JP7206743B2 - Cleaning blade, cleaning device, process cartridge, and image forming apparatus - Google Patents

Description

The present invention relates to cleaning blades, cleaning devices, process cartridges, and image forming apparatuses.

2. Description of the Related Art Conventionally, in electrophotographic copiers, printers, facsimiles, etc., a cleaning blade has been used as a cleaning means for cleaning the surface of a member to be cleaned such as an image carrier to remove residual toner and other objects to be cleaned. ing.

For example, in Patent Document 1, ``A cleaning blade that contacts the surface of a member to be cleaned to clean powder from the surface of the member to be cleaned includes a strip-shaped elastic blade and a ridge at the tip of the elastic blade. and a surface layer having a pencil hardness of 7H or more and a coefficient of friction of 0.1 or more and 0.3 or less."

Further, Japanese Patent Application Laid-Open No. 2002-200000 discloses a cleaning device provided in an image forming apparatus for removing toner from the surface of a rotationally driven image carrier, wherein the edge portion is brought into contact with the surface of the image carrier to clean the toner. A rotating brush is provided on the upstream side of the blade in the rotation direction of the image carrier to supply lubricant by bringing the tip of the brush into contact with the surface of the image carrier, and the blade of the blade A cleaning device characterized in that the material has an impact resilience of 10 to 45% and a Young's modulus of 5 to 11 MPa.

In addition, Patent Document 3 discloses that "at least a part of the surface of a plate-like substrate made of a rubber-like elastic body has a surface layer containing oxygen and gallium elements, and oxygen in the surface layer A blade for an image forming apparatus, wherein the content of is 15 atomic % or more.".

JP 2009-223071 A Japanese Patent Application Laid-Open No. 2007-163708 JP 2009-237158 A

In cleaning means using a cleaning blade, for example, the cleaning blade is pressed against the surface of a member to be cleaned (for example, an image carrier) to dam up and scrape off an object to be cleaned (for example, residual toner) present on the member to be cleaned. Remove by dropping.
Here, for example, in order to meet the recent demand for higher image quality, polymerized toner having a small particle size and a nearly spherical shape formed by a polymerization method or the like is sometimes used. When removing the polymerized toner remaining on the surface of the image carrier with a cleaning blade, the polymerized toner may slip through the gap between the cleaning blade and the surface of the image carrier, resulting in poor cleaning.

As a method of suppressing the cleaning failure due to slip-through, there is a method of increasing the pressure on the member to be cleaned while decreasing the hardness of the cleaning blade. However, in the above method, the abrasion of the cleaning blade and the member to be cleaned may be accelerated due to the increased frictional force of the cleaning blade on the member to be cleaned.
On the other hand, as a method of reducing the rubbing force on the member to be cleaned, there is a method of providing a surface layer containing a metal oxide on the surface of the cleaning blade. When a cleaning member provided with the above-described surface layer is used, the sliding friction force on the member to be cleaned is reduced and wear is suppressed, but the hardness of the cleaning blade increases, making it difficult to obtain initial cleaning performance. be.

Therefore, an object of the present invention is to improve the initial cleaning performance and aging performance compared to a cleaning blade in which the first layer containing a metal oxide and the third layer, which is an elastic layer having a permanent elongation of 2% or less, are in direct contact with each other. To provide a cleaning blade which satisfies both the maintenance of cleaning and the maintenance of cleaning.

The above problems are solved by the following means.

<1>
a first layer comprising a metal oxide;
a second layer which is an elastic layer having a Young's modulus of 4 MPa or more and 8 MPa or less;
a third layer, which is an elastic layer having a permanent elongation of less than 2%;
are provided in this order.

<2>
The cleaning blade according to <1>, wherein the first layer has a thickness of 0.1 μm or more and 5.0 μm or less.

<3>
The cleaning blade according to <2>, wherein the first layer has a thickness of 0.5 μm or more and 5.0 μm or less.

<4>
The cleaning blade according to any one of <1> to <3>, wherein the thickness of the second layer is 20 to 10000 times the thickness of the first layer.

<5>
The cleaning blade according to any one of <1> to <4>, wherein the metal oxide is an oxide of a Group 13 element.

<6>
The cleaning blade according to <5>, wherein the metal oxide is gallium oxide.

<7>
The cleaning blade according to any one of <1> to <6>, wherein the second layer has a Young's modulus of 4 MPa or more and 5.5 MPa or less.

<8>
a first layer having a dynamic friction coefficient of 0.05 or more and 0.5 or less and a Young's modulus of 10 MPa or more and 200,000 MPa or less;
a second layer which is an elastic layer having a Young's modulus of 4 MPa or more and 8 MPa or less;
a third layer, which is an elastic layer having a permanent elongation of less than 2%;
are provided in this order.

<9>
A cleaning device comprising the cleaning blade according to any one of <1> to <8>.

<10>
A process cartridge including the cleaning device according to <9> and detachable from an image forming apparatus.

<11>
an image carrier;
charging means for charging the surface of the image carrier;
electrostatic latent image forming means for forming an electrostatic latent image on the surface of the charged image carrier;
developing means for developing an electrostatic latent image formed on the surface of the image carrier with a developer containing toner to form a toner image;
a transfer means for transferring the toner image onto the surface of a recording medium;
the cleaning device according to <9>, which cleans the surface of the image carrier;
An image forming apparatus comprising:

According to the invention according to <1>, <5>, or <6>, the first layer containing a metal oxide and the third layer, which is an elastic layer having a permanent elongation of less than 2%, are provided in direct contact with each other. Provided is a cleaning blade that achieves both initial cleaning performance and cleaning maintenance over time compared to a cleaning blade.

According to the invention relating to <2>, there is provided a cleaning blade that suppresses deterioration in cleaning performance due to cracks in the first layer, compared to the case where the thickness of the first layer exceeds 5.0 μm.

According to the invention according to <3>, even if the thickness of the first layer is 0.5 μm or more and 5.0 μm or less, the first layer containing a metal oxide and the elastic layer having a permanent elongation of less than 2% Provided is a cleaning blade that achieves both initial cleaning performance and cleaning maintenance over time compared to a cleaning blade provided in direct contact with the three layers.

According to the invention according to <4>, there is provided a cleaning blade in which deterioration of cleaning performance due to cracks in the first layer is suppressed compared to the case where the thickness of the second layer exceeds 10000 times the thickness of the first layer. be done.

According to the invention according to <7>, a cleaning blade is provided that is superior in initial cleaning performance compared to the case where the second layer has a Young's modulus of more than 5.5 MPa.

According to the invention according to <8>, the first layer has a dynamic friction coefficient of 0.05 or more and 0.5 or less and a Young's modulus of 10 MPa or more and 200,000 MPa or less, and the elastic layer has a permanent elongation of less than 2%. Provided is a cleaning blade that achieves both initial cleaning performance and cleaning maintenance over time compared to a cleaning blade provided in direct contact with the third layer.

According to the invention according to <9>, <10>, or <11>, the first layer containing the metal oxide and the third layer, which is an elastic layer having a permanent elongation of less than 2%, are provided in direct contact with each other. A cleaning device, a process cartridge, or an image forming apparatus equipped with a cleaning blade that achieves both initial cleaning performance and maintenance of cleaning performance over time as compared with a cleaning blade is provided.

FIG. 2 is a schematic diagram showing an example of the layer structure of the cleaning blade according to the first aspect; FIG. 3 is a schematic diagram showing an example of the arrangement of the cleaning blade according to the first aspect when in use; It is a schematic diagram which shows an example of the film-forming apparatus used for formation of a 1st layer. 1 is a schematic diagram showing an example of an image forming apparatus according to an exemplary embodiment; FIG. 1 is a schematic cross-sectional view showing an example of a cleaning device according to an embodiment; FIG. FIG. 4 is a diagram for explaining a method of calculating a pressing force NF of a cleaning blade;

An embodiment that is an example of the present invention will be described below.
The descriptions of "parts by mass" and "% by mass" are synonymous with "parts by weight" and "% by weight", respectively.

[Cleaning blade]
<First Aspect>
A cleaning blade according to a first aspect includes a first layer containing a metal oxide, a second layer that is an elastic layer having a Young's modulus of 4 MPa or more and 8 MPa or less, and a third layer that is an elastic layer having a permanent elongation of less than 2%. and are provided in this order.
FIG. 1 shows an example of the layer structure of the cleaning blade according to the first aspect. The cleaning blade 10 shown in FIG. 1 includes a first layer 14 containing a metal oxide, a second layer 16 that is an elastic layer having a Young's modulus of 4 MPa or more and 8 MPa or less, and a second layer 16 that is an elastic layer having a permanent elongation of less than 2%. It is composed of three layers 18 and .
Although the cleaning blade 10 shown in FIG. 1 has the first layer 14, the second layer 16, and the third layer 18 in direct contact with each other, the present invention is not limited to this. The cleaning blade according to the first aspect may have at least the first layer, the second layer, and the third layer in this order, and if necessary, may further have other layers (such as an adhesive layer). may be

Next, the arrangement of the cleaning blade according to the first aspect during use will be described. When using the cleaning blade, for example, the end of the cleaning blade is pressed against the surface of the member to be cleaned (for example, the image carrier) to block and scrape off the cleaning target (for example, residual toner) on the member to be cleaned. Remove. That is, the cleaning blade is arranged and used so as to come into contact with the surface of the member to be cleaned during use.

