CN1782916A - Semiconductive resin composition and semiconductive member - Google Patents

Abstract

A semiconductive resin composition comprises (A) an oxyalkylene polymer having one or more hydrosilylizable alkenyl groups in each molecule, (B) a compound having two or more hydrosilyl groups in each molecule, (C) a hydrosilylizing catalyst, and (D) an ionic conductivity imparting agent or (E) a nonionic surfactant. A semiconductive member having a resistance little varying because of environment and applied voltage and little varying after continuous use, and preferably used as an electrophotographic member, comprising a metallic support member, a semiconductive elastic layer formed on the outer peripheral surface of the metallic support member, and one or more surface layers formed on the semiconductive elastic layer. The semiconductive member has a specific resistance and a specific resistance ratio.

Description

Semi-conducting resin composition and semiconductive member

The application is that national applications number is 01820085.0, international application no is PCT/JP01/10604, international filing date the dividing an application for the international application of " semi-conducting resin composition and semiconductive member " that be Dec 5 calendar year 2001, denomination of invention.

Technical field

The present invention relates to semiconduction composition and semiconduction rubber therefrom.In more detail, the semiconductive member that relates to middle semiconduction composition, semiconduction rubber and this semiconduction compositions that use such as roller formation around the metallicity support component of assembling in the image recording structure that for example adopts the electrofax mode.

In addition, the present invention relates generally to the semiconductive member that adopts in the device of electrofax modes such as adopting duplicating machine, printer or facsimile recorder receiving trap.In detail, the middle copying parts that the device middle copying device that relate to the developing parts that is suitable in the developing apparatus of the electro-photography apparatus that adopts a composition electrostatic development mode, adopts the electrofax mode adopts, duplicate parts, be installed in roller, electrophotography live part and magnetic drum etc. in the image recording structure.

Background technology

Add the electric conductivity imparting agent in resin binder, the way that makes semiconduction rubber is extremely general, has 10 but be difficult to be controlled at ⁷～10 ¹¹The semiconduction zone of Ω cm left and right sides specific insulation, in addition, give technology by the electric conductivity that adopts electronic conductivity electric conductivity imparting agents such as carbon black, be difficult to evenly disperse in system, there are variety of issue in the sample fluctuation and the voltage-dependent of the electrical characteristics of resulting half electrical conductance rubber.

As the way that addresses these problems, have been found that: the semiconduction roller that adopt nonionic surfactant, preferably adopts polyoxyethylene compound to constitute as the electric conductivity imparting agent, in semiconductor regions control easily, and the sample fluctuation and the voltage-dependent of electrology characteristic are minimum.Yet, the semiconduction roller that obtains like this, according to occasion, the nonionic surfactant of giving the composition interpolation as electric conductivity has the danger of oozing out.

In addition, be accompanied by the progress of Electronic Photographing Technology in recent years, in image processing systems such as dry type electrophotographic device, as charged usefulness, develop and supply part such as to use with, toner supply with, duplicating, adopt the elastomeric parts of semiconduction to cause concern, electrostatic roller, developer roll, photocopying roll, toner supplying roller etc. are employed with the form with resilient roller.In the methods such as charged and duplicating that adopt resilient roller, the charged devices of this polymer member and original corona discharge (コ ロ ト ロ Application) etc. relatively, have and to obtain advantages such as necessary image organizator electrostatic potential and toner copy volume with lower supply voltage.

Wherein, adopting the elastomeric parts of above-mentioned semiconduction, use as the developing parts of the electro-photography apparatus of the composition electrostatic development mode of employing to have caused concern, on developer roll etc., adopt.Here, the so-called developing apparatus that adopts a composition electrostatic development mode, mean charged electrostatic developer is loaded on lip-deep semiconduction elastomeric element with thin layer, apply voltage by contact or near photoreceptor, whereby, on the sub-image that the developer Electrostatic Absorption is formed to photosensitive surface and the developing apparatus that develops.Adopt the developing parts of semiconduction elastic layer, the comparisons such as conductive rollers that on metal sleeve, form the electroconductive resin layer with original employing, the advantage that has be can and photoreceptor between form stable contact area (below be called jaw (ニ Star プ) zone), or photosensitive surface do not caused advantage such as damage.

In addition, adopt of duplicating parts use the caused concern of the elastomeric parts of above-mentioned semiconduction, as the middle copying magnetic drum as the dry type electrophotographic device.The so-called middle copying parts here mean the toner image that forms on the photoreceptor, duplicate, after the load, duplicate the parts of toner image once more on recording materials such as paper to parts from the photoreceptor.

In the past, the toner image on the photoreceptor directly duplicates on the image-carrier.Recently, the adaptation of electro-photography apparatus coloured image is sharply made progress, yet, in order to form coloured image, generally must form green grass or young crops, fuchsin, 4 color images such as yellow and black, and be overlapped with various photosensitive devices.But, when 4 color images are overlapped,, causing the color fluctuation because the recording materials dimensional stability is bad, picture quality reduces greatly.Therefore, overlapping the so-called middle copying mode of duplicating behind 4 color images on recording materials on middle copying parts receives publicity, uses.

In addition, adopt the elastomeric parts of above-mentioned semiconduction to receive publicity, be used for charged roller as the live part of dry type electrophotographic device.The so-called live part here is to apply voltage by the semiconduction elastomeric element is directly contacted photoreceptor, makes the charged parts of photosensitive surface.Adopt the elastomeric live part of semiconduction, compare with the charged device of the corona discharge of original use, its advantage that has is to adopt low supply voltage to give necessary carried charge to photoreceptor, and can suppress the ozone generation.

In the image recording structure that adopts above-mentioned electrofax mode, has the type that adopts the middle copying body.That is,, form electrostatic latent image, on this electrostatic latent image, make the adhering toner particle, obtain toner image by the image writing device adopting Charging system to make on the electrostatic latent image carrier of uniform charged.Adopt first copy device that described toner image is once duplicated on the middle copying body.In addition,, adopt second copy device its secondary to be duplicated on the recording materials such as paper used for recording, then,, obtain the document image type by making the toner image on paper used for recording etc. the toner image that on this middle copying body, forms.The middle copying body that uses in this pattern image recording structure can adopt drum for example, and is to use the middle copying body that forms the semiconduction elastic layer on the periphery of the sleeve of drum.Because on this middle copying body, duplicate toner image from electrostatic latent image carrier, so, its soft and high external diameter precision required.Promptly, middle copying body with drum is typically provided to the electrostatic latent image carrier with drum and pushes the toner image that forms mutually on electrostatic latent image carrier, by the jaw zone that forms between electrostatic latent image carrier and the middle copying body, duplicate on the middle copying body.Therefore, in order to obtain the picture quality of good copy image, must on certain above width, keep the machine direction width in jaw zone (following title width of jaw) necessarily, in order to form high-quality copy image, as the middle copying body, require its soft and high external diameter precision.Usually, have the middle copying body of this high external diameter precision, can obtain, but owing to will append grinding step, cost raises, and is unfavorable by attrition process semiconduction elastic layer.

And, in order to reduce the hardness of semiconduction elastic layer, to add plastifier etc. usually, still,, pollute photoreceptor because plastifier infiltrates into the surface, picture quality is reduced, perhaps, problems such as the ageing stability deterioration of the homogeneity that has a resistance, resistance.In addition, when elastic layer hardness was low, the problem of generation was the attrition process difficulty, be difficult to obtain fixed external diameter precision.In order to reduce hardness, the someone proposes to adopt the method for foams as elastic layer, and still, the problem of existence is that residual because of the permanent compression set generation that pressurization causes, it is big that external diameter becomes.Therefore, relate to all motions that improve rubber rollers external diameter precision and propose, still, actual conditions are that soft and external diameter precision height, inexpensive, practical middle copying body still can't obtain.

To being used for the semiconduction elastic body of these purposes, can adopt macromolecule elastic body or high molecular foam materials such as original rubber polyurethane.As being for the desired characteristic of these semiconduction elastic bodys, require and photoreceptor between have the rubber hardness that can form stable contact field, plastifier etc. do not ooze out, do not pollute photoreceptor etc. and, also require so-called 10 ⁴～10 ⁹The middle resistance region of Ω stably has the resistance value of regulation.

Generally speaking, adopt macromolecular elastomer or foaming body,, can adopt the method for adding metal or metal oxide powder, carbon black or sodium perchlorate plasma conductive material in order to obtain the parts of above-mentioned middle resistance region.Yet, adopt metal or metal oxide powder, carbon black etc., when the middle resistance region that resistance is controlled at as electroconductive component necessity such as electrophotographies, the problem of existence is, and the resistance positional fluctuation is big, and the voltage-dependent of resistance is big etc.

When the resistance positional fluctuation of developing parts was big, the developer level of load and carried charge produced fluctuation on the developing parts, are the reasons that causes image quality decrease.

In addition, duplicating the resistance positional fluctuation of parts when big when the centre, duplicating to the various duplicating processes of recording materials to middle copying, from the centre from photoreceptor, duplicate efficient and produce fluctuation, is the reason that causes image quality decrease.In addition, the middle copying parts are owing to be duplicating intermediary's parts of contacting to 2 kinds of duplicating processes of recording materials to middle copying, from the centre from above-mentioned photoreceptor, so, must have optimum resistance value corresponding to the resistance of photoreceptor and recording materials.Owing to the resistance value under the various voltages must be controlled at as the desired optimal resistance scope of middle copying parts, so problem is the voltage-dependent when middle photocopying materials resistance value when big, the range of control of resistance becomes very narrow.

In addition, when the resistance positional fluctuation of duplicating parts was big, the carried charge that is copied on the body fluctuateed, and becomes the reason of image quality decrease.In addition, because being copied the surface current potential rises along with duplicating, so, in order to control copy volume, must carry out Control of Voltage according to surface potential, but when the voltage-dependent of resistance is big, change owing to duplicate the resistance of parts, for the copy volume that is copied on the body is reached necessarily, must be useful on the complicated control gear of revising the resistance change.

In addition, when the resistance positional fluctuation of live part was big, the carried charge on the photoreceptor fluctuateed, and becomes the reason of image quality decrease.In addition, rise along with charged owing to being copied the surface current potential, so, in order to control carried charge, must carry out Control of Voltage according to surface potential, but when the voltage-dependent of resistance is big, because the resistance of live part changes, to reach necessarily in order making, must to be useful on the complicated control gear of revising the resistance change by the carried charge on the electrified body.

On the other hand, people are known in having the macromolecular material of polarity, by sneaking into sodium perchlorate plasma conductive material, can produce the polymer member that does not have the voltage-dependent problem of the positional fluctuation of resistance and resistance at middle resistance region in fact.The resistance of this polymer member in the hot and humid environment of 32.5 ℃, 85% (RH), big with the difference of resistance in the low temperature and low humidity environment of 15 ℃, 10% (RH), so the problem of generation is big or because the energising resistance variations is big continuously because of the difference resistance variations of environment for use.In order to suppress the influence of this environmental change to the resistance change, usually adopt temperature sensor, humidity sensor to carry out temperature, humidity control, change is revised to resistance, promptly, from temperature, humidity value predetermined electrical resistance value, change the in addition method of the control of electricity such as the voltage apply.In addition, in order to suppress to carry out the resistance value monitoring owing to switching on to the influence of resistance change continuously, change applies voltage method according to resistance value.Yet, in the ordinary course of things, the resistance Yin Wendu of this polymer member, humidity and the change that takes place is not with the replaceable variation of the such simple function of linear function, in addition, environmental turbulence is also lagged behind etc. if having time, so, can not carry out correct resistance prediction.Therefore, not having these influences fully, in fact is impossible.

In addition, present situation in recent years is, requires colorize, high speed, and is strict more to the requirement of picture quality, in order to carry out the correction of resistance change, need carry out complicated more control.

As the measure that addresses these problems, the spy opens flat 11-293128 communique and discloses the conductive composition that contains the quaternary ammonium salt with amido link in a kind of polarity macromolecular compound.Yet, even adopt this measure, can be the resistance in 32.5 ℃, 85% hot and humid environment, be controlled at degree about 20 times with the difference of resistance in 15 ℃, 10% low temperature and low humidity environment, the control gear that in fact still needs the influence of resistance variations that environmental turbulence is caused to carry out revisal.

Summary of the invention

The invention solves the shortcoming of this original semiconduction resilient material, provide a kind of and can easily be controlled at semiconductor regions to resistance, the fluctuation of electrology characteristic sample and the voltage-dependent that present are minimum, and, reduce electric conductivity and give composition and ooze out dangerous semiconduction composition, the semiconduction rubber and the semiconduction roller that obtain by said composition.

The purpose of this invention is to provide a kind of because of environment, to apply the resistance change that voltage causes minimum, and the resistance variations that causes because of use continuously is little, is suitable for the semiconductive member that uses as the electrophotography parts.

The resistance positional fluctuation that another purpose of the present invention provides a kind of roller is little, and resistance is different little during rotation and when static, and, can significantly suppress semiconduction roller because of resistance variations that environmental change causes.

Another object of the present invention provides a kind of resistance variations of causing because of environmental change of can significantly suppressing, need not complicated control just can obtain high-quality image, developing parts, the middle copying parts that the image property that particularly is suitable for high-quality such as color laser printing requires to be suitable in the purposes to use, duplicate parts, live part, and inexpensive, handling ease, can form stable jaw and have uniform high precision external diameter, adopt the preferred semiconduction magnetic drums that use such as middle copying body of the image recording structure of electrofax mode.

That is, the present invention relates to a kind of semiconduction composition, said composition contains and has the oxyalkylene based polymer that can carry out the alkenyl of hydrogenation silylation reactive more than 1 in (A) molecule; (B) compound of 2 above hydrogenation silicyls is arranged in the molecule; (C) hydrogenation silylanizing catalyzer and (D) ionic electric conductivity imparting agent.

In addition, also relate to a kind of semiconduction composition, said composition contains and has the oxyalkylene based polymer that can carry out the alkenyl of hydrogenation silylation reactive more than 1 in (A) molecule; (B) compound of 2 above hydrogenation silicyls is arranged in the molecule; (C) hydrogenation silylanizing catalyzer and (E) nonionic surfactant.

It is preferred that described oxyalkylene based polymer (A), molecule chain end have the alkenyl person that can carry out the hydrogenation silylation reactive.

Described compound (B) with hydrogenation silicyl, poly-organohydrogensiloxanes is preferred.

Described nonionic surfactant (E) composition, the polyoxyethylene based compound is preferred.

In addition, also relate to the semiconduction rubber that above-mentioned semiconduction composition curing is obtained.

Described rubber, the specific insulation that records under 20 ℃, the environment of relative humidity 60% is 10 ⁷～10 ¹¹Ω cm person is preferred.

In addition, also relate to the semiconduction elastic layer that above-mentioned semiconduction composition curing is obtained, around metal support component, form the semiconductive member that is constituted.

Described semiconductive member under 23 ℃, the environment of relative humidity 55%, applies parts resistance that the 100V DC voltage records 10 ⁵Ω above 10 ⁹The following person of Ω is preferred.

In addition, the semiconductive member that the present invention relates to, these parts are by metal support component, at the semiconduction elastic layer that forms on the outer peripheral face of this metal support component, again in the semiconductive member that superficial layer constituted more than 1 layer that forms on this outer peripheral face, this semiconductive member has following characteristic: (1) applies parts resistance that the 1000V DC voltage records 10 under 23 ℃, the environment of relative humidity 55% ⁵Ω above 10 ⁹Below the Ω; (2) under 23 ℃, the environment of relative humidity 55%, apply the parts resistance that 500V and 1000V DC voltage record and use R respectively ₅₀₀And R ₁₀₀₀During expression, R ₅₀₀/ R ₁₀₀₀Value more than 0.8 below 1.2; (3) under 15 ℃, the environment of relative humidity 10%, apply the parts resistance R that the 1000V DC voltage records _LLAnd under 32.5 ℃, the environment of relative humidity 85%, apply the parts resistance R that the 1000V DC voltage records _HHRatio R _LL/ R _HHBelow 10.

In addition, under 23 ℃, the environment of relative humidity 55%, be preferred while the parts resistance when making above-mentioned semiconductive member rotation apply the 1000V DC voltage in continuous 100 hours is the person below 2 times more than 0.5 times of initial stage parts resistance.

Also have, at 23 ℃, under the environment of relative humidity 55%, the resistance positional fluctuation that applies the parts of 1000V DC voltage mensuration is that 20% following person is preferred.

Also have, under 23 ℃, the environment of relative humidity 55%, when applying the 1000V DC voltage and measuring rotation and the parts resistance when static use R respectively _RotationAnd R _StaticDuring expression, R _Rotation/ R _StaticValue be that 1.5 following persons are preferred more than 0.7.

