CN101397374A - Conductive rubber member - Google Patents
Conductive rubber member Download PDFInfo
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- CN101397374A CN101397374A CNA2008101687504A CN200810168750A CN101397374A CN 101397374 A CN101397374 A CN 101397374A CN A2008101687504 A CNA2008101687504 A CN A2008101687504A CN 200810168750 A CN200810168750 A CN 200810168750A CN 101397374 A CN101397374 A CN 101397374A
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- Electrophotography Configuration And Component (AREA)
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Abstract
The invention relates to a conductive rubber member. The invention provides a conductive rubber member that is free from the problem of pollution and leakage like OPC and the like and that has following-up property with respect to deformation and small variation of resistance value. The conductive rubber member is a conductive rubber member provided with a surface processing layer 12a that is formed by immersing a surface layer portion of an outmost conductive elastic layer 12 endowed with conductivity in a surface processing solution at least comprising isocyanate components and organic solvents, the upper portion 12b at the surface side of the surface processing layer 12a has a density of the isocyanate components therein which is greater than that on the surface side, and the lower portion 12c at the lower side of the upper portion 12b has a density of the isocyanate components that gradually decreases inwardly.
Description
[technical field]
The present invention relates to be particularly suitable for the conductive rubber member of the conductive roll, cleaning balde (Network リ-ニ Application グ Block レ-De), transfer belt etc. of the charged roller, transfer roll, developer roll, toner supplying roller, clearer roller etc. of electro photography duplicating machine and printer or image processing systems such as ink jet type (ト Na-ジ ェ ッ ト) duplicating machine and printer.
[background technology]
Controlling the conducting rubber roller of electroconductibility after having caoutchouc elasticity, is very important in electronic camera technology, and the molecule itself that constitutes rubber seldom has the necessary resistivity (10 of technology as intrinsic resistance rate value
4～10
9Ω cm), have only as limited material acquisition practical applications such as Epicholorohydrins.In most cases for keeping needed Young's modulus, physical strength, humiture characteristic, use is added in chemically stable base materials such as silicon rubber or ethylene propylene rubber (EPDM), urethane after electrically conductive microparticle such as carbon black gives electroconductibility, in order to prevent pollution such as OPC, to adjust resistance and prevent to leak electricity and form coating.
In addition, the development of revealing in recent years along with the eutectic of the toner binder that is used for the electro photography duplicating machine, developer roll is pinched in order to form sufficient folder, guarantees that toning agent is charged, requires softization.As the material that satisfies above-mentioned requirements, proposed wholely to keep soft, simultaneously the hard developer roll (for example with reference to patent documentation 1) in surface by elastic layer, the coating that contains urethane resin, making of containing that the thin cured layer of isocyanic ester constitutes.
On the other hand, the formation of coating has the shortcoming of complex process, manufacturing cost increase, as the means that simply address this problem, has proposed pair roller top layer part and has carried out chemically treated method (for example with reference to patent documentation 2).Though this treatment process is effective, implements the tendency that there is its top layer part hardening in the surface-treated conductive roll.Roller through the soft processing, because the distortion of roller top layer part increases when using, thus servo-actuated required with respect to distortion, but part hard roller in top layer lacks servo-actuated, also there is the problem that causes resistance change owing to using in addition in the danger of existence damage OPC etc.
So,, do not form the conductive roll (with reference to patent documentation 3) of high rigidity even the front has also proposed to form surface-treated layer yet.But in this case, concrete example is difficult with the surface treatment liquid to the conductive elastic layer dipping as using, form relatively thinner surface-treated layer, can not get abundant effect sometimes, can not fully tackle service requirements in some cases as surface-treated layer.
[patent documentation 1] spy opens the 2005-283913 communique
[patent documentation 2] spy opens flat 5-158341 communique
[patent documentation 3] spy opens the 2007-199694 communique
[summary of the invention]
In light of this situation, the present invention to be to provide pollutions such as there not being OPC or leakage problem, has the servo-actuated with respect to distortion, and the little conductive rubber member of resistance change is as research topic.
The present invention's the 1st scheme that solves aforementioned problems is conductive rubber member, it is the conductive rubber member with surface-treated layer, this surface-treated layer is to form by the surface treatment liquid that the top layer part dipping to the outermost layer conductive elastic layer that is endowed electroconductibility contains isocyanate prepolymer composition and organic solvent at least, it is characterized in that face side top section at the aforementioned surfaces processing layer, compare with the surface, the density of inner aforementioned isocyanate prepolymer composition is big, and in the underclad portion of this top section downside, the density of aforementioned isocyanate prepolymer composition reduces gradually to inside.
The 2nd scheme of the present invention is conductive rubber member, it is characterized in that the aforementioned surfaces treatment solution further contains in the described conductive rubber member of the 1st scheme to be selected from least a of carbon black, vinylformic acid fluorine based polymer and vinylformic acid silica methane series polymkeric substance.
The 3rd scheme of the present invention is conductive rubber member, it is characterized in that the aforementioned surfaces treatment solution further contains the polyethers based polymer in the described conductive rubber member of the 1st or the 2nd scheme.
