat shape as shown in FIG. 10 (A), or a cylindrical shape as shown in FIG. 10 (B). And a rolled magnet 93B which is a magnetic material. As shown in FIGS. 10A and 10B, the carrier recovery member (magnet blade 93A, roll-shaped magnet 93B, etc.) is upstream of the process of the cleaning blade 91 and is not shown in the figure. It is preferable to be installed downstream of the transfer unit located upstream. Further, as the magnetic material, any known magnetic material including ferrite may be used.
It is preferable that the length of the carrier recovery member (length with respect to the axial direction of the image carrier) covers at least the entire area of the image carrier used for image formation. Further, it is desirable that the leading end of the carrier recovery member is in the following region when the surface of the image holding member is zero.
0 (mm) <tip position of carrier recovery member <3.0 (mm)

The roll-shaped magnet 93 </ b> B shown in FIG. 10B is rotated in the operation direction of the image carrier 92 or in the opposite direction by applying a rotational force by power (not shown). A scraper 95 made of, for example, SUS is in contact with the roll-shaped magnet 93B, and the scraper 95 is configured such that the magnet 93B can rotate while the tip of the scraper 95 is in contact with the surface of the roll-shaped magnet 93B. The carrier (and / or fine powder or the like) 94 adsorbed to the roll-shaped magnet 93B is separated from the roll-shaped magnet 93B by receiving a mechanical pressing force from the scraper 95, and the separated carrier and fine powder or the like 94 is separated from the scraper 95. Is dropped and recovered in the carrier recovery unit 96 adjacent to.
In this way, the roll-shaped magnet 93B adsorbs the carrier 94 adhering to the operating image carrier 92 well, so that the amount of carrier entering the cleaning blade 91 is reduced and the damage of the blade is reduced, and the lifetime of the entire apparatus is reduced. Lengthen.

  EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited only to these examples. In the following description, “part” means “part by mass”.

-Preparation of cleaning blade-
<Cleaning blade A1>
First, as a polyol component, polycaprolactone polyol (Daicel Chemical Industries, Plaxel 205, average molecular weight 529, hydroxyl value 212 KOHmg / g) and polycaprolactone polyol (Daicel Chemical Industries, Plaxel 240, average molecular weight 4155, hydroxyl value 27 KOHmg / g). ) And a soft segment material made of an acrylic resin containing 2 or more hydroxyl groups (Act Flow UMB-2005B, manufactured by Soken Chemical Co., Ltd.) at a ratio of 8: 2 (mass ratio). did.

Next, with respect to 100 parts of the mixture of the hard segment material and the soft segment material, 4,4′-diphenylmethane diisocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd., Millionate MT, hereinafter referred to as “MDI”) is used as the isocyanate compound. Part was added and reacted at 70 ° C. for 3 hours under a nitrogen atmosphere.
The amount of the isocyanate compound used in this reaction is selected so that the ratio of isocyanate group to hydroxyl group (isocyanate group / hydroxyl group) contained in the reaction system is 0.5.
Subsequently, 34.3 parts of the above isocyanate compound was further added and reacted at 70 ° C. for 3 hours under a nitrogen atmosphere to obtain a prepolymer.
In addition, the total amount of the isocyanate compound utilized when using the prepolymer is 40.56 parts.

  Next, the prepolymer was heated to 100 ° C., degassed for 1 hour under reduced pressure, and then mixed with 1,4-butanediol and trimethylolpropane (mass ratio = 60) with respect to 100 parts of the prepolymer. 7.14 parts of / 40) was added and mixed well for 3 minutes so as not to cause foaming, and a curing reaction was performed for 1 hour in a centrifugal molding machine with a mold adjusted to 140 ° C. to obtain a flat plate. This flat plate was cross-linked at 110 ° C. for 24 hours, cooled, and cut to a predetermined size to obtain a cleaning blade A1 having a thickness of 2 mm.

