JP2010285649A - Coating method - Google Patents

Abstract

An object of the present invention is to provide a method for producing a coating film for obtaining a ceramic coating film having a small composition variation and excellent uniform and dense surface smoothness.
A method of producing a coating by an aerosol deposition method in which a particulate material is mixed with a gas to form an aerosol and sprayed from a nozzle onto a substrate to form a deposited film, the fracture toughness value of the particulate material being 6 MPam ^{1 / By being} less than ^2, it is a method for producing a coating film which can obtain a ceramic coating film with little composition fluctuation and excellent uniform and dense surface smoothness.
[Selection] Figure 2

Description

  The present invention relates to a method for producing a coating film using an aerosol deposition method in which a material such as finely divided ceramics, metal, or metalloid is sprayed onto a substrate to form a film.

  In recent years, a new thin film formation method called an aerosol deposition method (hereinafter referred to as AD method) has been proposed as a method for forming an electronic ceramic material such as an oxide or a nitride material (see, for example, Patent Document 1). This method is a film formation method based on the normal temperature impact solidification phenomenon. A raw material that has been finely divided in advance is mixed with a gas such as helium, nitrogen, and oxygen to form an aerosol, which is then sprayed onto a substrate through a nozzle in a reduced pressure atmosphere. To form a film. The formed film is composed of fine crystal lumps having a diameter of several tens of nanometers, and has a dense structure without generating voids. This AD method has an extremely high film forming speed compared with the conventional forming methods such as sputtering, ion plating, and CVD, and it is not necessary to carry out a heat treatment process at a high temperature at room temperature. Since a dense and high hardness film can be obtained, it is a production method very suitable for the production of a ceramic film. Utilizing the features of these AD methods, manufacturing of high dielectric constant dielectric films required for integration of passive components such as capacitors, resistors, inductors, etc., and three-dimensional mounting, and piezoelectric elements used in printer heads of ink jet printers Application development to manufacturing and the like is being attempted.

  FIG. 6 is a basic configuration diagram of a conventional general AD method apparatus. The main components of the apparatus are a vacuum chamber 102, an aerosol generator 106 and a thin carrier pipe 112 connecting them, and an injection nozzle 101 is attached to the tip of this carrier pipe. In addition to the substrate holder 113, a vacuum pump 109 such as a rotary pump is installed in the vacuum chamber 102, and the pressure is reduced from several Pa to several kPa. The aerosol generator 106 is connected through a gas cylinder 111 for supplying gas and an introduction pipe 110. Fine particles 105 as a raw material are agitated and mixed with gas in an aerosol generator to be aerosolized, and are supplied to the injection nozzle 101 through an introduction pipe 112. As the gas flows due to the pressure difference between the aerosol generator and the vacuum chamber, the aerosol is transported from the aerosol generator to the vacuum chamber and accelerated through the slit-like spray nozzles, and sprayed onto the substrate 103 to form the coating 107. . In general, the opening width of the slit can be about 1 mm to about 100 mm. A film-forming region having a large area can be obtained by moving the spray nozzle relative to the substrate, and a relatively small region can be formed by fixing.

  The film formation mechanism of the above-described AD method is considered as follows using the normal temperature impact solidification phenomenon. That is, the aerosolized raw material fine particles having an average particle diameter of about 1000 nm collide with the substrate at a high speed to be crushed into fine particles of about 10 to 30 nm, and the surface finely broken by the pulverization is very active as a new surface Thus, the new surfaces cause strong interparticle bonding. Therefore, unlike the conventional sintering method, a ceramic film having a dense structure can be produced at a low temperature.

Japanese Patent Laid-Open No. 2001-3180

However, as a result of various investigations on material properties and film forming properties used in the AD method, the fracture toughness value of the material to be formed is very important. When the fracture toughness value of the material increases, the film is formed by the AD method. It is difficult to form a film on the substrate. This phenomenon of no film formation cannot be explained simply by a slow film formation speed, and even if the film is formed for a long time, a film having a certain thickness or more cannot be formed. In other words, with the conventional method, it is impossible to accurately control the composition that affects the characteristics, and it is difficult to require that the secondary raw material be included in a relatively large proportion of the main raw material. Become.
The present invention has been made in view of the above-described problems, and an object of the present invention is to provide a method for producing a coating film for obtaining a ceramic coating film having a small composition variation and excellent uniform and dense surface smoothness. To do.

