WO2012043303A1 - 電子写真機器用現像ロール - Google Patents
電子写真機器用現像ロール Download PDFInfo
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- WO2012043303A1 WO2012043303A1 PCT/JP2011/071370 JP2011071370W WO2012043303A1 WO 2012043303 A1 WO2012043303 A1 WO 2012043303A1 JP 2011071370 W JP2011071370 W JP 2011071370W WO 2012043303 A1 WO2012043303 A1 WO 2012043303A1
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- elastic layer
- rubber elastic
- developing roll
- ionic liquid
- layer
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G15/00—Apparatus for electrographic processes using a charge pattern
- G03G15/06—Apparatus for electrographic processes using a charge pattern for developing
- G03G15/08—Apparatus for electrographic processes using a charge pattern for developing using a solid developer, e.g. powder developer
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G15/00—Apparatus for electrographic processes using a charge pattern
- G03G15/06—Apparatus for electrographic processes using a charge pattern for developing
- G03G15/08—Apparatus for electrographic processes using a charge pattern for developing using a solid developer, e.g. powder developer
- G03G15/0806—Apparatus for electrographic processes using a charge pattern for developing using a solid developer, e.g. powder developer on a donor element, e.g. belt, roller
- G03G15/0818—Apparatus for electrographic processes using a charge pattern for developing using a solid developer, e.g. powder developer on a donor element, e.g. belt, roller characterised by the structure of the donor member, e.g. surface properties
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/12—Polysiloxanes containing silicon bound to hydrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0025—Crosslinking or vulcanising agents; including accelerators
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
Definitions
- the present invention relates to a developing roll for electrophotographic equipment.
- electrophotographic devices such as copiers, printers, facsimiles and the like that employ an electrophotographic method have been widely used.
- a latent image is formed on a latent image carrier such as a photosensitive drum, and toner is attached to the latent image and developed to be visualized as a toner image. Then, the toner image is transferred to a recording medium such as paper to form an image.
- a developing roll has been widely used as a developing member for developing a latent image.
- a rubber elastic layer composed of one or two layers on the outer peripheral surface of the shaft body, a surface layer formed on the outer peripheral surface of the rubber elastic layer, and the like are known.
- Patent Document 1 discloses that a liquid silicone rubber composition in which carbon black is dispersed is used as a material for an elastic layer in a developing roll having an elastic layer on the outer periphery of a shaft body.
- Patent Document 2 discloses a developing roll formed by forming a conductive rubber member made of a rubber-like elastic body containing a specific ionic liquid as a conductive agent on the outer periphery of a shaft body.
- the conventional developing roll has room for improvement in the following points. That is, since the developing roll of patent document 1 uses liquid silicone rubber as a main material of an elastic layer, it is low-hardness and shows favorable settling resistance. However, since the electron conductive carbon black is dispersed as the conductive agent, the resistance uniformity depends on the degree of dispersion of the carbon black. Moreover, since the liquid silicone rubber which is a matrix polymer is insulative, a conductive path at the molecular level is not ensured and the electrical response is inferior.
- this type of developing roll is required to have good charge attenuation. This is because if there is a difference in charge attenuating property in the circumferential direction or longitudinal direction of the roll, a difference in toner holding force is generated, leading to uneven density of the image. Further, if the charge attenuation is low, the toner cleaning property by the toner supply roll or the like deteriorates, and as a result, toner filming is likely to occur, and the problem arises that the fog density increases due to the decrease in chargeability. It is. However, the conventional developing roll is not sufficient in charge attenuation.
- a developing roll for an electrophotographic apparatus includes a shaft body and a rubber elastic layer formed on the outer periphery of the shaft body, and the rubber elastic layer is liquid or millable silicone. It is formed from a crosslinked product of a composition containing rubber, a crosslinking agent, an electronic conductive agent, and an ionic liquid, and the composition is based on 100 parts by mass of the total amount of the liquid or millable silicone rubber and the crosslinking agent. It is summarized that the ionic liquid is contained within a range of 0.1 to 5.1 parts by mass.
- the developing roll for an electrophotographic apparatus has a surface layer on the outer periphery of the rubber elastic layer, and the surface unevenness is formed on the surface of the surface layer due to the surface unevenness formed on the surface of the rubber elastic layer. It is preferable that surface irregularities are formed on the surface of the surface layer due to the roughness forming particles added to the surface layer.
- the ionic liquid preferably has an alkoxysilyl group in the molecular structure.
- the residual charge of the rubber elastic layer at the time of application is 15 V or less, and the charge decay rate of the rubber elastic layer after 1 second from the application stop is 80% or more. It is preferable that
- the uneven resistance in the longitudinal direction of the rubber elastic layer is within one digit.
- the matrix polymer constituting the rubber elastic layer is silicone rubber, a rubber elastic layer having low hardness and low rigidity can be obtained. Further, since the electronic conductive agent is dispersed in the rubber elastic layer, the volume resistance of the rubber elastic layer is lowered, and the resistance can be reduced. In addition, since a specific amount of ionic liquid is added to the composition forming the rubber elastic layer, there is no problem of bleed and bloom, and the volume resistance variation caused by the degree of dispersion of the electronic conductive agent is alleviated and uniform. Volume resistance is obtained. Furthermore, since it is excellent also in charge attenuation, electrical responsiveness can be improved.
- the developing roll of the present invention it is easy to suppress toner filming due to a decrease in cleaning properties due to a density unevenness of an image and a decrease in charge attenuation rate when the electrophotographic apparatus is used. Can contribute to higher image quality and higher durability.
- the toner transportability is uniform and reliable, so that it is easier to suppress the density unevenness of the image when the electrophotographic apparatus is used.
- the rubber elastic layer has a surface layer on the outer periphery, and the surface unevenness is formed on the surface of the surface due to the surface unevenness formed on the surface of the rubber elastic layer, the toner stress is reduced. Therefore, the filming suppression effect is excellent when the electrophotographic apparatus is used.
- the ionic liquid has an alkoxysilyl group in the molecular structure, it has excellent compatibility with the silicone rubber that is the matrix polymer of the rubber elastic layer. And the effect of relaxing the volume resistance variation due to the degree of dispersion of the electronic conductive agent by the ionic liquid is further enhanced. Thereby, volume resistance variation becomes smaller.
- the toner releasability is improved.
- toner filming hardly occurs in a low-temperature and low-humidity environment, and fog is improved.
- the resistance unevenness in the longitudinal direction of the rubber elastic layer is less than one digit and the resistance unevenness is small, the charge unevenness is reduced and the uniformity of the image density is improved. Further, when the rubber elastic layer has little charge attenuation unevenness, the charge unevenness is reduced and the uniformity of the image density is improved.
- step unevenness step-shaped image unevenness
- the developing roll for electrophotographic equipment (hereinafter, also referred to as “the developing roll”) will be described.