FIG. 2 schematically shows an example of the arrangement of the cleaning blade according to the first aspect when in use.
As shown in FIG. 2, when the cleaning blade 10 is used, the end portion 12 of the first layer 14 of the cleaning blade 10 contacts the member to be cleaned 20 in a locally warped state (ie, tucked state). there is As the member to be cleaned 20 moves in the direction of the arrow G while the end portion 12 remains in contact with the member to be cleaned 20 , the object to be cleaned T existing on the surface of the member to be cleaned 20 is moved to the end portion of the cleaning blade 10 . 12 is scraped and removed.

Since the cleaning blade according to the first aspect has the above configuration, both initial cleaning performance and cleaning maintenance performance over time are achieved. Although the reason is not clear, it is presumed as follows.

For example, when an image is formed using a polymerized toner having a small particle size and a nearly spherical shape formed by a polymerization method or the like, and then the polymerized toner remaining on the surface of the image carrier is to be removed by a cleaning blade, the cleaning blade and the image are formed. The polymerized toner may slip through the gap between the surface of the holder and the cleaning failure.

As a method of suppressing the cleaning failure due to slip-through, there is a method of increasing the pressure on the member to be cleaned while decreasing the hardness of the cleaning blade. In the above method, although the slip-through is suppressed and good cleaning performance can be obtained in the initial stage, the abrasion of the cleaning blade and the member to be cleaned increases due to the increase in the frictional force of the cleaning blade against the member to be cleaned, which accelerates the wear of the cleaning blade and the member to be cleaned. be. Further, when the abrasion is accelerated, it may be difficult to maintain good cleanability.
On the other hand, as a method of reducing the rubbing force on the member to be cleaned, there is a method of providing a surface layer containing a metal oxide on the surface of the cleaning blade. When the cleaning member provided with the surface layer is used, the hardness of the cleaning blade is increased, so that the edge of the cleaning blade is less likely to warp locally, and the contact area with the member to be cleaned is reduced, thereby improving the initial cleaning performance. It may become difficult to obtain sexuality.

On the other hand, in the first aspect, the second layer, which is an elastic layer whose Young's modulus is in the above range, is interposed between the first layer containing a metal oxide and the third layer, which is an elastic layer whose elongation set is in the above range. It has layers.
Therefore, when the residue is removed by bringing the first layer into contact with the member to be cleaned, the frictional force on the member to be cleaned is reduced due to the low coefficient of friction of the first layer, while the low Young's modulus of the second layer reduces It is considered that the contact area with the member to be cleaned is increased. That is, the cleaning blade in the first aspect is provided with the second layer having a low Young's modulus, so that even if the hardness of the surface in contact with the member to be cleaned (that is, the first layer) is high, local warpage at the end portion can be prevented. is likely to occur, and the contact area is considered to be large. As a result, poor cleaning due to passing through is less likely to occur, and deterioration of cleaning performance due to wear of the member to be cleaned and the cleaning blade is less likely to occur.

In addition, due to the low elongation set of the third layer, even if the cleaning blade is used for a long period of time and the tip of the cleaning blade is locally warped during use, the object to be cleaned may slip through due to fatigue. Hateful. In other words, when the cleaning blade wears out due to long-term use, the contact pressure on the member to be cleaned decreases, which may make it easier for the object to be cleaned to slip through. It is considered that the cleaning maintainability over time is improved because the occurrence of the

From the above, it is presumed that in the first aspect, both the initial cleanability and the cleaning maintainability over time are achieved.

<Second Aspect>
A cleaning blade according to a second aspect includes a first layer having a coefficient of dynamic friction of 0.05 or more and 0.5 or less and a Young's modulus of 10 MPa or more and 200,000 MPa or less, and an elastic layer having a Young's modulus of 4 MPa or more and 8 MPa or less. and a third layer, which is an elastic layer having a permanent elongation of less than 2%, are provided in this order.
In the cleaning blade according to the second aspect, the first layer, the second layer, and the third layer may be arranged in direct contact with each other, and if necessary, another layer (for example, an adhesive layer, etc.) may be further added. may have.
The layer structure and arrangement of the cleaning blade according to the second aspect are the same as those of the first aspect, and thus the description thereof is omitted.

Since the cleaning blade according to the second aspect has the above configuration, both initial cleaning performance and cleaning maintenance performance over time are achieved. Although the reason is not clear, it is presumed to be due to the same action as in the first mode.
Specifically, by providing the second layer, which is an elastic layer having a Young's modulus in the above range, between the first layer and the third layer, the low coefficient of friction of the first layer provides a sliding friction force on the member to be cleaned. It is thought that the low Young's modulus of the second layer increases the contact area with the member to be cleaned while the is decreased. As a result, poor cleaning due to passing through is less likely to occur, and deterioration of cleaning performance due to wear of the member to be cleaned and the cleaning blade is less likely to occur. In addition, due to the low elongation set of the third layer, even if the cleaning blade is used for a long period of time and the tip of the cleaning blade is locally warped during use, it is difficult for the object to be cleaned to slip through due to fatigue. It is considered that the maintenance of cleaning over time is improved.
From the above, it is presumed that in the second aspect, both the initial cleanability and the long-term cleaning maintainability are achieved.

Hereinafter, the first aspect and the second aspect may be collectively referred to as "this embodiment".
Each layer constituting the cleaning blade in this embodiment will be described in detail.

<First layer>
In the first aspect, the first layer preferably contains at least a metal oxide, and in the second aspect, the first layer preferably contains a metal oxide. Moreover, the first layer is preferably a layer containing a metal oxide as a main component (that is, the component with the highest content), and more preferably a layered material of a metal oxide.
Examples of the metal oxide layered material include a metal oxide CVD film, a metal oxide deposition film, a metal oxide sputter film, and the like. The layered material of metal oxide may be a layer containing at least one selected from hydrogen atoms and carbon atoms, if necessary.

As the metal oxide, a metal oxide containing a Group 13 element and oxygen (that is, an oxide of a Group 13 element) is preferable.
Examples of metal oxides containing a Group 13 element and oxygen include metal oxides such as gallium oxide, aluminum oxide, indium oxide, and boron oxide, or mixed crystals thereof, among which gallium oxide is particularly preferred. .
The metal oxide layer containing a Group 13 element and oxygen may optionally contain other elements (e.g., Zn, C, Si, Ge, Sn, N, Be, Mg, Ca, Sr, etc.). may contain.
In the layered material of a metal oxide containing a Group 13 element and oxygen, the sum of the element composition ratios of the Group 13 element, oxygen, and hydrogen with respect to all the elements constituting the layered material is 90 atomic % or more. is preferred. In addition, the sum of the above element composition ratios is preferably 95 atomic % or more, more preferably 96 atomic % or more, and even more preferably 97 atomic % or more.

Here, the confirmation of each element in the layered material, the element composition ratio, etc. are obtained by Rutherford back scattering (hereinafter referred to as "RBS"). Company RBS-400, using 3S-R10 as the system. For the analysis, CE&A's HYPRA program or the like is used.
The RBS measurement conditions are a He++ ion beam energy of 2.275 eV, a detection angle of 160°, and a grazing angle of 109° with respect to the incident beam.

Specifically, the RBS measurement is performed as follows. First, a He++ ion beam is vertically incident on the sample, the detector is set at 160° with respect to the ion beam, and the backscattered He signal is to measure. The composition ratio and film thickness are determined from the detected energy and intensity of He. Spectra may be measured at two detection angles to improve the accuracy of composition ratio and film thickness determinations. Accuracy is improved by measuring and cross-checking at two detection angles with different depth resolution and backscattering dynamics.
The number of He atoms backscattered by a target atom depends only on three factors: 1) the atomic number of the target atom, 2) the energy of the He atom before scattering, and 3) the scattering angle. The density is assumed by calculation from the measured composition and used to calculate the thickness. Density error is within 20%.

The element composition ratio of hydrogen is obtained by hydrogen forward scattering (hereinafter referred to as "HFS").
In the HFS measurement, NEC's 3SDH Pelletron is used as an accelerator, CE&A's RBS-400 is used as an end station, and 3S-R10 is used as a system. The HYPRA program from CE&A is used for the analysis. The HFS measurement conditions are as follows.
・He++ ion beam energy: 2.275 eV
・Detection angle: Grazing angle 30° with respect to 160° incident beam

HFS measurements pick up the signal of hydrogen scattered in front of the sample by setting the detector at 30° to the He++ ion beam and the sample at 75° from normal. At this time, the detector should be covered with aluminum foil to remove He atoms scattered with hydrogen. Quantification is performed by normalizing the hydrogen counts of the reference sample and the sample to be measured by the stopping power and then comparing them. A sample obtained by implanting H ions into Si and muscovite mica are used as reference samples.
Muscovite is known to have a hydrogen concentration of 6.5 atomic percent.
The H adsorbed on the outermost surface is corrected by, for example, subtracting the amount of H adsorbed on the clean Si surface.

The thickness of the first layer is, for example, in the range of 0.1 μm or more and 5.0 μm or less. From the viewpoint of suppressing cracking of the first layer, the thickness is preferably 0.1 μm or more and 3.0 μm or less, more preferably 0.1 μm or more and 1.0 μm or less, and even more preferably 0.1 μm or more and 0.5 μm or less.
If the first layer is too thick, the edges are less likely to warp, and the contact area with the member to be cleaned may be reduced. However, since the present embodiment has the second layer, even if the first layer is thick, the end portion is likely to warp compared to the case where the second layer is not provided. is likely to be good. From that point of view, the thickness of the first layer may be 0.5 μm or more and 5.0 μm or less, 0.6 μm or more and 5.0 μm or less, or more than 1.0 μm and 5.0 μm or less. good too.
The thickness of the first layer is calculated, for example, by observing the cross section of the cleaning blade with a microscope (manufactured by Keyence Corporation, Digital Microscope VHX-200) and averaging the measured values at five locations.

