JP4779909B2 - Cleaning blade, cleaning device, process cartridge, and image forming apparatus - Google Patents

Description

  The present invention relates to a cleaning blade used in a copying machine or the like that forms an image by electrophotography, and a cleaning device, a process cartridge, and an image forming apparatus using the same.

  In general, in the formation of an image in an electrophotographic method or an electrostatic recording method, an electrostatic latent image is formed on an image carrier such as a photosensitive member, and then the electrostatic latent image is developed with a developer to form a toner image. Subsequently, the toner image is transferred and fixed on a recording medium. An image forming apparatus that uses this type of image forming method is usually provided with a cleaning device in order to clean the toner remaining on the image carrier after the transfer of the toner image.

Various types of cleaning devices are known. Typically, a cleaning blade (usually using an elastic contact plate) is placed in contact with the image carrier, and the residual on the image carrier. A blade cleaning system that scrapes off toner with a cleaning blade is often employed.
In low and medium speed machines, a contact-type charging device such as a charging roll is widely used as a charging member for an image carrier. The contact-type charging device is widely used because it generates less ozone than the non-contact-type charging device using so-called corotron charging, and is environmentally friendly. This is because it is also unnecessary and is small and low cost.

  On the other hand, the contact-type charging device has a problem that the amount of discharge product adhering to the photoreceptor is much larger than the non-contact type charging device using corotron charging. This is because the contact type charging device is smaller than the non-contact type charging device with respect to the absolute amount of discharge products, but the discharge region is very close to the photoreceptor. For this reason, when the contact type charging device and the cleaning blade are used in combination, there arises a problem that the cleaning blade is worn out, chipped or twisted due to an increase in the friction coefficient, and the torque of the photosensitive member driving system is increased.

  In order to prevent these problems, conventionally, an apparatus has been proposed that removes discharge products on the surface of the image carrier and reduces the frictional force with the cleaning blade. For example, a method of removing discharge products by rubbing the surface of an image carrier with a sponge roll containing a magnetic brush or an abrasive (see, for example, Patent Documents 1 and 2) has been proposed. Further, a method of using a material having low friction and high hardness for the portion of the cleaning blade that contacts the image carrier (see, for example, Patent Document 3), and a portion of the cleaning blade that contacts the image carrier for high modulus (high hardness). A method of improving the wear resistance with the material of the cleaning blade itself has been proposed, such as a method using this material (see, for example, Patent Document 4).

In addition, when using a two-component development method using a developer composed of a magnetic carrier and a toner, the toner is developed by applying a predetermined development bias to the development roll and applying a development electric field between the development roll and the image carrier. The toner is transferred to the electrostatic latent image by the action, and in such a process, a part of the magnetic carrier is transferred to the surface of the image carrier by electrostatic attraction force, so-called BCO (Bead Carry Over) and The phenomenon called may occur.
On the other hand, a fine powder carrier (crushed carrier) generated in a developer manufacturing process or in a developing device is often sharp and fragmented, unlike a substantially spherical carrier. Therefore, when a toner image is transferred to a transfer material when BCO occurs, the fine powder carrier is buried in the surface of the image carrier by receiving a transfer electric field or a transfer pressure between the image carrier and the transfer material. In addition to being easy, it adheres to the surface of the image carrier as it is.

  The carrier attached to the surface of the image carrier is repeatedly brought into contact with the cleaning blade that contacts the surface of the image carrier as the image carrier is rotated. In order to prevent this, conventionally, an apparatus for collecting carriers adhering to the surface of the image carrier has been proposed. For example, a device that collects carriers by forming an electric field between the collecting member and the photosensitive member (see, for example, Patent Document 5), or a device that collects carriers by magnetic attraction (for example, Patent Document 6). , 7) has been proposed.

Also, a two-layer cleaning blade has been proposed from the viewpoint of preventing the cleaning blade from turning over and improving the cleaning performance (see, for example, Patent Documents 8 and 9).
JP-A-10-143039 JP-A-1-090479 JP 2001-343874 A JP 2003-241599 A JP-A-62-262074 JP-A-3-120577 Japanese Utility Model Publication No. 53-32599 JP-A-63-235977 JP 2005-164616 A

  However, a means for removing discharge products is added to the image forming apparatus for the purpose of improving the wear resistance of the cleaning blade, or the image forming apparatus adheres to the surface of the image holding member due to the generation of BCO, causing edge defects. It is not preferable to add a carrier collecting means for collecting the fine powder carrier from the viewpoints of downsizing and cost reduction. In particular, it is necessary to avoid that the sharp fragment-shaped carrier is transferred to the surface of the image holding member and buried during the transfer of the toner image. In this case, between the development process and the transfer process, the sharp debris-shaped carrier adhering to the surface of the image carrier must be removed without disturbing the toner image developed on the image carrier.

  Therefore, a stronger magnetic field or electric field is required to collect small-sized and sharp-shaped carrier particles attached to the image carrier than to collect normal-size carriers. It becomes. In order to realize a stronger magnetic field or electric field, it is necessary to bring the collecting means closer to the photoreceptor. However, if the collecting means is simply brought close to the photosensitive member, the collected carrier rubs the toner image on the image holding member during conveyance, so that the toner image is transferred onto the image holding member without disturbing the toner image. It is very difficult to completely remove the used carrier.

  On the other hand, in order to improve the abrasion resistance of the cleaning blade, if a material having a high hardness or a high modulus is used as a material for the portion in contact with the image carrier, generally the resistance is improved but the elasticity is lowered. . A decrease in elasticity means that the rubberiness is lost and it is difficult to stretch. Since it is difficult to stretch, when a foreign object such as a carrier piece buried in the surface of the image holding member due to the generation of BCO passes through the contact portion between the edge of the cleaning blade and the surface of the image holding member, the foreign material is deformed by the force that deforms the edge. Following this, the tip of the edge cannot be deformed and is easily chipped.

  In addition, high modulus (high hardness) materials have the disadvantage that the sag (permanent deformation) deteriorates due to the large permanent elongation. If the amount of sag increases, the contact pressure cannot be maintained. As inviting poor cleaning.

In order to prevent the edge of the cleaning blade from being chipped as described above, the hardness of the edge is deformed (extends) to some extent when a foreign object passes through the contact portion between the edge of the cleaning blade and the surface of the image carrier. It is advantageous that the edge tip is made of the above material. Further, from the viewpoint of preventing such sag as described above, a material having a certain degree of hardness is advantageous.
However, such a low-hardness material is inferior in wear resistance, so that good cleaning performance cannot be maintained over a long period of time.

  The present invention aims to solve the above problems. That is, the present invention provides a cleaning blade that is excellent in wear resistance and chipping resistance and that can effectively prevent the occurrence of sag and maintain good cleaning performance for a long period of time. It is an object of the present invention to provide a cleaning device, a process cartridge, and an image forming apparatus that are used.

The above object is achieved by the present invention described below. That is, the cleaning blade of the present invention is
<1> A cleaning blade that contacts the surface of the member to be cleaned and cleans the surface of the member to be cleaned , containing at least one selected from an acrylic resin, a polybutadiene resin, and an epoxy resin , a first layer contacting said is composed of a back layer not in contact with the member to be cleaned surface, the material of the first layer, meets the following formula (1) to (3), of the material of the back layer The cleaning blade is characterized in that the rate of change in hardness at 10 to 60 ° C. is smaller than that of the material of the first layer .
Formula (1) 7.4 ≦ M ≦ 17
Formula (2) 0.039 ≦ α ≦ 0.105
Formula (3) 535 ≧ S ≧ 380
[In the formulas (1) to (3), M represents a 100% modulus (MPa), and α represents a strain amount change (Δ strain amount) when the strain amount is 100% to 200% in the stress-strain curve. Represents the ratio of the stress change (Δ stress) to {Δ stress / Δ strain amount = (stress at strain amount of 200% −stress at strain amount of 100%) / (200−100)} (MPa /%). It represents the elongation at break (%) measured based on JIS K6251 (using dumbbell-shaped No. 3 test piece). ]

Moreover, the cleaning device of the present invention comprises:
<2> A cleaning device including the cleaning blade according to <1>.