In addition, (ア ス カ-C) hardness is preferred the following person of 60 degree to A Sika-C.

Also have, under 23 ℃, the environment of relative humidity 55%, apply the parts resistance that 100V and 1000V DC voltage measure and use R respectively ₁₀₀And R ₁₀₀₀During expression, R ₁₀₀/ R ₁₀₀₀Value be preferred 10 following persons more than 1.0.

In addition, outside diameter tolerance is preferred the following person of 100 μ m.

Above-mentioned semiconduction elastic layer is preferred by the solidfied material constitutor of the electric conductivity solidification compound that contains following component: (A) have the oxyalkylene based polymer that can carry out the alkenyl of hydrogenation silylation reactive more than 1 in the molecule; (B) compound of 2 above hydrogenation silicyls is arranged in the molecule; (C) hydrogenation silylanizing catalyzer and (E) nonionic surfactant.

In addition, the present invention relates to charged roller, this charged roller is by metal support component, at the semiconduction elastic layer that forms on the outer peripheral face of this support component, again in the charged roller that superficial layer constituted more than 1 layer that forms on this outer peripheral face, this charged roller has following characteristic: (1) applies roller resistance that the 1000V DC voltage records 10 under 23 ℃, the environment of relative humidity 55% ⁵Ω above 10 ⁹Below the Ω; (2) under 23 ℃, the environment of relative humidity 55%, apply the roller resistance that 500V and 1000V DC voltage record and use R respectively ₅₀₀And R ₁₀₀₀During expression, R ₅₀₀/ R ₁₀₀₀Value more than 0.8 below 1.2; (3) under 15 ℃, the environment of relative humidity 10%, apply the roller resistance R that the 1000V DC voltage records _LLAnd under 32.5 ℃, the environment of relative humidity 85%, apply the roller resistance R that the 1000V DC voltage records _HHRatio R _LL/ R _HHBelow 10.

In addition, the present invention relates to developer roll, this developer roll is by metal support component, at the semiconduction elastic layer that forms on the outer peripheral face of this support component, again in the developer roll that superficial layer constituted more than 1 layer that forms on this outer peripheral face, this developer roll has following characteristic: (1) applies roller resistance that the 1000V DC voltage records 10 under 23 ℃, the environment of relative humidity 55% ⁵Ω above 10 ⁹Below the Ω; (2) under 23 ℃, the environment of relative humidity 55%, apply the roller resistance that 500V and 1000V DC voltage record and use R respectively ₅₀₀And R ₁₀₀₀During expression, R ₅₀₀/ R ₁₀₀₀Value more than 0.8 below 1.2; (3) under 15 ℃, the environment of relative humidity 10%, apply the roller resistance R that the 1000V DC voltage records _LLWith, under 32.5 ℃, the environment of relative humidity 85%, apply the roller resistance R that the 1000V DC voltage records _HHRatio R _LL/ R _HHBelow 10.

In addition, the present invention relates to the middle copying roller, this middle copying roller is by metal support component, at the semiconduction elastic layer that forms on the outer peripheral face of this support component, again in the middle copying roller that superficial layer constituted more than 1 layer that forms on this outer peripheral face, this middle copying roller has following characteristic: (1) applies roller resistance that the 1000V DC voltage records 10 under 23 ℃, the environment of relative humidity 55% ⁵Ω above 10 ⁹Below the Ω; (2) under 23 ℃, the environment of relative humidity 55%, apply the roller resistance that 500V and 1000V DC voltage record and use R respectively ₅₀₀And R ₁₀₀₀During expression, R ₅₀₀/ R ₁₀₀₀Value more than 0.8 below 1.2; (3) under 15 ℃, the environment of relative humidity 10%, apply the roller resistance R that the 1000V DC voltage records _LLWith, under 32.5 ℃, the environment of relative humidity 85%, apply the roller resistance R that the 1000V DC voltage records _HHRatio R _LL/ R _HHBelow 10.

In addition, the present invention relates to photocopying roll, this photocopying roll is by being by metal support component, at the semiconduction elastic layer that forms on the outer peripheral face of this support component, again in the photocopying roll that superficial layer constituted more than 1 layer that forms on this outer peripheral face, this photocopying roll has following characteristic: (1) applies roller resistance that the 1000V DC voltage records 10 under 23 ℃, the environment of relative humidity 55% ⁵Ω above 10 ⁹Below the Ω; (2) under 23 ℃, the environment of relative humidity 55%, apply the roller resistance that 500V and 1000V DC voltage record and use R respectively ₅₀₀And R ₁₀₀₀During expression, R ₅₀₀/ R ₁₀₀₀Value more than 0.8 below 1.2; (3) under 15 ℃, the environment of relative humidity 10%, apply the roller resistance R that the 1000V DC voltage records _LLWith, under 32.5 ℃, the environment of relative humidity 85%, apply the roller resistance R that the 1000V DC voltage records _HHRatio R _LL/ R _HHBelow 10.

Description of drawings

Fig. 1 is the mode chart of semiconduction roller of the present invention.

Fig. 2 is the pie graph of the middle copying type electro-photography apparatus of image recording structure one embodiment.

Fig. 3 is the pie graph of another embodiment of presentation video pen recorder.

Fig. 4 is the pie graph of the another embodiment of presentation video pen recorder.

Fig. 5 is the mode chart of expression developer roll and peripheral structure thereof.

Fig. 6 is the mode chart of middle copying magnetic drum of the present invention.

Fig. 7 is used for the mensuration electrode mode figure that the resistance positional fluctuation is measured.

Embodiment

Semi-conducting resin composition of the present invention is to contain following component: (A) have the oxyalkylene based polymer that can carry out the alkenyl of hydrogenation silylation reactive more than 1 in the molecule; (B) compound of 2 above hydrogenation silicyls is arranged in the molecule; (C) hydrogenation silylanizing catalyzer; And (D) ionic electric conductivity imparting agent or (E) nonionic surfactant.Low viscosity, curing back soft saw it is preferred from the viewpoint of processability before said composition was solidified.

Above-mentioned polymkeric substance (A), it is the composition that is cured with above-claimed cpd (B) generation hydrogenation silylation reactive, owing to have the alkenyl that can carry out the hydrogenation silylation reactive more than 1 in the molecule, so, the hydrogenation silylation reactive takes place and become the macromolecule shape and be cured.Contained alkene radix in the above-mentioned polymkeric substance (A), from with the viewpoint of carrying out the hydrogenation silylation reactive as the compound (B) of hardening agent, must be more than 1, yet, elasticity from as rubber the time considers, during straight chain molecule, wishes terminally to have 2 alkenyls at two of molecule, and the branch period of the day from 11 p.m. to 1 a.m of side chain is being arranged, wish that molecular end has 2 above alkenyls.One of composition feature of the present invention is to be easy to set for soft.In order to bring into play this feature, the alkene radix of molecular end is preferably in more than 2, yet, comparing with the molecular weight of polymkeric substance (A), the alkene radix becomes upright and outspoken when too much, and the tendency that is difficult to obtain good caoutchouc elasticity is arranged.

The solidfied material hardness of described composition must suitably be selected according to purposes etc., yet, when common A Sika-C hardness surpasses 60 when spending, because damage is caused on the surfaces such as photoreceptor of opposed usefulness sometimes, so, be preferably in below 60 degree.

The so-called alkenyl here so long as the group that contains the activated carbon-to-carbon double bond of hydrogenation silylation reactive gets final product, is not particularly limited.As above-mentioned alkenyl, can enumerate aliphatic unsaturated hydrocarbon bases such as vinyl, allyl, methyl ethylene, propenyl, butenyl group, pentenyl or hexenyl, ring type unsaturated alkyls such as cyclopropanyl, cyclobutane base, cyclopentenyl or cyclohexenyl group, or methylpropenyl etc.

Here, as the method that in polymkeric substance, imports alkenyl, can enumerate, for example endways, main chain or side chain have the organic polymer of functional groups such as hydroxyl, alkoxide group, by with have the organic compound reaction that above-mentioned functional group is shown reactive reactive group and alkenyl, alkenyl is imported the method for end, main chain or side chain, but be not limited to these.In addition, as having the example that above-mentioned functional group is shown the organic compound of reactive reactive group and alkenyl, can enumerate C such as acrylic acid, methacrylic acid, vinyl acetate, chloroacrylic acid or bromoacrylic acid ₃～C ₂₀Unsaturated fatty acid, carboxylic acid halides, acid anhydrides etc., and chloro-carbonic acid allyl (base) ester (CH ₂=CHCH ₂OCOCl) or bromine formic acid allyl ester (CH ₂=CHCH ₂-OCOBr) wait C ₃～C ₂₀The carboxylic acid halide that replaces of unsaturated fatty acid, allyl chloride, allyl bromide, bromoallylene, vinyl (chloromethyl) benzene, allyl (chloromethyl) benzene, allyl (bromomethyl) benzene, allyl (chloromethyl) ether, allyl (chlorine methoxyl) benzene, 1-butenyl group (chloromethyl) ether, 1-hexenyl (chlorine methoxyl) benzene or allyl oxygen (chloromethyl) benzene etc.

Described alkenyl, hope imports the end of polymkeric substance (A).When this alkenyl imports polymer ends, make semiconduction composition of the present invention solidify the solidfied material that obtains, be easy to become soft, high-intensity tendency.

Described polymkeric substance (A) is characterized in that, only by adding the resistance that a spot of electric conductivity imparting agent just is adjusted to regulation easily.And, adopt and suitably select the conduction imparting agent, by applying voltage, can be reduced to desirable scope to the resistance change.

In addition, reach soft for making composition of the present invention solidify the rubber that obtains, described repetitive is that the propylene oxide based polymer of oxypropylene group unit is preferred.That is, its advantage of composition of the present invention is not adopt plastifier etc. that photoreceptor is had dysgenic additive, and A Sika-C hardness is easy to obtain the little composition of compression set below 60 degree.

Here, above-mentioned so-called oxyalkylene based polymer, mean constitute in the backbone units more than 30%, preferred is the polymkeric substance that is made of oxyalkylene units more than 50%.As the unit beyond the contained oxyalkylene units, can enumerate the used compound of initial substance when making with 2 above active hydrogens as polymkeric substance, for example, from the unit of ethylene glycol, bis-phenol based compound, glycerine, trimethylolpropane or pentaerythrite etc.Also have, concerning the propylene oxide based polymer, also can be and multipolymer (also comprising graft polymer) from the unit of formations such as oxirane, epoxy butane.

As the molecular weight of above-mentioned oxyalkylene based polymer, from the good viewpoint of the balance of reactivity and softization, number-average molecular weight (Mn) reaches 1000～50000th, and is preferred.More preferably 5000～40000, especially preferred is 5000～30000.When number-average molecular weight less than 1000 the time, when this solidification compound is solidified, be difficult to obtain sufficient mechanical property (rubber hardness, length growth rate) etc.On the other hand, when number-average molecular weight surpassed 50000, the molecular weight of per 1 alkenyl that contains in the molecule increased, because steric hindrance makes reactive the reduction, or in most cases made and solidified insufficiently, and in addition, viscosity is too high, and processability has the tendency that degenerates.

Also have, so-called number-average molecular weight of the present invention means with the chloroform give mobile phase, the value that the GPC (gel permeation chromatography) of employing Aquapak A-440 post records.

The compound (B) that the present invention uses, so long as have in the molecule 2 above hydrogenation silicyls compound can there is no particular limitation, be preferred but hydrogenation monosilane radix is 2～40.When hydrogenation monosilane radix contained in the molecule surpasses 40, still have many hydrogenation silicyls to remain in the solidfied material after the curing, be the reason that causes hole and crack tendency, when hydrogenation monosilane radix is lower than 2, aspect hardening, problem is arranged sometimes.

Also have, in the present invention, what is called has 1 described hydrogenation silicyl, has meant that 1 H is bonded on the Si, to SiH ₂, have 2 hydrogenation silicyls, and be bonded in the H on the Si, be bonded in different Si respectively and go up the person, its curable is good, considers it is preferred from caoutchouc elasticity.

As above-claimed cpd (B), it is preferably a kind of can enumerating poly-organohydrogensiloxanes.Here said poly-organohydrogensiloxanes means the silicone compounds that has alkyl or hydrogen atom on the silicon atom.During about its structure particular instantiation, can enumerate usefulness

(2＜m+n≤50,2＜m, 0≤n are that the backbone c atoms number is that 2～20 hydrocarbon also can contain the phenyl more than 1 as R),

(0＜m+n≤50,0＜m, 0≤n are that the backbone c atoms number is that 2～20 hydrocarbon also can contain the phenyl more than 1 as R).

Chain, the ring compound of expressions such as (3≤m+n≤20,2＜m≤19,0≤n＜18 are that the backbone c atoms number is that 2～20 hydrocarbon also can contain the phenyl more than 1 as R), and usefulness with these unit more than 2:

(1≤m+n≤50,1≤m, 0≤n are that the backbone c atoms number is that 2～20 hydrocarbon also can contain the phenyl more than 1,2≤1, R as R ²Be the organic group of 2～4 valencys, R ¹Be the organic group of divalent, but R ¹Also can be different from R ²Structure).

(0≤m+n≤50,0≤m, 0≤n are that the backbone c atoms number is that 2～20 hydrocarbon also can contain the phenyl more than 1,2≤1, R as R ²Be the organic group of 2～4 valencys, R ¹Be the organic group of divalent, but R ¹Also can be different from R ²Structure).

(3≤m+n≤50,1≤m, 0≤n are that the backbone c atoms number is that 2～20 hydrocarbon also can contain the phenyl more than 1,2≤1, R as R ²Be the organic group of 2～4 valencys, R ¹Be the organic group of divalent, but R ¹Also can be different from R ²Structure) etc. the expression compound.

In addition, when using these (B) compositions, reach (E) intermiscibility of composition with (A) composition, (C) composition, (D) composition, or the good person of the dispersion stabilization in system is preferred.Particularly when the viscosity of whole system was hanged down, when using with the low person's conduct of above-mentioned each composition intermiscibility (B) composition, generation was separated, and causes curing bad sometimes.In addition, also can cooperate the little filler of particle diameters such as silicon dioxide attritive powder as dispersed auxiliary agent.

With (A) composition, (C) composition, (D) composition and (E) intermiscibility of composition, or the better person of dispersion stabilization, during concrete example, can enumerate:

(n is 6～12)

(2＜k＜35,0＜1＜10, R is the alkyl of carbon number more than 8) etc.

The addition of above-claimed cpd (B), with respect to the alkenyl total amount of polymkeric substance (A), it is preferred that the degree that reaches 0.8～5.0 equivalent with the hydrogen atom of the silicon atom combination of compound (B) is used.When the alkenyl total amount with respect to above-mentioned polymkeric substance (A), the hydrogen atom of the silicon atom combination of described compound (B) has the crosslinked inadequate tendency that becomes during less than 0.8 equivalent.In addition, when surpassing 5.0 equivalents,, the big tendency of change in physical is arranged owing to solidify the influence of the hydrogen atom of the residual silicon atom combination in back.Particularly when wanting to suppress this influence, the degree that its consumption reaches 1.0～2.0 equivalents is more preferably.

About the hydrogenation silylanizing catalyzer as (C) of the present invention composition, there is no particular limitation, can use catalyzer arbitrarily.During concrete example, can enumerate the metal chlorides such as various complex compounds, rhodium, ruthenium, iron, aluminium, titanium of chloroplatinic acid, simple substance platinum, chloroplatinic acid (comprise alcohol etc. complex compound), platinum, supported solid platinum person on carriers such as aluminium oxide, silicon dioxide, carbon black; Platinum-vinylsiloxane complex compound { for example, Pt _n(ViMe ₂SiOSiMe ₂Vi) _n, Pt[(MeViSiO) ₄] _m; Platinum-phosphine complex compound { for example, Pt (PPh ₃) ₄, Pt (PBu ₃) ₄; Platinum-phosphate complex compound { for example, Pt[P (OPh) ₃] ₄, Pt[P (OBu) ₃] ₄(in the formula, Me represents that methyl, Bu represent that butyl, Vi represent that vinyl, Ph represent phenyl, and n, m represent integer), Pt (diacetone) ₂, in addition, platinum-hydrocarbon compound of putting down in writing in No. 3159601 instructions of people's such as Ashby United States Patent (USP) and No. 3159662 instructionss, and the platinum alkoxide catalysis of putting down in writing in No. 32209722 instructions of United States Patent (USP) of people such as Lamoreaux.

In addition, as the catalyzer example beyond the platinum compounds, can enumerate RhCl (PPh ₃) ₃, RuCl ₃, Rh/Al ₂O ₃, RuCl ₃, IrCl ₃, FeCl ₃, AlCl ₃, PdCl ₂2HO, NiCl ₂, or TiCl ₄Deng.These catalyzer both can use separately, also can more than 2 kinds and use.Consider chloroplatinic acid, platinum-alkene complex, platinum-vinylsiloxane complex compound or Pt (diacetone) from catalytic activity ₂Deng being preferred.

