CN1347940A - Conductive rubber composition and the conductive rubber roller and rubber belt - Google Patents

Conductive rubber composition and the conductive rubber roller and rubber belt Download PDF

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CN1347940A
CN1347940A CN 01135484 CN01135484A CN1347940A CN 1347940 A CN1347940 A CN 1347940A CN 01135484 CN01135484 CN 01135484 CN 01135484 A CN01135484 A CN 01135484A CN 1347940 A CN1347940 A CN 1347940A
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rubber
conductive rubber
roller
rubber composition
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CN1169877C (en
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服部高幸
沟口哲朗
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Sumitomo Rubber Industries Ltd
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Sumitomo Rubber Industries Ltd
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Abstract

The invention aims to promote decrease in compression set, improvement in processability and reduction in a vulcanization time, to prevent ozone deterioration and to control the hardness appropriate as a roller, while keeping the volume resistivity of an electroconductive rubber composition low used for a roller and the like. An ethylene oxide/propylene oxide/allyl glycidyl ether terpolymer (A) having a copolymerization ratio of ethylene oxide/propylene oxide/allyl glycidyl ether of 50-95 mole %/1-49 mole %/1-10 mole % and a number-average molecular weight Mn of at least 10,000, an acrylonitrile butadiene rubber (B) and an epichlorohydrin rubber (C) are admixed so that relationships of 0.01<=b/(a+b+c)<=0.75 and 0.01<=a/c<=2.00 are satisfied, where a, b and c are the weight of (A), (B) and (C), respectively.

Description

The conductive rubber roller and the rubber tape of conductive rubber composition and use said composition
Technical field
The relevant conductive rubber composition of the present invention and used the conductive rubber roller and the conductive rubber band of this conductive rubber composition, it can be used for effectively duplicating machine, printer etc. charged roller, video picture roller, toner supply roller, duplicate roller, duplicate belt etc.
Background technology
Be used for charged roller, video picture roller, the toning agent supply roller of this duplicating machine, printer etc., duplicate roller, duplicate belt, suitable stable resistance value must be arranged.
In the past, the method of giving this roller and belt electroconductibility has electroconductive stuffings such as the powder that mixes metal oxide in the rubber and carbon black to obtain the method for electronic conduction rubber, with use urethanes, acrylonitrile butadiene rubber (NBR), the method for epichloro hydrin rubber plasma conductive rubber.
Used fusion that the conduction roller and the conduction belt of the electronic conduction rubber of above-mentioned conductive filler material are arranged, its resistance is relevant with impressed voltage, has the problem that does not possess fixed resistor.When especially using carbon black as conductive filler material, no stable correlationship between the volume intrinsic resistivity of sooty addition and rubber.And the carbon black addition changes slightly and just causes resistance drastic change sometimes, so the control of resistance is very difficult.The volume intrinsic resistivity of conductive rubber material be configured as that the resistance of roller can be converted with formula described later behind the roller, different and different with roll form.
Owing to be difficult to conductive filler material is evenly dispersed in the rubber, there is the uneven problem of resistance at the length direction and the width of roller and belt.Even the ununiformity very big resistance lowered, in the so small scope of μ m level, resistance is inhomogeneous still to be existed.Therefore, digitizing, the colorize of develop rapidly recently in the technology of high picture qualityization, have the tendency of not using electronic conduction rubber and being ready to use ionic conduction rubber especially.
As the conductive agent of above-mentioned ionic conduction rubber, the electroconductibility oligopolymer and the electroconductibility plasticizer (number-average molecular weight Mn is below 10,000) that contain polyether structures such as polyethylene oxide are arranged.But, use the ionic conduction rubber of above-mentioned conductive agent to have the problem of easily polluting photoreceptor.
Except above said, use the method for acrylonitrile butadiene rubber (NBR) and urethanes in addition, but can not obtain 10 9.6Volume intrinsic resistivity (the resistance 10 of roller that Ω cm is above 8.2Ω cm), can not adapt to copying band, more low-resistance requirement when duplicating roller and making colored purposes.And the NBR ozone resistance is also bad.
Thereby above-mentioned purposes and a part of charged roller, video picture roller, toner supply roller etc. often mix use with epichloro hydrin rubber or with other materials separately, have proposed various motions.
The spy opens and has proposed to contain 40~10 moles of % Epicholorohydrins (epichlorohydrin) for 2000-63656 ' number, 60~90 moles of % oxyethane, and the semiconductive material of the ether based copolymer of 0~10 mole of % glycidyl allyl ether, its volume intrinsic resistivity is low.
Specially permit and proposed to use independent or propylene oxide and oxyethane for No. 2647117 30~98 moles of % propylene oxide, the rubber that 0~60 mole of % Epicholorohydrin and the fusion of 0~15 mole of % unsaturated epoxide are got up, good caoutchouc elasticity is the video picture roller of purpose under the low temperature to keep, an example as unsaturated epoxide has used glycidyl allyl ether.
When using epichloro hydrin rubber separately, be 10 though can obtain the volume intrinsic resistivity 8.1(resistance of roller is 10 to Ω cm 8.8Ω cm) such lower resistance but then, when compressive permanent strain increases, exists and will prolong curing time and unpractical problem.