The process cartridge of the present invention is
<3> A process cartridge that is detachable from the image forming apparatus and includes the cleaning device according to <2>.

Furthermore, the image forming apparatus of the present invention includes:
<4> An image forming apparatus comprising: a member to be cleaned; and a cleaning blade that contacts the surface of the member to be cleaned and cleans the surface of the member to be cleaned, and uses the cleaning blade according to <1> as the cleaning blade It is.

  As described above, according to the present invention, cleaning that is excellent in wear resistance and chipping resistance, effectively prevents the occurrence of sag, and can maintain good cleaning performance over a long period of time. A blade, and a cleaning device, a process cartridge, and an image forming apparatus using the blade can be provided.

(Cleaning blade)
The cleaning blade of the present invention comprises at least one selected from an acrylic resin, a polybutadiene resin, and an epoxy resin in the cleaning blade that contacts the surface of the member to be cleaned and cleans the surface of the member to be cleaned. a first layer in contact with the cleaning member surface, the is composed of a back layer not in contact with the member to be cleaned surface, the material of the first layer, meets the following formula (1) to (3), the back The rate of change in hardness at 10 to 60 ° C. of the material of the layer is smaller than that of the material of the first layer .
Formula (1) 7.4 ≦ M ≦ 17
Formula (2) 0.039 ≦ α ≦ 0.105
Formula (3) 535 ≧ S ≧ 380
However, in the formulas (1) to (3), M represents a 100% modulus (MPa), and α is a strain amount change (Δ strain amount) when the strain amount is 100% to 200% in the stress-strain curve. The ratio of stress change (Δ stress) {Δ stress / Δ strain amount = (stress at strain amount of 200% −stress at strain amount of 100%) / (200−100)} (MPa /%), S is JIS It represents the elongation at break (%) measured based on K6251 (1993 / use of dumbbell-shaped No. 3 test piece).

  First, the cleaning blade of the present invention is a cleaning blade excellent in both wear resistance and chipping resistance by using a material satisfying the above formulas (1) to (3) for the first layer. In addition, the composition consisting of multiple layers of the first layer and the back layer can effectively prevent the occurrence of sag, and these effects maintain good cleaning performance over a long period of time. can do.

  Here, the cleaning blade of the present invention may have a two-layer configuration in which the second layer as the back layer is provided on the back surface of the first layer that contacts the surface of the member to be cleaned. The back surface layer which consists of several layers, such as a 2nd layer and a 3rd layer, may be provided in the back surface. In the following, the present invention will be described in detail by taking up a two-layer cleaning blade comprising a first layer and a second layer as a back layer.

-First layer-
In the cleaning blade of the present invention, since the material of the first layer that contacts the surface of the member to be cleaned satisfies the formula (1), the cleaning blade 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. On the other hand, if it exceeds 29.42 MPa (300 kgf / cm ² ), the first layer material is too hard, the followability to the member to be cleaned is deteriorated, and good cleaning properties cannot be exhibited. In addition, the surface of the member to be cleaned may be easily damaged.
Incidentally, the 100% modulus M is Ru der range of 7.4 ~ 17 MPa.

Moreover, since the first layer material satisfies the formulas (2) and (3), the chip resistance is excellent.
When α shown in the formula (2) exceeds 0.294, the first layer material lacks flexibility. Therefore, with the occurrence of BCO, foreign matter existing on the surface of the member to be cleaned, such as foreign matter buried or fixed on the surface of the image carrier, particularly foreign matter embedded or fixed on the surface, When a large stress is repeatedly applied to the tip of the first layer of the cleaning blade by repeatedly passing through the contact portion of the cleaning blade, it cannot be deformed so that this stress can be dispersed efficiently. Will occur. Therefore, since chipping occurs early, good cleaning properties cannot be maintained over a long period of time.
In addition, α is Ru der 0.039 more than 0.105 or less.

Further, when the elongation at break S shown in the formula (3) is less than 250%, the tip of the first layer is stretched when the foreign matter on the surface of the member to be cleaned collides with the tip of the first layer with a strong force. As a result, it becomes impossible to follow and deform, and 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.
Incidentally, the elongation at break S is Ri der less 535% or more 380%, preferably other hand larger for edge chipping, if the breaking elongation S is greater than 500% may increase the followability to the member to be cleaned (adhesion), The frictional force with the member to be cleaned is increased, and as a result, the wear (edge wear) at the tip of the first layer is likely 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 of the first layer in contact with the surface of the member to be cleaned exceeds the use 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 of the first layer 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 of the first layer that comes into contact with the surface of the member to be cleaned tends to decrease as the temperature lowers when 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 stick-and-slip behavior at the tip of the first layer 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 while the posture of the first layer tip is maintained, so that local plastic deformation is likely to occur. When such local plastic deformation occurs, the adhesion between the tip of the first layer and the member to be cleaned may be lowered, and a cleaning failure may easily occur. In order to suppress such local plastic deformation, it is preferable that the tip of the first layer always has a stick-and-slip behavior, and for this purpose, a temperature 10 which is a substantial lower limit of the use environment temperature. In an environment of ° C or higher, the rebound resilience R is preferably 10% or higher, more preferably 15% or higher, and still more preferably 20% or higher.
The rebound resilience R can be measured based on JISK6255 (1996) as described above.

The 100% modulus M shown in the formula (1) is measured at a tensile speed of 500 mm / min using a dumbbell-shaped No. 3 test piece in accordance with JISK6251 (1993). Asked. 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 JISK6251 (1993), a dumbbell-shaped No. 3 test piece was used and measured at a tensile speed of 500 mm / min, and obtained from stress at 100% strain and 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 of the first layer that comes into contact with the surface of the member to be cleaned, the glass transition temperature of the soft segment material and the hard segment material described later, the temperature dispersion is measured by a viscoelasticity measuring device, It was determined as the peak temperature of tan δ (loss tangent).

Here, the tan δ value is derived from the storage and loss elastic modulus described below.
When a sinusoidal distortion is applied to the linear elastic body in a steady vibration manner, the stress is expressed by the following equation (4). | E ^* | is called the complex elastic modulus. Further, from the theory of rheology, the elastic body component is represented by equation (5), and the viscous body component is represented by equation (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 shown in Equation (7), and is called “loss sine”. The larger the value, the more the linear elastic body has rubber elasticity. .
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 using a 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 first layer material used in the cleaning blade of the present invention is excellent in both wear resistance and chipping resistance, and can maintain good cleaning performance for a long period of time.
For this reason, in order to deal with foreign matter existing on the surface of the member to be cleaned, particularly foreign matter buried or fixed on the surface, such as foreign matter buried or fixed on the surface of the image carrier with the occurrence of BCO, 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, the cleaning device, and the image forming apparatus provided with the cleaning blade of the present invention, and to reduce the maintenance cost. In particular, the above-described merit can be further enjoyed with a process cartridge or an image forming apparatus provided with both the image carrier having improved surface wear resistance and the cleaning blade of the present invention.

The material satisfying the formulas (1) to (3) is not particularly limited as long as it is an elastomer material containing at least one selected from an acrylic resin, a polybutadiene resin, and an epoxy resin, but an elastomer material including a hard segment and a soft segment It is particularly preferred that 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 −30 ° 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 within the range of 30 to 100 ° C. The glass transition temperature of the material constituting the soft segment (hereinafter sometimes referred to as “soft segment material”) is preferably −100 to − It is preferably within the range of 50 ° C, and more preferably within the range of -90 to -60 ° C.

In addition, when using the hard segment material and the soft segment material having the glass transition temperature as described above, the mass ratio of the material constituting the hard segment to the total amount of the hard segment material and the 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 first layer becomes insufficient, and the early cleaning causes a failure to maintain good cleaning properties for a long period of time. There is. In addition, when the hard segment material ratio exceeds 96% by mass, the tip of the first layer 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. In addition, when the weight average molecular weight exceeds 4000, the permanent deformation of the polyurethane resin constituting the hard segment increases, and the tip of the first layer cannot maintain the contact pressure against the member to be cleaned, resulting in poor cleaning. May occur.
Examples of the polyurethane resin used as the hard segment material as described above include Daicel Chemical Industries, Plaxel 205, Plaxel 240, and the like.

