CN1321427C - Semi-conductive rubber part - Google Patents
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- CN1321427C CN1321427C CNB2004100978025A CN200410097802A CN1321427C CN 1321427 C CN1321427 C CN 1321427C CN B2004100978025 A CNB2004100978025 A CN B2004100978025A CN 200410097802 A CN200410097802 A CN 200410097802A CN 1321427 C CN1321427 C CN 1321427C
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Abstract
To provide a semiconductive rubber member causing no substantial sticking of foreign matter represented by a toner outer additive for a long period through reducing the surface free energy of the rubber member while maintaining its electrical properties' uniformity and design values' repeated reproducibility, excellent in processability and substantially exhibiting no surface defects including molding unevenness and cracks. This semiconductive rubber member is obtained by compounding 100 pts. mass of an ionically conductive rubber including a rubber having polyether linkages with 0.1-5 pt(s). mass of a wax. In this rubber member, it is preferable that the rubber having the polyether linkages to be used consists of a polymer made from a halogen-containing ether-based monomer and, when desired, a halogen-free ether-based monomer and/or a copolymerizable unsaturated epoxide-based monomer.
Description
Technical field
The present invention relates to semi-conductive rubber part, more particularly, the present invention relates to semi-conductive rubber part a kind of parts as the developer roll that in image processing system, contact etc., that external additive such as toner is difficult for adhering to and having the processing characteristics of excellence with toner.
Background technology
In recent years, the image processing system of laser printer etc. high speed and high image qualityization hastily.For this reason, in the initial stage process that image forms, require photoreceptor directly related and contiguous parts high precision int, high durableization and high speed (response is fast) and the characteristic homogenization in parts thereof with picture quality.Particularly for the parts that need conductivity, require when resistance value is adjusted to setting, electrical characteristics such as the resistance value in parts are homogeneous very.
As semi-conductive rubber part, be extensive use of the elastomer of electron conduction in the past.
The electron conduction elastomer is that to have added with the conductive carbon be the elastomer of the electroconductive stuffing of representative.Described electron conduction elastomer is owing to its conductivity can change along with gap between the particle of electroconductive stuffing, therefore, even add the filler of isodose, but the absolute value of resistance reaches the resistance value of each point in parts also easily owing to the dispersity of filler produces difference.
Therefore, in recent years, replace the elastomeric trend of electron conduction in expansion rapidly with the ionic conductivity elastomer.
In addition, under the requirement of above-mentioned image processing system high image qualityization, high precision int, with to the research of various conductive components accordingly, the technological innovation of toner (toner also claims ink powder) is also being carried out.In the past, the what is called pulverizing toner of small particle diameter is pulverized, made to the material that has added pigment, electric conducting material etc. and carried out mixing in resin with various mixing extruders was a main flow.But this pulverizing toner will realize that the following particle diameter of 10 μ m is very difficult.For this reason, but small particle diameterization to the use of the polymerization toner below the 10 μ m in expansion rapidly.The reason that realizes such small particle diameterization easily is that the polymerization toner is the toner that is not attended by pulverizing process, for example, as long as polymerization and dry in solution just can form toner.
When using the following small particle diameter toner of above-mentioned 10 μ m, have such problem that had not in the past had: promptly, toner condenses when keeping easily, thereupon producing the toner shape because polymerization and spheroidization, toner surface area diminish, are difficult for charged etc.
For addressing the above problem, in present employed toner, added the particulate that is called external additive (external additive).This external additive is the particle about tens of～hundreds of nm, to prevent the toner caking, and in order to make toner charged rapidly, be extensive use of at present have with the toner opposite charges or approach uncharged material, concrete have metal oxides such as silicon dioxide, titanium oxide, aluminium oxide.
In addition, in the polymerization toner, because easy this advantage of the design that toner is formed uses the one component system of carrier to receive an acclaim.In one component system, accept toner equably, the toner of accepting verily be supplied to the developer roll that is depicted in the sub-image on the photoreceptor and become from the past magnetic roller and use rubber-like semiconduction rubber rollers.
Compare with the magnetic roller that uses carrier, therefore the developer roll that uses one-component system, requires the semiconduction rubber rollers to have following performance because the toner transport sector is different with the charged mechanism of toner.
At first, the transport sector that toner is transferred to photoreceptor depends on the electrostatic force by toner electric charge and the decision of development electric field.The development electric field is at the sub-image (being electric charge) of photoreceptor and be applied between the developing bias current potential on the developer roll by decisions such as the kind of development electrode, position relations.
The used developer roll that is made of magnetic roller in using the two component system of carrier, its development electrode forms perpendicular fringe (erecting) shape arranged carrier according to the magnetic force from developer roll and developer roll surface and forms.Therefore, can bring into play electricity, magnetic action, make the transmission of toner easy.
In contrast to this, because the developer roll that is made of the semiconduction rubber rollers that uses in the one component system can not be brought into play magnetic force, therefore, its developer roll surface as electrode end surface must evenly form.That is, require developer roll to have high accuracy.
And when applying bias potential on developer roll, Potential distribution is homogeneous very.
Must make its electrical characteristics value very uniform developer roll in developer roll repeatedly by designed again.Particularly, requirement is even as the resistance value of the representation parameter of electrical characteristics value.
In the charged function aspects of toner, magnetic roller in the past, its carrier particle that adds with toner are the principal elements of control toner charging property, therefore, less require developer roll to have the function that makes toner charged.
In contrast, owing to do not contain carrier, therefore, require it to have the function of control toner charging property on the developer roll of one-component system.
Charging property control for toner requires when giving the toner charging property, and also requirement can be kept the charging property of being given.
Toner charging property deficiency, electrostatic force deficiency then, toner can verily not transferred to the sub-image of photoreceptor, and this becomes the bad reason of various images.The bad example of image has: concentration occurs along with the rotation of developer roll changing video picture ghost image, image fog etc.
From above viewpoint, scale with molecular level moves the ion that various so-called ionic conductivity elastomers with ehter bond such as chloropropylene oxide form owing to its water decomposition in elastomer inside, therefore has conductivity, thus, different with electronic conductive material, need not consider that the dispersiveness of filler just can obtain electrical characteristics.Thereby obtain the uniformity of above-mentioned resistance value easily, and because it has the very high feature of reproducing by design load of performance, and be widely used in various conductive rolls.
Yet, making water decomposition and obtain this situation of conductivity and can know from the ionic conductivity elastomer, the compatibility of itself and water is very high, and the free energy of roller sub-surface increases.
The ionic conductivity elastomer that will have such characteristic is used for developer roll, its result, developer roll is when adding press contacts repeatedly with other parts or material (toner, toner external additive, toner donor rollers, toner control with scraping blade, also comprise photoreceptor etc. sometimes), because free energy is big, therefore, the external additive of particularly counting about 10nm～hundreds of nm as metal oxide is very easy to stick to roller surfaces.Therefore, when continuing to use as developer roll, roller surfaces is different with A-stage, that is, the problem that exists the top layer to be coated fully by the toner external additive.
In addition, also there is such problem in the toner external additive: be accompanied by use, toner is by paper, be transferred between photoreceptor and the transfer roll etc., paper contacts with photoreceptor, and compositions such as the silicon dioxide in the paper, calcium carbonate stick on the photoreceptor, infiltrate developer roll (according to circumstances, also comprising toner cartridge) along with the photoreceptor rotation, the paper composition and the external additive that infiltrate are same, can produce harmful effect to developer roll.
For the problems referred to above, various solutions have been proposed so far.
For example, Japan Patent open communique 2001-357735 number (patent documentation 1) provides a kind of electroconductive component of using other the polymer-coated top layers different with the ionic conductivity elastomer.
But if be coated with, then owing to electrical characteristics can change along with the dispersiveness of filler contained in coating thickness, the smears etc., therefore, the homogeneity of the electrical characteristics that the ionic conductivity elastomer is had, the reproducibility repeatedly of design load can suffer damage.And, there is manufacturing cost to rise to be difficult to the problem of avoiding on this suitability for industrialized production.
