JP2013045040A - Method for manufacturing intermediate transfer belt, intermediate transfer belt, and image forming apparatus - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an intermediate transfer belt having a surface layer with durability such as abrasion resistance and scratch resistance, and filming resistance and forming no crack when removing toner by a cleaning member after secondary transfer, and an image forming apparatus using the intermediate transfer belt.SOLUTION: In the method for manufacturing the intermediate transfer belt including at least a single surface layer on a substrate, for use in an electro-photographic image forming apparatus, the surface layer is formed by applying a surface layer-forming coating liquid that includes an activation energy ray curable monomer, a siloxane graft type copolymer having a main chain that has a monomer unit including a benzene ring, and an activation energy ray curable monomer including a benzene ring expressed by a general formula D; and irradiating the film with an activation energy ray.

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 (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).

  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).

JP 2004-191554 A JP 2010-15143 A

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.

Moreover, it turned out that the technique of patent document 2 has the following faults.
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.

  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.

  The present invention has been made in view of the above situation, and the purpose thereof is excellent in durability such as abrasion resistance and scratch resistance and filming resistance in the removal of toner by the cleaning member after the secondary transfer, and It is an object of the present invention to provide an intermediate transfer belt having a surface layer free from cracks and an image forming apparatus using the intermediate transfer belt.

In order to improve the durability of the surface layer of the intermediate transfer belt, the present inventor has examined whether the durability when used for a long time is inferior when using a siloxane graft copolymer for the surface layer, The following was found.
1. The Si concentration in the portion at a depth of 0.5% from the surface is high with respect to the total thickness of the surface layer, and hardly exists at a depth of 2% or more from the surface.
2. As a result, when the toner is removed by the blade or brush, the cleaning member is pressed against the surface of the intermediate transfer belt and the stress is concentrated, so that the surface layer is scraped, and the surface layer surface in contact with the blade or brush has a low Si concentration. It is in a state.
3. For this reason, the slipperiness of the surface layer in contact with the blade or the brush is lowered, and when the toner is removed by the cleaning member such as the blade or the brush, the contact surface with the surface layer of the blade in a state of being pressed by the cleaning member. When the toner is sandwiched between the surface layer and the surface layer moves relatively, the surface layer is scraped by the toner and scratches are generated.
4). When the Si concentration is low, the releasability of the toner on the intermediate transfer belt is deteriorated, and when the toner is removed by a blade or a brush, the toner or the external additive of the toner is pressed against the intermediate transfer belt. Filming that locally covers the intermediate transfer belt occurs.
5. When the Si concentration is low, the adhesion between the toner and the intermediate transfer belt becomes strong (the releasability is poor), and when the toner is secondarily transferred from the intermediate transfer belt to a transfer medium such as paper, The toner is not transferred to the transfer medium and remains on the intermediate transfer belt, and the transfer rate is lowered.

  For these reasons, when used for a long time, the scratch resistance by the toner is simultaneously increased, the releasability of the intermediate transfer belt is increased, the filming resistance is increased, and the adhesion between the toner and the intermediate transfer belt is reduced. In order to increase the transfer rate, it has been found that Si existing in the surface layer needs to be present not only in the surface but also in the depth direction.

As a result of investigating whether Si concentrates on the surface when using a siloxane graft copolymer resin, it was estimated that this was due to the following phenomenon.
1. Since the siloxane graft copolymer has a high hydrophobicity, it has a low affinity with a mixed resin and easily migrates to the surface.
2. Since the grafted siloxane moiety is highly hydrophobic, it tends to be oriented on the surface side.

  As a result of further investigation, the surface layer has an active energy ray-curable monomer (A) and a siloxane graft copolymer (B) having a main chain composed of a monomer unit containing a benzene ring. It has been found that Si can be present in the depth direction without concentrating on the surface.

  However, it has been found that cracks occur when an active energy ray-curable monomer is used in combination with a siloxane graft copolymer having a main chain composed of a monomer unit containing a benzene ring.

It was estimated that the following phenomenon was caused as a result of examining whether an active energy ray-curable monomer and a siloxane graft copolymer having a main chain composed of a monomer unit containing a benzene ring were used in combination. did.
1. The compatibility between the active energy ray-curable monomer and the siloxane graft copolymer having a main chain composed of a monomer unit containing a benzene ring is poor.
2. The curing shrinkage of the active energy ray-curable monomer is larger than that of the siloxane graft copolymer having a main chain composed of monomer units containing a benzene ring. For this reason, a crack occurs without being able to cope with the stress generated by continuously winding between rolls for a long time.