- FIG. 1 is a circumferential sectional view schematically showing an example of the present developing roll.
- FIG. 2 is a circumferential sectional view schematically showing another example of the developing roll.
- the developing roll 10 includes at least a shaft body 12 and a rubber elastic layer 14 formed on the outer periphery of the shaft body 12.
- the rubber elastic layer 14 may be composed of a single layer as shown in FIG. 1, or may be composed of a plurality of layers as shown in FIG.
- FIG. 2 shows an example in which the rubber elastic layer 14 is composed of two layers.
- the inner layer is the base layer 14a
- the layer formed on the outer periphery of the base layer 14a is the intermediate layer 14b such as a resistance adjustment layer.
- the rubber elastic layer 14 may be composed of three or more layers.
- a surface layer 16 may be formed on the outer peripheral surface of the rubber elastic layer 14. The surface layer 16 is useful mainly for protecting the surface of the rubber elastic layer 14 and for imparting functions such as toner transportability.
- the surface modification of the rubber elastic layer 14 may be performed instead of the formation of the surface layer 16.
- the surface of the rubber elastic layer 14 can be protected and functions such as toner transportability can be imparted as in the case of forming the surface layer 16.
- the rubber elastic layer 14 is composed of a crosslinked body of a silicone rubber composition.
- the rubber elastic layer 14 consists of two or more layers, at least one layer should just be comprised from the crosslinked body of the silicone rubber composition.
- the silicone rubber composition contains at least liquid silicone rubber or millable silicone rubber, a crosslinking agent, an electronic conductive agent, and an ionic liquid.
- liquid or millable silicone rubber those generally known as a polyorganosiloxane base polymer can be used, and the organic group in the polyorganosiloxane base polymer is a monovalent substituted or unsubstituted hydrocarbon group.
- An alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group or a dodecyl group, an aryl group such as a phenyl group, an aralkyl group such as a ⁇ -phenylethyl group or a ⁇ -phenylpropyl group.
- an unsubstituted hydrocarbon group such as chloromethyl group and 3,3,3-trifluoropropyl group.
- methyl groups are frequently used because of their ease of synthesis.
- polydiorganosiloxanes in which at least two of the organic groups bonded to silicon atoms in one molecule are alkenyl groups (vinyl group, allyl group, butenyl group, pentenyl group, hexenyl group, etc.) are generally used.
- a chain-like one is particularly preferably used, but the present invention is not limited to these, and it is also possible to partially use one having no alkenyl group or a branched or cyclic polyorganosiloxane.
- the silicone rubber used in the silicone rubber composition is preferably a liquid silicone rubber from the viewpoint of dimensional accuracy and the like.
- liquid or millable silicone rubber of the present invention can be obtained by applying a known silicone rubber curing mechanism, and can be cured by crosslinking with an organic peroxide or by addition reaction. Is common.
- organic peroxides such as benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, p-methylbenzoyl peroxide, o-methylbenzoyl peroxide.
- organic peroxide crosslinking agents such as oxide, dicumyl peroxide, cumyl-t-butyl peroxide, 2,5-dimethyl-2,5-di-t-butylperoxyhexane, di-t-butyl peroxide are used.
- dicumyl peroxide cumyl-t-butyl peroxide, 2,5-dimethyl-2,5-di-t-butylperoxyhexane, and di-t-butyl peroxide are preferable because they give particularly low compression set.
- the crosslinking agent in the case of applying crosslinking by addition reaction is an organohydrogenpolysiloxane having at least two hydrogen atoms (hydrosilyl groups) bonded to a silicon atom in one molecule, and the hydrosilyl group in the molecule. Acts as a crosslinking agent for curing the composition by crosslinking with an alkenyl group bonded to a silicon atom in the liquid or millable silicone rubber by a hydrosilylation addition reaction.
- organohydrogenpolysiloxanes include trimethylsiloxy group-blocked methylhydrogenpolysiloxanes at both ends, trimethylsiloxy group-blocked dimethylsiloxane / methylhydrogensiloxane copolymers at both ends, and dimethylhydrogensiloxy group-blocked dimethyl at both ends.
- Polysiloxane both ends dimethylhydrogensiloxy group-blocked dimethylsiloxane / methylhydrogensiloxane copolymer, both ends trimethylsiloxy group-blocked methylhydrogensiloxane / diphenylsiloxane copolymer, both ends trimethylsiloxy group-blocked methylhydrogensiloxane Diphenylsiloxane / dimethylsiloxane copolymer, a copolymer comprising (CH 3 ) 2 HSiO1 / 2 units and SiO4 / 2 units, (CH 3 ) Examples thereof include a copolymer comprising 2 HSiO1 / 2 units, SiO4 / 2 units, and (C 6 H 5 ) SiO3 / 2 units.
- a carbon-based electronic conductive agent can be suitably used.
- the carbon-based electronic conductive agent include carbon black, carbon nanotube, fullerene and the like. Of these, carbon black is preferably used from the viewpoints of cost and the like, which are excellent in dispersibility in the composition and facilitate resistance reduction.
- the ionic liquid is an ionic substance that is liquid at room temperature.
- Specific examples of the ionic liquid include those having a cation (cation) represented by the following general formulas (1) to (4), for example, cyclic amidine ions such as imidazolium ions, pyridiniums, and the like.
- Organic cations such as ions, ammonium ions, sulfonium and phosphonium ions are used as cations.
- the anions include AlCl 4 ⁇ , Al 2 Cl 7 ⁇ , NO 3 ⁇ , BF 4 ⁇ , PF 6 ⁇ , CH 3 COO ⁇ , CF 3 COO ⁇ , CF 3 SO 3 ⁇ , (CF 3 SO 2 ) 2 N ⁇ , (CF 3 SO 2 ) 3 C ⁇ , AsF 6 ⁇ , SbF 6 ⁇ , F (HF) n ⁇ , CF 3 CF 2 CF 2 CF 2 SO 3 ⁇ , (CF 3 CF 2 SO 2 ) 2 N ⁇ , CF 3 CF 2 CF 2 COO — and the like can be mentioned.
- R 1 represents a hydrocarbon group having 4 to 10 carbon atoms
- R 2 and R 3 represent hydrogen or an alkyl group having 1 to 8 carbon atoms, and may contain a hetero atom.
- R 3 is not present when the nitrogen atom contains a double bond.
- R 4 represents a hydrocarbon group having 2 to 10 carbon atoms
- R 5 , R 6 and R 7 each represents hydrogen or an alkyl group having 1 to 8 carbon atoms, and may contain a hetero atom.
- R 8 represents a hydrocarbon group having 2 to 10 carbon atoms
- R 9 and R 10 represent hydrogen or an alkyl group having 1 to 8 carbon atoms, and may contain a hetero atom.