The 4th scheme of the present invention is conductive rubber member, it is characterized in that aforementioned polyethers based polymer has active hydrogen in the described conductive rubber member of the 3rd scheme.
The 5th scheme of the present invention is conductive rubber member, it is characterized in that aforementioned polyethers based polymer is an epichloro hydrin rubber in the described conductive rubber member of the 4th scheme.
The 6th scheme of the present invention is conductive rubber member, it is characterized in that in the described conductive rubber member of the 1st～5 any one party case at least aly giving aforementioned conductive elastic layer electroconductibility by what electron conduction gave that material and ionic conductivity give material.
The 7th scheme of the present invention is conductive rubber member, it is characterized in that the described conductive rubber member of the 1st～6 any one party case is roll forming or sheet.
If pollutions such as not having OPC or leakage problem can be provided, have the little conductive rubber member of servo-actuated, resistance change with respect to distortion according to the present invention.
[description of drawings]
[Fig. 1] is the sectional drawing as the conductive roll of conductive rubber member one example of the present invention.
[Fig. 2] is expression test example 5 results' diagram.
[Fig. 3] is expression test example 5 results' diagram.
[Fig. 4] is expression test example 5 results' diagram.
[Fig. 5] is expression test example 5 results' diagram.
[nomenclature]
10 conductive rolls
11 plugs
12 elastic layers
The 12a surface-treated layer
The 12b top section
The 12c underclad portion
[embodiment]
Conductive rubber member of the present invention is based on following opinion and finishes, in the conductive rubber member that has by surface-treated layer that the conductive elastic layer top layer part dipping surface treatment liquid that is endowed electroconductibility is formed, make in the conductive elastic layer skin section and divide the surface-treated layer that forms, than the surface, layer segment makes inner isocyanate prepolymer composition density big thereon, and the density at the underclad portion isocyanate prepolymer composition of this top section downside reduces gradually to inside, make the underclad portion of surface-treated layer adjust resistance value and prevent to sew thus with the same playing in the past, prevent the function that pollution substance is separated out internally simultaneously, and the hardness that the top section of the surface-treated layer by forming its upper strata can suppress top layer part raises, have servo-actuated, will be reduced to minimum the damage of object members such as OPC with respect to distortion.
Fig. 1 represents the sectional drawing as the conductive roll of conductive rubber member one example of the present invention.Conductive roll 10 has in rubber substrate the electroconductibility of interpolation and gives material and moulding, sulfurized conductive elastic layer 12 on plug 11 as shown in Figure 1, and the skin section of elastic layer 12 is divided and formed the surface-treated layer 12a that uses the surface treatment liquid that contains isocyanate prepolymer composition and organic solvent to form.Here surface-treated layer 12a contains the top section 12b and the underclad portion 12c below it of face side.Top section 12b be the density of isocyanate prepolymer composition of its inner dipping greater than the surface, for example be from the surface to the zone of inside for increasing gradually, underclad portion 12c is the zone that the density of isocyanate prepolymer composition reduces gradually from surface lateral inside.Here the so-called top section 12b that exists means the zone of the density of the isocyanate prepolymer composition that has inside greater than face side, otherwise also we can say to exist, can not have isocyanate prepolymer composition in fact the most surperficial of top section 12b at least to the more little zone of the density of face side isocyanate prepolymer composition.So in addition top section 12b, be not be with the interface of underclad portion 12c as problem, but because its existence can form the state that the hardness on top layer is lower than inner hardness.In addition, top section 12b is because to make the hardness on its top layer be that soft exists (than the low hardness of underclad portion 12c), so thickness at least will be more than 1 μ m, more than the preferred 10 μ m.More than the zone that preferred especially top section 12b distortion when using formation folder is pinched and exist, for example about preferred 10～100 μ m of thickness.In addition about preferred 100～1000 μ m of the thickness of underclad portion 12c.The thickness of top section 12b and underclad portion 12c for example can grind the conductive rubber member surface, measures the rubber hardness or the resistance value at each position and predicts.
The elastic layer 12 of conductive roll 10 of the present invention adds electroconductibility and gives forming materials sulfuration and form in rubber substrate.Here as rubber substrate, can enumerate urethane, epichloro hydrin rubber, paracril (NBR), styrene-butadiene rubber(SBR) (SBR), chloroprene rubber etc.
Give material as electroconductibility in addition, can use electron conductions such as carbon black, metal powder to give material or ionic conduction is given material, perhaps mix and use its two.Give material as ionic conduction and can enumerate organic salt, inorganic salts, metal complex, ionic liquid etc.Can enumerate lithium perchlorate, quaternary ammonium salt, sodium trifluoroacetate etc. as organic salt, inorganic salts.As metal complex, can enumerate iron halide-ethylene glycol etc. in addition, specifically can enumerate described in No. 3655364 communique of Japanese Patent.Ionic liquid is at room temperature to be to be also referred to as the normal temperature melting salt by the melting salt of liquid on the other hand, refers in particular to fusing point below 70 ℃, preferred melting salt below 30 ℃.Specifically can enumerate the spy opens described in the 2003-202722 communique.
