JP2006023725A - Conductive roller and image forming device equipped therewith - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a conductive roller in which a drying process in mass production can be omitted or shortened, the electrostatic chargeability to toner or a photosensitive drum is more improved than heretofore and a marked improvement in sharpness is possible, and to provide an image forming device which is equipped with such conductive roller and can form proper images. <P>SOLUTION: The conductive roller 1 is equipped with a shaft 2, an elastic layer 3 formed on the outer periphery of the shaft 2, a first resin coating layer 4 of ≤10<SP>6</SP>Ωcm for volume resistivity, formed on the outer peripheral surface of the elastic layer 3 and a second resin coating layer 5 of ≥10<SP>10</SP>Ωcm in volume resistivity, formed on the outer peripheral surface of the first resin coating layer 4, wherein at least either of the first resin coating layer 4 and the second elastic layer 5 includes a UV-curing resin, and the image forming device is equipped with such a conductive roller 1. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a conductive roller and an image forming apparatus provided with the conductive roller, and more particularly to a conductive roller used in an image forming apparatus such as an electrophotographic apparatus such as a copying machine or a printer or an electrostatic recording apparatus. .

  In an electrophotographic image forming apparatus such as a copying machine or a printer, as a developing method for visualizing a latent image by supplying toner to a photosensitive drum or the like holding a latent image and attaching the toner to the latent image on the photosensitive drum. A pressure development method is known. In the pressure development method, for example, after the photosensitive drum is charged to a constant potential, an electrostatic latent image is formed on the photosensitive drum by an exposure machine, and further, a developing roller carrying toner is placed on the electrostatic latent image. Development is performed by bringing the toner into contact with the latent image on the photosensitive drum in contact with the held photosensitive drum.

  In addition, the corona discharge method has been conventionally used for charging the photosensitive drum. However, in the corona discharge method, it is necessary to apply a high voltage of 6 to 10 kV, which is not preferable from the viewpoint of ensuring the safety of the apparatus. Furthermore, since harmful substances such as ozone are generated during corona discharge, it is not preferable from the viewpoint of environment. On the other hand, a contact charging method has been proposed in which a charging roller is brought into contact with the photosensitive drum and a voltage is applied between the photosensitive drum and the charging roller to charge the photosensitive drum.

  The developing roller in the pressure developing method and the charging roller in the contact charging method must rotate while securely holding the state in close contact with the photosensitive drum, so that the outer periphery of the shaft made of a highly conductive material such as metal In addition, a semiconductive elastic body in which carbon black or metal powder is dispersed in an elastomer such as silicone rubber, acrylonitrile-butadiene rubber (NBR), ethylene-propylene-diene rubber (EPDM), epichlorohydrin rubber (ECO), polyurethane, etc. Or a semiconductive elastic layer made of a foam obtained by foaming these. In addition, a resin coating layer may be further formed on the surface of the elastic layer for the purpose of controlling chargeability and adhesion to the toner and preventing contamination of the photosensitive drum by the elastic layer.

  Further, in addition to the developing roller and the charging roller, a toner supply roller for supplying toner to the developing roller, a transfer roller for transferring toner attached to the latent image on the photosensitive drum to a recording medium, and a photosensitive drum after transfer A conductive roller having a structure in which a semiconductive elastic layer is formed on the outer periphery of the shaft as described above, and a resin coating layer is further formed on the surface of the elastic layer, such as a cleaning roller for removing toner remaining on the surface. A roller is used.

  Conventionally, in the conductive roller, the resin coating layer is obtained by dipping the conductive roller body composed of a shaft and an elastic layer into a solvent-based or aqueous coating liquid or spraying the coating liquid on the conductive roller body. Later, it is formed by drying and curing with heat or hot air. In this case, since long drying is required, a long drying line is necessary for mass production. In addition, the resin coating layer is required to have subtle electrical conductivity and surface condition depending on its use, but the quality distribution is affected by variations in temperature distribution and air volume in the drying line, which greatly affects the performance of the resin coating layer. There was a problem.

  On the other hand, as a method for forming a stable quality resin coating layer without requiring a long drying line, an ultraviolet curable resin is applied to the surface of the elastic layer of the conductive roller and cured to form the resin coating layer. A technique has been proposed (see Patent Document 1).

JP 2002-310136 A

  However, the conductive roller in which the resin coating layer containing the ultraviolet curable resin is disposed on the outer peripheral surface of the elastic layer is superior to the conductive roller having no resin coating layer, but is still improved. There is a need for a conductive roller that is further excellent in chargeability with respect to toner and that can greatly improve image quality.

  Accordingly, an object of the present invention is to solve the above-mentioned problems of the prior art, omit or shorten the drying step in mass production, improve the charging property with respect to the toner or the photosensitive drum, and greatly improve the image quality. It is an object of the present invention to provide a conductive roller capable of performing the above. Another object of the present invention is to provide an image forming apparatus provided with such a conductive roller and capable of forming a good image.

  As a result of diligent studies to achieve the above object, the present inventors have found that in a conductive roller having a resin coating layer disposed on the surface of an elastic layer, the resin coating layer is a conductive resin coating layer containing a conductive agent. And a non-conductive resin coating layer that does not contain a conductive agent. By placing the non-conductive resin coating layer on the outer surface of the roller, the charging property of the conductive roller on the toner or photosensitive drum is greatly increased. Furthermore, by using an ultraviolet curable resin for at least one of the conductive resin coating layer and the non-conductive resin coating layer and forming it by ultraviolet irradiation, the drying process in mass production can be omitted or shortened. The present inventors have found that variations in the performance of the resin coating layer due to variations in temperature distribution and air volume in the operation line can be reduced, and the present invention has been completed.

That is, the conductive roller of the present invention includes a shaft, an elastic layer formed on the outer periphery of the shaft, and a first resin coating having a volume resistivity of 10 ⁶ Ω · cm or less formed on the outer peripheral surface of the elastic layer. And a second resin coating layer having a volume resistivity of 10 ¹⁰ Ω · cm or more formed on the outer peripheral surface of the first resin coating layer, the conductive roller comprising: the first resin coating layer; At least one of the second resin coating layers contains an ultraviolet curable resin. Here, the ultraviolet curable resin is obtained by curing a resin and / or compound polymerizable by ultraviolet rays by ultraviolet irradiation.

  In a preferred example of the conductive roller of the present invention, the first resin coating layer contains a conductive agent, and the second resin coating layer does not contain a conductive agent.

  In another preferred embodiment of the conductive roller of the present invention, the second resin coating layer contains at least one selected from the group consisting of fluorine-containing resins and compounds, and silicon-containing resins and compounds. Here, the fluorine-containing resin and compound and the silicon-containing resin and compound may be ultraviolet curable or non-ultraviolet curable.

  In another preferred embodiment of the conductive roller of the present invention, the second resin coating layer contains a fluorine-containing ultraviolet curable resin and / or a silicon-containing ultraviolet curable resin.

  In another preferred embodiment of the conductive roller of the present invention, the second resin coating layer includes at least one selected from the group consisting of a non-ultraviolet curable fluorine-containing resin and compound, and a silicon-containing resin and compound, and an ultraviolet ray. And curable resin. Here, as the non-ultraviolet curable fluorine-containing resin and / or compound, fluorine-containing (meth) acrylate resin and / or compound, fluorine-containing olefin resin and / or compound, fluorine-containing ether resin and / or Compound, fluorine-containing ester-based resin and / or compound, fluorine-containing epoxy-based resin and / or compound, fluorine-containing urethane-based resin and / or compound are preferable, and as the non-UV curable silicon-containing resin and / or compound, Silicon-containing (meth) acrylate resins and compounds, and silicone resins are preferred. The ultraviolet curable resin may be an ultraviolet curable resin that does not contain fluorine or silicon, or may be a fluorine and / or silicon-containing ultraviolet curable resin.

  In another preferred embodiment of the conductive roller of the present invention, the first resin coating layer has a coating liquid containing a conductive agent and a resin and / or compound polymerizable by ultraviolet rays on the outer peripheral surface of the elastic layer. After coating, the resin and / or compound that can be polymerized by ultraviolet rays are cured by ultraviolet irradiation. Here, the coating liquid preferably contains a photopolymerization initiator. Moreover, as the resin and / or compound that can be polymerized by ultraviolet rays, resins and / or compounds having a double bond between carbon atoms that can be polymerized by ultraviolet rays are preferable, and (meth) acrylate monomers and oligomers are more preferable.

  In another preferred embodiment of the conductive roller of the present invention, the second resin coating layer is applied to the outer peripheral surface of the first resin coating layer with a coating liquid containing a resin and / or compound that can be polymerized by ultraviolet rays. Thereafter, the resin and / or compound that can be polymerized by ultraviolet rays is cured by ultraviolet irradiation. Here, the coating liquid preferably contains a photopolymerization initiator. Moreover, as the resin and / or compound that can be polymerized by ultraviolet rays, resins and / or compounds having a double bond between carbon atoms that can be polymerized by ultraviolet rays are preferable, and (meth) acrylate monomers and oligomers are more preferable.

  In another preferred embodiment of the conductive roller of the present invention, the second resin coating layer containing at least one selected from the group consisting of the fluorine-containing resin and compound and the silicon-containing resin and compound is (1) polymerized by ultraviolet rays. Coating liquid containing at least one selected from the group consisting of possible fluorine-containing resins and compounds and silicon-containing resins and compounds, (2) non-UV curable fluorine-containing resins and compounds, and groups consisting of silicon-containing resins and compounds A coating solution containing at least one selected from the group consisting of a resin and / or a compound that is polymerizable by ultraviolet rays and does not contain fluorine and silicon, and (3) a non-ultraviolet curable fluorine-containing resin and compound, a silicon-containing resin, and At least one selected from the group consisting of compounds, a fluorine-containing resin polymerizable by ultraviolet rays, and A resin that can be polymerized by the ultraviolet ray by applying an ultraviolet ray to the outer peripheral surface of the first resin coating layer after applying any one of a coating liquid containing at least one selected from the group consisting of a compound and a silicon-containing resin and a compound. And at least one of the compounds is cured. Here, the coating liquid preferably contains a photopolymerization initiator.

  The resin and / or compound that can be polymerized by ultraviolet rays and does not contain fluorine and silicon are preferably resins and / or compounds having a double bond between carbon atoms that can be polymerized by ultraviolet rays, and do not contain fluorine and silicon (meth). More preferred are acrylate monomers and oligomers.

  The fluorine-containing resin and / or compound that can be polymerized by ultraviolet rays is preferably a resin and / or compound having a double bond between carbon atoms that can be polymerized by ultraviolet rays, and compounds derived from fluoroolefins and fluoro (meth) Acrylates are more preferred.

  The silicon-containing resin and / or compound that can be polymerized by ultraviolet rays is preferably a resin and / or compound having a double bond between carbon atoms that can be polymerized by ultraviolet rays. Oils and (meth) acryloxyalkylsilanes are more preferred.

  An image forming apparatus according to the present invention includes the conductive roller.