<Cleaning blade A2>
As the hard segment material, the same hard segment material as used for the production of the cleaning blade A1 is used, and as the soft segment material, a polybutadiene resin containing two or more hydroxyl groups (Idemitsu Kosan Co., Ltd., R-45HT) is used. The hard segment material and the soft segment material were mixed at a ratio of 8: 2.
A cleaning blade was produced in the same manner as in Example 1 except that this mixture was used to obtain a cleaning blade A2.

<Cleaning blade A3>
As the hard segment material, the same hard segment material as that used for the production of the cleaning blade A1 is used. 150), the hard segment material and the soft segment material were mixed in a ratio of 8: 2.
A cleaning blade was produced in the same manner as in Example 1 except that this mixture was used to obtain a cleaning blade A3.

<Cleaning blade A4>
The cleaning blade A1 was produced in the same manner as the cleaning blade A1, except that the mixing ratio of the hard segment material and the soft segment material was changed to 9: 1 in the production of the cleaning blade A1, and a cleaning blade A4 was obtained.

<Cleaning blade A5>
A cleaning blade A5 was obtained in the same manner as the cleaning blade A1, except that the mixing ratio of the hard segment material and the soft segment material was changed to 96: 4 in the production of the cleaning blade A1.

<Cleaning blade A6>
A cleaning blade A6 was obtained in the same manner as the cleaning blade A1, except that the mixing ratio of the hard segment material and the soft segment material was changed to 98: 2 in the preparation of the cleaning blade A1.

<Cleaning blade B1>
Instead of a mixture of a hard segment material and a soft segment material, only a polyol component is used, and 100 parts of Coronate 4086 (manufactured by Nippon Polyurethane Industry Co., Ltd.) used as this polyol component is used as an isocyanate compound, Nipponran 4038 (Japan) A cleaning blade was produced in the same manner as in Example 1 except that 6.8 parts of Polyurethane Industry Co., Ltd. were used, and a cleaning blade B1 was obtained.

<Cleaning blade B2>
Instead of a mixture of a hard segment material and a soft segment material, only a polyol component is used, and 100 parts of Coronate 4370 (manufactured by Nippon Polyurethane Industry Co., Ltd.) used as this polyol component is used as an isocyanate compound, Nipponran 4379 (Japan) A cleaning blade was produced in the same manner as in Example 1 except that 75 parts of Polyurethane Industry Co., Ltd. was used, and a cleaning blade B2 was obtained.

<Cleaning blade B3>
Instead of a mixture of a hard segment material and a soft segment material, only a polyol component is used, and 100 parts of Coronate 4370 (manufactured by Nippon Polyurethane Industry Co., Ltd.) used as this polyol component is used as an isocyanate compound, Nipponran 4379 (Japan) A cleaning blade was prepared in the same manner as in Example 1 except that 85 parts of Polyurethane Industry Co., Ltd. was used, and a cleaning blade B3 was obtained.

  The physical property values of the cleaning blade described above are shown in Table 9 and Table 10 below.

-Production of photoconductor-
<Photoreceptor A1>
To 170 parts of n-butyl alcohol in which 4 parts of polyvinyl butyral resin (S-REC BM-S, manufactured by Sekisui Chemical Co., Ltd.) was dissolved, 30 parts of an organic zirconium compound (acetylacetone zirconium butyrate) and an organic silane compound (γ-aminopropyltrimethoxy) 3 parts of silane) was added, mixed and stirred to obtain a coating solution for forming an undercoat layer.
This coating solution is dip-coated on an aluminum support having an outer diameter of 40 mm roughened by a honing treatment, air-dried at room temperature for 5 minutes, and then the support is heated to 50 ° C. for 10 minutes, It was placed in a constant temperature and humidity chamber at 50 ° C. and 85% RH (dew point 47 ° C.), and a humidification hardening acceleration treatment was performed for 20 minutes. Then, it put in the hot air dryer and dried for 10 minutes at 170 degreeC, and formed the undercoat layer.