Manufacture method to surface-treated layer 12a is not particularly limited, and for example can form with removing the surface treatment liquid that partly is penetrated in the elastic layer 12 behind the impermeable surface treatment solution in elastic layer 12 again.Specifically can be to be coated with the 1st surface treatment liquid elastic layer 12 being immersed in the 1st surface treatment liquid that contains isocyanate prepolymer composition or waiting to elastic layer 12 with spraying, after the 1st surface treatment liquid being penetrated into carry out in the elastic layer 12 handle the first time, with this elastic layer 12 be immersed in do not contain isocyanate prepolymer composition or isocyanate prepolymer composition concentration significantly be lower than the 1st surface treatment liquid to clean in the 2nd surface treatment liquid of organic solvent or with the 2nd surface treatment liquid, remove the isocyanate prepolymer composition that is immersed in the most surperficial thus and carry out the 2nd time and handle, and carry out that dry solidification forms.
Two stage processing so both can be carried out continuously, also can carry out with the operation of separating, and carry out the 1st processing with the 1st surface treatment liquid after, must carry out the 2nd time with the 2nd surface treatment liquid and handle before isocyanate prepolymer composition solidifies.After handling for the 1st time, for make elastic layer whole surface evenly carry out the 2nd time and handle, when the remaining organic solvent in elastic layer surface does not volatilize, carry out the 2nd processing when more preferably contact continuously after preferred handle for the 1st time with air.
As two sections processing of successive, can enumerate be immersed in elastic layer in the 1st surface treatment liquid after, mention elastic layer on one side, spray on one side the 2nd surface treatment liquid method or use the 1st surface treatment liquid and the 2nd surface treatment liquid is the treatment solution that is separated, elastic layer is moved to method (phase separation method) the 2nd surface treatment liquid from the 1st surface treatment liquid.Phase disengagement method can also be by making elastic layer be undertaken by the method for mentioning again from the 2nd surface treatment liquid after injecting the 2nd surface treatment liquid form layers on the 1st surface treatment liquid under the state that elastic layer is immersed in the 1st surface treatment liquid.
On the other hand, handle in order evenly to carry out the 2nd subsurface with operation separately on the whole surface of elastic layer, preferably when the remaining organic solvent in elastic layer surface does not volatilize or organic solvent roughly evenly carry out the 2nd time under the evaporable state (partial desiccation state) on the whole surface of elastic layer and handle.If there is difference in the drying regime of elastic layer surface organic solvent, then exists to produce and handle uneven danger.
Here the 1st surface treatment liquid is the treatment solution that dissolves isocyanate prepolymer composition in organic solvent at least.
As isocyanate prepolymer composition contained in the 1st surface treatment liquid, can enumerate 2,6-tolylene diisocyanate (TDI), 4,4 '-diphenylmethanediisocyanate (MDI), to phenylene vulcabond (PPDI), 1,5-naphthalene diisocyanate (NDI) and 3,3-dimethyl diphenyl-4,4 '-vulcabond isocyanate compounds such as (TODI) and aforesaid polymer and sex change body etc.Can also enumerate the prepolymer that contains polyvalent alcohol and isocyanic ester.
Here the organic solvent that is used for the 1st surface treatment liquid, so long as can dissolve isocyanate prepolymer composition, the solvent of the aftermentioned polyethers based polymer that contains as required, vinylformic acid fluorine based polymer and vinylformic acid silica methane series polymkeric substance, then be not particularly limited, can use elastic layer 12 than the organic solvent that is easier to flood and make elastic layer 12 swellings, kind with rubber substrate is different and different, can use organic solvents such as ethyl acetate, methylethylketone (MEK), methyl iso-butyl ketone (MIBK) (MIBK), toluene.When using phase disengagement method, along with the solvent that is used for the 2nd surface treatment liquid is different and different, can use produce the non-proton property polar solvent that is separated as non-polar solvents such as hexanes as the 1st surface treatment liquid, for example N-Methyl pyrrolidone, N, organic solvents such as dinethylformamide (DMF), dimethyl sulfoxide (DMSO) (DMSO), acetonitrile.
Can also contain the polyethers based polymer in other the 1st surface treatment liquid.Here the polyethers polymkeric substance preferably dissolves in the polymkeric substance of organic solvent, also preferably has active hydrogen in addition and can react the polymkeric substance that carries out chemical bonding with isocyanate prepolymer composition.
As preferred, polyethers based polymer, for example can enumerate epichloro hydrin rubber with active hydrogen.Here said epichloro hydrin rubber is meant the epichloro hydrin rubber of uncured state.Epichloro hydrin rubber is because it can give surface-treated layer electroconductibility and elasticity, so preferred.The end of epichloro hydrin rubber has active hydrogen (hydroxyl), but preferably has the epichloro hydrin rubber of hydroxyl, allyl group isoreactivity hydrogen in the unit.As epichloro hydrin rubber, can enumerate Epicholorohydrin homopolymer, Epicholorohydrin-ethylene oxide copolymer, Epicholorohydrin-glycidyl allyl ether multipolymer, Epicholorohydrin-ethylene oxide-glycidyl allyl ether terpolymer or their derivative etc.
