CN100412131C - Conductive rubber composition, conductive polymer composition, conductive vulcanized rubber, conductive rubber roller and conductive rubber band - Google Patents
Conductive rubber composition, conductive polymer composition, conductive vulcanized rubber, conductive rubber roller and conductive rubber band Download PDFInfo
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Abstract
The present invention provided an electroconductive rubber composition reduced in specific volume resistivity and compression set, excellent in ozone resistance and suppressed in photoreceptor contamination and to obtain a rubber product suppressed in generation of toxic gases when incinerated after used and the like and friendly to the environment. A non-halogen quaternary ammonium salt is compounded with an electroconductive polymer in an amount of at least 0.1 pt.wt. and at most 7.0 pts.wt. based on 100 pts.wt. of the electroconductive polymer, where the electroconductive polymer is obtained by mixing an ethylene oxide/propylene oxide/allyl glycidyl ether terpolymer (A) having an ethylene oxide/propylene oxide/allyl glycidyl ether copolymerization ratio of 50-95 mole %/1-49 mole %/1-10 mole % and a number-average molecular weight Mn of at least 10,000 with an acrylonitrile butadiene rubber (B) in a (A):(B) weight ratio of 70:30 to 5:95. The invention also provides a non-halogen polymer and a non-halogen composition of the non-halogen quaternary ammonium salt of sulphur acid. This composition can make the rubber produce such as the electroconductive rubber roller and the like.
Description
Technical field
The present invention relates to composition, electroconductibility vulcanized rubber, conducting rubber roller and the conducting rubber band of conductive rubber composition, electric conductive polymer.More specifically relate to the charged roller that can be effective to duplicating machine and printer etc., video picture roller, inking roller, duplicate the above-mentioned conducting rubber product of roller, copying band etc.
Background technology
The charged roller, video picture roller, inking roller, duplicating roller and the copying band that are used for duplicating machine and printer etc. all must possess suitable stable resistance value.
In the past, give above-mentioned roller and string rubber and comprise that with the method for electroconductibility employing sneaked into the method for the electron conduction rubber of electroconductibility weighting agents such as metal oxide powder and carbon black in rubber; Adopt the method for urethanes, paracril (NBR), epichloro hydrin rubber plasma conducting rubber.
Adopt the conductive roller of above-mentioned electron conduction rubber of having sneaked into the electroconductibility weighting agent or the resistance value of conducting rubber band to depend on the voltage that applies, have the problem that does not possess rated value of resistance.Particularly use under the situation of carbon black as the electroconductibility weighting agent, there are not stable relations between the volume intrinsic resistance of the addition of carbon black and rubber, and the acute variation that minimum variation all can cause resistance value takes place in the addition of carbon black, so be difficult to the controlling resistance value.
In addition, the volume intrinsic resistance of conducting rubber material and the roller resistance value that is configured as behind the roller convert according to fixed pattern described later, and these values change according to the variation of the shape of roller (or string rubber).
Homogeneous disperses in the rubber because the electroconductibility weighting agent is difficult in, so also have the length direction and the inhomogenous problem of the resistance value on the width of roller and string rubber.And, even the difference of resistance value reduces, also still there is the interior resistance value difference of small scope of μ m level.For above-mentioned reasons, in today that high image quality technology such as digitizing, colorization are maked rapid progress, the trend of electron conduction rubber has just appearred replacing with ionic conductivity rubber.
On the other hand, the conductive agent of above-mentioned ionic conductivity rubber is electroconductibility oligopolymer and the electroconductibility softening agent (Mn is below 10000) that polyoxyethylene etc. contains polyether structure.But, used the ionic conductivity rubber of above-mentioned conductive agent to have the problem of polluting photoreceptor easily.
Except the above, adopt the method for paracril (NBR) and urethanes in addition, but the volume intrinsic resistance value of gained elastomeric material is 10
9.6(resistance value of roller is 10 to Ω cm
8.2Ω), when being used for copying band and duplicating roller waiting chromaticity, can not adapt to the requirement of low-resistance value.In addition, also there is the not good problem of ozone resistance in NBR.
Therefore, proposed to use separately generally speaking epichloro hydrin rubber or be mixed for schemes such as such use, the charged roller of part, video picture roller, inking roller with other materials.
In addition, the quaternary ammonium salt of also having attempted sneaking into high chloro acid ion or chloride ion in paracril (NBR), urethanes, epichloro hydrin rubber plasma conducting rubber improves degree of ionization, realizes low-resistance method.
For example, the conductive agents such as quaternary ammonium salt that Japanese Patent has openly disclosed to contain organic rubbers such as paracril and epichloro hydrin rubber, carbon black, perchloric acid for communique 2000-17118 number are the composition of the electric conductive polymer of feature, said composition can reduce the difference of resistance value, reduces compression set with soft.
In addition, Japanese Patent has disclosed the rubber combination of the acquisitions such as quaternary amine of sneaking into perchloric acid in paracril, epichloro hydrin rubber etc. open the flat 9-132677 of communique number, and this rubber combination can easily be given electroconductibility, and resistance value is easy to control.
Though the composition resistance value difference of the electric conductive polymer that Japanese Patent is open communique 2000-17118 number is less, can reduce compression set, there is the problem that to pollute photoreceptor.And, use behind the quaternary ammonium salt of perchloric acid and contain chlorine in the composition, so use the back to exist and produce deleterious hydrogen chloride gas or using burn off to handle, heat and cut off to make it to decompose because of the different problems that produce dioxin of treatment condition to carry out circulation time.
The rubber combination that Japanese Patent is open the flat 9-132677 of communique number not only can not fully reduce compression set, and owing to containing chlorine in the composition behind the quaternary ammonium salt that has used perchloric acid, so with above-mentioned same, burn off after use may occur producing deleterious hydrogen chloride gas with the problem of dioxin in handling.
Same as the epichloro hydrin rubber of ionic-conductive polymer and neoprene (CR), chlorinatedpolyethylene (CPE), chlorosulfonated polyethylene (CSM), vinylchlorid (PVC), during forming, polymkeric substance contains the chlorine of one of halogen.Therefore, when adopting epichloro hydrin rubber to be electric conductive polymer,, may produce deleterious hydrogen chloride gas Huo dioxin with above-mentioned same.
In recent years, environmental problem is just obtaining very high attention, and the generation of toxic gas Huo dioxin also becomes very big social concern.Therefore, toxic gas can not be produced when wishing to develop burn off early with the material of dioxin as the composition of electric conductive polymer etc., and wishes that this material can be recycled.
In addition, for the volume intrinsic resistance is descended, in composition of electric conductive polymer etc., sneak into the quaternary ammonium salt that high chloro acid ion or chloride ion etc. contain halogen (particularly chlorine), or epichloro hydrin rubber etc. is when containing the electric conductive polymer of halogen (particularly chlorine), because the part of halogens such as chlorine wherein can cause side reaction, so there is the problem of the obvious deterioration of compression set.
The present invention is the invention of finishing in view of the above problems.But one of purpose of the present invention provides inhibition of sintering produces toxic substance when removing, can be recycled, the volume intrinsic resistance is lower, compression set is less and ozone resistance well, can not polluted the conductive rubber composition of photoreceptor.But two of purpose of the present invention provides mat heat after the use with above-mentioned effect same or cuts off and the composition of the electric conductive polymer that easily is decomposed.Three of purpose of the present invention provides weather resistance and dimensional stability good and conducting rubber roller and conducting rubber band that environment is had no adverse effects.
