JP5414308B2 - Manufacture of elastic rollers for electrophotography - Google Patents

Description

  The present invention relates to an image forming apparatus such as a printer or a copying machine, and a method for manufacturing an electrophotographic elastic roller used in an electrophotographic process cartridge.

  An image forming unit is installed inside the main body of the electrophotographic recording apparatus, and an image is formed through processes of cleaning, charging, latent image formation, development, transfer, and fixing. The image forming unit includes a photosensitive drum which is an image carrier, and further includes a cleaning unit, a charging unit, a latent image forming unit, a developing unit, and a transfer unit. The developer image on the photosensitive drum formed by the image forming unit is transferred onto a recording material by a transfer member, conveyed, and then discharged as a recording image fixed by being heated and pressed by a fixing unit.

  An example of a printer using an electrophotographic system is shown. In a one-component contact development type printer, the photosensitive drum is uniformly charged by a charging roller or a corona charger, and an electrostatic latent image is formed by a laser. Next, the developer in the developing container is applied onto the developing roller with an appropriate triboelectric charge by the developer applying roller and the developer regulating member, and development with the developer is performed at the contact portion between the photosensitive drum and the developing roller. Thereafter, the developer on the photosensitive drum is transferred onto a recording sheet by a transfer roller. Subsequently, the developer is fixed by the heat applied by the fixing roller and the pressure applied by the pressure roller, and the developer remaining on the photosensitive drum is removed by the cleaning blade, and the series of processes is completed.

  In an electrophotographic apparatus using a developing roller, the developing roller is in pressure contact with the photosensitive drum and the developer regulating member. When developing, the developer is in pressure contact with the developing roller and the photosensitive drum, and between the developing roller and the developer regulating member. The developer that is not transferred to the photosensitive drum is peeled off by the developer application roller, returned to the developing container again, stirred in the container, and conveyed again onto the developing roller by the developer application roller. As these steps are repeated, a load due to friction or the like is applied to the developer. Therefore, for the purpose of reducing the load on the developer, the developing roller has a configuration in which an elastic layer having appropriate elasticity is provided around the shaft core body. Further, since the developing roller and the charging roller always rotate in contact with other members, it is necessary to keep the contact state stable, and thus high dimensional accuracy is required as a roller. If the contact state cannot be kept stable, the amount of developer supplied may vary, the pressure distribution on the photosensitive drum may vary, and image density unevenness may occur.

  In recent years, the need for colorization and high image quality of electrophotography has increased, and there has been a strict demand for highly accurate outer dimensions and suppression of thickness unevenness for an electrophotographic elastic roller. As a method for producing an elastic roller, a coating method using an annular coating head has been conventionally known (see Patent Document 1). According to this, the restriction of the coating process due to the viscosity of the liquid material and the thickness of the liquid material layer is removed to some extent, and the liquid material is directly applied on the outer periphery of the shaft core body with a simpler device, and it is good and uniform A liquid material layer can be formed. In addition, in the coating method using the annular coating head, in order to prevent the coated liquid material from dripping in the direction of gravity and to further improve the dimensional accuracy, the space between the shaft core and the annular coating head is reduced. There is a method of inserting a detachable ring-shaped member (see Patent Document 2).

JP 2006-293015 A JP 2007-130589 A

  By the way, as one method for improving the adhesiveness of the elastic layer to the shaft core body, an adhesive layer may be provided between the shaft core body and the elastic layer. And in order to make the adhesiveness of a shaft core body and an elastic layer favorable, it is preferable to give sufficient thickness to an adhesive layer. However, when the adhesive layer is formed thick, the thickness unevenness may become a problem. That is, as described above, in the coating process using the annular coating head, when a ring-shaped member is inserted between the shaft core body and the annular coating head, the clearance between the shaft core body and the ring-shaped member is narrowed. The adhesive layer and the ring-shaped member may interfere with each other and the adhesive layer may be scraped off. Such scraping of the adhesive layer can contribute to poor appearance of the roller.

  Accordingly, an object of the present invention is to provide a method for producing an electrophotographic elastic roller that is excellent in adhesiveness between an elastic layer and a shaft core even when it is thin, and that effectively suppresses appearance defects.

An electrophotographic elastic roller manufacturing method according to the present invention includes a shaft core body, an adhesive layer formed on the outer periphery of the shaft core body, and an elastic layer formed on the outer periphery of the adhesive layer. A method for producing an electrophotographic elastic roller in which the elastic layer is bonded to the shaft core through the adhesive layer,
A step of applying an adhesive to the outer periphery of the shaft core, a step of curing the adhesive by ultraviolet irradiation to form an adhesive layer, and an annular coating head comprising the shaft core formed with the adhesive layer. the outer periphery of the center arranged so that shaft concentric, while relatively moving the annular coating head against the mandrel, the adhesive layer by ejecting liquid rubber from the annular coating head Applying liquid rubber on top;
A step of heat-curing the applied liquid rubber to form an elastic layer, and the adhesive is at least an organoalkoxysilane having an epoxy group, a photocationic polymerization initiator, and a silane coupling having a vinyl group An adhesive is contained, and the thickness of the adhesive layer is 10 nm to 100 nm.

  Even if the adhesive layer according to the present invention is thin, the adhesive layer is excellent in adhesion between the shaft core and the elastic layer. For this reason, when the liquid material is applied using the annular coating head, it is possible to prevent the adhesive layer from being scraped even if the shaft core and the ring-shaped member interfere with each other. As a result, it is possible to reduce the occurrence of defective appearance of the roller. Furthermore, an epoxy group-containing organoalkoxysilane is used as a material for the adhesive layer, and curing is performed by irradiation with ultraviolet rays, so that excessive heat is hardly generated. Therefore, phase separation during volatilization of the solvent such as thermosetting hardly occurs, and a uniform film can be obtained. As a result, unevenness in the electrical resistance value of the roller in the longitudinal direction and the circumferential direction of the roller can be suppressed, and consequently, unevenness in image density can be reduced.

It is a block diagram showing the outline of the elastic roller of this invention. It is sectional drawing showing the outline of the elastic roller of this invention. It is sectional drawing showing the outline of the ring coat machine of this embodiment. It is a schematic explanatory drawing of the optical position detector used for this invention. It is a figure showing the ring coating head of this embodiment. It is a schematic explanatory drawing of an example of how to obtain | require the cyclic | annular coating head position coordinate with respect to the reference | standard of this invention. It is a schematic explanatory drawing of the manufacturing method of the elastic roller which concerns on this invention. It is a schematic explanatory drawing of the manufacturing method of the elastic roller which concerns on this invention. It is a schematic explanatory drawing of the manufacturing method of the elastic roller which concerns on this invention. It is a schematic explanatory drawing of the manufacturing method of the elastic roller which concerns on this invention. It is a schematic explanatory drawing of the shake measuring apparatus used for the shake measurement of this invention. 1 is a configuration diagram illustrating an outline of an image forming apparatus of the present invention.

  Hereinafter, a method for producing an electrophotographic elastic roller and an electrophotographic elastic roller according to the present invention will be described in detail.

An electrophotographic elastic roller manufacturing method according to the present invention includes a shaft core, an adhesive layer formed on the outer periphery of the shaft core, and an elastic layer formed on the outer periphery of the adhesive layer. The layer is a method for producing an electrophotographic elastic roller bonded to the shaft core through an adhesive layer. This method uses an annular coating head for forming an elastic layer on the outer periphery of the shaft core body, and includes the following manufacturing steps (1) to (5).
(1) A step of applying an adhesive to the outer periphery of the shaft core body.
(2) A step of curing the adhesive by ultraviolet irradiation to form an adhesive layer.
(3) A step of mounting a ring-shaped member around the shaft core body on which the adhesive layer is formed.
(4) A step of discharging and applying liquid rubber on the outer periphery of the adhesive layer using an annular coating head.
(5) A step of heat-curing the applied liquid rubber to form an elastic layer.

  The adhesive applied to the outer periphery of the shaft core in the step (1) contains at least an organoalkoxysilane having an epoxy group, a photocationic polymerization initiator, and a silane coupling agent having a vinyl group. The thickness of the adhesive layer formed in the step (2) is 10 nm to 100 nm.

(Shaft core)
The shaft core used in the present invention functions as an electrode and a support member. The shaft core body may be plated with chromium, nickel, if necessary, on a metal or alloy of iron, aluminum, copper alloy, stainless steel. Moreover, you may comprise with materials, such as a synthetic resin. The shape is preferably a columnar shape or a cylindrical shape with a hollow center. The outer diameter of the shaft core can be determined as appropriate, but is usually in the range of 4.0 mm to 20.0 mm in diameter.

(Adhesive composition)
As described above, the adhesive used in the present invention contains at least an organoalkoxysilane having an epoxy group, a photocationic polymerization initiator, and a silane coupling agent having a vinyl group. Suitable solvents that can be used for the adhesive include, for example, alcohols such as ethanol and 2-butanol, ethyl acetate, methyl ethyl ketone, and mixtures thereof.

  An organoalkoxysilane having an epoxy group and a silane coupling agent are essential components for enhancing the adhesion between the shaft core and the elastic layer. The epoxy group contained in one molecule of the organoalkoxysilane is 1 or 2 or more and is not particularly limited. The adhesive can further contain an organoalkoxysilane having no epoxy group as the organoalkoxysilane. In this case, the content of the organoalkoxysilane having an epoxy group in the organoalkoxysilane component is preferably in the range of 1% to 50% of the entire organoalkoxysilane component.

