JP2009161782A - Atmospheric plasma processing apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an atmospheric plasma processing apparatus capable of consistently depositing a thin film of high film uniformity on a cylindrical base material with high productivity. <P>SOLUTION: The atmospheric plasma processing apparatus comprises at least one pair of base material driving units for rotating a cylindrical base material, at least one pair of electrodes, a high frequency power source connected to the electrodes, and a gas feed section for feeding gas containing thin film depositing gas. The base material driving unit moves the cylindrical base material along opposing surfaces of the opposing electrodes. The electrodes excite the gas fed from the gas feed section by the high frequency electric field by the high frequency power source under the atmospheric pressure or under the pressure in a vicinity thereof. By exposing the cylindrical base material moved along the opposing surfaces of the electrodes by at least one pair of base material driving units opposing each other to the excited gas, thin films can be deposited on at least two cylindrical base materials at the same time. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an atmospheric pressure plasma processing apparatus used for surface treatment of a cylindrical substrate.

  In general, as a method for providing a high-functional thin film on a substrate by performing a surface treatment, for example, a dry film forming method using a vacuum such as a sputtering method, a vacuum deposition method, an ion plating method or the like has been used. .

  Since such a film forming method requires vacuum equipment, the equipment cost is high. Furthermore, since continuous production was not possible and the film forming speed was low, there was a problem that productivity was low.

  As a method for overcoming the disadvantages of low productivity due to the use of these vacuum devices, Japanese Patent Application Laid-Open No. 61-238961, etc., generates a discharge plasma under atmospheric pressure, and obtains a high treatment effect by the discharge plasma. Plasma processing methods have been proposed.

  This atmospheric pressure plasma treatment method is performed at a low cost on the surface of a substrate or the like, which is discharged under atmospheric pressure or near atmospheric pressure, plasma-excited reactive gas introduced into the discharge space, and disposed between the electrodes, In addition, the functional thin film can be easily formed.

  In this atmospheric pressure plasma treatment method, if the base material can be placed between the electrodes, the thin film can be formed by placing between the electrodes.

  Moreover, if a base material cannot be mounted between electrodes, a thin film can be formed by spraying the excited plasma on the base material.

  For this reason, surface treatment can be performed without particular limitation, such as a film shape, a sheet shape, and a three-dimensional shape such as a lens shape.

  For example, an atmospheric pressure plasma processing apparatus has been proposed in which a surface of a cylindrical base material is surface-treated using an atmospheric pressure plasma processing method (see, for example, Patent Documents 1 and 2).

  However, in the method proposed in the patent document, the surface of the electrode disposed at the position facing the substrate on which the film is formed is also continuously exposed to the reactive gas (excitation gas), so that the surface is contaminated. It will be.

  For this reason, when continuous surface treatment is performed for a long time, powder generated due to contaminants on the electrode surface is taken into the thin film on the surface of the substrate, resulting in deterioration of surface smoothness and film hardness. For example, it may cause a deterioration in the quality of the thin film formed.

  Furthermore, the deposition of contaminants on the electrode surface causes plasma discharge and gas flow non-uniformity, resulting in defects such as streaks due to uneven film thickness and non-uniform film quality. End up.

  In order to prevent such problems from occurring, it is necessary to remove contaminants on the electrode surface, which hinders productivity and increases costs.

  As a technique for preventing contamination of the electrode surface facing the substrate to be treated, the substrate to be treated is conveyed on each surface of the opposed roller electrodes, and plasma discharge is performed between the roller electrodes. An atmospheric pressure plasma treatment method for surface treatment has been proposed (see, for example, Patent Documents 3 and 4).

  However, these proposed methods, in the case of resin substrates that are vulnerable to heat, suppress the exposure time of the excitation gas per plasma discharge treatment and the power density applied to the plasma discharge in order to prevent thermal damage. In many cases, the desired film thickness of the functional thin film cannot be obtained by a single plasma discharge treatment.

  For this reason, it is necessary to divide the plasma discharge treatment into a plurality of times, which reduces productivity, and requires a large processing device such as a plurality of plasma processing devices arranged and continuously processed, leading to a reduction in economic efficiency.

Further, such a proposed atmospheric pressure plasma processing apparatus has a problem that it is difficult to stably form a thin film on a continuous cylindrical base material.
JP 2000-355772 A JP 2003-160868 A JP 2003-154255 A JP 2001-279457 A

  The present invention has been made in view of the above problems, and an object of the present invention is to provide an atmospheric pressure plasma processing apparatus that can stably form a thin film with high film uniformity on a cylindrical base material with high productivity. There is.

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

1. At least one pair of opposed substrate drive units for rotating the cylindrical substrate;
At least one pair of opposing electrodes;
A high-frequency power source connected to at least one of the electrodes and applying a high-frequency electric field to the opposing region of the electrode;
A gas supply part for supplying a gas containing a thin film forming gas to the opposing region of the electrode,
Each of the base material driving units moves the cylindrical base material along the facing surface of the facing electrode,
The electrode excites the gas supplied from the gas supply unit by the high-frequency electric field from the high-frequency power source under atmospheric pressure or a pressure in the vicinity thereof,
By exposing the cylindrical substrate moved along the opposing surface of the electrode by the substrate driving unit to the excited gas,
At the same time, at least two of the cylindrical base materials are subjected to a surface treatment.

2. The gas supply unit is provided on the upstream side in the driving direction of the cylindrical base material in the opposed region of the electrode,
2. The atmospheric pressure plasma processing apparatus according to claim 1, further comprising a gas exhaust unit that exhausts unnecessary gas at a downstream side in the driving direction of the cylindrical base material in a region facing the electrode.

  3. 3. The atmospheric pressure plasma processing apparatus according to item 1 or 2, wherein the electrode has a box shape or a plate shape.

  4). 3. The atmospheric pressure plasma processing apparatus according to item 1 or 2, wherein the electrode has a belt shape that can rotate.

  5). 3. The atmospheric pressure plasma processing apparatus according to item 1 or 2, wherein the electrode has a rotatable cylindrical shape.

  6). 6. The atmospheric pressure plasma processing apparatus according to any one of 1 to 5, wherein the surface treatment includes at least a thin film formation on a cylindrical base material surface.

  7. The cylindrical substrate on which the surface treatment or thin film formation has been performed is an endless belt-shaped intermediate transfer member used in an electrophotographic image forming apparatus. Atmospheric pressure plasma processing equipment.

8). At least one pair of opposed substrate drive units for rotating the cylindrical substrate;
At least one pair of opposing electrodes;
A high-frequency power source connected to at least one of the electrodes and applying a high-frequency electric field to the opposing region of the electrode;
A gas supply unit for supplying a gas containing a thin film forming gas to the opposing region of the electrode;
An excitation gas injection unit that injects the excited gas by exciting the gas supplied from the gas supply unit by the high-frequency electric field from the high-frequency power source under atmospheric pressure or a pressure in the vicinity thereof,
The excitation gas injection unit injects the gas excited toward a substrate facing region that moves while the cylindrical substrate is opposed by the substrate driving unit,
Atmospheric pressure plasma treatment, wherein the surface treatment of at least two cylindrical substrates is performed simultaneously by exposing the jetted gas to the cylindrical substrate that moves while facing the substrate facing region. apparatus.

9. The excitation gas injection unit is provided on the upstream side in the driving direction of the cylindrical base material in the base material facing region,
9. The atmospheric pressure plasma processing apparatus according to claim 8, further comprising a gas exhaust unit that exhausts unnecessary gas on the downstream side in the drive direction of the cylindrical base material in the base material facing region.

  10. The atmospheric pressure plasma processing apparatus according to any one of 8 to 9, wherein the surface treatment includes at least thin film formation on a cylindrical base material surface.

  11. 11. The cylindrical substrate on which the surface treatment or thin film formation has been performed is an endless belt-shaped intermediate transfer member used in an electrophotographic image forming apparatus. Atmospheric pressure plasma processing equipment.

  By the above means, it was possible to provide an atmospheric pressure plasma processing apparatus capable of stably forming a thin film with high film uniformity on a cylindrical substrate with high productivity.

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

  First, an atmospheric pressure plasma processing method (hereinafter also referred to as an atmospheric pressure plasma CVD method) used in the atmospheric pressure plasma processing apparatus of the present embodiment will be described.

  The atmospheric pressure plasma processing method is a method in which a mixed gas of a discharge gas and a raw material gas (reactive gas) is introduced into a discharge space under atmospheric pressure or a pressure near atmospheric pressure, and the mixed gas is excited by discharge to form a substrate. For example, surface processing such as thin film formation, surface oxidation treatment, and roughening may be used.

  Here, the processing method which forms a thin film on a base material among these surface treatments is pointed out.

  The method is described in JP-A-11-133205, JP-A-2000-185362, JP-A-11-61406, JP-A-2000-147209, JP-A-2000-121804, etc. Also called the atmospheric pressure plasma method).

  Accordingly, a highly functional thin film can be formed with high productivity.

  Here, the vicinity of atmospheric pressure represents a pressure of 20 kPa to 110 kPa, preferably 93 kPa to 104 kPa.

  Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. However, the description in this section does not limit the technical scope of the claims or the meaning of terms.

  In each of the following drawings, an atmospheric pressure plasma processing apparatus forms a functional thin film on the surface of a cylindrical substrate K according to the purpose.

  First, a first atmospheric pressure plasma processing apparatus having a fixed electrode and having a discharge region and a film forming region in the same region will be described.

  FIG. 1 is a schematic configuration diagram showing an example of a first atmospheric pressure plasma processing apparatus having fixed electrodes.

The first atmospheric pressure plasma processing apparatus 1 excites the thin film forming gas supplied from the gas supply unit by a high frequency electric field from a high frequency power source under atmospheric pressure or a pressure in the vicinity thereof,
By exposing the cylindrical substrate moved along the opposing surface of the electrode by the substrate driving unit to the excited gas,
At the same time, a thin film is formed on at least two cylindrical substrates, which will be described in detail below.

The first atmospheric pressure plasma processing apparatus 1 includes at least one type of substrate conveyance unit 10 (at least one pair of opposed substrate drive units that rotate the cylindrical substrate) that conveys the cylindrical substrate K;
A pair of opposed electrodes 20 for plasma discharge;
A power supply 30 for supplying high-frequency power to each of the pair of electrodes 20;
At least a mixed gas (thin film forming gas) of the source gas and the discharge gas is generated in the discharge region Z (shaded portion) where discharge is performed by the high-frequency power supplied from the power supply 30, and the mixed gas G is supplied to the discharge space Z. A mixed gas supply unit 40;
And an exhaust part 50 for exhausting the used exhaust gas G ′.

  A region where the pair of electrodes 20 face each other is a discharge region Z.

  And the base material conveyance part 10, the electrode 20, the mixed gas supply part 40, and the exhaust part 50 are accommodated in the discharge container not shown which reduces that air flows in into the discharge space Z etc. from the outside.

  The base material transport unit 10 includes a first base material transport unit 11 and a second base material transport unit 12 disposed to face the first base material transport unit 11.

And the 1st base material conveyance part 11 and the 2nd base material conveyance part 12, respectively, drive roller 101 which conveys cylindrical base material K so that it may rotate in the direction of arrow a,
At least one pair of driven rollers 102 driven to rotate by a driving roller 101 through a cylindrical substrate K;
And a drive motor 103 that rotationally drives the drive roller 101 in the direction of arrow b.

  Here, the 1st base material conveyance part 11 and the 2nd base material conveyance part 12 move the cylindrical base material K along the opposing surface of the 1st electrode 21 and the 2nd electrode 22 which oppose. Let

  Further, the urging roller 104 for applying a predetermined tension to the cylindrical base material K is pulled in the direction of the arrow c by a tension applying means (not shown) to apply a predetermined tension to the cylindrical base material K.

  The tension applying means cancels the application of tension when the cylindrical base material K is changed, and makes it easy to change the cylindrical base material K. For example, it moves in the direction opposite to the arrow c direction to release the tension of the cylindrical base material K.

The electrode 20 is disposed between the upstream driven roller 102a and the downstream driven roller 102b of the pair of driven rollers 102 of the first base material transport unit 11 and the second base material transport unit 12, respectively. Has been
The first electrode 21 disposed in the first base material transport unit 11 is connected to the first high-frequency power source 31, and the second electrode 22 disposed in the second base material transport unit 12 is the second. Is connected to the power source 32.

  The opposing regions of the first electrode 21 and the second electrode 22 that are arranged to face each other form a discharge space Z.

  And the 1st electrode 21 and the 2nd electrode 22 are coat | covered with the dielectric material mentioned later on the surface.

  Further, the first electrode 21 and the second electrode 22 have substantially the same width as that of the cylindrical base material K, and have a box shape extending in the conveyance direction of the cylindrical base material K.

  The first electrode 21 slightly protrudes to the discharge region Z side from the extended battle connecting the tangent line between the upstream driven roller 102a and the downstream driven roller 102b. The electrode 21 can be closely attached.

  Similarly, the cylindrical substrate K can be in close contact with the second electrode 22.

  In the power source 30, a first high frequency power source 31 is connected to the first electrode 21, and a second high frequency power source 32 is connected to the second electrode 22.

  The first high frequency power supply 31 outputs a high frequency voltage Vω1 having a frequency ω1 and is applied to the first electrode 21.

  The second high frequency power supply 32 outputs a high frequency voltage Vω 2 having a frequency ω 2 and is applied to the second electrode 22.

  Then, the high frequency voltage Vω1 applied to the first electrode 21 and the high frequency voltage Vω2 applied to the second electrode 22 generate an electric field Eω1ω2 in which the frequencies ω1 and ω2 are superimposed in the discharge space Z.

  Then, the mixed gas G is excited by the electric field Eω1ω2 to be turned into plasma, and a film corresponding to the raw material gas contained in the mixed gas G is deposited on the surface of the cylindrical substrate K.

  Therefore, discharge and thin film deposition are performed in substantially the same region (the discharge region and the film forming region are in the same region).

  The mixed gas supply unit 40 generates a mixed gas G (thin film forming gas) in which a raw material gas for forming a functional thin film and a rare gas such as nitrogen gas or argon gas are mixed, and the mixed gas G is supplied from the gas supply nozzle 41. , And supplied to the discharge space Z (region facing the electrode 20).

  The exhaust unit 50 sucks used exhaust gas G ′ containing particles and the like by a blower (not shown) and exhausts the exhaust gas to the outside of the first atmospheric pressure plasma processing apparatus 1.

  As described above, the urging roller 104 of the base material transport unit 10 moves in the direction opposite to the arrow c direction, for example, in order to make it easy to change the cylindrical base material K when the cylindrical base material K is changed. The tension of the cylindrical substrate K is released.

  Similarly, the driving roller 101, the driven roller 102a, and the driven roller 102b are preferably configured so that the belt can be easily attached and detached.

  For example, it is possible to provide a cantilever structure that supports these rollers on the side opposite to the operation side, and to provide a variable angle mechanism that tilts in a direction that reduces the tension when the cylindrical base material K is replaced.

  Further, when the cylindrical base material K is continuously conveyed, a meandering sensor for detecting meandering of the cylindrical base material K is provided, and the angle of the urging roller 104 is changed based on the output of the meandering sensor to meander. May be reduced.

  In the first atmospheric pressure plasma processing apparatus 1 as described above, at least two substrates can be processed at the same time, and the processing capacity per unit of time can be increased.

  Further, since the first electrode 21 and the second electrode 22 are processed while being always covered with the cylindrical base material K, they are not directly exposed to the excited mixed gas G.

  For this reason, the surface of the electrode is not contaminated, and the powder generated due to the contaminant on the electrode surface is taken into the thin film on the substrate surface when continuous surface treatment is performed for a long time. In addition, it is possible to prevent deterioration of the quality of a thin film to be formed, such as deterioration of surface smoothness and film hardness.

  Further, due to non-uniformity of the plasma discharge and gas flow due to the deposition of contaminants on the electrode surface, there will be no occurrence of defects such as streaks due to uneven thickness of the thin film to be formed and non-uniform film quality.

  In addition, since the electrode 20 has a box shape extending in the conveyance direction of the cylindrical base material K, the discharge time is extended, and the discharge energy per unit area can be reduced.

  For this reason, the temperature of the cylindrical base material K does not increase, and the selection range of the material of the cylindrical base material K can be expanded.

  FIG. 2 is a schematic configuration diagram showing an example of a second atmospheric pressure plasma processing apparatus having a belt-like electrode.

  The second atmospheric pressure plasma processing apparatus 2 is different from the first atmospheric pressure plasma processing apparatus 1 described with reference to FIG. 1 in that the discharge region and the film forming region are in the same region. Only the electrode 20 described in (1) is different.

  Therefore, the description of the first base material transport unit 11 and the second base material transport unit 12, the first high frequency power source 31 and the second high frequency power source 32, and the mixed gas supply unit 40 and the exhaust unit 50 is omitted. To do.

  Hereinafter, the electrode 60 will be described.

  The electrode 60 is disposed between the upstream driven roller 102a and the downstream driven roller 102b of the pair of driven rollers 102 in the first base material transport unit 11 and the second base material transport unit 12, respectively. Has been.

The electrode 60 is driven by the second driving roller 602 (the driving roller 6021 on the first base material transport unit 11 side, the second base material transport unit 12 side) driven at the same peripheral speed as the driving roller 101. Drive roller 6022);
An electrode belt 603 (electrode belt 6031 on the first base material transport unit 11 side, second base material transport unit 12) whose contact surface with the second drive roller 602 is a conductor and whose opposite surface is coated with a dielectric material to be described later. Side electrode belt 6032),
A driven roller 601 (a driven roller 6011 on the first base material transport unit 11 side, a driven roller 6012 on the second base material transport unit 12 side).

  The electrode belt 6031 is driven by a driving roller 6021 and rotates at the same speed as the cylindrical substrate K while being in close contact with the cylindrical substrate K.