  According to the present invention, in the conductive roller having the resin coating layer disposed on the surface of the elastic layer, the resin coating layer is composed of the first conductive resin coating layer and the second non-conductive resin coating layer. Then, the second resin coating layer is disposed on the outer surface of the roller, and furthermore, an ultraviolet curable resin is used for at least one of the first resin coating layer and the second resin coating layer, thereby eliminating or shortening the drying process in mass production. In addition, the charging property with respect to the toner or the photosensitive drum is greatly improved as compared with the conventional case, and it is possible to provide a conductive roller capable of greatly improving the image quality. Further, it is possible to provide an image forming apparatus including such a conductive roller and capable of forming a good image.

Below, the conductive roller of this invention is demonstrated in detail, referring a figure. FIG. 1 is a cross-sectional view of an example of a conductive roller of the present invention. The illustrated conductive roller 1 includes a shaft 2, an elastic layer 3 formed on the outer periphery of the shaft 2, a first resin coating layer 4 formed on the outer peripheral surface of the elastic layer 3, and the first resin. And a second resin coating layer 5 formed on the outer peripheral surface of the coating layer 4. Here, the first resin coating layer 4 has a volume resistivity of 10 ⁶ Ω · cm or less, the second resin coating layer 5 has a volume resistivity of 10 ¹⁰ Ω · cm or more, and the first resin coating layer. At least one of 4 and the 2nd resin coating layer 5 contains ultraviolet curable resin.

  In the conductive roller 1 of the present invention, an ultraviolet curable resin is used for at least one of the first resin coating layer 4 and the second resin coating layer 5, so that it is long in the formation of a resin coating layer using an ultraviolet curable resin. Since there is no need for time drying, the drying step in mass production can be omitted or shortened. That is, the first resin coating layer 4 and / or the second resin coating layer 5 of the conductive roller 1 of the present invention is, for example, a coating liquid (first resin coating layer) containing a resin and / or compound that can be polymerized by ultraviolet rays. 4 is preferably added to the outer surface of the elastic layer 3 and / or the first resin coating layer 4 and then irradiated with ultraviolet rays, and a resin that can be polymerized by ultraviolet rays and / or Alternatively, since the compound is formed by curing, the drying step is not essential, and further, the first resin coating layer 4 and / or the second resin coating layer 5 is formed at the stage of irradiation with ultraviolet rays. Variations in the performance of the first resin coating layer 4 and / or the second resin coating layer 5 due to variations in temperature distribution and air volume in the line can be eliminated.

In the conductive roller 1 of the present invention, the volume resistivity of the first resin coating layer 4 is 10 ⁶ Ω · cm or less, and the volume resistivity of the second resin coating layer 5 is 10 ¹⁰ Ω · cm or more. Therefore, the chargeability of the conductive roller 1 with respect to the toner or the photosensitive drum is greatly improved. Here, the first resin coating layer 4 preferably contains a conductive agent, and the second resin coating layer 5 preferably does not contain a conductive agent.

  Furthermore, in a preferred embodiment of the conductive roller 1 of the present invention, the second resin coating layer 5 is at least one selected from the group consisting of fluorine-containing resins and compounds and silicon-containing resins and compounds (ultraviolet curable type). The surface energy of the second resin coating layer 5 can be reduced, and the conductive roller 1 has a low surface frictional resistance and is long. It is hard to wear even if used for a long period of time and has excellent durability.

  The shaft of the conductive roller of the present invention is not particularly limited as long as it has good conductivity. For example, a metal core made of a metal such as iron, stainless steel, or aluminum, or a hollow interior is hollowed out. A metal shaft such as a metal cylinder can be used.

  The elastic layer of the conductive roller of the present invention includes an elastomer and a conductive agent, and includes other components such as a filler as necessary. Examples of the elastomer used for the elastic layer include silicone rubber, ethylene-propylene-diene rubber (EPDM), acrylonitrile-butadiene rubber (NBR), natural rubber, styrene-butadiene rubber (SBR), butyl rubber, chloroprene rubber, acrylic rubber, and epichloro. Examples include hydrin rubber (ECO), ethylene-vinyl acetate copolymer (EVA), polyurethane, and mixtures thereof. Among these, silicone rubber, EPDM, ECO, and polyurethane are preferable. In the elastic layer, the elastomer may be used as a foam by chemically foaming the elastomer using a foaming agent, or mechanically entraining and foaming air like a polyurethane foam.

  The shaft and the elastic layer may be integrated using a reaction injection molding method (RIM molding method). That is, it is possible to integrate the shaft and the elastic layer by mixing and injecting two kinds of monomer components constituting the raw material component of the elastic layer into a cylindrical mold and performing a polymerization reaction. As a result, the time required from injection of raw materials to demolding can be shortened, and production costs can be greatly reduced.

  When silicone rubber is used for the elastic layer, the silicone rubber may be general millable silicone rubber (HCR) or liquid silicone rubber (LSR). In addition, when using liquid silicone rubber, it is preferable to form an elastic layer by liquid injection molding (LIM: Liquid injection Molding). The above liquid silicone rubber contains vinyl group-containing polyorganosiloxane with organohydrogenpolysiloxane, reinforcing filler such as silica, conductive agent, platinum-based catalyst, reaction inhibitor, silicone oil, and other various additives. After being injected into a mold having a predetermined shape, it is molded by heat curing.

（式中、Ｒ¹は、それぞれ独立して一価の炭化水素基であり、ｎは100〜10,000の整数である）で表される化合物が好ましい。ここで、Ｒ¹における、一価の炭化水素基としては、メチル基、エチル基、プロピル基、ブチル基及びペンチル基等のアルキル基、ビニル基及びアリル基等のアルケニル基、シクロヘキシル基等のシクロアルキル基、フェニル基等のアリール基、ベンジル基等のアラルキル基等が挙げられる。 The vinyl group-containing polyorganosiloxane has two or more reactive groups in the molecule, and examples of the reactive group include an alkenyl group and a hydroxyl group. As the vinyl group-containing polyorganosiloxane, the following formula (I):

In the formula, R ¹ is each independently a monovalent hydrocarbon group, and n is an integer of 100 to 10,000. Here, the monovalent hydrocarbon group in R ¹ includes an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group and a pentyl group, an alkenyl group such as a vinyl group and an allyl group, and a cyclohexyl group such as a cyclohexyl group. Examples include alkyl groups, aryl groups such as phenyl groups, and aralkyl groups such as benzyl groups.

（式中、Ｒ²は、それぞれ独立して水素又は一価の炭化水素基であり、ｍは10〜1,000の整数である）で表され、分子中に２個以上のケイ素−水素結合を有する化合物が好ましい。ここで、Ｒ²における、一価の炭化水素基としては、メチル基、エチル基、プロピル基、ブチル基及びペンチル基等のアルキル基、ビニル基及びアリル基等のアルケニル基、シクロヘキシル基等のシクロアルキル基、フェニル基等のアリール基、ベンジル基等のアラルキル基等が挙げられる。 Examples of the organohydrogenpolysiloxane include the following formula (II):

(Wherein R ² is each independently hydrogen or a monovalent hydrocarbon group, m is an integer of 10 to 1,000), and has two or more silicon-hydrogen bonds in the molecule. Compounds are preferred. Here, the monovalent hydrocarbon group in R ² includes alkyl groups such as methyl group, ethyl group, propyl group, butyl group and pentyl group, alkenyl groups such as vinyl group and allyl group, and cyclohexane such as cyclohexyl group. Examples include alkyl groups, aryl groups such as phenyl groups, and aralkyl groups such as benzyl groups.

  In addition, as a conductive agent contained in the liquid silicone rubber, a conductive agent generally used for an elastic layer to be described later can be used, and as a platinum catalyst, platinous chloride, chloroplatinic acid, alcohol-modified chloroplatinic acid can be used. Examples of the reaction inhibitor include methylvinylcyclotetrasiloxane, acetylene alcohols, siloxane-modified acetylene alcohol, hydroperoxide and the like.

  Examples of the conductive agent used for the elastic layer include an electronic conductive agent and an ionic conductive agent. Electronic conductive agents include conductive carbon such as ketjen black and acetylene black, carbon black for rubber such as SAF, ISAF, HAF, FEF, GPF, SRF, FT and MT, and carbon black for color subjected to oxidation treatment. , Pyrolytic carbon black, natural graphite, artificial graphite, antimony-doped tin oxide, ITO, tin oxide, titanium oxide, zinc oxide and other metal oxides, nickel, copper, silver, germanium and other metals, polyaniline, polypyrrole, polyacetylene, etc. Conductive whiskers such as conductive polymer, carbon whisker, graphite whisker, titanium carbide whisker, conductive potassium titanate whisker, conductive barium titanate whisker, conductive titanium oxide whisker, and conductive zinc oxide whisker. The blending amount of the electronic conductive agent is preferably in the range of 1 to 50 parts by mass, more preferably in the range of 5 to 40 parts by mass with respect to 100 parts by mass of the elastomer.

  Examples of the ionic conductive agent include tetraethylammonium, tetrabutylammonium, dodecyltrimethylammonium, hexadecyltrimethylammonium, benzyltrimethylammonium, modified fatty acid dimethylethylammonium, perchlorate, chlorate, hydrochloride, bromate, and the like. Ammonium salts such as salts, iodates, borofluorides, sulfates, ethyl sulfates, carboxylates, sulfonates; alkaline metals such as lithium, sodium, potassium, calcium, magnesium, alkaline earth metals Examples include perchlorate, chlorate, hydrochloride, bromate, iodate, borofluoride, sulfate, trifluoromethyl sulfate, and sulfonate. The compounding amount of the ionic conductive agent is preferably in the range of 0.01 to 10 parts by mass, more preferably in the range of 0.05 to 5 parts by mass with respect to 100 parts by mass of the elastomer. The said electrically conductive agent may be used individually by 1 type, may be used in combination of 2 or more type, and may combine an electronic conductive agent and an ionic conductive agent.

The elastic layer preferably has a resistance value of 10 ³ to 10 ¹⁰ Ωcm, more preferably 10 ⁴ to 10 ⁸ Ωcm, depending on the blending of the conductive agent. If the resistance value of the elastic layer is less than 10 ³ Ωcm, the electric charge may leak to the photosensitive drum or the like, or the conductive roller itself may be broken by voltage, and if it exceeds 10 ¹⁰ Ωcm, the ground cover tends to occur.

  The elastic layer may contain a crosslinking agent such as an organic peroxide and a vulcanizing agent such as sulfur in order to make the elastomer into a rubbery material, if necessary. Accelerators, vulcanization accelerators, vulcanization retarders, and the like may be included. In addition, the elastic layer further comprises a rubber compounding agent such as a filler, a peptizer, a foaming agent, a plasticizer, a softener, a tackifier, an anti-tacking agent, a separating agent, a release agent, a bulking agent, and a coloring agent. An agent may be contained.

  When the elastic layer is formed using polyurethane or EPDM as a base material, various charge control agents such as nigrosine, triaminophenylmethane, and cationic dyes, silicone resins, and silicone rubbers are used to control the toner charge amount on the surface. Fine powders such as nylon may be added. Here, the addition amount of the charge control agent is preferably in the range of 1 to 5 parts by mass with respect to 100 parts by mass of the polyurethane or EPDM, and the addition amount of the fine powder is relative to 100 parts by mass of the polyurethane or EPDM. A range of 1 to 10 parts by mass is preferred.

