WO2015098310A1 - 現像ロール被覆用ゴム部材及び画像形成装置用現像ロールの製造方法 - Google Patents
現像ロール被覆用ゴム部材及び画像形成装置用現像ロールの製造方法 Download PDFInfo
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- WO2015098310A1 WO2015098310A1 PCT/JP2014/079502 JP2014079502W WO2015098310A1 WO 2015098310 A1 WO2015098310 A1 WO 2015098310A1 JP 2014079502 W JP2014079502 W JP 2014079502W WO 2015098310 A1 WO2015098310 A1 WO 2015098310A1
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- Prior art keywords
- rubber
- particles
- coating layer
- coating
- developing roll
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- 0 *NN[*+]1CC1 Chemical compound *NN[*+]1CC1 0.000 description 1
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Classifications
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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
- G03G15/0808—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 developer supplying means, e.g. structure of developer supply roller
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
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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
Definitions
- the present invention relates to a method for producing a developing roll covering rubber member and a developing roll for an image forming apparatus. More specifically, the present invention has a uniform rough surface on the surface of the coating layer and a sufficient thickness while maintaining flexibility even on the convex portion.
- the present invention relates to a developing roll coating rubber member having a coating layer that can secure the thickness and realize non-adhesion and low friction, and a method for producing a developing roll for an image forming apparatus.
- a contact development system As a development process in a developing device of a recent non-magnetic one-component development system, a contact development system is known in which development is performed by uniformly pressing a developing roll on which a toner (developer) is adhered to a photosensitive member (FIG. 3). reference).
- the electrostatic latent image means forms an electrostatic latent image on the surface of the photosensitive drum based on predetermined image information, while the toner supply roller supplies toner to the surface of the developing roll,
- the supplied toner is regulated to a uniform thickness by a developer amount regulating member (hereinafter also referred to as “regulating blade”), and a uniform toner thin layer is formed on the surface of the developing roll.
- regulating blade developer amount regulating member
- the developing roll having the toner thin layer formed on the surface sequentially adheres the toner to the electrostatic latent image formed on the photosensitive drum at the nip portion or in the vicinity of the photosensitive drum. In this way, toner development is performed.
- the developing roll generally has a structure in which a rubber-like elastic body having conductivity is accumulated on a cylindrical surface of a core material made of a metal, a fibrous material, or a resin molded body. And, by providing a coating layer made of a resin on the surface of the rubber-like elastic body, (1) a problem that components contained in the rubber move to the surface and the counterpart material is contaminated, (2) volume resistance value Is a problem that changes greatly due to environmental changes, (3) a large dynamic friction coefficient, a problem that requires a large torque to rotate due to the frictional relationship with the contact partner member, and (4) a high adhesive property and friction coefficient Due to the characteristics, measures are taken against problems such as adhesion of toner, adhesion to the counterpart material, generation of frictional noise, and adhesion of dirt.
- Patent Document 1 discloses a method of forming a uniform rough surface by dispersing resin particles for roughening on the surface of the developing roll in order to make the surface of the developing roll a uniform rough surface.
- the toner layer particularly the convex portion on the surface of the developing roll is rubbed by the blade, so that frictional heat is generated by rubbing and is easily dissolved.
- the toner is dissolved, there is a problem that filming in which the toner adheres to the surface of the developing roll easily occurs. As the toner deteriorates, it becomes easier to dissolve and this problem is likely to occur.
- toners have a lower melting point and a smaller diameter, and are more easily dissolved by heat.
- Patent Document 2 discloses that the size of the particles to be blended in the surface layer is increased. A technique is disclosed.
- the toner transport amount will be biased or the toner charge amount will be non-uniform.
- the surface of the spherical particles is resin, it is hard, and depending on the type of toner, the toner may be damaged and filming may occur.
- Patent Document 3 Patent Document 4, and Patent Document 5 disclose a technique for reducing the toner stress by lowering the surface hardness of the concave portion that retains more toner than the convex portion formed on the surface.
- the coating layer contains hard particles, the toner stress is particularly large, and sufficient printing durability cannot be obtained.
- Patent Document 6 discloses a technique in which a silicone rubber binder is used as a binder and polymethylsilsesquioxane fine powder is used as resin particles.
- the binder is soft, but the polymethylsilsesquioxane fine powder is hard with resin particles, and the toner is deteriorated.
- the binder is a silicone rubber binder, adhesion to the rubber base layer is poor, and filming and toner adhesion may occur.
- Patent Document 7 discloses a coating layer in which particles are uniformly dispersed in a binder with a material having a low compression set, such as a silicone resin or a urethane resin.
- a material having a low compression set such as a silicone resin or a urethane resin.
- a polyurethane resin is preferably used as a material capable of maintaining stable triboelectric charging.
- the thickness of the coating layer has to be reduced.
- JP 09-269648 A Japanese Patent No. 3112489 Japanese Patent No. 5026902 Japanese Patent No. 5219575 JP 2005-258201 A Japanese Patent No. 3952428 JP 2010-128080 A
- the problems of the present invention are as follows: (1) a uniform rough surface is formed on the surface of the developing roll; (2) damage and toner stress to the counterpart member and toner while maintaining flexibility. (3) To provide a rubber member for coating a developing roll capable of realizing a non-adhesive and low friction, (3) ensuring a thickness sufficient to avoid the influence of rubber. It is in.
- Another object of the present invention is to provide a rubber member for coating a developing roll in which the coating rubber particles can be accumulated in the upper part of the layer even when the coating layer is thickened, and the above-mentioned problem can be solved.
- Another object of the present invention is to provide a method for producing a developing roll for an image forming apparatus using the above.
- a developing roll covering rubber member obtained by applying and curing a coating layer component around a developing roll having a rubber base layer,
- the coating layer component is (A) a liquid binder containing at least a polyol, an isocyanate compound, and a reactive silicone oil; (B) silicone rubber particles having a hardness (JIS K6253: 1997) durometer A (instantaneous) of 20 to 80 degrees and a rubber particle diameter of 0.2 to 10 ⁇ m; (C) a diluted solvent, The developing roll coating rubber member, wherein a ratio of the coating layer thickness after curing to the rubber particle diameter satisfies the rubber particle diameter / coating layer thickness ⁇ 0.3.
- diluting solvent is a diluting solvent that swells rubber particles.
- the surface of the coating layer is formed in a convex shape by the presence of the rubber particles, and the height of the convex portion forming the convex shape is in the range of 0.5 to 8.0 ⁇ m.
- the surface of the coating layer is formed in a convex shape due to the presence of the rubber particles, the spacing between the rubber particles is less than 5 ⁇ m, and the rubber particles are present in an aggregated state of 5 or more. 5.
- the developing roll coating rubber member according to any one of 1 to 4 above.
- a dispersion liquid is prepared by mixing and dispersing a binder containing at least a polyol, an isocyanate compound, and a reactive silicone oil, and a component of the coating layer containing a diluent solvent, Next, rubber particles composed of spherical silicone rubber particles having a hardness (JIS K6253: 1997) durometer A (instantaneous) of 20 to 80 degrees and 0.2 ⁇ m or more and less than 10 ⁇ m are mixed and dispersed in the dispersion.
- the rubber member surface has a uniform rough surface, and does not hinder the softness (trackability) of the rubber base material layer, while maintaining the flexibility even in the convex portion and contaminating the peripheral portion.
- Development roller coating rubber member having a coating layer capable of ensuring a sufficient thickness and realizing non-adhesion and low friction, and a developing roll for an image forming apparatus using the developing roll coating rubber member The manufacturing method of can be provided.
- vertical to the longitudinal direction of an example of the image development roll which can apply this invention
- the principal part expanded sectional view of the coating layer which comprises the rubber member for image development roll covering which concerns on this invention Schematic of an example of a developing device using a developing roll according to the present invention
- FIG. 1 is a cross-sectional view of a surface perpendicular to the longitudinal direction of an example of a developing roll to which the present invention can be applied.
- FIG. 2 shows an enlarged cross-sectional view of the main part of the coating layer constituting the developing roll covering rubber member according to the present invention.
- the developing roll coating rubber member of the present invention is obtained by coating and curing a coating layer component around a developing roll having a rubber base layer.
- the developing roll 1 has at least one rubber base layer 12 formed around the core material 11, and further a coating layer 13 formed around the rubber base layer 12.
- the rubber substrate layer of the developing roll includes silicone rubber, polyurethane elastomer, ethylene-propylene-diene rubber (EPDM), styrene-butadiene rubber (SBR), acrylonitrile-butadiene rubber (NBR), hydrogenated Examples thereof include acrylonitrile-butadiene rubber (HNBR), chloroprene rubber (CR), epichlorohydrin rubber (ECO), and the like, but are not particularly limited.
- silicone rubber is preferably used from the viewpoint of low hardness and little settling.
- the rubber base layer may include a conductive agent, a filler, an extender, a reinforcing agent, a processing aid, a curing agent, a vulcanization accelerator, a crosslinking agent, a crosslinking aid, an antioxidant, a plasticizer, as necessary.
- a conductive agent such as additives, ultraviolet absorbers, pigments, silicone oils, auxiliaries, and surfactants can be appropriately added.
