CN101333301A - Conductive rubber member - Google Patents
Conductive rubber member Download PDFInfo
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- CN101333301A CN101333301A CNA2008100963672A CN200810096367A CN101333301A CN 101333301 A CN101333301 A CN 101333301A CN A2008100963672 A CNA2008100963672 A CN A2008100963672A CN 200810096367 A CN200810096367 A CN 200810096367A CN 101333301 A CN101333301 A CN 101333301A
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Abstract
The object of the invention is to provide a conductive rubber member with stable resistance value and small dependability on environment. The conductive rubber member comprises a conductive elastic layer 12 which makes material be conductive through the conductivity thereof, the surface part of the conductive elastic layer 12 is immersed with a surface treatment liquid containing isocyanate and polymers with ionic conductivity to form a surface treatment layer 12a.
Description
Technical field
The present invention relates to be applicable to the conductive rubber member in electro photography duplicating machine and printer or the image processing systems such as ink jet type (ト Na one ジ ェ ッ ト formula) duplicating machine and printer, relate to the conductive rubber member that is specially adapted to conductive roll (Guide Electricity ロ one Le), scraper plate (プ レ one De), band (ベ Le ト) etc.
Background technology
The conductive roll of image processing systems such as electro photography duplicating machine and printer requires not pollute the character of photoreceptor etc. and electroconductibility etc.Use the goods of urethane, silicone rubber system in the past mostly, and then proposed on various elastic layers surface, to be provided with various overlays, surface-treated layer or lining tube (lining チ ュ one プ) (for example with reference to patent documentation 1～patent documentation 4).
Wherein, patent documentation 4 discloses a kind of charged member, low as cost, as can to have kept characteristic for a long time charged member, the applicant has carried out patent application, be to have to comprise the charged member that Epicholorohydrin is the elastic layer of rubber substrate, it has surface-treated layer, and described surface-treated layer is to contain at least a polymkeric substance, the electroconductibility selected by use from propylene fluorine based polymer and propylene siloxane-based polymers to pay the surface treatment liquid of material and isocyanate prepolymer composition and carry out surface treatment and form.
Conductive roll in this patent documentation 4 in order to pay electroconductibility, has cooperated electroconductibility such as carbon black to pay material in surface treatment liquid, is subjected to the influence of carbon black dispersion state easily but the problem that exists is the resistance value of roller integral body.
There is environmental factor dependence big when using other conductive agent, can not stablizes and carry out the problem that image forms.
In addition, the applicant discloses a kind ofly makes top layer zone impregnation surface treatment liquid, make its heat embrittlement and form the conductive rubber member of surface-treated layer, and wherein said surface treatment liquid is for paying agent with ionic conduction and heat-curable compounds is dissolved in (referring to the patent documentation 5) that forms in the solvent.This conductive rubber member is little to environmental factor dependence, and resistance value is stable, but under more harsh condition, resistance value changes a lot sometimes.
[patent documentation 1] Japanese kokai publication hei 6-175470 communique (claim etc.)
[patent documentation 2] Japanese kokai publication hei 5-281831 communique (claim etc.)
[patent documentation 3] Japanese kokai publication hei 4-214579 communique (claim 2, [0022] etc.)
[patent documentation 4] TOHKEMY 2002-040760 communique (claim etc.)
[patent documentation 5] TOHKEMY 2007-31703 number (claim etc.)
Summary of the invention
Problem of the present invention is In view of the foregoing, provides a kind of environmental factor dependence little, the conductive rubber member that resistance value is stable.
The present invention's the 1st scheme that solves above-mentioned problem is a conductive rubber member, it is characterized in that comprising by electroconductibility and pay the conductive elastic layer that material has been paid electroconductibility, the surface treatment liquid that contains isocyanate prepolymer composition and ionic-conductive polymer by the skin section impregnation at this conductive elastic layer forms surface-treated layer.
The 2nd scheme of the present invention is a conductive rubber member, it is characterized in that above-mentioned surface treatment liquid contains organic solvent in the described conductive rubber member of the 1st scheme, and above-mentioned organic solvent dissolution above-mentioned isocyanate prepolymer composition and above-mentioned ionic-conductive polymer.
The present invention's the 3rd scheme is a conductive rubber member, it is characterized in that in the described conductive rubber member of the 1st or the 2nd scheme, and above-mentioned ionic-conductive polymer is to be selected from least a in epichloro hydrin rubber, acrylonitrile butadiene rubber and the oxyalkylene.
The present invention's the 4th scheme is a conductive rubber member, it is characterized in that in the 1st～3 in the described conductive rubber member of either party case, above-mentioned surface treatment liquid contains carbon black.