  The hardness of the elastic layer is not particularly limited, but is preferably 80 degrees or less in terms of Asker C hardness, and more preferably 20 to 70 degrees. When the Asker C hardness of the elastic layer exceeds 80 degrees, the contact area between the conductive roller and the photosensitive drum may be reduced, and good development may not be performed. Also, when the conductive roller is used as a developing roller In addition, the toner is damaged, and the toner adheres to the photosensitive drum or the stratified blade. On the other hand, if the elastic layer is too low, when a conductive roller is used as a developing roller, the frictional force with the photosensitive drum or the stratified blade increases, which may cause image defects such as jitter. In addition, since the elastic layer is used in contact with a photosensitive drum, a stratified blade, or the like, even when the hardness is set to a low hardness, it is preferable to reduce the compression set as much as possible, specifically 20% or less. It is preferable that

  The surface roughness of the elastic layer is not particularly limited, but the JIS 10-point average roughness (Rz) is preferably 30 μm or less, and more preferably 1 to 20 μm. When the surface roughness (Rz) of the elastic layer exceeds 30 μm, the layer thickness of the toner layer and the uniformity of charging may be impaired. By setting the surface roughness to 30 μm or less, toner adhesion can be improved. In addition, it is possible to more reliably prevent image deterioration due to roller wear during long-term use. In order to obtain an appropriate surface roughness, the roller surface may be polished. However, if a polishing step is provided, the productivity of the roller is deteriorated and the manufacturing cost is increased. Therefore, it is preferable that the mold surface for molding the elastic layer is appropriately roughened, and the rough surface of the mold surface is transferred to the surface of the elastic layer to be molded to obtain the above surface roughness.

In the conductive roller of the present invention, it is necessary that at least one of the first resin coating layer and the second resin coating layer contains an ultraviolet curable resin, and the first resin coating layer preferably contains a conductive agent, The second resin coating layer preferably does not contain a conductive agent, and the first resin coating layer and the second resin coating layer may contain a known additive as required. In the conductive roller of the present invention, the volume resistivity of the first resin coating layer is 10 ⁶ Ω · cm or less, preferably 10 ³ to 10 ⁶ Ω · cm. The volume resistivity of the layer is 10 ¹⁰ Ω · cm or more, preferably 10 ¹⁰ to 10 ¹⁶ Ω · cm. If the volume resistivity of the first resin coating layer exceeds 10 ⁶ Ω · cm, fogging is likely to occur. By setting the volume resistivity of the second resin coating layer to 10 ¹⁰ Ω · cm or more, toner or photosensitive The chargeability of the drum is improved, and the image quality can be greatly improved. Here, the volume resistivity of the resin coating layer is determined by, for example, applying the coating liquid used for forming the resin coating layer on the copper plate, irradiating the coating liquid with ultraviolet rays, and curing the coating liquid with ultraviolet rays, and then measuring the copper plate and the measurement electrode. It can obtain | require by measuring resistance between.

In order to reduce the volume resistivity of the first resin coating layer to 10 ⁶ Ω · cm or less, it is usually necessary to use a conductive agent. As the conductive agent, the electronic conductive agent exemplified as the conductive agent for the elastic layer is used. In addition, an ionic conductive agent can be preferably used. In addition, when using an ultraviolet curable resin for a 1st resin coating layer, a carbon type electronic conductive agent, an ionic conductive agent, and a transparent conductive agent are preferable. Carbon-based electronic conductive agents include conductive carbon such as ketjen black and acetylene black, carbon black for rubber such as SAF, ISAF, HAF, FEF, GPF, SRF, FT, and MT, and color for which oxidation treatment has been applied. Examples thereof include carbon black, pyrolytic carbon black, natural graphite, and artificial graphite. In addition, as the transparent conductive agent, fine particles of metal oxide such as ITO, tin oxide, titanium oxide, and zinc oxide; fine particles of metal such as nickel, copper, silver, germanium: conductive titanium oxide whisker, conductive barium titanate Examples thereof include conductive whiskers such as whiskers. The blending amount of the electronic conductive agent is preferably 100 parts by mass or less with respect to 100 parts by mass of the resin constituting the first resin coating layer (that is, the total of the ultraviolet curable resin and the non-ultraviolet curable resin). The range of parts by mass is further preferable, and the range of 10 to 50 parts by mass is even more preferable. On the other hand, the blending amount of the ionic conductive agent is preferably 20 parts by mass or less, more preferably 0.01 to 20 parts by mass, and more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the resin constituting the first resin coating layer. A range is even more preferred.

When the first resin coating layer contains an ultraviolet curable resin, for example, the first resin coating layer may be formed by applying a coating liquid containing a conductive agent and a resin and / or compound polymerizable by ultraviolet rays to the outside of the elastic layer. After coating on the surface, it is formed by irradiating with ultraviolet rays and curing a resin and / or compound polymerizable by the ultraviolet rays. In the case where the second resin coating layer contains an ultraviolet curable resin, the second resin coating layer may be formed by, for example, applying a coating liquid containing a resin and / or compound polymerizable by ultraviolet rays to the outside of the first resin coating layer. After coating on the surface, it is formed by irradiating with ultraviolet rays and curing a resin and / or compound polymerizable by the ultraviolet rays. A first resin coating layer and / or a second resin coating is formed by curing a coating solution containing a resin and / or compound polymerizable by ultraviolet rays to form a first resin coating layer and / or a second resin coating layer. It is not necessary to prepare a long drying line for forming the layer, and furthermore, variations in the characteristics of the first resin coating layer and / or the second resin coating layer due to variations in various conditions of the drying process can be eliminated. Here, the coating liquid preferably further contains a reactive diluent, a photopolymerization initiator, and a photopolymerization accelerator, and may contain a known additive as necessary, and also contains a solvent. Preferably not. In addition, as a method of apply | coating a coating liquid to the surface of an elastic layer and / or 1st resin coating layer, a spray method, a roll coater method, a dipping method, a die coating method etc. are mentioned. Examples of the light source used for ultraviolet irradiation include a mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a metal halide lamp, and a xenon lamp. The conditions for ultraviolet irradiation are appropriately selected according to the type and application amount of the ultraviolet curable resin. For example, the irradiation intensity is preferably in the range of 100 to 700 mW / cm ² and the integrated light quantity of 200 to 3000 mJ / cm ² .

  In the resin coating layer containing the ultraviolet curable resin, the ratio of the ultraviolet curable resin and the non-ultraviolet curable resin and / or the compound is an ultraviolet curable resin with respect to a total of 100 parts by mass of the non-ultraviolet curable resin and the compound. Is preferably in the range of 10 to 10,000 parts by mass, more preferably in the range of 30 to 5000 parts by mass. If the blending amount of the UV curable resin with respect to 100 parts by mass of the non-UV curable resin and the compound is less than 10 parts by mass, the degree of crosslinking due to UV curing may be insufficient, and the coating strength may be lowered. If it exceeds, the target performance will not be demonstrated.

  Examples of the ultraviolet curable resin used for the first resin coating layer and / or the second resin coating layer include polyester resin, polyether resin, fluororesin, epoxy resin, amino resin, polyamide resin, acrylic resin, acrylic urethane resin, and urethane. Resins, alkyd resins, phenol resins, melamine resins, urea resins, silicone resins, polyvinyl butyral resins, vinyl ether resins, vinyl ester resins, and modified resins having specific functional groups introduced into these resins, etc. You may use individually by 1 type or in mixture of 2 or more types. Moreover, it is preferable to introduce a crosslinked structure in the first resin coating layer and / or the second resin coating layer in order to improve mechanical strength and environmental resistance.

  The ultraviolet curable resin is obtained by curing a resin and / or compound that can be polymerized by ultraviolet rays, preferably a resin and / or compound having a double bond between carbon atoms that can be polymerized by ultraviolet rays. In addition, the resin and / or compound that can be polymerized by ultraviolet rays may be used alone or in combination of two or more.

  As the resin and / or compound having a polymerizable double bond between carbon atoms used for forming the ultraviolet curable resin, a (meth) acrylate monomer and an oligomer are preferable. Here, as the (meth) acrylate monomer and oligomer, urethane (meth) acrylate, epoxy (meth) acrylate, ether (meth) acrylate, ester (meth) acrylate, polycarbonate (meth) acrylate, fluorine-based Examples thereof include monomers and oligomers such as (meth) acrylate and silicone-based (meth) acrylate. The (meth) acrylate oligomer includes polyethylene glycol, polyoxypropylene glycol, polytetramethylene ether glycol, bisphenol A type epoxy resin, phenol novolac type epoxy resin, adduct of polyhydric alcohol and ε-caprolactone, and the like (meth) It can be synthesized by reaction with acrylic acid or by urethanizing a polyisocyanate compound and a (meth) acrylate compound having a hydroxyl group.

  The urethane-based (meth) acrylate oligomer can be obtained by urethanization of a polyol, an isocyanate compound and a (meth) acrylate compound having a hydroxyl group. The epoxy-based (meth) acrylate oligomer is preferably a reaction product of a compound having a glycidyl group and (meth) acrylic acid, such as benzene ring, naphthalene ring, spiro ring, dicyclopentadiene, tricyclodecane, etc. A reaction product of a compound having a cyclic structure and a glycidyl group and (meth) acrylic acid is more preferable. Furthermore, the ether-based (meth) acrylate oligomer, the ester-based (meth) acrylate oligomer, and the polycarbonate-based (meth) acrylate oligomer are each composed of a polyol (polyether polyol, polyester polyol, and polycarbonate polyol) and (meth) acrylic acid. Obtained by reaction.

  The second resin coating layer of the conductive roller of the present invention preferably contains at least one of a fluorine-containing resin, a fluorine-containing compound, a silicon-containing resin, and a silicon-containing compound. When the second resin coating layer includes an ultraviolet curable resin and includes a fluorine and / or silicon-containing resin and / or a compound, the second resin coating layer includes, for example, (1) a fluorine-containing resin polymerizable by ultraviolet rays and A coating liquid comprising at least one selected from the group consisting of a compound and a silicon-containing resin and a compound; (2) at least one selected from the group consisting of a non-ultraviolet curable fluorine-containing resin and compound and a silicon-containing resin and compound; And a coating solution containing a resin and / or a compound that can be polymerized by ultraviolet rays and does not contain fluorine and silicon, and (3) a non-ultraviolet curable fluorine-containing resin and compound and a silicon-containing resin and compound. A fluorine-containing resin and compound that can be polymerized by ultraviolet rays, and a silicon-containing resin and compound. After applying any one of the coating liquids containing at least one selected from the group consisting of the resin resin and / or compound that can be polymerized by ultraviolet rays by irradiation with ultraviolet rays (that is, by ultraviolet rays) Polymerizable fluorine-containing resin and / or compound, silicon-containing resin and / or compound, resin and / or compound not containing fluorine and silicon) are cured. On the other hand, when the second resin coating layer does not include an ultraviolet curable resin and includes a fluorine and / or silicon-containing resin and / or a compound, the second resin coating layer includes, for example, a non-UV curable fluorine-containing resin and A coating liquid containing at least one selected from the group consisting of a compound and a silicon-containing resin and a compound is applied to the outer peripheral surface of the first resin coating layer, and then heated and dried. By including in the second resin coating layer at least one selected from the group consisting of a fluorine-containing resin and a compound and a silicon-containing resin and a compound (which may be an ultraviolet curable type or a non-ultraviolet curable type) Since the surface energy of the second resin coating layer is reduced and the frictional force of the second resin coating layer can be greatly reduced, the durability of the conductive roller can be greatly improved. Here, the resin and / or compound that can be polymerized by ultraviolet rays preferably have a double bond between carbon atoms that can be polymerized by ultraviolet rays.

