CN109280394A - A kind of semi-conductive silicone rubber roller material of high repeated charge and preparation method thereof - Google Patents
A kind of semi-conductive silicone rubber roller material of high repeated charge and preparation method thereof Download PDFInfo
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- 229920002379 silicone rubber Polymers 0.000 title claims abstract description 112
- 239000004945 silicone rubber Substances 0.000 title claims abstract description 103
- 239000000463 material Substances 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- HIHIPCDUFKZOSL-UHFFFAOYSA-N ethenyl(methyl)silicon Chemical compound C[Si]C=C HIHIPCDUFKZOSL-UHFFFAOYSA-N 0.000 claims abstract description 51
- 229920002943 EPDM rubber Polymers 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 9
- 239000006229 carbon black Substances 0.000 claims description 124
- 239000002253 acid Substances 0.000 claims description 49
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 48
- 239000000203 mixture Substances 0.000 claims description 48
- 229910021389 graphene Inorganic materials 0.000 claims description 45
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 44
- 238000000034 method Methods 0.000 claims description 29
- 230000020477 pH reduction Effects 0.000 claims description 28
- 239000006258 conductive agent Substances 0.000 claims description 27
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 26
- 229910017604 nitric acid Inorganic materials 0.000 claims description 26
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 21
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 21
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 21
- 150000001721 carbon Chemical class 0.000 claims description 16
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 12
- 229960004756 ethanol Drugs 0.000 claims description 10
- 235000019441 ethanol Nutrition 0.000 claims description 10
- 238000012986 modification Methods 0.000 claims description 7
- 230000004048 modification Effects 0.000 claims description 7
- 238000000498 ball milling Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- 239000013049 sediment Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 3
- 239000005977 Ethylene Substances 0.000 claims description 2
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims 2
- 240000007594 Oryza sativa Species 0.000 claims 1
- 235000007164 Oryza sativa Nutrition 0.000 claims 1
- 150000001336 alkenes Chemical class 0.000 claims 1
- 229910002804 graphite Inorganic materials 0.000 claims 1
- 239000010439 graphite Substances 0.000 claims 1
- 235000009566 rice Nutrition 0.000 claims 1
- 239000004408 titanium dioxide Substances 0.000 claims 1
- 238000007639 printing Methods 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 8
- 239000004065 semiconductor Substances 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 239000002131 composite material Substances 0.000 abstract description 3
- 229920001971 elastomer Polymers 0.000 description 23
- 239000005060 rubber Substances 0.000 description 23
- 239000003795 chemical substances by application Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 13
- 238000012360 testing method Methods 0.000 description 11
- 230000008569 process Effects 0.000 description 9
- 238000012545 processing Methods 0.000 description 8
- 230000008859 change Effects 0.000 description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 239000005864 Sulphur Substances 0.000 description 5
- 230000007246 mechanism Effects 0.000 description 5
- 239000004020 conductor Substances 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000000428 dust Substances 0.000 description 3
- 229920005558 epichlorohydrin rubber Polymers 0.000 description 3
- 239000004902 Softening Agent Substances 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000009434 installation Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 241000272525 Anas platyrhynchos Species 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
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- 239000012212 insulator Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
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- 238000006386 neutralization reaction Methods 0.000 description 1
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- 238000007670 refining Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
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- 230000006641 stabilisation Effects 0.000 description 1
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- 231100000419 toxicity Toxicity 0.000 description 1
- -1 vinylsiloxane Chemical class 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/16—Ethene-propene or ethene-propene-diene copolymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2383/04—Polysiloxanes
- C08J2383/07—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/16—Ethene-propene or ethene-propene-diene copolymers
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/001—Conductive additives
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
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Abstract
The present invention relates to semiconductive technical field of composite preparation, specifically disclose a kind of semi-conductive silicone rubber roller material and preparation method thereof of high repeated charge.The semi-conductive silicone rubber roller material of the high repeated charge is made of the raw material comprising following parts by weight: 50~90 parts of methyl vinyl silicone rubber；10~50 parts of ethylene propylene diene rubber；8~15 parts of conductive agglomerate A；5~12 parts of conductive agglomerate B；1~5 part of crosslinking agent.The volume resistivity of the semi-conductive silicone rubber roller material is in 0.42*104~0.88*104Ω cm is in semiconductor regions (i.e. about 105~109Ω cm) range, and its resistance is sufficiently stable, under hot and humid environment, does not ooze out the chemical substance of pollution photosensitive drums；In addition, the file printing durability is good, stable image output effect and permanent service life can guarantee.
Description
Technical field
The present invention relates to semiconductive technical field of composite preparation, and in particular to a kind of high repeated charge is partly led
Electric silica gel roller cylinder material and preparation method thereof.
Background technique
In recent years, it is set using offices such as the laser printer, laser integrated machines of electron image (electrofax) image-forming principle
It is standby to have obtained large-scale popularization and application.The semiconductives such as charging roller (PCR), developer roll (DVR), transfer roll, clearer, transfer belt
Rubber manufactured goods are cooperated with photosensitive drums, carbon dust, magnetic roller as key components and parts, constitute commonly known as " toner cartridge "
Drum powder box.
Since charging roller, developer roll are directly contacted with photosensitive drums, preciousness specific to the rubber material in polymer material
Elasticity makes it become only choosing.In order to restore the image of clear exquisiteness, charging roller, developer roll volume resistivity be in half
Conductive region (i.e. about 105~109Ω cm) range, and the variation degree of resistance is the smaller the better, it is smaller to show that material property is steady
It is fixed.
The electrically conducting manner of rubber material is broadly divided into two major classes, and one kind is Ionic conductivity, another kind of to lead for electron type
Electricity.
