JP5516430B2 - Intermediate transfer belt manufacturing method, intermediate transfer belt, and image forming apparatus - Google Patents

Description

  The present invention relates to an intermediate transfer belt manufacturing method, an intermediate transfer belt, and an image forming apparatus used in an electrophotographic image forming apparatus.

  In recent years, electrophotographic image forming apparatuses such as copying machines and laser printers have been strongly demanded for high image quality full color and high quality. As conventionally known, an electrophotographic image forming apparatus includes a charging member that uniformly charges a photosensitive member, an exposure member that forms an electrostatic latent image on the photosensitive member, and an electrostatic latent image that is converted into a toner image. A developing member for developing the toner image, a transfer member for transferring the obtained toner image to the transfer member, a fixing member for fixing the toner image on the transfer member, a cleaning member for cleaning residual toner on the photosensitive member, and an electrostatic on the photosensitive member. It has structural members such as a charge eliminating member that removes the latent image.

  An electrophotographic image forming apparatus supplies charged toner to an electrostatic latent image on a photoconductor in contact or non-contact manner, and transfers a toner image formed through a developing process to make the electrostatic latent image a visible image Then, after the primary transfer onto the intermediate transfer belt, the secondary transfer onto the transfer material and further fixing to form the final image. As an intermediate transfer member, an intermediate transfer belt using an endless belt as a substrate is known.

  In the transfer process, various mechanical and electrical external forces such as transfer charging and charge removal for primary transfer of the toner image to the intermediate transfer belt, and cleaning with a blade for removing the toner remaining on the intermediate transfer body after transfer are intermediate. Added to the transcript.

  For this reason, the intermediate transfer belt is required to have various characteristics such as durability against these external forces, that is, mechanical strength, wear resistance, electrical durability, and no filming.

  Durability refers to the performance that enables transfer to a transfer material for a long time. Since the surface of the intermediate transfer belt is secondarily transferred to a transfer material (for example, paper) and then cleaned by rubbing with a cleaning blade to remove residual toner, the surface smoothness is lost due to contact with the cleaning blade, Cracks occur and stable transfer of the toner image from the photoconductor becomes impossible. In addition, cracks (cracks) are generated by routing.

  Filming refers to a phenomenon in which the toner that remains without being removed is gradually collected after the surface of the intermediate transfer belt is cleaned with a cleaning blade after secondary transfer onto a transfer material (for example, paper). Reasons for the toner to remain include 1) toner entering a crack generated on the surface of the intermediate transfer belt, and 2) toner remaining in a recess formed on the surface by contact with a cleaning blade. At the place where filming occurs, the transfer rate decreases, image streaks and unevenness occur, and image quality cannot be improved.

  Many studies have been made on the durability of the intermediate transfer belt.

  For example, it has at least one heat-resistant resin on the surface of an image transfer belt that has excellent heat resistance and wear resistance and also has excellent releasability (or repellency), and the main chain portion has a polyimide structure, polybenzo 2. Description of the Related Art An image transfer belt is known that has an imidazole structure or a polyamide structure and is formed of a heat-resistant resin having a side chain portion of a polysiloxane structure that hangs down from a main chain portion (for example, a patent document) 1).

However, it has been found that the technique described in Patent Document 1 has the following drawbacks.
1) Since it is composed of only resin, the surface hardness is low and the transfer efficiency is poor.
2) Adhesion with toner is high and filming is likely to occur.
3) Poor releasability and poor cleaning with a rubber blade.

  Rubber latex and curing comprising at least three layers of a base layer, an elastic layer, and a surface layer, and the surface layer containing more than 1 part by weight of fluororubber with respect to 1 part by weight of fluororesin Or a water-based urethane resin containing a fluororesin and a silicone component and a curing agent, and the surface energy in the surface layer is 20 mN / m to 40 mN / m, In addition, an intermediate transfer belt having a hardness of 0.1 MPa to 1.5 MPa when pressed by 3 μm as measured with a nanoindenter is known (for example, see Patent Document 2).

However, it has been found that the technique described in Patent Document 2 has the following drawbacks.
1) Since the hardness is low, the wear resistance and scratch resistance are poor.
2) Since the hardness is low, the selection range of the cleaning member is narrowed. In particular, blade cleaning becomes difficult.
3) There is no description of factors for adjusting the resistance, and as a result resistance adjustment is difficult.

  Under such circumstances, a method for manufacturing an intermediate transfer belt having a surface layer having excellent durability such as abrasion resistance and scratch resistance due to removal of toner by a blade after secondary transfer, and an intermediate transfer manufactured by this manufacturing method Development of an image forming apparatus using the belt and the intermediate transfer belt is desired.

JP 2004-191554 A JP 2010-15143 A

  The present invention has been made in view of the above circumstances, and its purpose is a surface layer excellent in durability, such as abrasion resistance and scratch resistance, and filming resistance in the removal of toner by a cleaning member after secondary transfer. The present invention provides an intermediate transfer belt manufacturing method, an intermediate transfer belt manufactured by the manufacturing method, and an image forming apparatus using the intermediate transfer belt.

  The above object of the present invention has been achieved by the following constitution.

1. In a method for producing an intermediate transfer belt used in an electrophotographic image forming apparatus in which at least one surface layer is provided on a substrate,
The surface layer comprises one or more polyorganosiloxane chains, a vinyl copolymer having a number average molecular weight of 5,000 to 100,000 having three or more radical polymerizable double bonds, a polyfunctional (meth) acrylate, After applying a coating solution for forming a surface layer containing an active energy ray-curable composition having an active energy ray, the active energy ray is irradiated and formed .
The active energy ray-curable composition comprises 5 parts by volume of reactive metal oxide particles surface-treated with a compound having a radical polymerizable functional group with respect to 75 parts by volume of the active energy ray-curable composition. A method for producing an intermediate transfer belt, comprising 40 parts by volume .

2 . In an intermediate transfer belt used in an electrophotographic image forming apparatus in which at least one surface layer is provided on a substrate,
The surface layer is produced by the method for producing an intermediate transfer belt described in 1 above, and the active energy ray-curable composition used in the method for producing the intermediate transfer belt is surface-treated with a compound having a radical polymerizable functional group. An intermediate transfer belt comprising 5 to 40 parts by volume of the reactive metal oxide particles with respect to 75 parts by volume of the active energy ray-curable composition .

3 . An image forming apparatus using the intermediate transfer belt described in 2 above.

  In order to improve the slipperiness of the surface layer of the intermediate transfer belt, the present inventor removes the toner from the blade even if a surface layer using a fluorine resin or a silicone resin is provided on the surface. As a result of examining whether the durability such as abrasion resistance and scratch resistance due to aging is inferior, the following was found.

  1. When removing toner with a cleaning member such as a blade or brush, the surface layer is worn by rubbing with the cleaning member, or the toner is sandwiched between the contact surface with the surface layer of the blade and the surface layer in a pressed state. As the surface layer moves relatively, the surface layer is shaved by the toner and scratches are generated.

  2. When the toner is removed with a blade or a brush, the cleaning member is pressed against the surface of the intermediate transfer belt, so that stress is concentrated at a portion where the surface of the intermediate transfer belt is in contact with the blade. At this time, if the releasability of the toner on the intermediate transfer belt is poor, the toner or the external additive of the toner is pressed against the intermediate transfer belt, and filming that locally covers the intermediate transfer belt occurs. .

  3. When the toner is secondarily transferred from the intermediate transfer belt to a transfer medium such as paper, if the adhesion force between the toner and the intermediate transfer belt is strong, the toner is not transferred to the transfer medium and remains on the transfer belt. The transfer rate decreases.

  The phenomena shown in the above 1 to 3 were presumed to be due to the lack of slipperiness of the surface layer with long-term use.

  The reason why the slipperiness of the surface layer is lowered with long-term use is as a result of further investigation. As a result, the lubricant that forms the surface of the surface layer by the load applied to the surface layer (see 1 to 3 above) (for example, It was estimated that 1 part of fluororesin or silicone resin) was released.

From these, the abrasion resistance by the blade during transfer is increased, the abrasion scratch resistance by the toner is increased at the same time, the releasability of the intermediate transfer belt is increased and the filming resistance is increased, and the adhesion force between the toner and the intermediate transfer belt is increased. It has been found that it is important that the surface layer has the following structure in order to reduce the image quality and increase the transfer rate.
1. Prevents lubricant from falling off the surface layer of the intermediate transfer belt.
2. In order to increase the wear resistance, simultaneously increase the slipperiness and hardness of the surface layer.

  As a result of further investigation, the factors that have the most influence on the durability of the surface layer are insufficient hardness of the surface layer and the falling off of the lubricant, increasing the abrasion resistance by the blade, increasing the abrasion scratch resistance by the toner, In order to prevent the lubricant from falling off, it is possible to achieve the object and effect of the present invention by balancing the hardness and the coefficient of friction so that the materials constituting the surface layer have an integrated structure and fixing the lubricant. As will be understood, the present invention has been reached.

  Method for producing an intermediate transfer belt having a surface layer having excellent durability such as abrasion resistance and scratch resistance and filming resistance in the removal of toner by a cleaning member after secondary transfer, and an intermediate transfer belt produced by this production method And an image forming apparatus using the intermediate transfer belt.

1 is a schematic cross-sectional configuration diagram illustrating an example of an electrophotographic image forming apparatus that uses an intermediate transfer belt as an intermediate transfer member. FIG. 2 is a partially enlarged schematic cross-sectional view of an intermediate transfer belt of the intermediate transfer member shown in FIG. 1. FIG. 3 is a schematic manufacturing process diagram for manufacturing the intermediate transfer belt shown in FIG. 2. It is the schematic which shows an example of the hardening processing apparatus of the surface layer (protective layer) used at the hardening process process shown in FIG.

  The embodiment of the present invention will be described with reference to FIGS. 1 to 4, but the present invention is not limited to this.

  FIG. 1 is a schematic sectional view showing an example of an electrophotographic image forming apparatus using an intermediate transfer belt as an intermediate transfer member. This figure shows the case of a full-color image forming apparatus.

  In the figure, reference numeral 1 denotes a full-color image forming apparatus. The full-color image forming apparatus 1 includes a plurality of sets of image forming units 10Y, 10M, 10C, and 10K, an endless belt-shaped intermediate transfer body forming unit 7 as a transfer unit, and an endless belt-shaped paper feeding conveyance for conveying a recording medium P. And a belt type fixing device 24 as fixing means. A document image reading device SC is arranged on the upper part of the main body A of the full-color image forming apparatus 1.

  An image forming unit 10Y that forms a yellow image as one of different color toner images formed on each of the photoreceptors 1Y, 1M, 1C, and 1K is a drum-like photoreceptor as a first image carrier. 1Y, a charging unit 2Y disposed around the photoreceptor 1Y, an exposure unit 3Y, a developing unit 4Y, a primary transfer roller 5Y as a primary transfer unit, and a cleaning unit 6Y.

  An image forming unit 10M that forms a magenta image as another different color toner image is disposed around a drum-shaped photoconductor 1M as a first image carrier, and the photoconductor 1M. A charging unit 2M, an exposure unit 3M, a developing unit 4M, a primary transfer roller 5M as a primary transfer unit, and a cleaning unit 6M.

  Further, an image forming unit 10C for forming a cyan image as one of different toner images of different colors is disposed around a drum-shaped photoreceptor 1C as a first image carrier, and the photoreceptor 1C. The charging unit 2C, the exposure unit 3C, the developing unit 4C, the primary transfer roller 5C as the primary transfer unit, and the cleaning unit 6C are provided.

  In addition, an image forming unit 10K that forms a black image as one of other different color toner images is disposed around a drum-shaped photosensitive member 1K as a first image carrier, and the photosensitive member 1K. It has a charging unit 2K, an exposure unit 3K, a developing unit 4K, a primary transfer roller 5K as a primary transfer unit, and a cleaning unit 6K.

  The endless belt-shaped intermediate transfer body unit 7 has an endless intermediate transfer belt 70 as a semiconductive endless belt-shaped second image carrier that is wound around a plurality of rollers and rotatably supported.