  The total content of fluorine and silicon in the second resin coating layer including at least one selected from the group consisting of the fluorine-containing resin and compound and the silicon-containing resin and compound is preferably in the range of 0.1 to 50% by mass, The range of ˜30% by mass is more preferable. When the total content of fluorine and silicon in the second resin coating layer is less than 0.1% by mass, the characteristics of silicon and fluorine may not be sufficiently exhibited, and durability may be insufficient. And adhesion between the lower layer and the solubility and dispersibility may deteriorate.

  As the resin and / or compound containing a double bond between carbon atoms that can be polymerized by ultraviolet rays and not containing fluorine and silicon, (meth) acrylate monomers and oligomers not containing fluorine and silicon are preferable. Examples include monomers and oligomers such as (meth) acrylate, epoxy (meth) acrylate, ether (meth) acrylate, ester (meth) acrylate, and polycarbonate (meth) acrylate. These (meth) acrylate oligomers can be synthesized as described above.

  As the resin and / or compound having a double bond between carbon atoms polymerizable by ultraviolet rays and containing fluorine, compounds derived from fluoroolefins and fluoro (meth) acrylates are preferable. The fluorine-containing resin and / or compound having a polymerizable double bond between carbon atoms may be a monomer or an oligomer, and may be a mixture of a monomer and an oligomer. The fluorine content of the fluorine-containing resin and / or compound having a polymerizable double bond between carbon atoms is preferably in the range of 0.05 to 80% by mass, more preferably in the range of 0.08 to 80% by mass, and 0.1 to 80%. A mass% range is particularly preferred.

As the fluoroolefin used in the compound derived from the fluoroolefin, an olefin having 2 to 12 carbon atoms in which one or more hydrogen atoms are substituted with fluorine is preferable. Specifically, vinyl fluoride [CFH = CH ₂ , fluorine content 41% by mass], vinylidene fluoride [CF ₂ = CH ₂ , fluorine content 59% by mass], trifluoroethylene [CF ₂ = CFH, fluorine content 70% by mass], tetrafluoroethylene [CF ₂ = CF ₂ , fluorine content 76 mass%], hexafluoropropene [CF ₃ CF = CF ₂ , fluorine content 76 mass%], (perfluorobutyl) ethylene [CF ₃ (CF ₂ ) ₃ CH = CH _2, fluorine content 69 wt%, (perfluorohexyl) ethylene _{[CF 3 (CF 2) 5} CH = CH 2, fluorine content 71 wt%, (perfluorooctyl) ethyl Emissions _{[CF 3 (CF 2) 7} CH = CH 2, fluorine content 72 wt%, (perfluorodecyl) ethylene _{[CF 3 (CF 2) 9} CH = CH 2, fluorine content 73 wt%, chloro Trifluoroethylene [CF ₂ = CFCl, fluorine content 49% by mass], 1-methoxy- (perfluoro-2-methyl-1-propene) [(CF ₃ ) ₂ C = CFOCH ₃ , fluorine content 63% by mass 1,4-divinyloctafluorobutane [CH ₂ ═CH— (CF ₂ ) ₄ —CH═CH ₂ , fluorine content 60% by mass], 1,6-divinyldodecafluorohexane [CH ₂ ═CH— ( CF ₂ ) ₆ —CH═CH ₂ , fluorine content 64% by mass], 1,8-divinylhexadecafluorooctane [CH ₂ ═CH— (CF ₂ ) ₈ —CH═CH ₂ , fluorine content 67% by mass ] Etc. are mentioned.

The fluoro (meth) acrylates are preferably alkyl (meth) acrylates having 5 to 16 carbon atoms in which one or more hydrogen atoms are substituted with fluorine. Specifically, 2,2,2-tri Fluoroethyl acrylate [CF ₃ CH ₂ OCOCH═CH ₂ , fluorine content 37% by mass] 2,2,3,3,3-pentafluoropropyl acrylate [CF ₃ CF ₂ CH ₂ OCOCH═CH ₂ , fluorine content 47 mass%], 2- (perfluorobutyl) ethyl acrylate [CF ₃ (CF ₂ ) ₃ CH ₂ CH ₂ OCOCH═CH ₂ , fluorine content 54 mass%], 3- (perfluorobutyl) -2-hydroxy acrylate _{[CF 3 (CF 2) 3} CH 2 CH (OH) CH 2 OCOCH = CH 2, fluorine content 49 wt%], 2- (perfluorohexyl) ethyl acrylate [CF ₃ (CF _{2) 5 H 2 CH 2 OCOCH = CH 2} , fluorine content 59 wt%], 3- (perfluorohexyl) -2-hydroxypropyl acrylate _{[CF 3 (CF 2) 5} CH 2 CH (OH) CH 2 OCOCH = CH 2 , Fluorine content 55% by mass], 2- (perfluorooctyl) ethyl acrylate [CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ OCOCH═CH ₂ , fluorine content 62% by mass], 3- (perfluorooctyl) -2-hydroxypropyl acrylate [CF ₃ (CF ₂ ) ₇ CH ₂ CH (OH) CH ₂ OCOCH═CH ₂ , fluorine content 59 mass%], 2- (perfluorodecyl) ethyl acrylate [CF ₃ (CF ₂ ) ₉ CH ₂ CH ₂ OCOCH═CH ₂ , fluorine content 65 mass%], 2- (perfluoro-3-methylbutyl) ethyl acrylate [(CF ₃ ) ₂ CF (CF ₂ ) ₂ CH ₂ CH ₂ OCOCH═CH ₂ , Fluorine content 57 mass%], 3- (perfluoro-3-methylbutyl) -2-hydroxypropyl acrylate [(CF ₃ ) ₂ CF (CF ₂ ) ₂ CH ₂ CH (OH) CH ₂ OCOCH = CH ₂ , fluorine Content 52 mass%], 2- (perfluoro-5-methylhexyl) ethyl acrylate [(CF ₃ ) ₂ CF (CF ₂ ) ₄ CH ₂ CH ₂ OCOCH = CH ₂ , fluorine content 61 mass%], 3 -(Perfluoro-5-methylhexyl) -2-hydroxypropyl acrylate [(CF ₃ ) ₂ CF (CF ₂ ) ₄ CH ₂ CH (OH) CH ₂ OCOCH = CH ₂ , fluorine content 57 mass%], 2 -(Perfluoro-7-methyloctyl) ethyl acrylate [(CF ₃ ) ₂ CF (CF ₂ ) ₆ CH ₂ CH ₂ OCOCH═CH ₂ , fluorine content 64 mass], 3- (perfluoro-7-methyloctyl ) -2-Hydroxypropyl acrylate [(C _{3) 2 CF (CF 2)} 6 CH 2 CH (OH) CH 2 OCOCH = CH 2, fluorine content 60 wt%], 1H, 1H, 3H- tetrafluoropropyl acrylate _{[CHF 2 CF 2 CH 2 OCOCH} = CH ₂ , fluorine content 41% by mass], 1H, 1H, 5H-octafluoropentyl acrylate [CHF ₂ (CF ₂ ) ₃ CH ₂ OCOCH = CH ₂ , fluorine content 53% by mass], 1H, 1H, 7H-dodeca Fluoroheptyl acrylate [CHF ₂ (CF ₂ ) ₅ CH ₂ OCOCH═CH ₂ , fluorine content 59 mass%], 1H, 1H, 9H-hexadecafluorononyl acrylate [CHF ₂ (CF ₂ ) ₇ CH ₂ OCOCH═CH _2, the fluorine content of 63 wt%], IH-1-(trifluoromethyl) trifluoroethyl acrylate _{[(CF 3) 2 CHOCOCH =} CH 2, fluorine content 51 wt%, 1 , IH, 3H-hexafluorobutyl acrylate _{[CF 3 CHFCF 2 CH 2 OCOCH} = CH 2, fluorine content 48 wt%, 2,2,2-trifluoroethyl methacrylate _{[CF 3 CH 2 OCOC (CH} 3) = CH ₂ , fluorine content 34% by mass], 2,2,3,3,3-pentafluoropropyl methacrylate [CF ₃ CF ₂ CH ₂ OCOC (CH ₃ ) = CH ₂ , fluorine content 44% by mass], 2 -(Perfluorobutyl) ethyl methacrylate [CF ₃ (CF ₂ ) ₃ CH ₂ CH ₂ OCOC (CH ₃ ) = CH ₂ , fluorine content 51% by mass], 3- (perfluorobutyl) -2-hydroxypropyl methacrylate [CF ₃ (CF ₂ ) ₃ CH ₂ CH (OH) CH ₂ OCOC (CH ₃ ) = CH ₂ , fluorine content 47 mass%], 2- (perfluorohexyl) ethyl methacrylate [CF ₃ (CF ₂ ) ₅ CH _{2 H 2 OCOC (CH 3) =} CH 2, fluorine content 57 wt%], 3- (perfluorohexyl) -2-hydroxypropyl methacrylate _{[CF 3 (CF 2) 5} CH 2 CH (OH) CH 2 OCOC ( CH ₃ ) = CH ₂ , fluorine content 53 mass%], 2- (perfluorooctyl) ethyl methacrylate [CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ OCOC (CH ₃ ) = CH ₂ , fluorine content 61 mass %], 3-perfluorooctyl-2-hydroxypropyl methacrylate [CF ₃ (CF ₂ ) ₇ CH ₂ CH (OH) CH ₂ OCOC (CH ₃ ) = CH ₂ , fluorine content 57 mass%], 2- ( Perfluorodecyl) ethyl methacrylate [CF ₃ (CF ₂ ) ₉ CH ₂ CH ₂ OCOC (CH ₃ ) = CH ₂ , fluorine content 63 mass%], 2- (perfluoro-3-methylbutyl) ethyl methacrylate [(CF _{3) 2 CF (CF 2)} 2 C _{2 CH 2 OCOC (CH 3)} = CH 2, fluorine content 55 wt%], 3- (perfluoro-3-methylbutyl) -2-hydroxypropyl methacrylate _{[(CF 3) 2 CF (} CF 2) 2 CH 2 CH (OH) CH ₂ OCOC (CH ₃ ) = CH ₂ , fluorine content 51 mass%], 2- (perfluoro-5-methylhexyl) ethyl methacrylate [(CF ₃ ) ₂ CF (CF ₂ ) ₄ CH ₂ CH ₂ OCOC (CH ₃ ) = CH ₂ , fluorine content 59 mass%], 3- (perfluoro-5-methylhexyl) -2-hydroxypropyl methacrylate [(CF ₃ ) ₂ CF (CF ₂ ) ₄ CH ₂ CH (OH) CH ₂ OCOC (CH ₃ ) = CH ₂ , fluorine content 56 mass%], 2- (perfluoro-7-methyloctyl) ethyl methacrylate [(CF ₃ ) ₂ CF (CF ₂ ) ₆ CH ₂ CH ₂ OCOC (CH ₃ ) = CH ₂ , fluorine content 62 mass%], 3- (par Fluoro-7-methyloctyl) -2-hydroxypropyl methacrylate [(CF ₃ ) ₂ CF (CF ₂ ) ₆ CH ₂ CH (OH) CH ₂ OCOC (CH ₃ ) = CH ₂ , fluorine content 59 mass%], 1H, 1H, 3H-tetrafluoropropyl methacrylate [CHF ₂ CF ₂ CH ₂ OCOC (CH ₃ ) = CH ₂ , fluorine content 51 mass%], 1H, 1H, 5H-octafluoropentyl methacrylate [CHF ₂ (CF ₂ ) ₃ CH ₂ OCOC (CH ₃ ) ═CH ₂ , fluorine content 51 mass%], 1H, 1H, 7H-dodecafluoroheptyl methacrylate [CHF ₂ (CF ₂ ) ₅ CH ₂ OCOC (CH ₃ ) ═CH ₂ , Fluorine content 57% by mass], 1H, 1H, 9H-hexadecafluorononyl methacrylate [CHF ₂ (CF ₂ ) ₇ CH ₂ OCOC (CH ₃ ) = CH ₂ , fluorine content 61% by mass], 1H-1- (Trifle Oromethyl) trifluoroethyl methacrylate [(CF ₃ ) ₂ CHOCOC (CH ₃ ) = CH ₂ , fluorine content 48 mass%], 1H, 1H, 3H-hexafluorobutyl methacrylate [CF ₃ CHFCF ₂ CH ₂ OCOC (CH ₃ ) = CH ₂ , fluorine content 46 mass%] and the like.

