JP2005121789A - Electroformed nickel belt, method for forming electroformed nickel belt, function separation type organic photoreceptor, photoreceptor unit and image forming apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To improve the durability of an electroformed nickel belt and to suppress decrease in the productivity of the electroformed nickel belt to the utmost. <P>SOLUTION: In an electroformed nickel belt 14 formed by an electroforming process, the intensity ratio [I(200)/I(111)] of crystalline orientation planes defined by the ratio of the peak intensity I on the (200) plane to the peak intensity I on the (111) plane measured by X-ray diffraction is formed to be 2.5 to 5.0 in a layer 14a in the inner circumference face side and in a layer 14b in the outer circumference face side, and is formed to be 0.5 to 2.0 in an intermediate layer 14c. Thereby, durability against compression and stretching is improved in the layer 14a in the inner circumference face side and in the layer 14b in the outer circumference face side. Although it takes time to form the layer 14a in the inner circumference face side and the layer 14b in the outer circumference face side, it does not take time to form the intermediate layer 14c, which suppresses large increase in the process time of electroforming for forming the electroforming nickel belt 14. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to an electroformed nickel belt, a method for forming an electroformed nickel belt, a function-separated organic photoreceptor, a photoreceptor unit, and an image forming apparatus.

  2. Description of the Related Art As a function-separated organic photoconductor used for an image forming apparatus such as a copying machine or a laser printer, a belt-shaped one having an electroformed nickel belt formed by electroforming as a base is known. Such a belt-shaped function-separated type organic photoreceptor is used for image formation by being hung on a plurality of rollers having an outer diameter of 16 to 20 mm and rotating under a tension of 20 to 50 N. The electroformed nickel belt, which is the base of such a function-separated organic photoconductor, has a thin film thickness of about 30 μm and is flexible, which is caused by bending during handling and accumulation of metal fatigue. The resulting image may be defective due to such cracks. For this reason, it is necessary to sufficiently enhance the durability of the electroformed nickel belt.

  In the electroformed nickel belt formed by electroforming, the deposition amount of the electrodeposited film is set to about 1 μm per minute from the viewpoint of productivity, and in order to produce an electroformed nickel belt having a thickness of about 30 μm. It takes about 30 minutes.

  When the structure of nickel metal deposited at a rate of about 1 μm per minute by conventional electroforming is viewed in terms of the intensity ratio of crystal orientation planes by X-ray diffraction, the layered structure with respect to the peak intensity I of the (111) plane that is a columnar structure The strength ratio [I (200) / I (111)] of the crystal orientation plane expressed by the peak intensity I of the (200) plane is formed in the range of 0.35 to 0.5, and the tensile or compressive force The peak intensity I of the (200) plane that is judged to be a strong lamellar structure tends to be slightly weak. If the peak intensity I of the (200) plane is increased, durability against metal fatigue can be further improved. Therefore, a layer having a large peak intensity I of the (200) plane can be produced without significantly reducing the production efficiency. It is desired to form.

  Various inventions for electroformed nickel belts have been proposed (see, for example, Patent Document 1). In the electroformed nickel belt of the invention of this Patent Document 1, the intensity ratio of the crystal orientation plane represented by the ratio of the peak intensity at the (200) plane to the peak intensity at the (111) plane measured by X-ray diffraction is It is 0.6 or more over the entire layer.

JP 2002-206188

  Since the deposition of the layer having a large peak intensity I on the (200) plane is performed under a low current, in order to increase the deposition amount on the (200) plane, it is necessary to reduce the current applied during electroforming. In order to form an electroformed nickel belt having a film thickness of about 30 μm, for example, the amount of deposition is 0.4 to 0.6 μm / min. It takes about a minute. For this reason, there exists a problem that productivity falls and it becomes a cost increase.

  An object of the present invention is to improve the durability of an electroformed nickel belt and to suppress the decrease in productivity of the electroformed nickel belt as much as possible.

  According to the first aspect of the present invention, in an electroformed nickel belt formed by electroforming, the crystal orientation plane represented by the peak intensity I of the (200) plane with respect to the peak intensity I of the (111) plane measured by X-ray diffraction. The strength ratio [I (200) / I (111)] is formed such that the inner diameter side layer and the outer diameter side layer are 2.5 to 5.0, and the inner diameter side layer and the inner diameter side layer The intermediate layer sandwiched between the outer diameter surface side layers is formed to have a thickness of 0.5 to 2.0.

  Therefore, the inner diameter side layer and the outer diameter side layer of the electroformed nickel belt are electrically charged in the range of the crystallographic plane strength ratio [I (200) / I (111)] of 2.5 to 5.0. The electroformed nickel belt formed has improved durability against compression and tension by forming a layered structure with a high peak strength I on the (200) plane that has strength against cracks. To do. Further, the strength ratio [I (200) / I (111)] of the crystal orientation plane formed by the normal production process is 0.5 for the intermediate layer sandwiched between the inner diameter side layer and the outer diameter side layer. By forming at ~ 2.0, a significant increase in electroforming time is suppressed.

  According to a second aspect of the present invention, in the electroformed nickel belt according to the first aspect, the film thicknesses of the inner diameter surface side and the outer surface side are each 1/5 to 1/3 of the total film thickness. The total film thickness is 30 ± 3 μm.

  Therefore, since the layer on the inner diameter surface side and the outer diameter surface side layer of the electroformed nickel belt become a layered structure and a layer having improved durability against compression and tension is formed in 5 to 10 μm, the entire electroformed nickel belt As a result, durability against compression and pulling is improved. In addition, since the formation of a layer that requires time for formation is 2/5 to 2/3 of the entire film thickness, a significant increase in electroforming time is suppressed.

  According to the third aspect of the present invention, in an electroformed nickel belt formed by electroforming, the crystal orientation plane represented by the peak intensity I of the (200) plane with respect to the peak intensity I of the (111) plane measured by X-ray diffraction. The strength ratio [I (200) / I (111)] is formed such that the outer diameter side layer is 2.5 to 5.0 and the outer side is other than 0.5 to 2.0. It is characterized by being.