  Therefore, in order to prevent the occurrence of cracks, it is necessary to improve the compatibility between the active energy ray-curable monomer and the siloxane graft copolymer having a main chain composed of monomer units containing a benzene ring. As a result of further investigation, it was found that an active energy ray-curable monomer containing a benzene ring was added to an active energy ray-curable monomer and a siloxane graft copolymer having a main chain composed of monomer units containing a benzene ring. Thus, it has been found that it is effective for improving compatibility and suppressing cracks due to curing shrinkage, and as soon as the present invention has been achieved.

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

1. In the 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 at least an active energy ray-curable monomer, a siloxane graft copolymer having a main chain having a monomer unit containing a benzene ring, and an active energy ray-curable monomer containing a benzene ring represented by the general formula D A method for producing an intermediate transfer belt, comprising: forming a surface layer-forming coating solution, and irradiating with an active energy ray.

(R1 is a hydrogen atom or a methyl group, R3 is an alkylene group having 1 to 6 carbon atoms, or an ether having 1 to 3 oxygen atoms, R4 is an alkyl group having 1 to 6 carbon atoms, R5 is a hydrogen atom or methyl group, ethyl A phenyl group, and may take a cyclic structure with respect to the central carbon atom.)
2. The siloxane graft copolymer is a polymer comprising at least a polysiloxane monomer represented by the following general formula A and a monomer containing a benzene ring represented by the following general formula B, and the polysiloxane monomer represented by the general formula A The method for producing an intermediate transfer belt as described in 1 above, wherein the monomer containing 10% to 30% and the monomer containing the benzene ring represented by the general formula B is polymerized in a proportion of 65% to 85% .

(R1 represents a hydrogen atom or a methyl group, and R2 represents an alkylene group having 1 to 6 carbon atoms.)

(R1 represents a hydrogen atom or a methyl group, R3 represents an alkylene group having 1 to 6 carbon atoms, or an ether having 1 to 3 oxygen atoms, and R4 represents an alkyl group having 1 to 6 carbon atoms.)
3. The surface layer forming coating solution comprises 5 to 100 parts of the siloxane graft copolymer and 100 parts of the active energy ray-curable monomer and the active energy ray-curable monomer containing a benzene ring. 3. The method for producing an intermediate transfer belt as described in 1 or 2 above, wherein 100 to 300 parts are contained per 100 parts of the copolymer.

  4). An intermediate transfer belt manufactured by the method for manufacturing an intermediate transfer belt according to any one of 1 to 3 above.

  5). 5. An image forming apparatus using the intermediate transfer belt described in 4 above.

  Uses an intermediate transfer belt with a surface layer that is excellent in durability and filming resistance such as abrasion resistance and scratch resistance in removing toner by a cleaning member after secondary transfer, and has no cracks. The image forming apparatus can be provided.

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 the intermediate transfer belt of the present invention 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 in which a surface layer 70b is provided on an annular endless belt-like base body 70a.

  The hardness of the annular endless belt-shaped 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 annular 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 annular 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 annular endless belt-like base body 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 resistance and image quality, 0.5 μm to 5 μm is preferable.

  The thickness F of the surface layer 70b was measured with a Fisherscope (registered trademark) mms manufactured by Fischer Instruments.

  The configuration of the annular endless belt-like base body 70a 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 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.

  The intermediate transfer belt 70 shown in the figure shows a case in which the surface layer 70b is provided on the annular endless belt-like substrate 70a. However, the annular endless belt-like substrate 70a and the surface layer 70b An elastic layer, an intermediate layer, or the like may be provided between the layers.

  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 a surface layer forming coating solution on the surface of an annular endless belt-like substrate used in the coating step shown in FIG.

  The intermediate transfer belt manufacturing process 9 relating to the method of manufacturing the intermediate transfer belt of the present invention includes a base manufacturing process 9a for manufacturing an annular endless belt-shaped base as a base, and an annular endless belt-shaped base manufactured. Curing treatment for curing the surface layer forming coating film formed in the coating step 9b for coating the surface layer forming coating solution on the surface, the surface layer forming coating solution preparing step 9c, and the surface layer forming coating solution coating step. Step 9d.

  In the substrate manufacturing process 9a, the annular endless belt-shaped substrate 70a 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. Further, it can be produced by a known method described in JP-A-61-95361, JP-A-64-22514, JP-A-3-180309, or the like. In manufacturing the endless belt, an appropriate treatment such as mold release treatment or defoaming treatment can be performed. The annular endless belt-like base body 70a (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.

  Details of the surface layer forming coating solution prepared in the surface layer forming coating solution preparing step 9c 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 supply unit 9b3 for an annular endless belt-like substrate 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 an annular endless belt-like substrate holding member attached to the elevating member 9b3d. The annular 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 annular endless belt-like base body. The holding member 9b3f is attached to the elevating member 9b3d so that the annular endless belt-like base body 70a that is held is positioned substantially at the center of the coating tank 9b2a.

