CN100430834C - Conductive rubber roller - Google Patents
Conductive rubber roller Download PDFInfo
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- CN100430834C CN100430834C CNB2006100757888A CN200610075788A CN100430834C CN 100430834 C CN100430834 C CN 100430834C CN B2006100757888 A CNB2006100757888 A CN B2006100757888A CN 200610075788 A CN200610075788 A CN 200610075788A CN 100430834 C CN100430834 C CN 100430834C
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- glycidyl ether
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Abstract
A conductive rubber roller comprising a conductive core material and provided thereon a rubber layer; the rubber layer being formed by using a rubber composition containing as rubber components at least a polar rubber and an ethylene oxide-propylene oxide-allyl glycidyl ether terpolymer; the ethylene oxide-propylene oxide-allyl glycidyl ether terpolymer having a melt peak temperature of from 20 to 30 DEG C. and a melt enthalpy change DeltaH of from 40 to 70 mJ/mg as measured with a differential scanning calorimeter; and the allyl glycidyl ether in the ethylene oxide-propylene oxide-allyl glycidyl ether terpolymer being in a copolymerization ratio of from more than 10 mol % to 20 mol % or less.
Description
Technical field
The present invention relates to be used for for example conducting rubber roller of electrofax copy device, printing machine, electrostatic recording apparatus of imaging device, but relate more specifically to conducting rubber roller as for example being transferred to the transfer roll of the transfer printing assembly on recording medium such as the paper based on the transferred image of toner image by it; This toner image forms and is retained on the image bearing member as the static sensitive parts by imaging mode such as electrophotographic processes or electrostatic recording process.
Background technology
In imaging device such as electrofax copy device and electrostatic recording apparatus, the contact electrification system is common, wherein will exert pressure to the surface of static sensitive parts to the conducting rubber roller that its maintenance applies voltage, so that its static electrification.On every side as the static sensitive parts (drum) of imaging heart, one step such as that conducting rubber roller is used for independently is charged, transfer printing.
In recent years, as the rubber components of this conducting rubber roller, use polar rubber such as acrylonitrile-butadiene rubber and chloropropylene oxide class rubber.Polar rubber has electric conductivity (ionic conductivity) because of there is polar group in polymkeric substance, and knownly is suitable for conducting rubber roller because of the diffusion of lower resistance and little resistive voltage dependence.
Under many circumstances, require the elastomeric layer of conducting rubber roller to have specific insulation and be less than or equal to 2 * 10
9Ω cm.When rubber components only was acrylonitrile-butadiene rubber, its vulcanizate had specific insulation about 2 * 10
9To 1 * 10
10Ω cm causes the electric conductivity deficiency.Simultaneously, acrylonitrile-butadiene rubber also has relatively poor ozone resistance, and therefore can not realize enough energising permanance.
Therefore, usually use a kind of like this method: have a specific insulation about 1 * 10 with known
7To 3 * 10
9Chloropropylene oxide class rubber and the acrylonitrile-butadiene rubber blending of Ω cm are controlled, and can realize required specific insulation (for example referring to Jap.P. No.3656904) like this.
In addition, in recent years, for adapting to colour imaging and high-quality imaging, requirement has more low-resistance conducting rubber roller, and adopt and wherein only to use chloropropylene oxide class rubber or to add the method (for example, referring to Japanese Patent Application Laid-Open No.2002-132020) of various types of ionic conductive agents as the quaternary ammonium salt that contains perchlorate or chloride ion.
Yet, adopting at conducting rubber roller under the situation of this rubber elastic material, its resistivity can change with the variation of environmental factor such as temperature and humidity, therefore the problem that exists picture quality to change with service environment.Especially, the existence of chloropropylene oxide class rubber is tending towards being subjected to humidity effect seriously to cause the problem of resistivity environment variation thus.Wherein adding pollution that the method for various ionic conductive agents such as quaternary ammonium salt also may cause because of the surface migration of ion, energising etc. causes resistivity to change in time.Therefore, in some cases, can not realize can with at a high speed and any energising permanance of adapting of long-life imaging.
Under chloropropylene oxide class rubber and situation that the quaternary ammonium salt that contains perchlorate or chloride ion mixes, compression set also may very seriously take place and produce poison gas and dioxin when burning, its reason is that for example chlorine causes subsidiary reaction.
Therefore, as can solution to the problems described above, constantly attempt wherein epoxy ethane-epoxy propane-allyl glycidyl ether ter-polymers being measured the method for sneaking in polar rubber such as acrylonitrile-butadiene rubber or the epichlorohydrin rubber according to the rules.Therefore this epoxy ethane-epoxy propane-allyl glycidyl ether ter-polymers comprises ether-oxygen bonds, has the function that metal cation in the stabilization of polymer etc. reduces resistance thus.This epoxy ethane-epoxy propane-allyl glycidyl ether ter-polymers also can with other rubber cross, reason be it have big polarity and with the superior compatibility of other polar rubber and also because allyl glycidyl ether have unsaturated link.Owing to be different from conductive agent such as quaternary ammonium salt, be not easy like this to cause and ooze out and the static sensitive component contamination.In addition, the not halogen-containing element of epoxy ethane-epoxy propane-allyl glycidyl ether, therefore it is reported the subsidiary reaction problem that does not have the chlorine that chloropropylene oxide class rubber may cause, and can obtain the fine good elastomeric material (for example referring to Japanese Patent Application Laid-Open No.2002-105305) that prevents compression set.
Also the report epoxy ethane-epoxy propane-allyl glycidyl ether that will have a specific copolymerization ratio is measured mixing according to the rules, obtain conducting rubber roller thus, this conducting rubber roller have than normally used employing comprise acrylonitrile-butadiene rubber and chloropropylene oxide class rubber blend rubber composition conducting rubber roller and adopt the low resistance of the conducting rubber roller of the rubber composition wherein add ionic conductive agent, good ozone resistance and circlet border dependence (for example, referring to Jap.P. No.3600517 and Japanese Patent Application Laid-Open No.2006-037042) more.