Moreover, as a soft segment material when using a polyurethane resin as a hard segment material, it is preferable to use (1) a resin having a functional group capable of reacting with an isocyanate group. The physical properties of this resin are as follows: (2) Glass transition temperature is 0 ° C. or lower, (3) Viscosity at 25 ° C. is in the range of 600-35000 mPa · s, (4) Weight average molecular weight is in the range of 700-3000. Preferably there is. If these physical properties are not satisfied, the moldability in producing the first layer member 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 (1) to (4) can be appropriately 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 property. 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, Acto Flow (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 such an epoxy resin, for example, in terms of molecular structure, a resin having a structure (flexible skeleton) that can increase the mobility of the main chain in the main chain structure is suitable. Examples thereof include an alkylene skeleton, a cycloalkane skeleton, a polyoxyalkylene skeleton, and the like, 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 in the range of 900 ± 100, the viscosity at 25 ° C. is preferably in the range of 15000 ± 5000 mPa · s, and more preferably in the range of 15000 ± 3000 mPa · s. preferable. As an epoxy resin which has such a characteristic, Dainippon Ink and Chemicals make, EPLICON EXA-4850-150 etc. can be mentioned, for example.

  As a method for producing the member for the first layer, a conventionally known method can be used according to the raw materials used for the production. For example, a sheet is formed using centrifugal molding, extrusion molding, or the like, and is formed into a predetermined shape. It can be produced by cutting.

-Back layer-
Since the cleaning blade of the present invention has a multi-layer structure in which a back layer is further provided on the back surface of the first layer described above, the back layer plays a role of supporting the first layer, and the single layer blade is formed. In comparison, it is possible to effectively prevent the occurrence of sag (permanent deformation) and maintain good cleaning performance over a long period of time.

-Sag (permanent deformation) suppression From the viewpoint of further reliably preventing the occurrence of sagging (permanent deformation), it is preferable that the permanent elongation of the material used for the back layer is smaller than the permanent elongation of the material of the first layer. . By providing a back surface layer having excellent permanent elongation properties on the back surface of the first layer, the back surface layer functions more effectively as a support layer in terms of suppressing drooping.
The ratio of the permanent elongation of the first layer material to the permanent elongation of the back layer material (first layer: back layer) is preferably 1: 0.1 to 1: 0.9, It is more preferably 1: 0.1 to 1: 0.7, and particularly preferably 1: 0.1 to 1: 0.6.

Here, a method for measuring the permanent elongation (%) will be described.
In accordance with JIS K6262 (1997), a strip-shaped test piece is used, and 100% tensile strain is applied and left for 24 hours.
Ts = (L2-L0) / (L1-L0) × 100
Ts: Permanent elongation
L0: Distance between marked lines before pulling
L1: Distance between marked lines when pulling
L2: Distance between marked lines after pulling

  What can be used for the back layer as a material having a smaller permanent elongation than the material of the first layer is determined by the relative relationship with the material of the first layer. Can be mentioned.

  As a main material, a prepolymer produced by mixing diphenylmethane-4,4-diisocyanate with dehydrated polytetramethyl ether glycol and reacting it, and using a combination of 1,4-butadiol and trimethylolpropane as curing agents Is preferred. In addition, you may add additives, such as a reaction regulator.

  The permanent elongation of the back layer can be controlled by adjusting the conventionally known methods, that is, the main materials and additives, their contents, and the like.

-Environmental dependency Moreover, it is preferable that the material for back layers listed above plays a role of supporting the first layer also from the viewpoint of environmental dependency. As described above, 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. The contact pressure of the cleaning blade, for example, with respect to the temperature change within the temperature range. It changes it is not preferable that, from the point of view, the hardness change ratio in at 10 to 60 ° C. of the material of the back layer is not smaller than the rate of change of the hardness of the material of the first layer. By providing a material with a small rate of change in hardness due to temperature changes as the back layer, the back layer supports the first layer in terms of environmentally dependent changes in contact pressure, and a cleaning blade that satisfactorily suppresses changes in contact pressure can do.
The ratio of the hardness change rate of the first layer material to the hardness change rate of the back layer material (first layer: back layer) is 1: 0.1 to 1: 0.9. Is more preferable, 1: 0.1 to 1: 0.8 is more preferable, and 1: 0.1 to 1: 0.7 is particularly preferable.

Here, a method for measuring the rate of change in hardness at 10 to 60 ° C. will be described.
According to JIS K6263 (1997), the hardness of samples stored in 10 ° C and 60 ° C constant temperature baths was measured using a durometer A type, and the difference between the hardness at 10 ° C and the hardness at 60 ° C. Asked.

Further, as described above, since the operating environment temperature of the cleaning blade is in the range of about 10 to 60 ° C., when the glass transition temperature Tg of the material of the back layer exceeds the operating environment temperature, the rubber-like property disappears, and the contact pressure of the cleaning blade May become unstable. Therefore, it is preferable that the glass transition temperature Tg of the material of the back layer is also not more than the lower limit (10 ° C.) of the use environment temperature, as in the first layer.
Tg can be measured by the same method as in the case of the first layer.

  As the method for producing the member for the back layer, a conventionally known method can be used according to the raw materials used for production. For example, a sheet is formed using centrifugal molding or extrusion molding, and is cut into a predetermined shape. It can be produced by processing.

-Manufacturing method of cleaning blade-
In addition, the cleaning blade of the present invention is produced by bonding the first layer and the back layer obtained as described above (a plurality of back layers in the case of three or more layers) to each other. be able to. As the bonding method, a double-sided tape, various adhesives and the like are preferably used.
Also, the cleaning blade of the present invention can be obtained by pouring the material of each layer with a time difference at the time of molding and bonding the materials without providing an adhesive layer.

The edge wear resistance and chipping resistance in the cleaning blade of the present invention are determined by the performance of the portion that contacts and rubs against the surface of the member to be cleaned, and from this viewpoint, the thickness of the first layer is 0.1 mm or more. It is more preferable that it is 0.3 mm or more.
In addition, the thickness of the first layer should be 35% or less with respect to the total thickness of the cleaning blade in order to exhibit the effect of support by the back layer (prevention of sagging, improvement of environmental dependency, etc.). Is more preferable, and more preferably 30% or less.
Furthermore, the thickness of the entire cleaning blade is preferably 1.5 to 2.5 mm, more preferably 1.8 to 2.2 mm, from the viewpoint that an appropriate stiffness to ensure an appropriate contact pressure is necessary. .

  When cleaning a member to be cleaned using the cleaning blade of the present invention, the member to be cleaned is not particularly limited as long as it is a member that requires surface cleaning in the image forming apparatus, For example, an intermediate transfer body, a charging roll, a transfer roll, a transfer material transport belt, a paper transport roll, and a detoning roll that further removes toner from a cleaning brush that removes toner from the image holding body may be used. In particular, an image carrier is particularly preferable.

  When the cleaning blade of the present invention is used, the surface of various members to be cleaned as described above can be suppressed while suppressing the occurrence of chipping caused by foreign matters such as carrier pieces buried or fixed on the surface of the image carrier by the generation of BCO. The toner, external additives, discharge products, talc, paper dust, and other deposits adhered to the toner can be stably cleaned over a long period of time.

(Cleaning device, process cartridge and image forming device)
Next, a cleaning device, a process cartridge, and an image forming apparatus using the cleaning blade of the present invention will be described.
The cleaning device of the present invention is not particularly limited as long as the cleaning blade that contacts the surface of the member to be cleaned and cleans the surface of the member to be cleaned is provided with the cleaning blade of the present invention. For example, as a configuration example of the cleaning device, a cleaning blade is fixed in a cleaning case having an opening on the member to be cleaned side so that the edge tip is on the opening side, and recovered from the surface of the member to be cleaned by the cleaning blade. For example, a configuration including a conveyance member (conveyance auger) that guides foreign matters such as the waste toner to the foreign matter collection container. Further, two or more cleaning blades of the present invention may be used in the cleaning device of the present invention.