In order to solve the above-mentioned problems, the present invention is a method for producing a coating film by an aerosol deposition method in which a particulate material is mixed with a gas to form an aerosol and sprayed from a nozzle onto a substrate to form a deposited film. A method for producing a coating film, wherein the fracture toughness value is less than 6 MPam ^1/2 .

  Thereby, it is possible to obtain a ceramic coating with little composition variation and excellent uniform and dense surface smoothness.

The schematic diagram which shows AD method using one nozzle which concerns on the Example of this invention The characteristic view which shows the relationship between the fracture toughness value and film-forming speed | rate which concerns on the Example of this invention The schematic diagram which shows AD method using two nozzles concerning the Example of this invention Schematic diagram showing the layer structure of a photoreceptor according to an embodiment of the present invention. 1 is a schematic configuration diagram of an electrophotographic apparatus according to an embodiment of the present invention. Schematic diagram showing the conventional AD method

According to the first aspect of the present invention, there is provided a method for producing a coating film by an aerosol deposition method in which a brittle particulate material is mixed with a gas to form an aerosol and sprayed from a nozzle onto a substrate to form a deposited film. Since the fracture toughness value of the material is less than 6 MPam ^1/2 , a film can be efficiently formed on the substrate, so there is little composition fluctuation in the mixing and lamination processes, and the composition ratio is arbitrarily controlled and stable. A film having film characteristics can be obtained.

  According to a second aspect of the present invention, there is provided a method for producing a coating according to the first aspect, wherein the fine particle material is composed of a plurality of materials, so that a composite film is produced when sprayed onto the substrate at the same time. I can do it.

  According to invention of Claim 3 of this invention, it is a manufacturing method of the film of Claim 2, Comprising: A laminated film can be easily produced by spraying a several material on a board | substrate alternately.

According to a fourth aspect of the present invention, there is provided a method for producing a coating according to the first aspect, wherein the particulate material is sprayed onto the deposited film with a fine particle material having a fracture toughness value of 6 MPam ^1/2 or more. Thus, the deposited film can be flattened.

Further, since the fracture toughness value of the fine particle material used for affirmation of flattening is 6 MPam ^1/2 or more, the fine particles used in the flattening step are prevented from being contained as impurities in the deposited film, and the surface smoothness of the deposited film is also prevented. Can be improved.

  Details of an embodiment of the present invention will be described below with reference to the drawings.

FIG. 1 is a schematic view of a film forming apparatus using the AD method of the present invention. The film forming apparatus of the present invention includes aerosol generators 6-a and 6-b for dispersing material particles 5-a and 5-b having different compositions in a carrier gas to form aerosols, and these aerosols 4-a and 4 It is composed of an injection nozzle 1 for spraying -b, and the whole is covered with a vacuum chamber 2. An exhaust pump 9 is connected to the vacuum chamber 2, and the vacuum chamber 2 is continuously exhausted during film formation. The substrate 3 is mounted on the substrate holder 13 and can be moved back and forth and left and right as necessary. Gas cylinders 11-a and 11-b for introducing a carrier gas are connected to the aerosol generators 6-a and 6-b via introduction pipes 10-a and 10-b. The leading ends of the introduction pipes 10-a and 10-b are located in the vicinity of the bottom surface inside the aerosol generators 6-a and 6-b, and are disposed so as to be buried in the material particles 5-a and 5-b. The material particles 5-a and 5-b are blown up by sending carrier gas from the gas cylinders 11-a and 11-b to generate aerosols 4-a and 4-b. The generated aerosols 4-a and 4-b are supplied to the ejection nozzle 1 through the introduction pipe 12. The aerosol sprayed from the spray nozzle 1 is crushed by being sprayed onto the substrate, and becomes a deposited film 7 on the substrate 3. Whether the deposited film 7 is a mixed film or a laminated film is determined by opening and closing the switching valves 8-a and 8-b. That is, in order to obtain a mixed coating, both the switching valves 8-a and 8-b are opened and the mixed aerosol is ejected from the ejection nozzle 1. In order to obtain a laminated film, one of the switching valves 8-a and 8-b is opened, and the opening and closing thereof are alternately switched. The number of opening and closing of the switching valves 8-a and 8-b is the number of layers of the laminated coating. The material particles 5-a and 5-b used in the above steps are both made of a material having a fracture toughness value of less than 6 MPam ^1/2, so that the deposited film formed on the substrate is made of the material particles 5-a and 5-b. It becomes possible to obtain a mixed film containing both compositions or a laminated film in which single layer films having individual compositions are laminated.