As other preferred, polyethers based polymer with active hydrogen, can also enumerate and have hydroxyl or allylic polymkeric substance, for example can enumerate polyvalent alcohol, glycol etc.Such polyethers based polymer possesses the group that contains active hydrogen with two ends and compares, and preferred only possess the polymkeric substance that contains active hydrogen group at a side end.In addition, number average molecular weight is preferred 300～1000, and this is because can give surface-treated layer with elastic reason.As such polyethers based polymer, for example can enumerate polyalkylene glycol mono methyl ether, polyalkylene glycol dme, allylation ether, polyalkylene glycol glycol (Port リ ア Le キ レ Application グ リ コ-Le ジ オ-Le), polyalkylene glycol triol (Port リ ア Le キ レ Application グ リ コ-Le ト リ オ-Le) etc.
By add the polyethers based polymer in surface treatment liquid, can improve the flexibility or the intensity of surface-treated layer like this, its result can avoid the surface abrasion of conductive rubber member, or the damage danger of the photosensitive surface of contact with it.
In addition, can also contain the polymkeric substance that is selected from vinylformic acid fluorine based polymer and vinylformic acid silica methane series polymkeric substance in the 1st surface treatment liquid.
The vinylformic acid fluorine based polymer and the vinylformic acid silica methane series polymkeric substance that can be used in the 1st surface treatment liquid are to dissolve in specified solvent and can react the polymkeric substance that carries out chemical bonding with isocyanate prepolymer composition.Vinylformic acid fluorine based polymer is the fluorine based polymer as the solvent soluble with hydroxyl, alkyl or carboxyl, for example can enumerate the segmented copolymer or derivatives thereof of acrylate and vinylformic acid fluorinated alkyl etc.In addition, vinylformic acid silica methane series polymkeric substance is the solvent soluble siloxane-based polymers, for example can enumerate the segmented copolymer of acrylate and silicon Acrylote oxyalkyl ester or their derivative etc.
Give material as electroconductibility in other the 1st surface treatment liquid and can also add acetylene black, section's qin carbon black (ヶ ッ チ ェ Application Block ラ ッ Network), East Sea carbon black carbon blacks such as (ト-カ Block ラ ッ Network).
The carbon black that is used for the 1st surface treatment liquid is with respect to preferred 0～40 weight % of isocyanate prepolymer composition.If too many, then can produce come off, problem such as rerum natura reduction is unfavorable.
Vinylformic acid fluorine based polymer in other the 1st surface treatment liquid and vinylformic acid silica methane series polymkeric substance with respect to isocyanate prepolymer composition 100 mass parts, preferably make the total amount of vinylformic acid fluorine based polymer and vinylformic acid silica methane series polymkeric substance reach 2～30 mass parts.If be less than 2 mass parts, then the effect that carbon black etc. is remained in the surface-treated layer reduces.On the other hand, if the amount of polymkeric substance is too many, then have the problem that resistance value raises, discharge characteristic reduces of charged roller, or isocyanate prepolymer composition is less relatively, existence can not form the problem of effective surface-treated layer.
The 2nd surface treatment liquid is the treatment solution based on organic solvent, then is not particularly limited so long as can remove the treatment solution of the isocyanate prepolymer composition that is penetrated into the top layer of elastic layer 12 part, but does not preferably contain the treatment solution of isocyanate prepolymer composition.When containing isocyanate prepolymer composition, the concentration of preferred isocyanate composition significantly is lower than the 1st surface treatment liquid.
Can be used in the organic solvent of the 2nd surface treatment liquid, the same with the organic solvent that is used for the 1st surface treatment liquid can be the organic solvent of dissolving isocyanate prepolymer composition, but preferably compares organic solvent that does not more dissolve isocyanate prepolymer composition or the organic solvent that more is difficult to make the elastic layer swelling on operation with the organic solvent of the 1st surface treatment liquid.If use the solvent of the identical or dissolving isocyanate prepolymer composition more than it of organic solvent with the 1st surface treatment liquid or make the solvent of elastic layer swelling, then be not only top layer part, and remove to the danger of the isocyanate prepolymer composition of the elastic layer internal contamination that prevents to be equivalent to underclad portion also higherly, on operation, must to implement accurate temperature treatment or time management.
The above-mentioned solvent that can preferably use as the organic solvent of the 2nd surface treatment liquid in handling that is separated is to the non-polar solvent of isocyanate prepolymer composition as poor solvent, for example can enumerate hexane or hexanaphthene etc.Such organic solvent has and can form thin and the advantage of top section uniformly.
On the other hand, handle if need not be separated and when adopting other method to carry out two stage processing, can use the polar solvent of isocyanate prepolymer composition as the 2nd surface treatment liquid as good solvent, equally with the organic solvent of the 1st surface treatment liquid ethyl acetate, methylethylketone (MEK) can be enumerated, butylacetate or N-Methyl pyrrolidone etc. can also be enumerated.When using such organic solvent to handle, can form thicker top section, top section is thick more, can constitute the roller of soft more.
For dry solidification, be not particularly limited, so long as being solidified, isocyanate prepolymer composition gets final product, have and be cooled to the following temperature of isocyanate prepolymer composition zero pour, then by the method for the moisture-curing in the atmosphere or after under reduced pressure making solvent evaporates, by the method that heat or moisture are cured, generally behind Air drying, carry out heat treated as required.At this moment Heating temperature for example is 40～150 ℃.