  As the ball screw 9b3a rotates, the elevating member 9b3d moves in the vertical direction, so that the annular endless belt-like base body 70a held by the holding member 9b3f attached to the elevating member 9b3d becomes the surface inside the coating tank 9b2a. The coating liquid is applied to the surface of the annular endless belt-like substrate 70a by being immersed in the layer forming coating liquid S and then being pulled up.

  The speed at which the annular endless belt-shaped 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 uniformity, 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 annular endless belt-like substrate 70a using the dip coating apparatus shown in FIG. 2, the active energy rays are irradiated in the curing treatment step 9d to form the surface layer. A coating film is formed by curing the 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 coating the surface layer forming coating solution S on the surface of the annular endless belt-like substrate 70a is not particularly limited, and a known coating method can be applied. I can do it. Examples thereof include an annular coating method using an annular coating tank, a spray coating method, and a coating method using an ultrasonic atomizer.

  The curing process 9d uses the curing processing apparatus 2 (see FIG. 4). A curing process is performed by irradiating the surface layer forming coating film with active energy rays in the curing process step 9d, and the surface layer 70b shown in FIG. 1 is formed. The curing apparatus 2 (see FIG. 4) will be described with reference to FIG.

  In the case where the intermediate transfer belt has an elastic layer or an intermediate layer between the annular endless belt-like substrate 70a and the surface layer 70b, the elastic layer and the intermediate layer are also formed by using the dip coating apparatus shown in this figure. Is possible.

  FIG. 4 is a schematic view showing an example of a surface 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 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 70b of the annular endless belt-like substrate 70a. The curing apparatus has an active energy ray irradiation device 201 and a holding device 202 for a cylindrical or columnar member 3 holding an annular endless belt-like substrate 70a having a coating film for forming a surface layer formed on the surface. doing. The active energy ray irradiation device 201 is disposed at a position facing the cylindrical or columnar member 3, and is held on the cylindrical or columnar member 3 held by the holding device 202 and holding the annular endless belt-like base body 70 a. The active energy ray is irradiated to the coating film for forming the surface layer. The surface layer 70b is formed by irradiating the coating film for forming the surface layer with active energy rays to perform a curing process.

  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 annular endless belt-like base body 70a).

  L indicates the distance between the irradiation port 201c and the surface layer-forming coating film surface of the annular 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 heat-dried. 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 generally specified depending on the type of the active energy ray curable resin to be used, but is preferably within a temperature range in which the solvent can be sufficiently dried and the polymerization initiator is not deteriorated. The temperature range is preferably 60 ° C to 150 ° C, more preferably 80 ° C to 120 ° C, and particularly preferably 90 ° C to 100 ° C.

  Using the apparatus shown in FIGS. 3 and 4, at least an active energy ray-curable monomer, a siloxane graft copolymer having a main chain composed of monomer units containing a benzene ring, and an active energy ray-curable type containing a benzene ring After applying the surface layer forming coating solution containing the monomer, the surface layer is formed by irradiating active energy rays, and the intermediate transfer belt having the configuration shown in FIG.

  1. Even if the surface is scraped due to contact with the cleaning member due to long-term use, the presence of Si also in the thickness direction of the intermediate transfer belt reduces the slippage of the surface, and the blade after secondary transfer Scratches due to the removal of toner due to the toner can be reduced, and cracks that occur during film formation can be prevented.

  2. Even if the surface is scraped by contact with a cleaning member due to long-term use, the presence of Si also in the thickness direction of the intermediate transfer belt reduces the surface energy of the surface layer and reduces the friction coefficient. In addition, the toner releasability is improved. As a result, the filming resistance is improved.

  3. Even if the surface is scraped due to contact with a cleaning member due to long-term use, the presence of Si also in the thickness direction of the intermediate transfer belt reduces the surface energy of the surface layer, and toner releasability. By improving, 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.

  Next, the surface layer forming coating solution according to the method for producing the intermediate transfer belt of the present invention will be described.

(Configuration of surface layer forming coating solution)
The coating solution for forming a surface layer used in the present invention comprises at least an active energy ray-curable monomer, a siloxane graft copolymer having a main chain composed of a monomer unit containing a benzene ring, and an active energy ray-curable type containing a benzene ring. The composition has a monomer. It is good also as a structure which added the metal oxide fine particle to the coating liquid for surface layer formation as needed.

  The number average molecular weight of the siloxane graft copolymer having a main chain composed of a monomer unit containing a benzene ring used in the present invention is crystallization, productivity, surface hardness, function as an intermediate transfer belt, etc. It is preferably from 000 to 100,000.

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

(Preparation method of surface layer forming coating solution)
The surface layer forming coating solution used in the present invention can be prepared as follows.