Ionic conductivity rubber carries out conduction by the ion coordination of high probability, since this is from certain types of rubber
The characteristic that material itself has, electric conductivity is naturally relatively stable, and external alive correlation is also weaker, is currently
The mainstream electrically conducting manner of electron image imaging device.Such as representative epichlorohydrin rubber (epichlorohydrin rubber), volume electricity
Resistance rate is inherently 107~1010Ω cm range, commercialization is universal rapidly in recent years.In general ion can also be added to lead
Electric agent adjusts resistivity.In order to improve certain disadvantages of ionic conduction rubber, have been developed based on ionic conduction rubber, then mix
Close the way of the dual electrically conducting manner of electronic conductive material (such as conductive black).But ionic conduction rubber substrate is right first
Water has natural compatibility, is easy to wet, and surface adhesion degree rises, to adhere to carbon dust and its additive, seriously affects
Print quality.Secondly, especially sensitive to humidity variation, the variation degree of resistance is very big, and material property is unstable.
Third, ionic conductive agent is easy to happen surface migration, photosensitive drums are contaminated.Representative epichlorohydrin rubber is vulcanizing
Acid product can be also generated in reaction, it is necessary to acid absorbent neutralization be added, in order to adjust rubber hardness, the use of softening agent is also compared
Generally.The chemical complexing agent for participating in reaction is numerous, such as: vulcanizing agent, acid absorbent, softening agent, anti-aging agent, is prevented vulcanization accelerator
Burnt agent etc..The dedicated chemical complexing agent in part has a degree of toxicity to environment and human body.
Electronic conduction rubber is exactly the material that electronic conduction type is added to ionic conductivity rubber clone, so that rubber obtains
Obtain electric conductivity.Most of rubber almost insulate or semi-insulating, due to the limitation of electronic image system image-forming principle, should not use
Metal class conductive material, so, in fact conductive carbon black is the preferred electronic conductive material being particularly suitable for.In comparative maturity
Conduction field (volume resistivity about 10 completely-3~103Ω cm), have been carried out for conductive carbon black largely has for a long time
Effect research, but the method that these researchs are related to simply can not directly be diverted to semiconductive field, because of the conduction of the two
Mechanism has marked difference, and semiconductive field question is complicated and sensitive.Simple says, complete conduction generally requires that big component is added
The conductive carbon black of (more than tens of parts) obtains very high distributed density, and electrical conduction mechanism belongs to " closely to be connect between conducting particles
Touching forms conductive channel ".Semiconductive then needs to be added the conductive carbon black of appropriate component, component more to a certain degree, conductive machine
Reason tendency " contact is conductive "；Component is few to a certain extent, electrical conduction mechanism then tend to quantum mechanics scope " electron tunnel is worn
More, electron channel is formed "；Reducing again is exactly insulator " non-conductive ".Since semiconductor regions electrical conduction mechanism is complicated, mutual shadow
It rings, within this range, volume resistivity can occur six, seven the huge of the order of magnitude and be widely varied.Following factors can half-and-half be led
Volume resistivity in electric range affects: the fine difference (due to weighing difference or dust collector) of carbon black loading, carbon black
Structural damage (in refining glue process, structure caused by by shearing force is destroyed) degree is inconsistent, and carbon black is in sizing material
Middle bad or even material charge number the difference of dispersion also brings along fluctuation.So the variation degree that obtain resistance is small, performance is steady
Fixed material not a duck soup, in addition electrical conduction mechanism is complicated, the lifting of applied voltage will lead to the variation conversion of conductive path, with
And the factors such as durability dielectric loss are also not easily solved so that significant change occurs therewith for volume resistivity.
In addition, charging roller, developer roll are after undergoing a large amount of practical print jobs, the variation degree that resistance is lost is smaller
It is better, show that material property is stablized.Stable resistance band comes stable image output effect and permanent service life.
Summary of the invention
The technical problem to be solved by the invention is to provide a kind of semi-conductive silicone rubber roller materials of high repeated charge
Material and preparation method thereof.The semi-conductive silicone rubber roller material property is stablized, especially after being used for multiple times, resistance
Variation degree is small.
Above-mentioned technical problem to be solved by this invention, is achieved by following technical solution:
A kind of semi-conductive silicone rubber roller material of high repeated charge, is made of the raw material comprising following parts by weight:
50~90 parts of methyl vinyl silicone rubber；10~50 parts of ethylene propylene diene rubber；8~15 parts of conductive agglomerate A；It is conductive
5~12 parts of mother particle B；1~5 part of crosslinking agent.
Preferably, the semi-conductive silicone rubber roller material of the high repeated charge, by including following parts by weight
Raw material is made:
60~80 parts of methyl vinyl silicone rubber；20~40 parts of ethylene propylene diene rubber；10~12 parts of conductive agglomerate A；It is conductive
8~10 parts of mother particle B；1~5 part of crosslinking agent.
It is further preferred that the semi-conductive silicone rubber roller material of the high repeated charge, by comprising weighing as follows
The raw material of amount part is made:
80 parts of methyl vinyl silicone rubber；20 parts of ethylene propylene diene rubber；10~12 parts of A of conductive agglomerate A conductive agglomerate；It leads
8~10 parts of electric mother particle B；1~5 part of crosslinking agent.
Preferably, conductive agglomerate A is prepared by the inclusion of the method for following steps:
(1) preparation of conductive agent: the mixed acid that carbon black and graphene mixing are placed on the concentrated sulfuric acid and concentrated nitric acid composition is molten
In liquid, 5~10h of back flow reaction, carbon black and graphene mixture after must being acidified after washing is dry are carried out at 70~90 DEG C；It connects
By after acidification carbon black and graphene mixture be scattered in dehydrated alcohol, be then added n-octyl amine, heating reflux reaction 8~
16h is filtered, washed sediment and is dried to get the conductive agent；
(2) up to conductive agglomerate after the conductive agent that step (1) is prepared and methyl vinyl silicone rubber melt blending；
Wherein, the weight ratio of carbon black and graphene is 3~5:1 in step (1), the total weight of carbon black and graphene with mix
The amount ratio of acid solution is 1g:20~50mL, and the volume ratio of the concentrated sulfuric acid and concentrated nitric acid is 1~3:1~3 in mixed acid solution；Acid
The amount ratio of carbon black and graphene mixture and dehydrated alcohol after change is 1:10~20mL；Carbon black and graphene after acidification is mixed
The weight consumption ratio for closing object and n-octyl amine is 1:1~2；
The weight consumption of conductive agent and methyl vinyl silicone rubber ratio is 1:1~3 in step (2).