Disclosed epichloro hydrin rubber or oxyethane/glycidyl allyl ether/epoxy propane copolymer is admixed in the general commercially available epichloro hydrin rubber goes in the aforementioned communique, when reducing resistance, be difficult for taking place bleeding, therefore can make the rubber coated pressure bowl that does not pollute photoreceptor.
That is, owing to contain oxyethane, make most of ion stabilizedization and realized low resistance, because the copolymerization of propylene oxide has suppressed crystallization, because the copolymerization of glycidyl allyl ether is polluted bleeding and photoreceptor and is difficult to take place.
But, in above-mentioned fusion, compare with common widely used diene series rubber, bad as the performance of roller aspect physical propertiess such as compressive permanent strain and hardness and the processing characteristics aspect, thereby have the practical problem that is not suitable for.Especially, find that when the fusion ratio of above-mentioned ethylene oxide/propylene oxide/glycidyl allyl ether multipolymer was incorrect, compressive permanent strain increased, and has the big problem of dimensional change during as roller according to present inventor's experiment.
Aforementioned spy opens disclosed semi-conductivity material 2000-63656 number, because used the high epichloro hydrin rubber of ethylene oxide content that can make ion stabilizedization, can reduce the volume intrinsic resistivity, but the hardness as roller is too high, there is shortcoming physical properties aspect and processing characteristics aspect, mattness produces wrinkle, and squeezed state has problem.When it was used separately, compressive permanent strain increased, and has the big shortcoming of dimensional change during as roller, and during with other mixed with polymers, when its kind and proportioning were incorrect, resistance rose, and had the practical problem that is not suitable for.
Equally, No. 2647117 disclosed video picture roller of above-mentioned special permission also has the shortcoming of physical properties aspects such as hardness and processing characteristics aspect, simultaneously, the proportioning of ethylene oxide/propylene oxide/glycidyl allyl ether multipolymer does not specify in the appropriate scope, so compressive permanent strain and hardness are all big, with above-mentioned the same, there is the practical problem that is not suitable for.
If the blended amount of epichloro hydrin rubber is many, curing time is just long, simultaneously, widely used rubber phase ratios such as epichloro hydrin rubber and acrylonitrile butadiene rubber (NBR) and chloroprene rubber, price is very high, if blended amount surpasses necessary amount, roller of making so and belt cost are just high, have the practical problem that is not suitable for.
Summary of the invention
In view of the above-mentioned problems, problem of the present invention is correctly to set the fusion material and the proportioning of conductive rubber composition, try hard to when keeping low volume intrinsic resistivity, reduce compressive permanent strain, improve processing characteristics, shorten curing time, and do not worsened by ozone, hardness as roller is suitable, provides to be used for colored conductive rubber composition with conductive rubber roller and conductive rubber band especially effectively.
For solving above-mentioned problem, the invention provides conductive rubber composition, it is characterized in that, mixed by following material: the copolymerization ratio of ethylene oxide/propylene oxide/glycidyl allyl ether is that 50~95 moles of %/1~49 mole %/1~10 mole of %, number-average molecular weight Mn is 10, epoxy ethane-epoxy propane more than 000-glycidyl allyl ether terpolymer (A), acrylonitrile butadiene rubber (B), epichloro hydrin rubber (C).
The weight of above-mentioned epoxy ethane-epoxy propane-glycidyl allyl ether terpolymer (A), acrylonitrile butadiene rubber (B), epichloro hydrin rubber (C) is respectively a, b and c, and they satisfy following relational expression:
0.01≤b/(a+b+c)≤0.75
0.01≤a/c≤2.00。
As mentioned above, in the conductive rubber composition of the present invention, the mutual copolymerization ratio of epoxy ethane-epoxy propane-glycidyl allyl ether terpolymer is specific, and this terpolymer mixes with specific ratio with epichloro hydrin rubber.Therefore, can obtain the irrealizable practicality of ionic conduction rubber in the past, i.e. low resistance, compressive permanent strain is little, and dimensional stability height when making roller or belt.
Simultaneously, (NBR) mixes into specific ratios acrylonitrile butadiene rubber, in the scope of not losing ozone resistance, improved compressive permanent strain, can realize softization, improve processing characteristics, shorten curing time, when making the pulley type belt, the surface is glossy, non-wrinkle, squeezed state is splendid.
Therefore, good physicals (compressive permanent strain, hardness, curing time etc.) and processing characteristics is provided for low conductive rubber roller and the conductive rubber band of volume intrinsic resistivity.And in mixture as described above, according to using epichloro hydrin rubber separately in the past, or epichloro hydrin rubber mixes with NBR in the volume intrinsic resistivity scope that can realize, can reduce expensive epichloro hydrin rubber blended amount, realizes that cost reduces.
Above-mentioned epoxy ethane-epoxy propane-glycidyl allyl ether terpolymer (A), acrylonitrile butadiene rubber (B), epichloro hydrin rubber (C) weight separately are respectively a, b, c, satisfy the relation of 0.01≤b/ (a+b+c)≤0.75 when mixing.