The organoalkoxysilane having an epoxy group preferably includes an organoalkoxysilane having an epoxy group having a structure represented by the following formula (1).
Ra-Z-Si- (OR) ₃ formulas (1)
In the above formula (1), Ra is an epoxy group, Z is an alkylene group having 1 to 6 carbon atoms, and R is a lower alkyl group having 1 to 3 carbon atoms. In the structure represented by the above formula (1), it is more preferable that Z is a propyl group and R is an ethyl group. It is possible to control the flexibility of the adhesive layer by changing the length of the alkylene chain, which is an organic component.

In addition to the organoalkoxysilane having an epoxy group, it is preferable to contain an organoalkoxysilane having a structure represented by the following formula (2).
Rb-Si- (OR) ₃ formula (2)
In the above formula (2), Rb is a linear alkyl group having 1 to 21 carbon atoms, and R is a lower alkyl group having 1 to 3 carbon atoms as in the above formula (1). In the structure represented by the above formula (2), it is more preferable that Rb is a hexyl group and R is a methyl group.

  A group capable of cationic polymerization is cleaved by ultraviolet irradiation. As a result, the organoalkoxysilanes can be cross-linked. As the cationic photopolymerization initiator, it is preferable to use an onium salt of Lewis acid or Bronsted acid in which the epoxy group exhibits high reactivity.

  By curing the adhesive layer by ultraviolet irradiation in this way, it is difficult for excessive heat to be generated, so that phase separation during volatilization of the solvent such as thermosetting hardly occurs and a uniform film can be obtained.

(Adhesive viscosity)
The viscosity of the adhesive used in the present invention is preferably 0.8 mPa · s to 1.8 mPa · s. In particular, the viscosity of the adhesive is more preferably 1.0 mPa · s to 1.6 mPa · s. If the viscosity of the adhesive is less than 0.8 mPa · s, the thickness of the adhesive layer when the adhesive is applied to the outer periphery of the shaft core and cured is less than 10 nm, and the shaft core and the elastic layer are bonded. Does not have enough effect. Further, when the viscosity of the adhesive is 1.8 mPa · s or more, the thickness of the adhesive layer becomes 100 nm or more, and the coating unevenness is increased. When the coating unevenness increases, unevenness of the electrical resistance value as a roller also occurs, resulting in image density unevenness.

(Application and curing of adhesive)
As illustrated in FIGS. 1 and 2, the developing roller of the present invention includes an adhesive layer 103 made of the above-mentioned adhesive provided on the surface of the shaft core body 101 and an elastic provided around the adhesive layer. The layer 102 is included. In order to manufacture the developing roller of the present invention, first, an adhesive is applied to the surface of the shaft core body 101.
As a method of application, a general coating machine such as a roll coater or a spray coater may be used, or an adhesive may be soaked in a sponge or the like and may be applied by hand. Specifically, for example, a sponge soaked with an adhesive is pressed against a core bar rotating at 60 rpm with a load of 100 g and slid at a speed of 10 mm / sec. A layer can be obtained. Next, the adhesive applied to the shaft core 101 is cured with ultraviolet rays to form the adhesive layer 103. For irradiation with ultraviolet rays, a high pressure mercury lamp, a metal halide lamp, a low pressure mercury lamp, an excimer UV lamp, or the like can be used. Among these, an ultraviolet ray source rich in light having an ultraviolet wavelength of 150 nm to 480 nm is used. . Note that the cumulative amount of ultraviolet light is defined below.
UV integrated light quantity (mJ / cm ² ) = UV intensity (mW / cm 2) × irradiation time (sec)
The irradiation amount of ultraviolet rays may be appropriately selected according to the effects of ultraviolet ray curing and surface treatment, and the preferable accumulated ultraviolet light amount is in the range of about 100 to 100,000 mJ / cm ² .

(Hardness of adhesive layer)
The hardness of the adhesive layer formed by curing the adhesive of the present invention is preferably 4H or more and 8H or less in pencil hardness. If the pencil hardness is less than 4H, the adhesive layer may be scraped off when the adhesive layer and the ring-shaped member come into contact with each other when the elastic layer material is applied. The scraping of the adhesive layer contributes to poor appearance of the roller. On the other hand, if the hardness of the adhesive layer is 9H or more, cracks may occur in the adhesive layer. Cracks in the adhesive layer are also undesirable because they cause poor appearance of the roller and uneven image density.

(Coating unevenness of adhesive layer)
The coating unevenness of the adhesive layer formed by applying and curing the adhesive of the present invention is preferably as small as possible, and is preferably 10 nm or less in the longitudinal direction and the circumferential direction of the roller. If the coating unevenness of the adhesive layer is 10 nm or more, the electrical resistance value in the roller may be uneven, and density unevenness may also occur in the image due to this.

(Formation of elastic layer)
FIG. 3 shows a schematic explanatory diagram of a coating machine having an annular coating head that can be suitably used in the method for producing a developing roller of the present invention. In the present invention, the coating machine is hereinafter referred to as a ring coat machine.

  In this ring coat machine, a column 32 is attached substantially vertically on a gantry 31, and a precision ball screw 33 is attached substantially vertically on the gantry 31 and the column 32. Reference numeral 44 denotes a linear guide, and two linear guides 44 are attached to the column 32 in parallel with the precision ball screw 33. A linear motion guide (hereinafter referred to as LM guide) 34 connects a linear guide 44 and a precision ball screw 33, and a rotary motion is transmitted from a servo motor 35 via a pulley 36 so that the linear motion guide 34 can be moved up and down. An annular coating head fixing table 45 is attached to the column 32. An annular coating head position correction XY stage 46 is attached to the annular coating head fixing table 45, and an annular coating head 38 is attached on the annular coating head position correction XY stage 46. 4 is a view of the mechanism around the annular coating head position correcting XY stage 46 as viewed from directly above, and the back side in FIG. 4 is the LM guide side in FIG. Here, the X direction is the left-right direction in FIG. 4, and the Y direction is the front-rear direction in FIG. The annular coating head position correcting XY stage 46 is provided with a driving mechanism in both XY directions (horizontal directions) and is driven by a stepping motor. Further, as shown in FIG. 4, the annular coating head fixing table 45 has a pair of LED position detectors 48 in the XY directions for detecting the position of the shaft core and the position of the coating head. A total of 2 sets are attached. A laser may be used as a light source for optical position detection. Thus, in order to improve the accuracy of position detection of the measurement object, it is preferable that two or more sets of LED position detectors 48 are attached. The LED position detector 48 includes a pair of a light projecting unit and a light receiving unit, and detects the position of the measurement object from the difference in luminance of the received light.

  A bracket 37 is attached to the LM guide 34. A shaft core body position correction XY stage 47 is attached to the bracket 37, and a shaft core body lower holding shaft 39 that holds and fixes the shaft core body 101 on the shaft core body position correction XY stage 47 is substantially vertical. It is attached. The central axis of the shaft core upper holding shaft 40 that holds the shaft core body 101 of the roller on the opposite side is attached to the upper portion of the bracket 37, and the shaft core upper holding shaft 40 faces the shaft core lower holding shaft 39. And it arrange | positions so that it may become substantially concentric, and the shaft core body is hold | maintained. The central axes of the annular coating heads 38 are respectively supported so as to be parallel to the moving direction of the shaft core lower holding shaft 39 and the shaft core upper holding shaft 40. Further, when the shaft core lower holding shaft 39 and the shaft core upper holding shaft 40 are moved up and down, the central axis of the discharge port formed as an annular slit opened inside the annular coating head 38 and the shaft core lower shaft The center axis of the holding shaft 9 and the shaft core holding shaft 40 is adjusted to be substantially concentric.

  The liquid material supply port 41 is connected to a supply valve 43 via a pipe 42. The material supply valve 43 includes a mixing mixer, a material supply pump, a material fixed amount discharge device, and a material tank in front of the material supply valve 43, and can discharge the liquid material so that the amount per unit time is constant. The liquid material is weighed from a material tank by a material dispensing device and mixed by a mixing mixer. Thereafter, the liquid material mixed by the material supply pump is sent from the material supply valve 43 to the supply port 41 via the pipe 42.

  The liquid material fed from the supply port 41 passes through the flow path in the annular coating head 38 and is discharged from the nozzle of the annular coating head 38 (FIG. 3). In order to make the layer thickness of the liquid material constant, the discharge amount from the annular coating head nozzle and the supply amount from the material supply pump are made constant, and the shaft core body 101 held in the direction of the central axis of the shaft core body Move upward. As a result, the shaft core body 101 moves in the axial direction relative to the annular coating head 38, and a roll-shaped layer 102 made of a liquid material is formed on the outer periphery of the shaft core body 101. An elastic roller can be manufactured according to the present invention using a ring coater having the annular coating head. FIG. 5 is a sectional view of the annular coating head. A material is supplied from the material supply port 54, passes through the slit 51, and is discharged onto the inner peripheral surface of the coating head. The annular coating head is composed of an outer part 52 and an inner part 53.