The first layer may be provided at least in the contact area with the member to be cleaned, but from the viewpoint of ease of manufacture, the first layer should be provided so as to cover the entire surface of the second layer opposite to the third layer. may be

(Characteristics of first layer)
In the first aspect, it is preferable that the coefficient of dynamic friction of the first layer is 0.05 or more and 0.5 or less and the Young's modulus of the first layer is 10 MPa or more and 200,000 MPa or less. In the second aspect, the dynamic friction coefficient of the first layer is 0.05 or more and 0.5 or less, and the Young's modulus of the first layer is 10 MPa or more and 200,000 MPa or less.
Examples of the layer having both the coefficient of dynamic friction and the Young's modulus within the above range include the layer containing the aforementioned metal oxide.

The dynamic friction coefficient of the first layer is more preferably 0.1 or more and 0.4 or less, more preferably 0.1 or more and 0.2 or less. When the coefficient of dynamic friction of the first layer is within the above range, compared with the case where the coefficient of dynamic friction is larger than the above range, the frictional force on the member to be cleaned is reduced, the wear of the cleaning blade is suppressed, and the cleaning maintainability over time is good. becomes.
The Young's modulus of the first layer is more preferably 20 MPa or more and 200,000 MPa or less, and even more preferably 50 MPa or more and 200,000 MPa or less. In this embodiment, since the second layer is provided, even if the Young's modulus of the first layer is within the above range, the end of the cleaning blade tends to warp locally, and the contact area with the member to be cleaned is less likely to decrease.

The coefficient of dynamic friction of the first layer is the coefficient of dynamic friction of the surface of the first layer opposite to the second layer. Values measured in an environment with a humidity of 55% are used.

Also, the Young's modulus is measured using a nanoindentation method. Specifically, PICODENTOR HM500 manufactured by Fisher Instruments Co., Ltd. and a Berkovich type diamond indenter are used to measure the indentation depth-load curve, apply a load at a maximum indentation depth of 1000 nm, and then unload. Determine the slope of the unloading curve when , as Young's modulus.

(Method of forming the first layer)
For example, various vapor deposition methods (eg, PVD: physical vapor deposition method, CVD: chemical vapor deposition method) are used to form the first layer. Specifically, for example, plasma CVD method (e.g., microwave plasma CVD method, DC plasma CVD method, high frequency plasma CVD method, magnetic field plasma CVD method, etc.), ion beam sputtering method, ion beam vapor deposition method, reactivity A plasma sputtering method, an unbalanced magnetron sputtering method, a molecular beam epitaxy method, and the like can be mentioned. Among these, the plasma CVD (Chemical Vapor Deposition) method is preferable from the viewpoint of high film forming speed and high coverage.

The first layer is formed, for example, on the second layer side surface of the base material (for example, plate-like base material) in which the second layer and the third layer are laminated, by the vapor phase film forming method or the like.
Hereinafter, an example of a film forming apparatus used for forming the first layer will be described with a specific example shown in the drawings. Although the following description shows a method for forming a layer containing gallium, oxygen, and hydrogen, the present invention is not limited to this, and a well-known forming method may be applied depending on the composition of the target layer. good.

FIG. 3 is a schematic diagram showing an example of a film forming apparatus used for forming the first layer.
As shown in FIG. 3, the film forming apparatus 100 includes a vacuum vessel 101 having a partition portion 101a, a film forming jig 103 holding a plate-like substrate 112, and a discharge portion including a high frequency power supply portion 105a and a discharge electrode 105b. 105, a process gas supply unit 107 connected to the supply port 107a for supplying the process gas, a material gas supply unit 109 for connecting the supply port 109a for supplying the material gas, an exhaust device 111 connected to the exhaust port 111a, have

In the film forming apparatus shown in FIG. 3, an exhaust device 111 is provided at one end of the vacuum vessel 101 via an exhaust port 111a, and an exhaust device 111 (exhaust port 111a) of the vacuum vessel 101 is provided. A supply port 107a for supplying a process gas, a supply port 109a for supplying a material gas, and a discharge section 105 are provided on the opposite side.
A film forming jig 103 for holding a plate-like substrate 112 is provided inside the vacuum vessel 101 . This film forming jig 103 has a polygonal cross section and has a function of holding the plate-like substrate 112 on this side. The film forming jig 103 is rotated in the direction of the arrow by a rotating device (not shown) while holding the plate-like substrate 112 .

The discharge section 105 is composed of a discharge electrode 105b having a discharge surface provided on the side of the exhaust device 111 (exhaust port 111a), and a high-frequency power supply section 105a connected to the surface of the discharge electrode 105b opposite to the discharge surface. there is
A supply port 107 a for supplying a process gas is provided near the discharge electrode 105 b and connected to the process gas supply section 107 .
Further, a supply port 109a for supplying the material gas is provided at a location opposite to the supply port 107a with respect to the partition portion 101a. there is

One end of the vacuum chamber 101 is fixed to the inner wall of the vacuum chamber 101, and the other end faces the film formation jig 103 with a minute gap so as not to come into contact with the rotating film formation jig 103 and the plate-like substrate 112 held by it. It has a partition portion 101a.
This partition part 101a separates the area where the discharge electrode 105b inside the vacuum vessel 101 and the process gas are supplied from the supply port 107a, and the area where the material gas is supplied from the supply port 109a, with the exception of the minute gap. used to separate The position of the partition 101 a is set according to the length of one side of the film formation jig 103 (the size of the plate-like substrate 112 ), and does not need to be in the center of the vacuum vessel 101 .

Formation of the first layer is performed, for example, as follows.
First, a process gas is introduced from the supply port 107a, and high-frequency electric power having a frequency of 13.56 MHz, for example, is supplied from the high-frequency power source 105a to the discharge electrode 105b. At this time, plasma is formed so that the light emitting region radially expands from the discharge surface side of the discharge electrode 105b to the exhaust port 111a side. Here, the process gas introduced from the supply port 107a flows in the vacuum vessel 101 from the region including the discharge electrode 105b to the exhaust port 111a side.
The discharge electrode 105b may be surrounded by an earth shield.

Here, the process gas includes at least oxygen and is nitrogen, hydrogen, or a rare gas such as helium or argon.

Next, a non-single-crystal film containing gallium and oxygen is formed on the surface of the plate-like substrate 112 by introducing, for example, trimethylgallium (material gas) diluted with hydrogen as a carrier gas through the supply port 109a. be.

The temperature at which the surface layer is formed during film formation is not particularly limited, but the surface temperature of the plate-like substrate 112 is preferably in the range of 10°C to 100°C, more preferably in the range of 20°C to 60°C.
The temperature of the surface of the plate-like substrate 112 may be controlled by at least one of heating and cooling means (not shown in the figure), or may be left to the natural temperature rise during discharge. When heating the plate-like substrate 112 , a heater may be installed at a location adjacent to the plate-like substrate 112 . When cooling the plate-like substrate 112 , cooling gas or liquid may be circulated inside the film-forming jig 103 holding the plate-like substrate 112 .
If it is desired to avoid an increase in the temperature of the surface of the plate-like substrate 112 due to discharge, it is effective to adjust the high-energy gas flow that hits the surface of the plate-like substrate 112 . In this case, conditions such as gas flow rate, discharge output and pressure are adjusted so as to obtain the required temperature. Moreover, in order to prevent the temperature rise of the plate-like substrate 112 due to the temperature rise of the discharge electrode 105b itself due to discharge, a cooling gas or liquid may be circulated inside the discharge electrode.

Here, as the material gas, an organometallic compound containing gallium such as trimethylgallium, triethylgallium, or t-butylgallium is used.
These liquids and solids are vaporized and used alone or in a mixed state by bubbling with a carrier gas.
Moreover, you may mix two or more types of these.

When forming the surface layer mainly containing gallium and oxygen, it is preferable that active hydrogen exists in the vacuum vessel 101 . Active hydrogen may be supplied from hydrogen gas used as a carrier gas or hydrogen atoms contained in an organometallic compound.

The plasma generating means of the film forming apparatus 100 shown in FIG. 3 uses a high-frequency power supply unit, but is not limited to this. A system or a helicon plasma system may be used. Moreover, in the case of a high-frequency oscillator, either an inductive type or a capacitive type may be used.
Furthermore, two or more of these devices may be used in combination. For example, a remote plasma device that supplies active hydrogen from the process gas supply port 107a may be added. Also, two or more devices of the same type may be used. A high-frequency oscillation device is preferable in order to suppress the temperature rise of the surface of the plate-like substrate 112 due to plasma irradiation, but a device for preventing heat irradiation may be provided.

When two or more different plasma generators (plasma generating means) are used, discharge may be generated at the same pressure at the same time. Also, a pressure difference may be provided between the discharging area and the film-forming area (the portion where the plate-like substrate is installed). These devices may be arranged in series with respect to the gas flow formed in the film forming apparatus from the portion into which the gas is introduced to the portion from which the gas is discharged. You may arrange|position so that it may oppose.