In addition, Japan Patent open communique 2000-63656 number (patent documentation 2) provides a kind of like this technical scheme: use the semiconduction material of being made up of the ether based copolymer to form the charged roller and the developer roll of image processing system.Yet, as the 3rd page of left hurdle 13-16 of this communique capable as described in, the rubber layer that forms with such material because its prerequisite is, the surface needs coating, therefore, also there are the problems referred to above in the developer roll made from above-mentioned semiconduction material etc.
In addition, the open communique No. 1996292640 (patent documentations 3) of Japan Patent discloses such technical scheme: with the ultraviolet irradiation epichlorohydrin rubber of 200-450nm and the mixed rubber of unsaturated rubber, reduce frictional resistance.
Yet, only reduce coefficient of friction by ultraviolet irradiation, the free energy of roller surfaces is increased, can't prevent effectively that the metal oxide about foreign matter, especially tens of nm such as toner external additive from adhering to.In addition, when reducing frictional resistance, only use the ultraviolet irradiation of 200-450nm, its effect is also little.
Also have, ionic conductivity elastomer and acrylonitrile-butadiene rubber widely used rubber phase ratios such as (NBR), its viscosity height, when especially containing a large amount of oxyalkylene, this tendency is more obvious.Its result, poor, the breakages such as the appearance shaping is irregular, cracking of inflow extrudability, the rubber when metal pattern is shaped.
For this reason, this type of problem various investigations have been carried out.
For example, Japan Patent open communique 1996-110701 number (patent documentation 4) provides a kind of manufacture method of developer roll, it is characterized in that described method comprises following operation: in epichlorohydrin rubber, add allyl glycidyl ether and use at least a vulcanization forming in sulphur and the organosulfur compound, the operation of formation elastic layer.
Yet, in the composition of above-mentioned elastic layer,, can not say so fully from improving the angle of processability.In fact, in the embodiment of this communique, attempt to add stearic acid and improve processability.But aliphatic acid such as stearic acid are low molecules, therefore, exist aliphatic acid to ooze out, pollute the possibility of other parts.In addition, because aliphatic acid itself is adhesiveness material, therefore, the possibility that not only toner external additive, and toner also adheres on the developer roll becomes very big.
In addition, Japan Patent open communique 2002-194203 number (patent documentation 5) record is added calcium carbonate and is improved processing characteristics.But behind the fillers such as interpolation calcium carbonate, under many situations, the free energy of roller surfaces can increase, and the problem that foreign matters such as above-mentioned toner external additive adhere to can become more obvious.
For the developer roll that uses chloropropylene oxide, also attempt outside filler, adding the various performances (Japan Patent-No. 3273484 (patent documentation 6)) that resin improves developer roll.But it is very difficult low-gravity resin evenly being incorporated in the full-bodied rubber.
Patent documentation 1: open communique 2001-357735 number of Japan Patent
Patent documentation 2: open communique 2000-63656 number of Japan Patent
Patent documentation 3: open communique 1996-292640 number of Japan Patent
Patent documentation 4: open communique 1996-110701 number of Japan Patent
Patent documentation 5: open communique 2002-194203 number of Japan Patent
Patent documentation 6: No. the 3273484th, Japan Patent
Summary of the invention
The objective of the invention is to, a kind of like this semi-conductive rubber part is provided, and described semi-conductive rubber part can be at the situation decline low surface free energy of the reproducibility repeatedly of keeping the homogeneity of electrical characteristics, design load, make with the toner external additive and be that the impurity of representative does not adhere in fact chronically, the processing characteristics excellence, cannot see blemish such as irregular, the cracking of being shaped basically.
For reaching this purpose, the invention provides a kind of semi-conductive rubber part, it is characterized in that, described semi-conductive rubber part contains the ionic conductivity rubber constituent of the rubber with polyethers key, and,, mixed the wax of 0.1-5 mass parts with respect to these rubber constituent 100 mass parts.
The present inventor is to realize simultaneously preventing that adhesions such as toner external additive and raising processability from being purpose, carried out deep research, found that, in containing the ionic conductivity rubber of rubber, mix wax, can improve processability, blemish such as irregular, the cracking of preventing to be shaped, and can reduce surface free energy, can prevent adhesion such as toner external additive for a long time with polyethers key.
Semi-conductive rubber part of the present invention has overcome the shortcoming of existing surface free energy height of the ionic conductivity rubber that contains the rubber with polyethers key and poor in processability by mixing wax.
That is, by mixing the wax of 0.1-8 mass parts, wax can be present in the rubber top layer, like this, can reduce surface free energy, and the toner external additive is adhered to.
And, by in rubber, mixing wax,, also can be shaped easily even contain the high viscosity rubber such as chloropropylene oxide of a large amount of oxyalkylenes, and can suppress cracking and stop rubber along with the time by the ozone deterioration.
In addition, because wax is compared with aliphatic acid, have higher molecular weight, therefore, if the 0.1-8 mass parts just can not oozed out from the surface and pollute other parts, it is big that its adhesiveness can significantly not become yet.Like this,, just can obtain very big effect by mixing this simple adjustment of wax, therefore, the use of extension ion conducting rubber greatly.
When semiconduction rubber rollers of the present invention is used as developer roll, can prevents that the toner external additive from adhering to and processability is good, and can prevent to ftracture, make at an easy rate high-precision roller.
Also have, semi-conductive rubber part of the present invention, different with the technology of face coat, can keep as the electrical characteristics homogeneity of ionic conductivity rubber feature and the reproducibility repeatedly of design load.
Used wax among the present invention is not so long as normal temperature has especially and limits down for the organic substance that becomes low-viscosity (mobile) liquid after solid, the heating get final product.Can use in native paraffin, synthetic wax or processing, the modified waxes any.The example of native paraffin has animality waxes such as shellac wax; Vegetalitas waxes such as Brazil wax, candelila wax or rice wax; Pertroleum wax such as paraffin or microwax; Mineral such as montan wax or ceresine wax, or the like.
Synthetic wax is except polypropylene wax, Tissuemat E, Fischer-Tropsch wax, and its example also can be enumerated high-grade aliphatic ester, fatty acid amide, ketone-amine, hydrogenation wet goods.
Example as processing, modified waxes has: the wax of raw material has been carried out the oxidized petroleum waves of oxidation etc. with chemicals, airborne oxygen, the wax that above-mentioned wax has been carried out processing or modification as raw material, with chemical, physical means.
Preferably pertroleum wax or its processing of the wax that uses among the present invention, modified waxes.Described pertroleum wax is paraffin or microwax better.
Above-mentioned paraffin from the decompression distillation distillate oil separate, purifying obtains, normal temperature is the wax of solid shape down, by carbon number distribution about 20-40, molecular weight is that hydrocarbon about 300-550 is formed, and is main component with straight-chain hydrocarbons (just paraffin).The fusing point great majority are about 40-70 ℃.
Above-mentioned microwax from decompression distillation residue or heavy distillate that part is separated, purifying obtains, normal temperature is the wax of solid shape down, by carbon number about 30-60, molecular weight is that hydrocarbon about 500-800 is formed, and mostly is branched-chain hydrocarbons (different paraffin), saturated cyclic hydrocarbons (ring paraffin).Therefore, the crystallization of paraffin is less, and molecular weight is big, and fusing point is about 60-90 ℃.
In the present invention, above-mentioned pertroleum wax is good with fusing point at about wax more than 50 ℃.In addition, from the angle of the easy formation of the dispersiveness rubber composition, aftermentioned oxide-film, preferably fusing point is at about wax below 100 ℃.
For preventing the pollution to other parts such as photoreceptors, the fusing point of wax is about about 60-80 ℃ better, about 65-75 ℃ of left and right sides You Jia.