The present invention's the 5th scheme is a conductive rubber member, it is characterized in that in the 1st～4 in the described conductive rubber member of either party case, above-mentioned conductive elastic layer comprises rubber substrate, and this rubber substrate contains epichloro hydrin rubber.
The present invention's the 6th scheme is a conductive rubber member, it is characterized in that the described conductive rubber member of either party case is the roller shape in the 1st～5, it is tabular or banded to scrape.
According to the present invention, owing to used the surface treatment liquid that contains isocyanate prepolymer composition and ionic-conductive polymer, thus can provide environmental factor dependence little, the conductive rubber member that resistance value is stable.
Description of drawings
Fig. 1 is to use the sectional view of conductive roll of an example of conductive rubber member of the present invention.
Fig. 2 is the explanatory view of test example 1 measuring method.
Nomenclature
10 conductive rolls
11 plugs (core gold)
12 conductive elastic layers
The 12a surface-treated layer
Embodiment
A following example as conductive rubber member of the present invention is that example describes the present invention in detail with the conductive roll.
Fig. 1 has been to use the sectional view of conductive roll of an example of conductive rubber member of the present invention.
Shown in Fig. 1 (a), conductive roll 10 has conductive elastic layer 12 on plug 11, and the skin section of conductive elastic layer 12 forms surface-treated layer 12a.Surface-treated layer 12a is by impregnation surface treatment liquid in the skin section of conductive elastic layer 12, and makes its sclerosis and form one with conductive elastic layer 12.
Shown in Fig. 1 (b), conductive roll 10 also can have the optional layer 13 that is provided with between plug 11 and conductive elastic layer 12 and plug 11.At this, the optional layer that is provided with can be foaming layer between conductive elastic layer 12 and plug 11, also can be non-foam layer, and then can also be the structure more than 1 layer.In this case, the superiors are that the conductive elastic layer that satisfies following condition gets final product.
Certainly, conductive elastic layer 12 can be entity (ソ リ ッ De) (not having foaming), also can be cavernous body (ス Port Application ジ) (foam).And then for conductive elastic layer 12, outside surface can be ground, and also can not ground.
Conductive elastic layer 12 used base materials to the conductive roll 10 of present embodiment do not have particular restriction, can enumerate and for example contain epichloro hydrin rubber, urethane, acrylonitrile butadiene rubber (NBR), neoprene (CR), styrenerubber (SBR), acrylic rubber (ACM), ethylene propylene rubber (EPDM), silicone rubber (Q) etc., preferably use epichloro hydrin rubber.Because epichloro hydrin rubber can make elastic layer have electroconductibility, thus preferred.
As epichloro hydrin rubber, can enumerate Epicholorohydrin homopolymer, Epicholorohydrin-ethylene oxide copolymer, Epicholorohydrin-glycidyl allyl ether multipolymer, Epicholorohydrin-ethylene oxide-glycidyl allyl ether terpolymer, Epicholorohydrin-ethylene oxide-propylene oxide-glycidyl allyl ether tetrapolymer or derivatives thereof etc., these can use separately, also can will also use more than 2 kinds.Also can suitably mix other elastomeric material in the epichloro hydrin rubber.As blendable rubber substrate, can enumerate acrylonitrile butadiene rubber (NBR), urethane, neoprene (CR), styrenerubber (SBR) etc.
As urethane, can preferably enumerate polyethers is that urethane, polyester are urethane, polycarbonate-based urethane etc.As these urethane, casting type (notes type イ プ) is arranged but the urethane of mixed type (ミ ラ Block Le イ プ) etc., preferably so-called casting type polyurethane by the reaction of ammonia ester polyol and polyisocyanates is obtained.As with the isocyanic ester of polyol reaction, for example can use 3 functional isocyanate monomers such as triphenylmethane triisocyanate, three (isocyanate group phenyl) thiophosphatephosphorothioate, bicycloheptane triisocyanate, hexamethylene diisocyanate cyanurate (ヌ レ one ト) modified polyisocyanate (3 aggressiveness: 3 officials can, 5 aggressiveness: 4 officials can), the mixture of polymeric MDI (Port リ メ リ ッ Network MDI) etc.The mixture of polyisocyanates that these 3 officials can be above and 2 general functional isocyanate compounds is also passable.Example as 2 functional isocyanate compounds, can enumerate 2,4-tolylene diisocyanate (TDI), 4,4 '-diphenylmethanediisocyanate (MDI), PPDI (PPDI), 1,5-naphthalene diisocyanate (NDI), 3,3-dimethyl diphenyl-4,4 '-vulcabond (TODI) and two ends have modification bodies such as the prepolymer of these isocyanic ester and polymer etc.