- Q represents a nitrogen, phosphorus, or sulfur atom
- R 11 , R 12 , R 13 , and R 14 represent hydrogen or an alkyl group having 1 to 8 carbon atoms, and may contain a hetero atom.
- octyltrimethylammonium bis (trifluoromethanesulfonyl) imide octyltrimethylammonium trifluoromethanesulfonate
- 1-butyl-3-methylpyridinium bis (trifluoromethanesulfonyl) imide 1-butyl-3- Methylpyridinium trifluoromethanesulfonate
- 1-hexyl-3-methylpyridinium trifluoromethanesulfonate 1-hexyl-3-methylpyridinium trifluoromethanesulfonate
- diallyldimethylammonium bis (trifluoromethanesulfonyl) imide diallyldimethylammonium trifluoromethanesulfonate
- glycidyltrimethylammonium bis (trifluoromethanesulfonyl) examples include imide, glycidyltrimethylammonium / trifluoromethanes
- the ionic liquid may have an alkoxysilyl group in the molecular structure.
- the rubber elastic layer 14 is excellent in compatibility with the silicone rubber that is the matrix polymer, the dispersity of the ionic liquid in the matrix polymer is increased, and the volume resistance variation due to the dispersity of the electronic conductive agent is increased. The effect that is alleviated by is increased. Thereby, volume resistance variation becomes smaller.
- the alkoxysilyl group may be contained in the cation structure of the ionic liquid, or may be contained in the anion structure of the ionic liquid, but is preferably contained in the cation structure.
- ionic liquid having an alkoxysilyl group in the molecular structure include those having a cation (cation) represented by the following general formula (5).
- R 14 cyclic, linear organic group
- R 15 at least (CH 2 ) n is included (where n is an integer)
- R 16 alkyl group (—CH 3 , —C 2 H 5 etc.)
- R 14 —N may be an ammonium compound.
- R 14 is a cyclic organic group
- R 14 -N represents a 5-membered ring such as pyrrole, pyrrolidine or imidazole, a 6-membered ring such as pyridine or pyrimidine, a pyrimidine ring such as indole, quinoline, isoquinoline or purine, and an imidazole ring.
- nitrogen-containing heterocyclic compounds such as condensed rings. These ring structures may contain oxygen, sulfur and the like in addition to nitrogen.
- R 14 —N may not be a ring structure but may be an aliphatic hydrocarbon group having 1 to 18 carbon atoms (including an unsaturated bond). Specific examples include quaternary ammonium salts represented by the following general formula (6).
- R 17 is an aliphatic hydrocarbon group having 1 to 18 carbon atoms (for example, —C 8 H 17 ), and R 18 to R 19 are alkyl groups having 1 to 4 carbon atoms.
- R 15 includes at least a methylene group (CH 2 ) n.
- the number of methylene groups is preferably in the range of 1-18.
- R 15 may contain a functional group such as a urethane group, an ester group, an amide group, an amino group, a thioether group, a hydroxyl group, and an aromatic ring.
- a salt of a cation and an anion made of the above ammonium compound is used as the ionic liquid having an alkoxysilyl group in the molecular structure.
- the anion is not particularly limited, but bis (trifluoromethanesulfonyl) imide anion [(CF 3 SO 2 ) 2 N ⁇ ] (TFSI) is preferably used.
- TFSI bis (trifluoromethanesulfonyl) imide anion
- As anions other than TFSI for example, AlCl 4 ⁇ , Al 2 Cl 7 ⁇ , NO 3 ⁇ , BF 4 ⁇ , PF 6 ⁇ , CH 3 COO ⁇ , CF 3 COO ⁇ , CF 3 SO 3 ⁇ , (CF 3 SO 2 ) 3 C ⁇ , AsF 6 ⁇ , SbF 6 ⁇ , F (HF) n ⁇ , CF 3 CF 2 CF 2 CF 2 SO 3 ⁇ , (CF 3 CF 2 SO 2 ) 2 N ⁇ , CF 3 CF 2 CF 2 COO- and the like can be mentioned.
- ionic liquid having an alkoxysilyl group in the molecular structure include those represented by the following formulas (7) to (14).
- the above-mentioned composition includes platinum catalyst such as fine platinum, platinum black, platinum-supported activated carbon, platinum-supported silica, chloroplatinic acid, chloroplatinic acid alcohol solution, platinum olefin complex, platinum alkenylsiloxane complex, etc. Etc. may be contained. Further, reinforcing fillers such as fumed silica, crystalline silica, wet silica, fumed titanium oxide, and the like may be contained.
- These reinforcing fillers are, for example, surface-modified with organosilicon compounds such as organoalkoxysilanes, organohalosilanes, organosilazanes, diorganosiloxane oligomers whose molecular chain ends are blocked with silanol groups, and cyclic organosiloxanes. May be.
- organosilicon compounds such as organoalkoxysilanes, organohalosilanes, organosilazanes, diorganosiloxane oligomers whose molecular chain ends are blocked with silanol groups, and cyclic organosiloxanes. May be.
- organosilicon compounds such as organoalkoxysilanes, organohalosilanes, organosilazanes, diorganosiloxane oligomers whose molecular chain ends are blocked with silanol groups, and cyclic organosiloxanes. May be.
- Various additives such as
- the above-mentioned silicone rubber composition which is a material for forming the rubber elastic layer 14, contains 0.1% of the ionic liquid with respect to 100 parts by mass of the total amount of the liquid silicone rubber or millable silicone rubber and the crosslinking agent. It is contained within the range of up to 5.1 parts by mass.
- the lower limit of the ionic liquid is preferably 0.15 parts by mass or more, and more preferably 0.2 parts by mass or more.
- the upper limit of the ionic liquid is preferably 5.0 parts by mass or less, more preferably 4.0 parts by mass or less, and still more preferably 3.0 parts by mass or less.
- the rubber elastic layer 14 is composed of the above-described crosslinked silicone rubber composition so that the residual charge of the rubber elastic layer 14 at the time of application is 15 V or less. More preferably, it is 12 V or less. When the residual charge is 15 V or less, there is little variation in charge, and thus density unevenness hardly occurs.
- the rubber elastic layer 14 is composed of the above-mentioned crosslinked silicone rubber composition, so that the charge attenuation rate of the rubber elastic layer 14 after 1 second from application stop is 80% or more. It is preferable. More preferably, it is 85% or more.
- the charge decay rate is 80% or more, the charge decay is excellent and the toner releasability is improved. In particular, toner filming hardly occurs in a low-temperature and low-humidity environment, and fog is improved.
