WO2012042755A1 - 帯電部材、プロセスカートリッジおよび電子写真装置 - Google Patents
帯電部材、プロセスカートリッジおよび電子写真装置 Download PDFInfo
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- WO2012042755A1 WO2012042755A1 PCT/JP2011/004993 JP2011004993W WO2012042755A1 WO 2012042755 A1 WO2012042755 A1 WO 2012042755A1 JP 2011004993 W JP2011004993 W JP 2011004993W WO 2012042755 A1 WO2012042755 A1 WO 2012042755A1
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- 0 CC(CCCC1)C1=* Chemical compound CC(CCCC1)C1=* 0.000 description 6
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/337—Polymers modified by chemical after-treatment with organic compounds containing other elements
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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
- G03G15/02—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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L85/00—Compositions of macromolecular compounds obtained by reactions forming a linkage in the main chain of the macromolecule containing atoms other than silicon, sulfur, nitrogen, oxygen and carbon; Compositions of derivatives of such polymers
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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
- G03G15/02—Apparatus for electrographic processes using a charge pattern for laying down a uniform charge, e.g. for sensitising; Corona discharge devices
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- 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
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31652—Of asbestos
- Y10T428/31663—As siloxane, silicone or silane
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- 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
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31652—Of asbestos
- Y10T428/31667—Next to addition polymer from unsaturated monomers, or aldehyde or ketone condensation product
Definitions
- the present invention relates to a charging unit used in an electrophotographic apparatus, a process cartridge using the same, and an electrophotographic apparatus.
- the charging member that contacts the electrophotographic photosensitive member and charges the photosensitive member has an elastic layer containing rubber in order to secure a nip width between the photosensitive member and the charging member. Since such an elastic layer usually contains a low molecular weight component, the low molecular weight component may bleed on the surface of the charging member and adhere to the surface of the photoreceptor when used for a long time. Then, streaky unevenness may appear in the electrophotographic image formed using the photoconductor to which the low molecular weight component is attached. Such a phenomenon is particularly prominent when an electrophotographic image is formed using an electrophotographic apparatus placed in a stopped state for a long time in a high temperature and high humidity environment.
- Patent Document 1 discloses a charging in which the peripheral surface of the elastic layer is covered with an organic-inorganic hybrid coating to suppress bleeding of the low molecular weight component to the surface. A roll is disclosed.
- the present inventors examined the charging roll provided with the organic-inorganic hybrid coating described in Patent Document 1, the organic-inorganic hybrid coating had a low crosslinking density. This seems to be because the organic-inorganic hybrid coating attaches importance to flexibility. Therefore, it has been recognized that the film thickness of the organic-inorganic hybrid coating needs to be submicron or more in order to reliably suppress bleeding of low molecular weight components.
- the surface layer of the charging member is preferably thin. Also, in order to form a surface layer with a uniform thickness, it is preferable that the surface layer is thin.
- an object of the present invention is to provide a charging member provided with a surface layer that can more surely suppress the seepage of a low molecular weight component from an elastic layer.
- Another object of the present invention is to provide a process cartridge and an electrophotographic apparatus that can stably form a high-quality electrophotographic image.
- the present invention has a substrate, an elastic layer, and a surface layer, the surface layer has a Si—O—Ta bond, and a structural unit represented by the following structural formula (1) and the following structure
- a charging member containing a polymer compound having a structural unit represented by the formula (2) is provided:
- R 1 and R 2 each independently represents any one of the structural formulas (3) to (6).
- R 3 to R 7 , R 10 to R 14 , R 19 , R 20 , R 25 and R 26 are each independently hydrogen or an alkyl group having 1 to 4 carbon atoms.
- R 8 , R 9 , R 15 to R 18 , R 23 , R 24 and R 29 to R 32 are each independently hydrogen or an alkyl group having 1 to 4 carbon atoms.
- R 21 , R 22 , R 27 and R 28 each independently represent hydrogen, oxygen, an alkoxy group having 1 to 4 carbon atoms, or an alkyl group having 1 to 4 carbon atoms n, m, l, q , S and t are each independently an integer of 1 or more and 8 or less, p and r are each independently an integer of 4 or more and 12 or less, x and y are each independently 0 or 1
- the symbol “*” represents the bonding site to the silicon atom in the structural formula (1), and the symbol “**” represents the bonding portion to the oxygen atom in the structural formula (1).
- a process cartridge comprising the charging member and an electrophotographic photosensitive member disposed in contact with the charging member and configured to be detachable from the main body of the electrophotographic apparatus.
- an electrophotographic apparatus comprising the charging member and an electrophotographic photosensitive member disposed in contact with the charging member.
- the present invention it is possible to obtain a charging member having a surface layer that can more reliably suppress bleeding even with a thin film thickness.
- FIG. 1 is a configuration diagram of an electrophotographic apparatus according to the present invention.
- 2 is a 17 O-NMR spectrum of the condensate prepared in Example 1.
- 2 is a 29 Si-NMR spectrum of a cured film formed from the coating material for forming a surface layer prepared in Example 1.
- FIG. 3 is a 13 C-NMR spectrum of a cured film formed from the surface layer-forming paint prepared in Example 1.
- FIG. It is explanatory drawing of the crosslinking reaction in the formation process of the surface layer which concerns on this invention. It is a figure which shows the chemical structure of the high molecular compound which concerns on this invention. It is a figure which shows the chemical structure of the high molecular compound which concerns on this invention.
- FIG. 1 is a cross-sectional view in a direction perpendicular to the axis of a charging member (charging roller) having a roller shape according to the present invention.
- This charging roller has a structure in which an elastic layer 102 and a surface layer 103 are sequentially laminated on a substrate 101. Other layers may exist between the base and the elastic layer. *
- a substrate such as iron, copper, stainless steel, aluminum, nickel, or an alloy thereof can be used.
- Rubbers and thermoplastic elastomers used for the elastic layer of conventional charging members can be used alone or in combination of two or more. Specific examples of rubber are given below. 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, or alkyl ether rubber.
- thermoplastic elastomers examples include styrene elastomers and olefin elastomers.
- examples of commercially available styrene-based elastomers include “Lavalon” manufactured by Mitsubishi Chemical Corporation and “Septon Compound” manufactured by Kuraray Co., Ltd.
- examples of commercially available olefin elastomers include the following. The product name “Thermo Run” manufactured by Mitsubishi Chemical Corporation, the product name “Milastomer” manufactured by Mitsui Petrochemical Industry Co., Ltd., the product name “Sumitomo TPE” manufactured by Sumitomo Chemical Co., Ltd., and the product manufactured by Advanced Elastomer Systems Co., Ltd. Name “Santplane”.