Must in conductive elastic layer 12, add electroconductibility and pay material.That is: conductive elastic layer 12 is to form added the rubber combination sulfuration that electroconductibility pays material in rubber substrate.Pay material as electroconductibility, preferably pay the various carbon blacks of material, can use also that electron conductions such as metal-powder are paid material, ionic conduction is paid material or the two mixture as electron conduction.Pay material as ionic conduction, can enumerate organic salt, inorganic salts, metal complex, ionic liquid etc.As organic salt, inorganic salts, can enumerate lithium perchlorate, quaternary ammonium salt, sodium trifluoroacetate etc.As metal complex, can enumerate halogenation ethylene glycol and close iron (III) (Ha ロ ゲ Applicationization second iron one エ チ レ Application グ リ コ-Le) etc., specifically can enumerate the Diethylene Glycol iron(ic) chloride complex compound (III) (ジ エ チ レ Application グ リ コ one Le one saltization the 2nd iron Wrong body) put down in writing in No. 3655364 communique of Japan special permission etc.On the other hand, ionic liquid is to be under the room temperature to be also referred to as the normal temperature melting salt by the melting salt of liquid, referring in particular to fusing point is below 70 ℃, and is preferred below 30 ℃.Specifically can enumerate two (trifluoromethyl sulphonyl) imines (1-エ チ Le-3-メ チ Le イ ミ グ ゾ リ ウ system PVC ス (ト リ Off Le オ ロ メ チ Le ス Le Off オ ニ Le) イ ミ De) of the 1-ethyl 3-Methylimidazole of putting down in writing in the TOHKEMY 2003-202722 communique, 1-butyl-3-ethyl imidazol(e) (trifluoromethyl sulphonyl) imines (1-Block チ Le-3-エ チ Le イ ミ グ ゾ リ ウ system ト リ Off Le オ ロ メ チ Le ス Le Off オ ニ Le) イ ミ De) etc.
Electroconductibility is paid material and be there is no need to add to more than the requirement, the preferred use near the amount that need to obtain the resistance value minimum quantity.Add aequum to when above, as follows, form surface-treated layer after, be difficult to obtain required medium resistance value (middle opposing), for example 10
4～10
7Medium resistance value about Ω.For example, under the situation of carbon black, can use below the 10 weight %, preferably use the following degree of 7 weight %.
Surface-treated layer 12a makes its sclerosis by impregnation surface treatment liquid in the skin section of conductive elastic layer 12, forms one with the skin section of conductive elastic layer 12 and is provided with.This surface-treated layer 12a forms by the surface treatment liquid that impregnation contains isocyanate prepolymer composition and ionic-conductive polymer at least.Density sparse gradually form and conductive elastic layer 12 from the surface to inside with isocyanate prepolymer composition and ionic-conductive polymer forms one.Surface treatment liquid contained be meant in the skin section that is immersed in conductive elastic layer 12 conductive elastic layer 12 is flooded the specified time in surface treatment liquid, perhaps surface treatment liquid is coated on the conductive elastic layer 12, perhaps utilizes method such as spraying to make surface treatment liquid be impregnated into the skin section of conductive elastic layer 12.
Surface treatment liquid contains organic solvent, and organic solvent preferably dissolves isocyanate prepolymer composition and ionic-conductive polymer at least.
Said herein ionic-conductive polymer is meant to have polar group, and demonstrates 1.0 * 10
4～1.0 * 10
9Ω, preferred 1.0 * 10
7～1.0 * 10
9The polymer of the medium resistance value of Ω.
Ionic-conductive polymer is dissolved in above-mentioned organic solvent preferably, more preferably can pay elastic.Because improved flexibility, the intensity of surface-treated layer, the result has not had the roller surface to be worn, the possibility of (when connecing the The Ru) photosensitive surface of damage contact.As such ionic-conductive polymer, for example can enumerate acrylonitrile butadiene rubber (NBR), epichloro hydrin rubber, contain the polymkeric substance of alkylidene group oxygen (alkylene oxide) etc.As epichloro hydrin rubber, can enumerate Epicholorohydrin homopolymer, Epicholorohydrin-ethylene oxide copolymer, Epicholorohydrin-glycidyl allyl ether multipolymer, Epicholorohydrin-ethylene oxide-glycidyl allyl ether terpolymer, Epicholorohydrin-ethylene oxide-propylene oxide-glycidyl allyl ether tetrapolymer or derivatives thereof etc.As the polymkeric substance that contains alkylidene group oxygen, can enumerate ethylene oxide homopolymer, ethylene oxide-propylene oxide copolymer, ethylene oxide-glycidyl allyl ether multipolymer, ethylene oxide-propylene oxide-glycidyl allyl ether terpolymer or derivatives thereof etc.Ionic-conductive polymer can use separately, also can and use.