  The electrode belt 6032 is driven by a driving roller 6022 and rotates at the same speed as the cylindrical substrate K while being in close contact with the cylindrical substrate K.

  The driven roller 6011 is connected to the first high frequency power supply 31 and supplies high frequency power from the first high frequency power supply 31 to the electrode belt 6031.

  The driven roller 6012 is connected to the second power source 32 and supplies high-frequency power from the second power source 32 to the electrode belt 6032.

  The opposing regions of the first electrode 61 and the second electrode 62 that are arranged to face each other form a discharge space Z.

  Then, the mixed gas G is excited by the electric field Eω1ω2 generated in the discharge space Z to be turned into plasma, and a film corresponding to the raw material gas contained in the mixed gas G is deposited on the surface of the cylindrical substrate K.

  Therefore, discharge and thin film deposition are performed in substantially the same region (the discharge region and the film forming region are in the same region).

  Further, the electrode belt 6031 and the electrode belt 6032 have substantially the same width as the width of the cylindrical substrate K.

  The driven roller 6011 and the driving roller 6021 slightly protrude to the discharge region Z side from the extended battle connecting the tangent line between the upstream driven roller 102a and the downstream driven roller 102b. Can be in close contact with the first electrode 61 (electrode belt 6031).

  Similarly, the cylindrical base material K can be in close contact with the second electrode 62 (electrode belt 6032).

  In the second atmospheric pressure plasma processing apparatus 2 as described above, at least two substrates can be processed at the same time, and the processing capacity per unit of time can be increased.

  In addition, since the first electrode 61 (electrode belt 6031) and the second electrode 62 (electrode belt 6032) are always covered with the cylindrical base material K, the treatment is performed on the excited mixed gas G. There is no direct exposure.

  For this reason, the surface of the electrode is not contaminated, and the powder generated due to the contaminant on the electrode surface is taken into the thin film on the substrate surface when continuous surface treatment is performed for a long time. In addition, it is possible to prevent deterioration of the quality of a thin film to be formed, such as deterioration of surface smoothness and film hardness.

  Further, due to non-uniformity of the plasma discharge and gas flow due to the deposition of contaminants on the electrode surface, there will be no occurrence of defects such as streaks due to uneven thickness of the thin film to be formed and non-uniform film quality.

  Further, since the electrode 60 has a belt shape extending in the conveyance direction of the cylindrical substrate K, the discharge time is extended, and the discharge energy per unit area can be reduced.

  For this reason, the temperature of the cylindrical base material K does not increase, and the selection range of the material of the cylindrical base material K can be expanded.

  FIG. 3 is a schematic configuration diagram showing an example of a third atmospheric pressure plasma processing apparatus having a plurality of roller electrodes.

  FIG. 3A shows an example in which a plurality of roller electrodes are arranged to face each other, and FIG. 3B shows an example in which a plurality of roller electrodes are arranged to face each other in a staggered manner. Yes.

  First, an example in which a plurality of roller electrodes are arranged to face each other will be described with reference to FIG.

  The third atmospheric pressure plasma processing apparatus 3 is different from the first atmospheric pressure plasma processing apparatus 1 described with reference to FIG. 1 in that the discharge region and the film forming region are in the same region (FIG. 1). Only the electrode 20 described in (1) is different.

  Therefore, the description of the first base material transport unit 11 and the second base material transport unit 12, the first high frequency power source 31 and the second high frequency power source 32, and the mixed gas supply unit 40 and the exhaust unit 50 is omitted. To do.

  Hereinafter, the electrode 70 will be described.

  The electrode 70 is disposed between the upstream driven roller 102a and the downstream driven roller 102b of the pair of driven rollers 102 in the first base material transport unit 11 and the second base material transport unit 12, respectively. Has been.

  The electrode 70 is rotated dependently by the cylindrical base material K, and rotates at the same speed as the cylindrical base material K while being in close contact with the cylindrical base material K (the first base material transport unit 11). Side roller electrode 701 and second base material transport unit 12 side roller electrode 702).

  The roller electrode 701 is connected to the first high frequency power supply 31 and is supplied with high frequency power from the first high frequency power supply 31.

  Further, the roller electrode 702 is connected to the second power source 32 and is supplied with high frequency power from the second power source 32.

  The roller electrode 701 and the roller electrode 702 are disposed at positions facing each other, and a facing area of each facing roller forms a discharge space Z ′.

  Then, the mixed gas G is excited by the electric field Eω1ω2 generated in the discharge space Z ′ to be turned into plasma, and a film corresponding to the raw material gas contained in the mixed gas G is deposited on the surface of the cylindrical substrate K.

  Therefore, discharge and thin film deposition are performed in substantially the same region (the discharge region and the film forming region are in the same region).

  Further, the roller electrode 701 and the roller electrode 702 have substantially the same length as the width of the cylindrical substrate K.

  The roller electrode 701 and the roller electrode 702 slightly protrude to the discharge region Z ′ side from the extended battle connecting the tangent line between the upstream driven roller 102a and the downstream driven roller 102b. K can be in close contact with the first electrode 71 (roller electrode 701).

  Similarly, the cylindrical base material K can be in close contact with the second electrode 72 (roller electrode 702).

  Next, an example in which a plurality of roller electrodes are arranged so as to face each other in a staggered manner will be described with reference to FIG.

  The third atmospheric pressure plasma processing apparatus 3 ′ shown in FIG. 3B is different from the third atmospheric pressure plasma processing apparatus 3 shown in FIG.

  For this reason, the electrode 80 will be described below.

  The electrode 80 is disposed between the upstream driven roller 102a and the downstream driven roller 102b of the pair of driven rollers 102 in the first base material transport unit 11 and the second base material transport unit 12, respectively. Has been.

  The electrode 80 is rotated dependently by the cylindrical base material K, and rotates at the same speed as the cylindrical base material K while being in close contact with the cylindrical base material K (the first base material transport unit 11). Side roller electrode 801 and second base material transport unit 12 side roller electrode 802).

  The roller electrode 801 is connected to the first high frequency power supply 31 and is supplied with high frequency power from the first high frequency power supply 31.

  The roller electrode 802 is connected to the second power source 32 and is supplied with high frequency power from the second power source 32.

  The roller electrode 801 and the roller electrode 802 are arranged at positions facing each other in a zigzag shape when viewed from the axial direction, and opposing areas of the rollers facing each other form a discharge space Z ′.

  Then, the mixed gas G is excited by the electric field Eω1ω2 generated in the discharge space Z ′ to be turned into plasma, and a film corresponding to the raw material gas contained in the mixed gas G is deposited on the surface of the cylindrical substrate K.

  Therefore, discharge and thin film deposition are performed in substantially the same region (the discharge region and the film forming region are in the same region).

  Further, the roller electrode 801 and the roller electrode 802 have substantially the same length as the width of the cylindrical substrate K.

  The roller electrode 801 and the roller electrode 802 slightly protrude to the discharge region Z ′ side from the extended battle connecting the tangent line between the upstream driven roller 102a and the downstream driven roller 102b. K can be in close contact with the first electrode 81 (roller electrode 801).

  Similarly, the cylindrical base material K can be in close contact with the second electrode 82 (roller electrode 802).

  In the third atmospheric pressure plasma processing apparatus 3 as described above, at least two substrates can be processed at the same time, and the processing capacity per unit of time can be increased.

  In addition, the first electrode 81 (roller electrode 701 and roller electrode 801) and the second electrode 82 (roller electrode 702 and roller electrode 802) are processed while being always covered with the cylindrical base material K. Therefore, it is not directly exposed to the excited mixed gas G.

  For this reason, the surface of the electrode is not contaminated, and the powder generated due to the contaminant on the electrode surface is taken into the thin film on the substrate surface when continuous surface treatment is performed for a long time. In addition, it is possible to prevent deterioration of the quality of a thin film to be formed, such as deterioration of surface smoothness and film hardness.

  Further, due to non-uniformity of the plasma discharge and gas flow due to the deposition of contaminants on the electrode surface, there will be no occurrence of defects such as streaks due to uneven thickness of the thin film to be formed and non-uniform film quality.

  In addition, since a plurality of the electrodes 70 and 80 are arranged in the conveying direction of the cylindrical substrate K, the discharge time is extended, and the discharge energy per unit area can be reduced.

  For this reason, the temperature of the cylindrical base material K does not increase, and the selection range of the material of the cylindrical base material K can be expanded.

  FIG. 4 is a schematic configuration diagram showing an example of a fourth atmospheric pressure plasma processing apparatus having fixed electrodes and active gas flow paths.

  The fourth atmospheric pressure plasma processing apparatus 4 is different from the first atmospheric pressure plasma processing apparatus 1 described with reference to FIG. 1 in that the discharge region and the film forming region are in the same region. Only the electrode 20 described in (1) is different.

  Therefore, the description of the first base material transport unit 11 and the second base material transport unit 12, the first high frequency power source 31 and the second high frequency power source 32, and the mixed gas supply unit 40 and the exhaust unit 50 is omitted. To do.

  Hereinafter, the electrode 90 will be described.

