JP2008209835A - Intermediate transfer body and image forming apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an intermediate transfer body excellent in transferability and surface hardness and having excellent durability (mold releasability, resistance to void failure and resistance to crack) even after it is used or kept over a long term under severe environment, and an image forming apparatus equipped with the same. <P>SOLUTION: The intermediate transfer body has a first silicon oxide layer whose carbon content is ≥0.5 atm.% and ≤10 atm.% and a second silicon oxide layer whose carbon content is <0.5 atm.% from a base material side on the base material, and has a barrier layer containing silicon oxide at a position on a surface side from the first silicon oxide layer with respect to the base material. The barrier layer is set so that film thickness is 5 to 20 nm, average film density is 2.1 to 2.3 g/cm<SP>3</SP>, and carbon content is <0.1 atm.%. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an intermediate transfer body and an intermediate transfer body for synthesizing and transferring a toner image for each color for a color image in an electrophotographic apparatus such as an electronic copying machine, a laser beam printer, a facsimile, or an electrostatic recording apparatus. The present invention relates to an image forming apparatus including

  Conventionally, an image forming method using an intermediate transfer member is known as a method for transferring a toner image on an electrophotographic photosensitive member (hereinafter also simply referred to as a photosensitive member) to a recording material. This method is known as an electrophotographic photosensitive member. In the process of transferring the toner image from the toner to the recording material, another transfer process is performed. After the primary transfer from the electrophotographic photosensitive member to the intermediate transfer member, the primary transfer image of the intermediate transfer member is secondarily transferred to the recording material. To get the final image. This method is often employed as a multiple transfer method for each color toner image in a so-called full-color image forming apparatus that reproduces a color-separated document image using subtractive color mixing with toners such as black, cyan, magenta, and yellow. .

  However, in this multiple transfer system using the intermediate transfer member, the transfer of the primary transfer and the secondary transfer is performed twice, and toner of four colors is superimposed on the transfer member. Image defects are likely to occur.

  In general, it is known that the transfer efficiency can be improved by treating the toner surface with an external additive such as silica for toner transfer failure. However, the stress from the toner stirring member in the developing device, the stress received from the regulating blade for forming the toner layer on the developing roller, the stress received between the photosensitive member and the developing roller, etc. There is a problem that sufficient transfer efficiency cannot be obtained because silica is detached or embedded in the toner, and a cleaning device is required to scrape off the toner remaining on the intermediate transfer member from the intermediate transfer member with a blade. .

  On the other hand, the intermediate transfer member has a problem of a hollow failure. It is known that this void failure is mainly affected by the surface energy of the intermediate transfer member, and the toner image formed on the image carrier is transferred to the intermediate transfer member due to the decrease of the surface energy of the intermediate transfer member. After transferring to the body, when transferring the toner image transferred to the intermediate transfer body to the transfer paper (secondary transfer), the transfer is not performed sufficiently, and the toner image remains on the intermediate transfer body, This is a failure in which an untransferred area on the transfer paper becomes a white spot.

  In order to increase the secondary transfer efficiency of the intermediate transfer member against the above white spot failure, the surface of the intermediate transfer member is coated with an inorganic compound thin film (for example, silicon oxide, aluminum oxide, etc.) to improve the peelability of the toner image. There are proposals for improving the transfer efficiency to recording paper and the like (see, for example, Patent Documents 1 and 2).

  In Patent Documents 1 and 2, in order to improve the releasability of the toner from the intermediate transfer member, a layer of silicon oxide or aluminum oxide is formed on the surface of the intermediate transfer member. However, when an endurance test was performed on the intermediate transfer member produced by this method in an actual image forming apparatus, there was a problem that the oxide layer was peeled off from the surface layer by repeated bending operations, and silicon oxide was deposited by vapor deposition. In addition, since silicon oxide, aluminum oxide, or the like is formed by sputtering, there is a problem that a large facility such as a vacuum apparatus is required.

  On the other hand, in view of the above problems, there is a method of forming an inorganic compound thin film (for example, silicon oxide, aluminum oxide, etc.) by an atmospheric pressure plasma treatment method as a method for improving the secondary transfer property of the intermediate transfer member. In the case of forming a compound thin film, the first layer (adhesion layer) and the second layer (surface layer, hard film) from the viewpoint of achieving excellent durability (for example, thin film adhesion to the base material, surface thin film hardness). ) May be adopted. In this laminated structure, in order to give a stress relaxation function to the first layer, the reaction conditions of the auxiliary gas (for example, nitrogen gas, hydrogen gas, etc.) are set so as not to complete the thin film formation with the raw material. Control is performed so that the carbon content in the thin film is constant. However, since the raw materials are not changed to inorganic compounds in this way, the first layer is formed in a state where unreacted raw materials (for example, siloxane compounds) are contained in the film. In such a state, when used or stored for a long period of time, the unreacted raw material compound moves between the layers and causes bleed out on the surface, thereby reducing the surface energy of the surface of the intermediate transfer member. This will result in further promotion of white failure.

In addition, a method of forming an inorganic coating layer on the surface of the intermediate transfer member has been proposed (see, for example, Patent Document 3). In the method proposed in Patent Document 3, it is known that if a large amount of colloidal silica added to the inorganic coating layer is added, toner releasability is improved and transfer efficiency is improved. Repeating the operation causes cracks in the inorganic coating layer, so that it is impossible to add more than a certain amount. Therefore, there has been a problem that sufficient releasability cannot be exhibited and transfer efficiency cannot be increased beyond a certain level.
JP-A-9-212004 JP 2001-347593 A JP 2000-206801 A

  The present invention has been made in view of the above problems, and its purpose is excellent in transferability and surface hardness, and excellent durability (release) even after being used or stored for a long time in a harsh environment. And an image forming apparatus provided with the intermediate transfer member having high resistance, white spot failure resistance, and crack resistance.

  The above object of the present invention is achieved by the following configurations.

1. A first silicon oxide layer having a carbon content of 0.5 atomic% or more and 10 atomic% or less on the base material side and a second carbon content of less than 0.5 atomic% from the base material side. And a barrier layer containing silicon oxide at a position on the surface side of the first silicon oxide layer with respect to the substrate, the barrier layer having a thickness of 5 nm or more, An intermediate transfer member, characterized in that it is 20 nm or less, has an average film density of 2.1 g / cm ³ or more and 2.3 g / cm ³ or less, and has a carbon content of less than 0.1 atomic%.

  2. 2. The intermediate transfer member according to 1 above, wherein an average film density of the barrier layer is higher than an average film density of each of the first silicon oxide layer and the second silicon oxide layer.

3. ^3. The intermediate transfer member according to 1 or 2, wherein an average film density of the first silicon oxide layer is 1.8 g / cm ³ or more and less than 2.1 g / cm ³ .

4). 4. The intermediate transfer member according to any one of items 1 to 3, wherein an average film density of the second silicon oxide layer is 2.1 g / cm ³ or more and 2.3 g / cm ³ or less. .

  5. At least one layer selected from the first silicon oxide layer, the second silicon oxide layer, and the barrier layer has a thin film forming gas in a discharge space formed between opposing electrodes under atmospheric pressure or a pressure in the vicinity thereof. Formed by an atmospheric pressure plasma CDV method for forming a silicon oxide thin film by exciting a gas by applying a high frequency electric field to the discharge space and exposing the substrate to the excited gas. 5. The intermediate transfer member according to any one of 1 to 4, wherein the intermediate transfer member is formed.

  6). All the layers of the first silicon oxide layer, the second silicon oxide layer, and the barrier layer contain a thin film forming gas in a discharge space formed between opposing electrodes under atmospheric pressure or a pressure in the vicinity thereof. Formed by an atmospheric pressure plasma CDV method of forming a silicon oxide thin film by exciting the gas by applying a high frequency electric field to the discharge space and exposing the substrate to the excited gas. The intermediate transfer member according to any one of 1 to 5, wherein the intermediate transfer member is characterized in that:

  7. In the image forming apparatus for developing the surface of the image bearing member to form a toner image, transferring the toner image to an intermediate transfer member, and further transferring the toner image to a transfer paper, the intermediate transfer member is any one of the above-described one to six An image forming apparatus comprising the intermediate transfer member according to item 1.

