Patent Application
20140017605
The present invention relates to a film having a novel structure and an apparatus including the film. The present invention also relates to an electrophotographic photosensitive member including the film as a surface layer and a process cartridge and an electrophotographic apparatus each including the electrophotographic photosensitive member.
There is a technique for controlling friction by adopting a particular surface profile. For example, in the field of industrial machine materials, PTL 1 discloses that friction between a bearing member and a shaft can be decreased by providing raised portions on the surface of the bearing member.
PTL 3 discloses that friction of a slider of a magnetic head can be decreased by providing a honeycomb texture on a surface of the slider.
In one application to an organic function member, PTL 2 discloses that asperities on a surface (outer surface) of a toner image carrier, such as an electrophotographic photosensitive member or an intermediate transfer member, can facilitate the removal of toner particles remaining on the surface and prevent a cleaning blade from becoming caught on the surface (blade curling).
PTL 4 discloses that asperities including a smooth convex protrusion on a surface of an electrophotographic photosensitive member can prevent a cleaning blade from becoming reversed.
In accordance with another technique, a member contains a lubricant to control friction.
However, asperities on the surface may be worn away by friction for a long period of time. This increases the friction coefficient of the surface.
The present invention provides a film that is resistant to an increase in the friction coefficient resulting from the wearing of asperities after long-term use and an apparatus including the film. The present invention also provides an electrophotographic photosensitive member including the film as a surface layer and a process cartridge and an electrophotographic apparatus each including the electrophotographic photosensitive member.
In accordance with a first aspect of the present invention, a film has a first portion and a second portion having different hardnesses, wherein the first portion has hardness (H1 [GPa]) in the range of 0.01 to 3 GPa as determined by a continuous stiffness measurement, and the ratio (H2/H1) of the hardness (H2 [GPa]) of the second portion as determined by the continuous stiffness measurement to the hardness (H1 [GPa]) of the first portion as determined by the continuous stiffness measurement is in the range of 1.2 to 30,
the first portion forms a first surface region of the film, and the second portion forms a second surface region of the film,
each of the first portion and the second portion extends to a depth of 75% or more of the thickness of the film, and
in a 1 mm×1 mm square region disposed on an arbitrary position of the surface of the film, the second surface region accounts for 10% to 80% by area of the square region, and the first surface region and the second surface region account for 50% or more by area of the square region.
In accordance with a second aspect of the present invention, an apparatus includes a member containing the film and a contact member configured to come into contact with a surface of the film at a certain speed.
In accordance with a third aspect of the present invention, an electrophotographic photosensitive member includes the film as a surface layer.
In accordance with a fourth aspect of the present invention, a process cartridge is detachably attachable to a main body of an electrophotographic apparatus, and the process cartridge support: an electrophotographic photosensitive member, and a cleaning unit for cleaning a surface of the electrophotographic photosensitive member. The electrophotographic photosensitive member is the electrophotographic photosensitive member according to the third aspect, and the cleaning unit has a cleaning blade configured to come into contact with a surface of the electrophotographic photosensitive member.
In accordance with a fifth aspect of the present invention, an electrophotographic apparatus comprises: an electrophotographic photosensitive member, a charging unit, an exposure unit, a developing unit, a transfer unit, and a cleaning unit for cleaning a surface of the electrophotographic photosensitive member. The electrophotographic photosensitive member is the electrophotographic photosensitive member according to the third aspect, and the cleaning unit has a cleaning blade coming into contact with the surface of the electrophotographic photosensitive member.
In the film according to the first aspect of the present invention, the first portion has a lower hardness and is more easily worn away than the second portion. Thus, repeated use of the film depresses the first portion and raises the second portion. These asperities can result in the surface area of the film in contact with a contact member being decreased and friction between the film and the contact member being decreased. Repeated use of the film wears away the first portion having low hardness rather than the second portion having high hardness. This allows the asperities including the raised second portion to be maintained such that a difference in height between the first portion and the second portion is substantially constant even with long-term use. Thus, the film can have a low friction coefficient for a long period of time.
