JP2006323402A - Elastic member of semiconductive polymer, and oa component using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an elastic member of a semiconductive polymer, having characteristics that are superior, in both the voltage dependence and environmental dependence of the electrical resistance. <P>SOLUTION: An elastic member of a semiconductive polymer, comprising a conductive composition containing a conductive polymer and a binder polymer, is provided, wherein the elastic member satisfies both characteristics of (A) dispersion of 1.5 digits or smaller between the electrical resistance at an applied voltage of 1V and the electrical resistance at an applied voltage of 133V under the environment of 25°C×50%RH, and (B) a dispersion of one digit or smaller, between the electrical resistance at an applied voltage of 10V under the environment of 15°C×10%RH, and the electrical resistance at an applied voltage of 10V under the environment of 35°C×85%RH. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a semiconductive polymer elastic member and an OA component using the same, and more specifically, a developing roll, a charging roll, a transfer roll, a toner supply roll, a charge eliminating roll, a paper feed roll, a transport roll, and a cleaning roll. , A semiconductive polymer elastic member used as at least a part of constituent members of OA (Office Automation) parts such as a developing blade, a charging blade, a cleaning blade, and a transfer belt, and an OA component using the same Is.

  In general, in order to use a semiconductive polymer elastic member used for OA parts such as a developing roll, it is essential to control electric resistance. Therefore, conventionally, the electrical resistance is controlled by blending an ion conductive agent or an electronic conductive agent with a binder polymer such as resin or rubber.

Since the ionic conductive agent dissolves in the binder polymer, there is an advantage that the variation in conductivity is small, the variation in electric resistance when the voltage is changed is small, and the voltage dependency of the electric resistance is excellent. However, since the ionic conductive agent has a conductivity development mechanism based on ion conduction, if the electric resistance is 1 × 10 ⁷ Ω · cm or more, the ion conduction in the binder polymer is good. The conductivity can be controlled. However, when the electric resistance is less than 1 × 10 ⁷ Ω · cm, ion conduction is difficult to occur, and the conductivity is difficult to control. In addition, ionic conductive agents are easily affected by moisture, etc., and the electrical resistance fluctuates by two orders of magnitude under conditions of high temperature and high humidity and low temperature and low humidity. There are many restrictions.

  On the other hand, an electronic conductive agent such as carbon black is less susceptible to moisture and the like, has little fluctuation in electric resistance under conditions of high temperature and high humidity and low temperature and low humidity, and is excellent in environmental dependency of electric resistance and low electric resistance. It is suitable for use as an OA component. However, since it is difficult to uniformly disperse the electronic conductive agent in the binder polymer, variation in electric resistance is large, and it is difficult to control the conductivity. In addition, even when dispersed relatively uniformly, the mechanism of conductivity development is due to the tunnel effect or hopping phenomenon in which electrons are transmitted between the carbons in the binder polymer by a high voltage, so the electric resistance when the voltage is changed Fluctuation is large and the voltage dependence of electrical resistance is inferior.

  The present invention has been made in view of such circumstances, and a semiconductive polymer elastic member excellent in both the voltage dependency of electrical resistance and the environmental dependency of electrical resistance, and an OA component using the same. The purpose is to provide.

In order to achieve the above object, the present invention provides a semiconductive polymer elastic member using a conductive composition containing a conductive polymer and a binder polymer, and the elastic member has the following ( A semiconductive polymer elastic member that satisfies the characteristics of both A) and (B) is a first gist. Moreover, this invention makes the 2nd summary the OA component which used the said semiconductive polymer elastic member for at least one part of the structural member of OA component.
(A) In an environment of 25 ° C. × 50% RH, the fluctuation between the electric resistance when a voltage of 1 V is applied and the electric resistance when a voltage of 133 V is applied is 1.5 digits or less.
(B) The variation between the electric resistance when a voltage of 10 V is applied in an environment of 15 ° C. × 10% RH and the electric resistance when a voltage of 10 V is applied in an environment of 35 ° C. × 85% RH is 1 Less than digits.

  That is, the present inventors have intensively studied to obtain a semiconductive polymer elastic member excellent in both the voltage dependency of electrical resistance and the environmental dependency of electrical resistance. As a result, in an environment of 25 ° C. × 50% RH, the fluctuation between the electric resistance when a voltage of 1 V was applied and the electric resistance when a voltage of 133 V was applied was 1.5 digits or less, and 15 ° C. The fluctuation between the electric resistance when a voltage of 10 V is applied in an environment of × 10% RH and the electric resistance when a voltage of 10 V is applied in an environment of 35 ° C. × 85% RH is less than one digit. It has been found that the intended purpose can be achieved by using a conductive polymer elastic member, and the present invention has been achieved.

The semiconductivity in the semiconductive polymer elastic member of the present invention means that the electric resistance measured according to the method described in SRIS 2304 is in the range of 1 × 10 ¹² Ω · cm or less. .

  As described above, the semiconductive polymer elastic member of the present invention has a voltage dependency of electrical resistance in the range of 1V to 133V of 1.5 digits or less and an electrical resistance variation of 1 digit. Since it is below, it is excellent in both the voltage dependence of electrical resistance and the environmental dependence of electrical resistance. As a result, since the semiconductive polymer elastic member of the present invention can control the electric resistance depending on the applied voltage to be constant, for example, in the developing roll, the toner layer forming property and the charging property can be stabilized. The current control with the photosensitive member can be stabilized, and the transfer performance can be stabilized because the transfer of the toner on the photosensitive member is performed by controlling the voltage even with the transfer member. Furthermore, it is also effective as a current control element such as a sensor material or an actuator utilizing such a difference in electrical characteristics.

Moreover, when the electrical resistance of the semiconductive polymer elastic member of the present invention is in the range of 10 ⁶ to 10 ¹² Ω · cm, electrical characteristics suitable for OA parts can be provided.

  Furthermore, when the electrical resistance when the semiconductive polymer elastic member of the present invention is 100% stretched is 1.3 digits or less of the electrical resistance when not stretched, it is stable against variations in shape. Because it shows electrical characteristics, there are few electrical fluctuations during use with large deformations and electrical deterioration with long-term use, it can keep the image quality at a high level, and it does not break down the delicate toner with low melting point at high speed. Suitable for flexible members that can be printed.

  Next, an embodiment of the present invention will be described.

  The semiconductive polymer elastic member of the present invention can be obtained using a conductive composition containing a conductive polymer and a binder polymer.

  The conductive polymer is not particularly limited, but a conductive polymer having a surfactant structure is preferably used.

  The conductive polymer having the surfactant structure can be produced, for example, by a method such as chemical oxidative polymerization with an oxidizing agent in the presence of a conductive polymer raw material monomer and a surfactant.

  The raw material monomer for the conductive polymer is not particularly limited as long as it has electrical conductivity. For example, aniline (including aniline salts such as aniline hydrochloride in addition to aniline derivatives), pyrrole, thiophene, alkylthiophene, Ethylenedioxythiophene, isonaftthiophene, 3-thiophene-β-ethanesulfonic acid, dichenothiophene, acetylene, paraphenylene, phenynevinylene, furan, selenophene, tellurophene, isothianaphthene, paraphenylene sulfide, paraphenylene oxide, Examples include vinylene sulfide.

