WO2012043777A1 - 帯電部材及びその製造方法 - Google Patents
帯電部材及びその製造方法 Download PDFInfo
- Publication number
- WO2012043777A1 WO2012043777A1 PCT/JP2011/072492 JP2011072492W WO2012043777A1 WO 2012043777 A1 WO2012043777 A1 WO 2012043777A1 JP 2011072492 W JP2011072492 W JP 2011072492W WO 2012043777 A1 WO2012043777 A1 WO 2012043777A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- general formula
- condensate
- charging member
- surface layer
- carbon atoms
- Prior art date
Links
Images
Classifications
-
- 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
- G03G15/02—Apparatus for electrographic processes using a charge pattern for laying down a uniform charge, e.g. for sensitising; Corona discharge devices
- G03G15/0208—Apparatus for electrographic processes using a charge pattern for laying down a uniform charge, e.g. for sensitising; Corona discharge devices by contact, friction or induction, e.g. liquid charging apparatus
- G03G15/0216—Apparatus for electrographic processes using a charge pattern for laying down a uniform charge, e.g. for sensitising; Corona discharge devices by contact, friction or induction, e.g. liquid charging apparatus by bringing a charging member into contact with the member to be charged, e.g. roller, brush chargers
- G03G15/0233—Structure, details of the charging member, e.g. chemical composition, surface properties
-
- 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
- C08G77/48—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 in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
- C08G77/56—Boron-containing linkages
-
- 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
- C08G77/48—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 in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
- C08G77/58—Metal-containing linkages
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on 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; Coating compositions based on derivatives of such polymers
- C09D183/14—Coating compositions based on 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; Coating compositions based on derivatives of such polymers in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
-
- 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
- G03G15/02—Apparatus for electrographic processes using a charge pattern for laying down a uniform charge, e.g. for sensitising; Corona discharge devices
- G03G15/0258—Apparatus for electrographic processes using a charge pattern for laying down a uniform charge, e.g. for sensitising; Corona discharge devices provided with means for the maintenance of the charging apparatus, e.g. cleaning devices, ozone removing devices G03G15/0225, G03G15/0291 takes precedence
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24479—Structurally defined web or sheet [e.g., overall dimension, etc.] including variation in thickness
Definitions
- the present invention relates to a charging member used in an electrophotographic apparatus or the like and a method for manufacturing the charging member.
- the electrophotographic apparatus includes a charging member that contacts the outer surface of the photosensitive member to charge the outer surface, a developing member for forming a toner image on the electrostatic latent image formed on the outer surface of the photosensitive member, and a photosensitive member.
- An electrophotographic member such as a cleaning member for removing the adhering toner is used.
- the charging member generally has a support and an elastic layer (conductive elastic layer) provided on the support from the viewpoint of sufficiently ensuring a contact nip with the photoreceptor. Further, in order to suppress adhesion of a developer or the like to the surface of the elastic layer, a surface layer is generally provided on the surface of the elastic layer.
- Patent Document 1 describes a charging member in which a surface layer made of polysiloxane having a fluorinated alkyl group and an oxyalkylene group is formed by a so-called sol-gel method. Low surface free energy is achieved by the fluorinated alkyl group site, which makes it difficult for the toner and external additives used for the toner to stick to the surface even after repeated use over a long period of time. As a result, it is described that even if it is used in a DC contact charging system, it can be used as a charging member capable of stable charging and image output for a long period of time. Further, as one of methods for suppressing the adhesion of dirt to the surface of an electrophotographic member, as described in Patent Document 2, the surface layer contains coarse particles, and the surface of the surface layer is appropriately roughened. There is a known method to make it.
- an object of the present invention is to provide a charging member and a method for manufacturing the same, in which the surface is appropriately roughened without using coarse particles, and the adhesion of dirt to the surface can be suppressed.
- a charging member having a support, an elastic layer, and a surface layer, wherein the surface layer includes a polymer compound having a Si-OM bond, and the polymer
- the compound has at least one selected from structural units represented by the following general formula (1) and the following general formula (2), and a structural unit represented by the following general formula (3).
- a crack extending from the surface to the elastic layer, and the edge of the crack is raised in a convex shape, whereby the charging member is provided with a charging member having a roughened surface.
- M is any element selected from the group consisting of Ti, Zr, and Hf.
- M is a Ta element.
- R 1 and R 2 each independently represent any of the following general formulas (4) to (7).
- R 3 to R 7 , R 10 to R 14 , R 19 , R 20 , R 25 and R 26 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a hydroxyl group, a carboxyl group or an amino group.
- R 8 , R 9 , R 15 to R 18 , R 23 , R 24 and R 29 to R 32 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
- R 21 , R 22 , R 27 and R 28 each independently represent a hydrogen atom, an alkoxyl group having 1 to 4 carbon atoms, or an alkyl group having 1 to 4 carbon atoms.
- n, m, l, q, s and t each independently represent an integer of 1 or more and 8 or less.
- p and r each independently represents an integer of 4 or more and 12 or less.
- x and y each independently represents 0 or 1.
- the symbol “*” and the symbol “**” each represent a bonding site to a silicon atom and an oxygen atom in the general formula (3).
- the polymer compound is a hydrolytic condensate of a hydrolyzable compound having a structure represented by the following general formula (12), and a structure represented by the following general formulas (13) to (16).
- a method for producing a charging member which is a cross-linked product with at least one hydrolytic condensate of a hydrolyzable compound having (I) Hydrolytic condensate of a hydrolyzable compound having a structure represented by the general formula (12) and hydrolytic condensate of a hydrolyzable compound having a structure represented by the general formulas (13) to (16)
- Obtaining a liquid condensate containing at least one of the products (Ii) obtaining a coating material for forming a surface layer containing the liquid condensate and a photopolymerization initiator; (Iii) A coating film of the paint is formed on the elastic layer disposed on the outer periphery of the support, and the hydrolytic condensate R 33 of the hydrolysis condensate in the
- R 33 represents any of the following general formulas (17) to (20), and R 34 to R 36 each independently represents an alkyl group having 1 to 4 carbon atoms.
- R 37 to R 53 each independently represents an alkyl group having 1 to 9 carbon atoms.
- R 54 to R 58 , R 59 to R 65 , R 66 , R 67 and R 72 and R 73 are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, A hydroxyl group, a carboxyl group or an amino group is shown.
- R 57 , R 58 , R 62 to R 65 , R 70 , R 71 , and R 76 to R 79 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
- n ′, m′l ′, q ′, s ′ and t ′ each independently represent an integer of 1 or more and 8 or less.
- p ′ and r ′ each independently represent an integer of 4 or more and 12 or less.
- the symbol “*” represents the bonding position with the silicon atom of the general formula (12).
- the polymer compound comprises a hydrolysis condensate of a hydrolyzable compound having a structure represented by the general formula (12) and a structure represented by the general formulas (13) to (16).
- a method for producing a charging member comprising the steps of crosslinking a decomposition condensate to cure the coating film and forming a surface layer.
- R 80 represents an alkyl group having 1 to 21 carbon atoms or a phenyl group
- R 81 to R 83 each independently represents an alkyl group having 1 to 4 carbon atoms.
- the number of contact points with the photosensitive member is controlled, and by reducing the contact area with the photosensitive member, adhesion of toner and external additives is suppressed even during long-term use, and the surface is less likely to become dirty. As a result, a charging member that can maintain uniform charging over a long period of time can be obtained.
- FIG. 1 is a schematic cross-sectional view showing a state of cracks on the surface of a charging member according to the present invention.
- FIG. 2 is a diagram showing an example of the configuration of a charging member according to the present invention.
- FIG. 3 is a cross-sectional view of an electrophotographic apparatus according to the present invention.
- FIG. 4 is a schematic diagram showing an example of a developing device.
- FIGGS. 5A and 5B It is explanatory drawing of an example of the surface state of the charging member based on this invention.
- 6A and 6B are views showing the shape of cracks on the surface of the charging member according to the present invention. [FIG.
- FIG. 7 It is explanatory drawing of the relationship between the kind of metal element in the surface layer based on this invention, and an elasticity modulus.
- FIG. 8 is an O1s spectrum diagram showing an analysis result by ESCA.
- FIG. 9 is an explanatory diagram of a crosslinking reaction according to the present invention.
- FIG. 10A and 10B It is explanatory drawing of the chemical structure of the high molecular compound which concerns on this invention.
- FIG. 2 shows a cross section of a charging member according to an embodiment of the present invention.
- the charging member includes a support 101, a conductive elastic layer 102, and a surface layer 103.
- FIG. 1 is an enlarged cross-sectional view of the vicinity of the surface of the charging member.
- the charging member has a crack 104 extending from the surface to the elastic layer 102.
- the edge 104 of the crack 104 is raised in a convex shape.
- the surface of the charging member is roughened by the raised edge portion 105.
- FIG. 5A is a top view (binarization) of the surface of the charging member
- FIG. 5B is a bird's-eye view thereof.
- innumerable cracks 104 exist on the surface of the charging member.
- the edge 105 of the crack 104 is raised in a convex shape.
- FIG. 6A is an example of the shape of the crack 104 existing on the surface of the charging member.
- FIG. 6B shows the surface unevenness along the lines 1 to 5 in FIG. 6A, the horizontal axis is the line direction ( ⁇ m), and the vertical axis is the depth direction ( ⁇ m). The thickness of the surface layer is 2 ⁇ m.
- a metal (alloy) support made of iron, copper, stainless steel, aluminum, aluminum alloy or nickel.
- the conductive elastic layer one type or two or more types of elastic bodies such as rubber used in the conventional elastic layer (conductive elastic layer) of the charging member can be used.
- the rubber include the following. Urethane rubber, silicone rubber, butadiene rubber, isoprene rubber, chloroprene rubber, styrene-butadiene rubber, ethylene-propylene rubber, polynorbornene rubber, styrene-butadiene-styrene rubber, acrylonitrile rubber, epichlorohydrin rubber and alkyl ether rubber.
- the electroconductivity can be set to a predetermined value by appropriately using a conductive agent in the conductive elastic layer.
- the electrical resistance value of the conductive elastic layer can be adjusted by appropriately selecting the type and amount of the conductive agent, and the preferred range of the electrical resistance value is 10 2 to 10 8 ⁇ . The range is 10 3 to 10 6 ⁇ .
- a conductive agent for the conductive elastic layer conductive carbon such as ketjen black EC, acetylene black, carbon for rubber, carbon for color (ink) subjected to oxidation treatment, and pyrolytic carbon should be used. You can also.
- graphite such as natural graphite and artificial graphite can be used as a conductive agent for the conductive elastic layer.
- An inorganic or organic filler or crosslinking agent may be added to the conductive elastic layer.
- the hardness of the conductive elastic layer is 60 degrees or more and 85 degrees or less in MD-1 from the viewpoint of suppressing the deformation of the charging member when the charging member and the photoreceptor to be charged are brought into contact with each other. It is preferably 70 degrees or more and 80 degrees or less. If MD-1 is in the said range, it will become easier to control the crack depth of this electroconductive elastic layer using the cure shrinkage of a coating film.
- Rz surface roughness
- the conductive elastic layer is formed on the support by a known method such as extrusion molding, injection molding, compression molding, or the like, by mixing the raw materials of the conductive elastic body with a closed mixer or the like.