  Each color image formed by the image forming units 10Y, 10M, 10C, and 10K is sequentially transferred and synthesized on the rotating endless intermediate transfer belt 70 by the primary transfer rollers 5Y, 5M, 5C, and 5K. A color image is formed. A recording medium P such as paper as a recording medium accommodated in the paper feeding cassette 20 is fed by the paper feeding / conveying means 21, passes through a plurality of intermediate rollers 22 A, 22 B, 22 C, 22 D, and a registration roller 23, and is secondary. A color image is transferred onto a recording medium (transfer material) P at a time by being conveyed to a secondary transfer roller 5A as a transfer means.

  The recording medium (transfer material) P onto which the color image has been transferred is fixed by the fixing device 24 to which the heat roller fixing device 270 is attached, and is sandwiched between the discharge rollers 25 and placed on the discharge tray 26 outside the apparatus. Placed.

  On the other hand, after the color image is transferred to the recording medium (transfer material) P by the secondary transfer roller 5A, the endless intermediate transfer belt 70 in which the recording medium (transfer material) P is separated by curvature is removed by the cleaning means 6A. Is done.

  During the image forming process, the primary transfer roller 5K is always in pressure contact with the photoreceptor 1K. The other primary transfer rollers 5Y, 5M, and 5C are in pressure contact with the corresponding photoreceptors 1Y, 1M, and 1C, respectively, only during color image formation.

  The secondary transfer roller 5A comes into pressure contact with the intermediate transfer belt 70 only when the recording medium (transfer material) P passes through the secondary transfer roller 5A and secondary transfer is performed.

  Further, the housing 8 can be pulled out from the apparatus main body A through the support rails 82L and 82R. The housing 8 includes image forming units 10Y, 10M, 10C, and 10K, and an endless belt-shaped intermediate transfer body forming unit 7.

  The image forming units 10Y, 10M, 10C, and 10K are arranged in tandem in the vertical direction. An endless belt-shaped intermediate transfer body unit 7 is disposed on the left side of the photoreceptors 1Y, 1M, 1C, and 1K in the figure. The endless belt-shaped intermediate transfer body unit 7 includes an endless intermediate transfer belt 70 that can be rotated by winding rollers 71, 72, 73, 74, and 76, primary transfer rollers 5Y, 5M, 5C, and 5K, and a cleaning unit 6A. have.

  The image forming units 10Y, 10M, 10C, and 10K and the endless belt-shaped intermediate transfer body unit 7 are integrally pulled out from the main body A by the drawer operation of the housing 8.

  In this manner, the outer peripheral surfaces of the photoreceptors 1Y, 1M, 1C, and 1K are charged and exposed to form a latent image on the outer peripheral surface, and then a toner image (developed image) is formed by development, and an endless belt-like intermediate transfer The toner images of the respective colors are superposed on the belt 70, transferred to a recording medium (transfer material) P in a lump, and fixed and fixed by pressure and heating by the belt type fixing device 24. In the present invention, the time of image formation includes latent image formation and transfer of a toner image (developed image) to a recording medium P to form a final image.

  The photoreceptors 1Y, 1M, 1C, and 1K after the toner image is transferred to the recording medium P are transferred by the cleaning units 6Y, 6M, 6C, and 6K disposed on the photoreceptors 1Y, 1M, 1C, and 1K. After cleaning the toner remaining on the photoreceptor, the charging, exposure and development cycle described above is entered, and the next image formation is performed.

  In the color image forming apparatus, an elastic blade is used as a cleaning member of the cleaning unit 6A for cleaning the intermediate transfer member. Further, means (11Y, 11M, 11C, 11K) for applying a fatty acid metal salt to each photoconductor is provided. As the fatty acid metal salt, the same fatty acid metal salt as used in the toner can be used.

  The present invention relates to a method for manufacturing an intermediate transfer belt used in an electrophotographic image forming apparatus shown as an example in the figure, an intermediate transfer belt manufactured by this method, and an image forming apparatus using the intermediate transfer belt. It is.

  2 is a partially enlarged schematic sectional view of an intermediate transfer belt of an intermediate transfer member used in the image forming apparatus shown in FIG.

  In the figure, reference numeral 70 denotes an intermediate transfer belt. The intermediate transfer belt has a configuration having a surface layer 70b on an endless belt-like substrate 70a.

  The hardness of the endless belt-like substrate 70a is preferably 20 MPa to 200 MPa in consideration of mechanical strength, image quality, manufacturing cost, and the like.

  The thickness E of the endless belt-shaped substrate 70a is preferably 50 μm to 250 μm in consideration of mechanical strength, image quality, manufacturing cost, and the like.

  The hardness of the surface layer 70b is universal hardness (HU) (DIN 50359), and is preferably 0.60 GPa or more in consideration of scratches by the blade, abrasion, durability, transfer rate, filming, image quality, image quality, etc. Is more preferably 0.7 GPa to 1 GPa.

  Hardness shows the value measured on condition of the following using ultra micro hardness meter "H-100V (made by Fischer Instruments)."

Measurement conditions Measuring instrument: Micro hardness tester “H-100V (Fischer Instruments Co., Ltd.)”
Indenter shape: Vickers indenter (a = 136 °)
Measurement environment: 20 ° C, 60% RH
Maximum test load: 2mN
Loading speed: 2mN / 10sec
Maximum load creep time: 5 sec
Unloading speed: 2mN / 10sec
The measurement was performed by different methods for the surface layer 70b and the endless belt-like substrate 70a. About the surface layer 70b, it apply | coated and hardened so that it might become thickness 2 micrometers on the aluminum plate of thickness 1mm, and measured 30 points | pieces at random from 10 points | pieces. The endless belt-like substrate 70a was placed on an aluminum plate having a thickness of 1 mm, and measurement was performed at 5 points at equal intervals in the axial direction and 10 to 30 points in the circumferential direction. The average value of each is taken as universal hardness (HU).

  For the intermediate transfer belt, the unevenness of the universal hardness (HU) depending on the location in the circumferential direction is the difference between the maximum value and the minimum value with respect to the average value per sample, and the universal hardness (HU). In consideration of transfer unevenness, image density unevenness, image quality, and the like when the toner image is transferred to the intermediate transfer belt, 20% or less is preferable. The unevenness of universal hardness is a value obtained from the following formula.

Unevenness of universal hardness = (maximum hardness in the circumferential direction on the same axis−minimum hardness in the circumferential direction on the same axis) / maximum hardness in the circumferential direction on the same axis. The thickness F of the surface layer 70b is the transfer rate and durability. In consideration of filming and image quality, 0.5 μm to 5 μm is preferable.

  The thickness of the surface layer was measured with a Fisherscope (registered trademark) mms manufactured by Fischer Instruments.

  The structure of the endless belt-like base body 70a is not particularly limited, and may be a single layer or may be composed of two layers. In this figure, the case where it consists of one layer is shown.

  The configuration of the surface layer 70b is not particularly limited, and may be one layer or two layers. In this figure, the case where it consists of one layer is shown.

The surface free energy of the surface layer 70b is preferably 30 J / m ² or less in consideration of filming resistance, transferability, and the like. Furthermore, 25 J / m ² to 20 J / m ² is more preferable.

  The surface free energy indicates a value measured using Kyowa Interface Science Co., Ltd. DropMaster.

  The measurement is performed on the surface layer 70b at random from 10 to 30 points, and the average value thereof is defined as the surface free energy.

  FIG. 3 is a schematic manufacturing process diagram for manufacturing the intermediate transfer belt shown in FIG. FIG. 3A is a schematic flow chart for manufacturing the intermediate transfer belt shown in FIG. FIG. 3B is a schematic view showing an example of a coating apparatus for coating the surface layer forming coating solution on the surface of the substrate used in the coating process shown in FIG.

  The intermediate transfer belt manufacturing process 9 relating to the method of manufacturing the intermediate transfer belt according to the present invention includes a substrate manufacturing process 9a for manufacturing an endless belt-shaped substrate as a substrate, and a surface layer formation on the surface of the manufactured endless belt-shaped substrate. A coating step 9b for applying a coating solution; a coating solution preparation step 9c for forming a surface layer; and a curing treatment step 9d for curing the coating film for forming a surface layer formed in the coating solution coating step for forming a surface layer. ing.

  In the substrate manufacturing process 9a, the endless belt-shaped substrate 101 shown in FIG. 2 is manufactured by a conventionally known general manufacturing method. For example, a resin as a material can be melted by an extruder, formed into a cylindrical shape by an inflation method using an annular die, and then cut into a ring to produce an annular endless belt-like substrate. In addition, the polyamic acid solution is developed in a ring shape by an appropriate method such as a method of immersing the polyamic acid solution in the outer peripheral surface of the cylindrical mold, a method of applying to the inner peripheral surface, a method of further centrifuging, or a method of filling the casting mold The developed layer is dried and formed into a bell-shaped shape, and the molded product is heat-treated to convert the polyamic acid into an imide and recover it from the mold, etc. (JP-A 61-95361, JP-A 64-22514, JP-A 3-180309, etc.). In manufacturing the endless belt, an appropriate treatment such as mold release treatment or defoaming treatment can be performed. The endless belt-like substrate 101 (see FIG. 2) preferably has conductivity by dispersing a conductive agent in a resin.

  In the surface layer forming coating liquid preparation step 9c, the surface layer forming coating liquid preparation container 9c1, the stirrer 9c2, and the liquid sending for sending the prepared surface layer forming coating liquid to the coating liquid supply tank 9b5 of the dip coating apparatus 9b1 A tube 9c3 is used.

  The surface layer forming coating solution prepared in the surface layer forming coating solution preparing step 9c has a number average molecular weight of 5,000 having one or more polyorganosiloxane chains and three or more radical polymerizable double bonds. The composition has a 100,000 active vinyl copolymer and an active energy ray-curable composition having a polyfunctional (meth) acrylate. Moreover, it is preferable to make it the structure which added the reactive metal oxide fine particle to the coating liquid for surface layer formation as needed. Details of the surface layer forming coating solution will be described later.

  Reference numeral 9b1 denotes a dip coating apparatus used in the coating step 9b. The dip coating apparatus 9b1 has a coating unit 9b2 and a substrate supply unit 9b3 for an intermediate transfer belt. The application unit 9b2 receives an application tank 9b2a, an overflow liquid receiving tank 9b4 disposed on the upper part of the application tank 9b2a for receiving the application liquid overflowing from the opening 9b2a1 of the application tank 9b2a, an application liquid supply tank 9b5, and a liquid supply And a pump 9b6.

  The coating tank 9b2a has a structure in which a bottom portion 9b2a2 and a side wall 9b2a3 are raised from the peripheral surface of the bottom portion 9b2a2, and an upper portion is an opening portion 9b2a1. Reference numeral 9b2a4 denotes a coating liquid supply port for the surface layer forming coating liquid S sent from a liquid feeding pump 9b6 provided at the bottom 9b2a2 of the coating tank 9b2a. The coating tank 9b2a has a cylindrical shape in which the diameter of the opening 9b2a1 and the diameter of the bottom 9b2a2 are the same.

  Reference numeral 9b41 denotes a lid of the overflow tank 9b4, which has a hole 9b42 in the center. Reference numeral 9b43 denotes a coating liquid return port for returning the coating liquid in the overflow tank 9b4 to the coating liquid supply tank 9b5. S represents the coating solution for forming the surface layer. Reference numeral 9b8 denotes a stirring blade provided in the coating liquid supply tank 9b5.

  The supply unit 9b3 includes a ball screw 9b3a, a drive unit 9b3b that rotates the ball screw 9b3a, a control unit 9b3c that controls the rotation speed of the ball screw 9b3a, an elevating member 9b3d that is screwed to the ball screw 9b3a, and the rotation of the ball screw 9b3a. Along with this, there is a guide member 9b3e for moving the elevating member 9b3d in the vertical direction (the arrow direction in the figure). Reference numeral 9b3f denotes a holding member for the endless belt-like substrate of the intermediate belt attached to the elevating member 9b3d. The endless belt-like base body 70a is held on the surface of a cylindrical or columnar member 3 (see FIG. 4) that matches the diameter of the endless belt-like base body. The holding member 9b3f is attached to the elevating member 9b3d so that the held endless belt-like base body 101 of the intermediate belt is positioned substantially at the center of the coating tank 9b2a.