  The surfactant is not particularly limited, and examples thereof include anionic surfactants such as long-chain alkyl sulfates, cationic surfactants such as long-chain alkyl ammonium salts, and neutral surfactants. can give. These may be used alone or in combination of two or more.

  Examples of the long-chain alkyl sulfate of the anionic surfactant include dodecyl sulfonic acid, dodecyl benzene sulfonic acid, pentadecyl sulfonic acid, naphthalene sulfonic acid and the like.

  Examples of the long-chain alkylammonium salt of the cationic surfactant include cetyltrimethylammonium bromide.

  Examples of the oxidizing agent include ammonium persulfate, hydrogen peroxide, ferric chloride, and the like.

  The mixing ratio of the raw material monomer and the surfactant of the conductive polymer is preferably a molar ratio of raw material monomer / surfactant = 1 / 0.03 to 1/3, particularly preferably raw material monomer / surfactant. Agent = 1 / 0.05 to 1/2. That is, when the molar ratio of the surfactant is lowered, the compatibility and dispersibility with the binder polymer are lowered, and conversely, when the molar ratio of the surfactant is increased, the effect of the surfactant on the ionic conductivity is increased. This is because the electronic conductivity of the conductive polymer is reduced.

  The number average molecular weight (Mn) of the conductive polymer is preferably in the range of 500 to 100,000, particularly preferably in the range of 1000 to 20000.

  The binder polymer used together with the conductive polymer is not particularly limited, and examples thereof include acrylic-based, urethane-based, fluorine-based, polyamide-based, epoxy-based, rubber-based elastomers or resins. These may be used alone or in combination of two or more. Among these, acrylic and rubber elastomers or resins are preferable in terms of excellent compatibility with the conductive polymer.

  Examples of the acrylic elastomer or resin include polymethyl methacrylate (PMMA), polyethyl methacrylate, polymethyl acrylate, polyethyl acrylate, polyhydroxy methacrylate, acrylic silicone resin, acrylic fluorine resin, and known acrylic monomers. Polymerized products and the like can be mentioned.

  Examples of the urethane-based elastomer or resin include ether-based, ester-based, acrylic-based, aliphatic-based urethane, and those obtained by copolymerizing a silicone-based polyol or a fluorine-based polyol. The urethane elastomer or resin may have a urea bond or an imide bond.

  Examples of the fluoroelastomer or resin include polyvinylidene fluoride (PVDF), vinylidene fluoride-tetrafluoroethylene copolymer, vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene copolymer, and the like. It is done.

  Examples of the polyamide-based elastomer or resin include alcohol-soluble methoxymethylated nylon.

  Examples of the epoxy elastomer or resin include bisphenol A type, epoxy novolac resin, brominated type, polyglycol type, polyamide combined type, silicone modified, amino resin combined type, and alkyd resin combined type.

  Examples of the rubber elastomer or resin include natural rubber (NR), butadiene rubber (BR), acrylonitrile butadiene rubber (NBR), hydrogenated NBR (H-NBR), styrene butadiene rubber (SBR), and isoprene rubber (IR). ), Urethane rubber, chloroprene rubber (CR), epichlorohydrin rubber (ECO), ethylene propylene diene polymer (EPDM), fluoro rubber, styrene-butadiene block copolymer (SBS), styrene-ethylene-butylene-styrene block A known thermoplastic polymer such as a polymer (SEBS) can be used.

  The number average molecular weight (Mn) of the binder polymer is preferably in the range of 500 to 2,000,000, particularly preferably in the range of 2,000 to 800,000.

  The mixing ratio of the conductive polymer raw material (the total amount of the conductive polymer raw material monomer and the surfactant) and the binder polymer is a weight ratio, and the conductive polymer raw material / binder polymer = 1/99 to 40. The range of / 60 is preferable, and the raw material / binder polymer of the conductive polymer is particularly preferably 4/96 to 35/65. That is, if the weight ratio of the raw material of the conductive polymer is less than 1, the effect on the conductivity is small. Conversely, if the weight ratio of the raw material of the conductive polymer exceeds 40, the conductive composition becomes hard and brittle. This is because the physical properties of the composition are lowered.

  In addition to the conductive polymer and the binder polymer, the conductive composition may contain an ionic conductive agent, an electronic conductive agent, a crosslinking agent, and the like.

  Examples of the ionic conductive agent include lithium perchlorate, quaternary ammonium salts, borates, surfactants, and the like. These may be used alone or in combination of two or more.

  In addition, the blending ratio of the ionic conductive agent is 100 in total from the viewpoint of physical properties and electrical characteristics. The total of the raw material of the conductive polymer having a surfactant structure (total amount of raw material monomer and surfactant) and the binder polymer is 100. The range of 0.01 to 5 parts is preferable with respect to parts by weight (hereinafter abbreviated as “parts”), particularly preferably 0.5 to 2 parts.

Examples of the electronic conductive agent include carbon black, c-ZnO (conductive zinc oxide), c-TiO ₂ (conductive titanium oxide), c-SnO ₂ (conductive tin oxide), graphite, and the like.

  In addition, the blending ratio of the electronic conductive agent is 5 with respect to a total of 100 parts of the conductive polymer raw material (total amount of raw material monomer and surfactant) and the binder polymer from the viewpoint of physical properties and electrical characteristics. A range of ˜30 parts is preferred, with 8-20 parts being particularly preferred.

  Examples of the crosslinking agent include urea resins such as sulfur, isocyanate, blocked isocyanate, and melamine, epoxy curing agents, polyamine curing agents, and peroxides.

  In addition, the blending ratio of the crosslinking agent is based on 100 parts in total of the conductive polymer raw material (total amount of raw material monomer and surfactant) and the binder polymer from the viewpoint of physical properties, adhesion, and liquid storage property. The range of 1 to 30 parts is preferable, and the range of 3 to 10 parts is particularly preferable.

  In addition to the above components, the conductive composition may contain a crosslinking accelerator, a catalyst, an anti-aging agent, a dopant and the like as necessary.

  Examples of the crosslinking accelerator include sulfenamide-based crosslinking accelerators, dithiocarbamate-based crosslinking accelerators, amines, and organic tin-based catalysts.

  The said electrically conductive composition can be manufactured as follows, for example. That is, first, a conductive polymer is produced according to the method described above. Next, a binder polymer is blended with the conductive polymer, and an ionic conductive agent, an electronic conductive agent, a crosslinking agent, and the like are blended as necessary. And an electroconductive composition can be obtained by knead | mixing these using kneading machines, such as a roll, a kneader, a Banbury mixer. The conductive polymer is preferably soluble in a solvent or can be present as a colloidal solution, and the binder polymer is preferably soluble in a solvent.

  Furthermore, according to the above-mentioned method, while producing a conductive polymer, you may disperse | distribute this conductive polymer in a binder polymer using a high shear disperser. Use of such a high shear disperser is preferable because the particle size of the conductive polymer becomes smaller and becomes compatible or uniformly finely dispersed in the binder polymer. Further, the particle size (median diameter) of the conductive polymer is preferably 1 μm or less. In the production of the conductive composition, it is desirable that the purification after the synthesis of the conductive polymer is not completely dried in order to prevent aggregation of the conductive polymer.