- the conductive elastic layer is bonded onto the support via an adhesive as necessary.
- the conductive elastic layer formed on the support is vulcanized as necessary.
- the heating zone is divided into two, and the vulcanization is performed in the second zone after the first zone is maintained at a temperature lower than the vulcanization temperature and the gas component is sufficiently removed.
- the surface layer includes a polymer compound having a Si-OM bond, and the polymer compound includes at least one of structural units represented by the following general formula (1) and the following general formula (2), Moreover, it has at least 1 sort (s) of the structural unit shown by following General formula (3).
- M is any element selected from the group consisting of Ti, Zr, and Hf.
- M is a Ta element.
- R 1 and R 2 each independently represent any of the following general formulas (4) to (7).
- R 3 to R 7 , R 10 to R 14 , R 19 , R 20 , R 25 and R 26 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a hydroxyl group, a carboxyl group or an amino group.
- R 8 , R 9 , R 15 to R 18 , R 23 , R 24 and R 29 to R 32 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
- R 21 , R 22 , R 27 , and R 28 each independently represent a hydrogen atom, an alkoxyl group having 1 to 4 carbon atoms, or an alkyl group having 1 to 4 carbon atoms.
- n, m, l, q, s and t each independently represent an integer of 1 or more and 8 or less.
- p and r each independently represents an integer of 4 or more and 12 or less.
- x and y each independently represents 0 or 1.
- the symbol “*” and the symbol “**” each represent a bonding position to a silicon atom and an oxygen atom in the general formula (3).
- R 1 in the formula (3) is a structure represented by the formula (4)
- R 2 is a structure represented by the formula (5)
- Si—O— A part of the structure of a polymer compound having a Ti bond in the molecule is shown in FIG. 10A.
- R 1 in the formula (3) is a structure represented by the formula (4)
- R 2 is a structure represented by the formula (7)
- FIG. 10B shows a part of the structure of a polymer compound having a Si—O—Ti bond in the molecule.
- R 1 and R 2 in the general formula (3) are preferably those represented by any of the following general formulas (8) to (11).
- the presence of the organic chain makes it possible to control the elastic modulus of the surface layer, or to control the brittleness and flexibility as the film properties of the surface layer.
- the presence of an organic chain structure, particularly an ether moiety improves the adhesion of the surface layer to the elastic layer.
- N, M, L, Q, S and T are each independently an integer of 1 or more and 8 or less, and x 'and y' each independently represent 0 or 1. Further, the symbol “*” and the symbol “**” each represent a bonding site to a silicon atom and an oxygen atom in the general formula (3).
- the atomic ratio M / Si between M and silicon is preferably 0.10 or more and 12.50 or less. More preferably, it is 0.50 or more and 10.00 or less. If this value is 0.10 or more, generation of cracks due to curing shrinkage is easy, and a surface roughening effect is produced. Moreover, if it is 12.50 or less, the preservative of the condensate obtained and its dilution liquid will be stabilized.
- the polymer compound includes a hydrolysis condensate of a hydrolyzable compound having a structure represented by the following general formula (12) and a hydrolyzable compound having a structure represented by the following general formulas (13) to (16).
- the charging member is preferably a cross-linked product with at least one of the hydrolysis-condensation products. That is, since the hydrolysis-condensation product is greatly shrunk at the time of crosslinking, the surface layer made of the crosslinked product is cracked.
- the hydrolysis condensate has extremely high adhesion to the elastic layer. Therefore, when the hydrolysis condensate is crosslinked on the elastic layer to form a surface layer, the elastic layer is cracked by the shrinkage force at the time of crosslinking. As a result, the edge of the crack rises and the surface of the charging member is roughened.
- R 33 represents any one of the following general formulas (17) to (20), and R 34 to R 36 each independently represents an alkyl group having 1 to 4 carbon atoms.
- R 37 to R 53 each independently represents an alkyl group having 1 to 9 carbon atoms.
- R 54 to R 58 , R 59 to R 65 , R 66 , R 67 , R 72 and R 73 are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, Or a hydroxyl group, a carboxyl group, or an amino group is shown.
- R 57 , R 58 , R 62 to R 65 , R 70 , R 71 and R 76 to R 79 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
- n ′, m ′, l ′, q ′, s ′ and t ′ each independently represent an integer of 1 to 8.
- p ′ and r ′ each independently represent an integer of 4 or more and 12 or less.
- the symbol “*” represents the bonding position with the silicon atom of the general formula (12).
- hydrolyzable zirconium compound having the structure represented by the general formula (14) are shown below.
- hydrolyzable hafnium compound having the structure represented by the general formula (15) are shown below.
- hydrolysable silane compound which has a structure shown by General formula (20) is shown.
- (20-1) 3- (3,4-epoxycyclohexyl) methyloxypropyltrimethoxysilane
- (20-2) 3- (3,4-epoxycyclohexyl) methyloxypropyltriethoxysilane.
- the polymer compound comprises a hydrolysis condensate of a hydrolyzable compound having a structure represented by the general formula (12) and hydrolyzate of a hydrolyzable compound having a structure represented by the general formulas (13) to (16). It is preferably a crosslinked product of at least one kind of decomposition condensate and a hydrolysis condensate of a hydrolyzable compound having a structure represented by the following general formula (21). Such a cross-linked product can form a crack of the present invention by curing shrinkage during the formation of the cross-linked product. Further, the material composition of the surface of the charging member can be constituted by a single system that does not include a filler. Furthermore, it is possible to reduce the thickness of the surface layer.
- R 80 represents an alkyl group having 1 to 21 carbon atoms or a phenyl group
- R 81 to R 83 each independently represents an alkyl group having 1 to 4 carbon atoms.
- hydrolyzable silane compound having the structure represented by the general formula (21) are shown below.
- R 80 is a hydrolyzable silane compound having a linear alkyl group having 6 to 10 carbon atoms
- R 80 is a phenyl group. It is preferable to combine a hydrolyzable silane compound having In this case, the compatibility with the solvent is good even if the monomer structure is changed by the hydrolysis / condensation reaction.
- the metal element M any element selected from the group consisting of Ti, Zr, Hf, and Ta is used.
- the size of fine particles generated during synthesis differs as shown in FIG. , Ta ⁇ Hf ⁇ Zr ⁇ Ti tends to increase.
- the difference in the reaction rate of M or the valence reflects.
- the particle size in the synthesized solution is small, the modulus of elasticity tends to increase.
- the size of the fine particles determines the denseness of the film (surface layer). It is presumed that the elastic modulus is affected. In other words, the more dense the coating, the greater the degree of cure shrinkage, and this magnitude relationship directly affects the surface crack, that is, the effect on cure shrinkage, affecting the way the convex edges of the cracks rise. It has been found.
- a standard for the film thickness of the surface layer is 0.10 to 2.50 ⁇ m, particularly 0.15 to 2.00 ⁇ m. This is because a crack from the surface layer to the elastic layer can be easily generated due to curing shrinkage of the coating film for forming the surface layer. Moreover, as a result, the effect that the edge of the crack rises in a convex shape is increased, which is advantageous in roughening the surface. Further, the volume resistivity of the surface layer is 10 10 to 10 16 ⁇ ⁇ cm.
- the charging member of the present invention has a crack from the surface to the elastic layer, which is caused by curing shrinkage of the coating film, and the edge of the crack bulges in a convex shape. It is roughened.
- the size of the crack can be expressed as surface roughness Rz and crack depth Ry. Further, the height of the convex bulge at the edge of the crack is preferably about 0.5 ⁇ m or more and 35.0 ⁇ m or less.
- the surface roughness Rz of the charging member is 5 ⁇ m to 25 ⁇ m, particularly 7 ⁇ m to 22 ⁇ m, and more Is preferably 10 ⁇ m or more and 20 ⁇ m or less.
- the crack depth Ry of the charging member indicates the distance between the maximum height of the crack edge (convex portion) of the surface layer and the maximum depth including the crack of the conductive elastic layer generated after curing shrinkage. That is, the crack depth Ry on the surface of the charging member is necessarily larger than the crack depth y from the surface of the conductive elastic layer, including the maximum height of the crack edge (convex portion) of the surface layer. .
- the charging member according to the present invention can be manufactured, for example, by a method including the following steps (1) to (3).
- Process (1) At least one selected from the group consisting of a hydrolyzable silane compound represented by the general formula (12) and a hydrolyzable compound represented by the general formulas (13) to (16), the general formula (21).
- a hydrolyzable silane compound represented by the general formula (12) and a hydrolyzable compound represented by the general formulas (13) to (16)
- the mixture containing the hydrolyzable silane compound, water, and alcohol shown in (2) is heated and refluxed to hydrolyze and condense the hydrolyzable compound in the mixture to obtain a liquid condensate.
- first stage reaction heating hydrolyzable silane compound represented by general formula (12) or hydrolyzable silane compound represented by general formula (12) and general formula (21) in the presence of water and alcohol A reaction for obtaining a condensate intermediate containing a hydrolyzable condensate of a hydrolyzable silane compound by performing refluxing and hydrolysis / condensation.
- Second stage reaction at least one hydrolyzable compound selected from the above-mentioned condensate intermediate and a compound group having a structure represented by general formulas (13) to (16) in the presence of water and alcohol A reaction in which the final condensate is obtained by heating and refluxing, followed by hydrolysis and condensation.
- the hydrolysis of the general formulas (13) to (16) is very fast. Therefore, when all the hydrolyzable compounds are hydrolyzed at once, only the hydrolyzable compounds of the general formulas (13) to (16) react selectively, and white turbidity / precipitation tends to occur. Therefore, in order to obtain a polymer compound in which the element “M” is uniformly contained in the molecule, it is preferable to go through a two-step reaction process as described above.
- the reaction proceeds smoothly even if the hydrolysis / condensation reaction is not divided into two stages.
- the M / Si ratio is 0.30 to 12.50 (region where the concentration of M is high)
- the ratio WR (molar ratio) of the addition amount of water with respect to the hydrolyzable silane compound at the time of synthesizing the hydrolysis condensate is 0.3 or more and 6.0 or less.
- the value of WR is preferably 1.2 or more and 3.0 or less. If the amount of water added is within the above range, the degree of condensation during synthesis can be easily controlled. In addition, it is easy to control the condensation rate, and is effective in improving the storage stability of the hydrolyzed condensate or its diluted solution. Moreover, if it is in the said range, since it can synthesize
- a primary alcohol a mixed system of a primary alcohol and a secondary alcohol, or a mixed system of a primary alcohol and a tertiary alcohol may be used.
- a mixed system of a primary alcohol and a secondary alcohol or a mixed system of a primary alcohol and a tertiary alcohol may be used.
- Particularly preferred are ethanol, a combination of methanol and 2-butanol, and a combination of ethanol and 2-butanol.
- Process (2) A photopolymerization initiator is added to the condensate obtained in step (1) as necessary, and a solvent is added as necessary to adjust to an appropriate solid content concentration to prepare a coating for forming a surface layer.
- a solvent is added as necessary to adjust to an appropriate solid content concentration to prepare a coating for forming a surface layer.
- an appropriate solvent considering volatility may be used in addition to the solvent used for the synthesis in order to improve the coating property of the paint.
- Suitable solvents include 2-butanol, ethyl acetate, methyl ethyl ketone, or a mixture thereof.