  As the ball screw 9b3a rotates, the lifting member 9b3d moves in the vertical direction, so that the endless belt-like base body 101 of the intermediate belt held by the holding member 9b3f attached to the lifting member 9b3d becomes the surface in the coating tank 9b2a. The coating liquid is applied to the surface of the endless belt-like substrate 101 of the intermediate belt by being immersed in the layer forming coating liquid S and then being pulled up.

  The speed at which the endless belt-like substrate 70a is pulled up needs to be appropriately changed depending on the viscosity of the surface layer forming coating solution S to be used. For example, when the coating solution has a viscosity of 10 mPa · s to 200 mPa · s, In consideration of coating film thickness, drying, etc., 0.5 mm / sec to 15 mm / sec is preferable. After applying the surface layer forming coating solution S to the surface of the endless belt-like substrate 70a of the intermediate belt using the dip coating apparatus shown in FIG. 2, the surface layer is irradiated by the active energy ray in the curing treatment step 9d. A coating film is formed by curing the forming coating film. You may heat-dry a coating film before hardening. The drying temperature is preferably 60 ° C to 100 ° C.

  This figure explains the dip coating method, but the method for applying the surface layer forming coating solution S to the surface of the endless belt-like substrate 101 of the intermediate belt is not particularly limited, and a known coating method can be applied. I can do it. For example, a dip coating method, an annular coating method using an annular coating tank, a spray coating method, a coating method using an ultrasonic atomizer, and the like can be mentioned.

  The curing process 9d uses the curing apparatus 2 (see FIG. 3). In the curing treatment step 9d, the coating film for forming the surface layer is irradiated with active energy rays to perform the curing treatment, and the surface layer 102 shown in FIG. 1 is formed. The curing apparatus 2 will be described with reference to FIG.

  FIG. 4 is a schematic view showing an example of a surface layer (protective layer) curing treatment apparatus used in the curing treatment step shown in FIG. FIG. 4A is a schematic perspective view showing an example of a surface layer (protective layer) curing treatment apparatus used in the curing treatment step shown in FIG. FIG. 4B is a schematic enlarged cross-sectional view along the line AA ′ shown in FIG.

  In the figure, reference numeral 2 denotes an apparatus for curing the surface layer of the endless belt-like substrate 70a. The curing processing apparatus includes an active energy ray irradiation apparatus 201 and a holding apparatus 202 for a cylindrical or columnar member 3 that holds an endless belt-like base body 70a (see FIG. 2) having a surface layer forming coating film formed on the surface. And have. The active energy ray irradiation device 201 is disposed at a position facing the cylindrical or columnar member 3, and is a surface layer on the cylindrical or columnar member 3 held by the holding device 202 and holding the endless belt-like substrate 70a. An active energy ray is irradiated to the coating film for formation. A curing process is performed by irradiating the surface layer-forming coating film with active energy rays to form a surface layer 70b shown in FIG.

  The active energy ray irradiation apparatus 201 includes a housing 201a, an active energy ray source 201b housed inside the housing 201a, and an energy control device (not shown) of the active energy ray source 201b. The active energy ray irradiation device 201 is fixedly disposed on a frame (not shown) of the curing processing device 2. Reference numeral 201c denotes an active energy ray irradiation port provided at the bottom of the casing 201a (a surface facing the surface of the endless belt-like base body 70a).

  L represents the distance between the irradiation port 201c and the surface layer-forming coating film surface of the endless belt-like substrate 70a. The distance L can be appropriately set depending on the intensity of the active energy ray, the type of the surface layer forming coating film, and the like.

  The holding device 202 includes a first holding table 202a, a second holding table 202b, and a driving motor 202c.

  The driving motor 202c is disposed on the first holding table 202a, and the cylindrical or columnar member 3 is a rotating shaft of the driving motor 202c via an attachment shaft and a connecting member of the cylindrical or columnar member 3. It is connected to the.

  The second holding base 202b is provided with a bearing portion 202d that receives the other mounting shaft of the cylindrical or columnar member 3, so that when the active energy ray irradiation device 201 irradiates the active energy ray, it is driven. The cylindrical or columnar member 3 can be held while being rotated by the rotation of the motor 202c.

  The rotational speed (circumferential speed) of the cylindrical or columnar member 3 when irradiating the active energy rays is preferably 10 mm / s to 300 mm / s in consideration of curing unevenness, hardness, curing time, and the like.

  This figure shows a case where the active energy ray irradiating apparatus 201 is fixed and the cylindrical or columnar member 3 is rotated to irradiate the active energy ray. Alternatively, the active energy ray irradiation device 201 may be moved along the periphery of the cylindrical member 3. Moreover, although this figure has shown the case where the cylindrical or columnar member 3 is set horizontally, it is needless to say that the cylindrical or columnar member 3 may be set vertically.

  The active energy ray that can be used in the present invention can be used without limitation as long as it is an energy source that activates the formed active energy ray-curable resin with ultraviolet rays, electron beams, γ rays, and the like. An electron beam is preferred. In particular, ultraviolet rays are preferable because they are easy to handle and high energy can be easily obtained. As the ultraviolet light source, any light source that generates ultraviolet light can be used. For example, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, or the like can be used. An ArF excimer laser, a KrF excimer laser, an excimer lamp, synchrotron radiation, or the like can also be used. In order to irradiate the spot-like active energy rays, it is preferable to use an ultraviolet laser.

  Moreover, an electron beam can be used similarly. The electron beam is from 50 keV to 1000 keV, preferably from 100 keV emitted from various electron beam accelerators such as cockroft Walton type, bandegraph type, resonant transformer type, insulated core transformer type, linear type, dynamitron type, and high frequency type. An electron beam having an energy of 300 keV can be given.

The irradiation conditions vary depending on individual light sources, the irradiation amount of light, curing unevenness, hardness, curing time, taking into account the cure rate and the like, 100 mJ / cm ² or more, more preferably, 120 mJ / cm ² from 200 mJ / cm ² Particularly preferred is 150 mJ / cm ² to 180 mJ / cm ² . The amount of irradiation light indicates a value measured by UIT250 (manufactured by USHIO INC.).

  The irradiation time of the active energy ray is preferably from 0.5 seconds to 5 minutes, and more preferably from 3 seconds to 2 minutes from the viewpoint of curing efficiency and work efficiency of the active energy ray curable resin.

  In the present invention, the atmosphere at the time of irradiation with active energy rays can be cured without problems in an air atmosphere, but the oxygen concentration in the atmosphere is 5% or less, particularly 1% or less in consideration of curing unevenness, curing time, and the like. It is preferable that In order to obtain this atmosphere, it is effective to introduce nitrogen gas or the like.

  The oxygen concentration indicates a value measured by an oxygen concentration meter OX100 (manufactured by Yokogawa Electric Corporation) for atmospheric gas management.

  Moreover, in this invention, in order to advance the hardening reaction of an active energy ray efficiently, the coating film for surface layer formation can also be heated. Although there is no restriction | limiting in particular as a heating method, For example, blowing of heating air is mentioned. The heating temperature cannot be defined unconditionally depending on the type of active energy ray curable resin to be used, but is preferably within a temperature range that does not affect the coating film for forming the surface layer, and preferably 40 ° C to 100 ° C. Further, it is preferably 40 ° C. to 80 ° C., particularly preferably 40 ° C. to 60 ° C.

  Next, materials related to the method for manufacturing the intermediate transfer belt of the present invention will be described.

(Vinyl copolymer)
The vinyl copolymer having a number average molecular weight of 5,000 to 100,000 having one or more polyorganosiloxane chains and three or more radical polymerizable double bonds used in the present invention is, for example, A monomer (a) having a heavy bond and a polyorganosiloxane group, a monomer (b) other than the monomer (a) having a reactive functional group having a radical polymerizable double bond, and further if necessary The monomer (a) and the vinyl polymer (A) obtained by radical polymerization of the monomer (c) having a radical polymerizable double bond other than the monomer (b), and the reactive functional group It can be obtained by reacting a compound (B) having a reactive functional group and a radically polymerizable double bond.

  A vinyl copolymer having a number average molecular weight of 5,000 to 100,000 having one or more polyorganosiloxane chains and three or more radical polymerizable double bonds is obtained by combining the monomer (a) with radical polymerization. It can also be obtained by polymerizing the monomer (c ′) having two or more ionic double bonds and, if necessary, the monomer (c). When the amount of the monomer (c ′) is small, the desired vinyl copolymer can be obtained without gelation. Further, it is possible to make gelation more difficult by protecting a part or all of the monomer (c ′) by adding a part of the radical polymerizable double bond as a blocking group.

  When the number average molecular weight of the vinyl copolymer is less than 5,000, it is not preferable because it is easy to crystallize and the productivity is remarkably deteriorated.

  When the number average molecular weight of the vinyl copolymer exceeds 100,000, the surface hardness of the surface layer is lowered, and the function as a transfer belt is adversely affected.

  A number average molecular weight shows the value measured by the gel permeation chromatography (Gel Permeation Chromatography) Shimadzu Corp. make.

  The monomer (a) having a radical polymerizable double bond and a polyorganosiloxane chain used in the present invention is, for example, a compound represented by the following general formula (1), and lowers the surface free energy of the surface layer. Is to do.

(In the formula, R ¹ represents CH ₂ ═CHCH—COO— (CH ₂ ) m—, CH ₂ ═C (CH ₃ ) —COO— (CH ₂ ) m—, CH ₂ ═CH— (CH ₂ ) m— Or CH ₂ ═C (CH ₃ ) — (CH ₂ ) m—, where m is an integer from 0 to 10, R ² represents hydrogen, a methyl group, or the same functional group as R ¹ , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ represent an alkyl group or a phenyl group, and n represents a positive integer.)
The hydrogen represented by R ¹ to R ⁸ may be substituted with a known substituent other than hydrogen as long as the effects of the present invention are not lost.

  Specific examples of the monomer (a) having a radical polymerizable double bond and a polyorganosiloxane chain include, for example, one-end vinyl group-containing polyorganosiloxane compounds such as TSL9705 manufactured by Toshiba Silicone Co., Ltd., Chisso Corporation Examples thereof include one-terminal (meth) acryloxy group-containing polyorganosiloxane compounds such as Silaplane FM-0711, FM-0721, and FM-0725.

  A monomer (a) can be used 1 type or in mixture of 2 or more types according to required performance.

  The copolymerization ratio of the monomer (a) in the vinyl polymer (A) depends on the surface weight free energy on the surface layer of the intermediate transfer belt and the compatibility with other components contained in the active energy ray-curable composition. In consideration of coating properties such as adhesion to an endless belt-like substrate, toughness, solubility of the polymer in a solvent, and the like, from 1% by mass based on the total mass of monomers constituting the polymer The content is preferably 80% by mass, more preferably 5% by mass and 50% by mass, and particularly preferably 10% by mass to 45% by mass.

  The monomer (b) other than the monomer (a) having a radical polymerizable double bond and a reactive functional group introduces a radical polymerizable double bond into the vinyl polymer (A) polymerized in the first stage. It is a starting point, and the introduced radical polymerizable double bond is set by crosslinking with an active energy ray to suppress the bleeding of the vinyl polymer and form a tough partition wall.

  Examples of the reactive functional group include a hydroxy group, a carboxyl group, an isocyanate group, and an epoxy group.

  Specific examples of the monomer (b) having a hydroxy group include 2-hydroxyethyl (meth) acrylate, 1-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth). Examples include acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, polytetramethylene glycol mono (meth) acrylate, and hydroxystyrene.

  Specific examples of the monomer (b) having a carboxyl group include acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, and citraconic acid.

  Specific examples of the monomer (b) having an isocyanate group include (meth) acryloyloxyethyl isocyanate, (meth) acryloyloxypropyl isocyanate, 2-hydroxyethyl (meth) acrylate, and 4-hydroxybutyl (meth). Examples thereof include those obtained by reacting a hydroxyalkyl (meth) acrylate such as acrylate with a polyisocyanate such as toluene diisocyanate and isophorone diisocyanate.

  Specific examples of the monomer (b) having an epoxy group include glycidyl methacrylate, glycidyl cinnamate, glycidyl allyl ether, glycidyl vinyl ether, vinylcyclohexane monoepoxide, 1,3-butadiene monoepoxide, and the like. A monomer (b) can be used 1 type or in mixture of 2 or more types according to required performance.