  The intermediate transfer according to the present invention has excellent transferability and surface hardness, and has excellent durability (releasability, white spot failure resistance, crack resistance) even after being used or stored for a long time in a harsh environment. It was possible to provide a body and an image forming apparatus including the body.

  Hereinafter, the best mode for carrying out the present invention will be described in detail.

As a result of intensive studies in view of the above problems, the present inventors have found that the first silicon oxide layer having a carbon content of 0.5 atomic% or more and 10 atomic% or less on the base material side from the base material side. And a second silicon oxide layer having a carbon content of less than 0.5 atomic%, and a barrier containing silicon oxide at a position on the surface side of the substrate relative to the first silicon oxide layer The barrier layer has a film thickness of 5 nm or more and 20 nm or less, an average film density of 2.1 g / cm ³ or more and 2.3 g / cm ³ or less, and a carbon content of 0.1 atom. The intermediate transfer member is characterized by being less than a few percent, and has excellent transferability and surface hardness, and excellent durability (releasability, whiteness) even after being used or stored for a long time in harsh environments. It was possible to realize an intermediate transfer member having resistance to dropout failure and cracking).

  That is, a first silicon oxide layer (adhesion layer, stress relaxation layer) having a high carbon content and a low density and a second silicon oxide having a low carbon content and a high density are formed on a substrate constituting the intermediate transfer member. In an intermediate transfer body having a layer (surface layer, cured film layer), an unreacted thin film forming raw material (mainly a siloxane compound mainly remaining in the layer when the first layer is formed) In order to prevent the compound having a large surface energy lowering ability) from diffusing into the second layer (which is often the surface layer), causing bleed out and lowering the surface energy, the unreacted raw material is included. By providing a high-density barrier layer in a specific film thickness range that does not substantially contain carbon, that is, the carbon content is less than 0.1 atomic%, on the upper portion of the first silicon oxide layer, Of the unreacted raw material compound contained in the first silicon oxide layer located at By blocking the diffusion of silicon 2 into the silicon oxide layer or providing a barrier layer as the outermost layer, excellent transferability, surface hardness, and crack resistance are maintained, and due to diffusion to the surface and bleeding out. This prevents whiteout failures.

  Details of the present invention will be described below.

  The intermediate transfer member of the present invention is suitably used in image forming apparatuses such as electrophotographic copying machines, printers, facsimiles, etc., and the toner image carried on the surface of the photoreceptor is primarily transferred to the surface and transferred. Any toner image may be used as long as the image is held and the held toner image is secondarily transferred onto the surface of an object to be transferred such as recording paper, and may be a belt-like transfer member or a drum-like transfer member.

  First, the configuration of an image forming apparatus equipped with the intermediate transfer member of the present invention will be described using a tandem type full-color copying machine as an example.

  FIG. 1 is a cross-sectional configuration diagram illustrating an example of a configuration of a color image forming apparatus.

  The color image forming apparatus 1 is called a tandem full-color copying machine, and mainly includes an automatic document feeder 13, a document image reading device 14, a plurality of exposure means 13Y, 13M, 13C, and 13K. A plurality of sets of image forming units 10Y, 10M, 10C, and 10K, an intermediate transfer body unit 17, a paper feeding unit 15, and a fixing unit 124 are included.

  An automatic document feeder 13 and a document image reading device 14 are arranged on the upper part of the main body 12 of the color image forming apparatus 1, and an image of the document d conveyed by the automatic document feeder 13 is stored in the document image reading device 14. Reflected and imaged by the optical system, read by the line image sensor CCD.

  An analog signal obtained by photoelectrically converting a document image read by the line image sensor CCD is subjected to analog processing, A / D conversion, shading correction, image compression processing, and the like in an image processing unit (not shown), and then exposure means. Drum-shaped photoconductors 11Y, 11M, 11C, and 11K serving as first image carriers that are transmitted as digital image data for the respective colors to 13Y, 13M, 13C, and 13K, and corresponding to the exposure units 13Y, 13M, 13C, and 13K. A latent image of image data of each color is formed.

  The image forming units 10Y, 10M, 10C, and 10K are arranged in a vertical column, and rollers 171, 172, 173, and 174 are wound around the left side of the photoreceptors 11Y, 11M, 11C, and 11K so as to be rotatable. An intermediate transfer member 170 according to the present invention, which is a second semiconducting endless belt-shaped image carrier, is disposed. The intermediate transfer member 170 is driven in the direction of the arrow through a roller 171 that is rotationally driven by a driving device (not shown).

  The image forming unit 10Y that forms a yellow image includes a charging unit 12Y, an exposure unit 13Y, a developing unit 14Y, a primary transfer roller 15Y as a primary transfer unit, and a cleaning unit 16Y disposed around the photoreceptor 11Y.

  The image forming unit 10M that forms a magenta image includes a photoreceptor 11M, a charging unit 12M, an exposure unit 13M, a developing unit 14M, a primary transfer roller 15M as a primary transfer unit, and a cleaning unit 16M.

  The image forming unit 10C that forms a cyan image includes a photoreceptor 11C, a charging unit 12C, an exposure unit 13C, a developing unit 14C, a primary transfer roller 15C as a primary transfer unit, and a cleaning unit 16C.

  The image forming unit 10K that forms a black image includes a photoreceptor 11K, a charging unit 12K, an exposure unit 13K, a developing unit 14K, a primary transfer roller 15K as a primary transfer unit, and a cleaning unit 16K.

  The toner replenishing means 141Y, 141M, 141C, and 141K replenish toner to the developing devices 14Y, 14M, 14C, and 14K, respectively.

  Here, the primary transfer rollers 15Y, 15M, 15C, and 15K are selectively operated according to the type of image by a control unit (not shown), and the intermediate transfer member 170 is placed on the corresponding photoreceptors 11Y, 11M, 11C, and 11K. Press to transfer the image on the photoreceptor.

  In this manner, the images of the respective colors formed on the photoreceptors 11Y, 11M, 11C, and 11K by the image forming units 10Y, 10M, 10C, and 10K are rotated by the primary transfer rollers 15Y, 15M, 15C, and 15K. The images are sequentially transferred onto the intermediate transfer body 170 to form a combined color image.

  That is, the intermediate transfer member primarily transfers the toner image carried on the surface of the photosensitive member to the surface, and holds the transferred toner image.

  Further, the recording paper P, which is a recording medium accommodated in the paper feeding cassette 151, is fed by the paper feeding means 15, and then passes through a plurality of intermediate rollers 122A, 122B, 122C, 122D, and a registration roller 123, and then the secondary paper. The toner image is conveyed to a secondary transfer roller 117 serving as a transfer unit, and the combined toner image on the intermediate transfer member is collectively transferred onto the recording paper P by the secondary transfer roller 117. That is, the toner image held on the intermediate transfer member is secondarily transferred onto the surface of the transfer object.

  Here, the secondary transfer means 6 presses the recording paper P against the intermediate transfer body 170 only when the recording paper P passes through the secondary transfer means 6 and performs secondary transfer.

  The recording paper P onto which the color image has been transferred is subjected to fixing processing by the fixing device 124, sandwiched between the paper discharge rollers 125, and placed on a paper discharge tray 126 outside the apparatus.

  On the other hand, after the color image is transferred to the recording paper P by the secondary transfer roller 117, the residual toner is removed by the cleaning unit 8 from the intermediate transfer member 170 that has separated the curvature of the recording paper P.

  Here, the intermediate transfer member may be replaced with a rotating drum-shaped intermediate transfer drum as described above.

  Next, the configuration of the primary transfer rollers 15Y, 15M, 15C, and 15K as the primary transfer means that contacts the intermediate transfer body 170 and the secondary transfer roller 117 will be described.