  As the carrier gas, for example, an inert gas such as helium, argon, or krypton, nitrogen, air, oxygen, or the like can be used. The gas cylinders 11-a and 11-b may be the same gas or different gases. It does not matter. It is important to select the optimum carrier gas type according to the characteristics such as the mechanical characteristics and powder characteristics of the material particles used.

FIG. 2 shows the relationship between the fracture toughness value of the film obtained by using the AD method and the film formation speed. A film formation speed of zero means that no film is formed on the substrate. Incidentally, various different fracture toughness values in the figure are obtained by depositing different raw material particles, and as specific materials, yttria, aluminum nitride, silicon carbide, in order from the lowest fracture toughness value in the figure, Aluminum oxide. From each value of the fracture toughness value left indicated sequentially in ^{FIGS, 1.0Pam 1/2, 3.0Pam 1/2, 4.0Pam} 1/2, a 5.6Pam ^1/2, from these points An approximate curve is obtained, and the fracture toughness value at which the deposition rate becomes zero is 6.0 Pam ^1/2 .

  The film formation conditions such as the gas flow rate and the gas type are all performed under the same conditions, and the film thicknesses are all constant and approximately 5 microns. The individual raw material particles used in this example were treated with a ball mill, a jet mill, or the like in order to make the size uniform, thereby obtaining particles having an average particle diameter D50 of approximately 1 micron. Further, in order to eliminate the influence of moisture as much as possible and make the state of the raw material powder uniform, heat treatment was performed at 200 ° C. for 1 hour in a vacuum as a pretreatment.

As shown in FIG. 2, the fracture toughness value and the film formation rate by the AD method are closely related. As the fracture toughness value increases, the film formation rate decreases, and the fracture toughness value at which the film formation rate becomes zero is approximately 6 MPam. ^It can be expected to be about ^1/2 . That is, this suggests that it is difficult to form a film having a fracture toughness value of 6 MPm ^1/2 or more by the AD method. Naturally, the film formation rate of the film formed by the AD method is greatly influenced by the film formation conditions such as the gas flow rate, the type of gas, and the particle size of the powder. On the other hand, the fracture toughness value of the film is slightly affected by these conditions, but does not change greatly, and is determined by the characteristics of the substance itself. Therefore, the slope of FIG. 2 changes depending on the film forming conditions, but the intercept with the X axis does not change and is around the fracture toughness value of 6 MPm ^1/2 .

  The fracture toughness value is measured using the indentation method (IF method) of JIS R1607, and the fracture toughness value is obtained from the size of the dent when the sample is dented and the length of the crack. is there. In this example, a test was performed at a load pressure of 0.05 N using a micro hardness tester HMV-2T manufactured by Shimadzu Corporation as a measuring device. In addition, for the sake of accuracy, five points at different locations were measured for one sample and averaged.

Table 1 summarizes the relationship between the fracture toughness values of various brittle materials and the success or failure of film formation in the AD method. The fracture toughness value was measured using the same measuring apparatus as described above, and the load pressure was 10N. When the film formability was confirmed by visual observation, the case where the film was not formed on the substrate was marked as x. Note that the fracture toughness value shown here is different from the fracture toughness value shown in FIG. 1, not the film value but the sintered body value. The results shown in this table show the same tendency as the results shown in FIG. That is, it is concluded that it is difficult to form a film having a fracture toughness value of 6 MPam ^1/2 or more by the AD method.