Addition to above-mentioned hydrogenation silylanizing catalyzer (C) is not particularly limited, but to 1 mole of the alkenyl of above-mentioned polymkeric substance (A) 10 ^-1～10 ^-8It is preferred using in the molar range, particularly 10 ^-2～10 ^-6Use in the molar range and be more preferably.In addition, hydrogenation silylanizing catalyzer, owing to generally have corrosivity in high price, the tendency that has a large amount of generation hydrogen that solidfied material is foamed is so consumption surpasses 10 ^-1Mole is unfavorable.

In addition, as (D) composition ionic conductivity imparting agent that uses among the present invention, can enumerate the electric conductivity imparting agent of periodic table group II metal salt such as periodic tables such as lithium, sodium or potassium the 1st family's slaine and complex compound, Ca or Ba and electric conductivity such as complex compound, cationic surfactant, anionic surfactant or amphoteric surfactant thereof.

As above-mentioned periodic table the 1st family's slaine, concrete can enumerate LiCF ₃SO ₃, NaClO ₄, LiAsF ₆, LiBF ₄, alkali metal salt such as LiI, LiCl, LiBr, NaSCN, KSCN, NaCl, NaI or KI etc.As above-mentioned periodic table group II metal salt, can enumerate Ca (ClO ₄) ₂, Ba (ClO ₄) ₂Deng.In addition,, can enumerate 1 as the complex compound of these salt, the complex compound of polyvalent alcohol such as 4-butylene glycol, ethylene glycol, polyglycol, propylene glycol or polyglycol and derivant thereof, or glycol monoethyl ether, or with complex compound of unit alcohol such as ethylene glycol monoethyl ether etc.In addition, in addition, with electric conductivity plastifier such as complex compound of plastifier such as amino modified DOP, DBP and high chloro acid ion etc.

As above-mentioned cationic surfactant, can enumerate quaternary ammonium salts such as lauryl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride, OTAC, DTAC, hexadecyltrimethylammonium chloride, tetraethyl ammonium perchlorate, tetrabutyl ammonium perchlorate, tetrabutyl fluorine borated amine or tetraethyl fluorine borated amine; In addition, as the anionic surfactant, can enumerate organic sulfonate, higher alcohol oxirane addition sulfuric acid, high alcohol phosphate salt or higher alcohol oxirane addition phosphate ester salt; In addition, as amphoteric surfactant, can enumerate lauryl betaine, stearyl betaine or dimethyl alkyl lauryl betaine etc.

The addition of above-mentioned (D) composition is with respect to preferred 0.01～100 weight portion of polymkeric substance 100 weight portions of (A) composition, more preferably 0.1～50 weight portion.When addition is lower than 0.01 weight portion, the conduction ability of giving that the obtains inadequate tendency that becomes.And when surpassing 100 weight portions, danger such as oozing out increases, or the physical strength of causing semiconduction rubber has significantly reduced tendency.

Above-mentioned (D) composition and intermiscibility as the polymkeric substance (A) of principal component resin base-material, or dispersion stabilization is good, and the semiconduction zone (specific insulation 10 that generally is being difficult to control ⁷～10 ¹¹Ω cm) controls as easy as rolling off a logly, consider it is preferred for a short time from conduction fluctuation and voltage-dependent.

The non-ionic surfactant (E) that the present invention uses is to be used for rubber of the present invention is stably given the composition of electric conductivity.Above-mentioned so-called non-ionic surfactant means the surfactant that is not dissociated into ion in aqueous solution, for example, and ether type, Etheric ester type, ester type and nitrogenous type surfactant.As ether type non-ionic surfactant, for example, can enumerate polyxyethylated, alkyl phenyl ether, alkyl allyl formaldehyde condensation polyoxyethylene ether, polyoxyethylene polyoxypropylene block copolymer or polyoxyethylene polyoxyethyl propyl alkyl ether.As the Etheric ester type non-ionic surfactant, for example, can enumerate the polyoxyethylene ether of glycerine ester, the polyoxyethylene ether of sorbitan ester or the polyoxyethylene ether of sorbitol ester.As ester type non-ionic surfactant, for example, can enumerate cithrol, glycerine ester, polyglycerol ester, sorbitan ester, propylene glycol ester or sucrose ester.As nitrogenous type surfactant, for example, can enumerate fatty acid alkanol amides, polyoxyethylene fatty acid acid amides, polyoxyethylene alkyl amine or amine oxide.

Wherein, the polyoxyethylene based compound, owing to mix with the polymkeric substance (A) as the resin binder of major component, the viewpoint of the semiconduction rubber that a kind of conductive characteristic stability is extremely excellent from providing, the undulatory property of conductive characteristic and voltage-dependent are little sees it is preferred.Above-mentioned so-called polyoxyethylene based compound means in the repetitive that constitutes main chain and contains ethylene oxide unit 50% above person, not used by the special ground that limits to known in the past product.In addition, the number-average molecular weight of polyoxyethylene based compound is preferably less than 10000, more preferably less than 5000, especially preferably less than 3000.When number-average molecular weight reaches 10000 when above, see it is unfavorable from the viewpoint of mobile operation, particularly for a long time at polyoxyethylene repetitive content, because the crystallinity of compound uprises, so the balance that mixes in the semiconduction rubber has the danger that destruction is taken place.

It is preferred that above-mentioned polyoxyethylene based compound, the hydroxyl value that molecule contains on average reach below 1.2.When molecule contained hydroxyl, because (B) effect of the minor amount of water that contains in composition, (C) composition and the system, the danger of foaming increased, and the situation that is difficult to obtain good solidfied material is arranged.

In addition, the oozing out of above-mentioned in order to prevent (E) composition, the alkenyl that imports hydrogenatable silylation reactive in the suitable molecule is good.At this moment, the alkene radix that imports in the molecule is being preferred below 1.2 on average.When described alkenyl during greater than 1.2, to by (A) composition and (B) 3 yuan of cross-linked structures forming of composition exert an influence, mechanical properties such as the compression set of composition have the tendency of decline.Above-mentioned (E) composition when curing reaction, by the hydrogenation silylation reactive, carries out chemical bond with Si-H base as (B) composition of hardening agent, finally enters in the cross-linked structure after the curing.Therefore, have reduction and ooze out dangerous tendency.In above-mentioned (E) composition, be not preferred to the active low carbon-to-carbon unsaturated bond person of hydrogenation silylanizing.

In addition, as the alkenyl in above-mentioned (E) composition, same with (A) composition, so long as contain to the activated carbon-to-carbon double bond person of hydrogenation silylanizing can there is no particular limitation, for example, can enumerate unsaturated aliphatic hydrocarbon bases such as vinyl, allyl, methyl ethylene, propenyl, butenyl group, pentenyl or hexenyl, ring type unsaturated alkyls such as cyclopropanyl, cyclobutane base, cyclopentenyl or cyclohexenyl group, perhaps methylpropenyl etc.

In addition, above-mentioned (E) composition, the person is preferred not have the reactive hydrogen in its molecule.Preferred available compound with following general formula (1) expression is as example:

R(CH ₂CH ₂O) _nOR’ (1)

(R: the alkenyl of carbon number 1～20, the alkyl of R '=carbon number 1～20, the aryl of carbon number 1～20, n is 1～500 integer, n 〉=3rd is preferred).

Object lesson as above-mentioned alkenyl, can enumerate methyl, ethyl, propyl group, isopropyl, butyl, isobutyl, the second month in a season-butyl, tert-butyl, amyl group, isopentyl, neopentyl, uncle-amyl group, hexyl or isohesyl etc., object lesson as aryl, can enumerate phenyl, tolyl, 2,4,6-trimethylphenyl, xylyl, cumenyl, naphthyl, benzyl, benzhydryl, phenethyl or trityl etc.

Object lesson as the polyoxyethylene based compound, can enumerate polyoxyethylene polyols fatty acid part ester, polyoxyethylene fatty acid ester, polyoxyethylenated castor oil, polyoxyethylene alkyl amines such as polyoxyethylene alkyl ether, polyoxyethylene alkenyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene polystyrene phenyl ether, polyoxyethylene-oxypropylene glycol, polyoxyethylene-oxypropylene alkyl ether, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene glycerine fatty acid ester or contain polyoxyethylene groups organopolysiloxane etc., but be not limited to these.

The addition of above-mentioned (E) composition, can be adjusted the back according to desirable conductive characteristic adds, but, when above-mentioned (E) composition has possibility and carries out the alkenyl of hydroxylating in molecule, must not hinder because of (A) composition and (B) formation of the 3 dimension cross-linked structures that produce of the hydrogenation silylation reactive of composition.That is, when the addition of (E) composition was superfluous, (B) Si-H of composition base was owing to consume with the hydrogenation silylation reactive of the alkenyl of (E) composition, so, 3 tie up cross-linked structures and form and become insufficient by what (A) composition caused.According to this fact, (E) addition of composition, it is preferred reaching 0.01～100 weight portion with respect to polymkeric substance 100 weight portions of (A) composition.0.1～100 weight portion more preferably, especially preferred is 0.5～70 weight portion, particularly preferably is 0.5～50 weight portion, most preferably 1～50 weight portion.When addition is lower than 0.01 weight portion, the resulting conduction ability of the giving inadequate tendency that becomes.And when surpassing 100 weight portions, oozing out the danger that waits rises, and the remarkable tendency of decline of physical strength that causes semiconduction rubber is arranged.

As above-mentioned (D) composition of electric conductivity imparting agent and (E) in the composition,, be preferred from aspects such as the voltage-dependent of ionic conductivity imparting agent (D) resistance are little.In addition, non-ionic surfactant (E) from the aspects such as environmental stability height of resistance, is preferred.Also have, these electric conductivity imparting agents both can use separately, also can more than 2 kinds and use.

Above-mentioned electric conductivity imparting agent (D) or addition (E) reach the following person of 30 weight % with respect to the total amount of (A)～(C) composition, from the mechanical-physical character of elastic layer this point of big variation do not take place and consider it is preferred.In addition, the electric conductivity imparting agent of electron conduction particularly, when addition is big, because the voltage-dependent of resistance becomes big, so, for voltage-dependent being suppressed in the desirable scope, below the preferred 20 weight %, more preferably below 10 weight %.

Here, to above-mentioned reduction of oozing out danger, for example, can measure by the gel fraction of elastic layer and estimate.As the assay method of gel fraction, can cut the fragment about 0.01～0.5g from the elastic layer of roller, put into the prior weight (W that surveyed ₁) the metal mesh bag in, gravimetry (W once more ₂).With its under the environment of 23 ℃ of temperature, relative humidity 55% in acetone dipping after 24 hours, with 80 ℃ air driers dryings 3 hours.Survey its weight (W ₃), calculate according to following formula, the weight % as being not dissolved in acetone, obtain gel fraction:

Gel fraction (%)=(W ₃-W ₁)/(W ₂-W ₁) * 100

This result can think (A), (B) and (C) composition beyond the principal ingredient, enters the desired value of cross-linked structure degree by chemical bond, and this value is more near 100%, and the danger of oozing out is littler.

In addition, only using above-mentioned electric conductivity imparting agent (D) or (E) time, giving ability inadequate occasion in electric conductivity, the composition that adds as further giving electric conductivity can add alkali metal salt in composition of the present invention.Described alkali metal salt, so long as periodic table the 1st family's slaine such as lithium, sodium, potassium and complex compound thereof get final product, there is no particular limitation.

As above-mentioned alkali metal salt, concrete can enumerate NaClO ₄, LiClO ₄, LiAsF ₆, LiBF ₄, LiPF ₆, LiCF ₃SO ₃, alkali metal salt such as LiI, LiCl, LiBr, NaSCN, KSCN, NaCl, NaI or KI etc.In addition, as with the complex compound of these salt, can enumerate 1, the complex compound of polyvalent alcohol such as 4-butylene glycol, ethylene glycol, polyglycol, propylene glycol or polyglycol and derivant thereof, or the complex compound of monohydroxy alcohols such as glycol monoethyl ether, ethylene glycol monoethyl ether etc.In addition, can also enumerate, with above-mentioned beyond plastifier such as amino modified DOP, the DBP of usefulness and high chloro acid ion's electric conductivity plastifier such as complex salt etc.The addition of described alkali metal salt is 0.001～5 weight portion, and 0.01～1 weight portion is preferred.When addition is less than 0.001 weight portion, the resulting conduction ability of the giving inadequate tendency that becomes.In addition, when surpassing 5 weight portions, the physical strength of resulting semiconduction rubber has significantly reduced tendency.

In addition, in above-mentioned composition,, can use the bin stability modifying agent in order to improve bin stability.As this bin stability modifying agent, can adopt as the known general stabilizing agent of the preserving stabilizer of above-claimed cpd (B), desirable purpose can there is no particular limitation as long as can reach.Concrete can adopt compound, organic phosphorus compound, organosulfur compound, nitrogen-containing compound, tin based compound or the organic peroxide etc. that contain the aliphatics unsaturated link.Can enumerate 2-[4-morpholinodithio base sulfide more specifically, benzothiazole, thiazole, the 2-butyne dicarboxylic ester, the diethylacetylene dicarboxylic ester, butylated hydroxytoluene, butylated hydroxyanisole (BHA), vitamin E, 2-(4-morpholinodithio (モ Le Off オ ジ ニ Le ジ チ オ)) benzothiazole, 3-methyl-1-butene-3-alcohol, the organosiloxane that contains the acetylene unsaturated group, the organosiloxane that contains the ethene unsaturated group, acetylene alcohol, 3-methyl isophthalic acid-butyl-3-alcohol, the diallyl fumarate, the diallyl maleate ester, the diethyl fumarate, the diethyl maleic acid ester, the dimethyl maleic acid ester, the 2-allyl acetonitrile, 2, the 3-dichloropropylene, 2-butyne carboxylate or quinoline etc., but be not limited to these.Wherein, consider that from the useful life and both all satisfied viewpoints of voltinism of tachy steroling thiazole, dimethyl maleate are particularly preferred.Also have, described bin stability modifying agent both can use separately, also can be used in combination more than 2 kinds.

In addition, in composition of the present invention, can also add the filler that is used to improve processability and cost, preserving stabilizer, antioxidant, softening agent, plastifier, ultraviolet light absorber, lubricant, pigment etc.As the object lesson of above-mentioned filler, fine silica powder end particularly, especially specific surface area reaches 50～380m ²Micropowder silicon dioxide about/g is preferred, wherein, carries out the surface-treated hydrophobic silica, and the effect that improves to the good direction of roller intensity is big owing to having, so be particularly preferred.Described softening agent, plasticizer dosage are to be preferred below 150 weight portions with respect to (A) composition 100 weight portions.If become above-mentioned addition when above, the tendency that produces problems such as oozing out is arranged.

Can also in described composition, be added to raising as required and give resin cohesive imparting agent, the cohesive of various substrate adherence.As the example of cohesive imparting agent, can enumerate various silane coupling agents and epoxy resin etc.The silane coupling agent that particularly has functional groups such as epoxy radicals, methacryl or vinyl, little to the curable influence of composition, cohesive is effective, is easy to a large amount of uses.But operable silane coupling agent is not limited to these.In addition, can add these catalysts and silane coupling agent or epoxy resin and usefulness.In addition, there is no particular limitation to give resin to cohesive, can use normally used cohesive imparting agent.As object lesson, can enumerate phenolics, phenol-formaldehyde resin modified, cyclopentadiene-phenolics, xylene resin, coumarone resin, petroleum resin, terpene resin, terpene phenol resin or rosin ester resin etc.Also have, when using them, must consider influence the hydrogenation silylation reactive.

Make the semiconduction composition of the invention described above solidify the semiconduction rubber that obtains, very easily specific insulation is controlled at general unmanageable semiconduction zone (specific insulation 10 ⁷～10 ¹¹Ω cm).Here, the specific insulation of semiconduction rubber of the present invention is measured according to JISK-6911.In addition,, have only the semiconduction rubber part to be cured, can estimate its specific insulation with other method when when base material superimposed layer semiconduction rubber such as metal are made.

In addition, usually semiconduction rubber has the character of resistance decline when applying high voltage and carry out resistance measurement, the voltage-dependent of conductive characteristic is big, and, this specific character, for example, in the time of in be installed in the image recording structure that adopts the electrofax mode as roller, because the Control of Voltage complexity is unfavorable.And with regard to this respect, making semiconduction composition of the present invention solidify the semiconduction rubber that obtains, the voltage-dependent of its conductive characteristic is minimum.Also have, the voltage-dependent of the conductive characteristic in this semiconduction rubber, for example, double conducting rubber is after placing 24 hours under the constant temperature and humidity condition of 20 ℃ of temperature, humidity 60%, measure specific insulation under the condition that applies voltage 100V and 1000V, the logarithm value [LOG (R100/R1000)] of the ratio of specific insulation (R100) that can be by applying 100V and the specific insulation (R1000) that applies 1000V is estimated.