  Therefore, the outer diameter surface layer of the electroformed nickel belt is electrodeposited in the range of the crystal orientation plane strength ratio [I (200) / I (111)] of 2.5 to 5.0, and the metal of the layer is deposited. By forming the crystal structure into a layered structure having a high peak strength I on the (200) plane having strength against cracking, the formed electroformed nickel belt has improved durability against compression and tension. Further, by forming the strength ratio [I (200) / I (111)] of the crystal orientation plane formed in the normal production process except for the outer diameter surface side at 0.5 to 2.0, electroforming treatment A significant increase in time is suppressed.

  The invention according to claim 4 is an electroformed nickel belt formed by an electroforming process. The crystal orientation plane represented by the peak intensity I of the (200) plane with respect to the peak intensity I of the (111) plane measured by X-ray diffraction. The strength ratio [I (200) / I (111)] is formed such that the layer on the inner diameter side is 2.5 to 5.0, and the layer other than the inner diameter side is 0.5 to 2.0. It is characterized by.

  Therefore, the layer on the inner diameter side of the electroformed nickel belt is electrodeposited in the range of the crystal orientation plane strength ratio [I (200) / I (111)] of 2.5 to 5.0, and the metal crystal of the layer is deposited. By forming the structure into a layered structure having a high peak strength I on the (200) plane having strength against cracks, the formed electroformed nickel belt has improved durability against compression and tension. In addition to the inner diameter side, the strength ratio [I (200) / I (111)] of the crystal orientation plane formed in the normal production process is formed at 0.5 to 2.0, so that the electroforming time Is significantly suppressed.

  The invention according to claim 5 is the electroformed nickel belt according to claim 3 or 4, wherein the strength ratio [I (200) / I (111)] of the crystal orientation plane is formed to 2.5 to 5.0. The film thickness on the outer surface side or the inner surface side is ½ to 2/3 of the total film thickness, and the total film thickness is 30 ± 3 μm.

  Therefore, a layer having a layered structure and improved durability against compression and tension is formed on one of the inner diameter side layer and the outer diameter side layer of the electroformed nickel belt. The durability against compression and tension is improved as a whole cast nickel belt. In addition, since the formation of a layer that requires time for formation is 1/2 to 2/3 of the entire film thickness, a significant increase in electroforming time is suppressed.

  According to the sixth aspect of the present invention, in the electroformed nickel belt formed by electroforming, the crystal orientation plane represented by the peak intensity I of the (200) plane with respect to the peak intensity I of the (111) plane measured by X-ray diffraction. A plurality of layers having an intensity ratio [I (200) / I (111)] of 2.5 to 5.0 and a plurality of layers of 0.5 to 2.0 are alternately stacked from the inner surface side. It is characterized by being.

  Therefore, by repeatedly forming a layer having a crystal orientation plane intensity ratio [I (200) / I (111)] of 2.5 to 5.0 expressed by the peak intensity I of X-ray diffraction, the electroformed nickel belt It becomes a multilayer structure, and durability against compression and tensile force is improved. Further, a part of the electroformed nickel belt is formed into a layer having a crystal orientation plane strength ratio [I (200) / I (111)] of 2.5 to 5.0, and the other part is formed by a normal production process. By forming the strength ratio [I (200) / I (111)] of the crystal orientation plane to be 0.5 to 2.0, a significant increase in electroforming time is suppressed.

  A seventh aspect of the present invention is the electroformed nickel belt according to the sixth aspect, wherein the thickness ratio of the crystal orientation plane [I (200) / I (111)] is 2.5 to 5.0. Is 2 to 4 μm, and the total film thickness is 30 ± 3 μm.

  Therefore, it is possible to form 3 to 5 layers having a crystal orientation plane strength ratio [I (200) / I (111)] of 2.5 to 5.0, and to compress and pull the electroformed nickel belt. As a result, the electroforming process time is significantly prevented from increasing.

  The invention according to claim 8 is an electroformed nickel belt formed by electroforming, wherein the crystal orientation plane represented by the peak intensity I of the (200) plane with respect to the peak intensity I of the (111) plane measured by X-ray diffraction. A layer having an intensity ratio [I (200) / I (111)] of 2.5 to 5.0 and a layer of 0.5 to 2.0 are formed in a continuous roll shape. To do.

  Therefore, a layer having a crystal orientation plane strength ratio [I (200) / I (111)] of 2.5 to 5.0 is continuously formed in a roll shape, thereby compressing the electroformed nickel belt. Durability against tensile force is improved. In addition, since the layer having a crystal orientation plane strength ratio [I (200) / I (111)] of 0.5 to 2.0 is also continuously formed in a roll shape, the electroforming time is significantly increased. Is suppressed.

  The invention according to claim 9 is the electroformed nickel belt according to claim 8, wherein the thickness ratio of the crystal orientation plane [I (200) / I (111)] is 2.5 to 5.0. Is 0.05 to 0.15 μm, and the total film thickness is 30 ± 3 μm.

  Therefore, the layer having a crystal orientation plane strength ratio [I (200) / I (111)] of 2.5 to 5.0 is thin, and the time required to form this layer is shortened. A significant increase in casting processing time is suppressed.

According to a tenth aspect of the present invention, an electric current is passed between a cylindrical mold base material connected to a cathode of a power source and immersed in an electrolytic solution, and an anode immersed in the electrolytic solution. In a method for forming an electroformed nickel belt in which nickel is deposited on the surface of a mold base material, an electrodeposition current density between the cylindrical mold base material and a soluble active nickel pellet immersed as an anode in the electrolyte solution Of the crystal orientation plane expressed by the peak intensity I of the (200) plane with respect to the peak intensity I of the (111) plane measured by X-ray diffraction by applying an electrodeposition current of ² to 4 A / mm ² [I (200 ) / I (111)] of 2.5 to 5.0 on the cylindrical mold base material, and the electrodeposition current density between the cylindrical mold base material and the anode. There the X-ray diffraction by providing the conductive析電flow 4~6A / mm ² A layer having an intensity ratio [I (200) / I (111)] of the crystal orientation plane expressed by the peak intensity I of the (200) plane to the measured peak intensity I of the (111) plane is 0.5 to 2.0. Forming on a cylindrical mold base material.