In the above range with acrylonitrile butadiene rubber (NBR) when mixing, on the one hand, the physicals of NBR is very good, and (compressive permanent strain is low, and curing time is short in following specific curing system), second aspect, three's component of polymer (good especially in following specific curing system) crosslinked together well, the third aspect, especially the BNR that contains aqueous NBR can realize softization, so the physicals of composition (compressive permanent strain, hardness, curing time) is good.Mixed NBR (particularly containing aqueous NBR), polymer chain is movable easily, thus good processability, and ion transport efficiency height, so the volume intrinsic resistivity has also reduced.
Above-mentioned b/ (a+b+c) value was less than 0.01 o'clock, exist the physicals of processing characteristics and composition not reach the problem of improvement and the value of above-mentioned b/ (a+b+c) above 0.75 o'clock, ozone can take place makes it become bad situation, simultaneously, there is the problem that the volume intrinsic resistivity is raise in volume intrinsic resistivity rising because of NBR itself.
Above-mentioned again specific curing system is the system that the ratio fusion of sulphur/dibenzothiazyl disulfide/tetramethylthiuram monosulfide=1.5/1.5/0.5 or sulphur/2-mercaptobenzothiazole/tetramethylthiuram monosulfide=1.5/1.5/0.5 is got up.
With regard to above-mentioned acrylonitrile butadiene rubber (NBR), physicals is good and with above-mentioned epichloro hydrin rubber and above-mentioned epoxy ethane-epoxy propane-glycidyl allyl ether terpolymer the diene series rubber of high-compatibility to be arranged be suitable.Such rubber can be enumerated various NBR such as middle butyronitrile, middle high nitrile, high nitrile, high butyronitrile.
The copolymerization ratio of above-mentioned oxyethane (below be also referred to as EO)/propylene oxide (below be also referred to as PO)/glycidyl allyl ether (below be also referred to as AGE) takes 50~95 moles of %/1 ~ 49 mole %/1 ~ 10 mole of % that following reason is arranged.
In the conductive rubber composition, the performance of conductivity be because oxonium ion in the polymkeric substance and metallic cation (as nickel ion contained in the polymkeric substance protective agent etc.) by the ethylene oxide unit stabilization, because of the motion of polymer moieties molecule segment is transported.Therefore, think the ratio height of ethylene oxide unit just can make most ion stabilizedization, can bring into play low resistanceization.
But, after the ratio of oxyethane improved, the crystallization of oxyethane had taken place, hindered the motion of molecule segment, the volume intrinsic resistivity is risen.In order to suppress the crystallization of this oxyethane, make and the propylene oxide copolymerization.
The volume intrinsic resistivity scope of conductive rubber composition of the present invention is with 10 7.2Ω cm~10 8.9Ω cm is for well.The volume intrinsic resistivity is lower than 10 7.2Ω cm is difficult to realize that all excellent conductive rubber composition of each physicals becomes ionic conduction rubber, only relies on electronic conduction resins such as carbonaceous conductive; And greater than 10 8.9During Ω cm, when making roller and belt, duplicating, efficient charged, toner supply reduce, and the practical problem that is not suitable for is arranged.
The condition determination of volume intrinsic resistivity is that 23 ℃, relative humidity are that impressed voltage is 500 volts under 55% the fixed temperature and humidity condition.
Set above-mentioned oxyethane, propylene oxide, the mutual copolymerization ratio of glycidyl allyl ether terpolymer, and stipulate the part by weight of this terpolymer and epichloro hydrin rubber and the part by weight of acrylonitrile butadiene rubber, make the physical properties (compressive permanent strain of above-mentioned composition, hardness, curing time) and processing characteristics above-mentioned volume intrinsic resistivity is arranged again when being maintained.
Oxyethane is lower than 50 moles of % and propylene oxide surpasses 49 moles of %, and then the ionic stabilization is insufficient, reduces the weak effect of volume intrinsic resistivity.On the other hand, when oxyethane surpassed 95 moles of %, propylene oxide was lower than 1 mole of %, the problem that then has the volume intrinsic resistivity to rise too high.Aspect physical properties,, the practical problem that is unsuitable for is arranged during as roller and belt because crystallization too improves hardness.
With above-mentioned glycidyl allyl ether copolymerization, just might form crosslinkedly, thereby bleeding be difficult for to take place and pollute photoreceptor, can keep the elasticity of rubber simultaneously, improve physical properties.This glycidyl allyl ether unit itself has increased free volume as side chain again, can further suppress above-mentioned crystallization thereby can realize unprecedented low resistanceization.
The copolymerization ratio of glycidyl allyl ether is 1~10 mole of %, when being lower than 1 mole of %, easily produce bleeding, pollute photoreceptor, and on the other hand, when surpassing 10 moles of %, do not produce the effect that suppresses crystallization, the quantity of the cross-linking set after the sulfuration increases, and can not realize low resistanceization on the contrary, and makes deteriorations such as tensile strength, resistent fatigue characteristic, resistance to bend(ing).
Like this,, suppressed the crystallization of oxyethane, reduced the volume intrinsic resistivity with the glycidyl allyl ether copolymerization, on the other hand since with the copolymerization of glycidyl allyl ether, imported carbon-to-carbon double bond, can with other rubber cross.Owing to other rubber cross, can improve molecular weight, therefore, the blended amount of above-mentioned epoxy ethane-epoxy propane-glycidyl allyl ether terpolymer is many more also to be difficult for the generation bleeding and to pollute photoreceptor.