  Examples of the resin and / or compound containing silicon having a double bond between carbon atoms that can be polymerized by ultraviolet rays include reactive silicone oils at both ends, reactive silicone oils at one end, and (meth) acryloxyalkylsilanes. Is preferred. Further, as reactive silicone oils, those having a (meth) acryl group introduced at the terminal are preferable. The silicon content of the silicon-containing resin and / or compound having a polymerizable double bond between carbon atoms is preferably in the range of 0.01 to 40% by mass, more preferably in the range of 0.05 to 35% by mass, and 0.1 to 30%. A mass% range is particularly preferred.

（式中、ｐは繰り返し単位数である）で表されるシリコーンオイルが挙げられる。該両末端反応性シリコーンオイル類としては、市販品を利用することができ、例えば、信越化学工業(株)製の品名「Ｘ-２２-１６４Ａ」（粘度25mm²/s、官能基当量860g/mol）、品名「Ｘ-２２-１６４Ｂ」（粘度55mm²/s、官能基当量1630g/mol）、品名「Ｘ-２２-１６４Ｃ」（粘度90mm²/s、官能基当量2370g/mol）、東レ・ダウコーニング・シリコーン(株)製の品番「ＢＸ１６-１５２Ｂ」（粘度40cs/25℃、メタクリル基当量1300g/mol、25℃での比重0.97）、品番「ＢＹ１６-１５２」（粘度85cs/25℃、メタクリル基当量2800g/mol、25℃での比重0.97）、品番「ＢＸ２-１５２Ｃ」（粘度330cs/25℃、メタクリル基当量5100g/mol、25℃での比重0.97）等を用いることができる。 Examples of the both-end reactive silicone oils include the following formula (III):

(Wherein p is the number of repeating units). Commercially available products can be used as the both-end-reactive silicone oils, for example, “X-22-164A” (viscosity 25 mm ² / s, functional group equivalent 860 g / s) manufactured by Shin-Etsu Chemical Co., Ltd. mol), product name “X-22-164B” (viscosity 55 mm ² / s, functional group equivalent 1630 g / mol), product name “X-22-164C” (viscosity 90 mm ² / s, functional group equivalent 2370 g / mol), Toray・ Product number “BX16-152B” manufactured by Dow Corning Silicone Co., Ltd. (viscosity 40cs / 25 ° C, methacryl group equivalent 1300 g / mol, specific gravity 0.97 at 25 ° C), product number “BY16-152” (viscosity 85cs / 25 ° C) , Methacryl group equivalent 2800 g / mol, specific gravity 0.97 at 25 ° C.), product number “BX2-152C” (viscosity 330 cs / 25 ° C., methacryl group equivalent 5100 g / mol, specific gravity 0.97 at 25 ° C.), etc. can be used.

（式中、Ｒ³は、メチル基又はブチル基であり、ｑは繰り返し単位数である）で表されるシリコーンオイル及び下記式(V)：

で表されるシリコーンオイルが挙げられる。該片末端反応性シリコーンオイル類としては、市販品を利用することができ、例えば、信越化学工業(株)製の品名「Ｘ-２４-８２０１」（粘度25mm²/s、官能基当量2100g/mol）、品名「Ｘ-２２-１７４ＤＸ」（粘度60mm²/s、官能基当量4600g/mol）、品名「Ｘ-２２-２４２６」（粘度180mm²/s、官能基当量12000g/mol）、東レ・ダウコーニング・シリコーン(株)製の品番「ＢＸ１６-１２２Ａ」（粘度5cs/25℃、屈折率1.417、25℃での比重0.92）等を用いることができる。 Examples of the one-terminal reactive silicone oil include the following formula (IV):

(Wherein R ³ is a methyl group or a butyl group, q is the number of repeating units) and the following formula (V):

The silicone oil represented by these is mentioned. Commercially available products can be used as the one-terminal reactive silicone oils, for example, “X-24-8201” (viscosity 25 mm ² / s, functional group equivalent 2100 g / s) manufactured by Shin-Etsu Chemical Co., Ltd. mol), product name “X-22-174DX” (viscosity 60 mm ² / s, functional group equivalent 4600 g / mol), product name “X-22-2426” (viscosity 180 mm ² / s, functional group equivalent 12000 g / mol), Toray A product number “BX16-122A” manufactured by Dow Corning Silicone Co., Ltd. (viscosity 5cs / 25 ° C., refractive index 1.417, specific gravity 0.92 at 25 ° C.) or the like can be used.

Further, the (meth) acryloxyalkylsilanes include 3-methacryloxypropyldichloromethylsilane [CH ₂ ═C (CH ₃ ) COO (CH ₂ ) ₃ SiCl ₂ CH ₃ ], 3-acryloxypropyl dimethoxymethyl. silane _{[CH 2 = CHCOO (CH 2} ) 3 Si (OCH 3) 2 CH 3], 3- acryloxypropyltrimethoxysilane _{[CH 2 = CHCOO (CH 2} ) 3 Si (OCH 3) 3], 3- methacryl b propyl dimethoxy methyl silane _{[CH 2 = C (CH 3} ) COO (CH 2) 3 Si (OCH 3) 2 CH 3], 3- methacryloxypropyl trimethoxysilane _{[CH 2 = C (CH 3} ) COO (CH _{2) 3 Si (OCH 3)} 3], 3- methacryloxypropyl diethoxymethyl silane _{[CH 2 = C (CH 3} ) COO (CH 2) 3 Si (OC 2 H 5) 2 CH 3], 3- methacrylonitrile Shi propyltriethoxysilane _{[CH 2 = C (CH 3} ) COO (CH 2) 3 Si (OC 2 H 5) 3] , and the like. As the (meth) acryloxyalkylsilanes, commercially available products can be used. For example, product numbers “LS-2080”, “LS-2826”, “LS-2827” manufactured by Shin-Etsu Chemical Co., Ltd., “LS-3375”, “LS-3380”, “LS-4548”, “LS-5118”, and the like can be used.

  On the other hand, when at least one selected from the group consisting of a non-UV curable fluorine-containing resin and compound and a silicon-containing resin and compound is used for the second resin coating layer, the non-UV curable fluorine-containing resin and compound and silicon-containing As the resin and compound, those which are dispersed or dissolved in the coating solution are preferred. Here, as the non-ultraviolet curable fluorine-containing resin and / or compound, specifically, fluorine-containing (meth) acrylate resin and / or compound, fluorine-containing olefin resin and / or compound, fluorine-containing ether resin and And / or compounds, fluorine-containing ester resins and / or compounds, fluorine-containing epoxy resins and / or compounds, fluorine-containing urethane resins and / or compounds, and non-UV curable silicon-containing resins and / or compounds, Specific examples include silicon-containing (meth) acrylate resins and compounds having a plurality of siloxane bonds, silicone resins, alkoxysilanes, and polymers thereof. These non-ultraviolet curable fluorine-containing resins and compounds and silicon-containing resins and compounds may be used alone or in a combination of two or more.

  The fluorine content of the non-ultraviolet curable fluorine-containing resin and / or compound is preferably in the range of 2 to 80% by mass, and more preferably in the range of 2 to 70% by mass. When the fluorine content of the non-ultraviolet curable fluorine-containing resin and / or compound is less than 2% by mass, the effect of fluorine is insufficient, and when it exceeds 80% by mass, compatibility and dispersibility are problems. The silicon content of the non-ultraviolet curable silicon-containing resin and / or compound is preferably in the range of 2 to 70% by mass, and more preferably in the range of 2 to 50% by mass. If the silicon content of the non-ultraviolet curable silicon-containing resin and / or compound is less than 2% by mass, the silicon content will be low and the intended performance may not be achieved. Is unsuitable because it may decrease or dispersibility may decrease.

（式中、Ｘは、炭素数１〜２０のアルキレン基、パーフルオロアルキレン基又は部分フッ素化アルキレン基で、直鎖状及び分岐状のいずれでもよく、更には、これらアルキレン基、パーフルオロアルキレン基及び部分フッ素化アルキレン基中の主鎖又は側鎖中に酸素原子が介在したものであってもよく；Ｒ⁴は、水素、メチル基、塩素、フッ素又はシアノ基である）で表される化合物が好ましい。ここで、第２樹脂被覆層の耐久性を向上させる観点から、式(VI)中のＸが炭素数４以上のアルキレン基、パーフルオロアルキレン基又は部分フッ素化アルキレン基であるのが好ましく、炭素数６以上のアルキレン基、パーフルオロアルキレン基又は部分フッ素化アルキレン基であるのが更に好ましく、−(ＣＨ₂)₂−(ＣＦ₂)₇−であるのが特に好ましい。 As the non-ultraviolet curable fluorine-containing (meth) acrylate resin, perfluoroalkyl ester and partially fluorinated alkyl ester of (meth) acrylic acid, and perfluoroalkyl group or partially fluorinated alkyl group has an organic linking group. In addition to homopolymers of fluorine-containing (meth) acrylates such as (meth) acrylic acid ester and the like, the fluorine-containing (meth) acrylate and methyl, ethyl, butyl, octyl, dodecyl of (meth) acrylic acid And alkyl esters such as hydroxyethyl and hydroxybutyl; and copolymers with fluorine-free (meth) acrylates such as glycidyl esters. The copolymer may further be copolymerized with a small amount of polysiloxane group-containing (meth) acrylate. Here, the carbon number of the perfluoroalkyl group or the partially fluorinated alkyl group in the fluorine-containing (meth) acrylate is preferably in the range of 1-20. The fluorine-containing (meth) acrylate is represented by the following formula (VI):

(In the formula, X is an alkylene group having 1 to 20 carbon atoms, a perfluoroalkylene group or a partially fluorinated alkylene group, which may be linear or branched, and further, these alkylene groups and perfluoroalkylene groups. And a compound in which an oxygen atom may be present in the main chain or side chain in the partially fluorinated alkylene group; R ⁴ is hydrogen, methyl group, chlorine, fluorine or cyano group) Is preferred. Here, from the viewpoint of improving the durability of the second resin coating layer, X in the formula (VI) is preferably an alkylene group having 4 or more carbon atoms, a perfluoroalkylene group, or a partially fluorinated alkylene group. It is more preferably an alkylene group of 6 or more, a perfluoroalkylene group or a partially fluorinated alkylene group, and particularly preferably — (CH ₂ ) ₂ — (CF ₂ ) ₇ —.