- the elastic layer is configured to have a predetermined conductivity by appropriately using a conductive agent.
- a conductive agent As a standard of the electric resistance value of the elastic layer, it is 10 2 ⁇ or more and 10 8 ⁇ or less, and particularly 10 3 ⁇ or more and 10 6 ⁇ or less.
- the conductive agent used for the elastic layer include a cationic surfactant, an anionic surfactant, an amphoteric surfactant, an antistatic agent, and an electrolyte.
- the elastic layer preferably has an Asker C of 70 degrees or more, more preferably 73 degrees or more, from the viewpoint of suppressing deformation of the charging member when the charging member and the photosensitive member are brought into contact with each other. It is 92 degrees or less.
- the elastic layer that determines the shape of the charging member preferably has a so-called crown shape in which the thickness of the central portion is larger than the thickness of the end portion.
- the surface layer includes a high molecular compound having a Si—O—Ta bond and having a structural unit represented by the following structural formula (1) and a structural unit represented by the following structural formula (2).
- R 1 and R 2 each independently represents any one of structural formulas (3) to (6).
- R 3 to R 7 , R 10 to R 14 , R 19 , R 20 , R 25 and R 26 are each independently hydrogen, a straight chain having 1 to 4 carbon atoms or A branched alkyl group, carbonyl group, hydroxyl group, carboxyl group or amino group is shown.
- R 8 , R 9 , R 15 to R 18 , R 23 , R 24 and R 29 to R 32 each independently represent hydrogen or a linear or branched alkyl group having 1 to 4 carbon atoms.
- R 21 , R 22 , R 27 and R 28 each independently represent hydrogen, oxygen, an alkoxy group having 1 to 4 carbon atoms, or a linear or branched 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 “*” represents the bonding site to the silicon atom in the structural formula (1), and the symbol “**” represents the bonding site to the oxygen atom in the structural formula (1).
- FIG. 7A shows a part of the structure when R 1 in Structural Formula (1) is represented by Structural Formula (3) and R 2 is represented by Structural Formula (4).
- FIG. 7B shows part of the structure when R 1 in Structural Formula (1) is represented by Structural Formula (3) and R 2 is represented by Structural Formula (6). Show.
- the above polymer compound has a very dense cross-linked structure due to the Si—O—Ta bond. ing. Therefore, the surface layer containing such a polymer compound can highly suppress bleeding even when the film thickness is thin.
- R 1 and R 2 are preferably each independently selected from structures represented by the following structural formulas (7) to (10).
- the surface layer can be made stronger and more durable.
- the structure containing an ether group represented by the following structural formula (8) or (10) can further improve 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 .
- the symbol “*” represents the bonding site to the silicon atom in the structural formula (1), and the symbol “**” represents the bonding site to the oxygen atom in the structural formula (1).
- the atomic ratio of tantalum and silicon (Ta / Si) contained in the polymer compound is preferably 0.1 or more and 5.0 or less.
- Ta / Si is within the above numerical range, weakening of the polymer compound can be suppressed.
- the surface layer containing such a high molecular compound can more reliably suppress bleeding of low molecular weight components from the elastic layer, and has excellent durability.
- the polymer compound according to the present invention is obtained by subjecting a hydrolyzable silane compound represented by the following structural formula (11) and a hydrolyzable tantalum compound represented by the following structural formula (12) to dehydration condensation to produce a hydrolysis condensate. Get. Thereafter, a radically polymerizable group possessed by the hydrolyzed condensate, for example, an epoxy group is reacted to form a crosslink to obtain a crosslink. Condensation can be performed by mixing these hydrolyzable compounds and heating appropriately.
- R 33 represents any one selected from the structures represented by the following structural formulas (13) to (16).
- R 34 to R 36 each independently represents an alkyl group having 1 to 4 carbon atoms.
- R 37 to R 41 each independently represents an alkyl group having 1 to 9 carbon atoms.
- R 42 to R 44 , R 47 to R 49 , R 54 , R 55 , R 60 and R 61 are each independently hydrogen, a straight chain having 1 to 4 carbon atoms. Or a branched alkyl group, a hydroxyl group, a carbonyl group, a carboxyl group, a chlorocarbonyl group or an amino group.
- R 45 , R 46 , R 50 to R 53 , R 58 , R 59 and R 64 to R 67 each independently represent hydrogen or a linear or branched alkyl group having 1 to 4 carbon atoms.
- R 56 , R 57 , R 62 and R 63 each independently represent hydrogen, an alkoxy group having 1 to 4 carbon atoms, or a linear or branched alkyl group having 1 to 4 carbon atoms.
- CR 45 R 46 , CR 50 R 51 , CR 52 R 53 , CR 58 R 59 , CR 64 R 65 , CR 66 R 67 may be a carbonyl group.
- in at least any two carbons in R 42 , R 43 , R 44 , or (CR 45 R 46 ) n ′ , in R 47 , R 48 , R 49 , or (CR 50 R 51 ) m ′ At least any two of the carbons may together form a cycloalkane.
- R 54 and R 55 , or R 60 and R 61 may jointly form a cycloalkane.
- 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 “*” indicates the bonding position with the silicon atom in the structural formula (11).
- the polymer compound is a crosslinked product of a hydrolysis condensate of a hydrolyzable compound represented by structural formulas (11) and (12) and a hydrolyzable silane compound represented by structural formula (17) below. Is preferred.
- a cross-linked product can improve the electrical properties as the solubility and coating properties of the formulas (11) and (12) at the synthesis stage, and the film physical properties after curing.
- R 68 is an alkyl group having 1 to 21 carbon atoms, it is preferable for improving solubility and coatability.
- R 68 is a phenyl group, it contributes to improvement of electrical characteristics, particularly volume resistivity, which is preferable.
- R 68 represents an alkyl group having 1 to 21 carbon atoms or a phenyl group
- R 69 to R 71 each independently represents an alkyl group having 1 to 6 carbon atoms.
- R 68 represents an alkyl group having 1 to 21 carbon atoms or a phenyl group
- R 69 to R 71 each independently represents an alkyl group having 1 to 6 carbon atoms.
- R 68 represents an alkyl group having 1 to 21 carbon atoms or a phenyl group
- R 69 to R 71 each independently represents an alkyl group having 1 to 6 carbon atoms.
- R 68 represents an alkyl group having 1 to 21 carbon atoms or a phenyl group
- R 69 to R 71 each independently represents an alkyl group having 1 to 6 carbon atoms.
- R 68 represents an alkyl group having 1 to 21 carbon
- the above polymer compound may be prepared by preparing a coating for forming a surface layer containing such a hydrolyzable condensate, coating it to form a coating film, and then performing a crosslinking reaction to obtain a crosslinked product. it can.