- the rubber elastic layer 14 is composed of a crosslinked body of the above-described silicone rubber composition, so that the uneven resistance in the longitudinal direction of the rubber elastic layer 14 is within one digit. More preferably, such resistance unevenness is within 0.8 digits. If the resistance unevenness in the longitudinal direction of the rubber elastic layer 14 is within one digit, the resistance unevenness is small, so that the charge unevenness is reduced and the uniformity of the image density is improved. In addition, since uneven charging is reduced and the chargeability becomes uniform in this way, the surface unevenness of the developing roll 10 is less likely to appear in the image.
- the silicone rubber composition can be prepared, for example, as follows. That is, when liquid silicone rubber is used, various additives (excluding ionic liquid, cross-linking agent, catalyst) etc. such as liquid silicone rubber, electronic conductive agent, reinforcing filler added if necessary, etc. Mix using a mixer, Ross mixer, Hobart mixer, kneader mixer, etc., then add ionic liquid, crosslinking agent, catalyst if necessary, planetary mixer, Henschel mixer, Ross mixer, Hobart mixer, kneader mixer, roll It can prepare by kneading
- ionic liquid, the crosslinking agent, and the catalyst may be added at the first kneading.
- millable silicone rubber when millable silicone rubber is used, millable silicone rubber, electronic conductive agent, ionic liquid, reinforcing filler added as necessary, various additives such as catalyst (excluding crosslinking agent), etc., kneader mixer, roll, etc. And then adding a crosslinking agent or a retarder such as 1-ethynyl-1-cyclohexanol as necessary, and kneading with a roll or the like.
- the crosslinking agent may be added at the first kneading.
- urethane resin for example, urethane resin, polyamide resin, acrylic resin, acrylic silicone resin in a suitable solvent such as methyl ethyl ketone , Butyral resin, alkyd resin, polyester resin, fluororubber, fluororesin, mixture of fluororesin and fluororubber, silicone resin, acrylic modified silicone resin, silicone modified acrylic resin, fluorine modified acrylic resin, etc., as required ,
- a conductive solution such as carbon black as described above, an ion conductive agent such as quaternary ammonium salt, a particle for forming roughness such as urethane resin particles and acrylic resin particles, a plasticizer, a leveling agent, and the like. It can be used suitably.
- examples of the material for surface modification include a resin modifying silicone.
- examples of the resin modifying silicone include silicone alkoxy oligomers.
- an applicable solvent such as n-hexane can be used.
- the material for surface modification may contain a curing catalyst or the like, if necessary.
- the main developing roll 10 can be manufactured, for example, as follows. That is, when a liquid silicone rubber composition is used as the rubber elastic layer forming material, the shaft body 12 coated with an adhesive as required is coaxially set in the hollow portion of the roll molding die. Next, a liquid silicone rubber composition as a rubber elastic layer forming material is injected into a molding space between the inner peripheral surface of the hollow portion and the shaft body 12, and the mold is covered with the liquid silicone rubber composition. After heating and crosslinking under optimum conditions, cooling and demolding are performed. Thereby, the rubber elastic layer 14 can be formed along the outer peripheral surface of the shaft body 12.
- the millable silicone rubber composition as the rubber elastic layer forming material is directly applied to the outer peripheral surface of the shaft body 12 by a crosshead extrusion device.
- a cylindrical unvulcanized rubber layer made of a millable silicone rubber composition was formed on the outer peripheral surface of the shaft body 12, and this was crosslinked by heating under the optimum conditions for the millable silicone rubber composition. Then cool down. Thereby, the rubber elastic layer 14 can be formed along the outer peripheral surface of the shaft body 12.
- a surface layer forming material is applied to the surface of the rubber elastic layer 14 using various coating methods such as a roll coating method, a spray method, and a dipping method, and heat treatment is performed under conditions optimal for the surface layer forming material.
- the surface layer 16 is formed.
- the surface of the rubber elastic layer 14 is impregnated with a material for surface modification using various methods such as a roll coating method, a spray method, and a dipping method, and cured under conditions optimal for the material for the surface layer modification.
- the surface of the rubber elastic layer 14 is modified by performing treatment or the like. Basically, the main developing roll 10 can be manufactured in this way.
- the developing roll 10 preferably has surface unevenness formed on the surface of the surface layer 16 due to surface unevenness formed on the surface of the rubber elastic layer 14 or roughness-forming particles added to the surface layer 16. It is preferable that surface irregularities are formed on the surface of the surface layer 16 due to the above. This is because the toner transportability is uniform, and it is easier to suppress image density unevenness and filming when using an electrophotographic apparatus, in combination with the effect of improving the cleaning property by improving the charge attenuation. .
- mold transfer can be suitably used.
- surface irregularities may be formed on the wall surface of the hollow portion of the roll molding die described above, and surface irregularities may be imparted to the surface of the rubber elastic layer 14 by transfer during molding of the rubber elastic layer 14.
- electroless eutectoid plating in which fluororesin particles are co-deposited is applied to the wall surface of the hollow portion of the roll molding die.
- a method of forming a large number of pits on the surface of the layer can be exemplified. According to this method, fine surface irregularities can be easily formed on the surface of the rubber elastic layer 14.
- the surface of the rubber elastic layer 14 is formed as a smooth surface
- the surface layer 16 is formed using a surface forming material containing roughness forming particles, the surface of the surface layer 16 is caused by the roughness forming particles.
- Surface irregularities can be formed. According to this method, surface irregularities can be formed on the surface of the rubber elastic layer 14 at a relatively low cost.
- Rubber elastic layer forming material The following materials were prepared as rubber elastic layer forming materials. ⁇ Liquid silicone rubber> Vinyl group-containing dimethylpolysiloxane ⁇ 1> (Gelest, “DMS-V31”) ⁇ Millable silicone rubber> ⁇ Vinyl group-containing dimethylpolysiloxane ⁇ 2> (manufactured by KCC, “SF3901C”) ⁇ Crosslinking agent> Hydrosilyl group-containing dimethylpolysiloxane ⁇ 1> (Gelest, “HMS-301”) Hydrosilyl group-containing dimethylpolysiloxane ⁇ 2> (Gelest, “HMS-501”) ⁇ Electronic conductive agent> ⁇ Carbon black (Denka Black HS100, manufactured by Denki Kagaku Kogyo) ⁇ Ionic liquid> ⁇ Ionic liquid ⁇ 1> (octyltrimethylammonium bis (trifluoromethanesulfonyl) imide (oc
- Ionic liquid ⁇ 2> (1-butyl-3-methylpyridinium bis (trifluoromethanesulfonyl) imide (1-butyl-3-methylpyridinium chloride (reagent manufactured by Tokyo Chemical Industry Co., Ltd.) and bis (trifluoromethanesulfonyl) imide lithium ( Tokyo Chemical Co., Ltd. reagent) was added to an aqueous solvent and stirred at room temperature for 4 hours.