The thickness of top section 12b and underclad portion 12c, suitably adjusts isocyanate compound solidified temperature etc. at the concentration of kind that can be by with an organic solvent, the pickup of surface treatment liquid or the 1st surface treatment liquid.
Be arranged on the surface-treated layer 12a of elastic layer 12 top layer parts among the present invention, contain top section 12b and underclad portion 12c as mentioned above, part is set as one with them on the top layer of elastic layer 12.Such surface-treated layer 12a particularly underclad portion 12c mainly is that isocyanate prepolymer composition solidify to form, and the density of formation isocyanate prepolymer composition reduces the one of (gradually dredging) gradually to inside from the surface.Therefore can prevent that pollution substance such as softening agent from separating out to the conductive rollers surface, so form conductive roll to the stain resistance excellence of photoreceptor.In addition, because top section 12a, the hardness that can suppress top layer part raises, and has the servo-actuated with respect to distortion.
Relevant conductive rubber member of the present invention is suitable for the conductive roll, cleaning balde, transfer belt of charged roller, transfer roll, developer roll, toner supplying roller, clearer roller etc. as electro photography duplicating machine and printer or image processing systems such as ink jet type duplicating machine and printer etc.
[embodiment]
Followingly situation of the present invention is described, but the present invention is not subjected to the qualification of these embodiment according to embodiment.
(embodiment 1)
The manufacturing of＜roller 〉
At the trifunctional polyethers is to add ヶ ッ チ ェ Application Block ラ ッ Network EC (ヶ ッ チ ェ Application Block ラ ッ Network イ Application -Na シ ヨ Na Le corporate system) 3 weight parts and rising sun #60 (rising sun カ-ボ Application) 5 weight parts in polyvalent alcohol MN-3050 (the military field of Mitsui ヶ ミ カ Le system) 100 weight parts, make its dispersion reach the following degree of granularity 20 μ m, after the temperature adjustment to 80 ℃, under reduced pressure carry out 6 hours deaeration, dehydration operation, obtain A liquid.On the other hand, add to mix コ ロ ネ-ト C-HX (Japanese Port リ ウ レ Application corporate system) 10 weight parts in プ レ Port リ マ-ア ジ プ レ Application L100 (ユ ニ ロ イ ヤ Le corporate system) 22 weight parts, temperature adjustment to 80 ℃ obtains B liquid.A liquid and B liquid mixed and be injected in advance be provided with an axle (φ 8mm in central authorities, 1:270mm) and be preheated in 120 ℃ the iron pipe mold of diameter 23mm, heated 120 minutes down at 120 ℃, obtain being formed with the roller of conductive polyurethane layer on the axle surface of removing two end portions, to this roller surface grinding 1.5mm, obtain external diameter is adjusted to the roller (before handling) of 20mm.
The modulation of＜surface treatment liquid 〉
In acetonitrile 100 weight parts, add mixed dissolution プ レ Port リ マ-ア ジ プ レ Application L100 (ユ ニ ロ イ ヤ Le corporate system) 10 weight parts and make surface treatment liquid.
The surface treatment of＜roller 〉
The roller of making is immersed in the surface treatment liquid that keeps 23 ℃ after 60 seconds, in surface treatment liquid, slowly add hexanaphthene 100 weight parts and form phase-separated state, speed with 250mm/ minute is mentioned, and heating is 1 hour in the baking oven of 120 ℃ of maintenances, forms surface-treated layer by this method.
(embodiment 2)
The manufacturing of＜roller 〉
With respect to epichloro hydrin rubber (エ ピ Network ロ マ-CG-102; ダ イ ソ-corporate system) 100 weight parts, with the mixing perchloric acid tetraethyl ammonium of roller mixing machine (Northeast chemical company system) 0.5 weight part as conductive agent, as softening agent phthalic acid two (2-ethylhexyl) ester (DOP) 3 weight parts, zinc oxide (ZnO) 5 weight parts, as 2-mercaptoimidazoline (ア Network セ Le-22) 2 weight parts of vulcanizing agent, compression molding is carried out on surface at the metal system axle of diameter 6mm, obtains being formed with on the axle surface roller of epichloro hydrin rubber layer.Attrition process is carried out on this roller surface, obtain external diameter is adjusted to the roller (before handling) of 12mm.
The modulation of＜surface treatment liquid 〉
In methyl iso-butyl ketone (MIBK) 100 weight parts, add mixed dissolution isocyanate compound (HDI) 20 weight parts and make surface treatment liquid.
The surface treatment of＜roller 〉
The roller of making is immersed in the surface treatment liquid that keeps 23 ℃ after 30 seconds, speed with 250mm/ minute is mentioned, after becoming uniform partial desiccation state, be immersed in the butylacetate that keeps 23 ℃ and mention for 10 seconds, heating is 1 hour in the baking oven of 120 ℃ of maintenances, forms surface-treated layer thus.
(embodiment 3)
Making oven temperature in the surface treatment of roller is 150 ℃, in addition, carries out 1 identical operations with embodiment, makes the conductive roll of embodiment 3.