Further, when two different types of plasma generators are used under the same pressure, for example, when a microwave oscillator and a high-frequency oscillator are used, the excitation energy of the excited species may be greatly changed, and the film quality can be controlled. easier to do. Further, discharge may be performed at near atmospheric pressure (range of 300 to 1200 hPa). It is desirable to use He as a carrier gas when discharging near atmospheric pressure.

<Second layer>
The second layer is not particularly limited as long as it is an elastic layer having a Young's modulus of 4 MPa or more and 8 MPa or less.
Examples of materials used for the second layer include rubber elastic bodies, and specific examples include polyurethane rubber, polyimide rubber, silicone rubber, fluororubber, chloroprene rubber, and butadiene rubber. From the viewpoint of wear resistance, mechanical strength, oil resistance, and ozone resistance, the rubber elastic body preferably contains polyurethane rubber.
Moreover, the material used for the second layer and the material used for the third layer are preferably the same type of material from the viewpoint of adhesion between the second layer and the third layer. By using the same kind of material, it is easy to obtain a cleaning blade in which the second layer and the third layer are in direct contact and adhered to each other with high adhesive strength.
Materials of the same type include, for example, polyurethane rubbers, polyimide rubbers, silicone rubbers, fluororubbers, chloroprene rubbers, and butadiene rubbers. Among them, both the material used for the second layer and the material used for the third layer are preferably polyurethane rubber.
The details of the polyurethane rubber will be described later.

(Characteristics of second layer)
The Young's modulus of the second layer is 4 MPa or more and 8 MPa or less, preferably 4 MPa or more and 5.5 MPa or less, and more preferably 4 MPa or more and less than 5 MPa. When the Young's modulus of the second layer is within the above range, the contact area with the member to be cleaned is larger than when it is larger than the above range, and the contact area with the member to be cleaned is larger than when it is smaller than the above range. is suppressed.
The means for achieving the Young's modulus of the second layer within the above range varies depending on the material of the second layer and the like, but for example, a method of adjusting the compounding ratio at the time of forming the second layer can be mentioned. Specifically, for example, when the material of the second layer is a polyurethane rubber to be described later, a method of decreasing the Young's modulus of the second layer by decreasing the ratio of the polyisocyanate compound can be mentioned.

The elongation set of the second layer is not particularly limited, and is, for example, 0.1% or more and 5% or less. In this embodiment, since the elongation set of the third layer is small, even if the elongation set of the second layer is larger than the elongation set of the third layer, the cleaning maintainability over time can be obtained. From that point of view, the elongation set of the second layer may be more than 1% and 5% or less, more than 1.5% and 5% or less, or 2% or more and 5% or less.

Here, a method for measuring the permanent elongation (%) will be described.
Specifically, according to JIS K6262 (1997), a strip-shaped test piece is used, 100% tensile strain is applied and left for 24 hours.
Ts = (L2-L0)/(L1-L0) x 100
Ts: Permanent elongation
L0: Distance between gauge lines before pulling
L1: Distance between gauge lines when pulling
L2: Distance between marked lines after pulling If the sample to be measured is larger than the strip-shaped test piece specified in JIS K6262, cut out the strip-shaped test piece from the sample. Thus, the above measurements are performed. On the other hand, if the size of the sample is smaller than the size of the strip-shaped test piece, a strip-shaped test piece is formed from the same material as the sample, and the above measurement is performed on this strip-shaped test piece.

The thickness of the second layer is, for example, 100 μm or more and 1000 μm or less, preferably 200 μm or more and 800 μm or less, and more preferably 300 μm or more and 500 μm or less. When the thickness of the second layer is within the above range, cracking of the first layer is more likely to be suppressed than when it is thicker than the above range, and the contact area with the member to be cleaned is larger than when it is thinner than the above range. Cleanability tends to be good.
The thickness of the second layer is calculated, for example, by observing the cross section of the cleaning blade with a microscope (manufactured by Keyence Corporation, Digital Microscope VHX-200) and averaging the measured values at five locations.

The thickness of the second layer is preferably 20 to 200,000 times the thickness of the first layer, more preferably 200 to 100,000 times. When the ratio of the thickness of the second layer to the thickness of the first layer is within the above range, cracking of the first layer is more likely to be suppressed than when it is larger than the above range, and the thickness is less than when it is smaller than the above range. The contact area with the cleaning member is large, and the cleaning property tends to be good.

The thickness of the second layer is preferably thinner than the thickness of the third layer described later.
The thickness of the second layer is preferably 1.1 to 20 times the thickness of the third layer, more preferably 2 to 10 times, and preferably 3 to 6 times the thickness of the third layer. preferably
Similarly, the thickness of the third layer is calculated by, for example, observing the cross section of the cleaning blade with a microscope (manufactured by Keyence Corporation, Digital Microscope VHX-200) and averaging the measured values at five locations.

(polyurethane rubber)
The polyurethane rubber will be described below.
Polyurethane rubber is synthesized, for example, by polymerizing polyisocyanate and polyol. Moreover, you may use resin which has a functional group which can react with an isocyanate group other than a polyol. In addition, it is desirable that the polyurethane rubber has a hard segment and a soft segment.
Here, the terms "hard segment" and "soft segment" refer to the material that constitutes the former in the polyurethane rubber material, and the material that constitutes the latter is relatively harder than the material that constitutes the latter. means a segment made of a material that is relatively softer than the material that constitutes the former.

The combination of the material constituting the hard segment (hard segment material) and the material constituting the soft segment (soft segment material) is not particularly limited. Although it is possible to select from known resin materials so as to obtain a relatively soft combination in terms of strength, the following combinations are preferable in this embodiment.

- Soft segment material Polyether polyol is preferably used as the soft segment material. Polyether polyols are not particularly limited and include, for example, polycaprolactone, polyethylene glycol, polyoxytetramethylene glycol, polyoxypropylene glycol and the like.
Polyoxytetramethylene glycol is preferred due to the flexibility of the rubber and ease of control of microcrystals. In addition, the number average molecular weight of the polyoxytetramethylene glycol is preferably in the range of 500 or more and 5000 or less. When the number average molecular weight is 500 or more, the mechanical strength of the cleaning blade can be obtained. Further, when the number average molecular weight is 5000 or less, the mechanical strength of the cleaning blade does not become too high, and the decrease in workability due to the viscosity increase of the material is suppressed.

As the soft segment material, other polyols may be used, and the polyols include polyester polyols obtained by dehydration condensation of diols and dibasic acids, polycarbonate polyols obtained by reaction of diols and alkyl carbonates, and caprolactone-based polyols. polyols and the like. These may be used alone or in combination of two or more.

- Hard segment material A chain extender is preferably used as the hard segment material.
The chain extender is not particularly limited as long as it is conventionally known, and examples thereof include 1,4-butanediol (1,4-BD), ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, and hexane. Molecular weights of diols, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, xylene glycol, triethylene glycol, trimethylolpropane (TMP), glycerin, pentaerythritol, sorbitol, 1,2,6-hexanetriol, etc. 300 or less polyols. These may be used alone or in combination of two or more.

As the hard segment material, it is also desirable to use a resin having a functional group capable of reacting with an isocyanate group. Moreover, it is preferably a flexible resin, and more preferably an aliphatic resin having a linear structure from the viewpoint of flexibility. As specific examples, it is desirable to use an acrylic resin containing two or more hydroxyl groups, a polybutadiene resin containing two or more hydroxyl groups, an epoxy resin containing two or more epoxy groups, or the like.

When using a hard segment material and a soft segment material, the mass ratio of the material constituting the hard segment to the total amount of the hard segment material and soft segment material (hereinafter referred to as "hard segment material ratio") is 10% by mass or more and 30% by mass or less. is preferably within the range of 13% by mass or more and 23% by mass or less, more preferably 15% by mass or more and 20% by mass or less.
When the hard segment material ratio is within the above range, cracking of the first layer is suppressed compared to when it is less than the above range, and good cleaning performance is maintained over a long period of time. It does not become too hard compared to other materials, provides flexibility and extensibility, and tends to increase the contact area with the member to be cleaned.

- Polyisocyanate Polyisocyanates include, for example, 4,4'-diphenylmethane diisocyanate (MDI), 2,6-toluene diisocyanate (TDI), 1,6-hexane diisocyanate (HDI), and 1,5-naphthalene diisocyanate (NDI). , and 3,3-dimethylbiphenyl-4,4-diisocyanate (TODI).
In terms of ease of forming hard segment aggregates of the required size (particle diameter), polyisocyanates include 4,4′-diphenylmethane diisocyanate (MDI), 1,5-naphthalenediisocyanate (NDI), Hexamethylene diisocyanate (HDI) is more preferred.

The polyisocyanate content is preferably 10% by mass or more and 40% by mass or less, more preferably 15% by mass or more and 35% by mass or less, and even more preferably 20% by mass or more and 30% by mass or less, relative to the entire polyurethane rubber.
When the content of the polyisocyanate is within the above range, the amount of urethane bonds is secured and the desired hardness can be easily obtained compared to the case where the content is less than the above range, and the extensibility is improved compared to the case where it is more than the above range. As a result, the contact area with the member to be cleaned tends to increase.

Cross-linking agent Examples of the cross-linking agent include diols (bifunctional), triols (trifunctional), tetraols (tetrafunctional), etc. These may be used in combination. Moreover, you may use an amine compound as a crosslinking agent. In addition, it is desirable to be crosslinked using a trifunctional or higher crosslinking agent. Examples of trifunctional cross-linking agents include trimethylolpropane, glycerin, and triisopropanolamine.