Therefore, by passing an electrodeposition current density of ² to 4 A / mm ² between the cylindrical mold base material and the anode, the strength ratio [I (200) / I (111)] of the crystal orientation plane is 2.5. a layer of 5.0 is formed on the cylindrical mold base material, the strength of the crystal orientation surface by energizing the electric析電current density 4~6A / mm ² between the cylindrical mold base material and the anode A layer having a ratio [I (200) / I (111)] of 0.5 to 2.0 is formed on the cylindrical mold base material, and the durability of the electroformed nickel belt against compression and tensile force is improved. Suppressing a significant increase in electroforming time is realized.

  The eleventh aspect of the present invention is the method for forming an electroformed nickel belt according to the tenth aspect, wherein the electrolytic solution comprises nickel sulfamate 450 to 500 g / l, boric acid 30 to 40 g / l, nickel bromide 1 to 2 g / l. l, saccharin 50-100 ppm as the first brightener and compressive stress modifier of the deposited film, alkynediol 20-50 ppm as the second brightener, and alkylbenzene sulfonate 0.1-0.2 g / l as the surfactant It is characterized by being added.

  Therefore, nickel bromide acts as an anodic solubilizer for replenishing depleted metal ions, saccharin acts as a compressive stress modifier for the deposited film and a first brightener to release from the cylindrical metal matrix, Intensity ratio of crystal orientation plane expressed by peak intensity I of X-ray diffraction [I (200) / I (111)] 2.5 to 5.0 and 0.5 to 2.0 for forming a layered metal crystal Alkynediol acts as the second brightener, alkylbenzene sulfonate acts as the surfactant, improves durability against compression and tensile force of the electroformed nickel belt, and suppresses a significant increase in electroforming time. Is realized.

  A function-separated organic photoconductor according to a twelfth aspect of the invention is an alkyd and melamine resin using the electroformed nickel belt according to any one of the first to ninth aspects and titanium oxide fine particles of 0.3 μm or less as a light scattering agent. A thermosetting resinous subbing layer formed on the surface of the electroformed nickel belt by dispersing in a solution, a metal-free phthalocyanine and an azo pigment charge generating agent dispersed in a butyral resin solution, A charge generating layer formed on the pulling layer; and a charge transporting layer formed on the charge generating layer by mixing a stilbene compound as a charge generating agent in a polycarbonate resin solution.

  Therefore, this function-separated organic photoreceptor exhibits the same action as the invention according to any one of claims 1 to 9.

  A photoconductor unit according to a thirteenth aspect of the present invention comprises a function-separated organic photoconductor according to a twelfth aspect, and the function-separated organic photoconductor in contact with an inner peripheral surface of the function-separated organic photoconductor. And a plurality of rollers for supporting.

  Therefore, this photoconductor unit has the same action as the function-separated organic photoconductor according to claim 12, that is, the same action as the invention according to any one of claims 1 to 9.

  According to a fourteenth aspect of the present invention, there is provided an image forming apparatus according to the thirteenth aspect, the charging device for uniformly charging the outer peripheral surface of the function-separated organic photosensitive member, and the uniformly charged device. An exposure apparatus that writes an electrostatic latent image on the outer peripheral surface of the function-separated organic photoconductor, and a developer that develops the electrostatic latent image written on the outer peripheral surface of the function-separated organic photoconductor to form a toner image And a transfer device that transfers the developed toner image to a recording medium.

  Therefore, this image forming apparatus has the same operation as that of the photoconductor unit according to the thirteenth aspect, that is, the same operation as that of the invention according to any one of the first to ninth aspects.

  According to the invention described in any one of claims 1 to 9, durability against compression and tension of the electroformed nickel belt can be improved, and a significant increase in electroforming time can be suppressed.

  According to invention of Claim 10 or 11, the electrocast nickel belt which improved durability with respect to compression and a tension | tensile_strength can be manufactured, suppressing the great increase in electroforming process time.

  According to the invention of any one of claims 12 to 14, the same effect as that of the invention of any one of claims 1 to 9 can be obtained.

  An embodiment of the present invention will be described with reference to the drawings. FIG. 1 is a side view showing a schematic configuration of a color laser printer (hereinafter referred to as “printer”) as an image forming apparatus, FIG. 2 is a sectional view showing a function-separated organic photoconductor, and FIG. 3 is an electroformed nickel belt. FIG. 4 is a perspective view for explaining the state of cracks generated in the function-separated organic photoconductor.

  In the printer 1, a photoconductor unit 3 is disposed at a substantially central portion in a main body case 2. The photoconductor unit 3 includes a belt-like function-separated organic photoconductor 4, and the function-separated organic photoconductor. 4, a driving roller 5 having a diameter of 16 to 20 mm, a driven roller 6, a tension roller 7, and the like. A tension of 20 to 50 N is applied to the tension roller 7, and the function-separated organic photoconductor 4 is driven to rotate at a linear speed of 100 to 200 mm per second.

  Around the photoreceptor unit 3, a charging device 8 that uniformly charges the outer peripheral surface of the function-separated organic photoconductor 4, and an electrostatic charge on the outer peripheral surface of the uniformly charged function-separated organic photoconductor 4. An exposure device 9 for writing a latent image, four developing devices 10 for developing a latent electrostatic image written on the outer peripheral surface of the function-separated organic photoconductor 4 to form a toner image, and a function-separated organic photoconductor 4 An intermediate transfer belt 11 to which the upper toner image is intermediately transferred, a transfer device 12 for transferring the toner image transferred onto the intermediate transfer belt 11 to the recording medium S, and the like are disposed. The recording medium S to which the toner image has been transferred is subjected to fixing processing by heating and pressing in the fixing device 13, and the recording medium S on which the toner image has been fixed is discharged to the paper discharge unit 13a.

