JP4148470B2 - Conductive roller, image forming apparatus including the conductive roller, conductive belt, and image forming apparatus including the conductive belt - Google Patents

Description

The present invention relates to a conductive roller formed using a conductive elastomer composition , a conductive member including a conductive belt, and an image forming apparatus including the conductive member.
Specifically, it is effectively used for a developing roller, a charging roller, a transfer roller, a conductive roller such as a toner supply roller, and a conductive belt such as a transfer belt used in an image forming apparatus such as a copying machine, a printer, and a facsimile machine. In particular, although it has ionic conductivity, it has a very low electric resistance value as compared with the prior art.

  A charging roller, a developing roller, a toner supply roller, a transfer roller, a transfer belt, and the like used in an image forming apparatus such as a copying machine (copying machine), a printer, and a facsimile machine need to have an appropriate and stable electric resistance value. is there. Conventionally, as a method of imparting conductivity to this type of conductive roller or conductive belt, a method of using an electronically conductive elastomer composition in which a conductive filler such as metal oxide powder or carbon black is blended in a polymer And a method using an ion conductive elastomer composition such as urethane rubber, acrylonitrile butadiene rubber (NBR), epichlorohydrin rubber and the like.

  When an electronically conductive elastomer composition containing the above conductive filler is used, particularly in the required semiconducting region, the electrical resistance value changes abruptly due to a slight change in the amount of addition, so the control is very It becomes difficult to. Further, in the elastomer composition, since the conductive filler is difficult to uniformly disperse, there is a problem that the electric resistance value varies in the circumferential direction and the longitudinal direction of the roller and in the plane of the belt. Furthermore, the electric resistance value of the obtained conductive roller or conductive belt depends on the applied voltage, does not show a certain resistance value, and is particularly noticeable when carbon black is used.

  From the above viewpoints, digitalization, colorization, etc., which are remarkable in image quality improvement technology, in recent copiers and printers, an ion conductive elastomer composition is particularly preferred instead of an electronic conductive elastomer composition. Tend to be used.

  However, since it is generally difficult to reduce the electric resistance value only with an ion conductive elastomer, it has been proposed to add an ion conductive additive or the like. For example, since urethane and NBR alone have too high electrical resistance, various metal ion salts and quaternary ammonium salts are added, and various other proposals have been made.

  For example, in Japanese Patent Application Laid-Open Nos. 2001-2114050 and 2001-217090, a conductive polymer composition in which a lithium ion salt such as a lithium imide salt is added to a copolymer having an ethylene oxide polymerization ratio of 85% or more. A crosslinked polymer solid electrolyte wall made of a product is disclosed.

  Japanese Patent Application Laid-Open No. 2002-226714 discloses a highly antistatic rubber composition in which various amounts of metal salts are contained in various elastomers using a specific compound as a medium.

  However, the conductive polymer compositions disclosed in Japanese Patent Application Laid-Open Nos. 2001-2114050 and 2001-2170099 are used for battery walls, and the polymerization ratio of ethylene oxide is as high as 85% or more, so There is a problem that it cannot be used for products that are used in open systems at normal temperature and humidity, such as conductive rollers and conductive belts. Further, since the polymerization ratio of ethylene oxide is too high, the hardness is increased or the compression set is deteriorated, which is considered to be impractical for general products or for applications such as conductive rollers and conductive belts.

  In addition, the high antistatic rubber composition disclosed in JP-A-2002-226714 uses a specific low molecular weight compound as a medium, so that there is no problem as long as it is used for general-purpose rubber products. There is still room for improvement in terms of compression set, photoconductor contamination, raw material cost, etc., to be applied to products that require high performance such as conductive rollers and conductive belts such as printers and printers.

  In addition, additives such as various metal ion salts and quaternary ammonium salts may greatly deteriorate the compression set or contaminate the photoreceptor depending on the substance, and the resistance value cannot be lowered sufficiently. In some cases. In addition, urethane, NBR, and the like originally have a high electric resistance value, so that it is difficult to realize a low volume resistivity (volume specific resistance value) as described in the present invention, and further reduction in resistance is desired. In many cases, it is not suitable for practical use as a conductive member for a machine or a printer.

  Also, a method of applying ion conductive additives such as various metal ion salts and quaternary ammonium salts to an ion conductive elastomer composition having a lower electrical resistance than urethane or the like can be considered, but this method is not always sufficient. A low resistance value is not always obtained. Depending on the amount and type of the additive, physical properties such as compression set may be deteriorated, and the photoreceptor is often contaminated. In addition, depending on the type and blending amount of the salt, the increase in electrical resistance during continuous energization may be large and may not be practical.

In addition to the above, various printer conductive members are required to have sufficient mechanical properties such as wear resistance and strength when mounted on an actual machine, and when formed by electrophotography, toners and photoreceptors are used. Practically, the member surface must have various characteristics in addition to the resistance value, for example, the member surface needs to have an appropriate charging property. In this case, since it is difficult to cope with the formation of a single ion conductive elastomer, it is necessary to optimize various properties by blending various elastomers in order to compensate for the performance required by the intended use. is there. However, when the ion conductive elastomer obtained by the conventional technique is blended with an elastomer for imparting the required characteristics, there is a problem that the electric resistance value of each member becomes high. Therefore, such an elastomer can be blended only within a range satisfying a predetermined resistance value. As a result, when this blend is used, insufficient strength, poor wear resistance, or the like has occurred.
In particular, since a developing roll and a charging roll are components that are the core of image formation in a printer that forms an image with electrostatic force, it is necessary to sufficiently charge a member to be charged such as a toner or a photoreceptor. In addition, since an extremely low electric resistance value is required in the design of the machine, a sufficient amount of the elastomer cannot be blended as described above, and the chargeability of the surface of the developing roll or the charging roll cannot be adjusted appropriately. As a result, there is a problem that the toner and the photoconductor as the member to be charged cannot be sufficiently charged and an appropriate image cannot be obtained. In particular, these tendencies are conspicuous as problems such as early image degradation during long-term use.
JP 2001-2104050 A JP 2001-217209 A JP 2002-226714 A

The present invention has been made in view of the above-mentioned problems, and can achieve an unprecedented low resistance value while suppressing variations in electrical resistance, and has an appropriate hardness without deteriorating physical properties such as compression set. object is a formed of a conductive elastomer composition comprising, providing transfer roller for a color copying machine or color printer, a charging roller, a transfer belt, a suitable conductive roller and the conductive belts as a cleaning blade or the like It is said.

In order to solve the above-described problems, the present invention firstly includes a conductive roller formed from a conductive elastomer composition having the following configuration, and a conductive elastomer composition having the same configuration as the conductive roller. And a conductive belt formed .
The conductive elastomer composition is a vulcanized rubber composition having an epichlorohydrin-ethylene oxide-allyl glycidyl ether copolymerization ratio of 45-10 mol% / 55-80 mol% / 0-10 mol%. In addition to an oxide binary copolymer and / or epichlorohydrin rubber that is an epichlorohydrin-ethylene oxide-allyl glycidyl ether terpolymer as an ion conductive elastomer component, a fluoro group (F-) and a sulfonyl group (-SO _2- ) And a tris (fluoroalkylsulfonyl) methane salt, which is a salt having an anion having an anion) of 0.1 part by weight with respect to 100 parts by weight of the total polymer component including the ion conductive elastomer component. 01 heavy And the salt is dispersed in the ion conductive elastomer component without using a medium comprising a low molecular weight polyether compound or a low molecular weight polar compound having a molecular weight of 10,000 or less. ,
The volume resistivity described in JIS K6911 measured under an applied voltage of 100 V when the ionic conductive elastomer component is imparted with conductivity by adding only the salt without imparting conductivity with the electronic conductive agent. 10 to the power of 6.9 [Ω · cm] or less,
The compression set measured at a measurement temperature of 70 ° C., a measurement time of 24 hours, and a compression rate of 25% according to “Method of permanent strain test of vulcanized rubber and thermoplastic rubber” described in JIS K6262 is 30% or less,
Hardness measured by type E durometer according to JIS K6253 is you equal to or less than 75 degrees.

The present inventor made a number of ion conductive additives, earnestly researched various formulations, and accumulated experiments. As a result, a salt of bisfluoroalkylsulfonylimide, which is a salt having an anion having a fluoro group (F—) and a sulfonyl group (—SO ₂ —), and / or tris (fluoro ) with respect to the ion conductive elastomer component When a salt of ( alkylsulfonyl) methane is added, a salt with an anion having a fluoro group (F−) and a sulfonyl group (—SO ₂ —) has a very high degree of dissociation, resulting in Since it shows a large solubility, it has been found that a very large conductivity can be obtained, so that the volume resistivity can be lowered and physical properties such as compression set and hardness are not deteriorated.

  Therefore, it is possible to obtain an extremely low resistance value that cannot be realized by the conventional ion conductive elastomer composition, a small compression set, and an appropriate hardness when used as a roller or a belt. Therefore, a conductive roller and a conductive belt having a very low volume resistivity can be supplied with good physical properties (low compression set, low hardness), and can be made suitable for practical use. This makes it possible to obtain a good image with little variation while reducing power consumption.

The volume resistivity according to JIS K6911 were measured under the applied voltage of 100V in the case of imparting conductivity by adding only the upper Kishio in the ion conductive elastomer component without imparting conductivity by electron-conductive agent If the rate is 10 6.9 [Ω · cm] or less, if the conductive elastomer composition is used as a developing roller or a charging roller of a copying machine or a printer, toner or This is because the charging efficiency of the photosensitive member is lowered and is not suitable for practical use. For example, when used as a developing roller, when the toner charged by the developing roller is conveyed from the developing roller to the photoconductor, the voltage drop increases if the resistance value of the developing roller is large. The electric field, which is the potential difference, becomes small, and image formation cannot be performed as designed. Also, when used as a charging roller, if the resistivity is higher than the above, it is necessary to apply a very large voltage, making it unsuitable for practical use.
The volume resistivity is preferably as small as possible, but the lower limit is about 10 to the power of 5.0 [Ω · cm], preferably 10 to the power of 6.0 [Ω · cm] or more. The volume resistivity was measured under the condition of a constant temperature and humidity of 23 ° C. and a relative humidity of 55% under an applied voltage of 100 V and the volume resistivity described in JIS K6911.