The number-average molecular weight Mn that makes the terpolymer of above-mentioned epoxy ethane-epoxy propane-glycidyl allyl ether is more than 10,000, is in order to prevent the cause of bleeding and pollution photoreceptor.
The weight of above-mentioned epoxy ethane-epoxy propane-glycidyl allyl ether terpolymer (A), epichloro hydrin rubber (C) is respectively a and c, mixes by following relational expression:
0.01≤a/c≤2.00。
Here, when above-mentioned a/c value less than 0.01 the time, then can not realize low resistanceization, on the other hand, when the a/c value greater than 2.00 the time, compressive permanent strain increases, or poor processability, simultaneously, the volume intrinsic resistivity does not reduce.
Specifically, above-mentioned a/c value is in 0.01 to 0.50 scope, and along with the increase of terpolymer, the volume intrinsic resistivity reduces equally, but then is almost definite value between 1.00 and 2.00.On the contrary, when the value of a/c surpassed 2.00, the volume intrinsic resistivity increased, and has produced above-mentioned problem.
Above-mentioned acrylonitrile butadiene rubber (B) preferably contains aqueous acrylonitrile butadiene rubber.The acrylonitrile butadiene rubber that contains aqueous acrylonitrile butadiene rubber, particularly wherein acrylonitrile content is high, with above-mentioned ter-polymers (A) and epichloro hydrin rubber (C) good consistency is arranged, after mixing, or when extruding, can make rubber surface good very effectively, and the hardness of sulfide is reduced, so most suitable.Especially, acrylonitrile butadiene rubber (NBR) is the mixture of high molecular NBR and aqueous NBR, can prevent that photoreceptor from polluting, and make rubber combination keep good physical properties, so particularly suitable.Concrete ニ Star ボ-Le that Japanese ゼ ォ Application company produces, the DN223 of enumerating.
In the present invention, because the mixture ratio of EO-PO-AGE terpolymer is suitable, and the kind of sulfur-crosslinked promotor is suitable, so compressive permanent strain is low, preferably is no more than 30% with the compressive permanent strain value under the solid test piece occasion of method of JIS K6262 record described later.Above-mentioned compressive permanent strain value surpasses at 30% o'clock, and when making roller, the variation of size is excessive, so be not suitable for practicality.When especially using as foam material, because the different more or less difference of expansion ratio and foaming form, but the compressive permanent strain value under this solid state should be with below 30%.
The optimum vulcanization time of conductive rubber composition of the present invention is preferably in 1 minute to 40 minutes the scope.If less than one minute, then there is the rubescent problem of rubber the optimum vulcanization time in mixing and extrusion process, only curing time surpasses 40 minutes then the problem that yields poorly.
When conductive rubber composition of the present invention was used for the solid duplicating roller of color printer, its hardness (Asker-c hardness) was preferably in 50~75 the scope.Hardness may easily produce the problem of surface tackiness and pollute photoreceptor, and hardness surpassed at 75 o'clock, because really up to the mark, when installing on the printer, might bring physical injury to miscellaneous parts such as photoreceptor and middle copying belts less than 50 o'clock.When by foaming hardness being reduced, if hardness is too high under the solid state, it will be very difficult wanting not damage other physical properties and hardness is reduced to be suitable for practical hardness (30~50) by foaming.External diameter φ 15mm, the hardness of the solid duplicating roller of axle diameter phi 6mm is consistent with the block test piece hardness of vulcanized rubber described later.
Above-mentioned epichloro hydrin rubber, it can be the independent polymkeric substance of Epicholorohydrin, also can be the binary or the terpolymer of Epicholorohydrin (hereinafter referred to as EP) and oxyethane (EO) or glycidyl allyl ether (AGE), except being 10 at above-mentioned number-average molecular weight Mn, outside in the EO-PO-AGE terpolymer more than 000, in epichloro hydrin rubber, also can make EO, just have to reach more low-resistance advantage or/and the AGE copolymerization mixes both.
Especially, preferably contain oxyethane in the epichloro hydrin rubber, because the volume intrinsic resistivity is lower.Preferably contain glycidyl allyl ether in the epichloro hydrin rubber,, do not allow the volume intrinsic resistivity raise and can prevent that photoreceptor from polluting because can come crosslinkedly with sulphur.
The suitable ratio that contains of EP in the above-mentioned epichloro hydrin rubber: EO: AGE is 10~65 moles of %: 30~90 moles of %: 0.5~10 mole of %, that preferably is EP: EO: AGE=15~45 mole %: 50~75 moles of %: 3~7 moles of %.
The kind of vulcanization accelerator preferably mixes dibenzothiazyl disulfide and tetramethylthiuram monosulfide, and, increase the blended amount (be common usage quantity (1 weight part) 2-5 times) of sulphur and dibenzothiazyl disulfide.Also can use the surrogate 2-mercaptobenzothiazole of dibenzothiazyl disulfide etc.
Conductive rubber composition of the present invention is that above-mentioned terpolymer, epichloro hydrin rubber, acrylonitrile butadiene rubber, vulcanizing agent are reached various dopants (as vulcanization accelerator, filler, antioxidant, the protective agent etc.) melting mixing that mixes as required.Make conductive rubber by sulfuration.Melting mixing can carry out with usual practice.For example, known compounding rubber devices such as usefulness open type roller, sealed mixing roll descended mixing 2~10 minutes at 40~130 ℃.