- a known conductive agent such as an ionic conductive agent or an electronic conductive agent can be used.
- Examples of the ion conductive agent include LiCF 3 SO 3 , NaClO 4 , LiClO 4 , LiAsF 6 , LiBF 4 , NaSCN, KSCN, NaCl Group 1 metal salt, NH 4 Cl, (NH 4 ) 2 SO 4.
- NH 4 NO 3 ammonium salt Ca (ClO 4 ) 2 , Ba (ClO 4 ) 2 periodic table group 2 metal salt, these salts and 1,4-butanediol, ethylene glycol, polyethylene glycol, Complexes of propylene glycol, polypropylene glycol with polyhydric alcohols and derivatives thereof, complexes of these salts with ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, polyethylene glycol monomethyl ether, polyethylene glycol monoethyl ether monool, Cationicity of quaternary ammonium salts Examples thereof include anionic surfactants such as surfactants, aliphatic sulfonates, alkyl sulfate esters, and alkyl phosphate esters, and amphoteric surfactants of betaine.
- anionic surfactants such as surfactants, aliphatic sulfonates, alkyl sulfate esters, and alkyl phosphat
- Examples of the electronic conductive agent include carbon black, graphite carbon-based material, aluminum, silver, gold, tin-lead alloy, copper-nickel alloy metal or alloy, zinc oxide, titanium oxide, aluminum oxide, tin oxide, antimony oxide, Examples thereof include indium oxide, metal oxide of silver oxide, and materials obtained by applying conductive metal plating such as copper, nickel and silver to various fillers.
- conductive agents based on ionic conductive agents and electronic conductive agents can be used alone or in admixture of two or more in the form of powder or fiber.
- carbon black can be preferably used from the viewpoint of easy control of conductivity and economy.
- the coating layer component is (A) a liquid binder containing at least a polyol, an isocyanate compound, and a reactive silicone oil; (B) silicone rubber particles having a hardness (JIS K6253: 1997) durometer A (instantaneous) of 20 to 80 degrees and a rubber particle diameter of 0.2 ⁇ m or more and less than 10 ⁇ m; (C) a diluting solvent.
- ⁇ Binder> As the binder used in the present invention, an adhesive binder is used, and a rubber binder having a hardness (JIS K6253: 1997) durometer A (instantaneous) of 20 to 90 degrees is preferable. Specifically, a polyol and an isocyanate compound are used. Including reaction products of reactive silicone oils.
- rubber or an adhesive (primer) for treating the rubber surface may be further used.
- the binder used in the present invention is in a liquid state.
- the silicone rubber particles are separated from the liquid binder having poor compatibility, and the rubber particles migrate to the surface of the coating layer. Even if it is a coating layer thicker than a diameter, a convex part can be uniformly formed in the coating layer surface, and it is preferable.
- the primer is appropriately selected depending on the applicable rubber base material layer and binder, and isocyanate. Primers such as cage, silane and silicone are selected.
- the polyol used in the present invention is preferably a liquid at normal temperature (20 to 30 ° C.), and various polyols can be used. It is necessary to have charging properties, and the polyol is preferably one that can react with an isocyanate compound to form a coating layer (polyurethane) having a large triboelectric charge train.
- polyols include polyether polyols such as polyalkylene glycols such as polyethylene glycol, polypropylene glycol, tetramethylene glycol, and copolymers thereof.
- fluorine-containing polyols are particularly preferred.
- the fluorine-containing polyol not only reacts with the isocyanate compound to produce a coating layer having a larger triboelectric charge train, but also reduces the resistance environmental dependency of the resulting coating layer. As the fluorine content of the fluorine-containing polyol is higher, the triboelectric train becomes negatively larger.
- a copolymer (copolymer polyol containing an ethylene trifluoride monomer unit as a main component) having an ethylene trifluoride monomer as a main material and an ethylene tetrafluoride monomer as a main material.
- a copolymer (copolymer polyol containing a tetrafluoroethylene monomer unit as a main component) can be preferably exemplified.
- fluorine-containing polyols such as “Zeffle” (copolymer polyol containing a tetrafluoroethylene monomer unit as a main component) manufactured by Daikin Industries, Ltd. and “Lumiflon” manufactured by Asahi Glass Industry Co., Ltd. “(Copolymer polyol containing a trifluoromonohaloethylene monomer unit as a main component)” and “Defenser” manufactured by Dainippon Ink & Chemicals, Inc. are preferred.
- fluorine-containing polyols are mainly composed of, for example, a tetrafluoroethylene monomer, and a total of at least hydroxy monocarboxylic acid ester of acrylic acid and / or glycol monoester of acrylic acid copolymerized therewith. Contains 2 moles.
- fluorine-containing copolymer polyols are esterified with the above acrylate monomer (OH in the hydroxy monocarboxylic acid ester of acrylic acid, OH in the carboxyl group, and glycol monoester in acrylic acid). Not glycol OH).
- a copolymer polyol containing a tetrafluoroethylene monomer as a main component is particularly preferable.
- isocyanate compound used in the present invention examples include diisocyanates such as diphenylmethane diisocyanate (MDI), tolylene diisocyanate (TDI), hexamethylene diisocyanate (HDI), and their burettes, isocyanurates and urethanes. It can be preferably used.
- MDI diphenylmethane diisocyanate
- TDI tolylene diisocyanate
- HDI hexamethylene diisocyanate
- burettes isocyanurates and urethanes. It can be preferably used.
- isocyanate compounds are hexamethylene diisocyanate and its burette-modified product, isocyanurate-modified product, urethane-modified product, and the like.
- the reactive silicone oil used in the present invention can react with an isocyanate compound, and a reactive silicone oil having active hydrogen is preferably used.
- Reactive silicone oils having active hydrogen are, for example, silicone oils having amino groups (primary and / or secondary amino groups), silicone oils having mercapto groups, silicone oils having hydroxyl groups (eg having carboxyl groups) Silicone oils, silicone oils having phenolic OH groups, silicone oils having alcoholic OH groups, and the like are included.
- reactive silicone oils are commercially available as amino-modified silicone oil, mercapto-modified silicone oil, carboxyl-modified silicone oil, phenol-modified silicone oil, carbinol-modified silicone oil, and the like.
- any of the silicone oils having the reactive organic group only at one end or at both ends and / or in the side chain can be used.
- More preferable reactive silicone oil can be represented by the following general formula (1) or (2).
- each R represents —C 3 H 6 OC 2 H 4 OH or —C 3 H 6 OCH 2 —C (CH 2 OH) 2 C 2 H 5 , n Represents an integer of about 20 or less.
- Particularly preferred reactive silicone oils are those of the general formula (1) in which each R is —C 3 H 6 OC 2 H 4 OH, among which those with n of about 10 are particularly preferred. Such reactive silicone oils are also commercially available.
- a silicone oil having hydrogen bonded to silicon in the silicone skeleton can be used.
- the effect of softening the binder component can be obtained by adding reactive silicone oil.
- the binder component should be soft and soft, and the adhesiveness can be reduced by reducing the hardness by adding fluoroelastomer or silicone oil rather than reducing the hardness with a urethane binder. It is possible and preferable.
- the covering layer soft because it can follow the deformation of the rubber layer as the base material. If the coating layer is difficult to follow the deformation of rubber, etc., the coating layer will crack, and the rubber compounding agent will exude from the cracks, the toner will adhere to the cracks, the friction coefficient will change, and the roller will be changed early. May not be able to achieve its purpose.
- the silicone rubber particles used in the present invention preferably have a structure in which an organopolysiloxane such as dimethylpolysiloxane or a polyorganosilsesoxane is cross-linked, but is not particularly limited thereto. Commercially available silicone rubber particles can also be used.
- the toner conveyance amount and the rubber particle diameter can be adjusted within the range according to the size and shape of the toner so that the toner does not enter the dent.
- the particle diameter of the particles is preferably 0.2 ⁇ m to 10 ⁇ m, more preferably 0.8 ⁇ m to 5 ⁇ m.
- the coating layer surface is not uneven, and the toner and particles during printing cannot be in point contact. As a result, the impact of the toner cannot be absorbed (the contact resistance cannot be reduced), and the toner deteriorates, which is not preferable.
- the particle diameter of the silicone rubber particles exceeds 10 ⁇ m, the convex portions on the surface of the coating layer due to the particles become too high, the toner conveyance amount becomes too large, or the toner hits the convex surfaces of the rubber particles, and the toner deterioration proceeds. It is not preferable.
- the particles are too large, the surface roughness becomes too large, resulting in gritty or unevenness of the resulting image, and the fog characteristics are reduced.
- the particles are too large, it is difficult to form a uniform roughness over the entire surface of the coating layer. If the surface roughness of the roll varies, there is a risk that the toner transport amount is uneven and the toner charge amount is non-uniform.
- the hardness of the silicone rubber particles is preferably from 20 to 80 degrees, more preferably from 50 to 75 degrees, durometer A (instantaneous) (JIS K6253: 1997), but is appropriately selected according to the surface unevenness state.