  In manufacturing the elastic roller, first, the center position of the coating head is adjusted so that the holding shaft on the shaft core is at the center of the coating head. The LM guide shown in FIG. 3 is moved in the vertical direction, adjusted so that the tip of the shaft core holding shaft 40 falls within the measurement range of the LED position detector, and the position coordinates of the center of the shaft core holding shaft ( The X and Y coordinates on the horizontal plane) were read and used as the origin of the coordinates. Thereafter, in the measurement of all position coordinates, the origin of the coordinates is the center position coordinate of the holding shaft 40 on the shaft core body. Subsequently, the position of the annular coating head 38 is corrected. As a method for correcting the position of the coating head, for example, a method of obtaining and adjusting the position coordinates of the annular coating head by a contact method, or a reference pin is set on the annular coating head, and the position coordinates of the annular coating head The method of obtaining | requiring these by non-contact with an LED position detector etc. is mentioned.

  As an example, FIG. 6 shows a schematic explanatory diagram of a method for setting a reference pin on the annular coating head and obtaining the position coordinates of the annular coating head by an LED position detector. As shown in FIG. 6, a total of four pins 49 are erected on the annular coating head 38, two each for the X axis and the Y axis so as to be equidistant from the central axis of the annular coating head 38. . First, an LED position detector 48 (not shown in FIG. 6) measures the distance between the shaft core holding shaft 40 and the pin placed on the annular coating head. At that time, as shown in FIG. 6, the annular coating head position correcting XY stage 46 is driven so that the distances X1, X2, Y1, and Y2 are X1 = X2 and Y1 = Y2. By passing through this step, the center position coordinates of the annular coating head relative to the shaft core holding shaft are obtained relatively.

  FIG. 7 to FIG. 10 show schematic explanatory views of the elastic roller manufacturing method according to the present invention.

  The shaft core body 101 is gripped in the vertical axis direction by the shaft core upper holding shaft 40 and the shaft core lower holding shaft 39. At this time, a detachable ring-shaped member 301 is attached to a portion in front of the material outlet portion 56 of the coating head in the traveling direction (the direction indicated by the arrow A in FIG. 7A). As a result, the elastic layer material discharged from the elastic layer material outlet 56 at the start of coating is prevented from leaking in the direction of travel of the coating head relative to the shaft core (in the direction of arrow A). The elastic layer material can be applied to the peripheral surface with high dimensional accuracy.

  After the coating of the elastic layer material on the outer peripheral surface of the shaft core is completed, the ring-shaped member 301 is removed from the rear of the traveling direction (arrow A direction) from the material outlet portion 56 of the coating head.

  In the present invention, gripping the shaft core in the vertical axis direction means gripping the end of the shaft core so that the shaft core is in the vertical direction as shown in FIG. The LM guide descends (not shown) while the shaft core 101 is gripped in the vertical axis direction. At this time, as shown in FIG. 8B, the LED position detector 48 causes, for example, two central position coordinates (X in the horizontal plane) of the axial direction (longitudinal direction) positions 101-1 and 101-2 of the axial core body. And Y coordinate). The position in the longitudinal direction of the shaft core body for detecting the horizontal position coordinates depends on the length of the shaft core body, but usually, two points are preferably selected from both ends of the shaft core body, preferably within 80 nm, more preferably within 50 nm. The one closer to the end is preferable in terms of accuracy. Next, out of two arbitrarily selected axial core measurement points 101-1 and 101-2, the central position coordinate of 101-2 is used as a reference. Correction is performed by the shaft core position correction XY stage 47 so that the center position coordinate of the shaft core measurement point 101-1 is directly below the center of the shaft core measurement point 101-2 (FIG. 9A). Thereby, the tilting of the shaft core body can be corrected, and thereby the bias of the elastic layer when the liquid material is applied can be corrected.

  A mechanical error (X and Y directions) occurs when the apparatus is moved up and down while discharging the liquid material from the annular coating head 38 and moving the held shaft core 101 upward in the vertical direction. There is. In that case, the position of the annular coating head during discharge of the liquid material may be synchronized (X and Y directions) in accordance with the mechanical error (FIG. 9B).

Hereinafter, a mechanical error that occurs when the apparatus is moved up and down is referred to as a running error of the apparatus. At this time, the annular coating head position is moved by the annular coating head position correction XY stage. In this case, the position coordinates (X and Y) of the master are detected in advance by the LED position detector 48, and the running error of the apparatus is obtained. When the annular coating head 38 is moved in the horizontal direction in synchronization with the running error of the apparatus during coating, the running error of the apparatus can be canceled and a liquid material layer having a more uniform thickness can be provided. At this time, the axial coating body may be moved in the horizontal direction in synchronization with the running error of the apparatus while the annular coating head is fixed. Through the above steps, a cylindrical (roller-shaped) layer 102 made of a liquid material is formed on the outer periphery of the shaft core 101 (FIG. 10A). Then, the holding shaft on the shaft core body is raised, the shaft core body is removed from the ring coater (FIG. 10 (b)), and the elastic roller is manufactured by heating and curing.
The process for manufacturing such an elastic roller with a small run-out is summarized as follows.
-The process of measuring the running error of the device.
A process of detecting the center position coordinate of the shaft core body and correcting the tilting of the shaft core body.
A step of correcting the position of the annular coating head so that the position coordinates of the annular coating head coincide with the center position coordinates of the shaft core in the horizontal direction.
-And the position correction process of the annular coating head and / or the shaft core synchronized with the running error of the apparatus at the time of liquid material coating.

(Elastic layer thickness)
The thickness of the elastic layer is usually preferably in the range of 0.5 mm to 6.0 mm. More preferably, it is 2.0 mm-4.0 mm. When the thickness of the elastic layer is 0.5 mm or less, for example, in the case of a developing roller, the elasticity of the elastic layer cannot be obtained, and the stress on the developer cannot be reduced. In addition, when the thickness of the elastic layer is 6.0 mm or more, even in the vertical ring coater, dripping in the gravity direction occurs due to the weight of the liquid material, which may deteriorate the outer diameter size and the shake. As shown in FIG. 11, the run-out measurement is performed by causing the shaft core body supporting member 202 vertically mounted on the reference surface plate 201 to grip the shaft core body exposed portion of the elastic roller and using the grip portion as a fulcrum. Rotate. The change in the distance between the roller and the surface plate at this time was measured with a non-contact position detector (LS-5000 manufactured by Keyence Corporation) arranged perpendicular to the shaft core, and the maximum value of the distance between the roller and the surface plate was The difference between the minimum values is obtained as a value. The difference between the maximum value and the minimum value of the distance between the roller and the surface plate is obtained at a pitch of 1 cm in the axial direction of the elastic layer, and the maximum value among the difference values is taken as the value of deflection of the elastic layer. The deflection that can be preferably used as the elastic roller is preferably 60 μm or less, more preferably 50 μm or less, and even more preferably 30 μm or less, although it depends on the grade and durability of the apparatus. By setting the thickness to 30 μm or less, it is possible to prevent the stress applied to the other members from being biased and prevent the stress from being accelerated and causing the wear and deterioration of the portion to be accelerated. Can prevent the occurrence of density unevenness.

(Yield stress of liquid material)
The yield stress of the liquid material applied to the outer periphery of the shaft core with the annular coating head is preferably 20 Pa to 600 Pa. Yield stress (often called the yield point) is the critical stress below which a sample behaves as a solid. When the yield stress is exceeded, structural destruction of the three-dimensional network structure formed by the agglomerated filler occurs, and the sample starts to flow. Deformation continues indefinitely due to the applied stress, and even if the stress is removed, it does not return to its original shape. That is, since the mass of the material increases as the thickness of the coating film increases, the material easily flows in the direction of gravity. In order to prevent the flow from occurring, it is necessary to have a sufficient yield stress to counteract its own weight. By having a sufficient yield stress with respect to the thickness of the coating film, a molded product having a stable shape and good dimensional accuracy can be obtained. A more preferable range of the yield stress is 100 Pa or more and 400 Pa or less. When the yield stress is in the range of 20 Pa or more and 600 Pa or less, the dimensional accuracy with respect to the coating thickness can be maintained and the balance with the smoothness of the coating surface can be achieved in the best condition. When the yield stress exceeds 600 Pa, the leveling effect of the material at the time of coating is too small, causing difficulties such as generation of streaks or unevenness on the surface after coating. If the pressure is less than 20 Pa, the yield stress is too small for gravity to maintain the shape after the coating film is formed, so that the shape is deformed and the outer diameter dimensional difference with respect to the coating thickness of the elastic roll increases. The roll cannot withstand use. The dimensional accuracy that can be suitably used as an elastic roll depends on the grade and durability of the image forming apparatus. It is. If it exceeds 3%, the stress applied to the other members is biased, which may cause accelerated wear and deterioration of the portion where the stress is large, or cause image defects due to the loss of the balance of charge and developer supply.

(Liquid rubber)
The liquid material in the present invention is a polymer having fluidity for at least a certain period of time at room temperature, and is cured by heating or aging. Specific examples include liquid diene rubbers such as liquid butadiene rubber, liquid isoprene rubber, liquid nitrile rubber, liquid chloroprene rubber, and liquid ethylene-propylene rubber, liquid silicone rubber, and liquid urethane rubber. Such rubber | gum may be used independently or may be used in mixture of 2 or more types. Among these, since it is important that the elastic layer has sufficient deformation recovery force, it is preferable to use liquid silicone rubber or liquid urethane rubber as the liquid material.