Secondly, the present invention provides a conductive roller formed from a conductive elastomer composition having the following configuration, and a conductive belt formed from a conductive elastomer composition having the same configuration as the conductive roller. And offers.
The elastomer composition is a vulcanized rubber composition, and an epichlorohydrin-ethylene oxide copolymer having an epichlorohydrin-ethylene oxide-allyl glycidyl ether copolymerization ratio of 45-10 mol% / 55-80 mol% / 0-10 mol%. An ionic conductive elastomer component composed of a primary copolymer and / or epichlorohydrin rubber which is a terpolymer of epichlorohydrin-ethylene oxide-allyl glycidyl ether, chloroprene rubber, acrylonitrile butadiene rubber, ethylene-propylene-diene copolymer rubber (EPDM) ), natural rubber, isoprene rubber, styrene-butadiene rubber, butyl rubber, as well as blends of one or more rubbers selected from the group consisting of acrylic rubber, fluoro group (F-) and a sulfonyl group (-SO 2 - _a) The salt of bisfluoroalkylsulfonylimide and / or the salt of tris (fluoroalkylsulfonyl) methane, which is a salt provided with an anion, is 0 with respect to 100 parts by weight of the total polymer component including the ion conductive elastomer component and the rubber. The ion-conductive elastomer component and the rubber are contained without using a medium comprising a low molecular weight polyether compound or a low molecular weight polar compound having a molecular weight of 10,000 or less. Distributed in
The conductivity obtained by adding the above-mentioned salt to the ion conductive elastomer has a volume resistivity described in JIS K6911 measured under an applied voltage of 100 V of 10 8.5 [Ω · cm] or less,
The compression set measured at a measurement temperature of 70 ° C., a measurement time of 24 hours, and a compression rate of 25% according to “Permanent strain test method of vulcanized rubber and thermoplastic rubber” described in JIS K6262 is 30% or less. the shall be the feature.

In order to ensure the practicality as a conductive member such as an elastomer having a small ion conductivity to the ion conductive elastomer, chloroprene rubber, acrylonitrile butadiene rubber, ethylene-propylene-diene copolymer rubber (EPDM), natural rubber, isoprene rubber, When an elastomer composition is blended with one or more kinds of cross-linked rubbers selected from the group consisting of styrene butadiene rubber, butyl rubber, and acrylic rubber , when the resistance is slightly increased, a fluoro group (F-) and a sulfonyl group ( A salt with an anion having —SO ₂ —) is added to make the volume resistivity of the conductive elastomer composition 10 to the 8.5th power [Ω · cm] or less.
The conductive elastomer composition thus formed can have a volume resistivity as low as 10 8.5 [Ω · cm] or less even when various necessary elastomers are blended as described above. Therefore, as described above as a problem, for example, when used as a developing roll or a charging roll, it is extremely useful when blending various elastomers with an ion conductive elastomer in order to impart appropriate chargeability to the roll surface. However, even if the same elastomer is blended with the ion conductive elastomer obtained by the prior art, it becomes impossible to put it to practical use because of its high resistance. It is possible to provide various conductive rolls excellent in the above.

In the present invention, polyethylene glycol, polypropylene glycol or polyether polyol having a low molecular weight (generally from several hundred to several thousand) is added to the ion conductive elastomer component or a blend of the ion conductive elastomer component and the rubber. In order to blend the above-mentioned salts without using a polyether compound such as a low molecular weight polyester polyol, a medium composed of a polar compound such as adipic acid ester, phthalic acid ester, etc., bleed, transition contamination, copying machine, printer it can be obtained Ishirube conductive roller such cause photoreceptor contamination, and the conductive belts in applications.

It is conceivable to dissolve and disperse the salt as described above in a polyether polyol or polyester polyol having a low molecular weight (molecular weight of 10,000 or less) and then react with an isocyanate compound to form a polyurethane having a low electrical resistance value. Since this low molecular weight polyol cannot react, there remains anxiety in terms of contamination of the photoreceptor. Therefore, the present invention is not conventional in that the above-mentioned salt can be dispersed without using a low molecular weight compound that causes such contamination, and the volume resistivity is 10 6.9 [Ω · cm] or less. It is excellent in that a low electrical resistance value can be obtained.
Further, the ion conductive elastomer may be one or more selected from the group consisting of chloroprene rubber, acrylonitrile butadiene rubber, ethylene-propylene-diene copolymer rubber (EPDM), natural rubber, isoprene rubber, styrene butadiene rubber, butyl rubber, and acrylic rubber. Even when the rubber to be crosslinked is blended, the volume resistivity can be reduced to 10 8.5 [Ω · cm] or less without using a low molecular weight compound that causes contamination.

As described above, the compression set of the conductive roller and the conductive belt of the present invention was measured at a measurement temperature of 70 ° C., a measurement time of 24 hours, and a compression rate of 25 according to the vulcanized rubber permanent strain test method described in JIS K6262. The value of compression set measured in% is 30% or less, more preferably 25% or less, and still more preferably 20% or less. Further, when it is used in constant contact with a photoreceptor such as some developing rolls or charging rolls or transported while being in contact, it is particularly preferably 10% or less.
This is because if the compression set value is larger than 30%, the dimensional change when it becomes a roller or belt becomes too large to be suitable for practical use, and there is a problem in durability and accuracy maintenance of the image forming process system. This is because it occurs.
The lower limit is preferably 1% or more in terms of optimization of vulcanization conditions and stable mass productivity.

Moreover, the hardness of the conductive elastomer composition for forming the first inventions of the conductive roller and the conductive belt has a hardness measured by type E durometer according to JIS K6253 is 75 degrees or less. This is because the softer the nip, the larger the nip, the greater the efficiency of transfer, charging, development, etc., or the advantage that the mechanical damage to other members such as the photoreceptor can be reduced. In addition, although it is so preferable that it is soft, in the case of a solid, 40 degrees or more and 70 degrees or less are more preferable, and 50 degrees or more and 70 degrees or less are more preferable.
On the other hand, above for the second inventions of the conductive roller and the conductive belt conductive elastomer composition forming a chloroprene rubber ionic conductive elastomer component, acrylonitrile-butadiene rubber, ethylene - propylene - diene copolymer rubber (EPDM ), One or more cross-linked rubbers selected from the group consisting of natural rubber, isoprene rubber, styrene butadiene rubber, butyl rubber, acrylic rubber, and 10 8.5 [Ω. In terms of practicality, the hardness is not limited to the above range because it has a relatively low volume resistivity of cm] and high charging characteristics. Preferably, the hardness measured by a type E durometer described in JIS K6253 is 40 degrees or more and 88 degrees or less.
This is preferably 45 degrees or more and less than 88 degrees, and more preferably 50 degrees or more and less than 80 degrees in order to obtain nip stability or higher chargeability. The most optimal range is 50 degrees or more and less than 70 degrees. From the viewpoint of obtaining such a preferable hardness, it is extremely effective to use the elastomer used in the first invention.

Furthermore, the conductive elastomer composition forming the conductive roller and the conductive belt of the present invention has a volume change rate when immersed in distilled water at 40 ± 1 ° C. and 22 ± 0.25 hours in accordance with JIS K6258. Is less than 50%.
Thereby, sufficient water resistance can be ensured, so that high performance can be maintained even under normal temperature and humidity.

  The ion conductive elastomer component is preferably contained in an amount of 5% by weight to 100% by weight with respect to 100% by weight of the total elastomer composition. It is because it becomes possible to make volume resistivity low by setting it as the said range. In order to obtain a low resistance, about 100% by weight is most preferable, and in the case of adding another polymer, 90% by weight or more and 95% by weight or less is suitable for the stability of production. On the other hand, when controlling the practical characteristics such as chargeability, it is 5% by weight or more and 80% by weight or less, more preferably 10% by weight or more and 50% by weight or less, and further preferably 10% by weight or more and 30% by weight or less.

First, as the ion-conductive elastomer component of the second invention, epi-chloro hydrin - ethylene oxide binary copolymer or / and epi-chloro-hydrin - ethylene oxide - epi-chloro allyl glycidyl ether terpolymer Hydrin rubber is used.
That is, first, second epi-chloro-hydrin in the invention of - using epi-chloro hydrin copolymerization ratio of the allyl glycidyl ether is from 45 to 10 mole% / 55 to 80 mole% / 0-10 mol% - ethylene oxide Yes.
The copolymerization ratio is set based on the following reason, and the volume resistivity is set while maintaining the physical properties (compression set, hardness) of the conductive elastomer composition.

That is, epi-chloro hydrin - ethylene oxide - in a terpolymer composed of allyl glycidyl ether, ions of conductivity is exhibited, the lithium oxonium ions and metal cations such as in the polymer (e.g., during addition salt Cations such as ions, nickel ions contained in the polymer anti-aging agent, etc.) are stabilized by the ethylene oxide unit and are transported by the segmental motion of the molecular chains of the part. Therefore, it is considered that a higher ratio of ethylene oxide units can stabilize many ions and realize lower resistance.
However, if the ratio of ethylene oxide is increased too much, crystallization of ethylene oxide occurs and the segmental movement of the molecular chain is hindered, so the volume resistivity increases conversely. Such crystallization also causes an increase in hardness and a deterioration in compression set. In order to suppress this crystallization by ethylene oxide, ethylene oxide is made 80 mol% or less. On the other hand, when ethylene oxide is less than 55 mol%, ion stabilization becomes insufficient, and the effect of reducing volume resistivity becomes small.
Furthermore, when the ethylene oxide ratio exceeds 80 mol%, the affinity with water is too high, the shape changes due to moisture absorption, the water resistance tends to deteriorate, and it becomes difficult to use in an environment of normal temperature and humidity. It becomes unsuitable for the use of the present invention. Further, when the tack comes out and is used for a roller or a belt, the photosensitive member is contaminated. The ethylene oxide ratio is more preferably 65 mol% or more and 75 mol% or less.

When the epi-chloro-hydrin exceeds 45 mol%, the effect of ethylene oxide as described above can no longer the amount of ethylene oxide to more than 55 mol% it is difficult to obtain. On the other hand, epi-chloro hydrin hardly ethylene oxide content is less than 10 mol% to 80 mol% or less, tend to occur problems such as described above. Incidentally, the epi-chloro hydrin is is not more than 35 mol% to 15 mol%, more preferably.
Epichlorohydrin of the epihalohydrin Ru can be easily obtained from the easily produced. And the low electrical resistance etc. are realizable by setting it as the said copolymerization ratio.

By copolymerizing the allyl glycidyl ether, cross-linking is possible, thereby making it difficult to cause bleeding and contamination of the photoreceptor, and imparting rubber elasticity to improve physical properties. In addition, since the allyl glycidyl ether unit itself obtains a free volume as a side chain, the above crystallization can be further suppressed, and thus, an unprecedented reduction in resistance can be realized.
If the copolymerization ratio of allyl glycidyl ether exceeds 10 mol%, the number of cross-linking points after vulcanization will increase, making it difficult to achieve low resistance, and the tensile strength, fatigue properties, flex resistance, etc. will deteriorate. It's easy to do. Moreover, it is preferable that an allyl glycidyl ether shall be 2 mol% or more. This is because if it is less than 2 mol%, bleeding or photoconductor contamination is likely to occur, crystallization is likely to occur, and it is difficult to effectively reduce the resistance value. In addition, it becomes difficult to increase the vulcanization speed, which may cause a slight problem regarding productivity.
Thus, by copolymerizing allyl glycidyl ether, while suppressing the crystallization of ethylene oxide and lowering the volume resistivity, while introducing a carbon-carbon double bond by copolymerization of allyl glycidyl ether, Cross-linking with other rubber is possible. By co-crosslinking with other rubber, bleeding and photoconductor contamination can be prevented. Furthermore, since the molecular weight can be increased by co-crosslinking with other rubber, bleeding and photoconductor contamination are less likely to occur.