As a charge generating material, gallium chloride phthalocyanine is used, and a mixture of 15 parts, 10 parts of vinyl chloride-vinyl acetate copolymer resin (VMCH, manufactured by Nippon Union Carbide) and 300 parts of n-butyl alcohol is obtained with a sand mill. A dispersion was obtained by dispersing for 4 hours. This dispersion was dip-coated on the undercoat layer and dried to form a charge generation layer having a thickness of 0.2 μm.
Next, 40 parts of N, N′-bis (3-methylphenyl) -N, N′-diphenylbenzidine and 60 parts of bisphenol Z polycarbonate resin (molecular weight 40,000) were added to 235 parts of tetrohydrofuran and 100 parts of monochlorobenzene. The coating solution obtained by sufficiently dissolving and mixing in the part was dip coated on the aluminum support formed up to the charge generation layer and dried at 120 ° C. for 40 minutes to form a charge transport layer having a thickness of 22 μm. .

  Subsequently, 2 parts of the compound (1) shown below and 2 parts of RESITOP PL4852 (manufactured by Gunei Chemical Co., Ltd.) were dissolved in 10 parts of isopropyl alcohol to obtain a coating solution for forming a protective layer. This protective layer-forming coating solution was dip-coated on the charge transport layer, air-dried at room temperature for 30 minutes, and then dried at 140 ° C. for 60 minutes to form a protective layer having a thickness of 4 μm, whereby Photoreceptor A1 was obtained. .

<Photoreceptor A2>
In preparation of the photoreceptor A1, except that 2 parts of alumina was added and dispersed in the coating solution for the charge transport layer to form a charge transport layer, and no protective layer was formed on the charge transport layer. Produced a photoreceptor A2 in the same manner as the photoreceptor A1.

<Photoreceptor B1>
A photoreceptor B1 was produced in the same manner as the photoreceptor A1, except that no protective layer was formed in the production of the photoreceptor A1.

  The physical property values of the photoreceptor described above are shown in Table 11 below.

(Production of toner)
-Preparation of resin particle dispersion-
A mixture of 370 g of styrene, 30 g of n-butyl acrylate, 8 g of acrylic acid, 24 g of dodecanethiol, and 4 g of carbon tetrabromide was dissolved in 6 g of a nonionic surfactant (Nonipol 400: manufactured by Sanyo Chemical Industries) and anion Ion exchange in which 4 g of ammonium persulfate is dissolved in 10 ml of a surfactant (Neogen SC: manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) dissolved in 550 g of ion exchange water in a flask and then mixed and mixed slowly for 10 minutes. 50 g of water was added. After carrying out nitrogen substitution, while stirring the inside of the flask, it was heated in an oil bath until the contents reached 70 ° C., and emulsion polymerization was continued for 5 hours. As a result, a resin particle dispersion was prepared in which resin particles having an average particle size of 150 nm, a glass transition temperature Tg of 58 ° C., and a weight average molecular weight Mw of 11500 were dispersed. The solid content concentration of this dispersion was 40% by mass.

-Preparation of colorant dispersion (1)-
Carbon black (Mogal L: manufactured by Cabot) 60 g, nonionic surfactant (Nonipol 400: manufactured by Sanyo Chemical Co., Ltd.) 6 g, and ion-exchanged water 240 g were mixed and dissolved, and then a homogenizer (Ultra Turrax T50: IKA). The colorant dispersant (1) was prepared by dispersing the colorant (carbon black) particles having an average particle diameter of 250 nm by dispersing with an optimizer.

-Preparation of colorant dispersion (2)-
A homogenizer (Ultra Turrax T50) was prepared by mixing 60 g of Cyan pigment (CI Pigment Blue 15: 3), 5 g of a nonionic surfactant (Nonipol 400: manufactured by Sanyo Chemical Co., Ltd.), and 240 g of ion-exchanged water. : Manufactured by IKA Co., Ltd.) for 10 minutes, and then dispersed with an optimizer to prepare a colorant dispersant (2) in which colorant (Cyan pigment) particles having an average particle diameter of 250 nm are dispersed. did.

-Preparation of colorant dispersion (3)-
A homogenizer (Ultra Turrax T50: IKA) was prepared by mixing 60 g of Magenta pigment (CI Pigment Red 122), 5 g of a nonionic surfactant (Nonipol 400: manufactured by Sanyo Kasei Co., Ltd.), and 240 g of ion-exchanged water. The colorant dispersant (3) in which the colorant (Magenta pigment) particles having an average particle diameter of 250 nm are dispersed was prepared by stirring for 10 minutes using a product manufactured by the same company.