  The high shear disperser is a high-speed bead mill using ceramic beads such as glass or zirconia, a sand mill, a ball mill, a three roll, a pressure kneader, a colloid mill using a grinding force, or the like.

  Examples of the solvent include organic solvents such as m-cresol, methanol, methyl ethyl ketone (MEK), and toluene.

In the present invention, the greatest feature is that the semiconductive polymer elastic member using the conductive composition satisfies both the following characteristics (A) and (B).
(A) In an environment of 25 ° C. × 50% RH, fluctuation between the electric resistance when a voltage of 1 V is applied and the electric resistance when a voltage of 133 V is applied (difference between the maximum value and the minimum value of the electric resistance: Voltage dependency) is 1.5 digits or less.
(B) Fluctuation between the electric resistance when a voltage of 10 V is applied in an environment of 15 ° C. × 10% RH and the electric resistance when a voltage of 10 V is applied in an environment of 35 ° C. × 85% RH (environment) Dependency) is 1 digit or less.

  The evaluation of the voltage dependence of the electrical resistance was performed by measuring the electrical resistance when a voltage of 1 V was applied and the electrical resistance when a voltage of 133 V was applied in an environment of 25 ° C. × 50% RH, respectively. 1V / 133V), and the logarithmic difference of the electrical resistance is indicated as the number of fluctuation digits.

  In addition, the evaluation of the fluctuation (environment dependence) of the electrical resistance due to the environment is based on the electrical resistance at the low temperature and low humidity (15 ° C. × 10% RH) and the high temperature and high humidity (35 ° C. × 85%) under the condition of the applied voltage of 10V. % RH), and the logarithmic difference of the electrical resistance is expressed as a variable digit by Log (15 ° C. × 10% RH / 35 ° C. × 85% RH).

The semiconductive polymer elastic member using the conductive composition has an electric resistance of 10 ⁶ to 10 ¹² Ω · cm when a voltage of 10 V is applied in an environment of 25 ° C. × 50% RH. It is preferable to be within the range. That is, when the electrical resistance is less than 10 ⁶ Ω · cm, since the electric resistance is too low, leakage occurs, the tendency of the advantages of the image is reduced is seen as OA parts, contrary to 10 ¹² Ω · cm This is because the electrical resistance is too high, the charge up occurs and the control as the OA component tends to be difficult.

  In the semiconductive polymer elastic member using the conductive composition, the electrical resistance when 100% stretched is preferably an increase of 1.3 digits or less of the electrical resistance when not stretched. . That is, if the increase in electrical resistance exceeds 1.3 digits, the electrical resistance changes when used by being deformed by a flexible member, making it difficult to control as an OA component, resulting in image characteristics such as density unevenness. This is because there is a risk of adverse effects. In addition, the measurement of the electrical resistance fluctuation before and after the 100% elongation is performed by, for example, punching a semiconductive polymer elastic member using the conductive composition into a strip shape (10 mm width, 100 mm length), Measure the electrical resistance of 10V applied when it is stretched to 100% in an environment of 25 ° C x 50% RH, and change the electrical resistance before and after stretching (by digit). ).

  As an OA component using the semiconductive polymer elastic member of the present invention, for example, as shown in FIG. 1, a base layer 2 is formed on the outer peripheral surface of the shaft body 1, and an intermediate layer 3 is formed on the outer peripheral surface. Further, there is a conductive roll in which a surface layer 4 made of the semiconductive polymer elastic member of the present invention is formed on the outer peripheral surface thereof.

  The shaft body 1 is not particularly limited, and for example, a metal core made of a metal solid body, a metal cylinder body hollowed out inside, or the like is used. Examples of the material include stainless steel, aluminum, and iron plated. Moreover, an adhesive agent, a primer, etc. can be apply | coated on the shaft 1 as needed. The adhesive, primer, etc. may be made conductive as necessary.

  The material for the base layer 2 is not particularly limited, and examples thereof include silicone rubber, polyurethane elastomer, EPDM, SBR, NBR and the like. Among these, silicone rubber is particularly preferable because it has low hardness and little sag. In addition, when silicone rubber is used as the material for the base layer 2, a step of activating the silicone rubber surface by corona discharge, plasma discharge, or the like, and a step of applying a primer thereafter may be performed.

A conductive agent may be appropriately added to the base layer 2 material. As the conductive agent, carbon black has been conventionally used, graphite, potassium titanate, iron _{oxide, c-TiO 2, c-} ZnO, c-SnO 2, an ion conductive agent (quaternary ammonium salt, borate Salt, surfactant, etc.).

  The material for the intermediate layer 3 is not particularly limited, and examples thereof include NBR, hydrogenated acrylonitrile-butadiene rubber (H-NBR), polyurethane elastomer, CR, natural rubber, BR, IIR and the like. Among these, H-NBR is particularly preferable from the viewpoint of adhesiveness and coating solution stability.

  The material for the intermediate layer 3 includes a conductive agent, a vulcanizing agent such as sulfur, a vulcanization accelerator such as guanidine, thiazole, sulfenamide, dithiocarbamate, thiuram, stearic acid, zinc white (ZnO), a softening agent. Etc. may be added as appropriate. Note that the same conductive agent as described above is used.

  The conductive roll shown in FIG. 1 can be produced, for example, as follows. That is, first, each component of the base layer 2 material is kneaded using a kneader or the like to prepare the base layer 2 material. Further, each component of the intermediate layer 3 material is kneaded using a kneader such as a roll, the organic solvent is added to the mixture, mixed, and stirred to prepare the intermediate layer 3 material (coating solution). To do. Furthermore, the conductive composition as the material for the surface layer 4 is prepared according to the method described above.

  Next, as shown in FIG. 2, the shaft body 1 is prepared, and an adhesive, a primer, and the like are applied to the outer peripheral surface as necessary, and then the shaft body is placed in a cylindrical mold 6 in which the lower lid 5 is fitted. Set 1 Next, after casting the material for the base layer 2, an upper lid 7 is fitted on the cylindrical mold 6. Next, the entire roll mold is heated to vulcanize the base layer 2 material (150 to 220 ° C. × 30 minutes) to form the base layer 2. Subsequently, the shaft body 1 on which the base layer 2 is formed is demolded, and the reaction is completed as necessary (80 to 200 ° C. × 4 hours). Next, a corona discharge treatment is performed on the roll surface as necessary. Further, a coupling agent is applied to the roll surface as necessary. Then, a coating liquid as a material for the intermediate layer 3 is applied to the outer periphery of the base layer 2, or a roll having the base layer 2 formed is dipped in the coating liquid and pulled up, followed by drying and heat treatment. Thus, the intermediate layer 3 is formed on the outer periphery of the base layer 2. Further, after applying a composition (coating liquid) as a material for the surface layer 4 on the outer periphery of the intermediate layer 3 or immersing and lifting the roll having the intermediate layer 3 formed in the composition (coating liquid) The surface layer 4 is formed on the outer periphery of the intermediate layer 3 by performing drying and heat treatment. The coating method of the coating liquid is not particularly limited, and conventionally known dipping method, spray coating method, roll coating method and the like can be mentioned. In this way, it is possible to produce a conductive roll in which the base layer 2 is formed along the outer peripheral surface of the shaft body 1, the intermediate layer 3 is formed on the outer periphery, and the surface layer 4 is formed on the outer periphery. .