As the wax that uses among the present invention, its object lesson has: the commodity that the emerging chemical industry of imperial palace Co., Ltd. produces " SUNNOC ", " SUNNOC N " by name, " OZONOC 33 "; The commodity that Seiko KCC produces " SUNTIHTS ", " SUNTIHT R " by name, " SUNTIHT C ", " SUNTIHT Z "; The commodity that chemical industry Co., Ltd. of Kawaguchi produces " OZOGUARD MC ", " OZOGUARD K " by name, " OZOGUARD G " etc.
The content of wax is the 0.1-5 mass parts with respect to rubber constituent 100 mass parts, and is better about the 1-3 mass parts.More than 5 mass parts, then there is wax to ooze out, pollute the anxiety of other parts from the surface as wax content.And if below 0.1 mass parts, the effect that then is difficult to obtain raising processability of the present invention and reduces surface free energy.
The example that has the polyethers key and have the rubber of ionic conductivity has: but be that monomer is or/and the polymer that the unsaturated epoxide system of copolymerization forms by the ether of ether-based monomer and not Halogen optionally.
More particularly, the example of the execution mode of above-mentioned rubber has:
(1) homopolymers of forming by ether-based monomer,
(2) by ether-based monomer and not the ether of Halogen be the copolymer formed of monomer,
(3) but by ether-based monomer, not the ether of Halogen be the unsaturated epoxide of monomer and copolymerization be the copolymer formed of monomer,
(4) but be the copolymer that monomer is formed by the unsaturated epoxide of ether-based monomer and copolymerization.
Wherein, the execution mode of above-mentioned (3) is better, and is good especially with chloropropylene oxide-oxirane-allyl glycidyl ether copolymer.
The example of above-mentioned ether-based monomer has chloropropylene oxide or epibromohydrin etc., wherein, is good with chloropropylene oxide.
Ether as above-mentioned not Halogen is giving an example of monomer, and saturated oxyalkylene class such as oxirane, expoxy propane, epoxy butane, oxidation iso-butane or styrene oxide etc. are arranged.They can distinguish use separately, also can be used in combination more than two kinds.Wherein, from buying equal angles, optimization ethylene oxide and expoxy propane easily.When using oxirane and expoxy propane simultaneously, the mol ratio of both (ethylene oxide/propylene oxide) is 10/90～90/10 preferably, is 15/85～85/15 better, is good with 20/80～80/20 especially.
But the unsaturated epoxy as above-mentioned copolymerization is giving an example of monomer, just like butadiene monoxide, 1, and 2-epoxy-5-hexene, 1, the unsaturated oxyalkylene class of 2-epoxy-7-octene etc.; Glycidol ethers as allyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, chloroethyl glycidol ether or acetate ethylene oxidic ester etc.; As glycidic ester class of glycidyl methacrylate or glycidyl acrylate etc. etc.Wherein, be good with the glycidol ethers, allyl glycidyl ether is good especially.
In above-mentioned copolymer, the content ratio of each monomer is not particularly limited.For example, the amount of ether-based monomer is 30-100 mole % preferably, is 35-90 mole % better, and 40-80 mole % is good especially.
The ether of Halogen is not that the amount of monomer is 0-70 mole % preferably, is 10-65 mole % better, and 20-60 mole % is good especially.
Unsaturated epoxy is that the amount of monomer is 0-15 mole % preferably, is 1-10 mole % better, and 1-8 mole % is good especially.
As having the polyethers key but do not have ionic conductivity rubber for example, but by by the ether of Halogen not be monomer, and the unsaturated epoxy of optionally copolymerization be the polymer that monomer is formed.
More particularly, as the execution mode of above-mentioned rubber, can enumerate:
(1) by the ether of Halogen not be the homopolymers formed of monomer,
(2) but be monomer and the unsaturated epoxy of copolymerization is the copolymer that monomer is formed by the ether of Halogen not.
Wherein, the execution mode of preferably above-mentioned (2) is good with epoxy ethane-epoxy propane-allyl glycidyl ether copolymer especially.
Be monomer by the ether of Halogen not and but the unsaturated epoxy of copolymerization is in the copolymer formed of monomer, the content ratio of each monomer is being not particularly limited.For example, be preferably, the amount of ether-based monomer is about 70-99 mole %, is about 1-30 mole % but the unsaturated epoxy of copolymerization is the amount of monomer.
For the ether of Halogen not is but that the unsaturated epoxy of monomer and copolymerization is a monomer, can enumerate and above-mentioned same example.
In the present invention, can in above-mentioned rubber with polyethers key, mix other rubber.
As described other rubber, can enumerate various unsaturated rubbers or thermoplastic elastomer etc., also can be various forms of rubber such as copolymer rubber, mixed rubber.
Particularly, can enumerate acrylic-nitrile rubber, acrylonitrile-butadiene rubber, chloroprene rubber, butadiene rubber, styrene butadiene rubbers, butyl rubber, fluorubber, isoprene rubber, polyurethane rubber, silicon rubber etc.
Particularly, as other rubber, preferably using polar rubber, chlorine is rubber.Because mix polar rubber, compare when only using rubber with polyethers key, can improve the chargeding performance of semi-conductive rubber part of the present invention sometimes for toner.
During in particular as developer roll, when the toner positively charged, mix chloroprene rubber, when toner is electronegative, mix acrylonitrile-butadiene rubber, can obtain comprising the good developer roll of processability.
Like this, when in aforesaid rubber with polyethers key, mixing other rubber, the content ratio with rubber of polyethers key preferably account for about 20 quality % of total rubber composition above, less than 100 quality %.
Use has the polyethers key, when not having the rubber of ionic conductivity, as mentioned above, with the ionic conductivity building rubber compound, or adds ionic conductive agent.
The preferably above-mentioned ionic conductivity rubber of the ionic conductivity rubber that is used in combination with polyethers key.
In addition, there is no particular limitation to the ionic conductive agent that added, can use known material, for example, and antistatic agent or charge control agent etc.
Above-mentioned antistatic agent can be electrostatic latent image video picture in the past with the arbitrary substance that uses in the toner.
As the antistatic agent of negative charging, can enumerate 2: 1 type containing metal azo dyes, aromatic hydroxy-carboxylic, the metal complex of aromatic dicarboxylic acid, the sulfamide derivative of copper phthalocyaine dye, sulfonamide dyestuff of copper phthalocyanine etc.
Except quaternary ammonium compound, alkyl pyridine compound, alkyl methyl pyridine compounds, for example also have various nigrosine based dyes etc. as the antistatic agent of Positively chargeable.
The example of above-mentioned charge control agent has metal-organic complex, slaine, huge legendary turtle compound, Monoazo metal complex, acetylacetone metal complex, hydroxycarboxylic acid metal complex, polycarboxylic acids metal complex, polyalcohol metal complex etc.In addition, its example also has the carboxylic acid derivates such as slaine, carboxylic acid anhydrides, ester class of quaternary ammonium salt, carboxylic acid, condensation polymer of aromatic series based compound etc.In addition, also can use bisphenols, calixarenes phenol derivatives such as (calixarene) etc.
Also have,, also can use imido grpup lithium, perchloric acid sodium salt (NaClO as ionic conductive agent
4) or lithium perchlorate salt (LiClO
4).Wherein, be preferably, use imido grpup lithium, quaternary ammonium salt or perchloric acid sodium salt.
When mixing ionic conductive agent, its incorporation can suitably be selected, but with respect to rubber constituent 100 mass parts, is preferably the 0.1-2 mass parts.
Also can in ionic conductivity rubber of the present invention, mix the electron conduction agent.
The example of described electron conduction agent has:
Known electrical conductivity Carbon blacks such as ケ Star チ エ Application Block ラ Star Network, furnace black or acetylene black;
The conductive metal oxides such as titanium oxide, tin oxide or graphite that zinc oxide, potassium titanate, antimony mix;
LiClO
4, LiCF
3SO
3, NaClO
4, LiAsF
6, LiBF
4, slaine such as NaSCN, KSCN, NaCl;
Or electrolyte such as various quaternary ammonium salts, phosphate etc.