In order to realize low resistanceization and low the pollution, the most handy sulphur vulcanizes as curing system.If further use hydrotalcite, see better certainly from the low angle of polluting.Vulcanize available common way and carry out, for example add to depress and in vulcanizing boiler, vulcanize, also can carry out post cure as required at water vapor.
Be shaped with above-mentioned conductive rubber composition and make conductive rubber roller and conductive rubber band.Conductive rubber composition of the present invention is because to have low volume intrinsic resistivity and a compressive permanent strain little, the advantage of other physical propertiess (hardness, curing time) and processing characteristics, the conductive rubber roller made from it.Be applicable to that as low-resistance roller at the color photocopying roller, charged roller, toner supply roller and video picture roller etc. require low-resistance occasion to be suitable for especially.
Above-mentioned conductive rubber roller can be made with ordinary method, such as, above-mentioned conductive rubber composition (mixing thing) is formed tubulose with single shaft extrusion machine preformation, with this preformed articles under 160 ℃ through 10~60 minutes the sulfuration finish after, insert axle, cut into desired size behind the glazed surface and make always known the whole bag of tricks such as roller and all can use.Curing time can (for example キ ュ ラ ス ト メ-) mensuration be determined only curing time with rheometer with the sulfuration test.As required, can be about said temperature with curing temperature.
Above-mentioned conductive rubber band, available always known the whole bag of tricks, for example above-mentioned conductive rubber composition (mixing thing) is squeezed into band shape with extrusion machine after, 160 ℃ carry out 10~60 minutes the sulfuration, make the rubber tape body.As required, can be about said temperature with curing temperature.
Description of drawings
Fig. 1 is the sketch of conduction roller of the present invention.
Fig. 2 is the sketch of conductive rubber band of the present invention.
Nomenclature
1 is the conductive rubber roller
2 is axle
3 is the conductive rubber band
Embodiment
Embodiments of the present invention below are described.Conductive rubber composition of the present invention is characterised in that, mix by following material: the copolymerization ratio of ethylene oxide/propylene oxide/glycidyl allyl ether be 50~95 moles of %/1~49 mole %/1~10 mole %/, number-average molecular weight Mn is 10, epoxy ethane-epoxy propane more than 000-glycidyl allyl ether terpolymer (A), acrylonitrile butadiene rubber (B), epichloro hydrin rubber (C)
The weight of above-mentioned epoxy ethane-epoxy propane-glycidyl allyl ether terpolymer (A), acrylonitrile butadiene rubber (B), epichloro hydrin rubber (C) is respectively a, b and c, and they satisfy following relational expression:
0.01≤b/(a+b+c)≤0.75
0.01≤a/c≤2.00。
Above-mentioned acrylonitrile butadiene rubber (B) has used and has contained aqueous acrylonitrile butadiene rubber, rubber (acrylonitrile content is 31.5%) that acrylonitrile content is high.
Vulcanizing agent and various dopant fusion are as required joined in the above-mentioned rubber combination after good, carry out melting mixing with known compounding rubber devices such as closed mixing machines.Can make the conductive rubber composition that can be used for conductive rubber roller etc. like this, its volume intrinsic resistivity maintain low-level on, reduce compressive permanent strain simultaneously again, improve processing characteristics, shorten curing time, and not by the ozone deterioration, also suitable as its hardness of roller.
The mixing thing intact above-mentioned sulfuration is pre-formed into tubulose with the single shaft extrusion machine, and this preformed articles under 160 ℃, after sulfuration in 10~60 minutes, is inserted axle, cuts into desired size behind the glazed surface, makes to duplicate and uses roller.As shown in Figure 1, above-mentioned duplicating is columnar with conductive rubber roller 1 basically, and axle 2 was inserted in interior week.
Made the conductive rubber roller with above-mentioned conductive rubber composition in the present embodiment and used roller, but this conductive rubber composition also can be used for conductive rubber rollers such as charged roller, video picture roller, toner supply roller certainly as duplicating again.But conductive rubber composition also fusion is used as foaming roller etc. with various whipping agents.
As shown in Figure 2, make the conductive rubber band 3 that duplicates belt etc. with conductive rubber composition.Conductive rubber band 3 is by plural leather belt roller 4 tensionings, and the straight line portion 5 of sides carries sheet material such as paper and transports forward above the conductive rubber band 3 that revolution is moved, and difference is according to circumstances duplicated toning agent on the paper from photoreceptor.
Embodiment 1~3 and comparative example 1~6, the adulterant that the fusion of being put down in writing by following table 1 and table 2 forms is made conductive rubber composition through mixing and sulfuration.Made solid duplicating rubber coated pressure bowl by the conductive rubber composition of present embodiment and comparative example.