The content of invention
In order to finish one of purpose of the invention described above, conductive rubber composition is provided, the copolymerization ratio that comprises in the said composition by ethylene oxide/propylene oxide/glycidyl allyl ether is 50～95 moles of %/1～49 mole %/1～10 mole of %, number-average molecular weight Mn is at the epoxy ethane-epoxy propane more than 10000-glycidyl allyl ether terpolymer (A) and paracril (B), according to (A): (B)=electric conductive polymer that 70: 30～5: 95 weight ratio mixes, corresponding to the above-mentioned electric conductive polymer of 100 weight parts, having mixed the following non-halogen of above 7.0 weight parts of 0.1 weight part is quaternary ammonium salt.
As mentioned above, having used non-halogen with specified proportion in the conductive rubber composition of the present invention is quaternary ammonium salt, so can not cause the side reaction of electric conductive polymer and halogen component, can alleviate compression set.In addition, can also realize the raising with ozone resistance of reducing of volume intrinsic resistance simultaneously.
As mentioned above, special stipulation the copolymerization ratio of epoxy ethane-epoxy propane-glycidyl allyl ether terpolymer, and mix this terpolymer and paracril (NBR) with specified proportion.Under the prerequisite that does not influence ozone resistance, the incidence of compression set is descended like this.
In addition, owing to do not use Halogen electric conductive polymer such as epichloro hydrin rubber, so, can not produce objectionable impuritiess such as hydrogen chloride gas even non-halogen system: compositions as a whole carries out processing such as burn off after use yet.
So just can provide the ionic conductivity rubber that possesses in the past can not realize the good rerum natura as conducting rubber roller and conducting rubber band (the volume intrinsic resistance is little, compression set is little, ozone resistance well, can not pollute photoreceptor, dimensional stability is good), and environment is had no adverse effects, be fit to practical rubber item.
Above-mentioned epoxy ethane-epoxy propane-glycidyl allyl ether terpolymer (A) and paracril (B) are according to (A): (B)=and 70: 30～5: 95 weight ratio mixes.
In the afore mentioned rules scope be because if the weight ratio of paracril (B) less than above-mentioned weight ratio, then not only the incidence of compression set increases, and can pollute photoreceptor; Paracril (B) if weight ratio greater than above-mentioned weight ratio, then not only can cause the ozone deterioration, the volume intrinsic resistance of NBR self is increased, cause the volume intrinsic resistance to improve.
Can obtain to use separately the not available low resistance of paracril according to above-mentioned weight ratio mixing in the past, and ozone resistance is also increased, when being used for conducting rubber roller or conducting rubber band, has surface luster, non-wrinkled and squeezed state is good.
The copolymerization ratio of above-mentioned oxyethane (hereinafter referred to as EO)/propylene oxide (hereinafter referred to as PO)/glycidyl allyl ether (hereinafter referred to as AGE) is that the reason of 50～95 moles of %/1～49 mole %/1～10 mole of % is as described below.
The electroconductibility of conductive rubber composition can bring into play be because polymkeric substance in oxonium ion and metallic cation (for example, the nickel ion that comprises in the oxidation inhibitor of polymkeric substance etc.) or ammonium ion (obtaining) by quaternary ammonium salt influenced and stabilization by ethylene oxide unit etc., shift by the molecule segment motion of this part.Therefore, the higher polymkeric substance of the ratio of ethylene oxide unit can make most of ion stabilizedization, realizes low resistanceization.
But, if the ratio of oxyethane is too high, then can cause the crystallization of oxyethane, hinder the molecule segment motion, the volume intrinsic resistance is improved.In order to suppress the crystallization of oxyethane, make itself and propylene oxide copolymerization.
The volume intrinsic resistance of conductive rubber composition of the present invention better is 10
7.0Ω cm～10
9.0In the scope of Ω cm.If this is less than 10 because of the volume intrinsic resistance value
7.0Ω cm then can't make ionic conductivity rubber with this conductive rubber composition, depend on electron conduction weighting agents such as carbonaceous conductive.In addition, if the volume intrinsic resistance value greater than 10
9.0Ω cm during then as rubber coated pressure bowl and string rubber, duplicates, efficient such as charged and inking descends, and is not suitable for actual use.
In temperature is that 23 ℃, relative humidity are under 55% the fixed temperature and humidity condition determination attitude, applies the voltage of 500V, measures the volume intrinsic resistance value.
For the rerum natura of keeping above-mentioned conductive rubber composition (compression set is little, ozone resistance well, can not pollute photoreceptor, dimensional stability is good), and make it possess above-mentioned volume intrinsic resistance value, set the mutual copolymerization ratio of the terpolymer of above-mentioned oxyethane, propylene oxide, glycidyl allyl ether, and the when non-halogen of the mixed weight of regulation ter-polymers and the paracril mixed weight ratio that is quaternary ammonium salt.
If the ratio of 50 moles of % of the ratio deficiency of oxyethane and propylene oxide surpasses 49 moles of %, then the ionic stabilization is abundant inadequately, and the volume intrinsic resistance value is reduced.If the ratio of oxyethane surpasses 1 mole of % of ratio less than of 95 moles of % and propylene oxide, then there is the too high problem of volume intrinsic resistance value.In addition, because of rerum natura and crystallization excessively improve hardness, be not suitable as roller and string rubber and use.
Above-mentionedly be difficult for so not only causing that by producing crosslinkedly albefaction (frosting), bleeding and photoreceptor pollute, caoutchouc elasticity is increased with the glycidyl allyl ether copolymerization.In addition, this glycidyl allyl ether unit itself so can suppress above-mentioned crystallization, can be realized unexistent low resistanceization as the side chain volume that can gain freedom.
The copolymerization ratio of glycidyl allyl ether is that 1～10 mole of % is because if 1 mole of % of less than, bleeding and photoreceptor then take place easily to be polluted, if surpass 10 moles of %, then can not obtain the effect of above-mentioned inhibition crystallization, though the cross-linking set after the sulfuration is more, but can not realize low resistanceization, and deterioration all such as tensile strength, fatigue characteristic and resistance to bend(ing).
As mentioned above,, can suppress the crystallization of oxyethane, the volume intrinsic resistance is descended by the copolymerization of glycidyl allyl ether.On the other hand, the copolymerization by glycidyl allyl ether has imported carbon-to-carbon double bond, can realize crosslinked with other rubber.Crosslinked by with other rubber can prevent bleeding and pollute photoreceptor.In addition, by with other rubber cross, also can increase molecular weight, so, also be difficult to cause bleeding and pollute photoreceptor even sneak into the terpolymer of a large amount of above-mentioned epoxy ethane-epoxy propane-glycidyl allyl ethers.
The number-average molecular weight Mn of the terpolymer of above-mentioned epoxy ethane-epoxy propane-glycidyl allyl ether (hereinafter referred to as the EEO-PO-AGE terpolymer) is being because can prevent bleeding and pollute photoreceptor more than 10000.
Corresponding to the above-mentioned electric conductive polymer of 100 weight parts, non-halogen is that the blending ratio of quaternary ammonium salt is below 7.0 weight parts more than 0.1 weight part.
Blending ratio is to be less than 0.1 weight part, then the decline poor effect of volume intrinsic resistance because if non-halogen is quaternary ammonium salt in above-mentioned scope; Surpass 7.0 weight parts if non-halogen is quaternary ammonium salt, then can pollute photoreceptor.