  The electrode 90 is disposed between the upstream driven roller 102a and the downstream driven roller 102b of the pair of driven rollers 102 of the first base material transport unit 11 and the second base material transport unit 12, respectively. Has been.

The electrode 90 is a pair of electrodes 20 ′ (electrode 21 ′ on the first base material transport unit 11 side, second base material transport unit 12 side) that performs plasma discharge of the mixed gas G 1 of the source gas and the discharge gas. Electrode 22 '),
The flow path Y of the mixed gas G1 excited by the electrode 20 ′ and turned into plasma, and the roller 901 (the roller 9011 on the first base material transport unit 11 side, the roller 9012 on the second base material transport unit 12 side), Have.

  The electrode 21 ′ is connected to the first high frequency power supply 31, and high frequency power is supplied from the first high frequency power supply 31.

  The electrode 22 ′ is connected to the second power supply 32, and high frequency power is supplied from the second power supply 32.

  The opposing regions of the electrode 21 ′ and the electrode 22 ′ that are disposed to face each other form a discharge space Z.

  The electrodes 21 ′ and 22 ′ are covered with a dielectric material to be described later.

Further, the electrode 21 ′ and the electrode 22 ′ have substantially the same width as the width of the cylindrical substrate K,
One end thereof is located in the vicinity of the upstream driven roller 102a, and the other end has a box shape extending to the middle between the driven roller 102a and the downstream driven roller 102b.

  The electrode 21 ′ slightly protrudes to the discharge region Z side from the extended battle connecting the tangent line between the upstream driven roller 102a and the downstream driven roller 102b, and the cylindrical base material K thus protrudes from the electrode 21 ′. Close contact is possible.

  Similarly, the cylindrical substrate K can be in close contact with the electrode 22 '.

  A gas flow path in which the facing region of the cylindrical base material K from the downstream end in the conveying direction of the facing region between the electrode 21 ′ and the electrode 22 ′ to the facing portion of the driven roller 102 is activated in the discharge region Z. Y is formed.

  The high-frequency voltage Vω1 applied to the first electrode 21 ′ from the first high-frequency power supply 31 and the high-frequency voltage Vω2 applied to the second electrode 22 ′ from the second high-frequency power supply 32 are applied to the electric field in the discharge space Z. Eω1ω2 is generated.

  A film corresponding to the source gas contained in the mixed gas G excited by the electric field Eω1ω2 and excited into plasma is deposited on the surface of the cylindrical substrate K.

  Further, a film corresponding to the source gas is further deposited on the surface of the base material K while the mixed gas G1 that is further excited and turned into plasma flows through the flow path Y.

  As described above, in the fourth atmospheric pressure plasma processing apparatus 4, the discharge and thin film deposition are performed in substantially the same region (the discharge region and the film formation region are in the same region), and only the thin film deposition rod. And a part for performing the operation.

  In the fourth atmospheric pressure plasma processing apparatus 4 as described above, at least two substrates can be processed at the same time, and the processing capacity per unit of time can be increased.

  Further, since the first electrode 21 ′ and the second electrode 22 ′ are processed while being always covered with the cylindrical base material K, they are not directly exposed to the excited mixed gas G.

  For this reason, the surface of the electrode is not contaminated, and the powder generated due to the contaminant on the electrode surface is taken into the thin film on the substrate surface when continuous surface treatment is performed for a long time. In addition, it is possible to prevent deterioration of the quality of a thin film to be formed, such as deterioration of surface smoothness and film hardness.

  Further, due to non-uniformity of the plasma discharge and gas flow due to the deposition of contaminants on the electrode surface, there will be no occurrence of defects such as streaks due to uneven thickness of the thin film to be formed and non-uniform film quality.

  Further, since the electrode 21 'and the electrode 22' are formed in a box shape extending in the conveying direction of the cylindrical base material K, the discharge time is extended and the discharge energy per unit area can be reduced.

  For this reason, the temperature of the cylindrical base material K does not increase, and the selection range of the material of the cylindrical base material K can be expanded.

  Furthermore, by providing the flow path Y through which the mixed gas G1 that has been excited and turned into plasma flows, it is possible to continuously deposit a film on the cylindrical base material K without applying energy (heating). Thus, the selection range of the material of the cylindrical base material K can be expanded.

  FIG. 5 is a schematic configuration diagram showing an example of a plasma jet type fifth atmospheric pressure plasma processing apparatus.

The fifth atmospheric pressure plasma processing apparatus 5 excites the discharge gas supplied from the discharge gas supply unit by a high-frequency electric field from a high-frequency power source at atmospheric pressure or a pressure near the atmospheric pressure, and injects the excited gas. An injection unit;
A thin film forming gas supply section for ejecting the thin film forming gas toward the outlet of the excitation gas injection section,
Injecting the mixed gas of the discharge gas excited by the excitation gas injection unit and the thin film formation gas ejected from the thin film formation gas supply unit toward the substrate facing region where the cylindrical base material moves while facing,
By exposing the mixed gas to the moving cylindrical base material, a thin film is simultaneously formed on at least two cylindrical base materials.

  The fifth atmospheric pressure plasma processing apparatus 5 is different from the first atmospheric pressure plasma processing apparatus 1 to the fourth atmospheric pressure plasma processing apparatus 4 described with reference to FIGS. It is different to have separated.

  That is, the electrode (corresponding to the electrode 20 described in FIG. 1) and the mixed gas supply unit 40 are different.

  For this reason, description about the 1st base material conveyance part 11 and the 2nd base material conveyance part 12, the 1st high frequency power supply 31, the 2nd high frequency power supply 32, and the exhaust part 50 is abbreviate | omitted.

  The discharge gas supply device 45 supplies the discharge gas G <b> 2 to the region facing the electrode of the plasma jet generator 46.

  The thin film forming gas supply unit 47 generates a raw material gas (thin film forming gas) for forming a functional thin film, and supplies a mixed gas G3 of the raw material gas (thin film forming gas) and the carrier gas to the tip of the electrode of the plasma jet generator 46. Supply.

  Then, the plasma jet generator 46, which is an excitation gas injection unit, supplies a pair of opposed electrodes 461 and 462 spaced apart by a predetermined distance, and a gas mixture G3 of a source gas (thin film forming gas) and a carrier gas to the tip. And an opening.

  A first high frequency power supply 31 is connected to the electrode 461, and a high frequency voltage Vω1 having a frequency ω1 is applied thereto.

  The second high frequency power supply 32 is connected to the electrode 462, and a high frequency voltage Vω2 having a frequency ω2 is applied thereto.

  Note that the electrode 461 and the electrode 462 are covered with a dielectric material to be described later.

  Then, an electric field Eω1ω2 is generated in a region where the electrodes 461 and 462, which are discharge regions, are opposed to each other, and the discharge gas G2 supplied from the discharge gas supply device 45 is excited under atmospheric pressure or a pressure in the vicinity thereof.

  The discharge gas G2 excited by the plasma jet generation unit 46, the raw material gas (thin film formation gas) supplied from the thin film formation gas supply unit 47, and the mixed gas G3 of the carrier gas are at the tip of the plasma jet generation unit 46. Mix and activate.

  The activated mixed gas G1 has a deposition region X in which a film corresponding to the source gas is deposited (the cylindrical substrate K is opposed to the first substrate transport unit 11 and the second substrate transport unit 12). While moving to the substrate facing region).

  The mixed gas G1 released in the activated state flows toward the exhaust part 50 through the deposition region X where the two cylindrical substrates K face each other, and the two cylinders are conveyed with the deposition region X interposed therebetween. The activated mixed gas G1 is exposed to the cylindrical substrate K, and a film corresponding to the raw material gas is simultaneously deposited on the surfaces of the two cylindrical substrates K.

  In other words, the excited discharge gas, the raw material gas (thin film forming gas), and the carrier gas mixed gas are discharged (spouted) onto the cylindrical base material K that moves while facing each other across the deposition region X, and activated. By exposing the released mixed gas to the cylindrical substrate K, a thin film is simultaneously formed on at least two cylindrical substrates.

  In the fifth atmospheric pressure plasma processing apparatus 5 as described above, at least two substrates can be processed at the same time, and the processing capacity per unit of time can be increased.

Further, in order to deposit a film on the cylindrical base material K while the cylindrical base material K is transported in the deposition region X,
When continuous surface treatment is performed for a long time, powder generated due to contaminants on the electrode surface is taken into the thin film on the surface of the substrate, resulting in deterioration of surface smoothness and film hardness. The deterioration of the quality of the thin film to be formed can be prevented.

  Further, by providing the deposition region X extending in the conveyance direction of the cylindrical base material K, it becomes possible to extend the film forming time, the temperature of the cylindrical base material K is not increased, and the cylindrical base material K The selection range of materials can be expanded.

  In addition, by separating the discharge region and the film forming region, it is possible to increase the discharge energy in the plasma jet generating unit 46, and the selection range of the gas to be used can be expanded.

  Further, the discharge gas supply device 45 and the thin film forming gas supply unit 47 are separated, and the thin film is deposited by mixing the thin film forming gas after exciting the discharge gas, thereby preventing the thin film deposition at the plasma jet generating unit 46. In addition, a thin film can be efficiently formed on the cylindrical substrate K.