  The non-ultraviolet curable fluorine-containing (meth) acrylate-based resin may have a functional group capable of crosslinking reaction in the molecule, and the functional group capable of crosslinking reaction includes a hydroxyl group, a thiol group, and a carboxyl group. , Amino group, isocyanate group, aziridinyl group, glycidyl group, alkoxysilyl group, silanol group, cyclocarbonate group, acid anhydride group, vinyl group, enol ether group, thioether group, active ester group, acetoacetate group, metal salt, Examples include metal oxides and those obtained by blocking these functional groups with various blocking agents. As the compound that reacts with the functional group capable of crosslinking reaction, a reactive polyfunctional compound having two or more reactive functional groups in the molecule can be used, and the reactive functional group includes the above-described crosslinking reaction. The same functional groups as possible functional groups can be mentioned. As said reactive polyfunctional compound, an organic epoxy compound and an organic polyisocyanate compound are preferable from a viewpoint of industrial usefulness.

  Examples of the organic epoxy compound include compounds having two or more glycidyl groups, and specifically include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, glycerol polyglycidyl ether, diglycerol polyglycidyl ether, sorbitol polyglycidyl. Ether, polyethylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin polyglycidyl ether, diglycerin polyglycidyl ether, tri Methylolpropane polyglycidyl ether, spiroglycol diglycidyl ether, various Carboxymethyl resins.

  Specific examples of the organic polyisocyanate compound include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2, 4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, 3,3'-dimethyl-4,4'-biphenylene diisocyanate, 3,3'-dimethoxy-4,4'-phenylene diisocyanate, 3,3'-dichloro -4,4'-biphenylene diisocyanate, 1,5-naphthalene diisocyanate, 1,5-tetrahydronaphthalene diisocyanate, tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, dodecamethylene diisocyanate, trimethylhexamethylene diisocyanate 1,3-cyclohexylene diisocyanate, 1,4-cyclohexylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, hydrogenated xylylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 3, , 3′-dimethyl-4,4′-dicyclohexylmethane diisocyanate and the like, dimers and trimers thereof, and isocyanate groups of these compounds are converted to phenols, oximes, alcohols, active methylenes, mercaptans, acids And polyisocyanates partially blocked with amides, imides, amines, imidazoles, ureas, carbamates, imines or sulfites.

  Specific examples of the non-ultraviolet curable fluorine-containing olefin resin include polyvinylidene fluoride, polytetrafluoroethylene, vinylidene fluoride-tetrafluoroethylene copolymer, ethylene-tetrafluoroethylene copolymer, and vinylidene fluoride. -Tetrafluoroethylene-hexafluoropropylene terpolymer, tetrafluoroethylene-hexafluoropropylene copolymer, vinylidene fluoride-hexafluoropropylene copolymer, polyvinyl fluoride, polyvinyl fluoride ether, fluoride vinyl ether-tetrafluoro An ethylene copolymer etc. are mentioned. The fluorine-containing polyolefin resin is obtained by polymerizing or copolymerizing fluorine-containing olefin monomers such as vinyl fluoride, vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, and vinyl fluoride ether.

  As the non-ultraviolet curable silicon-containing (meth) acrylate resin, in addition to a homopolymer of a silicon-containing (meth) acrylate such as a polysiloxane group-containing (meth) acrylate, the silicon-containing (meth) acrylate and ( Examples thereof include alkyl esters of (meth) acrylic acid such as methyl, ethyl, butyl, octyl and dodecyl; hydroxyalkyl esters such as hydroxyethyl and hydroxybutyl; and copolymers with silicon-free (meth) acrylates such as glycidyl ester. It is done. The copolymer further has a (meth) acrylic acid perfluoroalkyl ester and partially fluorinated alkyl ester, and a perfluoroalkyl group or partially fluorinated alkyl group linked via an organic linking group (meth). A small amount of a fluorine-containing (meth) acrylate such as an acrylate ester may be copolymerized. The polysiloxane group-containing (meth) acrylate includes (meth) acrylic acid ester in which a (meth) acryloyl group is linked to one or both ends of the polysiloxane chain via a divalent linking group. Can be mentioned.

  The non-ultraviolet curable silicone resin is, for example, a polymer having a three-dimensional network structure obtained by hydrolyzing and polymerizing organochlorosilanes, and mainly includes trifunctional monomers such as methyltrichlorosilane and phenyltrichlorosilane. As a monomer, a bifunctional monomer such as dimethyldichlorosilane and diphenyldichlorosilane and a monofunctional monomer such as chlorosilane are optionally combined. A modified silicone resin obtained by alkyd modification, polyester modification, epoxy modification or phenol modification of the silicone resin can also be used. In addition, as the non-ultraviolet curable silicon-containing resin and / or compound, silicates that are alkoxysilanes (silicate esters) and polymers obtained by polymerizing them can also be used. Examples of these silicates include methyl silicate and ethyl silicate. , Propyl silicate, butyl silicate and the like. These non-ultraviolet curable silicon-containing resins and / or compounds may be used alone or in combination of two or more.

  When a resin and / or compound that can be polymerized by ultraviolet rays is blended in the coating liquid, a reactive diluent having a polymerizable double bond may be blended in the coating liquid as necessary. By blending a reactive diluent having a polymerizable double bond into the coating solution, the viscosity of the coating solution can be adjusted. As the reactive diluent, a monofunctional, bifunctional or polyfunctional polymerizable compound having a structure in which (meth) acrylic acid is bonded to a compound containing an amino acid or a hydroxyl group by an esterification reaction or an amidation reaction is used. be able to. The compounding amount of the reactive diluent is preferably in the range of 10 to 200 parts by mass with respect to a total of 100 parts by mass of the resin and compound polymerizable by the ultraviolet rays.

  When a resin and / or compound that can be polymerized by ultraviolet rays is blended in the coating solution, it is preferable to blend a photopolymerization initiator in the coating solution. As the photopolymerization initiator, known ones can be used. For example, 4-dimethylaminobenzoic acid, 4-dimethylaminobenzoic acid ester, 2,2-dimethoxy-2-phenylacetophenone, acetophenone diethyl ketal, Benzophenone derivatives such as alkoxyacetophenone, benzyldimethyl ketal, benzophenone and 3,3-dimethyl-4-methoxybenzophenone, 4,4-dimethoxybenzophenone, 4,4-diaminobenzophenone, alkyl benzoylbenzoate, bis (4-dialkylaminophenyl) ) Ketones, benzyl derivatives such as benzyl and benzylmethyl ketal, benzoin derivatives such as benzoin and benzoin isobutyl ether, benzoin isopropyl ether, 2-hydroxy-2-methylpropiophenone, 1-hydroxy Chlohexyl phenyl ketone, xanthone, thioxanthone and thioxanthone derivatives, fluorene, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis (2 , 4,6-Trimethylbenzoyl) -phenylphosphine oxide, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1,2-benzyl-2-dimethylamino-1- (morpholinophenyl) -Butanone-1 and the like. These photoinitiators may be used individually by 1 type, and may use 2 or more types together. The blending amount of the photopolymerization initiator is preferably in the range of 0.1 to 10 parts by mass with respect to 100 parts by mass in total of the resin and compound polymerizable by ultraviolet rays.

  When a photopolymerization initiator is blended in the coating solution, a tertiary amine photopolymerization accelerator such as triethylamine or triethanolamine, or a phosphine such as triphenylphosphine is used to accelerate the polymerization reaction by the photopolymerization initiator. A photopolymerization accelerator, a thioether photopolymerization accelerator such as thiodiglycol, and the like may be further added to the coating solution. The addition amount of these photopolymerization accelerators is preferably in the range of 0.01 to 10 parts by mass with respect to 100 parts by mass in total of the resin and compound polymerizable by ultraviolet rays.

  When an ultraviolet curable resin is not used for the first resin coating layer, the resin used for the conventional resin coating layer can be used as the resin for forming the first resin coating layer, and the resin is particularly limited. However, it is preferable to use, for example, alcohol-soluble copolymerized polyamide, water-soluble acrylic resin, water-soluble butyral resin, acrylic emulsion, urethane dispersion, rubber latex, and the like. On the other hand, when an ultraviolet curable resin is not used for the second resin coating layer, the resin used for the conventional resin coating layer can be used as the resin for forming the second resin coating layer, and is not particularly limited. For example, in addition to the above-mentioned non-UV curable fluorine-containing resin and silicon-containing resin, polyester resin, polyether resin, epoxy resin, amino resin, polyamide resin, acrylic resin, acrylic urethane resin, urethane resin It is preferable to use alkyd resin, phenol resin, melamine resin, urea resin, polyvinyl butyral resin and the like. The first resin coating layer and the second resin coating layer that do not contain an ultraviolet curable resin are applied by heating and drying the coating liquid containing the resin on the outer peripheral surface of the elastic layer or the first resin coating layer. It is formed.

  The thickness of the first resin coating layer is preferably in the range of 3 to 30 μm, and more preferably in the range of 5 to 20 μm. On the other hand, the thickness of the second resin coating layer is preferably in the range of 1 to 20 μm, and more preferably in the range of 3 to 10 μm. If the thickness of the second resin coating layer is less than 1 μm, local discharge tends to occur, and white streaks tend to occur in the image. If the thickness exceeds 20 μm, the resistance value increases remarkably and the development bias is sufficient. In some cases, image defects may occur.

The conductive roller of the present invention preferably has an electric resistance of 10 ³ to 10 ¹⁰ Ω, more preferably 10 ⁴ to 10 ⁸ Ω. For example, when the conductive roller is used as a developing roller, gradation control is difficult if the resistance value of the conductive roller is less than 10 ³ Ω, and bias leakage occurs if the photosensitive drum or the like is defective. On the other hand, if the resistance value of the conductive roller exceeds 10 ¹⁰ Ω, the developing bias causes a voltage drop due to the high resistance of the conductive roller itself when developing toner on a photosensitive drum, etc. A sufficient developing bias cannot be secured, and a sufficient image density cannot be obtained. The resistance value can be measured, for example, by pressing the outer peripheral surface of the conductive roller against a flat plate or cylindrical counter electrode with a predetermined pressure, applying a voltage of 100 V between the shaft and the counter electrode, Can be sought. Note that it is important to appropriately and uniformly control the resistance value of the conductive roller in order to keep the electric field strength for moving the toner properly and uniformly.