The incorporation of above-mentioned electron conduction agent more particularly, is suitably selected in the scope of the resistance value that is not less than ionic conductivity rubber with NN resistance according to the kind of electron conduction agent, in the scope that does not influence ionic conductivity.For example, when using electrical conductivity Carbon black,, be the 5-30 mass parts preferably with respect to rubber constituent 100 mass parts, be the 10-20 mass parts better.
Escape for the static that prevents toner, can in ionic conductivity rubber of the present invention, mix the dielectric loss angle tangent adjustment filler that reduces dielectric loss angle tangent.
The various fillers such as calcium carbonate, clay or organic/inorganic pigment that the dielectric loss angle tangent adjustment has weak inductive carbon black, fatty acid treatment to cross with the example of filler, wherein, the calcium carbonate that preferred weak inductive carbon black, fatty acid treatment are crossed.
Above-mentioned weak inductive carbon black is meant that particle diameter is big, structural development is little, the carbon black little to the contribution of conductivity.Mix such carbon black, can access the function as the capacitor that produces by polarization and can not improve conductivity, thereby can control conductivity and do not damage the homogenization of resistance.
If use the above-mentioned weak inductive carbon black of primary particle size (primary particle diameter) more than (preferably at about 100nm) more than about 80nm, then can more effectively obtain above-mentioned effect.In addition, primary particle size below about 250nm, then can make surface roughness in the extreme little below about 500nm preferably.
Consider that from the little angle of surface area the shape of above-mentioned weak inductive carbon black is preferably spherical or approach sphere.
Can select various weak inductive carbon blacks, but being good with obtaining the oven process of big particle diameter or carbon black that cracking process is made easily, furnace black the best.With the classification of carbon black, preferred SRF, FT and MT.In addition, also can use carbon black as pigment.
In order to bring into play the effect that reduces dielectric loss angle tangent conscientiously, the incorporation of weak inductive carbon black is preferably in more than about 30 mass parts with respect to rubber constituent 100 mass parts.In addition, may damage other parts of contact with it for avoiding hardness to rise, and descend, be preferably in below about 70 mass parts for fear of resistance to wear.And, can keep the purpose of ionic conductivity in order to make ionic conductivity rubber, the incorporation that also requires the weak inductive carbon black is preferably in below about 70 mass parts with respect to rubber constituent 100 mass parts.
Wherein, with respect to rubber constituent 100 mass parts, the incorporation of furnace black is about 30-70 mass parts, is preferably about 35-60 mass parts.
The calcium carbonate of above-mentioned fatty acid treatment is because aliphatic acid is present in the interface of calcium carbonate, and is active higher than common calcium carbonate, and because easy the to be sliding property of aliphatic acid and high degree of dispersion and stable easily.In addition, by fatty acid treatment, can promote polarization.By above-mentioned two effects, the function as the capacitor in the rubber is strengthened, thereby can reduce dielectric loss angle tangent expeditiously.
The incorporation of the calcium carbonate of fatty acid treatment is about 40-80 mass parts with respect to rubber constituent 100 mass parts, is preferably about 40-70 mass parts.Be defined as above-mentioned about 40-80 mass parts, be because, be preferably in more than about 40 mass parts, and rise and the resistance change, be preferably in below about 80 mass parts for fear of hardness in order to bring into play the effect that reduces dielectric loss angle tangent conscientiously.
In semi-conductive rubber part of the present invention, can mix vulcanizing agent, processing aid, plasticizer, be subjected to additives such as sour agent or deterioration preventing agent.The total amount of these additives is preferably about the 0-70 mass parts with respect to rubber constituent 100 mass parts.Determine that the additive incorporation is other parts that damage contacts with it in order to prevent hardness from rising below about 70 mass parts.
Above-mentioned vulcanizing agent can be sulphur system, triazine derivatives system, thiocarbamide system, various monomers etc.They can use separately, also can share more than two kinds.
Sulphur is that the example of vulcanizing agent has sulphur powder, tetramethylthiuram disulfide and N, sulfur-containing organic compounds such as N-morpholine double dithio etc.
As thiocarbamide is vulcanizing agent, can use to be selected from tetramethyl thiourea, trimethyl thiourea, ethylene thiourea and (C
nH
2n+1NH)
2One or more thiocarbamides in the thiocarbamide of C=S (in the formula, n represents the integer of 1-10) expression etc.
The addition of vulcanizing agent is about more than 0.5 mass parts, below about 5 mass parts with respect to rubber constituent 100 mass parts, is preferably more than about 1 mass parts, below 3 mass parts.
With thiocarbamide is that vulcanizing agent (especially ethylene thiourea) vulcanizes the rubber that forms with epichlorohydrin rubber or chloropropylene oxide based polymer, if its compression set reaches about below 15%, then its durability becomes well, and, the precision when also guaranteeing attrition process easily.In addition, owing to can also improve the effect that forms oxide-film by ultraviolet ray, therefore, be particularly suitable for using in the present invention.
In this case, with respect to rubber constituent 100 mass parts, thiocarbamide be the addition of vulcanizing agent more than about 0.2 mass parts, below about 3 mass parts, be preferably more than about 1 mass parts, below about 2 mass parts.
In addition, can also be vulcanizing agent and usefulness with above-mentioned thiocarbamide with the sulphur powder.At this moment, with respect to rubber constituent 100 mass parts, the incorporation of sulphur powder is about the 0.1-2.0 mass parts.
As above-mentioned plasticizer, except various plasticizer such as for example dibutyl phthalate (DBP), dioctyl phthalate (DOP) or tricresyl phosphate, in the material as conductive agent, processing aid many plasticizer component are arranged also, for example, as aliphatic acid such as the stearic acid of processing aid or as the quaternary ammonium salt of ionic conductive agent etc.
With respect to rubber constituent 100 mass parts of above-mentioned rubber layer, the addition of these plasticizer component is preferably in below about 5 mass parts.By this interpolation, can prevent to form and occur oozing out when the oxide-film and pollute photoreceptor when preventing from printer is installed or during running.
Be subjected to sour agent as above-mentioned, hydrotalcite, マ Block サ ラ Star ト are suitable especially owing to also have excellent dispersiveness.In addition, as being subjected to sour agent, the various materials of acid acceptor effect can have been used.
With Halogen rubber (especially epichlorohydrin rubber or chloropropylene oxide based polymer) during as rubber constituent, with respect to rubber quality, the above-mentioned addition that is subjected to sour agent is preferably in more than about 1 quality %, below about 5 quality % more than about 1 quality %, below about 10 quality %.This is because in order to prevent the influence sulfuration and to pollute photoreceptor, be preferably in more than about 1 quality % by the addition of sour agent, and in order to prevent that hardness from rising, and be preferably in below about 10 quality % by the addition of sour agent.
The example of above-mentioned deterioration preventing agent has various age resistor etc.As this age resistor, various antioxidants are for example arranged.When using antioxidant, can form expeditiously, preferably the addition of antioxidant is suitably selected in order to make the oxide-film in the top layer part that to grant as required.
In semi-conductive rubber part of the present invention, the most handy ultraviolet ray or ozone irradiation top layer form oxide-film.This oxide-film preferably has the oxide-film of a plurality of C=O groups or C-O group etc.By forming oxide-film, can prevent toner disappear electricity, make toner charged expeditiously, and can significantly reduce coefficient of friction.Its result, toner and the more difficult adhesion of toner external additive.
Oxide-film is by carrying out processing such as ultraviolet irradiation or ozone irradiation and rubber layer top layer partial oxidation being formed on the semi-conductive rubber part surface, wherein, forming oxide-film with ultraviolet irradiation and have the advantage that the processing time is short, cost is low, is preferable therefore.The available known method of processing that is used to form above-mentioned oxide-film is carried out.