  The semiconductive polymer elastic member of the present invention is not limited to the member for the surface layer 4 of the conductive roll shown in FIG. 1, but is used for the member for the base layer 2, the member for the intermediate layer 3, etc. It is also possible. The semiconductive polymer elastic member of the present invention is not limited to a roll member such as a conductive roll, but may be a belt member such as a transfer belt or a paper feed belt, a cleaning blade, a developing blade, a charging blade, or the like. It can also be used for OA parts such as blade members. Furthermore, the semiconductive polymer elastic member of the present invention can also be used for electronic members such as sensors, antistatic materials and actuators that utilize the electrical characteristics of OA parts.

  Next, examples will be described together with comparative examples.

  First, prior to Examples and Comparative Examples, the following compositions were prepared. And using these compositions, the conductive coating film or the foam sheet (henceforth "conductive coating film etc.") was produced, and the postscript evaluation was performed.

[Composition 1]
First, 1 mol of aniline and 1 mol of a surfactant (dodecylbenzenesulfonic acid) are oxidatively polymerized in water in the presence of 1 mol of an oxidizing agent (ammonium persulfate), and then an unreacted substance is removed with methanol. A polyaniline having a structure was obtained. Next, in an undried state, 20 parts of an active ingredient (non-volatile content) of polyaniline having this surfactant structure, and 80 parts of polymethyl methacrylate (PMMA) [number average molecular weight 20000] as a binder polymer The resulting mixture was kneaded at 80 ° C. for 10 minutes using a kneader to prepare a composition. And this composition was extrusion-molded and the electroconductive thin film of thickness 100 micrometers was produced.

[Composition 2]
First, 1 mol of aniline and 1 mol of a surfactant (dodecylbenzenesulfonic acid) were oxidatively polymerized in water in the presence of 1 mol of an oxidizing agent (ammonium persulfate), then unreacted substances were removed with methanol, and m-cresol. Was added to obtain a polyaniline solution having a surfactant structure. Next, 80 parts of polymethyl methacrylate (PMMA) [number average molecular weight 20000], which is a binder polymer, is dissolved in 500 parts of a solvent (m-cresol), and then the active ingredient (nonvolatile content) of the polyaniline solution is dissolved. ) 20 parts were added and kneaded using three rolls to prepare a composition (coating solution). And this composition (coating liquid) was apply | coated on the SUS304 board, and the 100-micrometer-thick electroconductive coating film was produced.

[Composition 3]
First, 1 mol of aniline and 0.05 mol of a surfactant (dodecylbenzenesulfonic acid) were oxidatively polymerized in water in the presence of 1 mol of an oxidizing agent (ammonium persulfate), and then unreacted substances were removed with methanol. -Cresol was added to obtain a polyaniline solution having a surfactant structure. Next, after dissolving 89.5 parts of polymethyl methacrylate (PMMA) [number average molecular weight 20000] as a binder polymer in 500 parts of a solvent (m-cresol), an active ingredient of the polyaniline solution ( (Non-volatile content) 10.5 parts was added and kneaded using three rolls to prepare a composition (coating solution). And this composition (coating liquid) was apply | coated on the SUS304 board, and the 100-micrometer-thick electroconductive coating film was produced.

[Composition 4]
First, 1 mol of aniline and 2 mol of a surfactant (dodecylbenzenesulfonic acid) were oxidatively polymerized in water in the presence of 1 mol of an oxidizing agent (ammonium persulfate), then unreacted substances were removed with methanol, and m-cresol was obtained. Was added to obtain a polyaniline solution having a surfactant structure. Next, after dissolving 66.7 parts of polymethyl methacrylate (PMMA) [number average molecular weight 20000] which is a binder polymer in 500 parts of a solvent (m-cresol), an active ingredient of the polyaniline solution ( (Non-volatile content) 33.3 parts was added and kneaded using three rolls to prepare a composition (coating solution). And this composition (coating liquid) was apply | coated on the SUS304 board, and the 100-micrometer-thick electroconductive coating film was produced.

[Composition 5]
First, 1 mol of aniline and 1 mol of a surfactant (dodecylbenzenesulfonic acid) were oxidatively polymerized in water in the presence of 1 mol of an oxidizing agent (ammonium persulfate), then unreacted substances were removed with methanol, and m-cresol. Was added to obtain a polyaniline solution having a surfactant structure. Next, 96 parts of polymethyl methacrylate (PMMA) [number average molecular weight 20000], which is a binder polymer, is dissolved in 500 parts of a solvent (m-cresol), and then the active ingredient (nonvolatile content) of the polyaniline solution is dissolved. 4 parts were added and kneaded using 3 rolls to prepare a composition (coating solution). And this composition (coating liquid) was apply | coated on the SUS304 board, and the 100-micrometer-thick electroconductive coating film was produced.

[Composition 6]
First, 1 mol of aniline and 1 mol of a surfactant (dodecylbenzenesulfonic acid) were oxidatively polymerized in water in the presence of 1 mol of an oxidizing agent (ammonium persulfate), then unreacted substances were removed with methanol, and m-cresol. Was added to obtain a polyaniline solution having a surfactant structure. Next, 65 parts of polymethyl methacrylate (PMMA) [number average molecular weight 20000], which is a binder polymer, is dissolved in 500 parts of a solvent (m-cresol), and then the active ingredient (nonvolatile content) of the polyaniline solution is dissolved. 35 parts were added and kneaded using 3 rolls to prepare a composition (coating solution). And this composition (coating liquid) was apply | coated on the SUS304 board, and the 100-micrometer-thick electroconductive coating film was produced.

[Composition 7]
Soluble nylon (made by Teikoku Chemical Co., EF30T) was used instead of polymethylmethacrylate, and 400 parts of methanol and 100 parts of water were used instead of 500 parts of m-cresol. Other than that was carried out similarly to the composition 2, and produced the electrically conductive coating film.

[Composition 8]
Instead of polymethylmethacrylate, polyurethane (Nihon Miractran, carbonate-based TPU E980) was used, and instead of 500 parts of m-cresol, 200 parts of methyl ethyl ketone (MEK) and 300 parts of tetrahydrofuran (THF) were used. It was dispersed with a high shear disperser (Dynomill 3200 rpm, bead particle size 0.8 mm). Other than that was carried out similarly to the composition 2, and produced the electrically conductive coating film.

[Composition 9]
A conductive coating film was produced in the same manner as the composition 8 except that a high shear disperser was not used.

[Composition 10]
Instead of polymethylmethacrylate, an acrylic fluorine-based resin (Dai Nippon Ink Chemical Co., Ltd., Defensa TR230K) was used, and in place of 500 parts of m-cresol, 200 parts of methyl ethyl ketone (MEK) and 300 parts of toluene were used. Other than that was carried out similarly to the composition 2, and produced the electrically conductive coating film.