- the coating material for forming the surface layer can be prepared by the following steps.
- a tantalum compound (C) is prepared.
- Step Hydrolyzable silane compound (A) and hydrolyzable silane compound (B) are mixed, water (D) and alcohol (E) are added, and hydrolysis / condensation is performed by heating under reflux. A condensate of a decomposable silane compound is obtained.
- the hydrolyzable silane compound (B) may be used as necessary, and the hydrolyzable tantalum compound (C) is added simultaneously with the hydrolyzable compound (A) and the like.
- the step can be omitted.
- hydrolyzable silane compound (B) examples are shown below. These can be used alone or in combination of two or more.
- hydrolyzable tantalum compound (C) examples are shown below. These can be used alone or in combination of two or more.
- hydrolyzable silane compound (A), hydrolyzable silane compound (B), and hydrolyzable tantalum compound (C) preferably satisfies the formula (20) in terms of molar ratio.
- A represents the number of moles of the hydrolyzable silane compound (A) represented by the formula (11).
- B represents the number of moles of the hydrolyzable silane compound (B) represented by the formula (17).
- C represents the number of moles of the hydrolyzable tantalum compound (C) represented by the formula (17). If the value of C / (A + B) is 0.1 or more, a surface layer having a high crosslinking density and a high bleeding effect can be obtained, and if it is 5.0 or less, the surface layer forming paint is cloudy. And precipitation can be suppressed and storage stability can be improved. Furthermore, it is preferable to satisfy Formula (21).
- the amount of water (D) added is the ratio of the number of moles of water D to the total number of moles (A + B) of the hydrolyzable silane compounds (A) and (B), Ror (D / ( A + B)) is preferably 0.3 or more and 6.0 or less. Ror is more preferably 1.2 or more and 3.0 or less. If Ror is 0.3 or more, the condensation reaction is sufficiently carried out to suppress the remaining unreacted monomer, and a film having a high crosslinking density can be obtained. If Ror is 6.0 or less, the condensation reaction rate is high, and it is possible to suppress the formation of white turbidity and precipitation in the surface layer-forming coating material. Can be suppressed.
- Alcohol (E) is used to make the silane tantalum condensate compatible.
- the alcohol (E) a primary alcohol, a secondary alcohol, a tertiary alcohol, a mixed system of a primary alcohol and a secondary alcohol, or a mixed system of a primary alcohol and a tertiary alcohol is used. Is preferred.
- the alcohol ethanol, a mixed solution of methanol and 2-butanol, and a mixed solution of ethanol and 2-butanol are particularly preferable from the viewpoint of compatibility with the condensate and coating properties.
- the process photopolymerization initiator (G) is used for crosslinking the silane tantalum condensate.
- the photopolymerization initiator (G) Lewis acid or Bronsted acid onium salts and cationic polymerization catalysts may be used.
- the cationic polymerization catalyst include borate salts, imide compounds, triazine compounds, azo compounds, and peroxides.
- an aromatic sulfonium salt or an aromatic iodonium salt is preferable from the viewpoints of sensitivity, stability, and reactivity.
- Particularly preferred cationic polymerization catalysts include bis (4-tert-butylphenyl) iodonium salt and a compound represented by formula (18) (trade name: Adekaoptomer-SP150, manufactured by Asahi Denka Kogyo Co., Ltd.).
- a compound represented by the formula (19) (trade name: Irgacure 261, manufactured by Ciba Specialty Chemicals) can also be suitably used.
- the photopolymerization initiator (G) is preferably used by previously dissolving it in a solvent such as alcohol or ketone, for example, methanol or methyl isobutyl ketone, in order to improve the compatibility with the coating material for forming the surface layer.
- a solvent such as alcohol or ketone, for example, methanol or methyl isobutyl ketone
- the surface layer-forming paint is adjusted to a concentration suitable for coating using a solvent in order to improve the coatability.
- a solvent examples include alcohols such as ethanol, methanol and 2-butanol, and ketones such as ethyl acetate, methyl ethyl ketone and methyl isobutyl ketone, and these can also be used as a mixture.
- a mixed solution of ethanol and 2-butanol is preferable.
- methods such as coating using a roll coater, dip coating, and ring coating can be used.
- the silane tantalum condensate is cross-linked in the coating film formed by applying the surface layer-forming paint on the elastic layer by the above method.
- Crosslinking can be formed by irradiating an active energy ray and cleaving and polymerizing an epoxy group in the silane tantalum condensate with a photopolymerization initiator (G).
- the active energy ray to be used ultraviolet rays are preferable because radicals of the photopolymerization initiator (G) can be generated at low temperatures and the crosslinking reaction can proceed.
- the crosslinking reaction By allowing the crosslinking reaction to proceed at a low temperature, it is possible to suppress the rapid volatilization of the solvent from the coating film, to prevent phase separation and wrinkle generation in the coating film, and to provide a surface layer with high adhesion strength to the elastic layer. Can be formed.
- the surface layer with high adhesion strength to the elastic layer is used when the charging member is used in an environment where changes in temperature and humidity are abrupt, and even if the volume of the elastic layer fluctuates due to changes in temperature and humidity, it suppresses the occurrence of wrinkles and cracks can do.
- the thermal deterioration of the elastic layer can be suppressed during the progress of the crosslinking reaction, it is also possible to suppress a decrease in the electrical characteristics of the elastic layer in the manufacturing process.
- a supply source of ultraviolet rays a high pressure mercury lamp, a metal halide lamp, a low pressure mercury lamp, an excimer UV lamp, or the like can be used, and among these, those that supply ultraviolet rays having a wavelength of 150 nm or more and 480 nm or less are preferable.
- the ultraviolet rays can be irradiated by adjusting the supply amount according to the irradiation time, lamp output, and the distance between the lamp and the surface layer, and the irradiation amount of the ultraviolet rays can be graded within the irradiation time.
- the integrated light quantity of ultraviolet rays can be selected as appropriate.
- the cumulative amount of ultraviolet light can be obtained from the following equation.
- UV integrated light quantity [mJ / cm 2 ] UV intensity [mW / cm 2 ] ⁇ irradiation time [s]
- the integrated light amount of ultraviolet rays can be measured using an ultraviolet integrated light amount meter UIT-150-A or UVD-S254 (both trade names) manufactured by USHIO INC.
- the integrated light amount of ultraviolet rays can be measured using an ultraviolet integrated light amount meter UIT-150-A or VUV-S172 (both trade names) manufactured by Ushio Electric Co., Ltd.