For example, when carrying out ultraviolet irradiation, though according to the kind of the surface of rubber layer and the distance between the ultra-violet lamp, rubber etc. and different, be preferably with about 100-400nm wavelength, be more preferably with about 100-200nm wavelength, good especially be about ultraviolet irradiation 3-30 minute with about 184.9nm or 253.7nm wavelength.
Will be before oxide-film forms apply voltage and be 50V the time ohmmeter be shown R50, will be after oxide-film forms apply voltage 50V the time ohmmeter be shown R50a, then from the disappear electric obstruction effect and the consideration of the balance between the deterioration of top layer of toner, exposure intensity (logR50a-logR50) preferably is about about 0.2-15.0.
Form when the oxide-film, during especially as developer roll, in order to be formed uniformly oxide-film, best grinding component surface in advance.Specifically, the maximal roughness Rmax on surface is preferably 2.0-15.0 μ m, is more preferably, and the average surface roughness Rz on surface is about 8 μ m.
Maximal roughness Rmax, surface roughness Rz press JIS B0601 (1994) and measure.
Like this, by forming oxide-film, though wax might ooze out under the high temperature under the situations such as shipping (how wet) environment, because high rigidityization (densification) effect that oxide-film produced can stop the generation of oozing out effectively.
The image that semi-conductive rubber part of the present invention can be used for the electro-photography apparatus of office automation equipment such as laser beam printer, ink-jet printer, photocopier, facsimile machine or ATM aptly forms in the mechanism etc.
Wherein, especially be suitable as developer roll, particularly being suitable for non-magnetic mono-component is the developer roll that toner is supplied to photoreceptor.
Video picture mode in the image formation mechanism of electro-photography apparatus is according to the relation of photoreceptor and developer roll, roughly be divided into contact and contactless, but semi-conductive rubber part of the present invention can be used for any mode, especially is suitable for and the non-contacting developer roll of photoreceptor.
Also have, semi-conductive rubber part of the present invention also is suitable for the parts that contact with toner.In addition, also be suitable for the charged roller that makes photosensitive drums similarly charged.Charged roller have the contact-type that contacts with photoreceptor and with the discontiguous non-contact type of photoreceptor, semi-conductive rubber part of the present invention can be used for above-mentioned any mode.
If semi-conductive rubber part of the present invention is used as charged roller, then can prevent from not to be transferred on intermediate transfer element, the page class, and the toner that remains on the photoreceptor, toner external additive, paper powder etc. are sticked to occur on the charged roller charged bad, can prevent that maybe breakage from appearring in live part sometimes.
Have, semi-conductive rubber part of the present invention also is suitable as clearer or the cleaning blade that is used to remove the impurity (for example, toner, toner external additive, paper powder etc.) that sticks on photoreceptor, the charged roller etc. again.If as clearer or cleaning blade, the recovery of the toner of then removing, toner external additive just becomes easily, and, can prevent the toner deterioration, toner is utilized again thereby can alleviate the mechanical stress that applies when the recovery.In addition, also can prevent the sclerosis that causes by toner external additive, paper powder etc., the cleaning member that alleviates damage photoreceptor, charged roller etc.
In addition, semi-conductive rubber part of the present invention also can be used as be used for toner image from photoreceptor be transferred to the toner donor rollers of transfer roll, the transmission toner of transfer belt, transfer paper, with transfer belt from the driven roller of interior side drive etc.
When the developer roll, the roller resistance value in the time of preferably will applying voltage and be 500V is set at 10 with semi-conductive rubber part of the present invention
5Ω～10
7Ω.
The electric current of crossing for control flows, suppress the bad generation of image, prevent that the roller resistance value is preferably in 10 to the photoreceptor discharge
5More than the Ω.On the other hand, for the efficient of keeping toner supply etc. and prevent that toner is transferred to and occur developer roll voltage when the photoreceptor and descend, toner can not be transferred to photoreceptor, image from developer roll effectively later on and occur badly that the roller resistance value is preferably in below about 107 Ω.In addition, in this case, the specific volume resistance of semi-conductive rubber part of the present invention is preferably in 10
8Below the Ω.
Structure to semi-conductive rubber part of the present invention is unqualified, can be individual layer, also can wait sandwich construction and make 2 layers according to desired properties.
When making sandwich construction, will in containing the ionic conductivity rubber of the rubber with polyethers key, 100 mass parts mix the rubber layer of 0.1-5 mass parts wax as outermost layer.
On the other hand, when making individual layer, only constitute (outermost layer) by the rubber layer that has mixed 0.1-5 mass parts wax in the ionic conductivity rubber that contains rubber in 100 mass parts with polyethers key.
When making above-mentioned single layer structure,, therefore, suitable especially because the rerum natura deviation is little, can cheaply make.
Shape to above-mentioned semi-conductive rubber part is unqualified, can be according to user mode, suitably select shapes such as roller shape, tabular, band shape.
As mentioned above, in the present invention, by this composition of wax that mixes in containing the ionic conductivity rubber of the rubber with polyethers key is regulated, the homogeneity of the electrical characteristics that the ionic conductivity rubber that forms had, the reproducibility repeatedly of design load can be do not damaged when coating ionic conductivity rubber components surface, and the advantage of manufacturing cost can be hanged down.
In addition,, processability is improved, and inflow extrudability, the rubber when metal pattern is shaped is become well, therefore, not be prone to breakages such as shaping is irregular, cracking owing to mix wax.
And, mix the surface free energy that wax can successfully reduce semi-conductive rubber part.Its result, for example, when being used for the developer roll of image processing system, can make with the toner external additive is that the impurity of representative does not adhere in fact chronically, prevents to adhere to the image disorder that takes place, parts breakage etc. by impurity.
Especially as developer roll, being that mode that non magnetic toner is supplied with photoreceptor non-contactly is when using, owing to mix wax in ionic conductivity rubber with one-component, improved processability, therefore, roller can be made high accuracy, and can make toner stick to photosensitive surface equably.In addition, developer roll requires to have the function that makes toner charged, owing to make ionic conductivity, can make it have the function that makes the charged function of toner and keep charging property.That is, ionic conductivity rubber because of ion within it portion move with molecular level and have conductivity, thus, make the electrical characteristics that Potential distribution is even, roller is inner also even, can make resistance value keep homogeneous.Its result can make the toner homogeneous charged, and can keep its charging property.
Thus, the developer roll made from semi-conductive rubber part of the present invention can be used for the non magnetic toner of one-component is supplied to non-contactly the situation of photoreceptor aptly.
Description of drawings
Fig. 1 is the schematic diagram of the semi-conductive rubber part of the present invention of roll shape.
Fig. 2 is the figure of assay method that shows the resistance of semiconduction rubber rollers.
Fig. 3 is the figure of assay method that shows the frictional force of semiconduction rubber rollers.
Fig. 4 is the figure of evaluation method that shows the surface free energy of semiconduction rubber rollers.
Embodiment
Below, describe with reference to the better embodiment of accompanying drawing semi-conductive rubber part of the present invention.
As shown in Figure 1, the semiconduction rubber rollers made from semi-conductive rubber part of the present invention 10 have drum rubber layer 1, be pressed into the cylindrical mandrel 2 of its hollow bulb.Rubber layer 1 and mandrel 2 usefulness conductive adhesives are bonding.The top layer part of rubber layer 1 makes the oxide-film 1a that the rubber oxidation is formed by ultraviolet irradiation.But also can not establish the oxide-film 1a of top layer part.
In the present embodiment, the thickness of rubber layer 1 is 8mm, and mandrel 2 is the cylindrical of diameter 10mm.
Rubber layer 1 contains the epichlorohydrin rubber that has ionic conductivity as having the rubber of polyethers key, and preferably the copolymerization ratio of oxirane (EO)/chloropropylene oxide (EP)/allyl glycidyl ether (AGE) is the copolymer of 56 moles of %/40 mole %/4 moles of %.
In rubber layer 1, with respect to rubber constituent 100 mass parts, mix the wax of 0.1-5 mass parts, to improve processability and to reduce surface free energy.