In addition,, also there is the problem of polluting photoreceptor if mix a large amount of above-mentioned EO-PO-AGE terpolymers, and the problem that compression set is serious and hardness rises.If under the prerequisite that does not cause these problems, control combined amount, just be difficult to realize low resistanceization.But by mixing non-halogen is quaternary ammonium salt, even reduce the consumption of EO-PO-AGE terpolymer, also can effectively realize low resistanceization.Not only can keep like this low resistance can also the contaminated solution photoreceptor etc. problem.
By mixing non-halogen is quaternary ammonium salt, can reduce the consumption of the EO-PO-AGE terpolymer of high price, realizes low resistanceization, so can reduce cost.
Preferably contain aqueous paracril (NBR) in the above-mentioned paracril (B).
If use the paracril (NBR) that contains aqueous NBR, then polymer chain easily shifts, and processibility is also fine, and the raising of ionic transport efficiency, so the volume intrinsic resistance descends.In addition, because extrusion characteristics is good, so non-wrinkled appearance can obtain to have the conductive roller and the conducting rubber band of excellent surface state.
The consistency that contains higher paracril of acrylonitrile content in the paracril of aqueous paracril and above-mentioned EO-PO-AGE terpolymer (A) is better, mix the back or the rubber surface when extruding very good, and the effect that the hardness of sulfide is descended is also very good.
Can prevent that as the high molecular NBR of paracril (NBR) and the mixture of aqueous NBR photoreceptor is contaminated, and the maintenance of the rerum natura of rubber combination is good, so be fit to actual the use.Specifically comprise ニ ッ Port-Le DN223 (trade(brand)name) that Japanese ゼ オ Application Co., Ltd. produces etc.
As above-mentioned paracril (NBR), be preferably the higher diene series rubber of consistency with the terpolymer of above-mentioned epoxy ethane-epoxy propane-glycidyl allyl ether.This rubber comprise middle nitrile, in various NBR such as high nitrile, high nitrile, high nitrile.So just can obtain the lower composition of resistance value.
Conductive rubber composition of the present invention is that to mix above-mentioned EO-PO-AGE terpolymer, paracril and non-halogen in the afore mentioned rules scope be quaternary ammonium salt, and contains vulcanizing agent and the non-halogen system: compositions of the various additives of sneaking into as required (vulcanization accelerator, weighting agent, be subjected to sour agent and protective agent etc.).
The electroconductibility vulcanized rubber that conductive rubber composition of the present invention obtains through sulfuration not only has lower volume intrinsic resistance value and compression set is less, ozone resistance well, can not pollute photoreceptor.In addition, because this rubber is non-halogen system: compositions, so can not produce toxic gas during burn off.Therefore, used the resistance value of the conducting rubber roller of this rubber and conducting rubber band lower, above-mentioned other rerum naturas are also fine, are specially adapted to the painted field that requires low-resistance value with duplicating roller and charged roller, inking roller and video picture roller, copying band etc.Owing to can not produce toxic gas during burn off,, environment be had no adverse effects so easily be decomposed with cutting off by heat.
To comprise non-halogen based polymer and non-halogen be that the non-halogen of quaternary ammonium salt is the composition of electric conductive polymer in order to finish two of purpose of the present invention, to the invention provides.
As mentioned above, it is quaternary ammonium salt that the composition of electric conductive polymer of the present invention has used non-halogen, can not cause the side reaction as the polymkeric substance and the halogen component of base material, so can realize reducing the generation of compression set and the decline of volume intrinsic resistance simultaneously.In addition, be quaternary ammonium salt owing to used non-halogen based polymer and non-halogen, making composition in its entirety is non-halogen system: compositions, so even use the back to carry out processing such as burn off, also can not produce objectionable impuritiess such as hydrogen chloride gas.
Like this, can provide the ionic conductivity rubber that possesses in the past low resistance, the compression set that can't realize less and dimensional stability good, conducting rubber roller or conducting rubber band that environment is had no adverse effects.
In the composition of electric conductive polymer of the present invention, the addition that above-mentioned non-halogen is quaternary ammonium salt can be the kind decision of quaternary ammonium salt according to used polymkeric substance and non-halogen.
In addition, be the low resistance that quaternary ammonium salt can't be realized can realize using NBR, urethanes etc. separately the time by mixing non-halogen, the composition that contains the electric conductive polymer of this non-halogen based polymer also can be realized low resistance.
It is that a kind of electric conductive polymer or multiple non-halogen are electric conductive polymer that above-mentioned non-halogen based polymer can adopt the multipolymer known in the past non-halogen such as (EO-PO-AGE multipolymers) that is selected from urethanes, NBR, ethylene oxide/propylene oxide/glycidyl allyl ether.Wherein, consider, preferably adopt urethane, NBR, EO-PO-AGE multipolymer from realizing low-resistance angle.
In addition, do not influencing under low-resistance prerequisite, also can sneak into the polymkeric substance of the electroconductibility that does not possess non-halogen system.The above-mentioned polymkeric substance that does not possess the electroconductibility of non-halogen system comprises synthetic polyisoprene (IR), styrene-butadiene rubber(SBR) (SBR), divinyl rubber various synthetic rubber such as (BR), or natural rubber (NR), and styrene-ethylene/butylene-styrene multipolymer (SEBS), styrene-ethylene/propylene-styrene multipolymer (SEPS), styrene-ethylene-ethylene/propene-styrol copolymer thermoplastic elastomers such as (SEEPS).
Preferably contain NBR in the above-mentioned non-halogen based polymer.By containing NBR, can make ion stabilizedization, easily shift and improve the ionic transport efficiency, so the volume intrinsic resistance is descended, also can alleviate compression set.
The volume intrinsic resistance value of the composition of electric conductive polymer of the present invention better is 10
7.0Ω cm～10
9.5In the scope of Ω cm.If this is less than 10 because of the volume intrinsic resistance value
7.0Ω cm then can't make ionic conductivity rubber with the composition of this electric conductive polymer, depend on electron conduction weighting agents such as carbonaceous conductive.In addition, if the volume intrinsic resistance value greater than 10
9.5Ω cm during then as rubber coated pressure bowl and string rubber, duplicates, efficient such as charged and inking descends, and is not suitable for actual use.
In temperature is that 23 ℃, relative humidity are under 55% the fixed temperature and humidity condition determination, applies the voltage of 500V, measures the volume intrinsic resistance value.
In addition, the above-mentioned non-halogen based polymer in the composition of electric conductive polymer of the present invention preferably contains the unitary polymkeric substance of oxyethane (EO).
The electroconductibility of conductive rubber composition can bring into play be because polymkeric substance in oxonium ion and metallic cation (for example, the nickel ion that comprises in the protective agent of polymkeric substance etc.) or ammonium ion (obtaining) by quaternary ammonium salt influenced and stabilization by ethylene oxide unit etc., shift by the molecule segment motion of this part.Therefore, the higher polymkeric substance of the ratio of ethylene oxide unit can make most of ion stabilizedization, realizes low resistance.
Above-mentioned effect also is like this for NBR.NBR has cyano group, because cyano group possesses stronger electron attractivity, and the deflection nitrogen-atoms so πDian Zi distributes, cyano group is just electronegative like this.Corresponding to this, form the directed matrix of joining cloth of positively charged ion work in the molecule, ion is transferred by the thermal motion of rubber molecule, obtains electroconductibility.