  The image forming apparatus of the present invention includes the above-described conductive roller in which the charging property with respect to the toner or the photosensitive drum is significantly improved as compared with the conventional one, and can form an excellent image stably. The image forming apparatus of the present invention is not particularly limited except that the conductive roller is used, and can be manufactured by a known method. Here, in the image forming apparatus of the present invention, the conductive roller is preferably used as one or more of a developing roller, a charging roller, a toner supply roller, a transfer roller, and a cleaning roller, and particularly used as a developing roller. preferable.

  The image forming apparatus of the present invention will be described in detail below with reference to the drawings. FIG. 2 is a partial cross-sectional view of an example of the image forming apparatus of the present invention. The image forming apparatus in the illustrated example supplies a photosensitive drum 6 that holds an electrostatic latent image, a charging roller 7 that is positioned near (upward in the drawing) of the photosensitive drum 6 and charges the photosensitive drum 6, and toner 8. A toner supply roller 9, a developing roller 10 disposed between the toner supply roller 9 and the photosensitive drum 6, a stratification blade 11 provided in the vicinity (upper part in the drawing) of the developing roller 10, and a photosensitive drum 6 is provided with a transfer roller 12 located in the vicinity of 6 (downward in the drawing) and a cleaning roller 13 disposed adjacent to the photosensitive drum 6. The image forming apparatus of the present invention can further include a known component (not shown) that is usually used in the image layer forming apparatus.

  In the illustrated image forming apparatus, the charging roller 7 is brought into contact with the photosensitive drum 6 and a voltage is applied between the photosensitive drum 6 and the charging roller 7 to charge the photosensitive drum 6 to a constant potential. Then, an electrostatic latent image is formed on the photosensitive drum 6 by an exposure machine (not shown). Next, the photosensitive drum 6, the toner supply roller 9, and the developing roller 10 rotate in the direction of the arrow in the figure, so that the toner 8 on the toner supply roller 9 is sent to the photosensitive drum 6 through the developing roller 10. It is done. The toner 8 on the developing roller 10 is adjusted to a uniform thin layer by the stratifying blade 11 and rotates while the developing roller 10 and the photosensitive drum 6 are in contact with each other, so that the toner 8 is transferred from the developing roller 10 to the photosensitive drum 6. It adheres to the electrostatic latent image and the latent image becomes visible. The toner 8 attached to the latent image is transferred to a recording medium such as paper by the transfer roller 12, and the toner 8 remaining on the photosensitive drum 6 after the transfer is removed by the cleaning roller 13. Here, in the image forming apparatus of the present invention, one or more of the charging roller 7, the toner supply roller 9, the developing roller 10, the transfer roller 12, and the cleaning roller 13 are provided with the above-described conductive roller having excellent toner chargeability. By using it, an excellent image can be stably formed over a long period of time.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.

Example 1
SANNICS FA952 [Sanyo Kasei Kogyo Co., Ltd. polyether polyol, OH value = 37] 100 parts by mass, SRX274C [Toray Dow Corning Silicone Co., Ltd. foam stabilizer] 1 part by mass, TOYOCAT NP [Tosoh Corporation amine catalyst] 2.8 parts by mass, 1.5 parts by mass of TOYOCAT EP [amine catalyst manufactured by Tosoh Corporation] and 59 parts by mass of Sunfoam IC-716 [Sanyo Chemical Co., Ltd. Tolylene Diisocyanate] were mechanically stirred and foamed.

  Next, a metal shaft with an outer diameter of 8.0 mm and a length of 240 mm is arranged from one side opening of a metal cylindrical mold having an inner diameter of 16 mm and a length of 250 mm, and the surface is fluorinated. Was injected from the foaming machine.

  Next, the mold in which the foamed polyurethane raw material was injected was heated in an oven at 80 ° C. for 20 minutes and then removed from the mold, and a roller body having an elastic layer made of urethane foam having an outer diameter of 16 mm and a foam part with an overall length of 230 mm Produced.

The coating liquid containing the first layer resin coating layer composition shown in Table 1 is applied to the outer peripheral surface of the roller body with a roll coater, and heated and dried at 100 ° C. for 1 hour in a hot air circulation type heating oven, and then shown in Table 1. Apply the coating solution containing the second resin coating layer with a roll coater, and irradiate ultraviolet rays at an irradiation intensity of 400 mW and an integrated light intensity of 1000 mJ / cm ² while rotating the roller using the UNICURE UVH-0252C device manufactured by Ushio Electric Co., Ltd. As a result, the coating liquid was instantly cured to form an elastic resin coating layer, and a developing roller having a resin coating layer on the outer peripheral surface of the roller body was obtained. The toner charge amount and toner transport amount of the obtained developing roller are evaluated by a known method, and the developing roller is incorporated in the image forming apparatus, and the image density, the presence of halftone spots, the presence of fogging, and the density difference between the leading and trailing edges are measured. Evaluated by a known method, and further adhered to the toner on the developing roller surface after printing 10,000 sheets, and incorporated into the developing roller image forming apparatus, and examined image density, presence of halftone spots, presence of fogging, and difference in front and rear end density. . These results are shown in Table 1.

(Example 2)
100 parts by mass of Nipol IR2200L (manufactured by Zeon Corporation) with Mooney viscosity ML _{1 + 4} (100 ° C.) of 70, 60 parts by mass of LIR-30 (manufactured by Kuraray) with an average molecular weight of 29,000, carbon black TB # 5500 (manufactured by Tokai Carbon Co., Ltd.) 28 A rubber composition was prepared by kneading 5 parts by mass, 5 parts by mass of zinc oxide, 1 part by mass of stearic acid, and 9 parts by mass of perhexa C-40 (manufactured by NOF Corporation) using a 55 L kneader. The rubber composition was extruded into a cylindrical shape using a crosshead type extruder manufactured by Mitsuba Manufacturing Co., Ltd., to a cored bar with an outer diameter of φ8 mm to which an adhesive had been attached, to obtain an unvulcanized rubber / cored bar integral molding. This was set in a cylindrical mold, vulcanized at 175 ° C. for 20 minutes under a pressure of 3.2 × 10 ⁶ Pa. The pressure of the split mold was released to obtain a rubber roller, and further vulcanized in an oven at 180 ° C. for 4 hours. The obtained roller was plunge-type polished to a diameter of 16 mm with a rotating grindstone to obtain a rubber roller. A developing roller was produced in the same manner as in Example 1 except that the resin coating layer was formed on the outer peripheral surface of the roller body using the coating liquid having the composition shown in Table 1. Table 1 shows the physical properties and performance of the obtained developing roller.

Example 3
50 parts by mass of carbon black TB # 5500 (manufactured by Tokai Carbon) with respect to 100 parts by mass of EPDM having an iodine value of 36 and a Mooney viscosity ML _{1 + 4} (100 ° C.) of 39, Nobelite A (manufactured by Nippon Flour Industries) as calcium carbonate 36 parts by weight, 60 parts by weight of Diana Process Oil PW90 (made by Idemitsu Kosan), 3 parts by weight of zinc white, 2 parts by weight of stearic acid, 1 part by weight of vulcanization accelerator 2-mercaptothiazole, 1.5 parts by weight of sulfur, foaming agent Neo Cerbon N 6 parts by mass of # 1000M (manufactured by Eiwa Kasei Kogyo) were kneaded using a 55 L kneader to prepare a foamed rubber composition. The foamed rubber composition was extruded into a cylindrical shape using a cross-head type extruder from Mitsuba Manufacturing Co., Ltd. to a cored bar having an outer diameter of φ8 mm to which an adhesive had been attached, to obtain an unvulcanized rubber / cored bar integrally molded product. This was set in a cylindrical mold, vulcanized and foamed at 175 ° C. for 20 minutes under a pressure of 3.2 × 10 ⁶ Pa. The pressure of the split mold was released to obtain a foamed rubber roller with a skin layer, and further vulcanized in an oven at 180 ° C. for 4 hours. The obtained roller was plunge-type polished to a diameter of φ16 mm with a rotating grindstone to obtain a foamed rubber roller. The resin coating layer was formed on the outer peripheral surface of the roller body using the coating liquid having the composition shown in Table 1, and the curing of the first resin coating layer was the same as the curing of the second resin coating layer of Example 1 with ultraviolet rays. A developing roller was produced in the same manner as in Example 1 except for the above. Table 1 shows the physical properties and performance of the obtained developing roller.

Example 4
After adding 1.6 parts by weight of conductive carbon and 0.15 parts by weight of dibutyltin dilaurate to 100 parts by weight of a trifunctional and 9,000 molecular weight polyether polyol obtained by adding propylene oxide to glycerin, sufficiently stirring and mixing, and then stirring for 20 minutes under reduced pressure This was defoamed and used as a polyol component. The hydroxyl value of the polyol component was 19 mgKOH / g. On the other hand, polypropylene glycol-modified polymeric MDI having an NCO content of 11% was degassed as an isocyanate component for 20 minutes while stirring under reduced pressure to obtain an isocyanate component. The polyol component and isocyanate component are mixed at a high speed of 3000 rpm with a two-component casting machine so that the ratio of the polyol component to the isocyanate component is 101.75 / 13.70 (isocyanate index: 103). Was poured into a cylindrical mold set with a core metal of φ8 mm, and heated and cured in a hot air circulation oven at 90 ° C. for 60 minutes. A urethane roller with a cored bar was taken out from the cylindrical mold to obtain a roller. A developing roller was produced in the same manner as in Example 3 except that the resin coating layer was formed on the outer peripheral surface of the roller body using the coating liquid having the composition shown in Table 1. Table 1 shows the physical properties and performance of the obtained developing roller.

(Example 5)
SANNICS FA952 [Sanyo Kasei Kogyo Co., Ltd. polyether polyol, OH value = 37] 100 parts by mass, SRX274C [Toray Dow Corning Silicone Co., Ltd. foam stabilizer] 1 part by mass, TOYOCAT NP [Tosoh Corporation amine catalyst] 2.8 parts by mass, 1.5 parts by mass of TOYOCAT EP [amine catalyst manufactured by Tosoh Corporation] and 59 parts by mass of Sunfoam IC-716 [Sanyo Chemical Co., Ltd. Tolylene Diisocyanate] were mechanically stirred and foamed.

  Next, a metal shaft with an outer diameter of 6.0 mm and a length of 240 mm is arranged from one side opening of a metal cylindrical mold having an inner diameter of 12 mm and a length of 250 mm, and the surface is fluorinated. Was injected from the foaming machine.

  Next, the mold in which the foamed polyurethane raw material was injected was heated in an oven at 80 ° C. for 20 minutes and then demolded, and a roller body having an elastic layer made of urethane foam having an outer diameter of 12 mm and a foam part having an overall length of 230 mm Produced.

The coating liquid containing the first layer resin coating layer composition shown in Table 1 is applied to the outer peripheral surface of the roller body with a roll coater, and heated and dried at 100 ° C. for 1 hour in a hot air circulation type heating oven, and then shown in Table 1. Apply the coating solution containing the second resin coating layer with a roll coater, and irradiate ultraviolet rays at an irradiation intensity of 400 mW and an integrated light intensity of 1000 mJ / cm ² while rotating the roller using the UNICURE UVH-0252C device manufactured by Ushio Electric Co., Ltd. As a result, the coating solution was instantly cured to form an elastic resin coating layer, and a charging roller having a resin coating layer on the outer peripheral surface of the roller body was obtained. The obtained charging roller is evaluated by a known method, and the charging roller is incorporated into an image forming apparatus, and the image density, the presence / absence of halftone spots, the presence / absence of fogging, and the leading / lower end density difference are evaluated by a known method. The toner adhesion on the surface of the charging roller after printing 10,000 sheets, and the charging roller image were incorporated into an image forming apparatus, and the image density, the presence or absence of halftone spots, the presence or absence of fogging, and the difference between the leading and trailing edge densities were examined. These results are shown in Table 1.

