JP4762574B2 - Semiconductive member for image processing apparatus - Google Patents

Description

The present invention relates to members, parts, elements, and materials for use in electrophotographic image forming apparatuses in copying machines, laser printers, facsimiles, composite OA devices, and the like, and in particular, contamination prevention and durability improvement. The present invention relates to a semiconductive member for an image processing apparatus including an image forming capable of forming an image and a material used for an outermost layer of the member.
In particular, the present invention relates to an outermost layer material used for a semiconductive member for an image processing apparatus including image formation capable of preventing contamination, imparting flame retardancy, and improving durability.
Further, the present invention relates to an outermost layer material used for a semiconductive member for an image processing apparatus capable of highly preventing contamination and improving durability by using a conductive agent containing an ionic conductor together with an electronic conductor. The present invention also relates to an image forming apparatus equipped with such a semiconductive member.

  2. Description of the Related Art Conventionally, in electrophotographic image processing / image forming apparatuses such as copying machines and printers, members, parts, elements, and units that require appropriate electrical conductivity, such as roller-shaped, cylindrical, or cylindrical parts and elements. Is often used. For example, conventionally, in a copying machine and a printer, semiconductive rollers such as a charging roller and a transfer roller are provided so as to rotate in contact with the photoreceptor, and each has a unique 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, and even if used for a long time. , Toner powder, paper dust, other dust and other contaminants do not adhere to or cause contamination, and it is difficult to transfer these contaminants to other components, parts, elements, etc. It is necessary that the image does not produce a deteriorated image.

  In the following, regarding toner adhesion / contamination as a typical contaminant, copying machines, printers, and the like have recently increased demands 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, the lowering of the melting point of the toner and the reduction in the particle size and the spheroidization of the toner for energy saving and higher image quality cause toner adhesion to the roller-like semiconductive member such as a charging roller or a transfer roller. If toner adheres to or adheres to such a semiconductive member, 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 toner from adhering to the surface of a semiconductive member 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 roller-like conductive member used for a charging roller or the like, a member having a structure in which a conductive elastic body layer is provided on a conductive metal core and a resistance adjusting layer is further provided on the conductive elastic body layer is known. (For example, see Patent Documents 1 to 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. Therefore, as an improvement, there has been known one in which an ionic conductive agent is added to make the electrical characteristics uniform (see, for example, Patent Document 18), but the contamination resistance is not always satisfied.

  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 a conductive agent is not dispersed, and the substance is formed on the elastic layer. The thing of the structure which has the surface layer which consists of a non-adhesive substance with higher non-adhesion is known (for example, refer patent document 5, 6).

Here, as the electrical resistance substance, epichlorohydrin-ethylene oxide-allyl glycidyl ether terpolymer, epichlorohydrin-ethylene oxide binary copolymer alone or a mixture thereof of epichlorohydrin rubber (1 × 10 ^7). ~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 film dust adhesion of paper dust and toner and preventing photoreceptor contamination due to 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) but _{further, Mg (1-X) Al} X (OH) 2 (CO 3) (X / 2) · mH 2 O A charging member containing a hydrotalcite compound represented by (for example, see Patent Document 15) it has been proposed respectively.

  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.

  Further, in order to prevent combustion due to causes such as discharge breakdown of the outermost layer, it is necessary to impart flame retardancy to these members. However, when a flame retardant is added to the outermost layer in order to impart flame retardancy, there is a problem that the outermost layer oozes out and easily causes photoconductor contamination. As an improvement, attempts have been made to add tetrabromobisphenol A or a derivative thereof (see, for example, Patent Document 18). However, this improvement is not sufficient for releasability and prevention of bleeding of low molecular weight substances from rubber members.

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 JP 2001-72733 A

  The present invention has been made in consideration of the above-described circumstances, and suppresses paper dust, toner, etc. from adhering to the outermost layer of the semiconductive elastic layer, and further prevents bleeding from the outermost and inner parts. Prevents contamination of the photoconductor, suppresses electrical conductivity, suppresses environmental fluctuations, resolves image quality degradation problems, improves slipperiness, provides wear resistance, and improves durability of semiconductive materials The object is to provide a semiconductive member for image processing including image formation with improved properties, and particularly for image processing apparatus including image formation capable of preventing contamination, imparting flame retardancy, and improving durability. The purpose is to provide a semiconductive member and the outermost layer material used therefor, and furthermore, by using a conductive agent containing an ionic conductor together with an electronic conductor, a high degree of contamination prevention and durability improvement is possible. For image processing equipment And to provide a conductive member, and the outermost layer material for use therein.

As a result of intensive studies to solve the above problems, the present invention contains an inorganic filler and a conductive agent having at least a plate-like structure in the outermost layer in an image processing semiconductive member including image formation. In addition, by containing at least an electron conductive agent and an ionic conductive agent as the conductive agent, by preventing bleeding, the photosensitive member is prevented from being contaminated, and the problem of image quality deterioration is solved without impairing the conductivity. It has been found that a semiconductive member for image formation of an electrophotographic method can be obtained which has improved slipperiness, imparted abrasion resistance and improved durability of the semiconductive member,
In addition, by containing at least one inorganic filler having a plate-like structure and a conductive agent and at least one flame retardant in the outermost layer, it prevents bleed, thereby preventing photoreceptor contamination and without impairing conductivity. , Semi-conducting for electrophotographic image processing that improves the durability and safety of semi-conductive members by improving the slipperiness, imparting wear resistance and flame resistance, and solving the problem of image quality degradation Finding that the material is obtained,
Furthermore, the outermost layer contains at least an inorganic filler having a plate-like structure and a conductive agent, and at least an electron conductive agent and a polymer matrix-supporting ionic conductive agent are contained as the conductive agent, thereby preventing bleeding and photosensitivity. An electronic device that prevents body contamination, does not impair electrical conductivity, suppresses environmental fluctuations, eliminates image quality degradation problems, improves slipperiness, provides wear resistance, and improves durability of semiconductive members The inventors have found that a photographic-type semiconductive member for image processing can be obtained, and have reached the present invention.

Thus, although the above object is achieved by the present invention, the present invention can be divided into the following three groups for convenience of understanding.
The present invention in the first group and the present invention in the second group are reference inventions.
[First Group of the Invention]
(1) A semiconductive member used in an electrophotographic image forming apparatus, wherein the constituent material constituting the outermost layer contains at least an inorganic filler having a plate-like structure and a conductive agent, and the conductive agent Contains at least an electron conductive agent and an ionic conductive agent.

[Second Group of the Invention]
(2) A semiconductive member for use in an electrophotographic image forming apparatus, the constituent material constituting the outermost layer of which is an inorganic filler having at least a plate-like structure, a conductive agent, and at least one flame retardant A semiconductive member for an image processing apparatus, comprising:
(3) The semiconductive member for an image processing apparatus as described in (2) above, wherein the flame retardant is at least a phosphorus compound.
(4) The semiconductivity for an image processing apparatus as described in (2) or (3) above, wherein the flame retardant is at least a phosphorus compound and a halogen compound or a halogen-containing phosphorus compound. Sexual member.
(5) The semiconductivity for an image processing apparatus according to any one of (2) to (4), wherein the flame retardant contains at least a nitrogen-containing phosphorus compound. Sexual member.
(6) The ionic conductive agent is contained as the conductive agent, and the counter anion of the ionic conductive agent is PF6. Any one of the items (2) to (5), Semiconductive member for image processing apparatus.

[Third Group of the Invention]
(7) A semiconductive member used in an electrophotographic image forming apparatus, wherein the constituent material constituting the outermost layer contains at least an inorganic filler and a conductive agent having a plate-like structure, and the conductive agent Contains at least an electron conducting agent and a polymer matrix-supporting ion conducting agent.
(8) The semiconductive member for an image processing apparatus according to (7), wherein the polymer matrix of the polymer matrix-supporting ionic conductive agent is a crosslinked polymer.
(9) The semiconductive member for an image processing apparatus according to (7) or (8), wherein the polymer matrix of the polymer matrix-supporting ion conductive agent is a fluorine-based polymer.
(10) The cross-linkable polymer is formed by cross-linking polymerization of a cross-linkable polymerizable composition containing a monofunctional monomer and a polyfunctional monomer, and includes a hetero atom other than carbon. The semiconductive member for an image processing apparatus according to claim 8 or 9.

The present invention includes a semiconductive member for an image processing apparatus according to a preferred embodiment as described below, and these semiconductive members are mounted on the image forming apparatus by themselves or other members. In addition, it performs image processing such as image formation in cooperation with parts, units, and the like.
(11) The semiconductive member for an image processing apparatus according to any one of (1) to (10), wherein the conductive agent further contains at least a silicone compound.
(12) The semiconductive member for an image processing apparatus according to any one of (1) to (10), wherein the conductive agent further contains at least a fluorinated silicone compound. .
(13) The image processing apparatus half described in any one of (1) to (10), wherein the conductive agent further contains a silicone compound having at least a reactive group. Conductive member.
(14) The image processing apparatus according to any one of (1) to (10), wherein the conductive agent contains a fluorinated silicone compound having at least a reactive group. Semiconductive member.
(15) The constituent material constituting the outermost layer further contains at least a polyol compound and an isocyanate compound, and any one of the items (1) to (10), Semiconductive member for image processing apparatus.
(16) The constituent material constituting the outermost layer further contains at least a fluorine polyol compound and an isocyanate compound. Any one of the items (1) to (10), The semiconductive member for image processing apparatuses as described.
(17) Any one of (1) to (10) above, wherein the constituent material constituting the outermost layer further contains at least a fluorine polyol compound, an acrylic resin and an isocyanate compound. The semiconductive member for an image processing apparatus according to item 1.
(18) Any of the items (1) to (10), wherein the constituent material constituting the outermost layer further contains at least a fluorine polyol compound, an acrylic polyol compound and an isocyanate compound. A semiconductive member for an image processing apparatus according to claim 1.