Table 1
Adulterant Adulterant detail (material name (=trade name) manufacturers) Embodiment 1 Embodiment 2 Embodiment 3
EO-PO-AGE multipolymer (EO: PO: AGE=90: 6: 4) ZSN8030 Japan ゼ ォ Application ????40 ????47.5 ??????12.5
Epichloro hydrin rubber (EO: PO: AGE=56: 40: 4) ェピクロマ-CG102 ダィソ- ????40 ????47.5 ??????12.5
Acrylonitrile butadiene rubber ニツポ-ルDN223 Japan ゼ ォ Application ????20 ????5 ??????75
Mineral filler 1 Light calcium carbonate Ball tail カ Le シ ゥ system ????20 ????20 ??????20
Synthetic hydrotalcite DHT-4A-2 The consonance chemistry ????1.2 ????1.43 ??????0.375
Zinc oxide Silver R Dong Bangya lead ????5 ????5 ??????5
Stearic acid 4931 ュニケマォ-ストラリア ????1 ????1 ??????1
Vulcanizing agent 1 Sulfur flour Crane sees chemistry ????1.5 ????1.5 ??????1.5
Vulcanization accelerator 1 ノクヤラ-DM The emerging chemical industry of imperial palace ????1.5 ????1.5 ??????1.5
Vulcanization accelerator 2 ノクヤラ-TS The emerging chemical industry of imperial palace ????0.5 ????0.5 ??????0.5
Volume intrinsic resistivity (during 500V) (denary logarithm value) ????7.4 ????7.2 ??????8.9
Processing characteristics is estimated ????○ ????△ ??????○
Optimum vulcanization time t c(100) [minute] ????20 ????33 ??????24
Compressive permanent strain (estimating) with solid rubber test piece, [%] ????19 ????27 ??????15
Ozone deterioration test (estimating) with the rubber sheet ????○ ????○ ??????△
Hardness (Asker-C) ????21 ????73 ??????63
Table 2
Adulterant Adulterant detail (material name (=trade name) manufacturers) Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Comparative example 5 Comparative example 6
EO-PO-AGE multipolymer (E O: PO: AGE=90: 6: 4) ZSN?80?30 Japan ゼ ォ Application ????0 ????50 ????10 ????0 ????75 ????100
Epichloro hydrin rubber (EO: PO: AGE=56: 40: 4) ェピクロマ-CG102 ダィソ- ????100 ????50 ????10 ????0 ????0 ????0
Acrylonitrile butadiene rubber ニツポ-ルDN223 Japan ゼ ォ Application ????0 ????0 ????80 ????100 ????25 ????0
Mineral filler 1 Light calcium carbonate Ball tail カ Le シ ゥ system ????20 ????20 ????20 ????20 ????20 ????20
Synthetic hydrotalcite DHT-4A-2 The consonance chemistry ????3 ????1.5 ????0.3 ????0 ????0 ????0
Zinc oxide Silver R Dong Bangya lead ????5 ????5 ????5 ????5 ????5 ????5
Stearic acid 4931 ュニケマォ-ストラリア ????1 ????1 ????1 ????1 ????1 ????1
Vulcanizing agent 1 Sulfur flour Crane sees chemistry ????1.5 ????1.5 ????1.5 ????1.5 ????1.5 ????1.5
Vulcanization accelerator 1 ノクヤラ-DM The emerging chemical industry of imperial palace ????1.5 ????1.5 ????1.5 ????1.5 ????1.5 ????1.5
Vulcanization accelerator 2 ノクヤラ-TS The emerging chemical industry of imperial palace ????0.5 ????0.5 ????0.5 ????0.5 ????0.5 ????0.5
Volume intrinsic resistivity (during 500V) (denary logarithm value) ????8.2 ????7.4 ????9.5 ????9.7 ????7.8 ????7.6
Processing characteristics is estimated ????○ ????△ ????○ ????○ ????× ????×
Optimum vulcanization time t c(100) [minute] (no torque peak)>60 ????37 ????26 ????33 ????14 ????47
Compressive permanent strain (estimating) with solid rubber test piece, [%] ????32 ????33 ????14 ????10 ????30 ????44
Ozone deterioration test (estimating) with the rubber sheet ????○ ????○ ????× ????× ????○ ????○
Hardness (Asker-C) ????69 ????75 ????62 ????60 ????34 ????86
Top (till vulcanization accelerator) numerical value in each table all is weight.ED representative ring oxidative ethane, PO representative ring Ethylene Oxide, AGE represents glycidyl allyl ether.
In each table, acrylonitrile butadiene rubber is the aqueous acrylonitrile butadiene rubber (ニ Star Port-Le DN223, acrylonitrile content are 31.5%) that contains 50 weight part ratios in the conventional high-molecular weight vinyl cyanide divinyl rubber of per 100 weight parts.Vulcanization accelerator 1 is a dibenzothiazyl disulfide, vulcanization accelerator 2 is-vulcanize tetra methylthiuram.
(embodiment 1~3)
As shown in table 1, EO-PO-AGE terpolymer (Mn80,000), epichloro hydrin rubber (Mn140,000), acrylonitrile butadiene rubber are pressed the proportioning of afore mentioned rules and mixed, obtain conductive rubber composition.
(comparative example 1~6)
As shown in table 2, only use EO-PO-AGE ter-polymers (Mn80,000), only use epichloro hydrin rubber (Mn140,000), the proportioning of the only conductive rubber composition made from acrylonitrile butadiene rubber, and acrylonitrile butadiene rubber is in specialized range resulting conductive rubber composition in addition.
