JP2005292418A - Semiconductive member for image formation - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a semiconductive member for electrophotographic image formation, such as a charging member or a transfer member, which prevents contamination of a photoreceptor, causes neither deterioration in conductivity nor image degradation, and has improved lubricity, imparted wear resistance and excellent durability, by suppressing adhesion of paper dust, toner, etc., in a contact charging means of an image forming apparatus and preventing bleeding from within the means or from within the means and from an outermost layer film. <P>SOLUTION: The semiconductive member for image formation is characterized in that a material constituting an outermost layer of a contact-charging means of an electrophotographic image forming apparatus contains at least a crosslinked fluorocarbon resin, an inorganic filler having a platy structure and conductive particles. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a material used for an electrophotographic image forming apparatus in a copying machine, a laser printer, a facsimile, a composite OA apparatus thereof, and the like, and particularly used for an image forming charging member capable of preventing contamination and improving durability. It relates to the outer layer material.

  2. Description of the Related Art Conventionally, in a copying machine or a printer, semiconductive rollers such as a charging roller and a transfer roller are provided so as to rotate in contact with a photoreceptor, and each has a function. For example, the charging roller is used as a charging roller charging member for a photosensitive member on which an electrostatic latent image is formed. The charging roller is pressed against and brought into contact with the surface of the photosensitive member. The charging roller rotates relative to each other to charge the surface of the photoreceptor. As described above, the charging roller, the transfer roller, and the like are in contact with the photoreceptor and rotate, and are required to have appropriate conductivity for charging.

  In recent years, copying machines, printers, and the like have been increasingly demanded for high speed, long life, high image quality, and energy saving. For example, in order to save energy, a low-temperature fixing method is adopted to lower the melting point of the toner, and in order to improve the image quality, the toner particle size is reduced by polymerization or made spherical. It is.

  However, lowering the melting point of the toner and making the particle size finer and spherical for energy saving and higher image quality are likely to cause toner adhesion to a semiconductive roller such as a charging roller or transfer roller, When toner adheres to or adheres to such a semiconductive roller, image quality deterioration becomes a problem. In other words, the increase in the number of sheets to pass increases the overall resistance of the semiconductive roller such as a charging roller due to toner adhesion, and causes a partial resistance change due to non-uniform adhesion of toner, resulting in deterioration of image quality. Will occur.

  In order to prevent such image quality deterioration, it is only necessary to prevent the toner from adhering to the surface of the semiconductive roller such as a charging roller. For example, the outermost layer is formed of a conventional hydrophilic resin such as N-methoxymethylated nylon. The roller used is not effective in preventing resistance fluctuation and toner adhesion to the roller surface under high temperature and high humidity.

  Conventionally, as a conductive roller used for a charging roller or the like, a roller having a structure in which a conductive elastic body layer is provided on a conductive metal core and a resistance adjustment layer is further provided on the conductive elastic body layer is known. (For example, refer patent documents 1-4).

  That is, the conductive roller having such a structure is generally made of an elastic material of synthetic rubber such as silicone rubber, ethylene propylene rubber, nitrile rubber, urethane rubber mixed with conductive particles.

  In the above-mentioned semiconductive roller, liquids such as various process oils and softeners are added to the elastic material to reduce the hardness. Therefore, the surface of the semiconductive roller is protected with various resins such as urethane and nylon. A layer was provided to prevent bleeding and photoconductor contamination.

  However, for example, if these semiconductive rollers are left for a long time under high temperature and high humidity, the resin component may be hydrolyzed and fixed to the latent image carrier, or the above rubber may be removed from pinholes in the coating film. These environmental resistance characteristics are not always satisfied, for example, the middle component oozes out and bleeds to contaminate the photoreceptor.

  More specifically, when a conductive roller having such a structure is used as a charging roller, an intermediate layer and an outermost layer must be provided in order to prevent image defects and contamination of the photoreceptor due to charging failure and the like. There is a problem, which results in a multi-layer structure and high costs. In addition, since the electrical characteristics of the conductive elastic layer are obtained by contact between the mixed conductive powders, there is a problem that uneven charging easily occurs due to non-uniformity of electrical characteristics.

  On the other hand, as a conductive roller that solves such problems, the surface of the conductive core bar has an elastic layer made of an electrically intermediate resistance material in which conductive particles are not dispersed. The thing of the structure which has the surface layer which consists of a non-adhesive substance whose non-adhesiveness is higher than a substance is known (for example, refer patent document 5, 6).

Here, as an electrical resistance substance, epichlorohydrin-ethylene oxide-allyl glycidyl ether terpolymer, epichlorohydrin-ethylene oxide binary copolymer alone or a mixture thereof epichlorohydrin rubber (1 × 10 ^{7) is used.} ~1 × ¹⁰ 10 Ω · cm) has been mentioned, non as the adhesive material, a fluorine-containing crosslinked copolymer obtained fluorine-containing copolymer was a component of fluoroolefin and hydroxyl group-containing vinyl ether is crosslinked with an isocyanate Polymers are mentioned. However, these fluororesin compounds alone are not sufficient in preventing the filming adhesion of paper dust and toner and preventing the photoreceptor from being contaminated by bleeding.

  Although it has been proposed to add silicone oil as an anti-adhesion agent for paper dust / toner, etc., it is effective for preventing the adhering of paper dust / toner etc., but the silicone oil has a reactive group. If not, the silicone oil itself will contaminate the photoreceptor. In the case of a silicone oil having a reactive group, it reacts within the coating film, and the contamination of the photoreceptor is reduced without causing bleeding itself. The effect of preventing the bleeding of the compound was low (see, for example, Patent Documents 7 to 10).

In addition to the above, a roller (for example, see Patent Document 11) in which the base material is urethane and is formed by curing a hydrophobic polyol (fluorine polyol) and isocyanate is provided with a fluororesin bleed prevention layer, and an isocyanate crosslinking agent A semiconductive roller (for example, see Patent Document 12) cured with a conductive roller (for example, see Patent Document 13) using a fluorine-crosslinked copolymer crosslinked with an isocyanate cross-linking agent as a non-adhesive substance. A semiconductive roller obtained by crosslinking a modified acrylate resin, a fluorine olefin resin, and a non- (fluorine modified) acrylate resin having an OH group with a compound (polyisocyanate compound) that reacts with an OH group (see, for example, Patent Document 14) Is further represented by Mg _(1-X) Al _X (OH) ₂ (CO ₃ ) _{(X / 2)} · mH ₂ O A charging member containing a lucite compound (see, for example, Patent Document 15) has been proposed.

  In addition, a charging member (see, for example, Patent Document 16) provided with a surface layer made of a resin mainly composed of a polymer compound of fluorine polyol and polyisocyanate is further provided with a film obtained by curing polyester polyol or acrylic polyol with isocyanate. Provided charging members and transfer members (see, for example, Patent Document 17) have been proposed.

However, it is used for the above-mentioned semiconductive elastic layer, and bleed from the semiconductive member used for the outermost layer as a conventional fluororesin compound to prevent paper powder / toner adhesion and to provide releasability with silicone oil. With materials and the like that prevent the above, it has not been sufficient to prevent bleeding to the surface of the semiconductive member and to prevent contamination of the photoreceptor.
Japanese Patent Laid-Open No. 1-142569 JP-A-4-311972 Japanese Patent Laid-Open No. 7-140760 Japanese Patent Publication No. 7-58403 JP-A-6-266206 JP-A-7-160155 Japanese Patent Publication No. 08-020794 JP 11-167273 A JP 2000-31003 A JP 2002-214880 A JP-A-8-208087 JP-A-9-226973 Japanese Patent Application Laid-Open No. 10-45953 JP-A-10-268613 JP 2000-310218 A JP-A-8-101563 JP-A-8-314233

  The present invention has been made in consideration of the above-described circumstances, and suppresses the adhesion of paper dust, toner, etc. to the outermost layer of the semiconductive elastic layer, and further prevents bleeding from the inside, thereby Image-forming semi-conductors that prevent body contamination, eliminate conductivity problems, eliminate image quality degradation problems, improve slipperiness and wear resistance, and improve the durability of semiconductive members. An object is to provide a conductive member.