-Preparation of colored dispersion (4)-
A homogenizer (Ultra Turrax T50: IKA) was prepared by mixing 90 g of Yellow pigment (CI Pigment Yellow 180), 5 g of a nonionic surfactant (Nonipol 400: manufactured by Sanyo Kasei Co., Ltd.), and 240 g of ion-exchanged water. The colorant dispersant (4) in which colorant (Yellow pigment) particles having an average particle diameter of 250 nm were dispersed was prepared by stirring for 10 minutes using

-Preparation of release agent dispersion-
100 g of paraffin wax (HNP0190: manufactured by Nippon Seiwa Co., Ltd., melting point 85 ° C.), 5 g of a cationic surfactant (Sanisol B50: manufactured by Kao Corporation), and 240 g of ion-exchanged water are mixed and heated to 95 ° C. After dispersing for 10 minutes in a stainless steel flask using a homogenizer (Ultra Turrax T50: manufactured by IKA), the dispersion was performed with a pressure discharge type homogenizer, and release agent particles having an average particle diameter of 550 nm were dispersed. A release agent dispersion was prepared.

-Production of toner base particles K1-
234 parts of a resin particle dispersion, 30 parts of a colorant dispersion (1), 40 parts of a release agent dispersion, 0.5 part of polyaluminum hydroxide (Pho2S manufactured by Asada Chemical Co., Ltd.), and 600 parts of ion-exchanged water, After mixing and dispersing in a round stainless steel flask using a homogenizer (Ultra Turrax T50: manufactured by IKA), the flask was heated to 40 ° C. with stirring in a heating oil bath. After 30 minutes hold at 40 ° C., a volume-average particle diameter D ₅₀ was confirmed to 4.5μm aggregated particles are generated. Further, when the temperature of the heating oil bath was raised and held at 56 ° C. for 1 hour, the volume average particle diameter D ₅₀ of the aggregated particles was 5.3 μm. Thereafter, 26 parts of the resin particle dispersion was added to the dispersion containing the aggregated particles, and then the temperature of the heating oil bath was set to 50 ° C. and held for 30 minutes. After the pH of the system is adjusted to 7.0 by adding a 1N sodium hydroxide solution to the dispersion containing the aggregated particles, the stainless steel flask is sealed, and the stirring is continued to 80 ° C. using a magnetic seal. Heated and held for 4 hours. After cooling, the reaction product was filtered off, washed four times with ion exchange water, and then freeze-dried to produce toner mother particles K1. The volume average particle diameter _{D 50} of the toner mother particles K1 is 5.9 [mu] m, the average value of the shape factor SF1 of 132.

-Production of toner base particles C1-
Toner base particles C1 were prepared in the same manner as the toner base particles K1, except that the color particle dispersion liquid (2) was used instead of the color particle dispersion liquid (1). The volume average particle diameter D ₅₀ of the toner base particles C1 is 5.8 μm, and the average value of the shape factor SF1 is 131.

-Production of toner base particles M1-
Toner mother particles M1 were prepared in the same manner as the toner mother particles K1, except that the colored particle dispersion (3) was used instead of the colored particle dispersion (1). The volume average particle diameter D ₅₀ of the toner base particles M1 is 5.5 μm, and the average value of the shape factor SF1 is 135.

-Production of toner base particles Y1-
Toner base particles Y1 were prepared in the same manner as the toner base particles K1, except that the color particle dispersion liquid (4) was used instead of the color particle dispersion liquid (1). The volume average particle diameter _{D 50} of the toner mother particles Y1 is 5.9 [mu] m, the average value of the shape factor SF1 of 130.

-External additives-
100 parts of each of the toner base particles K1, C1, M1, and Y1, 1 part of anatase type titanium oxide (average particle diameter 20 nm, i-butyltrimethoxysilane treatment), silica (prepared by sol-gel method, volume average particle diameter) 140 nm, HMDS (hexamethyldisilazane) treatment 2 parts, cerium oxide (volume average particle size 0.7 μm) 0.8 part, zinc stearate (ZNS-S: manufactured by Asahi Denka Kogyo Co., Ltd.) 0.3 part After blending for 15 minutes at a peripheral speed of 30 m / s using a 5-liter Henschel mixer, coarse particles were removed using a sieve having an opening of 45 μm to prepare a toner.