In rubber layer 1, mixed sulphur powder as vulcanizing agent, as the ethylene thiourea of vulcanization accelerator, as the hydrotalcite that is subjected to sour agent.Their addition is with respect to rubber constituent 100 mass parts, for about the 1-10 mass parts.
In addition, a kind of in the calcium carbonate with the weak inductive carbon black that reduces the dielectric loss angle tangent effect or fatty acid treatment or both have been mixed in the rubber layer 1.The addition of weak inductive carbon black is with respect to rubber constituent 100 mass parts, and for about the 30-70 mass parts, the addition of the calcium carbonate of fatty acid treatment is the 40-80 mass parts with respect to rubber constituent 100 mass parts.
Again, in the rubber layer 1, as having the polyethers key but there is not the rubber of ionic conductivity, use the polyethers based copolymer, be more preferably the copolymer that uses oxirane (EO)/expoxy propane (PO)/allyl glycidyl ether (AGE) to form, also can make up with above-mentioned chloropropylene oxide.
Again, use acrylonitrile-butadiene rubber, also can make up with above-mentioned epichlorohydrin rubber as other rubber that does not have the polyethers key.Like this, during with two kinds of rubber blendings,, epichlorohydrin rubber is accounted for more than 50 mass parts with respect to rubber constituent 100 mass parts.
With above-mentioned rubber composition mixing after, be extruded into cylindricly with extruder, make preform, it is cut into given size after, obtain preform.This preform is dropped in the vulcanizer, in the crosslinked temperature sulfuration of rubber constituent.After the sulfuration, mandrel is installed in the cylindric rubber layer, makes the roller shape.
Then, divide formation oxide-film 1a in order to following method in the skin section of rubber layer 1.
With cylinder grinder mixing roll surface, mirror finish is carried out on the pair roller surface, make roll surface roughness Rz below the 8 μ m, maximum surface roughness Rmax is about 2-15 μ m, after the washing, with ultraviolet irradiation machine irradiation ultraviolet radiation (184.9nm and/or 253.7nm), form oxide-film.
Specifically,, with official hour (be about 1-15 minute preferably, be about 5-10 minute better) irradiation ultraviolet radiation, amount to, every 90 degree at the circumferencial direction of roller at the whole peripheral formation oxide-film of roller circumferencial direction rotation 4 times.
Also can be processed to form roll shape, replace above-mentioned extrusion process method that roller is shaped by following pressurization.
That is, make rubber sheet, the sulfuration that rubber sheet is wound in the pressing mold is used on the axle, its press cure is become required tubulose, then mandrel is installed in the rubber layer cylindraceous, make the roller shape with above-mentioned rubber composition.
The semi-conductive rubber part of the present invention that obtains like this has excellent processability and surface free energy and reduces, its result, and foreign matters such as toner external additive are difficult for adhering to.
Specifically,, semi-conductive rubber part of the present invention is measured, recorded frictional force below the 585g weight with the method for putting down in writing among the following embodiment as estimating the whether suitable short-cut method of surface free energy.
In addition, the resistance when representing to apply voltage 500V with R, then the roller logR that is made of above-mentioned semi-conductive rubber part is about 5.5-6.1.And, will be before described oxide-film forms apply voltage and be 50V the time ohmmeter be shown R50, will be after oxide-film forms apply voltage 50V the time ohmmeter be shown R50a, then logR50a-logR50 is about about 0.2-1.5, better about about 0.2-0.4.
Also have, the compression set that the method that the roller that is made of above-mentioned semi-conductive rubber part is put down in writing with JIS K6301 records is about 9.5-10.5%.
To make said structure by the roller 10 that above-mentioned semi-conductive rubber part is formed, when installing as the developer roll in the laser printer, behind lettering 5% on 3000, the adhesion of impurity such as toner, toner external additive or paper powder does not appear, in addition, the wax that does not also occur mixing oozes out.
Embodiment
Make the roller of the embodiment 1-6 that constitutes by semi-conductive rubber part of the present invention and the roller of comparative example 1-3 respectively, measure their characteristic.
With Banbury mixer with the interpolation materials of 1,2 records of tabulating down mixing after, extrude, be processed into the tubulose of external diameter φ 18mm, internal diameter φ 9.5mm with extruder.This tube is installed in sulfuration with on the axle, in vulcanizer, after 1 hour, is installed on the axle of the φ 10mm that has been coated with conductive adhesive in 160 ℃ of sulfurations, bonding in 160 ℃ stove.Then, make end formedly, carry out transverse grinding with the cylinder grinder, and carry out mirror ultrafinish, be ground to the surface roughness of regulation with φ 16mm (tolerance 0.05) as correct grinding.
Behind the washing roller surfaces, except that comparative example 2, use ultraviolet irradiation, form oxide layer on the top layer.Concrete grammar is, use ultraviolet lamp (" PL21-200 ", SEN special light sources Co., Ltd. product), distance between roller and the ultra-violet lamp is made as 10cm, shine ultraviolet rays in 5 minutes (wavelength 184.9nm and 253.7nm) at circumferencial direction every 90 degree, make roller rotation 4 times, each 90 degree are at whole periphery (360 degree) the formation oxide-film of roller.
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | |
| GECO | 100 | 100 | 100 | 100 | 80 | 80 |
| The polyethers based polymer | 20 | |||||
| NBR | 20 | |||||
| Wax | 0.12 | 4.8 | 2 | 2 | 2 | 2 |
| The weak inductive carbon black | 50 | 50 | 50 | |||
| Calcium carbonate | 20 | 20 | 20 | |||
| Resistance (500V; The log value) | 5.88 | 5.7 | 5.81 | 5.7 | 6.1 | 5.5 |
| Resistance R 50 (50V; The log value) before the oxidation | 5.9 | 5.8 | 5.82 | 5.8 | 6.1 | 5.5 |
| Resistance R 50a (50V; The log value) after the oxidation | 6.27 | 6.1 | 6.18 | 6.1 | 6.45 | 5.7 |
| LogR50a-logR50 | 0.37 | 0.3 | 0.36 | 0.3 | 0.35 | 0.2 |
| Surface maximal roughness (Rmax; μ m) | 7.1 | 6.5 | 6 | 6.5 | 6 | 8 |
| Compression set (%) | 9.6 | 9.5 | 9.6 | 9.5 | 9.6 | 10.30 |
| Extrude processability | ○ | ◎ | ◎ | ◎ | ◎ | ◎ |
| Frictional force | 570 | 480 | 520 | 480 | 520 | 480 |
| The evaluation of surface free energy | ○ | ◎ | ◎ | ◎ | ○ | ○ |
| The initial stage picture appraisal | ○ | ○ | ○ | ◎ | ◎ | ◎ |
| Durability | ○ | ◎ | ◎ | ◎ | ◎ | ◎ |
| The performance that anti-toner external additive etc. adhere to | Slightly adhere to | Do not have and adhere to | Do not have and adhere to | Do not have and adhere to | Do not have and adhere to | Do not have and adhere to |
| The photoreceptor test for contamination | ◎ | ○ | ◎ | ◎ | ◎ | ○～◎ |
| Overall merit | ○ | ○～◎ | ○～◎ | ◎ | ◎ | ◎ |
Table 2
| Comparative example 1 | Comparative example 2 | Comparative example 3 | |
| GECO | 100 | 100 | 100 |
| The polyethers based polymer | |||
| NBR | |||
| Wax | 5.5 | ||
| The weak inductive carbon black | |||
| Calcium carbonate | 20 | 20 | 20 |
| Resistance (500V; The log value) | 5.65 | 5.65 | 5.88 |
| Resistance R 50 (50V; The log value) before the oxidation | 5.74 | 5.74 | 5.9 |
| Resistance R 50a (50V; The log value) after the oxidation | 6.03 | 5.74 | 6.35 |
| LogR50a-logR50 | 0.29 | 0 | 0.45 |
| Roll surface roughness (Rmax; μ m) | 6.5 | 6.5 | 6.6 |
| Compression set (%) | 9.4 | 9.4 | 9.3 |
| Extrude processability | △ | △ | ◎ |
| Frictional force (g is heavy) | 600 | 700 | 480 |
| The evaluation of surface free energy | × | ○～△ | ○ |
| The initial stage picture appraisal | ○ | × | ○ |
| Durability | △ | × | ○ |
| The performance that anti-toner external additive etc. adhere to | Adhere to | Adhere to | Wax oozes out |
| The photoreceptor test for contamination | ◎ | ◎ | × |
| Overall merit | ○～△ | × | × |
As the constituent in the conducting rubber roller of each embodiment and comparative example, use following material.