  As a result of intensive studies to solve the above problems, the present invention includes an inorganic filler having at least a crosslinked fluororesin and a plate-like structure and conductive particles in the outermost layer in the semiconductive member for image formation. By preventing bleeding, photoconductor contamination is prevented, and the problem of image quality deterioration is solved without impairing conductivity, improving slipperiness and providing wear resistance, and durability of semiconductive members. The present inventors have found that an electrophotographic semiconductive member for image formation having improved properties can be obtained, and have led to the present invention.

  In order to solve the above problems, the invention according to claim 1 is an inorganic filler having at least a cross-linked fluororesin and a plate-like structure as a material constituting the outermost layer of a member used in an electrophotographic image forming apparatus. And an image-forming semiconductive member containing conductive particles.

  According to a second aspect of the present invention, the constituent material used for the outermost layer contains at least a crosslinked fluororesin, an inorganic filler having a plate-like structure, conductive particles, and a silicone compound. Features a member.

  According to a third aspect of the present invention, in the image forming half, the constituent material used for the outermost layer contains at least a crosslinked fluororesin, an inorganic filler having a plate-like structure, conductive particles, and a fluorinated silicone compound. Features a conductive member.

  According to a fourth aspect of the present invention, there is provided an image in which the constituent material used for the outermost layer contains at least a crosslinked fluororesin, an inorganic filler having a plate-like structure, and a silicone compound having a conductive particle and a reactive group. Features a forming semiconductive member.

  Further, in the invention described in claim 5, the constituent material used for the outermost layer contains at least a crosslinked fluororesin, an inorganic filler having a plate-like structure, and a fluorinated silicone compound having a conductive particle and a reactive group. The image forming semiconductive member is characterized.

  Further, in the invention described in claim 6, the constituent material used for the outermost layer further contains at least a polyol compound and an isocyanate compound, and the semiconductivity for image formation according to any one of claims 2 to 5. Features a member.

  The invention according to claim 7 is the semiconductive member according to any one of claims 2 to 5, wherein the constituent material used for the outermost layer further contains at least a fluorine polyol compound and an isocyanate compound. Features.

  The invention according to claim 8 is the image formation according to any one of claims 2 to 5, wherein the constituent material used for the outermost layer further contains at least a fluorine polyol compound, an acrylic resin, and an isocyanate compound. Features a semi-conductive member.

  The invention according to claim 9 is the image according to any one of claims 2 to 5, wherein the constituent material used for the outermost layer further contains at least a fluorine polyol compound, an acrylic polyol compound, and an isocyanate compound. Features a forming semiconductive member.

  According to the present invention, in the semiconductive member for image formation, the outermost layer contains at least a cross-linked fluororesin, an inorganic filler having a plate-like structure, and conductive particles, thereby preventing bleeding from the inside and photosensitivity. It is possible to prevent body contamination, eliminate the problem of image quality deterioration without impairing conductivity, improve slipperiness, impart wear resistance, and improve the durability of semiconductive members Become.

  Further, in the semiconductive member for image formation, the outermost layer contains at least a crosslinked fluororesin, an inorganic filler having a plate-like structure and conductive particles, and at least a silicone compound. In addition, it prevents contamination of the photoconductor by preventing bleed from inside, eliminating the problem of deterioration of conductive image quality, improving slipperiness, imparting wear resistance, and improving durability. It can be realized.

  Further, in the semiconductive member for image formation, the outermost layer contains at least a cross-linked fluororesin and an inorganic filler having a plate-like structure and conductive particles and a fluorinated silicone compound, and the outermost layer has a cross-linked fluororesin. A plate-like inorganic filler and a conductive compound and a silicone compound having a reactive group; and a cross-linked fluororesin and a plate-like inorganic filler and a conductive particle and a fluorine having a reactive group in the outermost layer. By containing at least a fluorinated silicone compound, the effect of suppressing the adhesion of paper dust, toner, etc. to the outermost layer can be improved, and further, bleeding from the inside can be prevented, photoconductor contamination can be prevented, and conductivity can be prevented. It is possible to solve the problem of image quality degradation without impairing the properties, improve the slipperiness, impart wear resistance, and improve the durability of the semiconductive member.

  Furthermore, in the semiconductive member for image formation according to any one of claims 2 to 5, the outermost layer further contains at least a polyol compound and an isocyanate compound, and further contains at least a fluorine polyol compound and an isocyanate compound. In the case of a roller structure, etc., by suppressing the adhesion of paper dust and toner to the surface, further improving the releasability, and preventing bleeding from the inner and outermost coating films. To improve the followability of the outermost layer coating film, eliminate the problem of image quality degradation without impairing the conductivity, improve the slipperiness, impart wear resistance, and improve the durability of the semiconductive member Can do.

  6. The semiconductive member for image formation according to claim 2, wherein the outermost layer further contains at least a fluorine polyol compound, an acrylic resin and an isocyanate compound, and the outermost layer further contains at least a fluorine polyol compound and an acrylic polyol compound. By containing it, the effect of suppressing the adhesion of paper dust, toner, etc. to the outermost layer in particular can be improved, the releasability is further improved, and further bleeding from the inner and outermost layer coating is prevented. As a result, photoconductor contamination can be prevented. Also, in the case of a roller structure etc., the followability of the outermost layer coating film is improved, the adhesion to the conductive member is further improved, the outermost layer coating film is not peeled off, the conductivity is not impaired, and the image quality deterioration problem is Elimination can be achieved, slipperiness improvement and abrasion resistance can be imparted, and durability of the semiconductive member can be improved.

Hereinafter, the present invention will be described in detail.
In the image-forming semiconductive member of the present invention, the outermost layer is composed of a crosslinked fluororesin, a resin layer containing at least an inorganic filler having a plate-like structure and conductive particles, and the outermost layer includes these In addition to these components, a silicone compound, further a fluorinated silicone compound, a silicone compound having a reactive group, and a fluorination having a reactive group for imparting releasability depending on each application or as required. In order to improve the silicone compound and the like, improve coating properties, impart releasability, and the like, it may further contain various polyol compounds and isocyanate compounds, fluorine polyol compounds and isocyanate compounds, acrylic resins, acrylic polyol compounds, and the like.

  In addition, various additives such as leveling agents, antioxidants, flame retardants, anti-settling agents, antifoaming agents, corrosion inhibitors, solvents for dilution, thickeners, thixotropic agents, structural viscosity agents, etc. You may do it.

  The cross-linked fluororesin used in the present invention is produced by performing a cross-linking treatment by irradiating a predetermined amount of radiation while maintaining a temperature slightly higher than its melting point in an oxygen-free inert gasification atmosphere. It is a cross-linked fluororesin excellent in various properties such as wear resistance, creep resistance, and radiation resistance. In particular, the powder-crosslinked fluororesin was obtained by a method based on a production method such as JP 2000-186155 A, JP 2000-186157 A, JP 2002-317055 A, or JP 2002-317056 A. A cross-linked fluororesin was used. In addition, the general manufacturing method of these bridge | crosslinking fluororesins is disclosed by Unexamined-Japanese-Patent No. 6-116423 and Unexamined-Japanese-Patent No. 7-118423, and other fluororesins (tetrafluoroethylene-hexafluoropropylene copolymer ( FEP) and tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer (PFA)) are disclosed in JP-A-11-49867.

  By irradiation with ionizing radiation of 1 kGy or more in the absence of oxygen at a temperature equal to or higher than the crystal melting point of the fluororesin, a modified fluororesin (cross-linked fluororesin) having high strength and excellent radiation resistance and heat resistance is obtained. be able to.

  The mechanism by which the crosslinking reaction occurs when irradiated with radiation at a temperature above the crystalline melting point of PTFE is as follows. First, molecular chains are broken and fluorine atoms are desorbed by irradiation with radiation. Since the temperature is higher than the melting point, the molecular chain can move freely to some extent, and an opportunity is given to react the molecular chain terminal radical generated by the molecular chain breakage and the alkyl radical generated by the elimination of the fluorine atom. This reaction causes crosslinking.