The primary transfer rollers 15Y, 15M, 15C, 15K and the secondary transfer roller 6 are made of, for example, polyurethane, EPDM (ethylene tetrafluoroethylene copolymer), silicon on the peripheral surface of a conductive metal core such as stainless steel having an outer diameter of 8 mm. Solid state or foamed with a volume resistance of about 1 × 10 ⁵ to 1 × 10 ⁹ Ω · cm by dispersing conductive fillers such as carbon in rubber materials such as In a sponge state, it is formed by coating a semiconductive elastic rubber having a thickness of 5 mm and a rubber hardness of about 20 to 70 ° (Asker hardness C).

  Unlike the primary transfer rollers 15Y, 15M, 15C, and 15K, the secondary transfer roller 6 may come into contact with toner in the absence of the recording paper P. Therefore, the surface of the secondary transfer roller 6 is a semiconductive fluororesin. It is preferable to coat a material having good releasability such as urethane resin, and a peripheral surface of a conductive metal core such as stainless steel, a rubber or resin material such as polyurethane, EPDM, or silicon, and a conductive filler such as carbon. It is formed by coating a semiconductive material dispersed or containing an ionic conductive material with a thickness of about 0.05 to 0.5 mm.

  The intermediate transfer member of the present invention will be described below by taking the above-described intermediate transfer member 170 as an example.

  FIG. 2 is a cross-sectional view showing an example of the layer structure of the intermediate transfer member of the present invention.

The intermediate transfer member 170 in the present invention has a low-density first silicon oxide layer 176 having a carbon content of 0.5 atomic% or more and 10 atomic% or less on the surface of the substrate 175, and a first thereof. A high-density second silicon oxide layer 177 having a carbon content of less than 0.5 atomic% is provided on the upper portion of the silicon oxide layer 176. Further, as shown in FIG. Between the silicon oxide layer 176 and the second silicon oxide layer 177, the film thickness according to the present invention is 5 nm or more and 20 nm or less, and the average film density is 2.1 g / cm ³ or more and 2.3 g / cm ³ or less. Further, a high-density barrier layer 178 having a carbon content of less than 0.1 atomic% is provided. Further, as shown in FIG. 2 b), the barrier layer 178 according to the present invention may be provided on the outermost portion to prevent bleed-out of unreacted raw materials on the surface of the intermediate transfer body 170. Good.

  By adopting such a configuration, it is possible to obtain an intermediate transfer body 170 that has excellent releasability with toner and good transfer efficiency, and can bleed out unreacted raw materials to the surface even during repeated durable use. It is possible to suppress the occurrence of white spot failure and maintain excellent transfer performance over a long period of time.

  In the intermediate transfer member of the present invention, the carbon content of the barrier layer according to the present invention is less than 0.1 atomic%, and further, the carbon content of the first silicon oxide layer is 0.5 atomic%. As described above, the carbon content of the second silicon oxide layer is 10 atomic% or less and less than 0.5 atomic%. In particular, in the barrier layer according to the present invention, it is particularly preferable that the carbon content is less than 0.1 atomic% and no carbon atoms are contained. When the carbon content of the barrier layer is 0.1 atomic% or more, the barrier function is lowered, and the effect of preventing diffusion of unreacted raw materials from the first silicon oxide layer located in the lower layer is lowered.

  The atomic number concentration indicating the carbon content in the present invention is calculated by the following XPS method and is defined below.

Atomic concentration% = number of carbon atoms / number of all atoms × 100
In the present invention, the XPS surface analyzer used ESCALAB-200R manufactured by VG Scientific. Specifically, Mg was used for the X-ray anode, and measurement was performed at an output of 600 W (acceleration voltage: 15 kV, emission current: 40 mA). The energy resolution was set to be 1.5 eV to 1.7 eV when defined by the half width of a clean Ag3d5 / 2 peak.

  As a measurement, first, the range of the binding energy of 0 eV to 1100 eV was measured at a data acquisition interval of 1.0 eV to determine what elements were detected.

  Next, with respect to all the detected elements except the etching ion species, the data acquisition interval was set to 0.2 eV, and the photoelectron peak giving the maximum intensity was subjected to narrow scan, and the spectrum of each element was measured.

  The obtained spectrum is COMMON DATA PROCESSING SYSTEM manufactured by VAMAS-SCA-JAPAN (preferably Ver. 2.3 or later) so as not to cause a difference in the content calculation result due to a difference in measuring apparatus or computer. After being transferred to the top, the processing was performed with the same software, and the content value of each analysis target element (carbon, oxygen, silicon, titanium, etc.) was determined as the atomic concentration (at%).

  Before performing the quantitative process, a calibration of the Scale Scale was performed for each element, and a 5-point smoothing process was performed. In the quantitative process, the peak area intensity (cps * eV) from which the background was removed was used. For the background treatment, the method by Shirley was used. For the Shirley method, see D.C. A. Shirley, Phys. Rev. , B5, 4709 (1972).

In the intermediate transfer member of the present invention, the barrier layer according to the present invention has an average film density of 2.1 g / cm ³ or more and 2.3 g / cm ³ or less. The average film density of the silicon oxide layer is 1.8 g / cm ³ or more and less than 2.1 g / cm ³ , and the average film density of the second silicon oxide layer is 2.1 g / cm ³ or more, 2.3 g / cm It is preferable that it is cm ³ or less.

In particular, when the average film density of the barrier layer according to the present invention is less than 2.1 g / cm ³ , the barrier function is lowered, and diffusion of unreacted raw material from the first silicon oxide layer standing in the lower layer is prevented. Effect is reduced.

  Furthermore, it is preferable that the average film density of the barrier layer according to the present invention is higher than the average film density of each of the first silicon oxide layer and the second silicon oxide layer.

  The film density of the barrier layer and each silicon oxide layer defined in the present invention can be determined using known analysis means, but in the present invention, values determined by the X-ray reflectivity method are used.

  The outline of the X-ray reflectivity method is described in, for example, page 151 of the X-ray diffraction handbook (Science Electric Co., Ltd., 2000 International Literature Printing Co., Ltd.) 22 can be performed.

  Specific examples of measurement methods useful in the present invention are shown below.

  The measurement is performed using MXP21 manufactured by Mac Science. Copper is used as the target of the X-ray source and it is operated at 42 kV and 500 mA. A multilayer parabolic mirror is used for the incident monochromator. The incident slit is 0.05 mm × 5 mm, and the light receiving slit is 0.03 mm × 20 mm. Measurement is performed by the FT method with a step width of 0.005 ° and a step of 10 seconds from 0 to 5 ° in the 2θ / θ scan method. With respect to the obtained reflectance curve, Reflectivity Analysis Program Ver. Curve fitting is performed using 1 and each parameter is obtained so that the residual sum of squares of the actually measured value and the footing curve is minimized. From each parameter, the thickness and average film density of each layer can be determined.

  Next, each component of the intermediate transfer member of the present invention will be described.

(Base material)
As a substrate applicable to the intermediate transfer member of the present invention, a belt obtained by dispersing a conductive agent in a resin material can be preferably used. The resin used for the belt is not particularly limited, and so-called engineering plastic materials such as polycarbonate, polyimide, polyetheretherketone, polyvinylidene fluoride, ethylenetetrafluoroethylene copolymer, polyamide, and polyphenylene sulfide can be used. Moreover, carbon black can be used as a conductive agent. Carbon black can be used without particular limitation, and neutral carbon black may be used. The amount of the conductive agent used varies depending on the type of the conductive agent used, but it may be added so that the volume resistance value and the surface resistance value of the intermediate transfer member are within a predetermined range. On the other hand, 4 to 40 parts by mass are added. The base material used in the present invention can be produced by a conventionally known general method. For example, it can be manufactured by melting a resin as a material by an extruder, extruding it with an annular die or a T die, and rapidly cooling it.

(First silicon oxide layer, second silicon oxide layer and barrier layer)
Next, a barrier layer composed of the first silicon oxide layer, the second silicon oxide layer, and the silicon oxide according to the present invention is formed on the base material.

  In the first silicon oxide layer, the second silicon oxide layer, and the barrier layer in the present invention, the constituent material is silicon oxide.