- the cationic polymerization catalyst which is a photoinitiator in the coating material from a viewpoint of improving crosslinking efficiency in the case of the crosslinking reaction of the condensate in the process (3) mentioned later.
- the above cationic polymerizable group is an epoxy group. It is preferable to use an onium salt of an acid.
- Examples of other cationic polymerization catalysts include borate salts, compounds having an imide structure, compounds having a triazine structure, azo compounds, and peroxides.
- aromatic sulfonium salts and aromatic iodonium salts are preferable from the viewpoints of sensitivity, stability, and reactivity.
- bis (4-tert-butylphenyl) iodonium salt a compound having a structure represented by the following chemical formula (22) (trade name: Adekaoptoma-SP150, manufactured by Asahi Denka Kogyo Co., Ltd.), and the following chemical formula (23 ) (Trade name: Irgacure 261, manufactured by Ciba Specialty Chemicals) is preferable.
- the addition amount of the cationic polymerization catalyst as the photopolymerization initiator is preferably 1.0 to 3.0 parts by mass with respect to 100 parts by mass of the solid content of the hydrolyzable condensate. Within this range, the curing characteristics and the solubility of the photopolymerization initiator will be good.
- Step (3) The coating material prepared in the step (2) is applied on the conductive elastic layer formed on the substrate to form a coating film of the coating material.
- a coating method a known means, for example, coating using a roll coater, dip coating, ring coating, or the like can be used.
- a polymer compound can be formed by cleaving an epoxy group contained in the molecule of the condensate.
- examples of the crosslinking method include a method of irradiating active energy rays and a method of heating. And this coating film hardens
- the active energy ray ultraviolet rays are preferable. This is because if the cross-linking reaction is carried out by ultraviolet rays, it is possible to suppress deterioration of the conductive elastic layer due to thermal history, and thus it is possible to suppress a decrease in electrical characteristics of the conductive elastic layer.
- UV integrated light quantity [mJ / cm 2 ] UV intensity [mW / cm 2 ] ⁇ irradiation time [s]
- the adjustment of the integrated amount of ultraviolet light can be performed by the irradiation time, lamp output, and distance between the lamp and the irradiated object. Moreover, you may give a gradient to integrated light quantity within irradiation time.
- the cumulative amount of ultraviolet light can be measured using an ultraviolet cumulative light meter (trade names: UIT-150-A, UVD-S254, both manufactured by USHIO INC.).
- an excimer UV lamp the cumulative amount of ultraviolet light can be measured using an ultraviolet cumulative light meter (trade names: UIT-150-A, VUV-S172, both manufactured by USHIO INC.).
- n represents an integer of 1 or more.
- FIG. 3 shows an example of a schematic configuration of an electrophotographic apparatus provided with a process cartridge having the charging member of the present invention.
- This electrophotographic apparatus has a cylindrical photoreceptor 1 that is driven to rotate at a predetermined peripheral speed in the direction of an arrow about an axis 2.
- the photoreceptor may have a support, a photosensitive layer formed on the support, a charge injection layer, a surface layer, and the like.
- the surface of the rotationally driven photoconductor is uniformly charged to a predetermined positive or negative potential by the charging member 3, and then exposure light (not shown) output from exposure means (not shown) for slit exposure or laser beam scanning exposure.
- exposure light not shown
- an electrostatic latent image corresponding to the target image is formed.
- a DC voltage or a voltage obtained by superimposing an AC voltage on the DC voltage is applied to the charging member 3 from a voltage applying means (not shown).
- the electrostatic latent image formed on the surface of the photoreceptor 1 is supplied with a developer by a developing roller provided in the developing unit 5 and is reversely developed or normally developed to become a toner image.
- the toner image on the surface of the photoconductor 1 is transferred onto the transfer material such as paper that is conveyed between the photoconductor 1 and the transfer roller 6 in synchronization with the rotation of the photoconductor by a transfer bias applied to the transfer roller 6. Sequentially transferred to P.
- Examples of the developing means include jumping developing means, contact developing means, and magnetic brush means.
- As the transfer roller a transfer roller having an elastic layer adjusted to a medium resistance on a support can be used.
- the transfer material P onto which the toner image has been transferred is separated from the surface of the photoreceptor 1 and is introduced into the fixing unit 8, and is printed out as an image formed product (print, copy) on which the toner image is fixed. .
- the image formed product is introduced into the recirculation transport mechanism and reintroduced into the transfer unit.
- the surface of the photoreceptor 1 after the transfer of the toner image is cleaned by removing the developer (toner) remaining after the transfer by a cleaning means 7 such as a cleaning blade, and further subjected to a charge removal process by pre-exposure light from the pre-exposure means. After that, it is repeatedly used for image formation.
- a cleaning means 7 such as a cleaning blade
- pre-exposure is not always necessary.
- the photosensitive member 1, the charging member 3, the developing unit 5, and the cleaning unit 7 are integrated into a process cartridge 9, and is configured to be detachable from the electrophotographic apparatus main body using a guide unit 10 such as a rail of the electrophotographic apparatus main body.
- the cartridge can be appropriately selected from transfer means or the like, and can be attached to and detached from the electrophotographic apparatus main body.
- FIG. 4 is a schematic sectional view of the developing device of the developing means 5.
- an electrophotographic photosensitive drum 501 as an electrostatic latent image holding body that holds an electrostatic latent image formed by a known process is rotated in the direction of arrow B.
- a developing sleeve 508 as a developer carrying member carries a one-component developer 504 having magnetic toner supplied by a hopper 503 as a developer container, and rotates in the direction of arrow A. By doing so, the developer 504 is conveyed to the developing region D where the developing sleeve 508 and the photosensitive drum 501 face each other.
- a magnet roller 505 in which a magnet is inscribed is disposed in the developing sleeve 508 in order to magnetically attract and hold the developer 504 on the developing sleeve 508.
- the developing sleeve 508 used in the developing device of the present invention has a metal cylindrical tube 506 as a base and a conductive resin coating layer 507 coated thereon.
- a stirring blade 510 for stirring the developer 504 is provided in the hopper 503, a stirring blade 510 for stirring the developer 504 is provided.
- Reference numeral 513 denotes a gap indicating that the developing sleeve 508 and the magnet net roller 505 are not in contact with each other.
- the developer 504 is a triboelectric charge capable of developing the electrostatic latent image on the photosensitive drum 501 by friction between the magnetic toner constituting the developer and the conductive resin coating layer 507 on the developing sleeve 508. Get a charge.
- a ferromagnetic metal magnetic regulation blade 502 is provided as a developer layer thickness regulating member.
- the magnetic regulating blade 502 is suspended from the hopper 503 so as to face the developing sleeve 508 with a gap width of about 50 to 500 ⁇ m from the surface of the developing sleeve 508.
- a magnetic force line from the magnetic pole N 1 of the magnet roller 505 concentrates on the magnetic regulation blade 511, so that a thin layer of the developer 504 is formed on the developing sleeve 508.
- the developer (toner) used in the present invention is preferably in a range of mass average particle diameter of 4 ⁇ m or more and 11 ⁇ m or less regardless of the type. If such a toner is used, the toner charge amount or image quality and image density are balanced.
- the binder resin for the developer (toner) generally known resins can be used, and examples thereof include vinyl resins, polyester resins, polyurethane resins, epoxy resins, phenol resins, etc. Among them, vinyl resins, Polyester resins are preferred.
- a charge control agent can be included in the toner particles (internal addition) or mixed with the toner particles (external addition) for the purpose of improving charging characteristics. This is because the charge control agent enables optimal charge amount control according to the development system.
- positive charge control agent examples include modified products of nigrosine, triaminotriphenylmethane dyes and fatty acid metal salts; tributylbenzylammonium-1-hydroxy-4-naphthosulfonate, tetrabutylammonium tetrafluoroborate and the like.
- organometallic compounds and chelate compounds are effective as the negative charge control agent.
- organometallic compounds and chelate compounds include aluminum acetylacetonate, iron (II) acetylacetonate, 3,5-ditertiary butyl salicylate, etc., particularly acetylacetone metal complexes, monoazo metal complexes, naphthoic acid or salicylic acid metal complexes or salts. Is preferred.
- the magnetic material When the developer (toner) is a magnetic developer (toner), the magnetic material includes iron oxide-based metal oxides such as magnetite, maghemite, and ferrite; magnetic metals such as Fe, Co, and Ni; Formulated with alloys with metals such as Al, Co, Cu, Pb, Mg, Ni, Sn, Zn, Sb, Be, Bi, Cd, Ca, Mn, Se, Ti, W, V, and mixtures thereof To do. In that case, you may make these magnetic materials also serve as a coloring agent.
- iron oxide-based metal oxides such as magnetite, maghemite, and ferrite
- magnetic metals such as Fe, Co, and Ni
- Formulated with alloys with metals such as Al, Co, Cu, Pb, Mg, Ni, Sn, Zn, Sb, Be, Bi, Cd, Ca, Mn, Se, Ti, W, V, and mixtures thereof To do. In that case, you may make these magnetic materials also serve as a coloring agent.
- pigments and dyes conventionally used in this field can be used, and they may be appropriately selected and used.
- a release agent in the developer (toner) for example, an aliphatic hydrocarbon wax such as low molecular weight polyethylene, low molecular weight polypropylene, microcrystalline wax, paraffin wax, carnauba wax, Fischer-Tropsch wax, Suitable are waxes based on fatty acid esters such as sazol wax and montan wax.
- inorganic fine powders such as silica, titanium oxide and alumina are externally added to the developer (toner) in order to improve environmental stability, charging stability, developability, fluidity, storage stability and cleaning properties. That is, it is preferably present in the vicinity of the developer surface.
- silica fine powder is preferable.
- part means “part by mass”.
- thermosetting adhesive containing metal and rubber (trade name: METALOC N-33, manufactured by Toyo Chemical Laboratories Co., Ltd.) and drying it at a temperature of 80 ° C. for 30 minutes, It was further dried at a temperature of 120 ° C. for 1 hour.
- the kneaded product I is extruded coaxially onto the support with the adhesive layer into a cylindrical shape having an outer diameter of 8.75 to 8.90 mm, and the end is cut.
- An unvulcanized conductive elastic layer (length: 242 mm) was laminated on the outer periphery of the substrate.
- the roller was vulcanized using a continuous heating furnace having two zones with different temperature settings.
- the first zone was set at a temperature of 80 ° C. and allowed to pass in 30 minutes
- the second zone was set at a temperature of 160 ° C. and allowed to pass for 30 minutes
- the unvulcanized conductive elastic layer was vulcanized.
- Both ends in the width direction of the vulcanized conductive elastic layer were cut to make the length of the conductive elastic layer portion in the axial direction 232 mm. Furthermore, the surface of the conductive elastic layer was polished with a rotating grindstone, and formed into a crown shape with an end diameter of 8.26 mm and a center diameter of 8.5 mm. This was designated as a conductive elastic roller 1.
- Ten-point average roughness (Rz) and maximum depth (Ry) were measured in accordance with Japanese Industrial Standard (JIS) B0601 (1994). As measurement conditions, an evaluation length of 8.0 mm, a cutoff value of 0.8 mm, a feed rate of 0.5 mm / s, and a filter characteristic 2CR were used.
- the hardness was measured using a micro rubber hardness meter (MD-1 capa, manufactured by Kobunshi Keiki Co., Ltd.).