- the thickness of the surface layer thus formed is preferably 10 nm or more and 100 nm or less. By controlling the thickness within the above range, the effect of suppressing bleeding of low molecular weight components from the elastic layer can be more reliably obtained. In addition, it is possible to suppress uneven application of the coating material for forming the surface layer when forming the surface layer, and to form a uniform coating film. Moreover, it is preferable also in terms of appearance and cost.
- the molar ratio of the hydrolyzable silane compound (A), hydrolyzable silane compound (B), and hydrolyzable tantalum compound (C) satisfies the formula (20). In this case, it is preferably more than 50% and 75% or less.
- DC is an index representing the degree of condensation with respect to all groups bonded to the silicon atom, and is calculated using the formula (22).
- n is the number of hydrolyzable functional groups of the hydrolyzable silane compound, for example, alkoxy groups, and is 3 in the case of the hydrolyzable silane compounds (A) and (B), If ⁇ is represented by T, it can be obtained from equation (23).
- T 0 to T 3 represent component amounts in which the number of hydrolyzed portions condensed with the hydrolyzable silane compound is 0 to 3, respectively. If DC exceeds 50%, a dense film having a high bleeding suppression effect can be obtained. When all the functional groups of the silane compound having the hydrolyzable functional group 3 are condensed, the condensation rate is 75%. When the condensation rate exceeds 75%, the paint has a high viscosity, resulting in poor coating properties, white turbidity, or separation.
- a silane tantalum condensate obtained by hydrolyzing 3-glycidoxypropyltrimethoxysilane and a hydrolyzable tantalum compound (C) as the component (A) is used as a group capable of cationic polymerization.
- the epoxy group of such a silane tantalum condensate undergoes chain polymerization in the presence of a cationic polymerization catalyst (described as R + X ⁇ in FIG. 6), and the polymerization proceeds in a chain manner.
- n represents an integer of 1 or more.
- FIG. 1 An example of an electrophotographic apparatus provided with a process cartridge having a charging member according to the present invention is shown in FIG.
- the cylindrical electrophotographic photosensitive member 1 is disposed in contact with the charging member 3 (roller-shaped charging member in FIG. 2) of the present invention, and is driven to rotate at a predetermined peripheral speed around the shaft 2 in the arrow direction. Is done.
- the surface of the electrophotographic photosensitive member 1 that is driven to rotate is uniformly charged to a predetermined positive or negative potential by the charging member 3.
- exposure light (image exposure light) 4 output from exposure means (not shown) such as slit exposure or laser beam scanning exposure
- the surface of the electrophotographic photoreceptor 1 is subjected to static corresponding to the target image.
- An electrostatic latent image is formed.
- a voltage of only 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).
- a voltage ( ⁇ 1000 V) of only DC voltage was applied to the charging member.
- the dark portion potential was ⁇ 500 V and the light portion potential was ⁇ 150 V.
- the electrostatic latent image formed on the surface of the photoreceptor 1 is developed (reversal development or normal development) with toner contained in the developer of the developing unit 5 to become a toner image.
- the developing means include jumping developing means, contact developing means or magnetic brush means, but from the viewpoint of improving toner scattering, contact developing means are preferred.
- contact developing means is used. Adopted.
- the toner image formed on the surface of the electrophotographic photosensitive member 1 is sequentially transferred onto a transfer material (such as paper) P by a transfer bias from a transfer unit (such as a transfer roller) 6.
- the transfer material P is taken out and supplied from a transfer material supply means (not shown) to a contact portion between the electrophotographic photoreceptor 1 and the transfer means 6 in synchronization with the rotation of the electrophotographic photoreceptor 1.
- the transfer material P onto which the toner image has been transferred is separated from the surface of the photoreceptor 1, introduced into the fixing unit 8, and subjected to image fixing, thereby being printed out as an image formed product (print, copy).
- the surface of the photosensitive member 1 is cleaned by a cleaning means (cleaning blade or the like) 7 to remove the transfer residual developer (toner). Further, after being subjected to charge removal processing by pre-exposure light (not shown) from a pre-exposure means (not shown), it is repeatedly used for image formation.
- pre-exposure is not always necessary.
- the process cartridge of the present invention includes the above-described photoreceptor 1 and the charging member 3, and is configured by integrally connecting other means selected from the developing means 5, the transfer means 6, the cleaning means 7, and the like. can do.
- the process cartridge is configured to be detachable from an electrophotographic apparatus main body such as a copying machine or a laser beam printer.
- the electrophotographic photosensitive member 1, the charging member 3, the developing unit 5, and the cleaning unit 7 are integrally supported to form a process cartridge 9. This is detachably attached to the main body of the electrophotographic apparatus using guide means 10 such as a rail of the main body of the electrophotographic apparatus.
- the mixture was heated to reflux at 120 ° C. for 20 hours to obtain a condensate intermediate 1.
- the concentration of the condensate intermediate 1 was 28.0% by mass as a solid content (mass ratio based on the total weight of the solution assuming that all hydrolyzable silane compounds were dehydrated and condensed).
- the cured film of the coating liquid 1 was formed by the following procedures, the chemical structure was analyzed, and the degree of condensation (DC%) was calculated. That is, the coating liquid 1 was applied on a degreased aluminum sheet having a thickness of 100 ⁇ m. After drying, UV light with a wavelength of 254 nm was irradiated using a low-pressure mercury lamp (Harrison Toshiba Lighting Co., Ltd.) so that the integrated light amount was 9000 mJ / cm 2 , and the coating solution 1 was crosslinked and cured to obtain a cured film. . The obtained cured film was scraped off with a glass plate and pulverized using an agate mortar to prepare a sample powder for measurement.
- DC% degree of condensation
- This sample was measured for 29 Si-NMR spectrum using a nuclear magnetic resonance apparatus (JMN-EX400 JEOL).
- the obtained spectrum data is shown in FIG.
- the peak at ⁇ 46 to ⁇ 40 ppm is the T 0 component
- the peak at ⁇ 55 to ⁇ 47 ppm is the T 1 component
- the peak at ⁇ 61 to ⁇ 54 ppm is the T 2 component
- the peak at ⁇ 71 to ⁇ 61 ppm is T 3 component.
- the T 3 component indicates a state in which a silicon atom having one bond with an organic group has three bonds with another silicon atom or a tantalum atom via an oxygen atom.
- the degree of condensation of the hydrolyzable functional group bonded to Si was measured from the formula (23).