  The copolymerization ratio of the monomer (b) in the vinyl polymer (A) is determined by taking into consideration the scratch resistance, hardness, surface free energy, etc. of the surface layer of the intermediate transfer belt, and the total amount of monomers constituting the polymer. The content is preferably 10% by mass to 90% by mass based on the mass, more preferably 30% by mass to 90% by mass, and particularly preferably 40% by mass to 85% by mass.

  The monomer (c) having a radical polymerizable double bond other than the monomer (a) and the monomer (b) is compatible with the vinyl polymer and other components contained in the radiation curable composition. And improvement in physical properties such as hardness, toughness and scratch resistance of the surface layer of the intermediate transfer belt.

  Monomers (c) include (I) acrylic acid derivatives, (II) aromatic vinyl monomers, (III) olefinic hydrocarbon monomers, (IV) vinyl ester monomers, and (V) vinyl. Halide monomer, (VI) vinyl ether monomer and the like.

  (I) Specific examples of (meth) acrylic acid derivatives include alkyl (meth) acrylates such as (meth) acrylonitrile, methyl (meth) acrylate, butyl (meth) acrylate, ethylhexyl (meth) acrylate, and stearyl (meth) acrylate. , Benzyl (meth) acrylate and the like.

  Specific examples of the (II) aromatic vinyl monomer include styrenes such as styrene, methylstyrene, ethylstyrene, chlorostyrene, monofluoromethylstyrene, difluoromethylstyrene, and trifluoromethylstyrene.

  Specific examples of the (III) olefinic hydrocarbon monomer include ethylene, propylene, butadiene, isobutylene, isoprene, 1,4-pentadiene and the like.

  Specific examples of the (IV) vinyl ester monomer include vinyl acetate.

  Specific examples of the (V) vinyl halide monomer include vinyl chloride and vinylidene chloride.

  Specific examples of the (VI) vinyl ether monomer include vinyl methyl ether. These monomers may be used in combination of two or more.

  The copolymerization ratio of the monomer (c) in the vinyl polymer (A) is determined by considering the improvement in compatibility between the vinyl polymer and the other components contained in the radiation curable composition. It is preferably 0 to 89% by mass based on the total mass of the monomer.

  The vinyl polymer (A) can be synthesized by a known method, for example, solution polymerization. Solvents used during polymerization include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, ethyls such as tetrahydrofuran, dioxane, ethylene glycol dimethyl ether and diethylene glycol dimethyl ether, aromatics such as benzene, toluene, xylene and cumene, and acetic acid. Esters such as ethyl and butyl acetate can be used. Two or more solvents may be mixed and used. The monomer concentration during polymerization is preferably from 0 to 80% by mass.

  Examples of the polymerization initiator include ordinary peroxides or azo compounds such as benzoyl peroxide, azoisobutylvalenonitrile, azobisisobutyronitrile, di-t-butyl peroxide, t-butyl perbenzoate, and t-butyl. Peroctoate, cumene hydroxy peroxide and the like are used, and the polymerization temperature is preferably 50 ° C to 140 ° C, more preferably 70 ° C to 140 ° C.

  The preferred number average molecular weight of the resulting vinyl polymer (A) is 5,000 to 100,000.

  The vinyl polymer (A) having a reactive functional group and a polyorganosiloxane chain thus obtained is added with a compound (B) having a functional group capable of reacting with the reactive functional group and a radical polymerizable double bond. By reacting, a polymer having a radical polymerizable double bond and a polyorganosiloxane chain is obtained.

  The proportion of the vinyl polymer (A) and the compound (B) in which the number of functional groups that can react with the reactive functional group is 100% with respect to the number of reactive functional groups of the vinyl polymer (A). It is preferable to make it react with. Of course, the reaction may be performed at a rate of less than 100% as long as the photoreactivity is not impaired.

  As the combination of the reactive functional group and the functional group capable of reacting with the reactive functional group, various known combinations and reaction methods as shown below can be employed.

  1) When the reactive functional group is a hydroxy group, typical reactive functional groups include an acid halogen group and an isocyanate group. Specifically, (meth) acrylic acid chloride or methacryloxyethyl isocyanate By this reaction, a radical polymerizable double bond can be introduced. The reaction with (meth) acrylic acid chloride proceeds by adding a catalyst to a polymer solution having a polyorganosiloxane chain and a hydroxyl group, adding (meth) acrylic acid chloride and heating. As the solvent, ketones such as 2-butanone, methyl isobutyl ketone and cyclohexanone, esters such as ethyl acetate, propyl acetate and butyl acetate, and ether solutions such as ethylene glycol dimethyl ether and dioxolane can be used. As the catalyst, triethylamine, dimethylbenzylamine and the like are preferable, and the amount of the catalyst is 0.1% by mass to 1% by mass with respect to the solid content. The reaction is carried out in air to suppress gelation, the reaction temperature is 80 ° C. to 120 ° C., and the reaction time is 1 hour to 24 hours.

  The reaction with methacryloxyethyl isocyanate is carried out by using a metal compound such as tin octylate, tin dibutyldilaurate or zinc octylate as a catalyst in a solution of a polymer having a polyorganosiloxane chain and a hydroxyl group, or triethylamine, tributylamine or dimethylbenzyl. A tertiary amine such as amine is added as 0.05 PHR to 1 PHR (Per Hundred Resin) catalyst, and methacryloxyethyl methacrylate is added under heating. As the solvent, ketones such as 2-butanone, methyl isobutyl ketone and cyclohexanone, esters such as ethyl acetate, propyl acetate and butyl acetate, and ether solutions such as ethylene glycol dimethyl ether and dioxolane can be used.

  2) When the reactive functional group is an epoxy group, a typical reactive functional group includes a carboxyl group. Specifically, a radical polymerizable double bond is formed by reaction with (meth) acrylic acid. Can be introduced. The reaction with (meth) acrylic acid proceeds by adding a catalyst to a polymer solution having a polyorganosiloxane chain and an epoxy group, adding (meth) acrylic acid and heating. As the reaction conditions, the same conditions as in 1) the case where the reactive functional group is a hydroxy group are recommended, but the catalyst is most preferably a tertiary amine. Examples of the compound having a carboxyl group and a radical polymerizable double bond include pentaerythritol triacrylate succinic anhydride adduct and (meth) acryloxyethyl phthalate in addition to (meth) acrylic acid.

  3) When the reactive functional group is an isocyano group, a typical reactive functional group includes a hydroxyl group. Specifically, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) Examples include acrylate, ε-caprolactone adduct of hydroxyethyl (meth) acrylate, and the like. The reaction conditions are preferably the same as those in the above 1) when the reactive functional group is a hydroxy group.

(Multifunctional (meth) acrylate)
The polyfunctional (meth) acrylate related to the method for producing an intermediate transfer belt of the present invention has two or more (meth) acryloyloxy groups in one molecule, and wear resistance and toughness of the surface layer of the intermediate transfer belt. It is used to develop the properties and adhesion. Specific examples include bis (2-acryloxyethyl) -hydroxyethyl-isocyanurate, 1,6-hexanediol diacrylate, 1,4-butanediol diacrylate, 1,9-nonanediol diacrylate, Bifunctional monomers such as neopentyl glycol diacrylate, hydroxypivalate neopentyl glycol diacrylate, urethane acrylate; trimethylolpropane triacrylate, pentaerythritol triacrylate, tris (acryloxyethyl) isocyanurate, ditrimethylolpropane tetra Acrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, urethane acrylate, polyhydric alcohol, polybasic acid, (meth) acrylic acid, etc. Synthetic esters compounds, for example a polyfunctional monomer such as trifunctional or more ester compounds synthesized from trimethylolethane / succinic acid / acrylic acid = 2/1/4 mol, and the like. In order to give the coating film a hard coat property, it is desirable to use a polyfunctional acrylate having three or more functions.

  The content of the monomer (a) having a polyorganosiloxane chain is from 0.01% by mass on the basis of the entire nonvolatile content mass of the active energy ray-curable composition relating to the method for producing an intermediate transfer belt of the present invention. It can be 10% by mass. A vinyl copolymer having a number average molecular weight of 5,000 to 100,000 having one polyorganosiloxane chain and three or more radical polymerizable double bonds, which relates to the method for producing an intermediate transfer belt of the present invention, is active. Since the energy ray curable composition is concentrated on the surface when it is applied to an endless belt-like substrate, sufficiently low surface free energy can be expressed even if the amount of the monomer (a) is small. .

(Photopolymerization initiator)
The active energy ray-curable composition relating to the method for producing an intermediate transfer belt of the present invention can also use a photopolymerization initiator. Examples of photopolymerization initiators include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ale, acetoin, butyroin, toluoin, benzyl, benzophenone, p-methoxybenzophenone, diethoxyacetophenone, methylphenylglyoxy Rate, ethylphenylglyoxylate, 4,4-bis (dimethylaminobenzophenone), 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 1- (4-isopropylphenyl) ) Carbonyl compounds such as 2-hydroxy-2-methylpropan-1-one: Sulfur compounds such as tetramethylthiuram disulfide and tetramethylthiuram disulfide: Azo Azo compounds such as sisobutyronitrile and azobis-2,4-dimethylvaleronitrile: peroxide compounds such as benzoyl peroxide and ditertiary butyl peroxide: phosphine oxide compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide I can list them. These photopolymerization initiators are from 0.1% by mass to 20% by mass, preferably from 1% by mass to 10% by mass in consideration of the polymerization initiation effect, the hardness of the surface layer, etc. in the entire active energy ray-curable composition. % Is preferably used. The photopolymerization initiator can be used not only in one type but also in combination.

(Other additives)
In the active energy ray-curable composition of the present invention, an organic solvent, a light stabilizer, an ultraviolet absorber, a catalyst, a colorant, an antistatic agent, a lubricant, a leveling agent, an antifoaming agent, and a polymerization accelerator are optionally included. It is possible to include additional components such as antioxidants, flame retardants, infrared absorbers, surfactants, and surface modifiers.

  The organic solvent is contained in the active energy ray-curable composition from the standpoints of uniform solubility and dispersion stability of the active energy ray-curable composition, as well as adhesion to the endless belt-like substrate and smoothness and uniformity of the coating. The organic solvent is not particularly limited as long as it satisfies the above performance. Specific examples include organic solvents such as alcohols, hydrocarbons, halogenated hydrocarbons, ethers, ketones, esters, and polyhydric alcohol derivatives.

  One or more commercially available polyorganosiloxane chains, a vinyl copolymer having a number average molecular weight of 5,000 to 100,000 having three or more radical polymerizable double bonds, a polyfunctional (meth) acrylate, Examples of the coating solution for forming a surface layer containing the active energy ray-curable composition having the above include Full Shade RS (manufactured by Toyo Ink Manufacturing Co., Ltd.).

[Reactive metal oxide fine particles]
The reactive metal oxide fine particle used in the present invention is a metal oxide fine particle surface-treated with a compound having a radical polymerizable functional group, and the metal oxide fine particle is surface treated with a compound having a radical polymerizable functional group. Can be obtained.

[Metal oxide fine particles]
The metal oxide fine particles used in the present invention may be metal oxide fine particles including transition metals, such as silica (silicon oxide), magnesium oxide, zinc oxide, lead oxide, aluminum oxide, tantalum oxide, and indium oxide. Examples include metal oxide fine particles such as bismuth oxide, yttrium oxide, cobalt oxide, copper oxide, manganese oxide, selenium oxide, iron oxide, zirconium oxide, germanium oxide, tin oxide, titanium oxide, niobium oxide, molybdenum oxide, and vanadium oxide. Of these, particles of titanium oxide, alumina, zinc oxide, tin oxide and the like are preferable, and alumina and tin oxide are particularly preferable.

  As these metal oxide fine particles, those produced by a general production method such as a gas phase method, a chlorine method, a sulfuric acid method, a plasma method, or an electrolytic method are used.

  The number average primary particle size of the metal oxide fine particles is preferably in the range of 1 nm to 300 nm. Particularly preferred is 3 nm to 100 nm. When the particle size is small, the wear resistance is not sufficient, and when the particle size is large, the writing light may be scattered, or the particles may hinder photocuring and the wear resistance may be insufficient.