- ⁇ Ionic liquid ⁇ 7> In the synthesis of ionic liquid 6, (2-hydroxyethyl) trimethylammonium chloride was replaced with 1- (2-hydroxyethyl) pyridinium chloride (manufactured by CHEMICALLAND 21).
- ⁇ Ionic liquid ⁇ 8> Under an N 2 atmosphere, 60 mmol of [2- (acryloyloxy) ethyl] trimethylammonium chloride (manufactured by SIGMA-ALDRICH) and 59 mmol of (3-aminopropyl) trimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed at 100 ° C. For 72 hours.
- Ionic liquid ⁇ 10> In the synthesis of the ionic liquid 8, (3-aminopropyl) trimethoxysilane was changed to (3-mercaptopropyl) trimethoxysilane (reagent manufactured by Tokyo Chemical Industry Co., Ltd.) and [2- (acryloyloxy) ethyl] trimethylammonium chloride was changed to It was synthesized in place of [2- (methacryloyloxy) ethyl] trimethylammonium chloride (a reagent manufactured by Tokyo Chemical Industry Co., Ltd.).
- Example 2 Production of developing rolls according to Examples and Comparative Examples (Examples 1 to 4, Comparative Examples 1 to 5) Each of the vinyl group-containing dimethylpolysiloxane, carbon black, fumed silica, and crystalline silica was put into a planetary mixer and mixed for 30 minutes so that the composition shown in Table 1 described later was obtained, and then the hydrosilyl group-containing dimethylpolysiloxane. , 1-ethynyl-1-cyclohexanol, platinum catalyst, ionic liquid (Comparative Example 4 is an ionic conductive agent), mixed for 30 minutes, and degassed under reduced pressure to obtain a liquid silicone rubber as a rubber elastic layer forming material A composition was prepared.
- the liquid silicone rubber composition prepared above was press-molded under the conditions of 170 ° C. ⁇ 10 minutes, and then the secondary curing was performed under the conditions of 200 ° C. ⁇ 4 hours. Sheet and ring were made.
- a shaft (diameter 6 mm, made of SUS304, solid) is coaxially set in a roll molding die having a cylindrical hollow portion, and the liquid silicone rubber composition prepared above is filled between the die / shaft. Then, heat crosslinking was performed under the conditions of 170 ° C. ⁇ 10 minutes. Thereafter, the developing roll was removed and subjected to secondary curing under conditions of 200 ° C. ⁇ 4 hours, and a rubber elastic layer (outer diameter 12 mm, layer thickness 3 mm) was formed along the outer peripheral surface of the shaft body. A was produced.
- urethane resin Nippon Polyurethane, “Nipporan 5196”
- 40 parts by mass of carbon black (“Denka Black HS100”, manufactured by Denki Kagaku Kogyo”
- urethane resin particles Negami Kogyo Co., Ltd., “Art Pearl U-600T”
- methyl ethyl ketone as roughness forming particles were further added to and mixed with this mixture, and then isocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd., “ The surface layer forming material was prepared by adding 45 parts by weight of Coronate L ").
- a developing layer B was prepared by forming a surface layer of 10 ⁇ m. Note that surface irregularities are formed on the surface of the surface layer due to the roughness-forming particles added to the surface layer.
- Example 5 in order to form surface irregularities on the surface of the rubber elastic layer by transfer, the following roll molding dies were prepared. That is, nickel sulfate hexahydrate 20 g / L, sodium hypophosphite monohydrate 25 g / L, lactic acid (complexing agent) 27 g / L, propionic acid (complexing agent) 2.5 g / L, PTFE particles (Average particle diameter 0.2 ⁇ m) 2.0 g / L and lauryltrimethylammonium chloride 0.4 g / L were blended to prepare each plating bath having a pH of 4.8.
- an electroless eutectoid plating is applied to the inner peripheral surface of the cylindrical hollow portion by immersing a roll molding die having the cylindrical hollow portion in each of the plating baths, and the electroless eutectoid plating layer (thickness) A roll molding die having 15 ⁇ m) on the mold surface was produced.
- the plating conditions were such that the temperature of the plating bath was 90 ° C. and the plating time was 90 minutes.
- the cross section of the obtained mold for roll forming was observed with a scanning electron microscope, it was confirmed that many pits were formed on the surface of the electroless eutectoid plating layer.
- a shaft body (diameter 6 mm, made of SUS304, solid) is coaxially set in a roll mold having a large number of pits on the wall surface of the cylindrical hollow portion, and the embodiment
- heat crosslinking was performed under the conditions of 170 ° C. ⁇ 10 minutes.
- the mold was removed and secondary curing was performed at 200 ° C. for 4 hours.
- a rubber elastic layer (outer diameter: 12 mm, layer thickness: 3 mm, surface unevenness due to mold transfer was observed along the outer peripheral surface of the shaft body. ) was formed.
- the surface layer forming material prepared in the same manner as in Example 1 except that the urethane particles as roughness forming particles were not added was applied to the surface of the developing roll A using a roll coater, By performing oven crosslinking under the conditions of 180 ° C. ⁇ 60 minutes, a surface layer having a thickness of 10 ⁇ m was formed on the outer periphery of the rubber elastic layer, and a developing roll B was produced. Note that surface irregularities are formed on the surface of the surface layer due to surface irregularities formed by mold transfer formed on the surface of the rubber elastic layer.
- Example 6 and 7 Comparative Examples 6 and 7
- Each of the vinyl group-containing dimethylpolysiloxane, carbon black, fumed silica, platinum catalyst, and ionic liquid was kneaded with a kneader for 15 minutes so as to have the composition shown in Table 2 below. Thereafter, 1-ethynyl-1-cyclohexanol and hydrosilyl group-containing dimethylpolysiloxane were kneaded with two rolls to prepare a millable silicone rubber composition as a rubber elastic layer forming material.
- the millable silicone rubber composition prepared above was press-molded under the conditions of 170 ° C. ⁇ 10 minutes, and then subjected to secondary curing under the conditions of 200 ° C. ⁇ 4 hours, Sheet and ring were made.
- the above-prepared millable silicone rubber composition is extruded directly onto the outer peripheral surface of the shaft body (diameter 6 mm, made of SUS304, solid) by a crosshead extrusion device, so that the outer peripheral surface of the shaft body is millable.
- a cylindrical unvulcanized rubber layer made of a silicone rubber composition was formed.
- secondary crosslinking is performed under conditions of 200 ° C. ⁇ 4 hours, and a rubber elastic layer (outer diameter 12 mm, layer thickness) along the outer peripheral surface of the shaft body. 3 mm) was produced.
- Example 2 the surface layer forming material prepared in Example 1 was coated on the surface of the developing roll A by using a roll coater, and this was oven-crosslinked under the conditions of 180 ° C. ⁇ 60 minutes, whereby rubber was obtained.