The total polymer component 100 parts by weight containing the ion conductive elastomer component, the fluoro group (F-) and a sulfonyl group (-SO ₂ -) salts with anions having the above 0.01 parts by weight 20 and containing Mutoshi at a ratio of less parts.
The above range is because the effect of improving the conductivity is hardly seen when it is smaller than 0.01 parts by weight, and the demerit that the cost increases compared to the effect of improving the conductivity when it is larger than 20 parts by weight. This is because is larger.
In addition, More preferably, it is 0.2 to 10 weight part, More preferably, it is 0.4 to 6 weight part.

The conductive elastomer composition forming the conductive roller and the conductive belt of the present invention is a bisfluoroalkyl which is a salt having an anion having a fluoro group (F—) and a sulfonyl group (—SO ₂ —). It includes salts of sulfonylimides and / or salts of tris (fluoroalkylsulfonyl) methane.
The salt described above has a high degree of dissociation in polyethylene oxide since the anion is stable because charges are delocalized by a strong electron-attracting effect, and a particularly high ionic conductivity can be realized. Thus, a fluoro group (F-) and a sulfonyl group (-SO 2 _-) of bisfluoroalkylsulfonylimide a salt having an anion with a salt or / and tris (fluoroalkyl sulfonyl) blending a salt of methane As a result, low electric resistance can be efficiently realized. Therefore, by appropriately adjusting the blending of the polymer components, it is possible to suppress the problem of photoconductor contamination while maintaining low electric resistance.

The salt having an anion having a fluoro group (F—) and a sulfonyl group (—SO ₂ —) is preferably a lithium salt, but may be a salt of an alkali metal, a group 2A, or other metals. It is also possible to obtain a salt having a cation as represented by the following chemical formulas (Chemical Formula 1, Chemical Formula 2). In the formula, R _{1 to} R ₆ are each an alkyl group having 1 to 20 carbon atoms or a derivative thereof, and R _{1 to} R ₄ , and R ₅ and R ₆ may be the same or different. Among these, a trimethyl type quaternary ammonium cation in which three of R _{1 to} R ₄ are methyl groups and the other one is an alkyl group having 4 to 20 carbon atoms, preferably 6 to 20 carbon atoms, or a derivative thereof. The salt consisting of is particularly preferred because the positive charge on the nitrogen atom can be stabilized by three methyl groups having strong electron donating properties, and the compatibility with the polymer can be improved by other alkyl groups or derivatives thereof. In addition, in the cation of the chemical formula 2, R ₅ or R ₆ is preferably a methyl group or an ethyl group because it is easier to stabilize the positive charge on the nitrogen atom if it has an electron donating property. In this way, by stabilizing the positive charge on the nitrogen atom, the stability as a cation can be increased, and the salt can have a higher degree of dissociation and thus excellent conductivity imparting performance.

Specifically, as a salt of a bisfluoroalkylsulfonylimide or / and a salt of tris (fluoroalkylsulfonyl) methane, which is a salt having an anion having a fluoro group (F—) and a sulfonyl group (—SO ₂ —) is, for _{example, L iN (SO 2 CF 3} ) 2, LiC (SO 2 CF 3) 3 and the like.

A salt of bisfluoroalkylsulfonylimide and / or a salt of tris (fluoroalkylsulfonyl) methane, which is a salt having an anion having a fluoro group (F—) and a sulfonyl group (—SO ₂ —), has a molecular weight of 1 It is dispersed in the conductive elastomer composition without using a medium comprising a low molecular weight polyether compound or a low molecular weight polar compound having a molecular weight of 10,000 or less. The salt is preferably dispersed uniformly. Of the above-mentioned salts , bisfluoroalkylsulfonylimide salts such as LiN (SO ₂ CF ₃ ) ₂ have very good solubility in polyethylene oxide chains and the like, and can further plasticize polyethylene oxide chains and the like. Therefore, the addition can reduce the hardness and reduce the environmental dependency of the volume resistivity, which is very preferable. In particular, lithium-bis (trifluoromethanesulfonyl) imide (LiN (SO ₂ CF ₃ ) ₂ ) can be easily and uniformly dispersed by adding it directly to an ion conductive rubber such as an epihalohydrin rubber, and can be compressed permanently. This is very preferable because the strain characteristics can be improved and the hardness is hardly affected.

The epichlorohydrin-ethylene oxide-allyl glycidyl ether terpolymer can be used alone, or the epichlorohydrin-ethylene oxide-allyl glycidyl ether terpolymer and a mixture of chloroprene rubber or acrylonitrile butadiene rubber can be used. When used in combination with chloroprene rubber, the resistance value and vulcanization speed can be controlled more easily, and chloroprene rubber is a general-purpose rubber and is less expensive, thereby reducing the compound cost. When obtaining a particularly low volume resistivity, a weight ratio of (the terpolymer: chloroprene rubber) = (50:50) to (100: 0) is preferable.
In addition, the epichlorohydrin-ethylene oxide-allyl glycidyl ether terpolymer is used alone, or the epichlorohydrin-ethylene oxide-allyl glycidyl ether terpolymer is an epichlorohydrin rubber and an ethylene-propylene-diene copolymer rubber (EPDM). ), One or more rubbers composed of natural rubber, isoprene rubber, styrene butadiene rubber, butyl rubber, acrylic rubber, and the like can be blended as necessary.

The conductive elastomer composition forming the conductive roller and conductive belt of the present invention is a vulcanized rubber composition. The conductive elastomer composition is preferably crosslinked using sulfur and thioureas in combination, or crosslinked using sulfur and a triazine derivative. By taking advantage of each cross-linking system, the ratio of both sulfur and thiourea or sulfur and triazine derivatives is appropriately selected, so that the cross-linking speed, compression set, electrical resistance value, etc. are at the required level. It is possible to adjust. Furthermore, in the production of the foam roller, it is possible to dramatically suppress the decrease in the vulcanization speed and the decrease in the crosslinking density due to the foaming agent, and it is possible to obtain a roller having a high strength and a very good foam shape.

The thioureas are selected from the group consisting of tetramethylthiourea, trimethylthiourea, ethylenethiourea, and thiourea represented by (C _n H _{2n + 1} NH) ₂ C═S (n = 1 to an integer of 1 to 10). Species or multiple thioureas can be used.

  As the triazine derivative, one or more compounds selected from the group consisting of 2,4,6-trimercapto-S-triazine or 2-dialkylamino-4,6-dimercapto-S-triazine are used. be able to. From the viewpoint of the vulcanization rate, 2-dialkylamino-4,6-dimercapto-S-triazine is preferable.

Appropriate amounts of the sulfur and thioureas or sulfur and triazine derivatives can be selected depending on the type of accelerator used.
Specifically, sulfur is blended at a ratio of 0.1 to 5.0 parts by weight, preferably 0.2 to 2 parts by weight, with respect to 100 parts by weight of all polymer components. Is good.
The above range is because when the amount is less than 0.1 parts by weight, the vulcanization rate of the entire composition is slowed down, and the productivity is likely to deteriorate. On the other hand, if the amount is larger than 5.0 parts by weight, the compression set may increase, or sulfur and the accelerator may bloom.

Thioureas may be blended in a total proportion of 0.0009 mol to 0.0800 mol, preferably 0.0015 mol to 0.0400 mol, per 100 g of all polymer components.
The triazine derivative may be blended in an amount of 0.0004 mol to 0.0500 mol, preferably 0.0010 mol to 0.0300 mol, with respect to 100 g of all polymer components.
By blending in the above range, the vulcanization can be made tight, making it difficult to cause bloom and photoconductor contamination, and not much disturbing the molecular motion of the polymer, so low electrical resistance and compression set are achieved. It is also possible to improve mechanical properties such as
Further, when the foam 2, foam 3 or foam 6 shown in FIG. 6 to be described later is used as a foam or a foam roller, it is possible to reduce cross-linking inhibition by the foaming agent, and furthermore, it is sufficiently fast for practical use. Vulcanization rate can be set.
(Sulfur: thioureas) = (5: 1) to (1: 8) is preferably blended at a weight ratio.
(Sulfur: triazine derivative) = (3: 1) to (1: 2) is preferably blended at a weight ratio.

The conductive elastomer composition for forming the conductive roller and the conductive belt of the present invention includes an electronic conductive conductive material such as carbon black or conductive zinc for the purpose of improving the environmental dependency of the electrical resistance value. You may mix | blend an agent in the range which does not impair ionic conductivity completely.

  In the case of continuous vulcanization, a thiourea type, a combination of sulfur and thioureas, or a combination of sulfur and a triazine derivative is suitable because it has a suitably short scorch time.

Conductive elastomer composition forming the conductive roller and the conductive belt of the present invention is used as a vulcanized rubber.

Part of the cation generated from the salt having an anion having the fluoro group (F-) and the sulfonyl group (-SO _2- ) is converted into a single ion to stabilize the conductivity and improve the conductivity when added in a small amount. Can be planned. It is more preferable that 0.5% or more is single ionized. Thereby, it is possible to obtain a more stable electrical conductivity and a lower electric resistance value with addition of a smaller amount of metal salt, and more preferably 1% to 20% single ionization.
Single ionization means adsorption of one of cations or anions generated by dissociation of the salt by an ion adsorbent so that the other ion can move relatively freely in the system. Refers to that.

  In order to increase the vulcanization speed, a sulfur vulcanization system, a vulcanization system using sulfur and thioureas in combination, or a vulcanization system using sulfur and a triazine derivative in combination is preferable. Further, it is more preferable to use hydrotalcite from the viewpoint of low contamination. Vulcanization can also be performed by an ordinary method. For example, vulcanization may be performed in a vulcanization can under pressure of steam, or secondary vulcanization may be performed as necessary. Further, for possible blending, a method by continuous vulcanization may be performed.

In addition, hydrotalcite is preferably blended in an amount of 1 to 15 parts by weight, more preferably 2 to 10 parts by weight with respect to 100 parts by weight of the polymer containing halogen. In this way, when formulating hydrotalcite as acid acceptor, ions due to halogens generated during vulcanization of polymers containing halogen, such as epi-chloro Hidoringo beam is vulcanization inhibitor to be captured by the hydrotalcite And photoconductor contamination can be prevented. Moreover, since it is excellent also in dispersibility, since there is little influence on the physical property by kneading | mixing state or a process, it is preferable.

The conductive roller and conductive belt using the conductive elastomer composition of the present invention are excellent in that they have a low volume resistivity, a small compression set, and a low hardness. Is suitable for color transfer rollers, charging rollers, toner supply rollers, development rollers, and conductive belts when a low electrical resistance value is required, such as a transfer belt. .
In addition, since the conductive elastomer composition used in the present invention can be formed by using two or more kinds of elastomer components including an elastomer that imparts chargeability, a charging roller or toner for charging a photoreceptor is charged. A conductive member such as a developing roller that conveys toner to the latent image on the photoreceptor is particularly suitable.
Therefore, a conductive roller and a conductive belt having desired performance can be designed with a very high degree of freedom.