  The number average primary particle size of the metal oxide fine particles is a photographic image (excluding aggregated particles) obtained by taking an enlarged photograph of 10,000 times with a scanning electron microscope (manufactured by JEOL Ltd.) and randomly capturing 300 particles with a scanner. ) Automatic image processing analyzer LUZEX AP (Nireco Corp.) software version Ver. The value which calculated the number average primary particle size using 1.32 is shown.

  A compound having a radical polymerizable functional group used for surface treatment of metal oxide fine particles will be described.

  The compound having a radical polymerizable functional group used for the surface treatment of the metal oxide fine particles includes a functional group having a carbon / carbon double bond and a polar group such as an alkoxy group coupled with a hydroxyl group on the surface of the metal oxide fine particles. Compounds having the same molecule are preferred.

  As the compound having a radical polymerizable functional group, a compound having a functional group that is polymerized (cured) by irradiation with active energy rays such as ultraviolet rays and electron beams to become a resin such as polystyrene and polyacrylate is preferable. A silane compound having a reactive acryloyl group or methacryloyl group is particularly preferred because it can be cured in a light amount or in a short time.

  The metal oxide fine particles surface-treated with the compound having a radical polymerizable functional group used in the present invention can be produced, for example, by reacting a compound represented by the following formula (2) with the metal oxide fine particles. I can do it.

(Wherein R ⁹ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aralkyl group having 1 to 10 carbon atoms, R ¹⁰ is an organic group having a reactive double bond, X is a halogen atom, an alkoxy group, an acyloxy group) A group, an aminoxy group, and a phenoxy group, and n is an integer of 1 to 3.)
Examples of the compound represented by the general formula (2) will be given below.

_{S-1 CH 2 = CHSi (} CH 3) (OCH 3) 2
_{S-2 CH 2 = CHSi (} OCH 3) 3
S-3 CH ₂ = CHSiCl _{3
S-4 CH 2 = CHCOO (} CH 2) 2 Si (CH 3) (OCH 3) 2
_{S-5 CH 2 = CHCOO (} CH 2) 2 Si (OCH 3) 3
_{S-6 CH 2 = CHCOO (} CH 2) 2 Si (OC 2 H 5) (OCH 3) 2
_{S-7 CH 2 = CHCOO (} CH 2) 3 Si (OCH 3) 3
_{S-8 CH 2 = CHCOO (} CH 2) 2 Si (CH 3) Cl 2
_{S-9 CH 2 = CHCOO (} CH 2) 2 SiCl 3
_{S-10 CH 2 = CHCOO (} CH 2) 3 Si (CH 3) Cl 2
S-11 CH ₂ = CHCOO (CH ₂ ) ₃ SiCl _{3
S-12 CH 2 = C (} CH 3) COO (CH 2) 2 Si (CH 3) (OCH 3) 2
_{S-13 CH 2 = C (} CH 3) COO (CH 2) 2 Si (OCH 3) 3
_{S-14 CH 2 = C (} CH 3) COO (CH 2) 3 Si (CH 3) (OCH 3) 2
_{S-15 CH 2 = C (} CH 3) COO (CH 2) 3 Si (OCH 3) 3
_{S-16 CH 2 = C (} CH 3) COO (CH 2) 2 Si (CH 3) Cl 2
_{S-17 CH 2 = C (} CH 3) COO (CH 2) 2 SiCl 3
_{S-18 CH 2 = C (} CH 3) COO (CH 2) 3 Si (CH 3) C l2
_{S-19 CH 2 = C (} CH 3) COO (CH 2) 3 SiCl 3
_{S-20 CH 2 = CHSi (} C 2 H 5) (OCH 3) 2
S-21 CH ₂ ═C (CH ₃ ) Si (OCH ₃ ) _{3
S-22 CH 2 = C (} CH 3) Si (OC 2 H 5) 3
_{S-23 CH 2 = CHSi (} OCH 3) 3
_{S-24 CH 2 = C (} CH 3) Si (CH 3) (OCH 3) 2
_{S-25 CH 2 = CHSi (} CH 3) Cl 2
_{S-26 CH 2 = CHCOOSi (} OCH 3) 3
_{S-27 CH 2 = CHCOOSi (} OC 2 H 5) 3
_{S-28 CH 2 = C (} CH 3) COOSi (OCH 3) 3
_{S-29 CH 2 = C (} CH 3) COOSi (OC 2 H 5) 3
_{S-30 CH 2 = C (} CH 3) COO (CH 2) 3 Si (OC 2 H 5) 3
Moreover, you may use the silane compound which has the following radical polymerizable functional group other than the compound of the said General formula (2).

  In addition, although it is a compound outside this invention, there exist the following as an epoxy-type compound used conventionally well.

  These silane compounds can be used alone or in admixture of two or more.

[Production method of reactive metal oxide fine particles]
Next, a method for producing metal oxide fine particles (reactive metal oxide fine particles) surface-treated with a compound having a radical polymerizable functional group is an example in which a silane compound represented by the general formula (2) is used. Explained. In the surface treatment, a wet media dispersion type apparatus is used by using 0.1 to 200 parts by mass of a silane compound as a surface treatment agent and 50 to 5000 parts by mass of a solvent for 100 parts by mass of metal oxide fine particles. It is preferable to process.

  In addition, the slurry containing the metal oxide fine particles and the silane compound (solid particle suspension) is wet-dispersed, whereby the aggregate of the metal oxide fine particles is crushed and at the same time the surface treatment of the metal oxide fine particles proceeds. Thereafter, the solvent is removed to form powder, so that metal oxide fine particles surface-treated with a uniform and finer silane compound can also be obtained.

  The surface treatment amount of the compound having a radical polymerizable functional group (the coating amount of the compound having a radical polymerizable functional group) is preferably from 0.1% by mass to 60% by mass with respect to the metal oxide fine particles. Especially preferably, it is 5 mass% or more and 40 mass% or less.

  The surface treatment amount of the compound having a radical polymerizable functional group is determined by heat-treating the metal oxide fine particles after the surface treatment at 550 ° C. for 3 hours, and quantitatively analyzing the ignition residue with fluorescent X-rays. It is determined in terms of molecular weight.

  The wet media dispersion type device is filled with beads as media in a container, and further agitated disk mounted perpendicular to the rotation axis is rotated at high speed to crush and disperse the aggregated particles of metal oxide fine particles. There is no problem as long as the metal oxide fine particles are sufficiently dispersed and can be surface-treated when the surface treatment is performed on the metal oxide fine particles. Various styles such as continuous type and batch type can be adopted. Specifically, a sand mill, ultra visco mill, pearl mill, glen mill, dyno mill, agitator mill, dynamic mill, etc. can be used. These dispersive devices are pulverized and dispersed by impact crushing, friction, cutting, shear stress, etc., using a grinding medium such as balls and beads. As beads used in the sand grinder mill, balls made of glass, alumina, zircon, zirconia, steel, flint stone and the like can be used, but those made of zirconia or zircon are particularly preferable. Further, as the size of the beads, those having a diameter of about 1 mm to 2 mm are usually used, but in the present invention, those having a diameter of about 0.3 mm to 1.0 mm are preferably used.

  Various materials such as stainless steel, nylon and ceramic can be used for the disk and container inner wall used in the wet media dispersion type apparatus. In the present invention, the disk and container inner wall made of ceramic such as zirconia or silicon carbide are particularly used. Is preferred.

  By the wet treatment as described above, metal oxide fine particles surface-treated with the silane compound of the general formula (2) having a radical polymerizable functional group can be obtained.

[Fluorine resin having a radical polymerizable unsaturated bond / siloxane graft resin]
A radically polymerizable unsaturated bond means an unsaturated bond between carbon atoms. The fluororesin / siloxane graft type resin having a radically polymerizable unsaturated bond part used in the present invention refers to a copolymer having a repeating unit containing at least a fluorine atom and a repeating unit having a siloxane structure. For example, an organic solvent-soluble fluororesin (D) having a radically polymerizable unsaturated bond moiety via a urethane bond (hereinafter, sometimes simply referred to as a radically polymerizable fluororesin) 2 mass% to 70 mass%, A single-end radical-polymerizable polysiloxane (E) represented by the formula (3) and / or the general formula (4), a radical-polymerizable fluororesin (D) via a urethane bond under a radical polymerization reaction condition; A graft obtained by copolymerizing 15% by mass to 94% by mass of a radically polymerizable monomer (F) (hereinafter sometimes referred to as a non-reactive radically polymerizable monomer) that does not react other than a polymerization reaction by bonding. A copolymer is mentioned.

  The molecular weight of the graft copolymer is not particularly limited, but the weight average molecular weight is preferably determined by polystyrene-equivalent GPC (gel permeation chromatography) in consideration of film-forming properties, weather resistance, crosslinking density, and the like. Is in the range of about 5,000 to 2,000,000 (more preferably about 10,000 to 1,000,000).

[Wherein R ¹¹ is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , and R ¹⁶ may be the same or different from each other, A hydrocarbon group having 1 to 10 carbon atoms, and n is an integer of 2 or more]

[Wherein R ¹⁷ is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , and R ²² may be the same or different from each other, A hydrocarbon group having 1 to 10 carbon atoms, p is an integer of 0 to 10, and q is an integer of 2 or more.
The organic solvent-soluble fluororesin (C) having a radically polymerizable unsaturated bond moiety through a urethane bond used in the present invention is, for example, an organic solvent-soluble fluororesin (A-1) having a hydroxyl group and a radical having an isocyanate group. It can be obtained by reacting with a polymerizable monomer (C-2).

  The organic solvent-soluble fluororesin (C-1) having a hydroxyl group is not particularly limited as long as it contains at least a hydroxyl group-containing monomer portion and a polyfluoroparaffin portion as its constituent components. As a unit, what contains the repeating unit represented by General formula (5) and General formula (6) is mentioned.

[Wherein R ²³ and R ²⁴ may be the same or different independently for each repeating unit, and may be a hydrogen atom, a halogen atom (for example, a fluorine atom or a chlorine atom), a carbon number of 1 to 10 Carbon substituted with one or more alkyl groups (for example, methyl group or ethyl group), aryl groups having 6 to 8 carbon atoms (for example, phenyl group), halogen atoms (for example, fluorine atom or chlorine atom) One or a plurality of alkyl groups of 1 to 10 (for example, trifluoromethyl group, 2,2,2-trifluoroethyl group, or trichloromethyl group), or halogen atoms (for example, fluorine atom or chlorine atom) A substituted aryl group having 6 to 8 carbon atoms (for example, a pentafluorophenyl group, and x is an integer of 2 or more)

[In the formula, R ²⁵ independently represents a hydrogen atom, a halogen atom (for example, a fluorine atom or a chlorine atom), an alkyl group having 1 to 10 carbon atoms (for example, a methyl group or an ethyl group), An aryl group having 6 to 8 carbon atoms (for example, a phenyl group), an alkyl group having 1 to 10 carbon atoms (for example, a trifluoromethyl group) substituted with one or more halogen atoms (for example, fluorine atoms or chlorine atoms) , 2,2,2-trifluoroethyl group, or trichloromethyl group), or an aryl group having 6 to 8 carbon atoms substituted with one or more halogen atoms (for example, fluorine atom or chlorine atom) (for example, R ²⁶ is a divalent group selected from OR ^27a group, CH ₂ OR ^27b group, and COOR ^27c group independently for each repeating unit. R ^27a , R ^27b , and R ^27c are each an alkylene group having 1 to 10 carbon atoms (for example, a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, or a hexamethylene group), 10 is a cycloalkylene group (for example, cyclohexylene group), an alkylidene group having 2 to 10 carbon atoms (for example, isopropylidene group), and a divalent group selected from 6 to 10 carbon atoms, y is an integer of 2 or more Is)
Furthermore, the organic solvent-soluble fluororesin (D-1) having a hydroxyl group can contain, for example, a repeating unit represented by the general formula (5) as a constituent component. By including the repeating unit represented by the general formula (5), the solubility in an organic solvent can be improved.