(Preparation method of surface layer forming coating solution without using metal oxide fine particles)
The coating solution for forming a surface layer used in the present invention contains 5 to 50 parts of a siloxane graft copolymer having a main chain composed of a monomer unit containing a benzene ring with respect to 100 parts of the active energy ray-curable monomer. 100 parts to 300 parts of an active energy ray-curable monomer containing a benzene ring represented by the formula (D) is added to 100 parts to 300 parts of a siloxane graft copolymer, and an organic solvent is added so that the misfire content is 3% to 10%. It can be prepared by adding a photopolymerization initiator.

(R1 is a hydrogen atom or a methyl group, R3 is an alkylene group having 1 to 6 carbon atoms, or an ether having 1 to 3 oxygen atoms, R4 is an alkyl group having 1 to 6 carbon atoms, R5 is a hydrogen atom or methyl group, ethyl A phenyl group, and may take a cyclic structure with respect to the central carbon atom.)
The active energy ray-curable monomer compound containing a specific benzene ring represented by the general formula (D) is shown below.

(Preparation method of surface layer forming coating solution using metal oxide fine particles)
The organic solvent is added so that the non-volatile content is 30% to 200 parts of the non-volatile content of 100 parts of the coating liquid for forming the surface layer without using the fine metal oxide particles so that the non-volatile content is 3% to 10%. It can be prepared by adding a photopolymerization initiator after being dispersed by 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.

  Hereinafter, the materials constituting the surface layer forming coating solution used in the present invention will be described.

(Active energy ray-curable monomer)
As the active energy ray-curable monomer used in the present invention, various monomers having a carbon / carbon double bond can be used.

  The active energy ray-curable monomer is preferably a radically polymerizable monomer that is polymerized (cured) by irradiation with active energy rays such as ultraviolet rays or electron beams to become a resin, and in particular, a styrene monomer or an acrylic monomer. , Methacrylic monomers, vinyl toluene monomers, vinyl acetate monomers, and N-vinyl pyrrolidone monomers are preferred. Among them, an acrylic monomer having an acryloyl group or a methacryloyl group is particularly preferable because it can be cured with a small amount of light or in a short time.

  In the present invention, these radical polymerizable monomers may be used alone or in combination.

Below, an example of an acrylic monomer is shown among radically polymerizable monomers. An acrylic monomer is a compound having an acryloyl group (CH ₂ ═CHCO—) or a methacryloyl group (CH ₂ ═CCH ₃ CO—). Moreover, the Ac group number (acryloyl group number) mentioned below represents the number of acryloyl groups or methacryloyl groups.

  However, in the above, R and R 'are respectively shown below.

  In addition, although it is a compound outside this invention, there exist the following as an oxetane compound known well conventionally.

  In the present invention, the acrylic monomer preferably has 2 or more functional groups, particularly preferably 4 or more. In the acrylic monomer, the ratio of the molecular weight M of the compound having an acryloyl group or methacryloyl group to the number Ac of the acryloyl group or methacryloyl group (Ac / M, number of acryloyl groups or methacryloyl groups / molecular weight) is greater than 0.005. Is preferred. When such a compound is used and Ac / M is increased by increasing the polymerization reaction rate, a release layer of a fixing belt having a high film density can be formed.

  Examples of compounds having Ac / M greater than 0.005 include No. 1 in the exemplified compounds. 1 to 19, 21, 23, 26, 28, 30, 31 to 33, 35, 37, 40 to 44.

  Furthermore, it is particularly preferable that the acrylic monomer has a reactive acryloyl group and the Ac / M is in a range satisfying a condition that is larger than 0.005 and smaller than 0.012.

  By using in this relationship range, the crosslinking density is increased, and the abrasion resistance of the release layer of the fixing belt is improved.

  In the present invention, two or more curable compounds having different functional group densities may be mixed and used.

(Siloxane graft copolymer with a main chain consisting of monomer units containing a benzene ring)
A method for synthesizing a siloxane graft copolymer having a main chain composed of monomer units containing a benzene ring used in the present invention will be described.

  A siloxane graft copolymer having a main chain composed of monomer units containing a benzene ring 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 10% by mass 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 hydroxyperoxide 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 siloxane graft copolymer is 5,000 to 100,000.

(Siloxane graft copolymer with a main chain consisting of monomer units containing a benzene ring)
A siloxane graft copolymer having a main chain composed of monomer units containing a benzene ring and having a number average molecular weight of 5,000 to 100,000 used in the present invention is 10% polysiloxane monomer represented by the following general formula (A). It can be obtained by polymerizing 30% of a monomer containing a benzene ring represented by the following general formula B at a ratio of 65% to 85%.

  In addition to the polysiloxane monomer represented by the following general formula (A) and the monomer containing the benzene ring represented by the following general formula B, an acrylic monomer represented by the following general formula (C) is added and polymerized. You can also

(R1 represents a hydrogen atom or a methyl group, and R2 represents an alkylene group having 1 to 6 carbon atoms.)