When the cleaning blade of the present invention is used for cleaning the image carrier, the force NF (Normal Force) against which the cleaning blade is pressed against the image carrier is 2. The range of 0 to 5.0 gf / mm is preferable, the range of 3.0 to 4.0 gf / mm is more preferable, and the length d that the tip of the cleaning blade bites into the image carrier is 0.00. It is preferably in the range of 4 to 1.6 mm, more preferably in the range of 0.8 to 1.2 mm, and the angle W / A (Working Angle) at the contact portion between the cleaning blade and the image holding member is 8. It is preferably in the range of 0.1 to 14.0 °, more preferably in the range of 11 to 13 °, and it hits 1 mm in the axial direction of the cleaning blade. Preferably the Young's modulus E is in the range of 60~130gf / mm ^2, and more preferably in the range of 80~100gf / mm ^2.

When cleaning, an abrasive or a lubricant is interposed between the cleaning blade and the image carrier, and the NF, the biting length, the angle W / A, and the Young's modulus E are adjusted within the above-described ranges. Since the cleaning blade of the present invention exhibits a characteristic that it extends well following the rotation of the image carrier, it is possible to increase the amount of abrasive and lubricant held in the contact portion between the cleaning blade and the image carrier.
Therefore, when the amount of the abrasive held in the close contact portion is increased, it is possible to improve the scraping property of the discharge product that is the cause of image drift as a result, and the lubricant held in the close contact portion As the amount increases, it is possible not only to improve the scraping property of the discharge product, but also to reduce the wear of the blade tip and the photoreceptor.
As a supply source of the abrasive or lubricant, an abrasive or lubricant externally added to the toner, a solid abrasive that contacts a medium such as a brush that contacts the image carrier, or the like can be used.

Further, the image holding member is positioned on the upstream side of the rotation direction of the image holding member with respect to the rotation direction of the image holding member and on the downstream side of the toner image transfer portion. It is preferable to provide a toner holding member so as to come into contact.
In this case, since the discharge product on the surface of the toner holding member and the toner image holding member attached to the toner holding member is removed, the image drift due to the discharge product can be significantly reduced. In addition, since friction between the cleaning blade and the image carrier is reduced, blade wear can be reduced over a long period of time.

The toner holding member is preferably vibrated parallel or perpendicular to the rotation direction of the image holding member. By virtue of the vibration of the toner holding member, the discharge products are more efficiently removed, and the image blur can be further suppressed.
Further, the toner is accumulated in a region downstream of the rotation direction of the image carrier with respect to the rotation direction of the image carrier from the side where the toner holding member is provided and upstream of the rotation direction where the cleaning blade is provided. It is also preferable to form As a result, the toner in the toner reservoir adsorbs the discharge product, so that the image drift can be further suppressed.

As a material constituting the portion of the toner holding member that comes into contact with the image holding body, for example, a nonwoven fabric or a brush can be used, and a cloth made of other fibers may be used. When a non-woven fabric is used, a sponge is attached to the lower part of the non-woven fabric and the sponge is fixed to SUS or a metal shaft. The non-woven fabric may be rolled.
As the power for vibrating the toner holding member, an external power source such as a motor may be used, or the driving force of the image holding body or other image forming apparatus may be transmitted to the toner holding member via a gear or the like. . The period of vibration is preferably 0.1 to 5 seconds so that the toner does not leave the toner holding member.

In addition, when the cleaning blade is fixed to the cleaning device main body via a metal leaf spring so that the cleaning blade faces upward with respect to the direction of gravity, the toner reservoir is made of resin such as polyester on the sheet metal. It is possible to form the tape by uniformly sticking the tape made of in the axial direction of the cleaning blade. Here, the tip of the tape is attached so as to protrude from the tip of the cleaning blade.
As a result, the toner removed by the cleaning blade accumulates in the area partitioned by the tape, and when a certain amount or more of toner accumulates in the partitioned area, it contacts the image carrier.

A part of the toner accumulated in the toner reservoir in this way comes into contact with the image carrier and adsorbs the discharge product on the surface of the image carrier, and as a result, image blur due to the discharge product can be suppressed.
The amount of toner retained in the toner reservoir can be adjusted by changing the material, length, or thickness of the tape, and the toner in the toner reservoir can be circulated by providing a hole through which the toner can be removed. It is also possible to improve the scraping property of the discharge product by forming a toner reservoir with newly entered toner as needed. In addition, when positively utilizing the scraping property with respect to the discharge product due to the toner reservoir, the pressing force of the toner holding member against the image holding member is reduced so that the discharge product is placed between the toner holding member and the toner reservoir. Only a fixed amount may be removed.

On the other hand, charging of the image carrier is performed using discharge by a charging means such as a charging roll, and the amount of discharge required to charge the surface of the image carrier to a predetermined potential depends on the thickness of the image carrier, the image It varies depending on the temperature and humidity around the forming device.
Regarding the film thickness of the image carrier, since the discharge amount for obtaining a specific charging potential is generally smaller as the image carrier is smaller, the amount of discharge products generated can be minimized by adjusting the discharge amount according to the film thickness. It is possible to limit to the limit. Also, the higher the temperature and the higher the humidity, the smaller the amount of discharge for obtaining a specific charging potential. Therefore, by adjusting the amount of discharge according to the temperature or humidity, the amount of discharge products generated can be minimized. It is possible. The amount of discharge is defined by the AC current Iac of the scorotron or charging roll used as the charging means.
Therefore, by detecting the film thickness and temperature / humidity of the image carrier by some means, and defining the minimum amount of discharge based on the result, the amount of discharge products that cause image flow can be reduced. It is also effective to suppress it. As a result, even if image flow occurs, the degree becomes relatively light. In addition, if the cleaning blade of the present invention is used in such a situation, it is easy to remarkably suppress image flow.

  On the other hand, the process cartridge of the present invention is provided with the cleaning device of the present invention as a cleaning device that contacts the surface of one or more members to be cleaned such as an image carrier or an intermediate transfer member and cleans the surface of the member to be cleaned. If it is, it will not specifically limit, For example, the aspect etc. which are detachable with respect to an image forming apparatus are mentioned including the image holding body and the cleaning apparatus of this invention which cleans the surface of this image holding body. For example, in the case of a so-called tandem machine having an image carrier corresponding to each color toner, the cleaning device of the present invention can be provided for each image carrier. In addition to the cleaning device of the present invention, a cleaning brush or the like may be used as necessary.

-Image carrier (photoreceptor)-
As an image carrier used in a process cartridge or an image forming apparatus, a known photoconductor such as an organic photoconductor, an inorganic photoconductor such as an amorphous silicon photoconductor or a selenium photoconductor can be used. An organic photoreceptor having excellent advantages in terms of manufacturability and discardability is preferably used.
The organic photoreceptor is not particularly limited as long as it has a configuration in which at least a photosensitive layer is provided on a conductive substrate. In the present invention, a charge generation layer and a charge transport layer are provided on a conductive substrate. An organic photoreceptor having function-separated photosensitive layers laminated in this order is suitable for the expression of the cleaning effect. Further, a surface protective layer can be provided on the surface of the photosensitive layer, if necessary, or an intermediate layer can be provided between the photosensitive layer and the conductive substrate, or between the photosensitive layer and the surface protective layer, if necessary.

  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.
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 transport 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, but are not limited to, hole transporting compounds. These charge transport materials can be used alone or in combination of two or more. 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.
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. m and n are integers of 0-2.

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.

  Additives such as antioxidants, light stabilizers, and heat stabilizers are added to the photosensitive layer to prevent photoconductor deterioration caused by ozone, oxidizing gas, or light or heat generated in the copying machine. can do. 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.

In addition, at least one kind of electron accepting substance can be contained for the purpose of improving sensitivity, reducing residual potential, and reducing fatigue during repeated use. Examples of the electron acceptor usable in the photoreceptor used in the present invention include succinic anhydride, maleic anhydride, dibromomaleic anhydride, phthalic anhydride, tetrabromophthalic anhydride, tetracyanoethylene, tetracyanoquinodimethane, Examples include o-dinitrobenzene, m-dinitrobenzene, chloranil, dinitroanthraquinone, trinitrofluorenone, picric acid, o-nitrobenzoic acid, p-nitrobenzoic acid, and phthalic acid. Of these, benzene derivatives having electron-withdrawing substituents such as fluorenone, quinone and Cl, CN, NO ₂ are particularly preferred.