- the measurement of vibration was performed using a high-precision laser measuring machine LSM-430v manufactured by Mitutoyo Corporation.
- the outer diameter is measured using the measuring device, and the difference between the maximum outer diameter value and the minimum outer diameter value is defined as the outer diameter difference run. This measurement is performed at five points, and the average of the five outer diameter difference shakes is measured. The value was the runout of the object to be measured.
- a conductive elastic roller 2 and a conductive elastic roller 3 were obtained in the same manner as the conductive elastic roller 1 except that the surface polishing conditions of the vulcanized conductive elastic layer were changed. Further, a conductive elastic roller was obtained in the same manner as the conductive elastic roller 1 except that the component (2-2) in the amount shown in Table 2 was used instead of the component (2-1). A conductive elastic roller 4 and a conductive elastic roller 5 were obtained in the same manner as the conductive elastic roller 3 except that the surface polishing conditions of the vulcanized conductive elastic layer of the conductive roller were changed.
- the amount of the component (2-3) shown in Table 1 was used, and the conductive elasticity was changed except that the surface polishing conditions of the vulcanized conductive elastic layer were changed.
- the conductive elastic roller 6 and the conductive elastic roller 7 were produced in the same manner as the roller 1.
- These conductive elastic rollers 2 to 7 were evaluated in the same manner as the conductive elastic roller 1.
- the evaluation results of the conductive elastic rollers 1 to 7 are shown in Table 2 below.
- an oil bath set at a temperature of 120 ° C. was installed on a stirrer with a temperature runaway prevention mechanism, and the flask was immersed in the oil bath and stirred at a rotational speed of 750 rpm.
- the contents of the flask reached a temperature of 120 ° C. after 20 minutes.
- the 1st step reaction was performed by performing heating-refluxing for 20 hours, and the condensate intermediate 1 was obtained.
- the condensate 1 was diluted with ethanol, solid content was adjusted to 1.3 mass%, and the dilution liquid of the condensate 1 was obtained.
- the storage stability of the diluted solution of the obtained condensate 1 was evaluated according to the following criteria.
- an aromatic sulfonium salt [trade name: Adekaoptomer SP-150, manufactured by Asahi Denka Kogyo Co., Ltd.] as a photocationic polymerization initiator was diluted to 10% by mass with methanol. Then The amount of the photocationic polymerization initiator is 3.0 parts by mass with respect to 100 parts by mass of the solid content of the diluted solution of the condensate 1 prepared by the same method as described in Evaluation (1). A diluted solution of a photocationic polymerization initiator was added. A solvent prepared by mixing ethanol and 2-butanol at 1: 1 (mass ratio) was added to adjust the theoretical solid content concentration to 7.0 mass%. This was designated coating solution 1.
- the coating liquid 1 was spin-coated on the degreased surface of an aluminum sheet having a thickness of 100 ⁇ m.
- the spin coater 1H-D7 (trade name: manufactured by Mikasa Co., Ltd.) was used.
- spin coating conditions the rotation speed was 300 rpm and the rotation time was 2 seconds.
- the coating film of the coating liquid 1 was dried, the coating film was irradiated with ultraviolet rays having a wavelength of 254 nm to cure the coating film.
- the cumulative amount of ultraviolet light received by the coating film was 9000 mJ / cm 2 .
- a low-pressure mercury lamp manufactured by Harrison Toshiba Lighting Co., Ltd.
- the cured film was peeled from the aluminum sheet and pulverized using an agate mortar to prepare a sample for NMR measurement. This sample was measured for 29 Si-NMR spectrum and 13 C-NMR spectrum using a nuclear magnetic resonance apparatus (trade name: JMN-EX400, manufactured by JEOL).
- Condensate intermediates 2 to 7 were prepared in the same manner as the condensate intermediate 1 except that the composition shown in Table 5 below was used. Details of the compounds represented by the abbreviations (EP-1 to EP-5, He, Ph) in Table 5 are shown in Table 11.
- Example 1 Preparation of charging rollers 1-1 to 1-3
- ⁇ Formation of surface layer> Three conductive elastic rollers 1 prepared in the above [1] are prepared, and a coating No. is applied to the outer periphery of the conductive elastic layer of each conductive elastic roller 1.
- the detected O1s spectrum is separated into peaks (Ti—O—Ti bond, Si—O—Ti bond, Si—O—Si bond) corresponding to each bonding mode (see FIG. 8), and the presence of those peaks Thus, it was confirmed that each chemical bond was present in the surface layer.
- each charging roller and the electrophotographic photosensitive member are assembled in a process cartridge (product name: “HP 35A (CB435A)”, manufactured by HP) which integrally supports them.
- the process cartridge was mounted on a laser beam printer (trade name: “HP Laser Jet P1006 Printer”, manufactured by HP) for vertical output of A4 paper.
- This laser beam printer has a printing speed of 17 sheets / min and an image resolution of 600 dpi.
- the electrophotographic photosensitive member incorporated in the process cartridge together with the charging roller is an organic electrophotographic photosensitive member in which an organic photosensitive layer having a layer thickness of 8.0 ⁇ m is formed on a support.
- the organic photosensitive layer is a laminated type photosensitive layer formed by laminating a charge generation layer and a charge transport layer containing polycarbonate (binder resin) from the support side, and the charge transport layer is an electrophotographic photoreceptor. It is a surface layer.
- the developer (toner) used in the laser beam printer is a mixture of a developer binder resin with a colorant, a charge control agent, a release agent, inorganic fine particles, and the like.
- the format is appropriately selected according to the developing device.
- a magnetic one-component developer was used.
- an image was used on an A4 size paper in which a horizontal line having a width of 2 dots and an interval of 118 spaces was formed in a direction perpendicular to the rotation direction of the electrophotographic photosensitive member. Further, the output was performed in an environment of 25 ° C./55% RH, and image formation was performed in a so-called intermittent mode in which the rotation of the electrophotographic photosensitive member was stopped for 7 seconds every time one sheet was printed. Thus, an image forming operation for outputting 1000 images per day was performed over 2 days, and a total of 2000 electrophotographic images were output. About the halftone image formed in this way, the presence or absence and generation
- AA No horizontal streak caused by uneven charging due to poor charging is observed.
- Paint No. 15 and charging rollers 15-1 to 15-6 were prepared in the same manner as the charging roller 1 except that the conductive elastic roller 1 was changed to the conductive rollers 2 to 7. These were subjected to evaluations (3) to (8).
- Example 16 to 29 ⁇ Preparation of Surface Layer Forming Coating Materials 16-1 to 16-3, 17-1 to 17-3, 18-1 to 18-3>
- the coatings 16-1 to 16-3, 17-1 to 17-3, and 18-1 to 18 for forming the surface layer are the same as the coatings 1-1 to 1-3 except that the condensates 16 to 18 are used. -3 was prepared.
- the charging rollers 16-1 to 16-3, 17-1 to 17-3, 18-1 to 18-3, 19-1 to 19-3, 20 are the same as in Example 1 except that the above-described paint is used.
- -1 to 20-2, 21-1 to 21-3, and 22 to 29 were prepared. These were subjected to evaluations (3) to (8).
- Paint No. 30 and the charging rollers 30-1 to 30-6 were prepared in the same manner as the charging roller 1 except that the conductive elastic roller 1 was changed to the conductive rollers 2 to 7. These were subjected to evaluations (3) to (8).
- Examples 31 to 44 ⁇ Preparation of Surface Layer Forming Coating Materials 31-1 to 31-3, 32-1 to 32-3, 33-1 to 33-3>
- the coatings 31-1 to 31-3, 32-1 to 32-3, and 32-1 to 33 for forming the surface layer are the same as the coatings 1-1 to 1-3 except that the condensates 31 to 33 are used. -3 was prepared.
- the charging rollers 31-1 to 31-3, 32-1 to 32-3, 33-1 to 33-3, 34-1 to 34-3, and 35 are the same as in Example 1 except that the above paint is used.
- -1 to 35-2, 36-1 to 36-3, and 37 to 44 were prepared. These were subjected to evaluations (3) to (8).
- Paint No. 45, and the charging rollers 45-1 to 45-6 were prepared in the same manner as the charging roller 1 except that the conductive elastic roller 1 was changed to the conductive rollers 2 to 7. These were subjected to evaluations (3) to (8).
- Example 46 to 60 ⁇ Preparation of surface layer forming coatings 46-1 to 46-3, 47-1 to 47-3, 48-1 to 48-3>
- the coatings 46-1 to 46-3, 47-1 to 47-3 and 48-1 to 48 for forming the surface layer are the same as the coatings 1-1 to 1-3 except that the condensates 46 to 48 are used.
- -3 was prepared.
- the charging rollers 46-1 to 46-3, 47-1 to 47-3, 48-1 to 48-3, 49-1 to 49-3, 50 are the same as in Example 1 except that the above paint is used.
- -1 to 50-2, 51-1 to 51-3, and 52 to 59 were prepared. These were subjected to evaluations (3) to (8).
- Paint No. The charging rollers 60-1 to 60-6 were prepared in the same manner as the charging roller 1 except that the conductive elastic roller 1 was changed to the conductive rollers 2 to 7 and the conductive elastic roller 1 was changed to the conductive rollers 2 to 7. These were subjected to evaluations (3) to (8). The results of evaluations (3) to (8) of the charging roller according to Examples 1 to 60 are shown in Tables 12 to 15.