The first portion 11 has a lower hardness than the second portion 10, and is more easily worn away than the second portion with use while the film is in contact with the contact member at a certain speed. As illustrated in
Variations in appearance caused by light scattering can be decreased by substantially equalizing the refractive index of the first portion 11 with the refractive index of the second portion 10. This can reduce the deterioration of resolution in optical members. Thus, the present invention can be suitably embodied in electrophotographic applications.
As illustrated in
A film according to an embodiment of the present invention may be manufactured by irradiating a polymer film made of a monomer of an ultraviolet-curable resin or an electron beam curable resin, such as an acrylate, an unsaturated polyester, an epoxy, an oxetane, or a vinyl ether, (and a lubricant described below, if necessary) with ultraviolet rays or an electron beam through a photomask or an electron beam mask. The first portion and the second portion may be formed by altering the cross-linking density of the polymer film so as to have different hardnesses.
Examples of the monomer of the ultraviolet-curable resin or the electron beam curable resin include, but are not limited to, the following compounds.
A film according to an embodiment of the present invention may also be manufactured by pouring a solution of polycarbonate, polyarylate, polystyrene, polyethylene, or another resin (and a lubricant described below, if necessary) into a brass pinholder having many fine micrometer- or even nanometer-size rods in a certain direction and drying the solution.
As illustrated in
The lubricant 512 may be solid or semisolid.
Examples of the solid lubricant include, but are not limited to, particles of polymerized fluorine-containing compounds, layered oxides, such as mica and talc, layered hydrocarbon compounds, such as graphite, metal sulfides, such as molybdenum disulfide, silicone, melamine cyanurate, and boron nitride. Examples of the fluorine-containing compounds include, but are not limited to, tetrafluoroethylene, chlorotrifluoroethylene, hexafluoroethylenepropylene, vinyl fluoride, vinylidene fluoride, and chlorodifluoroethylene. The solid lubricant may be tetrafluoroethylene polymer particles, that is, polytetrafluoroethylene particles.
The lubricant in the form of particles may have an average particle size in the range of 0.01 to 10 μm.
Examples of the semisolid lubricant include, but are not limited to, fluorine grease (thickener: polytetrafluoroethylene or the like, base oil: perfluoropolyether or the like), silicone grease (thickener: lithium soap or the like, base oil: phenylmethylpolysiloxane, dimethylpolysiloxane, or the like), fluorosilicone grease (thickener: lithium soap or the like, base oil: fluorosilicone or the like), ester grease (thickener: urea, lithium soap, or the like), and polyphenyl ether grease containing a polyphenyl ether, such as pentaphenyl ether or tetraphenyl ether, as a base oil (thickener: bentonite or the like).
The lubricant content of the film may be 20% by volume or less of the volume of the film. An increase in the lubricant content of the film tends to make it more difficult to make a difference in hardness between the first portion and the second portion of the film by ultraviolet or electron beam irradiation. These lubricants may be used alone or in combination or may be used in combination with a dispersant.
The size of the lubricant may be equal to or smaller than the size of the second portion. An increase in the size of the lubricant tends to make it more difficult to make a difference in hardness between the first portion and the second portion of the film by ultraviolet or electron beam irradiation.
The first portion and the second portion may have any shape so as to result in decreases in the surface area of the film in contact with a contact member and friction between the film and the contact member. In the case that the first portion forms a depressed portion and the second portion forms a raised portion, the shape may be a hole form, a pillar form, a line and space (L&S) form, a square form, or a honeycomb form. In order to decrease friction between the film and a contact member by the action of air trapped in a closed space or prevent a lubricant abrasion powder accumulated in a closed space from flowing out of the wearing surface, the closed space may be of a hole form, a square form, or a honeycomb form, particularly a honeycomb form, as viewed from the top.
As described above, in a 1 mm×1 mm square region disposed on an arbitrary position of the surface of the film, the second surface region accounts for 10% to 80% by area of the square region and preferably 20% to 70% so as to more effectively decrease friction and wearing. When the second surface region accounts for less than 10% by area, the raised second portion has too small a contact area to support the load of the contact member and may be broken. When the second surface region accounts for more than 80% by area, the second portion has a large contact area with the contact member, resulting in an insufficient friction decreasing effect and a high friction coefficient.