- the hardness is less than 20 degrees durometer A (instantaneous)
- the shape of the rubber particles cannot be maintained when contacting the mating material, and the silicone rubber itself will not be destroyed or returned to its original size.
- the friction coefficient increases, and adhesion occurs, which is not preferable.
- the silicone rubber particles used in the present invention are made of a silicone cured product having rubber elasticity having a linear organopolysiloxane block represented by the general formula (3) in the molecular structural formula.
- R 1 is an alkyl group such as a methyl group, an ethyl group, a propyl group or a butyl group, an aryl group such as a phenyl group or a tolyl group, an alkenyl group such as a vinyl group or an allyl group, or ⁇ -phenylethyl Group, aralkyl group such as ⁇ -phenylpropyl group, monovalent halogenated hydrocarbon group such as chloromethyl group, 3,3,3-trifluoropropyl group, epoxy group, amino group, mercapto group, acryloxy group, A group selected from one or two or more monovalent organic groups having 1 to 20 carbon atoms selected from a reactive group-containing organic group such as a methacryloxy group, 90% by mole or more of which is a methyl group It is preferable.
- a is preferably an integer of 5 to 5,000, more preferably an integer of 10 to 1,000.
- a is less than 5, the characteristics of the linear organopolysiloxane are not sufficiently obtained, and thus the effect of lowering hardness and improving lubricity cannot be obtained sufficiently, and the maximum value of a is not particularly defined. If it is more than 5,000, production of silicone rubber fine particles becomes difficult.
- Curing is preferably performed by general crosslinking of silicone rubber and by addition reaction.
- Silicone rubber particles can be produced by a method of curing in a high temperature spray-drying method, a method of curing in an organic solvent, a method of curing this after being made into an emulsion, or the like. Since the production of the silicone rubber fine particles of the invention uses the silicone rubber spherical fine particles as an aqueous dispersion, this is preferably a method of curing in the emulsion particles of silicone.
- the silicone rubber particles used in the present invention may be a resinous polymer having an organosilsesquioxane unit represented by the general formula (4) as a structural unit.
- R 2 represents an alkyl group such as a methyl group, an ethyl group, a propyl group or a butyl group, an aryl group such as a phenyl or tolyl group, an alkenyl group such as a vinyl group or an allyl group, ⁇ -phenylethyl Group, aralkyl group such as ⁇ -phenylpropyl group, monovalent halogenated hydrocarbon group such as chloromethyl group, 3,3,3-trifluoropropyl group, epoxy group, amino group, mercapto group, acryloxy group
- the polyorganosilsesquioxane resin and other surface treatments may be uniformly coated on the entire surface of the rubber particles, or a part of the surface may be coated.
- An organoalkoxysilane represented by the following general formula (5) may be surface-treated on the surface of the silicone rubber spherical particles used in the present invention.
- R 2 represents the same monovalent organic group as in the general formula (4)
- R 3 represents an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group, or a butyl group.
- the compatibility of the resulting silicone particles with the base material and the lubricating properties can be expected to be further improved.
- rubber particles are dispersed with a ball mill, attritor, basket mill, sand mill, sand grinder, dyno mill, disperse mat, SC mill, spike mill, agitator mill, etc. If not, disperse with ultrasonic, homogenizer, ultrasonic homogenizer, nanomizer, desolver, disper, high-speed impeller disperser, etc.
- the surface of the silicone rubber particles may be treated with a silane coupling agent, silica, metal oxide or the like for non-adhesiveness, lubricity, wear resistance, and aggregation prevention.
- Rubber hardness JIS-A 30 degrees, no functional group Rubber hardness JIS-A 30 degrees, no functional group
- EP-2600 average particle diameter 2 ⁇ m, rubber hardness JIS-A 40 degree, no functional group
- EP-2601 average particle diameter 2 ⁇ m, rubber hardness JIS-A 40 degrees, functional group epoxy group
- E-2720 average particle size 2 ⁇ m, rubber hardness JIS-A 70 degrees, functional group methacryl group
- DY 33-430M average particle diameter 4 ⁇ m, rubber Hardness JIS-A 30 °, no functional group
- Toray Dow Corning “EP-2720”, “EP-9215 Cosmetics Powder”, “9701 Cosmetics Powder”, etc. can be used.
- ⁇ Diluted solvent there are an aqueous solvent and an organic solvent solvent, and a low boiling solvent and a high boiling solvent can be combined depending on the drying speed.
- the solid content concentration ratio with the diluent solvent is preferably in the range of 3 to 50 wt%, more preferably 5 to 30 wt%. %.
- the solid content concentration is low, liquid sag occurs at the time of coating, and drying becomes slow.
- the concentration is high, roughness and thickness control of the coating surface become difficult.
- the rubber particles swell in the coating liquid, and the repellency and dents of the coating layer can be eliminated.
- the coating solution can be applied in the coating solution so that the settling of the rubber particles can be delayed and can uniformly protrude on the rubber surface.
- organic solvents such as methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), tetrahydrofuran (THF), acetone, ethyl acetate, butyl acetate, toluene, xylene, heptane, cyclohexanone, isophorone are preferable.
- MEK methyl ethyl ketone
- MIBK methyl isobutyl ketone
- THF tetrahydrofuran
- acetone ethyl acetate
- butyl acetate butyl acetate
- toluene xylene
- heptane cyclohexanone
- isophorone is preferable.
- the heating temperature and time are appropriately set so that the rubber particles return to the original size by heating.
- the silicone rubber particles are preferably in the range of 3 to 30% by weight, more preferably 5 to 20% by weight as the solid content (% by weight). is there.
- the solid content ratio of the silicone rubber particles exceeds 30% by weight, the hardness of the surface of the coating layer is reduced, and many convex shapes are formed on the surface, which promotes non-adhesion and low friction, but reduces wear resistance.
- there are problems such as a decrease in the strength of the film, a decrease in adhesion to the rubber base material layer, and an increase in the toner conveyance amount.
- the solid content ratio of the rubber is less than 3% by weight, there is no convex formation of rubber particles on the surface of the coating layer, non-adhesion and low friction are lost, stress reduction on the counterpart material is lost, and printing defects are lost. Since it occurs, it is not preferable.
- the isocyanate compound is preferably in the range of 10 to 70% by weight, more preferably 30 to 60% by weight in terms of solid content by weight. If it is less than 10% by weight, the adhesiveness, strength, and abrasion resistance of the rubber are lowered. If it exceeds 70% by weight, the deterioration of the toner, adhesion with the toner, and deterioration of printing characteristics due to the embedment of the added rubber particles are not preferable.
- the polyol (for example, fluorine-containing polyol) is preferably in the range of 10 to 40% by weight, more preferably 10 to 30% by weight as the solid content by weight.
- the reactive silicone oil is preferably in the range of 10 to 70% by weight, more preferably 30 to 60% by weight in terms of solid content by weight.
- the binder is preferably adjusted so that the hardness (JIS K6253: 1997) durometer A (instantaneous) is 20 to 80 degrees.
- Toner deterioration can be prevented by adjusting the hardness of the coating layer to the same level as rubber.
- the hardness JIS K6253: 1997) durometer A (instantaneous) is less than 20 degrees, there are problems such as deterioration of wear resistance of the binder and occurrence of adhesion.
- ⁇ Surface shape> As for the shape of the surface of the coating layer, surface irregularities are formed by the silicone rubber particles accumulated on the surface.
- the number of rubber particles exposed on the surface can be determined by the particle diameter and the blended amount of rubber particles.
- the number of rubber particles in 50 ⁇ m 2 is preferably 200 or more, more preferably 500 or more.
- the number is less than 200, as described above, the rubber particles are less likely to form irregularities on the surface, and the toner cannot contact the toner during printing and cannot absorb the impact of the toner, resulting in deterioration of the toner.
- the particle size and the agglomeration size should be large according to the surface pressure, and it is better that there is a certain gap between the particles.
- the particle size is determined according to the toner size and the transport amount, the particle interval is shorter, the smaller the gap is, the better the toner does not enter the gap, and the particles are more agglomerated. good.
- the surface convex height is preferably 0.5 to 8.0 ⁇ m. If it is smaller than 0.5 ⁇ m, the toner and particles are not in point contact, and the resistance of the toner cannot be reduced, which is not preferable. If it is larger than 8.0 ⁇ m, the toner enters the gaps between the particles and the toner stress increases, which is not preferable.
- a convex portion is formed by one spherical particle, and in other cases, the particles are aggregated to form a convex portion.
- the width of the opening of the recess between the rubber particles in the rubber particle aggregated portion is 10 ⁇ m or less, and the depth is preferably less than 5 ⁇ m.
- the particles have particles smaller than the toner particle diameter on the surface and support the toner with dots.
- the ratio of “rubber particle diameter / coating layer thickness” satisfies the above rubber particle diameter / coating layer thickness ⁇ 0.3.
- the thickness of the coating layer is preferably 5 ⁇ m or more. The thicker the coating layer, the more rubber particles are present in the coating layer.
- the coating layer thickness above a certain level, problems such as toner adhesion, adhesion to the mating material, generation of frictional noise, and contamination due to rubber properties such as high adhesion properties and friction coefficient can be sufficiently avoided. It is preferable because a thickness as much as possible can be secured.
