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 PDF

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CN109280394A
CN109280394A CN201811189494.7A CN201811189494A CN109280394A CN 109280394 A CN109280394 A CN 109280394A CN 201811189494 A CN201811189494 A CN 201811189494A CN 109280394 A CN109280394 A CN 109280394A
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conductive
carbon black
silicone rubber
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曾昭宇
何华明
梁剑春
刘兰香
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GUANGZHOU DERUM RUBBER PRODUCT CO Ltd
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GUANGZHOU DERUM RUBBER PRODUCT CO Ltd
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    • C08J3/20Compounding polymers with additives, e.g. colouring
    • C08J3/22Compounding polymers with additives, e.g. colouring using masterbatch techniques
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    • C08J2323/00Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02Characterised 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
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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

A kind of semi-conductive silicone rubber roller material of high repeated charge and preparation method thereof
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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Application publication date: 20190129