In Jap.P. No.3600517, under the situation of disclosed rubber composition, can obtain to have the conducting rubber roller of excellent ozone resistance.Yet, consider and realize low resistance, environmental factor dependence and, sought further improvement the resistance tocrocking of photosensitive part.In Japanese Patent Application Laid-Open No.2006-037042, under the disclosed rubber composition situation, can obtain to have the dependent conducting rubber roller of subenvironment.Yet, be difficult to realize low resistance and circlet border dependence very in some cases, and sought further improvement.
Summary of the invention
The objective of the invention is to address the above problem, and in the conducting rubber roller such as transfer roll, charged roller and developer roll that use polar rubber such as acrylonitrile-butadiene rubber and chloropropylene oxide class rubber, the roller change in resistance that causes because of energising permanance deterioration and environmental change that has low resistance, has small degree simultaneously is provided, and still keeps not taking place the conducting rubber roller of static sensitive component contamination.
Like this, as for addressing the above problem the result of broad research repeatedly, the inventor finds, use have the melting peak temperature in particular range measured by differential scanning calorimeter and fusion enthalpy change Δ H and wherein allyl glycidyl ether can obtain conducting rubber roller with the epoxy ethane-epoxy propane-allyl glycidyl ether ter-polymers of specific copolymerization ratio copolymerization, the origin cause of formation that this conducting rubber roller resistivity environment changes is lower, have low-resistivity simultaneously and keep the static photosensitive part not pollute, be retained in the good energising permanance of guaranteeing under the regular situation simultaneously.
Finished the present invention based on this discovery.
In other words, according to the present invention, provide conducting rubber roller, this conducting rubber roller is the conducting rubber roller that comprises the conductive cores material and rubber layer is set thereon;
Rubber layer forms by the rubber composition that use contains as the polar rubber at least of rubber components and epoxy ethane-epoxy propane-allyl glycidyl ether ter-polymers;
Epoxy ethane-epoxy propane-allyl glycidyl ether ter-polymers has the melting peak temperature measured with differential scanning calorimeter more than or equal to 20 ℃ and be less than or equal to 30 ℃ and more than or equal to 40mJ/mg and be less than or equal to the fusion enthalpy change Δ H of 70mJ/mg, measure with differential scanning calorimeter, and the copolymerization ratio of the allyl glycidyl ether in epoxy ethane-epoxy propane-allyl glycidyl ether ter-polymers is greater than 10mol% and is less than or equal to 20mol%.
According to the present invention, conducting rubber roller also is provided, it is above-mentioned conducting rubber roller, wherein, when the copolymerization ratio in epoxy ethane-epoxy propane-allyl glycidyl ether ter-polymers is respectively by a and b (mol%) expression when epoxypropane and allyl glycidyl ether, 10＜a+b≤30 and 10＜b≤20.
Conducting rubber roller also is provided, and it is above-mentioned conducting rubber roller, and wherein above-mentioned rubber composition further comprises more than or equal to 0.1 mass parts and is less than or equal to the ionic conductive agent of 10 mass parts, by 100 mass parts rubber components.
Conducting rubber roller further is provided, it is any in the above-mentioned conducting rubber roller, it comprises above-mentioned rubber composition, this rubber composition comprise more than or equal to 5 mass parts and be less than or equal to 70 mass parts have iodine sorption value more than or equal to 5mg/g and be less than or equal to 30mg/g and the oily absorption value of dibutyl phthalate (DBP) is less than or equal to the carbon black of 55ml/100g, be 100 mass parts based on the rubber components summation of rubber composition.
Conducting rubber roller further is provided, it is any in the above-mentioned conducting rubber roller, wherein, mixing is more than or equal to 5 mass parts and be less than or equal to the epoxy ethane-epoxy propane-allyl glycidyl ether ter-polymers of 20 mass parts, is 100 mass parts based on the rubber components summation of rubber composition.
Conducting rubber roller further is provided here, and it is any in the above-mentioned conducting rubber roller, and wherein polar rubber is any in acrylonitrile-butadiene rubber and the epichlorohydrin rubber or two kinds.
Conducting rubber roller further is provided, it is any in the above-mentioned conducting rubber roller, the image forming apparatus that this conducting rubber roller is used for wherein will forming on the static sensitive parts electrostatic latent image develops with developer, wherein conducting rubber roller is for being in the transfer roll on the static sensitive parts face-to-face.
Embodiment
As mentioned above, conducting rubber roller of the present invention be have little resistivity environment dependence, simultaneously have excellent energising permanance, have low-resistivity and keep not taking place the conducting rubber roller of static sensitive component contamination.Therefore, but conducting rubber roller of the present invention be applicable to by it and will be transferred to the transfer roll of the transfer member on recording medium such as the paper based on the transferred image of toner image; This toner image forms and is retained on the image bearing member as on the static sensitive parts by imaging mode such as xerography or electrostatic recording.
Describe conducting rubber roller of the present invention below in detail.
Conducting rubber roller of the present invention is made of conductive cores material and the setting rubber layer as elastomeric layer thereon basically.
Being used for elastomeric layer of the present invention (rubber layer) constitutes by containing as the polar rubber at least of rubber components and the rubber composition of epoxy ethane-epoxy propane-allyl glycidyl ether ter-polymers.