  According to the present invention, as described in item (1) above, a semiconductive member used in an electrophotographic image processing apparatus, wherein the constituent material constituting the outermost layer has at least a plate-like structure. The inorganic filler and the conductive agent are contained, and the conductive agent contains at least an electron conductive agent and an ionic conductive agent, thereby preventing bleeding from the inner and outermost layers and preventing contamination of the photoreceptor. Can improve the followability of the outermost coating film, eliminate the problem of image quality deterioration without impairing the conductivity, improve the slipperiness, impart wear resistance, and improve the durability of the semiconductive member It becomes possible to make it.

  In addition, as described in the above item (2), an inorganic filler which is a semiconductive member used in an electrophotographic image forming apparatus and which has at least a plate-like structure as a constituent material constituting its outermost layer By containing a conductive agent and at least one flame retardant, bleeding from the outermost layer and the inside can be prevented, contamination of the photoreceptor can be prevented, and image quality deterioration can be achieved without impairing conductivity. It is possible to improve the durability and safety of the semiconductive member by improving the slipperiness, imparting wear resistance and imparting flame retardancy.

  Furthermore, as described in the above item (3), when a phosphorus compound is used as the flame retardant, a polyphosphoric acid film is formed on the outermost layer surface during combustion, thereby suppressing the generation of flammable gas or by latent heat of evaporation. Due to the action of lowering the combustion temperature, flame retardant is considered, and safety is improved.

  In addition, as described in the above item (4), by using a phosphorus compound and a halogen compound in combination, it is possible to make the phosphorus compound flame retardant by using a halogen compound alone or in comparison with a phosphorus compound alone. In addition to the mechanism, —OOH or —OH radical generated during combustion contributes to radical deactivation by halogen, particularly bromine, can cut off the combustion cycle, and can suppress the spread of fire. Further, it is considered that the halogen gas generated by the thermal decomposition of the halogen compound suppresses the combustible gas on the combustion surface and thus has a self-extinguishing property. Moreover, since it has a synergistic effect by using together, it can be made flame-retardant in a small amount.

  Furthermore, as described in the above item (5), when a nitrogen-containing phosphorus compound is used among the phosphorus compounds, the carbonization characteristic of the nitrogen-containing compound is imparted, and the outermost surface layer The shutdown of oxygen supply and generation of combustible gas from the inside can be suppressed, and further flame retardancy can be achieved.

  Further, as described in the above item (6), self-extinguishing properties can be imparted by using the counter anion PF6 of the ionic conductive agent in combination with the flame retardant as the conductive agent. The reason is unknown, but probably the deactivation of -OOH and -OH radicals due to the generation of -F radicals during the decomposition reaction of PF6, the shutdown of oxygen supply due to the formation of polyphosphoric acid surface film, and the generation of combustible gas from the inside It is thought to suppress. In addition, it is considered that the flame retardant works more effectively by the synergistic effect of the flame retardant.

  Furthermore, as described in the item (7), the inorganic filler has at least a plate-like structure as a constituent material constituting the outermost layer, which is a semiconductive member used in an electrophotographic image forming apparatus. And a conductive agent, and the conductive agent contains at least an electron conductive agent and a polymer matrix-carrying ion conductive agent, thereby preventing bleeding, preventing photoconductor contamination, and not impairing conductivity. In addition, it is possible to suppress environmental fluctuations, to solve the problem of image quality deterioration, to improve slipperiness and to provide wear resistance, and to improve the durability of the semiconductive member.

  In addition, as described in the above item (8), the polymer matrix of the ionic conductive agent supported on the polymer matrix of the constituent material used for the outermost layer is a cross-linked polymer, so that particularly from the inner and outermost layers. Prevents bleeding, prevents photoconductor contamination, improves the followability of the outermost coating layer, does not impair electrical conductivity, suppresses environmental fluctuations, eliminates the problem of conductive image quality degradation, improves slipperiness, and abrasion resistance It becomes possible to realize wear resistance and durability improvement.

  Further, as described in the above item (9), the polymer matrix of the ionic conductive agent supported on the polymer matrix of the constituent material used for the outermost layer is a fluoropolymer, so that the paper powder / toner is particularly formed on the outermost layer. It is possible to improve the effect of suppressing the adhesion, etc., the releasability is further improved, the bleeding from the inner and outermost layers is prevented, the photoreceptor contamination is prevented, and the followability of the outermost layer coating is improved. It is possible to improve and suppress the environmental fluctuation without impairing the conductivity, to solve the problem of deterioration of the conductive image quality, to improve the slipping property, to provide the wear resistance, to improve the durability and to improve the safety.

  Further, as described in the above item (10), the polymer matrix of the ionic conductive agent supporting the polymer matrix of the constituent material used for the outermost layer is a crosslinkable polymer, and the crosslinkable polymer is a monofunctional monomer. It is formed by cross-linking polymerization of a cross-linkable polymerizable composition containing a polyfunctional monomer, and by containing hetero atoms other than carbon, it prevents bleed from the inner and outermost layers, and causes contamination of the photoconductor. , Improving the followability of the outermost layer coating, without impairing conductivity, suppressing environmental fluctuations, eliminating the problem of degradation of conductive image quality, improving slipperiness, imparting wear resistance, and improving durability It can be realized.

  In addition, as described in the above item (11), by further containing at least a silicone compound, it is possible to suppress paper dust, toner, and the like from adhering to the outermost layer, and to prevent bleeding from the inner and outermost layers. By preventing the photoconductor contamination, improving the followability of the outermost layer coating, eliminating the problem of deterioration of the conductive image quality without impairing the conductivity, improving the slipperiness, imparting wear resistance, durability It is possible to improve the performance.

  Furthermore, as described in the above item (12), it further contains at least a fluorinated silicone compound, and also contains a silicone compound having a reactive group as described in the above item (13), By containing at least the fluorinated silicone compound having a reactive group as described in the item (14), the effect of suppressing the adhesion of paper powder, toner, etc. to the outermost layer can be improved. Furthermore, bleeding from the inner and outermost layers is prevented, contamination of the photoreceptor is prevented, followability of the outermost layer coating is improved, and the problem of image quality deterioration is solved without impairing electrical conductivity, and slipperiness is improved. Abrasion resistance can be imparted and the durability of the semiconductive member can be improved.

  Furthermore, as described in the item (15), the outermost layer further contains at least a polyol compound and an isocyanate compound, and as described in the item (16), further contains at least a fluorine polyol compound and an isocyanate compound. By suppressing the adhesion of paper dust, toner, etc. to the outermost layer, further improving the releasability, preventing bleeding from the inner and outermost coating film, preventing photoconductor contamination, Also, in the case of a roller structure etc., the followability of the outermost layer coating film is improved, the problem of image quality deterioration is solved without impairing the conductivity, the sliding property is improved, the wear resistance is given, and the semiconductive member Durability can be improved.

  Furthermore, as described in the above item (17), the outermost layer further contains at least a fluorine polyol compound, an acrylic resin and an isocyanate compound, and further as described in the above item (18), the fluorine polyol compound and the acrylic compound. By containing at least a polyol compound, it is possible to improve the effect of suppressing the adhesion of paper dust, toner, etc. to the outermost layer, and further improve the releasability, and further from the inner and outermost coating films. By preventing bleeding, contamination of the photoreceptor 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.
[First Group of the Invention]
The semiconductive member for image processing including image formation of the first group of the present invention is used for electrophotographic image processing, and the outermost layer has an inorganic filler having at least a plate-like structure and It is composed of a resin layer containing a constituent material containing a conductive agent, and contains at least an electron conductive agent and an ionic conductive agent as the conductive agent, and the outermost layer corresponds to each application in addition to these components. Or if necessary, a silicone compound for imparting release properties, further a fluorinated silicone compound, a silicone compound having a reactive group, a fluorinated silicone compound having a reactive group, etc. Various types of polyol compounds and isocyanate compounds, fluorine polyol compounds and isocyanate compounds, acrylic resins, acrylic polyol compounds, etc. It may have.

  In the first group of the present invention, the use ratio of the inorganic filler having a plate-like structure and the conductive agent, the electron conductive agent and the ionic conductive agent is not particularly limited, and depends on various situations, for example, the target volume resistivity. Determined.

[Second Group of the Invention]
The second group of semiconductive members for an image processing apparatus including the image forming of the present invention is used for electrophotographic image processing, and the outermost layer has an inorganic filling having at least a plate-like structure. It is composed of a resin layer containing an agent, a conductive agent and at least one flame retardant. In addition to these components, the outermost layer has releasability depending on each application or as necessary. A silicone compound for imparting, further a fluorinated silicone compound, a silicone compound having a reactive group, a fluorinated silicone compound having a reactive group, etc., and a polyol compound for improving coating properties, imparting releasability, etc. And isocyanate compounds, fluorine polyol compounds and isocyanate compounds, acrylic resins, acrylic polyol compounds, etc., and phosphorus compounds and halogens to impart flame retardancy Compounds, halogen-phosphorus compounds, nitrogen-containing phosphorus compound may variously containing PF6 salt.

  That is, the flame retardant used in the second group of the present invention includes, but is not limited to, organic phosphorus compounds and halogen compounds. In particular, phosphorus compounds are preferable because they form a film of polyphosphoric acid on the outermost surface during combustion, and suppress shutdown of oxygen supply and generation of combustible gas from the inside. In addition, halogen compounds can have flame retardant effects due to synergistic effects with phosphorus compounds, and if they are mixed, the amount of flame retardant added can be reduced, preventing the effect on pollution. it can. A halogen-containing phosphorus-based compound has the same effect. If the amount of the flame retardant itself can be reduced, it is more effective because it does not affect the performance of the image forming semiconductive member.

  Specifically, the phosphorus compounds include trimethyl phosphate, dimethyl ethyl phosphate, methyl ethyl propyl phosphate, methyl diethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, methyl ethylene phosphate, methyl trimethylene phosphate, trimethylol phosphate. Examples of halogen-containing phosphorus compounds include trichloroethyl phosphate, tris (dichloropropyl) phosphate, trischloropropyl phosphate, trisdichloropropyl-chloropropyl phosphate, bischloropropyl-dichloropropyl phosphate, bischlorooctyl dichloropropyl Phosphate, triphenyl phosphate, tris (dibromopro ) Phosphate, chlorophosphate, bromophosphate, tri (trifluoroethyl) phosphate, methyl phosphate (ditrifluoroethyl), ethyl phosphate (ditrifluoroethyl), diethyl phosphate (trifluoroethyl), propyl phosphate ( Ditrifluoroethyl), dipropyl phosphate (trifluoroethyl), tri (pentafluoropropyl) phosphate, methyl phosphate (dipentafluoropropyl), dimethyl phosphate (pentafluoropropyl), ethyl phosphate (dipentafluoropropyl) ), Diethyl phosphate (pentafluoropropyl), butyl phosphate (dipentafluoropropyl), etc., and nitrogen-containing phosphorus compounds include phosphonyl chloride derivatives, phosphonoamides, diethylbis (hydroxyethyl) aminomethyl Sufeto like. Examples of the halogen-containing compound, dibromo-dichloropropane, tetrabromide ethane, four the like bromide butane, but are not limited thereto.