[Wherein, R ²⁸ independently represents a hydrogen atom, a halogen atom (for example, a fluorine atom or a chlorine atom), an alkyl group having 1 to 10 carbon atoms (for example, a methyl group or an ethyl group for each repeating unit) ), An aryl group having 6 to 10 carbon atoms (for example, a phenyl group), an alkyl group having 1 to 10 carbon atoms (for example, trifluoro) substituted with one or more halogen atoms (for example, fluorine atoms or chlorine atoms) A methyl group, a 2,2,2-trifluoroethyl group, or a trichloromethyl group), or an aryl group having 6 to 10 carbon atoms substituted with one or more halogen atoms (for example, fluorine atom or chlorine atom) ( For example, a pentafluorophenyl ^{group), R 29} is independently in each repeat ^unit, an ^{oR 30a} group or ^{OCOR 30b group, R 30a} and ^{R 30b} is Hydrogen atom, halogen atom (eg, fluorine atom or chlorine atom), alkyl group having 1 to 10 carbon atoms (eg, methyl group or ethyl group), aryl group having 6 to 10 carbon atoms (eg, phenyl group), carbon A cycloalkyl group having 6 to 10 carbon atoms (for example, cyclohexyl group), an alkyl group having 1 to 10 carbon atoms substituted with one or more halogen atoms (for example, fluorine atom or chlorine atom) (for example, trifluoromethyl group) , 2,2,2-trifluoroethyl group, or trichloromethyl group), or an aryl group having 6 to 10 carbon atoms substituted with one or more halogen atoms (for example, fluorine atom or chlorine atom) (for example, A zeta is an integer of 2 or more]
The organic solvent-soluble fluororesin (D-1) can be used alone or in combination of two or more.

  The radical polymerizable monomer (D-2) having an isocyanate group is not particularly limited as long as it is a monomer containing an isocyanate group and a portion having radical polymerization, but has an isocyanate group, It is preferable to use a radical polymer monomer having no other functional group (for example, a hydroxyl group or a polysiloxane chain). As a radically polymerizable monomer (D-2) which has a suitable isocyanate group, the radically polymerizable monomer represented, for example by General formula (8) and General formula (9) is mentioned.

[Wherein R ³¹ represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, such as an alkyl group having 1 to 10 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, Or a hexyl group), an aryl group having 6 to 10 carbon atoms (for example, a phenyl group), or a cycloalkyl group having 3 to 10 carbon atoms (for example, a cyclohexyl group), and R ³² is an oxygen atom or 1 carbon atom. To 10 linear or branched divalent hydrocarbon groups, such as alkylene groups having 1 to 10 carbon atoms (for example, methylene group, ethylene group, trimethylene group, or tetramethylene group), from 2 carbon atoms 10 alkylidene groups (for example, isopropylidene group), or arylene groups having 6 to 10 carbon atoms (for example, phenylene group, tolylene group, or xylylene) ), Or cycloalkylene group having a carbon number of 3 to 10 (e.g., cyclohexylene group)]

[Wherein, R ³³ represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, such as an alkyl group having 1 to 10 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, Or a hexyl group), an aryl group having 6 to 10 carbon atoms (for example, a phenyl group) or a cycloalkyl group having 3 to 10 carbon atoms (for example, a cyclohexyl group), and R ³⁴ is an oxygen atom or a group having 1 carbon atom. 10 linear or branched divalent hydrocarbon groups, for example, an alkylene group having 1 to 10 carbon atoms (for example, a methylene group, an ethylene group, a trimethylene group, or a tetramethylene group), 2 to 10 carbon atoms An alkylidene group (for example, isopropylidene group), or an arylene group having 6 to 10 carbon atoms (for example, a phenylene group, a tolylene group, or a xylylene group) , Or cycloalkylene group having a carbon number of 3 to 10 (e.g., cyclohexylene group)]
(Preparation method of surface layer forming coating solution)
Active energy having one or more polyorganosiloxane chains, a vinyl copolymer having a number average molecular weight of 5,000 to 100,000 having three or more radical polymerizable double bonds, and a polyfunctional (meth) acrylate A coating solution for forming a surface layer containing a wire curable composition can be prepared as follows.

(Method for preparing coating solution for forming surface layer without using reactive metal oxide fine particles)
Other than the monomer (a) having 1 to 80% by mass of the monomer (a) having a radical polymerizable double bond and a polyorganosiloxane chain, and having a radical polymerizable double bond and a reactive functional group Monomer (b) 10 mass% to 90 mass%, and monomer (c) having a radical polymerizable double bond other than monomer (a) and monomer (b) (0 mass%) To 1 part by volume of a vinyl polymer (A) obtained by polymerizing a monomer containing from 89% by mass to a compound containing a functional group capable of reacting with a reactive functional group and the radical polymerizable double bond ( B) can be prepared by adding 10 to 100 parts by volume of an organic solvent so that the nonvolatile content is 3% to 20% and adding a photopolymerization initiator.

(Preparation method of surface layer forming coating solution using reactive metal oxide fine particles)
Other than the monomer (a) having 1 to 80% by mass of the monomer (a) having a radical polymerizable double bond and a polyorganosiloxane chain, and having a radical polymerizable double bond and a reactive functional group Monomer (b) 10 mass% to 90 mass%, and monomer (c) having a radical polymerizable double bond other than monomer (a) and monomer (b) (0 mass%) To 100 parts by volume of a vinyl polymer (A) obtained by polymerizing a monomer containing 89% by mass of a monomer and a compound having a functional group capable of reacting with a reactive functional group and the radical polymerizable double bond ( B) can be prepared by preparing 10 to 100 parts by volume and 5 to 40 parts by volume of reactive metal oxide fine particles, and then dispersing them with a wet media dispersion type apparatus. Wet media dispersion type device is filled with beads as a medium in a container, and further agitation disk mounted perpendicular to the rotation axis is rotated at high speed to crush and disperse the aggregated particles of metal oxide fine particles. For example, various types such as a vertical type, a horizontal type, a continuous type, and a batch type can be adopted. Specifically, a sand mill, ultra visco mill, pearl mill, glen mill, dyno mill, agitator mill, dynamic mill, etc. can be used. These dispersive devices are pulverized and dispersed by impact crushing, friction, cutting, shear stress, etc., using a grinding medium such as balls and beads.

  As beads used in the sand grinder mill, balls made of glass, alumina, zircon, zirconia, steel, flint stone and the like can be used, but those made of zirconia or zircon are particularly preferable. Further, as the size of the beads, those having a diameter of about 1 mm to 2 mm are usually used, but in the present invention, those having a diameter of about 0.3 mm to 1.0 mm are preferably used.

  Various materials such as stainless steel, nylon and ceramic can be used for the disk and container inner wall used in the wet media dispersion type apparatus. In the present invention, the disk and container inner wall made of ceramic such as zirconia or silicon carbide are particularly used. Is preferred.

  The end point of the dispersion is preferably a dispersion state in which the rate of change of the light transmittance at 405 nm from 1 hour before becomes 3% or less after the solution obtained by coating the dispersion with a wire bar on the PET film is naturally dried. More desirably, it is preferably 1% or less.

  A coating solution for forming a surface layer can be obtained by the dispersion treatment as described above.

(Endless belt base)
Next, as the endless belt-like substrate of the intermediate transfer belt of the present invention, for example, polycarbonate, polyphenylene sulfide (PPS), PVDF (polyvinylidene fluoride), polyimide, PEEK (polyether ether ketone), polyester, polyamide, polyphenylene sulfide. Resin materials such as polycarbonate, polyvinylidene fluoride (PVDF), polyfluoroethylene-ethylene copolymer (ETFE), and resin materials mainly composed of these. Furthermore, it is also possible to use a material obtained by blending these resin materials and elastic materials.

  Examples of the elastic material include polyurethane, chlorinated polyisoprene, NBR, chloropyrene rubber, EPDM, hydrogenated polybutadiene, butyl rubber, and silicone rubber. These may be used alone or in combination of two or more.

  Among the resin materials, polyimide resin is preferable from the viewpoint of mechanical properties. Specifically, as a polyimide resin material, a polypyromellitic acid imide resin material such as DuPont Kapton HA, a polybiphenyltetracarboxylic acid imide resin material such as Ube Industries, Upilex S, Polybenzophenone tetracarboxylic imido acid resin materials such as Upilex R from Ube Industries, Ltd., LARC-TPI (thermoplastic polyimide resin) from Mitsui Toatsu Chemical Industries, Ltd., and the like.

  A surface layer comprising a vinyl copolymer having a number average molecular weight of 5,000 to 100,000 having one or more polyorganosiloxane chains and three or more radical polymerizable double bonds, and a polyfunctional (meth) acrylate After applying the surface layer forming coating solution containing the active energy ray-curable composition, the following effects can be obtained by irradiating the active energy rays to form the surface layer.

  1. By combining a plurality of reactive sites of the vinyl copolymer and the polyfunctional (meth) acrylate, the crosslinking density is increased, and a coating film having high hardness, high crosslinking density, and high toughness can be formed. As a result, even if it is used for a long period of time, there is no decrease in the slipperiness estimated to be accompanied by the removal of the lubricant on the surface, the wear resistance is improved, and scraping and scratches can be reduced.

  2. By containing a resin having a polyorganosiloxane chain, the surface energy of the intermediate transfer belt is reduced and the friction coefficient can be reduced, so that the toner releasability is improved. As a result, the filming resistance is improved.

  3. As a result of high hardness and improved releasability of the toner, the deformation of the surface layer of the intermediate transfer belt when the toner is pushed into the intermediate transfer belt due to the high hardness is reduced, and the contact area with the toner is reduced. Since the toner releasability is improved, the adhesion force between the toner and the intermediate transfer belt can be reduced, so that the transfer rate is improved in the secondary transfer.

  Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In the examples, parts and% represent parts by mass and% by mass. The number average molecular weight of the polymer was measured by GPC (polystyrene conversion).

Example 1
An intermediate transfer belt having the substrate / surface layer structure shown in FIG. 2 was produced by the following method.

(Preparation of coating solution for surface layer formation)
By the method shown below, as shown in Table 1, a coating solution for forming a surface layer was prepared. 1-1 to 1-12.

(Synthesis of IPDI adduct)
After heating 222 parts of isophorone diisocyanate (IPDI) to 80 ° C. in a 1 L four-necked flask under air, 116 parts of 2-hydroxyethyl acrylate and 0.13 part of hydroquinone are added dropwise over 2 hours, and then 3 parts at 80 ° C. By reacting for a time, a compound (IPDI adduct molecular weight 338) having one liquid isocyanate group and one vinyl group was obtained.

(Preparation of solution No. 1-a having vinyl polymer)
1 part methacryloxy group-containing polysiloxane compound ("Silaplane FM-0721" manufactured by Chisso Corporation), 3 parts, 2-hydroxyethyl methacrylate, 14 parts, butyl methacrylate, 3 parts, methyl ethyl ketone (MEK), 100 parts, cooling tube, stirring device, temperature Charge to a four-necked flask equipped with a meter, heat up to 80 ° C. with stirring under a nitrogen stream, add 3 parts of azobisisobutyronitrile, conduct a polymerization reaction for 2 hours, and further azobisisobutyronitrile. 1 part was added and polymerization was carried out for 2 hours. Then, 41 parts of IPDI adduct and 1 part of tin octylate dissolved in 10 parts of methyl ethyl ketone (MEK) were added dropwise in about 10 minutes, followed by reaction for 2 hours. Cyclohexanone was added to this solution so that the non-volatile content was 10% to obtain a solution having a vinyl polymer having a number average molecular weight of about 4,000. 1-a.

(Preparation of solution No. 1-b having vinyl polymer)
4 parts of polysiloxane compound containing one-end methacryloxy group ("Silaplane FM-0721" manufactured by Chisso Corporation), 12 parts of 2-hydroxyethyl methacrylate, 3 parts of butyl methacrylate, 100 parts of methyl ethyl ketone (MEK), cooling tube, stirring device, temperature Charge into a four-necked flask equipped with a meter, heat up to 80 ° C. with stirring under a nitrogen stream, add 1 part of azobisisobutyronitrile, conduct a polymerization reaction for 2 hours, and further azobisisobutyronitrile. 1 part was added and polymerization was carried out for 2 hours. Then, 51 parts of IPDI adduct and 1 part of tin octylate dissolved in 20 parts of methyl ethyl ketone (MEK) were added dropwise in about 10 minutes, followed by reaction for 2 hours after the addition. Cyclohexanone was added to this solution so that the nonvolatile content was 10% to obtain a solution having a vinyl polymer having a number average molecular weight of about 5,000. 1-b.