(1) has the rubber of polyethers key
Rubber with ionic conductivity
Epichlorohydrin rubber (GECO); (described rubber constituent is that the copolymerization ratio of oxirane (EO)/chloropropylene oxide (EP)/allyl glycidyl ether (AGE) is the chloropropylene oxide based polymer of 56 moles of %/40 mole %/4 moles of % to " the EPICHLOMER CG102 " that DAISO Co., Ltd. produces.)
The rubber that does not have ionic conductivity
Polyethers key based copolymer; (described rubber constituent is the copolymer by oxirane (EO)/expoxy propane (PO)/allyl glycidyl ether (AGE) is formed to " the ゼ オ ス パ Application 8100 " that Japan ZEON Co., Ltd. produces.)
(2) other rubber
Acrylonitrile-butadiene rubber (NBR); " the Nipol 401LL " that Japan ZEON Co., Ltd. produces
(3) wax
" the SUNNOC N " that the emerging chemical industry of imperial palace Co., Ltd. produces
(4) other composition
The weak inductive carbon black; " rising sun #15 " that rising sun CARBON Co., Ltd. produces
Calcium carbonate; " the SUPER S " that Marno Calcium Co., Ltd. produces
Sulphur powder (vulcanizing agent)
Ethylene thiourea (vulcanizing agent); " ACCEL22-S " that KCC of Kawaguchi produces
Hydrotalcite (being subjected to sour agent); " DHT-4A-2 " that Kyowa Chemical Industry Co., Ltd produces
In embodiment 1-6 and comparative example 1-3, all be the sulphur powder that in rubber constituent 100 mass parts, has mixed 0.5 mass parts, the ethylene thiourea of 1.2 mass parts and the hydrotalcite of 3 mass parts.
The following characteristic of each embodiment that mensuration makes like this and the semiconduction rubber rollers of comparative example.It the results are shown in table 1 and table 2.
(resistance measurement)
As shown in Figure 2, the rubber layer 1 that has inserted mandrel 2 is overlapped on the aluminium drum 3, with be connected in power supply 4+the lead front end of the internal resistance r (100 Ω) of side is connected in an end face of aluminium drum 3, and the lead front end that will be connected in a side of power supply 4 is connected in the other end of mandrel 2, measure.Detection is applied to the voltage of the internal resistance r of said wires, as detecting voltage V.In this device, will apply voltmeter and be shown E, resistance R=r * E/ (V-r) then, but-the r item can be considered very little, like this, and R=r * E/V.Add the load of 500g at the two ends of mandrel 2 respectively, under state, detect voltage V when applying voltage E and being 50V or 500V, calculate R by following formula with measuring 1000 4 seconds with 30rpm rotation.Said determination carries out under the constant temperature and humidity condition of 23 ℃ of temperature, relative humidity 55%.
Before ultraviolet irradiation formation oxide-film, making and applying voltage E is 50V, measures resistance with said method.(mensuration of surperficial maximal roughness Rmax)
Surface maximal roughness Rmax presses JIS B 0601 (1994) and measures.
(mensuration of the permanent compression set of rubber)
Carry out under 70 ℃ of temperature of mensuration, 24 hours condition of minute by JIS K6262 " the scrag test method of vulcanized rubber ".
(extruding the evaluation of processability)
When the rubber composition extrusion molding with embodiment and comparative example, the surface state of the rubber that affirmation is with the naked eye extruded.Surface essentially no concavo-convex being expressed as " ◎ ", there is small concavo-convex being expressed as " zero " on the surface, surface irregular being expressed as " △ ".
(mensuration of frictional force)
With device evaluation shown in Figure 3 coefficient of friction by the semiconduction rubber rollers of embodiment and comparative example making.
In the device of Fig. 3, will be placed on the sheet material 31 by the semiconduction rubber rollers 10 that embodiment and comparative example are made, polyester film 32 is clipped between sheet material 31 and the rubber rollers 10.
Again, sheet material 31 is by the material Teflon easily sliding with respect to film 32
Form.Add the load of 200g at the two ends of roller, under this state, with film 32 tractive in the direction of arrows.The tensile force (g is heavy) of the film during with rubber rollers 10 rotations is as frictional force.
(evaluation of surface free energy)
Use method shown in Figure 4, estimate the surface free energy of the semiconduction rubber rollers of making by embodiment and comparative example.
(initial stage picture appraisal)
Each rubber rollers of embodiment and comparative example go up being installed at commercially available laser printer (LP2000C, EPSON company product) is as developer roll, and the semi-tone image of printing black (degree for) 25% is observed the deep or light irregular of this moment.Do not have blockyly for " ◎ " fully, slightly blocky is " zero ", deep or light irregular be " * " significantly.
(Evaluation of Durability)
Each rubber rollers of embodiment and comparative example go up being installed at commercially available laser printer (LP2000C, EPSON company product) is as developer roll, behind lettering 5% on 3000, and the semi-tone image of printing black (degree for) 25%, relatively gained image and initial stage image.
That both images do not change fully is " ◎ ", and be " zero " of minor variations is arranged, and vicissitudinous is " △ ", and what be changed significantly is " * ".
(preventing the evaluation of the performance of adhesions such as toner external additive)
As developer roll, behind lettering 5% on 3000, take out above-mentioned roller in last each rubber rollers that embodiment and comparative example are installed of commercially available laser printer (LP2000C, EPSON company product), the toner that detects by an unaided eye, external additive or paper powder have or not adhesion.
(photoreceptor test for contamination)
After above-mentioned endurance test, keeping is 1 month under 32.5 ℃, the condition of relative humidity 90%.Then, deceive the semi-tone printing of (look for) 25% with this printer, it is pollution-free that the printed article that detects by an unaided eye has, and estimates.
Free of contamination fully is " ◎ ", being of slight pollution (in printing 5 time the pollution that does not influence use of eliminating the degree of not seeing to naked eyes) " zero ", serious pollution (, also can find out the pollution that printed article is unusual) even print more than 5 for " * ".
Table 1 and table 2 show, compare with 2 semiconduction rubber rollers with comparative example 1, semiconduction rubber rollers of the present invention extrude excellent in workability.In addition, frictional force is also little, and the evaluation of surface free energy is also good, and impurity such as toner external additive are difficult for adhering to.
In addition, self-evident during the initial stage with the laser printer of semiconduction rubber rollers of the present invention as developer roll, even long-term the use also can provide the printing image of high-quality homogeneous.In addition, the semiconduction rubber rollers of the present invention such wax of semiconduction rubber rollers of example 3 is without comparison oozed out, and therefore, can not pollute photoreceptor basically.
In order further to investigate the pressure processing and the surface free energy of semi-conductive rubber part of the present invention, the rubber rollers of having made embodiment 7 and comparative example 4 has been carried out following experiment.
(embodiment 7 and comparative example 4)
With adding material shown in the table 3, make the rubber sheet of thick 3mm by the half finished rubber roller, the sulfuration that is wound in the pressing mold is used on the axle, press cure becomes the tubulose of external diameter φ 18mm, internal diameter φ 12.5mm, then be installed on the axle of the φ 14mm that has been coated with conductive adhesive, bonding in 160 ℃ stove.Then,, make transverse grinding, and grind as correct grinding, be ground to the surface roughness of regulation with φ 16mm (tolerance 0.05) with the mirror barreling with the cylinder grinder with end formed.