  The liquid urethane rubber is obtained from an isocyanate (curing agent) and a polymer polyol (main agent). Specific examples of the isocyanate include diphenylmethane diisocyanate (MDI), tolylene diisocyanate (TDI), naphthalene diisocyanate (NDI), hexamethylene diisocyanate (HDI), and the like. These isocyanates may be used alone or in admixture of two or more. Examples of the polymer polyol include polyester polyol, polyether polyol, caprolactone ester polyol, polycarbonate ester polyol, and silicone polyol. These weight average molecular weights are usually 500 or more and 5000 or less. More specifically, polyethylene adipate (PEA), polybutylene adipate (PBA), polyhexylene adipate, a copolymer of ethylene adipate and butylene adipate, and the like can be used as the polyester polyol. Further, as the polyether polyol, polycaprolactone, polyoxytetramethylene glycol, polyoxypropylene glycol and the like can be used. These polyols may be used alone or in combination of two or more. If necessary, the liquid urethane prepolymer can be mixed with a conductive agent, a chain extender, a crosslinking agent, a catalyst, and the like.

  In particular, it is more preferable to use an addition reaction cross-linkable liquid silicone rubber because it has good processability, high dimensional accuracy stability, and excellent productivity such that no reaction by-product is generated during the curing reaction. The liquid silicone rubber is a composition containing, for example, an organopolysiloxane (A liquid) and an organohydrogenpolysiloxane (B liquid), and further containing a catalyst and other additives as appropriate.

(Conducting agent and filler)
Examples of the conductive agent that can be included in the liquid rubber include carbon powders such as acetylene black, ketjen black, PAN-based carbon black, and pitch-based carbon black. Although the amount of mixing depends on the type, the amount contained in the liquid rubber is preferably in the range of 5% by mass to 20% by mass. When the amount is less than 5% by mass, the amount is not sufficient for exhibiting electrical conductivity. When the amount is more than 20% by mass, the balance with the amount of polymer is poor, and preferable mechanical properties as a roll used in electrophotography cannot be obtained.

It is preferable to adjust the volume resistivity of the elastic layer in the range of 1.0 × 10 ³ Ω · cm to 5.0 × 10 ⁶ Ω · cm by adjusting the addition amount of the conductive agent. In addition to the conductive agent, other additives for rubber such as the following fillers and cross-linking agents can be added to the elastic layer as needed.

  Examples of the filler that can be included in the liquid rubber include the following inorganic fillers. Fumed silica, wet silica, quartz fine powder, diatomaceous earth, carbon black, zinc oxide, basic magnesium carbonate, activated calcium carbonate, magnesium silicate, aluminum silicate, titanium dioxide, talc, mica powder, aluminum sulfate, calcium sulfate , Barium sulfate, glass fiber etc. The surface of these fillers may be hydrophobized by treating with an organosilicon compound such as polydiorganosiloxane. The filling amount of the filler is preferably in the range of 5% by mass to 20% by mass contained in the liquid rubber.

  Examples of the crosslinking agent that can be contained in the liquid rubber include conventionally known sulfur, organic peroxides, hydrosilyl crosslinking agents, and the like. Further, a vulcanization accelerator may be used in combination in order to increase the vulcanization efficiency by the sulfur vulcanizing agent and peroxide.

(Curing method)
The layer of the liquid material applied to the outer periphery of the shaft core body is cured by heat treatment with infrared heating to obtain an elastic roller. The surface of the layer of liquid material has adhesiveness. For this reason, infrared heating is preferred as a heat treatment method, which is non-contact, simple in apparatus, and capable of uniformly heat-treating the liquid material layer on the outer periphery of the shaft core in the longitudinal direction. At this time, heat treatment is uniformly performed in the circumferential direction by fixing the infrared heating device and rotating the axial body provided with a cylindrical (roller-shaped) uncured material layer made of a liquid material in the circumferential direction. The heat treatment temperature on the surface of the coating solution depends on the liquid material to be used, but for example, in the case of addition reaction cross-linked liquid silicone rubber, it is preferably 100 ° C. or higher and 250 ° C. or lower at which the silicone rubber curing reaction starts.

  Here, for the purpose of stabilizing physical properties of the elastic layer obtained by curing the liquid material layer, removing reaction residues and unreacted low molecular components in the elastic layer, the elastic layer after infrared heating is further subjected to heat treatment. Secondary curing may be performed. Then, both ends of the elastic layer are pierced to make the elastic layer as long as necessary, and the starting end and the terminal end when the liquid material is formed on the shaft core, which is likely to be abnormal when forming the elastic layer, are removed in advance. It is also preferable.

(Surface layer)
A surface layer may be further provided on the outer peripheral side of the elastic layer formed as described above from the viewpoints of wear resistance, developer triboelectric chargeability and releasability. Examples of the material for forming the surface layer include various polyamides, fluororesins, hydrogenated styrene-butylene resins, urethane resins, silicone resins, polyester resins, phenol resins, imide resins, and olefin resins. These materials may be used alone or in combination of two or more. Various additives are added to these materials as necessary.

  These materials constituting the surface layer are dispersed using a conventionally known dispersion apparatus using beads such as a sand mill, a paint shaker, a dyno mill, and a ball mill. The obtained dispersion for forming the surface layer is applied to the surface of the elastic layer by a spray coating method or a dipping method. The thickness of the surface layer is preferably 5 μm to 50 μm. 5 μm or more is preferable from the viewpoint of preventing low molecular weight components from seeping out and contaminating the photosensitive drum, and 50 μm or less is preferable from the viewpoint of preventing the roller from becoming hard and thereby causing developer fusing. preferable. More preferably, it is 10 micrometers-30 micrometers.

  The elastic roller of the present invention can be used as a developing roller. An example of a general process cartridge and an electrophotographic apparatus equipped with the developing roller of the present invention is shown as a schematic diagram in FIG. This will be described below with reference to FIG.

  The image forming apparatus includes four image forming units 10a to 10d for forming yellow, cyan, magenta, and black developer images, respectively, and is provided in a tandem manner. The specifications of the photoconductor 11, the charging device 12, the beam 13 from the image exposure device (not shown), the developing device 14, the cleaning device 15, and the transfer roller 16 are basically the four image forming units 10a to 10 in the basic configuration. 10d is the same. However, the adjustment may be slightly different depending on the characteristics of each color developer. The photosensitive member 11, the charging device 12, the developing device 14, and the cleaning device 15 are integrated to form a detachable process cartridge. The process cartridge according to the present invention includes a developing cartridge type including the developing device 14.

  The developing device 14 includes a developing container 6 that contains a one-component developer 5 and a developing roller 1 that is located in an opening extending in the longitudinal direction in the developing container 6 and that is opposed to the photosensitive drum 11. The electrostatic latent image on the photosensitive drum 11 is developed and visualized. Also provided is a developer supply roller 7 for supplying the one-component developer 5 to the developing roller 1 and scraping the one-component developer 5 carried on the developing roller 1 from the developing roller 1 without being used for development. Yes. Further, a developing blade 8 that regulates the carrying amount of the one-component developer 5 on the developing roller 1 and frictionally charges is provided.

  The surface of the photosensitive drum 11 is uniformly charged to a predetermined polarity and potential by the charging device 12, and image information is irradiated as a beam 13 from the image exposure device onto the surface of the charged photosensitive drum 11, so that an electrostatic latent image is obtained. Is formed. Next, a one-component developer is supplied onto the formed electrostatic latent image from the developing device 14 using the elastic roller of the present invention as the developing roller 1, and a developer image is formed on the surface of the photosensitive drum 11. As the photosensitive drum 11 rotates, the developer image is transferred to a transfer material 25 such as paper that is supplied in synchronization with the rotation when the developer image comes to a position facing the transfer roller 16.

  In FIG. 12, four image forming units 10 a to 10 d are formed so as to overlap a predetermined color image on one transfer material 25 in series. Therefore, the transfer material 25 is synchronized with the image formation of each image forming unit, that is, the image formation is synchronized with the insertion of the transfer material 25. For this purpose, the transfer roller 17 for transporting the transfer material 25 is sandwiched between the photosensitive drum 11 and the image transfer device 16 so that the drive roller 18, the tension roller 19, and the driven roller 20 of the transfer conveyor belt 17. It is laid around. The transfer material 25 is conveyed to the transfer conveyance belt 17 in a form that is electrostatically adsorbed by the action of the adsorption roller 21. Reference numeral 22 denotes a supply roller for supplying the transfer material 25.

  The transfer material 25 on which the image has been formed is peeled off from the transfer conveyance belt 17 by the action of the peeling device 23 and sent to the fixing device 24. The developer image is fixed on the transfer material 25, and the printing is completed. On the other hand, the photosensitive drum 11 after the transfer of the developer image to the transfer material 25 is further rotated, the surface is cleaned by the cleaning device 15, and is neutralized by a neutralization device (not shown) as necessary. Thereafter, the photosensitive drum 11 is used for the next image formation. In FIG. 12, reference numerals 26 and 27 denote bias power sources for the image transfer device 16 and the suction roller 21, respectively.

  Here, the apparatus for transferring the developer images of the respective colors directly onto the tandem type transfer material has been described. However, any apparatus that uses the elastic roller of the present invention as the developing roller may be used. Examples thereof include a monochrome single-color image forming apparatus and an image forming apparatus that forms a color image by temporarily superimposing developer images of respective colors on a transfer roller or a transfer belt and collectively transfers the image onto a transfer member. In addition, an image forming apparatus in which each color developing unit is arranged on a rotor or arranged in parallel with a photosensitive drum may be used. Further, instead of the process cartridge, a photosensitive drum, a charging device, a developing device, and the like may be directly incorporated in the image forming apparatus.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, these do not limit this invention at all.