- a developing layer B was prepared by forming a surface layer having a thickness of 10 ⁇ m on the outer periphery of the elastic layer. Note that surface irregularities are formed on the surface of the surface layer due to the roughness-forming particles added to the surface layer.
- Example 8 to 15 Along with the outer peripheral surface of the 2 mm thick sheet, ring, and shaft body in the same manner as in Example 1, except that the ionic liquids ⁇ 3> to ⁇ 10> shown in Table 3 below are used instead of the ionic liquid ⁇ 1>. Then, a developing roll A having a rubber elastic layer (outer diameter 12 mm, layer thickness 3 mm) and a developing roll B having a surface layer having a thickness of 10 ⁇ m formed on the outer periphery of the rubber elastic layer were prepared.
- Example 16 In the same manner as in Example 1, a developing roll A in which a rubber elastic layer (outer diameter 12 mm, layer thickness 3 mm) was formed along the outer peripheral surface of a 2 mm thick sheet, ring, and shaft body was produced. Next, after the developed developing roll A was immersed in the following surface modifying solution at room temperature for 10 minutes, the silicone alkoxy oligomer was cured by leaving it in a room temperature and humidity environment for 24 hours, and the surface of the rubber elastic layer was high. Hardened developing roll B was produced.
- a rubber elastic layer outer diameter 12 mm, layer thickness 3 mm
- KR-500 manufactured by Shin-Etsu Chemical Co., Ltd.
- D-20 manufactured by Shin-Etsu Chemical Co., Ltd.
- Example 17 A rubber elastic layer along the outer peripheral surface of the 2 mm-thick sheet, ring, and shaft body in the same manner as in Example 6 except that the ionic liquid ⁇ 1> was changed to the ionic liquid ⁇ 3> shown in Table 2 to be described later.
- a developing roll A having an outer diameter of 12 mm and a layer thickness of 3 mm and a developing roll B having a surface layer having a thickness of 10 ⁇ m formed on the outer periphery of the rubber elastic layer were prepared.
- compression set About the said shaping
- Each developing roll A is brought into line contact with the metal drum, and the metal drum is rotationally driven in a state where a load of 500 g is applied to both ends of the core metal of the roll.
- Each developing roll A is rotated around at 60 rpm, and DC 10 V is applied. In this state, the electrical resistance between the shaft body and the metal drum was measured, and the variation in the circumferential direction was obtained.
- the average value in the circumferential direction is taken as the electrical resistance value at a predetermined position in the longitudinal direction, the electrical resistance values are measured at a total of three points at both ends and the center of each developing roll A, and the difference between the maximum value and the minimum value was defined as longitudinal resistance unevenness.
- Each developing roll B is incorporated into a cartridge of a commercially available color laser printer (manufactured by HP, Color Laser jet 3800), solid images are produced in an LL environment (15 ° C. ⁇ 10% RH), and the image density is measured with a Macbeth densitometer. Then, density unevenness was obtained from the variation.
- Each developing roll B is incorporated in a cartridge of a commercially available color laser printer (manufactured by HP, Color Laser jet 3800), and images are transferred through 6000 sheets in an environment of 32.5 ° C. ⁇ 85% RH, and then the roll The appearance was enlarged and observed with a microscope (VK-9510, manufactured by Keyence Corporation). At this time, “ ⁇ ” indicates that no toner adheres to the roll surface, and “ ⁇ ” indicates that the toner adheres to the roll surface, but the change is slight and does not affect the image. A case where the toner adhered to the surface and the amount of conveyance was changed or the image was uneven was indicated as “x”.
- Tables 1 to 3 collectively show the composition of the composition and the evaluation results of the produced developing roll.
- Comparison of Table 1 to Table 3 shows the following. That is, in the developing roll according to Comparative Example 1, in the silicone rubber composition used as the material of the rubber elastic layer, the mass part of the ionic liquid with respect to 100 parts by mass of the total amount of the silicone rubber and the crosslinking agent has a lower limit defined in the present application. It is below. Therefore, the charge decay rate is low, and density unevenness is likely to occur.
- the mass part of the ionic liquid with respect to 100 mass parts of the total amount of the silicone rubber and the crosslinking agent exceeds the upper limit specified in the present application. Yes. Therefore, bleed and bloom of ionic liquid were observed.
- the developing rolls according to Comparative Examples 3 and 6 do not contain an ionic liquid in the silicone rubber composition used as the material for the rubber elastic layer.
- an ionic conductive agent that is solid at room temperature is contained in the silicone rubber composition used as the material of the rubber elastic layer in place of the ionic liquid. Therefore, the charge decay rate is extremely low, and density unevenness is particularly likely to occur. Moreover, the variation in volume resistance was large.
- the developing roll according to Comparative Example 5 does not contain an electronic conductive agent in the silicone rubber composition used as the material for the rubber elastic layer. Therefore, the volume resistance is too high to reduce the resistance. Therefore, it can be said that it is inferior to the performance as a developing roll, without evaluating others.
- the developing rolls according to the examples can achieve low hardness, low settling, and low resistance without causing bleed bloom, etc., and more uniform volume resistance can be obtained, and charge attenuating property can be obtained. It was confirmed that it was excellent.
- the surface of the rubber elastic layer has a surface layer, and surface irregularities are formed on the surface of the surface due to surface irregularities formed on the surface of the rubber elastic layer.
- the filming suppression effect is particularly excellent. This is because the toner stress is easily lowered due to the unevenness on the surface of the surface layer, and it is easier to suppress filming in combination with the effect of improving the charge decay rate.
- Examples 8 to 15 and 17 an ionic liquid having an alkoxysilyl group in the molecular structure is used. Compared to other examples having no alkoxysilyl group in the molecular structure, the volume resistance It was confirmed that the number of digits of variation and the number of longitudinal resistance irregularities were small, and the variation of electrical resistance was further reduced.