The content of the cross-linking agent is preferably 2% by mass or less, more preferably 1.5% by mass or less, and even more preferably 1.0% by mass or less, relative to the entire polyurethane rubber. When the content of the cross-linking agent is within the above range, molecular motion is less likely to be restrained by chemical cross-linking than when the content is above the above range, making it easier to obtain the required hardness.

- Catalyst Examples of catalysts include amine compounds such as tertiary amines, quaternary ammonium salts, and organic metal compounds such as organic tin compounds.
Examples of the tertiary amine include trialkylamines such as triethylamine, tetraalkyldiamines such as N,N,N',N'-tetramethyl-1,3-butanediamine, aminoalcohols such as dimethylethanolamine, Ethoxylated amines, ethoxylated diamines, ester amines such as bis(diethylethanolamine) adipate, triethylenediamine (TEDA), cyclohexylamine derivatives such as N,N-dimethylcyclohexylamine, N-methylmorpholine, N-(2-hydroxy morpholine derivatives such as propyl)-dimethylmorpholine; piperazine derivatives such as N,N'-diethyl-2-methylpiperazine and N,N'-bis-(2-hydroxypropyl)-2-methylpiperazine;

Examples of the quaternary ammonium salts include 2-hydroxypropyltrimethylammonium octylate, 1,5-diazabicyclo[4.3.0]nonene-5(DBN) octylate, 1,8-diazabicyclo [5.4.0] undecene-7(DBU)-octylate, DBU-oleate, DBU-p-toluenesulfonate, DBU-formate, 2-hydroxypropyltrimethylammonium-formate and the like. be done.

Examples of the organic tin compounds include dialkyltin compounds such as dibutyltin dilaurate and dibutyltin di(2-ethylhexoate), stannous 2-ethylcaproate, and stannous oleate.

Among these catalysts, the tertiary ammonium salt triethylenediamine (TEDA) is used from the viewpoint of hydrolysis resistance, and the quaternary ammonium salt is preferably used from the viewpoint of workability. Among quaternary ammonium salts, 1,5-diazabicyclo[4.3.0]nonene-5(DBN) octylate, 1,8-diazabicyclo[5.4.0]undecene-, which have high reaction activity 7(DBU)-octylate and DBU-formate are preferably used.

The content of the catalyst is preferably in the range of 0.0005% by mass to 0.03% by mass, more preferably 0.001% by mass to 0.01% by mass, based on the total polyurethane rubber.
These are used alone or in combination of two or more.

-Method for Producing Polyurethane Rubber A general method for producing polyurethane, such as a prepolymer method or a one-shot method, is used to produce the polyurethane rubber member constituting the contact member in the present embodiment. The prepolymer method is suitable for this embodiment because it yields a polyurethane having excellent strength and abrasion resistance, but is not limited by the manufacturing method.

Polyurethane rubber can be obtained, for example, by molding a composition obtained by blending an isocyanate compound, a cross-linking agent, a catalyst, and the like with the above-described polyol (eg, hard segment material and soft segment material).
The amounts and ratios of the polyol, polyisocyanate, cross-linking agent, and catalyst to be added are adjusted within the required range.

The weight average molecular weight of the polyurethane rubber is desirably in the range of 1,000 to 4,000, more desirably in the range of 1,500 to 3,500.
In addition, the measurement of a weight average molecular weight is performed by a gel permeation chromatography (GPC). Specifically, HPLC1100 manufactured by Tosoh Corporation is used as a measuring apparatus, a column TSKgel GMHHR-M+TSKgel GMHHR-M (7.8 mm ID 30 cm) manufactured by Tosoh Corporation is used, and a chloroform solvent is used for measurement. The weight average molecular weight is calculated from this measurement result using a molecular weight calibration curve prepared from a monodisperse polystyrene standard sample.

<Third layer>
The third layer is not particularly limited as long as it is an elastic layer having a permanent elongation of less than 2%.
Examples of the material used for the third layer include rubber elastic bodies, and specific examples include polyurethane rubber, polyimide rubber, silicone rubber, fluororubber, propylene rubber, and butadiene rubber. From the viewpoint of wear resistance, mechanical strength, oil resistance, and ozone resistance, the rubber elastic body preferably contains polyurethane rubber.
The details of the polyurethane rubber are as described above.
However, when the third layer contains polyurethane rubber, the weight average molecular weight of the polyurethane rubber contained in the third layer is, for example, 2000 or more and 3500 or less, preferably 2500 or more and 3000 or less. The content of the cross-linking agent in the polyurethane rubber contained in the third layer is preferably 1% by mass or more and less than 2% by mass, more preferably 1% by mass or more and less than 1.5% by mass.

(Characteristics of third layer)
The elongation set of the third layer is less than 2%, preferably 0.1% or more and less than 2%, more preferably 0.1% or more and 1.5% or less, further preferably 0.1% or more and 1% or less. . When the elongation set of the third layer is within the above range, compared with the case where the elongation set of the third layer is larger than the above range, it is possible to prevent the cleaning blade from slipping through the object to be cleaned due to the decrease in the contact pressure caused by the cleaning blade weakening over time. be done. Preferably, the elongation set of the third layer is less than the elongation set of the second layer. It should be noted that the smaller the permanent elongation of the third layer, the better, but it is difficult to form a layer with a permanent elongation of less than 0.1%.
Means for achieving the above range of elongation set of the third layer vary depending on the material of the third layer, but for example, a method of adjusting the compounding ratio and molecular weight at the time of forming the third layer can be mentioned. Specifically, for example, when the material of the third layer is the aforementioned polyurethane rubber, the elongation set value tends to vary by changing the content of the cross-linking agent, the molecular weight of the polyol used as the soft segment material, and the like. .

The Young's modulus of the third layer is not particularly limited, and is, for example, 3 MPa or more and 10 MPa or less, preferably 5 MPa or more and 8 MPa or less, more preferably 5 MPa or more and 6 MPa.
When the Young's modulus of the third layer is within the above range, there is an advantage that it can sufficiently contact the photoreceptor compared to the case where it is larger than the above range, and the entire blade is prevented from turning over compared to when it is smaller than the above range. It has the advantage of being able to

The thickness of the third layer is, for example, 1000 μm or more and 1800 μm or less, preferably 1200 μm or more and 1700 μm or less, and more preferably 1300 μm or more and 1500 μm or less.
The total thickness of the first layer, the second layer, and the third layer is preferably 1.4 mm or more and 2.5 mm or less, more preferably 1.5 mm or more and 2.2 mm or less, and 1.6 mm or more and 2.0 mm or less. is more preferred.

<Method for manufacturing cleaning blade>
For the cleaning blade according to the present embodiment, for example, a laminate of a second layer and a third layer is used as a base material, and the first layer is formed on the surface of the base material on the second layer side by the method described above.
Examples of the method for producing the base material in which the second layer and the third layer are laminated include a method in which the second layer and the third layer are produced respectively, and then bonded to each other using a double-sided tape, various adhesives, or the like. In addition, a material for forming the second layer (e.g., second layer-forming composition) and a material for forming the third layer (e.g., third layer-forming composition) are placed in a mold at different times. By molding after pouring into the substrate, bonding between materials may be obtained to obtain a substrate in which the second layer and the third layer are laminated.

<Application>
The member to be cleaned by the cleaning blade according to the present embodiment is not particularly limited as long as it requires surface cleaning. For example, if it is used in an image forming apparatus, it may be an image carrier, an intermediate transfer member, a charging roll, a transfer roll, a transfer material transport belt, a paper transport roll, etc., and remove toner from the image carrier. Also included are detoning rolls and the like that further remove toner from the cleaning brush. In this embodiment, it is particularly preferable that the member to be cleaned is an image carrier.

[Cleaning Device, Process Cartridge, and Image Forming Apparatus]
Next, a cleaning device, a process cartridge, and an image forming apparatus using the cleaning blade according to this embodiment will be described.
The cleaning device of this embodiment is not particularly limited as long as it includes the cleaning blade of this embodiment as a cleaning blade that contacts the surface of the member to be cleaned and cleans the surface of the member to be cleaned. For example, as an example of the configuration of the cleaning device, a cleaning blade is fixed in a cleaning case having an opening on the side of the member to be cleaned so that the tip of the edge faces the opening, and the cleaning blade recovers from the surface of the member to be cleaned. Another example is a configuration including a conveying member that guides foreign matter such as waste toner to a foreign matter collection container. Further, two or more cleaning blades of the present embodiment may be used in the cleaning device of the present embodiment.

On the other hand, the process cartridge of this embodiment includes the cleaning device of this embodiment as a cleaning device that contacts the surface of one or more members to be cleaned, such as an image carrier and an image carrier, and cleans the surface of the member to be cleaned. It is not particularly limited as long as it is For example, an image forming apparatus including an image carrier and the cleaning device of the present embodiment for cleaning the surface of the image carrier can be detachably attached to the image forming apparatus. For example, in the case of a so-called tandem machine having image carriers corresponding to toners of different colors, the cleaning device of this embodiment may be provided for each image carrier. In addition, a cleaning brush or the like may be used together with the cleaning device of the present embodiment.

An image forming apparatus according to this embodiment includes an image carrier, charging means for charging the surface of the image carrier, and electrostatic latent image forming means for forming an electrostatic latent image on the charged surface of the image carrier. , developing means for developing an electrostatic latent image formed on the surface of the image carrier with a developer containing toner to form a toner image, and transfer means for transferring the toner image onto the surface of a recording medium. and a cleaning device according to the present embodiment for cleaning the surface of the image carrier.