  Each of the four developing devices 10 stores toners of different colors (black, cyan, magenta, yellow), and the toner colors stored when these developing devices 10 are selectively driven. The toner image is formed.

  As shown in FIG. 2, the function-separated organic photoreceptor 4 has an electroformed nickel belt 14 formed by electroforming as a base, and a thermosetting resinous undercoat layer 15, a charge generation layer 16, The charge transport layer 17 is formed by sequentially laminating. The thermosetting resinous undercoat layer 15 is a thermosetting resinous layer having a film thickness of 3 to 8 μm formed by coating a film by dispersing alkyd in a melamine resin solution. The charge generation layer 16 is a layer having a film thickness of 0.1 to 0.5 μm formed by coating a charge generation agent such as phthalocyanine and an azo pigment in a butyral resin solution. The charge transport layer 17 is a layer having a film thickness of 20 to 30 μm formed by mixing a stilbene compound as a charge transport agent in a polycarbonate resin solution to form a coating film. Here, the photosensitive layer (thermosetting resinous undercoat layer 15, charge generation layer 16, charge transport layer 17) is A4 size recording medium S and has a printing durability equivalent to 40,000 to 50,000 sheets. The electroformed nickel belt 14 serving as the base may crack in the electroformed nickel belt 14 near the number of printing durability and cause image defects due to the metal fatigue characteristic of the electroformed nickel thin film.

  The electroformed nickel belt 14 which is the base of the function-separated organic photoconductor 4 is subjected to a tensile force and a compressive force due to repeated rotation on the outer periphery of the driving roller 5, the driven roller 6 and the tension roller 7. Causes fatigue and cracks. In particular, when the outer diameter of the rollers 5, 6 and 7 is 15 mm or less, the bent state of the electroformed nickel belt 14 tends to return from the original state in the elastic deformation range, and the tendency due to plastic deformation is likely to be mixed and metal fatigue tends to occur. And durability tends to be lowered.

  The electroformed nickel belt 14 as the base of the function-separated organic photoconductor 4 is manufactured at a temperature of 300 ° C. or higher when a fluororesin release layer is formed, like an electroformed nickel belt for heat fixing, Since the use conditions of 160 to 200 ° C. as the heating temperature at the time of fixing do not last for a long time, the electroformed nickel belt 14 is thermally affected by sulfur embrittlement due to the eutectoid of sulfur contained in the electrolyte chemical during electrodeposition. However, depending on the electrocasting conditions, the metal crystals tend to have a unique structure and tend to cause metal fatigue and cracks.

  When the electroformed nickel belt 14 formed by the electroforming process is used as a base, the electrolytic solution composition and the electrolytic solution composition are maintained and managed in a stable state, and replenishment of metal ions consumed by electrodeposition is performed. If sufficient electrolytic formation is ensured, the orientation state of the metal crystal structure depends on the current density during electrodeposition, and affects the durability of the film when repeatedly subjected to tensile and compressive forces.

An electroformed nickel belt as a base of a function-separated organic photoreceptor that is mounted on an image forming apparatus and has a market has an electrodeposition current of 4 to 5 A / mm ² in an electroforming process. The amount of precipitation is about 1 μm per minute and is formed to a thickness of 30 μm. The degree of orientation of the metal crystal is measured by X-ray diffraction, and the peak of the (200) plane with respect to the peak intensity I of the (111) plane The strength ratio [I (200) / I (111)] of the crystal orientation plane expressed by strength I is formed in the range of 0.35 to 0.4.

  The intensity ratio [I (200) / I (111)] of the crystal orientation plane is as small as 0.35 to 0.4 because the brightener in the electrolyte composition is composed of only the first brightener. And the intensity ratio [I (200) / I (111)] of the crystal orientation plane is 0.5 to 2.0, or 2.5 to 5.0. This is not possible without using two brighteners and gloss plating.

When the second brightener is used in combination with bright plating and the electrodeposition current density is 4 to 6 A / mm ² , the strength ratio of the crystal orientation plane is in the range of 0.5 to 2.0, and the electrodeposition current density is 2 When reduced to ˜4 A / mm ² , the strength ratio of the crystal orientation plane is in the range of ^2.5 to 5.0, and the layered structure becomes stronger. When the electrodeposition current density is 7 A / mm ² or more, the strength ratio of the crystal orientation plane is in the range of 0.3 to 0.4, and the layered structure tends to be mixed with the columnar structure. The strength is lowered, and a columnar structure is formed in the film thickness direction of the electroformed nickel belt to be formed, so that protrusions of 1 to 5 μ are easily formed.

When the electrodeposition current density is decreased from 4-6 A / mm ² to 2-4 A / mm ² , the layered structure becomes stronger and the metal crystal structure becomes more elastically deformed. The production efficiency is lowered by 0.4 to 0.6 μm per minute. Therefore, in the present embodiment, the electrodeposition current densities of 4 to 6 A / mm ² and ² to 4 A / mm ² are mixed to form an electrodeposited film, and the (111) plane peak intensity I measured by X-ray diffraction is measured. The layer 14a on the inner diameter side and the layer on the outer diameter side where the intensity ratio [I (200) / I (111)] of the crystal orientation plane expressed by the peak intensity I of the (200) plane is 2.5 to 5.0 14b, and the intermediate layer 14c sandwiched between the inner surface 14a and the outer surface 14b has a crystal orientation plane strength ratio [I (200) / I (111)] of 0.5 to It is formed to be 2.0. As a result, durability against compression and tension is improved, and a significant increase in electroforming time is suppressed.

FIG. 3 shows that the electroplating nickel belt 14 is obtained by using the second brightener together with the first brightener in the electrolytic solution composition and mixing the electrodeposition current densities 4 to 6 A / mm ² and ² to 4 A / mm ^2. The process of forming and the manufacturing process of the function-separated organic photoreceptor 4 using the electroformed nickel belt 14 as a base are shown.