The conductive roller can be prepared by a conventional method. For example, the kneaded material for the conductive elastomer composition is preformed into a tube shape with a single-screw extruder, and the preform is added at 160 ° C. for 15 to 70 minutes. After the vulcanization, various conventionally known methods such as inserting and bonding a core metal and polishing the surface and then cutting it into a required dimension to form a roller can be used. The vulcanization time may be determined by determining the optimum vulcanization time using a vulcanization test rheometer (eg, curast meter). Further, the vulcanization temperature may be determined by raising or lowering the temperature as necessary. In order to reduce the photoreceptor contamination and compression set, it is preferable to set the conditions so that a sufficient vulcanization amount can be obtained.
When a conductive elastomer composition for the purpose of obtaining a low electrical resistance value is used for the conductive elastomer composition forming the conductive roller and conductive belt of the present invention, the roller resistance value at an applied voltage of 100 V is 10 It is preferably ^3.5 [Ω] or more and 10 ^5.5 [Ω] or less, and more preferably 10 ^4.0 [Ω] or more and 10 ^5.0 [Ω] or less.
Moreover, a foaming agent etc. may be mix | blended and a conductive foam roll may be formed, a surface layer may be coated with a coating agent, or a tube may be tubing and used.

Further, the conductive belt, the kneaded product for the conductive elastomer composition was molded by extrusion in a belt shape by an extruder, 160 ° C., carried out 15 to 70 minutes vulcanization, making the belt body Various conventionally known methods, such as, can be used. The vulcanization temperature may be determined by raising or lowering the temperature as necessary.

Further, the conductive roller such as the developing roller and the charging roller in consideration of the charging property of the present invention preferably has a roller resistance value of 10 ^5.0 Ω or more and 10 ^7.0 Ω or less at an applied voltage of 100 V, more preferably 10 ^5.0 Ω or more. More preferably, it is 10 ^6.5 Ω or less. The above range is because if it is less than 10 ^5.0 Ω, current flows too much and image defects are likely to occur, and there is a possibility of discharge to the photoreceptor. On the other hand, if it is larger than 10 ^7.0 Ω, the efficiency of toner supply and the like is lowered and it is difficult to be practically used. Further, when the toner moves to the photosensitive member, a voltage drop of the developing roller occurs, and thereafter, the toner cannot be reliably conveyed from the developing roller to the photosensitive member, resulting in an image defect.

As described above, the conductive roller of the present invention preferably has a dielectric loss tangent of about 0.1 to 1.5 when a voltage of 100 Hz is applied. In the electrical characteristics of the conductive roller, the dielectric loss tangent is an index indicating the degree of influence of the current flow (conductivity) and the capacitor component (capacitance), and is a parameter indicating the phase delay when an alternating current is applied. However, it shows the size of the capacitor component ratio when voltage is applied. That is, in the case of a conductive roller, the dielectric loss tangent is the relationship between the amount of charge generated when the toner contacts the developing roller at a high pressure by the amount regulating blade and the amount of charge that escapes onto the roller before being conveyed to the photoreceptor. And is an index indicating the charge amount of the toner immediately before contact with the photoreceptor. If the dielectric loss tangent is large, it is easy to pass electricity (charge) and the polarization is difficult to proceed. Conversely, if the dielectric loss tangent is small, the polarization is difficult to pass electricity (charge).
Therefore, in the case of a conductive roller, the smaller the dielectric loss tangent, the higher the capacitor characteristics of the roller, and the toner charge caused by frictional charging can be maintained without escaping from the roller. That is, chargeability can be added to the toner, and the added chargeability can be maintained. In order to obtain such an effect, the dielectric loss tangent is set to 1.5 or less. More preferably, it is 0.1 or more and 1.0 or less.
Further, the dielectric loss tangent is set to about 0.1 or more in order to avoid the amount of the filler from increasing and becoming hard, or to avoid the deterioration of the surface due to the formation of an excessive oxide film.

  The conductive member formed of the conductive elastomer composition and the conductive member including the conductive belt has a surface roughness Rz of 1 μm to 8 μm and a surface friction coefficient of 0.1 to 1.5. Is preferable.

The surface roughness Rz is set to 1 μm or more and 8 μm or less. When the surface roughness Rz is reduced to 8 μm or less, the surface of the conductive roller and the conductive belt only has irregularities smaller than the particle diameter of the toner, and uniform toner conveyance This is because not only the toner fluidity but also the fluidity of the toner is improved, and as a result, the efficiency with which the toner is charged is extremely high. Further, when the surface roughness Rz exceeds 8 μm, the toner having a particle size of about 10 μm is difficult to be separated from the toner, and the toner may adhere when used endurancely. On the other hand, if it is smaller than 1 μm, there is no sufficient force to convey the toner and the printed dots are not stable. Preferably, they are 2 micrometers or more and 5 micrometers or less.
The surface roughness Rz is measured according to JIS B0601 (1994).

  The surface friction coefficient is preferably 0.1 to 1.5. This is because when the ratio exceeds 1.5, stress such as shearing force cannot be reduced between the toner supply roller or the amount regulating blade received by the toner and the developing roller. Further, the toner is not separated easily and causes deterioration of the toner during durable use. On the other hand, if the value is smaller than 0.1, the toner slips and cannot transfer a sufficient amount of toner. This is also because the print density is low because the toner transport amount is insufficient.

  The surface layer of the conductive member is preferably an oxide film. The oxide film is preferably an oxide film having a C═O group or a C—O group. By having the oxide film, the toner is sufficiently charged and the oxide film becomes a dielectric layer to prevent the toner charge from escaping, which is effective in reducing the friction coefficient and adjusting the dielectric loss tangent.

  The oxide film is preferably formed by ultraviolet irradiation or / and ozone irradiation. In particular, it is preferable to form an oxide film by ultraviolet irradiation because the processing time is fast and the cost is low. The treatment for forming the oxide film can be performed according to a known method. For example, in the case of performing ultraviolet irradiation, although depending on the distance between the surface layer and the ultraviolet lamp, the type of rubber, and the like, the wavelength of about 100 nm to 400 nm, more preferably about 100 nm to 200 nm is applied for 30 seconds to 30 minutes, preferably It is better to irradiate about 1 to 10 minutes. In addition, it is preferable to select the intensity | strength of ultraviolet rays, and irradiation conditions (time, the temperature in a tank, distance) within the range used as the dielectric loss tangent and friction coefficient in this invention.

Furthermore, the present invention relates to an image forming apparatus and comprising the conductive rows La of the present invention, provides an image forming apparatus comprising the conductive belt of the present invention .

  Specifically, as the conductive roller, a charging roller for uniformly charging the photosensitive drum, a developing roller for charging the toner and transporting it to the photosensitive member, a toner image from the photosensitive member to a sheet or an intermediate transfer belt, etc. And a toner supply roller for conveying the toner. Examples of the conductive belt include a transfer belt, an intermediate transfer belt, and a fixing belt. Charging or discharging is performed by bringing the surface of such a conductive member into contact with an object to be charged, and an image forming apparatus such as a printer, a copying machine, or a facsimile provided with the conductive member has electric characteristics. Since it is good, power consumption is small, and a good and uniform image can be obtained over a long period of time.

As is clear from the above description, the conductive roller and the conductive belt of the present invention have the fluoro group (F--) with respect to the ionic conductive elastomer component that provides a stable electric resistance with little variation in electric resistance. ) And a salt containing an anion having a sulfonyl group (—SO ₂ —) is formed from a conductive elastomer composition, so that a very large electric conductivity is obtained while ensuring physical properties such as compression set and hardness. You can get a degree. Therefore, in spite of the ionic conductivity, the volume resistivity value is very low, the compression set is small, and the hardness as a roller or belt can be made appropriate.

In addition, when only the required copolymerization ratio of epichlorohydrin-ethylene oxide-allyl glycidyl ether is used as the ion conductive elastomer component, and the conductive elastomer composed of epichlorohydrin-ethylene oxide-allyl glycidyl ether and the above-mentioned conductivity such as chloroprene. In any case using conductive elastomer with lower conductivity than conductive elastomer and / or ionic conductive elastomer blended with non-conductive elastomer, salt with anion having specific fluoro group and sulfonyl group is required Since it mix | blends in the ratio, the electroconductive roller and electroconductive belt formed from the electroconductive elastomer composition used as required volume resistance value can be obtained.

Thus, the conductive roller and the conductive elastomer composition for use in the conductive belt of the present invention, ing the composition of the low resistance of utility which could not be achieved by the conventional conductive elastomer composition. In concrete terms, charging, developing, in rollers and belts such as toner supply, while reducing power consumption, can be obtained with less variation good image, a charging roller, developing roller, toner supply roller, a transfer Even in a process requiring a relatively low resistance, such as a belt, a transfer roller, a color copying machine or a color printer, it can be suitably used as a conductive roller and a conductive belt. Furthermore, by using a conductive roller and / or a conductive belt, an image forming apparatus such as a copying machine, a printer, a facsimile, etc., which consumes less power and can stably obtain a good and uniform image over a long period of time. Can be provided.

Hereinafter, embodiments of the present invention will be described with reference to the drawings.
The conductive elastomer composition used for the conductive roller and the conductive belt of the present invention has a copolymerization ratio of epichlorohydrin / ethylene oxide / allyl glycidyl ether as an ionic conductive elastomer component of 45 to 10 mol% / 55 to 80 mol% / As the epichlorohydrin rubber of 0 to 10 mol%, the copolymerization ratio of epichlorohydrin (hereinafter referred to as EP) / ethylene oxide (hereinafter referred to as EO) / allyl glycidyl ether (hereinafter referred to as AGE) is 23 mol% / 73 mol% / 4 mol% of epichlorohydrin rubber is used.
2 parts by weight of lithium-bis (trifluoromethanesulfonyl) imide is blended with 100 parts by weight of the epichlorohydrin rubber as a salt having an anion having a fluoro group (F—) and a sulfonyl group (—SO ₂ —).

The salt having an anion having a fluoro group (F-) and a sulfonyl group (-SO _2- ) uses the above-described epichlorohydrin rubber as an elastomer component as a base material, and is therefore described in JP-A No. 2002-226714. It is uniformly dispersed in the substrate without using a medium composed of a low molecular weight polyether compound having a molecular weight of 10,000 or less or a low molecular weight polar compound.

  Also, after blending vulcanizing agents, vulcanization accelerators, and various other compounding agents (inorganic filler, hydrotalcite, zinc oxide, stearic acid) as necessary, publicly known open rolls, closed kneaders, etc. A conductive elastomer composition is provided by melt-kneading using a rubber kneader and vulcanization.

The above-mentioned salt having an anion having a fluoro group (F-) and a sulfonyl group (-SO _2- ) is added and kneaded and uniformly dispersed at the stage where various compounding agents and elastomer components are uniformly mixed by kneading. You may let them. Alternatively, a master batch kneaded in advance in a polymer component such as epichlorohydrin rubber may be prepared, and a target compounded rubber may be obtained using the master batch.
In particular, a fluoro group (F-) and a sulfonyl group (-SO ₂ -) When the amount of salt with an anion less and less than 1 part by weight with, the salt is contained 40 wt% or less 1 wt% or more It is preferable to use a masterbatch because it can prevent deviation from the target concentration.

The produced conductive elastomer composition has a volume resistivity described in JIS K6911 measured under an applied voltage of 100 V of 10 6.6 [Ω · cm], described in JIS K6262, “vulcanized rubber and The compression set measured at 70 ° C., the measurement time of 24 hours, the compression rate of 25% in the method of “determining the permanent set of thermoplastic rubber” is 29%, and the hardness measured with the type E durometer described in JIS K6253 is 70 degrees.
Thereby, it is possible to reduce the compression set while keeping the volume resistivity low, and to make the hardness of the roller, the belt, etc. appropriate.