(Preparation of solution No. 1-c having vinyl polymer)
20 parts of polysiloxane compound containing one-end methacryloxy group (“Silaplane FM-0721” manufactured by Chisso Corporation), 70 parts of glycidyl methacrylate, 10 parts of butyl methacrylate, 200 parts of methyl isobutyl ketone (MIBK), cooling tube, stirring device, thermometer Was added to a four-necked flask equipped with a nitrogen gas stream, heated to 90 ° C. while stirring under a nitrogen stream, added with 3 parts of azobisisobutyronitrile, and subjected to a polymerization reaction for 2 hours. Further, azobisisobutyronitrile 1 Polymerization was carried out for 2 hours by adding a portion. Next, the temperature was raised to 100 ° C., the inflowing gas was changed from nitrogen to air, 0.7 part of dimethylbenzylamine was added, 35 parts of acrylic acid was added dropwise in about 10 minutes, and the reaction was carried out for 10 hours after the addition.

  Cyclohexanone was added to this solution so that the non-volatile content was 10% to obtain a solution having a vinyl polymer having a number average molecular weight of about 17,000. 1-c.

(Preparation of solution No. 1-d having vinyl polymer)
15 parts of one-terminal methacryloxy group-containing polysiloxane compound ("Silaplane FM-0721" manufactured by Chisso Corporation), 70 parts of 2-hydroxyethyl methacrylate, 15 parts of butyl methacrylate, and 200 parts of methyl ethyl ketone (MEK) were added to a condenser, a stirring device, and a temperature. Charge to a four-necked flask equipped with a meter, heat up to 80 ° C. with stirring under a nitrogen stream, add 3 parts of azobisisobutyronitrile, conduct a polymerization reaction for 2 hours, and further azobisisobutyronitrile. 1 part was added and polymerization was carried out for 2 hours. Then, 204 parts of IPDI adduct and 1 part of tin octylate dissolved in 20 parts of methyl ethyl ketone (MEK) were added dropwise in about 10 minutes, followed by reaction for 2 hours. Cyclohexanone was added to this solution so that the non-volatile content was 10% to obtain a solution having a vinyl polymer having a number average molecular weight of about 20,000. 1-d.

(Preparation of solution No. 1-e having vinyl polymer)
25 parts of methacryloxy group-containing polysiloxane compound ("Silane Plain FM-0721" manufactured by Chisso Corporation), 30 parts of methacryloyloxyethyl isocyanate, 45 parts of butyl methacrylate, 200 parts of methyl ethyl ketone (MEK), cooling tube, stirring device, temperature Charge to a four-necked flask equipped with a meter, raise the temperature to 80 ° C. with stirring under a nitrogen stream, add 1.6 parts of azobisisobutyronitrile, conduct a polymerization reaction for 2 hours, and then add azobisisobutyrate. Polymerization was performed for 2 hours by adding 0.4 part of nitrile. Next, a solution prepared by dissolving 25.2 parts of 2-hydroxyethyl methacrylate and 0.6 part of tin octylate with 20 parts of methyl ethyl ketone (MEK) was dropped in about 10 minutes and reacted for 2 hours after dropping. Cyclohexanone was added to this solution so that the nonvolatile content was 20%, and a solution having a vinyl polymer having a number average molecular weight of about 24,000 was obtained. 1-e.

(Preparation of solution No. 1-f having vinyl polymer)
50 parts of a terminal methacryloxy group-containing polysiloxane compound ("Silaplane FM-0721" manufactured by Chisso Corporation), 60 parts of methacryloyloxyethyl isocyanate, 90 parts of butyl methacrylate, and 400 parts of methyl ethyl ketone (MEK) are cooled, stirrer, thermometer Was added to a four-necked flask with stirring under a nitrogen stream, the temperature was raised to 80 ° C., and 3.2 parts of azobisisobutyronitrile was added to carry out a polymerization reaction for 2 hours. Further, azobisisobutyro 0.8 parts of nitrile was added and polymerization was performed for 2 hours. Next, 50 parts of 2-hydroxyethyl methacrylate and 1.2 parts of tin octylate dissolved in 40 parts of methyl ethyl ketone (MEK) were added dropwise in about 10 minutes, and reacted for 2 hours after the addition. Cyclohexanone was added to the solution so that the non-volatile content was 20% to obtain a solution having a vinyl polymer having a number average molecular weight of about 50,000. 1-f.

(Preparation of solution No. 1-g having vinyl polymer)
60 parts of polysiloxane compound containing one-end methacryloxy group (“Silaplane FM-0721” manufactured by Chisso Corporation), 210 parts of 2-hydroxyethyl methacrylate, 60 parts of butyl methacrylate, and 400 parts of methyl ethyl ketone (MEK) were added to a condenser, a stirring device, and a temperature. Charge into a four-necked flask equipped with a meter, heat up to 80 ° C. with stirring under a nitrogen stream, add 1 part of azobisisobutyronitrile, conduct a polymerization reaction for 2 hours, and further azobisisobutyronitrile. Two parts were added and polymerization was performed for 2 hours. Then, 816 parts of IPDI adduct and 1 part of tin octylate dissolved in 80 parts of methyl ethyl ketone (MEK) were added dropwise in about 10 minutes, followed by reaction for 2 hours after the addition. Cyclohexanone was added to this solution so that the non-volatile content was 10% to obtain a solution having a vinyl polymer having a number average molecular weight of about 80,000. 1-g.

(Preparation of solution No. 1-h having vinyl polymer)
75 parts of one-terminal methacryloxy group-containing polysiloxane compound ("Silaplane FM-0721" manufactured by Chisso Corporation), 350 parts of 2-hydroxyethyl methacrylate, 75 parts of butyl methacrylate, and 600 parts of methyl ethyl ketone (MEK) were mixed with a condenser, a stirring device, and a temperature. Charge to a four-necked flask equipped with a meter, raise the temperature to 80 ° C. with stirring under a nitrogen stream, add 15 parts of azobisisobutyronitrile, conduct a polymerization reaction for 2 hours, and further azobisisobutyronitrile. 5 parts were added and polymerization was performed for 2 hours. Then, 1020 parts of IPDI adduct and 1 part of tin octylate dissolved in 100 parts of methyl ethyl ketone (MEK) were added dropwise in about 10 minutes, followed by reaction for 2 hours after the addition. Cyclohexanone was added to this solution so that the non-volatile content was 10% to obtain a solution having a vinyl polymer having a number average molecular weight of about 100,000. 1-h.

(Preparation of solution No. 1-i having vinyl polymer)
90 parts of polysiloxane compound containing one-end methacryloxy group ("Silaplane FM-0721" manufactured by Chisso Corporation), 420 parts of 2-hydroxyethyl methacrylate, 90 parts of butyl methacrylate and 600 parts of methyl ethyl ketone (MEK) were added to a condenser, a stirring device, and a temperature. Charge to a four-necked flask equipped with a meter, raise the temperature to 80 ° C. while stirring under a nitrogen stream, add 18 parts of azobisisobutyronitrile, conduct a polymerization reaction for 2 hours, and further azobisisobutyronitrile. 6 parts were added and polymerization was carried out for 2 hours. Then, IPDI adduct 1224 parts and tin octylate 1 part dissolved in 100 parts of methyl ethyl ketone (MEK) were added dropwise in about 10 minutes, followed by reaction for 2 hours. Cyclohexanone was added to this solution so that the non-volatile content was 10% to obtain a solution having a vinyl polymer having a number average molecular weight of about 120,000. 1-i.

(Preparation of solution No. 1-j having a polysiloxane compound)
One-terminal methacryloxy group-containing polysiloxane compound ("Silaplane FM-0711" manufactured by Chisso Corporation) was dissolved in cyclohexanone to obtain a solution having a polysiloxane compound having a concentration of 20%. 1-j. The number average molecular weight of the polysiloxane compound was about 1,000.

(Preparation of solution No. 1-k having polysiloxane compound)
One end methacryloxy group-containing polysiloxane compound (“Silaplane FM-0721” manufactured by Chisso Corporation) was dissolved in cyclohexanone to obtain a solution having a polysiloxane compound having a concentration of 20%. 1-k. The number average molecular weight of the polysiloxane compound was about 5,000.

(Preparation of coating solution for surface layer formation)
Solution No. having each vinyl polymer prepared. Solution No. 1-a to 1-i and polysiloxane compound no. 1-j, 1-k and polyfunctional (meth) acrylate are mixed so as to have the mass shown in Table 1 in terms of solid content, and 4 g of Irgacure 184 (manufactured by BASF Japan Ltd.) is used as a photopolymerization initiator. A coating solution for forming a surface layer having a solid content of 40% was prepared by adding 1 g of Irgacure 374 (manufactured by BASF Japan Ltd.) and cyclohexanone. 1-1 or 1-12.

  Incidentally, it has a vinyl copolymer having a number average molecular weight of 5,000 to 100,000 having one or more polyorganosiloxane chains and three or more radical polymerizable double bonds, and a polyfunctional (meth) acrylate. A commercially available full-shade RS (manufactured by Toyo Ink Manufacturing Co., Ltd.) as the surface layer forming coating solution containing the active energy ray-curable composition was used as the surface layer forming coating solution. 1-13.

(Preparation of endless belt-like substrate)
N-methyl-2-pyrrolidone (NMP) solution of polyamic acid composed of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (BPDA) and p-phenylenediamine (PDA) (European made by Ube Industries) S (solid content: 18% by mass)) and dried oxidized carbon black (SPECIAL BLACK4 (Degussa, pH 3.0, volatile content: 14.0%)) with respect to 100 parts by mass of the polyimide resin solid content. , Added to 23 parts by mass, using a collision type disperser (GeanusPY made by Seanas), with a pressure of 200 MPa, a minimum area of 1.4 mm ² , colliding after two divisions, and again passing through the path dividing into two parts five times And mixed to obtain a polyamic acid solution containing carbon black.

  The polyamic acid solution containing carbon black is applied to the inner surface of the cylindrical mold to a thickness of 0.5 mm via a dispenser, rotated at 1500 rpm for 15 minutes to form a spread layer having a uniform thickness, and then rotated at 250 rpm. Hot air at 60 ° C. was applied for 30 minutes from the outside of the mold, and then heated at 150 ° C. for 60 minutes. Thereafter, the temperature was raised to 360 ° C. at a rate of 2 ° C./min, and further heated at 360 ° C. for 30 minutes to remove the solvent, remove dehydrated ring-closing water, and complete the imide conversion reaction. Thereafter, the temperature was returned to room temperature, and the mold was peeled from the mold to produce an endless belt-like substrate having a total thickness of 0.1 mm.

(Application)
(Application of coating solution for surface layer formation)
Using the coating apparatus shown in FIG. 3 on the surface of the prepared endless belt-like substrate, each surface layer forming coating solution No. 1 prepared by the dip coating method was used. After forming a coating film for forming a surface layer from 1-1 to 1-13 so that the dry film thickness becomes 2 μm, ultraviolet rays are used as active energy rays, and coating for forming the surface layer is performed using a curing treatment apparatus shown in FIG. The film was cured to form a surface layer, and an intermediate transfer belt was prepared. 101 to 113. When irradiating ultraviolet rays, the light source was fixed and the cylindrical substrate holding the intermediate transfer belt was rotated at a peripheral speed of 60 mm / s.

Coating conditions Coating solution supply rate: 1 l / min
Lifting speed: 4.5mm / min
Ultraviolet irradiation conditions Type of light source: High-pressure mercury lamp (H04-L41: manufactured by Eye Graphics Co., Ltd.)
Distance from irradiation port to surface of coating film for surface layer formation: 100 mm
Irradiation quantity: 1 J / cm ²
Irradiation time (time during which the substrate is rotated): 240 seconds Evaluation With respect to 101 to 113, the transfer rate, scratch resistance, abrasion resistance, and filming resistance were evaluated by the following methods as substitute characteristics of durability, and the results of evaluation according to the following evaluation rank are shown in Table 2.

Transfer rate evaluation method The intermediate transfer belt produced was remodeled so that the bizhub PRO C6500 (laser exposure, reversal development, intermediate transfer tandem color multi-function machine) manufactured by Konica Minolta Business Technologies, Inc. was remodeled, and the exposure amount was appropriate. The A4 image with a cyan printing rate of 100% was output on neutral paper at (20 ° C., 50% RH).