  Further, the first silicon oxide layer, the second silicon oxide layer, and the barrier layer according to the present invention may all be composed of silicon oxide, or may contain other compounds as necessary.

  In the present invention, before the first silicon oxide layer is formed on the substrate, the substrate surface is subjected to surface treatment such as corona treatment, flame treatment, plasma treatment, glow discharge treatment, roughening treatment, chemical treatment, and the like. May be.

  In the intermediate transfer member of the present invention, the thickness of the barrier layer is 5 nm or more and 20 nm or less. When the thickness of the barrier layer is less than 5 nm, the barrier function is lowered, and the effect of preventing diffusion of unreacted raw material from the first silicon oxide layer that is positioned in the lower layer is lowered. On the other hand, if the thickness of the barrier layer exceeds 20 nm, the barrier film itself becomes brittle, leading to cracks and a decrease in adhesion.

  The film thickness of the first silicon oxide layer in the present invention is generally 1 nm to 5000 nm, preferably 3 nm to 3000 nm. The film thickness of the second silicon oxide layer is approximately 1 nm to 5000 nm, preferably 3 nm to 3000 nm. When the film thickness of the first inorganic oxide layer is less than 1 nm or more than 5000 nm, cracks and peeling easily occur during repeated use. In addition, when the second inorganic oxide layer is less than 1 nm, scratches are likely to occur, and the toner releasability and transfer efficiency are insufficient, and when it exceeds 5000 nm, film cracking or Peeling occurs.

  Next, a method for forming the first silicon oxide layer, the second silicon oxide layer, and the barrier layer according to the present invention will be described.

  In the intermediate transfer member of the present invention, the method for forming the first silicon oxide layer, the second silicon oxide layer, and the barrier layer is not particularly limited, and examples thereof include a vacuum deposition method, a molecular beam epitaxial growth method, and an ion cluster beam method. , Dry process such as low energy ion beam method, ion plating method, CVD method, sputtering method, atmospheric pressure plasma CVD method, spray coating method, spin coating method, blade coating method, dip coating method, casting method, roll coating Examples include wet processes such as coating methods such as coating, bar coating, and die coating, and patterning methods such as printing and ink jetting. The wet process includes a method of applying and drying a liquid in which fine particles of silicon oxide are dispersed in an arbitrary organic solvent or water using a dispersion aid such as a surfactant as required, or an oxide precursor such as an alkoxide. A so-called sol-gel method in which a body solution is applied and dried is used.

  In the intermediate transfer member of the present invention, in particular, at least one layer selected from the first silicon oxide layer, the second silicon oxide layer, and the barrier layer is between the electrodes facing each other under atmospheric pressure or a pressure in the vicinity thereof. A gas containing a thin film forming gas is supplied to the formed discharge space, a high frequency electric field is applied to the discharge space to excite the gas, and a substrate is exposed to the excited gas to form a silicon oxide thin film Preferably, the first silicon oxide layer, the second silicon oxide layer, and the barrier layer are all formed by the atmospheric pressure plasma CDV method. It is preferable from the viewpoint that the object effect of the present invention can be further exhibited.

  This atmospheric pressure plasma CVD method does not require a decompression chamber or the like, and is a film forming method capable of high speed film formation and high productivity. In addition, a film formed by the atmospheric pressure plasma CVD method has a uniform and smooth surface, and it is possible to relatively easily form a film with very little internal stress.

A specific method for forming the first silicon oxide layer, the second silicon oxide layer, and the barrier layer (inorganic oxide: SiO ₂ ) by the atmospheric pressure plasma CVD method will be described below.

  Atmospheric pressure plasma CVD (hereinafter also referred to as “atmospheric pressure plasma method”) is a method in which a discharge gas is excited and discharged under atmospheric pressure or a pressure near atmospheric pressure, and a source gas and / or a reactive gas are discharged into a discharge space. Introducing, exciting, and forming a thin film on a substrate, and methods thereof are disclosed in JP-A-11-133205, JP-A-2000-185362, JP-A-11-61406, JP-A-2000-147209, JP-A-2000-121804 and the like. By this atmospheric pressure plasma method, a highly functional thin film can be formed with high productivity. The atmospheric pressure or the vicinity thereof here represents a pressure of 20 kPa to 110 kPa, preferably 93 kPa to 104 kPa.

  Next, an apparatus and method for forming each silicon oxide layer and barrier layer of the intermediate transfer member according to the present invention by the atmospheric pressure plasma CVD method and various gases used therefor will be described.

  FIG. 3 is a schematic view showing an example of an atmospheric pressure plasma processing apparatus applicable to the production of the intermediate transfer member.

  In FIG. 3, the intermediate transfer body manufacturing apparatus 2 (direct method in which the discharge space and the thin film deposition region are substantially the same) has a first silicon oxide layer 176, a second silicon oxide layer 177 and a barrier layer 178 on a substrate 175. A roll electrode 20 and a driven roller 201 that are wound around a base material 175 of an endless belt-shaped intermediate transfer body 170 and rotated in the direction of the arrow, and a first silicon oxide layer 176 on the surface of the base material 175. The atmospheric pressure plasma CVD apparatus 3 is a film forming apparatus for forming the second silicon oxide layer 177 and the barrier layer 178.

  The atmospheric pressure plasma CVD apparatus 3 includes at least one set of fixed electrodes 21 arranged along the outer periphery of the roll electrode 20, a discharge space 23 in which discharge is performed in a region where the fixed electrode 21 and the roll electrode 20 face each other, A mixed gas supply device 24 that generates a mixed gas G of at least a raw material gas and a discharge gas and supplies the mixed gas G to the discharge space 23; a discharge vessel 29 that reduces the inflow of air into the discharge space 23 and the like; A first power source 26 connected to the roll electrode 20, a second power source 25 connected to the fixed electrode 21, and an exhaust unit 28 that exhausts the used exhaust gas G ′.

  The mixed gas supply device 24 (indicated by three stations in FIG. 3) includes a source gas for forming each of the first silicon oxide layer 176, the second silicon oxide layer 177, and the barrier layer 178, and nitrogen gas or argon. A rare gas such as a gas or helium gas, and a gas for controlling the decomposition of the raw material gas are supplied to the discharge space 23.

  Here, the gas for controlling the decomposition of the raw material gas (raw material decomposition control gas) represents a gas containing an active element in the molecular structure, for example, H, O, N, S, F, B , Cl, P, Br, I, As, Se, and the like. A gas containing an element having activity may be used alone or in combination. Further, from the viewpoint of controlling the carbon content of the thin film to be formed, the gas containing the element having activity may contain C in the molecular structure, or may be mixed with the gas containing C in the molecular structure.

  Further, the driven roller 201 is urged in the direction of the arrow by the tension urging means 202 and applies a predetermined tension to the base material 175. The tension urging means 202 cancels the urging of the tension when the base material 175 is changed, and the base material 175 can be easily changed.

  The first power supply 26 outputs a voltage having a frequency ω1, the second power supply 25 outputs a voltage having a frequency ω2, and generates an electric field V in which the frequencies ω1 and ω2 are superimposed on the discharge space 23 by these voltages. . Then, in the case of a film (a in FIG. 2) corresponding to the source gas contained in the mixed gas G by converting the discharge gas into plasma by the electric field V, the first silicon oxide layer 176, the barrier layer 178, and the second silicon oxide layer 177 is deposited on the surface of the substrate 175.

  Of the plurality of fixed electrodes, a plurality of fixed electrodes positioned on the downstream side in the rotation direction of the roll electrode and a mixed gas supply device are stacked so that the silicon oxide layers are stacked, and the thickness of the silicon oxide layer is adjusted. May be.

  For example, in the configuration shown in a) of FIG. 2, the first silicon oxide layer 176 is formed by a mixed gas supply device and a fixed electrode located on the most downstream side in the rotation direction of the roll electrode among the plurality of fixed electrodes, A barrier layer 178 is formed by the second fixed electrode located upstream and the mixed gas supply device, and a second silicon oxide layer 177 is formed by the third fixed electrode and mixed gas supply device located on the most upstream side. be able to. By continuously forming the film in this manner, productivity can be improved and adhesion of the first silicon oxide layer 176, the barrier layer 178, and the second silicon oxide layer 177 can be improved, and further durability can be improved. An intermediate transfer member can be produced.