A conductive roller 1 composed of the conductive roller shown in FIG. 1 is formed from the conductive elastomer composition. The conductive roller 1 has a substantially cylindrical shape, and a shaft core (core metal) 2 is inserted on the inner periphery thereof.
The conductive roller 1 is obtained by taking a ribbon of melt-kneaded kneaded material from a kneader, putting it into an extruder, extruding it into a hollow tube, and cutting the tube into an appropriate length. A vulcanized rubber tube is obtained by vulcanizing the cut tube at a required temperature for a required time. A metal core is inserted into the rubber tube and the surface is polished to form a conductive roller 1.

  In this embodiment, the conductive roller is a charging roller, but it may be a transfer roller, a developing roller, a toner supply roller, or the like. Moreover, it is good also as a foaming roller etc. by mix | blending various foaming agents.

  Further, as shown in FIG. 2, a conductive belt 3 such as a transfer belt is produced from the conductive elastomer composition. The conductive belt 3 is stretched by two or more pulleys 4 and carries a sheet material 6 such as paper or a toner image on the linear portion 5 on the upper side of the rotating conductive belt 3 and transports it. In some cases, toner or the like is transferred from the photoreceptor to paper.

As images forming device conductive roller or a conductive belts of the present invention is used, a color having a transfer roller, a charging roller, a photoreceptor, an intermediate transfer belt, fixing roller, the toner, a mirror, a structure in which a cleaning blade or the like And a monochrome (black and white) printer using a printer, a transfer roller, and a developing roller. In addition, it can be used as various image forming apparatuses such as copying machines, printers, and facsimiles.

Examples of the present invention, reference examples and comparative examples will be described in detail below.
For Examples 1 to 8, Reference Examples 1 to 3 and Comparative Examples 1 to 6, materials (compounds) composed of the formulations shown in Table 1 and Table 2 below were kneaded, and this Example and Reference Example And the electroconductive roller was produced from the electroconductive elastomer composition of a comparative example.
In addition, a kneaded product obtained by kneading the materials (compounding chemicals) having the composition shown in Table 1 and Table 2 is taken out of the ribbon from the kneader, extruded by a roller head extruder, and formed into a sheet shape. The slab sheet for physical property evaluation of each example , each reference example, and each comparative example, and a test piece used for compression set measurement and hardness measurement were prepared.

The numerical values in the upper part (up to the vulcanization accelerator) in each table are parts by weight. The abbreviation EP represents epichlorohydrin, EO represents ethylene oxide, AGE represents allyl glycidyl ether, and PO represents propylene oxide. Mn represents a number average molecular weight, and Mw represents a weight average molecular weight. In each table, vulcanization accelerator 1 is dibenzothiazyl disulfide, vulcanization accelerator 2 is tetramethylthiuram monosulfide, vulcanization accelerator 3 is di-ortho-tolylguanidine, vulcanization agent 2 is ethylenethiourea, Vulcanizing agent 3 was 2-di-n-butylamino-4,6-dimercapto-s-triazine.
As the epichlorohydrin rubber 1, a prototype obtained by polymerization according to the method described in JP-A No. 2000-63656 was used.

  In Table 2, the non-chlorine ammonium salt is the quaternary ammonium salt of gluconic acid having the structure shown in FIG. 3, and the chlorinated quaternary ammonium salt is the quaternary ammonium salt shown in FIG. The high-performance ion conductive additive was prepared by dissolving 20% by weight of lithium-bis (trifluoromethanesulfonyl) imide in dibutoxyethoxyethyl adipate. The lithium-bis (trifluoromethanesulfonylimide) in the table was synthesized by a conventionally known method described in JP 2001-288193 A or the like.

More specifically, a kneaded product obtained by kneading the materials (compounding chemicals) having the composition shown in Tables 1 and 2 was taken out from the kneader, put into a φ60 mm extruder, and extruded into a hollow tube shape. This raw rubber tube was cut to an appropriate length and then vulcanized at 160 ° C. for 15 to 70 minutes to obtain a vulcanized rubber tube.
Prepare a cylindrical shaft that is the same shape as the charging roller shaft mounted on the Ricoh copier IMAGEIO MF2730, apply hot-melt adhesive to it, and insert it into the vulcanized rubber tube obtained earlier Then, after heating and bonding, the surface was polished and finished to the target dimensions to produce conductive rubber rollers of Examples , Reference Examples and Comparative Examples. These rollers had an outer diameter of 14 mmφ, an inner diameter (shaft diameter) of 8 mmφ, and an axial rubber length of 317 mm, and the same dimensions as those of the charging roller mounted on the Ricoh copier IMAGEIO MF2730.

(Examples 1-8, Reference Examples 1-3 )
As shown in Table 1, Examples 1 to 7 and Reference Examples 1 to 3 are EP-EO-AGE terpolymers (EP: EO: AGE) in which the copolymerization ratio is within the range of the present invention. = 23: 73: 4), and Example 8 used an EP-EO binary copolymer (EP: EO = 39: 61).
In Examples 1 to 4 and 6 to 8 , lithium-bis (trifluoromethanesulfonyl) imide was used as a salt having an anion having a fluoro group (F—) and a sulfonyl group (—SO ₂ —). Reference Examples 1 to 3 used lithium trifluoromethanesulfonate. In Example 5 , lithium-tris (trifluoromethanesulfonyl) methane) was used.
The compounding ratio was as shown in Table 1, and a conductive elastomer composition was obtained.

(Comparative Examples 1 to 6)
As shown in Table 2, in Comparative Examples 1, 3, 4, and 5, EP-EO-AGE terpolymers having the same copolymerization ratio as in Example 1 were used. Comparative Example 2 uses an EP-EO-AGE terpolymer (EP: EO: AGE = 63: 34.5: 2.5), and Comparative Example 6 uses an EO-PO-AGE terpolymer (EO). : PO: AGE = 90: 4: 6).
In Comparative Examples 2 and 6, lithium-bis (trifluoromethanesulfonyl) imide, which is a salt having an anion having a fluoro group (F—) and a sulfonyl group (—SO ₂ —), was blended.
Comparative Example 3 was formulated with a non-chlorine quaternary ammonium salt, Comparative Example 4 with a chlorinated quaternary ammonium salt, and Comparative Example 5 with a high performance ionic conductive additive.
Comparative Example 1 did not contain an ion conductive additive.
The compounding ratio was as shown in Table 2, and a conductive elastomer composition was obtained.

The following characteristic measurements were performed on the conductive elastomer compositions of the above examples , reference examples and comparative examples. The results are shown in the lower part of Tables 1 and 2.

(Measurement of hardness)
About the said test piece for compression set measurement, the hardness under the load of 1000g was measured using the type E durometer of JISK6253 (durometer E hardness).

(Measurement of volume resistivity)
The above 130 × 130 × 2 mm slab sheet was measured using a super high resistance microammeter R-8340A manufactured by Advantest Corporation under a constant temperature and humidity condition of 23 ° C. and a relative humidity of 55%. The measurement method was in accordance with the volume resistivity (volume resistivity) measurement method described in JIS K6911, and the applied voltage at the time of measurement was 100V.
The common logarithm log ₁₀ R [Ω · cm] is displayed in Tables 1 and 2.

(Measurement of compression set)
The compression set measurement specimen prepared as described above was measured at a measurement temperature of 70 ° C. and a measurement time of 24 hours in accordance with the provisions of “Permanent strain test method for vulcanized rubber and thermoplastic rubber” described in JIS K6262. The compression rate was 25%.
When making a foam, there will be some difference depending on the foaming ratio and foaming form, but when the compression set of this solid specimen is 30% or more, the dimensional change when it becomes a roller becomes too large and practical. There is a high possibility that it will no longer be suitable.

(Photoconductor contamination test)
32.5 ° C. in a state where the slab sheets of Examples, Reference Examples and Comparative Examples are pressed against the photoreceptor set in the cartridge (cartridge type C4127X) of Laser Jet 4050 type laser beam printer manufactured by Hewlett-Packard Company. Store for 2 weeks at 90% relative humidity. Thereafter, the slab sheet was removed from the photoconductor, halftone printing was performed with the printer using the photoconductor, the printed material was observed with the naked eye, and the presence or absence of smudges on the printed material was determined according to the following criteria.
○: As long as the printed material is visually confirmed, there is no contamination. △: Mild contamination (contamination that can be removed to the extent that it cannot be visually recognized by imprinting 5 sheets)
×: Severe contamination (contamination that can be seen by looking at the printed matter even if 5 or more sheets are imprinted)

(Water resistance survey)
Measure the volume change rate when immersed in distilled water at 40 ± 1 ° C. and 22 ± 0.25 hours according to JIS K6258 for 130 mm × 130 mm × 2 mm slab sheets of Examples, Reference Examples and Comparative Examples, Based on the value, water resistance was determined according to the following criteria.
A volume change rate of less than 50% was evaluated as “◯” (no problem in water resistance), and 50% or more as “x” (problem in water resistance).

The roller resistance values were measured for the rollers of the above Examples , Reference Examples and Comparative Examples.
(Measurement of roller resistance)
As shown in FIG. 5, the roller resistance value R is an internal resistance r (100Ω) in which a conductive roller 11 having a cored bar 12 is mounted on an aluminum drum 13 having a diameter of 30 mm and connected to the positive side of the power source 14. The leading end of the conducting wire was connected to one end surface of the aluminum drum 13 and the leading end of the conducting wire connected to the negative side of the power source 14 was connected to the other end surface of the conductive roller 11 for measurement. In this apparatus, when the applied voltage is E, the roller resistance R is R = r × E / (V−r), but the term of −r is regarded as minute this time, and R = r × E / V. . In a state where a load F of 500 g is applied to both ends of the core metal 2 and rotated at 30 rpm, 100 detection voltages V are measured for 4 seconds when the applied voltage E is 100 V, and R is calculated from the above equation. . The average value of the 100 calculated R values was used as the roller resistance. The common logarithm log ₁₀ R [Ω] is displayed in Tables 1 and 2.

(cost)
Example calculates the raw material cost per unit volume of Reference Examples and Comparative Examples, the prices of Example 4 △ a (Yes), × a higher 10% or more than the price of this Example 4 (unsuitable) Tables 1 and 2 show 10% or more cheaper as good (good). Further, the price close to the price of the fourth embodiment, that is, the price within 10% of the price of the fourth embodiment is set to Δ (possible).

  As can be seen from Table 1, the conductive elastomer composition of Example 1 has lithium-bis (trifluoro) with respect to 100 parts by weight of the EP-EO-AGE terpolymer having a copolymerization ratio in the range of the present invention. 2 parts by weight of romethanesulfonyl) imide is used, and sulfur and thiazole accelerators and thiuram accelerators are used as the vulcanization system, so the volume resistivity value is 10 to the 6.6th power [Ω · cm] In addition, the compression set and hardness were practically appropriate values. Further, there was no photoconductor contamination and the cost result was good, and it was confirmed that the rubber roller had excellent characteristics. Furthermore, since the volume change rate when immersed in distilled water at 40 ° C. ± 1 ° C. and 22 ± 0.25 hours in accordance with JIS K6258 was 30%, the level of water resistance (◯) was satisfactory.