The outermost surface of the image carrier is preferably composed of a layer containing fluorine resin particles such as PTFE (polytetrafluoroethylene) or a layer containing a resin having a crosslinked structure.
When the photosensitive layer of the image carrier is a function-separated type photosensitive layer in which a charge generation layer and a charge transport layer are laminated in this order on a conductive substrate, the charge transport layer contains fluorine-based resin particles. Alternatively, the surface protective layer provided on the charge transport layer may contain a resin having a crosslinked structure.

When a charge transport layer containing fluororesin particles is provided on the surface of the image carrier, the friction force between the cleaning blade and the surface of the image carrier is reduced to reduce scratches and wear on the surface of the image carrier and the edge of the edge of the cleaning blade. Suppression and wear can be suppressed, the life of the image carrier can be extended, and the gap between the image carrier and the cleaning blade can be suppressed for long-term use. Become.
The content in the case where the fluorine resin particles are added to the charge transport layer is preferably 0.1 to 40% by mass, more preferably 1 to 30% by mass, particularly with respect to the total amount of the material constituting the charge transport layer. Is preferably 3 to 10% by mass. If the content is less than 0.1% by mass, the effect of reducing the friction due to the dispersion of the fluororesin particles may be insufficient when the charger of the image carrier is a contact charger. On the other hand, if it exceeds 40% by mass, the light transmission property and charge transport property of the charge transport layer are remarkably lowered, and the residual potential may be increased by repeated use.

The fluororesin particles that can be used in the present invention include ethylene tetrafluoride resin, trifluoroethylene chloride resin, hexafluoropropylene resin, vinyl fluoride resin, vinylidene fluoride resin, difluoride dichloride. It is desirable to appropriately select one or two or more of ethylene resins and copolymers thereof, but particularly preferred are tetrafluoroethylene resin and vinylidene fluoride resin.
Moreover, the primary average particle diameter of the fluororesin particles is preferably 0.05 to 1 μm, and more preferably 0.1 to 0.5 μm. When the primary average particle size is less than 0.05 μm, aggregation at the time of dispersion may easily proceed, and when it exceeds 1 μm, image quality defects may easily occur.

When a surface protective layer containing a resin having a crosslinked structure is provided on the surface of the image carrier, 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 cross-linked structure have excellent body wear properties, 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 more preferable that the resin having a crosslinked structure further contains a charge transporting material.
Although various materials can be used as the resin having a crosslinked structure, phenolic resins, urethane resins, siloxane resins and the like are preferable in terms of characteristics, and those made of siloxane resins are particularly preferable. Of these, those having a structure derived from the compounds represented by the 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 transporting ability, D is a flexible subunit, R ² is hydrogen, an alkyl group, a substituted or unsubstituted aryl group, and Q is a hydrolyzed group. Represents a decomposable 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 each a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a phenyl group substituted with an alkoxy group having 1 to 4 carbon atoms, or an unsubstituted phenyl group; It is selected from aralkyl groups having 7 to 10 carbon atoms and 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.

As the specific structure of Ar ₅ in the formula (III), when k = 0 is, _Ar 1 to Ar ₄ of the m = 1 of the structure shown in the structural group 1, when k = 1 is , 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 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) to 26, but the present invention is not limited thereto.

In addition, 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, an 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 (VI) 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). Tri- and tetrafunctional alkoxysilanes are preferable for improving the strength of the film, and bi- and monofunctional alkoxysilanes are preferable for improving flexibility and film-forming properties.

  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 as shown in 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, an alkyl group, a substituted or unsubstituted aryl group, Q represents a hydrolyzable group, and a represents an integer of 1 to 3.
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. Examples of such resins 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, acetoacetal, or the like (for example, SREC B manufactured by Sekisui Chemical Co., Ltd.) , K, etc.), 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 has been 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 those having an average particle diameter of 1 to 100 nm, preferably 10 to 30 and dispersed in an organic or alkaline solvent such as an alcohol, ketone or ester. A commercially available product can be used. The solid content of colloidal silica in the outermost surface layer is not particularly limited, but is 0.1 to 50% by mass in the total solid content of the outermost surface layer in terms of film forming properties, electrical characteristics, and strength. Is used, preferably 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. That is, 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 maintain good wear resistance and contamination resistance adhesion over a long period of time. The content of the silicone particles in the outermost 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 in the total solid content of the outermost surface layer. It is.

Other particles include fluorine-based particles such as ethylene tetrafluoride, ethylene trifluoride, propylene hexafluoride, vinyl fluoride, vinylidene fluoride, and "8th Polymer Materials Forum Lecture Proceedings p89". Particles made of a resin obtained by copolymerizing the fluororesin and a monomer having a hydroxyl group as shown in FIG. 1, ZnO—Al ₂ O ₃ , SnO ₂ —Sb ₂ O ₃ , In ₂ O ₃ —SnO ₂ , ZnO—TiO Examples thereof include semiconductive metal oxides such as ₂ , 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.

  The exposure rate of the particles to the protective layer surface is preferably 40% or less. If 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 member, 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 wear of the cleaning member 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 protective layer, which is effective in improving the potential stability and image quality when the environment changes. Antioxidants include the following compounds, such as “Sumizer BHT-R”, “Sumizer MDP-S”, “Sumizer BBM-S”, “Sumizer WX-R”, “Sumizer NW” as hindered phenols, “Sumilizer BP-76”, “Sumilizer BP-101”, “Sumilizer GA-80”, “Sumilizer GM”, “Sumilizer GS” or more manufactured by Sumitomo Chemical Co., Ltd., “IRGANOX1010”, “IRGANOX1035”, “IRGANOX10X”, “98” ”,“ IRGANOX1135 ”,“ IRGANOX1141 ”,“ IRGANOX1222 ”,“ IRGANOX1330 ”,“ IRGANOX1 25WL ”,“ IRGANOX1520L ”,“ IRGANOX245 ”,“ IRGANOX259 ”,“ IRGANOX3114 ”,“ IRGANOX3790 ”,“ IRGANOX5057 ”,“ IRGANOX565 ”or more manufactured by Ciba Specialty Chemicals, Inc.,“ Adekastab AO-20 ”,“ Adekastab A ” "ADK STAB AO-40", "ADK STAB AO-50", "ADK STAB AO-60", "ADK STAB AO-70", "ADK STAB AO-80", "ADK STAB AO-330" and more As the amine system, “Sanol LS2626”, “Sanol LS765”, “Sanol LS770”, “Sanol LS744”, “Tinuvin 144”, “Tinuvin 622LD”, “Mark LA57”, “Mark LA67”, “Mark LA62”, “Mark LA68”, “Mark LA63”, “Smilizer-TPS”, “Smilizer-TP-D” as thioether system, “Mark 2112” as phosphite system, “Mark PEP · 8 ”,“ Mark PEP · 24G ”,“ Mark PEP · 36 ”,“ Mark 329K ”,“ Mark HP · 10 ”, 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 coating solution used for forming the protective layer or a catalyst when preparing the coating solution. 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 Alkaline catalysts such as sodium, calcium hydroxide, ammonia, triethylamine, etc., and solid catalysts insoluble in the system shown below 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.) ); Levacit SPC-108, Levacit 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 resin such as Nafion-H (manufactured by DuPont); Amberlite IRA-400, Amberlite IRA-45 (manufactured by Rohm and Haas) ) And the like; 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 acid 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 appropriately 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. 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. Such catalysts include, in addition to those described above, 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) Organic aluminum compounds such as aluminum tris (trifluoroacetylacetonate) and aluminum tris (hexafluoroacetylacetonate) It is possible to use.

  Besides organic aluminum compounds, organic compounds such as dibutyltin dilaurate, dibutyltin dioctiate, 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 such multidentate ligands include those shown below and those derived therefrom, but the present invention is not limited to these.