(R1 represents a hydrogen atom or a methyl group, R3 represents an alkylene group having 1 to 6 carbon atoms, or an ether having 1 to 3 oxygen atoms, and R4 represents an alkyl group having 1 to 6 carbon atoms.)

(R1 represents a hydrogen atom or a methyl group, and R4 represents an alkyl group having 1 to 6 carbon atoms.)
Next, specific polysiloxane monomers represented by the general formula (A) are shown below.

  Next, specific monomers containing a benzene ring represented by the general formula (B) are shown below.

  Next, specific acrylic monomers represented by the general formula (C) are shown below.

  A commercially available compound can also be used as the siloxane graft copolymer having a main chain composed of monomer units containing a benzene ring used in the present invention. Examples of commercially available siloxane graft copolymers include Saimak series manufactured by Toagosei Co., Ltd. For example, GS-30, GS-101, US-270, US-350, US-352, US-380, etc. are mentioned.

[Metal oxide fine particles]
The metal oxide fine particles used in the present invention may be metal oxide fine particles including transition metals, for example, silica (silicon oxide), magnesium oxide, zinc oxide, lead oxide, aluminum oxide, tantalum oxide, 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 titanium oxide and alumina 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 in consideration of wear resistance, scattering of writing light, inhibition of photocuring and the like. Particularly preferred is 3 nm to 100 nm.

  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.

  In the present invention, in addition to the metal oxide fine particles, metal oxide fine particles obtained by surface-treating the above metal oxide fine particles with various surface treatment agents can be used. Examples of the surface treatment agent include hexamethylsilazane, methyltrimethoxysilane, methyl hydrogen silicone oil, and the like.

(Photopolymerization initiator)
The surface layer forming coating solution used in 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 used in terms of the uniform solubility and dispersion stability of the active energy ray-curable composition, and also the adhesion to the endless belt-like substrate and the smoothness and uniformity of the coating, and is particularly limited as an organic solvent. It does not have to be a material that satisfies the above performance. Specific examples include organic solvents such as alcohols, hydrocarbons, halogenated hydrocarbons, ethers, ketones, esters, and polyhydric alcohol derivatives.

(Annular endless belt-shaped substrate)
Next, as an annular endless belt-like substrate for the intermediate transfer belt of the present invention, for example, polycarbonate, polyphenylene sulfide (PPS), PVDF (polyvinylidene fluoride), polyimide, PEEK (polyether ether ketone), polyester, Examples thereof include resin materials such as polyamide, polyphenylene sulfide, 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, polypyromellitic acid imide based imide resin material such as Kapton HA from DuPont Co., Ltd., polybiphenyltetracarboxylic imide based resin material such as Upilex S from Ube Industries, Ltd., 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.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.

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)
(Synthesis of siloxane graft copolymer with main chain consisting of monomer units containing benzene ring)
As shown in Table 1, a siloxane graft copolymer having a main chain composed of monomer units containing a benzene ring was synthesized by the method shown below and From 1-i to 1-to.

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

(Synthesis of Siloxane Graft Copolymer No. 1-I)
(A) 20 parts of polysiloxane monomer (exemplary monomer A2), (B) 80 parts of monomer containing benzene ring (exemplary monomer B1), and 200 parts of MIBK were equipped with a condenser, a stirrer, and a thermometer. Charge into a four-necked flask, raise the temperature to 90 ° C. while stirring under a nitrogen stream, add 3 parts of azobisisobutyronitrile, conduct a polymerization reaction for 2 hours, and then add 1 part of azobisisobutyronitrile. The reaction was terminated when the number average molecular weight reached 20000.

(Synthesis of Siloxane Graft Copolymer No. 1-B)
(A) 15 parts of polysiloxane monomer (Exemplary monomer A3), (B) 85 parts of monomer containing benzene ring (Exemplary monomer B1), 200 parts of MIBK, equipped with a condenser, a stirrer, and a thermometer Charge into a four-necked flask, raise the temperature to 90 ° C. while stirring under a nitrogen stream, add 3 parts of azobisisobutyronitrile, conduct a polymerization reaction for 2 hours, and then add 1 part of azobisisobutyronitrile. The reaction was terminated when the number average molecular weight reached 30,000.

(Synthesis of Siloxane Graft Copolymer No. 1-C)
(A) 25 parts of a polysiloxane monomer (exemplary monomer A1), (B) 75 parts of a monomer containing a benzene ring (exemplary monomer B1), and 200 parts of MIBK were equipped with a condenser, a stirrer, and a thermometer. Charge into a four-necked flask, raise the temperature to 90 ° C. while stirring under a nitrogen stream, add 3 parts of azobisisobutyronitrile, conduct a polymerization reaction for 2 hours, and then add 1 part of azobisisobutyronitrile. The reaction was terminated when the number average molecular weight reached 50,000.