In addition, the fluctuation of the conductive characteristic sample of semiconduction rubber is big usually, but makes semiconduction composition of the present invention solidify the semiconduction rubber that obtains, and the fluctuation of conductive characteristic sample is minimum.Also have, conductive characteristic sample fluctuation in this semiconduction rubber, for example, double conducting rubber is after placing 24 hours under the constant temperature and humidity condition of 20 ℃ of temperature, humidity 60%, measure specific insulation under the condition that applies voltage 100V and 1000V, the logarithm value [LOG (Rmax/Rmin)] of ratio that can be by maximum resistance measured value (Rmax) and most low-resistance measured value (Rmin) is estimated.

Described semiconduction rubber, for example, inject composition of the present invention in the mould with desired shape molding space after, make by heating.Concrete, for example, to carry out moulding, but be liquid and productive viewpoint from composition by liquid injection moulding, extrusion modling or compression moulding etc., liquid injection moulding is preferred.

Composition of the present invention for example, adopts the duty metallic catalyst by the Si-H base addition reaction of alkenyl to be made its curing.Therefore, curing rate is very fast, and it is suitable carrying out online production.Make the temperature of composition heat cured of the present invention, 80～180 ℃ is preferred.When more than 80 ℃ the time, carry out the hydrogenation silylation reactive sharp, can make its curing at short notice.

Semiconductive member of the present invention, in the center is provided with the metal die of metallicity support component 203 or cylindrical sleeve 204, semiconduction composition of the present invention pour into a mould, injection, extrusion modling etc., make easily by being heating and curing in suitable temperature, time.In above-mentioned semiconductive member, around metallicity support component 203 or cylindrical sleeve 204, form conductive elastic layer 202.On this conductive elastic layer, can also form superficial layer 201.Fig. 1 illustrates the mode chart that uses the semiconduction roller of the present invention of roller as parts, and Fig. 6 illustrates the mode chart of middle copying magnetic drum of the present invention.

Described semiconductive member, (parts resistance is 10 very easily parts resistance to be controlled at general unmanageable semiconduction zone ^5～10Ω), fluctuation of the sample of parts resistance and voltage-dependent also can reach very little.The parts resistance so-called of the present invention here means that a parts flatly is placed on the sheet metal, respectively adds the 500g loading at the both ends of parts conductive shaft along the sheet metal direction respectively, applies the resistance value that DC voltage records between axle and sheet metal.

Described semiconductive member, under 23 ℃, the environment of relative humidity 55%, parts resistance must reach 10 when applying the 100V DC current ⁵～10 ⁹Ω.Particularly, 10 ⁷～10 ⁹Ω is preferred.When being lower than 10 ⁵During Ω, the problem of generation is with the opposed parts that contact of semiconductive member tendencies such as superfluous electric current flows through to be arranged, when surpassing 10 ⁹During Ω, the semiconductive member surface has and is easy to charged tendency.

In addition, another semiconductive member 110 of the present invention, be by metal support component 203, the semiconduction elastic layer 202 that on this support component outer peripheral face, forms, the semiconductive member that constitutes in the superficial layer more than 1 layer 201 that forms on this outer peripheral face again, wherein, (1) under 23 ℃, the environment of relative humidity 55%, the parts resistance that records when applying the 1000V DC voltage reaches 10 ⁵Ω above 10 ⁹Below the Ω; (2) under 23 ℃, the environment of relative humidity 55%, apply the parts resistance that 500V and 1000V DC voltage record and use R respectively ₅₀₀And R ₁₀₀₀During expression, R ₅₀₀/ R ₁₀₀₀Value reach more than 0.8 below 1.2; (3) under 15 ℃, the environment of relative humidity 10%, apply the parts resistance R that the 1000V DC voltage records _LLWith under 32.5 ℃, the environment of relative humidity 85%, apply the parts resistance R that the 1000V DC voltage records _HHRatio R _LL/ R _HHBelow 10.

As parts of the present invention, as long as can be as the electrophotography parts can there is no particular limitation.For example, can enumerate duplicate with parts, middle copying with parts, develop with parts, charged with parts or toner supply with parts etc.Wherein, be preferred as duplicating with the semiconduction roller of parts with parts, middle copying.Described semiconduction roller, concrete can enumerate, and for example electrophotography device charged roller, developer roll, photocopying roll, feed roll, clearer, photographic fixing are with backer roll or magnetic drum etc.

Adopt Fig. 2, the middle copying type electro-photography apparatus of image recording structure one embodiment is illustrated.

The surface of the Electrophtography photosensor 101 of coating photoreceptor material formation on the aluminum tubular conductor, make uniform charged with charged roller (charged device) 102, then, adopt send from writing station 104a, according to the scan exposure light 104b of image information, on photosensitive surface, form electrostatic latent image.This electrostatic latent image by in the developer, develops visual corresponding to the developer 105a of the chrominance signal of the electrostatic latent image of this formation.This visual toner image, at the duplicating zone P1 that Electrophtography photosensor 101 contacts with middle copying magnetic drum 110, between middle copying magnetic drum 110 and photoreceptor 101, apply voltage by not shown power supply, so that duplicate toward the surface of middle copying magnetic drum 110 from Electrophtography photosensor 101.Photosensitive surface after the duplicating, irradiation removes electricity from the light that removes electric light 108, removes by purification plant 103 at the toner that photosensitive surface is residual.Above-mentioned operation is carried out repeatedly, each chromosome is developed visual as developer 105b, 105c, the 105d of information look different developer, duplicate successively, be stacked on the middle copying magnetic drum 110 from photosensitive surface, lamination forms a plurality of toner images on middle copying magnetic drum surface.Color toner image in the 110 surperficial laminations formation of middle copying magnetic drum, by transmitting with paper transfer roller 109, the contact area of the recording materials 112 between duplicating parts 106 at middle copying magnetic drum 110 and roll forming, by the voltage that between middle copying magnetic drum 110 and duplicating parts 106, applies, from duplicating parts 106 toward recording materials 112 dislocation charges, whereby, make Electrostatic Absorption, duplicate together to the recording materials surface on charged recording materials surface.Duplicate together to the toner image on recording materials 112 surfaces and be transferred to fixing device 107, by these fixing device 107 photographic fixing in addition.

The another embodiment of image recording structure is described by Fig. 3 in addition.

This image recording structure has: corresponding to black (K), yellow (Y), fuchsin (M), cyan (C) 4 looks, there is cylindric photoreceptor 101K, 101Y, 101M, the 101C of photographic layer on the surface; Make each same charged charged roller (charged device) 102K, 102Y, 102M, 102C of these photoreceptors; On same charged photoreceptor, shine image writer 104K, 104Y, 104M, the 104C that image light forms electrostatic latent image respectively; Place K, Y, M, 4 developer 105K, 105Y of C developer of all kinds, 105M, 105C; With 22 of contacting, the first middle copying magnetic drum 110 cylindraceous among above-mentioned 4 photoreceptor 101K, 101Y, 101M, the 101C; The second middle copying magnetic drum 111 cylindraceous that contacts with these 2 middle copying magnetic drums, for overlapping on the second middle copying magnetic drum 111 toner image that duplicates, a collection of roller shape duplicating parts 106 that duplicate on the recording materials 112 that transmit by transfer roller 109; Toner image on the recording materials 112 is carried out the fixing device 107 of photographic fixing.

On each toner 101K, 101Y, 101M, 101C, form the electrostatic latent image of correspondence of all kinds, by each developer 105K, 105Y, 105M, 105C, by the formation toner image of all kinds of toner development of all kinds.Toner image of all kinds on each photoreceptor toner 101K, 101Y, 101M, 101C after per 2 kinds of colors are overlapped on duplicating to the first middle copying magnetic drum 110, makes 4 looks overlap on the second middle copying magnetic drum 111.Toner image on the second middle copying magnetic drum 111, by being applied to the voltage between the second middle copying magnetic drum 111 and the duplicating parts 106, electric charge moves to recording materials 112 from photocopying materials 106, Electrostatic Absorption is on charged recording materials surface, a collection of duplicate on the recording materials 112 after, by fixing device 107, photographic fixing in addition on these recording materials 112.

In addition, by Fig. 4 the another embodiment of image recording structure is described.

This image recording structure has: corresponding to black (K), yellow (Y), fuchsin (M), cyan (C) 4 looks, there is cylindric photoreceptor 101K, 101Y, 101M, the 101C of photographic layer on the surface; Contact with certain pressure with these photoreceptors, with photoreceptor between by apply DC voltage or alternately apply exchange, DC voltage, make live part 102K, 102Y, 102M, the 102C of photosensitive surface uniform charged; On same charged photoreceptor, shine image writer 104K, 104Y, 104M, the 104C that image light forms electrostatic latent image respectively; Place K, Y, M, 4 developer 105K, 105Y of C developer of all kinds, 105M, 105C; The banded middle copying parts 118 that contact with above-mentioned 4 photoreceptor 101K, 101Y, 101M, 101C; Be the toner image that coincidence on these middle copying parts 118 is duplicated, a collection of roller shape that duplicates on the recording materials 112 that transmitted by transfer roller 109 duplicates parts 106; Toner image on the recording materials 112 is carried out the fixing device 107 of photographic fixing.

In addition, with Fig. 5 the developing apparatus of use based on an embodiment of developing parts of the present invention is illustrated.

Developer roll (developing parts) the 113rd is by the semiconduction elastic layer 202 that forms around conductive shaft (support component) 203, according to superficial layer 201 formations that need form on this semiconduction elastic layer 202.Be stored in the toner 116 in the toner container 115, load on reliably by donor rollers 114 on the surface of developer roll 113, pushed by the control assemblies such as control panel 117 that are installed in the toner container 115, carried out the contact electrification frictional electrification, formed toner thin layer.By making on the electrostatic latent image of this toner thin layer attached to photoreceptor 101 surfaces, form toner image.To developer roll 113 and donor rollers 114, control panel 117, must adjust their surface potential, in most cases apply DC current.Usually in order to prevent that toner from leaking from the developer roll both ends, the both ends of pair roller and end sides are carried out the sealing of toner with felt etc., and be not shown to this.

Above-mentioned metallicity holding components 203, can enumerate as concrete example, to stainless steel, iron impose plating or by aluminium axle, cylindric aluminum pipe being carried out the cylinder of machining processes, the corrosion resistant plate bending is made into cylindric, and by these coupling part Laser Processings being made the seamless roller person of welding.

Above-mentioned parts 203 desired functions are to support semiconduction elastic layer 202 and superficial layer 201, keep the shape of regulation.By machining such as machined into attrition process and draw figuration processing such as processing extrusion process, so long as the conductive material of processing gets final product easily, and to its material and job operation without limits.

Above-mentioned elastic layer 202 desired major functions, for the electric charge of supplying with by support component 203 is sent to superficial layer 201 necessary electric conductivity, with form stable contact area between the parts that semiconductive member 110 contacts, promptly form the necessary hardness in jaw zone, and be in the necessary external diameter homogeneity of the even width of jaw of whole axial formation.

The resistance of above-mentioned semiconductive member, under 23 ℃, the environment of relative humidity 55%, when applying the 1000V DC voltage and measuring, parts resistance must reach 10 ⁵～10 ⁹Ω.When being lower than 10 ⁵During Ω, and there is superfluous electric current to flow through between the contact component, becomes the reason of various image deflects, when being higher than 10 ⁹During Ω, the electric current that flows through between contact component is few, and contact component can not be fully charged, becomes the reason of image deflects.The lower limit of resistance is 10 ⁵Ω, and 10 ⁶Ω is better.

Above-mentioned semiconductive member, the character that has is: when resistance measurement, apply voltage when high resistance descend, yet this specific character must be carried out Control of Voltage as semiconductive member the time, is unfavorable.Consider from this viewpoint, under 23 ℃, the environment of relative humidity 55%, apply the parts resistance that 500V and 1000V DC voltage record and use R respectively ₅₀₀And R ₁₀₀₀During expression, R ₅₀₀/ R ₁₀₀₀Value must be 0.8～1.2.Work as R ₅₀₀/ R ₁₀₀₀Value greater than 1.2 or less than 0.8 o'clock owing to can not regard the resistive element of certain value as, so, must have special control circuit to make current value reach constant.R ₅₀₀/ R ₁₀₀₀The lower limit of value is 0.9, and the upper limit 1.1 is preferred.

In addition, in using the various environment of electro-photography apparatus, in order to obtain the uniform image quality, as long as 15 ℃ of normally used temperature humidity lower limit, the environment lower member resistance R of relative humidity 10% _LLWith similarly as the parts resistance R under 32.5 ℃ of the upper limit, the environment of relative humidity 85% _HHRatio R _LL/ R _HHBelow 10, just can use special control gear as the constant resistance body.In addition, if R _LL/ R _HHBelow 5, even in the purposes of colored printing that requires special high quality graphic etc., also needn't adopt special control gear, so be desirable.

In addition, the character that above-mentioned semiconductive member has is that when the resistance of parts was passed in time and changed when continuous energising, picture quality also had the character that changes in time.Picture quality changes minimum in order to make continuous use, under normally used 23 ℃, the environment of relative humidity 55%, while making the parts rotation apply the 1000V DC voltage that applies usually continuous 100 hours, it is preferred that parts resistance reaches 0.5～2 times of parts initial resistance.When initial resistance variations surpasses 2 times, very big with the difference of initial pictures quality, same when less than 0.5 times, with the difference of the initial pictures quality tendency greatly that becomes.

The resistance positional fluctuation of above-mentioned semiconductive member, under 23 ℃, the environment of relative humidity 55%, when applying the 1000V DC voltage and measuring, must be below 20%.When surpassing 20%, as the static of the image processing system of dry type electrophotographic device etc. with, develop with or duplicating when parts such as using, the tendency of the main cause that becomes image quality decrease is arranged.Be limited to 20% on the positional fluctuation, but be preferred below 10%.

In addition, change for the above-mentioned parts resistance of revisal, the method that adopts is, measure the parts resistance when static, near the control method of the voltage this value on the parts of control when putting on actual act etc., but when static and the parts resistance during rotation when big-difference is arranged very, because the revisal difficulty of parts resistance change, so, wish when static and the parts resistance difference during rotation little.That is, under 23 ℃, the environment of relative humidity 55%, apply normally used 1000V DC voltage equally normally used, when measuring rotation and the roller resistance when static use R respectively _RotateAnd R _StaticDuring expression, R _Rotate/ R _StaticValue is necessary for 0.7～1.5.At this moment, monitor roller resistance when static, the change of revisal parts resistance easily.R _Rotate/ R _StatiValue on be limited to 1.5, but 1.3 is preferred.On the other hand, lower limit is 0.7, and 0.9 is preferred.Work as R _Rotate/ R _StaticValue less than 0.7 or greater than 1.5 o'clock, the resistance value monitoring when static, sometimes can not be correctly in addition revisal of the change of component resistance value, so, sometimes for the mechanism of complexity must be arranged parts resistance change carrying out revisal.

In recent years, more and more stricter to image high quality, the multifunction requirement of electro-photography apparatus, therefore, wish that semiconductive member uses in wideer voltage range.When using in this purposes, particularly described semiconductive member applies the parts resistance that 100V and 1000V DC voltage record and uses R respectively under 23 ℃, the environment of relative humidity 55% ₁₀₀And R ₁₀₀₀During expression, R ₁₀₀/ R ₁₀₀₀Value be 0.1～10th, preferred.Particularly, R ₁₀₀/ R ₁₀₀₀Be 0.5～2 o'clock, owing to needn't control especially, so be preferred.Work as R ₁₀₀/ R ₁₀₀₀Value less than 0.1, or greater than 10 o'clock, the resistive element of certain value did not reach, so, have special control circuit to make current value reach certain.

In addition, during the outside dimension low precision of the semiconductive member that formation superficial layer 201 obtains on the outer peripheral face of above-mentioned semiconduction elastic layer 202, because above-mentioned width of jaw instability, so, the obvious variation of the picture quality of duplicating.Therefore, the profile deviation of parts is preferably below 100 μ m, more preferably below 60 μ m.Just in this point, use above-mentioned semiconduction composition, the semiconductive member 110 that adopts the above-mentioned method of forming to make even back processing such as do not grind, still obtains the goods of this high outside dimension precision easily, and it is particularly preferred having this characteristics.Also have, here, the outside diameter tolerance of so-called above-mentioned parts means the radius variation of parts, parts is rotated measure: be set in the reference point that leaves on the component locations and the distance of parts outer peripheral face, obtain from its maximal value and minimum value.