  Hereinafter, the electrodes used in each of the above atmospheric pressure plasma processing apparatuses will be described.

  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 each electrode, and each roller electrode has at least one electrode surface to withstand the discharge caused by the strong electric field. The following dielectric is coated.

  FIG. 6 is a schematic configuration diagram showing an example of an electrode used in the atmospheric pressure plasma processing apparatus.

FIG. 6A is a partial sectional view of electrodes used in the first atmospheric pressure plasma processing apparatus 1, the fourth atmospheric pressure plasma processing apparatus 4, and the fifth atmospheric pressure plasma processing apparatus 5.
FIG. 6B is a partial sectional view of an electrode used in the second atmospheric pressure plasma processing apparatus 2.
FIG. 6C is a partial cross-sectional view of electrodes used in the third atmospheric pressure plasma processing apparatuses 3 and 3 ′.

In FIG. 6A,
The structure of the electrode 20 (21, 22) and the electrodes 461, 462 of the plasma jet generating unit 46 will be described. Ceramics with respect to a conductive base material 201 (hereinafter also referred to as “electrode base material”) such as metal. After the thermal spraying, a ceramic coating treated dielectric 202 (hereinafter also simply referred to as “dielectric”) sealed with an inorganic material is used.

  As the ceramic material used for thermal spraying, alumina, silicon nitride, or the like is preferably used. Among these, alumina is more preferably used because it is easily processed.

  Alternatively, the electrode may be constituted by a combination in which the electrode base material 201 is covered with a lining dielectric (not shown) 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 electrode base material 201 include metals such as silver, platinum, stainless steel, aluminum, titanium, and iron. Stainless steel is preferable from the viewpoint of processing.

  In the present embodiment, the electrode base material 201 of the electrodes 20, 461, 462 is preferably a stainless jacket roller base material having a cooling means with cooling water.

In FIG. 6B,
The configuration of the electrode 60 (electrode belt 603) will be described.
It is desirable that the surface of the base material 203 (hereinafter also referred to as “belt electrode base material” 203) is covered with a solid dielectric 204.

  Examples of the solid dielectric 204 include plastics such as polytetrafluoroethylene and polyethylene terephthalate, rubbers such as chloroprene rubber and silicon rubber, glass, or silicon oxide, or metal oxides such as aluminum oxide, zirconium oxide, and titanium oxide. Or composite metal oxides, such as barium titanate, etc. can be mentioned.

  Examples of the belt electrode base material 203 include metals such as silver, platinum, copper, stainless steel, aluminum, titanium, and iron.

In the present embodiment, there is a cooling means by bringing gas or liquid into contact with the back surface of the belt electrode 60,
More preferably, the rollers 601 and 602 are jacket rollers through which cooling water can flow.

In FIG. 6C,
The structure of the roller electrodes 701 and 801 will be described. Similarly to FIG. 6A, after spraying ceramics on a conductive base material 201 such as metal (hereinafter also referred to as “electrode base material”), an inorganic material is used. And a ceramic coating treated dielectric 202 (hereinafter, also simply referred to as “dielectric”) that has been sealed.

  As the ceramic material used for thermal spraying, alumina, silicon nitride, or the like is preferably used. Among these, alumina is more preferably used because it is easily processed.

  Alternatively, the electrode may be constituted by a combination in which the electrode base material 201 is covered with a lining dielectric (not shown) 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 electrode base material 201 include metals such as silver, platinum, stainless steel, aluminum, titanium, and iron. Stainless steel is preferable from the viewpoint of processing.

  In the present embodiment, the electrode base material 201 of the roller electrode 701 (801) is preferably a stainless steel jacket roller base material having a cooling means using cooling water.

  The cylindrical base material on which the thin film is formed using the first to fifth atmospheric pressure plasma processing apparatuses 1 to 5 described above is an endless belt-like intermediate transfer body (intermediate transfer belt) used for an electrophotographic image forming apparatus. ) Is preferable.

  And the following can be used as the base material.

  As a base material of the intermediate transfer belt, a belt formed by dispersing a conductive agent in a resin material or an elastic material can be used.

  These base materials may be used alone or in combination of two or more, and a belt composed of a combination of a laminate of these resin material and elastic material can also be used.

  As the resin used for the belt, so-called engineering plastic materials such as polycarbonate, polyimide, polyetheretherketone, polyvinylidene fluoride, ethylenetetrafluoroethylene copolymer, polyamide, and polyphenylene sulfide can be used.

  Elastic materials include isoprene rubber, butadiene rubber, styrene / butadiene rubber, acrylonitrile / butadiene rubber, nitrile rubber, hydrogenated nitrile rubber, fluorine rubber, silicone rubber, ethylene / propylene rubber, chloroprene rubber, acrylic rubber, butyl rubber, urethane Rubber materials such as rubber, chlorosulfonated polyethylene rubber, epichlorohydrin rubber, natural rubber and polyether rubber, and elastomers such as polyurethane, polystyrene / polybutadiene block polymer, polyolefin, polyethylene, chlorinated polyethylene, ethylene / vinyl acetate copolymer, etc. Can be used.

  In order to reduce the hardness, the elastic layer may be a foam. In this case, the density is suitably from 0.1 g / cm3 to 0.9 g / cm3.

  Moreover, carbon black can be used as a conductive agent.

  As the carbon black, neutral or acidic carbon black can be used.

  The amount of the conductive filler used varies depending on the type of the conductive filler to be used, but may be added so that the volume resistance value and the surface resistance value of the intermediate transfer belt are within a predetermined range. It is 10-20 mass parts with respect to this, Preferably it is 10-16 mass parts.

  The base material used in the present embodiment 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.

  The gas used in the mixed gas supply unit 40 and the mixed gas supply device 45 described above is a raw material gas for forming a functional thin film, for example, an inorganic oxide layer, an inorganic nitride layer, an inorganic carbide layer, etc. A rare gas such as nitrogen gas or argon gas is preferably used.

  In the atmospheric pressure plasma processing apparatuses 1 to 5, a functional thin film is formed on the cylindrical base material by the above-described method. This functional thin film is obtained by measuring the carbon atom content by XPS measurement. It is preferable to contain not more than atomic%.

  A mixed gas (discharge gas) is plasma-excited between the electrodes, the source gas having carbon atoms present in the plasma is radicalized and exposed to the surface of the cylindrical substrate K.

  And the carbon containing molecule | numerator and carbon containing radical which were exposed to the surface of this cylindrical base material K are contained in the formed thin film.

  The discharge gas used in the atmospheric pressure plasma processing apparatuses 1 to 5 refers to a gas that is plasma-excited under the plasma processing conditions as described above, for example, nitrogen, argon, helium, neon, krypton, xenon, etc., and mixtures thereof. Is mentioned.

  As a raw material gas for forming the functional thin film, an organic metal compound that is gaseous or liquid at room temperature, particularly an alkyl metal compound, a metal alkoxide compound, or an organometallic complex compound is used. The phase state of these raw materials does not necessarily need to be a gas phase at normal temperature and normal pressure, and can be a liquid phase as long as it can be vaporized through heating, decompression, etc. by melting, evaporation, sublimation, etc. It can also be used in a solid phase.

  The source gas contains a component that is in a plasma state in the discharge space and forms a thin film, and is an organometallic compound, an organic compound, an inorganic compound, or the like.

  For example, as a silicon compound, silane, tetramethoxysilane, tetraethoxysilane (TEOS), tetra n-propoxysilane, tetraisopropoxysilane, tetra n-butoxysilane, tetra t-butoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane , Diethyldimethoxysilane, diphenyldimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, phenyltriethoxysilane, (3,3,3-trifluoropropyl) trimethoxysilane, hexamethyldisiloxane, bis (dimethylamino) dimethyl Silane, bis (dimethylamino) methylvinylsilane, bis (ethylamino) dimethylsilane, N, O-bis (trimethylsilyl) acetamide, bis (trimethylsilyl) carbodiimi , Diethylaminotrimethylsilane, dimethylaminodimethylsilane, hexamethyldisilazane, hexamethylcyclotrisilazane, heptamethyldisilazane, nonamethyltrisilazane, octamethylcyclotetrasilazane, 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) methane, cyclopentadienyltrimethylsilane, phenyldimethylsilane, phenyltrimethylsila , Propargyltrimethylsilane, tetramethylsilane, trimethylsilylacetylene, 1- (trimethylsilyl) -1-propyne, tris (trimethylsilyl) methane, tris (trimethylsilyl) silane, vinyltrimethylsilane, hexamethyldisilane, octamethylcyclotetrasiloxane, tetramethyl Examples include, but are not limited to, cyclotetrasiloxane, hexamethylcyclotetrasiloxane, M silicate 51, and the like.

  Titanium compounds include organometallic compounds such as tetradimethylaminotitanium, metal hydrogen compounds such as monotitanium and dititanium, metal halogen compounds such as titanium dichloride, titanium trichloride, and titanium tetrachloride, tetraethoxy titanium, tetraisopropoxy titanium And metal alkoxides such as tetrabutoxytitanium, but are not limited thereto.