- the particle diameter is small and the thickness is small and the ratio exceeds 0.3, the rubber particles on the surface of the coating layer are often buried in the binder, and the toner and particles are not in point contact, reducing the resistance of the toner. I can't.
- the ratio exceeds 0.3 and the number of rubber particles is less than 200, the rubber particles on the surface of the coating layer are often buried in the binder, and the toner and particles are in point contact. The toner resistance cannot be reduced.
- the ratio of “rubber particle diameter / coating layer thickness” is preferably less than 0.3.
- the particle diameter is 0.3 or more, the above-mentioned problem occurs. If the polished surface cannot be filled, and there are traces of a polishing step at the time of printing or if it is thin, the exposure of particles increases and the toner conveyance amount increases. On the other hand, if it is thin, the unevenness of rubber polishing is not filled with the coating, which causes deterioration of the toner. Moreover, the problem that wear resistance falls also arises.
- the rubber particles are uniformly present on the surface of the coating layer, so that the particle portions become non-adhesive and have low friction, and the surface hardness decreases.
- a manufacturing method of a developing roll for an image forming apparatus according to the present invention comprises: applying and forming a rubber base material layer around a core material; In a method for producing a developing roll for an image forming apparatus in which a coating layer is formed around a binder, a binder containing at least a polyol, an isocyanate compound, and a reactive silicone oil and a component of the coating layer containing a diluting solvent are mixed and dispersed.
- a dispersion liquid is prepared, and then, rubber particles composed of spherical silicone rubber particles having a hardness (JIS K6253: 1997) durometer A (instantaneous) of 20 to 80 degrees and 0.2 ⁇ m or more and less than 10 ⁇ m are mixed with the dispersion liquid.
- the coating dispersion is applied to the periphery of the elastic rubber layer, dried and cured to form a coating layer. It is a method of forming.
- the coating layer when the coating layer is formed, it is preferable to apply the coating dispersion, maintain the liquid state for a predetermined time, move the rubber particles to the upper layer in the layer, and then cure.
- the rubber particles when the rubber particles are moved to the upper layer portion in the layer, the rubber particles are moved so that the surface exposed particle change rate obtained by the following calculation formula before and after curing of the coating layer becomes a surface state of 500% or more. It is preferable to make it.
- the developing roll coating rubber member of the present invention can be obtained by applying, drying and / or baking the constituent materials of the coating layer.
- an adhesive in advance before applying the rubber member of the present invention.
- the coating method is not particularly limited, and can be performed by a known coating method such as a dipping method, a spray method, a roll coating method, a doctor blade method, a flow coating method, or the like.
- Drying conditions can be set as appropriate, but are preferably performed at room temperature to 150 ° C. for 5 to 20 minutes.
- Calcination may not be performed, but it is preferably performed at room temperature to 230 ° C. for about 5 to 120 minutes, and can be appropriately set according to the heat resistance of the rubber.
- Silicone rubber particles are blended in a binder, uniformly dispersed, and applied to the surface of the rubber base layer, so that the surface of the coating layer has a uniform surface roughness, and the coating layer is kept soft to provide low adhesion and low friction. be able to.
- Convex silicone rubber particles that come into contact with the mating member are soft and point contact, and are less dependent on the hardness of the binder, reducing stress on the mating surface, reducing adhesion, and reducing friction .
- the resin component used in the toner component and the silicone do not stick, and the convexity of the silicone rubber particles makes a point contact, Stress can be reduced and toner deterioration can be prevented.
- rubber particles other than silicone such as EPDM, SBR, and urethane, are not preferred because they are sticky.
- the surface of the coating layer is formed in a convex shape due to the presence of the rubber particles, the spacing between the rubber particles is less than 5 ⁇ m, and the rubber particles are present in an aggregated state of 5 or more. It is preferable. It is preferable that the distance between the rubber particles formed in a convex shape is shorter because the surface structure is such that the toner does not enter the opening between the rubber particles.
- silicone rubber particle shape is spherical or substantially spherical rubber beads, the surface of the roll becomes point contact, and the toner is transported without stress. At low loads, rubber particles that retain or recover the shape of a sphere or a substantially sphere are preferred.
- the coating solution has sedimentation and uniform application is difficult.
- the coating solution has sedimentation and uniform application is difficult.
- the rubber particles if a solvent that swells the rubber particles is used, sedimentation can be further reduced and uniform application can be achieved. Furthermore, the rubber increases the viscosity of the coating agent and improves the coating property.
- silicone rubber particles reduces the frictional wear resistance, but it can be improved by adding a binder or a lubricating component.
- Example 1 ⁇ Creation of coating layer composition solution (coating solution)> ⁇ Fluorine-containing polyol (solid content concentration 50%) (“Zeffle GK510” manufactured by Daikin Industries, Ltd.) 35.0 parts by weight ⁇ Urethane modified hexamethylene diisocyanate (solid content concentration 80%) (“Duranate E402-80B” manufactured by Asahi Kasei Corporation) 79.4 parts by weight Reactive silicone oil (“X-22-160AS” manufactured by Shin-Etsu Chemical Co., Ltd.) 50.0 parts by weight-Diluting solvent; 249.4 parts by weight of butyl acetate
- a dispersion liquid in which a binder and a diluent solvent were mixed was prepared.
- Silicone rubber particles (“EP-2720” manufactured by Toray Dow Corning Co., Ltd .: hardness (JIS K6253: 1997) durometer A (instantaneous) 70 degrees, average particle diameter 2 ⁇ m (1-2 ⁇ m)) 14.6 wt. Parts were mixed to obtain a coating dispersion (1).
- the coating dispersion (1) was prepared in advance by high-speed stirring with a bead mill and then stirred for 10 minutes with a stirrer to prepare a coating dispersion (2).
- a primer “KBP-40” manufactured by Shin-Etsu Silicone Co., Ltd. was spray-coated on the surface of the rubber-coated roller, and then the coating dispersion (2) was spray-coated on the coated surface. Thereafter, the coating film was cured by heating at 160 ° C. for 40 minutes to form a developing roll covering rubber member as a coating layer, and a developing roller was manufactured.
- the thickness of the surface coating layer at this time was as shown in Table 1.
- Toner transport amount The toner on the developing roll after passing through the developing blade is sucked and the toner accumulated on the filter paper is weighed to measure the toner amount (mg / cm 2 ) per unit area. did. The results are shown in Table 1. Conveyance amount is preferably 0.4 ⁇ 0.6mg / cm 2, more preferably from 0.4 ⁇ 0.55mg / cm 2. If it is more than this, the toner consumption increases, which is not preferable. Further, the smaller the transport amount, the better the torque fuel consumption, but if it is less than 0.4 mg / cm 2 , the printing becomes thin, which is not preferable.
- HL-2240D in a low temperature and low humidity environment (15 ° C., 25% RH), A 3000-sheet endurance test was performed at a density of 1% / sheet, and after 2500 sheets, an image pattern with black solid portions provided in four places, top, bottom, left and right, was printed, and a black and white transmission densitometer ("X-rite310T” manufactured by X-rite Corporation) ), The transmission density was measured at a total of 12 points (one black solid part / 3 points), and the average value was calculated. The results are shown in Table 1. When the image density is 1.9 or more, it can be evaluated that the image density is good.
- Example 2 In Example 1, 14.6 parts by weight of silicone rubber particles (manufactured by Toray Dow Corning) (rubber hardness (JIS K6253: 1997) durometer A (instantaneous) 70 degrees, average particle diameter 2 ⁇ m (1-2 ⁇ m)) A coating dispersion was prepared in the same manner except that the amount was changed to 9 parts by weight. Thereafter, a rubber base material layer was prepared in the same manner as in Example 1, evaluated in the same manner as in Example 1, and the results are shown in Table 1.
- Example 3 silicone rubber particles (manufactured by Toray Dow Corning) (rubber hardness (JIS K6253: 1997) durometer A (instantaneous) 70 degrees, average particle size 2 ⁇ m (1 to 2 ⁇ m)) were converted into silicone rubber particles (Shin-Etsu Chemical Co., Ltd.).
- a coating dispersion was prepared in the same manner except that the rubber hardness (JIS K6253: 1997) durometer A (instant) was 75 degrees and the average particle diameter was 2 ⁇ m (0.7 to 5 ⁇ m)). Then, except having changed the thickness of the coating layer into 10 micrometers, the rubber base material layer was created similarly to Example 1, and it evaluated similarly to Example 1, The result was shown in Table 1.
- Example 4 A coating dispersion was prepared in the same manner as in Example 1. Then, except having changed the thickness of the coating layer into 10 micrometers, the rubber base material layer was created similarly to Example 1, and it evaluated similarly to Example 1, The result was shown in Table 1.
- Example 1 silicone rubber particles (manufactured by Toray Dow Corning) (rubber hardness (JIS K6253: 1997) durometer A (instantaneous) 70 degrees, average particle size 2 ⁇ m (1 to 2 ⁇ m)) were converted into silicone rubber particles (Shin-Etsu Chemical Co., Ltd.).