It is further preferred that the amount ratio of carbon black and graphene mixture and dehydrated alcohol in step (1) after acidification is
1:12mL；The weight consumption ratio of carbon black and graphene mixture and n-octyl amine after acidification is 1:1.5.
It is further preferred that the weight consumption of conductive agent and methyl vinyl silicone rubber ratio is 1:2 in step (2).
Preferably, the conductive agglomerate B is prepared by the inclusion of the method for following steps:
(1) preparation of modified carbon black: carbon black is placed in the mixed acid solution of the concentrated sulfuric acid and concentrated nitric acid composition, 70~90
5~10h of back flow reaction is carried out at DEG C, must be acidified carbon black after washing is dry；Then acidification carbon black is mixed with nano-titanium dioxide
It is placed on progress 4~6h of ball milling in dehydrated alcohol, is modified carbon black to obtain the final product after removing ethyl alcohol drying；
(2) up to conductive female after the modification carbon black that step (1) is prepared and methyl vinyl silicone rubber melt blending
Grain；
Wherein, the amount ratio of carbon black and mixed acid solution is 1g:20~50mL, dense sulphur in mixed acid solution in step (1)
The volume ratio of acid and concentrated nitric acid is 1~3:1~3；The weight ratio for being acidified carbon black and nano-titanium dioxide is 1:1~3；It is acidified carbon black
It is 1g:8~20mL with the total weight of nano-titanium dioxide and the amount ratio of dehydrated alcohol；Modified carbon black and methyl in step (2)
The weight ratio of vinylsiloxane rubber is 1:1~3.
It is further preferred that the amount ratio of carbon black and mixed acid solution is 1g:20~30mL in step (1), mixed acid is molten
The volume ratio of the concentrated sulfuric acid and concentrated nitric acid is 1:2 in liquid；The weight ratio of acidification carbon black and nano-titanium dioxide is 1:1 in step (1)；
The amount ratio of the total weight and dehydrated alcohol that are acidified carbon black and nano-titanium dioxide is 1g:10~15mL.
It is further preferred that the weight ratio of modified carbon black and methyl vinyl silicone rubber is 1:2 in step (2).
The present invention also provides a kind of preparation method of the semi-conductive silicone rubber roller material of high repeated charge, it includes
Following steps:
Methyl vinyl silicone rubber, ethylene propylene diene rubber, conductive agglomerate A, conductive agglomerate B and crosslinking agent are placed in double roller
The uniformly semi-conductive silicone rubber roller material up to the high repeated charge is kneaded in open mill or rotor mixer.
Preferably, 3 times or more thin logical processing are carried out in mixing process.
The utility model has the advantages that (1) the present invention provides a kind of conductive silicon rubber roller materials of high repeated charge；Described
The volume resistivity of conductive silicon rubber roller material is in 0.42*104~0.88*104Ω cm is in semiconductor regions (i.e. about 105
~109Ω cm) range；(2) the conductive silicon rubber roller material of the high repeated charge described in ethylene propylene diene rubber and
Methyl vinyl silicone rubber can make the condition that " electron tunnel passes through " occurs between conductive black can be more wide as substrate
Pine is conducive to " electron tunnel passes through, and forms electron channel " and realizes conduction in other words；(3) conductive black of the present invention
The method is used to prepare conductive silicon rubber roller composites after being prepared into conductive agglomerate through the invention, relative to it
His mode, on the one hand can further decrease volume resistivity；On the other hand its resistance is sufficiently stable, embodiment it is demonstrated experimentally that
Its R250Relative to R500Variation degree and R1000Relative to R500Variation degree from the point of view of, in 8~25% ranges；It is much small
In other modes；(4) conductive agglomerate A and conductive agglomerate B is prepared by two kinds of method of modifying in electric carbon black of the present invention,
Volume resistivity, printing when combining form by the way that conductive agglomerate A and B is added can cooperate with raising to be used alone after being added is durable
Property, for resistance variations degree less than 25%, performance is very superior after printing 20000 times, this explanation performance after multiple charge and discharge
Variation less, to ensure that image output effect after a large amount of printings, substantially increases the service life of material；(4) in addition,
The conductive silicon rubber roller material of high repeated charge of the present invention does not ooze out pollution sense under hot and humid environment
The chemical substance of light drum.
Specific embodiment
The present invention is explained further below in conjunction with specific embodiment, but embodiment does not do any type of limit to the present invention
It is fixed.