  Examples of aluminum compounds include aluminum n-butoxide, aluminum s-butoxide, aluminum t-butoxide, aluminum diisopropoxide ethyl acetoacetate, aluminum ethoxide, aluminum hexafluoropentanedionate, aluminum isopropoxide, aluminum III 2,4- Pentandionate, dimethylaluminum chloride and the like are exemplified, but not limited thereto.

  Examples of the zinc compound include zinc bis (bis (trimethylsilyl) amide), zinc 2,4-pentanedionate, zinc 2,2,6,6-tetramethyl-3,5-heptanedionate and the like. Not.

  Zirconium compounds include zirconium t-butoxide, zirconium diisopropoxide bis (2,2,6,6-tetramethyl-3,5-heptanedionate, zirconium ethoxy, zirconium hexafluoropentanedionate), zirconium isopropoxy. , Zirconium 2-methyl-2-butoxide, zirconium trifluoropentandionate, and the like, but are not limited thereto.

  These raw materials may be used alone or in combination of two or more components.

  Further, the hardness of the functional thin film formed by the atmospheric pressure plasma processing apparatuses 1 to 5 can be adjusted by the film forming speed, the additive gas amount ratio, or the like.

  The cylindrical base material provided with the functional thin film formed by the atmospheric pressure plasma processing apparatuses 1 to 5 is an endless belt-shaped intermediate transfer body (hereinafter also referred to as an intermediate transfer belt) used in an electrophotographic image forming apparatus. Preferably there is.

  The intermediate transfer member according to the present invention is a member used for an image forming apparatus such as an electrophotographic copying machine, a printer, a facsimile, etc., and primarily transfers a toner image carried on the surface of the photosensitive member to the surface, The transferred toner image is held, and the held toner image is secondarily transferred onto the surface of an object to be transferred such as recording paper.

  In general, the intermediate transfer belt has a substrate and a surface layer composed of at least one layer on the surface of the substrate, and the surface hardness of the surface layer is 3 GPa or more and 11 GPa or less as measured by a nanoindentation method. Preferably there is.

In the electrodes arranged at the opposed positions in the atmospheric pressure plasma processing apparatuses 1 to 5,
One electrode (for example, the first electrode 21 in FIGS. 1 and 4, the first electrode 61 in FIG. 2, the roller electrodes 701 and 801 in FIG. 3, and the electrode 461 in FIG. 5) is supplied from the first power supply 25. A first high-frequency voltage Vω1 of frequency ω1 is applied;
The other electrode (for example, the second electrode 22 in FIGS. 1 and 4, the second electrode 62 in FIG. 2, the roller electrodes 702 and 802 in FIG. 3, and the electrode 462 in FIG. 5) is supplied from the second power source 26. A high frequency voltage Vω2 having a frequency ω2 is applied.

  As a result, an electric field (electric field strength Eω1ω2) corresponding to a voltage obtained by multiplying the high frequency voltage Vω1 (electric field strength Eω1) and the high frequency voltage Vω2 (electric field strength Eω2) is generated between one electrode and the other electrode. The current I1 flows through one electrode, the current I2 flows through the other electrode, and plasma is generated between the roller electrodes.

Here, the relationship between the frequency ω1 and the frequency ω2, and the relationship between the electric field strength Eω1, the electric field strength Eω2, and the electric field strength IV at which discharge of the discharge gas is started,
When ω1 <ω2, Eω1 ≧ IV> Eω2 or Eω1> IV ≧ Eω2 is satisfied,
The output density of the second high frequency electric field is 1 W / cm ² or more.

Since the electric field strength IV for starting the discharge of nitrogen gas is 3.7 kV / mm, the electric field strength Eω1 applied from at least the first power supply 25 is 3.7 kV / mm or more,
The electric field strength Eω2 applied from the second high frequency power supply 26 is preferably 3.7 kV / mm or less.

Moreover, as the 1st high frequency power supply 31 applicable to the 1st-5th atmospheric pressure plasma processing apparatuses 1-5,
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
A8 SEREN IPS 100-460kHz L3000
And the like, and any of them can be used.

As the second high frequency power supply 32,
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
B6 Pearl Industry 20-99.9MHz RP-2000-20 / 100M
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 embodiment, the power supplied between the electrodes facing each other from the first and second high frequency power supplies supplies power (power density) of 1 W / cm ² or more to the one electrode to excite the discharge gas. Plasma is generated to form a thin film.

The upper limit value of power supplied to the one electrode is preferably 50 W / cm ² , more preferably 20 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.

Also, by supplying power (power density) of 1 W / cm ² or more, preferably 5 W / cm ² or more to the other electrode, the power density can be improved while maintaining the uniformity of the high frequency electric field. I can do it.

The upper limit value of the power supplied to the other electrode is preferably 50 W / cm ² .

  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.

  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 a pulse mode that performs ON / OFF intermittently. Either of them may be adopted, but at least the other electrode is supplied. As for the high frequency, the continuous sine wave is preferable because a finer and better quality film can be obtained.

Between the one electrode and the first high-frequency power supply 31, a first filter 31a is installed,
The current from the other high-frequency power supply 32 to the one high-frequency power supply 31 is made difficult to pass, and the current from the second high-frequency power supply 32 to one electrode is grounded to make it easier to pass.

Further, a second filter 32a is installed between the other electrode and the second high-frequency power source 32,
The current from one high-frequency power supply 31 to the other high-frequency power supply 32 is made difficult to pass, and the current from the first high-frequency power supply 31 to the other electrode is grounded to facilitate the passage.

  In the above description, the relationship between the electrode and the power source may be that the second high frequency power source 32 is connected to the one electrode and the first high frequency power source 32 is connected to the other electrode.

  In particular, when a rare gas such as argon is used as the discharge gas, one of the one electrode and the other electrode 20b may be connected to the ground and a power source may be connected to the other electrode. good.

  In this case, it is preferable to use the second high-frequency power source 32 from the viewpoint that a dense thin film can be formed.

Hereinafter, the present invention will be specifically described with reference to examples. However, the embodiment of the present invention is not limited thereto.
(Production of cylindrical substrate)
A cylindrical base material 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 part by mass Each of the above materials was put into a single screw extruder and melt kneaded to obtain a resin mixture. At the tip of the single screw extruder, a slit-shaped annular die having a seamless belt-shaped discharge port was attached, and the kneaded resin mixture was extruded in the form of a seamless belt.

The extruded seamless belt-shaped resin mixture is extrapolated to a cylindrical cooling cylinder provided at the discharge destination of the single-screw extruder, cooled, and solidified to form an endless cylindrical substrate for the intermediate transfer belt. Obtained. The thickness of the obtained base material was 120 μm.
Examples 1 to 4 (Comparative Examples 1 and 2)
(Production of Intermediate Transfer Belt 1: Example 1)
The produced cylindrical base material is mounted as the cylindrical base material K of the atmospheric pressure plasma processing apparatus composed of the opposed parallel plate electrodes shown in FIG. 1, and the cylindrical base material K is transported at a speed of 150 m / min. As a surface layer, a silicon oxide layer having a thickness of 250 nm was formed under the following formation conditions. At this time, as the dielectric covering each of the parallel plate electrodes 20 (21) and 20 (22) of the atmospheric pressure plasma processing apparatus, a single-walled one-mm thick alumina coated by ceramic spraying was used. The gap between the discharge spaces Z1 formed between the parallel plate electrodes 20 (21) and 20 (22) was set to 0.5 mm at the narrowest portion.

  Moreover, the metal base material which coat | covered the dielectric material of each parallel plate electrode is a stainless steel jacket specification which has the heating and cooling function by water circulation, and each parallel plate electrode is circulated by circulating 60 degreeC water during plasma discharge. A plasma treatment was carried out while keeping the surface temperature of the toner 100 constant, and 100 intermediate transfer belts K were continuously produced. The surface of each parallel plate electrode after the production was not found to be contaminated with dirt.

The source gas was heated to generate steam, mixed and diluted with preheated N ₂ gas and O ₂ gas, and then supplied to the discharge space Z1 from the mixed gas supply device (nozzle) 41. . An exhaust nozzle 50 was provided on the opposite side of the mixed gas supply device, and the pressure in the exhaust nozzle 50 was adjusted to be kept at −50 Pa, and exhaust gas after the plasma reaction was exhausted outside the system.
<Silicon oxide layer formation conditions>
Discharge gas: N ₂ gas, 3 slm per 1 cm processing width
Reaction gas: 21% by volume of O ₂ gas with respect to the total gas
Source gas: 0.1% by volume of tetraethoxysilane (TEOS) based on the total gas
Low frequency side power supply: High frequency power supply (50 kHz), 5 W / cm ² manufactured by Shinko Electric Co., Ltd.
High frequency side power supply: Broadband high frequency power supply (60.0 MHz) manufactured by Pearl Industrial Co., Ltd., 5 W / cm ²
(Preparation of Intermediate Transfer Belt 2: Example 2)
The produced cylindrical base material is mounted as the cylindrical base material K of the atmospheric pressure plasma processing apparatus constituted by the opposed parallel belt electrodes shown in FIG. While continuously transporting at a transport speed of 150 m / min, a silicon oxide layer was formed as a surface layer with a thickness of 250 nm under the same formation conditions as in Example 1. At this time, the dielectrics covering the belt electrodes 60 (61) and 60 (62) of the atmospheric pressure plasma processing apparatus were all coated with a 1 mm thick polytetrafluoroethylene film.