- a coating dispersion was prepared in the same manner except that the rubber hardness (JIS K6253: 1997) durometer A (instant) was 75 degrees and the average particle diameter was 2 ⁇ m (0.7 to 5 ⁇ m)). Then, except having changed the thickness of the coating layer into 5 micrometers, the rubber base material layer was created similarly to Example 1, and it evaluated similarly to Example 1, and the result was shown in Table 1.
- Example 1 Comparative Example 1
- silicone rubber particles manufactured by Toray Dow Corning
- rubber hardness JIS K6253: 1997) durometer A (instantaneous) 70 degrees, average particle size 2 ⁇ m (1-2 ⁇ m)
- a coating dispersion was prepared in the same manner except that the part was changed to part.
- a rubber base material layer was prepared in the same manner as in Example 1, evaluated in the same manner as in Example 1, and the results are shown in Table 1.
- Example 2 silicone rubber particles (manufactured by Toray Dow Corning) (rubber hardness (JIS K6253: 1997) durometer A (instantaneous) 70 degrees, average particle diameter 2 ⁇ m (1-2 ⁇ m)) were used as silicone rubber particles (manufactured by Momentive). ) (Rubber hardness (JIS K6253: 1997) durometer A (instant) 95 degrees, average particle diameter 2 ⁇ m (1 to 3 ⁇ m)). Thereafter, a rubber base material layer was prepared in the same manner as in Example 1, evaluated in the same manner as in Example 1, and the results are shown in Table 1.
- Example 3 silicone rubber particles (manufactured by Toray Dow Corning) (rubber hardness (JIS K6253: 1997) durometer A (instantaneous) 70 degrees, average particle size 2 ⁇ m (1 to 2 ⁇ m)) were converted into silicone rubber particles (Shin-Etsu Chemical Co., Ltd.). A coating dispersion was prepared in the same manner except that the rubber hardness (JIS K6253: 1997) durometer A (instant) was 30 degrees and the average particle size was 5 ⁇ m (1 to 15 ⁇ m). Thereafter, a rubber base material layer was prepared in the same manner as in Example 1, evaluated in the same manner as in Example 1, and the results are shown in Table 1.
- Example 4 In Example 1, 50.0 parts by weight of reactive silicone oil was 0 parts by weight, silicone rubber particles (manufactured by Toray Dow Corning) (rubber hardness (JIS K6253: 1997) durometer A (instantaneous) 70 degrees, average particle diameter A coating dispersion was prepared in the same manner except that 14.6 parts by weight (2 ⁇ m (1-2 ⁇ m)) was changed to 3.1 parts by weight. Thereafter, a rubber base material layer was prepared in the same manner as in Example 1, evaluated in the same manner as in Example 1, and the results are shown in Table 1.
- a dispersion was prepared as follows. In a nitrogen atmosphere, 100 parts by weight of polytetramethylene glycol ("PTG1000SN” manufactured by Hodogaya Chemical Co., Ltd.) and 21.2 parts by weight of isocyanate ("Millionate MT” manufactured by Nippon Polyurethane Industry Co., Ltd.) are mixed stepwise in the solvent methyl ethyl ketone. The reaction was carried out at 80 ° C. for 6 hours to prepare a polyurethane polyol prepolymer.
- PTG1000SN polytetramethylene glycol
- isocyanate MT manufactured by Nippon Polyurethane Industry Co., Ltd.
- composite silicon powder (“KMP-601” manufactured by Shin-Etsu Chemical Co., Ltd .; volume average particle size 15 ⁇ m) as core / shell particles was added in an amount of 30 parts by weight to a solid content concentration of 70 parts by weight.
- the mixture was stirred with a propeller blade, dispersed and mixed to obtain a coating solution.
- a rubber base material layer was prepared in the same manner as in Example 1, evaluated in the same manner as in Example 1, and the results are shown in Table 1.
- Comparative Example 6 In Comparative Example 5, composite silicon powder (KMP-601 manufactured by Shin-Etsu Chemical Co., Ltd .; volume average particle size 15 ⁇ m) was used as the core-shell particle, and composite silicon powder (“X-52-7030” manufactured by Shin-Etsu Chemical Co., Ltd.) was used. A coating solution was prepared in the same manner except that the volume average particle size was changed to 1.0 ⁇ m. Thereafter, a rubber base material layer was prepared in the same manner as in Example 1, evaluated in the same manner as in Example 1, and the results are shown in Table 1.
- Example and Comparative Example 4 are compared, when reactive silicone oil is not included, the dynamic friction coefficient becomes large (lower friction coefficient is not sufficient), the flexibility is poor, and the number of particles on the roll surface is very high. It can be confirmed that it decreases. As a result, printing vertical stripes are seen at an early stage. The image density cannot be maintained.