Because of electric conductivity that epoxy ethane-epoxy propane-the allyl glycidyl ether ter-polymers manifests belongs to such fact: in polymkeric substance with the oxonium ion of ethylene oxide unit coordination or metal cation with the sub-chain motion continuous motion of strand, change those strands simultaneously with its coordination.Like this, have ethylene oxide unit at high proportion those strands can with more polyion coordination, reach stable thus and can realize low resistance.Yet if the ratio of ethylene oxide unit is too high, the crystallization of initial ring oxidative ethane suppresses the sub-chain motion of strand thus, causes high specific insulation unfriendly.Therefore, with epoxypropane and oxirane copolymerization, can provide randomness to keep not taking place crystallization suitably to ethylene oxide unit like this.They and allyl glycidyl ether copolymerization also make can with other rubber cross, might reduce like this and ooze out and the static sensitive component contamination.In addition, allyl glycidyl ether unit and epoxypropane are similar, also have the non crystallized function of retaining ring oxidative ethane, help to realize low resistance thus.
Be used for epoxy ethane-epoxy propane of the present invention-allyl glycidyl ether ter-polymers, necessary is, this ter-polymers have with differential scanning calorimeter measure more than or equal to 20 ℃ and be less than or equal to 30 ℃ melting peak temperature and more than or equal to 40mJ/mg and be less than or equal to the fusion enthalpy change Δ H of 70mJ/mg, and the copolymerization ratio of allyl glycidyl ether is for greater than 10mol% and be less than or equal to 20mol%, is preferably greater than or equals 11mol% and be less than or equal to 15mol%.
In addition, the melting peak temperature that will measure with differential scanning calorimeter and fusion enthalpy change Δ H are as the crystallizability index of polymer compound.
Therefore, if melting peak temperature greater than 30 ℃ and fusion enthalpy change Δ H greater than 70mJ/mg, then epoxypropane and allyl glycidyl ether can not enough make oxirane keep non-crystallizable, can suppress the sub-chain motion of strand like this, can not realize low resistance thus.
On the other hand, if melting peak temperature less than 20 ℃ and fusion enthalpy change Δ H less than 40mJ/mg, then epoxypropane and allyl glycidyl ether can enough make oxirane keep non-crystallizable, but can not expect to realize low resistance, the strand of epoxy ethane-epoxy propane-allyl glycidyl ether ter-polymers has so too high degree of freedom in vulcanized rubber in addition, to such an extent as to especially can not obtain enough circlets border dependence in high temperature and high humidity environment.
If the copolymerization ratio of allyl glycidyl ether is for being less than or equal to 10mol%, then promptly use melting peak temperature that differential scanning calorimeter measures and fusion enthalpy change Δ H in above-mentioned scope, can obtain to have the conducting rubber roller of excellent energising permanance, but owing to almost there is not crosslinking points, therefore may exist and ooze out or surface migration, and the strand of epoxy ethane-epoxy propane-allyl glycidyl ether ter-polymers has so too high degree of freedom in vulcanized rubber, to such an extent as to especially in high temperature and high humidity environment, can not obtain enough circlets border dependence, so might bring picture quality to change with service environment.Also such problem can take place: when adding ionic conductive agent, it oozes out and pollutes the static sensitive parts thus.On the other hand, if the copolymerization ratio of allyl glycidyl ether is greater than the 20mol% of top scope, then can obtain to have little resistivity environment dependence and good to the resistant to pollution conducting rubber roller of photosensitive part, but because too many on the contrary crosslinking points, so destroyed the degree of freedom of epoxy ethane-epoxy propane-allyl glycidyl ether ter-polymers, be difficult to realize low resistance thus and cause bad tensile property, fatigue behaviour, resistance to bend(ing) energy etc., or cause crosslinked too high rigidity.
In addition, consider compatibility, resistance value etc., the oxirane and the epoxypropane that are used for epoxy ethane-epoxy propane of the present invention-allyl glycidyl ether ter-polymers can preferably have such copolymerization ratio: when during respectively by a and b (mol%) expression, being preferably 10＜a+b≤30 and 10＜b≤20 in the epoxypropane of epoxy ethane-epoxy propane-allyl glycidyl ether ter-polymers and allyl glycidyl ether copolymerization ratio.
Consider and prevent to ooze out and prevent the static sensitive component contamination, epoxy ethane-epoxy propane-allyl glycidyl ether ter-polymers also can have number-average molecular weight more than or equal to 10,000, its scope is suitably up to making ter-polymers mediate the molecular weight of mediating under the temperature usually.
The combined amount that is used for epoxy ethane-epoxy propane of the present invention-allyl glycidyl ether ter-polymers can be preferably more than or equal 5 mass parts and be less than or equal to 20 mass parts, by 100 mass parts rubber components gross masses.If its combined amount less than 5 mass parts, then is difficult to the effect that fine acquisition realizes low resistance and high-durability because of epoxy ethane-epoxy propane-allyl glycidyl ether ter-polymers.If combined amount surpasses 20 mass parts, then be tending towards making rubber rollers to have big resistance environmental factor dependence and might pollute the static sensitive parts.
Among the present invention,, can preferably add ionic conductive agent for strengthening the concentration of ionophore in rubber to realize low resistance.The addition of ionic conductive agent can be preferably more than or equal 0.1 mass parts and be less than or equal to 10 mass parts, by 100 mass parts rubber components.If this amount then can not obtain to provide the effect of ionic conductivity less than 0.1 mass parts.Even its amount can not be expected bigger ionic conduction effect again greater than 10 mass parts, exist simultaneously to be exuded to the possibility that the static sensitive component contamination is caused on the roller surface.
In addition, the allyl glycidyl ether in epoxy ethane-epoxy propane-allyl glycidyl ether ter-polymers has unsaturated link, and can with other rubber cross.Therefore, the copolymerization ratio of different allyl glycidyl ethers changes the performance of oozing out of ionic conductive agent.
If the copolymerization ratio of allyl glycidyl ether is lower than the 10mol% of the scope of the invention, then the crosslinking points existence is oozed out or the possibility of surface migration owing to almost not having with elastomeric material.On the other hand, if the copolymerization ratio of allyl glycidyl ether surpasses the 20mol% of the scope of the invention, then can obtain to resist the effect with surface migration of oozing out of ionic conductive agent, but because a lot of crosslinking points of existence and other elastomeric material, so degree of freedom of meeting saboteur chain, influence the stabilization of ion thus and suppress to realize low resistance, cause crosslinked too high rigidity simultaneously.