The manufacture method of semiconductive member 110 of the present invention is not particularly limited, and can adopt original known various parts-moulding methods.For example, in the center is provided with the metal die of the metal support component 203 that SUS etc. makes, the semiconduction composition is adopted various forming methods such as extrusion molding, compression moulding, injection moulding, reaction injection molding (RIM), liquid injection moulding (LIM), moulding by casting carry out moulding, adopt suitable temperature and time to make and be heating and curing, moulding semiconduction elastic layer 202 around metal support component 203.Here, as the manufacture method of semiconductive member of the present invention, because for the semiconduction composition that forms elastic layer is a liquid, so, consider that from productivity, processability liquid injection moulding is preferred.At this moment, the semiconduction composition also can full solidification by other back solidification method after making its semi-solid preparation.In addition, as required, also can be provided with one or more 201 layers in the outside of above-mentioned semiconduction elastic layer.

Above-mentioned elastic layer 202 is made of preferably the solidfied material of the electric conductivity solidification compound that contains following component: have in above-mentioned (A) molecule more than 1 in the oxyalkylene based polymer, above-mentioned (B) molecule of alkenyl that can the hydrogenation silylation reactive compound of 2 above hydrogenation silicyls, above-mentioned (C) hydrogenation silylanizing catalyzer are arranged; And, above-mentioned (E) non-ionic surfactant.Above-mentioned composition is low viscous before curing, and is soft after solidifying, and sees it is preferred from processability.

On this conductive elastic layer 202, the resin that constitutes superficial layer 201 is adopted methods such as spraying process, dip coated method or rolling method, the thickness of coating regulation by carrying out drying, make its curing in the temperature of regulation, can obtain semiconductive member 110 of the present invention.

Concrete major component as above-mentioned superficial layer 201 is not particularly limited, but from the viewpoint of conductive characteristic, contains-NHCO-key and from the viewpoint of environmental stability, have polycarbonate skeleton-ROCO ₂The resin of-repetitive constitutes as the main resin combination of forming and get final product, both can be polyamide or polyurethane and with the hybrid resin of polycarbonate, also can be to have in 1 molecule-NHCO-key and-ROCO ₂The polycarbonate polyurethane of-two kinds of repetitives etc.

As above-mentioned polycarbonate polyurethane ,-ROCO ₂-skeleton-the R base is preferred for persons such as ester ring type alkyl or straight chained alkyls.Wherein, reach well balanced viewpoint from the soft of superficial layer and low water absorption and consider that-R base is preferred for straight chained alkyl.

In addition, above-mentioned polycarbonate polyurethane is the compound that obtains by polycarbonate polyol and polyisocyanates reaction.Polycarbonate polyol is that polyvalent alcohol photoreactive gas, chloro-carbonate, dialkyl carbonate or the condensation of carbonic acid diallyl obtain.As polyvalent alcohol, preferably use 1,6-hexanediol, 1,4-butylene glycol, 1,3 butylene glycol or 1,5-pentanediol etc., the number-average molecular weight of polycarbonate polyol (Mn) is preferred in about 300～15000 scopes.Polycarbonate polyol preferably uses separately, but with polyester polyol, polyether glycol or polyester-polyether glycol and with good.

As with the polyisocyanates of polycarbonate polyol reaction, can use toluene diisocyanate (TDI), diphenyl-methane-4,4 '-diisocyanate (MDI), xylylene diisocyanate (XDI), hexamethylene diisocyanate (HDI), hydrogenation MDI, hydrogenation TDI or isophorone diisocyanate (IPDI) etc.Wherein, be easy to get calmly and the balance of characteristics such as cost, electrology characteristic, mechanical property etc. considers that it is preferred adopting hydrogenation MDI or IPDI.

On the other hand,, cause the equable viewpoint consideration of resistance, also can use the resin combination of acrylic acid-vinyl carboxylates based copolymer as major component from environmental changes such as temperature, humidity as the major component of above-mentioned superficial layer 201.This acrylic acid-vinyl carboxylates based copolymer, the total amount that is acrylate monomer composition, methacrylate monomers composition and vinyl carboxylates monomer component contains in resinous principle more than the 50 weight %, the multipolymer that preferred 80 weight % are above, described vinyl carboxylates monomer component contains in resinous principle more than the 3 weight %, more than the preferred 5 weight %, the more preferably above multipolymer of 10 weight %.

As described acrylate monomer composition, consider from the viewpoint that can well carry out polymerization, can enumerate methyl acrylate, ethyl acrylate, butyl acrylate or 2-EHA etc.

In addition,, consider, can enumerate methyl methacrylate, Jia Jibingxisuanyizhi or butyl methacrylate etc. from the viewpoint that can well carry out polymerization as described methacrylate monomers composition.Wherein, from the viewpoint that is easy to obtain, methyl methacrylate is preferred.

In addition,, consider, can enumerate vinyl acetate, propionate, valeric acid vinyl acetate or isovaleric acid vinyl acetate etc. from the viewpoint that can well carry out polymerization as described vinyl carboxylates monomer component.Wherein, from be easy to obtain, the good electronegative viewpoint of toner, it is preferred adopting vinyl acetate.

In addition, in above-mentioned superficial layer 201, consider, can add various adjuvants such as conductive agent, various filler or silane coupling agent as required from resistance adjustment, surface configuration adjustment or to the viewpoints such as cohesive of conductive elastic layer 202.

Coating process to above-mentioned superficial layer 201 is not particularly limited, and for example above-mentioned resin is dissolved in solvent, and making solid constituent reach 5～15% ground, to adopt spraying process or the coating of dip coated method be easy.At this moment, in order to improve the overlay film of superficial layer solution, can add various adjuvants such as leveling agent as required.

The thickness of described superficial layer 201 can be set in suitable value according to used material, composition and purposes etc., be not particularly limited, but common 5～50 μ m is preferred.When thinner than 5 μ m, abrasion performance descends, and long-time permanance has the tendency of decline.When thicker than 50 μ m, the wrinkle that results from the polar expansion rate variance of above-mentioned elastic layer 202 is easy to produce, or problem such as compression deformation increasing has the tendency of generation.

In addition, the thickness of described elastic layer 202 must be not particularly limited according to settings in good time such as purposes, but common 1～10mm is preferred.When thickness was thinner than 1mm, the hardness of semiconduction elastic layer 202 reduced, and the tendency that is difficult to guarantee to contact fully amplitude is arranged.And when surpassing 10mm, undesired deformation such as be distorted easily under user mode becomes the reason of image deflects easily.

In the image recording structure that adopts parts of the present invention to use as the middle copying magnetic drum, the thickness of described semiconduction elastic layer 202 is 3～8mm, and the hardness of magnetic drum is A Sika-below C hardness 60 degree preferably.When the thickness of described semiconduction elastic layer 202 surpassed 8mm, it is irregular that fluctuation takes place circumferential speed, and the toner image quality of duplicating on middle copying magnetic drum 110 has disorderly tendency.In addition, when than 3mm hour, be difficult to obtain desirable width of jaw.The hardness of magnetic drum is low more, is effectively for obtaining stable wide width of jaw, but during the hardness step-down of magnetic drum, problems such as compression set is big takes place, so usually, it is suitable that A Sika-C hardness reaches more than 20 degree.

Below by specific embodiment the present invention is illustrated.

Embodiment 1

Embodiment 1

With respect to terminal polyoxypropylene (the カ ネ カ サ イ リ Le ACX004-N of (A) allyl, Kanegafuchi Chemical Industry Co., Ltd's system) 100g, mix (D) ionic electric conductivity imparting agent (LV-70, rising sun electrification Co., Ltd. system) 10g, then, in this potpourri, take by weighing (B) poly-organohydrogensiloxanes (ACX-004-C, Kanegafuchi Chemical Industry Co., Ltd's system) 7g, (C) two (1,3-divinyl-1,1,3, the 3-tetramethyl disiloxane) (platinum content is 13.2 * 10 to platinum complex catalyst ^-5Mmol/ μ L, xylene solution) 88 μ L and as the 1-ethyl-1-cyclohexanol 0.1g of bin stability modifying agent, and evenly mix, composition obtained.After above-mentioned composition carried out deaeration in 60 minutes with vacuum defoamation stirring apparatus (シ-テ Star Network Co., Ltd. system), the semiconduction composition that obtains packed into apply in the aluminum metal container with the fluororesin sheet, under 140 ℃, 15 minutes condition of heating, be pressed, obtain 5 sheet solidfied materials that 2mm is thick.

To resulting sheet semiconduction rubber, after placing 24 hours under the environment of 20 ℃ of temperature, relative humidity 60%, under the condition that applies voltage 100V and 1000V, measure specific insulation.To resulting measurement result, apply the mean value (R100) of the specific insulation of 100V and apply mean value (R1000) expression of the specific insulation of 1000V with 5 blocks of sheet materials, voltage-dependent is estimated in logarithm value [LOG (R100/R1000)] with the ratio of R100 and R1000.In addition, calculate the logarithm value [LOG (Rmax/Rmin)] of the ratio of 5 middle maximum resistance measured values (Rmax) and most low-resistance measured value (Rmin), the fluctuation of assess sample resistance.Cooperation table and evaluation result are shown in table 1.

Embodiment 2

Beyond cooperation (D) ionic electric conductivity imparting agent (LV-70, rising sun electrification Co., Ltd. system) 2g, the sheet solidfied material is made in operation similarly to Example 1.Cooperation table and evaluation result are shown in table 1.

Embodiment 3

Beyond cooperation (D) ionic electric conductivity imparting agent (LV-70, rising sun electrification Co., Ltd. system) 0.5g, the sheet solidfied material is made in operation similarly to Example 1.Cooperation table and evaluation result are shown in table 1.

Embodiment 4

Beyond cooperation (D) ionic electric conductivity imparting agent (エ レ ガ Application LD-204, NOF Corp's system) 2g, the sheet solidfied material is made in operation similarly to Example 1.Cooperation table and evaluation result are shown in table 1.

Embodiment 5

Beyond cooperation (D) ionic electric conductivity imparting agent (エ レ ガ Application LD-204, NOF Corp's system) 0.5g, the sheet solidfied material is made in operation similarly to Example 1.Cooperation table and evaluation result are shown in table 1.

Comparative example 1

With respect to terminal polyoxypropylene (カ ネ カ サ イ リ Le ACX004-N, the Kanegafuchi Chemical Industry Co., Ltd's system) 100g of (A) allyl, add product as carbon black (#3030B, the Mitsubishi chemical Co., Ltd's system) 5g of electric conductivity imparting agent, in addition mixing with 3 rollers.Then, take by weighing in this potpourri (B) poly-organohydrogensiloxanes (ACX-004-C, Kanegafuchi Chemical Industry Co., Ltd's system) 7g, (platinum content is 13.2 * 10 to platinum complex catalyst in (C) two (1,3-divinyl-1,1,3,3-tetramethyl disiloxane) ^-5Mmol/ μ L, xylene solution) 88 μ L and as the 1-ethyl-1-cyclohexanol 0.1g of bin stability modifying agent, and evenly mix, composition obtained.Above-mentioned composition is operated similarly to Example 1, obtained 5 sheet solidfied materials that 2mm is thick.Cooperation table and evaluation result are shown in table 1.

Table 1

	Trade name	Unit	Embodiment	1	Embodiment 2	Embodiment 3	Embodiment 4	Embodiment 5	Comparative example 1
										(A) composition	ACX004-N	g	100	100	100	100	100	100
(B) composition	ACX004-C	g	7	7	7	7	7	7
									(C) composition	Pt vinylsiloxane complex compound	μL	88	88	88	88	88	88
(D) composition	LV-70	g	10	2	0.5
									エレガンLD-204	g				2	0.5
	The electric conductivity imparting agent	Carbon black #3030B	g														5
The storage-stable modifying agent									1-ethinyl-1-cyclohexanol	g	0.1	0.1	0.1	0.1	0.1	0.1
	Estimate	R100	Ωcm	4.9×10 8	9.3×10 8	1.0×10 9	1.0×10 9	1.3×10 9									9.8×10 9
R1000									Ωcm	4.5×108	8.1×108	9.8×108	8.8×108	1.2×109	4.1×10 9
		Voltage-dependent LOG (R 100/R 1000)		0.04	0.04	0.01	0.06	0.03								0.38
Sample fluctuation LOG (R MAXR MIN)										0.18	0.25	0.13	0.10	0.09	1.37

From the above result who illustrates as can be known, the semiconduction rubber that obtains from semiconduction composition of the present invention, the sample fluctuation of electrology characteristic is minimum, and, the electricity dependence is also little, as electronic conduction type electric conductivity imparting agent, compare with the occasion of general use carbon black, can see that sample fluctuation and voltage-dependent are extremely excellent.

Embodiment 6

With respect to terminal polyoxypropylene (the カ ネ カ サ イ リ Le ACX004-N of (A) allyl, Kanegafuchi Chemical Industry Co., Ltd's system) 300g, mix (D) ionic electric conductivity imparting agent (エ レ ガ Application LD-204, NOF Corp's system) 3g, then, in this potpourri, take by weighing (B) poly-organohydrogensiloxanes (ACX-004-C, Kanegafuchi Chemical Industry Co., Ltd's system) 20g, (C) two (1,3-divinyl-1,1,3, the 3-tetramethyl disiloxane) (platinum content is 13.2 * 10 to platinum complex catalyst ^-5Mmol/ μ L, xylene solution) 210 μ L and as the dimethyl maleate 105 μ L of bin stability modifying agent, and evenly mix, composition obtained.After above-mentioned composition carried out deaeration in 60 minutes with vacuum defoamation stirring apparatus (シ-テ Star Network Co., Ltd. system), the semiconduction composition that obtains, inject in the roller forming metal mold with injection pressure 1MPa, under 140 ℃, 20 minutes condition of heating, obtain being provided with around the axle that 5 SUS at diameter 8mm make the semiconduction roller of the semiconduction elastic layer of thick 3mm, long 230mm.

To resulting roller, under the environment of 23 ℃ of temperature, relative humidity 55%, when applying voltage 100V and 1000V, measure roller resistance.To resulting measurement result, apply the resistance mean value (R100) of 100V and apply roller resistance mean value (R1000) expression of 1000V with 5 rollers, voltage-dependent is estimated with the logarithm value [LOG (R100/R1000)] of the ratio of R100 and R1000.In addition, calculate the logarithm value [LOG (Rmax/Rmin)] of the ratio of 5 middle maximum resistance measured values (Rmax) and most low-resistance measured value (Rmin), the fluctuation of assess sample resistance.Cooperation table and evaluation result are shown in table 2.

Comparative example 2

With respect to terminal polyoxypropylene (カ ネ カ サ イ リ Le ACX004-N, the Kanegafuchi Chemical Industry Co., Ltd's system) 300g of (A) allyl, add carbon black (MA220, Mitsubishi chemical Co., Ltd's system) 24g as the electric conductivity imparting agent, in addition mixing with 3 rollers.Then, take by weighing in this potpourri (B) poly-organohydrogensiloxanes (ACX-004-C, Kanegafuchi Chemical Industry Co., Ltd's system) 20g, (platinum content is 13.2 * 10 to platinum complex catalyst in (C) two (1,3-divinyl-1,1,3,3-tetramethyl disiloxane) ^-5Mmol/ μ L, xylene solution) 210 μ L and as the dimethyl maleate 105 μ L of bin stability modifying agent, and evenly mix, composition obtained.Above-mentioned composition is operated similarly to Example 6, made 5 semiconduction rollers.Cooperation table and evaluation result are shown in table 2.

Table 2

	Trade name	Unit	Embodiment 6	Comparison array 2
					(A) composition	ACX004-N	g	300	300
(B) composition	ACX004-C	g	20	20
					(C) composition	Pt vinylsiloxane complex compound	μL	210	210
(D) composition	エレガンLD-204	g	3
					The electric conductivity imparting agent	Carbon black MA220	g		24
The storage-stable modifying agent	Dimethyl maleate	μL	105	105
					Estimate	R100	Ω	3.4×10 8	1.7×10 8
R1000	Ω	3.3×10 8	8.8×10 7
				Voltage-dependent LOG (R 100/R 1000)			0.01	0.29
Sample fluctuation LOG (R MAXR MIN)		0.01	0.37

From above result as can be known, the fluctuation of the sample of the electrology characteristic of semiconductive member of the present invention is minimum, and electric dependence is also little, as electronic conduction type electric conductivity imparting agent, compares with the occasion that adopts general carbon black, and sample fluctuation and voltage-dependent are extremely excellent.

Embodiment 2

Embodiment 7

Except mixing as beyond polyoxyethylene alkenyl ether (ノ ニ オ Application E205S, the NOF Corp's system) 10g of (E) composition, the sheet solidfied material is made in operation similarly to Example 1.Cooperation table and evaluation result are shown in table 3.