(Example 6)
100 parts by mass of Nipol IR2200L (manufactured by Zeon Corporation) with Mooney viscosity ML _{1 + 4} (100 ° C.) of 70, 60 parts by mass of LIR-30 (manufactured by Kuraray) with an average molecular weight of 29,000, carbon black TB # 5500 (manufactured by Tokai Carbon Co., Ltd.) 28 A rubber composition was prepared by kneading 5 parts by mass, 5 parts by mass of zinc oxide, 1 part by mass of stearic acid, and 9 parts by mass of perhexa C-40 (manufactured by NOF Corporation) using a 55 L kneader. The rubber composition was extruded into a cylindrical shape using a cross-head type extruder from Mitsuba Manufacturing Co., Ltd. to a cored bar with an outer diameter of φ6 mm to which an adhesive had been attached, to obtain an unvulcanized rubber / cored bar integral molding. This was set in a cylindrical mold, vulcanized at 175 ° C. for 20 minutes under a pressure of 3.2 × 10 ⁶ Pa. The pressure of the split mold was released to obtain a rubber roller, and further vulcanized in an oven at 180 ° C. for 4 hours. The obtained roller was plunge-type polished to a diameter of 12 mm with a rotating grindstone to obtain a rubber roller. A charging roller was produced in the same manner as in Example 5 except that the resin coating layer was formed on the outer peripheral surface of the roller body using the coating liquid having the formulation shown in Table 2. Table 2 shows the physical properties and performance of the obtained charging roller.

(Example 7)
50 parts by mass of carbon black TB # 5500 (manufactured by Tokai Carbon) with respect to 100 parts by mass of EPDM having an iodine value of 36 and a Mooney viscosity ML _{1 + 4} (100 ° C.) of 39, Nobelite A (manufactured by Nippon Flour Industries) as calcium carbonate 36 parts by weight, 60 parts by weight of Diana Process Oil PW90 (made by Idemitsu Kosan), 3 parts by weight of zinc white, 2 parts by weight of stearic acid, 1 part by weight of vulcanization accelerator 2-mercaptothiazole, 1.5 parts by weight of sulfur, foaming agent Neo Cerbon N 6 parts by mass of # 1000M (manufactured by Eiwa Kasei Kogyo) were kneaded using a 55 L kneader to prepare a foamed rubber composition. The foamed rubber composition was extruded into a cylindrical shape using a cross-head type extruder manufactured by Mitsuha Seisakusho to a cored bar with an outer diameter of φ6 mm to which an adhesive had been attached to obtain an unvulcanized rubber / cored bar integrally molded product. This was set in a cylindrical mold, vulcanized and foamed at 175 ° C. for 20 minutes under a pressure of 3.2 × 10 ⁶ Pa. The pressure of the split mold was released to obtain a foamed rubber roller with a skin layer, and further vulcanized in an oven at 180 ° C. for 4 hours. The obtained roller was plunge-type polished to a diameter of 12 mm with a rotating grindstone to obtain a foamed rubber roller. The resin coating layer was formed on the outer peripheral surface of the roller body using the coating liquid having the composition shown in Table 2, and the curing of the first resin coating layer was the same as the curing of the second resin coating layer of Example 5 with ultraviolet rays. A charging roller was produced in the same manner as in Example 5 except that the above was performed. Table 2 shows the physical properties and performance of the obtained charging roller.

(Example 8)
Liquid silicone LIM liquid # 2090 (made by Toray Dow Corning Silicone) is stirred and degassed, then injected into a cylindrical mold set with a core metal with an outer diameter of φ6 mm, and hot air is circulated at 120 ° C for 30 minutes It was heated and cured in an oven. A roller with a cored bar was taken out from the cylindrical mold and cured by heating in a hot air circulation oven at 200 ° C. for 4 hours to obtain a roller. A charging roller was manufactured in the same manner as in Example 7 except that the resin coating layer was formed on the outer peripheral surface of the roller body using the coating liquid having the formulation shown in Table 2. Table 2 shows the physical properties and performance of the obtained charging roller.

(Comparative Example 1)
A developing roller was produced in the same manner as in Example 1 except that the resin coating layer was formed using the coating liquid having the formulation shown in Table 2. Table 2 shows the physical properties and performance of the obtained developing roller.

(Comparative Example 2)
A charging roller was produced in the same manner as in Example 8 except that the resin coating layer was formed using the coating liquid having the composition shown in Table 2. Table 2 shows the physical properties and performance of the obtained charging roller.

Evaluation methods:
(1) Image evaluation Image forming device: Commercially available laser printer Cartridge color: Cyan (2) Surface roughness Surfcom 590A (manufactured by Tokyo Seimitsu)
(3) Resistance value
R8340A ULTRA HIGH RESISTANCE METER (manufactured by ADVANTEST)
Measurement conditions: 100V applied voltage between shaft and roller surface
Measured with a load of 500g on both ends of the roller

  As is apparent from Tables 1 and 2, the conductive roller of the example is excellent in chargeability with respect to the toner. Therefore, an image forming apparatus incorporating the conductive roller as a developing roller can provide a good image over a long period of time. Could be formed.

It is sectional drawing of an example of the electroconductive roller of this invention. 1 is a partial cross-sectional view of an example of an image forming apparatus of the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Conductive roller 2 Shaft 3 Elastic layer 4 1st resin coating layer 5 2nd resin coating layer 6 Photosensitive drum 7 Charging roller 8 Toner 9 Toner supply roller 10 Developing roller 11 Layering blade 12 Transfer roller 13 Cleaning roller

Claims (21)

A shaft, an elastic layer formed on the outer periphery of the shaft, a first resin coating layer having a volume resistivity of 10 ⁶ Ω · cm or less formed on the outer peripheral surface of the elastic layer, and the first resin coating layer A conductive roller provided with a second resin coating layer having a volume resistivity of 10 ¹⁰ Ω · cm or more formed on the outer peripheral surface;
At least one of the first resin coating layer and the second resin coating layer contains an ultraviolet curable resin.   The conductive roller according to claim 1, wherein the first resin coating layer includes a conductive agent, and the second resin coating layer does not include a conductive agent.   2. The conductive roller according to claim 1, wherein the second resin coating layer includes at least one selected from the group consisting of a fluorine-containing resin and a compound and a silicon-containing resin and a compound.   The conductive roller according to claim 3, wherein the second resin coating layer contains a fluorine-containing ultraviolet curable resin and / or a silicon-containing ultraviolet curable resin.   The said 2nd resin coating layer contains at least 1 sort (s) selected from the group which consists of a non-ultraviolet curable fluorine-containing resin and compound, a silicon-containing resin, and a compound, and an ultraviolet curable resin, It is characterized by the above-mentioned. The conductive roller described in 1.   The second resin coating layer is at least one selected from the group consisting of a non-ultraviolet curable fluorine-containing resin and compound, a silicon-containing resin and a compound, a fluorine-containing ultraviolet curable resin and / or a silicon-containing ultraviolet curable resin. The conductive roller according to claim 4 or 5, characterized by comprising:   The non-ultraviolet curable fluorine-containing resin and / or compound is at least one selected from the group consisting of fluorine-containing (meth) acrylate resins and compounds, and fluorine-containing olefin resins and compounds. The conductive roller according to claim 5 or 6.   7. The non-ultraviolet curable silicon-containing resin and / or compound is at least one selected from the group consisting of silicon-containing (meth) acrylate resins and compounds, and silicone resins. The conductive roller described in 1.   The first resin coating layer is a resin that can be polymerized with ultraviolet rays by irradiating with ultraviolet rays after applying a coating liquid containing a conductive agent and a resin and / or compound polymerizable with ultraviolet rays to the outer peripheral surface of the elastic layer. The conductive roller according to claim 2, wherein the compound is cured.   After the second resin coating layer is applied to the outer peripheral surface of the first resin coating layer with a resin and / or compound that can be polymerized by ultraviolet rays, the resin and / Alternatively, the conductive roller according to claim 1, wherein the compound is cured.   The conductive roller according to claim 9 or 10, wherein the resin and / or compound polymerizable by ultraviolet rays is a resin and / or compound having a carbon-carbon double bond polymerizable by ultraviolet rays.   The conductive roller according to claim 11, wherein the resin and / or compound having a carbon-carbon double bond polymerizable by ultraviolet rays is a (meth) acrylate monomer and / or oligomer.   The second resin coating layer containing at least one selected from the group consisting of the fluorine-containing resin and compound and the silicon-containing resin and compound is (1) a fluorine-containing resin and compound that can be polymerized by ultraviolet rays, and a silicon-containing resin and compound. A coating liquid containing at least one selected from the group consisting of: (2) non-ultraviolet curable fluorine-containing resins and compounds; and at least one selected from the group consisting of silicon-containing resins and compounds; And (3) a non-ultraviolet curable fluorine-containing resin and compound, and at least one selected from the group consisting of a silicon-containing resin and a compound, and ultraviolet rays. Polymerizable fluorine-containing resins and compounds and silicon-containing resins and compounds Or at least one of a resin and a compound that can be polymerized by the ultraviolet rays by irradiating with ultraviolet rays, and then applying at least one of a coating liquid containing at least one selected from the above to the first resin coating layer. The conductive roller according to claim 3, wherein   The resin and / or compound that is polymerizable by ultraviolet rays and does not contain fluorine and silicon are resins and / or compounds having a double bond between carbon atoms that can be polymerized by ultraviolet rays. Conductive roller.   The resin and / or compound having a carbon-carbon double bond polymerizable by ultraviolet rays and not containing fluorine and silicon is a (meth) acrylate monomer and / or oligomer containing no fluorine and silicon. The conductive roller according to claim 14.   The conductive roller according to claim 13, wherein the fluorine-containing resin and / or compound polymerizable by ultraviolet rays is a resin and / or compound having a double bond between carbon atoms polymerizable by ultraviolet rays.   The resin and / or compound having a carbon-carbon double bond polymerizable by ultraviolet rays and containing fluorine is a compound derived from fluoroolefins and / or fluoro (meth) acrylates. The conductive roller according to claim 16.   The conductive roller according to claim 13, wherein the silicon-containing resin and / or compound polymerizable by ultraviolet rays is a resin and / or compound having a carbon-carbon double bond polymerizable by ultraviolet rays.   Resins and / or compounds having a double bond between carbon atoms that can be polymerized by ultraviolet rays and containing silicon are reactive silicone oils at both ends, reactive silicone oils at one end, and (meth) acryloxyalkylsilanes. The conductive roller according to claim 18, wherein the conductive roller is at least one selected from the group consisting of:   The conductive roller according to claim 9, wherein the coating liquid contains a photopolymerization initiator.   An image forming apparatus comprising the conductive roller according to claim 1.

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