(Measurement of adhesive layer thickness)
An adhesive was applied on the outer periphery of the shaft core, and then cured by ultraviolet irradiation to form an adhesive layer. Next, preparation for measuring the thickness of the adhesive layer was performed using a thin film measuring apparatus “F20-EXR” (trade name, manufactured by FILMETRICS). First, a baseline was captured using a shaft core body to which no adhesive layer was applied. Next, the film structure to be analyzed was set, and the estimated approximate film thickness was input. The wavelength range was set to 400 nm to 1000 nm as the data range to be analyzed thereafter. After making the above preparations, the thickness of the adhesive layer is measured at a total of nine locations, three in the longitudinal direction of the shaft core at regular intervals from the end and three in the circumferential direction. The average value obtained was taken as the thickness of the adhesive layer.

(Measurement of coating unevenness of adhesive layer)
As described above, the thickness of the adhesive layer was measured at a total of nine locations. As a result, the difference between the maximum value and the minimum value obtained was determined, and this value was defined as coating unevenness of the adhesive layer.

(Measurement of adhesive viscosity)
The viscosity of the adhesive was measured based on the viscosity-measurement method of the liquid of JIS Z8803 using a Ubelode type viscometer which is a kind of capillary viscometer after adjusting the coating temperature to 25 ° C.

(Measures pencil hardness of adhesive layer)
The viscosity of the adhesive was adjusted to 1.3 mPa · s so that the thickness of the adhesive layer after curing was 30 nm. Further, a metal plate made of SUS having a thickness of 1 mm and a smooth surface was washed and dried. Thereafter, the adhesive was soaked in a sponge and applied onto a metal plate, and the adhesive was cured by ultraviolet irradiation to obtain an adhesive layer. Next, the pencil hardness of the adhesive layer was measured based on the mechanical properties of the paint film according to JIS K-5600-5-4, Part 5 Section 4 of the coating general test method.

Example 1
(Preparation of liquid material)
Liquid molecular chain terminal vinyl-blocked dimethylpolysiloxane
(Molecular weight Mw = 100,000) 80% by mass
Carbon black (Denka black powder made by Denki Kagaku Kogyo) 7% by mass
Silica (manufactured by Nippon Aerosil Co., Ltd .: trade name: AEROSIL50) 13% by mass
The above materials were mixed and defoamed for 30 minutes using a planetary mixer to obtain a liquid silicone rubber base material having a yield stress of 210 [Pa]. Furthermore, 0.02 part of an isopropyl alcohol solution of chloroplatinic acid (platinum content 3 mass%) was added to 100 parts of this base material and mixed to obtain a mixture A. Further, 1.5 parts of an organohydrogenpolysiloxane having a viscosity of 10 cps (SiH content 1 mass%) was added to 100 parts of the base material and mixed to obtain a mixture B. The mixture A and the mixture B were set in the raw material tank 1 and the raw material tank 2, respectively, and sent to a static mixer using a pressure feed pump to mix the mixture A and the mixture B at a ratio of 1: 1.

(Adhesive adjustment)
The following components were mixed in a 300 ml eggplant flask, then stirred at room temperature for 30 minutes, and then heated under reflux on an oil bath set at 120 ° C. for 20 hours to give a hydrolyzable silane compound condensate I. Got. When the mass ratio with respect to the total weight of the solution of the polysiloxane polymer assuming that all the hydrolyzable silane compounds were dehydrated and condensed was defined as the solid content, the solid content of the condensate I was 28.0% by mass.
・ Glycidoxypropyltriethoxysilane (GPTES) (hydrolyzable silane compound)
[Product name: KBE-403, manufactured by Shin-Etsu Chemical Co., Ltd.]
43.60 g (0.157 mol)
・ Hexyltrimethoxysilane (HeTMS) (hydrolyzable silane compound)
[Product name: KBM-3063, manufactured by Shin-Etsu Chemical Co., Ltd.]
41.90 g (0.203 mol)
・ Water 38.90g
・ Ethanol 68.55g
Next, a mixed solvent of 2-butanol 36.00 g / ethanol 234.00 g was added to 10.00 g of the condensate I to obtain a solid content of 1.0% by mass. The following photocationic polymerization initiator and vinyl group-containing silane coupling agent were mixed with 10.0 g of the condensate diluted to a solid content of 1.0% by mass as described above to obtain an adhesive in the present invention.
Aromatic sulfonium salt [trade name: Adekaoptomer SP-150, manufactured by Asahi Denka Kogyo Co., Ltd.] diluted to 10% by mass with methyl isobutyl ketone (MIBK) 0.1 g
・ Vinyltriethoxysilane [Product name: SILQUEST A-171 SILANE, manufactured by Momentive Performance Materials Japan LLC] 1.0 g
The viscosity of the adhesive was 1.0 mPa · s.

(Application and curing of adhesive)
The shaft core was washed with MEK (methyl ethyl ketone) and dried. Thereafter, an adhesive was soaked into the sponge, and the adhesive was applied to the shaft core body by hand coating. This was irradiated with ultraviolet light having a wavelength of 254 nm so that the integrated light amount was 9000 mJ / cm ² , and the adhesive was cured and dried by a crosslinking reaction to form an adhesive layer. A low-pressure mercury lamp manufactured by Harrison Toshiba Lighting Co., Ltd. was used for ultraviolet irradiation. Moreover, the thickness of the adhesive layer was 15 nm, the coating unevenness was 5 nm, and the pencil hardness measured by the above-mentioned method was 7H.

(Preparation for creating elastic rollers)
A vertical ring coater having an annular coating head 38 of the form shown in FIG. 3 was used. In manufacturing the elastic roller, first, the position coordinates of the center of the annular coating head were measured based on the position coordinates of the holding shaft 40 on the shaft core body. Hereinafter, in the measurement of all position coordinates, the origin of the coordinates is assumed to be the holding shaft 40 on the shaft core. First, the position coordinates (X and Y) of the holding shaft 40 on the shaft core were detected by the LED position detector 48, and the coordinates were determined as the origin. Next, the shaft core holding shaft 40 was fixed inside the annular coating head 38. Thereafter, the distance between the shaft on the shaft core and the pin placed on the annular coating head was measured by the LED position detector 48, and the position coordinates (X and Y) at the center of the annular coating head were calculated. Next, the position coordinates of the center of the annular coating head were adjusted so that X1 = X2 and Y1 = Y2 in FIG. As a result, the center position coordinate of the holding shaft 40 on the shaft core and the center position coordinate of the annular coating head 38 can be matched in the horizontal direction.

  Next, the tilt correction of the shaft core lower holding shaft 39 with respect to the shaft core upper holding shaft 40 was performed. The center position coordinate of the shaft core lower holding shaft 39 is measured by the LED position detector 48, and the center position of the shaft core lower holding shaft 39 is aligned with the center position coordinate of the shaft core upper holding shaft 40 in the horizontal direction. The coordinates were adjusted. Thereby, the tilt correction of the shaft core holding shaft and the shaft core lower holding shaft can be performed.

(Create elastic roller)
The upper end of the shaft core lower holding shaft 39 was positioned above the annular coating head through the annular coating head 38. At this time, a detachable ring-shaped member 301 is attached to a portion ahead of the material discharge port 57 of the coating head in the traveling direction (the direction indicated by arrow A in FIG. 7A). In this state, the iron shaft core having a length of 280.0 mm and an outer diameter of φ6.0 mm set on the shaft core lower holding shaft 39 is vertically gripped by lowering the shaft core upper holding shaft 40. did. Thereafter, when the shaft core gripped by the LM guide 34 is lowered, the LED position detector 48 causes two position coordinates (X and Y) at a distance of 14.0 mm and 266.0 mm from the end of the shaft core body. ) Was detected. Next, the position coordinates of the shaft core lower holding shaft 39 were adjusted so that the position coordinates of these two locations coincide in the horizontal direction. As a result, the tilt of the shaft core can be corrected. The inner diameter of the ring-shaped member 301 used is φ6.2 mm, and has a clearance of about 0.1 mm with respect to the outer diameter φ6 mm of the shaft core body. The outer diameter of the ring-shaped member 301 is φ12.0 mm, which is substantially the same as the inner diameter φ12.0 mm of the annular coating head, and the entire outer peripheral surface is in contact with the annular coating head.

  Thereafter, the shaft core holding shaft was raised in the vertical direction at a speed of 60 mm / s to move the shaft core. At that time, the annular coating head 38 was simultaneously moved in the horizontal direction by an amount equivalent to the running error of the coating apparatus determined in advance (FIG. 9A). While correcting the position of the annular coating head, the rubber material is discharged at 5.04 ml / sec from an annular slit opened inside the annular coating head, and a cylindrical shape made of a rubber material on the outer periphery of the shaft core ( A layer of rubber material was formed on the roll shape. The shaft core body was removed from the ring coater, and a roller having an uncured molded product layer (hereinafter, uncured roller) was produced.

  This uncured roller is rotated at 60 rpm around the shaft core body, and infrared light (output 1000 W) is applied to the surface of the uncured molded product layer using an infrared heating lamp “HYL25” (trade name) manufactured by Hibeck Co., Ltd. Irradiate for 4 minutes to cure. The distance between the surface of the molded product layer and the lamp at the time of infrared irradiation was 60 mm, and the temperature of the molded product layer surface was 170 ° C. After that, secondary curing is performed in an electric furnace at 170 ° C. for 1 hour for the purpose of stabilizing the physical properties of the cured rubber elastic layer and removing reaction residues and unreacted low molecular components in the rubber elastic layer. It was. Through the above steps, an elastic roller having an outer diameter of Φ12.0 mm, a layer thickness of 3.0 mm, and a length of the elastic layer in the longitudinal direction of 240.0 mm was obtained on the outer periphery of the shaft core body.