  In the electroforming process 20 using the nickel sulfamate solution, since it takes 30 minutes or more to form one electrodeposited film, a plurality of SUS cylindrical metal molds 21 are arranged in a line according to the number of production per hour. Deploy.

  An auxiliary electrode 22 is disposed at the lower end of the cylindrical metal mother die 21 in a conductive manner inside the cylindrical metal mother die body 25 via insulating materials 23 and 24, and can be easily attached to and detached from the carrier 26 for conveyance. After being attached by the slide plate 27 and transported to the standby position 28 of the electroforming process, each process step of polishing, cleaning, electroforming, preliminary cleaning, finish drying, and mold release is performed.

  In the polishing step (A), the surface of the cylindrical metal matrix body 25 is wet-polished with a polishing cloth 29 while maintaining a mirror surface of 0.05 to 0.1 μm or less, and the electrodeposited film is peeled off during the formation of the electrodeposited film. The surface is activated so as not to occur.

  In the cleaning step (B), the activated surface is cleaned with warm pure water and the nonwoven fabric 30 so that no projections are formed on the electrodeposited film due to polishing residues, and the cylindrical metal mold body 25 is heated to 40 ° C. Warm up.

  In the electroforming step (C), boric acid 30 to 40 g / l, nickel bromide 1 to 2 g / l as an anodic dissolving agent, first brightener and compression of the deposited film in a solution of nickel sulfamate 450 to 550 g / l Add saccharin 50-100ppm as stress modifier, alkynediol 20-50ppm as second brightener, add 0.1-0.2g / l of alkylbenzene sulfonate as surfactant to prevent defects such as pits Then, the liquid temperature is heated to 55 to 60 ° C. to obtain an electrolytic solution.

  In addition, an ion-permeable diaphragm cathode case 31 is used for enhancing the effect of air stirring of the electrolytic solution and preventing the formation of protrusions and pits on the surface of the electrodeposited film due to foreign matters in the electrolytic solution. The metal mold 21 is rotated at 6 to 10 rpm, the distance between the cylindrical metal mold body 25 and the anode plate is set to 80 to 120 mm, a predetermined electrodeposition current is applied, and the strength ratio of the desired crystal orientation plane is determined. As a layer structure, a film thickness of 30 ± 3 μm is formed.

  Replenishment of nickel metal ions consumed by repeated electroforming is performed by a titanium case 34 in which 8-12 mm soluble active nickel pellets containing 0.01-0.03% sulfur are covered with slime-containing diaphragms 32,33. , 35 is used as an anode, and a current having a desired electrodeposition current density is supplied between the cylindrical metal base body 25 and the active nickel pellets are dissolved in accordance with the electrodeposition current. Replenish. This makes it possible to reduce the number of times nickel metal ions that are consumed are replenished by dissolving the nickel sulfamate, suppress fluctuations in the metal ions in the electrolyte, maintain the electrolyte composition stably, and facilitate management. Become.

  The cylindrical metal master body 25 is connected to the cathodes of the power supplies 38 and 39 via the energizing shaft 36 and the sliding electrode 37. The titanium cases 34 and 35 in the electrolytic solution are connected to anodes from power sources 38 and 39, respectively, and are supplied with a desired electrodeposition current.

For example, the intensity ratio [I (200) / I (111)] of the crystal orientation plane represented by the peak intensity I of the (200) plane to the peak intensity I of the (111) plane measured by X-ray diffraction is The crystal orientation plane of the intermediate layer 14c is between 2.5 and 5.0 between the layer 14a and the outer diameter side layer 14b and is sandwiched between the inner diameter side layer 14a and the outer diameter side layer 14b. When the electroformed nickel belt 14 having a film thickness of 30 ± 3 μm and having a strength ratio [I (200) / I (111)] of 0.5 to 2.0 is formed, the power source 38 Intensity ratio of crystal orientation plane expressed by peak intensity I of (200) plane with respect to peak intensity I of (111) plane of X-ray diffraction by supplying a current with a deposition current density of ² to 4 A / mm ² [I (200) / I (111)] in the range of 2.5 to 5.0 as the inner surface 14a Form, continuously supply 38 or after the formation of the intermediate layer 14c of the power source 39 becomes color electrostatic析電current density 4~6A / mm ² current is supplied, continuously supply 38 or power supply 39 color electrostatic析電current density A current of ² to 4 A / mm ² is supplied to form the outer surface 14b. Since the interface of each layer is activated by continuously forming it in the electrolytic solution, the electroformed nickel belt 14 having a film thickness of 30 ± 3 μm can be obtained without releasing each layer.

The electroformed nickel belt 14 can be operated with a single power source, but depending on the power source capacity and power system, the electrodeposition current density is independently supplied with currents of ² to 4 A / mm ² and 4 to 6 A / mm ² , Alternatively, in the case of supplying simultaneously by the layer configuration, two power supply systems are used. The equipment will be supported by the layer structure, power capacity, and power supply system to be adopted.

  In the pre-cleaning step (D), the electrolytic solution adhering to the cylindrical metal matrix 21 is washed and removed, and a shower is taken during the pulling up to remove and clean the electrolytic solution almost completely, thereby contaminating the pure water in the drying step. Do not.

  In the finish drying step (E), the electrodeposited film formed on the surface of the cylindrical metal mold body 25 is heated to 60 to 70 ° C. for pure water cleaning and drying, and washed with an air knife or the like when being pulled up. To promote drying and form a surface free of stains.