When paying material and use electron conduction to pay material as electroconductibility, by the organic solvent in the surface treatment liquid is impregnated in the conductive elastic layer 12, conductive elastic layer 12 swelling a little, produce minute groove, chain structure (conductive path) once was cut off, and isocyanate prepolymer composition at least and ionic-conductive polymer in the surface treatment liquid are filled in this minute groove.After removing organic solvent, the chain structure that isocyanate prepolymer composition stops the electroconductibility of conductive elastic layer 12 to pay material returns to the state before the swelling, on the other hand, ionic-conductive polymer company structure that cut electroconductibility is paid material has played ligation.That is: because being situated between, these isocyanate prepolymer compositions and ionic-conductive polymer be that cut electroconductibility pays in the chain structure of material, so the conductive path of conductive roll 10 skin section forms following state, promptly form the state of the medium resistance part that contains isocyanate prepolymer composition and ionic-conductive polymer halfway, with the state before the surface treatment different, that is: reconstituted how many states of increasing of resistance.
Paying agent as electroconductibility uses situation that ionic conductivity pays agent too, because the organic solvent in the surface treatment liquid is impregnated in the conductive elastic layer 12, conductive elastic layer 12 swelling a little produces fine groove, and isocyanate prepolymer composition at least in the surface treatment liquid and ionic-conductive polymer are filled in this fine groove.At this moment, do not pay company's structure (conductive path) that material forms in the conductive elastic layer 12 by electron conduction, but owing to presenting high-resistance isocyanate prepolymer composition intermediary at ionic-conductive polymer, so can make resistance keep lowly.
Isocyanate prepolymer composition has the tendency of skin section (surface-treated layer 12a) hardening that makes conductive elastic layer 12, by also using ionic-conductive polymer, surface-treated layer 12a can keep elasticity (flexibility).
Isocyanate prepolymer composition and ionic-conductive polymer be with mode impregnation sparse gradually from the surface to inside, thus resistance to increase a surperficial side bigger, surface-treated layer 12a forms the oblique Layer of resistance dipping bed (Di Kang Pour).
The surface treatment liquid that will contain ionic-conductive polymer contains and is immersed in the conductive elastic layer 12, forms surface-treated layer 12a, can produce the conductive roll 10 with the electrical characteristic of wanting easily thus.As mentioned above, ionic-conductive polymer this to form the material of surface-treated layer 12a of medium resistance different as the such resistance value that dispersion reduces base material (conductive elastic layer 12) passed through of medium resistance and carbon black.That is: be not carbon black such pass through the material that dispersion state changes resistance value.Can as ionic conductive agent, not pollute the photoreceptor of roller surface, contact etc.And then, compare with ionic conductive agent, owing to be not subject to moisture effects, so used the environmental factor dependence of conductive roll 10 of the surface treatment liquid that contains ionic-conductive polymer little.
As isocyanate prepolymer composition contained in the surface treatment liquid, can enumerate 2,6-tolylene diisocyanate (TDI), 4,4 '-diphenylmethanediisocyanate (MDI), PPDI (PPDI), 1,5-naphthalene diisocyanate (NDI) and 3,3-dimethyl diphenyl-4,4 '-vulcabond (TODI) and above-mentioned polymer and modification body etc.Also can enumerate the prepolymer that polyvalent alcohol and isocyanic ester form.
As long as surface treatment liquid contains mentioned component, but also can further add carbon black, ionic conductive agents such as acetylene black, Ketjen black (ケ ッ チ ェ Application Block ラ ッ Network), ト one カ is black, further reduce resistance value.Contain ionic-conductive polymer by surface treatment liquid, can make surface-treated layer 12a have electroconductibility.Therefore, when adding carbon black, ionic conductive agent, even a small amount of interpolation also can obtain abundant effect.
The carbon black that uses in the surface treatment liquid is preferably 0～40 weight % with respect to isocyanate prepolymer composition.In the time of too much, can produce come off, problem such as resistance value deviation, not preferred.
In the scope that does not hinder characteristic, also can contain the polymkeric substance that is selected from propylene fluorine based polymer (ア Network リ Le Off ッ prime system Port リ マ one) and the propylene siloxane-based polymers (ア Network リ Le シ リ コ one Application is Port リ マ one) in the surface treatment liquid.
Propylene fluorine based polymer and propylene siloxane-based polymers be dissolve in the organic solvent of regulation, can with the material of isocyanate compound reaction carrying out chemical bonding.Propylene fluorine based polymer be dissolve in have hydroxyl, the fluorine based polymer of the solvent of alkyl or carboxyl, segmented copolymer, its derivative of acrylate and fluoroalkyl acrylate etc. are for example arranged.The propylene siloxane-based polymers is the siloxane-based polymers of solvent soluble, and segmented copolymer, its derivative of acrylate and silicon Acrylote oxyalkyl ester etc. are for example arranged.