  Among the flame retardant compounds, phosphorus compounds are particularly preferable, and among them, halogen-containing phosphorus compounds and nitrogen-containing phosphorus compounds combined with phosphorus compounds are preferable. A composite compound such as a halogen-containing phosphorus-based compound has an effect on flame retardancy in a smaller amount than a phosphorus compound alone. When a phosphorus compound is used as a flame retardant, a polyphosphoric acid film is formed during combustion, and the flame retardant can be considered due to the action of suppressing the generation of flammable gas or lowering the combustion temperature by latent heat of vaporization. In particular, it has the effect of making it flame retardant for oxygen-containing coating film resins.

  When the amount of the flame retardant as described above is large, the electroconductivity is lowered and the contamination is increased. In this case, the amount of the flame retardant added is preferably set to a range of 0.4 parts by weight or less, particularly preferably 0.01 to 0.2 parts by weight with respect to 100 parts by weight of the coating film component not containing the solvent. Range. By adding in such a range, flame retardancy can be obtained without affecting the contamination. When the amount is 0 part by weight, the effect on flame retardancy cannot be exhibited, and when the amount exceeds 0.4 part by weight, there is a possibility of causing contamination such as bleeding. When these flame retardants are added to the coating material, flame retardancy can be imparted, which is useful.

  Further, when an ion conductive agent having a counter anion of PF6 is added, not only the ion conductivity is high, but also self-extinguishing properties are imparted upon combustion. The reason is unknown, but it is thought to cause the thermal decomposition during combustion and form a polyphosphoric acid film on the surface of the outermost layer, so that it functions to shut down the oxygen supply and suppress flammable gas evaporation from the inside. It is done.

  In the second group of the present invention, the use ratio of the inorganic filler having a plate-like structure, the conductive agent, and the flame retardant is not particularly limited, and is determined according to various situations such as a target volume resistivity.

[Third Group of the Invention]
In addition, a third group of the semiconductive members for image processing including image formation according to the present invention is used for electrophotographic image processing, and the outermost layer has an inorganic filler having a plate-like structure, and It is composed of a resin layer containing a conductive agent, and contains at least an electron conductive agent and a polymer matrix-supporting ionic conductive agent as the conductive agent, and the outermost layer depends on each application in addition to these components Or if necessary, a silicone compound for imparting release properties, further a fluorinated silicone compound, a silicone compound having a reactive group, a fluorinated silicone compound having a reactive group, etc. Various types of polyol compounds and isocyanate compounds, fluorine polyol compounds and isocyanate compounds, acrylic resins, acrylic polyol compounds, etc. It may have.

As a polymer matrix-supporting ionic conductive agent, it is dispersed in the outermost layer and exhibits effects such as suppression of environmental fluctuations and suppression of conductive variation. By dispersing and supporting this ion conductive agent in a polymer matrix, it is possible to suppress environmental variability and to suppress variation in conductivity. This dispersion or loading is performed by dispersing and dissolving an ionic conductive agent in a polymerizable compound in a polymer matrix, then polymerizing by means such as heat or light, and further by cross-linking, etc. After dissolving, swelling, and dissolving, the solution can be volatilized and the like, and the like can be carried out by means such as containing an ionic conductive agent. In addition, an ion conductive polymer solid electrolyte or gel electrolyte can also be used.
Further, the polymer matrix-supporting ionic conductive agent can be controlled to a predetermined resistance value by being added in combination with a conductive agent such as carbon black.

  Examples of the polymer matrix in the third group of the present invention include polyethylene oxide, polypropylene oxide, polyacrylonitrile, polyurethane, polysiloxane, polyphosphazene, polyacrylate, and the like. Further, as the fluorine-based polymer, polyvinylidene fluoride, polyfluoride. Examples thereof include, but are not limited to, vinylidene fluoride-hexafluoropropylene copolymer. Furthermore, there may be mentioned polysiloxane having an ethylene oxide chain as a side chain or a crosslinked polymer having an ethylene oxide chain as a side chain or a main chain, such as those obtained by crosslinking urethane, acrylic, epoxy and the like. In particular, for a crosslinked polymer, a polymerizable compound containing a hetero atom other than carbon such as an oxygen atom, a nitrogen atom, or a sulfur atom in the molecule can be used. It is presumed that the heteroatoms other than carbon promote ionization of the ionic conductive agent, improve the ionic conductivity in the polymer matrix, and improve the strength. These polymer matrices can contain and carry an ion conductive agent.

  The type of the polymerizable compound is not particularly limited, and includes those that generate a polymer by causing a polymerization reaction such as thermal polymerization or actinic ray polymerization, but are monofunctional capable of forming a crosslinked polymer matrix. A combination of a monomer and a polyfunctional monomer is preferable, and it is particularly preferable to use a trifunctional monomer as the polyfunctional monomer.

  Examples of the polymerizable compound include monofunctional and polyfunctional (meth) acrylate monomers or prepolymers. In addition, (meth) acrylate in this specification means an acrylate or a methacrylate.

  Monofunctional acrylates include alkyl (meth) acrylates (methyl (meth) acrylate, butyl (meth) acrylate, trifluoroethyl (meth) acrylate, etc.), alicyclic (meth) acrylates, hydroxyalkyl (meth) acrylates (hydroxy Ethyl acrylate, hydroxypropyl acrylate, etc.), hydroxypolyoxyalkylene (oxyalkylene group preferably has 1 to 4 carbon atoms) (meth) acrylate (hydroxypolyoxyethylene (meth) acrylate, hydroxypolyoxypropylene (meth) acrylate, etc. ) And alkoxyalkyl (alkoxy group preferably has 1 to 4 carbon atoms) (meth) acrylate (methoxyethyl acrylate, ethoxyethyl acrylate, phenoxyethyl acrylate) Etc.) and the like.

  Specific examples of other (meth) acrylates include, for example, methylethylene glycol (meth) acrylate, ethylethylene glycol (meth) acrylate, propylethylene glycol (meth) acrylate, phenylethylene glycol, ethoxydiethylene glycol acrylate, methoxyethyl acrylate, methoxy Alkylpropylene such as diethylene glycol methacrylate, methoxytriethylene glycol acrylate, methoxytriethylene glycol methacrylate, methoxytetraethylene glycol methacrylate, and other alkylethylene glycol (meth) acrylates, ethylpropylene glycol acrylate, butylpropylene glycol acrylate, methoxypropylene glycol acrylate, etc. Recall (meth) acrylate.

  The (meth) acrylate may contain a heterocyclic group, and the heterocyclic group is a heterocyclic residue containing a heteroatom such as oxygen, nitrogen, or sulfur. Although the kind of heterocyclic group contained in this (meth) acrylate is not specifically limited, For example, the furfuryl (meth) acrylate and tetrahydrofurfuryl (meth) acrylate which have a furfuryl group and a tetrahydrofurfuryl group are preferable. Other (meth) acrylates having a heterocyclic group include furfuryl ethylene glycol (meth) acrylate, tetrahydrofurfuryl ethylene glycol (meth) acrylate, furfuryl propylene glycol (meth) acrylate, and tetrahydrofurfuryl propylene glycol (meth) acrylate. And alkylene glycol acrylate having a furfuryl group or a tetrahydrofurfuryl group.

  Furthermore, examples of the polyfunctional (meth) acrylate include a monomer or a prepolymer having two or more (meth) acryloyl groups. In particular, a trifunctional (meth) acrylate having three (meth) acryloyl groups is most preferable from the viewpoint of excellent ionic conductivity and strength. Examples of the polyfunctional (meth) acrylate include ethylene glycol dimethacrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol diacrylate, and EO-modified trimethylol. Examples include propane triacrylate, PO-modified trimethylolpropane triacrylate, butanediol (meth) acrylate, trimethylolpropane tri (meth) acrylate, and dipentaerythritol hexa (meth) acrylate. In order to form a crosslinked polymer matrix, a combination of a monofunctional monomer and a polyfunctional monomer is particularly preferable.

  Specific examples of the polymerization initiator for the monomer include, for example, a thermal polymerization initiator. Examples of the organic peroxide include isobutyl peroxide, lauroyl peroxide, benzoyl peroxide, m-toluoyl peroxide, 3, 3, 5 -Trimethylhexanoyl peroxide, t-butylperoxy-2-ethylhexanoate, t-butylperoxybivalate, cumylperoxyneodecanoate, t-butylperoxyneodecanoate, diisopropylperoxydi Carbonate, di- (2-ethoxyethyl) peroxydicarbonate, bis- (4-tert-butylcyclohexyl) peroxydicarbonate, di- (2-ethylhexyl) peroxydicarbonate, di- (n-propyl) per Oxydicarbonate, di- (meth Ciisopropyl) peroxydicarbonate, t-butylperoxydicarbonate, di- (3-methyl-3-methoxybutyl) peroxydicarbonate, diallylperoxydicarbonate, dicyclohexylperoxydicarbonate, etc. 2,2′-azobis- (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobisiso Examples include butyronitrile, 2,2′-azobis- (2-methylbutyronitrile), dimethyl-2,2′-azobisisobutyrate, and the like, but are not limited thereto.

  In particular, peroxydicarbonate-based compounds are thought to be produced by primary decomposition, and there is little difference in reactivity between R-OCO. And decarboxylated R-O., And they are produced by polymerization even if they start from two radical species. It is considered that it does not make a big difference in the structure of the polymer matrix. Therefore, a homogeneous polymer matrix can be obtained, which can be produced uniformly and has no uneven ionic conductivity. In addition, thermal polymerization can be performed particularly at low temperature and in a short time, and a high polymer matrix having high ionic conductivity can be obtained. Among the peroxydicarbonate compounds, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, and bis- (4-t-butylcyclohexyl) peroxydicarbonate are particularly preferable.