  For example, ionizing radiation is first irradiated to the starting fluororesin. The irradiation atmosphere is not particularly limited as long as the molecular chain is thereby cut off, whether in air, oxygen, vacuum, or inert gas. The radiation may be any of gamma rays, electron beams, X-rays, neutron rays, high-energy ions, etc., and it is sufficient that irradiation with a target amount is performed. The radiation dose is preferably about 0.1 kGy to 1000 kGy. If it is less than 0.1 kGy, the molecular chain scission effect is hardly reflected as the final change in the resin properties, and the resin properties hardly change even when irradiation is carried out in excess of 1000 kGy. The temperature of the atmosphere in this irradiation step is not particularly limited, and molecular chain scission can be achieved in any temperature range. However, the higher the temperature of the atmosphere at the time of irradiation, the more the molecular chain breakage is promoted. On the other hand, the movement of the molecular chain is limited at a low temperature near the liquid nitrogen temperature, and as a result, the cleavage is suppressed. Considering these and the preparation for handling, a temperature in the range from room temperature to the melting point of the fluororesin is preferable.

  Next, the fluororesin is cross-linked by irradiation with ionizing radiation at a temperature equal to or higher than the melting point in a vacuum or in an atmosphere in which oxidation by oxygen is suppressed by introducing an inert gas. The radiation dose at this time is preferably 1 kGy to 10 MGy. As in the case of molecular chain scission, cross-linking with an irradiation dose of less than 1 kGy cannot give a significant change in the resin properties after cross-linking, and the resin properties hardly change even when irradiation exceeds 10 MGy. The reason why irradiation is performed in an atmosphere in which oxidation by oxygen is suppressed is to prevent reaction active sites generated by radiation irradiation from preferentially reacting with oxygen and inhibiting the crosslinking reaction when oxygen is present. The reason for irradiating at an atmospheric temperature above the melting point is to activate the movement of the molecular chain by holding the fluororesin at a temperature above the melting point, and to increase the chance that the reaction active points generated in the molecular chain react. This is to form a crosslinked structure.

There is no restriction on the identity of the starting fluororesin, and the existing fluororesin can be used as it is. According to the present invention, the properties of the obtained cross-linked fluororesin can be widely changed by changing the amount of radiation required for molecular chain scission and the amount of radiation required for cross-linking while using the existing fluororesin. Is possible.
Examples of fluororesins include tetrafluoroethylene / hexafluoropropylene copolymer (FEP), tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer (PFA), and ethylene / tetrafluoroethylene copolymer (ETFE and PVdF). The selection of fluorine-based resins from the above, the mixing of two or more types of resins, the mixing of the same resins having different molecular weights, etc.

  In the present invention, by using a cross-linked fluororesin, the reason why the above-described effect is achieved is not clear, but the slipperiness and low friction properties, which are the characteristics resulting from the cross-linked structure of the cross-linked fluororesin, are improved. It is considered that the surface abrasion due to a cleaning blade or the like is suppressed and the durability of the image-forming semiconductive member is improved.

  The addition amount of the above-mentioned crosslinked fluororesin is preferably in the range of 0.1 to 30% by weight with respect to the outermost layer material, and is changed according to matching with the outermost layer material, discharge conditions, and the like. If the amount added exceeds 30% by weight, the film formability of the outermost layer, the strength of the coating film, etc. may be lowered. More preferably, it is 1 to 10% by weight.

  Next, the inorganic filler having a plate-like structure used in the present invention generally has a plate-like shape. Here, the plate shape referred to in the present invention refers to a structure in which two opposing surfaces (table surfaces) are particularly developed.

  As an inorganic filler having a plate-like structure used in the present invention, general-purpose talc, natural mica, synthetic mica, sericite, glass flake, natural hydrotalcite, synthetic talcite, magnesium hydroxide, plate-like are used as fillers. Examples thereof include, but are not limited to, aluminum hydroxide, plate-like iron oxide, plate-like calcium carbonate, graphite, and BN. Magnesium hydroxide, aluminum hydroxide, talcite and the like are preferable because they can impart a flame-retardant effect. The average particle size is preferably from 0.01 to 5 μm, more preferably from 0.1 to 1 μm. If it is less than 0.01 μm, the bleed prevention effect is suppressed, and if it exceeds 5 μm, there is a problem in image quality due to surface roughness.

  In the present invention, by using an inorganic filler having a plate-like structure, the reason why the above-mentioned effects are achieved is not clear, but by having a plate-like structure, the fillers overlap each other and exhibit a barrier function. Or it is thought that it suppresses that the low molecular substance from a semiconductive rubber layer is bleed | bleeded by adsorption | suction etc. of a bleed component between layers. Moreover, you may add fillers, such as clay, diatomaceous earth, and silica.

  The addition amount of the inorganic filler is preferably in the range of 0.1 to 30% by weight with respect to the outermost layer material, and is changed according to matching with the outermost layer material, discharge conditions, and the like. If the added amount is less than 0.1% by weight, the bleed suppressing effect is low, and if it exceeds 30% by weight, the film formability of the outermost layer, the coating strength may be lowered, and the like may occur. More preferably, it is 1 to 10% by weight.

As the conductive particles used in the present invention, inorganic or organic electron conductive particles having an average particle diameter of 0.01 to 5 μm are preferably used. Examples of the conductive particles include carbon black, graphite, carbon fluoride, various conductive metals or alloys such as aluminum, copper, nickel, stainless steel, tin oxide, indium oxide, titanium oxide, zinc oxide, tin oxide It is possible to use one or more fine powders such as various conductive metal oxides such as antimony oxide composite oxide and tin oxide-indium oxide composite oxide, and further, the surface of an insulating material subjected to conductive treatment. it can.
These conductive particles may be used alone or in combination of two or more.

Moreover, there is no restriction | limiting in particular as addition amount of these electroconductive particle, According to various situations, it is 0.01-40 weight% normally with respect to the total amount of outermost layer, Preferably it is added in the ratio of 5-20 weight%. The By adding conductive particles such as carbon black, the resistance can be controlled to a predetermined value. The surface layer preferably has a volume resistivity of 1 × 10 ³ to 1 × 10 ¹² Ω · cm, more preferably 1 × 10 ⁵ to 1 × 10 ¹⁰ Ω · cm.

  In the present invention, the use ratio of the crosslinked fluororesin and the inorganic filler having a plate-like structure and the conductive particles is not particularly limited, and is determined according to various situations, for example, target volume resistivity.

  In the present invention, the outermost layer of the semiconductive member is composed of the above-mentioned crosslinked fluororesin and a resin layer containing at least an inorganic filler having a plate-like structure and conductive particles, and constitutes the outermost layer used in the present invention. As the resin to be used, any of a thermoplastic resin and a thermosetting resin can be used.

  Examples of the thermoplastic resin include thermoplastic acrylic resins, thermoplastic urethane resins, and thermoplastic fluororesins. Examples of the thermosetting resin include polyester resins, amino resins, epoxy resins, thermosetting polyurethane resins, thermosetting acrylic resins, and respective fluorine-modified resins.

  In these, as this resin, what consists of a polyol compound and an isocyanate compound which make a coating film property favorable is preferable, for example. For example, examples of the polyol compound include polyester polyol, polyether polyol, polycarbonate polyol, acrylic polyol, fluorine polyol, and copolymerized polyols thereof.

  Further, for example, as polyester polyols, polyester polyols and polyesters obtained by condensation reaction of dibasic acids or reactive acid derivatives such as esters, acid halides, and acid anhydrides with glycols or amino alcohols alone or in mixtures. Amide polyols are mentioned.

Examples of the polycarbonate polyol include those obtained by a dealcoholization reaction between a polyhydric alcohol and ethylene carbonate, dimethyl carbonate, diethyl carbonate, diphenyl carbonate or the like.
Examples of the polyether polyol include polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol and the like obtained by ring-opening polymerization of ethylene oxide, propylene oxide, tetrahydrofuran and the like, and copolymers thereof.