The organic solvent that contains in the surface treatment liquid is so long as dissolve getting final product of isocyanate prepolymer composition and ionic-conductive polymer and these carbon blacks that contain as required, propylene fluorine based polymer and propylene siloxane-based polymers.Organic solvent is not had particular determination, for example can enumerate vinyl acetic monomer, methyl ethyl ketone (MEK), toluene.
This conductive rubber member of the present invention for example is applicable to conductive roll, scraper plate, travelling belt etc.
Followingly according to embodiment the present invention is described, the explanation of these embodiment is an example, and formation of the present invention is not limited to the following description.
Embodiment 1
The manufacturing of＜roller 〉
To 100 parts by weight of epichlorohydrin rubber (エ ピ Network ロ マ one CG-102, グ イ ソ one society's system) adds 0.5 weight part sodium trifluoroacetate in as conductive agent, 3 weight part zinc white, 2 weight part stearic acid, 1.5 weight part vulcanizing agents, (ロ one Le ミ キ サ one) is mixing with the roller mixing tank, under 160 ℃ * 30 minutes cure conditions with it after extrusion forming on the mandrel surface, its outside surface attrition process to predetermined outside diameter, is obtained forming on the mandrel surface roller component of elastic layer thus.
＜modulation surface treatment liquid 〉
In 100 weight part vinyl acetic monomers, add 15 weight part isocyanate compounds (MDI) and 3 parts by weight of epichlorohydrin rubber (エ ピ Network ロ マ one C; グ イ ソ one society's system), mixed dissolution is made surface treatment liquid.
The surface treatment of＜roller 〉
Surface treatment liquid is remained on 23 ℃, and with above-mentioned roller component dipping after 60 seconds, heating is 1 hour in remaining on 120 ℃ baking oven, forms surface-treated layer, makes the conductive roll of embodiment 1.
Embodiment 2
Use ball mill with 100 weight part vinyl acetic monomers, 2 weight part acetylene blacks (electrochemistry society system), 3 parts by weight of epichlorohydrin rubber (エ ピ Network ロ マ one C; グ イ ソ one society's system) dispersing and mixing is after 3 hours, add 15 weight part isocyanate compounds (MDI), mixed dissolution is made surface treatment liquid, forms surface-treated layer on the used roller component with this surface treatment liquid in embodiment 1, makes the conductive roll of embodiment 2.
Embodiment 3
Use ball mill with 100 parts by weight of toluene, 2 weight part acetylene blacks (electrochemistry society system), 8 weight part polyoxyethylene-polyoxytrimethylenes-glycidyl allyl ether terpolymer (ゼ オ ス パ Application 8030, Japan ゼ オ Application society system), 1 weight part propylene siloxane polymer (モ デ イ バ one FS700, Japan grease society system) 1 weight part propylene fluoropolymer (ノ バ Off ッ ソ, big day true qualities material system) dispersing and mixing is after 3 hours, add 10 weight part isocyanate compounds (MDI), mixed dissolution is made surface treatment liquid, in embodiment 1, form surface-treated layer on the used roller component with this treatment solution and embodiment 1 the same ground, make the conductive roll of embodiment 3.
Embodiment 4
The manufacturing of＜roller 〉
In 100 weight parts, add the black #5500 (East Sea カ one ボ Application society system) of 10 weight part ト, one カ, 25 weight part rising sun サ, one マ Le, 1.5 weight part サ Application セ ラ, one TET (three new chemical industry society systems), 1.5 weight part サ Application セ ラ, one CZ (three new chemical industry society systems), 1.0 weight part sulphur in the acrylonitrile butadiene rubber of high nitrile type, mixing with the roller mixing tank, under 160 ℃ * 30 minutes cure conditions after extrusion moulding on the mandrel surface, with the external diameter of outside surface attrition process, obtain on mandrel surface, forming the roller component of elastic layer to regulation.
＜modulation surface treatment liquid 〉
Use ball mill with 100 parts by weight of toluene, 2 parts by weight of epichlorohydrin rubber (エ ピ Network ロ マ one C; グ イ ソ one society's system), the acrylonitrile butadiene rubber of high nitrile type, 1 weight part propylene fluoropolymer (ノ バ Off ッ ソ in 1 weight part, big day true qualities material system) dispersing and mixing is after 3 hours, add 10 weight part isocyanate prepolymers (ア ジ プ レ Application L100, ユ ニ ロ イ ヤ Le society system), mixed dissolution is made surface treatment liquid.Use this treatment solution on above-mentioned roller component, to form surface-treated layer similarly to Example 1, make the conductive roll of embodiment 4.