As ionic conductive agent, can use arbitrary conventionally known various conductive agents.Especially preferably use at least a in quaternary ammonium salt and the season phosphonium salt.In addition,, exist polymkeric substance and halogen component to cause the possibility of subsidiary reaction, and exist and influence the possibility of rubber physical property because of for example compression set seriously occurring for the ionic conductive agent of halogen-containing component.Therefore, be used for quaternary ammonium salt of the present invention and season phosphonium salt can be preferably non-halogen compounds.
Being used for rubber composition of the present invention can be preferably: based on 100 mass parts rubber components, contain more than or equal to 5 mass parts and be less than or equal to the vulcanizate of the carbon black of 70 mass parts as the rubber composition of filler, this carbon black has iodine sorption value more than or equal to 5mg/g and be less than or equal to 30mg/g and the oily absorption value of dibutyl phthalate (DBP) is less than or equal to 55ml/100g.
In conducting rubber roller of the present invention, only use carbon black can make rubber composition have agent of low hygroscopicity, and make the gained conducting rubber roller have little resistance environmental factor dependence as filler.In addition, with the particle diameter index of iodine sorption value as carbon black.Have the iodine sorption value scope and be 5 to 30mg/g and mean that carbon black has sizable particle diameter.Simultaneously, the oily absorption value of dibutyl phthalate (DBP) is used as physical dimension index (related carbon black pellet).Having the oily absorption value of dibutyl phthalate (DBP) is less than or equal to 55ml/100g and means that structure almost occurs or relatively also growth.
If carbon black have iodine sorption value greater than 30mg/g or the oily absorption value of dibutyl phthalate (DBP) greater than 55ml/100g, then carbon black adds the fashionable percolation limit that is tending towards reaching on a small quantity at it, so has the height possibility of the electric conductivity that demonstration causes because of electronic conduction mechanism.Under electronic conduction system situation, there is the little advantage of resistance environmental factor dependence.Yet the problem of existence is that resistivity is come inhomogeneously and the voltage-dependent of resistance is taken place, and this is inappropriate for conducting rubber roller.On the other hand,, then must add so that the resilient material with regulation hardness to be provided in a large number, so cause bad kneading processing characteristics if carbon black has iodine sorption value and is lower than 5mg/g.
Has iodine sorption value more than or equal to 5mg/g and be less than or equal to 30mg/g and amount that carbon black that the oily absorption value of dibutyl phthalate (DBP) is less than or equal to 55ml/100g also can 5 to 70 mass parts adds, by 100 mass parts rubber components.If addition is less than 5 mass parts, then the effect as filler may so be not enough to as for making the gained vulcanized rubber have low-intensity, and vulcanized rubber may fragmentation or split when inserting the conductive cores material like this.On the other hand, if the carbon black addition is greater than 70 mass parts, what for to when using carbon black, there being the possibility that electronic conduction takes place, and rubber can have too high hardness unfavourably.In addition, carbon black can be preferably to add more than or equal to 5 mass parts and the amount that is less than or equal to 30 mass parts, the conducting rubber roller of Huo Deing can be guaranteed the roller resistance variations that causes because of environmental change and the permanance deterioration of switching on of less degree like this.
Be used for rubber composition of the present invention and comprise epoxy ethane-epoxy propane-allyl glycidyl ether ter-polymers as rubber components and at least a polar rubber in addition.Said composition can preferably comprise at least a as polar rubber in chloropropylene oxide class rubber and the acrylonitrile-butadiene rubber.There is not particular restriction for chloropropylene oxide class rubber.Commercially available is chloropropylene oxide homopolymer (ECH), chloropropylene oxide-ethylene oxide copolymer (ECH-EO), chloropropylene oxide-allyl glycidyl ether multipolymer (ECH-AGE), chloropropylene oxide-oxirane-allyl glycidyl ether ter-polymers (ECH-EO-AGE) or the like.Especially, preferably can sulfur vulcanization or the chloropropylene oxide-oxirane-allyl glycidyl ether ter-polymers (ECH-EO-AGE) of efficient vulcanization, more preferably the copolymerization ratio of oxirane is more than or equal to 40mol% in the chloropropylene oxide class rubber.
Chloropropylene oxide-oxirane-allyl glycidyl ether ter-polymers shows a kind of like this trend: the specific insulation of vulcanized rubber reduces with the copolymerization ratio increase of oxirane, therefore, if the copolymerization ratio of oxirane is less than 40mol%, then can reach the required resistance value difficulty of resilient material that is used for conducting rubber roller, to such an extent as to and epichlorohydrin rubber have so that big mixing ratio makes rubber have high environmental factor dependence.More preferably, the copolymerization ratio of the oxirane in the chloropropylene oxide class rubber can be more than or equal to 45mol% and is less than or equal to 80mol%.In addition, chloropropylene oxide class rubber can be the blend of homogenous material or two classes or multiclass material.
There is not particular restriction to being used for acrylonitrile-butadiene rubber of the present invention yet.Can use any commercial acrylonitrile-butadiene rubber.Especially preferably has average propylene nitrile content more than or equal to 15 quality % and be less than or equal to the acrylonitrile-butadiene rubber of 25 quality %.If it has average propylene nitrile content less than 15 quality %, then be difficult to realize the resistivity of stipulating.If it has average propylene nitrile content greater than 25 quality %, then rubber rollers is tending towards having big resistance environmental factor dependence.In addition, acrylonitrile-butadiene rubber can be the blend of homogenous material or two classes or multiclass material.