(Production roller development)
The following materials were mixed, MEK was added, and the mixture was dispersed with a sand mill for 1 hour.
Polyurethane polyol prepolymer “Takelac TE5060” (trade name, manufactured by Mitsui Takeda Chemical Co., Ltd.) 100 parts by mass.
-77 parts by mass of isocyanate “Coronate 2521” (trade name, manufactured by Nippon Polyurethane Co., Ltd.).
Carbon black “MA100” (trade name, manufactured by Mitsubishi Chemical Corporation) 24 parts by mass.

  After dispersion, MEK was further added to adjust the film thickness after coating and drying to 20 μm in the range of 20% by mass to 30% by mass to obtain a coating material for the surface layer.

  The prepared elastic roller was immersed in this paint, applied to the surface layer, and then naturally dried. Next, the coating film was cured by heat treatment at 140 ° C. for 60 minutes to obtain a developing roller on which a surface layer was formed.

(Visual inspection)
Each of the produced elastic roller and the developing roller having the elastic roller coated with the surface layer coating as described above was visually inspected and evaluated according to the following criteria. The results are shown in Table 3.
A: Adhesive adhesion is not recognized on both the elastic roller and the developing roller.
B: Adhesion of a minute adhesive is recognized on the elastic roller, but the influence is not recognized on the developing roller.
C: Remarkable adhesion of the adhesive is recognized on the elastic roller, and the influence is recognized on the developing roller.

(Image evaluation)
The created developing roller 1 was left to stand for 24 hours in an environment of a temperature of 23 ° C. and a humidity of 50%, and then subjected to aging. Thereafter, it was incorporated into an electrophotographic process cartridge used in the following electrophotographic image forming apparatus as a developing roller.
Image forming apparatus “HP Color LaserJet 3800 (trade name)” (manufactured by Hewlett-Packard Company).
Electrophotographic process cartridge: nominal life of 6000 sheets, A4 size, 5% printing rate, print cartridge: cyan.

Next, the electrophotographic process cartridge was incorporated in the image forming apparatus, and a durability test was performed in a continuous mode (21 sheets per minute output) under an environment of a temperature of 23 ° C. and a humidity of 50%. When the paper was passed, 3000 character images with a printing rate of 5% were continuously output. Thereafter, a solid image, a halftone image having an image density of 0.6 (measured using a Macbeth reflection densitometer RD918), and a character image are output one by one, and density unevenness (roller pitch) is visually observed. Evaluated by criteria. The results are shown in Table 3.
A: Good in all images.
B: Some density unevenness is confirmed in the halftone image, but there is no practical problem.
C: Although density unevenness is slightly confirmed in the solid image and the halftone image, there is no practical problem.
D: Remarkable density unevenness is confirmed in the solid image and the halftone image.

(Example 2)
The liquid material was adjusted in the same manner as in Example 1.

The adjustment of the adhesive was carried out by adding a mixed solvent of 4.50 g of 2-butanol / 29.00 g of ethanol to 10.00 g of the condensate I as in Example 1 so that the solid content was 6.5% by mass. The following photocationic polymerization initiator and vinyl group-containing silane coupling agent were mixed with 10.0 g of the condensate diluted to a solid content of 6.5% by mass as described above to obtain an adhesive.
Aromatic sulfonium salt [trade name: Adekaoptomer SP-150, manufactured by Asahi Denka Kogyo Co., Ltd.] diluted to 10% by mass with methyl isobutyl ketone (MIBK) 0.1 g
・ Vinyltriethoxysilane [Product name: SILQUEST A-171 SILANE, manufactured by Momentive Performance Materials Japan LLC] 1.0 g
The viscosity of the adhesive was 1.55 mPa · s.

  Next, as in Example 1, an adhesive was applied to the shaft core body and cured. The thickness of the adhesive layer was 57.5 nm, the coating unevenness was 10 nm, and the pencil hardness measured by the method described above was 5H. Thereafter, an elastic roller and a developing roller were prepared in the same manner as in Example 1, and appearance evaluation and image evaluation were performed. The results are shown in Table 3.

(Example 3)
The liquid material was adjusted in the same manner as in Example 1.

The following components were mixed in a 300 ml eggplant flask, then stirred at room temperature for 30 minutes, and then heated under reflux on an oil bath set at 120 ° C. for 20 hours to give a hydrolyzable silane compound condensate I. Got. The solid content of this condensate I (mass ratio with respect to the total weight of the polysiloxane polymer solution when it is assumed that all hydrolyzable silane compounds are dehydrated and condensed) is 28.0% by mass.
・ Glycidoxyhexyltriethoxysilane (GHeTES) (hydrolyzable silane compound)
50.11 g (0.157 mol)
・ Hexyltrimethoxysilane (HeTMS) (hydrolyzable silane compound)
[Product name: KBM-3063, manufactured by Shin-Etsu Chemical Co., Ltd.]
41.90 g (0.203 mol)
・ Water 38.90g
・ Ethanol 85.46g
Next, a mixed solvent of 18.00 g of 2-butanol / 112.00 g of ethanol was added to 10.00 g of the condensate I to obtain a solid content of 2.0% by mass.

  The same photocationic polymerization initiator and vinyl group-containing silane coupling agent as those in Example 1 were mixed with 10.0 g of the condensate diluted to a solid content of 2.0% by mass as described above to prepare an adhesive. The viscosity of the adhesive was 1.1 mPa · s. Next, as in Example 1, an adhesive was applied to the shaft core body and cured. The thickness of the adhesive layer was 19 nm, the coating unevenness was 5.5 nm, and the pencil hardness measured by the method described above was 6H. Thereafter, an elastic roller and a developing roller were prepared in the same manner as in Example 1, and appearance evaluation and image evaluation were performed. The results are shown in Table 3.

Example 4
The liquid material was adjusted in the same manner as in Example 1.

The following components were mixed in a 300 ml eggplant flask, then stirred at room temperature for 30 minutes, and then heated under reflux on an oil bath set at 120 ° C. for 20 hours to give a hydrolyzable silane compound condensate I. Got. The solid content of this condensate I (mass ratio with respect to the total weight of the polysiloxane polymer solution when it is assumed that all hydrolyzable silane compounds are dehydrated and condensed) is 28.0% by mass.
・ Glycidoxypropyltriethoxysilane (GPTES) (hydrolyzable silane compound)
[Product name: KBE-403, manufactured by Shin-Etsu Chemical Co., Ltd.]
43.60 g (0.157 mol)
・ Henicosyltrimethoxysilane (HenTMS) (hydrolyzable silane compound)
84.61 g (0.203 mol)
・ Water 25.93g
・ Ethanol 72.54g
Next, a mixed solvent of 18.00 g of 2-butanol / 112.00 g of ethanol was added to 10.00 g of the condensate I to obtain a solid content of 2.0% by mass. The same photocationic polymerization initiator and vinyl group-containing silane coupling agent as those in Example 1 were mixed with 10.0 g of the condensate diluted to a solid content of 2.0% by mass as described above to prepare an adhesive. The viscosity of the adhesive was 1.05 mPa · s. Next, as in Example 1, an adhesive was applied to the shaft core body and cured. The thickness of the adhesive layer was 17 nm, the coating unevenness was 6 nm, and the pencil hardness measured by the above method was 5H. Thereafter, an elastic roller and a developing roller were prepared in the same manner as in Example 1, and appearance evaluation and image evaluation were performed. The results are shown in Table 3.

(Example 5)
The liquid material was adjusted in the same manner as in Example 1.

The following components were mixed in a 300 ml eggplant flask, then stirred at room temperature for 30 minutes, and then heated under reflux on an oil bath set at 120 ° C. for 20 hours to give a hydrolyzable silane compound condensate I. Got. The solid content of this condensate I (mass ratio with respect to the total weight of the polysiloxane polymer solution when it is assumed that all hydrolyzable silane compounds are dehydrated and condensed) is 28.0% by mass.
・ Glycidoxyheptyltriethoxysilane (GHepTES) (hydrolyzable silane compound)
52.30 g (0.157 mol)
・ Hexyltrimethoxysilane (HeTMS) (hydrolyzable silane compound)
[Product name: KBM-3063, manufactured by Shin-Etsu Chemical Co., Ltd.]
41.90 g (0.203 mol)
・ Water 38.90g
・ 91.10g of ethanol
Next, a mixed solvent of 11.00 g of 2-butanol / 72.00 g of ethanol was added to 10.00 g of the condensate I to obtain a solid content of 3.0% by mass. The same photocationic polymerization initiator and vinyl group-containing silane coupling agent as those in Example 1 described below were mixed with 10.0 g of the condensate diluted to a solid content of 3.0% by mass as described above to prepare an adhesive. The viscosity of the adhesive was 1.2 mPa · s. Next, as in Example 1, an adhesive was applied to the shaft core body and cured. The thickness of the adhesive layer was 24 nm, the coating unevenness was 8 nm, and the pencil hardness measured by the above method was 4H. Thereafter, an elastic roller and a developing roller were prepared in the same manner as in Example 1, and appearance evaluation and image evaluation were performed. The results are shown in Table 3.