Embodiment 8

Except mixing as beyond polyoxyethylene alkenyl ether (ノ ニ オ Application E205S, the NOF Corp's system) 2g of (E) composition, the sheet solidfied material is made in operation similarly to Example 1.Cooperation table and evaluation result are shown in table 3.

Embodiment 9

Except mixing as beyond polyoxyethylene alkyl ether (ユ ニ オ Star Network ス MM500, the NOF Corp's system) 5g of (E) composition, the sheet solidfied material is made in operation similarly to Example 1.Cooperation table and evaluation result are shown in table 3.

Table 3

	Trade name	Unit	Embodiment 7	Comparison array 8	Embodiment 9
						(A) composition	ACX004-N	g	100	100	100
(B) composition	ACX004-C	g	7	7	7
						(C) composition	Pt vinylsiloxane complex compound	μL	88	88	88
(E) composition	ノニオンE205S	g	10	2
						ユニオツクス MM500	g			5
	The electric conductivity imparting agent	Carbon black #3030B	g
The storage-stable modifying agent						1-ethyl-1-encircles ethanol	g	0.1	0.1	0.1
	Estimate	R100	Ωcm	3.4×10 9	8.2×10 9						4.7×10 9
R1000						Ωcm	3.0×10 9	7.7×10 9	4.2×10 9
		Voltage-dependent LOG (R 100/R 1000)		0.05	0.03					0.05
Sample fluctuation LOG (R MAXR MIN)							0.04	0.07	0.08

From above result as can be known, the semiconduction rubber that obtains from semiconduction composition of the present invention, the sample fluctuation of its electrology characteristic is minimum, and, the electricity dependence is also little, as electronic conduction type electric conductivity imparting agent, to compare with the occasion that adopts general carbon black, sample fluctuation and voltage-dependent are extremely excellent.

Embodiment 10

Except mixing as beyond polyoxyethylene alkenyl ether (ノ ニ オ Application E205S, the NOF Corp's system) 15g of (E) composition, 5 semiconduction rollers are made in operation similarly to Example 6.Cooperation table and evaluation result are shown in table 4.

Comparative example 3

Beyond carbon black (MA220, the Mitsubishi chemical Co., Ltd system) 15g of interpolation as the electric conductivity imparting agent, operate equally with comparative example 2, make 5 semiconduction rollers.Cooperation table and evaluation result are shown in table 4.

Table 4

	Trade name	Unit	Embodiment 10	Comparison array 3
					(A) composition	ACX004-N	g	300	300
(B) composition	ACX004-C	g	20	20

(C) composition	Pt vinylsiloxane complex compound	μL	210	210
					(E) composition	ノニオンE205S	g	15
The electric conductivity imparting agent	Carbon black MA220	g		15
					The storage-stable modifying agent	Dimethyl maleate	μL	105	105
Estimate	R100	Ω	2.3×10 8	2.8×10 8
					R1000	Ω	2.0×10 8	1.7×10 8
	Voltage-dependent LOG (R 100/R 1000)		0.06	0.22
					Sample fluctuation LOG (R MAXR MIN)		0.03	0.41

From above result as can be known, semiconductive member of the present invention, the sample fluctuation of electrology characteristic is minimum, and electric dependence is also little, as electronic conduction type electric conductivity imparting agent, compares with the occasion that adopts general carbon black, and sample fluctuation and voltage-dependent are extremely excellent.

Embodiment 3

Embodiment 11

ACX004-N (Kanegafuchi Chemical Industry Co., Ltd's system) 300g with respect to (A) composition, mix polyoxyethylene allyl methyl ether (ユ ニ Le-Block PKA-5007 as (E) composition, Japan's grease system, molecular weight 400) 30g, then, take by weighing 21g in this potpourri as the compd B that shows structure under the having of (B) composition:

And as (C) composition two (1,3-divinyl-1,1,3,3-tetramethyl disiloxane) platinum complex catalyst (platinum content is 3 weight %, xylene solution) 210 μ L and as the dimethyl maleate 105 μ L of bin stability modifying agent, and evenly mix, obtain composition.Above-mentioned composition is operated similarly to Example 6, made 5 semiconduction rollers.Cooperation table and evaluation result are shown in table 5.

Embodiment 12

Change into the 48g except the ユ ニ Le-Block PKA-5007 that uses as (E) composition changes compd B that 105g, (B) composition use into, 5 semiconduction rollers are made in operation similarly to Example 11.Cooperation table and evaluation result are shown in table 5.

Embodiment 13

Except adopting polyoxyethylene-oxypropylene multipolymer allyl butyl ether (ユ ニ セ-Off PKA-5015, Japan's grease system, molecular weight 1600, ethenoxy unit content 75% in the main chain) 105g is as beyond (E) composition, employing compd B 20g conduct (B) composition, 5 semiconduction rollers are made in operation similarly to Example 11.Cooperation table and evaluation result are shown in table 5.

Embodiment 14

Except adding lithium perchlorate 0.5g again, 5 semiconduction rollers are made in operation similarly to Example 13.Cooperation table and evaluation result are shown in table 5.

Embodiment 15

In the prescription of embodiment 11, beyond (E) composition usefulness polyoxyethylene alkenyl ether (ノ ニ オ Application E205S, NOF Corp's system) 30g, (B) composition usefulness compd B 12g, 5 semiconduction rollers are made in operation similarly to Example 11.Cooperation table and evaluation result are shown in table 5.

Comparative example 4

With respect to terminal polyoxypropylene (カ ネ カ サ イ リ Le ACX004-N, the Kanegafuchi Chemical Industry Co., Ltd's system) 300g of (A) allyl, add carbon black (MA220, Mitsubishi chemical Co., Ltd's system) 15g as the electric conductivity imparting agent, in addition mixing with 3 rollers.Then, in this potpourri, take by weighing (B) compound B-11 2g, (C) two (1,3-divinyl-1,1,3,3-tetramethyl disiloxane) platinum complex catalyst (platinum content is 3 weight %, xylene solution) 210 μ L and as the dimethyl maleate 105 μ L of bin stability modifying agent, and evenly mix, obtain composition.Above-mentioned composition is operated similarly to Example 11, made 5 semiconduction rollers.Cooperation table and evaluation result are shown in table 5.

Table 5

	Trade name	Unit	Implementation column 11	Implementation column 12	Implementation column 13	Implementation column 14	Implementation column 15	Comparative example 4
									(A) composition	ACX004-N	g	300	300	300	300	300	300
(B) composition	Compd B	g	21	48	20	20	12	12
									(C) composition	Pt vinylsiloxane complex compound	μL	210	210	210	210	210	210
(E) composition	ユ ニ Le one プ PKA-5007	g	30	105
									ユ ニ セ one Off PKA-5015	g			105	105
	-	The lithium perchlorate	g				0.5
The electric conductivity imparting agent									ノニオンE205S	g					30
	Carbon black MA220	g						15
									The storage-stable modifying agent	Dimethyl maleate	μL	105	105	105	105	105	105
Estimate	R100	Ωcm	8.0×10 8	1.4×10 8	1.3×10 8	1.8×10 6	4.1×10 8	1.9×10 8
									R1000	Ωcm	7.6×10 8	1.4×10 8	1.2×10 8	1.5×10 6	3.6×10 8	8.0×10 7
	Voltage-dependent LOG (R 100/R 1000		0.02	0.00	0.03	0.08	0.06	0.38
									Sample fluctuation LOG (R MAX/R MIN		0.03	0.07	0.03	0.05	0.07	0.57
	Gel fraction	％	88	85	92	89	72	88

Shown in above the result as can be known, semiconductive member of the present invention, the sample fluctuation of electrology characteristic is minimum, and electric dependence is also little, as electronic conduction type electric conductivity imparting agent, compare with the occasion that adopts general carbon black, sample fluctuation and voltage-dependent are extremely excellent.In addition, when employing contains alkenyl polyoxyethylene based polymer as (E) composition, enter in the cross-linked structure by chemical bond, the danger of oozing out can reduce more.

Embodiment 4

The semiconduction roller of these embodiment and comparative example is that the stainless steel shaft surface with long 248mm, external diameter 16mm imposes prime treatment person as support component.

Embodiment 16

With respect to terminal polyoxypropylene (the カ ネ カ サ イ リ Le ACX 004-N of (A) allyl, Kanegafuchi Chemical Industry Co., Ltd's system) 100 weight portions, mix (B) poly-organohydrogensiloxanes (ACX-004-C, Kanegafuchi Chemical Industry Co., Ltd's system) 6.6 weight portions, (C) two (1,3-divinyl-1,1,3, the 3-tetramethyl disiloxane) (the platinum containing ratio is 3 weight % to platinum complex catalyst, xylene solution) 0.06 weight portion and (E) non-ionic surfactant (ノ ニ オ Application E205S, NOF Corp's system) 3 weight portions, deaeration is carried out in decompression (below the 10mmHg, 120 minutes).

Behind the above-mentioned composition that obtains of the interior injection of the metal die that is provided with above-mentioned axle, each metal die in 140 ℃ of heating 30 minutes, is solidified by making composition, on the periphery of axle, form the semiconduction elastic layer of thick about 5mm.The semiconduction elastic layer is under 21 ℃, the condition of relative humidity 60%, and A Sika-C hardness is 40 degree.

Then, with spraying process following solution is coated with (160 ℃ of dryings on semiconduction elastic layer surface, 30 minutes): with poly(ether-urethane) (Y258, Dainichiseika Color Chem's system) reaches in the solution of solid constituent 5% with MEK/dimethyl formamide=1/1 dilution, make carbon black (MA220, Mitsubishi chemical Co., Ltd's system) the resin solid composition is reached the dispersion soln of 10 weight portions, on the outer peripheral face of semiconduction elastic layer, form the superficial layer of 10 μ m, make the semiconduction roller.

The semiconduction roller that last method is made carries out following mensuration place 24 hours under 23 ℃, the environment of relative humidity 55% after under this environment.For this roller is applied voltage, investigate resistance variations, roller is placed on the aluminium sheet under the 1kg loading, (that is, whole roller is applied the state of 1kg loading), between aluminium sheet and axle, apply 100V, 500V and 1000V DC voltage, carry out R ₅₀₀And R ₁₀₀₀Measure.Roller is revolved at every turn turn 90 degrees and carry out altogether 4 times, with its mean value as roller resistance.The result is R ₅₀₀Be 1.5 * 10 ⁸Ω, R ₁₀₀₀Be 1.4 * 10 ⁸Ω, R ₅₀₀/ R ₁₀₀₀Be 1.07.

In addition, in order to measure the environmental factor dependence of roller resistance, with roller under 1. 15 ℃, the environment of relative humidity 10% (LL) and 2. under 32.5 ℃, the environment of relative humidity 85% (HH), after placing 24 hours respectively, then, 1., 2. under separately the environment roller is placed on the aluminium sheet, under the 1kg loading, between aluminium sheet and axle, apply the 1000V DC voltage, carry out the roller resistance R _LLAnd R _HHMeasure.The result is R _LLAnd R _HHBe respectively 2.0 * 10 ⁸Ω (R _LL) and 7.0 * 10 ⁷Ω (R _HH), R _LL/ R _HHBe 2.9.

Then, this roller is pushed with the 1kg loading in diameter 30mm stainless steel rider, the speed of changeing with per minute 30 makes the roller rotation on one side, applied the 1000V DC voltage 100 hours on one side, then, roller is placed on the aluminium sheet under the 1kg loading, between aluminium sheet and axle, applies the 1000V DC voltage, carry out R once more ₁₀₀₀Measurement result be 2.2 * 10 ⁸Ω is for voltage applies preceding 1.57 times.

In addition, in order to measure the positional fluctuation of roller resistance, be stated from the wide aluminum battery lead plate 302 of the 20mm shown in Fig. 7 on the mensuration electrode by 5 of 20mm arranged spaced on the electrical insulator 301, under the 1kg loading, by between each aluminium electrode and axle, applying the 1000V DC voltage, measure the resistance of each position.Will be in axial 5 mensuration, turn 90 degrees 4 places and carry out 20 mensuration altogether circumferentially revolving at every turn, the positional fluctuation of being obtained resistance by following formula is 12%:

The positional fluctuation of resistance=(minimum value of the maximal value-resistance of resistance) * 100/ (minimum value of the maximal value+resistance of resistance) * 2) (%)

In addition,, roller is rotated with the speed of changeing in 1 minute 30, the roller resistance R the when DC voltage that applies 1000V is simultaneously measured rotation by choking with the 1kg loading in the stainless steel rider that roller is placed on external diameter 30mm _RotateUnder this condition, with 10 times/second sample rate samplings 30 seconds, the result of calculation of its mean value was that roller resistance is 1.25 * 10 during rotation ⁸Ω.Above-mentioned R ₁₀₀₀Resistance R when static _Static, calculate R _Rotate/ R _StaticThe result be 0.89.

Embodiment 17

Except with beyond non-ionics (ユ ニ オ Star Network ス MM500, NOF Corp's system) 5 weight portions conduct (E) composition, operate similarly to Example 16, form the semiconduction elastic layer.A Sika-C the hardness of this elastic layer under 21 ℃, the condition of relative humidity 60% is 40 degree.

Then, operation similarly to Example 16 forms 10 μ m superficial layers on the outer peripheral face of described semiconduction elastic layer, make the semiconduction roller.

After placing 24 hours under 23 ℃, the condition of relative humidity 55%, operation is estimated similarly to Example 16 the semiconduction resilient roller of making.

The result is R ₅₀₀Be 1.0 * 10 ⁸Ω, R ₁₀₀₀Be 9.5 * 10 ⁷Ω, R ₅₀₀/ R ₁₀₀₀Be 1.05.In addition, roller resistance R _LLAnd R _HHBe respectively 2.0 * 10 ⁸Ω (R _LL) and 6.0 * 10 ⁷Ω (R _HH), R _LL/ R _HHBe 3.3.

In addition, apply the R of voltage after 100 hours continuously ₁₀₀₀Become 1.5 * 10 ⁸Ω is 1.58 times that apply continuously before the voltage.

In addition, the positional fluctuation of resistance is 5.5%.

In addition, R _RotateBe 8.5 * 10 ⁷Ω, similarly to Example 16, R ₁₀₀₀As R _Static, R _Rotate/ R _XstaticCheckout result be 0.89.

Comparative example 5

Except replacing (E) composition as beyond the conductive agent with carbon black (MA220, Mitsubishi chemical Co., Ltd's system) 5 weight portions, operation similarly to Example 16 forms the semiconduction elastic layer.A Sika-C the hardness of this elastic layer under 21 ℃, the condition of relative humidity 60% is 40 degree.

Then, operation similarly to Example 16 forms 10 μ m superficial layers on the outer peripheral face of described semiconduction elastic layer, make the semiconduction roller.

After placing 24 hours under 23 ℃, the condition of relative humidity 55%, operation is estimated similarly to Example 16 the semiconduction resilient roller of making.

The result is R ₅₀₀Be 3.5 * 10 ⁷Ω, R ₁₀₀₀Be 2.0 * 10 ⁷Ω, R ₅₀₀/ R ₁₀₀₀Be 1.75.In addition, roller resistance R _LLAnd R _HHBe respectively 2.0 * 10 ⁸Ω (R ^LL) and 1.0 * 10 ⁷Ω (R _HH), R _LL/ R _HHBe 20.

In addition, apply the R of voltage after 100 hours continuously ₁₀₀₀Become 4.5 * 10 ⁷Ω is 2.25 times that apply continuously before the voltage.

In addition, the positional fluctuation of resistance is 55%.

In addition, R _RotateBe 4.5 * 10 ⁷Ω, similarly to Example 16, R ₁₀₀₀As R _Static, R _Rotate/ R _StaticCheckout result be 2.25.

Embodiment 5

The semiconduction roller of these embodiment and comparative example is that the stainless steel shaft surface with long 248mm, external diameter 16mm imposes prime treatment person as support component, and the photocopying roll that is shaped to the roller shape is whole as duplicating parts.

Embodiment 18

Operation similarly to Example 16 forms the semiconduction elastic layer on the stainless steel shaft periphery.A Sika-C the hardness of this elastic layer under 21 ℃, the condition of relative humidity 60% is 40 degree.

Then, similarly to Example 16, make photocopying roll.

After placing 24 hours under 23 ℃, the condition of relative humidity 55%, operation is estimated similarly to Example 16 the photocopying roll of making.

The result is R ₅₀₀Be 1.5 * 10 ⁸Ω, R ₁₀₀₀Be 1.4 * 10 ⁸Ω, R ₅₀₀/ R ₁₀₀₀Be 1.07.In addition, R _LLAnd R _HHBe respectively 2.0 * 10 ⁸Ω (R _LL) and 7.0 * 10 ⁷Ω (R _HH), R _LL/ R _HHBe 2.9.