The preparation of the semi-conductive silicone rubber roller material of the high repeated charge of embodiment 1
Parts by weight of raw materials composition: 80 parts of methyl vinyl silicone rubber；20 parts of ethylene propylene diene rubber；12 parts of conductive agglomerate A；
8 parts of conductive agglomerate B；3 parts of crosslink agent DCP；
The conductive agglomerate A is prepared via a method which to obtain: (1) preparation of conductive agent: carbon black and graphene are mixed
It is placed in the mixed acid solution of the concentrated sulfuric acid and concentrated nitric acid composition, back flow reaction 6h is carried out at 80 DEG C, is obtained after washing is dry sour
Carbon black and graphene mixture after change；Then by after acidification carbon black and graphene mixture be scattered in dehydrated alcohol, so
After n-octyl amine is added, heating reflux reaction 12h is filtered, washed sediment and is dried to get the conductive agent；(2) will
Up to conductive agglomerate after conductive agent and methyl vinyl silicone rubber melt blending that step (1) is prepared；Wherein, step (1)
The weight ratio of middle carbon black and graphene is 4:1, and the amount ratio of the total weight and mixed acid solution of carbon black and graphene is 1g:
30mL, the volume ratio of the concentrated sulfuric acid and concentrated nitric acid is 1:3 in mixed acid solution；Carbon black and graphene mixture after acidification with it is anhydrous
The amount ratio of ethyl alcohol is 1:12mL；The weight consumption ratio of carbon black and graphene mixture and n-octyl amine after acidification is 1:1.5；Step
Suddenly the weight consumption of conductive agent and methyl vinyl silicone rubber ratio is 1:2 in (2)；
The conductive agglomerate B is prepared via a method which to obtain: (1) carbon black the preparation of modified carbon black: being placed in dense sulphur
In the mixed acid solution of acid and concentrated nitric acid composition, back flow reaction 6h is carried out at 80 DEG C, must be acidified carbon black after washing is dry；Then
Acidification carbon black is mixed with nano-titanium dioxide and is placed on progress ball milling 5h in dehydrated alcohol, up to modified after removing ethyl alcohol is dry
Carbon black；(2) up to conductive agglomerate after the modification carbon black that step (1) is prepared and methyl vinyl silicone rubber melt blending；
Wherein, the amount ratio of carbon black and mixed acid solution is 1g:25mL in step (1), the concentrated sulfuric acid and concentrated nitric acid in mixed acid solution
Volume ratio is 1:2；The weight ratio for being acidified carbon black and nano-titanium dioxide is 1:1；It is acidified the gross weight of carbon black and nano-titanium dioxide
The amount ratio of amount and dehydrated alcohol is 1g:15mL；The weight ratio of modified carbon black and methyl vinyl silicone rubber is 1 in step (2):
2；
The preparation method of the semi-conductive silicone rubber roller material of high repeated charge: by methyl vinyl silicone rubber, three
First EP rubbers, conductive agglomerate A, conductive agglomerate B and crosslink agent DCP, which are placed in two-roll mill, to be kneaded uniformly up to described
Semi-conductive silicone rubber roller material；It is sufficiently mixed to realize, 3 times thin logical processing is carried out in mixing process.
The preparation of the semi-conductive silicone rubber roller material of the high repeated charge of embodiment 2
Parts by weight of raw materials composition: 60 parts of methyl vinyl silicone rubber；40 parts of ethylene propylene diene rubber；15 parts of conductive agglomerate A；
5 parts of conductive agglomerate B；1 part of crosslink agent DCP；
The conductive agglomerate A is prepared via a method which to obtain: (1) preparation of conductive agent: carbon black and graphene are mixed
It is placed in the mixed acid solution of the concentrated sulfuric acid and concentrated nitric acid composition, back flow reaction 5h is carried out at 90 DEG C, is obtained after washing is dry sour
Carbon black and graphene mixture after change；Then by after acidification carbon black and graphene mixture be scattered in dehydrated alcohol, so
After n-octyl amine is added, heating reflux reaction 15h is filtered, washed sediment and is dried to get the conductive agent；(2) will
Up to conductive agglomerate after conductive agent and methyl vinyl silicone rubber melt blending that step (1) is prepared；Wherein, step (1)
The weight ratio of middle carbon black and graphene is 3:1, and the amount ratio of the total weight and mixed acid solution of carbon black and graphene is 1g:
20mL, the volume ratio of the concentrated sulfuric acid and concentrated nitric acid is 1:3 in mixed acid solution；Carbon black and graphene mixture after acidification with it is anhydrous
The amount ratio of ethyl alcohol is 1:10mL；The weight consumption ratio of carbon black and graphene mixture and n-octyl amine after acidification is 1:1；Step
(2) weight consumption of conductive agent and methyl vinyl silicone rubber ratio is 1:2 in；
The conductive agglomerate B is prepared via a method which to obtain: (1) carbon black the preparation of modified carbon black: being placed in dense sulphur
In the mixed acid solution of acid and concentrated nitric acid composition, back flow reaction 8h is carried out at 70 DEG C, must be acidified carbon black after washing is dry；Then
Acidification carbon black is mixed with nano-titanium dioxide and is placed on progress ball milling 6h in dehydrated alcohol, up to modified after removing ethyl alcohol is dry
Carbon black；(2) up to conductive agglomerate after the modification carbon black that step (1) is prepared and methyl vinyl silicone rubber melt blending；
Wherein, the amount ratio of carbon black and mixed acid solution is 1g:20mL in step (1), the concentrated sulfuric acid and concentrated nitric acid in mixed acid solution
Volume ratio is 1:3；The weight ratio for being acidified carbon black and nano-titanium dioxide is 1:1；It is acidified the gross weight of carbon black and nano-titanium dioxide
The amount ratio of amount and dehydrated alcohol is 1g:18mL；The weight ratio of modified carbon black and methyl vinyl silicone rubber is 1 in step (2):
3；
The preparation method of the semi-conductive silicone rubber roller material of high repeated charge: by methyl vinyl silicone rubber, three
First EP rubbers, conductive agglomerate A, conductive agglomerate B and crosslink agent DCP, which are placed in two-roll mill, to be kneaded uniformly up to described
Semi-conductive silicone rubber roller material；It is sufficiently mixed to realize, 3 times thin logical processing is carried out in mixing process.