Specifically, β-diketones such as acetylacetone, trifluoroacetylacetone, hexafluoroacetylacetone, and dipivaloylmethylacetone; acetoacetates 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 organic ligands as described above, inorganic ligands such as pyrophosphoric acid and triphosphoric acid can be exemplified. 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 those in which R ⁵ and R ⁶ in the following general formula (VII) are the same are particularly preferable. By making R ⁵ and R ^{6 the} same, the coordination power of the ligand near room temperature (20 ° C. to 25 ° C.) becomes strong, and the coating liquid can be further stabilized.

In general formula (VII), R ⁵ and R ⁶ each independently represent 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 And various other solvents can be used. As such a 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. .

  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 protective layer obtained by curing the coating solution in a high humidity state is effective in stabilizing the characteristics of the protective layer. Furthermore, depending on the application, the protective layer may be subjected to a surface treatment using hexamethyldisilazane, trimethylchlorosilane, or the like to make it hydrophobic.

  A resin layer having a charge transporting property and also including a resin having a cross-linked structure has excellent mechanical strength and sufficient photoelectric properties, so that it can be used as it is as a charge transport layer of a multilayer photoreceptor. You can also. 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 binder resins as those used for the charge generation layer and the charge transport layer can be used. The content of the charge generating material in the single-layer type photosensitive layer is about 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 solvent and coating method used for coating can be the same as described above. The film thickness is preferably about 5 to 50 μm, more preferably 10 to 40 μm.

-Toner-
The toner used in the image forming apparatus having the process cartridge and the cleaning apparatus of the present invention and the image forming apparatus of the present invention is not particularly limited as long as it is a known toner, but the toner has a shape factor SF of less than 140. Preferably there is. 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 SF is a value defined by the following equation (13).
Formula (13) SF = ML ² / (4A / π)
Here, ML represents the maximum toner length (μm), and A represents the toner projected area (μm ² ).

The shape factor SF 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 the 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 usually 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 such as: carnauba wax, rice wax, candelilla wax, tree wax, jojoba oil, etc .; animal waxes such as beeswax; montan wax, ozokerite, ceresin, paraffin wax, microcrystalline Examples thereof include mineral-based or petroleum-based waxes such as wax and Fischer-Tropsch wax, 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. Further, if necessary, a charge control agent usually used such as a quaternary ammonium salt, a nigrosine compound or a triphenylmethane pigment may be appropriately selected and contained.

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.
Further, the toner used in the present invention is appropriately externally added with inorganic particles such as silica and titania having an average particle diameter of about 10 to 300 nm, an abrasive of about 0.2 to 3 μm, and a lubricant of about 3 to 15 μm. be able to. The toner thus obtained can be mixed with, for example, a carrier made of ferrite beads having an average particle diameter of 35 μm to obtain a two-component developer.

-Specific examples of cleaning blades, image forming devices, and cleaning devices-
Next, specific examples of the cleaning blade of the present invention, and an image forming apparatus and a cleaning apparatus using the cleaning blade will be described in more detail with reference to the drawings.
FIG. 1 is a schematic diagram showing an example of an image forming apparatus according to the present invention, which shows a so-called tandem type image forming apparatus.
In FIG. 1, 21 is a main body housing, 22 and 22a to 22d are image forming engines, 23 is a belt module, 24 is a recording material supply cassette, 25 is a recording material conveyance path, 30 is each photosensitive unit, and 31 is a photosensitive drum. , 33 are each developing unit, 34 is a cleaning device, 35, 35a to 35d are toner cartridges, 40 is an exposure unit, 41 is a unit case, 42 is a polygon mirror, 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 roll, 68 is a paper discharge unit, 71 is a manual feed device, 72 is a feed roll, and 73 is Double-sided recording unit, 74 is a guide roll, 76 is a conveyance path, 77 is a conveyance roll, 230 is an intermediate transfer belt, 31,232 is the tension roll, 521 secondary transfer roll, 531 denotes a cleaning blade.

  The tandem type image forming apparatus shown in FIG. 1 has an image forming engine 22 (specifically, 22a to 22d) of four colors (black, yellow, magenta, and cyan in this embodiment) arranged in a main body housing 21. Above that, 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 disposed, while a recording material such as paper (see FIG. In addition, a recording material supply cassette 24 that accommodates a recording material is disposed, and a recording material conveyance path 25 that serves as a conveyance path for the recording material from the recording material supply cassette 24 is arranged 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, and each photosensitive unit 30, each developing unit 33, and one common exposure unit 40 are provided.
Here, the photosensitive unit 30 includes, for example, a photosensitive drum 31, a charging device (charging roll) 32 that charges the photosensitive drum 31 in advance, and a cleaning device 34 that removes residual toner on the photosensitive drum 31. It is an integrated sub-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 photosensitive unit 30 may be separated from the developing unit 33 to form a single process cartridge. In FIG. 1, 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 mirrors (see FIG. (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 via 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 material.

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

Further, in the present embodiment, a manual feed device (MSI) 71 is provided on the side of the main body housing 21, and the recording material on the manual feed device 71 is recorded by the feed roll 72 and the takeaway roll 62. It is sent out toward the material conveyance path 25.
Further, the main body housing 21 is provided with a double-sided recording unit 73. The double-sided recording unit 73 discharges the recording material on which single-sided recording has been performed when the double-sided mode in which image recording is performed on both sides of the recording material is selected. 67 is reversed and taken in by the guide roll 74 in front of the entrance, and the recording material is conveyed along the internal recording material 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 type image forming apparatus shown in FIG. 1 will be described in detail.
FIG. 2 is a schematic cross-sectional view showing an example of the cleaning device of the present invention, in which 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. 2, 32 is a charging roll (charging device), 331 is a unit case, 332 is a developing roll, 333 is a toner conveying member, 334 is a conveying paddle, 335 is a trimming member, 341 is a cleaning case, 342 is a cleaning blade, 344 Indicates a film seal and 345 indicates 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.

Next, the cleaning blade provided in the cleaning device 34 will be described in detail with reference to the drawings.
FIG. 3 is a schematic cross-sectional view showing an example of the cleaning blade of the present invention, and shows the cleaning blade 342 shown in FIG. 2 together with the photosensitive drum 31 in contact therewith. Here, in FIG. 3, 342a represents a cleaning first layer, and 342b represents a back layer.
The cleaning blade 342 shown in FIG. 3 includes a cleaning first layer 342a that comes into contact with the photosensitive drum 31, and a back layer 342b provided on the surface of the cleaning first layer 342a opposite to the surface on which the photosensitive drum 31 is provided. And consists of two layers.

  Here, the thickness of the cleaning first layer 342a is adjusted to 0.5 mm, and the thickness of the back layer 342b is adjusted to 1.5 mm. Note that the cleaning blade 342 can be manufactured by, for example, pasting the cleaning first layer 342a and the back layer 342b prepared in a sheet shape in advance using 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 in order with a time difference.

The contact pressure of the cleaning blade 342 with respect to the photosensitive drum 31 is set to about 2.0 to 5.0 gf / mm (= 2.0 to 6.0 × 10 ⁻³ × 9.8 N / mm).
In this embodiment, the cleaning blade of 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 cleaning used in the belt cleaning device 53 is used. The blade 531 may also be the cleaning blade of 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. . Here, a developing roll 332 is disposed at a position facing the opening of the unit case 331, and a toner conveying member 333 for agitating and conveying the developer is disposed in the unit case 331. Furthermore, a transport paddle 334 can be disposed between the developing roll 332 and the toner transport member 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.
When a two-component developer is used, the carrier piece may be buried or fixed on the surface of the photosensitive drum 31 with the generation of BCO. However, even in this case, since the cleaning device 34 includes the cleaning blade of the present invention, it is possible to maintain good cleaning performance while suppressing the occurrence of chipping over a long period of time.
As the toner used in the present embodiment, the toner described above can be used, but the shape factor SF is preferably less than 140 from the viewpoint of transferability and image quality.

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 material by the secondary transfer device 52, and the recording material to which the color toner image has been transferred undergoes a fixing process by the fixing device 66. The paper is discharged to a paper 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 such an 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. 4 is a schematic diagram showing an example of the method for fixing the cleaning blade of the present invention, in which 342 denotes a cleaning blade, 342c denotes a spring material, and 342d denotes a holder. As shown in FIG. 4, 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. 4, 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.