The rubber composition that is used for conducting rubber roller of the present invention also can optionally be added in other component that common available rubber uses.Those components that for example can optionally mix are vulcanizing agent such as sulphur or the compound that contains organic sulfur, various vulcanization accelerator, processing aid such as various lubricant or ointment, various antioxidant, various gas-development agent such as p, p '-oxo two (benzene sulfonyl hydrazides) (OBSH), azobisformamide (ADCA) or dinitrosopentamethylene tetramine (DPT), various blowing promotor such as urea, vulcanization aid such as zinc paste or stearic acid and various filler such as lime carbonate, talcum, silicon dioxide or clay.
Under situation of the present invention, because epoxy ethane-epoxy propane-allyl glycidyl ether ter-polymers has melting peak temperature in specialized range and the fusion enthalpy change Δ H that measures with differential scanning calorimeter, ion can more effectively be stablized, and so can realize low resistance and any variation of the resistivity that reduces to cause because of temperature and humidity.In addition, reduced any variation (especially between ambient temperature and moisture environment and hot and humid environment) by special ratios copolymerization allyl glycidyl ether, and further can keep not taking place photosensitive part and pollute because of the strand resistance that motion change causes in vulcanized rubber.Therefore, this makes might provide a kind of like this conducting rubber roller: this conducting rubber roller has low resistance, guarantees that the light activated element pollution does not take place for the very little resistance variations and the maintenance that cause because of temperature and humidity, keeps the high-durability feature that conducting rubber roller had that contains traditional epoxy ethane-epoxy propane-allyl glycidyl ether ter-polymers simultaneously.
As production method, conducting rubber roller of the present invention can obtain by the following method: by extruder unvulcanized conductive rubber composition is extruded into pipe, it is heated in sulfurator or continuous vulcanization stove prepare conductive rubber (resilient material) pipe thus, in this conductive rubber pipe, insert the conductive shaft that scribbles cementing agent then, then heating bonds together conductive shaft and conductive rubber pipe, and further polishing reaches the diameter with regulation until roller then.Also can use wherein not the vulcanized conducting rubber composition to extrude simultaneously, or the rubber composition that will extrude is packed into any conventionally known production method to vulcanize in the mould with the conductive shaft that scribbles cementing agent.Conducting rubber roller of the present invention in addition also can provide resin bed or similar layer in the periphery of elastomeric layer.
Conductive cores material as the conductive shaft that is used as conducting rubber roller of the present invention can use metal material such as iron, copper or stainless pole, and it preferably can have overall diameter 4 to 10mm.Electroplating processes can further be passed through in the surface of this rod, and purpose is antirust and scratch resistance is provided.
The imaging device that the electrostatic latent image that conducting rubber roller of the present invention is used for wherein will form on the static sensitive parts develops with developer, and this conducting rubber roller can be preferably the transfer roll that is arranged at face-to-face on the static light activated element.
Embodiment
Following the present invention will be by providing embodiment and comparative example is described in more detail.The present invention does not mean and limited by these embodiment.
The formula rate of the rubber composition that uses in embodiment and the comparative example and the test result of the conducting rubber roller that obtains provided in to 5 at table 1.In the prescription that provides therein, the unit of amount is a mass parts.
At first, raw material given below is used for embodiment and comparative example according to table 1 to 5 prescriptions that provide, and mediates, prepare the rubber composition of embodiment and comparative example thus by open roll refining machine.
-epoxy ethane-epoxy propane-allyl glycidyl ether ter-polymers (epoxy ethane-epoxy propane-allyl glycidyl ether copolymerization ratio (mol%): 87: 1: 12; Number-average molecular weight: 60,000; Trade name: ZEOSPAN 8010 is available from Nippon ZeonCo., Ltd.).
-Ditto (epoxy ethane-epoxy propane-allyl glycidyl ether copolymerization ratio (mol%): 94: 2: 4; Number-average molecular weight: 80,000; A kind of test products)
-Ditto (epoxy ethane-epoxy propane-allyl glycidyl ether copolymerization ratio (mol%): 77: 0.5: 22.5; Number-average molecular weight: 70,000; A kind of test products)
-Ditto (epoxy ethane-epoxy propane-allyl glycidyl ether copolymerization ratio (mol%): 74: 12: 14; Number-average molecular weight: 70,000; A kind of test products)
-Ditto (epoxy ethane-epoxy propane-allyl glycidyl ether copolymerization ratio (mol%): 89: 0.5: 10.5; Number-average molecular weight: 70,000; A kind of test products)
-Ditto (epoxy ethane-epoxy propane-allyl glycidyl ether copolymerization ratio (mol%): 87: 4: 9; Number-average molecular weight: 80,000; A kind of test products)
-Ditto (epoxy ethane-epoxy propane-allyl glycidyl ether copolymerization ratio (mol%): 90: 4: 6; Number-average molecular weight: 80,000; Trade name: Z E O SPAN 8030 is available from Nippon Zeon Co., Ltd.)
-acrylonitrile-butadiene rubber (acrylonitrile content: 18 quality %; Trade name: NIPOL DN401L; Available from Nippon Zeon Co., Ltd.)
-chloropropylene oxide class rubber (ethylene oxide content: 56mol%; Trade name: ZECHRON 3106; Available from Nippon Zeon Co., Ltd.)
-ionic conductive agent (quaternary ammonium salt, EO add-on type quaternary ammonium salt; Trade name: KS-555; Available from Kao Corporation)
-carbon black (carbon black A; Iodine sorption value: 14mg/g; DBP oil absorption value: 29ml/100g; Trade name: ASAHI#8; Available from Asahi Carbon Co., Ltd.)
-Ditto (black B; Iodine sorption value: 23mg/g; DBP oil absorption value 51ml/100g; Trade name: ASAHI#35; Available from Asahi Carbon Co., Ltd.)
-Ditto (carbon black C; Iodine sorption value: 25mg/g; DBP oil absorption value 87ml/100g; Trade name: ASAHI#55; Available from Asahi Carbon Co., Ltd.)
-filler (lime carbonate; Trade name: SUPER 3S; Available from Maruo CalciumCo., Ltd.)