When the cleaning blade of the present embodiment is used for cleaning the image carrier, the cleaning blade is worn while effectively cleaning residual toner, which is an object to be cleaned, and also allowing the lubricant (external additive) to pass through well. NF (Normal Force) with which the cleaning blade is pressed against the image carrier is preferably in the range of 1.3 gf/mm to 2.3 gf/mm, more preferably 1.6 gf/mm to 2.3 gf/mm. It is more preferably in the range of 0 gf/mm or less.

Here, the pressing force NF of the cleaning blade is calculated by the following equation.
・Formula: N=dEt ³ /4L ³
6, E is the Young's modulus of the cleaning blade, t is the thickness t of the cleaning blade shown in FIG. 6, and L is the thickness of the cleaning blade shown in FIG. It represents the free length (the length of the area not fixed by the fixture 346).

The biting amount d of the cleaning blade shown in FIG. 6 into the image carrier is preferably in the range of 0.8 mm or more and 1.2 mm or less, more preferably in the range of 0.9 mm or more and 1.1 mm or less.
The angle α (W/A, working angle) at the contact portion between the cleaning blade and the image carrier shown in FIG. It is more preferable to have
The set angle θ of the cleaning blade shown in FIG. 6 with respect to the image carrier is preferably 10° or more and 25° or less, more preferably 12° or more and 25° or less, and still more preferably 15° or more and 25° or less. The set angle θ is defined by a virtual line along the non-bent portion of the cleaning blade's ventral surface and a point where the virtual line contacts the surface of the member to be cleaned when the cleaning blade is in contact with the image carrier. means the angle (acute angle) at which the tangent line of

<Specific Examples of Image Forming Apparatus and Cleaning Device>
Next, specific examples of an image forming apparatus and a cleaning device using the cleaning blade of the present embodiment will be described in more detail with reference to the drawings.
FIG. 4 is a schematic diagram showing an example of the image forming apparatus of this embodiment, and shows a so-called tandem image forming apparatus.
In FIG. 4, 21 is a main body housing, 22, 22a to 22d are image forming units, 23 is a belt module, 24 is a recording medium supply cassette, 25 is a recording medium conveying path, 30 is each photoreceptor unit, and 31 is a member to be cleaned. 33, each developing unit; 34, a cleaning device; 35, 35a to 35d, toner cartridges; 40, an exposure unit; 41, a unit case; 61 is a delivery roll; 62 is a transport roll; 63 is a positioning roll; 66 is a fixing device; 67 is a discharge roll; 74 is a guide roll; 76 is a transport path; 77 is a transport roll; 230 is an intermediate transfer belt; represents a blade.

The tandem-type image forming apparatus shown in FIG. 4 has image forming units 22 (specifically 22a to 22d) of four colors (yellow, magenta, cyan, and black in this embodiment) arranged in a body housing 21. A belt module 23 containing an intermediate transfer belt 230 that is circulated and conveyed along the direction in which the image forming units 22 are arranged is disposed above the belt module 23 . A recording medium supply cassette 24 for storing the recording medium supply cassette 24 is provided, and a recording medium transport path 25 serving as a transport path for the recording medium from the recording medium supply cassette 24 is arranged in the vertical direction.

In this embodiment, the image forming units 22 (22a to 22d) are arranged in order from the upstream side in the circulation direction of the intermediate transfer belt 230, for example, for yellow, magenta, cyan, and black (arrangement is not necessarily in this order). ), and includes each photoreceptor unit 30 , each developing unit 33 , and one common exposure unit 40 .
Here, the photoreceptor unit 30 includes, for example, a photoreceptor drum 31 , a charging device (charging roll) 32 that charges the photoreceptor drum 31 in advance, and a cleaning device 34 that removes residual toner on the photoreceptor drum 31 . It is an integral sub-cartridge.

The developing unit 33 develops the electrostatic latent image formed on the charged photosensitive drum 31 by the exposure unit 40 with a corresponding color toner (for example, negative polarity in this embodiment). For example, it is integrated with a sub-cartridge composed of the photoreceptor unit 30 to form a process cartridge (so-called Customer Replaceable Unit).
It goes without saying that the photoreceptor unit 30 may be separated from the developing unit 33 and used as an independent process cartridge. In FIG. 4, reference numeral 35 (35a to 35d) denotes a toner cartridge for supplying toner of each color component 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 (not shown) corresponding to each photoreceptor unit 30 in a unit case 41. (not shown) are stored, 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 corresponding exposure point on the photosensitive drum 31 via the imaging lens and mirror. It is what I did.

Further, in the present embodiment, the belt module 23 has, for example, a pair of support rolls (one of which is a driving roll) 231 and 232 and an intermediate transfer belt 230 stretched therebetween. 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 . The toner image on the body drum 31 is electrostatically transferred to the intermediate transfer belt 230 side. Further, a secondary transfer device 52 is provided at a portion corresponding to the support roll 232 on the downstream side of the most downstream image forming unit 22d of the intermediate transfer belt 230, and transfers the primary transferred image on the intermediate transfer belt 230 to a recording medium. Secondary transfer (batch transfer) to .

In this embodiment, the secondary transfer device 52 includes a secondary transfer roll 521 that is arranged in pressure contact with the toner image holding surface of the intermediate transfer belt 230 and a secondary transfer roll 521 that is arranged on the back side of the intermediate transfer belt 230 . and a back roll (which also serves as the support roll 232 in this example) forming a counter electrode. Then, 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 back roll (support roll 232).
Furthermore, a belt cleaning device 53 is disposed on the upstream side of the most upstream image forming unit 22a of the intermediate transfer belt 230 to remove residual toner on the intermediate transfer belt 230. FIG.

Further, the recording medium supply cassette 24 is provided with a feed roll 61 for feeding the recording medium. Immediately after the feed roll 61, a transport roll 62 for feeding the recording medium is provided, and the secondary transfer portion is provided. A positioning roll 63 for supplying the recording medium to the secondary transfer portion at a predetermined timing is arranged in the recording medium conveying path 25 positioned immediately before. On the other hand, a fixing device 66 is provided in the recording medium transport path 25 located downstream of the secondary transfer portion, and a discharge roller 67 for discharging the recording medium is provided downstream of the fixing device 66. A discharged recording medium is accommodated in a discharge section 68 formed in the upper portion of the housing 21 .

Further, in this embodiment, a manual feeding device (MSI) 71 is provided on the side of the main body housing 21 , and the recording medium on this manual feeding device 71 is fed by a delivery roll 72 and a transport roll 62 . It is sent out toward the transport path 25 .
Further, a double-sided recording unit 73 is attached to the main body housing 21. This double-sided recording unit 73 ejects the recording medium on which one side has been recorded to a discharge roll when a double-sided mode for recording images on both sides of the recording medium is selected. 67 is reversed, the recording medium is taken inside by the guide roll 74 in front of the entrance, the recording medium is conveyed along the recording medium return conveying path 76 inside by the conveying roll 77, and is again supplied to the alignment roll 63 side. It is something to do.

Next, the cleaning device 34 arranged in the tandem image forming apparatus shown in FIG. 4 will be described in detail.
FIG. 5 is a schematic cross-sectional view showing an example of the cleaning device of the present embodiment, showing 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. It is a diagram.
5, 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, and 344 denotes a film seal, and 345 denotes a conveying member.

The cleaning device 34 has a cleaning case 341 containing residual toner and having an opening facing the photoreceptor drum 31 . A cleaning blade 342 is arranged at the lower edge of the opening of the cleaning case 341 so as to contact the photoreceptor drum 31 . 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 to maintain airtightness between the cleaning case 341 and the photosensitive drum 31 . Reference numeral 345 denotes a conveying member that guides the waste toner stored in the cleaning case 341 to a side waste toner container.

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

Further, the developing unit (developing device) 33 used in the present embodiment has a unit case 331 that accommodates developer and opens to face the photosensitive drum 31, as shown in FIG. 5, for example. Here, a developing roller 332 is arranged at a portion facing the opening of the unit case 331, and a toner conveying member 333 for agitating and conveying the developer is arranged inside the unit case 331. As shown in FIG. Further, a transport paddle 334 may be arranged between the developing roll 332 and the toner transport member 333 .
During development, after the developer is supplied to the developing roll 332 , the developer is conveyed to the developing area facing the photosensitive drum 31 while the layer thickness of the developer is regulated by, for example, the trimming member 335 .

In this embodiment, as the developing unit 33, for example, a two-component developer consisting of toner and carrier may be used, or a one-component developer consisting of only toner may be used.

Toner As the toner used in the present embodiment, a toner in which at least a lubricant is externally added as an external additive to toner particles is preferably used.
Further, the toner used in the present embodiment may be a dry toner such as pulverized toner, but is preferably a wet toner. The wet toner is not particularly limited as long as it is obtained by a known melt suspension method, emulsion aggregation/coalescing method, dissolution suspension method, or the like.
Liquid toners often have a smaller particle size than dry toners, and often have higher sphericity. According to the cleaning blade according to the present disclosure, by suppressing the occurrence of curling, image defects such as image contamination are easily suppressed even when the wet toner is used.

The volume average particle size (D50v) of the toner particles is preferably 2 μm or more and 10 μm or less, more preferably 4 μm or more and 8 μm or less.