  In the release step (F), one-side open / close-type release jigs 40 are attached to the outer diameter surfaces on both sides of the electrodeposited film formed with a film thickness distribution of 3 μm or less deposited on the cylindrical metal mold body 25. And a film thickness increasing portion 41 having a film distribution of 3 to 30 μm having a width of 20 to 30 mm formed on both ends of the cylindrical metal master body 25 and an unnecessary electrodeposition film due to excessive current on the auxiliary electrode 22 The adhesive tape is applied to the pointed-shaped portion 42 for starting peeling, peeled off in the circumferential direction, and the entire circumference of the film thickness increasing portion 41 is cut off while rotating the cylindrical metal mother die 21. The tool 40 is opened, and high-pressure air is sprayed between the cylindrical metal base body 25 and the electrodeposited film that has been easily peeled off due to the compressive stress at both ends. And drop it onto the cushion sponge 44 of the receiving jig 43 at the same time as the mold release. Start out. If the electroformed nickel belt 14 is manufactured through these steps, the electroformed nickel belt 14 can be manufactured with high productivity without causing a minute bend such as a kink, which is a problem in durability of the electroformed nickel belt 14. Become.

  The electrodeposited film (electroformed nickel belt 14) taken out by dropping on the receiving jig 43 is used as a base of the function-separated organic photoreceptor 4 of the printer 1, and a photosensitive layer (thermosetting resinous undercoat layer). 15, the charge generation layer 16 and the charge transport layer 17) are applied and baked at 130 to 140 [deg.] C. to form the function-separated organic photoconductor 4, which has a width necessary for use in the printer 1. A cutting step G is performed for cutting.

  In the cutting process G, the super-hard cutting metal rollers facing vertically are used, and the intermediate process product 4a of the function-separated organic photoconductor 4 is inserted into the lower roller 45 and placed thereon, and the upper roller 46 that has been waiting is placed. Is moved on the lower roller 45, and the entire periphery is cut while rotating both ends of the intermediate process product 4 a of the function-separated organic photoconductor 4 with the peripheral edge of the opposing roller blade having a shear clearance of 5 μm. A step is formed with a thickness of 0 to 0.05 mm, and a detent guide or the like at the time of image formation is formed on the back side as necessary. Also, depending on the application method of the photosensitive layer (thermosetting resinous undercoat layer 15, charge generation layer 16, charge transport layer 17), the photosensitive layer is applied after first cutting both ends in the state of the electroformed nickel belt 14. There is also a case.

  If the cut end portion 47 is used in the printer 1 with a step of 0.1 mm or more, the step portion becomes a crack starting point due to repeated bending load, and the durability is lowered.

  The intermediate process product 4a of the function-separated organic photoconductor 4 that has undergone this cutting step G has a cross-section of 300 ° C. or higher that expresses brittleness such as sulfur embrittlement that tends to occur in electroformed nickel metal at the time of cutting. Since it does not become high temperature, durability is not reduced and the finished product of the function-separated organic photoconductor 4 can be obtained.

  Since the printing durability in the printer 1 is usually in the range of 40,000 to 50,000 sheets with the recording medium S of A4, the base of the function-separated organic photoconductor 4 needs to have the same life or longer life. However, if it is safe even if it is structurally damaged, it may be equivalent to the life of the function-separated organic photoconductor 4, but the function separation using the electroformed nickel belt 14 which is a metal film as a base body. In the type organic photoconductor 4, if the substrate is broken, the fracture surface becomes sharp and an unexpected failure occurs. Therefore, it is necessary to increase the durability of the substrate as much as possible.

  In Table 1, the effect of Examples 1-5 and Comparative Examples 1-2 is described.

  In Example 1, the electroforming liquid composition was boric acid 30 to 40 g / l in a solution of nickel sulfamate 450 to 550 g / l, nickel bromide 1 to 2 g / l as an anodic dissolving agent, the first brightener and the deposited film. Saccharin 50 to 100 ppm as a compressive stress modifier and alkynediol 20 to 50 ppm as a second brightener, and 0.1 to 0.2 g / l of alkylbenzene sulfonate as a surfactant for preventing pits and the like 1 was added, and the liquid temperature was adjusted to 55 to 60 ° C.

The intensity ratio [I of the crystal orientation plane that can be expressed by the peak intensity I of the (200) plane with respect to the peak intensity I of the (111) plane of the X-ray diffraction of the electroformed nickel belt 14 serving as the base of the function-separated organic photoreceptor 4 (200) / I (111)] is 2.5 to 5.0 for the inner diameter side layer and the outer diameter side layer, and the inner diameter side layer and the outer diameter side layer are In the case of forming the film with a thickness ratio of 30 ± 3 μm in which the intensity ratio [I (200) / I (111)] of the sandwiched intermediate layer is 0.5 to 2.0, electrodeposition is performed from the power source 38. By supplying a current having a current density of 3 A / mm ² , the intensity ratio of the crystal orientation plane expressed by the peak intensity I of the (200) plane with respect to the peak intensity I of the (111) plane of X-ray diffraction [I (200) / I (111)] forms a layer of 2.5 to 5.0 on the inner diameter side to 1/5 to 1/3 of the entire film thickness, and continuously From 38 or power source 39 supplies a current to be conductive析電current density 5A / mm ^2, a layer of the intensity ratio of crystal orientation surface [I (200) / I (111 ) ] is 0.5 to 2.0 After forming as an intermediate layer, a current having an electrodeposition current density of 3 A / mm ² is continuously supplied from the power supply 38 or 39 to the peak intensity I of the (111) plane of X-ray diffraction on the outer diameter surface side. A layer having a crystal orientation plane intensity ratio [I (200) / I (111)] of 2.5 to 5.0 expressed by a peak intensity I of (200) plane is 1/5 to 1/3 of the entire film thickness. Form.

  Since the interface of each layer is activated by continuously forming it in the electrolytic solution, the electroformed nickel belt 14 having a film thickness of 30 ± 3 μm can be obtained without releasing each layer.

In Example 2, an electric current with an electrodeposition current density of 5 A / mm ² is supplied from the power source 38, and the intensity ratio [I (200) / I (111)] of the crystal orientation plane of X-ray diffraction is on the inner diameter side. A layer of 0.5 to 2.0 is formed to be 1/2 to 1/3 of the entire film thickness, and a layer having a crystal orientation plane strength ratio of 2.5 to 5.0 is continuously formed. Alternatively, an electroforming nickel belt 14 having a total film thickness of 30 ± 3 μm is obtained by supplying a current having an electrodeposition current density of 3 A / mm ² from a power source 39.