  When the thermal polymerization initiator is contained in an amount of 0.005 to 5 wt% with respect to the polymer matrix or polymerizable monomer after polymerization, further decomposition of the primary decomposition radicals can be suppressed. Furthermore, if it is the said initiator density | concentration, the polymer matrix formed by the superposition | polymerization is enough to hold | maintain an ion conductive agent, and an ion conductive polymer matrix with high ionic conductivity is obtained. Although the reason is unknown, especially when a peroxydicarbonate compound is used as an initiator, it is effective for obtaining a homogeneous polymer matrix having no polymerization unevenness in the case of an acrylate-based polar monomer. Therefore, it is possible to construct a good ion conductive polymer matrix.

  Examples of the photopolymerization initiator include carbonyl compounds, sulfur compounds and onium salts. As thermal polymerization initiators, azobisisovaleronitrile, azobisisobutyronitrile, benzoyl peroxide, lauroyl peroxide, ethyl methyl ketone peroxide, bis- (4-tert-butylcyclohexyl) peroxydicarbonate, diisopropylperoxy Examples thereof include peroxydicarbonates such as dicarbonate. Furthermore, a sensitizer and a storage stabilizer can be used together as necessary, and the above thermal polymerization initiator, photopolymerization initiator, and the like can be used in combination. These can be used alone or as a mixture of two or more.

Examples thereof include a coating film in which at least one kind of crosslinked polymer fine particles are prepared and the fine particles are uniformly dispersed in the outermost layer coating material. The particle diameter of the dispersed fine particles is preferably from 0.01 to 50 μm, more preferably from 0.1 to 5 μm. The fine particles are uniformly dispersed in the outermost layer, and within 1 mm ² , the fine particles are dispersed within a range of 2000 or less depending on the particle size of the fine particles. For example, when the particle size of the fine particles is 2 to 3 μm, about 50 to 200 particles are appropriate.

  In the third group of the present invention, the use ratio of the inorganic filler having a plate-like structure and the conductive agent, the electron conductive agent, and the polymer matrix-supported ionic conductive agent is not particularly limited, and various conditions such as a target volume resistance It is determined according to the rate.

[Detailed description of matters common to the first to third groups of the present invention]
In these first to third groups of the present invention, other leveling agents, antioxidants, flame retardants, anti-settling agents, antifoaming agents, corrosion inhibitors, solvents for dilution, thickeners, thixotropic agents Various additives such as a structural viscosity imparting agent may be contained.

  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 pollutant low molecular substance from the outermost layer coating film and a semiconductive rubber layer, an ionic conductive agent, etc. are bleed | bleeded by adsorption | suction 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 agent and electron conductive agent used in the present invention, an inorganic or organic electron conductive agent having an average particle diameter of 0.01 to 5 μm is preferably used. Examples of the electron conductive agent 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 electron conductive agents may be used alone or in combination of two or more.

Moreover, there is no restriction | limiting in particular as addition amount of these electron conductive agents, According to various conditions, 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 a conductive agent such as carbon black, the resistance can be controlled to a predetermined value. The resistance of the surface layer is preferably 1 × 10 ³ to 1 × 10 ¹² Ω · cm, more preferably 1 × 10 ⁵ to 1 × 10 ^{10 in} volume resistivity when used in combination with an ion conductive agent. Ω · cm.

  The conductive agent used in the present invention and the ion conductive agent used in combination include tetraethylammonium, tetrabutylammonium, lauryltrimethylammonium, dodecyltrimethylammonium, stearyltrimethylammonium, octadecyltrimethylammonium, hexadecyltrimethylammonium, benzyltrimethylammonium, modified Perchlorate such as aliphatic dimethylethylammonium, chlorate, hydrochloride, bromate, iodate, borofluoride, sulfate, alkyl sulfate, carboxylate, sulfonate, PF6 salt Ammonium salts such as BF4 salt, or alkali metal or alkaline earth metal perchlorate, chlorate, hydrochloride, bromate, iodine such as lithium, sodium, calcium, magnesium Salt, fluoroboric acid salts, trifluoromethyl sulfate, sulfonate, PF6 @ salts, and the like BF4 salt.

  The amount of the ion conductive agent used in combination is usually 0.01 to 5% by weight, preferably 0.1 to 2% by weight, based on the total amount of the outermost layer, depending on various situations. The If it is less than 0.01% by weight, the effect of the ionic conductive agent cannot be sufficiently exhibited, and the effect of suppressing variation in electric resistance cannot be sufficiently exhibited. On the other hand, if it exceeds 5% by weight, the ionic conductive agent by the inorganic filler having a plate-like structure is not preferable because it suppresses the effect of suppressing the seepage from the outermost layer and causes contamination of the photoreceptor.

By adding together with a conductive agent such as carbon black, the resistance value 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 outermost layer of the semiconductive member is composed of a resin layer containing at least the inorganic filler having the above plate-like structure, a conductive agent, an electron conductive agent and an ionic conductive agent, and is used in the present invention. As the resin constituting the outer layer, 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 and reactive acid derivatives such as esters, acid halides, and acid anhydrides, and glycols, amino alcohols and the like alone or in mixture. 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.

  Moreover, the fluorine resin which gives mold release property 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.

The suitable 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, particularly for obtaining 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 that is the same as that of the outermost layer 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 conducting the surface of an insulating material 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 based on 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. 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 by these formulations. 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.
Examples 1 to 12 of the first group and Examples 13 to 24 of the second group are reference examples.
[First Group of the Invention]
Example 1
First, a semiconductive member surface treatment solution having the following composition was prepared.
Polyvinylidene fluoride-tetrafluoroethylene-hexafluoropropylene terpolymer / acrylic resin (polymethyl methacrylate) mixed composition (Novafusso (registered trademark) PF250: manufactured by Dainippon Color Material Industries) 100 parts by weight Electronic conductive agent: oxidation Titanium (MT-150A: manufactured by Teika Co., Ltd.) 4.7 parts by weight Ion conductive agent: tetra n-butylammonium perchlorate (manufactured by Tokyo Chemical Industry)
0.2 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 Next, a 3 mm thick ternary epichlorohydrin rubber (GECO) elastic layer (volume resistivity R: 2.5 × 10 ⁷ Ω · cm, Log R: 7.4) is formed on an 8Φ cored bar. The adjustment liquid was spray-coated on the provided roller so that the film thickness after curing was 5 μm, and the semiconductive member of Example 1 (roller resistance R ′: 1.1 × 10 ⁶ Ω, Log R ′ : 6.0).
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.

Example 2
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 Electronic conductive agent: titanium oxide (MT-150A : Teika Co., Ltd.) 4.7 parts by weight Ion conductive agent: Tetra n-butylammonium perchlorate (Tokyo Kasei)
0.2 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 8 Φ core so that the film thickness after curing is 5 μm. The semiconductive member of Comparative Example 1 was produced by coating, 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 the NBR elastic layer whose resistance was adjusted with carbon on the cored bar was prepared, except that the 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.

  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 inorganic filler having a plate-like structure contained in the surface layer is inherent in the semiconductive member and the outermost layer. It can be seen that the problem of OPC contamination due to existing OPC contaminants has been solved.

Example 3
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 Electronic conductive agent: titanium oxide (MT-150A : Teika Co., Ltd.) 4.7 parts by weight Ion conductive agent: Tetra n-butylammonium perchlorate (Tokyo Kasei)
0.2 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 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 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 Materials Co., Ltd.) 100 parts by weight Electronic conductive agent: titanium oxide (MT-150A : Teika Co., Ltd.) 4.7 parts by weight Ion conductive agent: Tetra n-butylammonium perchlorate (Tokyo Kasei)
0.2 parts by weight Lubricant: Fatty acid amide (Kawaslip VL: Kawaken Fine Chemical) 1.2 parts by weight

Example 4
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 mixed composition (Novafusso (registered trademark) PF250: manufactured by Dainippon Color Materials Co., Ltd.) 100 parts by weight Electronic conductive agent: titanium oxide (MT-150A : Teika Co., Ltd.) 4.7 parts by weight Ion conductive agent: Tetra n-butylammonium perchlorate (Tokyo Kasei)
0.2 parts by weight Plate-like structure inorganic filler: synthetic hydrotalcite (DHT-4A (registered trademark): manufactured by Kyowa Chemical Industry Co., Ltd.) 0.14 parts by weight Silicone compound: fluorinated silicone compound (FMS-121: Chisso Corporation ) Made)
0.0032 parts by weight

Example 5
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 mixed composition (Novafusso (registered trademark) PF250: manufactured by Dainippon Color Materials Co., Ltd.) 100 parts by weight Electronic conductive agent: titanium oxide (MT-150A : Teika Co., Ltd.) 4.7 parts by weight Ion conductive agent: Tetra n-butylammonium perchlorate (Tokyo Kasei)
0.2 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 Silicone compound: Silanol-terminated silicone (DMS-S15: Chisso Corporation) Made)
0.0032 parts by weight

Example 6
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.