[Composition 11]
First, 1 mol of aniline and 1 mol of a surfactant (pentadecylbenzenesulfonic acid) were oxidatively polymerized in the presence of 1 mol of an oxidizing agent (ammonium persulfate), then unreacted substances were removed with methanol, toluene was added, A polyaniline solution having a surfactant structure was obtained. Next, 80 parts of H-NBR (manufactured by Zeon Corporation, Zetpol 0020) as the binder polymer, 1 part of sulfur as the cross-linking agent, and sulfenamide-based cross-linking accelerator (Noxeller CZ, manufactured by Ouchi Shinsei Chemical Co., Ltd.) 5 parts, 0.5 part of a dithiocarbamate-based crosslinking accelerator (Ouchi Shinsei Chemical Co., Ltd., Noxeller BZ) is kneaded using two rolls and dissolved in 200 parts of methyl ethyl ketone (MEK) and 300 parts of toluene. After that, 20 parts of an active ingredient (nonvolatile content) of the polyaniline solution was added to prepare a composition (coating solution). And after apply | coating this composition (coating liquid) on a SUS304 board, it heat-crosslinked at 150 degreeC for 30 minute (s), and produced the 100-micrometer-thick electroconductive coating film.

[Composition 12]
A conductive coating film was prepared in the same manner as the composition 11 except that 5 parts of acetylene black (Denka Black HS100, manufactured by Denki Kagaku Kogyo Co., Ltd.) was further added as a conductive agent.

[Composition 13]
Conductivity is the same as in composition 11, except that 1 part of quaternary ammonium salt (tetrabutylammonium hydrogen sulfate: TBAHS) and 1 part of borate (made by Nippon Carlit Co., Ltd., LR147) are further added as a conductive agent. A coating film was prepared.

[Composition 14]
First, 1 mol of pyrrole and 1 mol of a surfactant (pentadecylbenzenesulfonic acid) were oxidatively polymerized in the presence of 0.1 mol of an oxidizing agent (ferric chloride), and then unreacted substances were removed with methanol. Was added and filtered to remove moisture, thereby obtaining a polypyrrole solution having a surfactant structure. Next, 80 parts of polyurethane (manufactured by Nippon Milactolan, carbonate-based TPU E980) as a binder polymer is dissolved in 200 parts of methyl ethyl ketone (MEK) and 300 parts of tetrahydrofuran (THF), and then the effective component (nonvolatile content) of the polypyrrole solution is dissolved. ) 20 parts were added to prepare a composition (coating solution). And this composition (coating liquid) was apply | coated on the SUS304 board, and it heated for 30 minutes at 150 degreeC, and produced the 100-micrometer-thick conductive coating film.

[Composition 15]
First, 1 mol of 3,4-ethylenedioxythiophene and 1 mol of a surfactant (pentadecylbenzenesulfonic acid) were oxidatively polymerized in the presence of 0.2 mol of an oxidizing agent (ammonium persulfate) and then unreacted with methanol. The product was removed, and toluene was added to obtain a polythiophene solution having a surfactant structure. Next, 80 parts of polyurethane (manufactured by Nippon Milactolan, carbonate-based TPU E980) as a binder polymer is dissolved in 200 parts of methyl ethyl ketone (MEK) and 300 parts of tetrahydrofuran (THF), and then the active ingredient (nonvolatile content of the polythiophene solution) is dissolved. ) 20 parts were added to prepare a composition (coating solution). And this composition (coating liquid) was apply | coated on the SUS304 board, and it heated for 30 minutes at 150 degreeC, and produced the 100-micrometer-thick conductive coating film.

[Composition 16]
First, 1 mol of aniline and 0.3 mol of a surfactant (pentadecylbenzenesulfonic acid) are oxidized and polymerized in the presence of 1 mol of an oxidizing agent (ammonium persulfate), then unreacted substances are removed with methanol, and toluene is added. Thus, a polyaniline solution having a surfactant structure was obtained. Next, 80 parts of a binder polymer, polyurethane (manufactured by Nippon Milactolan, carbonate-based TPU E980), is dissolved in 200 parts of methyl ethyl ketone (MEK) and 300 parts of tetrahydrofuran (THF), and then the active ingredient (nonvolatile content of the polyaniline solution) is dissolved. ) 20 parts were added to prepare a composition (coating solution). And this composition (coating liquid) was apply | coated on the SUS304 board, and it heated for 30 minutes at 150 degreeC, and produced the 100-micrometer-thick conductive coating film.

[Composition 17]
90 parts of polyether polyol (manufactured by Sanyo Chemical Co., Ltd., FA718), 10 parts of polymer polyol (manufactured by Mitsui Chemicals, POP31-28), and 0.5 part of tertiary amine catalyst (manufactured by Kao Corporation, Kaulizer No. 31) And 0.05 parts of a tertiary amine catalyst (Toyocat HX-35, manufactured by Tosoh Corporation), 2 parts of a foaming agent (water), and 2 parts of a silicone foam stabilizer (manufactured by Nihon Unicar Company, Ltd., L-5309) Then, 20 parts of polyaniline having a surfactant structure prepared in the same manner as in composition 1 was blended in a dry state and kneaded using three rolls. And 8.8 parts of Crude MDI (Sumitomo Bayer Urethane Co., Ltd., Sumidur 44V20) was added to this, mixed using a casting machine, cast and foamed into a mold at 80 ° C., and then at 80 ° C. for 30 minutes. Heat treatment was performed to produce a 5-fold foamed sheet (300 mm × 300 mm, thickness 10 mm).

[Composition A]
100 parts of epichlorohydrin rubber (Osaka Soda Co., Ltd., Epichromer CG), 2 parts of a quaternary ammonium salt (LBA Co., Ltd., TBAHS) as a conductive agent, 10 parts of an acid acceptor (zinc oxide), and a thiourea crosslinking accelerator 3 parts (manufactured by Sanshin Chemical Co., Ltd., Sunseller 22C) were mixed and kneaded using three rolls, and then dissolved in 300 parts of methyl ethyl ketone (MEK) and 150 parts of toluene to prepare a composition (coating solution). Prepared. And after apply | coating this composition (coating liquid) on a SUS304 board, it heat-crosslinked at 150 degreeC for 30 minute (s), and produced the 100-micrometer-thick electroconductive coating film.

[Composition B]
100 parts of polyurethane (manufactured by Nippon Milactolan, carbonate-based TPU E980) was dissolved in 200 parts of methyl ethyl ketone (MEK) and 300 parts of tetrahydrofuran (THF), and then acetylene black (made by Denki Kagaku Kogyo, 7 parts of Denka Black HS100) were blended and kneaded using three rolls to prepare a composition. And this was heat-crosslinked at 150 ° C. for 30 minutes to prepare a conductive coating film having a thickness of 100 μm on a SUS304 plate.

[Composition C]
The amount of acetylene black (Denka Black HS100, manufactured by Denki Kagaku Kogyo Co., Ltd.) was changed to 20 parts. Other than that was carried out similarly to the composition B, and produced the electroconductive coating film.