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Abstract
Description
R14:環状、直鎖の有機基
R15:少なくとも(CH2)nを含む(但し、nは整数)
R16:アルキル基(-CH3、-C2H5等)
ゴム弾性層形成材料として、以下の材料を準備した。
<液状シリコーンゴム>
・ビニル基含有ジメチルポリシロキサン<1>(Gelest社製、「DMS-V31」)
<ミラブルシリコーンゴム>
・ビニル基含有ジメチルポリシロキサン<2>(KCC社製、「SF3901C」)
<架橋剤>
・ヒドロシリル基含有ジメチルポリシロキサン<1>(Gelest社製、「HMS-301」)
・ヒドロシリル基含有ジメチルポリシロキサン<2>(Gelest社製、「HMS-501」)
<電子導電剤>
・カーボンブラック(電気化学工業社製、「デンカブラックHS100」)
<イオン液体>
・イオン液体<1>(オクチルトリメチルアンモニウム・ビス(トリフルオロメタンスルホニル)イミド(オクチルトリメチルアンモニウムクロリド(東京化成社製試薬)とビス(トリフルオロメタンスルホニル)イミドリチウム(東京化成社製試薬)を水系溶媒に添加し、室温で4時間攪拌して調製した。)。
・イオン液体<2>(1-ブチル-3-メチルピリジニウム・ビス(トリフルオロメタンスルホニル)イミド(1-ブチル-3-メチルピリジニウムクロリド(東京化成社製試薬)とビス(トリフルオロメタンスルホニル)イミドリチウム(東京化成社製試薬)を水系溶媒に添加し、室温で4時間攪拌して調製した。)。
・イオン液体<3>
N2雰囲気下、3-メチルピリジン(東京化成社製試薬)を60mmolと3-クロロプロピルトリメトキシシラン(東京化成社製試薬)を55mmol混合し、90℃で72時間反応させた。冷却して析出した固体を酢酸エチルで2回洗浄した後、酢酸エチルを減圧で除去し、3-メチル-1-トリメトキシシリルプロピルピリジニウムクロリドの化合物を53mmol得た。これをアセトンで溶解し、ビス(トリフルオロメタンスルホニル)イミドリチウム(東京化成社製試薬)53mmolを加えた後、24時間室温で攪拌した。溶剤を減圧除去し、析出したリチウムクロリドをろ過することで3-メチル-1-トリメトキシシリルプロピルピリジニウムビス(トリフルオロメタンスルホニル)イミド(イオン液体3)の化合物を40mmol得た。
・イオン液体<4>
上記イオン液体3の合成において、3-メチルピリジンを1-メチルピペリジン(東京化成社製試薬)に換えて合成した。
・イオン液体<5>
上記イオン液体3の合成において、3-メチルピリジンを4-メチルモルホリン(東京化成社製試薬)に換えて合成した。
・イオン液体<6>
N2雰囲気下、(2-ヒドロキシエチル)トリメチルアンモニウムクロリド(東京化成社製試薬)を60mmolと3-イソシアネートプロピルトリエトキシシラン(東京化成社製試薬)を59mmol混合し、75℃で48時間反応させた。冷却して析出した固体を酢酸エチルで2回洗浄した後、酢酸エチルを減圧で除去し、イオン液体6のアニオンがクロリドの化合物を55mmol得た。これをアセトンで溶解し、ビス(トリフルオロメタンスルホニル)イミドリチウム(東京化成社製試薬)55mmolを加えた後、24時間室温で攪拌した。溶剤を減圧除去し、析出したリチウムクロリドをろ過することでイオン液体6の化合物を45mmol得た。
・イオン液体<7>
上記イオン液体6の合成において、(2-ヒドロキシエチル)トリメチルアンモニウムクロリドを1-(2-ヒドロキシエチル)ピリジニウムクロリド(CHEMICALLAND21社製)に換えて合成した。
・イオン液体<8>
N2雰囲気下、[2-(アクリロイルオキシ)エチル]トリメチルアンモニウムクロリド(SIGMA-ALDRICH社製)を60mmolと(3-アミノプロピル)トリメトキシシラン(東京化成社製試薬)を59mmol混合し、100℃で72時間反応させた。冷却して析出した固体を酢酸エチルで2回洗浄した後、酢酸エチルを減圧で除去し、イオン液体8のアニオンがクロリドの化合物を53mmol得た。これをアセトンで溶解し、ビス(トリフルオロメタンスルホニル)イミドリチウム(東京化成社製試薬)53mmolを加えた後、24時間室温で攪拌した。溶剤を減圧除去し、析出したリチウムクロライドをろ過することでイオン液体8の化合物を42mmol得た。
・イオン液体<9>
上記イオン液体8の合成において、(3-アミノプロピル)トリメトキシシランを(3-メルカプトプロピル)トリメトキシシラン(東京化成社製試薬)に換えて合成した。
・イオン液体<10>
上記イオン液体8の合成において、(3-アミノプロピル)トリメトキシシランを(3-メルカプトプロピル)トリメトキシシラン(東京化成社製試薬)に、また[2-(アクリロイルオキシ)エチル]トリメチルアンモニウムクロリドを[2-(メタクリロイルオキシ)エチル]トリメチルアンモニウムクロリド(東京化成社製試薬)に換えて合成した。
<触媒>
・白金触媒(Gelest社製、「SIP6830.3」)
<充填剤>
・ヒュームドシリカ(日本アエロジル社製、「アエロジルR972」)
・結晶性シリカ(龍森社製、「クリスタライトVX-S」)
<遅延剤>
・1-エチニル-1-シクロヘキサノール(東京化成社製、試薬)
<イオン導電剤(常温で固体)>
・テトラブチルアンモニウム過塩素酸塩(東京化成社製、試薬)
(実施例1~4、比較例1~5)
後述の表1に示す配合となるように、それぞれ、ビニル基含有ジメチルポリシロキサン、カーボンブラック、ヒュームドシリカ、結晶性シリカをプラネタリーミキサーに入れ、30分混合した後、ヒドロシリル基含有ジメチルポリシロキサン、1-エチニル-1-シクロヘキサノール、白金触媒、イオン液体(比較例4はイオン導電剤)を添加して30分混合し、減圧脱泡することにより、ゴム弾性層形成材料としての液状シリコーンゴム組成物を調製した。
先ず、ゴム弾性層の表面に表面凹凸を転写により形成するため、以下のロール成形金型を準備した。すなわち、硫酸ニッケル6水和物20g/L、次亜リン酸ナトリウム1水和物25g/L、乳酸(錯化剤)27g/L、プロピオン酸(錯化剤)2.5g/L、PTFE粒子(平均粒子径0.2μm)2.0g/L、ラウリルトリメチルアンモニウムクロライド0.4g/Lを配合し、pH4.8の各めっき浴を調製した。次いで、上記各めっき浴に、円柱状中空部を有するロール成形用金型を浸漬することにより、円柱状中空部の内周面に無電解共析めっきを施し、無電解共析めっき層(厚み15μm)を型面に有するロール成形用金型を作製した。この際、めっき条件は、めっき浴の温度を90℃、めっき時間を90分間とした。なお、得られたロール成形用金型の断面を、走査型電子顕微鏡により観察したところ、無電解共析めっき層の表面に多数のピットが形成されていることが確認された。