  Further, in order to improve the adhesion between the first silicon oxide layer 176 and the base material 175, nitrogen, helium, argon, or the like is formed upstream of the fixed electrode forming the first silicon oxide layer 176 and the mixed gas supply device. A gas supply device that supplies a gas such as oxygen or hydrogen and a fixed electrode may be provided to perform plasma treatment to activate the surface of the substrate 175.

  As still another form, one of the roll electrode and the fixed electrode may be connected to the ground, and the power supply may be connected to the other electrode. As the power source in this case, it is preferable to use the second power source because a dense thin film can be formed, and particularly preferable when a rare gas such as argon is used as the discharge gas.

  FIG. 4 is a schematic view showing another example of an atmospheric pressure plasma processing apparatus applicable to the production of an intermediate transfer member.

  The second production apparatus 2b for the intermediate transfer member forms a first silicon oxide layer, a second silicon oxide layer, and a barrier layer on a plurality of substrates (two in FIG. 4) at the same time. Primarily composed of a plurality of film forming apparatuses 2b1 and 2b2 for forming a silicon oxide layer on the surface of the substrate.

  The second manufacturing apparatus 2b (a method in which discharge and thin film deposition are performed between opposed roll electrodes in a modification of the direct system) is arranged in a substantially mirror image relation with a predetermined gap from the first film forming apparatus 2b1. A mixed gas G of at least a raw material gas and a discharge gas, which is disposed between the second film forming apparatus 2b2, the first film forming apparatus 2b1 and the second film forming apparatus 2b2, is generated in the discharge space 23b. And a mixed gas supply device 24b for supplying the mixed gas G.

  The first film forming apparatus 2b1 is a tension energizing unit that energizes the roll electrode 20a, the driven roller 201, and the driven roller 201 that rotate in the direction of the arrow by winding the base material 175 of an endless belt-shaped intermediate transfer member. The second film forming apparatus 2b2 has means 202 and a first power source 25 connected to the roll electrode 20a. The second film forming apparatus 2b2 is a roll that rolls around a base material 175 of an endless belt-like intermediate transfer member and rotates in the arrow direction. It has an electrode 20b, a driven roller 201, tension urging means 202 for urging the driven roller 201 in the direction of the arrow, and a second power source 26 connected to the roll electrode 20b.

  The third manufacturing apparatus 2b has a discharge space 23b in which discharge is performed in a region where the roll electrode 20a and the roll electrode 20b are opposed to each other.

  The mixed gas supply device 24b supplies the discharge space 23b with a source gas for forming a silicon oxide layer, a rare gas such as nitrogen gas, argon gas, or helium gas, and a gas for controlling the decomposition of the source gas.

  The first power supply 25 outputs a voltage having a frequency ω1, and the second power supply 26 outputs a voltage having a frequency ω2, and generates an electric field V in which the frequencies ω1 and ω2 are superimposed on the discharge space 23b. . Then, the mixed gas G is converted into plasma (excited) by the electric field V, and the plasma (excited) mixed gas is converted into the surface of the substrate 175 of the first film forming apparatus 2b1 and the surface of the substrate 175 of the second film forming apparatus 2b2. The film (silicon oxide layer) corresponding to the source gas contained in the plasma gas (excited) mixed gas is exposed to the substrate 175 of the first film forming apparatus 2b1 and the substrate 175 of the second film forming apparatus 2b2. It is simultaneously deposited and formed on the surface.

  Here, the roll electrode 20a and the roll electrode 20b facing each other are arranged with a predetermined gap therebetween.

  As yet another form, one of the roll electrode 20a and the roll electrode 20b may be connected to the ground, and the power supply may be connected to the other roll electrode. In this case, it is preferable to use the second power source for the formation of a dense thin film, and particularly preferable when a rare gas such as nitrogen gas, argon gas or helium gas is used as the discharge gas.

  The details of the thin film formation region of the atmospheric pressure plasma CVD apparatus for forming the silicon oxide layer on the substrate will be described below.

  FIG. 5 is a schematic diagram showing an example of the configuration of the thin film formation region in the atmospheric pressure plasma CVD apparatus.

  FIG. 5 shows the thin-film formation region at the broken line in the atmospheric pressure plasma CVD apparatus shown in FIG.

  With reference to FIG. 5, an example of an atmospheric pressure plasma CVD apparatus suitably used for forming the first silicon oxide layer 176 will be described.

  The atmospheric pressure plasma CVD apparatus 3 includes at least one pair of rollers that are detachably wound around a base material and driven to rotate, and at least one pair of electrodes that perform plasma discharge. Among the pair of electrodes, One electrode is one roller of the pair of rollers, and the other electrode is a fixed electrode facing the one roller through the base material, and the one roller and the fixed electrode are opposed to each other An intermediate transfer body manufacturing apparatus in which the substrate is exposed to plasma generated in a region to deposit and form the silicon oxide layer. For example, when nitrogen is used as a discharge gas, a high voltage is applied by one power source. It is preferably used for starting discharge stably and continuing discharge by applying a high frequency with the other power source.

  As described above, the atmospheric pressure plasma CVD apparatus 3 includes the mixed gas supply device 24, the fixed electrode 21, the first power source 25, the first filter 25a, the roll electrode 20, and the driving means 20a for driving and rotating the roll electrode in the arrow direction. It has the 2nd power supply 26 and the 2nd filter 26a, and plasma discharge is performed in the discharge space 23, the mixed gas G which mixed the raw material gas containing organic substance, and discharge gas is excited, and the excited mixed gas G1 is exposed to the substrate surface 175a, and a silicon oxide layer containing carbon is deposited and formed on the surface.

A first high frequency voltage having a frequency ω ₁ is applied to the fixed electrode 21 from the first power source 25, and a high frequency voltage having a frequency ω ₂ is applied to the roll electrode 20 from the second power source 26. whereby an electric field frequency omega ₂ and is superimposed is generated at the frequency omega ₁ and the electric field strength V ₂ at electric field intensity V ₁ between the fixed electrode 21 and role electrode 20, a current I ₁ to the fixed electrode 21 The current I ₂ flows through the roll electrode 20 and plasma is generated between the electrodes.

Here, the relationship between the frequency ω1 and the frequency ω2 and the relationship between the electric field strength V ₁ , the electric field strength V _2, and the electric field strength IV at which discharge of the discharge gas is started are ω ₁ <ω ₂ and V ₁ ≧ IV > V ₂ or V ₁ > IV ≧ V ₂ is satisfied, and the output density of the second high-frequency electric field is 1 W / cm ² or more.

Since the electric field intensity IV for starting the discharge of nitrogen gas is 3.7 kV / mm, the electric field intensity V ₁ applied from at least the first power supply 25 is 3.7 kV / mm or more, and the second high frequency power supply 60 field intensity V ₂ to be applied from the it is preferable to 3.7 kV / mm or less.

In addition, as the first power source 25 (high frequency power source) that can be used for the first atmospheric pressure plasma CVD apparatus 3,
Applied power symbol Manufacturer Frequency Product name A1 Shinko Electric 3kHz SPG3-4500
A2 Shinko Electric 5kHz SPG5-4500
A3 Kasuga Electric 15kHz AGI-023
A4 Shinko Electric 50kHz SPG50-4500
A5 HEIDEN Research Laboratories 100kHz * PHF-6k
A6 Pearl Industry 200kHz CF-2000-200k
A7 Pearl Industry 400kHz CF-2000-400k
And the like, and any of them can be used.

As the second power source 26 (high frequency power source),
Applied power supply symbol Manufacturer Frequency Product name B1 Pearl Industry 800kHz CF-2000-800k
B2 Pearl Industry 2MHz CF-2000-2M
B3 Pearl Industry 13.56MHz CF-5000-13M
B4 Pearl Industry 27MHz CF-2000-27M
B5 Pearl Industry 150MHz CF-2000-150M
And the like, and any of them can be used.