The preparation of the semi-conductive silicone rubber roller material of the high repeated charge of embodiment 3
Parts by weight of raw materials composition: 50 parts of methyl vinyl silicone rubber；50 parts of ethylene propylene diene rubber；10 parts of conductive agglomerate A；
10 parts of conductive agglomerate B；5 parts of crosslink agent DCP；
The conductive agglomerate A is prepared via a method which to obtain: (1) preparation of conductive agent: carbon black and graphene are mixed
It is placed in the mixed acid solution of the concentrated sulfuric acid and concentrated nitric acid composition, back flow reaction 6h is carried out at 80 DEG C, is obtained after washing is dry sour
Carbon black and graphene mixture after change；Then by after acidification carbon black and graphene mixture be scattered in dehydrated alcohol, so
After n-octyl amine is added, heating reflux reaction 10h is filtered, washed sediment and is dried to get the conductive agent；(2) will
Up to conductive agglomerate after conductive agent and methyl vinyl silicone rubber melt blending that step (1) is prepared；Wherein, step (1)
The weight ratio of middle carbon black and graphene is 5:1, and the amount ratio of the total weight and mixed acid solution of carbon black and graphene is 1g:
20mL, the volume ratio of the concentrated sulfuric acid and concentrated nitric acid is 1:1 in mixed acid solution；Carbon black and graphene mixture after acidification with it is anhydrous
The amount ratio of ethyl alcohol is 1:15mL；The weight consumption ratio of carbon black and graphene mixture and n-octyl amine after acidification is 1:2；Step
(2) weight consumption of conductive agent and methyl vinyl silicone rubber ratio is 1:2 in；
The conductive agglomerate B is prepared via a method which to obtain: (1) carbon black the preparation of modified carbon black: being placed in dense sulphur
In the mixed acid solution of acid and concentrated nitric acid composition, back flow reaction 5h is carried out at 90 DEG C, must be acidified carbon black after washing is dry；Then
Acidification carbon black is mixed with nano-titanium dioxide and is placed on progress ball milling 8h in dehydrated alcohol, up to modified after removing ethyl alcohol is dry
Carbon black；(2) up to conductive agglomerate after the modification carbon black that step (1) is prepared and methyl vinyl silicone rubber melt blending；
Wherein, the amount ratio of carbon black and mixed acid solution is 1g:20mL in step (1), the concentrated sulfuric acid and concentrated nitric acid in mixed acid solution
Volume ratio is 2:1；The weight ratio for being acidified carbon black and nano-titanium dioxide is 1:2；It is acidified the gross weight of carbon black and nano-titanium dioxide
The amount ratio of amount and dehydrated alcohol is 1g:10mL；The weight ratio of modified carbon black and methyl vinyl silicone rubber is 1 in step (2):
3；
The preparation method of the semi-conductive silicone rubber roller material of high repeated charge: by methyl vinyl silicone rubber, three
First EP rubbers, conductive agglomerate A, conductive agglomerate B and crosslink agent DCP, which are placed in two-roll mill, to be kneaded uniformly up to described
Semi-conductive silicone rubber roller material；It is sufficiently mixed to realize, 3 times thin logical processing is carried out in mixing process.
The preparation of 1 semi-conductive silicone rubber roller material of comparative example
Parts by weight of raw materials composition: 80 parts of methyl vinyl silicone rubber；20 parts of ethylene propylene diene rubber；20 parts of conductive agglomerate A；
3 parts of crosslink agent DCP；
The conductive agglomerate A is prepared via a method which to obtain: (1) preparation of conductive agent: carbon black and graphene are mixed
It is placed in the mixed acid solution of the concentrated sulfuric acid and concentrated nitric acid composition, back flow reaction 6h is carried out at 80 DEG C, is obtained after washing is dry sour
Carbon black and graphene mixture after change；Then by after acidification carbon black and graphene mixture be scattered in dehydrated alcohol, so
After n-octyl amine is added, heating reflux reaction 12h is filtered, washed sediment and is dried to get the conductive agent；(2) will
Up to conductive agglomerate after conductive agent and methyl vinyl silicone rubber melt blending that step (1) is prepared；Wherein, step (1)
The weight ratio of middle carbon black and graphene is 4:1, and the amount ratio of the total weight and mixed acid solution of carbon black and graphene is 1g:
30mL, the volume ratio of the concentrated sulfuric acid and concentrated nitric acid is 1:3 in mixed acid solution；Carbon black and graphene mixture after acidification with it is anhydrous
The amount ratio of ethyl alcohol is 1:12mL；The weight consumption ratio of carbon black and graphene mixture and n-octyl amine after acidification is 1:1.5；Step
Suddenly the weight consumption of conductive agent and methyl vinyl silicone rubber ratio is 1:2 in (2)；
The preparation method of the semi-conductive silicone rubber roller material of high repeated charge: by methyl vinyl silicone rubber, three
First EP rubbers, conductive agglomerate A and crosslink agent DCP, which are placed in two-roll mill, to be kneaded uniformly up to the semiconductive silicon rubber
Rubber roller cylinder material；It is sufficiently mixed to realize, 3 times thin logical processing is carried out in mixing process.
The comparative example the difference from embodiment 1 is that, in ingredient only contain conductive agglomerate A, do not contain conductive agglomerate B.
The preparation of 2 semi-conductive silicone rubber roller material of comparative example
Parts by weight of raw materials composition: 80 parts of methyl vinyl silicone rubber；20 parts of ethylene propylene diene rubber；20 parts of conductive agglomerate B；
3 parts of crosslink agent DCP；
The conductive agglomerate B is prepared via a method which to obtain: (1) carbon black the preparation of modified carbon black: being placed in dense sulphur
In the mixed acid solution of acid and concentrated nitric acid composition, back flow reaction 6h is carried out at 80 DEG C, must be acidified carbon black after washing is dry；Then
Acidification carbon black is mixed with nano-titanium dioxide and is placed on progress ball milling 5h in dehydrated alcohol, up to modified after removing ethyl alcohol is dry
Carbon black；(2) up to conductive agglomerate after the modification carbon black that step (1) is prepared and methyl vinyl silicone rubber melt blending；
Wherein, the amount ratio of carbon black and mixed acid solution is 1g:25mL in step (1), the concentrated sulfuric acid and concentrated nitric acid in mixed acid solution
Volume ratio is 1:2；The weight ratio for being acidified carbon black and nano-titanium dioxide is 1:1；It is acidified the gross weight of carbon black and nano-titanium dioxide
The amount ratio of amount and dehydrated alcohol is 1g:15mL；The weight ratio of modified carbon black and methyl vinyl silicone rubber is 1 in step (2):
2；
The preparation method of the semi-conductive silicone rubber roller material of high repeated charge: by methyl vinyl silicone rubber, three
First EP rubbers, conductive agglomerate B and crosslink agent DCP, which are placed in two-roll mill, to be kneaded uniformly up to the semiconductive silicon rubber
Rubber roller cylinder material；It is sufficiently mixed to realize, 3 times thin logical processing is carried out in mixing process.