The drive rollers 601 (6011) and 601 (6012) of each belt electrode have a stainless steel jacket specification having heating and cooling functions by water circulation, and each belt electrode is circulated by circulating water at 60 ° C. during plasma discharge. The plasma treatment was performed while keeping the surface temperature of the film constant. As in Example 1, 100 intermediate transfer belts K were continuously produced. The roller electrodes after the production were not found to be contaminated with dirt that would hinder processing.
(Preparation of intermediate transfer belt 3: Example 3)
The produced cylindrical base material is mounted as the cylindrical base material K of the atmospheric pressure plasma processing apparatus constituted by the opposed double roller electrode shown in FIG. 3A, and the cylindrical base material is the same as in Example 1. While continuously transporting K at a transport speed of 150 m / min, a silicon oxide layer was formed as a surface layer with a thickness of 250 nm under the same formation conditions as in Example 1. At this time, as the dielectric covering each of the roller electrodes 701 and 702 of the atmospheric pressure plasma processing apparatus, the one coated with 1 mm thick alumina by ceramic spraying was used.

In addition, the metal base material coated with the dielectric of each roller electrode is a stainless steel jacket specification having heating and cooling functions by water circulation, and the surface of each roller electrode is circulated by circulating water at 60 ° C. during plasma discharge. Plasma treatment was performed while keeping the temperature constant. As in Example 1, 100 intermediate transfer belts K were continuously produced. The belt electrodes after completion of the production were not observed to be contaminated with dirt that would hinder processing.
(Preparation of intermediate transfer belt 4: Example 4)
100 intermediate transfer belts K were continuously formed in the same manner as in Example 3 except that the produced cylindrical base material was an atmospheric pressure plasma processing apparatus composed of opposed double roller electrodes as shown in FIG. Made. The belt electrodes after completion of the production were not observed to be contaminated with dirt that would hinder processing.
(Preparation of intermediate transfer belt 5: Comparative Example 1)
In the production of the intermediate transfer belt 1, an atmospheric pressure plasma processing apparatus having a single substrate transport unit similar to that shown in FIG. 3 of Japanese Patent Application Laid-Open No. 2007-017666 is used as the atmospheric pressure plasma processing apparatus. 100 intermediate transfer belts 5 were continuously produced in the same manner except for the above. In the production of the intermediate transfer belt 5, every time 10 pieces were processed, an operation of removing the surface contamination of the fixed electrode 21 at the position facing the cylindrical base material was performed.
(Preparation of Intermediate Transfer Belt 6: Comparative Example 2)
In the production of the intermediate transfer belt 5, 100 intermediate transfer belts 3 were continuously produced in the same manner except that the operation for removing the surface contamination of the fixed electrode 21 was not performed at all.
<Evaluation>
Among the intermediate transfer belts produced according to the above method, the following evaluation was performed on the last produced intermediate transfer belt.
[Measurement of surface hardness of thin film]
The thin film surface hardness (GPa) of the silicon oxide film of each produced intermediate transfer belt 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 (250 nm). The surface hardness (GPa) of the thin film was measured under the condition that the indentation depth was sufficiently small.
[Measurement of surface roughness]
According to the following method, 10-point average roughness (Rz) was measured.

As an atomic force microscope (AFM), the SPI3800N probe station and SPA400 multifunctional unit manufactured by Seiko Instruments Inc./SII Nanotechnology Co., Ltd. were used as measuring devices. DF20 was used. In the DFM mode (Dynamic Force Mode), a measurement area of 10 μm square was measured, and 10-point average roughness (Rz) was calculated from the obtained three-dimensional data.
[Measurement of film thickness of surface thin film (silicon oxide film)]
The thickness (nm) of the silicon oxide film of each of the produced intermediate transfer belts was obtained from the analysis result of the reflection spectrum using a reflection spectral film thickness meter FE-3000 (manufactured by Otsuka Electronics Co., Ltd.). It was confirmed in advance that the analysis result of the film thickness and the film thickness actually measured by electron microscope observation of the cross section (surface layer portion) of the intermediate transfer belt almost coincided with each other.

The film thickness was measured at intervals of 15 mm in the width direction and in the circumferential direction within the range involved in the drawing on the surface of each intermediate transfer belt. The variation width from the designed film thickness of 250 nm was measured, and this was used as a measure of thin film uniformity.
[Image quality evaluation by color laser printer]
As a color laser printer, a magiccolor 5440DL manufactured by Konica Minolta Business Technology was used, the internal intermediate transfer belt was removed, and the intermediate transfer belts 1 to 3 prepared above were mounted. As the toner, a polymerized toner having an average particle diameter of 6.5 μm is used, and Konica Minolta CF paper (manufactured by Konica Minolta Business Technology) is used with red (yellow and magenta toner), blue (magenta and cyan toner), green (yellow and yellow and toner). (Cyan toner) and black using a document in which the density of the solid image is changed in five levels from low to high for each color, printing is performed, and the unevenness of the output image and the toner density are visually observed. The image quality was evaluated according to

○: Image unevenness and density reduction are not recognized in all density regions. Δ: Image unevenness does not occur in all density regions, but density is slightly low in high density images. ×: Image unevenness occurs in all density regions. And the density of the obtained image is low [Evaluation of cleaning suitability]
After cleaning the surface of each intermediate transfer member with a cleaning blade using the color laser printer, the surface state of each intermediate transfer member is visually observed to confirm the toner adhesion state, and the cleaning suitability is evaluated according to the following criteria. went.

○: No toner adhesion is observed
Δ: Slight toner adhesion is observed, but there is no problem in practical use. X: Clear toner wiping off has occurred, and there are practical problems. Table 1 shows the results obtained as described above.

As is clear from the results shown in Table 1, the intermediate transfer belts 1 to 4 produced by the atmospheric pressure plasma processing apparatus of the present invention have a thin film uniformly formed on the surface, and both the hardness and the surface roughness of the thin film are It can be seen that it is good and has excellent properties as an intermediate transfer belt. On the other hand, although the intermediate transfer belt 5 of the comparative example had a uniform thin film formed on the surface, the hardness and surface roughness of the formed thin film were slightly inferior to those of the intermediate transfer belts 1 to 4, and the intermediate transfer by an actual machine. Also in evaluation as a belt, it was slightly inferior to the intermediate transfer belts 1 to 4. Further, the time required for producing 100 intermediate transfer belts was about four times that of the intermediate transfer belts 1 to 4 of the present invention. In addition, the intermediate transfer belt 6 that did not perform any electrode cleaning process at the time of thin film formation has streaks due to uneven thickness of the surface layer in the circumferential direction of the cylinder, and the thin film formation is uneven. Moreover, the whole was cloudy and was observed as a powder. Moreover, the surface hardness and surface roughness of the formed thin film were also inferior, and the measured value depending on the location was varied. Further, in the actual machine evaluation, strong image unevenness was recognized and the quality required for the intermediate transfer belt was not satisfied.
Examples 5 to 6 (Comparative Example 3)
An elastic layer and a silicon oxide layer as described below were provided on the surface of the polyphenylene sulfide intermediate transfer belt (cylindrical substrate) before treatment.
(Production of elastic layer)
On the outer periphery of “cylindrical substrate K”, “elastic layer 1” made of chloroprene rubber and having a thickness of 50 μm was provided by dipping coating.
(Production of silicon oxide layer)
A silicon oxide layer having a thickness of 100 nm was provided on the cylindrical substrate having the elastic layer 1 in the same manner as in Example 1.
(Preparation of Intermediate Transfer Belt 7: Example 5)
The produced cylindrical base material is mounted as the cylindrical base material K of the atmospheric pressure plasma processing apparatus constituted by the opposed parallel plate electrodes shown in FIG. 4, and the cylindrical base material K is transported at a speed of 100 m / min. As a surface treatment, treatment with fluorinated alkylsilane (FAS, CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (OC ₂ H ₅ ) ₃ ) was performed for 1 minute. At this time, the dielectric covering each of the parallel plate electrodes 20 ′ (21 ′) and 20 ′ (22 ′) of the atmospheric pressure plasma processing apparatus is a single-walled alumina coated by ceramic spraying. It was used. Further, the narrowest portion of the gap of the discharge space Z5 formed between the parallel plate electrodes 20 ′ (21 ′) and 20 ′ (22 ′) was set to 1.0 mm.

  Moreover, the metal base material which coat | covered the dielectric material of each parallel plate electrode is a stainless steel jacket specification which has a heating and cooling function by water circulation, and each parallel plate electrode is circulated by circulating 75 degreeC water during plasma discharge. A plasma treatment was carried out while keeping the surface temperature of the toner 100 constant, and 100 intermediate transfer belts K were continuously produced. The surface of each parallel plate electrode after the production was not found to be contaminated with dirt.