Various average particle diameters of toner particles are measured using Coulter Multisizer II (manufactured by Beckman Coulter, Inc.) and using ISOTON-II (manufactured by Beckman Coulter, Inc.) as an electrolytic solution.
In the measurement, 0.5 mg or more and 50 mg or less of the measurement sample is added to 2 ml of a 5% aqueous solution of a surfactant (preferably sodium alkylbenzenesulfonate) as a dispersant. This is added to 100 ml or more and 150 ml or less of the electrolytic solution.
The electrolytic solution in which the sample was suspended was subjected to dispersion treatment for 1 minute with an ultrasonic disperser, and the particle size distribution of particles having a particle size in the range of 2 μm to 60 μm was measured by Coulter Multisizer II using an aperture with an aperture diameter of 100 μm. Measure. Note that the number of particles to be sampled is 50,000.
Based on the measured particle size distribution, a cumulative distribution is drawn from the smaller diameter side for the particle size range (channel) divided based on the measured particle size distribution.

Examples of the lubricant externally added to the toner particles include silica particles, higher fatty acid metal salt particles (eg, zinc stearate particles), fluororesin particles (eg, polytetrafluoroethylene (PTFE) particles), boron nitride particles, and the like. mentioned.

Each particle externally added to the toner particles may be subjected to a hydrophobic treatment on the surface.

The average diameter of the lubricant externally added to the toner particles is preferably 50 nm or more and 1000 nm or less, more preferably 100 nm or more and 500 nm or less, and even more preferably 100 nm or more and 350 nm or less.

The average diameter of the lubricant is obtained by observing 100 primary particles after dispersing the lubricant in resin particles (polyester, weight average molecular weight Mw = 50000) having a particle diameter of 100 µm with a SEM (Scanning Electron Microscope) device. Equivalent circle mean diameter, which is the 50% diameter (D50v) in the cumulative frequency of equivalent circle diameters obtained by image analysis of .

The external addition amount of the external additive is, for example, preferably 0.01% by mass or more and 5% by mass or less, more preferably 0.01% by mass or more and 2.0% by mass or less, relative to the toner particles.

Next, the operation of the image forming apparatus according to this embodiment will be described. First, when each image forming unit 22 (22a to 22d) forms a single-color toner image corresponding to each color, the single-color toner image of each color is sequentially superimposed on the surface of the intermediate transfer belt 230 so as to match the original document information. be transcribed. Subsequently, the color toner image transferred to the surface of the intermediate transfer belt 230 is transferred to the surface of the recording medium by the secondary transfer device 52, and the recording medium onto which the color toner image has been transferred is subjected to fixing processing by the fixing device 66. , is discharged to the discharge unit 68 .
On the other hand, in each image forming unit 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. be.
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 member instead of being directly fixed to the frame member inside the cleaning device 34 as shown in FIG.

EXAMPLES The present embodiment will be described in detail below with reference to Examples, but the present embodiment is not limited to these Examples. In the following description, "parts" and "%" are all based on mass unless otherwise specified.

[Example 1]
<Preparation of Third Layer Forming Composition 1>
Polyoxytetramethylene glycol [PTMG] (manufactured by Hodogaya Chemical Co., Ltd., PTG2000, average molecular weight 2000, hydroxyl value 56.5 KOHmg/g) was used as the soft segment material of the polyol component (indicated as "PTMG" in the table). ).
1,4-butanediol (manufactured by Mitsubishi Chemical Corporation) was used as a chain extender (that is, hard segment material) (indicated by "BD" in the table).
As the polyisocyanate, 4,4′-diphenylmethane diisocyanate (MDI, manufactured by Nippon Polyurethane Industry Co., Ltd., Millionate MT) was used (indicated as “MDI” in the table).
Trimethylolpropane (manufactured by Mitsubishi Gas Chemical Company, Inc.) was used as a cross-linking agent (shown as "TMP" in the table).
As a catalyst, 1,8-diazabicyclo(5.4.0)undecene-7]-octylate (DBU, manufactured by San-Apro Co., Ltd., -U-CAT SA 102) was used.

Polyisocyanate (MDI) is added to the mixture of the soft segment material (PTMG) and the hard segment material (1,4-butanediol), and reacted at 70 ° C. for 6 hours in a nitrogen atmosphere to obtain prepolymer 1. got
The addition amounts of the soft segment material, the hard segment material, and the polyisocyanate were adjusted so that the molar ratios were the values shown in Table 1.

Next, this prepolymer 1 was heated to 100° C. and defoamed under reduced pressure for 1 hour. Thereafter, a cross-linking agent (trimethylolpropane) and a catalyst (DBU) were added to the prepolymer 1, and mixed for 3 minutes without entraining bubbles to prepare a composition 1 for forming a third layer.
The amount of the cross-linking agent added was adjusted so that the molar ratio would be the value shown in Table 1.
The amount of catalyst added was 0.005 parts per 100 parts of prepolymer 1.

<Preparation of Second Layer Forming Composition 1>
As a soft segment material of the polyol component, polycaprolactone polyol (PLAXEL 240 manufactured by Daicel Corporation, average molecular weight 4155, hydroxyl value 27 KOHmg/g) was used (indicated as "CL" in the table).
1,4-butanediol (manufactured by Mitsubishi Chemical Corporation) was used as a chain extender (that is, hard segment material) (indicated by "BD" in the table).
As the polyisocyanate, 4,4′-diphenylmethane diisocyanate (MDI, manufactured by Nippon Polyurethane Industry Co., Ltd., Millionate MT) was used (indicated as “MDI” in the table).
Trimethylolpropane (manufactured by Mitsubishi Gas Chemical Company, Inc.) was used as a cross-linking agent (shown as "TMP" in the table).
As a catalyst, 1,8-diazabicyclo(5.4.0)undecene-7]-octylate (DBU, manufactured by San-Apro Co., Ltd., -U-CAT SA 102) was used.

Polyisocyanate (MDI) is added to the mixture of the soft segment material (polycaprolactone polyol) and the hard segment material (1,4-butanediol), reacted at 80 ° C. for 2 hours under a nitrogen atmosphere, and pre-treated. Polymer 2 was obtained.
The addition amounts of the soft segment material, the hard segment material, and the polyisocyanate were adjusted so that the molar ratios were the values shown in Table 1.

Thereafter, a cross-linking agent (trimethylolpropane) and a catalyst (DBU) were added to the prepolymer 2 and mixed to prepare a composition 1 for forming a second layer.
The amount of the cross-linking agent added was adjusted so that the molar ratio would be the value shown in Table 1.
The amount of catalyst added was 0.005 parts per 100 parts of prepolymer 2.

<Preparation of a base material in which the second layer and the third layer are laminated>
The composition for forming the third layer and the composition for forming the second layer are poured in order into a centrifugal molding machine whose mold is adjusted to 140 ° C. so that each thickness is as shown in Table 1, and cured for 1 hour. reacted. Then, it was aged and heated at 110° C. for 24 hours, cooled, and then cut to obtain a plate-like substrate 1 having a width of 8 mm and a thickness of 2 mm.
The weight average molecular weight of the polyurethane rubber in the second layer was 4,000, and the weight average molecular weight of the polyurethane rubber in the third layer was 3,000.

<Formation of first layer>
A first layer made of hydrogen-containing gallium oxide was formed on the second layer side surface of the obtained plate-like substrate 1 . The first layer was formed using a film forming apparatus (film forming apparatus 100 shown in FIG. 3).
First, the plate-like substrate 1 is placed on a substrate supporting member (film formation jig 103 in FIG. 3) in the film formation chamber (vacuum vessel 101 in FIG. 3) of the film formation apparatus, and the inside of the film formation chamber is It was evacuated until the pressure reached 0.1 Pa. This evacuation was carried out within 5 minutes after completion of replacement of the high-concentration oxygen-containing gas.

Next, He-diluted 40% oxygen gas (flow rate 1.6 sccm) and hydrogen gas (flow rate 50 sccm) were supplied from the gas introduction pipe (supply port 109a in FIG. 3) to the flat plate electrode (discharge electrode 105b in FIG. 3) with a diameter of 85 mm. is introduced into a film formation chamber provided with a radio frequency power supply unit (high frequency power supply unit 105a in FIG. 3) and a matching circuit (not shown in FIG. 3), a radio wave of 13.56 MHz is set to an output of 150 W with a tuner. Discharge was performed from the flat plate electrode by matching. The reflected wave at this time was 0W.
Next, trimethylgallium gas (flow rate: 1.9 sccm) was introduced into the film formation chamber from a shower nozzle through a gas introduction pipe. At this time, the reaction pressure in the deposition chamber measured by a Barathron vacuum gauge was 5.3 Pa. In this state, the plate-like substrate 1 was rotated at a speed of 500 rpm to form a film for 68 minutes to form a first layer having a thickness of 0.2 μm on the surface of the plate-like substrate 1 .
A cleaning blade was obtained as described above.

[Examples 2 to 5]
The types and amounts of the soft segment material, hard segment material, polyisocyanate, and cross-linking agent used for the preparation of the third layer-forming composition and the second layer-forming composition are shown in Table 1, and each layer A cleaning blade was obtained in the same manner as in Example 1, except that the thickness was as shown in Table 1.
The hard segment material (chain extender) used in the preparation of the composition for forming the second layer of Example 2 was 1,3-propanediol (manufactured by Mitsubishi Chemical Corporation) ("PD" in the table )

[Comparative Example 1]
A cleaning blade was obtained in the same manner as in Example 1, except that the first layer was not provided.