Therefore, the better combination of above-mentioned non-halogen based polymer is NBR and the higher polymkeric substance of EO content.Wherein, best is the mixture of higher epoxy ethane-epoxy propane-glycidyl allyl ether (EO-PO-AGE) terpolymer of NBR, EO content, and this mixture can effectively reduce the volume intrinsic resistance.
Above-mentioned EO-PO-AGE terpolymer possesses the good mechanical rerum natura, and the NBR higher with the consistency of EO-PO-AGE terpolymer, especially middle nitrile, in after various NBR such as high nitrile, high nitrile mix, can obtain all good compositions of rerum naturas such as compression set and hardness.
In addition, because above-mentioned EO-PO-AGE terpolymer uses as non-halogen based polymer, sneaking into non-halogen therein is quaternary ammonium salt, can effectively reduce resistance, so can reduce the consumption of the EO-PO-AGE terpolymer of high price, realizes low resistance.Therefore, by with non-halogen be that quaternary ammonium salt is used in combination, when reducing cost, can also effectively reduce resistance.
Perhaps, adding above-mentioned non-halogen in the urethanes of not chloride halogen such as grade is quaternary ammonium salt, under the situation of the composition of acquisition electric conductive polymer, adding non-halogen in polyalcohols polyol etc. is quaternary ammonium salt and 1, polyols such as 4-butyleneglycol, add tensio-active agent and various additive more as required, fully stir.After the stirring, decompression deaeration is down handled, and adds isocyanic ester and catalysts then, injects mould, and heating cure obtains desirable roller or string rubber.
In addition, adding non-halogen in urethanes is quaternary ammonium salt, under the situation of the composition of acquisition electric conductive polymer, as mentioned above, stirs the back and injects mould, then by solidifying the composition that just can obtain electric conductive polymer of the present invention.
The composition of electric conductive polymer of the present invention is that to comprise non-halogen based polymer, non-halogen be quaternary ammonium salt, vulcanizing agent and the non-halogen system: compositions of the various additives of blended (vulcanization accelerator, weighting agent, be subjected to sour agent, protective agent etc.) as required.
The composition of electric conductive polymer of the present invention has lower volume intrinsic resistance, and compression set is less, and because it is non-halogen system: compositions, so can not produce toxic gas during burn off.Therefore, used the resistance value of conducting rubber roller of said composition lower, be specially adapted to paintedly require the field of low-resistance value with duplicating roller and charged roller, inking roller and video picture roller, copying band etc.Owing to can not produce toxic gas by heat with cutting off when being decomposed, so environment is had no adverse effects yet.
Above-mentioned non-halogen in the composition of conductive rubber composition of the present invention or electric conductive polymer is that quaternary ammonium salt can use the quaternary ammonium salt of sulfonic acid or the quaternary ammonium salt of glyconic acid, the quaternary ammonium salt of glucono-lactone.
To non-halogen is that the skeleton structure of quaternary ammonium salt is conscientiously studied the back and found that the degree of ionization of above-mentioned 3 kinds of ammonium salts is high especially, thus can effectively realize low resistance, and can reduce compression set, can also suppress pollution to photoreceptor.
Non-halogen be quaternary ammonium salt except above-mentioned 3 kinds, also can use the quaternary ammonium salt of sulfuric acid, nitric acid etc.These all are the salt of the stronger acid of acidity, can keep the not chloride structure that waits halogen.
Specifically, non-halogen is that quaternary ammonium salt has the structure with following formula 1 (changing 1) expression.
(changing 1)
The object lesson of sulfonic acid quaternary ammonium salt comprises that M is the salt (trade(brand)name: KP-4728, Kao Corp's system) of tosic acid residue in the following formula.
The object lesson of the quaternary ammonium salt of glucono-lactone comprises that M is the salt (trade(brand)name: KP-4729, Kao Corp's system) of glucono-lactone residue in the following formula.
The composition of melting mixing conductive rubber composition of the present invention or electric conductive polymer of the present invention makes the electroconductibility vulcanized rubber after the sulfuration.Melting mixing can adopt ordinary method to carry out.For example, with known compounding rubber devices such as open roller, closed mixing rolls, under 40 ℃～130 ℃ the temperature mixing about 2～10 minutes.
Scrag test method according to the vulcanized rubber of JIS K6262 record, under the minute of 70 ℃ mensuration temperature and 24 hours, the compression set rate that records the electroconductibility vulcanized rubber that conductive rubber composition of the present invention obtains through sulfidizing is below 25%.
If above-mentioned compression set value is greater than 25%, the dimensional change when then being configured as roller is excessive, is not suitable for actual use.When particularly using (becoming sponge), because of frothing percentage and foaming form can produce some differences as foam.Therefore, this value is preferably in the above-mentioned scope.
Because vulcanized rubber satisfies low resistance and low contaminative simultaneously, to add the vulcanized rubber that sulphur makes be suitable so adopt.As promotor, better be to be used in combination dibenzothiazyl disulfide and tetramethylthiuram monosulfide.Also available 2-mercaptobenzothiazole etc. replaces dibenzothiazyl disulfide.
If the sulfuration system of Sulfur (S)/dibenzothiazyl disulfide (DM)/tetramethylthiuram monosulfide (TS) or Sulfur (S)/2-mercaptobenzothiazole (M)/tetramethylthiuram monosulfide (TS) is used for the mixture of the higher high molecular EO-PO-AGE terpolymer of NBR or NBR and EO content, then can finish crosslinking copolymerization effectively, also can reduce pollution, and reduce compression set photoreceptor.
The sulfuration system that possesses suitable vulcanizing agent and vulcanization accelerator comprises the sulfuration system that the mixed according to Sulfur/dibenzothiazyl disulfide/tetramethylthiuram monosulfide or Sulfur/2-mercaptobenzothiazole/tetramethylthiuram monosulfide=1.5/1.5/0.5 forms.
So not only can shorten curing time, also can make above-mentioned EO-PO-AGE terpolymer and paracril crosslinking copolymerization well, reduce pollution photoreceptor.
Sulfuration can adopt ordinary method to carry out.For example, can add in the sulfuration cylinder of depressing at water vapor and vulcanize, perhaps carry out sulfidizing, also can carry out post cure as required and handle by the method for press vulcanization.
In addition, also can utilize peroxide cure system to carry out sulfidizing.By combining, can suppress pollution to photoreceptor with post cure.
Above-mentioned conducting rubber roller can make according to ordinary method.For example, make the mixture of the composition of above-mentioned conductive rubber composition or electric conductive polymer be configured as tubulose with the single shaft extrusion machine in advance, under 160 ℃ the temperature to the heating of this preformed articles after 10～60 minutes, insert plug, after the surface ground, size cutting according to the rules obtains known in the past the whole bag of tricks such as roller.Curing time can by sulfuration test with mobilometer (for example, キ ュ ラ ス ト メ one ) try to achieve just when.In addition, Heating temperature can be done suitably to adjust near said temperature as required.Use under the situation of urethane, can be according to the raw material of sneaking into, 80 ℃ of solidification treatment of carrying out about 12 hours.
After with Press forming machine the mixture press molding of the composition of above-mentioned conductive rubber composition or electric conductive polymer being band shape,, making known in the past the whole bag of tricks such as string rubber and just can make above-mentioned conducting rubber band in 160 ℃ of heating 10～60 minutes.Heating temperature can be done suitably to adjust near said temperature as required.
Simple declaration to accompanying drawing
Fig. 1 is the sketch of conducting rubber roller of the present invention.
Fig. 2 is the sketch of conducting rubber band of the present invention.