(Synthesis of Siloxane Graft Copolymer No. 1-ni)
(A) 30 parts of a polysiloxane monomer (exemplary monomer A2), (B) 70 parts of a monomer (exemplary monomer B2) containing a benzene ring, and 200 parts of MIBK, equipped with a condenser, a stirrer, and a thermometer Charge into a four-necked flask, raise the temperature to 90 ° C. while stirring under a nitrogen stream, add 3 parts of azobisisobutyronitrile, conduct a polymerization reaction for 2 hours, and then add 1 part of azobisisobutyronitrile. The reaction was terminated when the number average molecular weight reached 20000.

(Synthesis of Siloxane Graft Copolymer No. 1-E)
(A) 20 parts of polysiloxane monomer (exemplary monomer A4), (B) 80 parts of monomer containing benzene ring (exemplary monomer B1), and 200 parts of MIBK were equipped with a condenser, a stirrer, and a thermometer. Charge into a four-necked flask, raise the temperature to 90 ° C. while stirring under a nitrogen stream, add 3 parts of azobisisobutyronitrile, conduct a polymerization reaction for 2 hours, and then add 1 part of azobisisobutyronitrile. The reaction was terminated when the number average molecular weight reached 20000.

(Synthesis of Siloxane Graft Copolymer No. 1-F)
(A) 20 parts of polysiloxane monomer (exemplary monomer A2), (B) 65 parts of monomer containing benzene ring (exemplary monomer B1), (C) 15 parts of acrylic monomer (exemplary monomer C1), MIBK200 Was added to a four-necked flask equipped with a condenser, a stirrer, and a thermometer, and the temperature was raised to 90 ° C. while stirring with a nitrogen stream, and 3 parts of azobisisobutyronitrile was added and polymerized for 2 hours. The reaction was performed, and 1 part of azobisisobutyronitrile was further added. The reaction was terminated when the number average molecular weight reached 30000.

(Synthesis of Siloxane Graft Copolymer No. 1-To)
(A) 20 parts of polysiloxane monomer (exemplary monomer A1), (B) 70 parts of monomer containing benzene ring (exemplary monomer B2), (C) 10 parts of acrylic monomer (exemplary monomer C1), and MIBK200 Was added to a four-necked flask equipped with a condenser, a stirrer, and a thermometer, and the temperature was raised to 90 ° C. while stirring with a nitrogen stream, and 3 parts of azobisisobutyronitrile was added and polymerized for 2 hours. The reaction was carried out, and 1 part of azobisisobutyronitrile was further added. The reaction was terminated when the number average molecular weight reached 20000.

(Preparation of commercially available siloxane graft copolymer 1-h with a main chain consisting of monomer units containing a benzene ring)
Saimac GS-101 (manufactured by Toagosei Co., Ltd.) was prepared and designated 1-h.

  Although the siloxane graft copolymer may contain a solvent, the following “parts” and “%” relate to the non-volatile content unless otherwise indicated, and exclude the solvent (volatile content).

(Preparation of active energy ray-curable monomer)
The active energy ray-curable monomers shown in Table 2 were prepared and From a to d.

(Preparation of active energy ray-curable monomer containing benzene ring)
An active energy ray-curable monomer containing a benzene ring shown in Table 3 was prepared. D1 to D4.

(Preparation of coating solution for surface layer formation)
The prepared active energy ray-curable monomer No. Siloxane graft copolymer No. 1 having a main chain consisting of monomer units containing a benzene ring and a to d prepared. Active energy ray-curable monomer No. 1 containing 1-i to 1-chi and a benzene ring. D1 to D4 were used, and as shown in Table 4, a coating solution for forming a surface layer having a composition shown below having a solid content of 4% was prepared. 1-1 to 1-22.

(Preparation of coating solution for forming comparative surface layer)
The prepared active energy ray-curable monomer No. a, b, d and a siloxane graft copolymer No. 1 having a main chain composed of monomer units containing a prepared benzene ring. As shown in Table 4, a coating solution for forming a surface layer having a solid content of 4% as shown in Table 4 was prepared. 1-23 to 1-25.

(Preparation of Comparative Surface Layer Forming Coating Solution No. 1-23)
Except for the active energy ray-curable monomer containing a benzene ring, the surface layer forming coating solution No. A coating solution for forming a surface layer was prepared in the same manner as in 1-4, and the coating solution for forming a comparative surface layer No. 1 was prepared. 1-23.

(Preparation of comparative surface layer forming coating solution No. 1-24)
Except for the active energy ray-curable monomer containing a benzene ring, the surface layer forming coating solution No. The surface layer forming coating solution was prepared in the same manner as in 1-10, and the comparative surface layer forming coating solution No. 1-10 was prepared. 1-21.