By the way, as described in the catalog issued by each manufacturer, the fracture toughness value of the sintered body is, for example, 5.5 MPam ^{1/2 for} silicon nitride N800 manufactured by Asahi Glass Co., Ltd., and silicon nitride SN manufactured by Kyocera Corporation. Even if -240 is the same material as 7.0 MPam ^1/2 , a slight difference will occur due to differences in sintering conditions and measurement conditions by the manufacturer. In general, the film formation by the AD method has a great influence on the success or failure of the film formation and the film formation speed depending on the powder state (particle size, dry state), the incident angle of the aerosol, the gas flow rate, the gas type, and the like. Therefore, when determining whether or not a material can be formed, if an attempt is made to form a film of a single material under only one condition, and judging from the result, an incorrect result is derived. The film formation results shown in Table 1 show that various raw material particles (manufacturer, average particle diameter, heat treatment conditions, etc.) and various film formation conditions (gas type, gas flow rate, nozzle-substrate distance, etc.) Since the results are comprehensively studied, the results are not limited to materials of specific manufacturers or specific film forming conditions, but are universal results for the AD method. In other words, from the results shown in FIG. 2 and (Table 1), a new finding was concluded that it was difficult to form a brittle material having a high fracture toughness value and a value of 6 MPam ^1/2 or more by the AD method. It will be. Note that the reason why the fracture toughness value affects the film formability of the AD method is considered to be the following mechanism. The fracture toughness value is a kind of measure showing the resistance to fracture of a material having a crack in the surface or inside. Therefore, when a material having a high fracture toughness value is used in the AD method, the raw material particles temporarily collide with the substrate. Even if there is a crack in the film, it is less likely to be completely crushed and an active new surface that is indispensable for growing as a film cannot be obtained. As a result, it becomes impossible to grow as a film on the substrate. In addition, in order to improve this, even if the collision energy is increased by devising the film formation conditions, the etching effect is increased, and the etching rate exceeds the film formation rate. You will not be able to grow. Therefore, it becomes difficult to form a film having a high fracture toughness value by the AD method.

  FIG. 3 is a schematic view of an AD method film forming apparatus for producing a mixed film and a laminated film using a plurality of spray nozzles according to an embodiment of the present invention. The film forming apparatus shown in FIG. 1 produces a mixed film and a laminated film with one spray nozzle by opening and closing the switching valves 8-a and 8-b, whereas the film forming apparatus shown in FIG. This is a method for producing a film using two independent spray nozzles. When the film is continuously formed using the two injection nozzles shown in FIG. 3, by controlling the focal position where the aerosol and the substrate injected from the individual injection nozzles 1-a and 1-b collide, A mixed film and a laminated film can be arbitrarily produced. That is, when producing a mixed film, it is possible to set the focal point A and the focal point B (shown in FIG. 3) to substantially the same position. On the other hand, the laminated film can be produced by setting the focal point A and the focal point B apart.

  Table 2 shows the characteristics of the mixed film when various brittle materials were produced using the AD method film forming apparatus of FIG. For comparison with the present example, Comparative Examples 1 and 2 show the characteristics of a single composition film made by the AD method and not mixed. Silicon carbide coatings have very good wear properties and are applied to cutting tools, bearings, and the like, but have low resistance and transmittance, and are characteristics that should be improved depending on various electronic devices. It is clear from Table 2 that the addition of alumina and yttria to silicon carbide improves the resistance and transmittance, and the characteristics of titanium oxide are improved by mixing with alumina as well as silicon carbide. ing. The merit of mixing silicon carbide can be used as a surface coating material for displays that require abrasion resistance while requiring transparency, such as electronic paper and touch panel liquid crystal. The merit in the case of titanium oxide is that it can be used for a charge generation layer or a charge transport layer for a photoreceptor because the light absorption characteristics change when mixed. Whether or not a mixed film is formed is confirmed not only by the characteristics shown in Table 2, but also by composition analysis using an electron probe microanalyzer (EPMA). In this embodiment, the composition ratio of the mixed film is controlled by the powder mill conditions and the film forming conditions such as flow rate gas, and the composition ratio of the film obtained this time is approximately 0.8 for the main material and 0.2 for the auxiliary material. 2.

  In the film deposition apparatus of the AD method described in FIG. 3, the positional relationship between the individual spray nozzles is arranged at a position that is not symmetrical in terms of angle, but is not particularly limited to this. It can be varied according to the film speed and the mixing composition ratio. In general, the film forming speed is higher when spraying at normal incidence than when spraying from an oblique direction, even if the same material is used. Therefore, it is only necessary to select optimum film forming conditions in consideration of this. Further, the number of injection nozzles is not particularly limited, and two or more nozzles may be used in accordance with the number of materials to be mixed and the number of materials to be laminated.