In addition, apply the R of voltage after 100 hours continuously ₁₀₀₀Become 2.2 * 10 ⁸Ω is 1.57 times that apply continuously before the voltage.

Embodiment 19

Similarly to Example 17, on the stainless steel shaft periphery, form the semiconduction elastic layer.A Sika-C the hardness of this elastic layer under 21 ℃, the condition of relative humidity 60% is 40 degree.

Then, similarly to Example 17, make photocopying roll.

After placing 24 hours under 23 ℃, the condition of relative humidity 55%, operation is estimated similarly to Example 16 the photocopying roll of making.

The result is R ₅₀₀Be 1.0 * 10 ⁸Ω, R ₁₀₀₀Be 9.5 * 10 ⁷Ω, R ₅₀₀/ R ₁₀₀₀Be 1.05.In addition, the R of roller resistance _LLAnd R _HHBe respectively 2.0 * 10 ⁸Ω (R _LL) and 6.0 * 10 ⁷Ω (R _HH), R _LL/ R _HHBe 3.3.

In addition, apply the R of voltage after 100 hours continuously ₁₀₀₀Become 1.5 * 10 ⁸Ω is 1.58 times that apply continuously before the voltage.

Comparative example 6

Same with comparative example 5, on the stainless steel shaft periphery, form the semiconduction elastic layer.The A Si card C hardness of this elastic layer under 21 ℃, the condition of relative humidity 60% is 40 degree.

Then, same with comparative example 5, make photocopying roll.

After placing 24 hours under 23 ℃, the condition of relative humidity 55%, operation is estimated similarly to Example 16 the photocopying roll of making.

The result is R ₅₀₀Be 3.5 * 10 ⁷Ω, R ₁₀₀₀Be 2.0 * 10 ⁷Ω, R ₅₀₀/ R ₁₀₀₀Be 1.75.In addition, the R of roller resistance _LLAnd R _HHBe respectively 2.0 * 10 ⁸Ω (R _LL) and 1.0 * 10 ⁷Ω (R _HH), R _LL/ R ^HHBe 20.

In addition, apply the R of voltage after 100 hours continuously ₁₀₀₀Become 4.5 * 10 ⁷Ω is 2.25 times that apply continuously before the voltage.

Then, evaluation to the duplicating characteristic of embodiment in the embodiment 5 and the photocopying roll shown in the comparative example (amount of remaining toner, duplicate stain and image in the middle of comes off), it is the laser beam printing (device of putting down in writing among Fig. 2) of middle copying type, with the spherical toner of the green grass or young crops (C) of using mean grain size 6 μ m, fuchsin (M), yellow (Y) and black (K) 4 looks, output image carries out under various environment.

The copy image on the middle copying roller, on paper, carry out secondary with the photocopying roll of making and duplicate.In described secondary duplicates, be 1000V at the duplicating voltage of the photocopying roll that disposes later of middle copying roller and paper, the peripheral speed of roller is 100mm/ second.In addition, the contact pressure of photocopying roll and middle copying body roller is at electric conductivity backing roll two ends, makes line pressure 150g/cm with spring device, output line image, employed intermediate color pattern, character pattern, carries out picture appraisal and estimates the duplicating characteristic.In addition, adopt C, M, each 4 colour toners of Y, K to carry out above-mentioned evaluation, and the picture quality of carrying out between the toner compare.The result shows, adopts the embodiment of the photocopying roll of making according to the foregoing description 18 and 19, and its line image, employed intermediate color pattern all obtain the preferable image quality, do not find the difference between 4 colour toners.In addition, photocopying roll duplicates with identical duplicating voltage under low temperature and low humidity and under hot and humid, and also not seeing picture quality has big difference.

Yet the photocopying roll of comparative example 6 has broken line owing to find low concentration employed intermediate color pattern under the low temperature and low humidity environment, so, duplicating voltage being brought up to 1500V duplicate, the result is that the broken line of employed intermediate color pattern reduces, but still sees the poor of 4 looks a small amount of degree.In addition, also find the axial concentration fluctuation of roller.

Embodiment 6

The live part of these embodiment and comparative example is with long 248mm, imposes prime treatment person as holding components on the surface of the stainless steel shaft of external diameter 16mm, and with the charged roller that is shaped as roll shape as whole live parts.

Embodiment 20

Operation similarly to Example 16 forms the semiconduction elastic layer on the stainless steel shaft periphery.A Sika-C the hardness of described elastic layer under 21 ℃, the condition of relative humidity 60% is 40 degree.

Then, charged roller is made in operation similarly to Example 16.

The charged roller of making, under 23 ℃, the condition of relative humidity 55%, place 24 hours after similarly to Example 16 operation estimate.

The result is R ₅₀₀Be 1.5 * 10 ⁸Ω, R ₁₀₀₀Be 1.4 * 10 ⁸Ω, R ₅₀₀/ R ₁₀₀₀Be 1.07.In addition, R _LLAnd R _HHBe respectively 2.0 * 10 ⁸Ω (R _LL) and 7.0 * 10 ⁷Ω (R _HH), R ^LL/ R _HHBe 2.9.

In addition, apply the R of voltage after 100 hours continuously ₁₀₀₀Be 2.2 * 10 ⁸Ω is 1.57 times that apply continuously before the voltage.

Embodiment 21

Operation similarly to Example 17 forms the semiconduction elastic layer on the stainless steel shaft periphery.The A Si card C hardness of described elastic layer under 21 ℃, the condition of relative humidity 60% is 40 degree.

Then, charged roller is made in operation similarly to Example 17.

The charged roller of making, under 23 ℃, the condition of relative humidity 55%, place 24 hours after similarly to Example 16 operation estimate.

The result is R ₅₀₀Be 1.0 * 10 ⁸Ω, R ₁₀₀₀Be 9.5 * 10 ⁷Ω, R ₅₀₀/ R ₁₀₀₀Be 1.05.In addition, roller resistance R _LLAnd R _HHBe respectively 2.0 * 10 ⁸Ω (R _LL) and 6.0 * 10 ⁷Ω (R _HH), R _LL/ R _HHBe 3.3.In addition, apply the R of voltage Ω after 100 hours continuously ₁₀₀₀Become 1.5 * 10 ⁸Ω is 1.58 times that apply continuously before the voltage.

Comparative example 7

Operate equally with comparative example 5, on the stainless steel shaft periphery, form the semiconduction elastic layer.A Sika-C the hardness of described elastic layer under 21 ℃, the condition of relative humidity 60% is 40 degree.

Then, operate equally, make charged roller with comparative example 5.

The charged roller of making, under 23 ℃, the condition of relative humidity 55%, place 24 hours after similarly to Example 16 operation estimate.

The result is R ₅₀₀Be 3.5 * 10 ⁷Ω, R ₁₀₀₀Be 2.0 * 10 ⁷Ω, R ₅₀₀/ R ₁₀₀₀Be 1.75.In addition, roller resistance R _LL. and R _HHBe respectively 2.0 * 10 ⁸Ω (R _LL) and 1.0 * 10 ⁷Ω (R _HH), R _LL/ R _HHBe 20.

In addition, apply the R of voltage after 100 hours continuously ₁₀₀₀Become 4.5 * 10 ⁷Ω is 2.25 times that apply continuously before the voltage.

Then, the embodiment in the embodiment 6 and the charged roller shown in the comparative example charged roller as the laser printer of putting down in writing among Fig. 2.LL (15 ℃, 10%Rh), NN (23 ℃, 55%Rh), (32.5 ℃ of HH, under various environment 85%Rh), make medium tone image output with C, M, various 4 colour toners of Y, K,, carry out the charged characteristic evaluation by picture qualities such as the cutting marks of medium tone relatively, color dim spots.The result shows, do not find the cutting marks of medium tone image, color dim spot etc. when using the charged roller of making according to embodiment 20 and 21.In addition, charged roller can adopt same condition to duplicate under low temperature and low humidity and under hot and humid, does not find that environment causes the difference of medium tone image color.

Yet the charged roller of comparative example 7 is under the low temperature and low humidity environment, and low concentration medium tone image cuts marks, so, improve to duplicate voltage and show to the result that 1500V duplicates, the minimizing that cuts marks of medium tone image, but find that the reduction degree of 4 looks poor.In addition, also find the axial concentration fluctuation of roller.

Embodiment 7

The developing parts of these embodiment and comparative example, carried out prime treatment person as support component with the stainless steel shaft surface of external diameter 12mm, the developer roll that is shaped to roll forming is all as developing parts.

Embodiment 22

Operation similarly to Example 16 forms the semiconduction elastic layer on the stainless steel shaft periphery.A Sika-C the hardness of described elastic layer under 21 ℃, the condition of relative humidity 60% is 40 degree.

Then, developer roll is made in operation similarly to Example 16.

The developer roll of making, under 23 ℃, the condition of relative humidity 55%, place 24 hours after similarly to Example 16 operation estimate.

The result is R ₅₀₀Be 1.5 * 10 ⁸Ω, R ₁₀₀₀Be 1.4 * 10 ⁸Ω, R ₅₀₀/ R ₁₀₀₀Be 1.07.In addition, R _LLAnd R _HHBe respectively 2.0 * 10 ⁸Ω (R _LL) and 7.0 * 10 ⁷Ω (R _HH), R _LL/ R _HHBe 2.9.

In addition, apply the R of voltage after 100 hours continuously ₁₀₀₀Be 2.2 * 10 ⁸Ω is 1.57 times that apply continuously before the voltage.

Embodiment 23

Operation similarly to Example 17 forms the semiconduction elastic layer on the stainless steel shaft periphery.A Sika-C the hardness of described elastic layer under 21 ℃, the condition of relative humidity 60% is 40 degree.

Then, developer roll is made in operation similarly to Example 17.

The developer roll of making, under 23 ℃, the condition of relative humidity 55%, place 24 hours after similarly to Example 16 operation estimate.

The result is R ₅₀₀Be 1.0 * 10 ⁸Ω, R ₁₀₀₀Be 9.5 * 10 ⁷Ω, R ₅₀₀/ R ₁₀₀₀Be 1.05.In addition, roller resistance R _LLAnd R _HHBe respectively 2.0 * 10 ⁸Ω (R _LL) and 6.0 * 10 ⁷Ω (R _HH), R _LL/ R _HHBe 3.3.

In addition, apply the R of voltage after 100 hours continuously ₁₀₀₀Become 1.5 * 10 ⁸Ω is 1.58 times that apply continuously before the voltage.

Comparative example 8

Operate equally with comparative example 5, on the stainless steel shaft periphery, form the semiconduction elastic layer.A Sika-C the hardness of described elastic layer under 21 ℃, the condition of relative humidity 60% is 40 degree.

Then, operate equally, make developer roll with comparative example 5.

The developer roll of making, under 23 ℃, the condition of relative humidity 55%, place 24 hours after similarly to Example 16 operation estimate.

The result is R ₅₀₀Be 3.5 * 10 ⁷Ω, R ₁₀₀₀Be 2.0 * 10 ⁷Ω, R ₅₀₀/ R ₁₀₀₀Be 1.75.In addition, roller resistance R ^LLAnd R _HHBe respectively 2.0 * 10 ⁸Ω (R _LL) and 1.0 * 10 ⁷Ω (R _HH), R _LL/ R _HHBe 20.

In addition, apply the R of voltage after 100 hours continuously ₁₀₀₀Become 4.5 * 10 ⁷Ω is 2.25 times that apply continuously before the voltage.

Then, for estimating the developing property of the developer roll made from embodiment in the embodiment 7 and comparative example 6, be installed in as the developer roll of the developing apparatus of putting down in writing among Fig. 5 and carry out image output in the laser printer.And carry out following evaluation (15 ℃ of LL, 10%Rh), NN (23 ℃, 55%Rh), HH (32.5 ℃, under various environment 85%Rh), make medium tone image output with C, M, various 4 colour toners of Y, K, carry out picture qualities such as the cutting marks of medium tone, color dim spot relatively.The result shows, does not find that the medium tone image cuts marks, the color dim spot when adopting the developer roll of making according to the foregoing description 22 and 23.In addition, charged roller can adopt same condition to duplicate under low temperature and low humidity and under hot and humid, does not find that environment causes the difference of medium tone image color.

Yet the charged roller of comparative example 8 is under hot and humid environment, and particularly the medium tone image color in high concentration one side thickens, and entire image is thin out under the low temperature and low humidity environment, finds that low concentration medium tone image cuts marks.In addition, the color dim spot of medium tone image is compared during with the developer roll that adopts embodiment to make and is become big, can not get preferable image.

Embodiment 8

The middle copying magnetic drum of these embodiment and comparative example imposes prime treatment person to the aluminium sleeve surface of long 248mm, external diameter 32mm, wall thickness 2mm as support component.

Embodiment 24

Operation similarly to Example 16 forms the semiconduction elastic layer on the periphery of aluminium sleeve.A Sika-C the hardness of described elastic layer under 21 ℃, the condition of relative humidity 60% is 40 degree.

Then, the middle copying magnetic drum is made in operation similarly to Example 16.

The middle copying magnetic drum of making, under 23 ℃, the condition of relative humidity 55%, place 24 hours after similarly to Example 16 operation estimate.

The result is R ₅₀₀Be 1.5 * 10 ⁸Ω, R ₁₀₀₀Be 1.4 * 10 ⁸Ω, R ₅₀₀/ R ¹⁰⁰⁰Be 1.07.In addition, R _LLAnd R _HHBe respectively 2.0 * 10 ⁸Ω (R _LL) and 7.0 * 10 ⁷Ω (R _HH), R _LL/ R _HHBe 2.9.

In addition, apply the R of voltage after 100 hours continuously ₁₀₀₀Be 2.2 * 10 ⁸Ω is 1.57 times that apply continuously before the voltage.

Embodiment 25

Operation similarly to Example 17 forms the semiconduction elastic layer on the periphery of aluminium sleeve.A Sika-C the hardness of described elastic layer under 21 ℃, the condition of relative humidity 60% is 40 degree.

Then, the middle copying magnetic drum is made in operation similarly to Example 17.

The middle copying magnetic drum of making, under 23 ℃, the condition of relative humidity 55%, place 24 hours after similarly to Example 16 operation estimate.

The result is R ₅₀₀Be 1.0 * 108 Ω, R ₁₀₀₀Be 9.5 * 10 ⁷Ω, R ₅₀₀/ R ₁₀₀₀Be 1.05.In addition, roller resistance R _LLAnd R _HHBe respectively 2.0 * 10 ⁸Ω (R _LL) and 6.0 * 10 ⁷Ω (R _HH), R _LL/ R _HHBe 3.3.

In addition, apply the R of voltage after 100 hours continuously ₁₀₀₀Become 1.5 * 10 ⁸Ω is 1.58 times that apply continuously before the voltage.

Comparative example 9

Operate equally with comparative example 5, on the aluminum casing periphery, form the semiconduction elastic layer.A Sika-C the hardness of described elastic layer under 21 ℃, the condition of relative humidity 60% is 40 degree.

Then, operate equally, make the middle copying magnetic drum with comparative example 5.

The middle copying magnetic drum of making, under 23 ℃, the condition of relative humidity 55%, place 24 hours after similarly to Example 16 operation estimate.

The result is R ₅₀₀Be 3.5 * 10 ⁷Ω, R ₁₀₀₀Be 2.0 * 10 ⁷Ω, R ₅₀₀/ R ₁₀₀₀Be 1.75.In addition, roller resistance R _LLAnd R _HHBe respectively 2.0 * 10 ⁸Ω (R _LL) and 1.0 * 10 ⁷Ω (R _HH), R _LL/ R _HHBe 20.

In addition, apply the R of voltage after 100 hours continuously ₁₀₀₀Become 4.5 * 10 ⁷Ω is 2.25 times that apply continuously before the voltage.

Then, for the duplicating characteristic of estimating embodiment in the embodiment 8 and the middle copying magnetic drum shown in the comparative example (amount of remaining toner, duplicate mottled and image in the middle of come off), install as the middle copying magnetic drum in the laser printer of the middle copying type of putting down in writing among Fig. 3.4 chromosphere shape toners of the cyan (C) of employing mean grain size 6 μ m, fuchsin (M), yellow (Y), black (K) carry out image output under various environment, estimated.

(15 ℃ of LL, 10%Rh), NN (23 ℃, 55%Rh), HH (32.5 ℃, under various environment 85%Rh), with the various 4 colour toners output of C, M, Y, K lines image, medium tone image, character image, carry out the evaluation map picture cut marks and picture quality such as color dim spot relatively.The result shows, does not find difference between 4 kinds of toners when adopting the middle copying magnetic drum of making according to embodiment 24 and 25.In addition, the poor image quality heteropole that causes under each environment such as LL environment, NN environment, HH environment is few, obtains the preferable image quality.