(Preparation of Comparative Surface Layer Forming Coating Liquid No. 1-25)
Except for the active energy ray-curable monomer containing a benzene ring, the surface layer forming coating solution No. A coating solution for forming a surface layer was prepared in the same manner as in 1-19, and the coating solution for forming a comparative surface layer No. 1-25.

(Coating solution composition for surface layer formation)
Active energy ray-curable monomer 70 parts by mass Siloxane graft copolymer having a main chain composed of monomer units containing a benzene ring
10 parts by mass Active energy ray-curable monomer containing a benzene ring 20 parts by mass Irgacure 184 (manufactured by BASF Japan) 1 part by mass Irgacure 379 (manufactured by BASF Japan) 3 parts by mass Cyclohexanone 500 parts by mass MIBK 2000 parts by mass

(Preparation of intermediate transfer belt)
(Preparation of annular endless belt-shaped 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 substrate was peeled off from the mold to produce an annular endless belt-like substrate having a total thickness of 0.1 mm.

(Application)
(Application of coating solution for surface layer formation)
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 so that the dry film thickness is 2 μm using the coating apparatus shown in FIG. Using ultraviolet rays as energy rays, the coating film for forming the surface layer was cured by the curing apparatus shown in FIG. 101 to 121. 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 For 101 to 121, the presence / absence of cracks (cracks), durability substitution characteristics, transfer rate, scratch resistance, abrasion resistance, and filming resistance were evaluated by the following methods, and evaluated according to the following evaluation ranks. The results are shown in Table 5.

Crack
Both ends of the produced intermediate transfer belt were visually observed to check for cracks.

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).

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

  Applying a coating solution for forming a surface layer comprising an active energy ray-curable monomer, a siloxane graft copolymer having a main chain composed of a monomer unit containing a benzene ring, and an active energy ray-curable monomer containing a benzene ring Sample No. having the formed surface layer. Nos. 101 to 122 were free from cracks, showed excellent results in transfer rate, scratch resistance, abrasion resistance, and filming resistance, and were confirmed to be excellent in durability.

  Sample No. having a surface layer prepared by removing the active energy ray-curable monomer containing a benzene ring. From 123 to 125, occurrence of cracks was confirmed. 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 coating solution for surface layer formation)
(Synthesis of siloxane graft copolymer with main chain consisting of monomer units containing benzene ring)
A siloxane graft copolymer No. 1 having a main chain composed of monomer units containing a benzene ring shown in Table 1 of Example 1 was used. When synthesizing 1-i, the compound A2 represented by the general formula A and the compound B1 represented by the general formula B are combined with the main chain of the siloxane graft copolymer of the monomer unit containing a benzene ring as shown in Table 6. The composition was synthesized by changing the ratio (%) and changed from No2-a to 2-f.

  The number average molecular weight indicates a value measured by the same measurement method as in Example 1.

(Preparation of coating solution for surface layer formation)
The surface layer forming coating solution No. 1 prepared in Example 1 was used. When preparing 1-1, the siloxane graft copolymer no. A coating solution for forming a surface layer was prepared by the same method except that 2-a to 2-f were used. 2-A to 2-F.

(Preparation of intermediate transfer belt)
Using the prepared coating solution for forming the surface layer, an intermediate transfer belt was prepared in the same manner as in Example 1, and Sample No. 201 to 206.

Evaluation The produced sample No. About 201 to 206, the presence / absence of cracks (cracks), substitution characteristics for durability, transfer rate, scratch resistance, abrasion resistance, and filming resistance were measured by the same method as in Example 1, and the same evaluation as in Example 1 The results of evaluation according to the rank are shown in Table 7.

  It was prepared using a siloxane graft copolymer obtained by reacting 15 to 35 parts of a polysiloxane monomer represented by the general formula A and 85 to 65 parts of a monomer containing a benzene ring represented by the general formula B. Sample No. Nos. 202 to 205 exhibited excellent performances in terms of crack transfer rate, scratch resistance, abrasion resistance, and filming resistance. Sample No. 1 was prepared using a siloxane graft copolymer in which 95% of the siloxane graft copolymer main chain is contained in the monomer unit containing a benzene ring. Sample No. 201 has a transfer rate, scratch resistance, abrasion resistance, and filming resistance to some extent. The result was inferior to 202-205. Sample No. 1 prepared using a siloxane graft copolymer obtained by reacting 40 parts of a polysiloxane monomer represented by the general formula A and 60 parts of a monomer containing a benzene ring represented by the general formula B was used. No. 206 has a little filming resistance (durability). The result was inferior to 202 to 205f. The effectiveness of the present invention was confirmed.