  The ejection width of the nozzle (FIG. 3 shows the depth direction) is not particularly limited, and the effect of the present invention can be exhibited without problems even with a nozzle having a width of several mm to a hundred mm.

Examples of material particles having a fracture toughness value of less than 6 MPam ^1/2 that can be used in the present invention include oxides such as aluminum oxide, yttria, titanium oxide, silicon oxide, and ferrite, nitrides such as aluminum nitride and titanium nitride, and silicon carbide. And carbides such as barium titanate, lead zirconate titanate, and forsterite.

By the way, it has been described so far that it is indispensable to use material particles having a fracture toughness value of less than 6 MPam ^1/2 in order to obtain a mixed film or a laminated film. However, one material particle has a fracture toughness value of 6 MPam ^{1 /} It has been found that using ^two or more materials is very effective for flattening the film formed. Conventionally, in order to improve the surface smoothness of the coating, the fine particle material is mixed with the gas to make an aerosol, and the deposition film is formed by spraying from the nozzle onto the substrate, and the fine particle material is mixed with the gas to make the aerosol. There has been proposed a production method in which a step of planarizing the surface of the deposited film by spraying on the surface is used in combination. However, if the material used in the planarization step is not properly selected, the fine particle material is included as an impurity in the film.

Therefore, in the present invention, by using a fine particle material having a fracture toughness value of 6 MPam ^1/2 or more in the planarization step, the fine particle material having a fracture toughness value of 6 MPam ^1/2 or more is not formed as a deposited film as described above. It becomes possible to prevent the fine particles themselves from being contained as impurities in the film. As a specific manufacturing method, in the AD method film forming apparatus shown in FIGS. 1 and 3, a leaf fracture toughness value of less than 6 MPam ^1/2 is used for the fine particle material to be a film, and a fracture toughness value of 6 MPam is used for one fine particle material. ^Flatten using ^1/2 or more. In FIG. 1, there are two methods of alternately performing the film forming process and the flattening process, or performing the flattening process after the film forming process is completed, and open and close the switching valves 8-a and 8-b. Can be implemented. In the embodiment using the two injection nozzles shown in FIG. 3, since the planarization can be performed in the process of growing the film, the flattening effect is great, and the film forming process and the flattening process are performed using one injection nozzle. Compared with the case, a flatter surface can be obtained. In addition, since the film forming process and the flattening process can be performed at the same time, the productivity is increased as compared with the case of switching one injection nozzle. In this case, the positional relationship between the focal point A and the focal point B is preferably separated.

Examples of material particles having a fracture toughness value of 6 MPam ^1/2 or more that can be used in the planarization step according to the present invention include zirconia, silicon nitride, and diamond. The effect of the present invention is not limited to the material particles described above, and other materials may be used. What is important in the present invention is that the fracture toughness value of the material used in the film-forming process is less than 6 MPam ^1/2 , and the fracture toughness value of the material used in the planarization process is 6 MPm ^1/2 or more.

  FIG. 4 is a schematic view showing the layer structure of the electrophotographic photosensitive member 20 produced by using the AD method of the present invention. In FIG. 4, 21 is a conductive support, 22 is a charge generation layer composed of an organic film, and 23 is a charge transport layer composed of a light-transmitting metal oxide film. It is formed in order. The charge transport layer 23 is formed by the AD method manufacturing method of the present invention shown in FIG. 1 or FIG.

  In order to be used as the charge transport layer 23, it has to have a function of reaching the charge generation layer 22 without absorbing in the wavelength band of the light to be exposed and transporting the generated charges to the surface of the electrophotographic photosensitive member. Don't be. In this example, a mixed film of titanium oxide and alumina was used as a charge transport layer as a material having the characteristics.