In Example 3, similarly, an electric current with an electrodeposition current density of 3 A / mm ² is supplied from the power source 38, and the intensity ratio [I (200) / I (111)] of the crystal orientation plane of X-ray diffraction is the inner surface. A layer of 2.5 to 5.0 is formed from the side so as to be 1/2 to 2/3 of the entire film thickness, and a layer having a crystal orientation plane strength ratio of 0.5 to 2.0 is continuously formed. The electroformed nickel belt 14 having a total film thickness of 30 ± 3 μm is obtained by supplying a current having an electrodeposition current density of 5 A / mm ² from the power source 38 or the power source 39.

In Example 4, the power source 38 or the power source 39 alternately supplies a current with an electrodeposition current density of 3 A / mm ² and a current with an electrodeposition current density of 5 A / mm ^2. After forming a layer having a strength ratio [I (200) / I (111)] of 2.5 to 5.0 with a thickness of 2 to 4 μm, a layer having a crystal orientation plane strength ratio of 0.5 to 2.5 is formed. The electroformed nickel belt 14 having a film thickness of 30 ± 3 μm is obtained by forming a thickness of 5 to 7 μm to form a plurality of layers.

In Example 5, a current having an electrodeposition current density of 3 A / mm ² from a power source 38 and a current having an electrodeposition current density of 5 A / mm ² from a power source 39 are continuously supplied, and the crystal orientation plane of X-ray diffraction Of the layer having a strength ratio [I (200) / I (111)] of 2.5 to 5.0 and a layer having a crystal orientation plane strength ratio of 0.5 to 2.0. The electroformed nickel belt 14 having a thickness of 30 ± 3 μm is obtained by continuously superposing and forming a thickness of 0.15 to 2 μm in a roll shape.

  A layer having a crystal orientation plane strength ratio [I (200) / I (111)] in the range of 2.5 to 5.0 when continuously superposed on the roll shape has a rotational speed of the cylindrical metal matrix 21. If 6 rpm, the thickness is 0.13 μm, and if 10 rpm, the thickness is 0.02 μm.

In Comparative Example 1, a current having an electrodeposition current density of 5 A / mm ² was continuously supplied from the power source 38 or the power source 39, and the intensity ratio [I (200) / I (111)] of the crystal orientation plane of X-ray diffraction. However, an electroformed nickel belt having a film thickness of 30 ± 3 μm is obtained with a single layer film of 0.5 to 2.0.

Comparative Example 2 is an electrocast nickel belt of a function-separated organic photoreceptor that is currently in practical use. The electroforming solution composition is 450 to 550 g / l nickel sulfamate, 40 g / l boric acid, and an odor as an anodic dissolver. 2 g / l of nickel fluoride, 50 to 100 ppm of sodium saccharin as a compressive stress adjusting agent for the first brightener and deposited film, 1000 to 1500 ppm of sodium naphthalene sulfonate, and 0.1 to 0.2 g of alkylbenzene sulfonate as a surfactant / L is added, the liquid temperature is set to 55 to 60 ° C., and nickel metal ions are replenished with soluble active nickel pellets of 8 to 12 mm containing 0.01 to 0.03% sulfur and slime-containing diaphragms 35 and 36. A case where the current is an electrodeposition current density of 5 A / mm ² is configured by putting it in titanium cases 34 and 35 coated with The same is fed between the cylindrical metal matrix body 25 rotating at 6 to 10 rpm and the anode to obtain an electroformed nickel belt having a film thickness of 30 ± 3 μm.

  In this electroformed nickel belt, the layer structure is a single layer, and the strength ratio [I (200) / I (111)] of the crystal orientation plane in the surface X-ray diffraction is 0.35 to 0.4. .

  The function-separated organic photoconductor formed by using the electroformed nickel belts of Examples 1 to 5 and Comparative Examples 1 and 2 as a base is used in a durability test machine having the same layout as the printer 1 shown in FIG. Assembling as a part, the durability test was done. The driving roller 5, the driven roller 6, and the tension roller 7 are each coated with a polyurethane rubber having an outer diameter of 16 mm. A tension of 20 to 50 N is applied by the tension roller 7, and the A4 size recording medium can be printed at a linear speed of 200 mm / sec. Forty to 50,000 sheets were driven to rotate.

  As a result, no zigzag crack A was generated in any of the seven samples at a rotational speed corresponding to 40,000 to 50,000 sheets from the cut steps at both ends where cracks were likely to occur. In the samples of Comparative Examples 1 and 2, when the A4 size recording medium equivalent to 5.2 to 58,000 sheets was rotated, a streak-like crack B started to occur, and the streak expanded at a rotation speed equivalent to 60,000 sheets or more. Then, the inside of the streak portion was cut (see FIG. 4). In the samples of Examples 1 to 5, it was found that streak-like cracks B did not occur within the image forming width even at a rotational speed equivalent to 60,000 sheets, and the function of the function-separated organic photoreceptor as a substrate was improved. did.