  Example 2 differs from Example 1 only in that 11 parts by weight of lithium-bis (trifluoromethanesulfonyl) imide is blended. The volume resistivity value was as low as 10 6.3 [Ω · cm], and the compression set and hardness were practically appropriate values. Although the photosensitive member was not contaminated and the cost evaluation was Δ, it was confirmed that the conductive roller had excellent characteristics. Further, as in Example 1, the water resistance was at a level with no problem.

  Example 3 differs from Example 1 only in that thioureas and guanidine accelerators are used as vulcanization accelerators for the vulcanizing agent. The volume resistivity value was as low as 10 to the 6.4th power [Ω · cm], the compression set was small and very excellent, and the hardness was also a practically appropriate value. There was no photoconductor contamination and the result of the cost was good, and it was confirmed that it had excellent characteristics as a conductive roller. There was no problem with respect to water resistance.

  Example 4 differs from Example 3 only in that 11 parts by weight of lithium-bis (trifluoromethanesulfonyl) imide is blended. The volume resistivity is as low as 10 to the power of 6.2 [Ω · cm], the compression set is small and very excellent, the hardness is also a practically appropriate value, and there is no contamination of the photoreceptor. Although cost evaluation is (triangle | delta), it has confirmed that it had the characteristic outstanding as a conductive roller. There was no problem with respect to water resistance.

Reference Example 1 is different from Example 2 only in that 11 parts by weight of lithium trifluoromethanesulfonate is blended in place of lithium-bis (trifluoromethanesulfonyl) imide. The volume resistivity is as low as 10 to the power of 6.7 [Ω · cm], the compression set and the hardness are also practically appropriate values, and there is no photoconductor contamination, and the cost result is ○, and the conductivity It was confirmed that the roller had excellent characteristics. There was no problem with respect to water resistance.

Reference Example 2 is different from Example 4 only in that 11 parts by weight of lithium trifluoromethanesulfonate is blended in place of lithium-bis (trifluoromethanesulfonyl) imide. The volume resistivity value is as low as 10 to the 6.5th power [Ω · cm], the compression set is very small and excellent, and the hardness is also a practically appropriate value. The result was also ◯, and it was confirmed that the conductive roller had excellent characteristics. There was no problem with respect to water resistance.

Reference Example 3, only in that blended with the anion adsorbent is different from Reference Example 2. The volume resistivity is as low as 10 to the power of 6.2 [Ω · cm], the compression set is small and very excellent, the hardness is also a practically appropriate value, and there is no contamination of the photoreceptor. The result of the cost was also ◯, and it was confirmed that the conductive roller had excellent characteristics. There was no problem with respect to water resistance.

Example 5, lithium - bis in place (trifluoromethanesulfonyl) imide, lithium - only in that tris (trifluoromethanesulfonyl) methane is mixed 2 parts by weight is different from example 1. The volume resistivity is as low as 10.sup.6.2 [.OMEGA..cm], the compression set is very small and excellent, and the hardness is also practically appropriate. Although the cost was Δ, it was confirmed that the conductive roller had excellent characteristics. There was no problem with respect to water resistance.

Example 6 uses sulfur and thioureas in combination as vulcanizing agents, and vulcanization accelerators are only used in combination with thiazole-based and thiuram-based materials and guanidine-based materials. Different. The volume resistivity is as low as 10 to the power of 6.7 [Ω · cm], the compression set is small and very excellent, the hardness is also a practically appropriate value, and there is no contamination of the photoreceptor. Evaluation was also (circle) and it has confirmed that it had the characteristic outstanding as a conductive roller. There was no problem with respect to water resistance.

Example 7 differs from Example 1 only in that sulfur and a triazine derivative are used in combination as a vulcanizing agent, and the blending ratio of thiazole type and thiuram type vulcanization accelerators is changed accordingly. The volume resistivity is as low as 10 to the 6.6 [Ω · cm], the compression set is small and very excellent, the hardness is also a practically appropriate value, and there is no contamination of the photoreceptor. Evaluation was also (circle) and it has confirmed that it had the characteristic outstanding as a conductive roller. There was no problem with respect to water resistance.

In Example 8 , instead of the EP-EO-AGE terpolymer used in Examples 1 to 7 and Reference Examples 1 to 3 , an EP-EO binary having a copolymerization ratio within the above-described preferred range. The difference from Example 3 is that only 100 parts by weight of a copolymer (EP: EO = 39: 61) is used. The volume resistivity is as low as 10 to the power of 6.7 [Ω · cm], the compression set is small and very excellent, the hardness is also a practically appropriate value, and there is no contamination of the photoreceptor. Evaluation was also (circle) and it has confirmed that it had the characteristic outstanding as a conductive roller. There was no problem with respect to water resistance.

As described above, in all of Examples 1 to 8 and Reference Examples 1 to 3 , the volume resistivity described in JIS K6911 measured under an applied voltage of 100 V is 10 to the 6.9th power [Ω · cm] or less. In addition, the size of compression set measured at a measurement temperature of 70 ° C. for a measurement time of 24 hours and a compression rate of 25% by the “method of permanent strain test of vulcanized rubber” described in JIS K6262 is 30% or less, The durometer E hardness was 75 degrees or less, there was no photoconductor contamination, and the cost was good or good.

In addition, as shown in Reference Example 3 , by adding an anion adsorbent to lithium trifluoromethanesulfonate, the volume resistivity can be further reduced as compared with the case of lithium trifluoromethanesulfonate alone, which is expensive. Since a volume resistivity reduction effect similar to that when a large amount of lithium-bis (trifluoromethanesulfonyl) imide is used is obtained, it is more advantageous in terms of cost.

On the other hand, as shown in Table 2, Comparative Example 1 was not limited to Examples 1 and 2 except that a salt having an anion having a fluoro group (F—) and a sulfonyl group (—SO ₂ —) was not blended. 5. Although the composition is different from that of Reference Example 1 , the volume resistivity value is larger than 10 to the power of 6.9 [Ω · cm], and the compression set is larger than 30%, which is unsuitable and suitable for practical use. There wasn't.

  Comparative Example 2 differs from Example 2 only in that the copolymerization ratio of the EP-EO-AGE terpolymer is outside the scope of the present invention. Even when 11 parts by weight of lithium-bis (trifluoromethanesulfonyl) imide was blended, the volume resistivity value was larger than 10 to the 6.9th power [Ω · cm], and the cost evaluation was Δ. The compression set was also very large.

Comparative Example 3 is a fluoro group (F-) and a sulfonyl group (-SO ₂ -) in place of the salt with an anion with, only in that blended with chlorine-ammonium salt Examples 1, 2, 5 Unlike the reference example 1 , the volume resistivity value was larger than 10 to the 6.9th power [Ω · cm], and the compression set was considerably large.

Comparative Example 4 is fluoro group (F-) and a sulfonyl group (-SO ₂ -) in place of the salt with an anion with, only in that blended with ammonium perchlorate salt Examples 1, 2, 5 Unlike Reference Example 1 , the compression set was very large and was not suitable for practical use.

Comparative Example 5 is a high performance ion conductive additive in which a salt having an anion having a fluoro group (F—) and a sulfonyl group (—SO ₂ —) is dispersed not in a direct addition but in a low molecular weight compound medium. It differs from Examples 1, 2, 5 and Reference Example 1 in that it was blended in the form. The compression set was large and unsuitable. Further, the contamination of the photosensitive member was also x, and it was not suitable for practical use as a conductive roller or a conductive belt.

  Comparative Example 6 differs from Example 1 only in that the ratio of the EO-PO-AGE terpolymer is EO: PO: AGE = 90: 4: 6. The volume resistivity value was an appropriate value of 10 to the power of 6.7 [Ω · cm], but the hardness was too high, and it was unsuitable due to contamination of the photoreceptor. There was also a problem with water resistance.

Further, by incorporating a foaming agent in the above examples were generated indicate to onset foam 1-6 in Table 3 below.
Foam 1-6 using the same as in Example 1 EP-EO-AGE terpolymer as the substrate, a fluoro group (F-) and a sulfonyl group - with an anion having a (-SO ₂₎ 2 parts by weight of a salt (lithium-bis (trifluoromethanesulfonyl) imide), 7.5 parts by weight of a foaming agent, and the other compounding agents shown in Table 3 were mixed and kneaded in the same manner as in Example 1 to conduct electricity. An elastomer composition for foam was obtained . It was used as the foamed agent 4,4'-oxybis (benzenesulfonyl hydrazide).

For foam 1, a chemical foaming agent was added to the blending components of Example 1, and sulfur (vulcanizing agent 1) was used as the vulcanizing agent.
For foam 2, a chemical foaming agent was added to the blending components of Example 6 , and sulfur (vulcanizing agent 1) and thioureas (vulcanizing agent 2) were used as vulcanizing agents.
The foam 3 was the same as the foam 2, and sulfur and thioureas were reduced from the foam 2 .
For foam 4, a chemical foaming agent was added to the blending components of Example 3, and only thioureas were used as vulcanizing agents.
Foam 5 was obtained by adding a chemical foaming agent to the blending components of Example 7 and using only a triazine derivative (vulcanizing agent 3) as a vulcanizing agent.
For the foam 6, a chemical foaming agent was added to the ingredients of Example 7 , and sulfur and triazine derivatives were used as vulcanizing agents.

  For foams 1-6, after sampling the optimum amount in an unvulcanized state, the “Die” of “Vulcanization Test by Vibrating Vulcanization Tester” of JIS standard with Nichigo Corporation Clastometer V-type VDR In accordance with “Vulcanization Test Method A”, a sine wave vibration having a low amplitude (1 ° in the present invention) that does not break is applied to the rubber specimen, the torque transmitted from the specimen to the upper die is measured, and the vulcanization shown in FIG. A curve was obtained. The temperature was 160 ° C.

  From FIG. 6 above, when the sulfur of the foams 2 and 3 and thioureas are used as the vulcanizing agent, when the sulfur of the foam 6 and the triazine derivative are used, only the sulfur of the foam 1 When only thioureas were used, it was confirmed that the crosslinking density was significantly increased and the vulcanization rate was greatly improved as compared with the case where only the triazine derivative of foam 5 was used.

As is clear from the above description, according to the present invention, a fluoro group (F-) and a sulfonyl group (-SO ₂ ) can be used for an ion conductive elastomer component that can provide stable electrical resistance with little variation in electrical resistance. Since it is formed from the electroconductive elastomer composition which mix | blended the salt provided with the anion which has-), very big electroconductivity can be obtained, ensuring physical properties, such as compression set and hardness. Thus, despite the ionic conductivity, the volume resistivity is very low, also on small compression set, as a roller or belt can be set to an appropriate Hardness.

Further, the copolymerization ratio of epi-chloro-hydrin / ethylene oxide / allyl glycidyl ether, a fluoro group (F-) and a sulfonyl group - for defining the proportion of salt with an anion having a (-SO ₂₎ Thus, a lower electrical resistance value can be realized at an appropriate cost, and it can also be suitable for use at room temperature and humidity.