後述の表2に示す配合となるように、それぞれ、ビニル基含有ジメチルポリシロキサン、カーボンブラック、ヒュームドシリカ、白金触媒、イオン液体(比較例7はイオン導電剤)をニーダーで15分間混練りした後、2本ロールで、1-エチニル-1-シクロヘキサノール、ヒドロシリル基含有ジメチルポリシロキサンを練り込んで、ゴム弾性層形成材料としてのミラブルシリコーンゴム組成物を調製した。
イオン液体<1>に代えて後述の表3に示すイオン液体<3>~<10>に変更した以外は実施例1と同様にして、2mm厚のシート、リング、軸体の外周面に沿ってゴム弾性層(外径12mm、層厚さ3mm)が形成された現像ロールAと、ゴム弾性層の外周に厚さ10μmの表層が形成された現像ロールBとを作製した。
実施例1と同様にして、2mm厚のシート、リング、軸体の外周面に沿ってゴム弾性層(外径12mm、層厚さ3mm)が形成された現像ロールAを作製した。次いで、作製した現像ロールAを下記の表面改質液に常温で10分間浸漬した後、常温常湿環境下で24時間放置することによりシリコーンアルコキシオリゴマーを硬化させて、ゴム弾性層表面近傍が高硬度化した現像ロールBを作製した。
<表面改質液>
n-ヘキサン100質量部にシリコーンアルコキシオリゴマー(信越化学工業社製「KR-500」)2質量部と、シリコーンアルコキシオリゴマーの硬化触媒(信越化学工業社製「D-20」)0.08質量部を溶解させることにより、表面改質液を調製した。
イオン液体<1>に代えて後述の表2に示すイオン液体<3>に変更した以外は実施例6と同様にして、2mm厚のシート、リング、軸体の外周面に沿ってゴム弾性層(外径12mm、層厚さ3mm)が形成された現像ロールAと、ゴム弾性層の外周に厚さ10μmの表層が形成された現像ロールBとを作製した。
2.1 シート物性
(硬度)
上記成形シートについて、JISK6253に準拠し、タイプAデュロメータを用い、デュロメータ硬さを測定した。
上記成形リングについて、JISK6262に準拠し、70℃、168時間、25%圧縮の条件にて圧縮永久歪みを測定した。
上記成形シートについて、JISK6271に準拠し、二重リング電極法にて、1V印加の条件にて、体積抵抗率を測定した。
上記成形したシートを40℃、95%RH湿熱環境に2週間放置し、その後のシート表面における導電剤のブリード、ブルームの有無を目視観察した。ブリード、ブルームが何ら認められなかったものを「○」とし、ブリード、ブルームが認められたものを×とした。
(体積抵抗バラツキ)
金属ドラム上に各現像ロールAを線接触させ、ロールの芯金の両端に各々500gの荷重をかけた状態で金属ドラムを回転駆動し、60rpmで各現像ロールAをつれ周り回転させ、DC10V印加した状態での軸体と金属ドラム間の電気抵抗を測定し、その周方向のバラツキを求めた。
図3に示すように、同じ外径の樹脂製ロール1(30mm幅)、金属製ロール2(20mm幅)、樹脂製ロール3(80mm幅)、金属製ロール4(20mm幅)、樹脂製ロール5(80mm幅)、金属製ロール6(20mm幅)、樹脂製ロール7(30mm幅)とを、この順に組み合わせてドラム8を構成した。このドラム8上に各現像ロールAを線接触させ、各現像ロールAの軸体の両端に各々500gの荷重をかけた状態でドラムを回転駆動し、60rpmで各現像ロールAをつれ周り回転させ、DC10V印加した状態での軸体と各金属製ロール間の電気抵抗を測定した。その周方向の平均値を長手方向における所定位置での電気抵抗値とし、各現像ロールAの両端部および中央部の合計3点で電気抵抗値を測定し、その最大値と最小値との差を長手方向抵抗ムラとした。
図4の模式図に示すように、23℃×53%RHの環境下、回転数60rpmで現像ロールA10を矢印方向に回転させながら、コロナ放電線20を用いて、100μAのコロナ電流を印加して現像ロールA10の表面を帯電した。そして、コロナ電流を印加した状態で現像ロールA10を回転させたまま、表面電位計22を現像ロールA10の一方端から他方端まで5mm/sで移動させて現像ロールA10表面の表面電位を測定し、その最大値を残留電荷とした。
図4の模式図に示すように、23℃×53%RHの環境下、回転数60rpmで現像ロールA10を矢印方向に回転させながら、コロナ放電線20を用いて、100μAのコロナ電流を印加して現像ロールA10の表面を帯電した。そして、上記コロナ放電線20から1/4周期分後方の位置に配した表面電位計22により現像ロールA10表面の表面電位を測定し、印加をオフしてから1秒間の表面電位変位量から電荷減衰率を求めた。
各現像ロールBを市販のカラーレーザープリンタ(HP社製、Color Laser jet 3800)のカートリッジに組み込み、ベタ画像出しをLL環境(15℃×10%RH)で行い、画像濃度をマクベス濃度計で測定し、そのバラツキから濃度ムラを求めた。
各現像ロールBを市販のカラーレーザープリンタ(HP社製、Color Laser jet 3800)のカートリッジに組み込み、32.5℃×85%RHの環境下で、画像出しを通紙6000枚行ない、その後のロール外観を顕微鏡((株)キーエンス製、VK-9510)で拡大し観察した。この際、ロール表面にトナーの付着が無かった場合を「◎」、ロール表面にトナーが付着しているが、軽微で搬送量の変化や画像に影響が出なかった場合を「○」、ロール表面にトナーが付着し、搬送量の変化や画像にムラが発生した場合を「×」とした。
Claims (5)
- 軸体と、前記軸体の外周に形成されたゴム弾性層とを有し、
前記ゴム弾性層は、
液状またはミラブルシリコーンゴムと、架橋剤と、電子導電剤と、イオン液体とを含む組成物の架橋体から形成されており、
前記組成物は、
前記液状またはミラブルシリコーンゴムおよび架橋剤の総量100質量部に対して、前記イオン液体を0.1~5.1質量部の範囲内で含有することを特徴とする電子写真機器用現像ロール。 - 前記ゴム弾性層の外周に表層を有し、
前記ゴム弾性層の表面に形成された表面凹凸に起因して前記表層の表面に表面凹凸が形成されている、もしくは、
前記表層に添加された粗さ形成粒子に起因して前記表層の表面に表面凹凸が形成されていることを特徴とする請求項1に記載の電子写真機器用現像ロール。 - 前記イオン液体が、分子構造中にアルコキシシリル基を有するものであることを特徴とする請求項1または2に記載の電子写真機器用現像ロール。
- 印加時における前記ゴム弾性層の残留電荷が15V以下であり、印加停止から1秒後における前記ゴム弾性層の電荷減衰率が80%以上であることを特徴とする請求項1から3のいずれか1項に記載の電子写真機器用現像ロール。
- 前記ゴム弾性層の長手方向の抵抗ムラが1桁以内であることを特徴とする請求項1から4のいずれか1項に記載の電子写真機器用現像ロール。
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