In closed mixing machine (DS10-40MWA-S, gloomy mountain (strain) makes manufacturing), undertaken mixing material shown in above-mentioned table 1, the table 2 respectively by blended amount separately.The rubber that takes out with ribbon from above-mentioned mixing roll is laminar with roller head extrusion machine extrusion molding, and thin slice is added in the metal die, with only time press vulcanization, makes and estimates the vulcanized rubber piece that physical properties is used under 160 ℃.
Each embodiment that makes as mentioned above and the conductive rubber composition of each comparative example are made following characteristic measurement.Its result is shown in lower part of above-mentioned table 1 and table 2.
(mensuration of volume intrinsic resistivity)
Make test block (130mm * 130mm * 2mm) by the above-mentioned vulcanized rubber piece of making, digital ultra-high resistance microgalvanometer R-8340 with ア De バ Application ス ト コ-Port レ-シ ョ Application corporate system, be under 55% the fixed temperature and humidity condition 23 ℃ and relative humidity, impressed voltage 500V measures volume specific resistance (volume intrinsic resistivity) the ρ V (Ω cm) that JIS K6911 is put down in writing.
In the occasion of the solid roller of individual layer homogeneous, the resistance R of roller (Ω) can be represented by following formula
R(Ω)=(ρV/2πν)log 10(r 1/r 2)
In the formula, ρ V is volume intrinsic resistivity (Ω cm), and ν is the width (cm) of rubber coated pressure bowl, r 1Be roller external diameter (mm), r 2External diameter (mm) for axle.
Here, the roller of making in embodiment and the comparative example is of a size of r 1=15, r 2=6, ν=21.8 with these value substitutions, become following formula in theory:
log 10R(Ω)=-2.5+log 10ρV
Therefore, volume intrinsic resistivity (Ω mm) is if 10 7.2~10 8.9(Ω cm), then the resistance R (Ω) of the solid photocopying roll of above-mentioned size becomes 10 4.7~10 6.4(Ω).
But measured value is, several 2.5 in the following formula becomes 1.3~2.0, and roller resistance R (Ω) is 10 5.2~10 7.6(Ω).
The denary logarithm value of the intrinsic resistivity of volume shown in table 1, the table 2.
(evaluation of processing characteristics)
Observe the surface of the rubber thin slice when pushing out after mixing, estimate and compare with following benchmark.
◎: glossy, non-wrinkle, squeezed state is splendid
Zero: tarnish, non-wrinkle, squeezed state is good
△: thin and shallow wrinkle are arranged, make behind the roller and do not hinder practicality through polishing, squeezed state still can.
*: wrinkle are many, and the polishing back is as the also inapplicable practicality of roller and dark, and squeezed state is very poor.
(evaluation of curing time)
After getting the sample of unvulcanized rubber composition of embodiment, comparative example of suitable amount, measure vulcanization curve with the キ ュ ラ ス ト メ- V-type VDR of Niri Shoji K. K.'s system." oscillatory type vulcanzing tester sulfuration test " and " mould sulfuration test A " according to the JIS specification, test piece applies the sine wave oscillations of the certain amplitude that does not reach Rogue program to rubber, never vulcanize the torque of measuring mould above test piece passes to until over cure, calculate tc (100) (maximum torque point) as the optimum vulcanization time index [minute], compare respectively.
(mensuration of compressive permanent strain)
According to the regulation of JISK6262 " vulcanized rubber permanent strain test method(s) ", do to measure temperature and be 70 ℃, minute and be 24 hours mensuration.
(ozone deterioration test)
According to the regulation of " the vulcanized rubber ozone deterioration test method " of JIS K6259 record, under 40 ℃ temperature condition, test, estimate the state of deterioration.But consider from the practical standpoint of conduction roller, get elongation 5%, ozone concn 2ppm, be 50,100,200,300 hours observing time after.Evaluation is carried out on block rubber.
Flawless after zero: 300 hour
△: crack in 50~300 hours
*: internal cutting off in 50~300 hours
(measurement of hardness)
With the vulcanized rubber piece of press vulcanization making 80mm * 45mm * 10mm as described above, with the durometer " SRIS0101 type " that polymer gauge (strain) is made, apply the load of 1,000 gram, sample is carried out measurement of hardness (Asker-C hardness).
As known from Table 1, the copolymerization ratio of ethylene oxide/propylene oxide/glycidyl allyl ether of embodiment 1, embodiment 2, embodiment 3 is that 90 moles of %/6 mole %/4 moles of %, number-average molecular weight Mn are 80,000 epoxy ethane-epoxy propane-glycidyl allyl ether terpolymer (EO-PO-AGE multipolymer) and epichloro hydrin rubber are 1.00 to mix with weight ratio, and be 0.20,0.05,0.75 to mix with acrylonitrile butadiene with the value of above-mentioned b/ (a+b+c), form conductive rubber composition.The value of above-mentioned b/ (a+b+c) is the conductive rubber composition of 0.020 embodiment 1, except the volume intrinsic resistivity is low to moderate 10 7.4Outside the Ω cm, processing characteristics, ozone resistance are all good, and optimum vulcanization time, compressive permanent strain, hardness all are the practical suitable values that, and can confirm to have excellent characteristic as rubber coated pressure bowl.