<Creation of carrier>
・ Styrene-acrylic resin (Hymer TB-1000, Sanyo Chemical Industries) 35 parts ・ Iron powder (particle size 2 μm, magnetization 93 emu / g at 1 kOe, Kanto Denki) 60 parts ・ Carbon black (black pearls 2000, manufactured by Cabot) 5 parts These materials were melt-kneaded and then pulverized and classified to prepare a resin carrier having an average particle size of 20 μm. Next, the obtained resin carrier was put into a centrifugal rotary mixer (Okada Seiko) and stirred to mechanically spheroidize the resin carrier. Next, 5 parts of nigrosine dye (Orient Chemical Co., Ltd.) as a charge control agent and 100 parts of the resin carrier are mixed and stirred using a Henschel mixer (Mitsui Miike Engineering Co., Ltd.), and the charge control agent is placed on the surface of the resin carrier. It was made to adhere electrostatically. Next, this was put into a centrifugal rotary mixer (Okada Seiko) and mixed to fix the nigrosine dye on the surface of the resin carrier. Next, 10 parts of polymethyl methacrylate having an average particle size of 0.4 μm and 100 parts of a resin carrier are mixed and stirred as a resin powder by a Henschel mixer (Mitsui Miike Engineering Co., Ltd.), and the charge control agent is statically applied to the surface of the resin carrier. Electrodeposited. Next, this mixture was put into a centrifugal rotary mixer (Okada Seiko) and mixed to form a resin coating on the surface of the resin carrier.

<Production of developer>
Further, 100 parts of the carrier obtained above and 5 parts of each color toner were stirred for 20 minutes at 40 rpm with a V-blender, and sieved with a sieve having an opening of 212 μm to prepare a developer.

[Examples 1-7 and Comparative Examples 1-6]
The above-described cleaning blades A1 to A6, B1 to B3 and the photoreceptors A1 to A2 and B1 are combined in an image forming apparatus (manufactured by Fuji Xerox Co., Ltd., DocuCenter Color 400CP) so as to have the combinations shown in Table 12 below. Further, the arrangement of the cleaning blade with respect to the photosensitive member (that is, the pressing force NF, the biting length d, and the angle W / A) is as shown in Table 12, and each color developer obtained as described above is used as follows. Evaluation was performed. The results are shown in Table 12 below.

  The evaluation methods and evaluation criteria for image flow, cleaning blade edge wear, and cleaning blade edge chipping shown in Table 12 are as follows.

-Image flow-
The evaluation of image flow was 1000 consecutive halftone images with an image area ratio of 5% on the entire surface of A4 paper (210 x 297 mm, manufactured by Fuji Xerox, P paper) in a high humidity environment (28 ° C, 85%). After printing, the apparatus was left in the same high humidity environment for 10 hours. After standing, a part of the photoreceptor was lightly wiped with a nonwoven fabric impregnated with pure water to clean the surface of the photoreceptor.
Subsequently, for the sample obtained by reprinting the same halftone image, the image portion corresponding to the portion lightly wiped with the nonwoven fabric (the image corresponding to the region where the discharge product causing the image flow is removed) An image density A and an image density B of an image portion corresponding to a portion not wiped off by the nonwoven fabric (an image corresponding to an area where adhesion of discharge products causing image flow has progressed and accumulated) are represented by X -Measured by a density measuring device (X-rite 404A) manufactured by Rite Co., Ltd., and the occurrence of image flow was evaluated from the difference between the image density A and the image density B (density difference Δ).
Image flow evaluation criteria are as follows. The allowable range is G0 to G2.
G0; density difference Δ = 0
G1; 0 <density difference Δ ≦ 0.05
G2; 0.05 <density difference Δ ≦ 0.1
G3; 0.1 <density difference Δ ≦ 0.2
G4; 0.2 <density difference Δ ≦ 0.3
G5; 0.3 <Density difference Δ