Landscapes
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Plasma & Fusion (AREA)
- General Physics & Mathematics (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Electrostatic Charge, Transfer And Separation In Electrography (AREA)
- Silicon Polymers (AREA)
- Polyethers (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Laminated Bodies (AREA)
Abstract
Description
ここで帯電部材としては、感光体との当接ニップを十分に確保する観点から、支持体および支持体上に設けられた弾性層(導電性弾性層)を有するものが一般的である。また、弾性層の表面への現像剤などの付着を抑制するために、弾性層の表面に表面層を設けることも一般的に行われている。
また、電子写真用部材の表面への汚れの付着を抑制する方法のひとつとして、特許文献2に記載されているように、表面層に粗い粒子を含有させ、表面層の表面を適度に粗面化する方法が知られている。
そこで本発明の目的は、粗い粒子を用いなくとも、表面が適度に粗面化されてなり、表面への汚れの付着を抑制し得る帯電部材およびその製造方法の提供にある。
MO4/2
MO5/2
(i)前記一般式(12)で示される構造を有する加水分解性化合物の加水分解縮合物と、前記一般式(13)~(16)で示される構造を有する加水分解性化合物の加水分解縮合物の少なくとも1種とを含む液状の縮合物を得る工程と、
(ii)該液状の縮合物と光重合開始剤とを含む表面層形成用の塗料を得る工程と、
(iii)該塗料の塗膜を、支持体の外周に配置された弾性層の上に形成し、該塗膜中の
該加水分解縮合物のR33のエポキシ基を開裂させることによりこれらの加水分解縮合物を架橋させ、表面層を形成する工程とを有する帯電部材の製造方法
が提供される。
一般式(13): Ti(OR37)(OR38)(OR39)(OR40)
一般式(14): Zr(OR41)(OR42)(OR43)(OR44)
一般式(15): Hf(OR45)(OR46)(OR47)(OR48)
一般式(16): Ta(OR49)(OR50)(OR51)(OR52)(OR53)
(i)前記一般式(12)で示される構造を有する加水分解性化合物の加水分解縮合物と、前記一般式(21)で示される構造を有する加水分解性化合物の加水分解縮合物と、前記一般式(13)~(16)で示される構造を有する加水分解性化合物の加水分解縮合物の少なくとも1種とを含む液状の縮合物を得る工程と、
(ii)該液状の縮合物と光重合開始剤とを含む表面層形成用の塗料を得る工程と、
(iii)該塗料の塗膜を、支持体の外周に配置された弾性層の上に形成し、該塗膜中の該加水分解縮合物のR33のエポキシ基を開裂させることによりこれらの加水分解縮合物を架橋させて該塗膜を硬化させ、表面層を形成する工程とを有する帯電部材の製造方法が提供される。
[図2]本発明に係る帯電部材の構成の一例を示す図である。
[図3]本発明に係る電子写真装置の断面図である。
[図4]現像装置の一例を示す模式図である。
[図5A及び5B]本発明に係る帯電部材の表面状態の一例の説明図である。
[図6A及び6B]本発明に係る帯電部材の表面の亀裂の形状を示す図である。
[図7]本発明に係る表面層中の金属元素の種類と弾性率との関係の説明図である。
[図8]ESCAによる解析結果を示すO1sスペクトル図である。
[図9]本発明に係る架橋反応の説明図である。
[図10A及び10B]本発明に係る高分子化合物の化学構造の説明図である。
支持体としては導電性を有するものが用いられる。具体例としては、以下のものが挙げられる。鉄、銅、ステンレス鋼、アルミニウム、アルミニウム合金又はニッケルで形成されている金属製(合金製)の支持体。
導電性弾性層には、従来の帯電部材の弾性層(導電性弾性層)に用いられているゴムなどの弾性体を1種または2種以上用いることができる。ゴムとしては以下のものが挙げられる。ウレタンゴム、シリコーンゴム、ブタジエンゴム、イソプレンゴム、クロロプレンゴム、スチレン−ブタジエンゴム、エチレン−プロピレンゴム、ポリノルボルネンゴム、スチレン−ブタジエン−スチレンゴム、アクリロニトリルゴム、エピクロルヒドリンゴムおよびアルキルエーテルゴム。
表面層は、Si−O−M結合を有している高分子化合物を含み、該高分子化合物は、下記一般式(1)及び下記一般式(2)で示される構成単位の少なくとも1種、並びに下記一般式(3)で示される構成単位の少なくとも1種を有している。
MO4/2
MO5/2
一般式(13): Ti(OR37)(OR38)(OR39)(OR40)
一般式(14): Zr(OR41)(OR42)(OR43)(OR44)
一般式(15): Hf(OR45)(OR46)(OR47)(OR48)
一般式(16): Ta(OR49)(OR50)(OR51)(OR52)(OR53)
以下に、本発明の帯電部材の製造方法を例示する。
本発明に係る帯電部材は、例えば、次の工程(1)~(3)を含む方法により製造することができる。
一般式(12)で示される加水分解性シラン化合物、及び一般式(13)~(16)で示される加水分解性化合物からなる群から選択される少なくとも1つ、任意成分としての一般式(21)で示される加水分解性シラン化合物、水、および、アルコールを含む混合液を加熱、還流させて、該混合液中の加水分解性化合物の加水分解、縮合を行って、液状の縮合物を得る。
第1段階反応:一般式(12)で示される加水分解性シラン化合物、または、一般式(12)及び一般式(21)で示される加水分解性シラン化合物を、水およびアルコールの存在下で加熱還流させて加水分解・縮合を行って、加水分解性シラン化合物の加水分解縮合物を含む縮合物中間体を得る反応。
第2段階反応:上記縮合物中間体、および、一般式(13)~(16)で示される構造を有する化合物群から選択される少なくとも1つの加水分解性化合物を、水およびアルコールの存在下で加熱還流させて、加水分解・縮合を行って最終的な縮合物を得る反応。
なお、M/Si比が0.10~0.30程度(Mの濃度が小さい領域)であれば、加水分解・縮合反応を2段階に分割しなくても反応は円滑に進行する。一方、M/Si比が0.30~12.50(Mの濃度が大きい領域)である場合は、上記したように2段階の反応により縮合物を調製することが好ましい。
工程(1)で得た縮合物に、必要に応じて光重合開始剤を加え、また、必要に応じて溶媒を加えて適当な固形分濃度に調整して、表面層形成用の塗料を調製する。
縮合物の固形分濃度の調整の際には、塗料の塗工性を向上させるために、合成に使用した溶剤以外に、揮発性を考慮した適当な溶剤を用いても良い。適当な溶剤としては、2−ブタノール、酢酸エチル、メチルエチルケトン、あるいは、これらを混合したものが挙げられる。
また、後述する工程(3)における縮合物の架橋反応の際に、架橋効率を向上させる観点から、光重合開始剤であるカチオン重合触媒を塗料に含有させておくことが好ましい。例えば、活性エネルギー線によって賦活化されるルイス酸のオニウム塩に対してエポキシ基は高い反応性を示すことから、上記のカチオン重合可能な基がエポキシ基である場合、カチオン重合触媒としては、ルイス酸のオニウム塩を用いることが好ましい。
工程(2)で調製した塗料を、基体上に形成した導電性弾性層の上に塗布し、該塗料の塗膜を形成する。塗布方法としては、公知の手段、例えば、ロールコーターを用いた塗布、浸漬塗布、リング塗布などを用いることができる。
活性エネルギー線としては、紫外線が好ましい。これは、架橋反応を紫外線によって行えば、熱履歴による導電性弾性層の劣化を抑制することができる為、導電性弾性層の電気的特性の低下を抑制することもできる。
紫外線積算光量[mJ/cm2]=紫外線強度[mW/cm2]×照射時間[s]
例えば、前記した一般式(12)に係る化合物としての、3−グリシドキシプロピルトリメトキシシランと、前記した一般式(13)~(16)からなる群から選択される少なくとも1つの加水分解性化合物とを加水分解させて得られる縮合物は、カチオン重合可能な基としてエポキシ基を有する。このような縮合物のエポキシ基は、カチオン重合触媒(図9中、R+X−と記載)の存在下で、エポキシ環が開環し、連鎖的に重合が進む。
その結果、MO4/2またはMO5/2を含むポリシロキサン同士が架橋し、硬化して本発明に係る高分子化合物が形成される。なお、図9中、nは1以上の整数を表す。
図3に、本発明の帯電部材を有するプロセスカートリッジを備えた電子写真装置の概略構成の一例を示す。この電子写真装置は、軸2を中心に矢印方向に所定の周速度で回転駆動される円筒状の感光体1を有する。感光体は支持体、支持体上に形成された感光層、電荷注入層、表面層等を有するものであってもよい。
回転駆動される感光体の表面は、帯電部材3により、正又は負の所定電位に均一に帯電され、次いで、スリット露光やレーザービーム走査露光の露光手段(不図示)から出力される露光光(画像露光光)4を受け、目的の画像に対応した静電潜像が形成される。
感光体1の表面に形成された静電潜像は、現像手段5に設けられる現像ローラにより現像剤が供給され反転現像又は正規現像されてトナー像となる。次いで、感光体1の表面のトナー像は、転写ローラ6に印加される転写バイアスによって、感光体1と転写ローラ6との間に感光体の回転と同期して搬送された紙等の転写材Pに順次転写される。
感光体1、帯電部材3、現像手段5、クリーニング手段7を一体化してプロセスカートリッジ9とし、電子写真装置本体のレール等の案内手段10を用いて電子写真装置本体に着脱可能な構造としている。上記部材の他、転写手段等から適宜選択してカートリッジ化し、電子写真装置本体に着脱可能とすることもできる。
513は、現像スリーブ508とマゲネットローラ505とが非接触状態にあることを示す間隙である。現像剤504は、現像剤を構成する磁性トナー相互間及び現像スリーブ508上の導電性樹脂被覆層507との摩擦により、感光体ドラム501上の静電潜像を現像することが可能な摩擦帯電電荷を得る。 図4の例では、現像領域Dに搬送される現像剤504の層厚を規制するために、現像剤層厚規制部材としての強磁性金属製の磁性規制ブレード502が設けられている。この磁性規制ブレード502は、現像スリーブ508の表面から約50~500μmのギャップ幅を持って現像スリーブ508に臨むように、ホッパ503から垂下されている。マグネットローラ505の磁極N1からの磁力線が磁性規制ブレード511に集中することにより、現像スリーブ508上に現像剤504の薄層が形成される。
現像剤(トナー)には帯電特性を向上させる目的で、荷電制御剤をトナー粒子に包含させること(内添)、又はトナー粒子と混合して用いること(外添)ができる。これは、荷電制御剤によって、現像システムに応じた最適の荷電量コントロールが可能となるためである。
以下に、具体的な実施例を挙げて本発明をさらに詳細に説明する。ただし、本発明はこれらに限定されるものではない。なお、実施例中の「部」は「質量部」を意味する。
<導電性弾性ローラ1の作成および評価>
表1に示す量の成分(1)、(2−1)、(3)、(4)及び(5)、を6Lニーダーで20分間混練し、次いで表1に示す量の成分(6)及び(7)を加え、オープンロールでさらに8分間混練することによって、混練物Iを得た。
導電性弾性ローラ1の導電性弾性層の表面の十点平均粗さ(Rz)、最大深さ(Ry)、硬度、および、外径差振れを評価した。結果を表1に示す。尚、最大深さRyは、粗さ曲線から、その平均線の方向に基準長さだけ抜き取り、この抜き取り部分の山頂線と谷底線との間隔を粗さ曲線の、縦倍率の方向に測定した値である。つまり基準測定長中の、表面層の亀裂縁部(凸部)の最大高さと、硬化収縮後に生じる導電性弾性層の亀裂を含んだ最大深さの距離を示す。
また、振れの測定は、ミツトヨ(株)製高精度レーザー測定機LSM−430vを用いて行った。詳しくは、該測定機を用いて外径を測定し、最大外径値と最小外径値の差を外径差振れとし、この測定を5点で行い、5点の外径差振れの平均値を被測定物の振れとした。
加硫した導電性弾性層の表面研磨条件を変更した以外は、導電性弾性ローラ1と同様にして導電性弾性ローラ2および導電性弾性ローラ3を得た。
また、成分(2−1)の代わりに、表2に示す量の成分(2−2)使用した以外は導電性弾性ローラ1と同様にして導電性弾性ローラを得た。この導電性ローラの加硫した導電性弾性層の表面研磨条件を変更した以外は導電性弾性ローラ3と同様にして導電性弾性ローラ4、および、導電性弾性ローラ5を得た。
<縮合物1の調製および評価>
〔第1段階反応〕
下記表3に記載した材料を300mlのナスフラスコに入れた。
下記表4の材料を300mlのナスフラスコに入れ、室温で3時間攪拌して、第2段階反応を行い最終的な縮合物1を合成した。
先ず、縮合物1の固形分を調整した。すなわち、アルミニウム製の計量カップの質量(A)を測定した。この計量カップを用いて、縮合物1を約2.000~3.000g(B)を精密天秤で秤量した。更に温度200℃、30分間オーブン中に放置し、水分蒸発後の質量(C)を測定し、次式により、固形分を算出した。
A:1ヶ月放置しても白濁・沈殿が無い状態である。
B:2週間程度から白濁化する状態である。
C:1週間程度から白濁化する状態である。
D:合成時に白濁・沈殿を生じる状態である。