(embodiment 4)
In surface treatment liquid, cooperate acetylene black 5 weight parts, in addition, carry out 1 identical operations, make the conductive roll of embodiment 4 with embodiment.
(comparative example 1)
Do not add hexanaphthene, in addition, carry out 1 identical operations, make the conductive roll of comparative example 1 with embodiment.
(comparative example 2)
In surface treatment liquid, do not add hexanaphthene behind the dipping, and, in addition, carry out 1 identical operations, make the conductive roll of comparative example 2 with embodiment with the roller surface that the sponge wiping that is impregnated with hexanaphthene is mentioned.
(comparative example 3)
Be not immersed in the N-BUTYL ACETATE, in addition, carry out 2 identical operations, make the conductive roll of comparative example 3 with embodiment.
(comparative example 4)
Roller is immersed in the surface treatment liquid back continuous impregnating in keeping 23 ℃ methyl iso-butyl ketone (MIBK) 30 seconds, in addition, carries out 2 identical operations, make the conductive roll of comparative example 4 with embodiment.
(comparative example 5)
Rubber rollers surface coated polyurethane coating (ネ オ レ ッ Star R-940 at embodiment 2; Nanmu originally changes into corporate system), continuous impregnating is heating 1 hour in keeping 120 ℃ baking oven after 10 seconds in keeping 23 ℃ butylacetate, with the roller that forms coating thus 5 conductive roll as a comparative example.
(test example 1): the microsclerometry of roller
Use microhardness tester (MD-1, polymer gauge Co., Ltd. system) to measure the rubber hardness (Hs) of the conductive roll of each untreated conductive roll, each embodiment and each comparative example.This result is shown in table 1,2.
(test example 2): the resistance value of roller is measured
To the conductive roll of each untreated conductive roll, each embodiment, each comparative example, measure the resistance value when impressed voltage is 100V.The mensuration of resistance value, under NN environment (23 ℃, 55%RH), roller is placed on the electrode member that contains the SUS304 plate, apply at the two ends of roller under the state of 500g load, use ULTRA HIGH RESISTANCE METER R8340A (ア of Co., Ltd. De バ Application テ ス ト system) to measure to apply voltage resistance value between plug and the electrode after 30 seconds.On sense of rotation, measure 8 places altogether for 45 ° in the each rotation of circumferential direction in addition, measure at this moment maximum value, minimum value, mean value respectively.This result is shown in table 1,2.
(test example 3): the observation of condition of surface
To the conductive roll of each embodiment, each comparative example, by the condition of surface of Visual Confirmation roller.When in apparent good order and condition, be designated as zero, be designated as △ when condition of surface is general, be designated as when condition of surface is bad *.This result is shown in following table 1,2.
(test example 4): picture appraisal
With the conductive roll of embodiment 1, comparative example 1,2 as developer roll; As charged roller, be installed in the image change that the laser printer of selling on the market (MICROLINE 9600PS Zhu formula Hui She Red デ- system) is gone up print cross 10,000 on paper under the NN environment (23 ℃, 55%RH) by Visual Confirmation after with the conductive roll of embodiment 2, comparative example 3～5 respectively.When image is good, be designated as zero, be designated as △ when image is general, be designated as when image is bad *.In addition also by Visual Confirmation roller condition of surface at this moment.This result is shown in following table 1,2.
(test example 5): the evaluation of grinding object again
To the conductive roll of each embodiment and each comparative example, grind rubber surface 0.05mm, 0.1mm, 0.3mm again after, carry out and test example 1 identical operations, measure the hardness (Hs) of rubber again.About resistance value, also carry out and test example 2 identical operations in addition, measure resistance value again.These results show table 3,4 and Fig. 2～5 in.
[table 1]
| Polyurethane base material | Embodiment 1 | Embodiment 3 | Embodiment 4 | Comparative example 1 | Comparative example 2 | |
| Microhardness (°) | 52.0 | 53.7 | 53.0 | 55.4 | 57.3 | 55.9 |
| Resistance value (Ω) | 7.24×10 6 | 7.11×10 7 | 5.52×10 7 | 1.12×10 8 | 2.39×10 8 | 1.20×10 8 |
| Resistance value (MAX/MIN ratio) | 5 | 4 | 4 | 4 | 4 | 112 |
| Condition of surface | - | Zero is good | Zero is good | Zero is good | Zero is good | * exist processing inhomogeneous |
| Picture appraisal | - | Zero is good | Zero is good | Zero is good | * roller surface produces wrinkle | * exist density unevenness even |
[table 2]
| The Epicholorohydrin base material | Embodiment 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | |
| Microhardness (°) | 46.2 | 48.2 | 52.4 | 46.7 | 54.2 |
| Resistance value (Ω) | 5.94×10 5 | 8.00×10 5 | 1.64×10 6 | 6.97×10 5 | 9.30×10 6 |
| Resistance value (MAX/MIN ratio) | 5 | 3 | 4 | 34 | 12 |
| Condition of surface | - | Zero is good | Zero is good | △ exists processing inhomogeneous | △ exists processing inhomogeneous |
| Picture appraisal | - | Zero is good | * roller surface produces the wrinkle photoreceptor and produces damage | △ exists density unevenness even | * roller surface cracks |
[table 3]
[table 4]
(test-results summary)
Can confirm to use the surface treatment liquid of phase-separated state to carry out the conductive roll of surface-treated embodiment 1,3,4, compare with carrying out in the past the conductive roll of surface-treated comparative example 1, microhardness and resistance value reduce.Also confirmed to carry out the conductive roll of surface-treated embodiment 2 in addition, compared that microhardness and resistance value also reduce with carrying out in the past the conductive roll of surface-treated comparative example 3 with operation separately.The image of embodiment 1～4 printed matter is good in the picture appraisal after crossing 10,000 on paper in addition.