- the 13 C-NMR spectrum of the sample was measured. The obtained spectrum is shown in FIG. From this spectrum, it was confirmed that no epoxy group was present in the cured film and all the epoxy groups were ring-opened. From the above, in the cured film formed from the coating liquid 1, all the epoxy groups in the raw material glycidoxypropylethoxysilane compound are ring-opened and crosslinked, and —SiO 3 / It was confirmed that it had two structural units. This evaluation 3 was confirmed in the same manner in the examples described later.
- the left and right turn-over was performed 20 times in total with a front roll rotation speed of 8 rpm, a rear roll rotation speed of 10 rpm, and a roll gap of 2 mm. Thereafter, the roll gap was set to 0.5 mm and thinning was performed 10 times to obtain a kneaded product I for an elastic layer.
- thermosetting adhesive (trade name: METALOC U) containing metal and rubber in a region up to 115.5 mm on both sides across the center of the cylindrical surface in the axial direction of the support (a region having an axial width of 231 mm).
- METALOC U thermosetting adhesive
- -20 manufactured by Toyo Chemical Laboratory Co., Ltd. This was dried at a temperature of 80 ° C. for 30 minutes, and further dried at a temperature of 120 ° C. for 1 hour.
- the kneaded product I was extruded into a cylindrical shape having an outer diameter of 8.75 to 8.90 mm coaxially around the core metal with an adhesive layer by extrusion molding using a cross head, and the end portion was cut.
- An elastic roller 1 in which an unvulcanized elastic layer was laminated on the outer periphery of the core metal was produced.
- the roller 1 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 this was also allowed to pass for 30 minutes to obtain a vulcanized elastic roller 2.
- both ends of the elastic layer portion (rubber portion) of the elastic roller 2 before surface polishing were cut so that the axial width of the elastic layer portion was 232 mm.
- the surface of the elastic layer portion was polished with a rotating grindstone (work rotation speed 333 rpm, grindstone rotation speed 2080 rpm, polishing time 12 sec).
- the crown shape has an end diameter of 8.26 mm and a center diameter of 8.50 mm, the surface 10-point average roughness (Rz) is 5.5 ⁇ m, the deflection is 18 ⁇ m, and the hardness is 73 degrees (Asker C )
- Elastic roller 3 (elastic roller after surface polishing).
- the ten-point average roughness (Rz) was measured according to JISB0601 (1994).
- the shake was measured 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 runs is measured. The value was the runout of the object to be measured.
- the Asker C hardness is measured in a temperature of 25 ° C. and a relative humidity of 55% RH by bringing a pusher of an Asker C-type hardness meter (manufactured by Kobunshi Keiki Co., Ltd.) into contact with the surface of the object to be measured. Performed under conditions.
- Each of the surface layer-forming paints 1-1 to 1-7 is applied to the peripheral surface of the elastic layer of the seven elastic rollers 3 by ring application (discharge amount: 0.120 ml / s, moving speed of the ring portion relative to the elastic roller: 85 mm / s, total discharge amount: 0.130 ml).
- the surface layer is formed by irradiating the coating film of each surface layer coating material with ultraviolet light having a wavelength of 254 nm so that the integrated light quantity becomes 9000 mJ / cm 2 and curing the coating film.
- a low-pressure mercury lamp manufactured by Harrison Toshiba Lighting Co., Ltd.
- the following evaluations were performed on the obtained charging rollers 1-1 to 1-7.
- the charging rollers 1-1 to 1-7 were incorporated in a process cartridge that is integrally supported together with the photosensitive member. At this time, a total load of 1 kg was applied to the charging roller. Then, it was left for 30 days under high temperature and high humidity (temperature 40 ° C., humidity 95% RH). Next, the process cartridge was left for 72 hours at room temperature and normal humidity (temperature 25 ° C., humidity 50% RH). This process cartridge was loaded into a laser beam printer (trade name: Color LaserJet 4700 Printer, manufactured by HP) capable of outputting A4 size paper in the vertical direction, and a black solid image was output as an electrophotographic image.
- a laser beam printer trade name: Color LaserJet 4700 Printer, manufactured by HP
- the developing method of this laser beam printer is a reversal developing method, the output speed of the transfer material is 164 mm / s, and the image resolution is 600 dpi.
- the photoreceptor is an organic electrophotographic photoreceptor having an organic photosensitive layer having a layer thickness of 19.0 ⁇ m on a support.
- the organic photosensitive layer is a laminated photosensitive layer in which a charge generation layer and a charge transport layer containing a modified polycarbonate (binder resin) are laminated from the support side, and this charge transport layer is the surface of the electrophotographic photoreceptor. It is a layer.
- the toner used in the laser beam printer is a so-called polymerized toner, and has a glass transition temperature of 63 ° C.
- This polymerized toner is obtained by adding silica fine particles and titanium oxide fine particles to particles obtained by suspension polymerization of a polymerizable monomer system containing a wax, a charge control agent, a dye, styrene, butyl acrylate and an ester monomer in an aqueous medium. Contains externally added toner particles.
- a polymerizable monomer system containing a wax, a charge control agent, a dye, styrene, butyl acrylate and an ester monomer in an aqueous medium.
- Table 4 the presence or absence of horizontal streaks due to the contact trace of the charging roller with the photosensitive member, and the density and length of the streaks, if any, are shown in Table 4 below. Evaluation was made according to the criteria. The criteria shown in Table 4 are based on the length of the horizontal stripe when a stripe having a width of about 1 mm on A4 vertical paper is targeted.
- the condensates 2 to 19 were changed in the same manner as the condensate 1 except that the types and amounts of the condensate intermediates 2 to 11 and the types and amounts of the hydrolyzable tantalum compounds were changed as shown in Table 7 below.
- Table 7 the compound types indicated by the abbreviations of the hydrolyzable tantalum compounds (Ta-1 to Ta-3) are also shown in Table 6 above.
- the condensates 2 to 19 obtained were evaluated [1] in the same manner as the condensate 1.
- Coating solutions 2 to 19 were prepared in the same manner as the coating solution 1 except that the condensates 2 to 19 were used. The above evaluations [2] to [3] were performed for each coating solution.
- a comparative coating liquid 20 was prepared in the same manner as the coating liquid 1 except that the comparative condensate 20 was used. About this, said evaluation [2] and [3] were performed.
- a comparative coating liquid 21 was prepared in the same manner as the coating liquid 1 except that the above-mentioned comparative condensate 21 was used and no photocationic polymerization initiator was added. About this, said evaluation [2] and [3] were performed. In the evaluation [2] and [3] for the comparative coating liquid 21, the coating film of the comparative coating liquid 21 was cured by heating at a temperature of 250 ° C. for 1 hour without using UV.
- the charging rollers 20 and 21 were produced in the same manner as in Example 1 except that the surface layer forming paint 1 of Example 1 was changed to the comparative coating liquids 20 and 21, and were used for evaluation [4] to [6]. did.