Example 3
The surface layer forming coating solution No. 1 prepared in Example 1 was used. When preparing 1-i, the amount of the siloxane graft copolymer and the amount of the active energy ray-curable monomer containing a benzene ring are changed as shown in Table 8 with respect to 100 parts of the active energy ray-curable monomer. In all other cases, a surface layer-forming coating solution was prepared in the same manner. 3-1 to 3-12. The amount of the siloxane graft copolymer and the amount of the active energy ray-curable monomer containing a benzene ring are parts relative to 100 parts of the active energy ray-curable monomer.

(Preparation of intermediate transfer belt)
The prepared coating solution for surface layer formation No. Samples Nos. 3-1 to 3-12 were prepared in the same manner as in Example 1, and an intermediate transfer belt was prepared. 301 to 312.

Evaluation The produced sample No. For 301 to 312, the transfer rate, scratch resistance, abrasion resistance, and filming resistance were measured by the same method as in Example 1 as substitute characteristics of durability, and the results of evaluation according to the same evaluation rank as in Example 1 are shown. 9 shows.

  The surface layer forming coating solution No. 5 was prepared by changing the amount of the siloxane graft copolymer from 5 parts to 100 parts with respect to 100 parts of the active energy ray-curable monomer constituting the surface layer forming coating solution. Sample Nos. 3-2 to 3-5 and 3-8 to 3-11 were used. Nos. 302 to 305 and 308 to 311 showed excellent performances in terms of cracks, transfer rate, scratch resistance, abrasion resistance, and filming resistance. The surface layer forming coating solution No. 1 was prepared with the amount of the siloxane graft copolymer being 4 parts per 100 parts of the active energy ray curable monomer constituting the surface layer forming coating solution. Sample No. 3 produced using 3-1 was used. No. 301 has a little filming resistance. The result was inferior to 302-305. The surface layer forming coating solution No. 1 was prepared with 110 parts of the siloxane graft copolymer based on 100 parts of the active energy ray curable monomer constituting the surface layer forming coating solution. Sample No. 3 prepared using 3-6 Sample No. 306 shows transfer rate, scratch resistance, and abrasion resistance to some extent. The result was inferior to 302-305.

  The surface layer forming coating solution No. 1 was prepared with the amount of the active energy ray curable monomer containing a benzene ring being 4 parts per 100 parts of the active energy ray curable monomer constituting the surface layer forming coating solution. Sample No. 3 prepared using 3-7 Sample No. 307 has a transfer rate of a little. The result was inferior to 302-305.

  The surface layer forming coating solution No. 1 was prepared with 110 parts of the active energy ray curable monomer containing the benzene ring as to 110 parts of the active energy ray curable monomer constituting the surface layer forming coating solution. Sample No. 3 prepared using 3-12 Sample No. 312 has a transfer rate, scratch resistance, abrasion resistance, and filming resistance to some extent. The result was inferior to 302-305. The effectiveness of the present invention was confirmed.

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 (5)

In the 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 at least an active energy ray-curable monomer, a siloxane graft copolymer having a main chain having a monomer unit containing a benzene ring, and an active energy ray-curable monomer containing a benzene ring represented by the general formula D A method for producing an intermediate transfer belt, comprising: forming a surface layer-forming coating solution, and irradiating with an active energy ray.

(R1 is a hydrogen atom or a methyl group, R3 is an alkylene group having 1 to 6 carbon atoms, or an ether having 1 to 3 oxygen atoms, R4 is an alkyl group having 1 to 6 carbon atoms, R5 is a hydrogen atom or methyl group, ethyl A phenyl group, and may take a cyclic structure with respect to the central carbon atom.) The siloxane graft copolymer is a polymer comprising at least a polysiloxane monomer represented by the following general formula A and a monomer containing a benzene ring represented by the following general formula B, and the polysiloxane monomer represented by the general formula A 2. The intermediate transfer belt according to claim 1, wherein 10% to 30% and a monomer containing the benzene ring represented by the general formula B can be polymerized at a ratio of 65% to 85%. Method.

(R1 represents a hydrogen atom or a methyl group, and R2 represents an alkylene group having 1 to 6 carbon atoms.)

(R1 represents a hydrogen atom or a methyl group, R3 represents an alkylene group having 1 to 6 carbon atoms, or an ether having 1 to 3 oxygen atoms, and R4 represents an alkyl group having 1 to 6 carbon atoms.)   The surface layer forming coating solution comprises 5 to 100 parts of the siloxane graft copolymer and 100 parts of the active energy ray-curable monomer and the active energy ray-curable monomer containing a benzene ring. The method for producing an intermediate transfer belt according to claim 1, wherein 100 to 300 parts are contained per 100 parts of the copolymer.   An intermediate transfer belt manufactured by the method for manufacturing an intermediate transfer belt according to claim 1.   An image forming apparatus using the intermediate transfer belt according to claim 4.

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