In contrast, carry out the conductive rollers of surface-treated comparative example 1 in the past, cross 10,000 on paper after the roller surface produce wrinkle, the conductive rollers of comparative example 3 also can be damaged photoreceptor, the image of printed matter is all bad simultaneously.
On the other hand, confirmed in surface treatment liquid, to use behind the dipping conductive roll of the comparative example 2 on the sponge wiper rolls surface that is impregnated with hexanaphthene, compare with the conductive roll of comparative example 1, its microhardness and resistance value reduce, and see since the inhomogeneous resistance value that causes of wiping than large deviation.In addition, can see in the image of print that in picture appraisal density unevenness is even, be evaluated as bad.In methyl iso-butyl ketone (MIBK), flood the conductive roll of the comparative example 4 in 30 seconds after in surface treatment liquid, soaking roller clearly, its microhardness, resistance value all are lower than the conductive roll of embodiment 2, and when being impregnated into the roller of inhomogeneous partial desiccation (part still is in the adhesional wetting state) in the solvent once more, the surface can produce be handled inhomogeneous and can be seen some deviations of resistance value, can see in the image of print that in picture appraisal density unevenness is even.Exceeded more than the required degree by the concentration reduction that is immersed in the isocyanic ester of surface-treated layer in the good solvent methyl iso-butyl ketone (MIBK) in addition, or can see that the OPC that is caused by softening agent pollutes.The conductive rollers of hence one can see that comparative example 2 and comparative example 4, the density that partly has an inner isocyanate prepolymer composition to the underclad portion that inside reduces gradually, are uneven texture greater than the density of the top section on surface and isocyanate prepolymer composition.
On the other hand, behind the pair roller coating composition liquid, in butylacetate, flood the conductive roll of the comparative example 5 in 10 seconds, by carrying out and comparative example 4 conductive rollers identical operations, be immersed in the roller of partial desiccation state in the solvent once more, it is inhomogeneous that its surface can produce processing, can see some deviations of resistance value.In addition, can see that in picture appraisal there is crackle on the roller surface, the picture appraisal of printed matter is bad.
To the conductive roll of each embodiment, each comparative example grinding object is estimated again the time, conductive roll as Fig. 2-5 illustrated embodiment 1～4, there is the zone that raises to inside from top layer in the rubber hardness of its top layer part, and forming the zone that its lower floor reduces, surface-treated layer contains top section and underclad portion as can be known as mentioned above.
Shown in Fig. 2,3, can confirm the conductive roll of embodiment 1,4, the regional oblique line of its rubber hardness about from the surface to thickness 0.1mm raises, and reduces at its later regional bend.And the regional oblique line of the resistance value of conductive roll of having confirmed embodiment 1,4 about from the surface to thickness 0.05mm raises, and reduces at its later regional bend to constitute the inclination impedance layer.Also be the same among the embodiment 2, rubber hardness and resistance value raise from the surface to the specific thickness oblique line, reduce at its later regional oblique line.
The conductive roll of embodiment 3 in addition, or owing to improved treatment temp, base material expands, isocyanate prepolymer composition be to the reason of internal divergence more, can confirm from the surface to thickness 0.05mm about the resistance value in zone raise largely.
On the other hand, carry out the conductive roll of surface-treated comparative example 1,3 in the past, confirmed from its surface, form the inclination impedance layer that rubber hardness or resistance value oblique line reduce to rubber inside.
The conductive roll of comparative example 4, confirmed from its surface to thickness 0.1mm about the zone, rubber hardness and resistance value oblique line raise.
The conductive roll of comparative example 5, from its surface grinding to thickness 0.05mm about, show and to grind identical rubber hardness of gum base materials and resistance value with rubber, confirmed that thus its surface is formed with coating.
Claims (7)
1. conductive rubber member, it is the conductive rubber member with surface-treated layer, this surface-treated layer is to form by the surface treatment liquid that the top layer part dipping to the outermost layer conductive elastic layer that is endowed electroconductibility contains isocyanate prepolymer composition and organic solvent at least, it is characterized in that face side top section at the aforementioned surfaces processing layer, the density of inner aforementioned isocyanate prepolymer composition is greater than the surface, and in the underclad portion of this top section downside, the density of aforementioned isocyanate prepolymer composition reduces gradually to inside.
2. the described conductive rubber member of claim 1 is characterized in that the aforementioned surfaces treatment solution further contains to be selected from least a of carbon black, vinylformic acid fluorine based polymer and vinylformic acid silica methane series polymkeric substance.
3. the described conductive rubber member of claim 1 is characterized in that the aforementioned surfaces treatment solution further contains the polyethers based polymer.