Embodiment 5
To 100 weight parts is that 3 functional polyethers are interpolation 7 weight part VALCAN XC (キ ャ ボ ッ ト society system) among the MN-3050 (Mitsui military field ケ ミ カ Le society system) of polyvalent alcohol, be dispersed to granularity and reach the following degree of 20 μ m, after the temperature adjustment to 80 ℃, under reduced pressure carry out deaeration, dehydration operation, obtain A liquid.Add 11 weight part コ ロ ネ, one ト C-HX (Japanese Port リ ウ レ Application society system) in addition in 25 weight part prepolymer ア ジ プ レ Application L100 (ユ ニ ロ イ ヤ Le society system), mix, temperature adjustment to 80 ℃ obtains B liquid.Above-mentioned A liquid and B liquid are mixed, under 120 ℃ * 120 minutes cure conditions, after the mandrel surface cast molding, outside surface is carried out attrition process, reach predetermined outside diameter, obtain forming the roller component of elastic layer at mandrel surface.
In embodiment 3, do not add acetylene black, and add 0.5 weight part lithium perchlorate, use this surface treatment liquid on above-mentioned roller component, to form surface-treated layer, make the conductive roll of embodiment 5.
Comparative example 1
In embodiment 2, do not add epichloro hydrin rubber (エ ピ Network ロ マ one C, ダ イ ソ one society's system), carry out surface treatment, make the conductive roll of comparative example 1.
Comparative example 2
In embodiment 1, do not add epichloro hydrin rubber (エ ピ Network ロ マ one C, グ イ ソ one society's system), add 1.0 weight part ammoniumper chlorate and carry out surface treatment, make the conductive roll of comparative example 2.
Comparative example 3
In embodiment 1, do not add isocyanate compound (MDI), add carboxylamine ester paint (ネ オ レ ッ Star R-940, nanmu originally changes into society's system), form the overlay of 30 μ m, make the conductive roll of comparative example 3.
Comparative example 4
In embodiment 4, do not add epichloro hydrin rubber (エ ピ Network ロ マ one C, グ イ ソ one society's system) and in the acrylonitrile butadiene rubber of high nitrile type, carry out surface treatment, make the conductive roll of comparative example 4.
Comparative example 5
In embodiment 5, do not add polyoxyethylene-polyoxytrimethylene-glycidyl allyl ether terpolymer (ゼ オ ス パ Application 8030, Japanese ゼ オ Application society system), carry out surface treatment, make the conductive roll of comparative example 5.
(test example 1) resistance measurement
Measure the resistance value of the conductive roll of each embodiment and each comparative example.As shown in Figure 2, conductive roll 10 is positioned on the electrode member 40 that comprises the SUS304 plate, apply the 100g load to the two ends of plug 11, under this state, (N/N:20 ℃ * 50%RH) use ultra-high resistance survey meter (ULTRA HIGH RESISTANCE METER) R8340A (ア of Co., Ltd. De バ Application テ ス ト system) to measure resistance value between plug 11 and the electrode member 40 of ambient temperature and moisture environment.The voltage that apply this moment is DC-100V, the results are shown in table 1 and table 2.
(test example 2) picture appraisal
With the conductive roll of embodiment 1～4 and comparative example 1～4 as charged roller, with the conductive roll of embodiment 5 and comparative example 5 as developer roll, be installed in (MICROLINE9600PS on the commercially available printer, Co., Ltd. is towards デ one system), (10 ℃ of LL environment, 30%RH), the NN environment (25 ℃, 50%RH) He under the HH environment (35 ℃, 85%RH) print, estimate the image of this print.Image is evaluated as zero when good, image is evaluated as △ when bad a little, be evaluated as when image is bad *.So-called " image is bad " is meant the state of finding to have density unevenness or deterioration etc.This results are shown in following table 1 and table 2.
(test example 3) OPC test for contamination
With the conductive roll of embodiment 1～4 and each comparative example 1～4 as charged roller, the conductive roll of embodiment 5 and comparative example 5 is as developer roll, be assembled on the toner cartridge (toner cartridge) of commercially available laser printer, squeeze with 500gf contacts with photoreceptor, each box is assembled in output image on the printer with box and each conductive roll keep 14 days in 50 ℃, the environment of 90%RH after.Estimate the image of this moment.Image is evaluated as zero when good, image is evaluated as △ when bad a little, be evaluated as when image is bad *.Said " image is bad " is meant the state of finding to have density unevenness or deterioration etc.With the OPC of microscopic examination contact and the surface of conductive roll.The results are shown in following table 1 and table 2.