Example 7
A semiconductive member of Example 8 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.
100 parts by weight of polyester polyol (Yurak (registered trademark) C-230U: manufactured by Hirono Chemical)
33 parts by weight of polyisocyanate (Eurach (registered trademark) PU-614: manufactured by Hirono Chemical)
Electron conducting agent: Carbon (Ketjen Black (registered trademark) EC: manufactured by Lion Akzo)
2.6 parts by weight Ion conductive agent: Tetra n-butylammonium perchlorate (manufactured by Tokyo Chemical Industry)
0.2 parts by weight Plate-like inorganic filler: Synthetic hydrotalcite (DHT-4A (registered trademark): manufactured by Kyowa Chemical Industry) 4.4 parts by weight Silicone compound: Silanol-terminated silicone (DMS-S15: Chisso Corporation) 0.1 parts by weight Toluene 50 parts by weight Xylene 50 parts by weight

Example 8
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 (Eurack (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 Electronic conductive agent: Carbon (Ketjen Black (registered trademark) ) EC: manufactured by Lion Akzo) 2.6 parts by weight Ionic conductive agent: tetra n-butylammonium perchlorate (manufactured by Tokyo Chemical Industry) 0.2 parts by weight Plate-like inorganic filler: synthetic hydrotalcite (DHT-4A (registered) Trademark): Kyowa Chemical Industry Co., Ltd.) 4.4 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

Example 9
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 (trademark) LF-601C curing agent: manufactured by Asahi Glass)
20 parts by weight Electronic Conductive Agent: Carbon (Ketjen Black (registered trademark) EC: manufactured by Lion Akzo)
2.6 parts by weight Ion conductive agent: Tetra n-butylammonium perchlorate (manufactured by Tokyo Chemical Industry)
0.2 parts by weight Plate-like inorganic filler: Synthetic hydrotalcite (DHT-4A (registered trademark): manufactured by Kyowa Chemical Industry) 4.4 parts by weight Silicone compound: Silanol-terminated silicone (DMS-S15: Chisso Corporation) Made)
0.1 parts by weight Toluene 50 parts by weight Xylene 50 parts by weight

Example 10
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 Electronic Conductive Agent: Carbon (Ketjen Black (registered trademark) EC: manufactured by Lion Akzo)
2.6 parts by weight Ion conductive agent: Tetra n-butylammonium perchlorate (manufactured by Tokyo Chemical Industry)
0.2 parts by weight Plate-like structure inorganic filler: Synthetic hydrotalcite (DHT-4A (registered trademark): manufactured by Kyowa Chemical Industry) 4.4 parts by weight Silicone compound: Silanol-terminated polyfluoropropylmethylsiloxane (FMS-9921: 0.1 part by weight Toluene 50 parts by weight Xylene 50 parts by weight

Table 2 shows the evaluation results of charging roller contamination after 60,000 copies of each roller obtained in Examples 3, 4, 5, 6 and Comparative Example 5.
Further, the semiconductive members (charging rollers) obtained in Examples 7, 8, 9, and 10 were obtained by examining 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 and 3 points at both ends Roller dirt density Standard deviation: Stain density deviation at the roller center and 3 points at both ends

From Table 2, it can be said that the dirt density of the charging rollers of Examples 3, 4, 5, and 6 when mounted on an actual machine is clearly lower than that of Comparative Example 5 in which no silicone compound is added.
Moreover, all the main resins of the surface treatment liquid used in Examples 7 to 10 have a polyol compound and an isocyanate compound. It can be said that the roller dirt density in Examples 3 to 6 and Examples 7 to 10 is clearly lower than that in Comparative Example 5 in which no silicone compound is added.

  Moreover, all the main resins of the surface treatment liquid used in Examples 7 to 10 have a polyol compound and an isocyanate compound. Comparing the roller dirt density of Examples 3-6 and Examples 7-10, it is clear that the dirt on each roller of Examples 7-10 is lower than that of Examples 3-6. Therefore, at least when a reactive silicone compound is used for the surface treatment liquid, it can be said that the effect of the silicone compound can be further enhanced 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 10 is the lowest compared to the dirt density of the other rollers, and the difference from the other Examples of roller dirt density can be said to be statistically significant. The surface treatment liquid of Example 10 contains a fluorinated silicone compound having a reactive group, a fluorine polyol compound, and an isocyanate compound.

Example 11
A semiconductive member surface treatment solution having the following composition was prepared.
Fluoropolyol (Lumiflon (registered trademark) LF-601C main agent: manufactured by 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 Electronic Conductive Agent: Carbon (Ketjen Black (registered trademark) EC: manufactured by Lion Akzo)
2.6 parts by weight Ion conductive agent: Tetra n-butylammonium perchlorate (manufactured by Tokyo Chemical Industry)
0.2 parts by weight Plate-like structure inorganic filler: Synthetic hydrotalcite (DHT-4A (registered trademark): manufactured by Kyowa Chemical Industry) 4.4 parts by weight Silicone compound: Silicone oil (DMS-T11: Chisso) 0.1 Part by weight Toluene 50 parts by weight Xylene 50 parts by weight Next, the above adjustment liquid is provided on a roller provided with an NBR elastic layer whose resistance is adjusted with carbon similar to that used in Example 2 having a thickness of 6 mm on an 18Φ core metal. A semiconductive member of Example 11 was prepared by spray coating 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 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 the cleaning property 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: Cleaning performance evaluation 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 the solid pattern corresponding part on the back of the evaluation sample in the above item 3. No toner contamination: cleaning property OK
Toner contamination present: cleaning ability NG
And evaluate.

Example 12
A semiconductive member of Example 12 was produced in exactly the same manner as in Example 11 except that the composition of the surface treatment liquid was changed to the following composition, and the paper dust adhesion characteristics as in Example 11 were evaluated.
Fluoropolyol (Lumiflon (registered trademark) LF-601C main agent: manufactured by Asahi Glass)
90 parts by weight polyisocyanate (Lumiflon (trademark) 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 Electronic Conductive Agent: Carbon (Ketjen Black (registered trademark) EC: manufactured by Lion Akzo)
2.6 parts by weight Ion conductive agent: Tetra n-butylammonium perchlorate (manufactured by Tokyo Chemical Industry)
0.2 parts by weight Plate-like inorganic filler: Synthetic hydrotalcite (DHT-4A (registered trademark): manufactured by Kyowa Chemical Industry) 4.4 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 produced in exactly the same manner as in Example 11 except that the composition of the surface treatment liquid was changed to the following composition, and the paper dust adhesion characteristics as in Example 11 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 Electronic Conductive Agent: Carbon (Ketjen Black (trademark) EC: manufactured by Lion Akzo)
2.8 parts by weight Silicone compound: Silicone oil (DMS-T11: Chisso) 0.1 part 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 11, Example 12, 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.

From Table 3, it can be seen that the paper dust adhesion characteristics are significantly improved in the transfer rollers of Examples 11 and 12 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.

[Second Group of the Invention]
Example 13
First, a semiconductive member surface treatment solution having the following composition was prepared.
Polyvinylidene fluoride-tetrafluoroethylene-hexafluoropropylene terpolymer / acrylic resin (polymethyl methacrylate) mixed composition (Novafusso (registered trademark) PF250: manufactured by Dainippon Color Material Industries) 100 parts by weight Electronic conductive agent: oxidation Titanium (MT-150A: manufactured by Teika Co., Ltd.) 4.9 parts by weight Plate-like structure inorganic filler: Synthetic hydrotalcite (DHT-4A
(Registered trademark): manufactured by Kyowa Chemical Industry Co., Ltd. 0.14 parts by weight Flame retardant: trimethyl phosphate 0.0032 parts by weight Next, a 3 mm thick ternary epichlorohydrin rubber (GECO) elastic layer (volume resistance) on an 8Φ cored bar The above adjustment liquid was spray-coated on a roller provided with a ratio R: 2.5 × 10 ⁷ Ω · cm, Log R: 7.4) so that the film thickness after curing was 5 μm. A semiconductive member (roller resistance R ′: 1.1 × 10 ⁶ Ω, Log R ′: 6.0) was produced.
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.

Example 14
In Example 13, instead of the ternary epichlorohydrin rubber (GECO) elastic layer, an NBR elastic layer having a resistance adjusted with carbon (volume resistivity R: 4.0 × 10 ⁶ Ω · cm, Log R: 6.6) The semiconductive member of Example 14 (roller resistance R ′: 1.8 × 10 ⁵ Ω, Log R ′: 5.2) was produced in the same manner as Example 13 except that The same evaluation test was conducted.

Comparative Example 7
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 Material Industries Co., Ltd.) 100 parts by weight Electroconductive agent: titanium oxide (MT-150A: manufactured by Teika Co., Ltd.) 4.9 parts by weight Flame retardant: trimethyl phosphate 0.0032 parts by weight Next, 8Φ cored bar The adjustment liquid was spray-coated on a roller provided with a 3 mm thick ternary epichlorohydrin rubber (GECO) elastic layer thereon so that the film thickness after curing was 5 μm. A member was prepared and the same evaluation test as in Example 13 was performed.

Comparative Example 8
In Comparative Example 7, in place of the ternary epichlorohydrin rubber (GECO) elastic layer, the same as in Comparative Example 7 except that an NBR elastic layer having a resistance adjusted with carbon similar to that used in Example 14 was used. Thus, a semiconductive member of Comparative Example 8 was produced, and the same evaluation test as in Example 13 was performed.

Comparative Example 9
In Example 13, except that the surface layer is not provided, a semiconductive member of Comparative Example 9 in which only the ternary epichlorohydrin rubber (GECO) elastic layer is provided on the cored bar is prepared as in Example 13, The same evaluation test as in Example 13 was performed.

Comparative Example 10
In Example 14, a semiconductive member of Comparative Example 4 having only the NBR elastic layer whose resistance was adjusted with carbon on the cored bar was prepared, except that the surface layer was not provided. The same evaluation test as in Example 13 was performed.
Table 4 shows the evaluation test results of the semiconductive members obtained in Examples 13 and 14 and Comparative Examples 7, 8, 9, and 10. In Table 4, the use ratio is parts by weight.

  From the results of Comparative Examples 9 and 10 in Table 4, 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 13 and 14 in Table 4 with the results of Comparative Examples 7 and 8, the inorganic filler having a plate-like structure contained in the surface layer is inherent in the semiconductive member and the outermost layer. It can be seen that the problem of OPC contamination due to existing OPC contaminants has been solved.