  Further, the fluoropolyol is a fluororesin having one or more groups (hydroxyl groups) that react with isocyanate. For example, a hydroxyl-containing fluororesin such as a tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, a hydroxyl-modified resin of tetrafluoroethylene-hexafluoropropylene-perfluoroalkyl vinyl ether copolymer, and the like can be given. Specifically, a FEVE (fluoroethylene unit and vinyl ether unit) alternating copolymer having a hydroxyl group can be mentioned.

  The acrylic polyol is an acrylic resin such as a copolymer of an acrylic monomer having a hydroxyl group and an acrylic ester. The hydroxyl groups are randomly arranged in the main chain of the acrylic resin. The hydroxyl group content ratio can be controlled by various copolymerization ratios. For example, AA / HPA / MMA / BMA / BA, AA / HPMA / MMA / BMA / BA (AA is acrylic acid, HPA is hydroxypropyl acrylate, HPMA is hydroxypropyl methacrylate, MMA is methyl methacrylate, BMA is butyl methacrylate, BA refers to butyl acrylate).

  Furthermore, examples of these copolymer polyols include polyester polycarbonate polyols, polyester polyether polyols, and the like using the above-described polyester polyols, polycarbonate polyols, and polyether polyols as copolymerization components.

  The isocyanate compound added as a crosslinking agent is a compound having two or more isocyanate groups in the molecule, and the same isocyanate as that generally used as a raw material for producing polyurethane can be used.

  Specifically, tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), naphthalene diisocyanate (NDI), tolidine diisocyanate (TODI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), phenylene diisocyanate, xylylene diisocyanate ( XDI), tetramethylxylylene diisocyanate (TMXDI), cyclohexane diisocyanate, lysine ester triisocyanate, undecane triisocyanate, hexamethylene triisocyanate, triphenylmethane triisocyanate, and polymers, derivatives, modified products, hydrogenated products of these isocyanate compounds Examples include the body.

  Of these, aliphatic or alicyclic isocyanates such as hexamethylene diisocyanate and isophorone diisocyanate, and polymers, derivatives and modified products thereof are particularly preferred from the viewpoint of ozone resistance and heat resistance.

  Examples of the auxiliary agent used in the urethane forming reaction include chain extenders such as glycols, hexanetriol, trimethylolpropane, amines, and crosslinking agents. The NCO / OH molar ratio between the polyol and the isocyanate compound is preferably 1.0 / 1.0 to 1.8 / 1.0.

  In addition, an uncrosslinked fluororesin that imparts releasability can also be contained. Examples of the fluororesin include polytetrafluoroethylene, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene-hexafluoropropylene-perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene-ethylene copolymer, polychloroethylene. Examples thereof include trifluoroethylene, chlorotrifluoroethylene-ethylene copolymer, tetrafluoroethylene-vinylidene fluoride copolymer, polyvinylidene fluoride, and polyvinyl fluoride.

  Reacting a hydroxyl group-containing fluororesin such as a tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer or a hydroxyl-modified resin of tetrafluoroethylene-hexafluoropropylene-perfluoroalkyl vinyl ether copolymer with an isocyanate compound as a fluoropolyol compound Gives a good coating film, which is preferable. These resins may be used alone or in combination of two or more.

  The reaction coating film of the above-mentioned fluorine polyol compound and isocyanate compound is to change the functional group of the side chain of the vinyl ether unit, for example, the type of alkyl group or alkylene group, to use a high molecular weight polyisocyanate compound as the isocyanate compound, etc. Thus, the elongation of the coating film and the friction coefficient can be arbitrarily adjusted. In particular, when the elongation and film hardness are adjusted, the flexibility of the outermost layer can be improved, whereby a member having excellent flexibility can be obtained. At that time, if the elongation is less than 50%, cracking may occur and the bleed prevention effect may be lost. Therefore, the elongation is preferably adjusted to 50% or more.

  When a reaction resin of these fluorine polyol compound and isocyanate compound is used, surface contamination of the charging member can be avoided. Specific examples include fluorine polyol compounds such as Campe (registered trademark) Freon HD (manufactured by Kansai Paint), Lumiflon (registered trademark) series (manufactured by Asahi Glass Co., Ltd.), Zaffle (registered trademark) series (manufactured by Daikin), hexa Examples thereof include an outermost coating film having a crosslinked structure obtained by reacting a polyol-added polyisocyanate compound such as a trimethylolpropane adduct of methylene diisocyanate and a trimethylolpropane adduct of tolylene diisocyanate and an amino resin such as a melamine resin.

  Moreover, in this invention, other resin can be added to the said resin as needed. Other resins include, for example, the acrylic resin, polyurethane resin, nylon resin, silicone resin, polyester resin, epoxy resin, cellulose, melamine resin, etc., but improved dispersibility, adhesion of the coating film to the conductive rubber part Acrylic resin is preferred from the viewpoint of improving the performance and electrostatic paper dust / toner antifouling property. These may be added alone or in combination as necessary. When using an acrylic resin here, the above-mentioned acrylic polyol may be used and the said isocyanate may be made to react as a polyol component.

  In the coating film, the releasability may be insufficient. Silicone compound, further fluorinated silicone compound, silicone compound having a reactive group for firmly fixing the releasable component by the coating film, reactive group It is preferable to add a fluorinated silicone compound or the like having the above, and by adding these compounds, it is possible to further improve the releasability against paper dust and toner adhesion.

  Examples of the silicone compound used in the present invention, further a fluorinated silicone compound, a silicone compound having a reactive group, and a fluorinated silicone compound having a reactive group are not particularly limited. For example, polyether-modified silicone oil, Higher fatty acid ester-modified silicone oils, methylstyryl-modified silicone oils, alkyl-modified silicone oils, and higher alkoxy-modified silicone oils are preferred. Polyether-modified silicone oils and higher fatty acid ester-modified silicone oils are particularly preferred from the viewpoints of good compatibility and high retention by fillers.

  Similarly, fluorinated silicone compounds include compounds generally referred to as fluorosilicone oils such as 3,3,3-trifluoropropylmethylsiloxane, 3,3,3-trifluoropropylmethylsiloxane-dimethylsiloxane copolymer, bis (Tridecafluorooctyl) tetramethylsiloxane, fluorosilicone grease, and the like are exemplified, but the invention is not limited to these. In addition, these also have the effect which contributes to the leveling of a coating-film solution, and it becomes the smoothness improvement of a coating film.

  The molecular weight of these silicone compounds and fluorinated silicone compounds is preferably in the range of 400-50000, particularly preferably in the range of 1000-20000. The blending ratio is preferably set in the range of 0.4 parts by weight or less, particularly preferably in the range of 0.01 to 0.2 parts by weight with respect to 100 parts by weight of the coating film component not containing the solvent. If it is 0 part by weight, a sufficient effect on the releasability cannot be exhibited, and if it exceeds 0.4 part by weight, it may cause contamination such as bleeding.

  In particular, a silicone compound having a reactive group and a fluorinated silicone compound having a reactive group are more preferable for the purpose of fixing a release component to the coating film because they are more effective in bleeding resistance.

  The silicone compound having a reactive group can appropriately select a curing reaction with an isocyanate cross-linking agent or a coating material, and can be incorporated in a large amount, which is effective for improving the releasability. Examples of the reactive group include an amino group, a hydroxyl group, a carboxyl group, an epoxy group, and an acrylic group.

  Specifically, carbinol-modified silicone oil, amino-modified silicone oil, carboxyl-modified silicone oil, mercapto-modified silicone oil, epoxy-modified silicone oil, methacryloxy-modified silicone oil, phenol-modified silicone oil and the like are preferable. Moreover, as a modified | denatured form of these reactive silicone compounds, a side chain type, a both terminal type, a single terminal type, and a side chain both terminal type are preferable.

  Similarly, examples of the fluorinated silicone compound having a reactive group include fluorinated silicone compounds such as vinyl end groups and silanol end groups. Specifically, vinyl-terminated trifluoropropylmethylsiloxane-dimethylsiloxane copolymer, silanol Examples include terminal polytrifluorotrifluoropropylmethylsiloxane. The fluorinated silicone compound having a reactive group can improve the releasability as well as the reactive silicone compound, and can further improve the effect of preventing the adhesion of dirt and bleeding by the fluorine group.