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Abstract
Description
また、かかる現象は、高温高湿環境下で、長時間に亘って停止した状態に置かれた電子写真装置を用いて電子写真画像を形成した場合に特に顕著に生じる。
ここで、帯電効率の観点からは、帯電部材の表面層の膜厚は薄い方が好ましい。また、均一な厚さの表面層を形成するうえでも、表面層の膜厚は薄い方が好ましい。
そこで、本発明の目的は、弾性層からの低分子量成分の染み出しをより確実に抑制することができる表面層を備えた帯電部材を提供することにある。また、本発明の他の目的は、高品位な電子写真画像を安定して形成することのできるプロセスカートリッジ、および、電子写真装置を提供することにある。
また、本発明によれば、上記帯電部材と、該帯電部材に当接して配置されている電子写真感光体とを備え、電子写真装置の本体に着脱可能に構成されているプロセスカートリッジが提供される。
更に、本発明によれば、上記帯電部材と、該帯電部材に当接して配置されている電子写真感光体とを備える電子写真装置が提供される。
基体としては、鉄、銅、ステンレス、アルミニウム、又はニッケルの金属や、これらの合金等の基体を用いることができる。
弾性層を形成する材料としては、従来の帯電部材の弾性層に用いられているゴムや熱可塑性エラストマーを1種または2種以上を組み合わせて用いることができる。ゴムの具体例を以下に挙げる。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、またはアルキルエーテルゴム等。
表面層は、Si-O-Ta結合を有し、かつ、下記構造式(1)で示される構成単位と、下記構造式(2)で示される構成単位とを有する高分子化合物を含む。
式(1)中、R1、R2は各々独立して、構造式(3)~(6)のいずれかを示す。
Ta(OR37)(OR38)(OR39)(OR40)(OR41) ・・・(12)
上記構造式(11)中、R33は下記構造式(13)~(16)で示される構造から選ばれる何れかを示す。R34~R36は各々独立して炭素数1~4のアルキル基を示す。構造式(12)中、R37~R41は各々独立して炭素数1~9のアルキル基を示す。
上記式(17)中、R68は炭素数1~21のアルキル基、またはフェニル基を示し、R69~R71は各々独立して炭素数1~6のアルキル基を示す。また、R68がフェニル基である加水分解性シラン化合物を含む場合、R68が炭素数1~21のアルキル基である加水分解性シラン化合物と併用することが、加水分解縮合反応を通して構造が変化しても溶媒との相溶性が良好であることから、好ましい。
(1)工程
モノマーとしての式(11)で示される加水分解性シラン化合物(A)と、式(17)で示される加水分解性シラン化合物(B)と、式(12)で示される加水分解性タンタル化合物(C)とを準備する。
(2)工程
加水分解性シラン化合物(A)と加水分解性シラン化合物(B)を混合し、水(D)、アルコール(E)を添加して、加熱還流により加水分解・縮合を行い、加水分解性シラン化合物の縮合物を得る。
(3)工程
得られた液に、加水分解性タンタル化合物(C)を添加し、混合し、適宜加熱して、加水分解・縮合を行い、加水分解性シラン化合物と加水分解性タンタル化合物の縮合物(シランタンタル縮合物ともいう。)を生成させ、縮合物含有液を得る。
(4)工程
縮合物含有液に光重合開始剤(G)を添加、混合する。
加水分解性シラン化合物(A)の具体例を以下に示す。これらは1種又は2種以上を組み合わせて用いることができる。
式(20)中、Aは、式(11)で示される加水分解性シラン化合物(A)のモル数を示す。
Bは、式(17)で示される加水分解性シラン化合物(B)のモル数を示す。
Cは、式(17)で示される加水分解性タンタル化合物(C)のモル数を示す。
そして、C/(A+B)の値が0.1以上であれば、架橋密度が高く、ブリーディング効果の高い表面層を得ることができ、5.0以下であれば、表面層形成用塗料に白濁や沈殿が生じるのを抑制し、保存性を向上させることができる。更に、式(21)を満たすことが好ましい。
添加する水(D)の添加量は、加水分解性シラン化合物(A)及び(B)の合計のモル数(A+B)に対する水のモル数Dとの比、Ror(D/(A+B))が、0.3以上、6.0以下であることが好ましい。Rorは1.2以上3.0以下であることがより好ましい。
Rorが0.3以上であれば、縮合反応が充分に行われ、未反応のモノマーが残存するのを抑制し、架橋密度の高い膜が得られる。Rorが6.0以下であれば、縮合反応の速度が速く、表面層形成用塗料に白濁や沈殿が生成するのを抑制することができ、また、極性が高くなって縮合物との相溶性が低下するのを抑制することができる。アルコール(E)は、シランタンタル縮合物を相溶させるために用いられる。
アルコール(E)としては、第1級アルコール、第2級アルコール、第3級アルコール、第1級アルコールと第2級アルコールの混合系、第1級アルコールと第3級アルコールの混合系を用いることが好ましい。アルコールとして、特に、エタノール、メタノールと2-ブタノールの混合溶液、エタノールと2-ブタノールの混合溶液が縮合物との相溶性や塗工性の観点から好ましい。
光重合開始剤(G)は、シランタンタル縮合物を架橋させるために用いる。光重合開始剤(G)としては、ルイス酸あるいはブレンステッド酸のオニウム塩、カチオン重合触媒を用いることもできる。カチオン重合触媒としては、例えば、ボレート塩、イミド化合物、トリアジン化合物、アゾ化合物、過酸化物等が挙げられる。
カチオン重合触媒としては、感度、安定性及び反応性の観点から、芳香族スルホニウム塩や芳香族ヨードニウム塩が好ましい。特に好ましいカチオン重合触媒として、ビス(4-tert-ブチルフェニル)ヨードニウム塩や、式(18)で示される化合物(商品名:アデカオプトマ-SP150、旭電化工業(株)製)を挙げることができる。
低温で架橋反応を進行させることにより、塗膜から溶剤が急速に揮発するのを抑制し、塗膜に相分離、シワが発生するのを抑制し、弾性層との密着強度が高い表面層を形成することができる。弾性層との密着強力が高い表面層は、帯電部材が温湿度の変化が急激な環境下で使用され、温湿度の変化による弾性層の体積が変動しても、シワやクラックの発生を抑制することができる。その上、架橋反応の進行時に弾性層の熱劣化を抑制することができるため、製造工程における弾性層の電気的特性の低下を抑制することもできる。
ここでDCはケイ素原子に結合する総ての基に対する縮合度合いを表す指標であり、式(22)を用いて算出する。
例えば、前記した成分(A)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、加水分解性タンタル化合物(C)とを加水分解させて得られるシランタンタル縮合物は、カチオン重合可能な基としてエポキシ基を有する。このようなシランタンタル縮合物のエポキシ基は、カチオン重合触媒(図6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、TaO5/2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6中、nは1以上の整数を表す。