(test example 4) printing test continuously
With the conductive roll of embodiment 1～4 and comparative example 1～4 as charged roller, the conductive roll of embodiment 5 and comparative example 5 is as developing roll, be installed on the commercially available laser printer, (35 ℃ of HH environment, after printing 10000 continuously 85%RH), under the LL environment, print, estimate the image of this print.The results are shown in table 1 and table 2.What image was good is evaluated as zero, and image is bad a little is evaluated as △, and image is bad is evaluated as *.Said " image is bad " is meant the state of finding to have density unevenness, deterioration etc.
Utilize and the resistance value of testing after example 1 identical method mensuration is printed 10000 continuously, the results are shown in following table 1 and the table 2.
Table 1
Table 2
The result sums up
As shown in table 1, will in surface treatment liquid, be dissolved with epichloro hydrin rubber embodiment 1, and with the embodiment 2 of carbon, use the conductive roll of the embodiment 3 of polyoxyethylene-polyoxytrimethylene-glycidyl allyl ether terpolymer under various environment, all to obtain evaluation well as the print image of charged roller printing.In the OPC test for contamination, the condition of surface on OPC surface and charged roller surface is all good, and the image of print might as well.Further, print the print image of test continuously, the resistance value and the resistance value at initial stage after printing is tested continuously relatively do not have big variation.That is: the resistance value of the conductive roll of embodiment 1～3 is stable.
Relative therewith, the conductive roll of comparative example 1 is used as the print image that charged roller is printed, the evaluation that the print image that prints in NN, HH environment obtains, but in the LL environment, discovery has the deep or light point that is caused by the resistance value deviation, obtains bad evaluation.Think that in the LL environment, the resistance value of charged roller increases, and show the deviation of the resistance value that the dispersion state by carbon black causes.In the OPC test for contamination, to slight crimping vestige, the image of print obtains bad a little evaluation at the roller surface observation.Resistance value after the printing test is compared with the resistance value at initial stage greatly and is raise continuously, causes the result of print image degradation.
On the other hand, the evaluation that the conductive roll of comparative example 2 is obtained in the NN environment as the print image of charged roller printing, but in the LL environment, obtain bad a little evaluation, in the HH environment, obtain bad evaluation.Think that this is owing to all used ionic conductive agent in rubber substrate and surface treatment liquid, in these two kinds of environment, the influence of the moisture significant result that becomes.In the OPC test for contamination, the pollution that caused by ionic conductive agent has all been found to think in OPC surface and roller surface, has also found the surperficial slight crimping vestige of roller, and the print image obtains bad evaluation.In printing was tested continuously, being evaluated as of print image was bad.
To use urethane resin to replace isocyanate compound, and the conductive roll of comparative example 3 that overlay is set with the mixture of itself and epichloro hydrin rubber is as the printed print image of charged roller, in test example 2, all obtain good result in the various environment, but printing test back (test example 4) obtains bad evaluation continuously.Find that roller fold occurred on the surface when charged roller surface is observed in the printing back continuously.Think this be owing to overlay and rubber layer to the tracing ability of displacement is different cause that stress is in its set of surfaces due to.Hence one can see that is provided with the importance of surface-treated layer.In the OPC test for contamination, do not find that the OPC surface is contaminated, but found some crimping vestiges that the evaluation of print image is bad a little on the charged roller surface.
To be rubber substrate with NBR, and the conductive roll of embodiment 4 that has dissolved epichloro hydrin rubber and NBR in the surface treatment liquid be as charged roller, the evaluation that printed print image all obtains in various environment in test example 2.In the OPC test for contamination, the condition of surface of OPC surface and charged roller is all good, and the image of print might as well.The print image of printing test might as well continuously.
The conductive roll that does not dissolve the comparative example 4 of epichloro hydrin rubber and NBR in the surface treatment liquid is used as the printed print image of charged roller, the evaluation that all obtains in the various environment in test example 2, but in printing is tested continuously,, obtain bad a little evaluation because of resistance value raises.Think that this is that the conductive path of skin section has produced due to the deviation owing to roller skin section repeated deformation.In the OPC test for contamination, the condition of surface on OPC surface and charged roller surface is all good, and the image of print might as well.
To with the carbamate rubber substrate, and the conductive roll that has dissolved the embodiment 5 of polyoxyethylene-polyoxytrimethylene-glycidyl allyl ether terpolymer in the surface treatment liquid is used as developer roll, the evaluation that printed print image all obtains in various environment.In the OPC test for contamination, the condition of surface on OPC surface and charged roller surface is all good, and the image of print might as well.The print image of printing test might as well continuously.
The conductive roll that does not have the comparative example 5 of dissolving polyoxyethylene-polyoxytrimethylene-glycidyl allyl ether terpolymer in the surface treatment liquid is used as the print image of developer roll printing, though the evaluation that in the various environment of test example 2, all obtains, but in printing is tested continuously, resistance value raises, and is evaluated as bad a little.The same with the conductive roll of comparative example 4, think that owing to roller skin section repeated deformation, the conductive path of top layer part produces due to the deviation.In the OPC test for contamination, not find to pollute, but find some crimping vestiges on the roller surface, being evaluated as of print image is bad a little.