Example 15
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 Industries Co., Ltd.) 100 parts by weight Electronic conductive agent: titanium oxide (MT-150A: manufactured by Teika Co., Ltd.) 4.7 parts by weight Ionic conductive agent: tetra n-butylammonium perchlorate (manufactured by Tokyo Chemical Industry)
0.2 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 Flame retardant: Tris (dibromopropyl) phosphate 0.0032 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 15 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 11
A semiconductive member of Comparative Example 11 was produced in exactly the same manner as in Example 15 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 15.
Polyvinylidene fluoride-tetrafluoroethylene-hexafluoropropylene terpolymer / acrylic resin mixed composition (Novafusso (registered trademark)
PF250: manufactured by Dainippon Color Industries Co., Ltd.) 100 parts by weight Electroconductive agent: titanium oxide (MT-150A: manufactured by Teika Co., Ltd.) 4.9 parts by weight Lubricant: fatty acid amide (Kawaslip VL: Kawaken Fine Chemical)
1.2 parts by weight

Example 16
A semiconductive member of Example 16 was prepared in exactly the same manner as in Example 15 except that the composition of the surface treatment liquid was changed to the following composition, and the same antifouling property as in Example 15 was evaluated.
Polyvinylidene fluoride-tetrafluoroethylene-hexafluoropropylene terpolymer / acrylic resin mixed composition (Novafusso (registered trademark)
PF250: manufactured by Dainippon Color Industries Co., Ltd.) 100 parts by weight Electronic conductive agent: titanium oxide (MT-150A: manufactured by Teika Co., Ltd.) 4.7 parts by weight Ionic conductive agent: tetra n-butylammonium perchlorate (manufactured by Tokyo Chemical Industry)
0.2 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 Flame retardant: diethyl bis (hydroxyethyl) aminomethyl phosphate
0.0032 parts by weight Silicone compound: fluorinated silicone compound (FMS-121: manufactured by Chisso Corporation)
0.0032 parts by weight

Example 17
A semiconductive member of Example 17 was produced in the same manner as in Example 15 except that the composition of the surface treatment liquid was changed to the following composition, and the same antifouling property as in Example 15 was evaluated.
Polyvinylidene fluoride-tetrafluoroethylene-hexafluoropropylene terpolymer / acrylic resin mixed composition (Novafusso (registered trademark)
PF250: manufactured by Dainippon Color Industries Co., Ltd.) 100 parts by weight Electronic conductive agent: titanium oxide (MT-150A: manufactured by Teika Co., Ltd.) 4.7 parts by weight Ionic conductive agent: tetra n-butylammonium perchlorate (manufactured by Tokyo Chemical Industry)
0.2 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 Flame retardant: diethyl bis (hydroxyethyl) aminomethyl phosphate
0.0032 parts by weight Silicone compound: Silanol-terminated silicone (DMS-S15: manufactured by Chisso Corporation)
0.0032 parts by weight

Example 18
The silicone compound of Example 17 was replaced with silanol-terminated polytrifluoropropylmethylsiloxane (FMS-9921: manufactured by Chisso Corporation), and the same weight part was added. A conductive member was prepared, and the same antifouling property as in Example 17 was evaluated.

Example 19
A semiconductive member of Example 19 was prepared in exactly the same manner as in Example 15 except that the composition of the surface treatment liquid was changed to the following composition, and the same antifouling property as in Example 15 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 Electronic Conductive Agent: Carbon (Ketjen Black (registered trademark) EC: manufactured by Lion Akzo)
2.6 parts by weight Ion conductive agent: Tetra n-butylammonium perchlorate (manufactured by Tokyo Chemical Industry)
0.2 parts by weight Plate-like inorganic filler: synthetic hydrotalcite (DHT-4A (registered trademark): manufactured by Kyowa Chemical Industry) 4.4 parts by weight Flame retardant: tri (ditrifluoroethyl phosphate) 0.1 weight Part Silicone compound: Silanol-terminated silicone (DMS-S15: manufactured by Chisso Corporation)
0.1 parts by weight Toluene 50 parts by weight Xylene 50 parts by weight

Example 20
A semiconductive member of Example 20 was produced in exactly the same manner as in Example 15 except that the composition of the surface treatment liquid was changed to the following composition, and the same antifouling property as in Example 15 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 Electronic Conductive Agent: Carbon (Ketjen Black (registered trademark) EC: manufactured by Lion Akzo)
2.6 parts by weight Ion conductive agent: Tetra n-butylammonium perchlorate (manufactured by Tokyo Chemical Industry)
0.2 parts by weight Plate-like structure inorganic filler: synthetic hydrotalcite (DHT-4A
(Registered trademark): Kyowa Chemical Industry Co., Ltd.) 4.4 parts by weight Flame retardant: Diethylbis (hydroxyethyl) aminomethyl phosphate
0.1 part 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

Example 21
A semiconductive member of Example 21 was prepared in exactly the same manner as in Example 15 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 15.
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 Electronic Conductive Agent: Carbon (Ketjen Black (registered trademark) EC: manufactured by Lion Akzo)
2.6 parts by weight Ion conductive agent: Tetra n-butylammonium perchlorate (manufactured by Tokyo Chemical Industry)
0.2 parts by weight Plate-like structure inorganic filler: synthetic hydrotalcite (DHT-4A
(Registered trademark): Kyowa Chemical Industry Co., Ltd.) 4.4 parts by weight Flame retardant: Tri (ditrifluoroethyl phosphate) 0.1 parts by weight Silicone compound: Silanol-terminated silicone (DMS-S15: manufactured by Chisso Corporation)
0.1 parts by weight Toluene 50 parts by weight Xylene 50 parts by weight

Example 22
A semiconductive member of Example 22 was prepared in exactly the same manner as in Example 15 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 15.
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 Electronic Conductive Agent: Carbon (Ketjen Black (registered trademark) EC: manufactured by Lion Akzo)
2.6 parts by weight Ion conductive agent: Tetra n-butylammonium perchlorate (manufactured by Tokyo Chemical Industry)
0.2 parts by weight Plate-like structure inorganic filler: synthetic hydrotalcite (DHT-4A (registered trademark)
4.4 parts by weight Flame retardant: Tris (dibromopropyl) phosphate 0.1 part by weight Silicone compound: Silanol-terminated polyfluoropropylmethylsiloxane (FMS-9921: manufactured by Chisso) 0.1 part by weight Toluene 50 Parts by weight xylene 50 parts by weight

Table 5 shows the result of charging roller contamination evaluation after 60,000 copies of each roller obtained in Examples 15, 16, 17, 18 and Comparative Example 11.
Further, the semiconductive members (charging rollers) obtained in Examples 17, 20, 21, and 22 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 5 shows the evaluation results of charging roller contamination after 60,000 copies of the rollers of Examples 19, 20, 21, and 22.
In addition, the usage-amount of the raw material in Table 5 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 and 3 points at both ends Roller dirt density Standard deviation: Stain density deviation at the roller center and 3 points at both ends

From Table 5, it can be said that the dirt density of the charging rollers of Examples 15, 16, 17, and 18 when mounted on an actual machine is clearly lower than that of Comparative Example 11 in which no silicone compound is added.
In addition, the main resin of the surface treatment liquid used in Examples 19 to 22 has a polyol compound and an isocyanate compound. It can be said that the roller dirt density of Examples 15 to 18 and Examples 19 to 22 is clearly lower than that of Comparative Example 11 in which no silicone compound is added.

  In addition, the main resin of the surface treatment liquid used in Examples 19 to 22 has a polyol compound and an isocyanate compound. Comparing the roller dirt density of Examples 15-18 and Examples 19-22, it is clear that the dirt of each roller of Examples 19-22 is lower than that of Examples 15-18. 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 semiconductive members of the items (14) and (15) are based on this result.

  Furthermore, the roller dirt density of Example 22 is the lowest compared to the dirt density of the other rollers, and the difference from the other examples of roller dirt density can be said to be statistically significant. The surface treatment liquid of Example 22 contains a fluorinated silicone compound having a reactive group, a fluorine polyol compound, and an isocyanate compound.

Example 23
A semiconductive member surface treatment solution having the following composition was prepared.
Fluoropolyol (Lumiflon (registered trademark) LF-601C main agent: manufactured by 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 Electronic Conductive Agent: Carbon (Ketjen Black (registered trademark) EC: manufactured by Lion Akzo)
2.6 parts by weight Ion conductive agent: Tetra n-butylammonium hexafluorophosphate (manufactured by Tokyo Chemical Industry) 0.2 parts by weight Plate-shaped inorganic filler: Synthetic hydrotalcite (DHT-4A (registered trademark))
4.4 parts by weight Flame retardant: Tris (dibromopropyl) phosphate 0.1 part by weight Silicone compound: Silicone oil (DMS-T11: Chisso) 0.1 part by weight Toluene 50 parts by weight Xylene 50 parts by weight Next, the film thickness after curing the adjustment liquid on a roller provided with an NBR elastic layer whose resistance is adjusted with carbon similar to that used in Example 2 having a thickness of 6 mm on an 18 Φ core metal is 15 μm. As described above, the semiconductive member of Example 23 was produced by spray coating.
This semiconductive member was mounted on a Ricoh Imagio Color 2800 as a secondary transfer roller, and 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. Cleaning performance evaluation (Note 2 = Same as 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 the cleaning property 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.

Example 24
A semiconductive member of Example 24 was produced in exactly the same manner as in Example 23 except that the composition of the surface treatment liquid was changed to the following composition, and the paper dust adhesion characteristics as in Example 23 were evaluated.
Fluoropolyol (Lumiflon (registered trademark) LF-601C main agent: manufactured by Asahi Glass)
90 parts by weight polyisocyanate (Lumiflon (trademark) 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 Electronic Conductive Agent: Carbon (Ketjen Black (registered trademark) EC: manufactured by Lion Akzo)
2.6 parts by weight Ion conductive agent: Tetra n-butylammonium hexafluorophosphate (manufactured by Tokyo Chemical Industry) 0.2 parts by weight Plate-shaped inorganic filler: Synthetic hydrotalcite (DHT-4A (registered trademark))
4.4 parts by weight Flame retardant: Tris (dibromopropyl) phosphate 0.1 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 12
A semiconductive member of Comparative Example 12 was prepared in exactly the same manner as in Example 24 except that the composition of the surface treatment liquid was changed to the following composition, and the paper dust adhesion characteristics as in Example 23 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 Co., Ltd.) 20 parts by weight Electroconductive agent: Carbon (Ketjen Black (registered trademark) EC: manufactured by Lion Akzo)
2.8 parts by weight Silicone compound: Silicone oil (DMS-T11: Chisso) 0.1 part by weight Toluene 50 parts by weight Xylene 50 parts by weight

Table 6 shows the evaluation results of paper dust adhesion characteristics of the secondary transfer rollers obtained in Example 23, Example 24, and Comparative Example 12. In addition, the usage-amount of the raw material in Table 6 is shown by a weight part.
Also, “good” in the paper dust adhesion characteristics in Table 6 indicates a case where no dirt is generated in the evaluation of 50K sheets.