The comparative example the difference from embodiment 1 is that, in ingredient only contain conductive agglomerate B, do not contain conductive agglomerate A.
The preparation of 3 semi-conductive silicone rubber roller material of comparative example
Parts by weight of raw materials composition: 80 parts of methyl vinyl silicone rubber；20 parts of ethylene propylene diene rubber；20 parts of conductive agglomerate；It hands over
3 parts of agent DCP of connection；
The conductive agglomerate is prepared via a method which to obtain: by after carbon black and methyl vinyl silicone rubber melt blending i.e.
Obtain conductive agglomerate；Wherein, the weight consumption of carbon black and methyl vinyl silicone rubber ratio is 1:2；
The preparation method of semi-conductive silicone rubber roller material: by methyl vinyl silicone rubber, ethylene propylene diene rubber, conductive mother
Grain and crosslink agent DCP, which are placed in two-roll mill, to be kneaded uniformly up to the semi-conductive silicone rubber roller material；For reality
It is now sufficiently mixed, 3 times thin logical processing is carried out in mixing process.
The comparative example the difference from embodiment 1 is that, the conductive agglomerate in the comparative example is directly by carbon black and ethylene methacrylic
Base silicon rubber melt blending is prepared, and is not first modified carbon black respectively using such as embodiment 1 conductive agglomerate A and B, so
It is prepared afterwards with methyl vinyl silicone rubber melt blending.
Experimental example 1
The preparation for the semi-conductive silicone rubber roller material that Examples 1 to 3 and comparative example 1~3 are prepared is prepared into
(rubber outside diameter 20mm, metal core axle diameter are 10mm, rubber part length to the development roller sample being equipped with to installation
235.5mm), hereinafter abbreviated as 1~3 sample of Examples 1 to 3 sample and comparative example；Following performance, tool are tested in applied voltage
Body the results are shown in Table 1.
(1) volume resistivity is tested: development roller sample to be evaluated adds outside under 500V voltage, is tested using volume resistivity
Instrument test volume resistivity；
(2) voltage dependence is tested: development roller sample to be evaluated is at standard test environment (23 DEG C, relative humidity 55%)
Under, apply 250 volts 500 volts and 1000 volts of DC voltages respectively, measurement resistance is respectively R250,R500And R1000.Using R500 as base
Quasi- value.Test test specimens R250Relative to R500Variation degree；And test specimens R1000Relative to R500Variation degree.Resistance
Variation degree it is the smaller the better, it is smaller show material property stablize.Office machine needs not be provided multiple voltage output or compensation, letter
Change structure and reduces cost.The value belongs to preferable less than 100% in test.Above-mentioned " variation degree " is used to express the stabilization of resistance
Property, it is defined as follows: the quasi- ╳ 100% of the variation degree=∣ quasi- ∣/R Ji of R variation-R Ji；
(3) durability test: testing developer roll after undergoing a large amount of practical print jobs, the variation journey that resistance is lost
Degree；Initial resistance: before installation printing, resistance R is measured0；Terminate resistance: after printing 20,000, measuring resistance R20000；The variation
It is the smaller the better, show that material property is stablized；Stable resistance band comes stable image output effect, and permanent use longevity
Life；The value belongs to preferable less than 100%；
(4) photosensitive drums test for contamination: development roller sample is mounted in a whole set of toner cartridge, set environment chamber condition: temperature
50 DEG C, relative humidity 80%.Standing time: 7 days.After printing set original text, detecting the presence of test roller has low molecular compound precipitation, feels
Light drum is without contaminated phenomenon.
The processability test result of 1. semi-conductive silicone rubber roller material of table
Its volume of semi-conductive silicone rubber roller material from 1 experimental data of table as can be seen that as described in Examples 1 to 3
Resistivity is in 0.42*104~0.88*104Ω cm is in semiconductor regions (i.e. about 105~109Ω cm) range.
From its R of semi-conductive silicone rubber roller material described in Examples 1 to 3250Relative to R500Variation degree and R1000
Relative to R500Variation degree from the point of view of, in 8~25% ranges；In this field, the value belongs to preferably less than 100%, and by this
The value of the invention semi-conductive silicone rubber roller material is far smaller than 100%, this illustrates that its resistance is sufficiently stable, effect ten
Divide protrusion.Especially, its R of semi-conductive silicone rubber roller material described in Examples 1 to 320000Relative to R0Variation degree it is small
In 25%, and the value belongs to preferably less than 100% in practice process；This illustrates semi-conductive silicone rubber described in Examples 1 to 3
Its resistance variations very little after printing 20000 is opened of roller material, file printing durability is good, can guarantee stable image output effect
Fruit and permanent service life.The semi-conductive silicone rubber roller material being wherein prepared under the formula of embodiment 1 and method
The stability and durability effect of effect are most significant.
It can be seen that its semi-conductive silicone rubber roller of 1~2 sample of comparative example from the data of comparative example 1~2 and embodiment 1
Its R of material20000Relative to R0Variation degree be respectively greater than 80% and 160%, this explanation is being made in semi-conductive silicone rubber roller
Conductive agglomerate A or conductive agglomerate B is used alone during standby cannot be guaranteed that material has good printing durability；And it will be conductive
Semi-conductive silicone rubber roller material its R that master batch A and conductive agglomerate B is prepared after being applied in combination20000Relative to R0Variation
Degree is greatly reduced less than 25%, and material can be substantially improved after conductive agglomerate A and conductive agglomerate B are applied in combination in this explanation
Durability.