  These silicone compounds having a reactive group are compatible with the resin and are uniformly dispersed in the coating film, which also contributes to the leveling of the coating film solution and improves the smoothness of the coating film. In particular, a silicone compound having an amino group, a hydroxyl group, or a carboxyl group can be fixed to the outermost layer coating film by a curing reaction with an isocyanate compound. The silicone compound having an epoxy group reacts with the active hydrogen of the fluororesin and is immobilized. As a result, the releasability of the outermost layer is improved and the frictional force is reduced, and furthermore, they can prevent bleeding of low-molecular substances in the conductive rubber component, and can also provide a barrier effect, and more contamination of the photoreceptor, Can reduce paper dust and toner adhesion. Furthermore, a large amount of the silicone compound can be contained, and the releasability is further improved.

  As for the silicone compound which has the said reactive group, and the fluorinated silicone compound which has a reactive group, what was set to the range of the molecular weight of 400-50000 is preferable, Most preferably, it is the range of 1000-20000.

  The blending ratio of the silicone compound having a reactive group and the fluorinated silicone compound having a reactive group should be set in a range of 0.4 parts by weight or less with respect to 100 parts by weight of a coating film component not containing a solvent. Is particularly preferable, and the range is 0.01 to 0.2 parts by weight. If it is 0 part by weight, a sufficient effect on the releasability cannot be exhibited, and if it exceeds 0.4 part by weight, it may cause contamination such as bleeding. When these silicone compounds and the like are added to the coating material, high release properties can be imparted, which is useful.

  The thickness of the outermost layer is not particularly limited, but is usually 50 μm or less, preferably 1 to 30 μm, and if it exceeds 50 μm, it becomes hard and the flexibility of the outermost layer may be impaired. , Not very preferable.

  In addition, it is preferable to use an aprotic polar solvent as an organic solvent used when dissolving these compounds to form a coating film for forming the outermost layer, and in particular, butyl acetate, cyclohexanone, toluene, xylene, dimethyl. A solvent such as formamide can be added.

  In addition, the outermost layer forming method is not particularly limited, but a coating material containing each component forming the layer is prepared, and the coating liquid application method is not particularly limited, and is conventionally known. Examples include a dipping method, a spray coating method, and a roll coating method.

An appropriate resistance when the semiconductive member of the present invention is a charging roller is preferably a volume resistivity of 1 × 10 ² to 1 × 10 ¹² Ω · cm in order to obtain a good image. It is preferably 1 × 10 ⁵ to 1 × 10 ¹⁰ Ω · cm. Further, if the outermost layer produced in this way has irregularities, the toner is clogged and causes image defects. Therefore, the outermost layer is preferably as smooth as possible. The charging roller using the semiconductive member thus produced can stably obtain an image free from printing omission, unevenness, and fogging, and is excellent in environmental resistance against temperature and humidity.

  The band semiconductive member of the present invention is used in, for example, a contact charging system as a charging roller, and the shape is not particularly limited as long as it is in contact with an object to be charged. As other forms, various shapes such as a plate shape and a block shape are applicable.

  In the case of a charging roller, a metal or plastic shaft may be provided inside these rollers. In addition, the structure in the case where the semiconductive member of the present invention is a charging roller includes an elastic layer and at least one coating layer, and an elastic body is used as the elastic layer and a resin layer is used as the coating layer. . Illustrated is a charging roller comprising a shaft made of metal or plastic, an elastic layer formed on the outer periphery of the shaft, and an outermost layer formed of a resin added with a conductive agent formed on the surface of the elastic layer. be able to.

  Although it does not specifically limit as an elastic layer used in the semiconductive member of this invention, It can form with the rubber | gum, resin, and foam which were conventionally used as an elastic layer. Specifically, polyurethane, silicone rubber, butadiene rubber, isoprene rubber, chloroprene rubber, styrene-butadiene rubber, ethylene-propylene rubber, norbornene rubber, styrene-butadiene-styrene rubber, epichlorohydrin rubber, fluorine rubber, acrylic rubber, etc. The rubber composition used as the base rubber may be mentioned, and two or more of these rubber materials may be blended.

  A conductive agent such as an ionic conductive agent or an electronic conductive agent can be added to the elastic layer to impart predetermined conductivity. Examples of ionic conductive agents include tetraethylammonium, tetrabutylammonium, lauryltrimethylammonium, dodecyltrimethylammonium, stearyltrimethylammonium, octadecyltrimethylammonium, hexadecyltrimethylammonium, benzyltrimethylammonium, and modified aliphatic dimethylethylammonium. Such as perchlorate, chlorate, hydrochloride, bromate, iodate, borofluoride, sulfate, alkyl sulfate, carboxylate, sulfonate, PF6 salt, BF4 salt etc. Ammonium salt or perchlorate, chlorate, hydrochloride, bromate, iodate, borofluoride of alkali metal or alkaline earth metal such as lithium, sodium, calcium, magnesium Trifluoromethyl sulfate, sulfonate, PF6 @ salts, and the like BF4 salt.

  Furthermore, examples of the electronic conductive agent include various conductive metals or alloys such as carbon black, graphite, aluminum, copper, nickel, stainless steel, tin oxide, indium oxide, titanium oxide, zinc oxide, tin oxide-antimony oxide composite. One kind or two or more kinds of fine powders such as oxides, various conductive metal oxides such as tin oxide-indium oxide composite oxide, and the like obtained by subjecting the surface of an insulating material to a conductive treatment can be used.

Moreover, there is no restriction | limiting in particular as addition amount of these electrically conductive agents, According to various situations, it selects suitably. In the case of an ionic conductive agent, the amount is usually 0.01 to 5 parts by weight, preferably 0.05 to 2 parts by weight with respect to 100 parts by weight of rubber. Moreover, in the case of an electronic conductive agent, it is 0.5-50 weight part normally, Preferably it is 1-40 weight part. By these prescriptions, it is preferable to adjust the volume resistivity of the elastic layer to 1 × 10 ³ to 1 × 10 ¹⁰ Ω · cm, particularly 1 × 10 ⁴ to 1 × 10 ⁸ Ω · cm. In addition, rubber additives such as a filler, a crosslinking agent, and a foaming agent can be added to the conductive elastic layer as necessary.

  Further, as the charging device using the semiconductive member of the present invention, for example, the charging roller which is the charging member of the semiconductive member of the present invention is driven to rotate while being in contact with the photosensitive drum which is the charged body, A charging device configured to charge the photosensitive drum by applying a DC voltage or a voltage obtained by superimposing an AC voltage on the DC voltage between the photosensitive drum and the charging roller by the voltage applying means can be exemplified. . The charging device using the semiconductive member of the present invention is not limited to this, and the form of the member to be charged and the charging member, the voltage applying method by the voltage applying means, or the like may be appropriately changed.

  Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited to these.

First, a semiconductive member surface treatment solution having the following composition was prepared.
Polyvinylidene fluoride-tetrafluoroethylene-hexafluoropropylene terpolymer / acrylic resin (polymethylmethacrylate) mixed composition (Novafusso (registered trademark) PF250: manufactured by Dainippon Color Industries) 100 parts by weight Conductive particles: oxidation Titanium (MT-150A: manufactured by Teika Co., Ltd.) 4.9 parts by weight Plate-like inorganic filler: Synthetic hydrotalcite (DHT-4A (registered trademark): manufactured by Kyowa Chemical Industry) 0.14 parts by weight Cross-linked fluororesin : PTFE radiation crosslinked particles (uncrosslinked fluororesin TLP10F-1: manufactured by Mitsui DuPont Fluorochemical Co., Ltd.) 0.20 parts by weight Next, a 3 mm thick ternary epichlorohydrin rubber (GECO) elastic layer (GECO) elastic layer (8 Φ core metal) The film thickness after curing the adjustment liquid on a roller provided with a volume resistivity R: 2.5 × 10 ⁷ Ω · cm, Log R: 7.4) is 5 μm. The semiconductive member of Example 1 (roller resistance R ′: 1.1 × 10 ⁶ Ω, Log R ′: 6.0) was produced by spray coating.
This semiconductive member was mounted as a charging roller in the Ricoh imagio photoconductor toner kit M, and left in an environment of 60 ° C.-30% RH for 10 days. Thereafter, the Ricoh imageio photoconductor toner kit M was mounted on the Ricoh Imageo MF-1530, an image was output, and an evaluation test was performed to determine whether there was any abnormality in the OPC portion where the semiconductive member was in contact.