As described above, in a 1 mm×1 mm square region disposed on an arbitrary position of the surface of the film, the first surface region and the second surface region account for 50% or more by area, preferably 90% or more by area, more preferably 100% by area, of the square region. When the first surface region and the second surface region account for less than 50% by area, the asperities including the depressed first portion and the raised second portion cannot maintain a low friction coefficient of the film for a long period of time.
As described above, the ratio (H2/H1) of the hardness (H2 [GPa]) of the second portion as determined by a continuous stiffness measurement to the hardness (H1 [GPa]) of the first portion as determined by the continuous stiffness measurement is in the range of 1.2 to 30 and is preferably in the range of 1.5 to 30 so as to more appropriately maintain a difference in height between the first portion and the second portion. When the ratio (H2/H1) of the hardness (H2 [GPa]) of the second portion as determined by a continuous stiffness measurement to the hardness (H1 [GPa]) of the first portion as determined by the continuous stiffness measurement is less than 1.2, this results in a small difference in wearing speed and accordingly a small difference in height between the first portion and the second portion, thus producing an insufficient friction decreasing effect. When the ratio (H2/H1) of the hardness (H2 [GPa]) of the second portion as determined by a continuous stiffness measurement to the hardness (H1 [GPa]) of the first portion as determined by the continuous stiffness measurement is more than 30, this results in a large difference in height between the first portion and the second portion, and the raised second portion cannot support the load of the contact member and may be broken.
As described above, the hardness (H1 [GPa]) of the first portion as determined by the continuous stiffness measurement is in the range of 0.01 to 3 GPa. When the hardness (H1 [GPa]) of the first portion as determined by a continuous stiffness measurement is 0.01 GPa or more, a difference in height between the first portion and the second portion can be appropriately maintained. When the hardness (H1 [GPa]) of the first portion as determined by a continuous stiffness measurement is 3 GPa or less, repeated use of the film can appropriately raise the second portion.
As described above, each of the first portion and the second portion extends to a depth of 75% or more of the thickness of the film. In order to maintain the asperities including the depressed first portion and the raised second portion for a longer period of time, each of the first portion and the second portion may extend to a depth of 90% or more of the thickness of the film. Each of the first portion and the second portion may pass through the film (extend to a depth of 100% of the thickness of the film). When each of the first portion and the second portion extends to a depth of less than 75% of the thickness of the film, the asperities including the depressed first portion and the raised second portion cannot be maintained for a long period of time.
The film may have a thickness in the range of 1 to 100 μm.
In the case that the first portion becomes a space depressed portion and the second portion becomes a linear raised portion with use, the first portion and the second portion may have a size in the range of 0.1 to 50 μm. The size of the second portion may be the width of the line in the line and space form, the hole diameter in the hole form, the pillar diameter in the pillar form, or a distance between opposite apexes in the honeycomb form. For another shape, the size of the second portion may be the smallest width in a continuous region of the second portion on the surface of the film.
In the case that the first surface region is surrounded by the second surface region, the maximum size of the closed space surrounded by the raised second portion may be in the range of 0.1 to 100 μm so that trapped air can decrease friction between the film and a contact member. The term “the maximum size of the closed space”, as used herein, refers to the hole diameter for the closed space of a circular hole form or the maximum distance between opposite apexes for the closed space of a honeycomb form. For the closed space of another form, the maximum size of the closed space is the maximum distance between two parallel lines that are in contact with the periphery of the closed space.
These sizes may easily be determined with an image analyzing apparatus, such as an image analyzing apparatus manufactured by Nireco Corp. (trade name: Luzex AP).