-vulcanizing agent (sulphur, S; Trade name: SULFAX PMC; Available from TsurumiKagaku Kogyo K.K.)
-vulcanization accelerator (dibenzothiazyl-disulfide, DM; Trade name: NOCCELER DM; Available from Ohuchi-Shinko Chemical IndustrialCo., Ltd.)
(the curing autumn is blue female, TET for-Ditto; Trade name: NOCCELER TET; Available from Ohuchi-Shinko Chemical Industrial Co., Ltd.)
-vulcanization aid (zinc paste; Trade name: Zinc Oxide JIS 2 is available from Hakusui Chemical Industries, Ltd.)
-Ditto (stearic acid; Trade name: LUNAC S20; Available from Kao company)
-gas-development agent (azobisformamide; Trade name: VINYFOR AC#LQ; Available from Eiwa Chemical Ind.Co., Ltd.)
-blowing promotor (urea; Trade name: CELLPASTE A; Available from EiwaChemical Ind.Co., Ltd.)
Conducting rubber roller for production example and comparative example, these rubber compositions are extruded into pipe separately with extruder, then vulcanize 30 minutes preparation tubular rubber vulcanizates down at 160 ℃ by sulfurator, then the conductive shaft of diameter 6mm is inserted the inner-diameter portion whose of this tubular rubber vulcanizate, obtain roller shape shape thus.This shape is polished so that it has external diameter 14mm.So produce conducting rubber roller.
Measure melting peak temperature and fusion enthalpy change Δ H
With differential scanning calorimeter (EXSTAR6000 DSC, make by SeikoInstruments Inc.), will about 10mg epoxy ethane-epoxy propane-allyl glycidyl ether ter-polymers temperature range-100 to 100 ℃ in the heating (rate of heat addition: 10 ℃/min), with this repetitive operation twice, wherein the melting peak temperature of epoxy ethane-epoxy propane-allyl glycidyl ether ter-polymers and fusion enthalpy change Δ H (mJ/mg) are calculated by the second melting peak.
Measuring roller resistivity (environmental factor dependence)
The conducting rubber roller produced is added press contacts with the aluminum drum of external diameter 30mm separately, in this way the load of 4.9N is put on separately the conductive shaft two end portions of roller.Under this state, roller is rotated with 0.5Hz (cycles/sec), and apply voltage 1 along conductive shaft and aluminum drum, 000V, in each environment of 10 ℃/15%RH (L/L), 23 ℃/55%RH (N/N) and 35 ℃/95%RH (H/H), measure its current value, wherein calculate the resistivity of roller by the Ohm law.Resistivity among the L/L that will so measure is carried out income value to number conversion divided by the resistivity among the H/H simultaneously, and it is poor to be expressed as the power (index) of environmental change.In the embodiment of the invention and comparative example, it is poor to change power according to following evaluation criteria assessment resistivity environment.
AA: the power difference of environmental change is for being less than or equal to 1.3 (very circlet border dependences).
A: the power difference of environmental change is 1.3 to being less than or equal to 1.8 (very circlet border dependences).
B: the power difference of environmental change is 1.8 to being less than or equal to 2.0 (moderate environment dependences).
C: the power difference of environmental change is greater than 2.0 (big environmental factor dependences).
Roller energising endurancing
At first, according to above-mentioned measuring roller resistivity, measure the resistivity of conducting rubber roller in 23 ℃/55%RH (N/N) environment, the resistivity of measurement is defined as the roller resistivity before the endurancing.
Then, conducting rubber roller is placed in 50 ℃ the environment, and the aluminum drum of itself and diameter 30mm is added press contacts, will put on the axle two end portions of roller at the 4.9N load on each side in this way.Under this state, roller is rotated with 0.2Hz, and apply 80 μ A steady currents 25 hours continuously along axle and aluminium drum.Subsequently, in 23 ℃/55%RH (N/N) environment, remeasure roller resistivity to obtain roller resistivity after the endurancing.Here, the resistivity of the resistivity after the endurancing before divided by endurancing carries out income value to number conversion, and it is poor to be expressed as the power of permanance.This difference is more little, can think that the energising permanance of conducting rubber roller is good more.In the embodiment of the invention and comparative example, assess the energising permanance by durable change power difference according to following evaluation criteria.
A: durable change power difference is for being less than or equal to 0.35 (favorable durability).
C: durable change power difference is greater than 0.35 (bad permanance)
Resistivity reduces test
The conducting rubber roller produced is added press contacts with the aluminum drum of external diameter 30mm separately, will put on the conductive shaft two end portions of roller at the 4.9N load on each side in this way.Under this state, roller is rotated with 0.5Hz, apply voltage 1 along conductive shaft and aluminum drum, 000V measures its current value in 23 ℃/55%RH (N/N) environment, wherein calculate the resistivity of roller by the Ohm law.In the embodiment of the invention and comparative example, the effect that reduces resistivity by with its with wherein do not contain epoxy ethane-epoxy propane-allyl glycidyl ether ter-polymers and rubber components only for the comparative example 1-6 of acrylonitrile-butadiene rubber (NBR) to assessment recently.
Evaluation criteria provides below.Here, the resistivity of each conducting rubber roller that obtains in embodiment and comparative example obtains change in resistance power difference divided by the resistivity of comparative example 1-6 and after carrying out income value to number conversion.
A: change in resistance power difference is-1.0 (big reduction effects) for to be less than or equal to.
C: change in resistance power difference is greater than-1.0 (little reduction effects).