Typical film characteristics of the composite film of titanium oxide and alumina formed by using the AD method of the present invention include a transmittance of 80% (wavelength: 800 nm) and an electric resistance (sheet resistance) of 2 × 10 at a film thickness of 5 μm. ^-13 Ω / □, surface roughness 40 nm. As film forming conditions, high-purity titanium oxide powder having a particle size distribution of D ₁₀ = 0.2 μm, D ₅₀ = 0.3 μm, and D ₉₀ = 0.5 μm, a particle size distribution of D ₁₀ = 0.3 μm, D ₅₀ = 0. An alumina powder of 5 μm and D ₉₀ = 0.8 μm was used. Nitrogen gas was used as the carrier gas, and individual optimization was achieved by varying the flow rate. For comparison, when titanium oxide having a single composition is formed using the same material particles as described above under the same film formation conditions, the electrical resistance (sheet resistance) of the film is 7 × 10 ⁻⁸ Ω / □, and the transmittance. It is confirmed that this example is more suitable for use as a charge transport layer of an electrophotographic photosensitive member.

  As the support 21, the support 21 itself has conductivity, for example, aluminum is representative, but other than that, aluminum alloy, copper, stainless steel, chromium, titanium, nickel, magnesium, indium, gold, Platinum, silver, iron, etc. can be used. In addition, aluminum, indium oxide, tin oxide, gold, etc. are formed into a film by vapor deposition etc. on a dielectric substrate such as plastic, and conductive fine particles are mixed into plastic or paper. A thing etc. can be used. These conductive supports 21 are required to have uniform conductivity, and smooth surface properties are also important. Since the smoothness of the surface of the support 21 greatly affects the uniformity of the charge generation layer 22 and the charge transport layer 23 formed thereon, the surface roughness is preferably 0.5 μm or less.

  Although FIG. 4 shows a configuration in which the charge generation layer 22 is formed directly on the support 21, an undercoat layer having an injection blocking function and an adhesion function is provided between the support 21 and the charge generation layer 22. You can also (not shown). Examples of the material for the undercoat layer include casein, polyvinyl alcohol, nitrocellulose, ethylene-acrylic acid copolymer, polyvinyl butyral, phenolic resin, polyamide, polyurethane, gelatin and the like, which exhibit insulating performance. Further, when the support is aluminum, an alumite treatment may be performed to form alumina having a thickness of several tens of μm as an undercoat layer.

  The charge generation layer 22 is not particularly specified. For example, metal phthalocyanines such as titanyl phthalocyanine, metal-free phthalocyanine, copper phthalocyanine, naphthalocyanines, and mixed crystals of these two phthalocyanines, azo compounds, selenium-tellurium, pyrylium compounds, perylene compounds, cyanine compounds, squalane compounds In addition to organic substances such as compounds and polycyclic quinone compounds, amorphous silicon, zinc oxide and the like can be mentioned.

  In order to improve printing durability, various protective films may be coated on the charge transport layer 23, and examples of the material include carbon, alumina, and silicon carbide. Further, as a method of forming these protective films, in addition to sputtering, CVD, etc., they may be formed by the AD method of this embodiment.

  FIG. 5 is a schematic configuration diagram of an electrophotographic apparatus 30 configured using the electrophotographic photosensitive member according to the present invention. The electrophotographic apparatus 30 shown in FIG. 5 has photoconductors 31, 32, 33, and 34 as four cylindrical or columnar image forming bodies, and a belt-like transfer body 35 extending over these. The intermediate transfer unit 36 and the like are included. Around the photosensitive members 31, 32, 33, and 34, there are charging devices (here, charging rollers) 37, 38, 39, and 40, an exposure device 41, and developing units 42 and 43 each having a developer storage portion above. 44, 45, and photoconductor cleaners 46, 47, 48, 49 are arranged. The intermediate transfer unit 36 is provided with a belt cleaner 51 for cleaning so-called residual toner that is not transferred onto the recording paper 50 but remains on the surface of the belt-shaped transfer body 35. Further, the belt-like transfer body 35 of the intermediate transfer unit 36 is the final one required to transfer the toner image formed and transferred by the photoreceptors 31, 32, 33, and 34 onto the recording paper 50. The transfer roller 52 abuts or faces the transfer roller 52. The fixing device 53 is means for fixing the toner image transferred to the recording paper 50.