Nomenclature: 1 is the conducting rubber roller, and 2 is the axle core, and 3 is the conducting rubber band, and 4 is belt pulley, and 5 is the linearity part, and 6 is sheet material.
The working of an invention mode
Below, embodiments of the present invention are described.
The conductive rubber composition of embodiments of the present invention 1 comprises electric conductive polymer, this polymkeric substance is that 90 moles of %/4 mole %/6 moles %, number-average molecular weight Mn are 80000 epoxy ethane-epoxy propane-glycidyl allyl ether terpolymer (A) and 75 weight part paracrils (B) by the copolymerization ratio of 25 weight part ethylene oxide/propylene oxide/glycidyl allyl ethers, promptly according to (A): (B)=25: 75 weight ratio mixes, corresponding to the above-mentioned electric conductive polymer of 100 weight parts, the non-halogen of having sneaked into 5 weight parts is quaternary ammonium salt.
In addition, corresponding to the above-mentioned electric conductive polymer of 100 weight parts, the vulcanizing agent (Sulfur) of 1.5 weight parts, the vulcanization accelerator 1 (dibenzothiazyl disulfide) of 1.5 weight parts, the vulcanization accelerator 2 (tetramethylthiuram monosulfide) of 0.5 weight part, the inorganic filler of 20 weight parts, the zinc oxide of 5 weight parts and the stearic acid of 1 weight part have also been mixed.Wherein, cl content is 0 weight %.
Above-mentioned non-halogen is that quaternary ammonium salt is the quaternary ammonium salt of glucono-lactone.In addition, above-mentioned paracril is the rubber that contains the aqueous paracril of 50 weight parts in the common paracril of 100 weight parts.
Is the above-mentioned conductive rubber composition that quaternary ammonium salt, vulcanizing agent and the various additives of sneaking into as required make with known compounding rubber device melting mixings such as closed mixing rolls by electric conductive polymer, non-halogen, carry out sulfidizing, obtain to can be used for the electroconductibility vulcanized rubber of conducting rubber roller etc.
According to the scrag test method of the vulcanized rubber of JIS K6262 record, the compression set rate of the above-mentioned electroconductibility vulcanized rubber that records under the minute of 70 ℃ mensuration temperature and 24 hours is 22%.
In temperature is that 23 ℃, relative humidity are under 55% the fixed temperature and humidity condition determination, applies the voltage of 500V, and the volume intrinsic resistance that records above-mentioned electroconductibility vulcanized rubber is 10
8.2
Make above-mentioned conductive rubber composition be configured as tubulose with the single shaft extrusion machine in advance, under 160 ℃ the temperature this preformed articles heating after 10～60 minutes, is being inserted plug, after the surface was ground, size cutting according to the rules obtained to duplicate and uses roller.As shown in Figure 1, above-mentioned duplicating usefulness conducting rubber roller 1 is the shape near cylinder, has inserted an axle core 2 in it week.
Because the volume intrinsic resistance of above-mentioned conductive rubber composition is lower, compression set is less, so can obtain dimensional stability and weather resistance is all good and ozone resistance good, and can reduce conducting rubber roller to the pollution of photoreceptor.In addition, because above-mentioned composition is non-halogen system: compositions,, can not produce dysgenic conducting rubber roller to environment so, can not produce pollution substance even can obtain after use, to carry out burn off etc. yet.
In addition, also can adopt the quaternary ammonium salt etc. of sulfonic acid is quaternary ammonium salt as non-halogen.
Comprising non-halogen based polymer and non-halogen in the composition of the electric conductive polymer of embodiments of the present invention 2 is quaternary ammonium salt, and said composition is non-halogen system: compositions.
Above-mentioned non-halogen based polymer comprises as containing epoxy ethane-epoxy propane-glycidyl allyl ether (EO-PO-AGE) terpolymer of the polymkeric substance of ethylene oxide unit and the mixture of paracril (NBR).
In the above-mentioned EO-PO-AGE terpolymer, the copolymerization ratio of ethylene oxide/propylene oxide/glycidyl allyl ether is 90 moles of %/4 mole %/6 moles of %, and number-average molecular weight Mn is 80000.
Above-mentioned EO-PO-AGE terpolymer and paracril are according to 25 weight parts: the weight ratio of 75 weight parts is mixed.
Combined amount as the quaternary ammonium salt of the above-mentioned non-halogen glucono-lactone that is quaternary ammonium salt is 5 weight parts.
Behind the various additives of in the composition of above-mentioned electric conductive polymer, sneaking into vulcanizing agent and adding as required, carry out sulfidizing with known compounding rubber device melting mixings such as closed mixing rolls, so just can obtain can be used for the electroconductibility vulcanized rubber of conducting rubber roller etc.
According to the scrag test method of the vulcanized rubber of JIS K6262 record, the compression set rate of the above-mentioned electroconductibility vulcanized rubber that records under the minute of 70 ℃ mensuration temperature and 24 hours is 22%.
In temperature is that 23 ℃, relative humidity are under 55% the fixed temperature and humidity condition determination, applies the voltage of 500V, and the volume intrinsic resistance that records above-mentioned electroconductibility vulcanized rubber is 10
8.2
Make the composition of above-mentioned electric conductive polymer be configured as tubulose with the single shaft extrusion machine in advance, under 160 ℃ the temperature this preformed articles heating after 10～60 minutes, is being inserted plug, after the surface ground, size cutting according to the rules with above-mentioned same, makes near duplicating roller cylindraceous.
Because the volume intrinsic resistance of the composition of above-mentioned electric conductive polymer is lower, compression set is less, so can obtain dimensional stability and all good conducting rubber rollers of weather resistance.And, because above-mentioned composition is non-halogen system: compositions, so, also can not produce the conducting rubber roller of pollution substance even can obtain after use, to carry out burn off etc.
Can only use above-mentioned EO-PO-AGE terpolymer as non-halogen based polymer, or use NBR, urethane etc. separately, also can use mixture with other components etc.
Also can use the quaternary ammonium salt etc. of sulfonic acid is quaternary ammonium salt as non-halogen.
In the above-mentioned embodiment, made the conducting rubber roller that uses with roller as duplicating by the composition of conductive rubber composition of the present invention or electric conductive polymer of the present invention.But the composition of above-mentioned conductive rubber composition or above-mentioned electric conductive polymer also can be used for the manufacturing of conducting rubber rollers such as charged roller, video picture roller, inking roller.In addition, also can be used and make foaming roller etc. with various whipping agents.
As shown in Figure 2, the composition by conductive rubber composition of the present invention or electric conductive polymer of the present invention makes conducting rubber band 3.Conducting rubber band 3 is by the belt pulley 4 open-shaped attitudes more than 2, is loaded with sending into of sheet material 6 such as paper on the upside linearity part 5 of the conducting rubber band 3 that moves around, and the toner image that will be produced on the photoreceptor is duplicated on the sheet material again.
Experiment 1
Below, the embodiment 1～5 and the comparative example 1～7 of conductive rubber composition of the present invention is elaborated.
In embodiment 1～5 and the comparative example 1～7, with closed mixing roll (DS10-40MWA-S, the gloomy mountain of Co., Ltd. makes made) respectively according to material mixture ratio amount (cooperation reagent) mixing raw material of following table 1 and table 2 record.The banded rubber press molding that will take out from above-mentioned mixing roll with the roller extrusion machine is a sheet then, in its mould of packing into, in 160 ℃ with press vulcanization between the most in good time, make rerum natura assessment vulcanized rubber flap.