Unless otherwise specified, the hardness of a film is measured by a continuous stiffness measurement. More specifically, the hardness of a film can be measured with an ultramicro hardness tester by the continuous stiffness measurement. The hardness of the first portion measured by the continuous stiffness measurement is herein referred to as H1 [GPa], and the hardness of the second portion measured by the continuous stiffness measurement is herein referred to as H2 [GPa]. In accordance with the continuous stiffness measurement, under the influence of micro vibration of an indenter during an indentation test, the response amplitude and the phase difference are measured as a function of time. With a continuous variation of the indentation depth, the initial gradient upon unloading is continuously determined. More specifically, a sample is subjected to an indentation loading/unloading test with a Berkovich indenter to obtain a load-indentation depth chart.
The area percentages of the first surface region and the second surface region can be calculated by detecting the deflection amplitude of a cantilever varying with a difference in surface viscoelasticity under the influence of vertical micro vibration of a sample to obtain a viscoelastic profile.
The present invention can be suitably embodied in electrophotographic applications. A film according to an embodiment of the present invention can be suitably used as a surface layer (outermost layer), such as a charge-transport layer or a protective layer, of an electrophotographic photosensitive member. In this case, the contact member may be a cleaning blade. The cleaning blade is generally made of urethane rubber.
The present invention can also be suitably embodied in functional components of automobiles. For example, a film according to an embodiment of the present invention may be applied to a surface of a windshield wiper or an openable and closable windowpane, with which a contact member comes into contact at a certain speed so as not to pass raindrops or snowflakes therebetween. A film according to an embodiment of the present invention may also be applied to the contact member that comes into contact with the windshield wiper or the windowpane.
The material and the layer structure of an electrophotographic photosensitive member will be described below.
An electrophotographic photosensitive member generally includes a support and a photosensitive layer disposed on the support.
The photosensitive layer may be a monolayer photosensitive layer that contains a charge-transport substance and a charge-generating substance or a multilayer (function-separated) photosensitive layer that includes a charge-generating sublayer containing a charge-generating substance and a charge-transport sublayer containing a charge-transport substance. The multilayer photosensitive layer has excellent electrophotographic characteristics. The multilayer photosensitive layer may be a normal photosensitive layer in which the charge-generating sublayer and the charge-transport sublayer are stacked on a support in this order and a reversed photosensitive layer in which the charge-transport sublayer and the charge-generating sublayer are stacked on the support in this order. The normal photosensitive layer has excellent electrophotographic characteristics. The charge-generating sublayer or the charge-transport sublayer may be a multilayer.
The support has high electrical conductivity (electroconductive support) and may be a metallic (alloy) support, for example, made of aluminum, an aluminum alloy, or stainless steel. The support may also be a metallic support or a plastic support each having an aluminum, aluminum alloy, or indium oxide-tin oxide alloy film formed by vacuum evaporation. The support may also be a plastic or paper support containing electroconductive particles, such as carbon black, tin oxide particles, titanium oxide particles, or silver particles, or a support made of an electroconductive binder resin. The support may be cylindrical or belt-shaped.
An electroconductive sublayer for preventing interference fringes caused by laser beam scattering or covering scratches of the support may be disposed between the support and the photosensitive layer (the charge-generating sublayer or the charge-transport sublayer) or an undercoat layer described below.
The electroconductive sublayer may be formed by applying a coating liquid for the electroconductive sublayer and drying and/or curing the coating liquid. The coating liquid for the electroconductive sublayer may be prepared by dispersing electroconductive particles, such as carbon black, metal particles, or metal oxide particles, and a binder resin in a solvent.
Examples of the binder resin for use in the coating liquid for the electroconductive sublayer include, but are not limited to, phenolic resin, polyurethane, polyamide, polyimide, polyamideimide, poly(amic acid), poly(vinyl acetal), epoxy resin, acrylic resin, melamine resin, and polyester.
Examples of the solvent for use in the coating liquid for the electroconductive sublayer include, but are not limited to, organic solvents, such as alcohols, sulfoxides, ketones, ethers, esters, aliphatic halogenated hydrocarbons, halogenated aromatic compounds, and aromatic compounds.
The electroconductive sublayer preferably has a thickness in the range of 1 to 40 μm, more preferably 2 to 20 μm.