1 is a side view illustrating a schematic configuration of a printer which is an image forming apparatus according to an embodiment of the present invention. It is sectional drawing which shows a function separation type organic type photoreceptor. It is a manufacturing process figure which shows the outline of the manufacturing process of an electroformed nickel belt and a function separation type organic type photoreceptor using it as a base. It is a perspective view explaining the mode of the crack which arises in a function separation type organic type photoreceptor.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Image forming apparatus 3 Photoreceptor unit 4 Function separation type organic type photoreceptor 5, 6, 7 Roller 8 Charging device 9 Exposure device 10 Developing device 12 Transfer device 14 Electroformed nickel belt 14a Inner diameter side layer 14b Outer diameter side Layer 14c Intermediate layer 15 Thermosetting resinous undercoat layer 16 Charge generation layer 17 Charge transport layer 25 Cylindrical mold base material 38, 39 Power supply

Claims (14)

In the electroformed nickel belt formed by electroforming process,
The intensity ratio [I (200) / I (111)] of the crystal orientation plane expressed by the peak intensity I of the (200) plane to the peak intensity I of the (111) plane measured by X-ray diffraction is The outer diameter surface layer is formed at 2.5 to 5.0, and the intermediate layer sandwiched between the inner diameter surface layer and the outer diameter surface layer is formed at 0.5 to 2.0. An electroformed nickel belt.   2. The film thicknesses of the inner diameter surface side and the outer surface side are 1/5 to 1/3 of the total film thickness, respectively, and the total film thickness is 30 ± 3 μm. The electroformed nickel belt described. In the electroformed nickel belt formed by electroforming process,
The intensity ratio [I (200) / I (111)] of the crystal orientation plane expressed by the peak intensity I of the (200) plane to the peak intensity I of the (111) plane measured by X-ray diffraction is a layer on the outer diameter plane side. Is formed at 2.5 to 5.0, and is formed at 0.5 to 2.0 except for the outer surface side. In the electroformed nickel belt formed by electroforming process,
The intensity ratio [I (200) / I (111)] of the crystal orientation plane expressed by the peak intensity I of the (200) plane to the peak intensity I of the (111) plane measured by X-ray diffraction is An electroformed nickel belt formed at 2.5 to 5.0, and formed at 0.5 to 2.0 except for the inner surface side.   The thickness ratio of the crystal orientation plane [I (200) / I (111)] is formed to be 2.5 to 5.0. 5. The electroformed nickel belt according to claim 3, wherein the electrocast nickel belt is 2/3 and the total film thickness is 30 ± 3 μm. In the electroformed nickel belt formed by electroforming process,
The intensity ratio [I (200) / I (111)] of the crystal orientation plane expressed by the peak intensity I of the (200) plane to the peak intensity I of the (111) plane measured by X-ray diffraction is 2.5 to 5.0. A plurality of layers and a plurality of layers of 0.5 to 2.0 are alternately laminated from the inner surface side.   The film thickness of the layer having a crystal orientation plane strength ratio [I (200) / I (111)] of 2.5 to 5.0 is 2 to 4 μm, and the total film thickness is 30 ± 3 μm. The electroformed nickel belt according to claim 6. In the electroformed nickel belt formed by electroforming process,
The intensity ratio [I (200) / I (111)] of the crystal orientation plane expressed by the peak intensity I of the (200) plane to the peak intensity I of the (111) plane measured by X-ray diffraction is 2.5 to 5.0. The electroformed nickel belt is characterized in that the layer and the layer of 0.5 to 2.0 are formed in a continuous roll shape.   The film thickness of the layer having a crystal orientation plane strength ratio [I (200) / I (111)] of 2.5 to 5.0 is 0.05 to 0.15 μm, and the total film thickness is 30 ± 3 μm. The electroformed nickel belt according to claim 8, wherein: Nickel is applied to the surface of the cylindrical mold base by energizing between the cylindrical mold base connected to the cathode of the power source and immersed in the electrolyte and the anode immersed in the electrolyte. In the method of forming the electroformed nickel belt to be deposited,
By applying an electrodeposition current having an electrodeposition current density of ² to 4 A / mm ² between the cylindrical mold base material and a soluble active nickel pellet immersed as an anode in the electrolytic solution, X-ray diffraction is performed. A layer having a crystal orientation plane intensity ratio [I (200) / I (111)] of 2.5 to 5.0 expressed by the peak intensity I of the (200) plane to the measured peak intensity I of the (111) plane is 2.5 to 5.0. Forming on a cylindrical mold base material;
An electrodeposition current density of 4 to 6 A / mm ² is applied between the cylindrical mold base material and the anode to give a peak intensity I of (111) measured by X-ray diffraction (200 A step of forming a layer having a crystal orientation plane intensity ratio [I (200) / I (111)] of 0.5 to 2.0 on the cylindrical mold base material, which can be expressed by a peak intensity I) of the plane;
A method for forming an electroformed nickel belt, comprising:   The electrolyte includes 450 to 500 g / l nickel sulfamate, 30 to 40 g / l boric acid, 1 to 2 g / l nickel bromide, 50 to 100 ppm saccharin as a first brightener and a compressive stress regulator for the deposited film, second The method for forming an electroformed nickel belt according to claim 10, wherein 20 to 50 ppm of alkyne diol is added as a brightening agent and 0.1 to 0.2 g / l of alkylbenzene sulfonate is added as a surfactant. An electroformed nickel belt according to any one of claims 1 to 9,
A thermosetting resinous subbing layer in which titanium oxide fine particles of 0.3 μm or less are dispersed in an alkyd and melamine resin solution as a light scattering agent to form a coating on the surface of the electroformed nickel belt;
A charge generation layer in which a metal-free phthalocyanine and an azo pigment charge generation agent are dispersed in a butyral resin solution and formed on the thermosetting resinous undercoat layer;
A charge transport layer in which a stilbene compound as a charge generator is mixed with a polycarbonate resin solution to form a coating on the charge generation layer;
A function-separated organic photoconductor comprising: A function-separated organic photoconductor according to claim 12,
A plurality of rollers in contact with the inner peripheral surface of the function-separated organic photoconductor to support the function-separated organic photoconductor,
A photoreceptor unit. The photoreceptor unit according to claim 13;
A charging device for uniformly charging the outer peripheral surface of the function-separated organic photoconductor;
An exposure apparatus that writes an electrostatic latent image on the outer peripheral surface of the uniformly charged function-separated organic photoreceptor,
A developing device that develops an electrostatic latent image written on the outer peripheral surface of the function-separated organic photoconductor to form a toner image;
A transfer device for transferring the developed toner image to a recording medium;
An image forming apparatus comprising:

Images