It can be seen that from the data of comparative example 3 and embodiment 1 and without any modification prepared by conductive mother to carbon black
Grain, the semi-conductive silicone rubber roller material further obtained, R250Relative to R500Variation degree and R1000Relative to R500's
Variation degree is all larger than 200%, R20000Relative to R0Variation degree be greater than 500%, significantly larger than embodiment 1, resistance value ten
It is point unstable, and print durability and be also greatly reduced.This illustrates that conductive material carbon black is not changed in accordance with the method for the present invention
Property processing, cannot get the semi-conductive silicone rubber roller material that resistance value is stable and printing durability is good.
Claims (10)
1. a kind of semi-conductive silicone rubber roller material of high repeated charge, which is characterized in that by including following parts by weight
Raw material is made:
50~90 parts of methyl vinyl silicone rubber；10~50 parts of ethylene propylene diene rubber；8~15 parts of conductive agglomerate A；Conductive agglomerate B
5~12 parts；1~5 part of crosslinking agent.
2. the semi-conductive silicone rubber roller material of high repeated charge according to claim 1, which is characterized in that by wrapping
Raw material containing following parts by weight is made:
60~80 parts of methyl vinyl silicone rubber；20~40 parts of ethylene propylene diene rubber；10~12 parts of conductive agglomerate A；Conductive agglomerate
8~10 parts of B；1~5 part of crosslinking agent.
3. the semi-conductive silicone rubber roller material of high repeated charge according to claim 1, which is characterized in that by wrapping
Raw material containing following parts by weight is made:
80 parts of methyl vinyl silicone rubber；20 parts of ethylene propylene diene rubber；10~12 parts of conductive agglomerate A；Conductive agglomerate B 8~10
Part；1~5 part of crosslinking agent.
4. the semi-conductive silicone rubber roller material of high repeated charge according to claim 1, which is characterized in that conductive
Master batch A is prepared by the inclusion of the method for following steps:
(1) preparation of conductive agent: carbon black and graphene being mixed and are placed in the mixed acid solution of the concentrated sulfuric acid and concentrated nitric acid composition,
5~10h of back flow reaction, carbon black and graphene mixture after must being acidified after washing is dry are carried out at 70~90 DEG C；Then will
Carbon black and graphene mixture after acidification are scattered in dehydrated alcohol, are then added n-octyl amine, 8~16h of heating reflux reaction,
It is filtered, washed sediment and is dried to get the conductive agent；
(2) up to conductive agglomerate after the conductive agent that step (1) is prepared and methyl vinyl silicone rubber melt blending；
Wherein, the weight ratio of carbon black and graphene is 3~5:1 in step (1), and the total weight and mixed acid of carbon black and graphene are molten
The amount ratio of liquid is 1g:20~50mL, and the volume ratio of the concentrated sulfuric acid and concentrated nitric acid is 1~3:1~3 in mixed acid solution；After acidification
Carbon black and the amount ratio of graphene mixture and dehydrated alcohol be 1:10~20mL；Carbon black and graphene mixture after acidification
Weight consumption ratio with n-octyl amine is 1:1~2；
The weight consumption of conductive agent and methyl vinyl silicone rubber ratio is 1:1~3 in step (2).
5. the semi-conductive silicone rubber roller material of high repeated charge according to claim 4, which is characterized in that step
(1) amount ratio of carbon black and graphene mixture and dehydrated alcohol in after acidification is 1:12mL；Carbon black and graphite after acidification
The weight consumption of alkene mixture and n-octyl amine ratio is 1:1.5.
6. the semi-conductive silicone rubber roller material of high repeated charge according to claim 4, which is characterized in that step
(2) weight consumption of conductive agent and methyl vinyl silicone rubber ratio is 1:2 in.
7. the semi-conductive silicone rubber roller material of high repeated charge according to claim 1, which is characterized in that described
Conductive agglomerate B be prepared by the inclusion of the method for following steps:
(1) preparation of modified carbon black: carbon black is placed in the mixed acid solution of the concentrated sulfuric acid and concentrated nitric acid composition, at 70~90 DEG C
5~10h of back flow reaction is carried out, carbon black must be acidified after washing is dry；Then carbon black will be acidified and mix postposition with nano-titanium dioxide
4~6h of ball milling is carried out in dehydrated alcohol, is modified carbon black to obtain the final product after removing ethyl alcohol drying；
(2) up to conductive agglomerate after the modification carbon black that step (1) is prepared and methyl vinyl silicone rubber melt blending；
Wherein, the amount ratio of carbon black and mixed acid solution is 1g:20~50mL in step (1), in mixed acid solution the concentrated sulfuric acid and
The volume ratio of concentrated nitric acid is 1~3:1~3；The weight ratio for being acidified carbon black and nano-titanium dioxide is 1:1~3；It is acidified carbon black and receives
The total weight of rice titanium dioxide and the amount ratio of dehydrated alcohol are 1g:8~20mL；Modified carbon black and ethylene methacrylic in step (2)
The weight ratio of base silicon rubber is 1:1~3.
8. the semi-conductive silicone rubber roller material of high repeated charge according to claim 7, which is characterized in that step
(1) amount ratio of carbon black and mixed acid solution is 1g:20~30mL in, the volume ratio of the concentrated sulfuric acid and concentrated nitric acid in mixed acid solution
For 1:2；The weight ratio of acidification carbon black and nano-titanium dioxide is 1:1 in step (1)；It is acidified the total of carbon black and nano-titanium dioxide
The amount ratio of weight and dehydrated alcohol is 1g:10~15mL.