- Example and Comparative Example 2 are compared, if the rubber particle hardness is durometer A (instantaneous) 95 degrees or more, the flexibility is lowered, the interval between the rubber particles is widened, and the aggregation state of the rubber particles is good. There wasn't. Dispersed printing vertical stripes are seen at an early stage, and the image density cannot be maintained. This is probably because the particles are not rubber but resin and the particles are hard, which damages the mating member and the toner and promotes toner deterioration.
- durometer A instantaneous
- the particle diameter / thickness ratio of the coating layer is 1.86, the number of particles on the surface is as small as 56, and the maximum particle diameter is 15 ⁇ m.
- the gap between the rubber particles on the surface of the coating layer is increased, the toner enters the gap, and the toner stress is increased.
- Comparative Example 5 there are many surface rubber particles, but this is thought to be due to the large amount of rubber particles blended with large surface protrusions because large particles were used. This is not because the rubber particles have moved to the surface, as can be seen from the change rate of the exposed particles on the coating layer surface before and after curing. Therefore, in Comparative Example 6 using particles smaller than Comparative Example 5, the number of surface particles is small.
- the rubber particles are the same as in the examples, and in Comparative Example 7 in which the dispersion liquid is different, the hardness, particle size, and blending amount of the rubber particles are the same as those in the examples, but the flexibility is low.
- the surface spacing and dispersion of the particles were also poor.
- the number of surface rubber particles has also decreased extremely. Since the coating layer component hardened immediately, it is considered that the rubber particles were hardened without being transferred to the surface.
- the roller can be used for a charging roll, a blade, a fixing roll, a fixing belt, a rubber member such as a supply roll.
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Abstract
Description
(1)現像ロールの表面において、均一な粗面を形成していること、
(2)柔軟性を維持しながら、相手部材やトナーに対してダメージや、トナーストレスなどを与えないこと、
(3)ゴムの影響を十分に回避できるだけの厚さを確保することができること、
(4)非粘着化、低摩擦化を実現できること、
が求められる。
ゴム基材層を有する現像ロールの周囲に、被覆層成分を塗布・硬化させて得られる現像ロール被覆用ゴム部材であり、
該被覆層成分は、
(A)ポリオール、イソシアネート化合物、及び反応性シリコーン油を少なくとも含む液状のバインダーと、
(B)硬度(JIS K6253:1997)デュロメータA(瞬時)が20~80度であり、ゴム粒子径が0.2~10μmのシリコーンゴム粒子と、
(C)希釈溶剤とを含み、
硬化後の被覆層厚みと前記ゴム粒子径の比が、前記ゴム粒子径/被覆層厚み<0.3を満足することを特徴とする現像ロール被覆用ゴム部材。
前記希釈溶剤が、ゴム粒子を膨潤させる希釈溶剤を用いることを特徴とする前記1記載の現像ロール被覆用ゴム部材。
前記ポリオールが、フッ素含有ポリオールであることを特徴とする前記1又は2記載の現像ロール被覆用ゴム部材。
前記被覆層の表面に、前記ゴム粒子が50μm2あたり200個以上存在することを特徴とする前記1~3の何れかに記載の現像ロール被覆用ゴム部材。
前記被覆層の表面が、前記ゴム粒子の存在によって凸状に形成され、該凸状を為す凸部の高さが0.5~8.0μmの範囲であることを特徴とする前記1~4の何れかに記載の現像ロール被覆用ゴム部材。
前記被覆層の表面が、前記ゴム粒子の存在によって凸状に形成され、前記ゴム粒子同士の間隔が5μm未満であり、かつ前記ゴム粒子が5個以上凝集した状態で存在することを特徴とする前記1~4の何れかに記載の現像ロール被覆用ゴム部材。
芯材の周囲にゴム基材層を塗布・形成し、
次いで、該ゴム基材層の周囲に被覆層を形成する画像形成装置用現像ロールの製造方法において、
ポリオール、イソシアネート化合物、および反応性シリコーン油を少なくとも含むバインダーと、希釈溶剤を含む前記被覆層の成分を混合・分散させて分散液を作製し、
次いで、該分散液に、硬度(JIS K6253:1997)デュロメータA(瞬時)が20~80度であり、0.2μm以上10μm未満の球状シリコーンゴム粒子からなるゴム粒子を混合し、分散せてコーティング用分散液を作製し、
該コーティング用分散液を、前記弾性ゴム層の周囲に塗布し、乾燥後硬化して、被覆層を形成する画像形成装置用現像ロールの製造方法。
被覆層を形成する際に、
該コーティング用分散液を塗布後、液状の状態を所定時間維持して、ゴム粒子を層内上層部に移動させた後、硬化させることを特徴とする前記7記載の画像形成装置用現像ロールの製造方法。
ゴム粒子を層内上層部に移動させる際に、
被覆層の硬化前後の下記算出式で求められる表面露出粒子変化率が500%以上の表面状態となるように該ゴム粒子を移動させることを特徴とする前記8記載の画像形成装置用現像ロールの製造方法。
<表面露出粒子変化率の算出式>
表面露出粒子変化率=(硬化後の表面粒子個数-硬化前の表面粒子個数)/硬化前の表面粒子個数×100%
(ここで、表面粒子個数は、キーエンス製レーザー顕微鏡「VK-9700」を用いて、3000倍の倍率で、被覆層表面の任意の三箇所を撮影し、画像中の50μm×50μmの範囲のゴム粒子個数を測定した値である。)
現像ロールのゴム基材層としては、シリコーンゴム、ポリウレタン系エラストマー、エチレン-プロピレン-ジエンゴム(EPDM)、スチレン-ブタジエンゴム(SBR)、アクリロニトリル-ブタジエンゴム(NBR)、水素添加アクリロニトリル-ブタジエンゴム(HNBR)、クロロプレンゴム(CR)、エピクロロヒドリンゴム(ECO)等が挙げられるが、特に限定されるものではない。
本発明において、被覆層成分は、
(A)ポリオール、イソシアネート化合物、及び反応性シリコーン油を少なくとも含む液状のバインダーと、
(B)硬度(JIS K6253:1997)デュロメータA(瞬時)が20~80度であり、ゴム粒子径が0.2μm以上10μm未満のシリコーンゴム粒子と、
(C)希釈溶剤
とを含む。
本発明に用いられるバインダーとしては、接着性を有するバインダーが用いられ、硬度(JIS K6253:1997)デュロメータA(瞬時)が20~90度のゴムバインダーが好ましく、具体的には、ポリオールとイソシアネート化合物、反応性シリコーン油の反応生成物を包含する。
本発明に用いられるシリコーンゴム粒子としては、ジメチルポリシロキサンなどオルガノポリシロキサン、ポリオルガノシルセスオキサンを架橋した構造が好ましいが、特にこれらに限定されるものではない。また、市販のシリコーンゴム粒子を用いることができる。
aは5~5,000の整数が好ましく、より好ましくは10~1,000の整数を表す。
aが5未満では、線状オルガノポリシロキサンの特徴が十分に出ないため、硬さ低下および潤滑性向上の効果が十分に得られなくなるし、aの最大値は特に定めるものではないが、実際に5,000より大きいとシリコーンゴム微粒子の製造が困難となる。
例えばメチルトリメトキシシラン、メチルトリエトキシキラン、メチルトリプロポキシシラン、メチルトリブトキシシラン、エチルトリメトキシシラン、プロピルトリメトキシシラン、ブチルトリメトキシシラン、N-(β-アミノエチル)-γ-アミノプロピルトリメトキシシラン、γ-グリシドキシプロピルトリメトキシシラン、ビニルトリメトキシシラン、フェニルトリメトキシシラン、γ-メタクリロキシプロピルトリメトキシシラン、γ-メルカプトプロピルトリメトキシシラン、3,3,3-トリフロロプロピルトリメトキシシラン、3,3,4,4,5,5,6,6,6-ノナフロロヘキシルトリメトキシシラン、3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-ヘプタデカフロロデシルトリメトキシシラン等を、単独あるいは2種以上の組合せで使用することができる。)
希釈溶剤としては、水系、有機溶剤系があり、乾燥速度に応じて、低沸点溶剤、高沸点溶剤を組み合わせることができる。
本発明の被覆層を構成するコーティング液の配合処方としては、固形分重量%(固形分比率)として、シリコーンゴム粒子が3~30重量%の範囲が好ましく、さらに好ましくは5~20重量%である。
被覆層の硬さとしては、好ましくは硬度(JIS K6253:1997)デュロメータA(瞬時)が20~80度になるようにバインダーが調整される。