An undercoat layer having a barrier function or an adhesive function to improve the adhesion of the photosensitive layer, improve charge injection from the support, or prevent the electrical breakdown of the photosensitive layer may be disposed between the support or the electroconductive sublayer and the photosensitive layer (the charge-generating sublayer or the charge-transport sublayer).
The undercoat layer may be formed by applying a coating liquid for the undercoat layer and drying and/or curing the coating liquid. The coating liquid for the undercoat layer may be prepared by dissolving a resin (binder resin) in a solvent.
Examples of the resin for use in the coating liquid for the undercoat layer include, but are not limited to, acrylic resin, ally resin, alkyd resin, ethylcellulose resin, an ethylene-acrylic acid copolymer, epoxy resin, casein resin, silicone resin, gelatin resin, phenolic resin, butyral resin, polyacrylate, polyacetal, polyamideimide, polyamide, poly(allyl ether), polyimide, polyurethane, polyester, polyethylene, polycarbonate, polystyrene, polysulfone, poly(vinyl alcohol), polybutadiene, polypropylene, and urea resin.
The undercoat layer may also be formed of aluminum oxide.
Examples of the solvent for use in the coating liquid for the undercoat layer include, but are not limited to, alcohols, sulfoxides, ketones, ethers, esters, aliphatic halogenated hydrocarbons, and aromatic compounds.
The undercoat layer preferably has a thickness in the range of 0.05 to 7 μm, more preferably 0.1 to 2 μm.
The charge-generating substance for use in the electrophotographic photosensitive member include, but are not limited to, azo pigments, such as monoazo, disazo, and trisazo; phthalocyanine pigments, such as metal phthalocyanine and nonmetal phthalocyanine; indigo pigments, such as indigo and thioindigo; perylene pigments, such as perylene acid anhydride and perylene acid imide; polycyclic quinone pigments, such as anthraquinone and pyrenequinone; squarylium dyes; pyrylium salts and thiapyrylium salts; triphenylmethane dyes; inorganic substances, such as selenium, selenium-tellurium, and amorphous silicon; quinacridone pigments; azulenium salt pigments; cyanine dyes; xanthene dyes; quinoneimine dyes; styryl dyes; cadmium sulfide; and zinc oxide. These charge-generating substances may be used alone or in combination.
In the case that the photosensitive layer is a multilayer photosensitive layer, examples of the binder resin for use in the charge-generating sublayer include, but are not limited to, acrylic resin, ally resin, alkyd resin, epoxy resin, diallyl phthalate resin, silicone resin, a styrene-butadiene copolymer, phenolic resin, butyral resin, benzal resin, polyacrylate, polyacetal, polyamideimide, polyamide, poly(allyl ether), polyarylate, polyimide, polyurethane, polyester, polyethylene, polycarbonate, polystyrene, polysulfone, poly(vinyl acetal), polybutadiene, polypropylene, methacrylate resin, urea resin, a vinyl chloride-vinyl acetate copolymer, and vinyl acetate resin. The binder resin may be butyral resin. These binder resins may be used alone or in combination as a mixture or a copolymer.
The charge-generating sublayer may be formed by applying a coating liquid for the charge-generating sublayer and drying and/or curing the coating liquid. The coating liquid for the charge-generating sublayer may be prepared by dispersing a charge-generating substance and a binder resin in a solvent. The dispersion may be performed with a homogenizer, an ultrasonic homogenizer, a ball mill, a sand mill, a rolling mill, a vibrating mill, an attritor, or a liquid-collision high-speed disperser. The ratio of the charge-generating substance to the binder resin may be in the range of 1:0.5 to 1:4 (mass ratio).
Examples of the solvent for use in the coating liquid for the charge-generating sublayer include, but are not limited to, organic solvents, such as alcohols, sulfoxides, ketones, ethers, esters, aliphatic halogenated hydrocarbons, halogenated aromatic compounds, and aromatic compounds.
The charge-generating sublayer preferably has a thickness in the range of 0.001 to 6 μm, more preferably 0.01 to 2 μm.
The charge-generating sublayer may contain an intensifier, an antioxidant, an ultraviolet absorber, and/or a plasticizer, if necessary.