  From Table 6, it can be seen that the paper dust adhesion characteristics of the transfer rollers of Example 23 and Example 24 are significantly improved compared to the transfer roller of Comparative Example 12 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.

  Moreover, when flame retardance evaluation was implemented according to UL94 about Example 13 to Example 24 and Comparative Example 11 and Comparative Example 12, in Examples 13 to 24, the addition of flame retardancy was recognized, and Comparative Example 11 and 12, no reduction in combustibility was observed.

[Group 3 of the present invention]
Synthetic Example (Ion Conductive Particles Supported on Polymer Matrix)
13.8 parts of ethoxydiethylene glycol acrylate as a monofunctional monomer, 0.2 parts of trimethylolpropane triacrylate as a polyfunctional monomer, and bis (4-t-butylcyclohexyl) peroxydicarbonate as a thermal polymerization initiator 0.056 parts was added, mixed and dissolved to prepare a thermally polymerizable solution. Further, 5.0 parts of the thermopolymerizable solution was mixed with 100.0 parts of n-hexane, dispersed, heated at 50 ° C., and polymerized to obtain particles of about 1 μm or less. In addition, this was separated by filtration, and then dispersed in the paint described in the examples (10 vol%) to perform spray coating molding.

Example 25
First, a semiconductive member surface treatment solution having the following composition was prepared.
Polyvinylidene fluoride-tetrafluoroethylene-hexafluoropropylene terpolymer / acrylic resin (polymethyl methacrylate) mixed composition (Novafusso (registered trademark) PF250: manufactured by Dainippon Color Material Industries) 100 parts by weight Electronic conductive agent: oxidation Titanium (MT-150A: manufactured by Teika Co., Ltd.) 4.7 parts by weight Polymer matrix ionic conductive agent: particle size 1 μm or less (polymer matrix: crosslinked particles: ethoxydiethylene glycol acrylate,
Trimethylolpropane triacrylate polymer) 5 parts by weight Among them, ionic conductive agent: tetra n-butylammonium perchlorate 0.2 parts by weight Plate-like inorganic filler: synthetic hydrotalcite (DHT-4A (registered trademark): Kyowa Chemical 0.14 parts by weight Next, a 3 mm thick ternary epichlorohydrin rubber (GECO) elastic layer (volume resistivity R: 2.5 × 10 ⁷ Ω · cm, Log R: 7. 4) The above-mentioned adjustment liquid was spray-coated on the roller provided with 4 μm so that the film thickness after curing was 5 μm, and the semiconductive member of Example 25 (roller resistance R ′: 1.1 × 10 ⁶ Ω) , LogR ′: 6.0).
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.

Example 26
In Example 25, instead of the ternary epichlorohydrin rubber (GECO) elastic layer, an NBR elastic layer having a resistance adjusted with carbon (volume resistivity R: 4.0 × 10 ⁶ Ω · cm, Log R: 6.6) A semiconductive member of Example 26 (roller resistance R ′: 1.8 × 10 ⁵ Ω, Log R ′: 5.2) was produced in the same manner as Example 25 except that the above-described example 25 was provided. The same evaluation test was conducted.

Comparative Example 13
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 Electronic conductive agent: titanium oxide (MT-150A : Teika Co., Ltd.) 4.7 parts by weight Polymer matrix ionic conductive agent: particle size 1 μm or less (polymer matrix: crosslinked particles: ethoxydiethylene glycol acrylate,
Trimethylolpropane triacrylate polymer) 5 parts by weight Of ionic conductive agent: tetra n-butylammonium perchlorate 0.2 parts by weight Next, a ternary epichlorohydrin rubber (GECO) elastic layer having a thickness of 3 mm on an 8Φ cored bar The adjustment liquid was spray-coated on a roller provided with a thickness of 5 μm to prepare a semiconductive member of Comparative Example 13, and the same evaluation test as in Example 25 was performed. .

Comparative Example 14
In Comparative Example 13, in place of the ternary epichlorohydrin rubber (GECO) elastic layer, the same as in Comparative Example 13 except that an NBR elastic layer having a resistance adjusted with carbon similar to that used in Example 26 was used. Thus, the semiconductive member of Comparative Example 14 was produced, and the same evaluation test as in Example 25 was performed.

Comparative Example 15
In Example 25, a semiconductive member of Comparative Example 15 having only a ternary epichlorohydrin rubber (GECO) elastic layer provided on a core bar, similar to Example 25, except that no surface layer is provided, The same evaluation test as in Example 25 was performed.

Comparative Example 16
In Example 26, the semiconductive member of Comparative Example 16 having only the NBR elastic layer whose resistance was adjusted with carbon on the mandrel was prepared and implemented, except that the surface layer was not provided. The same evaluation test as in Example 25 was performed.
Table 7 shows the evaluation test results of the semiconductive members obtained in Examples 25 and 26 and Comparative Examples 13, 14, 15, and 16. In Table 7, the use ratio is parts by weight.

  From the results of Comparative Examples 15 and 16 in Table 7, 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 25 and 26 in Table 7 with the results of Comparative Examples 13 and 14, the inorganic filler having a plate-like structure contained in the surface layer is inherent in the semiconductive member and the outermost layer. It can be seen that the problem of OPC contamination due to existing OPC contaminants has been solved.

Example 27
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 Electronic conductive agent: titanium oxide (MT-150A : Teika Co., Ltd.) 4.7 parts by weight Polymer matrix ionic conductive agent: particle size 1 μm or less (polymer matrix: crosslinked particles: ethoxydiethylene glycol acrylate,
Trimethylolpropane triacrylate polymer) 5 parts by weight Among them, ionic conductive agent: tetra n-butylammonium perchlorate 0.2 parts by weight Plate-like inorganic filler: synthetic hydrotalcite (DHT-4A (registered trademark): Kyowa Chemical 0.14 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 27 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 17
A semiconductive member of Comparative Example 17 was prepared in exactly the same manner as in Example 27 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 27.
Polyvinylidene fluoride-tetrafluoroethylene-hexafluoropropylene terpolymer / acrylic resin mixed composition (Novafusso (registered trademark) PF250: manufactured by Dainippon Color Materials Co., Ltd.) 100 parts by weight Electronic conductive agent: titanium oxide (MT-150A : Teika Co., Ltd.) 4.7 parts by weight Polymer matrix ionic conductive agent: particle size 1 μm or less (polymer matrix: crosslinked particles: ethoxydiethylene glycol acrylate,
Trimethylolpropane triacrylate polymer) 5 parts by weight Of which: Ion conductive agent: Tetra n-butylammonium perchlorate 0.2 parts by weight Lubricant: Fatty acid amide (Kawaslip VL: Kawaken Fine Chemicals) 1.2 parts by weight

Example 28
A semiconductive member of Example 28 was prepared in exactly the same manner as in Example 27 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 27.
Polyvinylidene fluoride-tetrafluoroethylene-hexafluoropropylene terpolymer / acrylic resin mixed composition (Novafusso (registered trademark) PF250: manufactured by Dainippon Color Materials Co., Ltd.) 100 parts by weight Electronic conductive agent: titanium oxide (MT-150A : Teika Co., Ltd.) 4.7 parts by weight Polymer matrix ionic conductive agent: particle size 1 μm or less (polymer matrix: ethoxydiethylene glycol acrylate,
Tetraethylene glycol diacrylate polymer) 5 parts by weight Of which: Ion conductive agent: Tetra n-butylammonium perchlorate 0.2 parts by weight Plate-like inorganic filler: Synthetic hydrotalcite (DHT-4A (registered trademark): Kyowa Chemical 0.14 parts by weight Silicone compound: Fluorinated silicone compound (FMS-121: manufactured by Chisso Corporation)
0.0032 parts by weight

Example 29
A semiconductive member of Example 29 was prepared in exactly the same manner as in Example 27 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 27.
Polyvinylidene fluoride-tetrafluoroethylene-hexafluoropropylene terpolymer / acrylic resin mixed composition (Novafusso (registered trademark) PF250: manufactured by Dainippon Color Materials Co., Ltd.) 100 parts by weight Electronic conductive agent: titanium oxide (MT-150A : Teika Co., Ltd.) 4.7 parts by weight Polymer matrix ionic conductive agent: particle size 1 μm or less (polymer matrix: crosslinked particles: ethoxydiethylene glycol acrylate,
Trimethylolpropane triacrylate polymer) 5 parts by weight Among them, ionic conductive agent: tetra n-butylammonium perchlorate 0.2 parts by weight Plate-like inorganic filler: synthetic hydrotalcite (DHT-4A (registered trademark): Kyowa Chemical 0.14 parts by weight Silicone compound: Silanol-terminated silicone (DMS-S15: manufactured by Chisso Corporation)
0.0032 parts by weight

Example 30
The silicone compound of Example 29 was replaced with silanol-terminated polytrifluoropropylmethylsiloxane (FMS-9921: manufactured by Chisso Corporation), and the same weight part was added. A conductive member was produced, and the same antifouling property as in Example 27 was evaluated.