  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, a member for the first layer was formed as follows.
First, as the 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 isocyanate compound used in this reaction was selected so that the ratio of isocyanate group to hydroxyl group contained in the reaction system (isocyanate group / hydroxyl group) was 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. 7.40 parts of / 40) was added, and mixed well for 3 minutes so as not to cause foam to prepare composition A1 for forming the first layer.

  Next, the composition A1 for forming the first layer was poured into a centrifugal molding machine whose mold was adjusted to 140 ° C., and a curing reaction was performed for 1 hour to form a flat plate-like first layer.

Moreover, composition A1 for 2nd layer formation prepared with the following method as a member for 2nd layers was prepared.
Diphenylmethane-4,4-diisocyanate was mixed with dehydrated polytetramethyl ether glycol and reacted at 120 ° C. for 15 minutes. Using.

  In addition, the adhesion between the first layer and the second layer is performed by pouring the composition for forming the second layer into a centrifugal molding machine after forming the first layer into a flat plate shape as described above, and curing the composition. A second layer was formed on the back side of the first layer.

  This flat plate is cooled at 110 ° C. for 24 hours and then cooled, cut into predetermined dimensions, and the first layer thickness is 0.5 mm, the second layer thickness is 1.5 mm (the thickness of the first layer relative to the total thickness). A cleaning blade A1 having a ratio of 25%) was obtained.

<Cleaning blade A2>
As the hard segment material, the same hard segment material as that 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 (made by 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 first layer and a second layer were formed in the same manner as the cleaning blade A1 except that the composition for forming the first layer was prepared using this mixture, to obtain a cleaning blade A2.

<Cleaning blade A3>
The hard segment material is the same hard segment material as that used for the cleaning blade A1, and the soft segment material is an epoxy resin containing two or more epoxy groups (Dainippon Ink Chemical Industries, EPICLON EXA-4850). -150), the hard segment material and the soft segment material were mixed in a ratio of 8: 2.
A first layer and a second layer were formed in the same manner as the cleaning blade A1 except that the composition for forming the first layer was prepared using this mixture, to obtain a cleaning blade A3.

<Cleaning blade A4>
In the production of the cleaning blade A1, the mixing ratio of the hard segment material and the soft segment material was 9: 1, and the composition for forming the first layer was prepared using this mixture. A first layer and a second layer were formed to obtain a cleaning blade A4.

<Cleaning blade A5>
In the production of the cleaning blade A1, the mixing ratio of the hard segment material and the soft segment material was set to 96: 4, and the composition for forming the first layer was prepared using this mixture. A first layer and a second layer were formed to obtain a cleaning blade A5.

<Cleaning blade A6>
In the production of the cleaning blade A1, the mixing ratio of the hard segment material and the soft segment material was set to 98: 2, and the composition for forming the first layer was prepared using this mixture. A first layer and a second layer were formed to obtain a cleaning blade A6.

<Cleaning blade B1>
A blade forming composition B1 was prepared using only the polyol component instead of the mixture of the hard segment material and the soft segment material.
Specifically, for 100 parts of Coronate 4086 (manufactured by Nippon Polyurethane Industry Co., Ltd.) as a polyol component, 6.8 parts of Nipponran 4038 (manufactured by Nippon Polyurethane Industry Co., Ltd.) is added as an isocyanate compound, and under a nitrogen atmosphere. The mixture was reacted at 70 ° C. for 3 hours to obtain a prepolymer.

  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. / 40) was added and mixed well for 3 minutes so as not to cause foaming to prepare blade-forming composition B1.

  Next, the blade-forming composition B1 was poured into a centrifugal molding machine whose mold was adjusted to 140 ° C., and cured for 1 hour to form a flat plate. This flat plate was cross-linked at 110 ° C. for 24 hours, cooled, cut to a predetermined size, and a single-layer cleaning blade B1 having a thickness of 2 mm was obtained.

<Cleaning blade B2>
To 100 parts of Coronate 4370 (manufactured by Nippon Polyurethane Industry Co., Ltd.) as a polyol component, 75 parts of Nipponran 4379 (manufactured by Nippon Polyurethane Industry Co., Ltd.) is added as an isocyanate compound and reacted at 70 ° C. for 3 hours in a nitrogen atmosphere. Thus, a prepolymer was obtained.
A single-layer cleaning blade B2 was obtained in the same manner as the cleaning blade B1, except that this mixture was used to prepare a blade-forming composition B2.

<Cleaning blade B3>
To 100 parts of Coronate 4370 (manufactured by Nippon Polyurethane Industry Co., Ltd.) as a polyol component, 85 parts of Nipponporan 4379 (manufactured by Nippon Polyurethane Industry Co., Ltd.) is added as an isocyanate compound and reacted at 70 ° C. for 3 hours in a nitrogen atmosphere. Thus, a prepolymer was obtained.
A single-layer cleaning blade B3 was obtained in the same manner as the cleaning blade B1, except that this mixture was used to prepare the blade-forming composition B3.

<Cleaning blade B4>
To 100 parts of Coronate 4370 (manufactured by Nippon Polyurethane Industry Co., Ltd.) as a polyol component, 90 parts of Nipponran 4379 (manufactured by Nippon Polyurethane Industry Co., Ltd.) as an isocyanate compound was added and reacted at 70 ° C. for 3 hours in a nitrogen atmosphere. Thus, a prepolymer was obtained.
A single-layer cleaning blade B4 was obtained in the same manner as the cleaning blade B1, except that the blade-forming composition B4 was prepared using this mixture.

<Cleaning blade B5>
A cleaning blade B5 having a two-layer structure was obtained in the same manner as the cleaning blade A1, except that the first layer was formed using the blade-forming composition B1 prepared in the production of the cleaning blade B1.

<Cleaning blade B6>
A cleaning blade B6 having a two-layer structure was obtained in the same manner as the cleaning blade A1, except that the first layer was formed using the blade-forming composition B2 prepared in the production of the cleaning blade B2.

<Cleaning blade B7>
A cleaning blade B7 having a two-layer structure was obtained in the same manner as the cleaning blade A1 except that the first layer was formed using the blade-forming composition B3 prepared in the production of the cleaning blade B3.

<Cleaning blade B8>
The first layer and the second layer were formed in the same manner as the cleaning blade B5 except that the second layer member was changed to one having a permanent elongation larger than that of the first layer as shown in Tables 9 to 11 below. A cleaning blade B8 was obtained.

<Cleaning blade B9>
The first layer and the second layer are formed in the same manner as the cleaning blade B5 except that the second layer member is changed to one having a hardness change rate larger than that of the first layer as shown in Tables 9 to 11 below. Thus, a cleaning blade B9 was obtained.

-Production of photoconductor-
<Photoreceptor A>
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 (23 ° C.) for 5 minutes, and then the support is brought to 50 ° C. for 10 minutes. The temperature was raised, and the mixture 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 is 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 24 μm Photoconductor A was obtained.

[Examples 1 to 3 and Comparative Examples 1 to 9]
The cleaning blades A1 to A3 and B1 to B9 described above were attached to an image forming apparatus (Fuji Xerox Co., Ltd., DocuCenter Color 400CP) as shown in the following table, and various evaluations were performed. The results are shown in the table below.
Moreover, the graph which shows the relationship between the distortion amount and stress of the member for 1st layer of the cleaning blade used for Examples 1-3 and the cleaning blade used for Comparative Examples 1-3 is shown in FIG.