Examples of the charge-transport substance for use in the electrophotographic photosensitive member include, but are not limited to, triarylamine compounds, hydrazone compounds, styryl compounds, stilbene compounds, pyrazoline compounds, oxazole compounds, thiazole compounds, and triarylmethane compounds. These charge-transport substances may be used alone or in combination.
In the case that the photosensitive layer is a multilayer photosensitive layer, examples of the binder resin for use in the charge-transport sublayer include, but are not limited to, acrylic resin, acrylonitrile resin, ally resin, alkyd resin, epoxy resin, silicone resin, phenolic resin, phenoxy resin, butyral resin, polyacrylamide, polyacetal, polyamideimide, polyamide, poly(allyl ether), polyarylate, polyimide, polyurethane, polyester, polyethylene, polycarbonate, polystyrene, polysulfone, poly(vinyl butyral), poly(phenylene oxide), polybutadiene, polypropylene, methacrylate resin, urea resin, poly(vinyl chloride) resin, and vinyl acetate resin. The binder resin may be polyarylate or polycarbonate. These resins may be used alone or in combination as a mixture or a copolymer.
The charge-transport sublayer may be formed by applying a coating liquid for the charge-transport sublayer and drying and/or curing the coating liquid. The coating liquid for the charge-transport sublayer may be prepared by dissolving a charge-transport substance and a binder resin in a solvent. The ratio of the charge-transport substance to the binder resin may be in the range of 2:1 to 1:2 (mass ratio).
Examples of the solvent for use in the coating liquid for the charge-transport sublayer include, but are not limited to, ketones, such as acetone and methyl ethyl ketone; esters, such as methyl acetate and ethyl acetate; aromatic hydrocarbons, such as toluene and xylene; ethers, such as 1,4-dioxane and tetrahydrofuran; and halogen-substituted hydrocarbons, such as chlorobenzene, chloroform, and carbon tetrachloride.
The charge-transport sublayer preferably has a thickness in the range of 5 to 30 μm, more preferably 6 to 25 μm.
The charge-transport sublayer may contain an antioxidant, an ultraviolet absorber, and/or a plasticizer, if necessary.
In the case that the photosensitive layer is a monolayer, the monolayer photosensitive layer may be formed by applying a coating liquid for the monolayer photosensitive layer and drying and/or curing the coating liquid. The coating liquid for the monolayer photosensitive layer may be prepared by dispersing the charge-generating substance, the charge-transport substance, and the binder resin in the solvent.
A protective layer for protecting the photosensitive layer may be disposed on the photosensitive layer. The protective layer may be formed by applying a coating liquid for the protective layer and drying and/or curing the coating liquid. The coating liquid for the protective layer may be prepared by dissolving the binder resin in a solvent.
The protective layer preferably has a thickness in the range of 0.01 to 10 μm, more preferably 0.1 to 7 μm.
These coating liquids may be applied by dip coating, spray coating, spinner coating, roller coating, Mayer bar coating, or blade coating.
In general, a contact member serving as a cleaning blade is strongly pressed against the surface of an electrophotographic photosensitive member to remove residual toner. Strongly pressing the contact member increases the rotation torque of the electrophotographic photosensitive member. Strongly pressing the contact member is likely to destroy asperities (particularly raised portions) formed on the surface of the electrophotographic photosensitive member.
A film according to an embodiment of the present invention can be used as a surface layer of an electrophotographic photosensitive member to decrease friction between the electrophotographic photosensitive member and a contact member and consequently decrease the rotation torque of the electrophotographic photosensitive member. A film according to an embodiment of the present invention used as a surface layer of an electrophotographic photosensitive member can also retain asperities on the surface for a long period of time. The asperities can result in a decrease in friction between the electrophotographic photosensitive member and a contact member and prevent cleaning blade from becoming caught on the surface layer (blade curling).