  Next, details of image formation will be described. First, the electrophotographic photosensitive member 31 according to the present invention is uniformly charged by the charging device 37 and then exposed by the exposure device 41, and the electrostatic latent image formed thereby is developed by the developing device 42. The toner image in which the electrostatic latent image is visualized is transferred to the belt-shaped transfer body 35 at a position facing or in contact with the belt-shaped transfer body 35 of the intermediate transfer unit 36. The toner images of other colors formed on the surface of the electrophotographic photosensitive member 32 are used as the first toner image as the second toner image in accordance with the timing at which the first toner image advances to a position where the first toner image contacts the electrophotographic photosensitive member 32. The toner image is transferred onto the toner image. Similarly, the third and fourth toner images are transferred in a superimposed manner to complete a four-color superimposed image. The superimposed image formed on the belt-like transfer member 35 of the intermediate transfer unit 36 is then collectively transferred to the recording paper 50 at a portion in contact with the final transfer roller 52, and is fixed to the recording paper 50 by the fixing device 53. A color image is formed on the recording paper 50.

  In the series of image forming processes, the toner that has not been transferred from the electrophotographic photosensitive member 31, 32, 33, 34 to the belt-like transfer member 35 is scraped off by the photosensitive member cleaners 46, 47, 48, 49. Generally, the photoreceptor cleaners 46, 47, 48, and 49 are configured by blades or the like, and the photoreceptor cleaners 46, 47, 48, and 49 are in contact (sliding) with the photoreceptors 31, 32, 33, and 34, respectively. The toner that was not transferred in step 1 is removed.

  Since the electrophotographic photoreceptors 31, 32, 33, and 34 according to the present invention have high wear resistance (durability), for example, when the process speed of the electrophotographic apparatus 30 is set to a higher speed, or a so-called heavy duty machine. It can also be suitably used in devices in fields where high throughput is required.

  As a result of operating the electrophotographic photosensitive member according to the present invention mounted on the electrophotographic apparatus 30 configured as described above, the image quality of the obtained image is the same as that of a conventional organic photosensitive member or amorphous silicon photosensitive member. It was confirmed that there was no inferiority compared to the fabricated one.

  In the above-described embodiments of the present invention, the case where the present invention is applied to an electrophotographic photosensitive member has been described. However, other devices such as piezoelectric films for inkjet heads, ceramic capacitors, insulating films for various devices such as semiconductors, coatings, etc. It has been confirmed that similar preferable results can be obtained when applied to a membrane.

  According to the method for producing a film of the present invention, the composition can be precisely controlled, and a mixed film and a laminated film can be formed without limiting the ratio of the composition ratio. Therefore, it is suitable for forming a film in various industrial equipment parts. Can be used for

DESCRIPTION OF SYMBOLS 1,1-a, 1-b Injection nozzle 2 Vacuum chamber 3 Substrate 4 Aerosol 5-a, 5-b Material particle 6-a, 6-b Aerosol generator 7 Deposition film 8-a, 8-b Switching valve 9 Exhaust pump 10-a, 10-b Introducing pipe 11-a, 11-b Gas cylinder 12 Introducing pipe 13 Substrate holder 20 Electrophotographic photosensitive member 21 Support 22 Charge generating layer 23 Charge transporting layer 30 Electrophotographic apparatus 31, 32, 33 34 Photosensitive member 35 Belt-shaped transfer member 36 Intermediate transfer unit 37, 38, 39, 40 Charging device (charging roller)
41 Exposure Device 42, 43, 44, 45 Developer 46, 47, 48, 49 Photoconductor Cleaner 50 Recording Paper 51 Belt Cleaner 52 Final Transfer Roller 53 Fixing Device

Claims (4)

A method for producing a coating by an aerosol deposition method in which a brittle particulate material is mixed with a gas to form an aerosol and sprayed from a nozzle onto a substrate to form a deposited film, wherein the fracture toughness value of the particulate material is less than 6 MPam ^1/2 A method for producing a coating film, characterized by comprising: The method for producing a coating film according to claim 1, wherein the fine particle material comprises a plurality of materials. The method for producing a coating film according to claim 2, wherein the plurality of materials are alternately sprayed on the substrate. The method for producing a coating film according to claim 1, wherein a fine particle material having a fracture toughness value of 6 MPam ^1/2 or more is sprayed on the deposited film.

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