[Composition D]
Silicone in which carbon was dispersed (manufactured by Shin-Etsu Chemical Co., Ltd., KE1350AB) was applied on a SUS304 plate to prepare a conductive coating film having a thickness of 100 μm.

[Composition E]
First, 1 mol of aniline and 1 mol of a surfactant (pentadecylbenzenesulfonic acid) were oxidized and polymerized in the presence of 1 mol of an oxidizing agent (ammonium persulfate), then unreacted substances were removed with methanol, and filtration was performed three times. The water was completely removed at 100 ° C. for 30 minutes to obtain polyaniline having a surfactant structure. Next, 80 parts of H-NBR (manufactured by Zeon Corporation, Zetpol 0020) as the binder polymer, 1 part of sulfur as the cross-linking agent, and sulfenamide-based cross-linking accelerator (Noxeller CZ, manufactured by Ouchi Shinsei Chemical Co., Ltd.) 5 parts, 0.5 part of a dithiocarbamate-based crosslinking accelerator (Ouchi Shinsei Chemical Co., Ltd., Noxeller BZ) is kneaded using two rolls and dissolved in 200 parts of methyl ethyl ketone (MEK) and 300 parts of toluene. After that, polyaniline having the surfactant structure was added and kneaded with three rolls to prepare a composition (coating solution). And after apply | coating this composition (coating liquid) on a SUS304 board, it heat-crosslinked at 150 degreeC for 30 minute (s), and produced the 100-micrometer-thick electroconductive coating film.

[Composition F]
90 parts of polyether polyol (manufactured by Sanyo Chemical Co., Ltd., FA718), 10 parts of polymer polyol (manufactured by Mitsui Chemicals, POP31-28), and 0.5 part of tertiary amine catalyst (manufactured by Kao Corporation, Kaulizer No. 31) And 0.05 parts of a tertiary amine catalyst (Toyocat HX-35, manufactured by Tosoh Corporation), 2 parts of a foaming agent (water), and 2 parts of a silicone foam stabilizer (manufactured by Nihon Unicar Company, Ltd., L-5309) And 3 parts of ketjen black were blended and kneaded using three rolls. And 8.8 parts of Crude MDI (Sumitomo Bayer Urethane Co., Sumidur 44V20) and 20.5 parts of tolylene diisocyanate (Mitsui Chemicals Co., Ltd., TDI-80) are added to this and mixed using a casting machine. Then, it was cast and foamed into a mold set at 80 ° C., and then heat-treated at 80 ° C. for 30 minutes to prepare a 5-fold foamed sheet (300 mm × 300 mm, thickness 10 mm).

  The electrical resistance was measured using the conductive coating film and the like thus obtained. In addition, the voltage dependence and environmental dependence of the electrical resistance were also evaluated. These results are shown in Tables 1 to 4 below.

[Electric resistance]
In an environment of 25 ° C. × 50% RH, the electrical resistance of the conductive coating film and the like when a voltage of 1 V was applied and when a voltage of 133 V was applied was measured according to SRIS 2304.

(Voltage dependency)
In accordance with the evaluation of the electrical resistance, the electrical resistance when a voltage of 1V was applied and the electrical resistance when a voltage of 133V were applied were measured in an environment of 25 ° C. × 50% RH, respectively. 133V), the difference in electrical resistance is indicated by the number of fluctuation digits.

(Environment dependency)
According to the evaluation of the electrical resistance, the electrical resistance at low temperature and low humidity (15 ° C. × 10% RH) and the electrical resistance at high temperature and high humidity (35 ° C. × 85% RH) are measured, respectively. Differences are shown in variable digits. The applied voltage at this time is 10V.

〔Particle size〕
The particle size (median diameter) of the conductive polymer dispersed in the binder polymer was measured using a particle size distribution meter LA920 manufactured by Horiba. In addition, about the thing which has not mix | blended the conductive polymer, the particle size (median diameter) of the electrically conductive agent was measured. In addition, since a filler other than carbon is used in combination, “−” is displayed for those in which the particle size of the conductive polymer cannot be measured accurately.

[Electric resistance fluctuation before and after 100% extension]
When the conductive coating film made of each of the above compositions is punched into a strip (10 mm width, 100 mm length), an electrode is applied to the marked line portion, and stretched to 100% in an environment of 25 ° C. × 50% RH The electrical resistance was measured, and the electrical resistance fluctuation (digit) before and after stretching was determined. The applied voltage at this time is 10V.

  From the results in the above table, the compositions B, C, D, and F containing the electronic conductive agent have remarkably large electrical resistance fluctuations before and after 100% elongation, whereas the conductive polymer (conductive having a surfactant structure). It can be seen that the compositions 7 to 17 using the conductive polymer have very small electrical resistance fluctuations before and after 100% elongation. This is because compositions B, C, D, and F are dispersed with an electronic conductive agent that becomes a conductive path, while compositions 7 to 17 have a conductive polymer that becomes a conductive path in a binder polymer. This seems to be because it is uniformly dispersed in a state where it is connected to. In addition, since the composition 1-6 did not expand | extend PMMA used as a binder polymer, the electrical resistance fluctuation | variation was not able to be measured, but it turns out that the voltage dependence of electrical resistance and the environmental dependence of electrical resistance are small. . From this, it is considered that the conductive polymers in the compositions 1 to 6 are also present in the binder polymer in the same form as the compositions 7 to 17.

[Preparation of developing roll]

[Example 1]
Silicone in which carbon is dispersed (KE1350AB, manufactured by Shin-Etsu Chemical Co., Ltd.) is cast into an injection mold in which a core metal (diameter 10 mm, made of SUS304) is set as a shaft body, and 150 ° C. × 45 minutes. After heating under conditions, the mold was removed and a base layer was formed along the outer peripheral surface of the shaft. The surface of the base layer was subjected to corona discharge treatment (condition: 0.3 kW × 20 seconds). Subsequently, the composition C prepared above was applied to the outer peripheral surface of the base layer to form an intermediate layer. Furthermore, a surface layer made of the composition 1 prepared above is formed on the surface of the intermediate layer, a base layer is formed on the outer peripheral surface of the shaft, an intermediate layer is formed on the outer peripheral surface, and a surface layer is formed on the outer peripheral surface. A developing roll formed of was prepared.

[Examples 2 to 18, Comparative Examples 1 to 5]
A developing roll was produced in the same manner as in Example 1 except that the compositions shown in Tables 5 to 8 below were used as the intermediate layer material and the surface layer material. However, in Comparative Examples 1 to 5, the surface of the base layer was subjected to corona discharge treatment (condition: 0.3 kW × 20 seconds), and then an intermediate layer or a surface layer was formed. In addition, “None” is displayed for those in which the base layer or the intermediate layer is not formed.

  Each characteristic was evaluated according to the following reference | standard using the developing roll of the Example goods and comparative example goods which were obtained in this way. These results are shown in Tables 5 to 8 below.