In
The rotating surface of the electrophotographic photosensitive member 1201 is positively or negatively charged by a charging unit 1203 and is then exposed to exposure light (image exposure light) 1204 emitted from an exposure unit (not shown). Thus, an electrostatic latent image of a target image is formed on the surface of the electrophotographic photosensitive member 1201. The charging unit may be a corona charging unit including a corotron or a scorotron or a contact charging unit including a roller, a brush, or a film. The voltage applied to the charging unit may be a direct-current voltage alone or a direct-current voltage on which an alternating voltage is superimposed. The exposure unit may be a slit exposure unit or a laser beam scanning exposure unit.
The electrostatic latent image formed on the surface of the electrophotographic photosensitive member 1201 is developed with toner of the developing unit 1205 to form a toner image. The development involves the contact or noncontact of magnetic or nonmagnetic single-component or two-component toner. Examples of the toner include, but are not limited to, polymerized toner manufactured by suspension polymerization or emulsion polymerization and spheroidized toner manufactured by mechanical grinding or spheroidizing. The toner may have a weight average particle size in the range of 4 to 7 μm and an average circularity in the range of 0.95 to 0.99.
The toner image formed on the surface of the electrophotographic photosensitive member 1201 is transferred to a medium (such as a paper sheet) 1207 by a transfer unit 1206. The medium 1207 is fed by a medium supply unit (not shown) between the electrophotographic photosensitive member 1201 and the transfer unit 1206 (contact portion) in synchronism with the rotation of the electrophotographic photosensitive member 1201.
The medium 1207 to which the toner image has been transferred is separated from the surface of the electrophotographic photosensitive member 1201. The toner image is then fixed by a fixing unit 1208. The image-formed medium (print or copy) is then output from the electrophotographic apparatus.
After the toner image has been transferred to the medium, residual toner on the surface of the electrophotographic photosensitive member 1201 is removed with a cleaning blade 1209 of a cleaning unit. The electricity on the surface of the electrophotographic photosensitive member 1201 is then removed with preexposure light 1210 emitted from a preexposure unit (not shown). The electrophotographic photosensitive member 1201 is then used in the next image forming.
Components selected from the electrophotographic photosensitive member 1201, the charging unit 1203, the developing unit 1205, the transfer unit 1206, and the cleaning unit (cleaning blade 1209) may be housed in a container as a process cartridge. The process cartridge may be detachably attached in a main body of an electrophotographic apparatus. In
Although the present invention will be further described in the following examples, the present invention is not limited to these examples.
An ultramicro hardness tester manufactured by MTS Systems Corp. (trade name: Nano Indenter DCM) was used in the measurement of hardness by the continuous stiffness measurement. The continuous stiffness measurement was performed with a Berkovich indenter made of diamond at room temperature (25° C.) in the atmosphere.
The area percentage of the second surface region was measured with a scanning probe microscope manufactured by SII NanoTechnology Inc. (trade name: S-image).
A photosensitive silicone polymer serving as a negative photoresist material manufactured by Shin-Etsu Chemical Co., Ltd. (trade name: SINR-3170PX) was applied to a silicon wafer by spinner coating to form a coating film. The coating film was then irradiated twice with ultraviolet rays. The first ultraviolet irradiation was performed over the entire surface of the coating film. The second ultraviolet irradiation was performed using a photomask having a line width of 4 μm and a space width of 4 μm. The first and second ultraviolet irradiances and irradiation times were determined such that the ratio of the hardness of a second portion (high hardness portion) to the hardness of a first portion (low hardness portion) was approximately 1.5 and that the hardness of the first portion (low hardness portion) was approximately 0.15 GPa. The coating film was then dried at 90° C. for 2 minutes. The dried film had a thickness of 17 μm.
In a 1 mm×1 mm square region disposed on an arbitrary position of the surface of the film, a second surface region formed of the second portion (high hardness portion) accounted for 51% by area of the square region, and a first surface region formed of the first portion (low hardness portion) and the second surface region accounted for 100% by area of the square region. The ratio of the hardness of the second portion (high hardness portion) to the hardness of the first portion (low hardness portion) was 1.6, and the hardness of the first portion (low hardness portion) was 0.14 GPa. Both the first portion (low hardness portion) and the second portion (high hardness portion) passed through the film.