Example 31
A semiconductive member of Example 31 was produced in exactly the same manner as in Example 27 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 27.
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 Electronic Conductive Agent: Carbon (Ketjen Black (registered trademark) EC: manufactured by Lion Akzo)
2.6 parts by weight Polymer matrix ionic conductive agent: particle size 1 μm or less (polymer matrix: crosslinked particles: ethoxydiethylene glycol acrylate,
Trimethylolpropane triacrylate polymer) 5 parts by weight Among them, ionic conductive agent: tetra n-butylammonium perchlorate 0.2 parts by weight Plate-like inorganic filler: synthetic hydrotalcite (DHT-4A (registered trademark): Kyowa Chemical 4.4) by weight Silicone compound: Silanol-terminated silicone (DMS-S15: manufactured by Chisso Corporation)
0.1 parts by weight Toluene 50 parts by weight Xylene 50 parts by weight

Example 32
A semiconductive member of Example 32 was produced in exactly the same manner as in Example 27 except that the composition of the surface treatment liquid was changed to the following composition, and the same antifouling property as in Example 27 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 Electronic Conductive Agent: Carbon (Ketjen Black (registered trademark) EC: manufactured by Lion Akzo)
2.6 parts by weight Polymer matrix ionic conductive agent: particle size 1 μm or less (polymer matrix: crosslinked particles: vinylidene fluoride
Hexafluoropropylene copolymer /
Elf Atchem Japan KAYNAR2851) 5 parts by weight Ion conductive agent: Tetra n-butylammonium perchlorate 0.2 parts by weight Plate-structured inorganic filler: Synthetic hydrotalcite (DHT-4A (registered trademark): Kyowa Chemical Industry 4.4 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

Example 33
A semiconductive member of Example 33 was produced in the same manner as in Example 27 except that the composition of the surface treatment liquid was changed to the following composition, and the same antifouling properties as in Example 27 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 Electronic Conductive Agent: Carbon (Ketjen Black (registered trademark) EC: manufactured by Lion Akzo)
2.6 parts by weight Polymer matrix ionic conductive agent: particle size 1 μm or less (polymer matrix: crosslinked particles: ethoxydiethylene glycol acrylate,
Trimethylolpropane triacrylate polymer) 5 parts by weight Among them, ionic conductive agent: tetra n-butylammonium perchlorate 0.2 parts by weight Plate-like inorganic filler: synthetic hydrotalcite (DHT-4A (registered trademark): Kyowa Chemical 4.4) by weight Silicone compound: Silanol-terminated silicone (DMS-S15: manufactured by Chisso Corporation)
0.1 parts by weight Toluene 50 parts by weight Xylene 50 parts by weight

Example 34
A semiconductive member of Example 34 was prepared in exactly the same manner as in Example 27 except that the composition of the surface treatment liquid was changed to the following composition, and the same antifouling property as in Example 27 was evaluated.
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 Electronic Conductive Agent: Carbon (Ketjen Black (registered trademark) EC: manufactured by Lion Akzo)
2.6 parts by weight Polymer matrix ionic conductive agent: particle size 1 μm or less (polymer matrix: crosslinked particles: ethoxydiethylene glycol acrylate,
Trimethylolpropane triacrylate polymer) 5 parts by weight Among them, ionic conductive agent: tetra n-butylammonium perchlorate 0.2 parts by weight Plate-like inorganic filler: synthetic hydrotalcite (DHT-4A (registered trademark): Kyowa Chemical 4.4 parts by weight Silicone compound: Silanol-terminated polyfluoropropylmethylsiloxane (FMS-9921: manufactured by Chisso) 0.1 part by weight Toluene 50 parts by weight Xylene 50 parts by weight

Table 8 shows the result of charging roller contamination evaluation after 60,000 copies of each roller obtained in Examples 27, 28, 29, and 30 and Comparative Example 17.
In addition, the semiconductive member (charging roller) obtained in Examples 31, 32, 33, and 34 was obtained by examining the influence of the combination of the surface treatment liquid main resin and the reactive silicone compound on the roller dirt. Table 8 shows the evaluation results of charging roller contamination after 60,000 copies of each of the rollers of Examples 31, 32, 33, and 34.
In addition, the usage-amount of the raw material in Table 8 is shown by a weight part.
The evaluation in Table 8 is shown below.
Roller dirt density average: Average dirt density at the center of the roller and 3 points at both ends Roller dirt density Standard deviation: Stain density deviation at the roller center and 3 points at both ends

From Table 8, it can be said that the dirt density of the charging rollers of Examples 27, 28, 29, and 30 when mounted on an actual machine is clearly lower than that of Comparative Example 17 in which no silicone compound is added.
Further, the main resin of the surface treatment liquid used in Examples 31 to 34 has a polyol compound and an isocyanate compound. It can be said that the roller dirt density of Examples 27 to 30 and Examples 31 to 34 is clearly lower than that of Comparative Example 17 in which no silicone compound is added.

  Further, the main resin of the surface treatment liquid used in Examples 31 to 34 has a polyol compound and an isocyanate compound. Comparing the roller dirt density of Examples 27-30 and Examples 31-34, it is clear that the dirt of each roller of Examples 31-34 is lower than that of Examples 27-30. 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 semiconductive members of the items (15) and (16) are based on such results.

  Further, the roller dirt density of Example 34 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 34 contains a fluorinated silicone compound having a reactive group, a fluorine polyol compound, and an isocyanate compound.

Example 35
A semiconductive member surface treatment solution having the following composition was prepared.
Fluoropolyol (Lumiflon (registered trademark) LF-601C main agent: manufactured by 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 Electronic Conductive Agent: Carbon (Ketjen Black (registered trademark) EC: manufactured by Lion Akzo)
2.6 parts by weight Polymer matrix ionic conductive agent: particle size 1 μm or less (polymer matrix: crosslinked particles: ethoxydiethylene glycol acrylate,
Trimethylolpropane triacrylate polymer) 5 parts by weight Among them, ionic conductive agent: tetra n-butylammonium perchlorate 0.2 parts by weight Plate-like inorganic filler: synthetic hydrotalcite (DHT-4A (registered trademark): Kyowa Chemical 4.4 parts by weight Silicone compound: Silicone oil (DMS-T11: Chisso) 0.1 part by weight Toluene 50 parts by weight Xylene 50 parts by weight Next, in Example 2 having a thickness of 6 mm on an 18Φ cored bar The above-mentioned adjustment liquid was spray-coated on a roller having an NBR elastic layer whose resistance was adjusted with carbon similar to that used for the coating so that the film thickness after curing was 15 μm. Produced.
This semiconductive member was mounted on a Ricoh Imagio Color 2800 as a secondary transfer roller, and 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. Cleaning performance evaluation (Note 3 = Same as Note 1 and Note 2)
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 the cleaning property 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.

Example 36
A semiconductive member of Example 36 was produced in exactly the same manner as in Example 35 except that the composition of the surface treatment liquid was changed to the following composition, and the paper dust adhesion characteristics as in Example 35 were evaluated.
Fluoropolyol (Lumiflon (registered trademark) LF-601C main agent: manufactured by Asahi Glass)
90 parts by weight polyisocyanate (Lumiflon (trademark) 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 Electronic Conductive Agent: Carbon (Ketjen Black (registered trademark) EC: manufactured by Lion Akzo)
2.6 parts by weight Polymer matrix ionic conductive agent: particle size 1 μm or less (polymer matrix: crosslinked particles: ethoxydiethylene glycol acrylate,
Trimethylolpropane triacrylate polymer) 5 parts by weight Among them, ionic conductive agent: tetra n-butylammonium perchlorate 0.2 parts by weight Plate-like inorganic filler: synthetic hydrotalcite (DHT-4A (registered trademark): Kyowa Chemical 4.4 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 18
A semiconductive member of Comparative Example 18 was produced in exactly the same manner as in Example 35 except that the composition of the surface treatment liquid was changed to the following composition, and the paper dust adhesion characteristics as in Example 35 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 Ion conductive agent: 7 parts by weight of lithium perchlorate Silicone compound: Silicone oil (DMS-T11: Chisso) 0.1 part by weight Toluene 50 parts by weight Xylene 50 parts by weight

Table 9 shows the results of evaluating the paper dust adhesion characteristics of the secondary transfer rollers obtained in Example 35, Example 36, and Comparative Example 18.
In addition, the usage-amount of the raw material in Table 9 is shown by a weight part.
Further, “good” of the paper dust adhesion characteristics in Table 9 indicates a case where no dirt is generated in the evaluation of 50K sheets.

  From Table 9, it can be seen that the paper dust adhesion characteristics of the transfer rollers of Example 35 and Example 36 are significantly improved compared to the transfer roller of Comparative Example 18 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.

Further, in the environmental test (left for 10 days in a 60 ° C.-30% RH environment), in Examples 25 to 36, there was no change in the roller volume resistance value, and the environment resistance was excellent. It was recognized that the resistance value was large and the fluctuation was large, resulting in missing prints, unevenness and fogging images, and inferior environmental resistance to temperature and humidity.

Claims (11)

A semiconductive member used in an electrophotographic image forming apparatus, wherein the constituent material constituting the outermost layer contains at least an inorganic filler having a plate-like structure and a conductive agent, and the conductive agent is at least are those containing electron conductive agent and a polymer matrix carrying an ion-conducting agent, Ri Oh the polymer matrix in crosslinked polymeric particles, crosslinked polymeric particles, fluorinated polymer or a monofunctional acrylate and 3 A semiconductive member for an image processing apparatus, which is a copolymer of a functional acrylate . The semiconductive member for an image processing apparatus according to claim 1 , wherein the fluorine-based polymer is a vinylidene fluoride-hexafluoropropylene copolymer . The semiconductive member for an image processing apparatus according to claim 1 , wherein the copolymer of the monofunctional acrylate and the trifunctional acrylate is an ethoxydiethylene glycol acrylate / trimethylolpropane triacrylate polymer . The semiconductive member for an image processing apparatus according to any one of claims 1 to 3, wherein the conductive agent further contains at least a silicone compound. The semiconductive member for an image processing apparatus according to any one of claims 1 to 3, wherein the conductive agent further contains at least a fluorinated silicone compound. The semiconductive member for an image processing apparatus according to claim 1, wherein the conductive agent further contains a silicone compound having at least a reactive group. The semiconductive member for an image processing apparatus according to claim 1, wherein the conductive agent contains at least a fluorinated silicone compound having a reactive group. The semiconductive member for an image processing apparatus according to any one of claims 1 to 3, wherein the constituent material constituting the outermost layer further contains at least a polyol compound and an isocyanate compound. The semiconductive member for an image processing apparatus according to any one of claims 1 to 3, wherein the constituent material constituting the outermost layer further contains at least a fluorine polyol compound and an isocyanate compound. . The image processing apparatus half according to any one of claims 1 to 3, wherein the constituent material constituting the outermost layer further contains at least a fluorine polyol compound, an acrylic resin, and an isocyanate compound. Conductive member. 4. The image processing apparatus according to claim 1, wherein the constituent material constituting the outermost layer further contains at least a fluorine polyol compound, an acrylic polyol compound, and an isocyanate compound. 5. Semiconductive member.