Table 1
Table 2
Embodiment 1～embodiment 5
Mixing above-mentioned non-halogen according to proportioning shown in the table 1 in proportioning EO-PO-AGE terpolymer as shown in table 1 and paracril is quaternary ammonium salt, makes the test film that is formed by conductive rubber composition according to the method described above.
Comparative example 1～comparative example 7
The EO-PO-AGE terpolymer that comparative example 1 is used and the proportioning of paracril are the proportioning of the present invention's regulation shown in the table 2, but unmixed non-halogen is quaternary ammonium salt,
In the comparative example 2, according to proportioning shown in the table 2, only having mixed non-halogen in paracril is quaternary ammonium salt 1.
The EO-PO-AGE terpolymer that comparative example 3 is used and the proportioning of paracril are outside the ratio range of the regulation of the present invention shown in the table 2, and wherein having mixed non-halogen is quaternary ammonium salt 2.
In comparative example 4 and the comparative example 5, though the proportioning of used EO-PO-AGE terpolymer and paracril is the proportioning of the present invention regulation shown in the table 2, non-halogen is that quaternary ammonium salt 1 (comparative example 4) and non-halogen are that the proportioning of quaternary ammonium salt 2 (comparative example 5) is all outside the ratio range of the regulation of the present invention shown in the table 2.
In the comparative example 6,, mixed the quaternary ammonium salt 1 that contains halogen according to proportioning shown in the table 2 though the proportioning of used EO-PO-AGE terpolymer and paracril is the proportioning of the present invention's regulation shown in the table 2.
Comparative example 7 has used paracril and epichloro hydrin rubber, but unmixed non-halogen is quaternary ammonium salt.
The characteristic of the test film that the conductive rubber composition of above each embodiment that makes and comparative example is formed is measured as described below, and it the results are shown in the Lower Half of above-mentioned table 1 and table 2.
Experiment 2
Below, the embodiment 6～10 and the comparative example 8～11 of the composition of electric conductive polymer of the present invention is elaborated.
In embodiment 6～10 and the comparative example 8～11, with closed mixing roll (DS10-40MWA-S, the gloomy mountain of Co., Ltd. makes made) respectively according to material mixture ratio amount (cooperation reagent) mixing raw material of following table 3 and table 4 record.The banded rubber press molding that will take out from above-mentioned mixing roll with the roller extrusion machine is a sheet then, in its mould of packing into, in 160 ℃ with press vulcanization between the most in good time, make rerum natura assessment vulcanized rubber flap.
Table 3
Table 4
Embodiment 11, comparative example 12 and 13 proportionings based on table 5 and table 6 record are added quaternary ammonium salt, 1 in polyether polyhydroxy-compound, 4-butyleneglycol and silicon are tensio-active agent, after stirring with general stirrer, each raw material homogeneous are disperseed.After the dispersion, decompression deaeration is down handled, and adds isocyanic ester and catalysts then, is injected into and makes the rerum natura assessment with in the mould of test film.At last, in 80 ℃ of curing 12 hours, make same rerum natura assessment test film.
Table 5
Table 6
As non-halogen based polymer, only used paracril (embodiment 8) or used styrene-butadiene rubber(SBR) and paracril, or used EO-PO-AGE terpolymer and paracril (embodiment 6～7, and embodiment 9～10) according to proportioning shown in the table 1.Sneaking into above-mentioned non-halogen according to proportioning shown in the table 3 therein is quaternary ammonium salt, makes test film by aforesaid method by the composition of electroconductibility polymerization.
In addition, as polyether polyhydroxy-compound, use polyether polyhydroxy-compound with branched table 5 record; As the short chain polyol, use 1, the 4-butyleneglycol.Mixing the above non-halogen according to proportioning shown in the table 5 is quaternary ammonium salt, makes test film (embodiment 11) by aforesaid method by the conductive polyurethane composition.
Comparative example 8～comparative example 11
In the comparative example 8, mix EO-PO-AGE terpolymer and paracril, also mixed the quaternary ammonium salt that contains halogen according to proportioning shown in the table 4.
In the comparative example 9, do not use the EO-PO-AGE terpolymer, mixed paracril and epichloro hydrin rubber, yet unmixed quaternary ammonium salt.
In the comparative example 10, only used paracril as non-halogen based polymer.In addition, in the comparative example 11, styrene-butadiene rubber(SBR) and paracril have been used.All unmixed quaternary ammonium salt in comparative example 10 and the comparative example 11.
The characteristic of the test film that the composition of the electric conductive polymer of above each embodiment that makes and each comparative example is formed is measured as described below, and it the results are shown in the Lower Half of above-mentioned table 3～table 6.
The numerical value unit of the upper part (till vulcanization accelerator) in above-mentioned each table all is a weight part.The unit of chlorinity is weight %, and the unit of compression set rate is %.In addition, abbreviation EO representative ring oxidative ethane, PO representative ring Ethylene Oxide, AGE represent that glycidyl allyl ether, EP represent Epicholorohydrin.
In addition, the paracril in above-mentioned each table is the rubber that contains the aqueous paracril of 50 weight parts in the common paracril of 100 weight parts, represents with weight part in each table.
What not halogen-containing quaternary ammonium salt (non-halogen is quaternary ammonium salt) 1 used is above-mentioned KP-4729 (glucono-lactone salt).What not halogen-containing quaternary ammonium salt (non-halogen is quaternary ammonium salt) 2 used is above-mentioned KP-4728 (tosilate).
In the comparative example, the quaternary ammonium salt that contains halogen 1 of use is the salt (コ one ミ Application 86P コ Application Network, Kao Corp's system) with chloride structure with following formula 2 (changing 2) expression.
(changing 2)
Vulcanization accelerator 1 is that dibenzothiazyl disulfide, vulcanization accelerator 2 are N for tetramethylthiuram monosulfide, vulcanization accelerator 3, N-dicyclohexyl-2-[4-morpholinodithio base sulfinyl amine, vulcanization accelerator 4 are that 2-(4 '-morpholino dithio) benzothiazole, vulcanization accelerator 5 are N, N '-diethyl thiourea.
The mensuration of volume intrinsic resistance value
As mentioned above, make vulcanized rubber sheet (130mm * 130mm * 2mm).With ア De バ Application テ ス ト コ one Port レ one シ, the digital ultra-high resistance small electric flowmeter R-8340A that Application company produces, in temperature is that 23 ℃, relative humidity are under 55% the fixed temperature and humidity condition, apply the voltage of 500V, measure volume specific resistance (volume intrinsic resistance value) the ρ V (Ω cm) of JIS K6911 record.
Volume intrinsic resistance value denary logarithm value representation in table 1～6.
When making the solid-state roller of individual layer homogeneous, the resistance R of roller (Ω) can be represented by the formula.
R(Ω)＝(ρV/2πv)log
10(r1/r2)
In the following formula, ρ V represents volume intrinsic resistance (Ω cm), and v represents roller rubber width (cm), and r1 represents roller external diameter (mm), and r2 represents an external diameter (mm).
For example, when the size of roller is r1=15, r2=6, v=21.8, in these value substitution following formulas, be shown below in theory: log
10R (Ω)=-2.5+log
10ρ V.
Therefore, be 10 as fruit volume intrinsic resistance value (Ω cm)
7.0～10
9.0(Ω cm), then the roller resistance value R (Ω) of the solid-state duplicating roller of following formula size is 10
4.5～10
6.5(Ω).