The raw material gas was heated to generate steam, mixed and diluted with preheated Ar gas, and then supplied to the discharge space Z1 from the mixed gas supply device (nozzle) 41. An exhaust nozzle 50 was provided on the opposite side of the mixed gas supply device, and the pressure in the exhaust nozzle 50 was adjusted to be kept at −20 Pa, and exhaust gas after the plasma reaction was exhausted out of the system.
<Alkyl fluoride surface treatment conditions>
Discharge gas: Ar gas, 1 slm per 1 cm processing width
Source gas: 0.01% by volume of fluoroalkylsilane (FAS) based on the total gas
High frequency power supply: Shinko Electric Co., Ltd. high frequency power supply (5 kHz), 5 W / cm ²
(The non-applied electrode is grounded)
(Preparation of Intermediate Transfer Belt 8: Example 6)
The produced cylindrical base material is mounted as a cylindrical base material K of an atmospheric pressure plasma processing apparatus constituted by the plasma jet electrode shown in FIG. While continuously transporting at a transport speed of min, as a surface treatment, treatment with fluorinated alkylsilane (FAS, CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (OC ₂ H ₅ ) ₃ ) was performed for 1 minute. At this time, as the dielectric covering the parallel electrodes 461 and 462 in the plasma jet nozzle of the atmospheric pressure plasma processing apparatus, a single-walled alumina coated with 1 mm thickness by ceramic spraying was used. Further, the gap between the discharge spaces Z6 formed between the parallel electrodes 461 and 462 was set to 1.0 mm.

In addition, the metal base material coated with the dielectric of each parallel electrode has a stainless steel jacket specification that has heating and cooling functions by water circulation. During plasma discharge, the surface temperature of the electrode is controlled by circulating water at 95 ° C. The plasma treatment was performed while keeping constant. In the same manner as in Example 5, 100 intermediate transfer belts K were continuously produced. The parallel electrodes after the completion of the production were not found to be contaminated with dirt that would hinder processing.
<Alkyl fluoride surface treatment conditions>
Discharge gas: Ar gas, 1 slm per 1 cm processing width
Source gas: 0.02% by volume of fluoroalkylsilane (FAS) with respect to the carrier gas Ar (0.5 slm per 1 cm treatment width)
The power source is the same as in Example 5.
(Preparation of intermediate transfer belt 9: Comparative Example 3)
In the production of the intermediate transfer belt 7, 100 intermediate transfer belts 9 were continuously formed except that the atmospheric pressure plasma processing apparatus was the atmospheric pressure plasma processing apparatus having the above-mentioned single substrate transport unit. Made. In the production of the intermediate transfer belt 9, the surface contamination of the fixed electrode 21 at the position facing the cylindrical base material is not removed.
(Measurement of water contact angle)
The water contact angle on the surface of each of the produced intermediate transfer belts was evaluated by a contact angle meter PG-X manufactured by Fibro system. 1 μl of water was dropped in a room at 25 ° C. and 50% RH, and the contact angle after 5 seconds from the dropping was adopted.

Water contact angles were measured at intervals of 15 mm in the width direction and in the circumferential direction within the range involved in the drawing of the surface of each intermediate transfer belt, and this was used as a measure of surface treatment uniformity.
[Image quality evaluation by color laser printer]
The same evaluation as in Examples 1 to 4 was performed.

  As is apparent from the results shown in Table 2, it can be seen that the intermediate transfer belts 7 and 8 produced by the atmospheric pressure plasma processing apparatus of the present invention are uniformly surface-treated and have excellent characteristics as an intermediate transfer belt. . On the other hand, it was shown that the intermediate transfer belt 9 of the comparative example has uneven surface treatment and inferior treatment state.

  FIG. 7 is an explanatory diagram of the layer configuration of the intermediate transfer belt.

  Hereinafter, the layer structure of the intermediate transfer belts 7 to 9 will be described with reference to FIG.

  The intermediate transfer belt 6 has an elastic layer 6b, a silicon oxide layer 6c, and an alkyl fluoride layer 6d on the surface of the substrate 6a.

  The base material layer 6a is, for example, PPS having a thickness of about 120 μm, the elastic layer 6b is, for example, chloroprene rubber, and at least one of the silicon oxide layer 6c and the alkyl fluoride layer 6d is an atmospheric pressure plasma processing apparatus. It is formed by.

It is a schematic block diagram which shows an example of the 1st atmospheric pressure plasma processing apparatus which has the fixed electrode. It is a schematic block diagram which shows an example of the 2nd atmospheric pressure plasma processing apparatus which has a belt-shaped electrode. It is a schematic block diagram which shows an example of the 3rd atmospheric pressure plasma processing apparatus which has a some roller electrode. It is a schematic block diagram which shows an example of the 4th atmospheric pressure plasma processing apparatus which has the fixed electrode and the flow path of active gas. It is a schematic block diagram which shows an example of the 5th atmospheric pressure plasma processing apparatus of a plasma jet system. It is a schematic block diagram which shows an example of the electrode used for the said atmospheric pressure plasma processing apparatus. FIG. 3 is an explanatory diagram of a layer configuration of an intermediate transfer belt.

Explanation of symbols

1, 2, 3, 4, 5 Atmospheric pressure plasma processing apparatus 11 1st base material conveyance part 12 2nd base material conveyance part 20 Electrode 21 1st electrode 22 2nd electrode 30 Power supply 31 1st high frequency power supply 32 Second high-frequency power source 40 Mixed gas supply unit 45 Mixed gas supply unit 46 Plasma jet generation unit 50 Exhaust unit 60, 70, 80, 90 Electrode 101 Drive roller 102 Followed roller G Mixed gas K Cylindrical substrate X Deposition region Z Discharge area

Claims (11)

At least one pair of opposed substrate drive units for rotating the cylindrical substrate;
At least one pair of opposing electrodes;
A high-frequency power source connected to at least one of the electrodes and applying a high-frequency electric field to the opposing region of the electrode;
A gas supply part for supplying a gas containing a thin film forming gas to the opposing region of the electrode,
Each of the base material driving units moves the cylindrical base material along the facing surface of the facing electrode,
The electrode excites the gas supplied from the gas supply unit by the high-frequency electric field from the high-frequency power source under atmospheric pressure or a pressure in the vicinity thereof,
By exposing the cylindrical substrate moved along the opposing surface of the electrode by the substrate driving unit to the excited gas,
At the same time, at least two of the cylindrical base materials are subjected to a surface treatment. The gas supply unit is provided on the upstream side in the driving direction of the cylindrical base material in the opposed region of the electrode,
2. The atmospheric pressure plasma processing apparatus according to claim 1, further comprising a gas exhaust unit configured to exhaust unnecessary gas on a downstream side in the driving direction of the cylindrical base material in a region facing the electrode. The atmospheric pressure plasma processing apparatus according to claim 1, wherein the electrode has a box shape or a plate shape. The atmospheric pressure plasma processing apparatus according to claim 1, wherein the electrode has a belt-like shape that can rotate. The atmospheric pressure plasma processing apparatus according to claim 1, wherein the electrode has a rotatable cylindrical shape. The atmospheric pressure plasma processing apparatus according to any one of claims 1 to 5, wherein the surface treatment includes at least a thin film formation on a cylindrical base material surface. The cylindrical substrate on which the surface treatment or thin film formation has been performed is an endless belt-shaped intermediate transfer member used in an electrophotographic image forming apparatus. Atmospheric pressure plasma processing equipment. At least one pair of opposed substrate drive units for rotating the cylindrical substrate;
At least one pair of opposing electrodes;
A high-frequency power source connected to at least one of the electrodes and applying a high-frequency electric field to the opposing region of the electrode;
A gas supply unit for supplying a gas containing a thin film forming gas to the opposing region of the electrode;
An excitation gas injection unit that injects the excited gas by exciting the gas supplied from the gas supply unit by the high-frequency electric field from the high-frequency power source under atmospheric pressure or a pressure in the vicinity thereof,
The excitation gas injection unit injects the gas excited toward a substrate facing region that moves while the cylindrical substrate is opposed by the substrate driving unit,
Atmospheric pressure plasma treatment, wherein the surface treatment of at least two cylindrical substrates is performed simultaneously by exposing the jetted gas to the cylindrical substrate that moves while facing the substrate facing region. apparatus. The excitation gas injection unit is provided on the upstream side in the driving direction of the cylindrical base material in the base material facing region,
The atmospheric pressure plasma processing apparatus according to claim 8, further comprising a gas exhaust unit that exhausts unnecessary gas at a downstream side of the base material facing region in the driving direction of the cylindrical base material. The atmospheric pressure plasma processing apparatus according to any one of claims 8 to 9, wherein the surface treatment includes forming a thin film on at least a cylindrical substrate surface. The cylindrical substrate on which the surface treatment or thin film formation has been performed is an endless belt-shaped intermediate transfer member used in an electrophotographic image forming apparatus. Atmospheric pressure plasma processing equipment.

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