評価結果を表2に示す。
次に、以下の方法で調製した縮合物1の硬化物について、核磁気共鳴装置(商品名:JMN−EX400、JEOL社製)を用いて、29Si−NMR、13C−NMRスペクトルを測定し、当該硬化物中に、一般式(3)の構造が存在していることを確認した。
評価(1)に記載の方法と同じ方法で調製した縮合物1の希釈液の固形分100質量部に対して、上記光カチオン重合開始剤の液量が3.0質量部となるように上記光カチオン重合開始剤の希釈液を加えた。これに、エタノールと2−ブタノールとを1:1(質量比)で混合した溶媒を加えて、理論固形分濃度を7.0質量%に調整した。これをコーティング液1とした。
次いで、硬化膜をアルミニウム製シートから剥離し、メノウ製の乳鉢を用いて粉砕し、NMR測定用試料を調製した。この試料を核磁気共鳴装置(商品名:JMN−EX400、JEOL社製)を用いて29Si−NMRスペクトル、および、13C−NMRスペクトルを測定した。
また、13C−NMRスペクトルよりエポキシ基が残存せず全て重合していることを確認した。以上のことより一般式(3)の構造を硬化膜内に有していることを確認した。
<縮合物中間体2~7の調製および評価>
下記表5に示す組成とした以外は、縮合物中間体1と同様にして縮合物中間体2~7を調製した。なお、表5中の略号(EP−1~EP−5、He、Ph)が表している化合物の詳細は表11に示す。
下記表6~9に示す組成とした以外は、縮合物1と同様にして縮合物2~60を調製し、評価(1)、および、評価(2)を行った。評価結果を表6~9に併せて示す。なお、表6~9中の略号(Tr−1~Tr−3、Zr−1~Zzr−3、Hf−1~Hf−3、および、Ta−1~Ta−3)が表している化合物の詳細は表11に示す。
縮合物中間体4を縮合物61として前記評価(1)及び評価(2)に供した。その結果を表10に示す。
<比較用の縮合物62~65の調製および評価>
下記表10に記載の組成とした以外は、縮合物中間体1と同様にして縮合物62~65を調製し、前記評価(1)に供した。その結果を表10に示す。なお、縮合物62~65は、合成中に白濁、沈殿を生じ、評価(2)を行うためのコーティング液を調製できなかったため、評価(2)は行っていない。
<表面層形成用塗料1−1~1−3の調製>
縮合物1に、エタノール:2−ブタノール=1:1(質量比)の混合溶媒を加えて、固形分濃度を0.7%、6.6%、および、13.1%に調整した。これらを各々塗料No.1−1、1−2および1−3とした。
<表面層の形成>
上記[1]で作成した導電性弾性ローラ1を3本用意し、各々の導電性弾性ローラ1の導電性弾性層の外周部に塗料No.1−1~1−3をリング塗布(吐出量:0.120ml/s、リング部のスピード:85mm/s、総吐出量:0.130ml)した。導電性弾性層の周面に形成された各塗料の塗膜に対して、波長が254nmの波長の紫外線を積算光量が9000mJ/cm2になるように照射した。これにより、塗料中の縮合物1を架橋させて表面層を形成した。なお、紫外線の照射には、の低圧水銀ランプ(ハリソン東芝ライティング(株)製)を用いた。このようにして帯電ローラ1−1~1−3を作成した。各帯電ローラについて以下の評価(3)~(8)を行った。
帯電ローラの表面の外観を目視にて観察し、以下の基準で表面層形成用の塗料の塗工状態を評価した。
A:塗工ムラが発生していない。
B:塗工ムラがローラの端部に一部発生している。
C:塗工ムラが全面に発生している。
上記膜厚の測定には、帯電ローラの軸に沿う方向の中央部において周方向4箇所をサンプリングし、断面方向を観察する。このとき観察装置としては、SEM(HITACHI社製:走査型電子顕微鏡)を用い、加速電圧5kV~20kV、倍率10000倍で確認できる。
評価(2)と同様の方法にて、100μmのアルミニウム製シートの脱脂した表面に、厚みが5.0μmの、縮合物1の硬化膜を形成した。この硬化膜に対して、表面皮膜物性試験(商品名:フィッシャースコープH100V;フィッシャーインストルメンツ社製)を用いて、圧子を測定対象の表面から0.5μm/7sで進入させた。このときの値を弾性率とした。
カラー3Dレーザー顕微鏡(商品名:VK−8700(株)キーエンス社製)を用いて、倍率1000倍(対物レンズ50倍)で各帯電ローラの表面を観察した。また、表面粗さ(Rzjis、Ry)に関しては、解析ソフト VK Analzerを用いて算出した。
各帯電ローラの表面層内のSi−O−Ti結合の存在をX線光電子分光分析(ESCA、Electron Spectroscopy for Chemical Analysis)により確認した。具体的には、ローラ表面の一部分を切断した。次いで、当該切断片をスパッタリング(スパッタリング条件:アルゴンガスを使用、1kV、1分)して表面の汚染を除去した。その後、この切断片について、X線光電子分光分析装置(商品名:Quantum2000;アルバックファイ社製、パスエネルギー(Pass Energy):140eV)を用いて、表面層内の化学結合様式を解析した。検出されたO1sスペクトルを、各結合様式に対応したピーク(Ti−O−Ti結合、Si−O−Ti結合、Si−O−Si結合)に分離し(図8参照)、それらのピークの存在により各化学結合が表面層内に存在することを確認した。
各帯電ローラを用い、以下に示す画像評価を行った。
AA:帯電不良による帯電ムラに起因する横スジが認められない。
A:画像端部に軽微に帯電ムラに起因する横スジが確認できる。
B:画像端部にハッキリと帯電ムラに起因する横スジが確認できる。
C:画像全面に軽微に帯電ムラに起因する横スジが確認できる。
D:画像全面に帯電ムラに起因する横スジが確認できる。
<表面層形成用塗料2−1~2−3、3−1~3−3の調製>
縮合物2を用いた以外は、塗料1−1~1−3と同様にして表面層形成用の塗料2−1~2−3、3−1~3−3を調製した。
<表面層形成用塗料4−1~4−3の調製>
縮合物4に、エタノール:2−ブタノール=1:1(質量比)の混合溶媒を加えて、固形分濃度を0.3%、6.6%、および、19.7%に調整した。これらを各々塗料No.4−1、4−2および4−3とした。
<表面層形成用塗料5−1~5−2の調製>
縮合物5に、エタノール:2−ブタノール=1:1(質量比)の混合溶媒を加えて、固形分濃度を0.3%、および、19.7%に調整した。これらを各々塗料No.5−1、および5−2とした。
<表面層形成用塗料6−1~6−3の調製>
縮合物6に、エタノール:2−ブタノール=1:1(質量比)の混合溶媒を加えて、固形分濃度を0.3%、6.6%、および、19.7%に調整した。これらを各々塗料No.6−1、6−2および6−3とした。
<表面層形成用塗料7~14の調製>
縮合物7~14の各々に、エタノール:2−ブタノール=1:1(質量比)の混合溶媒を加えて、固形分濃度を9.8%に調整した。これらを各々塗料No.7~14とした。
<表面層の形成および帯電ローラの評価>
上記の塗料を用いた以外は実施例1と同様にして帯電ローラ2−1~2−3、3−1~3−3、4−1~4−4、5−1~5−2、6−1~6−3、7~14を作成した。そして、これらを、評価(3)~(8)に供した。
<表面層形成用塗料15の調製>
縮合物15に、エタノール:2−ブタノール=1:1(質量比)の混合溶媒を加えて、固形分濃度を13.1%に調整した。これを塗料No.15とする。
<表面層の形成および帯電ローラの評価>
塗料No.15を用い、かつ、導電性弾性ローラ1を導電性ローラ2~7に変えた以外は帯電ローラ1と同様にして帯電ローラ15−1~15−6を作成した。これらを評価(3)~(8)の供した。
<表面層形成用塗料16−1~16−3、17−1~17−3、18−1~18−3の調製>
縮合物16~18を用いた以外は、塗料1−1~1−3と同様にして表面層形成用の塗料16−1~16−3、17−1~17−3、18−1~18−3を調製した。
<表面層形成用塗料19−1~19−3、21−1~21−3の調製>
縮合物19または21に、エタノール:2−ブタノール=1:1(質量比)の混合溶媒を加えて、固形分濃度を0.3%、6.6%、および、19.7%に調整した。これらを各々塗料No.19−1~19−3、21−1~21−3とした。
<表面層形成用塗料20−1~20−2の調製>
縮合物20に、エタノール:2−ブタノール=1:1(質量比)の混合溶媒を加えて、固形分濃度を0.3%、および、19.7%に調整した。これらを各々塗料No.20−1、および20−2とした。
<表面層形成用塗料22~29の調製>
縮合物22~29の各々に、エタノール:2−ブタノール=1:1(質量比)の混合溶媒を加えて、固形分濃度を9.8%に調整した。これらを各々塗料No.22~29とした。
<表面層の形成および帯電ローラの評価>
上記の塗料を用いた以外は実施例1と同様にして帯電ローラ16−1~16−3、17−1~17−3、18−1~18−3、19−1~19−3、20−1~20−2、21−1~21−3、22~29を作成した。そして、これらを、評価(3)~(8)に供した。
<表面層生成用塗料30の調製>
縮合物30に、エタノール:2−ブタノール=1:1(質量比)の混合溶媒を加えて、固形分濃度を13.1%に調整した。これを塗料No.30とした。
<表面層の形成および帯電ローラの評価>
塗料No.30を用い、かつ、導電性弾性ローラ1を導電性ローラ2~7に変えた以外は帯電ローラ1と同様にして帯電ローラ30−1~30−6を作成した。これらを評価(3)~(8)の供した。
<表面層形成用塗料31−1~31−3、32−1~32−3、33−1~33−3の調製>
縮合物31~33を用いた以外は、塗料1−1~1−3と同様にして表面層形成用の塗料31−1~31−3、32−1~32−3、33−1~33−3を調製した。
<表面層形成用塗料34−1~34−3、36−1~36−3の調製>
縮合物34または36に、エタノール:2−ブタノール=1:1(質量比)の混合溶媒を加えて、固形分濃度を0.3%、6.6%、および、19.7%に調整した。これらを各々塗料No.34−1~34−3、36−1~36−3とした。
<表面層形成用塗料35−1~35−2の調製>
縮合物35に、エタノール:2−ブタノール=1:1(質量比)の混合溶媒を加えて、固形分濃度を0.3%、および、19.7%に調整した。これらを各々塗料No.35−1、および35−2とした。
<表面層形成用塗料37~44の調製>
縮合物37~44の各々に、エタノール:2−ブタノール=1:1(質量比)の混合溶媒を加えて、固形分濃度を9.8%に調整した。これらを各々塗料No.37~44とした。
<表面層の形成および帯電ローラの評価>
上記の塗料を用いた以外は実施例1と同様にして帯電ローラ31−1~31−3、32−1~32−3、33−1~33−3、34−1~34−3、35−1~35−2、36−1~36−3、37~44を作成した。そして、これらを、評価(3)~(8)に供した。
<表面層生成用塗料45の調製>
縮合物45に、エタノール:2−ブタノール=1:1(質量比)の混合溶媒を加えて、固形分濃度を13.1%に調整した。これを塗料No.45とした。
<表面層の形成および帯電ローラの評価>
塗料No.45を用い、かつ、導電性弾性ローラ1を導電性ローラ2~7に変えた以外は帯電ローラ1と同様にして帯電ローラ45−1~45−6を作成した。これらを評価(3)~(8)の供した。
<表面層形成用塗料46−1~46−3、47−1~47−3、48−1~48−3の調製>
縮合物46~48を用いた以外は、塗料1−1~1−3と同様にして表面層形成用の塗料46−1~46−3、47−1~47−3、48−1~48−3を調製した。
<表面層形成用塗料49−1~49−3、51−1~51−3の調製>
縮合物49または51に、エタノール:2−ブタノール=1:1(質量比)の混合溶媒を加えて、固形分濃度を0.3%、6.6%、および、19.7%に調整した。これらを各々塗料No.49−1~49−3、51−1~51−3とした。
<表面層形成用塗料50−1~50−2の調製>
縮合物35に、エタノール:2−ブタノール=1:1(質量比)の混合溶媒を加えて、固形分濃度を0.3%、および、19.7%に調整した。これらを各々塗料No.50−1~50−2とした。
<表面層形成用塗料52~59の調製>
縮合物52~59の各々に、エタノール:2−ブタノール=1:1(質量比)の混合溶媒を加えて、固形分濃度を9.8%に調整した。これらを各々塗料No.52~59とした。
<表面層の形成および帯電ローラの評価>
上記の塗料を用いた以外は実施例1と同様にして帯電ローラ46−1~46−3、47−1~47−3、48−1~48−3、49−1~49−3、50−1~50−2、51−1~51−3、52~59を作成した。そして、これらを、評価(3)~(8)に供した。
<表面層生成用塗料60の調製>
縮合物60に、エタノール:2−ブタノール=1:1(質量比)の混合溶媒を加えて、固形分濃度を13.1%に調整した。これを塗料No.60とした。
<表面層の形成および帯電ローラの評価>
塗料No.60を用い、かつ、導電性弾性ローラ1を導電性ローラ2~7に変えた以外は帯電ローラ1と同様にして帯電ローラ60−1~60−6を作成した。これらを評価(3)~(8)の供した。
上記実施例1~60に係る帯電ローラの評価(3)~(8)の結果を表12~15に示す。
<表面層形成用塗料61−1~61−3の調製>
縮合物61を用いた以外は塗料1−1~1−3と同様にして表面層形成用の塗料61−1~61−3を調製した。
<表面層の形成および評価>
塗料61−1~61−3を用いた以外は、実施例1と同様にして帯電ローラ61−1~61−3を作成し、評価(3)~(8)に供した。