But in measured value, the numerical value 2.5 in the following formula becomes 1.3～2.0, and roller resistance value R (Ω) is 10
5.0～10
7.7(Ω).
(Ω cm) is 10 as the fruit volume intrinsic resistance value
7.0～10
9.5(Ω cm), then the roller resistance value R (Ω) of the solid-state duplicating roller of above-mentioned size is 10
4.5～10
7.0(Ω).
But in measured value, the numerical value 2.5 in the following formula becomes 1.3～2.0, and roller resistance value R (Ω) is 10
5.0～10
8.2(Ω).
The mensuration of compression set
Scrag test method according to JIS K6262[vulcanized rubber] regulation, in the minute of 70 ℃ mensuration temperature and 24 hours, measure.
The test for contamination of photoreceptor
Each the vulcanized rubber sheet that makes embodiment, comparative example is impaction state with photoreceptor in the seal box (seal box Type C 4127X) that is set at the Laser Jet 4000 type laser printers that ヒ ュ one レ ッ ト パ ッ カ one De company produces, is that 32.5 ℃, relative humidity are to place for 1 week under 90% the condition in temperature.Then, each vulcanized rubber sheet is removed from photoreceptor, carried out the half-tone printing, whether stain is arranged, on the visual observation printed matter according to following 3 criterion evaluations with the printer that this photoreceptor is housed.
Zero: no visual visible stain on the printed matter.
△: slight pollution (have to be less than 5 blocks of stains, but visual being difficult to differentiate, do not have problem in the use).
*: severe contamination (stain more than 5 being arranged, visual obvious).
The ozone resistance assessment
According to the regulation of [the ozone deterioration test method of vulcanized rubber] of JIS K6259 record, under 40 ℃ temperature condition, test the assessment deterioration condition.Consider that from the practicality of conductive roller extensibility is 5%, ozone concn is after 2ppm, observing time being respectively 50,100,200 hours.Test with the rubber test sheet, assess according to following benchmark.
Also leakless of test film after zero: 200 hour.
△: have the crack to produce in 50～200 hours.
*: test film fracture in 50～200 hours.
Can find out from table 1, in the conductive rubber composition of the present invention of embodiment 1～embodiment 5, corresponding to 100 weight part electric conductive polymers, having mixed the following non-halogen of above 7.0 weight parts of 0.1 weight part is quaternary ammonium salt, and wherein electric conductive polymer is 90 moles of %/4 mole %/6 moles of % by the copolymerization ratio of ethylene oxide/propylene oxide/glycidyl allyl ether, number-average molecular weight Mn be epoxy ethane-epoxy propane-glycidyl allyl ether terpolymer (EO-PO-AGE multipolymer) of 80,000 (A) and paracril (B) according to (A): (B)=70: 30～5: 95 weight ratio mixes.
The volume intrinsic resistance value of the test film that is formed by the conductive rubber composition of embodiment 1～embodiment 5 is 10
8.0～10
8.8(Ω cm), the compression set rate is 14%～24%.In the assessment of photoreceptor test for contamination, embodiment 1,3,5 is △, and embodiment 2 and 4 is zero.In the ozone resistance assessment, have only embodiment 2 to be △, other embodiment are zero.
As mentioned above, the volume intrinsic resistance value of embodiment 1～embodiment 5 is lower, compression set is also less, can not pollute photoreceptor, do not have problems in the use and ozone resistance good.In addition, the chloride rate of embodiment 1～5 all is 0.0%, since not chloride, so, can not produce hydrogenchloride and dioxin even after use, handle yet.
Among the embodiment 1～5, be quaternary ammonium salt, reduced the consumption of the EO-PO-AGE terpolymer of high price, realized low resistance, reduced cost by mixing non-halogen.
As shown in table 2, different on proportioning of comparative example 1 and embodiment 1 only are that unmixed non-halogen is quaternary ammonium salt, but because unmixed non-halogen is quaternary ammonium salt, so the volume intrinsic resistance value of comparative example 1 is 10
9.1Ω cm is higher than 10 of embodiment 1
8.2Ω cm.
In the comparative example 2, only used paracril as polymkeric substance, though wherein mixed not halogen-containing (non-halogen system) quaternary ammonium salt 1, its ozone resistance is not good.
Comparative example 3 is compared with the proportioning of the present invention's regulation with different only being of embodiment 1 on proportioning, and the proportional quantity of EO-PO-AGE terpolymer increases, and causes photoreceptor by severe contamination like this, exceeds standard.In addition, the compression set rate is 25%, and is also not ideal.
The proportional quantity of comparative example 4 and embodiment 1 different only being on proportioning compared with the proportionings of the present invention's regulation, not halogen-containing (non-halogen system) quaternary ammonium salt 1 increases, and causes photoreceptor by severe contamination like this, exceeds standard.In addition, the compression set rate is 25%, and is also not ideal.
The proportional quantity of comparative example 5 and embodiment 5 different only being on proportioning compared with the proportionings of the present invention's regulation, not halogen-containing (non-halogen system) quaternary ammonium salt 2 increases, and causes photoreceptor by severe contamination like this, exceeds standard.
Different on proportioning of comparative example 6 and embodiment 1 only are that replacing non-halogen with the quaternary ammonium salt that contains halogen is quaternary ammonium salt.Owing to wherein mixed the quaternary ammonium salt that contains halogen, so becoming, the compression set rate reaches 30% greatly, exceed standard.In addition, owing to mixed the quaternary ammonium salt that contains halogen, thus chloride, will produce hydrogenchloride and dioxin when after use, handling like this.
Comparative example 7 is to have mixed paracril and epichloro hydrin rubber but the composition of unmixed quaternary ammonium salt, owing to wherein mixed chloride epichloro hydrin rubber, so will produce hydrogenchloride and dioxin when handling after use.
Can find out from table 3, in the composition of the electric conductive polymer of the present invention of embodiment 6～embodiment 7 and embodiment 10, having mixed non-halogen in non-halogen based polymer is quaternary ammonium salt, wherein non-halogen based polymer by the copolymerization ratio of ethylene oxide/propylene oxide/glycidyl allyl ether be 90 moles of %/4 mole %/6 moles %, number-average molecular weight Mn be epoxy ethane-epoxy propane-glycidyl allyl ether terpolymer (EO-PO-AGE multipolymer) of 80,000 (A) and paracril (B) mix according to the weight ratio of 25: 75 and 75: 25.Embodiment 8 has only used paracril and has mixed the composition that non-halogen is the electric conductive polymer of the present invention of quaternary ammonium salt as non-halogen based polymer.Embodiment 9 has used the mixture of paracril and styrene-butadiene rubber(SBR) and has mixed the composition that non-halogen is the electric conductive polymer of the present invention of quaternary ammonium salt as non-halogen based polymer, is similarly the composition of electric conductive polymer of the present invention.Can find out that from table 5 embodiment 11 is the composition of electric conductive polymer of the present invention too, containing non-halogen in the urethane of non-chlorine, non-halogen system is quaternary ammonium salt.
The volume intrinsic resistance value of the test film that the composition of the electric conductive polymer of embodiment 6～embodiment 11 forms is 10
7.7Ω cm～10
9.0Ω cm, the compression set rate is 9.8%～25%, confirms that embodiment 6～11 has the superperformance that the volume intrinsic resistance value is lower, the compression set rate is less.In addition, the cl content in the composition of embodiment 6～11 is 0.0%, because wherein not chloride, so even also can not produce hydrogenchloride and dioxin when handling after use.