The value of above-mentioned b/ (a+b+c) is the conductive rubber composition of 0.05 embodiment 2, and the volume intrinsic resistivity is very low, is 10 7.2Ω cm, optimum vulcanization time, compressive permanent strain, hardness all are the practical suitable values that.Though the processing characteristics evaluation is △, wrinkle is unshowy, there is no obstruction in the practicality, can confirm to have excellent characteristic as rubber coated pressure bowl.
The value of above-mentioned b/ (a+b+c) is the conductive rubber composition of 0.75 embodiment 3, and the volume intrinsic resistivity almost has 10 8.9Ω cm is so high, but processing characteristics is very good, and ozone resistance is evaluated as △, and optimum vulcanization time, compressive permanent strain, hardness all are the practical suitable values that.Can confirm to have excellent characteristic as rubber coated pressure bowl.
On the other hand, as shown in table 2, the composition of comparative example 1 does not use the EO-PO-AGE multipolymer, has only used epichloro hydrin rubber, does not use acrylonitrile butadiene rubber yet, and its volume intrinsic resistivity almost has 10 8.2Ω cm is so high, and processing characteristics and ozone resistance are also all good, but does not have the peak value of torque when vulcanization curve is measured, and only curing time reached more than 60 minutes, and compressive permanent strain is also high, thereby is unsuitable for practicality.
The conductive rubber composition of comparative example 2 EO-PO-AGE multipolymer, but do not use acrylonitrile butadiene rubber, except that processing characteristics, each evaluation result of curing time were relatively poor, hardness, compressive permanent strain were also high, thereby are unsuitable for practicality.
The proportioning of the acrylonitrile butadiene rubber of comparative example 3 is higher than the scope of regulation, 4 of comparative examples have been used acrylonitrile butadiene rubber, each evaluation result of its processing characteristics, curing time, compressive permanent strain, hardness is all good, but except that the volume intrinsic resistivity was very high, the evaluation of ozone deterioration was also very poor.
The composition fusion of comparative example 5 EO-PO-AGE multipolymer and acrylonitrile butadiene rubber, but do not use epichloro hydrin rubber, its processing characteristics is very poor, hardness is also high, thereby inapplicable practicality.
Comparative example 6 has only used the EO-PO-AGE polymkeric substance, and processing characteristics is very poor, and hardness is also high, and compressive permanent strain is also high, thereby is unsuitable for practicality.
By above explanation as can be known, according to the present invention, with number-average molecular weight Mn is 10, epoxy ethane-epoxy propane-glycidyl allyl ether the terpolymer that forms more than 000, with specific copolymerization ratio, mix with epichloro hydrin rubber and acrylonitrile butadiene rubber with specific proportioning, can obtain that the volume intrinsic resistivity is low, compressive permanent strain is little, processing characteristics is improved and not by ozone institute deterioration, as the also suitable conductive rubber composition of the hardness of roller.
Like this, above-mentioned conductive rubber composition, the volume intrinsic resistivity is low, dimensional stability height when making roller or belt, and when extruding the surface glossy, no wrinkle can be made product fabulous, that excellent practicality is arranged.
Again, the shortening of curing time also may reduce the blended amount of expensive epichloro hydrin rubber, might realize the reduction of cost.
Therefore, as in the past conductive rubber composition irrealizable low resistance conductive rubber composition with practical value, can be used for various uses.Specifically,, require more low-resistance process, can both be used as the conductive rubber band of conductive rubber roller no matter be to duplicate belt and duplicate the roller or the rubber tape of colored usefulness, roller.

Claims (8)

1. conductive rubber composition is characterized in that, is mixed by following material:
The copolymerization ratio of ethylene oxide/propylene oxide/glycidyl allyl ether is that 50~95 moles of %/1~49 mole %/1~10 mole %, number-average molecular weight Mn are the epoxy ethane-epoxy propane-glycidyl allyl ether terpolymer (A) more than 10,000,
Acrylonitrile butadiene rubber (B),
Epichloro hydrin rubber (C),
The weight of above-mentioned epoxy ethane-epoxy propane-glycidyl allyl ether terpolymer (A), acrylonitrile butadiene rubber (B), epichloro hydrin rubber (C) is respectively a, b, c,
They satisfy following relation:
0.01≤b/(a+b+c)≤0.75
0.01≤a/c≤2.00。
2. conductive rubber composition as claimed in claim 1, its feature are that also above-mentioned acrylonitrile butadiene rubber (B) contains aqueous acrylonitrile butadiene rubber.
3. conductive rubber composition as claimed in claim 1, its feature are that also the scope of volume intrinsic resistivity is 10 7.2Ω cm~10 8.9Ω cm.
4. conductive rubber composition as claimed in claim 1, its feature is that also compressive permanent strain is lower than 30%.
5. the conductive rubber roller is characterized in that, has used the described conductive rubber composition of claim 1.
6. the conductive rubber roller is characterized in that, has used the described conductive rubber composition of claim 2.
7. the conductive rubber band is characterized in that, has used the described conductive rubber composition of claim 1.
8. the conductive rubber band is characterized in that, has used the described conductive rubber composition of claim 2.
CNB011354844A 2000-10-10 2001-10-10 Conductive rubber composition and the conductive rubber roller and rubber belt Expired - Fee Related CN1169877C (en)

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