Therefore, it can be used for various applications as a practical low resistance composition that could not be realized with a conductive member formed from a conventional conductive elastomer composition. Specifically, in a roller or belt for charging, developing, toner supply, etc., it is possible to obtain a good image with little variation while reducing power consumption, and a charging roller for a color copying machine or a color printer. Even in a process requiring a relatively low resistance such as a developing roller, a toner supply roller, a transfer belt, and a transfer roller, it can be suitably used as a conductive roller and a conductive belt. Furthermore, by using the conductive roller and / or the conductive belt, an image forming apparatus such as a copying machine, a printer, a facsimile, etc., which consumes less power and can stably obtain a good and uniform image over a long period of time. Can be provided.

Next, Examples 9 and 10 and Comparative Examples 7 and 8 will be described in detail.
Example 9, 10 and Comparative Examples 7 and 8, were kneaded comprising material (compounding chemicals) from the formulation described in Table 4 below, the conductive roller formed of a conductive elastomer composition of the present Examples and Comparative Examples Was made.

The numerical values and abbreviations in Table 4 are the same as those in Tables 1 to 3 above. The conductive rubber rollers of Examples 9 and 10 and Comparative Examples 7 and 8, the slab sheet for evaluating physical properties, and the production of test pieces were also described in Examples 1 to 8, Reference Examples 1 to 3 and Comparative Examples 1 to 6 described above. It is the same.

(Examples 9 and 10 )
EP-EO binary copolymer is in the range of copolymerization ratio present invention (EP: EO = 39: 61 ) and, in the NB R Example 9, by blending the polar rubber of Example 10 CR 1 part by weight of a salt (lithium-bis (trifluoromethanesulfonyl) imide) having an anion having a fluoro group and a sulfonyl group is blended with 100 parts by weight of the resulting blend rubber, and the other compounding agents shown in Table 4 Were mixed at each compounding ratio shown in Table 4 to obtain a conductive elastomer composition.

(Comparative Examples 7 and 8)
Comparative Example 7 is a blend rubber obtained by blending an EP-EO binary copolymer (EP: EO = 39: 61) having a copolymerization ratio outside the range of the present invention and NBR which is a polar rubber. 100 parts by weight are not blended with a salt having an anion having a fluoro group and a sulfonyl group, and the other blending agents listed in Table 4 are mixed at each blending ratio shown in Table 4 to provide conductivity. An elastomer composition was obtained.
Comparative Example 8 is based on 100 parts by weight of EP-EO-AGE terpolymer (EP: EO: AGE = 63: 34.5: 2.5) having a copolymerization ratio outside the range of the present invention. Then, without adding a salt having an anion having a fluoro group and a sulfonyl group, the other compounding agents shown in Table 4 were mixed at each compounding ratio shown in Table 4 to obtain a conductive elastomer composition. It was.

The characteristics of the conductive elastomer compositions of Examples 9 and 10 and Comparative Examples 7 and 8 produced as described above were measured by the method described above. The results are shown in the lower part of Table 4 above.

As can be seen from Table 4, Example 9 is composed of 40 parts by weight of an EP-EO binary copolymer (EP: EO = 39: 61) having a copolymerization ratio within the range of the present invention, and a polar rubber. 1 part by weight of a salt (lithium-bis (trifluoromethanesulfonyl) imide) having an anion having a fluoro group and a sulfonyl group is blended with 100 parts by weight of a blend rubber obtained by blending 60 parts by weight of NBR, Since sulfur and thiazole accelerators and thiuram accelerators are used as the vulcanization system, the volume resistivity is as low as 10 to the 8th power [Ω · cm], and the compression set and hardness are also low. It was a practically appropriate value, and it was confirmed that the rubber roller had excellent characteristics without contamination of the photoreceptor. Furthermore, it was a level ((circle)) which does not have a problem regarding water resistance.

Example 10 is a blend of 50 parts by weight of an EP-EO binary copolymer (EP: EO = 39: 61) having a copolymerization ratio within the range of the present invention and 50 parts by weight of CR which is a polar rubber. 1 part by weight of a salt having an anion having a fluoro group and a sulfonyl group (lithium-bis (trifluoromethanesulfonyl) imide) is blended with 100 parts by weight of the blended rubber, and the volume resistivity is 10 6 It was confirmed that the rubber roller had excellent properties as a rubber roller, with a low value of .9 [Ω · cm], a compression set and a hardness that were practically appropriate values, and no photoreceptor contamination. Furthermore, it was a level ((circle)) which does not have a problem regarding water resistance.

As described above, in Examples 9 and 10 , the volume resistivity described in JIS K6911 measured under an applied voltage of 100 V is 10 8.9 [Ω · cm] or less, and JIS K6262 Measured at a temperature of 70 ° C. for a measurement time of 24 hours and with a compression rate of 25% according to the described “Permanent Strain Test Method of Vulcanized Rubber”, the size of the compression set measured is 30% or less, and the durometer E hardness is 75 degrees or less. Furthermore, it was excellent without any photoconductor contamination.

On the other hand, as shown in Table 4, Comparative Example 7 is different from Example 9 only in that it does not contain a salt having an anion having a fluoro group and a sulfonyl group. It was larger than 10 8.5 [Ω · cm], unsuitable, and unsuitable for practical use.
In Comparative Example 8, an EP-EO-AGE terpolymer (EP: EO: AGE = 63: 34.5: 2.5) having a copolymerization ratio outside the range of the present invention was used as an elastomer component. Although it is a different composition from Example 9 in that a salt having an anion having a fluoro group and a sulfonyl group is not blended, the volume resistivity value is larger than 10 8.5 [Ω · cm], It was unsuitable and not suitable for practical use.

Furthermore, Examples 11 to 13 and Comparative Examples 9 to 11 will be described in detail.
In Examples 11 to 13 and Comparative Examples 9 to 11, a roller was produced by the method described above using the blending materials described in Tables 2 and 4 of Examples 9 and 10 and Comparative Examples 7 and 3 described in Table 5. Then, the dimensions of the rollers were set to two shapes: an outer diameter of 20 mmφ and an inner diameter (shaft diameter) of 10 mmφ, and an outer diameter of 16 mmφ and an inner diameter (shaft diameter) of 10 mmφ so that they could be mounted on a printer described later. However, Examples 11 and 12 and Comparative Examples 9 and 10 were changed from light calcium carbonate of inorganic filling 1 to light-treated Hakuenka CC (manufactured by Shiroishi Calcium Co., Ltd.) for the purpose of reducing dielectric loss tangent, and 40 weight Partly formulated. In Example 13 and Comparative Example 11, 50 parts by weight of light calcium carbonate of inorganic filling 1 was changed to light electric carbon black (“Asahi # 15” manufactured by Asahi Carbon Co., Ltd.).

For Examples 11-13 and Comparative Examples 9 to 11, after the roller as described above, bonded in an oven at mounted on the shaft of 10mmφ to 160 ° C., then forming the ends, according to Table 5 Were subjected to final polishing and finished to a predetermined surface roughness of 20 mmφ (tolerance 0.05), to produce a developing roller. Table 5 shows the surface roughness Rz of each Example and Comparative Example roller. The dielectric loss tangent was adjusted to about 1.5 for Examples 11 and 12 and Comparative Examples 9 and 10, and about 1.1 for Example 13 and Comparative Example 11. The dielectric loss tangent here is a measurement result at 100 Hz.

After washing the roller surface with water, Examples 11 to 13 and Comparative Examples 9 to 11 were further irradiated with ultraviolet rays to form an oxide layer on the surface layer. This uses an ultraviolet irradiator (“PL21-200” manufactured by Sen Special Light Source Co., Ltd.), and the distance between the roller and the ultraviolet lamp is 10 cm, and ultraviolet rays (wavelengths 184.9 nm and 253.7 nm) are emitted every 90 degrees in the circumferential direction. The irradiation was performed for a predetermined time (5 minutes), and the roller was rotated four times to form an oxide film on the entire circumference of the roller (360 degrees). In Examples 11 and 12 and Comparative Examples 9 and 10 irradiated with ultraviolet rays, the dielectric loss tangent was about 1.1, and in Examples 13 and 11 were about 0.5. The dielectric loss tangent here is a measurement result at 100 Hz.

The following characteristic measurements were performed on the developing rollers of Examples 11 to 13 and Comparative Examples 9 to 11 produced as described above. The results are shown in the lower part of Table 5 above. The roller resistance value was measured in the same manner as described above.

(Measurement of dielectric loss tangent)
As shown in FIG. 7, the metal plate 23 on which the rubber roller 21 is mounted and the shaft 22 are used as electrodes, an AC voltage of 100 Hz to 100 kHz is applied to the rubber roller 21, and an LCR meter ("AG-4411B" manufactured by Ando Electric Co., Ltd.) The R (resistance) component and the C (capacitor) component were measured separately. From the values of R and C, the dielectric loss tangent, impedance, phase angle, and the like were obtained by the following formula. The measurement temperature was 23 ° C. to 24 ° C. (room temperature).
Dissipation factor (tan δ) = G / (ωC)
G = 1 / R
Thus, the dielectric loss tangent is a value obtained as G / (ωC) when the electrical characteristics of one roller are modeled as two parallel equivalent circuits of a roller resistance component and a capacitor component.

(Measurement of surface roughness Rz)
The surface roughness Rz was measured according to JIS B 0601 (1994).

(Measurement of friction coefficient)
As shown in FIG. 8, a digital force gauge (“Model PPX-2T” manufactured by Imada Co., Ltd.) 31, a friction piece (commercially available OHP film) 32, a 20 g weight 34, and a conductive rubber roller 33 are included. the numerical values are measured with a digital force gauge 31 is substituted into equation Euler in that equipment, to calculate the coefficient of friction.

(Printing test)
In order to investigate toner separation, toner charging uniformity, and stability over time (durability), Example 11 was used in “LP2000C” manufactured by Epson Corporation, which uses a non-contact type negatively charged toner that is a commercially available printer. 12 and Comparative Examples 9 and 10, the rubber rollers of Example 13 and Comparative Example 11 were mounted on “HL1440” manufactured by Brother Industries, Ltd. using a positively charged toner that is a contact method. The performance was evaluated by checking.
The image evaluation (initial image) was uneven density when 100 half-tone images after 25% printing were printed. In addition, after printing, the toner immediately before the photoconductor is sucked with a charge amount measuring device (Q / m meter 2 (OHS.2A) manufactured by Trek Co.), the charge amount is measured, and the weight of the toner sucked is measured by a weight meter. The amount of static electricity per weight was calculated as the charge amount (μC / g), and the weight was recorded to the nearest 0.1 mg.
Durability evaluation (printing 3000 sheets) was evaluated as halftone stability by comparing 3000 parts printing, which is half of the display so that the toner box does not become empty, by comparing the wear of the seal part and the difference from the initial image. .