[Electric resistance]
With the surface of the developing roll pressed against the SUS plate, a load of 1 kg is applied to both ends of the developing roll, and the electrical resistance between the core of the developing roll and the surface of the developing roll pressed against the SUS plate is Measured according to SRIS 2304. The electrical resistance was measured when a voltage of 1 V was applied and when a voltage of 133 V was applied in an environment of 25 ° C. × 50% RH.

(Voltage dependency)
In accordance with the evaluation of the electrical resistance, the electrical resistance when a voltage of 1V was applied and the electrical resistance when a voltage of 133V were applied were measured in an environment of 25 ° C. × 50% RH, respectively. 133V), the difference in electrical resistance is indicated by the number of fluctuation digits.

(Environment dependency)
According to the evaluation of the electrical resistance, the electrical resistance at low temperature and low humidity (15 ° C. × 10% RH) and the electrical resistance at high temperature and high humidity (35 ° C. × 85% RH) are measured, respectively. Differences are shown in variable digits. The applied voltage at this time is 10V.

〔hardness〕
The hardness (type A) was measured according to JIS K 6253.

(Compression set)
According to JIS K 6262, compression set was measured under the conditions of a temperature of 70 ° C., a test time of 22 hours, and a compression rate of 25%.

(Development roll characteristics)
(Image unevenness)
The obtained developing roll was incorporated into a commercially available color printer, and images were printed in an environment of 20 ° C. × 50% RH. In the evaluation, the case where there was no density unevenness due to the developing roll in the halftone image and there were no fine line breaks or color unevenness was evaluated as ◯, and the case where density unevenness occurred was evaluated as x.

(Environmental change)
The environment when the obtained developing roll is incorporated in a commercially available color printer and images are printed in an environment of 15 ° C. × 10% RH and when images are printed in an environment of 35 ° C. × 85% RH Variation was evaluated. In the evaluation, a solid black image was printed, and when the change was 0.1 or less with a Macbeth densitometer, ○, and when it exceeded 0.1, x.

[Preparation of charging roll]

Example 19
Silicone in which carbon is dispersed (KE1350AB, manufactured by Shin-Etsu Chemical Co., Ltd.) is cast into an injection mold in which a core metal (diameter 10 mm, made of SUS304) is set as a shaft body, and 150 ° C. × 45 minutes. After heating under conditions, the mold was removed and a base layer was formed along the outer peripheral surface of the shaft. The surface of the base layer was subjected to corona discharge treatment (condition: 0.3 kW × 20 seconds). Subsequently, the composition 11 prepared above was applied to the outer peripheral surface of the base layer to form an intermediate layer. Furthermore, a surface layer made of the composition 2 prepared above is formed on the surface of the intermediate layer, a base layer is formed on the outer peripheral surface of the shaft, an intermediate layer is formed on the outer peripheral surface, and a surface layer is formed on the outer peripheral surface. A charging roll formed of was prepared.

[Examples 20 to 29, Comparative Examples 6 and 7]
A charging roll was produced in the same manner as in Example 19 except that the compositions shown in Table 9 to Table 11 below were used as the intermediate layer material and the surface layer material. In Example 24, the base layer material prepared in the same manner as the composition 17 was used. In addition, “None” was displayed for those in which no intermediate layer was formed.

  Using the charging rolls of Examples and Comparative Examples thus obtained, each characteristic was evaluated according to the following criteria. These results are shown in Tables 9 to 11 below. The electrical resistance, voltage dependency, environment dependency, hardness, and compression set were evaluated in accordance with the evaluation of the developing roll.

(Charging roll characteristics)
(Image unevenness)
The obtained charging roll was incorporated into a commercially available color printer, and images were taken out in an environment of 20 ° C. × 50% RH. In the evaluation, the density unevenness caused by the charging roll in the halftone image was not observed, and the thin line was not broken or the color misregistration was evaluated as ◯, and the density unevenness was evaluated as x.

(Environmental change)
The environment when the obtained charging roll is incorporated into a commercially available color printer and images are taken out in an environment of 15 ° C. × 10% RH and when images are taken out in an environment of 35 ° C. × 85% RH. Variation was evaluated. In the evaluation, a solid black image was printed, and when the change was 0.1 or less with a Macbeth densitometer, ○, and when it exceeded 0.1, x.

[Preparation of transfer roll]

Example 30
Silicone in which carbon is dispersed (KE1350AB, manufactured by Shin-Etsu Chemical Co., Ltd.) is cast into an injection mold in which a core metal (diameter 10 mm, made of SUS304) is set as a shaft body, and 150 ° C. × 45 minutes. After heating under conditions, the mold was removed and a base layer was formed along the outer peripheral surface of the shaft. The surface of the base layer was subjected to corona discharge treatment (condition: 0.3 kW × 20 seconds). Subsequently, the composition 11 prepared above was applied to the outer peripheral surface of the base layer to form an intermediate layer. Furthermore, a surface layer made of the composition 2 prepared above is formed on the surface of the intermediate layer, a base layer is formed on the outer peripheral surface of the shaft, an intermediate layer is formed on the outer peripheral surface, and a surface layer is formed on the outer peripheral surface. A transfer roll formed of was prepared.

[Examples 31 to 37, Comparative Examples 8 and 9]
A transfer roll was produced in the same manner as in Example 30, except that the compositions shown in Table 12 and Table 13 below were used as the intermediate layer material and the surface layer material. In Example 37, a base layer material prepared in the same manner as the composition 17 was used. In addition, “None” was displayed for those in which no intermediate layer was formed.

  Using the transfer rolls of the example product and the comparative product obtained in this way, each characteristic was evaluated according to the following criteria. These results are also shown in Table 12 and Table 13 below. The electrical resistance, voltage dependency, environment dependency, hardness, and compression set were evaluated in accordance with the evaluation of the developing roll.

(Transfer roll properties)
(Image unevenness)
The obtained transfer roll was incorporated into a commercially available color printer, and images were taken out in an environment of 20 ° C. × 50% RH. In the evaluation, the case where there was no density unevenness due to the transfer roll in the halftone image and there was no break in the fine lines or color misregistration was evaluated as ◯, and the case where the density unevenness occurred was evaluated as x.

(Environmental change)
The environment when the obtained transfer roll is incorporated in a commercially available color printer and images are printed in an environment of 15 ° C. × 10% RH and when images are printed in an environment of 35 ° C. × 85% RH. Variation was evaluated. In the evaluation, a solid black image was printed, and when the change was 0.1 or less with a Macbeth densitometer, ○, and when it exceeded 0.1, x.

[Production of transfer belt]

[Examples 38 to 45, Comparative Examples 10 and 11]
As the base layer material, intermediate layer material, and surface layer material, single-layer or multilayer intermediate transfer belts (endless belts) were produced using the compositions shown in Table 14 and Table 15 below. In addition, “None” is displayed for those in which the base layer or the intermediate layer is not formed.

  Using the transfer belts of the example product and the comparative product obtained as described above, each characteristic was evaluated according to the following criteria. These results are also shown in Table 14 and Table 15 below.

[Electric resistance]
A SUS rod having a diameter of 10 mm and a weight of 1 kg was placed inside the transfer belt, and the electrical resistance between the portion in contact with the SUS rod and the SUS rod was measured according to SRIS 2304. The electrical resistance was measured when a voltage of 1 V was applied and when a voltage of 133 V was applied in an environment of 25 ° C. × 50% RH.