Resistance photosensitive parts (photosensitive drums) pollute
Conducting rubber roller is contacted with the static sensitive parts of use among the laser printer LASER JET 4000N (being made by Hewlett-Packard Co.) separately, with 1, the 000g load imposes on roller conductive shaft two end portions, and it was placed 1 day in 40 ℃/95%RH environment.After placement, remove load, and with any sediment on the microscopic examination static sensitive parts.Then the static sensitive parts that use are installed in the printer box, and with the black image printing on 30 paper.The image that visually rank forms.The good assessment of scenario of image of wherein not seeing sediment and formation on the static sensitive parts is " A "; Although and will on the static sensitive parts, see sediment slightly but assessment of scenario that the image that forms can be tolerated in actual use is " B ".With the flagrant in actual use assessment of scenario of the image of wherein seeing sediment and formation on the static sensitive parts is " C ".
Roller resistivity unevenness
The conducting rubber roller produced is added press contacts with the aluminum drum of external diameter 30mm separately, in this way each 4.9N load is put on the conductive shaft two end portions of roller.Under this state, roller is rotated with 0.5Hz, apply voltage 1,000V along conductive shaft and aluminum drum.Measure the differential resistivity between maximal value and the minimum value, with it as the resistivity dispersion index.In addition, assess according to following evaluation criteria.
A: measured value is for being less than or equal to 1.1 (very little roller resistivity unevenness).
B: the resistance value of measurement greater than 1.1 to being less than or equal to 1.2 (little roller resistivity unevenness)
C: measured value is more than or equal to 1.2 (big roller resistivity unevenness).
Embodiment 1-1 and comparative example 1-1 to 1-6
The result who obtains provides in table 1 in the lump.
As shown in table 1, find out from embodiment 1-1 and comparative example 1-1 to 1-5: epoxy ethane-epoxy propane-allyl glycidyl ether ter-polymers is suitable when it in the scope that the present invention requires the time.More specifically, in comparative example 1-1, wherein compare with in the scope of the present invention those melting peak temperature higher and fusion enthalpy change Δ H is big and the copolymerization ratio of allyl glycidyl ether less than the scope of the invention, to such an extent as to oxirane has the effect that high crystal property like this brings little reduction resistivity.Simultaneously, because the copolymerization ratio of allyl glycidyl ether is little, therefore the roller that obtains has very big environmental factor dependence and bad photosensitive part resistance tocrocking.In addition, in comparative example 1-2, wherein compare with in the scope of the present invention those melting peak temperature low and fusion enthalpy change Δ H is less and the copolymerization ratio of allyl glycidyl ether greater than the scope of the invention, the crosslinking points of the allyl glycidyl ether roller that is attributable to obtain is so many, to such an extent as to the roller that obtains has very circlet border dependence and good photosensitive part resistance tocrocking, but brings the effect of little reduction resistivity.In addition, although the copolymerization ratio of allyl glycidyl ether within the scope of the present invention, but in comparative example 1-3, wherein compare melting peak temperature with in the scope of the present invention those low and fusion enthalpy change Δ H is less, the roller that obtains has not enough circlet border dependences and brings the effect of not enough reduction resistivity, and in comparative example 1-4, wherein compare melting peak temperature with in the scope of the present invention those higher and fusion enthalpy change Δ H is bigger, and the roller strap of acquisition comes the effect of not enough reduction resistivity.In addition, although melting peak temperature and fusion enthalpy change Δ H are within the scope of the present invention, but in comparative example 1-5, wherein the copolymerization ratio of allyl glycidyl ether is outside the scope of the invention, and the roller of acquisition has very big environmental factor dependence and bad photosensitive part resistance tocrocking.
On the other hand, among the embodiment 1-1 within the scope of the present invention, the roller of acquisition has circlet border dependence and good photosensitive part resistance tocrocking, keeps good energising permanance simultaneously.In addition, resistivity is effectively reduced.
Embodiment 2-1 to 2-4 and comparative example 2-1
The test result that obtains provides in table 2 in the lump.
As shown in table 2, find out that from embodiment 2-1 to 2-4 the combined amount that wherein is used for epoxy ethane-epoxy propane of the present invention-allyl glycidyl ether ter-polymers is preferably 5 to 20 mass parts.More specifically, among the embodiment 2-4 of its combined amount greater than 20 mass parts, the conducting rubber roller of acquisition shows big environmental factor dependence therein.
It can also be seen that, compare with embodiment 2-3, comparative example 2-1, it is not mixing under any epoxy ethane-epoxy propane-allyl glycidyl ether ter-polymers only with the conducting rubber roller of acrylonitrile-butadiene rubber and the control of chloropropylene oxide class rubber for resistance of conducting rubber roller, shows the energising permanance than wherein mixing poor according to the embodiment 2-3 of epoxy ethane-epoxy propane of the present invention-allyl glycidyl ether ter-polymers.
Embodiment 3-1 and comparative example 3-1
The test result that obtains provides in table 3 in the lump.
As shown in table 3, find out from embodiment 3-1 and comparative example 3-1, be used for rubber composition of the present invention and more preferably comprise ionic conductive agent.See that embodiment 3-1 identical with embodiment 1-1 except the ionic conductive agent that mixes 1 mass parts more effectively reaches low-resistivity, keeps the circlet border dependence that obtains among the embodiment 1-1 simultaneously.In addition, do not find the photosensitive part pollution problem.In contrast, for comparative example 3-1, wherein 1 mass parts ionic conductive agent is sneaked in the rubber composition that uses the epoxy ethane-epoxy propane-allyl glycidyl ether ter-polymers outside the scope of the invention, reduce the effect deficiency of resistivity, the roller of Huo Deing has big environmental factor dependence and further causes photosensitive part to pollute simultaneously.
Embodiment 4-1 to 4-5
The test result that obtains provides in table 4 in the lump.
As shown in table 4, find out from embodiment 4-1 and 4-5: be used for rubber composition of the present invention and preferably only use carbon black as filler, and for carbon black, press the rubber components summation meter of rubber composition, comprise 5 to 70 mass parts and have the carbon black that iodine sorption value 5 to 30m g/g and the oily absorption value of dibutyl phthalate (DBP) are less than or equal to 55ml/100g.