[Comparative Examples 2 to 4]
The types and amounts of the soft segment material, hard segment material, polyisocyanate, and cross-linking agent used for preparing the third layer-forming composition and the second layer-forming composition are shown in Table 2, and each layer A cleaning blade was obtained in the same manner as in Example 1, except that the thickness was as shown in Table 2.

[Comparative Example 5]
A cleaning blade was obtained in the same manner as in Example 1, except that the following isocyanate treatment was performed instead of forming the first layer.
<Isocyanate treatment>
The resulting plate-like substrate 1 is immersed in MDI (diphenylmethane diisocyanate) melted at 80° C. for 10 minutes to perform isocyanate treatment, thereby forming an isocyanate-treated layer on the surface of the plate-like substrate 1 on the second layer side. bottom.

[Comparative Example 6]
Example 1 except that a base material consisting of the third layer was produced without using the composition for forming the second layer, and the first layer was provided on the base material consisting of the third layer instead of the plate-shaped base material 1. A cleaning blade was obtained in the same manner as above.

[measurement]
Each thickness of the first layer, the second layer, and the third layer was determined by the method described above.
The dynamic friction coefficient of the first layer was determined by the method described above.
The Young's moduli of the first layer, second layer and third layer were determined by the method described above.
The elongation set of the second and third layers was determined by the method described above.
The results obtained are shown in Tables 3 and 4.

[evaluation]
<Evaluation of cleanability>
The resulting cleaning blade was mounted on a black-and-white image forming apparatus Docu Center III C3300 manufactured by Fuji Xerox Co., Ltd., and the pressing force NF (Normal Force) was set to 2.0 gf/mm and the angle W/A (Working Angle) was set to 10°. .
Further, a developer containing toner particles having a volume average particle diameter of 6 μm was used as the developer.
Photosensitivity after forming 1000 sheets of A4 paper (210 × 297 mm, Fuji Xerox Co., Ltd., P paper) with an image density of 40% in a high-temperature and high-humidity environment (temperature 28 ° C., humidity 85% RH). The surface of the body and the image on the 1000th sheet, and the surface of the photoreceptor and the image on the 10000th sheet after forming 10000 sheets of full-surface halftone images with an image density of 40% were visually observed and evaluated according to the following criteria. bottom. Tables 3 and 4 show the results.

-Evaluation criteria-
A: No problem in cleanability B: Fine toner slipping through, but no problem in terms of image quality C: Toner slipping through, slight white spots in the image, but acceptable range for image quality D: Toner slipping through, image quality Upper muscle occurs

<Blade wear evaluation>
The resulting cleaning blade was mounted on a black-and-white image forming apparatus Docu Center III C3300 manufactured by Fuji Xerox Co., Ltd., and the pressing force NF (Normal Force) was set to 2.0 gf/mm and the angle W/A (Working Angle) was set to 10°. .
As the developer, a developer containing a toner in which polymer resin particles, zinc stearate particles, and silica particles are externally added to toner particles was used.
In a high temperature and high humidity environment (temperature 28 ° C, humidity 85% RH), using A4 paper (210 × 297 mm, manufactured by Fuji Xerox Co., Ltd., P paper), test print (5% area ratio per color) Image of 10,000 prints were made. The depth of wear at the edge of the cleaning blade was observed from the cross-sectional side of the cleaning blade with a laser microscope VK-8510 manufactured by Keyence Corporation, and the maximum depth of the edge missing portion on the photoreceptor surface side was measured and evaluated according to the following evaluation criteria. . Note that A and B are allowable ranges. Tables 3 and 4 show the results.

-Evaluation criteria-
A: Tip wear depth: 3 µm or less and no wear marks Cleaning failure: Not occurred B: Tip wear depth: More than 3 µm and 5 µm or less Cleaning failure: Not occurred C: Tip wear depth: More than 5 µm Cleaning Defective: occurred

<Blade squeal evaluation>
The obtained cleaning blade was mounted on a black-and-white image forming apparatus Docu Center III C3300 manufactured by Fuji Xerox Co., Ltd., and the pressing force NF (Normal Force) was set to 2.0 gf/mm and the angle W/A (Working Angle) was set to 10°. 100 sheets of halftone images (image density 1%) are printed on A4 size paper in an environment of 28°C/85% RH. The hardness was evaluated according to the following criteria. Tables 3 and 4 show the results.

-Evaluation criteria-
A: Only the device driving sound can be heard
B: Slightly audible squeal of the cleaning blade other than the driving sound of the device.

<Evaluation of cleaning maintainability over time>
The resulting cleaning blade was mounted on a black-and-white image forming apparatus Docu Center III C3300 manufactured by Fuji Xerox Co., Ltd., and the pressing force NF (Normal Force) was set to 2.0 gf/mm and the angle W/A (Working Angle) was set to 10°. .
As the developer, a developer containing a toner in which polymer resin particles, zinc stearate particles, and silica particles are externally added to toner particles was used.
In a high temperature and high humidity environment (temperature 28 ° C, humidity 85% RH), using A4 paper (210 × 297 mm, manufactured by Fuji Xerox Co., Ltd., P paper), test print (5% area ratio per color) Image of 10,000 prints were made.

The amount of permanent deformation (μm) of the cleaning blade after that was measured as follows. Specifically, the process cartridge with the cleaning blade of each of the above examples attached so as to be in contact with the surface of the photoreceptor (image carrier) was placed in a constant temperature and high humidity environment (45° C., 95% RH). - It was left in a constant humidity bath for one week, and the difference in the biting amount of the cleaning blade before and after being left was taken as the amount of permanent deformation. The amount of encroachment was measured using a non-contact laser displacement meter (trade name: LK-035, manufactured by Keyence Corporation) capable of measuring the distance from the center of the photoreceptor to the tip of the edge of the cleaning blade. asked for a change in
In addition, the state of occurrence of image quality defects such as color streaks (image quality) in the 10000th image was visually evaluated according to the following criteria.
-Evaluation criteria-
A: No streaks were observed B: Slight streaks were observed in the image, but within an acceptable range C: Streaks were observed in the image and were unacceptable

From the above results, it can be seen that in the examples, compared to the comparative examples, both the initial cleaning property and the cleaning maintenance property over time are achieved.

10 cleaning blade 12 end 14 first layer 16 second layer 18 third layer 20 member to be cleaned 21 main body housing 22, 22a to 22d image forming unit 23 belt module 24 recording medium supply cassette , 25 recording medium transport path, 30 photoreceptor unit, 31 photoreceptor drum (image carrier/member to be cleaned), 32 charging roll, 33 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 delivery roll, 62 transport roll, 63 alignment roll, 66 fixing device, 67 discharge roll, 68 paper discharge section , 71 manual supply device, 72 delivery roll, 73 double-sided recording unit, 74 guide roll, 76 transport path, 77 transport roll, 100 film forming device, 101 vacuum container, 101a partition, 103 film forming jig, 105 discharge unit , 105a high-frequency power supply unit, 105b discharge electrode, 107 process gas supply unit, 107a supply port for supplying process gas, 109 material gas supply unit, 109a supply port for supplying material gas, 111 exhaust device, 111a exhaust port, 112 plate 230 intermediate transfer belt 231, 232 support roll 331 unit case 332 developing roll 333 toner conveying member 334 conveying paddle 335 trimming member 341 cleaning case 342 cleaning blade 344 film seal 345 conveying Member 346 Fixing tool 521 Secondary transfer roll 531 Cleaning blade T Object to be cleaned

Claims (10)

a first layer comprising a metal oxide;
a second layer which is an elastic layer having a Young's modulus of 4 MPa or more and 8 MPa or less;
a third layer, which is an elastic layer having a permanent elongation of less than 2%;
are provided in this order,
The first layer has a dynamic friction coefficient of 0.05 or more and 0.5 or less, and a Young's modulus of 10 MPa or more and 200,000 MPa or less ,
the third layer comprises polyurethane rubber;
The polyurethane rubber has a hard segment and a soft segment,
A cleaning blade , wherein the material constituting the soft segment contains polyether polyol . 2. The cleaning blade according to claim 1, wherein the first layer has a thickness of 0.1 [mu]m or more and 5.0 [mu]m or less. 3. The cleaning blade according to claim 2, wherein the first layer has a thickness of 0.5 [mu]m or more and 5.0 [mu]m or less. 4. The cleaning blade according to any one of claims 1 to 3, wherein the thickness of the second layer is 20 times or more and 10000 times or less the thickness of the first layer. The cleaning blade according to any one of claims 1 to 4, wherein the metal oxide is an oxide of a group 13 element. 6. The cleaning blade according to claim 5, wherein said metal oxide is gallium oxide. The cleaning blade according to any one of claims 1 to 6, wherein the second layer has a Young's modulus of 4 MPa or more and 5.5 MPa or less. A cleaning device comprising the cleaning blade according to any one of claims 1 to 7. A process cartridge, comprising the cleaning device according to claim 8, which is attachable to and detachable from an image forming apparatus. an image carrier;
charging means for charging the surface of the image carrier;
electrostatic latent image forming means for forming an electrostatic latent image on the surface of the charged image carrier;
developing means for developing an electrostatic latent image formed on the surface of the image carrier with a developer containing toner to form a toner image;
a transfer means for transferring the toner image onto the surface of a recording medium;
The cleaning device according to claim 8, which cleans the surface of the image carrier;
An image forming apparatus comprising:

Images