被覆層表面の形状は、表面に集積したシリコーンゴム粒子によって、表面凹凸が形成されている。
本発明に係る画像形成装置用現像ロールの製造方法は、芯材の周囲にゴム基材層を塗布・形成し、次いで、該ゴム基材層の周囲に被覆層を形成する画像形成装置用現像ロールの製造方法において、ポリオール、イソシアネート化合物、および反応性シリコーン油を少なくとも含むバインダーと、希釈溶剤を含む前記被覆層の成分を混合・分散させて分散液を作製し、次いで、該分散液に、硬度(JIS K6253:1997)デュロメータA(瞬時)が20~80度であり、0.2μm以上10μm未満の球状シリコーンゴム粒子からなるゴム粒子を混合し、分散せてコーティング用分散液を作製し、該コーティング用分散液を、前記弾性ゴム層の周囲に塗布し、乾燥後硬化して、被覆層を形成する方法である。
<表面露出粒子変化率の算出式>
表面露出粒子変化率=(硬化後の表面粒子個数-硬化前の表面粒子個数)/硬化前の表面粒子個数×100%
(ここで、表面粒子個数は、キーエンス製レーザー顕微鏡「VK-9700」を用いて、3000倍の倍率で、被覆層表面の任意の三箇所を撮影し、画像中の50μm×50μmの範囲のゴム粒子個数を測定した値である。)
<被覆層構成溶液(コーティング液)の作成>
・フッ素含有ポリオール(固形分濃度50%)(ダイキン工業社製「ゼッフルGK510」) 35.0重量部
・ウレタン変性ヘキサメチレンジイソシアネート(固形分濃度80%)(旭化成工業社製「デュラネートE402-80B」) 79.4重量部
・反応性シリコーンオイル(信越化学工業社製「X-22-160AS」)
50.0重量部
・希釈溶剤;酢酸ブチル 249.4重量部
作成した分散液に、シリコーンゴム粒子(東レダウコーニング社製「EP-2720」:硬度(JIS K6253:1997)デュロメータA(瞬時)70度、平均粒子径2μm(1~2μm))14.6重量部を混合し、コーティング用分散液(1)とした。
外径が10mmの鉄製のシャフト芯材に、体積抵抗率(JIS C 2139(2008))が106Ωcmで、硬度(JIS K6253:1997)デュロメータA(瞬時)が45度の導電性シリコーンゴムを被覆して、円筒研削盤の研磨によって、JIS B 0601(1994)による10点平均粗さを8μm(Ry)に調整し、外径が16mmのゴム基材層を形成し、ゴム被覆ローラとした。
予め、上記コーティング用分散液(1)をビーズミルで、高速撹拌して分散させた後、さらにスターラーで10分間撹拌することにより作成し、コーティング用分散液(2)を調製した。
上記ゴム被覆ローラの表面に、プライマーとして、信越シリコーン社製「KBP-40」をスプレー塗布し、次いで、その塗布面に、上記のコーティング用分散液(2)をスプレー塗布した。
その後、160℃40分加熱処理して、塗膜を硬化させ、被覆層である現像ロール被覆用ゴム部材を形成して、現像ローラを製作した。
この際の表面被覆層の厚みは表1に示すとおりであった。
実施例1で得られた現像ロール被覆用ゴム部材に対して、下記の項目について評価を行ない、結果を表1に示した。
ASTM D-1894(JIS K7125:1999、ISO8295:1995)に準じ、新東科学製表面性試験機「ヘイドン・トライボギア」によって、厚み2mmのゴムシート表面に、上記で得られたコーティング用分散液(2)を表1に示す厚さ(表面被覆層厚み:μm)になるように、スプレー塗布し、焼成後、動摩擦係数を測定した。その結果を表1に示した。
(試験条件)
相手材:直径10mmのSUS304鋼球、
移動速度:50mm/分、
荷重:0.49N、
振幅:50mm
得られた現像ロール被覆用ゴム部材について、JIS K5600-5-6:1999(ISO2409:1992)に準じ、碁盤目試験後テープ剥離試験を実施し、接着性を以下の基準で評価し、その結果を表1に示した。
<評価基準>
○:屈曲部のコーティング膜の剥れなし、カット線に波打ちなし
△:屈曲部のコーティング膜の剥れなし、カット線に波打ちあり
×:屈曲部のコーティング膜の剥れあり
上記ゴム被覆ローラ表面に、プライマー塗布後、コーティング用分散液(2)を厚さ10μmになるように、スプレー塗布し、焼成して、被覆用ゴム部材を形成した。
得られた被覆用ゴム部材の表層(被覆層)を厚さ5mmにスライスし、ゴムシートを形成し、そのシートを50%伸ばした状態で、目視により白色に変色するかどうかを確認し、また顕微鏡においてシート(被覆層)にクラックが発生したか否かを確認し、以下の基準で評価し、その結果を表1に示した。
<評価基準>
○:被覆層のクラックなし、白色変色なし
△:被覆層のクラックあり、白色変色あり
×:被覆層のクラックが大きく、白色変色あり
ゴム部材被覆層表面を、キーエンス製レーザー顕微鏡「VK-9700」を用いて、1000倍、3000倍の倍率で撮影し、被覆層表面からの粒子凸部の高さを評価し、その結果を表1に示した。
0.5μm以上8μm未満であれば、本発明のゴム部材の凸部高さとして好ましく、0.5μm未満または8μm以上であれば、好ましくない。
ゴム部材被覆層表面を、キーエンス製レーザー顕微鏡VK-9700を用いて、1000倍、3000倍の倍率で撮影し、ゴム粒子同士の間隔を計測し、その結果を表1に示した。
ゴム粒子同士の間隔がゴム粒子同士の間隔が5μm以下であれば好ましく、ゴム粒子同士の間隔が5μmより離れていれば好ましくない。
また同時に、顕微鏡において、粒子分散状態を以下の基準で評価し、その結果を表1に示した。
<評価基準>
○:5個以上の凝集部分がある
△:4個以下の凝集部分がある
×:粒子が表面写真から確認できない
コーティング塗布に形成された被覆層表面のゴム粒子単独を、キーエンス製レーザー顕微鏡「VK-9700」を用いて、3000倍の倍率で撮影し、10個の粒子径の算術平均により、平均粒子径を求め、これを粒子径とした。
また、被測定用現像ローラの任意の三箇所を、ロール表面と垂直に切断することにより、採取した断面サンプルを、キーエンス製レーザー顕微鏡「VK-9700」を用いて、3000倍の倍率で観察し、被覆層の厚みを求めた。
ゴム粒子径/被覆層厚みの値を算出し、その結果を表1に示した。
ゴム粒子径/被覆層厚み<0.3であれば好ましく、ゴム粒子径/被覆層厚み>0.3であれば好ましくない。
キーエンス製レーザー顕微鏡「VK-9700」を用いて、3000倍の倍率で、ローラ表面の任意の三箇所を撮影した。任意の三箇所を撮影することで、配合ゴム粒子による凸部の輪郭が黒色に表される。
この輪郭が黒色、かつ円形度0.5以上の部分をゴム粒子部と考えて、画像中の50μm×50μmの範囲のゴム粒子個数を測定し、結果を表1に示した。
ゴム粒子個数200個以上であれば好ましく、200個未満であれば好ましくない。
焼成前の被覆層表面の粒子個数を、上記「ロール表面の粒子個数の評価」と同様に数え、焼成前後のロール表面露出粒子個数の変化率を下記の式により求めた。その結果を表1に示した。
(焼成後の表面粒子個数-焼成前の表面粒子個数)/焼成前の表面粒子個数×100%
求めた値が900%以上であると、良好に粒子がロール表面に移行していると判断できる。
コーティング用分散液(2)を、ゴム基材層表面にスプレー塗布した後、室温で30分乾燥後、被覆層のベトツキの有無を指触により確認し、以下の基準で評価し、その結果を表1に示した。
<評価基準>
○:ベトツキがある
×:ベトツキがない
コーティング用分散液(2)を、ゴム基材層表面にスプレー塗布した後、160℃40分加熱処理により塗膜を硬化させ、室温で30分放置した後、被覆層のベトツキの有無を指触により確認し、以下の基準で評価し、その結果を表1に示した。
<評価基準>
○:ベトツキがない
×:ベトツキがある
現像ロール上にあって、現像ブレードを通過した後のトナーを吸引し、濾紙上に溜まったトナーを秤量して、単位面積当たりのトナー量(mg/cm2)を測定した。その結果を表1に示した。
搬送量は0.4~0.6mg/cm2が好ましく、さらに好ましくは0.4~0.55mg/cm2である。これより多いと、トナー消費量が多くなってしまい、好ましくない。また、搬送量は少ないほどトルク燃費が良いが、0.4mg/cm2未満であると、印刷が薄くなってしまい、好ましくない。
トナーが現像ブレードと繰り返し摺擦されることにより、現像ブレードにトナー固着が起こり、トナー固着凸部でトナーの供給阻害を引き起こし、黒ベタ画像において、縦白スジ状模様として現れる画像欠陥を評価した。
得られたゴム部材(現像ロール)を、市販のモノクロレーザープリンター(ブラザー株式会社製「HL-2240D」)のカートリッジ(ブラザー株式会社製「TN-27J」)に組み込んで、低温低湿環境下(15℃25%RH)、1%濃度/枚で3000枚通紙耐久試験を行い、500枚ごとに黒ベタ画像を印字し、縦スジの発生を目視で確認した。
縦スジ画像不良の判定基準は以下の通りに行なった。判定結果を表1に示した。
<判定基準>
○:通紙枚数2000枚において、縦スジ発生なし。
△:通紙枚数1500枚において、縦スジ発生あり。
×:通紙枚数1000枚以下において、縦スジ発生あり。
所定の枚数印刷後、トナーが現像ロールと感光体ドラム、規制ブレードとの繰り返しの摩擦による、現像ロール表面へのトナー成分の固着、いわゆるフィルミングを引き起こさずに、所望の黒ベタ画像濃度を維持できるか評価した。ロール仕様は、初期画像で目標濃度を得られていた。
各仕様のロールを市販のモノクロレーザープリンター(ブラザー株式会社製「HL-2240D」)のカートリッジ(ブラザー株式会社製「TN-27J」)に組み込んで、低温低湿環境下(15℃25%RH)、1%濃度/枚で3000枚通紙耐久試験を行い、2500枚後に黒ベタ部を上下左右4箇所設けた画像パターンを印字し、白黒透過濃度計(X-rite株式会社製「X-rite310T」)で、透過濃度の測定を合計12点(黒ベタ部 1箇所/3点)行い、平均値を算出した。その結果を表1に示した。
画像濃度が1.9以上であると画像濃度良好として評価できる。
高温環境下、長期保存した後、室温環境下で印字した場合における、現像ロールと感光体ドラム、規制ブレードとの当接部分で圧縮永久歪による凹み、またはトナー固着凸部が形成されることによるトナーの供給阻害によって、印字ベタ画像が横白スジ模様として表れる画像欠陥の程度を評価した。
各仕様のロールを市販のモノクロレーザープリンター(ブラザー株式会社製HL-2240D)のカートリッジ(ブラザー株式会社製TN-27J)に組み込んで、高温環境(40℃、90%RH)下、カートリッジをドラムユニットに装着した状態で120時間放置し、取り出して常温下に8時間以上放置した後、黒ベタ画像1枚、ハーフトーン画像20枚、黒ベタ画像1枚を連続印字した。
最後の黒ベタ画像に、周期的な横白スジ画像の発生があるかを目視で確認し、以下の基準で評価した。その結果を表1に示した。
<評価基準>
○:横スジなし
×:横スジあり
実施例1において、シリコーンゴム粒子(東レダウコーニング社製)(ゴム硬度(JIS K6253:1997)デュロメータA(瞬時)70度、平均粒子径2μm(1~2μm))14.6重量部を6.9重量部に変更した以外は、同様にコーティング用分散液を作成した。