As mentioned above, owing to used electric conductive polymer, so realized low resistance.Because having mixed non-halogen is quaternary ammonium salt, so the consumption of the EO-PO-AGE terpolymer of high price reduces in embodiment 6 and 7, realized low resistance, reduced cost.
Because only used paracril as polymkeric substance among the embodiment 8, so compare with embodiment 6～7 and embodiment 9～11, the compression set rate is 9.8%, and is especially little.In addition, be quaternary ammonium salt by mixing non-halogen, obtained to use separately in the past NBR the low resistance that can't obtain.
As shown in table 4, different on proportioning of comparative example 3 and embodiment 6 only are that having replaced non-halogen with chloride quaternary ammonium salt is quaternary ammonium salt, owing to wherein mixed chloride quaternary ammonium salt, so the compression set rate reaches 30% more greatly, exceed standard.In addition owing to mixed chloride quaternary ammonium salt, so wherein chloride, so just during the processing after use generation hydrogenchloride with dioxin.
Comparative example 9 is to have mixed paracril and epichloro hydrin rubber but the composition of unmixed quaternary ammonium salt, owing to wherein mixed chloride epichloro hydrin rubber, so can produce hydrogenchloride with dioxin during the processing after use.
Comparative example 10～comparative example 12 is compositions of halogen-containing electric conductive polymer not, but because unmixed non-halogen is quaternary ammonium salt, so the volume intrinsic resistance value reaches 10
9.6More than the Ω cm, exceed standard.
Different on proportioning of comparative example 13 and embodiment 11 only are to have mixed the quaternary ammonium salt that contains halogen, so its compression set rate increase reaches 29%.In addition, owing to contain chlorine, so can produce hydrogenchloride with dioxin during the processing after use.
As mentioned above, conductive rubber composition of the present invention, is mixed according to specified proportion more than 10000, according to the terpolymer and the paracril of the epoxy ethane-epoxy propane-glycidyl allyl ether of specific copolymerization ratio copolymerization by number-average molecular weight Mn.Therefore, it is the conductive rubber composition that a kind of volume intrinsic resistance value is lower, the compression set rate is less, pollution photoreceptor is suppressed and possesses good ozone resistance.
Because having used non-halogen in the conductive rubber composition of the present invention is quaternary ammonium salt, so not only can obtain lower volume intrinsic resistance value, also can reduce compression set.In addition, because composition in its entirety is a non-halogen system,, so just can not produce detrimentally affect to environment so, can not produce the objectionable impurities from halogen such as hydrogen chloride gas even after use, carry out burn off etc. yet.
As mentioned above, because practicality such as lower, weather resistance of volume intrinsic resistance value and dimensional stability are good, so used the rubber coated pressure bowl of conductive rubber composition of the present invention and string rubber to be applicable to copying band and to duplicate roller.Particularly require low-resistance field with product etc. in painted usefulness and high image quality, after can providing and can be used as conducting rubber roller and the use of conducting rubber band, using, even attempt is with hot or cut off and decomposed, can not produce toxic gas yet, decompose easily the product that environment is had no adverse effects.
Because having used non-halogen in the composition of electric conductive polymer of the present invention is quaternary ammonium salt, so not only can obtain lower volume intrinsic resistance value, also can reduce compression set.In addition, owing to contain non-halogen based polymer and non-halogen is quaternary ammonium salt,,, can not produce the objectionable impurities from halogen such as hydrogen chloride gas yet, so just can not produce detrimentally affect environment even after use, carry out burn off etc. so composition in its entirety is a non-halogen system.
As mentioned above, because practicality such as lower, weather resistance of volume intrinsic resistance value and dimensional stability are good, so used the rubber coated pressure bowl and the string rubber of the composition of electric conductive polymer of the present invention to be applicable to copying band and to duplicate roller.Particularly require low-resistance field with product etc. in painted usefulness and high image quality, can provide to can be used as after conducting rubber roller and conducting rubber band use, use, promptly use heat or cut off and decomposed, also can not produce toxic gas, decompose easily the product that environment is had no adverse effects.
Claims (5)
1. conductive rubber composition, it is characterized in that, the copolymerization ratio that comprises by ethylene oxide/propylene oxide/glycidyl allyl ether is 50～95 moles of %/1～49 mole %/1～10 mole of %, number-average molecular weight Mn is at the epoxy ethane-epoxy propane more than 10000-allyl glyceroether terpolymer (A) and paracril (B), according to (A): (B)=electric conductive polymer that 70: 30～5: 95 weight ratio mixes, corresponding to the above-mentioned electric conductive polymer of 100 weight parts, having mixed the following non-halogen of above 7.0 weight parts of 0.1 weight part is quaternary ammonium salt, and above-mentioned non-halogen is that quaternary ammonium salt is the sulfonic acid quaternary ammonium salt, glyconic acid quaternary ammonium salt or glucono-lactone quaternary ammonium salt.
2. conductive rubber composition as claimed in claim 1 wherein, contains aqueous paracril in the above-mentioned paracril (B).
3. electroconductibility vulcanized rubber, described vulcanized rubber obtains by the described conductive rubber composition of claim 1 is carried out sulfidizing, according to the scrag test method of the vulcanized rubber of JIS K6262 record, be that 70 ℃, minute are that the compression set rate that records under 24 hours the condition is below 25% measuring temperature.
4. the conducting rubber roller is characterized in that, has used the described electroconductibility vulcanized rubber of claim 3.
5. the conducting rubber band is characterized in that, has used the described electroconductibility vulcanized rubber of claim 3.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001009102A JP3540278B2 (en) | 2001-01-17 | 2001-01-17 | Conductive rubber composition, conductive vulcanized rubber, and conductive rubber roller and conductive rubber belt |
| JP009102/01 | 2001-01-17 | ||
| JP2001025898A JP2002226711A (en) | 2001-02-01 | 2001-02-01 | Conductive polymer composition, conductive vulcanized rubber, conductive rubber roller and conductive rubber belt |
| JP025898/01 | 2001-02-01 |
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|---|---|
| CN1366002A CN1366002A (en) | 2002-08-28 |
| CN100412131C true CN100412131C (en) | 2008-08-20 |
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| JP4925665B2 (en) * | 2003-11-17 | 2012-05-09 | 株式会社ブリヂストン | Conductive polymer member, transfer roller, and image forming apparatus |
| JP5297648B2 (en) * | 2007-12-21 | 2013-09-25 | キヤノン化成株式会社 | Conductive rubber roller |
| JP5875416B2 (en) * | 2011-03-22 | 2016-03-02 | キヤノン株式会社 | Conductive member for electrophotography |
| US20120251171A1 (en) | 2011-03-29 | 2012-10-04 | Canon Kabushiki Kaisha | Conductive member |
| JP6000580B2 (en) * | 2011-03-29 | 2016-09-28 | キヤノン株式会社 | Contact charging roller, developing member, conductive member and manufacturing method thereof, process cartridge, and electrophotographic apparatus |
| JP2017049488A (en) * | 2015-09-03 | 2017-03-09 | 富士ゼロックス株式会社 | Elastic member, charging device, process cartridge, and image forming apparatus |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2000017118A (en) * | 1998-07-02 | 2000-01-18 | Jsr Corp | Electroconductive rubber composition and electroconductive roll |
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| JP2000017118A (en) * | 1998-07-02 | 2000-01-18 | Jsr Corp | Electroconductive rubber composition and electroconductive roll |
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