(Example 6)
The liquid material was adjusted in the same manner as in Example 1.

The adjustment of the adhesive was carried out by adding a mixed solvent of 4.0 g of 2-butanol / 26.00 g of ethanol to 10.00 g of the condensate I as in Example 1 to obtain a solid content of 7.0% by mass. The following photocationic polymerization initiator and vinyl group-containing silane coupling agent were mixed with 10.0 g of the condensate diluted to 7.0% by mass as described above to obtain an adhesive.
Aromatic sulfonium salt [trade name: Adekaoptomer SP-150, manufactured by Asahi Denka Kogyo Co., Ltd.] diluted to 10% by mass with methyl isobutyl ketone (MIBK) 0.1 g
・ Vinyltriethoxysilane [Product name: SILQUEST A-171 SILANE, manufactured by Momentive Performance Materials Japan LLC] 1.0 g
The viscosity of the adhesive was 1.6 mPa · s.

  Next, as in Example 1, an adhesive was applied to the shaft core body and cured. The thickness of the adhesive layer was 65 nm, the coating unevenness was 15 nm, and the pencil hardness measured by the method described above was 4H. Thereafter, an elastic roller and a developing roller were prepared in the same manner as in Example 1, and appearance evaluation and image evaluation were performed. The results are shown in Table 3.

(Example 7)
The liquid material was adjusted in the same manner as in Example 1.

The adhesive was adjusted by adding a mixed solvent of 3.3 g of 2-butanol / 21.70 g of ethanol to 10.00 g of the condensate I as in Example 1 to obtain a solid content of 8.0% by mass. The following photocationic polymerization initiator and vinyl group-containing silane coupling agent were mixed with 10.0 g of the condensate diluted to a solid content of 8.0% by mass as described above to obtain an adhesive.
Aromatic sulfonium salt [trade name: Adekaoptomer SP-150, manufactured by Asahi Denka Kogyo Co., Ltd.] diluted to 10% by mass with methyl isobutyl ketone (MIBK) 0.1 g
・ Vinyltriethoxysilane [Product name: SILQUEST A-171 SILANE, manufactured by Momentive Performance Materials Japan LLC] 1.0 g
The viscosity of the adhesive was 1.7 mPa · s.

  Next, as in Example 1, an adhesive was applied to the shaft core body and cured. The thickness of the adhesive layer was 80 nm, the coating unevenness was 20 nm, and the pencil hardness measured by the method described above was 4H. Thereafter, an elastic roller and a developing roller were prepared in the same manner as in Example 1, and appearance evaluation and image evaluation were performed. The results are shown in Table 3.

(Example 8)
The liquid material was adjusted in the same manner as in Example 1.

The adjustment of the adhesive was carried out by adding a mixed solvent of 40.0 g of 2-butanol / 260.00 g of ethanol to 10.00 g of the condensate I as in Example 1 to obtain a solid content of 0.9% by mass. The following photocationic polymerization initiator and vinyl group-containing silane coupling agent were mixed with 10.0 g of the condensate diluted to 0.9% by mass as described above to obtain an adhesive.
Aromatic sulfonium salt [trade name: Adekaoptomer SP-150, manufactured by Asahi Denka Kogyo Co., Ltd.] diluted to 10% by mass with methyl isobutyl ketone (MIBK) 0.1 g
・ Vinyltriethoxysilane [Product name: SILQUEST A-171 SILANE, manufactured by Momentive Performance Materials Japan LLC] 1.0 g
The viscosity of the adhesive was 0.9 mPa · s.

  Next, as in Example 1, an adhesive was applied to the shaft core body and cured. The thickness of the adhesive layer was 12 nm, the coating unevenness was 4 nm, and the pencil hardness measured by the method described above was 8H. Thereafter, an elastic roller and a developing roller were prepared in the same manner as in Example 1, and appearance evaluation and image evaluation were performed. The results are shown in Table 3.

Example 9
The liquid material was adjusted in the same manner as in Example 1.

The following components were mixed in a 300 ml eggplant flask, then stirred at room temperature for 30 minutes, and then heated under reflux on an oil bath set at 120 ° C. for 20 hours to give a hydrolyzable silane compound condensate I. Got. The solid content of this condensate I (mass ratio with respect to the total weight of the polysiloxane polymer solution when it is assumed that all hydrolyzable silane compounds are dehydrated and condensed) is 28.0% by mass.
・ Glycidoxymethyltriethoxysilane (GMeTES) (hydrolyzable silane compound)
39.15 g (0.157 mol)
・ Methyltrimethoxysilane (MeTMS) (hydrolyzable silane compound)
27.66 g (0.203 mol)
・ Water 38.90g
・ Ethanol 20.66g
Next, a mixed solvent of 2-butanol 40.0 g / ethanol 260.00 g was added to the condensate I10.00 g to obtain a solid content of 0.9% by mass. The following photocationic polymerization initiator and vinyl group-containing silane coupling agent were mixed with 10.0 g of the condensate diluted to 0.9% by mass as described above to obtain an adhesive.
Aromatic sulfonium salt [trade name: Adekaoptomer SP-150, manufactured by Asahi Denka Kogyo Co., Ltd.] diluted to 10% by mass with methyl isobutyl ketone (MIBK) 0.1 g
・ Vinyltriethoxysilane [Product name: SILQUEST A-171 SILANE, manufactured by Momentive Performance Materials Japan LLC] 1.0 g
The viscosity of the adhesive was 0.9 mPa · s.

  Next, as in Example 1, an adhesive was applied to the shaft core body and cured. The thickness of the adhesive layer was 11 nm, the coating unevenness was 4 nm, and the pencil hardness measured by the method described above was 9H.

  Thereafter, an elastic roller and a developing roller were prepared in the same manner as in Example 1, and appearance evaluation and image evaluation were performed. The results are shown in Table 3.

(Example 10)
The liquid material was adjusted in the same manner as in Example 1.

Adjustment of the adhesive was carried out by adding a mixed solvent of 45.0 g of 2-butanol / 295.0 g of ethanol to 10.00 g of the condensate I as in Example 1 to obtain a solid content of 0.8% by mass. The following photocationic polymerization initiator and vinyl group-containing silane coupling agent were mixed with 10.0 g of the condensate diluted to a solid content of 0.8% by mass as described above to obtain an adhesive.
Aromatic sulfonium salt [trade name: Adekaoptomer SP-150, manufactured by Asahi Denka Kogyo Co., Ltd.] diluted to 10% by mass with methyl isobutyl ketone (MIBK) 0.1 g
・ Vinyltriethoxysilane [Product name: SILQUEST A-171 SILANE, manufactured by Momentive Performance Materials Japan LLC] 1.0 g
The viscosity of the adhesive was 0.80 mPa · s. Next, as in Example 1, an adhesive was applied to the shaft core body and cured. The thickness of the adhesive layer was 10 nm, the coating unevenness was 5 nm, and the pencil hardness measured by the method described above was 8H. Thereafter, an elastic roller and a developing roller were prepared in the same manner as in Example 1, and appearance evaluation and image evaluation were performed. The results are shown in Table 3.

(Example 11)
The liquid material was adjusted in the same manner as in Example 1.

The adjustment of the adhesive was carried out by adding a mixed solvent of 2.8 g of 2-butanol / 18.2 g of ethanol to 10.00 g of the condensate I as in Example 1 to obtain a solid content mass of 9.0% by mass. The following photocationic polymerization initiator and vinyl group-containing silane coupling agent were mixed with 10.0 g of the condensate diluted to a solid content of 9.0% by mass as described above to obtain an adhesive.
Aromatic sulfonium salt [trade name: Adekaoptomer SP-150, manufactured by Asahi Denka Kogyo Co., Ltd.] diluted to 10% by mass with methyl isobutyl ketone (MIBK) 0.1 g
・ Vinyltriethoxysilane [Product name: SILQUEST A-171 SILANE, manufactured by Momentive Performance Materials Japan LLC] 1.0 g
The viscosity of the adhesive was 1.80 mPa · s. Next, as in Example 1, an adhesive was applied to the shaft core body and cured. The thickness of the adhesive layer was 100 nm, the coating unevenness was 22 nm, and the pencil hardness measured by the method described above was 3H. Thereafter, an elastic roller and a developing roller were prepared in the same manner as in Example 1, and appearance evaluation and image evaluation were performed. The results are shown in Table 3.

(Comparative Example 1)
The liquid material was adjusted in the same manner as in Example 1.

The following components were mixed in a 300 ml eggplant flask, then stirred at room temperature for 30 minutes, and then heated under reflux on an oil bath set at 120 ° C. for 20 hours to give a hydrolyzable silane compound condensate I. Got. The solid content of this condensate I (mass ratio with respect to the total weight of the polysiloxane polymer solution when it is assumed that all hydrolyzable silane compounds are dehydrated and condensed) is 28.0% by mass.
・ Hexyltrimethoxysilane (HeTMS) (hydrolyzable silane compound)
[Product name: KBM-3063, manufactured by Shin-Etsu Chemical Co., Ltd.]
74.16 g (0.36 mol)
・ Water 38.90g
・ Ethanol 63.08g
Next, a mixed solvent of 24.00 g of 2-butanol / 153.00 g of ethanol was added to 10.00 g of the condensate I to obtain a solid content of 1.5% by mass.