In Example 1, instead of the ternary epichlorohydrin rubber (GECO) elastic layer, an NBR elastic layer whose volume is adjusted with carbon (volume resistivity R: 4.0 × 10 ⁶ Ω · cm, Log R: 6.6) The semiconductive member of Example 2 (roller resistance R ′: 1.8 × 10 ⁵ Ω, Log R ′: 5.2) was produced in the same manner as in Example 1 except that The same evaluation test was conducted.

[Comparative Example 1]
A semiconductive member surface treatment solution having the following composition was prepared.
Polyvinylidene fluoride-tetrafluoroethylene-hexafluoropropylene terpolymer / acrylic resin mixed composition (Novafusso (registered trademark) PF250: manufactured by Dainippon Color Materials Co., Ltd.) 100 parts by weight Conductive particles: Titanium oxide (MT-150A 4.9 parts by weight Next, the film thickness after curing the above adjustment liquid on a roller provided with a 3 mm thick ternary epichlorohydrin rubber (GECO) elastic layer on an 8Φ cored bar. The semiconductive member of Comparative Example 1 was prepared by spray coating so that the thickness was 5 μm, and the same evaluation test as in Example 1 was performed.

[Comparative Example 2]
In Comparative Example 1, in place of the ternary epichlorohydrin rubber (GECO) elastic layer, the same as in Comparative Example 1 except that an NBR elastic layer having a resistance adjusted with carbon similar to that used in Example 2 was used. Thus, the semiconductive member of Comparative Example 2 was produced, and the same evaluation test as in Example 1 was performed.

[Comparative Example 3]
In Example 1, except that the surface layer is not provided, a semiconductive member of Comparative Example 3 in which only the ternary epichlorohydrin rubber (GECO) elastic layer is provided on the cored bar is prepared as in Example 1, The same evaluation test as in Example 1 was performed.

[Comparative Example 4]
In Example 2, a semiconductive member of Comparative Example 4 having only an NBR elastic layer whose resistance was adjusted with carbon on a cored bar was prepared, except that a surface layer was not provided. The same evaluation test as in Example 1 was performed.
Table 1 shows the evaluation test results of the semiconductive members obtained in Examples 1 and 2 and Comparative Examples 1, 2, 3, and 4. In Table 1, the use ratio is parts by weight.

表１の比較例３、４の結果よりＯＰＣ汚染物質が三元系エピクロルヒドリンゴム（ＧＥＣＯ）弾性層、ＮＢＲ弾性層に内在している事が判る。又、表１の実施例１、２の結果と、比較例１、２の結果の対比により、表層に含有される架橋フッ素樹脂及び板状構造を有する無機充填剤が、半導電性部材によるＯＰＣ汚染の問題が解消している事が判る。

From the results of Comparative Examples 3 and 4 in Table 1, it can be seen that the OPC contaminant is inherent in the ternary epichlorohydrin rubber (GECO) elastic layer and the NBR elastic layer. Further, by comparing the results of Examples 1 and 2 in Table 1 with the results of Comparative Examples 1 and 2, the cross-linked fluororesin contained in the surface layer and the inorganic filler having a plate-like structure are OPC by a semiconductive member. It can be seen that the problem of contamination has been solved.

A semiconductive member surface treatment solution having the following composition was prepared.
Polyvinylidene fluoride-tetrafluoroethylene-hexafluoropropylene terpolymer / acrylic resin mixed composition (Novafusso (registered trademark) PF250: manufactured by Dainippon Color Materials Co., Ltd.) 100 parts by weight Conductive particles: Titanium oxide (MT-150A) 4.9 parts by weight Plate-like inorganic filler: Synthetic hydrotalcite (DHT-4A (registered trademark): manufactured by Kyowa Chemical Industry Co., Ltd.) 0.14 parts by weight Crosslinked fluororesin: PTFE radiation crosslinked particles (Uncrosslinked fluororesin TLP10F-1: manufactured by Mitsui DuPont Fluorochemical Co., Ltd.) 0.20 parts by weight Silicone compound: Silicone oil (DMS-T11: manufactured by Chisso Corporation)
0.0032 parts by weight Next, spray the adjustment liquid on a roller provided with a 3 mm thick ternary epichlorohydrin rubber (GECO) elastic layer on an 8Φ core so that the film thickness after curing is 5 μm. The semiconductive member of Example 3 was produced by coating.
This semiconductive member is mounted on a Ricoh Imagio Neo 270 as a charging roller, and after taking 60,000 copies with a 5% chart (A4), the dirt on both ends of the charging roller and the central portion are peeled off with tape, The dirt density of each tape measured with a densitometer (X-Rite 508: manufactured by X-Rite Inc.) was taken as the dirt characteristic value of the charging roller.

[Comparative Example 5]
A semiconductive member of Comparative Example 5 was prepared in exactly the same manner as in Example 3 except that the composition of the surface treatment liquid was changed to the following composition, and the same antifouling property as in Example 3 was evaluated.
Polyvinylidene fluoride-tetrafluoroethylene-hexafluoropropylene terpolymer / acrylic resin mixed composition (Novafusso (registered trademark) PF250: manufactured by Dainippon Color Material Industries) 100 parts by weight Conductive particles: Titanium oxide (MT-150A) 4.9 parts by weight Lubricant: Fatty acid amide (Kawaslip VL: Kawaken Fine Chemical)
1.2 parts by weight

A semiconductive member of Example 4 was produced in the same manner as in Example 3 except that the composition of the surface treatment liquid was changed to the following composition, and the same anti-smudge property as in Example 3 was evaluated.
Polyvinylidene fluoride-tetrafluoroethylene-hexafluoropropylene terpolymer / acrylic resin mixture composition (Novafusso (registered trademark) PF250: manufactured by Dainippon Color Industries) 100 parts by weight Conductive particles: Titanium oxide (MT-150A) 4.9 parts by weight Plate-like inorganic filler: Synthetic hydrotalcite (DHT-4A (registered trademark): manufactured by Kyowa Chemical Industry Co., Ltd.) 0.14 parts by weight Crosslinked fluororesin: PTFE radiation crosslinked particles (Uncrosslinked fluororesin TLP10F-1: manufactured by Mitsui DuPont Fluorochemical Co., Ltd.) 0.20 parts by weight Silicone compound: fluorinated silicone compound (FMS-121: manufactured by Chisso Corporation) 0.0032 parts by weight

A semiconductive member of Example 5 was produced in the same manner as in Example 3 except that the composition of the surface treatment liquid was changed to the following composition, and the same antifouling property as in Example 3 was evaluated.
Polyvinylidene fluoride-tetrafluoroethylene-hexafluoropropylene terpolymer / acrylic resin mixture composition (Novafusso (registered trademark) PF250: manufactured by Dainippon Color Industries) 100 parts by weight Conductive particles: Titanium oxide (MT-150A) 4.9 parts by weight Plate-like inorganic filler: Synthetic hydrotalcite (DHT-4A (registered trademark): manufactured by Kyowa Chemical Industry Co., Ltd.) 0.14 parts by weight Crosslinked fluororesin: PTFE radiation crosslinked particles (Uncrosslinked fluororesin TLP10F-1: manufactured by Mitsui DuPont Fluorochemical Co., Ltd.) 0.20 parts by weight Silicone compound: Silanol-terminated silicone (DMS-S15: manufactured by Chisso Corporation) 0.0032 parts by weight

  The silicone compound of Example 5 was replaced with silanol-terminated polytrifluoropropylmethylsiloxane (FMS-9921: manufactured by Chisso Corp.), and the same weight part was added. A conductive member was prepared, and the same antifouling property as in Example 3 was evaluated.