  A toner having a predetermined area (10 mm × 50 mm, 3 points) on the intermediate transfer belt was collected using a suction device, and the toner mass (S) before transfer was measured.

  Next, the transfer residual toner on the intermediate transfer belt is collected with a booker tape and pasted on a white sheet, and the transfer residual toner is measured using a spectrocolorimeter (Konica Minolta Sensing Co., Ltd., CM-2002). The transfer residual toner mass (T) was determined from the relationship between the pre-calibrated toner mass and the colorimetric value.

  The transfer rate (η) was determined as η = (1−T / S) × 100 (%).

Evaluation rank of transfer rate A: Transfer rate from 98% to 100%
○: Transfer rate is 95% or more and less than 98% △: Transfer rate is 90% or more and less than 95% ×: Transfer rate is less than 90% Scratch resistance evaluation method The produced intermediate transfer belt is manufactured by Konica Minolta Business Technologies, Inc. bizhub PRO C6500 (laser exposure / reverse development / intermediate transfer tandem color compound machine) was modified so that it could be evaluated, and mounted on an evaluation machine with optimized exposure, and YMCBk at (20 ° C., 50% RH). The surface state of the intermediate transfer belt was observed before and after printing 1 million sheets of A4 images with a color printing ratio of 2.5% on neutral paper, and the state of scratches generated within a range of 100 mm × 100 mm was evaluated.

Evaluation rank of scratch resistance ◎: No surface scratch after 1 million sheets printed ○: Surface scratch after 1 million sheets printed, less than 6 places △: Surface scratch after 6 million sheets printed, less than 11 places Generation x: Generation of 11 or more scratches on the surface after printing 1 million sheets Abrasion resistance evaluation method 1 million images were printed in the same manner as the scratch resistance evaluation, and the initial intermediate transfer belt thickness and 1 million The film thickness of the intermediate transfer belt after the sheet was evaluated. The film thickness of the intermediate transfer belt is measured at 10 random locations where the film thickness is uniform (the film thickness tends to be uneven at both ends, so at least 3 cm at both ends), and the average value is taken as the film thickness of the intermediate transfer belt. . The film thickness measuring device is an eddy current type film thickness measuring device EDDY560C (manufactured by HELMUT FISCHER GMBTE CO), and the difference in film thickness between the intermediate transfer belt before and after the actual shooting test is used as the film thickness depletion amount.

Evaluation rank of wear resistance ◎: Film thickness wear amount is less than 0.5 μm ○: Film thickness wear amount is from 0.5 μm to less than 1 μm △: Film thickness wear amount is from 1 μm to less than 2 μm ×: Film thickness wear amount is 2 μm or more Evaluation Method for Filming Resistance One million images were printed by the same method as the evaluation of scratch resistance, and the color difference ΔE between the initial and one million sheets was evaluated. The intermediate transfer belt was measured with a spectrocolorimeter (Konica Minolta Sensing Co., Ltd., CM-2002), and ΔE was calculated.

Evaluation rank of filming resistance ◎: ΔE is 0 or more and less than 1 ○: ΔE is 1 or more and less than 4 Δ: ΔE is 4 or more and less than 6 ×: ΔE is 6 or more

  A surface layer comprising a vinyl copolymer having a number average molecular weight of 5,000 to 100,000 having one or more polyorganosiloxane chains and three or more radical polymerizable double bonds, and a polyfunctional (meth) acrylate Sample No. 2 was prepared by applying a coating solution for forming a surface layer containing the active energy ray-curable composition and then irradiating and curing the active energy rays. It was confirmed that all of Nos. 102 to 108, 110, and 113 showed excellent performance in terms of transfer rate, scratch resistance, wear resistance, and filming resistance.

  An active energy ray having a surface layer of a vinyl copolymer having a number average molecular weight of 4,000 having one or more polyorganosiloxane chains and three or more radical polymerizable double bonds, and a polyfunctional (meth) acrylate Sample No. 1 was prepared by applying a surface layer forming coating solution containing a curable composition and then irradiating and curing with active energy rays. In No. 101, the siloxane component bleeds out on the surface, and the normal surface state was not obtained, resulting in poor transferability.

  An active energy ray having a surface layer of a vinyl copolymer having a number average molecular weight of 120,000 having one or more polyorganosiloxane chains and three or more radical polymerizable double bonds, and a polyfunctional (meth) acrylate Sample No. 1 was prepared by applying a surface layer forming coating solution containing a curable composition and then irradiating and curing with active energy rays. No. 109 had a large molecular weight, so that no hardness was obtained, resulting in poor transfer rate, abrasion resistance, and scratch resistance.

  It was prepared by applying a coating solution for forming a surface layer containing an active energy ray-curable composition having a polysiloxane compound containing one terminal methacryloxy group and a polyfunctional (meth) acrylate, and then irradiating and curing the active energy ray. Sample No. Nos. 111 and 112 were inferior in terms of transfer rate, scratch resistance, abrasion resistance and filming resistance. The effectiveness of the present invention was confirmed.

Example 2
An intermediate transfer belt having the substrate / surface layer structure shown in FIG. 2 was produced by the following method.

(Preparation of endless belt-like substrate)
The same endless belt-like substrate as the endless belt-like substrate prepared in Example 1 was prepared.

(Preparation of metal oxide fine particles)
The metal oxide fine particles shown in Table 3 were prepared and I was taken from Lee. The number average primary particle size of the metal oxide fine particles is a photographic image (excluding aggregated particles) obtained by taking an enlarged photograph of 10,000 times with a scanning electron microscope (manufactured by JEOL Ltd.) and randomly capturing 300 particles with a scanner. ) Automatic image processing analyzer LUZEX AP (Nireco Corp.) software version Ver. The value which calculated the number average primary particle size using 1.32 is shown.

(Preparation of reactive metal oxide fine particles)
The prepared metal oxide fine particles No. The compounds shown in Table 4 were prepared as compounds having a radical polymerizable functional group for treating the surface of A to E. A to H.

  The prepared compound No. having a radical polymerizable functional group The metal oxide fine particles No. prepared using A to H were prepared. The surface treatment of A to E was performed, and the reactive metal oxide fine particles No. 1 shown in Table 5 were used. 1-A to 1-Q were prepared.

(Production of reactive metal oxide particles)
Wet media dispersion using 15 parts by mass of a compound having a radical polymerizable functional group as a surface treating agent and 400 parts by mass of a solvent (a mixed solvent of toluene: isopropyl alcohol = 1: 1) with respect to 100 parts by mass of metal oxide particles. After dispersion using a mold apparatus, the solvent was removed to produce reactive metal oxide particles whose surface was treated with a compound having a radical polymerizable functional group.

  The surface treatment amount of the compound having a radical polymerizable functional group in the produced reactive metal oxide particles (the coating amount of the compound having a radical polymerizable functional group) was 12% by mass with respect to the metal oxide fine particles.

  The surface treatment amount of the compound having a radical polymerizable functional group is determined by heat-treating the metal oxide particles after the surface treatment at 550 ° C. for 3 hours, quantitatively analyzing the ignition residue with fluorescent X-ray, and calculating the molecular weight from the Si amount. The value obtained by conversion is shown.

(Preparation of coating solution for surface layer formation)
The surface layer forming coating solution No. 1 prepared in Example 1 was used. When preparing 1-2 and 1-12, reactive metal oxide fine particles No. 1 prepared as shown in Table 6 were prepared. 1-A to 1-Q were mixed, and zirconia beads having a diameter of 0.5 mm were charged with a horizontal circulation disperser (Dispermat: Eihiro Seiki) so that the filling rate would be 80%, and dispersed at 1000 rpm. A photopolymerization initiator (Irgacure 379: BASF Japan) was mixed with the dispersion liquid. The coating liquid for surface layer formation of 2-1 to 2-44 was prepared.

(Application of coating solution for surface layer formation)
Using the coating apparatus shown in FIG. 3 on the surface of the prepared endless belt-like substrate, each surface layer forming coating solution No. 1 prepared by the dip coating method was used. After forming a coating film for forming a surface layer from 2-1 to 2-44 so that the dry film thickness is 2 μm, ultraviolet rays are used as active energy rays, and coating for forming the surface layer is performed using a curing treatment apparatus shown in FIG. The film was cured to form a surface layer, and an intermediate transfer belt was prepared. 201 to 244. When irradiating ultraviolet rays, the light source was fixed and the cylindrical substrate holding the intermediate transfer belt was rotated at 60 mm / s.

Coating conditions Coating solution supply rate: 1 l / min
Lifting speed: 4.5mm / min
Ultraviolet irradiation conditions Type of light source: High-pressure mercury lamp (H04-L41: manufactured by Eye Graphics Co., Ltd.)
Distance from irradiation port to surface of coating film for surface layer formation: 100 mm
Irradiation quantity: 1 J / cm ²
Irradiation time (time during which the substrate is rotated): 240 seconds Evaluation Tables 201 to 244 show the results obtained by evaluating the transfer rate, scratch resistance, wear resistance, and filming resistance as durability substitute characteristics by the same method as in Example 1, and according to the same evaluation rank as in Example 1. 7 shows.

  The active energy ray-curable composition is prepared by including 5 to 40 parts by volume of reactive metal oxide fine particles subjected to reactive surface treatment with respect to 75 parts by volume of the active energy ray-curable composition. Sample No. 201 to 217, 219 to 221, 223 to 239, and 241 to 243 were all confirmed to be excellent in transfer rate, scratch resistance, abrasion resistance, and filming resistance.

  The active energy ray curable composition was prepared by adding 3 parts by volume of reactive metal oxide fine particles subjected to reactive surface treatment to 75 parts by volume of the active energy ray curable composition. 218 and 240 were confirmed to be somewhat inferior in transfer rate, scratch resistance, abrasion resistance, and filming resistance although there was no practical problem.

  The active energy ray curable composition was prepared by adding 50 parts by volume of reactive metal oxide fine particles subjected to reactive surface treatment to 75 parts by volume of the active energy ray curable composition. Nos. 222 and 244 have no problem in practical use because of a large filler ratio, but the coating properties are slightly poor and the film forming state is also slightly poor. Therefore, although there was no problem in practical use, it was confirmed that the transfer rate was slightly inferior.

DESCRIPTION OF SYMBOLS 1 Full-color image forming apparatus 2 Curing processing apparatus 201 Active energy ray irradiation apparatus 201b Active energy ray source 202 Holding apparatus 3 Cylindrical or cylindrical member 7 Endless belt-like intermediate transfer body formation unit 70 Intermediate transfer belt 70a Base body 70b Surface layer 9 Manufacturing Process 9a Substrate manufacturing process 9b Coating process 9b1 Immersion coating device 9b2 Coating section 9b2a Coating tank 9c Surface layer forming coating solution preparing process 9d Curing process

Claims (3)

In a method for producing an intermediate transfer belt used in an electrophotographic image forming apparatus in which at least one surface layer is provided on a substrate,
The surface layer comprises one or more polyorganosiloxane chains, a vinyl copolymer having a number average molecular weight of 5,000 to 100,000 having three or more radical polymerizable double bonds, a polyfunctional (meth) acrylate, After applying a coating solution for forming a surface layer containing an active energy ray-curable composition having an active energy ray, the active energy ray is irradiated and formed .
The active energy ray-curable composition comprises 5 parts by volume of reactive metal oxide particles surface-treated with a compound having a radical polymerizable functional group with respect to 75 parts by volume of the active energy ray-curable composition. A method for producing an intermediate transfer belt, comprising 40 parts by volume . In an intermediate transfer belt used in an electrophotographic image forming apparatus in which at least one surface layer is provided on a substrate,
The said surface layer is produced by the manufacturing method of the intermediate transfer belt of Claim 1, and the active energy ray hardening-type composition used for the manufacturing method of this intermediate transfer belt is surface-treated with the compound which has a radically polymerizable functional group. An intermediate transfer belt , wherein the reactive metal oxide particles are contained in an amount of 5 to 40 parts by volume with respect to 75 parts by volume of the active energy ray-curable composition . An image forming apparatus using the intermediate transfer belt according to claim 2 .

Images