  Of the above power supplies, * indicates a HEIDEN Laboratory impulse high-frequency power supply (100 kHz in continuous mode). Other than that, it is a high frequency power source that can apply only a continuous sine wave.

In the present invention, the power supplied between the electrodes facing each other from the first and second power sources supplies power (power density) of 1 W / cm ² or more to the fixed electrode 21 to generate plasma by exciting the discharge gas. To form a thin film. The upper limit value of the power supplied to the fixed electrode 21 is preferably 50 W / cm ² . The lower limit is preferably 1.2 W / cm ² . The discharge area (cm ² ) refers to an area in a range where discharge occurs in the electrode.

Further, by supplying power (power density) of 1 W / cm ² or more to the roll electrode 20, it is possible to improve the power density while maintaining the uniformity of the high frequency electric field. Thereby, a further uniform high-density plasma can be generated, and a further improvement in film forming speed and an improvement in film quality can be achieved. Preferably it is 2 W / cm ² or more. The upper limit value of power supplied to the roll electrode 20 is preferably 50 W / cm ² .

  Here, the waveform of the high-frequency electric field is not particularly limited. There are a continuous sine wave continuous oscillation mode called a continuous mode and an intermittent oscillation mode called ON / OFF intermittently called a pulse mode. Either of them may be adopted, but at least the high frequency supplied to the roll electrode 20 The continuous sine wave is preferable because a denser and better quality film can be obtained.

  In addition, a first filter 25 a is installed between the fixed electrode 21 and the first power supply 25 to facilitate passage of current from the first power supply 25 to the fixed electrode 21, and the second power supply 26. The current from the second power source 26 to the first power source 25 is less likely to pass through, and the second electrode 26 and the second power source 26 are connected between the second electrode 26 and the second power source 26. A filter 26a is installed to facilitate the passage of current from the second power source 26 to the roll electrode 20, ground the current from the first power source 21, and the first power source 25 to the second power source 26. It is designed to make it difficult for current to pass through.

  It is preferable to employ an electrode that can maintain a uniform and stable discharge state by applying a strong electric field as described above to the electrode, and the fixed electrode 21 and the roll electrode 20 have at least a resistance to discharge by a strong electric field. One electrode surface is coated with the following dielectric.

  In the above description, the relationship between the electrode and the power source may be that the second power source 26 is connected to the fixed electrode 21 and the first power source 25 is connected to the roll electrode 20.

  As still another form, one of the fixed electrode 21 and the roll electrode 20 may be connected to the ground, and the power source may be connected to the other electrode. As the power source in this case, it is preferable to use the second power source because a dense thin film can be formed, and particularly preferable when a rare gas such as argon is used as the discharge gas.

  FIG. 6 is a perspective view showing an example of a roll electrode.

  The structure of the roll electrode 20 will be described. In FIG. 6A, the roll electrode 20 is inorganic after a ceramic is sprayed on a conductive base material 200a (hereinafter also referred to as “electrode base material”) such as metal. It is composed of a combination in which a ceramic-coated dielectric 200b (hereinafter also simply referred to as “dielectric”) coated with a material is covered. As the ceramic material used for thermal spraying, alumina, silicon nitride, or the like is preferably used. Among these, alumina is more preferable because it is easily processed.

  Further, as shown in FIG. 6B, the roll electrode 20 'may be configured by a combination of a conductive base material 200A such as metal covered with a lining dielectric 200B provided with an inorganic material by lining. As the lining material, silicate glass, borate glass, phosphate glass, germanate glass, tellurite glass, aluminate glass, vanadate glass and the like are preferably used. Of these, borate glass is more preferred because it is easy to process.

  Examples of the conductive base materials 200a and 200A such as metal include metals such as silver, platinum, stainless steel, aluminum, and iron. Stainless steel is preferable from the viewpoint of processing.

  In this embodiment, the base material 200a, 200A of the roll electrode uses a stainless steel jacket roll base material having a cooling means by cooling water (not shown).

  FIG. 7 is a perspective view showing an example of a fixed electrode.

  In FIG. 7 (a), the fixed electrodes 21 and 21a, 21b of the prisms or prisms are sprayed with ceramics on the conductive base material 210c such as metal, and then the inorganic material is applied. The ceramic coating-processed dielectric 210d that has been sealed by using a combination is coated. In addition, as shown in FIG. 7B, the prismatic or prismatic fixed electrode 21 'is a combination of a conductive base material 210A such as metal coated with a lining dielectric 210B provided with an inorganic material by lining. You may comprise.

  Hereinafter, an example of a film forming process for depositing and forming a silicon oxide layer on the base material 175 in the process of manufacturing the intermediate transfer member will be described with reference to FIGS.

  3 and 5, after the base material 175 is stretched between the roll electrode 20 and the driven roller 201, a predetermined tension is applied to the base material 175 by the operation of the tension urging means 202, and then the roll electrode 20 is rotated at a predetermined rotation speed. Rotating drive.

  A mixed gas G is generated from the mixed gas supply device 24 and discharged to the discharge space 23.

  A voltage of frequency ω1 is output from the first power supply 25 and applied to the fixed electrode 21, and a voltage of frequency ω2 is output from the second power supply 26 and applied to the roll electrode 20, and these voltages enter the discharge space 23. An electric field V in which the frequencies ω1 and ω2 are superimposed is generated.

  The mixed gas G discharged into the discharge space 23 by the electric field V is excited to be in a plasma state. Then, the mixed gas G in a plasma state is exposed to the substrate surface, and a film of at least one layer selected from an inorganic oxide layer, an inorganic nitride layer, and an inorganic carbide layer by the source gas in the mixed gas G, that is, a first oxidation A silicon layer 176 is formed on the substrate 175.

  Similarly, the barrier layer 178 and the second silicon oxide layer 177 can be provided on the first silicon oxide layer thus formed.

  The discharge gas refers to a gas that is plasma-excited under the above conditions, and examples thereof include nitrogen, argon, helium, neon, krypton, xenon, and mixtures thereof.

  The source gas contains a component that forms a silicon oxide film, and examples thereof include organometallic compounds and organic compounds. Examples thereof include silane, tetramethoxysilane, tetraethoxysilane (TEOS), and tetra n-propoxy. Silane, tetraisopropoxysilane, tetra-n-butoxysilane, tetra-t-butoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diphenyldimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, phenyltriethoxysilane , (3,3,3-trifluoropropyl) trimethoxysilane, hexamethyldisiloxane, bis (dimethylamino) dimethylsilane, bis (dimethylamino) methylvinylsilane, bis (ethylamino) dimethyl Lan, N, O-bis (trimethylsilyl) acetamide, bis (trimethylsilyl) carbodiimide, diethylaminotrimethylsilane, dimethylaminodimethylsilane, hexamethyldisilazane, hexamethylcyclotrisilazane, heptamethyldisilazane, nonamethyltrisilazane, octamethyl Cyclotetrasilazane, tetrakisdimethylaminosilane, tetraisocyanatosilane, tetramethyldisilazane, tris (dimethylamino) silane, triethoxyfluorosilane, allyldimethylsilane, allyltrimethylsilane, benzyltrimethylsilane, bis (trimethylsilyl) acetylene, 1, 4-bistrimethylsilyl-1,3-butadiyne, di-t-butylsilane, 1,3-disilabutane, bis (trimethylsilyl) me , Cyclopentadienyltrimethylsilane, phenyldimethylsilane, phenyltrimethylsilane, propargyltrimethylsilane, tetramethylsilane, trimethylsilylacetylene, 1- (trimethylsilyl) -1-propyne, tris (trimethylsilyl) methane, tris (trimethylsilyl) silane, Examples include, but are not limited to, vinyltrimethylsilane, hexamethyldisilane, octamethylcyclotetrasiloxane, tetramethylcyclotetrasiloxane, hexamethylcyclotetrasiloxane, M silicate 51, and the like.

  These raw materials may be used alone as long as they form the silicon oxide layer having the carbon content, but two or more kinds of components may be mixed and used.