本発明に係る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一例を図2に示す。円筒状の電子写真感光体1は、本発明の帯電部材3(図2においてはローラ形状の帯電部材)に当接して配置されて、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。回転駆動される電子写真感光体1の表面は帯電部材3により、正または負の所定電位に均一に帯電される。次いで、スリット露光やレーザービーム走査露光等の露光手段(不図示)から出力される露光光(画像露光光)4を受けることで、電子写真感光体1の表面に、目的の画像に対応した静電潜像が形成される。
[実施例1]
<縮合物1の調製>
下記表1に示す成分を混合した後、室温で30分攪拌した。
(1)Si-O-Ta結合の有無
縮合物1について、Taの縮合状態を以下のように測定した。測定用試料として、縮合物中間体1の合成の際に用いたイオン交換水を、17O-H2O(7~9.9atm%、CIL社製)に代えた他は、縮合物1と同様にして本評価に供する縮合物1(以降、「評価用縮合物1」とする)を合成した。
得られた液状の評価用縮合物1について、核磁気共鳴装置(Avance500 BRUKER社製)を用いて17O-NMR測定を行った。その結果、図3に示すように、170~200ppmにSi-17O-Taのピークと、410~460ppmにTa-17O-Taのピークを有する基準スペクトルを得た。次いで、評価用縮合物1について17O-NMR測定を行い、得られたスペクトルから、Si-O-Ta結合の存在の有無を検出した。
上記評価[1](1)にて得た、評価用縮合物1の17O-NMRのスペクトルにおける、各ピークの積分値より、Si-O-Ta結合およびTa-O-Ta結合の数に対するTa-O-Ta結合の数の比、すなわち、(Ta-O-Ta)/{(Si-O-Ta)+(Ta-O-Ta)}を算出した。
縮合物1の25gに、光カチオン重合開始剤としての芳香族スルホニウム塩(商品名:アデカオプトマー SP-150、旭電化工業(株)製)のメチルイソブチルケトン10質量%液の2.00gを添加して、コーティング液1を調製した。
コーティング液1の安定性を、以下の基準により評価した。結果を表9に示す。
A:1ヶ月放置しても白濁・沈殿が無い状態。
B:2週間程度から白濁気味になる状態。
C:1週間程度から白濁気味になる状態。
D:合成時に白濁・沈殿を生じる状態。
以下の手順によりコーティング液1の硬化膜を形成し、その化学構造を分析し、また、縮合度(DC%)を算出した。
すなわち、脱脂した厚さ100μmのアルミニウム製シートの上にコーティング液1を塗布した。乾燥後、低圧水銀ランプ(ハリソン東芝ライティング(株)製)を用い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、コーティング液1を架橋、硬化し硬化膜を得た。得られた硬化膜をガラス板で削り取り、メノウ乳鉢を用いて粉砕し、測定用試料粉末を作製した。この試料を、核磁気共鳴装置(JMN-EX400 JEOL社)を用いて、29Si-NMRスペクトルを測定した。得られたスペクトルデータを図4に示す。検出されたスペクトルにおいて、-46~-40ppmのピークをT0成分、-55~-47ppmのピークをT1成分、-61~-54ppmのピークをT2成分、-71~-61ppmのピークをT3成分とする。ここで、T3成分とは、有機基との結合を1つ有するケイ素原子が、酸素原子を介して他のケイ素原子、または、タンタル原子との結合を3つ有する状態を示す。これらの検出値に基づき式(23)からSiに結合する加水分解官能基の縮合度を測定した。
また、試料の13C-NMRスペクトルを測定した。得られたスペクトルを図5に示す。このスペクトルから硬化膜中にエポキシ基が存在せず、総てのエポキシ基が開環したことを確認した。以上のことより、コーティング液1から形成される硬化膜において、原料のグリシドキシプロピルエトキシシラン化合物中のエポキシ基は総て開環、架橋し、且つ、式(1)中の-SiO3/2の構成単位を有していることを確認した。この評価3は、後述する実施例において、同様に確認できた。
<表面層形成用塗料1-1~1-7の調製>
上記コーティング液1を、エタノールと2-ブタノールとの混合液(エタノール:2-ブタノール=1:1(質量比))で希釈し、固形分濃度が、1.0質量%、0.1質量%、0.2質量%、0.5質量%、3.5質量%、4.0質量%、および5.0質量%の表面層形成用塗料1-1~1-7を調製した。
7本の弾性ローラ3の弾性層の周面に表面層形成用塗料1-1~1-7の各々を、リング塗布(吐出量:0.120ml/s、リング部の弾性ローラに対する移動速度:85mm/s、総吐出量:0.130ml)した。次いで、各表面層塗料の塗膜に対して、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、該塗膜を硬化させることによって表面層を形成し、帯電ローラ1-1~1-7を得た。
なお、紫外線の照射には低圧水銀ランプ(ハリソン東芝ライティング(株)製)を用いた。得られた帯電ローラ1-1~1-7について以下の評価を行った。
帯電ローラ1-1~1-7について、表面の外観を目視にて観察し、以下の基準により、その塗工性を評価した。結果を表10に示す。
A:帯電ローラの表面に全く塗工不良がない。
B:帯電ローラの表面の一部に塗工不良が生じた。
C:帯電ローラの表面の全領域に塗工不良が生じた。
帯電ローラ1-1~1-7の表面層の層厚を測定した。得られた帯電ローラの断面を、走査型透過電子顕微鏡(STEM 製品名:HD-2000、(株)日立ハイテクノロジーズ製)を用いて測定した。結果を、表10に示す。
帯電ローラ1-1~1-7を、感光体と共に一体に支持するプロセスカートリッジに組み込んだ。このとき帯電ローラには合計1kgの加重がかかるようにした。その後高温高湿下(温度40℃、湿度95%RH)に30日間放置した。次いで、当該プロセスカートリッジを、常温常湿下(温度25℃、湿度50%RH)に72時間放置した。このプロセスカートリッジを、A4サイズの紙を縦方向に出力可能なレーザービームプリンター(商品名:Color LaserJet 4700 Printer、HP社製)に装填し、電子写真画像として、黒のソリッド画像を出力した。
なお、このレーザービームプリンターの現像方式は反転現像方式であり、転写材の出力スピードは164mm/sであり、画像解像度は600dpiである。また、感光体は、支持体上に層厚19.0μmの有機感光層を有する有機電子写真感光体である。ここで、有機感光層は、支持体側から電荷発生層と変性ポリカーボネート(結着樹脂)を含有する電荷輸送層とを積層した積層型感光層であり、この電荷輸送層は電子写真感光体の表面層となっている。
また、上記レーザービームプリンターに使用したトナーは、いわゆる重合トナーであり、そのガラス転移温度は63℃、体積平均粒子径は6μmである。この重合トナーは、ワックス、荷電制御剤、色素、スチレン、ブチルアクリレートおよびエステルモノマーを含む重合性単量体系を水系媒体中で懸濁重合して得られた粒子に、シリカ微粒子および酸化チタン微粒子を外添してあるトナー粒子を含んでいる。
得られた電子写真画像における、帯電ローラの感光体との当接痕に起因する横スジの発生の有無、発生している場合にはそのスジの濃さ、および長さを下記表4に示す基準により評価した。表4に示す基準はA4縦用紙上で幅が1mm程度のスジを対象にしたときの横方向のスジの長さに基く。