(Voltage dependency)
In accordance with the evaluation of the electrical resistance, the electrical resistance when a voltage of 1V was applied and the electrical resistance when a voltage of 133V were applied were measured in an environment of 25 ° C. × 50% RH, respectively. 133V), the difference in electrical resistance is indicated by the number of fluctuation digits.

(Environment dependency)
According to the evaluation of the electrical resistance, the electrical resistance at low temperature and low humidity (15 ° C. × 10% RH) and the electrical resistance at high temperature and high humidity (35 ° C. × 85% RH) are measured, respectively. Differences are shown in variable digits. The applied voltage at this time is 10V.

[Transfer belt characteristics]
(Image unevenness)
The obtained transfer belt was incorporated into a commercially available color printer, and images were taken out in an environment of 20 ° C. × 50% RH. In the evaluation, a case where there was no density unevenness due to the transfer belt in the halftone image and no thin line breakage or color misregistration was indicated as ◯, and a case where density unevenness occurred was indicated as x.

(Environmental change)
The environment when the obtained transfer belt is incorporated into a commercially available color printer and images are printed in an environment of 15 ° C. × 10% RH and when images are printed in an environment of 35 ° C. × 85% RH. Variation was evaluated. In the evaluation, a solid black image was printed, and when the change was 0.1 or less with a Macbeth densitometer, ○, and when it exceeded 0.1, x.

[Production of toner supply roll]

Example 46
A sponge layer was formed along the outer peripheral surface of the shaft body using the composition 17 to prepare a toner supply roll having a single layer structure. That is, first, 90 parts of a polyether polyol (manufactured by Sanyo Chemical Co., Ltd., FA718), 10 parts of a polymer polyol (manufactured by Mitsui Chemicals, POP31-28), and a tertiary amine catalyst (manufactured by Kao Corporation, Kaulizer No. 31) 0.5 part, 0.05 part of tertiary amine catalyst (Tosoh Corporation, Toyocat HX-35), 2 parts of foaming agent (water), silicone foam stabilizer (manufactured by Nippon Unicar Company, L- 5309) 2 parts and 20 parts of polyaniline having a surfactant structure prepared in the same manner as in the above composition 1 were blended in a dry state and kneaded using three rolls. Then, 8.8 parts of Crude MDI (Sumitomo Bayer Urethane Co., Ltd., Sumidur 44V20) 8.8 parts were added and mixed using a casting machine, and this was set with a core bar (diameter 5 mm, made of SUS304) as a shaft body. After being cast and foamed in the toner supply roll molding, it was heated and foamed at 80 ° C. for 30 minutes. Thereafter, the mold was removed, the surface was polished, and a toner supply roll in which a sponge layer was formed along the outer peripheral surface of the shaft body was produced.

[Comparative Example 12]
A toner supply roll was produced in the same manner as in Example 46 except that the composition F was used in place of the composition 17.

  Using the toner supply rolls of the example product and the comparative example product thus obtained, each characteristic was evaluated according to the following criteria. These results are also shown in Table 16 below. The electrical resistance, voltage dependency, environment dependency, hardness, and compression set were evaluated in accordance with the evaluation of the developing roll.

[Toner supply roll characteristics]
(Image unevenness)
The obtained toner supply roll was incorporated into a commercially available color printer, and images were printed in an environment of 20 ° C. × 50% RH. Evaluation is when there is no density unevenness caused by the toner supply roll in the halftone image, the thin line is not broken or the toner is not scattered, printed on a white background, and the Macbeth densitometer shows a change of 0.1 or more Was marked with x.

(Environmental change)
When the obtained toner supply roll was incorporated into a commercially available color printer and imaged in an environment of 15 ° C. × 10% RH and when imaged in an environment of 35 ° C. × 85% RH, The environmental change was evaluated. In the evaluation, a solid black image was printed, and when the change was 0.1 or less with a Macbeth densitometer, ○, and when it exceeded 0.1, x.

  From the above results, it can be seen that all the examples are excellent in developing roll characteristics, charging roll characteristics, transfer roll characteristics, transfer belt characteristics, and toner supply roll characteristics. The reason is presumed as follows. That is, the composition which is the surface layer material of the example (in the case of a single layer structure, the constituent material of the layer) contains a conductive polymer and a binder polymer, and the special conductive polymer is contained in the binder polymer. It is finely dispersed or dissolved into a polymer alloy consisting of a composite of a special conductive polymer and binder polymer. It is presumed that this is because both of the characteristics of the electronic conductive agent, which are excellent in dependence, are provided.

  On the other hand, since the products of Comparative Examples 1 to 11 are inferior to at least one of the electrical resistance voltage dependency and the electrical resistance environment dependency, the developing roll characteristics, the charging roll characteristics, the transfer roll characteristics, and the transfer belt characteristics. It turns out that it is inferior to. It can be seen that the product of Comparative Example 12 has inferior toner supply roll characteristics due to the large voltage dependency of the electrical resistance.

It is sectional drawing of the electroconductive roll using the semiconductive polymer elastic member of this invention. It is sectional drawing which shows an example of the manufacturing method of the said electroconductive roll.

Explanation of symbols

1 shaft body 2 base layer 3 intermediate layer 4 surface layer

Claims (8)

A semiconductive polymer elastic member comprising a conductive composition containing a conductive polymer and a binder polymer, wherein the elastic member satisfies the following characteristics (A) and (B): A semiconductive polymer elastic member.
(A) In an environment of 25 ° C. × 50% RH, the fluctuation between the electric resistance when a voltage of 1 V is applied and the electric resistance when a voltage of 133 V is applied is 1.5 digits or less.
(B) The variation between the electric resistance when a voltage of 10 V is applied in an environment of 15 ° C. × 10% RH and the electric resistance when a voltage of 10 V is applied in an environment of 35 ° C. × 85% RH is 1 Less than digits. 2. The semiconductive polymer elastic member according to claim 1, which has an electric resistance in a range of 10 ⁶ to 10 ¹² Ω · cm when a voltage of 10 V is applied in an environment of 25 ° C. × 50% RH.   The semiconductive polymer elastic member according to claim 1 or 2, wherein the electrical resistance when stretched 100% is a rise of 1.3 orders of magnitude or less when not stretched.   The said binder polymer is soluble in a solvent, and the said conductive polymer is soluble in a solvent or a binder solution or can exist as a colloidal solution. Conductive polymer elastic member.   The semiconductive polymer elastic member according to any one of claims 1 to 4, wherein the conductive polymer is dispersed in a binder polymer with a particle size of 1 µm or less or is compatible with the binder polymer. .   The semiconductive polymer elastic member according to any one of claims 1 to 5, wherein the conductive polymer has a surfactant structure.   A semiconductive polymer having a surfactant structure is synthesized using a raw material monomer and a surfactant, and the conductive polymer is dispersed in a binder polymer using a high shear disperser. Conductive polymer elastic member. An OA component comprising the semiconductive polymer elastic member according to any one of claims 1 to 7 as at least a part of constituent members of an OA component.

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