In embodiment 7 and comparative example 4, use and embodiment 1-6 and comparative example 1-3 same material.But " the シ one ス ト 3 " that electrical conductivity Carbon black then uses East Sea CARBON Co., Ltd. to produce.
For the semiconduction rubber rollers of embodiment 7 that makes like this and comparative example 4, measure the roller resistance when applying 500V, and estimate surface free energy and pressure processing.The results are shown in table 3.The mensuration of the roller resistance when applying 500V and the evaluation of surface free energy are undertaken by method as hereinbefore.
Table 3
| Embodiment 7 | Comparative example 4 | |
| GECO | 100 | 100 |
| Wax | 2 | - |
| The sulphur powder | 0.5 | 0.5 |
| Ethylene thiourea | 1.2 | 1.2 |
| Hydrotalcite | 3 | 3 |
| Electrical conductivity Carbon black | 16 | 16 |
| |
10 | 10 |
| Resistance (500V; The log value) | 5.73 | 5.73 |
| The evaluation of surface free energy | ◎ | △ |
| The mobile rubber surface unity and coherence in writing cracking of pressure processing rubber | Good do not have | There is small cracking the slightly not good end of difference |
| Overall merit | ◎ | △ |
Table 3 shows, even in press molding, also can confirm, semi-conductive rubber part of the present invention has excellent processability.
As mentioned above, therefore semi-conductive rubber part of the present invention, can be used for the semi-conductive rubber part that requirement has good workability, high-precision processing and requires the electrical characteristics homogenization aptly owing to mixed wax in ionic conductivity rubber.Wherein, can be aptly as the semiconduction in the electro photography image processing system, require to have required flexible parts, roller, transport tape etc., especially can be aptly as becoming the developer roll that one-component is the carrier of non magnetic toner.And, also can be used as the charged roller that impurity such as toner, toner external additive, paper powder adhere to easily aptly, and also can be aptly as the clearer that these impurity are removed etc.
Symbol description
1 semiconduction rubber layer
The 1a oxide-film
2 mandrels
10 semiconduction rubber rollers
Claims (10)
1. a semi-conductive rubber part is characterized in that, in the ionic conductivity rubber constituent of 100 mass parts fusion the wax of 0.1-5 mass parts, wherein, comprise rubber in this ionic conductivity rubber constituent with polyethers key.
2. semi-conductive rubber part according to claim 1 is characterized in that, as described rubber constituent, uses by having the polyethers key and having the polymer that the ether-based monomer of ionic conductivity is formed.
3. semi-conductive rubber part according to claim 1 is characterized in that, as described rubber constituent, uses epichlorohydrin rubber.
4. semi-conductive rubber part according to claim 1, it is characterized in that, as described rubber constituent, to have mixed by the ether of Halogen not in ether-based monomer be that monomer is or/and the rubber of the polymer that the unsaturated epoxide of copolymerization is a monomer to be formed but use.
5. semi-conductive rubber part according to claim 4 is characterized in that, as described rubber constituent, uses chloropropylene oxide-oxyalkylene-allyl glycidyl ether copolymer.
6. semi-conductive rubber part according to claim 1 is characterized in that, as described wax, uses fusing point at paraffin more than 50 ℃, below 100 ℃ or microwax.
7. semi-conductive rubber part according to claim 1 is characterized in that, its top layer is formed with oxide-film by ultraviolet irradiation or ozone irradiation.
8. semi-conductive rubber part according to claim 1 is characterized in that, described semi-conductive rubber part is the developer roll in the image processing system.
9. semi-conductive rubber part according to claim 8 is characterized in that, described developer roll is used for non-contactly the non magnetic toner of one-component being supplied to photoreceptor.
10. semi-conductive rubber part according to claim 1 is characterized in that, described semi-conductive rubber part is charged roller, clearer or the cleaning blade in the image processing system.
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| JP2004035719 | 2004-02-12 | ||
| JP2004035719A JP2005225969A (en) | 2004-02-12 | 2004-02-12 | Semiconductive rubber member |
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| CN1655288A CN1655288A (en) | 2005-08-17 |
| CN1321427C true CN1321427C (en) | 2007-06-13 |
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| JP4856974B2 (en) * | 2005-02-22 | 2012-01-18 | キヤノン株式会社 | Charging device, process cartridge, and image forming apparatus |
| JP5188681B2 (en) * | 2006-04-14 | 2013-04-24 | 住友ゴム工業株式会社 | Semiconductive rubber member and developing roller comprising the rubber member |
| JP5021354B2 (en) | 2006-04-28 | 2012-09-05 | 住友ゴム工業株式会社 | Rubber member and developing roller comprising the rubber member |
| JP4234751B2 (en) | 2006-11-02 | 2009-03-04 | 住友ゴム工業株式会社 | Semiconductive rubber roll |
| JP2008191382A (en) * | 2007-02-05 | 2008-08-21 | Canon Chemicals Inc | Conductive rubber roller, image forming apparatus and transfer roller |
| JP5315620B2 (en) * | 2007-03-14 | 2013-10-16 | 株式会社リコー | Protective agent coating apparatus, process cartridge, and image forming apparatus |
| JP5320701B2 (en) * | 2007-07-31 | 2013-10-23 | 株式会社リコー | Image forming apparatus |
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5773024A (en) * | 1980-10-24 | 1982-05-07 | Canon Inc | Molded article |
| JPS6272747A (en) * | 1985-09-25 | 1987-04-03 | Kao Corp | Additive for epichlorohydrin rubber |
| US5733235A (en) * | 1994-11-22 | 1998-03-31 | Nippon Zeon Co., Ltd. | Rubber covered roll, rubber composition, and image-forming apparatus |
| CN1347940A (en) * | 2000-10-10 | 2002-05-08 | 住友橡胶工业株式会社 | Conductive rubber composition and the conductive rubber roller and rubber belt |
| CN1384906A (en) * | 1999-09-21 | 2002-12-11 | 美国维克托里克公司 | Pipe fitting gasket having enhanced surface properties |
| CN1389764A (en) * | 2002-05-20 | 2003-01-08 | 广州市刘氏橡塑制品有限公司 | Charge roll for laser image forming eqipment and its production process |
| CN1407023A (en) * | 2001-08-23 | 2003-04-02 | 住友橡胶工业株式会社 | Polymer composition for electric conductive roller electric conductive roller and belt |
-
2004
- 2004-02-12 JP JP2004035719A patent/JP2005225969A/en active Pending
- 2004-11-22 CN CNB2004100978025A patent/CN1321427C/en not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5773024A (en) * | 1980-10-24 | 1982-05-07 | Canon Inc | Molded article |
| JPS6272747A (en) * | 1985-09-25 | 1987-04-03 | Kao Corp | Additive for epichlorohydrin rubber |
| US5733235A (en) * | 1994-11-22 | 1998-03-31 | Nippon Zeon Co., Ltd. | Rubber covered roll, rubber composition, and image-forming apparatus |
| CN1384906A (en) * | 1999-09-21 | 2002-12-11 | 美国维克托里克公司 | Pipe fitting gasket having enhanced surface properties |
| CN1347940A (en) * | 2000-10-10 | 2002-05-08 | 住友橡胶工业株式会社 | Conductive rubber composition and the conductive rubber roller and rubber belt |
| CN1407023A (en) * | 2001-08-23 | 2003-04-02 | 住友橡胶工业株式会社 | Polymer composition for electric conductive roller electric conductive roller and belt |
| CN1389764A (en) * | 2002-05-20 | 2003-01-08 | 广州市刘氏橡塑制品有限公司 | Charge roll for laser image forming eqipment and its production process |
Non-Patent Citations (1)
| Title |
|---|
| 橡胶工业手册第二分册配合剂 王梦蛟等主编，250，化学工业出版社 1989 * |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2005225969A (en) | 2005-08-25 |
| CN1655288A (en) | 2005-08-17 |
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