In Examples 11 to 13 , an ultraviolet ray was irradiated to form an oxide layer on the surface layer, and the surface roughness Rz and the friction coefficient were within the range of the present invention. Therefore, the roller resistance value and the printing test were good. Further, when a non-contact type printer is used, there is a possibility of discharge when the roller resistance value is lower than the fifth power of 10. However, since Examples 11 and 12 had appropriate roller resistance values, discharge was also caused. Did not occur.
It has been found that by using the conductive roller of the present invention, it can be applied to any kind of printer regardless of the non-contact type or the contact type.

On the other hand, since Comparative Example 9 had a high roller resistance value and was not good in the printing test, the overall evaluation was not good.
In Comparative Examples 10 and 11, an oxide layer was formed on the surface layer and the production method of the present invention was used as a developing roller. However, since the blending was not within the scope of the present invention, it was not good in the printing test. Somewhat inferior.
This is because rubber such as chloroprene rubber (CR) and acrylonitrile butadiene rubber (NBR) that can improve the charge amount of the toner cannot be blended, or the electric resistance value cannot be lowered sufficiently.

  From the above results, it is possible to obtain a fluoro group for a blend rubber obtained by blending an EP-EO binary copolymer (EP: EO = 39: 61), which is an ion conductive elastomer, and a polar rubber such as NBR and CR. And a conductive rubber roller formed using a conductive elastomer composition containing a salt having a sulfonyl group-containing anion (lithium-bis (trifluoromethanesulfonyl) imide) is used as a developing roller. In addition, it was found that the volume resistivity of rubber can be lowered to 10 8.5 [Ω · cm] or less, and it has good characteristics in compression set, hardness, photoreceptor contamination, printing test, and the like.

It is the schematic of the electroconductive roller of this invention. It is the schematic of the electroconductive belt of this invention. It is a figure which shows the structure of the non-chloric acid quaternary ammonium salt used by the comparative example. It is a figure which shows the structure of the perchloric acid quaternary ammonium salt used by the comparative example. It is the schematic which shows the measuring apparatus of the electrical resistance value of an electroconductive roller. It is a figure which shows the vulcanization curve by the curastometer of the foams 1-6. It is the schematic which shows the measuring method of the dielectric loss tangent of an electroconductive roller. It is the schematic which shows the measuring method of the friction coefficient of an electroconductive roller.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Conductive roller 2 Shaft core 3 Conductive belt 4 Pulley 5 Linear part 6 Sheet material

Claims (18)

A conductive row La composed is formed from a conductive elastomer composition,
The conductive elastomer composition is a vulcanized rubber composition having an epichlorohydrin-ethylene oxide-allyl glycidyl ether copolymerization ratio of 45-10 mol% / 55-80 mol% / 0-10 mol%. In addition to an oxide binary copolymer and / or epichlorohydrin rubber that is an epichlorohydrin-ethylene oxide-allyl glycidyl ether terpolymer as an ion conductive elastomer component, a fluoro group (F-) and a sulfonyl group (-SO _2- The salt of bisfluoroalkylsulfonylimide and / or the salt of tris (fluoroalkylsulfonyl) methane, which is a salt provided with an anion having an ionic group), is added in an amount of 0. 01 heavy And the salt is dispersed in the ion conductive elastomer component without using a medium comprising a low molecular weight polyether compound or a low molecular weight polar compound having a molecular weight of 10,000 or less. ,
The volume resistivity described in JIS K6911 measured under an applied voltage of 100 V when the ionic conductive elastomer component is imparted with conductivity by adding only the salt without imparting conductivity with the electronic conductive agent. 10 to the power of 6.9 [Ω · cm] or less,
The compression set measured at a measurement temperature of 70 ° C., a measurement time of 24 hours, and a compression rate of 25% according to “Method of permanent strain test of vulcanized rubber and thermoplastic rubber” described in JIS K6262 is 30% or less,
A conductive member having a hardness measured by a type E durometer described in JIS K6253 of 75 degrees or less. A conductive row La composed is formed from a conductive elastomer composition,
The conductive elastomer composition is a vulcanized rubber composition having an epichlorohydrin-ethylene oxide-allyl glycidyl ether copolymerization ratio of 45-10 mol% / 55-80 mol% / 0-10 mol%. An ion conductive elastomer component comprising an epichlorohydrin rubber which is an epoxide hydride copolymer and / or epichlorohydrin-ethylene oxide-allyl glycidyl ether terpolymer, and chloroprene rubber, acrylonitrile butadiene rubber, ethylene-propylene-diene copolymer rubber (EPDM), natural rubber, isoprene rubber, styrene-butadiene rubber, butyl rubber, as well as blends of one or more rubbers selected from the group consisting of acrylic rubber, fluoro group (F-) and a sulfonyl group (-SO ₂ ) Salt of bisfluoroalkylsulfonylimide and / or tris (fluoroalkylsulfonyl) methane, which is a salt with an anion having a cation), based on 100 parts by weight of the total polymer component including the ion conductive elastomer component and the rubber. The salt is contained in a proportion of 0.01 parts by weight or more and 20 parts by weight or less, and the salt does not use a medium composed of a low molecular weight polyether compound or a low molecular weight polar compound having a molecular weight of 10,000 or less. Dispersed in the rubber,
The conductivity obtained by adding the above-mentioned salt to the ion conductive elastomer has a volume resistivity described in JIS K6911 measured under an applied voltage of 100 V of 10 8.5 [Ω · cm] or less,
The compression set measured at a measurement temperature of 70 ° C., a measurement time of 24 hours, and a compression rate of 25% according to “Permanent strain test method of vulcanized rubber and thermoplastic rubber” described in JIS K6262 is 30% or less. A conductive member characterized by the above. 3. The conductive roller according to claim 1, wherein the volume change rate when immersed in distilled water at 40 ± 1 ° C. and 22 ± 0.25 hours in accordance with JIS K6258 is less than 50%. The epichlorohydrin rubber has a copolymerization ratio of epichlorohydrin-ethylene oxide-allyl glycidyl ether of 35-15 mol% / 65-75 mol% / 0-10 mol% according to any one of claims 1 to 3. The conductive roller as described. Epichlorohydrin-ethylene oxide-allyl glycidyl ether terpolymer is used alone or mixed with the above epichlorohydrin-ethylene oxide-allyl glycidyl ether ternary copolymer with chloroprene rubber or acrylonitrile butadiene rubber,
The conductive roller according to any one of claims 1 to 4, wherein the conductive roller is cross-linked using sulfur and thioureas together, or cross-linked using sulfur and triazine derivatives together. Surface roughness Rz is at 1μm or more 8μm or less, the conductive roller according to any one of claims 1 to 5 and the friction coefficient of the surface is 0.1 to 1.5. The conductive roller according to any one of claims 1 to 6, wherein the surface layer is an oxide film. The conductive roller according to claim 7, wherein the surface oxide film is formed by ultraviolet irradiation or / and ozone irradiation. An image forming apparatus comprising the conductive roller according to claim 1.   A conductive belt formed from a conductive elastomer composition,
  The conductive elastomer composition is a vulcanized rubber composition having an epichlorohydrin-ethylene oxide-allyl glycidyl ether copolymerization ratio of 45-10 mol% / 55-80 mol% / 0-10 mol%. It contains an epichlorohydrin rubber which is an oxide binary copolymer and / or an epichlorohydrin-ethylene oxide-allyl glycidyl ether terpolymer as an ion conductive elastomer component, and also contains a fluoro group (F-) and a sulfonyl group (-SO ₂ The salt of bisfluoroalkylsulfonylimide and / or the salt of tris (fluoroalkylsulfonyl) methane, which is a salt having an anion having-), is 0 with respect to 100 parts by weight of the total polymer component including the ion conductive elastomer component. .01 parts by weight or more and 20 parts by weight or less, and the salt is dispersed in the ion conductive elastomer component without using a medium comprising a low molecular weight polyether compound or a low molecular weight polar compound having a molecular weight of 10,000 or less. Has been
  The volume resistivity described in JIS K6911 measured under an applied voltage of 100 V when the ionic conductive elastomer component is imparted with conductivity by adding only the salt without imparting conductivity with the electronic conductive agent. 10 to the power of 6.9 [Ω · cm] or less,
  The compression set measured at a measurement temperature of 70 ° C., a measurement time of 24 hours, and a compression rate of 25% according to “Method of permanent strain test of vulcanized rubber and thermoplastic rubber” described in JIS K6262 is 30% or less,
  A conductive belt having a hardness measured by a type E durometer described in JIS K6253 of 75 degrees or less.   A conductive belt formed from a conductive elastomer composition,
  The conductive elastomer composition is a vulcanized rubber composition having an epichlorohydrin-ethylene oxide-allyl glycidyl ether copolymerization ratio of 45-10 mol% / 55-80 mol% / 0-10 mol%. An ion conductive elastomer component comprising an epichlorohydrin rubber which is an epoxide hydride copolymer and / or epichlorohydrin-ethylene oxide-allyl glycidyl ether terpolymer, and chloroprene rubber, acrylonitrile butadiene rubber, ethylene-propylene-diene copolymer rubber (EPDM), natural rubber, isoprene rubber, styrene butadiene rubber, butyl rubber, blended with one or more rubbers selected from the group consisting of acrylic rubber, fluoro group (F-) and sulfonyl group (-SO ₂ The salt of bisfluoroalkylsulfonylimide and / or the salt of tris (fluoroalkylsulfonyl) methane, which is a salt with an anion having-), is added to 100 parts by weight of the total polymer component including the ion conductive elastomer component and the rubber. The ion conductive elastomer component is contained without using a medium composed of a low molecular weight polyether compound or a low molecular weight polar compound having a molecular weight of 10,000 or less. And dispersed in the rubber,
  The conductivity obtained by adding the above-mentioned salt to the ion conductive elastomer has a volume resistivity described in JIS K6911 measured under an applied voltage of 100 V of 10 8.5 [Ω · cm] or less,
  The compression set measured at a measurement temperature of 70 ° C., a measurement time of 24 hours, and a compression rate of 25% according to “Permanent strain test method of vulcanized rubber and thermoplastic rubber” described in JIS K6262 is 30% or less. Conductive belt characterized by   The conductive belt according to claim 10 or 11, which has a volume change rate of less than 50% when immersed in distilled water at 40 ± 1 ° C and 22 ± 0.25 hours in accordance with JIS K6258.   The epichlorohydrin rubber has a copolymerization ratio of epichlorohydrin-ethylene oxide-allyl glycidyl ether of 35-15 mol% / 65-75 mol% / 0-10 mol% according to any one of claims 10 to 12. The conductive belt described.   Epichlorohydrin-ethylene oxide-allyl glycidyl ether terpolymer alone or mixed with chloroprene rubber or acrylonitrile butadiene rubber in the epichlorohydrin-ethylene oxide-allyl glycidyl ether terpolymer,
  The conductive belt according to any one of claims 10 to 13, wherein the conductive belt is cross-linked by using sulfur and thioureas together or cross-linked by using sulfur and triazine derivatives together.   The conductive belt according to claim 10, wherein the surface roughness Rz is 1 μm or more and 8 μm or less, and the surface friction coefficient is 0.1 to 1.5.   The conductive belt according to claim 10, wherein the surface layer is an oxide film.   The conductive belt according to claim 16, wherein the surface oxide film is formed by ultraviolet irradiation and / or ozone irradiation.   An image forming apparatus comprising the conductive belt according to claim 10.

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