<縮合物2~19の調製>
用いる原料および量を表5に記載したように変更した以外は縮合物中間体1と同様にして縮合物中間体2~11を調製した。なお、表5中の原料の略号が示す化合物種を表6に示す。
縮合物2~19を用いた以外は、上記のコーティング液1と同様にしてコーティング液2~19を調製した。そして、各コーティング液について、上記の評価[2]~[3]を行った。
コーティング液2および3を用いて、実施例1と同様にして表面層形成用塗料2-1~2-5および3-1~3-5を調製した。なお、固形分濃度は、0.1質量%、0.2質量%、1.0質量%、4.0質量%および5.0質量%の5種類とした。これらの塗料を用いて実施例1と同様にして帯電ローラ2-1~2-5及び3-1~3-5を作製し、評価[4]~[6]に供した。
コーティング液4~7を用いて、実施例1と同様にして表面層形成用塗料4-1~4-3~7-1~7-3を調製した。なお、固形分濃度は、0.5質量%、1.0質量%、および3.5質量%の3種類とした。これらの塗料を用いて実施例1と同様にして帯電ローラ4-1~4-3、5-1~5-3、6-1~6-3、および、7-1~7-3を作製し、評価[4]~[6]に供した。
コーティング液8~19を用いて、実施例1と同様にして表面層形成用塗料8~19を調製した。なお、固形分濃度は、1.0質量%とした。これらの塗料を用いて実施例1と同様にして帯電ローラ8~19を作製し、評価[4]~[6]に供した。
<比較用縮合物20の調製>
下記表8に示す組成とした以外は縮合物1と同様にして比較用縮合物20を調製した。これについて、上記評価[1]を行った。
上記比較用縮合物20を用いた以外は、コーティング液1と同様にして比較用コーティング液20を調製した。これについて、上記評価[2]及び[3]を行った。
下記表8に示すように、加水分解性シラン化合物を用いず、加水分解性タンタル化合物、水、エタノールを混合し、室温で3時間攪拌して比較用縮合物21を得た。これについて、上記評価[1]を行った。
上記の比較用縮合物21を用い、かつ、光カチオン重合開始剤を添加しない以外は、コーティング液1と同様にして比較用コーティング液21を調製した。これについて、上記評価[2]及び[3]を行った。なお、比較用コーティング液21についての評価[2]および[3]に際して、比較用コーティング液21の塗膜の硬化には、UVを用いず、温度250℃で1時間加熱することにより行った。
実施例1の表面層形成用塗料1を比較用コーティング液20および21に変えた以外は、実施例1と同様にして帯電ローラ20及び21を作製し、評価[4]~[6]に供した。
2 軸
3 帯電部材
4 露光光
5 現像手段
6 転写手段
7 クリーニング手段
8 定着手段
9 プロセスカートリッジ
10 案内手段
P 転写材
101 軸芯体(基体)
102 弾性層
103 表面層
Claims (7)
- 基体、弾性層及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-Ta結合を有し、かつ、
下記構造式(1)で示される構成単位および下記構造式(2)で示される構成単位を有している、高分子化合物を含有していることを特徴とする帯電部材:
- 前記高分子化合物における、タンタルとケイ素との原子数比(Ta/Si)が0.1以上、5.0以下である請求項1又は2に記載の帯電部材。
- 前記高分子化合物が、下記構造式(11)で示される加水分解性シラン化合物と、下記構造式(12)で示される加水分解性タンタル化合物との加水分解縮合物の架橋物である請求項1から3のいずれか一項に記載の帯電部材:
- 請求項1から5のいずれか一項に記載の帯電部材と、該帯電部材に当接して配置されている電子写真感光体とを備え、電子写真装置の本体に着脱可能に構成されていることを特徴とするプロセスカートリッジ。
- 請求項1から5のいずれか一項に記載の帯電部材と、該帯電部材に当接して配置されている電子写真感光体とを備えていることを特徴とする電子写真装置。
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EP11828322.5A EP2624062A4 (en) | 2010-09-27 | 2011-09-06 | LOADING ELEMENT, PROCESS CARTRIDGE AND ELECTRO-PHOTOGRAPHIC DEVICE |
CN201180046556.9A CN103124932B (zh) | 2010-09-27 | 2011-09-06 | 充电构件、处理盒和电子照相设备 |
KR1020137009951A KR101454137B1 (ko) | 2010-09-27 | 2011-09-06 | 대전 부재, 프로세스 카트리지 및 전자 사진 장치 |
US13/371,200 US8501325B2 (en) | 2010-09-27 | 2012-02-10 | Charging member, process cartridge, and electrophotographic apparatus |
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US (1) | US8501325B2 (ja) |
EP (1) | EP2624062A4 (ja) |
JP (1) | JP5038524B2 (ja) |
KR (1) | KR101454137B1 (ja) |
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US8447214B2 (en) | 2010-09-30 | 2013-05-21 | Canon Kabushiki Kaisha | Charging member and process for its production |
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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 |
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Publication number | Publication date |
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KR101454137B1 (ko) | 2014-10-22 |
CN103124932A (zh) | 2013-05-29 |
KR20130079548A (ko) | 2013-07-10 |
EP2624062A1 (en) | 2013-08-07 |
JP2012093727A (ja) | 2012-05-17 |
CN103124932B (zh) | 2015-03-25 |
US8501325B2 (en) | 2013-08-06 |
JP5038524B2 (ja) | 2012-10-03 |
US20120141160A1 (en) | 2012-06-07 |
EP2624062A4 (en) | 2015-10-07 |
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