  In Example 6, instead of 0.20 parts by weight of crosslinked fluororesin: PTFE radiation crosslinked particles (uncrosslinked fluororesin TLP10F-1: manufactured by Mitsui DuPont Fluorochemical Co., Ltd.), PTFE radiation crosslinked particles (uncrosslinked fluororesin MP1300: A semiconductive member of Example 7 was prepared in the same manner as in Example 5 except that the same part by weight of Mitsui DuPont Fluoro Chemical Co.) was added, and the same antifouling property as in Example 3 was evaluated. .

A semiconductive member of Example 8 was produced in the same manner as in Example 3 except that the composition of the surface treatment liquid was changed to the following composition, and the same antifouling property as in Example 3 was evaluated.
Polyester polyol (Yurak (registered trademark) C-230U: manufactured by Hirono Chemical)
100 parts by weight Polyisocyanate (Yurak (registered trademark) PU-614: manufactured by Hirono Chemical) 33 parts by weight Carbon (Ketjen Black (registered trademark) EC: manufactured by Lion Akzo)
2.8 parts by weight Plate-like structure inorganic filler: Synthetic hydrotalcite (DHT-4A (registered trademark): manufactured by Kyowa Chemical Industry Co., Ltd.) 4.4 parts by weight Cross-linked fluororesin: PTFE radiation cross-linked particles (uncrosslinked pre-fluorinated resin TLP10F -1: Mitsui DuPont Fluorochemical Co., Ltd.) 2.4 parts by weight Silicone compound: Silanol-terminated silicone DMS-S15: manufactured by Chisso Corporation 0.1 part by weight Toluene 50 parts by weight Xylene 50 parts by weight

A semiconductive member of Example 9 was produced in exactly the same manner as in Example 3 except that the composition of the surface treatment liquid was changed to the following composition, and the stain resistance characteristics were evaluated in the same manner as in Example 3.
Polyester polyol (Eurach (registered trademark) C-230U: manufactured by Hirono Chemical Co., Ltd.) 100 parts by weight Polyisocyanate (Eurac (registered trademark) PU-614: manufactured by Hirono Chemical Co., Ltd.) 33 parts by weight Carbon (Ketjen Black (registered trademark) EC: Lion Akzo) 2.8 parts by weight Plate-like structure inorganic filler: Synthetic hydrotalcite (DHT-4A (registered trademark): manufactured by Kyowa Chemical Industry Co., Ltd.) 4.4 parts by weight Cross-linked fluororesin: PTFE radiation cross-linked particles (fluorine before uncross-linking) Resin TLP10F-1: manufactured by Mitsui DuPont Fluorochemical Co., Ltd.) 2.4 parts by weight Silicone compound: Silanol-terminated polytrifluoropropylmethylsiloxane (FMS-9921: manufactured by Chisso Corporation) 0.1 part by weight Toluene 50 parts by weight Xylene 50 Parts by weight

A semiconductive member of Example 10 was produced in the same manner as in Example 3 except that the composition of the surface treatment liquid was changed to the following composition, and the same antifouling property as in Example 3 was evaluated.
Fluoropolyol (Lumiflon (registered trademark) LF-601C main agent: manufactured by Asahi Glass) 100 parts by weight Polyisocyanate (Lumiflon (TM) LF-601C curing agent: manufactured by Asahi Glass)
20 parts by weight carbon (Ketjen Black (registered trademark) EC: manufactured by Lion Akzo)
2.8 parts by weight Plate-like structure inorganic filler: Synthetic hydrotalcite (DHT-4A (registered trademark): manufactured by Kyowa Chemical Industry Co., Ltd.) 4.4 parts by weight Cross-linked fluororesin: PTFE radiation cross-linked particles (uncrosslinked pre-fluorinated resin TLP10F -1: Mitsui DuPont Fluoro Chemical Co., Ltd.) 2.4 parts by weight Silicone compound: Silanol-terminated silicone (DMS-S15: manufactured by Chisso Corporation) 0.1 part by weight Toluene 50 parts by weight Xylene 50 parts by weight

A semiconductive member of Example 11 was produced in the same manner as in Example 3 except that the composition of the surface treatment liquid was changed to the following composition, and the stain resistance characteristics were evaluated in the same manner as in Example 3.
Fluoropolyol (Lumiflon (registered trademark) LF-601C main agent: manufactured by Asahi Glass) 100 parts by weight Polyisocyanate (Miflon (registered trademark) LF-601C curing agent: manufactured by Asahi Glass)
20 parts by weight Carbon (Ketjen Black (trademark) EC: manufactured by Lion Akzo) 2.8 parts by weight Plate-like structure inorganic filler: Synthetic hydrotalcite (DHT-4A (registered trademark): manufactured by Kyowa Chemical Industry) 4.4 Weight parts Cross-linked fluororesin: PTFE radiation cross-linked particles (uncrosslinked fluororesin TLP10F-1: manufactured by Mitsui DuPont Fluorochemical Co., Ltd.) 2.4 parts by weight Silicone compound: Silanol-terminated polyfluoropropylmethylsiloxane (FMS-9921: manufactured by Chisso) 0.1 parts by weight Toluene 50 parts by weight Xylene 50 parts by weight

Table 2 shows the results of charging roller contamination evaluation after 60,000 copies of each roller obtained in Examples 3, 4, 5, 6, and 7 and Comparative Example 5.
Further, the semiconductive members (charging rollers) obtained in Examples 8, 9, 10, and 11 were examined for the influence of the combination of the surface treatment liquid main resin and the reactive silicone compound on the roller dirt. Table 2 shows the result of charging roller contamination evaluation after 60,000 copies of each of the rollers of Examples 7, 8, 9, and 10.
In addition, the usage-amount of the raw material in Table 2 is shown by a weight part.
The evaluation in Table 2 is shown below.
Roller dirt density average: Average dirt density at the center of the roller, 3 points on both ends Roller dirt density standard deviation: Roller dirt density, deviation of the dirt density at 3 points on the center of the roller

表２より実機に搭載した際の実施例３、４、５、６、７の帯電ローラの汚れ濃度は、全くシリコーン化合物を添加していない比較例５に比較し明らかに低いと言える。
また実施例８〜１１に使用されている表面処理液のメイン樹脂は何れもポリオール化合物及びイソシアネート化合物を有するものである。実施例３〜７と実施例８〜１１のローラ汚れ濃度は、全くシリコーン化合物を添加していない比較例５に比較し明らかに低いと言える。
また実施例８〜１１に使用されている表面処理液のメイン樹脂は何れもポリオール化合物及びイソシアネート化合物を有するものである。実施例３〜７と実施例８〜１１のローラ汚れ濃度を比較すると、実施例８〜１１の各ローラの汚れが実施例３〜７のそれより低い事は明白である。従って、少なくとも、反応性を有するシリコーン化合物を表面処理液に使用する場合、処理液中にポリオール化合物及びイソシアネート化合物を含有させる事でシリコーン化合物の効果をより引き出す事が出来ると言える。請求項６及び７の発明はこの結果に基づくものである。
さらに、実施例１１のローラ汚れ濃度が他のローラに汚れ濃度に比較し最も低く、他の実施例ローラ汚れ濃度との差は統計的に有意と言える。尚、実施例１１の表面処理液には反応基を有するフッ素化シリコーン化合物とフッ素ポリオール化合物及びイソシアネート化合物が含まれている。

From Table 2, it can be said that the dirt density of the charging rollers of Examples 3, 4, 5, 6, and 7 when mounted on an actual machine is clearly lower than that of Comparative Example 5 in which no silicone compound is added.
In addition, the main resin of the surface treatment liquid used in Examples 8 to 11 has a polyol compound and an isocyanate compound. It can be said that the roller dirt density of Examples 3 to 7 and Examples 8 to 11 is clearly lower than that of Comparative Example 5 in which no silicone compound is added.
In addition, the main resin of the surface treatment liquid used in Examples 8 to 11 has a polyol compound and an isocyanate compound. Comparing the roller dirt density of Examples 3-7 and Examples 8-11, it is clear that the dirt of each roller of Examples 8-11 is lower than that of Examples 3-7. Therefore, at least when a reactive silicone compound is used in the surface treatment liquid, it can be said that the effect of the silicone compound can be further extracted by including a polyol compound and an isocyanate compound in the treatment liquid. The inventions of claims 6 and 7 are based on this result.
Further, the roller dirt density of Example 11 is the lowest compared to the dirt density of the other rollers, and the difference from the other Examples of roller dirt density is statistically significant. The surface treatment liquid of Example 11 contains a fluorinated silicone compound having a reactive group, a fluorine polyol compound, and an isocyanate compound.