-Edge wear-
When evaluating edge wear, use A4 paper (210 x 297 mm, manufactured by Fuji Xerox Co., Ltd., P paper) in a high-temperature and high-humidity environment (28 ° C, 85RH%) until the total number of revolutions of the photoconductor reaches 100K cycles. The wear at the tip of the cleaning blade after image formation using the image and the poor cleaning were evaluated and judged together.
In the test, the image density of the image to be formed was set to 1% in order to evaluate under severe conditions where the lubrication effect at the contact portion between the photosensitive member and the cleaning blade was reduced.

Subsequently, when the wear depth at the tip of the cleaning blade after the test was observed with a laser microscope VK-8510 manufactured by Keyence Corporation from the cross-sectional side of the cleaning blade, the maximum edge missing portion depth on the surface of the photoreceptor was measured.
In addition, the evaluation of cleaning failure is undecided by feeding A3 paper on which an untransferred solid image (solid image size: 400 mm × 290 mm) is formed between the photoconductor and the cleaning blade after the above test is completed. Immediately after the last edge of the received image in the conveying direction has passed through the contact area between the photoconductor and the cleaning blade, the actual machine is stopped and the presence or absence of toner rub-off is visually confirmed. The cleaning was defective.
In addition, when the portion for blocking the toner is missing due to wear or chipping at the tip of the cleaning blade, the larger the edge wear depth or chipping depth, the easier the cleaning failure occurs in the above test. The test is useful for qualitative evaluation of wear and chip of the cleaning blade tip.
The evaluation criteria for edge wear are shown below. The allowable range is G0 to G2.

G0: Edge wear depth of 3 μm or less and no wear, no cleaning failure occurred G1; Edge wear depth of 3 μm or less, no cleaning failure occurred G2: Edge wear depth of more than 3 μm and 5 μm or less, poor cleaning Not generated G3: Edge wear depth exceeds 3 μm and 5 μm or less, cleaning failure occurs G4: Edge wear depth exceeds 5 μm and 10 μm or less, cleaning failure occurs G5; Edge wear depth exceeds 10 μm, cleaning failure occurs

-Edge missing-
Edge chipping occurs when foreign matter attached to the surface of the photoreceptor passes many times through the contact portion between the photoreceptor and the cleaning blade. Therefore, the elasticity of the cleaning blade is reduced, and a 5 mm width is obtained every 5K cycles in a low-temperature and low-humidity (10 ° C., 15% RH) environment, which is a condition in which the stress when the cleaning blade collides with foreign matter is likely to increase. The depth and number of edge defects after running the photosensitive drum for 100 K cycles while producing the toner band were measured.
The edge missing depth was measured by measuring the depth of the edge missing portion on the photosensitive member surface side when the cross section side of the cleaning blade was observed with a laser microscope VK-8510 manufactured by Keyence Corporation. At this time, the number of chips having a width of 5 μm or more was evaluated. The evaluation criteria for edge defects are shown below. The allowable range is G0 to G2.

G0; (Number of chipping of 5 μm or more) 0 G1; 1 to 5 G2; 6 to 10 G3; 11 to 20 G4; 21 to 30 G5;

(A) is a schematic sectional view showing a contact portion between the cleaning blade and the image carrier, (B) is an enlarged view of the contact portion of (A), and (C) is a conventional cleaning blade and image. It is a figure which shows a contact part with a holding body. FIG. 6 is a schematic cross-sectional view for explaining an amount d of a cleaning blade that bites into an image carrier and an angle W / A at a contact portion between the cleaning blade and the image carrier. It is a schematic cross section showing a part of the image forming apparatus of the present invention provided with an abrasive supply means. (A) is a schematic sectional view showing a contact portion between the cleaning blade in which fine powder or the like is accumulated and the image carrier, and (B) is a contact between the cleaning blade in which the polymerization carrier (or filling carrier) is accumulated and the image carrier. It is a schematic sectional drawing which shows a part. 1 is a schematic diagram illustrating an example of an image forming apparatus of the present invention. It is a schematic cross section which shows an example of the cleaning apparatus of this invention. It is a schematic cross section which shows an example of the cleaning blade of this invention. It is a schematic diagram showing an example of a fixing method of the cleaning blade of the present invention. FIG. 3 is a schematic cross-sectional view showing a part of the image forming apparatus of the present invention including a toner holding member and a toner reservoir. (A) And (B) is a schematic cross section which shows a part of image forming apparatus of this invention provided with the magnetic type carrier collection | recovery member.