4. the described conductive rubber member of claim 3 is characterized in that aforementioned polyethers based polymer has active hydrogen.
5. the described conductive rubber member of claim 4 is characterized in that aforementioned polyethers based polymer is an epichloro hydrin rubber.
6. any described conductive rubber member of claim 1～5 is characterized in that aforementioned conductive elastic layer gives at least a electroconductibility that is endowed that material and ionic conductivity are given material by electron conduction.
7. conductive rubber member is characterized in that the described conductive rubber member of claim 1 is roll forming or sheet.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007256132 | 2007-09-28 | ||
| JP2007256132 | 2007-09-28 | ||
| JP2007-256132 | 2007-09-28 | ||
| JP2008245512A JP2009098669A (en) | 2007-09-28 | 2008-09-25 | Conductive rubber member |
| JP2008-245512 | 2008-09-25 | ||
| JP2008245512 | 2008-09-25 |
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| Publication Number | Publication Date |
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| CN101397374A true CN101397374A (en) | 2009-04-01 |
| CN101397374B CN101397374B (en) | 2013-01-02 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN 200810168750 Active CN101397374B (en) | 2007-09-28 | 2008-09-28 | Conductive rubber member |
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| Country | Link |
|---|---|
| JP (1) | JP2009098669A (en) |
| CN (1) | CN101397374B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102029751A (en) * | 2009-08-07 | 2011-04-27 | 新智德株式会社 | Conductive rubber member and charged roller |
| CN103443715A (en) * | 2011-08-22 | 2013-12-11 | 东海橡塑工业株式会社 | Developing roll for electrophotographic equipment |
| CN107365439A (en) * | 2017-07-30 | 2017-11-21 | 华南理工大学 | A kind of new neoprene vulcanization process |
| CN116140154A (en) * | 2023-04-10 | 2023-05-23 | 南一智能装备(常州)有限公司 | Coating machine is from membrane conveying swing arm roller mechanism |
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| JP2009223252A (en) * | 2008-03-19 | 2009-10-01 | Fuji Xerox Co Ltd | Conductive roll, image forming apparatus equipped with conductive roll, and method and device for manufacturing conductive roll |
| JP5366120B2 (en) * | 2008-08-11 | 2013-12-11 | シンジーテック株式会社 | Manufacturing method of rubber member |
| JP2011197543A (en) * | 2010-03-23 | 2011-10-06 | Konica Minolta Business Technologies Inc | Intermediate transfer body and image forming apparatus |
| JP2013132312A (en) * | 2011-12-26 | 2013-07-08 | Bridgestone Sports Co Ltd | Method of manufacturing golf ball, and golf ball |
| JP6048221B2 (en) * | 2013-03-01 | 2016-12-21 | 日本精工株式会社 | Rolling bearing unit for wheel support with seal ring |
| JP6637925B2 (en) * | 2017-05-31 | 2020-01-29 | 住友理工株式会社 | Electrophotographic equipment blade and method of manufacturing the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4065542B2 (en) * | 2004-07-23 | 2008-03-26 | キヤノン株式会社 | Method for producing electrophotographic roller |
| JP2006225552A (en) * | 2005-02-18 | 2006-08-31 | Canon Inc | Roller for electrophotography, and process cartridge and device of electrophotography using the same |
| JP5146982B2 (en) * | 2005-11-01 | 2013-02-20 | シンジーテック株式会社 | Conductive rubber member |
| JP5146983B2 (en) * | 2005-11-16 | 2013-02-20 | シンジーテック株式会社 | Conductive rubber member |
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2008
- 2008-09-25 JP JP2008245512A patent/JP2009098669A/en active Pending
- 2008-09-28 CN CN 200810168750 patent/CN101397374B/en active Active
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102029751A (en) * | 2009-08-07 | 2011-04-27 | 新智德株式会社 | Conductive rubber member and charged roller |
| CN103443715A (en) * | 2011-08-22 | 2013-12-11 | 东海橡塑工业株式会社 | Developing roll for electrophotographic equipment |
| CN103443715B (en) * | 2011-08-22 | 2016-08-17 | 住友理工株式会社 | Developer roller for electrophotographic equipment |
| CN107365439A (en) * | 2017-07-30 | 2017-11-21 | 华南理工大学 | A kind of new neoprene vulcanization process |
| CN107365439B (en) * | 2017-07-30 | 2020-02-18 | 华南理工大学 | Novel chloroprene rubber vulcanization method |
| CN116140154A (en) * | 2023-04-10 | 2023-05-23 | 南一智能装备(常州)有限公司 | Coating machine is from membrane conveying swing arm roller mechanism |
| CN116140154B (en) * | 2023-04-10 | 2023-07-04 | 南一智能装备(常州)有限公司 | Coating machine is from membrane conveying swing arm roller mechanism |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2009098669A (en) | 2009-05-07 |
| CN101397374B (en) | 2013-01-02 |
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Effective date of registration: 20160707 Address after: Tokyo, Japan, the port district, Zhi Zhi, Ding Ding, No. 12, No. 15 Patentee after: Nitto Kogyo KK Address before: Tokyo, Japan Patentee before: Nitto Kogyo KK |