その後、実施例1と同様に、ゴム基材層を作成し、実施例1と同様に評価し、その結果を表1に示した。
実施例1において、シリコーンゴム粒子(東レダウコーニング社製)(ゴム硬度(JIS K6253:1997)デュロメータA(瞬時)70度、平均粒子径2μm(1~2μm))をシリコーンゴム粒子(信越化学工業社製)(ゴム硬度(JIS K6253:1997)デュロメータA(瞬時)75度、平均粒子径2μm(0.7~5μm))に変更した以外は同様にコーティング用分散液を作成した。
その後、被覆層の厚みを10μmに変更した以外は、実施例1と同様にゴム基材層を作成し、実施例1と同様に評価し、その結果を表1に示した。
実施例1と同様にコーティング用分散液を作成した。
その後、被覆層の厚みを10μmに変更した以外は、実施例1と同様にゴム基材層を作成し、実施例1と同様に評価し、その結果を表1に示した。
実施例1において、シリコーンゴム粒子(東レダウコーニング社製)(ゴム硬度(JIS K6253:1997)デュロメータA(瞬時)70度、平均粒子径2μm(1~2μm))をシリコーンゴム粒子(信越化学工業社製)(ゴム硬度(JIS K6253:1997)デュロメータA(瞬時)75度、平均粒子径2μm(0.7~5μm))に変更した以外は同様にコーティング用分散液を作成した。
その後、被覆層の厚みを5μmに変更した以外は、実施例1と同様にゴム基材層を作成し、実施例1と同様に評価し、その結果を表1に示した。
実施例1において、シリコーンゴム粒子(東レダウコーニング社製)(ゴム硬度(JIS K6253:1997)デュロメータA(瞬時)70度、平均粒子径2μm(1~2μm))14.6重量部を0重量部に変更した以外は同様にコーティング用分散液を作成した。
その後、実施例1と同様に、ゴム基材層を作成し、実施例1と同様に評価し、その結果を表1に示した。
実施例1において、シリコーンゴム粒子(東レダウコーニング社製)(ゴム硬度(JIS K6253:1997)デュロメータA(瞬時)70度、平均粒子径2μm(1~2μm))をシリコーンゴム粒子(モメンティブ社製)(ゴム硬度(JIS K6253:1997)デュロメータA(瞬時)95度、平均粒子径2μm(1~3μm))に変更した以外は同様にコーティング用分散液を作成した。
その後、実施例1と同様に、ゴム基材層を作成し、実施例1と同様に評価し、その結果を表1に示した。
実施例1において、シリコーンゴム粒子(東レダウコーニング社製)(ゴム硬度(JIS K6253:1997)デュロメータA(瞬時)70度、平均粒子径2μm(1~2μm))をシリコーンゴム粒子(信越化学工業社製)(ゴム硬度(JIS K6253:1997)デュロメータA(瞬時)30度、平均粒子径5μm(1~15μm))に変更した以外は同様にコーティング用分散液を作成した。
その後、実施例1と同様に、ゴム基材層を作成し、実施例1と同様に評価し、その結果を表1に示した。
実施例1において、反応性シリコーンオイル50.0重量部を0重量部とし、シリコーンゴム粒子(東レダウコーニング社製)(ゴム硬度(JIS K6253:1997)デュロメータA(瞬時)70度、平均粒子径2μm(1~2μm))14.6重量部を3.1重量部に変更した以外は同様にコーティング用分散液を作成した。
その後、実施例1と同様に、ゴム基材層を作成し、実施例1と同様に評価し、その結果を表1に示した。
分散液を下記の通り作成した。
ポリテトラメチレングリコール(保土谷化学社製「PTG1000SN」)100重量部に溶剤メチルエチルケトン中で、イソシアネート(日本ポリウレタン工業社製「ミリオネートMT」)21.2重量部を段階的に混合して、窒素雰囲気下80℃にて6時間反応させ、ポリウレタンポリオールプレポリマーを作成した。
前記ポリウレタンポリオールプレポリマー100重量部とイソシアネート(三井武田ケミカル株式会社製「タケネートB830」;TMP変性TDI、f(平均官能基数)=3相当)7.2重量部を加えて、NCO当量を1.2となるようにした。
さらに有機溶剤として酢酸ブチルを277.9重量部加え、固形分濃度30%とし、分散液とした。
作成した分散液に、コア・シェル粒子として、複合シリコンパウダ(信越化学工業株式会社製「KMP-601」;体積平均粒子径15μm)を、固形分濃度70重量部に対して30重量部加え、プロペラ羽で撹拌し、分散、混合し、コーティング液とした。
その後、実施例1と同様に、ゴム基材層を作成し、実施例1と同様に評価し、その結果を表1に示した。
比較例5において、コア・シェル粒子として、複合シリコンパウダ(信越化学工業株式会社製KMP-601;体積平均粒子径15μm)を、複合シリコンパウダ(信越化学工業株式会社製「X-52-7030」;体積平均粒子径1.0μm)に変更した以外は同様にコーティング液を作成した。
その後、実施例1と同様に、ゴム基材層を作成し、実施例1と同様に評価し、その結果を表1に示した。
ウレタン樹脂(三洋化成社製散布練C-810S;固形分濃度60%)75重量部に、希釈溶剤として酢酸ブチル420重量部を添加したものを分散液とした。
作成した分散液に、シリコーンゴム粒子(信越化学工業社製)(ゴム硬度(JIS K6253:1997)デュロメータA(瞬時)75度、平均粒子径2μm(0.7~5μm))5重量部を添加し、コーティング液を作成した。
その後、実施例1と同様にゴム基材層を作成し、実施例1と同様に評価し、その結果を表1に示した。
実施例と比較例1を比較すると、粒子を全く含まなかった場合、動摩擦係数が大きくなることがわかる(低摩擦係数化が十分でない)。結果として、印刷縦スジ、横スジ画像不良(フィルミング)が早い段階で見られることとなる。画像濃度が維持できていない。
粒子がゴムでなく、樹脂であり、粒子が硬いため、相手部材やトナーにダメージを与えてしまい、トナー劣化が促進したためと考えられる。
比較例5については、表面ゴム粒子は多いが、これは、大きい粒子を用いたため、表面凸部も大きく、ゴム粒子を多量配合していることに起因すると考えられる。硬化前後の被覆層表面露出粒子変化率からもわかるとおり、ゴム粒子が表面に移動してきたからではない。
そのため、比較例5よりも小さい粒子を用いた比較例6では、表面粒子個数は少なくなっている。
トナー現像方式の現像装置に用いられる現像ロールの他、帯電ロール、ブレード、定着ロール、定着ベルト、供給ロールなどのゴム部材などにも用いることができる。
2:規制ブレード
3:供給ロール
4:感光体
5:トナー
11:芯材
12:ゴム基材層
13:被覆層
101:ゴム粒子
Claims (9)
- ゴム基材層を有する現像ロールの周囲に、被覆層成分を塗布・硬化させて得られる現像ロール被覆用ゴム部材であり、
該被覆層成分は、
(A)ポリオール、イソシアネート化合物、及び反応性シリコーン油を少なくとも含む液状のバインダーと、
(B)硬度(JIS K6253:1997)デュロメータA(瞬時)が20~80度であり、ゴム粒子径が0.2~10μmのシリコーンゴム粒子と、
(C)希釈溶剤とを含み、
硬化後の被覆層厚みと前記ゴム粒子径の比が、前記ゴム粒子径/被覆層厚み<0.3を満足することを特徴とする現像ロール被覆用ゴム部材。 - 前記希釈溶剤が、ゴム粒子を膨潤させる希釈溶剤を用いることを特徴とする請求項1記載の現像ロール被覆用ゴム部材。
- 前記ポリオールが、フッ素含有ポリオールであることを特徴とする請求項1又は2記載の現像ロール被覆用ゴム部材。
- 前記被覆層の表面に、前記ゴム粒子が50μm2あたり200個以上存在することを特徴とする請求項1~3の何れかに記載の現像ロール被覆用ゴム部材。
- 前記被覆層の表面が、前記ゴム粒子の存在によって凸状に形成され、該凸状を為す凸部の高さが0.5~8.0μmの範囲であることを特徴とする請求項1~4の何れかに記載の現像ロール被覆用ゴム部材。
- 前記被覆層の表面が、前記ゴム粒子の存在によって凸状に形成され、前記ゴム粒子同士の間隔が5μm未満であり、かつ前記ゴム粒子が5個以上凝集した状態で存在することを特徴とする請求項1~4の何れかに記載の現像ロール被覆用ゴム部材。
- 芯材の周囲にゴム基材層を塗布・形成し、
次いで、該ゴム基材層の周囲に被覆層を形成する画像形成装置用現像ロールの製造方法において、
ポリオール、イソシアネート化合物、および反応性シリコーン油を少なくとも含むバインダーと、希釈溶剤を含む前記被覆層の成分を混合・分散させて分散液を作製し、
次いで、該分散液に、硬度(JIS K6253:1997)デュロメータA(瞬時)が20~80度であり、0.2μm以上10μm未満の球状シリコーンゴム粒子からなるゴム粒子を混合し、分散せてコーティング用分散液を作製し、
該コーティング用分散液を、前記弾性ゴム層の周囲に塗布し、乾燥後硬化して、被覆層を形成する画像形成装置用現像ロールの製造方法。 - 被覆層を形成する際に、
該コーティング用分散液を塗布後、液状の状態を所定時間維持して、ゴム粒子を層内上層部に移動させた後、硬化させることを特徴とする請求項7記載の画像形成装置用現像ロールの製造方法。 - ゴム粒子を層内上層部に移動させる際に、
被覆層の硬化前後の下記算出式で求められる表面露出粒子変化率が500%以上の表面状態となるように該ゴム粒子を移動させることを特徴とする請求項8記載の画像形成装置用現像ロールの製造方法。
<表面露出粒子変化率の算出式>
表面露出粒子変化率=(硬化後の表面粒子個数-硬化前の表面粒子個数)/硬化前の表面粒子個数×100%
(ここで、表面粒子個数は、キーエンス製レーザー顕微鏡「VK-9700」を用いて、3000倍の倍率で、被覆層表面の任意の三箇所を撮影し、画像中の50μm×50μmの範囲のゴム粒子個数を測定した値である。)
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WO2019003901A1 (ja) * | 2017-06-27 | 2019-01-03 | Nok株式会社 | 現像ローラ |
JP7042591B2 (ja) | 2017-11-17 | 2022-03-28 | Nok株式会社 | シール部材 |
JP7422022B2 (ja) | 2020-07-02 | 2024-01-25 | 信越ポリマー株式会社 | 現像ローラ |
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JP7337177B2 (ja) * | 2019-08-26 | 2023-09-01 | Nok株式会社 | 帯電ロール |
JP7337176B2 (ja) * | 2019-08-26 | 2023-09-01 | Nok株式会社 | 帯電ロール |
JP7342136B2 (ja) * | 2019-08-29 | 2023-09-11 | Nok株式会社 | 帯電ロール |
EP4170433A4 (en) * | 2020-06-18 | 2023-11-15 | NOK Corporation | DEVELOPMENT ROLLER |
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