The evaluation methods and criteria shown in the above table are as follows.
-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 of the edge of the cleaning blade after image formation was used 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 edge tip 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 photoreceptor surface side was measured.
In addition, the evaluation of the cleaning failure is performed at a normal process speed between A3 paper on which a non-transferred solid image (solid image size: 400 mm × 290 mm) is formed after the above test is completed between the photosensitive member and the cleaning blade. The actual machine is stopped immediately after the end of the feeding direction of the unfixed image after passing through the contact portion between the photoconductor and the cleaning blade, and the presence or absence of toner rub-off is visually checked to make noticeable rubbing. The case where the omission was observed was regarded as poor cleaning.
In addition, when the part that blocks the toner is missing due to wear or chipping at the edge tip, the larger the edge wear depth or chipping depth, the more likely the cleaning failure to occur in the above test. Useful for qualitative evaluation of edge tip wear and chipping.
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 lowered, and a 5 mm width is obtained every 5K cycles in a low-temperature and low-humidity (10 ° C., 15% RH) environment where stress is likely to increase when the cleaning blade collides with foreign matter. 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;

-Photoconductor scratches-
The photoconductor scratches were run for 100,000 cycles, then a halftone image was printed, and the presence or absence of white streaks due to the photoconductor scratches was evaluated on the print. Evaluation criteria for photoconductor scratches are shown below. The allowable range is ◯.
○: No white streak on print ×: White streak on print

-Photoconductor wear rate-
The photoconductor wear rate was calculated as the photoconductor wear rate per 1000 cycles of the photoconductor by measuring the film thickness of the photoconductor before and after the test with an eddy current film thickness meter and calculating the difference between them.

-Sagging (permanent deformation) / Measurement of sagging amount-
The process cartridge with the cleaning blade attached is left in a constant temperature / humidity layer of 45 ° C and 95% RH, which is a high temperature / humidity environment, for 1 week. . The allowable range is 0.2 mm or less.
The amount of biting is measured with a non-contact laser displacement meter (manufactured by Keyence Corporation, product name: LK-035) capable of measuring the distance from the center of the photoconductor to the tip of the cleaning blade edge. Sought change.

-Environment dependency-
A constant temperature bath having a temperature of 10 ° C. and 60 ° C. is prepared in an environment of humidity 50% RH, and the cleaning blade is placed on the plate at 0 mm, 0.4 mm, 0.8 mm, 1.2 mm, and 1. The load applied to the plate when 6 mm was bite in was measured, and the difference in the slope of the load with respect to the amount of biting in the environment of 10 ° C. and 60 ° C. was determined as an indicator of environmental dependence (inclination in the environment of 10 ° C. ÷ 60 ° C. Tilt in the environment). It can be considered that the larger the index is, the greater the environmental dependency is, and the allowable range is 1.2 or less.
In addition, the load applied to the plate is measured by providing the load plate (trade name: LM-1KA, manufactured by Kyowa Denki Co., Ltd.) for measuring the load, and providing the plate with which the blade comes into contact. The load was measured while changing to the above numerical values.

-Cleaning performance-
At the normal process speed with the primary transfer turned off for the untransferred solid image (solid image size: 300 mm × 400 mm) after completion of each test of “edge chipping, photoconductor scratching, sag, environment dependency”. Immediately after the end of the conveyance direction of the unfixed solid image has been formed on the photoconductor and 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 rubbing is visually confirmed. The evaluation was made according to the following criteria.
○: No slip-through △: Scratch-through is observed but slight (no problem such as scraping appearing on the next print)
X: Remarkable abrasion is recognized

[Examples 4 to 6]
The cleaning blades A4 to A6 were attached to an image forming apparatus (manufactured by Fuji Xerox Co., Ltd., DocuCenter Color 400CP) as shown in the following table, and various evaluations such as local edge deformation were performed. The results are shown in the table below.

The evaluation method and evaluation criteria for the local deformation of the edge shown in the above table are as follows.
-Evaluation method of edge local deformation-
The local deformation of the edge is A4 paper (210 x 297 mm) until the cumulative number of revolutions of the photoconductor reaches 100 K cycles in a low-temperature and low-humidity environment (10 ° C, 15 RH%) where the rubber elasticity decreases and the stick and slip behavior becomes dull. , Manufactured by Fuji Xerox Co., Ltd., P paper), the deformation of the edge tip of the cleaning blade after image formation and the cleaning failure 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.

Then, when the deformation | transformation of the edge front-end | tip after a test was observed with the laser microscope VK-8510, it implemented by measuring the width length of the part in which the local deformation | transformation has generate | occur | produced in the width direction of an edge front-end | tip.
In addition, the evaluation of the cleaning failure is performed at a normal process speed between A3 paper on which a non-transferred solid image (solid image size: 400 mm × 290 mm) is formed after the above test is completed between the photosensitive member and the cleaning blade. Feed the paper, stop the actual machine immediately after the end of the unfixed image in the transport direction passes through the contact area between the photoconductor and the cleaning blade, and visually check whether the toner has passed through. The case where remarkable rubbing through was observed so as to correspond to the raised part was regarded as defective cleaning.
The evaluation criteria for edge local deformation are shown below.
○: No local deformation of the edge was observed, and no cleaning failure was caused due to this.
(Triangle | delta): Although local deformation | transformation of the edge was observed, the cleaning defect resulting from this did not generate | occur | produce.
X: Local deformation of the edge was observed, and a cleaning failure due to this was generated.

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. It is a graph which shows the relationship between the amount of distortion and stress of the cleaning blade used for the Example.

Explanation of symbols

21 Main body housing 22, 22a to 22d Image forming engine 23 Belt module 24 Recording material supply cassette 25 Recording material conveyance path 30 Photosensitive unit 31 Photoconductive 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 Takeaway roll 63 Registration roll 66 Fixing device 67 Discharge roll 68 Discharge unit 71 Manual feed device 72 Feed roll 73 Both sides Recording unit 74 Guide roll 76 Conveying path 77 Conveying roll 230 Intermediate transfer belts 231 and 232 Stretching roll 331 Unit case 332 Developing roll 333 Toner conveying member 334 Carrying Paddle 335 trimming member 341 the cleaning case 342 cleaning blade 342a cleaning first layer 342b back layer 342c spring member 342d holder 344 film seal 345 conveying auger 521 secondary transfer roll 531 a cleaning blade

Claims (10)

In the cleaning blade that contacts the surface of the member to be cleaned and cleans the surface of the member to be cleaned,
At least one selected from an acrylic resin, a polybutadiene resin, and an epoxy resin, and a first layer that contacts the surface of the member to be cleaned, and a back layer that does not contact the surface of the member to be cleaned.
Material of the first layer, meets the following formula (1) to (3),
A cleaning blade , wherein a rate of change in hardness of the back layer material at 10 to 60 ° C. is smaller than that of the material of the first layer .
Formula (1) 7.4 ≦ M ≦ 17
Formula (2) 0.039 ≦ α ≦ 0.105
Formula (3) 535 ≧ S ≧ 380
[In the formulas (1) to (3), M represents a 100% modulus (MPa), and α represents a strain amount change (Δ strain amount) when the strain amount is 100% to 200% in the stress-strain curve. Represents the ratio of the stress change (Δ stress) to {Δ stress / Δ strain amount = (stress at strain amount of 200% −stress at strain amount of 100%) / (200−100)} (MPa /%). It represents the elongation at break (%) measured based on JIS K6251 (using dumbbell-shaped No. 3 test piece). ]   The cleaning blade according to claim 1, wherein the breaking elongation S is 500 or less.   The cleaning blade according to claim 1 or 2, wherein a glass transition temperature of the material of the first layer is 10 ° C or less.   The cleaning according to any one of claims 1 to 3, wherein the rebound resilience measured based on JIS K6255 of the material of the first layer is 10% or more under an environment of a temperature of 10 ° C or more. blade.   The cleaning blade according to any one of claims 1 to 4, wherein a thickness of the first layer is 35% or less of a thickness of the entire cleaning blade.   The cleaning blade according to claim 1, wherein a permanent elongation of the material of the back layer is smaller than that of the material of the first layer. The cleaning blade according to any one of claims 1-6, wherein the glass transition temperature of the material of the back layer is 10 ° C. or less. A cleaning device comprising a cleaning blade according to any one of claims 1-7. A process cartridge that is detachable from the image forming apparatus and includes the cleaning device according to claim 8 . A member to be cleaned, and a cleaning blade that contacts the surface of the member to be cleaned and cleans the surface of the member to be cleaned.
An image forming apparatus using the cleaning blade according to any one of claims 1 to 7 as the cleaning blade.

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