  By providing at least three silicon oxide layers, that is, the first silicon oxide layer, the barrier layer, and the second silicon oxide layer on the surface of the substrate by the above method, the transferability is high, the cleaning property and An intermediate transfer member excellent in durability (whiteout resistance) can be provided.

  In each constituent layer, the carbon content specified in the present invention can be adjusted by the amount of the source gas, the amount of gas for controlling the decomposition of the source gas, and the setting conditions of the plasma discharge treatment apparatus.

  Hereinafter, the present invention will be specifically described with reference to examples. However, the embodiment of the present invention is not limited thereto.

Example 1
<Preparation of intermediate transfer member>
[Preparation of Intermediate Transfer Member 1]
[Preparation of substrate]
A substrate for an intermediate transfer member was produced according to the following method.

Polyphenylene sulfide resin (E2180, manufactured by Toray Industries, Inc.) 100 parts by mass Conductive filler (Furness # 3030B, manufactured by Mitsubishi Chemical Corporation) 16 parts by mass Graft copolymer (Modiper A4400, manufactured by NOF Corporation) 1 part by mass Lubricant (calcium montanate) 0.2 parts by mass Each of the above raw materials was put into a single screw extruder and melt-kneaded to obtain a resin mixture. Next, a slit-shaped annular die having a seamless belt-shaped discharge port was attached to the tip of the single screw extruder, and the kneaded resin mixture was extruded into a seamless belt shape. The extruded seamless belt-shaped resin mixture is extrapolated to a cylindrical cooling cylinder provided at the discharge destination, cooled and solidified to form a base material for a seamless cylindrical intermediate transfer member with a thickness of 120 μm. Produced.

[Formation of each silicon oxide layer]
A first layer (first silicon oxide layer) and a second layer (from the base material side) are formed from the base material side according to the following method using three atmospheric pressure plasma processing apparatuses shown in FIG. A silicon oxide layer (barrier layer) and a third layer (second silicon oxide layer) were sequentially formed to produce an intermediate transfer body 1.

(Formation of first layer: first silicon oxide layer)
A first silicon oxide layer having a thickness of 85 nm was formed on the prepared base material using the atmospheric pressure plasma processing apparatus shown in FIG. 5 under the following film formation conditions. In the atmospheric pressure plasma processing apparatus, as the dielectric covering each electrode, an opposing electrode was coated with 1 mm of alumina by a ceramic spray process. In addition, the metal base material coated with the dielectric of each roll electrode is a stainless steel jacket specification having heating and cooling functions by water circulation, and the temperature of the surface of the roll electrode is circulated by circulating water at 50 ° C. during plasma discharge. The plasma treatment was performed while maintaining a constant value. The electrode gap was set to 0.5 mm, and each film thickness was adjusted by adjusting the treatment time.

The carbon content measured by the above-mentioned XPS method (X Scientific Photoelectron Spectrometer (ESCALAB 200R) manufactured by VG Scientific) of the first layer formed according to the following film formation conditions is 5.0 atomic%. The average film density measured by the aforementioned X-ray reflectivity method (MXP21 manufactured by Mac Science) was 1.89 g / cm ³ .

<First-layer film formation conditions>
Discharge gas: Nitrogen gas (3.5 slm per 1 cm processing width)
Reaction gas: 1.0% by volume of oxygen gas with respect to the total gas
Source gas: 0.05% by volume of tetraethoxysilane (TEOS) based on the total gas
Low frequency side power supply power: HEIDEN Laboratory impulse high frequency power supply (100 kHz), 10 W / cm ²
High frequency side power supply: Broadband high frequency power supply (60.0 MHz) manufactured by Pearl Industry, 10 W / cm ²
(Formation of second layer: barrier layer)
Using the same atmospheric pressure plasma apparatus as that used for forming the first layer, the conditions are changed to the following thin film formation conditions, and a thickness of 10 nm and a carbon content of 0. A barrier layer having a number of atoms of less than 1% and an average film density of 2.21 g / cm ³ was formed. Here, the carbon content of less than 0.1 atomic% means that it is below the detection limit by XPS measurement, and includes 0 atomic%.

<The film formation conditions of the second layer (barrier layer)>
Discharge gas: Nitrogen gas (3.5 slm per 1 cm processing width)
Reaction gas: 21% by volume of oxygen gas with respect to the total gas
Source gas: 0.02% by volume of tetraethoxysilane (TEOS) with respect to the total gas
Low frequency side power supply power: HEIDEN Laboratory impulse high frequency power supply (100 kHz), 10 W / cm ²
High frequency side power supply: Broadband high frequency power supply (60.0 MHz) manufactured by Pearl Industry, 10 W / cm ²
(Formation of third layer)
In the same manner as the formation method up to the second layer, except that the oxygen gas concentration in the reaction gas is changed to 18% by volume with respect to the total gas, the thickness is increased on the second layer (barrier layer). A third layer having a thickness of 165 nm, a carbon content of 0.2 atomic%, and an average film density of 2.19 g / cm ³ was formed to produce an intermediate transfer body 1.

[Preparation of Intermediate Transfer Member 2]
In the production of the intermediate transfer member 1, the second layer (barrier layer) was not formed, and the intermediate transfer member 2 was produced in the same manner except that the thickness of the third layer was changed to 175 nm.

[Preparation of intermediate transfer members 3 to 6]
In the production of the intermediate transfer member 1, intermediate transfer members 3 to 6 were produced in the same manner except that the film thickness of the second layer (barrier layer) was changed to 3 nm, 6 nm, 18 nm, and 22 nm, respectively. In the production of each intermediate transfer member, the film thickness of the third layer was appropriately corrected so that the total film thickness was 260 nm.

[Preparation of Intermediate Transfer Member 7]
In the production of the intermediate transfer member 1, the thickness was 10 nm and the carbon content was 0.1%, except that the oxygen gas concentration during the formation of the second layer (barrier layer) was changed to 16% by volume with respect to the total gas. An intermediate transfer member 7 was produced in the same manner except that a second layer having 25 atomic% and an average film density of 2.14 g / cm ³ was formed.

[Preparation of Intermediate Transfer Member 8]
In the production of the intermediate transfer member 1, the thickness is 85 nm and the carbon content is the same except that the oxygen gas concentration at the time of forming the first layer (first silicon oxide layer) is changed to 12% by volume with respect to the total gas. An intermediate transfer member 8 was produced in the same manner except that a first layer having an amount of 0.4 atomic% and an average film density of 2.11 g / cm ³ was formed.

[Preparation of Intermediate Transfer Member 9]
In the production of the intermediate transfer member 1, the thickness was 85 nm in the same manner except that the oxygen gas concentration at the time of forming the first layer (first silicon oxide layer) was changed to 0.4% by volume with respect to the total gas. An intermediate transfer member 9 was produced in the same manner except that a first layer having a carbon content of 11.0 atomic% and an average film density of 1.67 g / cm ³ was formed.

[Preparation of Intermediate Transfer Member 10]
In the production of the intermediate transfer member 1, the thickness was 165 nm in the same manner except that the oxygen gas concentration at the time of forming the second layer (second silicon oxide layer) was changed to 10.0% by volume with respect to the total gas. An intermediate transfer member 10 was produced in the same manner except that a third layer having a carbon content of 0.6 atomic% and an average film density of 1.98 g / cm ³ was formed.

<Evaluation of intermediate transfer member>
Each characteristic evaluation was performed according to the following method about each produced said intermediate transfer body.

[Evaluation of secondary transferability of toner]
The secondary transferability of the toner was evaluated by a toner transfer rate representing a ratio of the toner mass of the toner image transferred onto the recording paper to the toner mass of the toner image formed on each intermediate transfer member.

  Using a printer (magiccolor 5440DL manufactured by Konica Minolta Business Technologies), the internal intermediate transfer belt was removed, and each of the produced intermediate transfer belts was mounted.