Explanation of symbols

1, 11, 16, 81, 91, 101 Cleaning blade 2, 12, 17, 82, 92, 102 Image carrier 3 Toner 4 Abrasive 5 Conventional cleaning blade 6 Conventional image carrier 13 Fine powder of carrier 14 etc. Polymerization Carrier (or filling carrier)
18 Brush 19 Solid abrasive 21 Main body housing 22, 22a-22d Image forming engine 23 Belt module 24 Recording medium supply cassette 25 Recording medium conveyance path 30 Photosensitive unit 31 Photosensitive drum 32 Charging roll 33 Each developing unit 34 Cleaning device 35, 35a to 35d Toner cartridge 40 Exposure unit 41 Unit case 42 Polygon mirror 51 Primary transfer device 52 Secondary transfer device 53 Belt cleaning device 61 Feed roll 62 Take away roll 63 Registration roll 66 Fixing device 67 Discharge roll 68 Discharge unit 71 Manual feed device 72 Feed roll 73 Double-sided recording unit 74 Guide roll 76 Transport path 77 Transport roll 83 Toner holding member 84 Toner 85 Tape 93A Magnet blade 93B All-shaped mug 94 Scraper 96 Carrier recovery unit 230 Intermediate transfer belts 231 and 232 Stretch roll 331 Unit case 332 Developing roll 333 Transport auger 334 Transport paddle 335 Trimming member 341 Cleaning case 342 Cleaning blade 342a Cleaning edge side layer 342b Back side layer 342c Spring material 342d Holder 344 Film seal 345 Conveyor auger 521 Secondary transfer roll 531 Cleaning blade

Claims (3)

A charging step for charging the surface of the image carrier, an exposure step for exposing the image carrier to form an electrostatic latent image based on image data, and transferring toner to the electrostatic latent image to form an electrostatic latent image on the image carrier. A developing step for forming a toner image on the surface, a transfer step for transferring the toner image on the image carrier to a recording medium, and a cleaning step for cleaning the surface of the image carrier after the toner image is transferred with a cleaning blade; Have
The coefficient of friction of the image carrier surface is 0.6 to 1.4,
The material of the portion of the cleaning blade that contacts the surface of the image carrier satisfies the following formulas (1) to (3):
An image forming method comprising: supplying an abrasive to a portion where the image carrier and the cleaning blade are in contact with each other.
Formula (1) 3.92 ≦ M ≦ 29.42
Formula (2) 0 <α ≦ 0.294
Formula (3) S ≧ 250
(In the formulas (1) to (3), M represents a 100% modulus (MPa), and α represents a strain amount change (Δ strain amount in a stress-strain curve in a range of 100% to 200% strain). ) Represents the ratio of stress change (Δstress) to Δ {stress / Δstrain amount = (stress at 200% strain−stress at 100% strain) / (200−100)} (MPa /%). (The elongation at break (%) measured based on JIS-K6251 (using dumbbell-shaped No. 3 test piece)).   2. The image forming method according to claim 1, wherein the surface roughness Rz of the surface of the image carrier measured based on JIS-B0601 is 0.01 to 2 μm. An image carrier, a charging unit for charging the surface of the image carrier, an exposure unit for exposing the image carrier to form an electrostatic latent image based on image data, and transferring toner to the electrostatic latent image. Developing means for forming a toner image on the image carrier, transfer means for transferring the toner image on the image carrier to a recording medium, and transferring the toner image in contact with the surface of the image carrier. A cleaning blade for cleaning the surface of the image carrier after,
An image forming apparatus that forms an image using the image forming method according to claim 1.

Images