Yet the middle copying magnetic drum of comparative example 9 can be seen medium tone image color defect spot, sees the difference of colourity under each environment such as LL environment, NN environment, HH environment.

Embodiment 9

The semiconduction magnetic drum of these embodiment and comparative example, carrying out machined near the aluminum tubular conductor two ends of long 248mm, external diameter 32mm, wall thickness 2mm, be pressed into flange toward this processing part with turning axle, and, turning axle with above-mentioned flange is a benchmark, the aluminium tube-surface is carried out machined into and attrition process, and external diameter tolerance+0.01mm is following, its surface of outside diameter tolerance precision 0.01mm still imposes prime treatment person though be finish-machined to, as support component (cylindrical sleeve).

Embodiment 26

Operation similarly to Example 16 forms the semiconduction elastic layer on the periphery of aluminum casing.

Then, poly(ether-urethane) (Y258, Dainichiseika Color Chem's system) reaches the made solution of solid constituent 5% with MEK/dimethyl formamide=1/1 dilution, on the surface that is applied to the semiconduction elastic layer on the surface of semiconduction elastic layer with spraying process and carry out (160 ℃ of dryings, 30 minutes), on the outer peripheral face of semiconduction elastic layer, form the superficial layer of 10 μ m, make the semiconduction magnetic drum.

The semiconduction magnetic drum that last method is made carries out following mensuration place 24 hours under 23 ℃, the environment of relative humidity 55% after under this environment.

A Sika-C type hardness tester meter that original adoption macromolecule gauge Co., Ltd. makes, to axial 3 x circumferential 4 totally 12 hardness measure, on average, obtaining A Sika-C hardness is 45.5 degree.

Then, to the R of this photocopying roll ₁₀₀, R ₅₀₀And R ₁₀₀₀Adopt method similarly to Example 1 to measure, the result who obtains is: R ₁₀₀Be 1.5 * 10 ⁸Ω, R ₅₀₀Be 1.5 * 10 ⁸Ω, R ₁₀₀₀Be 1.4 * 10 ⁸Ω, R ₁₀₀/ R ₁₀₀₀Be 1.07, R ₅₀₀/ R ₁₀₀₀Be 1.07.

In addition, R _LLAnd R _HHBe respectively 2.0 * 10 ⁸Ω (R _LL) and 7.0 * 10 ⁷Ω (R _HH), R _LL/ R _HHBe 2.9.

In addition, apply the R of voltage after 100 hours continuously ₁₀₀₀Become 2.2 * 10 ⁸Ω is 1.57 times that apply continuously before the voltage.

In addition, the exposed portions serve of the aluminum casing at magnetic drum two ends is placed on the V-block, while the Laser Outer Diameter Measuring Sensors that makes magnetic drum rotation キ-エ Application ス society manufacturing, axial 5 mensuration from the reference position poor apart from maximal value and minimum value to the magnetic drum end, measure the outside diameter tolerance of magnetic drum whereby.The result is that maximum deviation is 55 μ m, average 40 μ m.

Embodiment 27

Except adopting non-ionic surfactant (ユ ニ オ Star Network ス MM500, NOF Corp's system) 5 weight portions are as beyond (E) composition, and operation similarly to Example 26 forms the semiconduction elastic layer on the aluminum casing periphery, and, make the semiconduction magnetic drum at its surface formation superficial layer.

The semiconduction magnetic drum of making, under 23 ℃, the environment of relative humidity 55%, place 24 hours after, under this environment, carry out following mensuration

A Sika-C the hardness that adopts method similarly to Example 26 to measure is 46 degree.

Then, adopt method similarly to Example 16, the centre is duplicated the R of magnetic drum ₁₀₀, R ₅₀₀And R ₁₀₀₀The result who measures is: R ₁₀₀Be 1.0 * 10 ⁸Ω, R ₅₀₀Be 1.0 * 10 ⁸Ω, R ₁₀₀₀Be 9.5 * 10 ⁷Ω, R ₁₀₀/ R ₁₀₀₀Be 1.05, R ₅₀₀/ R ₁₀₀₀Be 1.05.In addition, roller resistance R _LLAnd R _HHBe respectively 2.0 * 10 ⁸Ω (R _LL) and 6.0 * 10 ⁷Ω (R _HH), R _LL/ R _HHBe 3.3.

In addition, apply the R of voltage after 100 hours continuously ₁₀₀₀Become 1.5 * 10 ⁸Ω is 1.58 times that apply continuously before the voltage.

Operation similarly to Example 26, the result who measures the magnetic drum outside diameter tolerance is that the deviation maximal value is 60 μ m, average out to 48 μ m.

Embodiment 28

Contain except employing beyond the semiconduction composition of electric conductivity imparting agent (LV-70, rising sun electrification Co., Ltd. system) 10 weight portions, operation similarly to Example 26 forms the semiconduction elastic layer on the aluminum casing outer peripheral face.

Then, except reach beyond the solution that makes after 20 weight portions disperse operation similarly to Example 26 with respect to resin solid as conductive agent carbon black contained in the superficial layer (3030B, Mitsubishi chemical Co., Ltd's system), form superficial layer, make the semiconduction magnetic drum.

Adopt method similarly to Example 26, the A Sika of mensuration-C hardness is 46 degree.

Then to the R of this middle copying magnetic drum ₁₀₀, R ₅₀₀And R ₁₀₀₀The result who adopts method similarly to Example 16 to measure: R ₁₀₀Be 1.6 * 10 ⁸Ω, R ₅₀₀Be 1.5 * 10 ⁷Ω, R ₁₀₀₀Be 1.4 * 10 ⁷Ω, R ₁₀₀/ R ₁₀₀₀Be 1.14, R ₅₀₀/ R ₁₀₀₀Be 1.07.

In addition, roller resistance R _LLAnd R _HHBe respectively 2.5 * 10 ⁷Ω (R _LL) and 1.0 * 10 ⁷Ω (R _HH), R _LL/ R _HHBe 2.5.

Operation similarly to Example 26, the result who measures the magnetic drum outside diameter tolerance is that the deviation maximal value is 60 μ m, average 48 μ m.

Comparative example 10

Conductive carbon black 10 weight portions, paraffin hydrocarbon ils 20 weight portions, zinc paste 5 weight portions, vulcanizing agent 2 weight portions, higher fatty acid 1.5 weight portions, nitrile butadiene rubber (NBR) 40 weight portions and EPDM60 weight portion are mixed 30 minutes with two rollers while cooling off, make compound.The compound that obtains is made the thick sheet of 5mm.This sheet material on the periphery of described cylindrical sleeve, in 160 ℃ of vulcanizing treatment 30 minutes, is formed the semiconduction elastic layer.The result who measures the external diameter precision after the sulfuration be deviation more than 0.1mm, so, carry out the surface grinding equating deviation is reached below the 100 μ m.

Then, operation similarly to Example 26 forms superficial layer on its surface, makes the semiconduction magnetic drum.

A Sika-C the hardness that adopts method similarly to Example 26 to measure is 70 degree.

According to the same procedure of embodiment 16 R to this middle copying magnetic drum ₁₀₀, R ₅₀₀And R ₁₀₀₀The result who measures is R ₁₀₀Be 2.0 * 10 ⁷Ω, R ₅₀₀Be 1.0 * 10 ⁷Ω, R ₁₀₀₀Be 1.8 * 10 ⁶Ω, R ₁₀₀/ R ₁₀₀₀Be 11.1, R ₅₀₀/ R ₁₀₀₀Be 5.56.

In addition, roller resistance R _LLAnd R _HHBe respectively 3.0 * 10 ⁶Ω (R _LL) and 1.0 * 10 ⁶Ω (R _HH), R _LL/ R _HHBe 3.0.

Operation similarly to Example 26, the result who measures the magnetic drum outside diameter tolerance is that the deviation maximal value is 75 μ m, average out to 65 μ m.

Then, the duplicating characteristic (residual quantity, the mottled and image hollow of duplicating) to embodiment in the embodiment 9 and the middle copying magnetic drum shown in the comparative example adopts the spherical toner of mean grain size 6 μ m to estimate under various environment.

Under the extruding of 50g/cm, make photoreceptor and middle copying magnetic drum bonding, under duplicating voltage 400V, toner image is once duplicated on the middle copying body from photoreceptor, again the copy image secondary on the middle copying magnetic drum is duplicated on the paper, estimate and duplicate characteristic.Also have, in secondary duplicated, the duplicating voltage of middle copying magnetic drum and the electric conductivity backing roll that disposes behind paper was that 1000V, magnetic drum peripheral speed are 100mm/ second.In addition, the contact pressure of electric conductivity backing roll and middle copying magnetic drum makes line pressure reach 150g/cm at the two ends of electric conductivity backing roll with spring device.

This result is, with the semiconduction magnetic drum of the foregoing description during as the middle copying magnetic drum, do not take place driving fit bad, the slurry that overflows does not take place, it is also good to duplicate characteristic.Particularly the middle copying magnetic drum of embodiment 26～28 even reach under low temperature and low humidity hot and humid time, also can duplicate under the same conditions.

Yet the middle copying magnetic drum of comparative example 10 can not form uniform jaw, duplicates the defect spot in the length direction generation of roller.In addition, under hot and humid, must reduce and duplicate voltage.In addition, with the photoreceptor Long contact time time, can see the pollution of photoreceptor.

The possibility of industrial utilization

According to conductive rollers provided by the invention, it can easily be controlled at the semiconduction zone to resistance, and in resulting semi-conductive roller, the fluctuation of the sample of electrology characteristic (roller resistance) and voltage-dependent are minimum, and, ooze out danger and be reduced.

According to semiconductive member provided by the invention, when the positional fluctuation of the variation in voltage of its resistance under hot and humid environment and the change of resistance under the low temperature and low humidity environment and resistance, the resistance variations of using continuously, resistance and rotation and the resistance difference when static minimum, be suitable for doing to duplicate with parts, develop with parts, charged with parts, supply with toner with electrophotography parts such as parts.

Particularly adopt the image recording structure of duplicating parts, middle copying parts, live part or the developing parts that the present invention relates to, minimum because of the picture quality change that environment for use causes, can obtain high-quality image.

Claims (12)

1. semiconductive member, it is by metal support component, the semiconduction elastic layer that forms on this support component outer peripheral face, the semiconductive member that constitutes at the superficial layer more than 1 layer that forms on this outer peripheral face again, and has the characteristic of following (1)～(3):

(1) under 23 ℃, the environment of relative humidity 55%, applies parts resistance that the 1000V DC voltage records 10 ⁵Ω above 10 ⁹Below the Ω;

(2) under 23 ℃, the environment of relative humidity 55%, apply the parts resistance that 500V and 1000V DC voltage measure and use R respectively ₅₀₀And R ₁₀₀₀R during expression ₅₀₀/ R ₁₀₀₀Value more than 0.8 below 1.2;

(3) under 15 ℃, the environment of relative humidity 10%, apply the parts resistance R that the 1000V DC voltage records _LLWith, under 32.5 ℃, the environment of relative humidity 85%, apply the parts resistance R that the 1000V DC voltage records _HHRatio R _LL/ R _HHBelow 10.

2. according to the semiconductive member of putting down in writing in the claim 1, also have, under 23 ℃, the environment of relative humidity 55%, be more than 0.5 times below 2 times of parts initial resistance while make described semiconductive member rotation apply the parts resistance of 1000V DC voltage in the time of 100 hours continuously.

3. according to the semiconductive member of record in the claim 1, also have, under 23 ℃, the environment of relative humidity 55%, apply parts resistance positional fluctuation that the 1000V DC voltage measures below 20%.

4. according to the semiconductive member of record in the claim 1, also have, under 23 ℃, the environment of relative humidity 55%, when applying the 1000V DC voltage and measuring rotation and the parts resistance when static use R respectively _RotateAnd R _StaticDuring expression, R _Rotate/ R _StaticValue more than 0.7 below 1.5.

5. according to the semiconductive member of record in the claim 1, also have, its A Sika-C hardness is below 60 degree.

6. according to the semiconductive member of record in the claim 1, also have, under 23 ℃, the environment of relative humidity 55%, apply the parts resistance that 100V and 1000V DC voltage record and be respectively R ₁₀₀And R ₁₀₀₀The time R ₁₀₀/ R ₁₀₀₀Value more than 0.1 below 10.

7. according to the semiconductive member of record in the claim 1, also have, its outside diameter tolerance is below the 100 μ m.

8. according to the semiconductive member of record in the claim 1, wherein said semiconduction elastic layer has the oxyalkylene based polymer that can carry out the alkenyl of hydrogenation silylation reactive more than 1 by containing in (A) molecule; (B) compound of 2 above hydrogenation silicyls is arranged in the molecule; (C) hydrogenation silylanizing catalyzer and (E) the solidfied material formation of the electric conductivity solidification compound of non-ionic surfactant.

9. charged roller, it is by metal support component, the semiconduction elastic layer that forms on this support component outer peripheral face, the charged roller that constitutes at the superficial layer more than 1 layer that forms on this outer peripheral face again, and has the characteristic of following (1)～(3):

(1) under 23 ℃, the environment of relative humidity 55%, applies roller resistance that the 1000V DC voltage records 10 ⁵Ω above 10 ⁹Below the Ω;

(2) under 23 ℃, the environment of relative humidity 55%, apply the roller resistance that 500V and 1000V DC voltage measure and use R respectively ₅₀₀And R ₁₀₀₀R during expression ₅₀₀/ R ₁₀₀₀Value more than 0.8 below 1.2;

(3) under 15 ℃, the environment of relative humidity 10%, apply the roller resistance R that the 1000V DC voltage records _LLWith, under 32.5 ℃, the environment of relative humidity 85%, apply the roller resistance R that the 1000V DC voltage records _HHRatio R _LL/ R _HHBelow 10.

10. developer roll, it is by metal support component, the semiconduction elastic layer that forms on this support component outer peripheral face, the developer roll that constitutes at the superficial layer more than 1 layer that forms on this outer peripheral face again, and has the characteristic of following (1)～(3):

(1) under 23 ℃, the environment of relative humidity 55%, applies roller resistance that the 1000V DC voltage records 10 ⁵Ω above 10 ⁹Below the Ω;

(2) under 23 ℃, the environment of relative humidity 55%, apply the roller resistance that 500V and 1000V DC voltage measure and use R respectively ₅₀₀And R ₁₀₀₀R during expression ₅₀₀/ R ₁₀₀₀Value more than 0.8 below 1.2;

(3) under 15 ℃, the environment of relative humidity 10%, apply the roller resistance R that the 1000V DC voltage records _LLWith, under 32.5 ℃, the environment of relative humidity 85%, apply the roller resistance R that the 1000V DC voltage records _HHRatio R _LL/ R _HHBelow 10.

11. middle copying roller, it is by metal support component, the semiconduction elastic layer that forms on this support component outer peripheral face, the middle copying roller that constitutes at the superficial layer more than 1 layer that forms on this outer peripheral face again, and has the characteristic of following (1)～(3):

(1) under 23 ℃, the environment of relative humidity 55%, applies roller resistance that the 1000V DC voltage records 10 ⁵Ω above 10 ⁹Below the Ω;

(2) under 23 ℃, the environment of relative humidity 55%, apply the roller resistance that 500V and 1000V DC voltage measure and use R respectively ₅₀₀And R ₁₀₀₀R during expression ₅₀₀/ R ₁₀₀₀Value more than 0.8～below 1.2;

(5) under 15 ℃, the environment of relative humidity 10%, apply the roller resistance R that the 1000V DC voltage records _LLAnd under 32.5 ℃, the environment of relative humidity 85%, apply the roller resistance R that the 1000V DC voltage records _HHRatio R _LL/ R _HHBelow 10.

12. a photocopying roll, it is by metal support component, the semiconduction elastic layer that forms on this support component outer peripheral face, the photocopying roll that constitutes at the superficial layer more than 1 layer that forms on this outer peripheral face again, and has the characteristic of following (1)～(3):

(1) under 23 ℃, the environment of relative humidity 55%, applies roller resistance that the 1000V DC voltage records 10 ⁵Ω above 10 ⁹Below the Ω;

(2) under 23 ℃, the environment of relative humidity 55%, apply the roller resistance that 500V and 1000V DC voltage record and use R respectively ₅₀₀And R ₁₀₀₀R during expression ₅₀₀/ R ₁₀₀₀Value more than 0.8 below 1.2;

(3) under 15 ℃, the environment of relative humidity 10%, apply the roller resistance R that the 1000V DC voltage records _LLAnd under 32.5 ℃, the environment of relative humidity 85%, apply the roller resistance R that the 1000V DC voltage records _HHRatio R _LL/ R _HHBelow 10.

Images