評価結果を表16に示す。
102 導電性弾性層
103 表面層
104 亀裂
Claims (7)
- 支持体、弾性層および表面層を有している帯電部材であって、該表面層は、Si−O−M結合を有している高分子化合物を含み、該高分子化合物は、下記一般式(1)及び下記一般式(2)で示される構成単位から選ばれる少なくとも1つ、並びに下記一般式(3)で示される構成単位を有しており、該帯電部材は、その表面から該弾性層に至る亀裂を有し、該亀裂はその縁部が凸状に盛り上がり、それによって該帯電部材は、該表面が粗面にされていることを特徴とする帯電部材:
一般式(1)
MO4/2
(上記一般式(1)において、Mは、Ti、ZrおよびHfからなる群から選ばれるいずれかの元素である);
一般式(2)
MO5/2
(上記一般式(2)において、Mは、Ta元素である);
一般式(3)
(上記一般式(3)中、R1およびR2はそれぞれ独立に以下の一般式(4)~(7)のいずれかを示す);
一般式(4)
一般式(5)
一般式(6)
一般式(7)
(上記R3~R7、R10~R14、R19、R20、R25およびR26は各々独立に水素原子、炭素数1~4のアルキル基、水酸基、カルボキシル基またはアミノ基を示す。R8、R9、R15~R18、R23、R24およびR29~R32は各々独立に水素原子、炭素数1~4のアルキル基を示す。R21、R22、R27およびR28は各々独立に水素原子または炭素数1~4のアルコキシル基、または炭素数1~4のアルキル基を示す。n、m、l、q、sおよびtは各々独立に1以上8以下の整数を示す。pおよびrは各々独立に4以上12以下の整数を示す。xおよびyは各々独立に0もしくは1を示す。記号「*」および記号「**」は各々、一般式(3)中のケイ素原子および酸素原子への結合部位を示す。)。 - 前記高分子化合物における、Mとケイ素との原子数比M/Siが0.10以上12.50以下である請求項1または2に記載の帯電部材。
- 前記高分子化合物が、下記一般式(12)で示される構造を有する加水分解性化合物の加水分解縮合物と、下記一般式(13)~(16)で示される構造を有する加水分解性化合物の加水分解縮合物の少なくとも1種との架橋物である請求項1~3のいずれかの一項に記載の帯電部材:
一般式(12): R33−Si(OR34)(OR35)(OR36)
一般式(13): Ti(OR37)(OR38)(OR39)(OR40)
一般式(14): Zr(OR41)(OR42)(OR43)(OR44)
一般式(15): Hf(OR45)(OR46)(OR47)(OR48)
一般式(16): Ta(OR49)(OR50)(OR51)(OR52)(OR53)
(上記一般式(12)中、R33は、下記一般式(17)~(20)のいずれかを示し、R34~R36は各々独立に炭素数1~4のアルキル基を示す。上記一般式(13)~(16)中、R37~R53は各々独立に炭素数1~9のアルキル基を示す;
一般式(17)
一般式(18)
一般式(19)
一般式(20)
(上記一般式(17)~(20)中、R54~R58、R59~R65、R66、R67、R72およびR73は各々独立に水素原子、炭素数1~4のアルキル基、水酸基、カルボキシル基またはアミノ基を示す。R57、R58、R62~R65、R70、R71およびR76~R79は各々独立に水素原子または炭素数1~4のアルキル基を示す。n’、m’、l’、q’、s’、t’は各々独立に1以上8以下の整数を示す。p’およびr’は各々独立に4以上12以下の整数を示す。また、記号「*」は一般式(12)のケイ素原子との結合位置を示す。))。 - 前記高分子化合物が、請求項4に記載の一般式(12)で示される構造を有する加水分解性化合物の加水分解縮合物と請求項4に記載の一般式(13)~(16)で示される構造を有する加水分解性化合物の加水分解縮合物の少なくとも1種と、下記一般式(21)で示される構造を有する加水分解性化合物の加水分解縮合物との架橋物である請求項1~3のいずれかの一項に記載の帯電部材:
一般式(21): R80−Si(OR81)(OR82)(OR83)
(上記一般式(21)中、R80は炭素数1~21のアルキル基またはフェニル基を示し、R81~R83は各々独立に炭素数1~4のアルキル基を示す)。 - 請求項4に記載の帯電部材の製造方法であって、
(i)前記一般式(12)で示される構造を有する加水分解性化合物の加水分解縮合物と、前記一般式(13)~(16)で示される構造を有する加水分解性化合物の加水分解縮合物の少なくとも1種とを含む液状の縮合物を得る工程と、
(ii)該液状の縮合物と光重合開始剤とを含む表面層形成用の塗料を得る工程と、
(iii)該塗料の塗膜を、支持体の外周に配置された弾性層の上に形成し、該塗膜中の
該加水分解縮合物のR33のエポキシ基を開裂させることによりこれらの加水分解縮合物を架橋させ、表面層を形成する工程とを有することを特徴とする帯電部材の製造方法。 - 請求項5に記載の帯電部材の製造方法であって、
(i)前記一般式(12)で示される構造を有する加水分解性化合物の加水分解縮合物と、前記一般式(21)で示される構造を有する加水分解性化合物の加水分解縮合物と、前記一般式(13)~(16)で示される構造を有する加水分解性化合物の加水分解縮合物の少なくとも1種とを含む液状の縮合物を得る工程と、
(ii)該液状の縮合物と光重合開始剤とを含む表面層形成用の塗料を得る工程と、
(iii)該塗料の塗膜を、支持体の外周に配置された弾性層の上に形成し、該塗膜中の該加水分解縮合物のR33のエポキシ基を開裂させることによりこれらの加水分解縮合物を架橋させて該塗膜を硬化させ、表面層を形成する工程とを有することを特徴とする帯電部材の製造方法。
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201180046496.0A CN103124931B (zh) | 2010-09-27 | 2011-09-22 | 充电构件及其制造方法 |
KR1020137009949A KR101477941B1 (ko) | 2010-09-27 | 2011-09-22 | 대전 부재 및 그 제조 방법 |
EP11829330.7A EP2624066B1 (en) | 2010-09-27 | 2011-09-22 | Charging member and method for producing same |
US13/345,477 US9372428B2 (en) | 2010-09-27 | 2012-01-06 | Charging member and method for manufacturing the same |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2010215811 | 2010-09-27 | ||
JP2010-215811 | 2010-09-27 |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US13/345,477 Continuation US9372428B2 (en) | 2010-09-27 | 2012-01-06 | Charging member and method for manufacturing the same |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2012043777A1 true WO2012043777A1 (ja) | 2012-04-05 |
Family
ID=45893214
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2011/072492 WO2012043777A1 (ja) | 2010-09-27 | 2011-09-22 | 帯電部材及びその製造方法 |
Country Status (6)
Country | Link |
---|---|
US (1) | US9372428B2 (ja) |
EP (1) | EP2624066B1 (ja) |
JP (2) | JP4954344B2 (ja) |
KR (1) | KR101477941B1 (ja) |
CN (1) | CN103124931B (ja) |
WO (1) | WO2012043777A1 (ja) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104335124A (zh) * | 2012-05-22 | 2015-02-04 | 佳能株式会社 | 充电构件、处理盒和电子照相设备 |
Families Citing this family (27)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4948666B2 (ja) * | 2010-08-17 | 2012-06-06 | キヤノン株式会社 | 帯電部材及びその製造方法 |
EP2624062A4 (en) | 2010-09-27 | 2015-10-07 | Canon Kk | LOADING ELEMENT, PROCESS CARTRIDGE AND ELECTRO-PHOTOGRAPHIC DEVICE |
CN103154827B (zh) | 2010-09-27 | 2015-07-01 | 佳能株式会社 | 充电构件、处理盒和电子照相设备 |
JP4942233B2 (ja) | 2010-09-27 | 2012-05-30 | キヤノン株式会社 | 帯電部材、プロセスカートリッジおよび電子写真装置 |
CN103124934B (zh) | 2010-09-30 | 2015-06-10 | 佳能株式会社 | 充电构件及其生产方法 |
WO2012111836A1 (ja) | 2011-02-15 | 2012-08-23 | キヤノン株式会社 | 帯電部材、その製法、プロセスカートリッジ及び電子写真装置 |
WO2012147301A1 (ja) | 2011-04-27 | 2012-11-01 | キヤノン株式会社 | 帯電部材、プロセスカートリッジ、電子写真装置、及び帯電部材の製造方法 |
EP2703902B1 (en) * | 2011-04-28 | 2016-03-23 | Canon Kabushiki Kaisha | Charging member, method for producing charging member, electrophotographic device, and processor cartridge |
CN103502895B (zh) * | 2011-04-28 | 2015-11-25 | 佳能株式会社 | 充电构件、处理盒和电子照相设备 |
WO2013145616A1 (ja) | 2012-03-29 | 2013-10-03 | キヤノン株式会社 | 電子写真用部材の製造方法及びコーティング液 |
JP6128424B2 (ja) * | 2012-10-25 | 2017-05-17 | 株式会社リコー | 画像形成装置及びプロセスカートリッジ |
JP6338354B2 (ja) * | 2013-11-06 | 2018-06-06 | 株式会社沖データ | 帯電装置、画像形成手段および画像形成装置 |
JP6541437B2 (ja) * | 2015-05-27 | 2019-07-10 | キヤノン株式会社 | 帯電部材、プロセスカートリッジおよび電子写真装置 |
US9910379B2 (en) | 2015-10-26 | 2018-03-06 | Canon Kabushiki Kaisha | Charging member with concave portions containing insulating particles and electrophotographic apparatus |
US9904199B2 (en) | 2015-10-26 | 2018-02-27 | Canon Kabushiki Kaisha | Charging member having outer surface with concave portions bearing exposed elastic particles, and electrophotographic apparatus |
US10317811B2 (en) | 2016-10-07 | 2019-06-11 | Canon Kabushiki Kaisha | Charging member, method for producing same, process cartridge and electrophotographic image forming apparatus |
JP7034815B2 (ja) | 2017-04-27 | 2022-03-14 | キヤノン株式会社 | 帯電部材、電子写真プロセスカートリッジ及び電子写真画像形成装置 |
JP7046571B2 (ja) | 2017-11-24 | 2022-04-04 | キヤノン株式会社 | プロセスカートリッジ及び電子写真装置 |
JP7187270B2 (ja) | 2017-11-24 | 2022-12-12 | キヤノン株式会社 | プロセスカートリッジ及び電子写真装置 |
CN112020678B (zh) | 2018-04-18 | 2022-11-01 | 佳能株式会社 | 导电性构件、处理盒和电子照相图像形成设备 |