  The same photocationic polymerization initiator and vinyl group-containing silane coupling agent as in Example 1 below were mixed with 10.0 g of the condensate diluted to a solid content of 1.5% by mass as described above to obtain an adhesive. The viscosity of the adhesive was 1.05 mPa · s. Next, in the same manner as in Example 1, an adhesive was applied to the shaft core and irradiated with ultraviolet rays. However, the adhesive layer did not cure.

(Comparative Example 2)
The liquid material was adjusted in the same manner as in Example 1.

The adjustment of the adhesive was carried out by adding a mixed solvent of 2-butanol 36.00 g / ethanol 234.00 g to 10.00 g of the condensate I as in Example 1 to a solid content of 1.0% by mass. The following vinyl group-containing silane coupling agent was mixed with 10.0 g of the condensate diluted to a solid content of 1.0% by mass as described above to obtain an adhesive.
・ Vinyltriethoxysilane [Product name: SILQUEST A-171 SILANE, manufactured by Momentive Performance Materials Japan LLC] 1.0 g
The viscosity of the adhesive was 1.0 mPa · s.

  Next, in the same manner as in Example 1, an adhesive was applied to the shaft core and irradiated with ultraviolet rays. However, the adhesive did not cure.

(Comparative Example 3)
The liquid material was adjusted in the same manner as in Example 1. The adjustment of the adhesive was carried out by adding a mixed solvent of 2-butanol 36.00 g / ethanol 234.00 g to 10.00 g of the condensate I as in Example 1 to a solid content of 1.0% by mass. The following photocationic polymerization initiator was mixed with 10.0 g of the condensate diluted to a solid content of 1.0% by mass as described above to obtain an adhesive in the present invention.
Aromatic sulfonium salt [trade name: Adekaoptomer SP-150, manufactured by Asahi Denka Kogyo Co., Ltd.] diluted to 10% by mass with methyl isobutyl ketone (MIBK) 0.1 g
The viscosity of the adhesive was 1.05 mPa · s.

  Next, in the same manner as in Example 1, an adhesive was applied to the shaft core and irradiated with ultraviolet rays. However, the adhesive layer did not cure.

(Comparative Example 4)
The liquid material was adjusted in the same manner as in Example 1.

The adhesive was adjusted by adding a mixed solvent of 24.00 g of 2-butanol / 153.00 g of ethanol to 10.00 g of the same condensate I as in Example 1 to obtain a solid content of 1.5% by mass. The following photocationic polymerization initiator and vinyl group-containing silane coupling agent were mixed with 10.0 g of the condensate diluted to a solid content of 1.5% by mass as described above to obtain an adhesive.
Aromatic sulfonium salt [trade name: Adekaoptomer SP-150, manufactured by Asahi Denka Kogyo Co., Ltd.] diluted to 10% by mass with methyl isobutyl ketone (MIBK) 0.1 g
・ Vinyltriethoxysilane [Product name: SILQUEST A-171 SILANE, manufactured by Momentive Performance Materials Japan LLC] 1.0 g
The viscosity of the adhesive was 1.05 mPa · s. Next, an adhesive was applied to the shaft core in the same manner as in Example 1, and left for 2 hours in a hot air circulating furnace adjusted to 160 ° C. instead of ultraviolet irradiation. However, the adhesive layer did not cure.

(Comparative Example 5)
The liquid material was adjusted in the same manner as in Example 1.

The adjustment of the adhesive was carried out by adding a mixed solvent of 2-butanol 73.00 g / ethanol 477.00 g to the same condensate I10.00 g as in Example 1 to obtain a solid content of 0.5% by mass. The following photocationic polymerization initiator and vinyl group-containing silane coupling agent were mixed with 10.0 g of the condensate diluted to a solid content of 0.5% by mass as described above to obtain an adhesive.
Aromatic sulfonium salt [trade name: Adekaoptomer SP-150, manufactured by Asahi Denka Kogyo Co., Ltd.] diluted to 10% by mass with methyl isobutyl ketone (MIBK) 0.1 g
・ Vinyltriethoxysilane [Product name: SILQUEST A-171 SILANE, manufactured by Momentive Performance Materials Japan LLC] 1.0 g
The viscosity of the adhesive was 0.5 mPa · s. Next, as in Example 1, an adhesive was applied to the shaft core body and cured. The thickness of the adhesive layer was 5 nm, the coating unevenness was 1 nm, and the pencil hardness measured by the method described above was 9H. Thereafter, an elastic roller was prepared in the same manner as in Example 1. However, since the shaft core and the elastic layer were not adhered, appearance evaluation and image evaluation were not performed.

(Comparative Example 6)
The liquid material was adjusted in the same manner as in Example 1.

The adjustment of the adhesive was carried out by adding a mixed solvent of 2.40 g of 2-butanol / 15.60 g of ethanol to 10.000 g of the condensate I as in Example 1 to obtain a solid content of 10.0% by mass. The following photocationic polymerization initiator and vinyl group-containing silane coupling agent were mixed with 10.0 g of the condensate diluted to 10.0% by mass as described above to obtain an adhesive.
Aromatic sulfonium salt [trade name: Adekaoptomer SP-150, manufactured by Asahi Denka Kogyo Co., Ltd.] diluted to 10% by mass with methyl isobutyl ketone (MIBK) 0.1 g
・ Vinyltriethoxysilane [Product name: SILQUEST A-171 SILANE, manufactured by Momentive Performance Materials Japan LLC] 1.0 g
The viscosity of the adhesive was 1.9 mPa · s. Next, as in Example 1, an adhesive was applied to the shaft core body and cured. The thickness of the adhesive layer was 120 nm, the coating unevenness was 25 nm, and the pencil hardness measured by the above method was B. Thereafter, an elastic roller and a developing roller were prepared in the same manner as in Example 1, and appearance evaluation and image evaluation were performed. The results are shown in Table 3.

(Comparative Example 7)
The liquid material was adjusted in the same manner as in Example 1.

As preparation of the adhesive, the following materials were mixed to obtain an adhesive.
・ Phenyltriethoxysilane (PhTES) 3.0g
[Product name: KBE-103, manufactured by Shin-Etsu Chemical Co., Ltd.]
・ N-hexane 96.0 g
・ Curing catalyst 1.0g
The viscosity of the adhesive was 1.8 mPa · s.

  Next, an adhesive was applied to the shaft core in the same manner as in Example 1, and left in a hot-air circulating furnace adjusted to 160 ° C. instead of ultraviolet irradiation for 2 hours to cure the adhesive layer. The thickness of the adhesive layer was 100 nm, the coating unevenness was 50 nm, and the pencil hardness measured by the method described above was 4B. Thereafter, an elastic roller and a developing roller were prepared in the same manner as in Example 1, and appearance evaluation and image evaluation were performed. The results are shown in Table 3.

  * Comparative Example 7 has different adhesive components. For details, see the comparative example in the specification.

* Measurement was not possible because the adhesive did not cure.

  * 1 In the second half of the durability test, the elastic layer was scraped only at the end (non-image area) of the developing roller.

        It is estimated that the adhesiveness between the adhesive layer and the elastic layer is inferior to that of Example 1.

  * 2 After the adhesive was cured, cracks were observed in part of the adhesive layer.

  * 3 Evaluation was not possible because the adhesive did not cure.

* 4 Evaluation was not performed because the adhesive layer and elastic layer did not adhere.

101 shaft core 102 elastic layer 103 adhesive layer

Claims (5)

A shaft core body, an adhesive layer formed on the outer periphery of the shaft core body, and an elastic layer formed on the outer periphery of the adhesive layer, and the elastic layer is disposed on the shaft through the adhesive layer. the manufacturing method of the electrophotographic elastic roller adhering to core,
Applying an adhesive to the outer periphery of the shaft core;
Curing the adhesive by ultraviolet irradiation to form an adhesive layer;
The shaft core body on which the adhesive layer is formed is disposed so as to be concentric with the central axis of the annular coating head , and the annular coating head is moved relative to the shaft core body while moving the annular core a step of applying a liquid rubber on the outer circumference of the adhesive layer by ejecting liquid rubber from coating head,
And heat-curing the applied liquid rubber to form an elastic layer,
The adhesive contains at least an organoalkoxysilane having an epoxy group, a photocationic polymerization initiator, and a silane coupling agent having a vinyl group.
The method for producing an electrophotographic elastic roller, wherein the adhesive layer has a thickness of 10 nm to 100 nm.   The method for producing an elastic roller for electrophotography according to claim 1, wherein the viscosity of the adhesive applied to the outer periphery of the shaft core is 1.0 mPa · s to 1.6 mPa · s.   The method for producing an elastic roller for electrophotography according to claim 1 or 2, wherein the adhesive layer has a pencil hardness of 4H or more and 8H or less. The adhesive contains a hydrolyzable silane compound having a structure represented by the formula (1) as the organoalkoxysilane having the epoxy group, and further comprising a hydrolyzable silane compound having a structure represented by the formula (2). method of manufacturing electrophotographic elastic roller according to any one of claims 1-3 containing:
Ra-Z-Si- (OR) ₃ formulas (1)
Rb-Si- (OR) ₃ formula (2)
[In the above formulas (1) and (2), Ra represents an epoxy group, Z represents an alkylene group having 1 to 6 carbon atoms, R represents an alkyl group having 1 to 3 carbon atoms, and Rb represents a carbon number. Represents a linear alkyl group of 1 to 21]. Each of the formulas (1) and the formula hydrolyzable silane compound represented by (2) The production of the electrophotographic elastic roller according to claim 4 glycidoxypropyl triethoxysilane and hexyltrimethoxysilane Method.

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