A semiconductive member surface treatment solution having the following composition was prepared.
Fluoropolyol (Lumiflon (registered trademark) LF-601C main agent: Asahi Glass)
90 parts by weight polyisocyanate (Lumiflon (trademark) LF-601C curing agent: manufactured by Asahi Glass)
18 parts by weight Acrylic resin (polymethyl methacrylate) 4 parts by weight Carbon (Ketjen Black (trademark) EC: manufactured by Lion Akzo) 2.8 parts by weight Plate-like inorganic filler: Synthetic hydrotalcite (DHT-4A (registered trademark) ): Kyowa Chemical Industry Co., Ltd.) 4.4 parts by weight Cross-linked fluororesin: PTFE radiation cross-linked particles (uncrosslinked fluororesin TLP10F-1: Mitsui DuPont Fluoro Chemical Co., Ltd.) 2.4 parts by weight Silicone compound: Silicone oil (DMS- T11: Chisso) 0.1 parts by weight Toluene 50 parts by weight Xylene 50 parts by weight Next, an NBR elastic layer having a resistance adjusted with carbon similar to that used in Example 2 having a thickness of 6 mm is provided on a 18 Φ cored bar. The semiconducting member of Example 12 was prepared by spray coating the adjusted liquid on the roller so that the film thickness after curing was 15 μm. .
This semiconductive member was mounted on a Ricoh Imagio Color 2800 as a secondary transfer roller, and the paper dust adhesion characteristics were evaluated.

The paper dust adhesion characteristics were measured by the following method.
Paper dust adhesion evaluation method i. Arbitrary documents are set on the Image Color 2800 document table.
ii. Place AR Color 100g (A3 version) in the paper feed tray and take 1000 copies.
iii. Evaluation of cleaning performance (Note 1)
iv. If the cleaning property is OK, the process returns to i, and i, ii, and iii are repeated again until the cleaning property becomes NG. In the case of cleaning ability NG, the total number of copies of AR Color (A3 version) that has been copied so far is counted to obtain paper dust adhesion characteristics.
* Note 1: Evaluation of cleaning performance Set A3 size chart with 1 or 2 solid band patterns on the platen.
2. Set A4 transfer paper horizontally on the A3 plate tray, and make 10 copies in a single color.
3. Next, make a single color copy and use it as a cleaning property evaluation sample.
4. The cleaning property is that the solid pattern corresponding part on the back of the evaluation sample in the above item 3 is not contaminated with toner: Cleaning property OK
Toner smudged: Cleanability NG
And evaluate.

A semiconductive member of Example 13 was prepared in exactly the same manner as in Example 12 except that the composition of the surface treatment liquid was changed to the following composition, and the paper dust adhesion characteristics as in Example 12 were evaluated.
Fluoropolyol (Lumiflon (registered trademark) LF-601C main agent: manufactured by Asahi Glass) 90 parts by weight Polyisocyanate (Lumiflon (TM) LF-601C curing agent: manufactured by Asahi Glass)
20 parts by weight Acrylic polyol (Hitaroid (registered trademark) 6500: manufactured by Hitachi Chemical Co., Ltd.) 10 parts by weight Carbon (Ketjen Black (registered trademark) EC: manufactured by Lion Akzo)
2.8 parts by weight Plate-like structure inorganic filler: Synthetic hydrotalcite (DHT-4A (registered trademark): manufactured by Kyowa Chemical Industry Co., Ltd.) 4.4 parts by weight Cross-linked fluororesin: PTFE radiation cross-linked particles (uncrosslinked pre-fluorinated resin TLP10F -1: Mitsui DuPont Fluoro Chemical Co., Ltd.) 2.4 parts by weight Silicone compound: Silicone oil (DMS-T11: manufactured by Chisso)
0.1 parts by weight Toluene 50 parts by weight Xylene 50 parts by weight

[Comparative Example 6]
A semiconductive member of Comparative Example 6 was prepared in exactly the same manner as in Example 12 except that the composition of the surface treatment liquid was changed to the following composition, and the paper dust adhesion characteristics as in Example 12 were evaluated.
Fluoropolyol (Lumiflon (registered trademark) LF-601C main agent: manufactured by Asahi Glass) 100 parts by weight Polyisocyanate (Lumiflon (trademark) LF-601C curing agent: manufactured by Asahi Glass)
20 parts by weight Fluororesin powder (MP102: manufactured by Mitsui DuPont Fluorochemical Co., Ltd.) 30 parts by weight Carbon (Ketjen Black (trademark) EC: manufactured by Lion Akzo) 2.8 parts by weight Silicone compound: Silicone oil (DMS-T11: Chisso) 0.1 parts by weight Toluene 50 parts by weight Xylene 50 parts by weight

Table 3 shows the evaluation results of the paper dust adhesion characteristics of the secondary transfer rollers obtained in Example 12, Example 13, and Comparative Example 6.
In addition, the usage-amount of the raw material in Table 3 is shown by a weight part.
Also, “good” of the paper dust adhesion characteristics in Table 3 indicates the case where no dirt is generated in the evaluation of 50K sheets.

表３より、表面処理液にアクリル成分を全く含まない比較例６の転写ローラに対し、実施例１２、実施例１３の転写ローラでは紙粉付着特性が大幅に改善されている事が判る。なお、この改善はすべり性向上に由来する事象も含まれていると推定される。

From Table 3, it can be seen that the paper dust adhesion characteristics are greatly improved in the transfer rollers of Example 12 and Example 13 compared to the transfer roller of Comparative Example 6 in which the surface treatment liquid does not contain any acrylic component. In addition, it is estimated that this improvement includes the phenomenon derived from the improvement of slipperiness.

Claims (9)

  The material constituting the outermost layer of a member used in an electrophotographic image forming apparatus contains at least a cross-linked fluororesin, an inorganic filler having a plate-like structure, and conductive particles. Element.   2. The semiconductive member for image formation according to claim 1, wherein the constituent material used for the outermost layer contains at least a crosslinked fluororesin, an inorganic filler having a plate-like structure, conductive particles, and a silicone compound. .   2. The semiconductive material for image formation according to claim 1, wherein the constituent material used for the outermost layer contains at least a crosslinked fluororesin, an inorganic filler having a plate-like structure, conductive particles, and a fluorinated silicone compound. Sexual member.   2. The image forming apparatus according to claim 1, wherein the constituent material used for the outermost layer contains at least a crosslinked fluororesin, an inorganic filler having a plate-like structure, and a silicone compound having a conductive particle and a reactive group. Semiconductive member for use.   The constituent material used for the outermost layer contains at least a crosslinked fluororesin, an inorganic filler having a plate-like structure, and a fluorinated silicone compound having a conductive group and a reactive group. Semiconductive member for image formation.   6. The semiconductive member for image formation according to claim 2, wherein the constituent material used for the outermost layer further contains at least a polyol compound and an isocyanate compound.   6. The image-forming semiconductive member according to claim 2, wherein the constituent material used for the outermost layer further contains at least a fluorine polyol compound and an isocyanate compound.   6. The image-forming semiconductive member according to claim 2, wherein the constituent material used for the outermost layer further contains at least a fluorine polyol compound, an acrylic resin, and an isocyanate compound.   6. The semiconductive member for image formation according to claim 2, wherein the constituent material used for the outermost layer further contains at least a fluorine polyol compound, an acrylic polyol compound, and an isocyanate compound. .