WO2019203225A1 (ja) | 2018-04-18 | 2019-10-24 | キヤノン株式会社 | 導電性部材、プロセスカートリッジ及び電子写真画像形成装置 |
WO2019203238A1 (ja) | 2018-04-18 | 2019-10-24 | キヤノン株式会社 | 導電性部材及びその製造方法、プロセスカートリッジ並びに電子写真画像形成装置 |
CN111989622B (zh) | 2018-04-18 | 2022-11-11 | 佳能株式会社 | 显影构件、处理盒和电子照相设备 |
CN112005173B (zh) | 2018-04-18 | 2023-03-24 | 佳能株式会社 | 导电性构件、处理盒和图像形成设备 |
US10558136B2 (en) | 2018-04-18 | 2020-02-11 | Canon Kabushiki Kaisha | Charging member, manufacturing method of charging member, electrophotographic apparatus, and process cartridge |
WO2019203227A1 (ja) | 2018-04-18 | 2019-10-24 | キヤノン株式会社 | 導電性部材、プロセスカートリッジ、および画像形成装置 |
JP2023058944A (ja) * | 2021-10-14 | 2023-04-26 | ヒューレット-パッカード デベロップメント カンパニー エル.ピー. | コーティング層を有する帯電部材 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002080785A (ja) * | 2000-09-11 | 2002-03-19 | Suzuka Fuji Xerox Co Ltd | 導電性有機・無機ハイブリッド皮膜 |
JP2006064750A (ja) * | 2004-08-24 | 2006-03-09 | Canon Chemicals Inc | 帯電用部材、プロセスカートリッジ及び画像形成装置 |
JP2006162802A (ja) * | 2004-12-03 | 2006-06-22 | Canon Inc | 画像形成装置 |
JP2007264611A (ja) * | 2006-02-28 | 2007-10-11 | Canon Inc | 帯電部材、プロセスカートリッジおよび電子写真装置 |
JP2009151159A (ja) * | 2007-12-21 | 2009-07-09 | Canon Inc | 帯電装置 |
Family Cites Families (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5200237A (en) * | 1990-10-01 | 1993-04-06 | Associated Universities, Inc. | Solid-gel precursor solutions and methods for the fabrication of polymetallicsiloxane coating films |
JP2004037786A (ja) * | 2002-07-03 | 2004-02-05 | Canon Inc | 帯電部材、これを用いた電子写真装置及びプロセスカートリッジ |
JP2004354489A (ja) * | 2003-05-27 | 2004-12-16 | Bridgestone Corp | 現像ローラ、その製造方法及び画像形成装置 |
JP4455454B2 (ja) | 2004-09-02 | 2010-04-21 | キヤノン株式会社 | 帯電部材、プロセスカートリッジおよび電子写真装置 |
CN100570502C (zh) * | 2004-12-28 | 2009-12-16 | 佳能株式会社 | 充电构件、处理盒和电子照相设备 |
DE602005027749D1 (de) | 2004-12-28 | 2011-06-09 | Canon Kk | Ladegerät, prozesskartusche und elektrofotografische vorrichtung |
KR100893985B1 (ko) * | 2004-12-28 | 2009-04-20 | 캐논 가부시끼가이샤 | 대전 부재, 공정 카트리지 및 전자 사진 장치 |
JP2006293004A (ja) * | 2005-04-11 | 2006-10-26 | Canon Chemicals Inc | 電子写真用帯電ローラ |
KR20100129344A (ko) | 2006-02-28 | 2010-12-08 | 캐논 가부시끼가이샤 | 대전 부재, 공정 카트리지 및 전자 사진 장치 |
US8064803B2 (en) | 2006-02-28 | 2011-11-22 | Canon Kabushiki Kaisha | Charging member, process cartridge, and electrophotographic apparatus |
TW200902596A (en) * | 2007-02-08 | 2009-01-16 | Dow Corning | Heteroelement siloxane compounds and polymers |
JP5110985B2 (ja) | 2007-06-29 | 2012-12-26 | キヤノン株式会社 | 接触式帯電部材、プロセスカートリッジ及び電子写真画像形成装置 |
WO2010050615A1 (ja) * | 2008-10-31 | 2010-05-06 | キヤノン株式会社 | 帯電部材、プロセスカートリッジ及び電子写真装置 |
JP4717959B1 (ja) | 2009-12-14 | 2011-07-06 | キヤノン株式会社 | 帯電部材、プロセスカートリッジ及び電子写真装置 |
JP5729988B2 (ja) * | 2009-12-15 | 2015-06-03 | キヤノン株式会社 | 帯電部材、プロセスカートリッジ及び電子写真装置 |
JP5264873B2 (ja) | 2009-12-28 | 2013-08-14 | キヤノン株式会社 | 帯電部材、プロセスカートリッジ及び電子写真装置 |
EP2605072B1 (en) | 2010-08-09 | 2017-06-28 | Canon Kabushiki Kaisha | Charging member, method for producing same, process cartridge, and electrophotographic device |
JP4948666B2 (ja) | 2010-08-17 | 2012-06-06 | キヤノン株式会社 | 帯電部材及びその製造方法 |
EP2607961B1 (en) | 2010-08-19 | 2016-09-14 | Canon Kabushiki Kaisha | Electrification member, process cartridge, and electrophotographic device |
JP5925051B2 (ja) | 2012-05-22 | 2016-05-25 | キヤノン株式会社 | 帯電部材、プロセスカートリッジ及び電子写真装置 |
-
2011
- 2011-09-15 JP JP2011202219A patent/JP4954344B2/ja active Active
- 2011-09-22 EP EP11829330.7A patent/EP2624066B1/en not_active Not-in-force
- 2011-09-22 KR KR1020137009949A patent/KR101477941B1/ko active IP Right Grant
- 2011-09-22 CN CN201180046496.0A patent/CN103124931B/zh active Active
- 2011-09-22 WO PCT/JP2011/072492 patent/WO2012043777A1/ja active Application Filing
-
2012
- 2012-01-06 US US13/345,477 patent/US9372428B2/en active Active
- 2012-03-09 JP JP2012052761A patent/JP2012113325A/ja not_active Withdrawn
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002080785A (ja) * | 2000-09-11 | 2002-03-19 | Suzuka Fuji Xerox Co Ltd | 導電性有機・無機ハイブリッド皮膜 |
JP2006064750A (ja) * | 2004-08-24 | 2006-03-09 | Canon Chemicals Inc | 帯電用部材、プロセスカートリッジ及び画像形成装置 |
JP2006162802A (ja) * | 2004-12-03 | 2006-06-22 | Canon Inc | 画像形成装置 |
JP2007264611A (ja) * | 2006-02-28 | 2007-10-11 | Canon Inc | 帯電部材、プロセスカートリッジおよび電子写真装置 |
JP2009151159A (ja) * | 2007-12-21 | 2009-07-09 | Canon Inc | 帯電装置 |
Non-Patent Citations (1)
Title |
---|
See also references of EP2624066A4 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104335124A (zh) * | 2012-05-22 | 2015-02-04 | 佳能株式会社 | 充电构件、处理盒和电子照相设备 |
Also Published As
Publication number | Publication date |
---|---|
EP2624066B1 (en) | 2016-03-16 |
JP4954344B2 (ja) | 2012-06-13 |
US20120107565A1 (en) | 2012-05-03 |
JP2012113325A (ja) | 2012-06-14 |
CN103124931A (zh) | 2013-05-29 |
EP2624066A4 (en) | 2014-11-05 |
US9372428B2 (en) | 2016-06-21 |
KR101477941B1 (ko) | 2014-12-30 |
KR20130079547A (ko) | 2013-07-10 |
CN103124931B (zh) | 2015-06-17 |
JP2012093720A (ja) | 2012-05-17 |
EP2624066A1 (en) | 2013-08-07 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP4954344B2 (ja) | 帯電部材及びその製造方法 | |
JP5943721B2 (ja) | 帯電部材、プロセスカートリッジ及び電子写真装置 | |
JP5943696B2 (ja) | 帯電部材、帯電部材の製造方法、電子写真装置およびプロセスカートリッジ | |
JP5925051B2 (ja) | 帯電部材、プロセスカートリッジ及び電子写真装置 | |
JP5943690B2 (ja) | 帯電部材、プロセスカートリッジ及び電子写真装置 | |
JP5038524B2 (ja) | 帯電部材、プロセスカートリッジおよび電子写真装置 | |
JP5264873B2 (ja) | 帯電部材、プロセスカートリッジ及び電子写真装置 | |
KR101512574B1 (ko) | 대전 부재, 프로세스 카트리지 및 전자 사진 장치 | |
JP4948666B2 (ja) | 帯電部材及びその製造方法 | |
JP4942233B2 (ja) | 帯電部材、プロセスカートリッジおよび電子写真装置 | |
JP2012063759A (ja) | 帯電部材、プロセスカートリッジ及び電子写真装置 | |
JP4942234B2 (ja) | 帯電部材、その製造方法及び電子写真装置 | |
JP5627385B2 (ja) | 現像剤担持体 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 201180046496.0 Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 11829330 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2011829330 Country of ref document: EP |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 20137009949 Country of ref document: KR Kind code of ref document: A |