  Polymerized toner having an average particle diameter of 6.5 μm was set in this printer, and printing was performed on Konica Minolta CF paper (manufactured by Konica Minolta Business Technologies) with each color of yellow, magenta, cyan, and black at the maximum toner density. Measure the optical (reflection) density of the toner adhesion amount transferred onto the print paper and the residual toner amount on the belt, and convert the measurement result to the toner amount according to the relationship between the optical density and the toner amount obtained in advance. The toner transfer rate (%) was determined, and the secondary transferability was evaluated according to the following criteria.

Transfer rate (%) = (amount of toner transferred onto test print paper / (amount of toner transferred onto test print paper + amount of residual toner on belt)) × 100
A: The transfer rate was 98% or more. B: The transfer rate was 95% or more and less than 98%. Δ: The transfer rate was 90% or more and less than 95%. X: The transfer rate was less than 90%. [Measurement of surface hardness]
The thin film surface hardness (GPa) of the silicon oxide film of each produced intermediate transfer member was measured by the nanoindentation method shown below.

  The measurement apparatus used was NANO Indenter XP / DCM (manufactured by MTS Systems / MTS Nano Instruments), using a diamond Berkovich indenter with a tip shape of an equilateral triangle, a maximum load setting of 25 μN, and a thickness of the silicon oxide layer (260 nm). The surface hardness (GPa) of the thin film was measured under the condition that the indentation depth was sufficiently small.

[Durability Evaluation 1: Continuous Output Suitability]
Using a printer similar to the above-mentioned evaluation of the secondary transfer property of the toner, a test pattern having a 5% image rate for each toner color on Konica Minolta CF paper (A4), and 200,000 in an environment of 23 ° C. and 50% RH. After printing the sheets, the presence or absence of image quality in the first and 200,000 prints was visually observed, and durability evaluation 1 was performed according to the following criteria.

◎ No change in the image on both the first and 200,000 prints, and no problem image failure is found ○ The first print shows no problem image failure, 200,000 copies A slight change is observed in the eye print, but the quality is acceptable for practical use. Δ: No trouble in the image that is a problem is observed in the first print, and a change is recognized in the 200,000 print. However, it is a quality acceptable for practical use. ×: No image failure that is a problem in the first print is recognized, but an obvious failure is recognized in the 200,000th print. XX: Image failure that is a problem in the first print is not recognized, but a strong image failure is recognized in the 200,000 print, and the quality is not practical. [Durability Evaluation 2: (High temperature and high humidity resistance)
In the same printer as the evaluation of the secondary transferability of the toner, each intermediate transfer member was subjected to a forced deterioration treatment in which it was left for 6 months in an environment of 35 ° C. and 85% RH. Print on the Minolta CF paper (A4) with a test pattern of 5% image rate for each toner color, visually observe the presence or absence of a defect in the output print, and evaluate durability 2 according to the following criteria: It was.

◎: Occurrence of hollow failure is not recognized at all ○: Extremely weak hollow failure is recognized in part, but it is of good quality △: Weak hollow failure is recognized in part, but is practically acceptable XX: Obvious hollow failure is recognized and is a problem that is practically problematic. XX: Strong hollow failure is recognized, and the quality is not suitable for practical use. It is shown in 2.

  As is clear from the results shown in Table 2, the printer using the intermediate transfer member having the configuration defined in the present invention is superior to the comparative example in the secondary transfer property of the toner, and also suppresses the occurrence of a defect in the void. It can also be seen that the intermediate transfer member is excellent in surface hardness and durability.

Example 2
<Preparation of intermediate transfer member>
[Preparation of intermediate transfer members 11 to 19]
In the production of the intermediate transfer members 1, 3 to 10 described in Example 1, the arrangement order of the second layer of the barrier layer and the third layer of the second silicon oxide layer is reversed, so that Similarly, the intermediate transfer member 11 (intermediate transfer member 1) is changed to the layer structure of the layer (first silicon oxide layer), the second layer (second silicon oxide layer), and the third layer (barrier layer). The intermediate transfer members 12 to 19 (change of the layer arrangement of the intermediate transfer members 3 to 11) were prepared.

<Evaluation of intermediate transfer member>
About each produced said intermediate transfer body, it carries out similarly to the method as described in Example 1, evaluation of the secondary transfer property of a toner, measurement of surface hardness, durability evaluation 1 (continuous output suitability), and durability. Evaluation 2 (high temperature and high humidity resistance) was evaluated, and the results obtained are shown in Table 3.

  As is clear from the results shown in Table 3, the printer using the intermediate transfer member having the configuration defined in the present invention is superior to the comparative example in the secondary transfer property of the toner, and also suppresses the occurrence of a void failure. It can also be seen that the intermediate transfer member is excellent in surface hardness and durability.

1 is a cross-sectional configuration diagram illustrating an example of a configuration of a color image forming apparatus. FIG. 3 is a cross-sectional view illustrating an example of a layer configuration of an intermediate transfer member of the present invention. It is the schematic which shows an example of the atmospheric pressure plasma processing apparatus applicable to manufacture of an intermediate transfer body. It is the schematic which shows another example of the atmospheric pressure plasma processing apparatus applicable to manufacture of an intermediate transfer body. It is a schematic diagram which shows an example of a structure of the thin film formation area | region in an atmospheric pressure plasma CVD apparatus. It is a perspective view which shows an example of a roll electrode. It is a perspective view which shows an example of a fixed electrode.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Color image forming apparatus 2 Manufacturing apparatus of intermediate transfer body 3 Atmospheric pressure plasma CVD apparatus 4 Atmospheric pressure plasma apparatus 17 Intermediate transfer body unit 20 Roll electrode 21 Fixed electrode 23 Discharge space 24 Mixed gas supply apparatus 25 1st power supply 26 2nd Power source 41 Thin film forming region 117 Secondary transfer roller 170 Intermediate transfer belt 175 Base material 176 First silicon oxide layer 177 Second silicon oxide layer 178 Barrier layer 201 Driven roller

Claims (7)

A first silicon oxide layer having a carbon content of 0.5 atomic% or more and 10 atomic% or less on the base material side and a second carbon content of less than 0.5 atomic% from the base material side. And a barrier layer containing silicon oxide at a position on the surface side of the first silicon oxide layer with respect to the substrate, the barrier layer having a thickness of 5 nm or more, An intermediate transfer member, characterized in that it is 20 nm or less, has an average film density of 2.1 g / cm ³ or more and 2.3 g / cm ³ or less, and has a carbon content of less than 0.1 atomic%. The intermediate transfer member according to claim 1, wherein an average film density of the barrier layer is higher than an average film density of each of the first silicon oxide layer and the second silicon oxide layer. The intermediate transfer member according to claim 1 or 2, wherein an average film density of the first silicon oxide layer is 1.8 g / cm ³ or more and less than 2.1 g / cm ³ . 4. The intermediate transfer according to claim 1, wherein an average film density of the second silicon oxide layer is 2.1 g / cm ³ or more and 2.3 g / cm ³ or less. body. At least one layer selected from the first silicon oxide layer, the second silicon oxide layer, and the barrier layer has a thin film forming gas in a discharge space formed between opposing electrodes under atmospheric pressure or a pressure in the vicinity thereof. Formed by an atmospheric pressure plasma CDV method of forming a silicon oxide thin film by exciting a gas by applying a high-frequency electric field to the discharge space and exposing the substrate to the excited gas. The intermediate transfer member according to any one of claims 1 to 4, wherein the intermediate transfer member is formed. All the layers of the first silicon oxide layer, the second silicon oxide layer, and the barrier layer contain a thin film forming gas in a discharge space formed between opposing electrodes under atmospheric pressure or a pressure in the vicinity thereof. Formed by an atmospheric pressure plasma CDV method of forming a silicon oxide thin film by exciting the gas by applying a high frequency electric field to the discharge space and exposing the substrate to the excited gas. The intermediate transfer member according to any one of claims 1 to 5, wherein In an image forming apparatus for developing a surface of an image carrier to form a toner image, transferring the toner image to an intermediate transfer member, and further transferring the toner image to a transfer paper, the intermediate transfer member is any one of claims 1 to 6. An image forming apparatus comprising the intermediate transfer member according to claim 1.

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