As from the foregoing, conductive rubber member of the present invention, little by in surface treatment liquid, cooperating isocyanate prepolymer composition and ionic-conductive polymer to obtain environmental factor dependence, even the also stable conductive rubber member of roller skin section repeated deformation resistance value.
Claims (6)
1. conductive rubber member, it is characterized in that comprising by electroconductibility and pay the conductive elastic layer that material has been paid electroconductibility, the surface treatment liquid that contains isocyanate prepolymer composition and ionic-conductive polymer by the skin section impregnation at above-mentioned conductive elastic layer forms surface-treated layer.
2. the described conductive rubber member of claim 1 is characterized in that above-mentioned surface treatment liquid contains organic solvent, and above-mentioned organic solvent dissolution above-mentioned isocyanate prepolymer composition and above-mentioned ionic-conductive polymer.
3. claim 1 or 2 described conductive rubber members is characterized in that above-mentioned ionic-conductive polymer is to be selected from least a in epichloro hydrin rubber, acrylonitrile butadiene rubber and the oxyalkylene.
4. the described conductive rubber member of claim 1 is characterized in that above-mentioned surface treatment liquid contains carbon black.
5. the described conductive rubber member of claim 1 is characterized in that above-mentioned conductive elastic layer comprises rubber substrate, and described rubber substrate contains epichloro hydrin rubber.
6. the described conductive rubber member of claim 1, it is characterized in that above-mentioned conductive rubber member be the roller shape, scrape tabular or banded.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007098797 | 2007-04-04 | ||
| JP2007098797 | 2007-04-04 | ||
| JP2008095724 | 2008-04-02 |
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| Publication Number | Publication Date |
|---|---|
| CN101333301A true CN101333301A (en) | 2008-12-31 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2008100963672A Pending CN101333301A (en) | 2007-04-04 | 2008-04-07 | Conductive rubber member |
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| Country | Link |
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| JP (1) | JP5190876B2 (en) |
| CN (1) | CN101333301A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102279547A (en) * | 2010-06-14 | 2011-12-14 | 柯尼卡美能达商用科技株式会社 | Intermediate transfer belt and image-forming apparatus |
| CN105372962A (en) * | 2014-08-08 | 2016-03-02 | 住友橡胶工业株式会社 | Electroconductive roller, and image forming apparatus |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5570208B2 (en) * | 2009-12-28 | 2014-08-13 | キヤノン株式会社 | Image forming apparatus and intermediate transfer belt manufacturing method |
| JP5937481B2 (en) * | 2012-10-03 | 2016-06-22 | バンドー化学株式会社 | Conductive roller for electrophotographic apparatus |
| JP7414469B2 (en) * | 2018-11-26 | 2024-01-16 | キヤノン株式会社 | Developing members, process cartridges, and electrophotographic image forming devices |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3731734B2 (en) * | 2000-05-16 | 2006-01-05 | 北辰工業株式会社 | Charging member |
| JP4144701B2 (en) * | 2003-03-14 | 2008-09-03 | シンジーテック株式会社 | Charging roll |
| JP2006039394A (en) * | 2004-07-29 | 2006-02-09 | Canon Chemicals Inc | Conductive roller |
| JP5213004B2 (en) * | 2005-06-20 | 2013-06-19 | シンジーテック株式会社 | Conductive rubber member and manufacturing method thereof |
| JP5093793B2 (en) * | 2005-07-08 | 2012-12-12 | シンジーテック株式会社 | Rubber member |
| 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 |
-
2008
- 2008-04-02 JP JP2008095724A patent/JP5190876B2/en not_active Expired - Fee Related
- 2008-04-07 CN CNA2008100963672A patent/CN101333301A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102279547A (en) * | 2010-06-14 | 2011-12-14 | 柯尼卡美能达商用科技株式会社 | Intermediate transfer belt and image-forming apparatus |
| CN102279547B (en) * | 2010-06-14 | 2014-12-31 | 柯尼卡美能达商用科技株式会社 | Intermediate transfer belt and image-forming apparatus |
| CN105372962A (en) * | 2014-08-08 | 2016-03-02 | 住友橡胶工业株式会社 | Electroconductive roller, and image forming apparatus |
| CN105372962B (en) * | 2014-08-08 | 2021-02-12 | 住友橡胶工业株式会社 | Conductive roller and image forming apparatus |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2008274262A (en) | 2008-11-13 |
| JP5190876B2 (en) | 2013-04-24 |
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Application publication date: 20081231 |