Find out from embodiment 4-2 and 4-3, this embodiment 4-2 and 4-3 show than wherein using the embodiment 4-1 circlet border dependence of lime carbonate as filler separately for wherein only having the situation of the carbon black of the oily absorption value of iodine sorption value and dibutyl phthalate (DBP) in above-mentioned scope as filler.In addition, embodiment 4-4, wherein the oily absorption value of iodine sorption value and dibutyl phthalate (DBP) is greater than above-mentioned scope, and even iodine sorption value and the oily absorption value of dibutyl phthalate (DBP) are in above-mentioned scope, embodiment 4-5, the carbon black that wherein mixes 75 mass parts also shows circlet border dependence separately, but is tending towards showing big roller resistivity unevenness.
As mentioned above, conducting rubber roller of the present invention as can be seen has little resistivity environment dependence, has excellent energising permanance simultaneously, further has low resistance and keeps not taking place the static sensitive component contamination.
The application requires the right of priority from the 2006-114434 of 2005-136059 that Japanese patent application No. is the 2005-136057 that submits in the 2005-136056 that submits in the 2005-136055 of submission on May 9th, 2005, on May 9th, 2005, on May 9th, 2005, the 2005-136058 that on May 9th, 2005 submitted to, on May 9th, 2005 submitted to and submission on April 18th, 2006, hereby it is incorporated into this paper with for referencial use.
Claims (7)
1. conducting rubber roller, it comprises conductive cores material and the rubber layer that is provided with thereon;
Described rubber layer contains as the polar rubber at least of rubber components and the rubber composition of epoxy ethane-epoxy propane-allyl glycidyl ether ter-polymers by use and forms;
Described epoxy ethane-epoxy propane-allyl glycidyl ether ter-polymers has and is greater than or equal to 20 ℃ and be less than or equal to 30 ℃ melting peak temperature and more than or equal to 40mJ/mg and be less than or equal to the fusion enthalpy change Δ H of 70mJ/mg, measure with differential scanning calorimeter; With
The copolymerization ratio of this allyl glycidyl ether in described epoxy ethane-epoxy propane-allyl glycidyl ether ter-polymers is to being less than or equal to 20mol% greater than 10mol%.
2. conducting rubber roller according to claim 1, wherein, copolymerization ratio in described epoxy ethane-epoxy propane-allyl glycidyl ether ter-polymers is a of mol% and b when representing by unit respectively when epoxypropane and allyl glycidyl ether, 10＜a+b≤30 and 10＜b≤20.
3. conducting rubber roller according to claim 1, wherein, described rubber composition further comprises more than or equal to 0.1 mass parts and is less than or equal to the ionic conductive agent of 10 mass parts, by 100 mass parts rubber components.
4. conducting rubber roller according to claim 1, it comprises described rubber composition, rubber components summation based on this rubber composition is 100 mass parts, this rubber composition comprises more than or equal to 5 mass parts and is less than or equal to the carbon black of 70 mass parts, and this carbon black has iodine sorption value more than or equal to 5mg/g and be less than or equal to 30mg/g and dibutyl phthalate oil absorption value is less than or equal to 55ml/100g.
5. conducting rubber roller according to claim 1, wherein mixing more than or equal to 5 mass parts and be less than or equal to the described epoxy ethane-epoxy propane-allyl glycidyl ether ter-polymers of 20 mass parts, is 100 mass parts based on the rubber components summation of described rubber composition.
6. conducting rubber roller according to claim 1, wherein said polar rubber are any in acrylonitrile-butadiene rubber and the epichlorohydrin rubber or two kinds.
7. conducting rubber roller according to claim 1, this conducting rubber roller is used for forming on the static sensitive parts electrostatic latent image is the image forming apparatus that develops with developer, and wherein said conducting rubber roller is the transfer roll that is arranged on Face to face on the static sensitive parts.
Applications Claiming Priority (13)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005136056 | 2005-05-09 | ||
| JP2005136058 | 2005-05-09 | ||
| JP2005-136056 | 2005-05-09 | ||
| JP2005-136058 | 2005-05-09 | ||
| JP2005136057 | 2005-05-09 | ||
| JP2005-136055 | 2005-05-09 | ||
| JP2005136059 | 2005-05-09 | ||
| JP2005-136059 | 2005-05-09 | ||
| JP2005136055 | 2005-05-09 | ||
| JP2005-136057 | 2005-05-09 | ||
| JP2005136055 | 2005-05-09 | ||
| JP2006-114434 | 2006-04-18 | ||
| JP2006114434 | 2006-04-18 |
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| Publication Number | Publication Date |
|---|---|
| CN1862405A CN1862405A (en) | 2006-11-15 |
| CN100430834C true CN100430834C (en) | 2008-11-05 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNB2006100757888A Expired - Fee Related CN100430834C (en) | 2005-05-09 | 2006-05-09 | Conductive rubber roller |
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| CN101928416A (en) * | 2010-08-24 | 2010-12-29 | 安徽中鼎橡塑制品有限公司 | Rubber coating of photocopier charging roller assembly and manufacturing process thereof |
| CN103172879B (en) * | 2013-04-03 | 2015-06-24 | 西南交通大学 | Method for preparing polar rubber/small organic molecule hybrid damping laminar composite material |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1347940A (en) * | 2000-10-10 | 2002-05-08 | 住友橡胶工业株式会社 | Conductive rubber composition and the conductive rubber roller and rubber belt |
| US20020128139A1 (en) * | 2000-12-18 | 2002-09-12 | Masayuki Hashimoto | Conductive rubber roller |
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2006
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1347940A (en) * | 2000-10-10 | 2002-05-08 | 住友橡胶工业株式会社 | Conductive rubber composition and the conductive rubber roller and rubber belt |
| US20020128139A1 (en) * | 2000-12-18 | 2002-09-12 | Masayuki Hashimoto | Conductive rubber roller |
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| CN1862405A (en) | 2006-11-15 |
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