9. the semi-conductive silicone rubber roller material of high repeated charge according to claim 7, which is characterized in that step
(2) weight ratio of modified carbon black and methyl vinyl silicone rubber is 1:2 in.
10. the preparation side of the semi-conductive silicone rubber roller material of high repeated charge according to any one of claims 1 to 9
Method, which is characterized in that comprise the following steps:
Methyl vinyl silicone rubber, ethylene propylene diene rubber, conductive agglomerate A, conductive agglomerate B and crosslinking agent are placed in double roller mill
The uniformly semi-conductive silicone rubber roller material up to the high repeated charge is kneaded in machine or rotor mixer.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110218396A (en) * | 2019-06-17 | 2019-09-10 | 湖南工业大学 | A kind of UV printing rubber roll and preparation method thereof |
| CN113881234A (en) * | 2021-10-12 | 2022-01-04 | 广州德润橡胶制品有限公司 | Silicone rubber material for preparing printing equipment roller |
| CN114437570A (en) * | 2020-11-05 | 2022-05-06 | 中国石油化工股份有限公司 | Preparation method of nano cross-linking agent for guanidine gum fracturing fluid and prepared cross-linking agent |
| CN115466462A (en) * | 2021-10-14 | 2022-12-13 | 苏州瑞高新材料有限公司 | Preparation method of 3D precision Ethylene Propylene Diene Monomer (EPDM) embossing roller die |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1298124A (en) * | 1999-11-29 | 2001-06-06 | 三星电子株式会社 | Charging roller for imaging equipment developing machine and method and apparatus for producing charging roller |
| JP3383536B2 (en) * | 1996-12-18 | 2003-03-04 | 信越化学工業株式会社 | Semiconductive silicone rubber composition and silicone rubber roll |
| CN1470559A (en) * | 2003-06-20 | 2004-01-28 | 山东大学 | Silicone rubber/EPDM combined conductive rubber and preparation method thereof |
| CN101055455A (en) * | 2006-04-14 | 2007-10-17 | 住友橡胶工业株式会社 | Semiconductor rubber member and developing roller composed of semiconductor rubber member |
| CN101451000A (en) * | 2007-01-24 | 2009-06-10 | 三星电子株式会社 | Roller rubber forming composition, rubber roller including the same, and imaging apparatus including the rubber roller |
| CN103176381A (en) * | 2011-12-22 | 2013-06-26 | 富士施乐株式会社 | Conductive roller, image-forming apparatus, and process cartridge |
| CN103857746A (en) * | 2011-10-07 | 2014-06-11 | 大曹株式会社 | Semi-conductive rubber composition |
-
2018
- 2018-10-12 CN CN201811189494.7A patent/CN109280394A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3383536B2 (en) * | 1996-12-18 | 2003-03-04 | 信越化学工業株式会社 | Semiconductive silicone rubber composition and silicone rubber roll |
| CN1298124A (en) * | 1999-11-29 | 2001-06-06 | 三星电子株式会社 | Charging roller for imaging equipment developing machine and method and apparatus for producing charging roller |
| CN1470559A (en) * | 2003-06-20 | 2004-01-28 | 山东大学 | Silicone rubber/EPDM combined conductive rubber and preparation method thereof |
| CN101055455A (en) * | 2006-04-14 | 2007-10-17 | 住友橡胶工业株式会社 | Semiconductor rubber member and developing roller composed of semiconductor rubber member |
| CN101451000A (en) * | 2007-01-24 | 2009-06-10 | 三星电子株式会社 | Roller rubber forming composition, rubber roller including the same, and imaging apparatus including the rubber roller |
| CN103857746A (en) * | 2011-10-07 | 2014-06-11 | 大曹株式会社 | Semi-conductive rubber composition |
| CN103176381A (en) * | 2011-12-22 | 2013-06-26 | 富士施乐株式会社 | Conductive roller, image-forming apparatus, and process cartridge |
Non-Patent Citations (4)
| Title |
|---|
| 张洁等: "电-热平衡态下不同电阻率-温度效应的导电硅橡胶的直流电流-电压特性", 《材料工程》 * |
| 橡胶工业原材料与装备简明手册编审委员会编著: "《橡胶工业原材料与装备简明手册2016年版》", 31 December 2016, 北京理工大学出版社 * |
| 汤慧萍等著: "《金属纤维多孔材料孔结构及性能》", 31 October 2016, 冶金工业出版社 * |
| 黄英等: "导电硅橡胶导电性和电热性的研究", 《橡胶工业》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110218396A (en) * | 2019-06-17 | 2019-09-10 | 湖南工业大学 | A kind of UV printing rubber roll and preparation method thereof |
| CN110218396B (en) * | 2019-06-17 | 2022-03-04 | 湖南工业大学 | A kind of UV printing rubber roller and preparation method thereof |
| CN114437570A (en) * | 2020-11-05 | 2022-05-06 | 中国石油化工股份有限公司 | Preparation method of nano cross-linking agent for guanidine gum fracturing fluid and prepared cross-linking agent |
| CN114437570B (en) * | 2020-11-05 | 2023-06-27 | 中国石油化工股份有限公司 | Preparation method of nano cross-linking agent for guanidine gum fracturing fluid and prepared cross-linking agent |
| CN113881234A (en) * | 2021-10-12 | 2022-01-04 | 广州德润橡胶制品有限公司 | Silicone rubber material for preparing printing equipment roller |
| CN115466462A (en) * | 2021-10-14 | 2022-12-13 | 苏州瑞高新材料有限公司 | Preparation method of 3D precision Ethylene Propylene Diene Monomer (EPDM) embossing roller die |
| CN115466462B (en) * | 2021-10-14 | 2024-05-03 | 苏州瑞高新材料股份有限公司 | Preparation method of 3D precise ethylene propylene diene monomer embossing roller die |
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Application publication date: 20190129 |