A film was prepared in the same manner as in Example 1-1 except that the first and second ultraviolet irradiances and irradiation times were determined such that the ratio of the hardness of the second portion (high hardness portion) to the hardness of the first portion (low hardness portion) was approximately 1.2 and that the hardness of the first portion (low hardness portion) was approximately 0.15 GPa. The dried film had a thickness of 16 μm.
In a 1 mm×1 mm square region disposed on an arbitrary position of the surface of the film, a second surface region formed of the second portion (high hardness portion) accounted for 53% by area of the square region, and a first surface region formed of the first portion (low hardness portion) and the second surface region accounted for 100% by area of the square region. The ratio of the hardness of the second portion (high hardness portion) to the hardness of the first portion (low hardness portion) was 1.2, and the hardness of the first portion (low hardness portion) was 0.16 GPa. Both the first portion (low hardness portion) and the second portion (high hardness portion) passed through the film.
A coating liquid for a charge-transport layer having the following composition was applied to a 100 mm×100 mm×0.75 mm aluminum sheet by Mayer bar coating and was dried to form the charge-transport layer having a thickness of 20 μm.
Coating Liquid for the Charge-Transport Layer
Bisphenol Z polycarbonate: 10 parts by mass
Compound having the following structural formula (101) (charge-transport substance): 9 parts by mass
Chlorobenzene: 100 parts by mass
A coating liquid for a surface layer having the following composition was applied to the charge-transport layer by spray coating to form a coating film having a thickness of 5 μm.
Coating Liquid for the Surface Layer
Compound having the structural formula (28) (radical polymerizable compound having a charge-transport structure): 10 parts by mass
Trimethylolpropane triacrylate: 10 parts by mass 2,2-dimethoxy-1,2-diphenylethane-1-one
(photopolymerization initiator, trade name: IRGACURE 651, manufactured by BASF): 1 part by mass
Chlorobenzene: 100 parts by mass
The coating film was then irradiated twice with ultraviolet rays. The first ultraviolet irradiation was performed over the entire surface of the coating film. The second ultraviolet irradiation was performed using a photomask having a line width of 4 μm and a space width of 4 μm. The first and second ultraviolet irradiances and irradiation times were determined such that the ratio of the hardness of a second portion (high hardness portion) to the hardness of a first portion (low hardness portion) was approximately 10 and that the hardness of the first portion (low hardness portion) was approximately 0.15 GPa. The coating film was then dried at 90° C. for 2 minutes. The dried surface layer (film) had a thickness of 5 μm.
In a 1 mm×1 mm square region disposed on an arbitrary position of the surface of the surface layer (film), a second surface region formed of the second portion (high hardness portion) accounted for 51% by area of the square region, and a first surface region formed of the first portion (low hardness portion) and the second surface region accounted for 100% by area of the square region. The ratio of the hardness of the second portion (high hardness portion) to the hardness of the first portion (low hardness portion) was 8.6, and the hardness of the first portion (low hardness portion) was 0.14 GPa. Both the first portion (low hardness portion) and the second portion (high hardness portion) passed through the film.
A coating liquid for a charge-transport layer having the following composition was applied to a 100 mm×100 mm×0.75 mm aluminum sheet by Mayer bar coating and was dried to form the charge-transport layer having a thickness of 20 μm.
Coating Liquid for the Charge-Transport Layer
Bisphenol Z polycarbonate: 10 parts by mass
Compound having the structural formula (101) (charge-transport substance): 9 parts by mass
Chlorobenzene: 100 parts by mass
A coating liquid for a surface layer having the following composition was applied to the charge-transport layer by spray coating to form a coating film having a thickness of 5 μm.
Coating Liquid for the Surface Layer
Compound having the structural formula (28) (radical polymerizable compound having a charge-transport structure): 10 parts by mass
Methyl ethyl ketone: 100 parts by mass
The coating film was then irradiated twice with an electron beam. The first electron beam irradiation was performed over the entire surface of the coating film. The second electron beam irradiation was performed using a metal mask having a line width of 4 μm and a space width of 4 μm. The electron beam irradiation was performed at an accelerating voltage of 30 kV under nitrogen purge. The first and second electron beam doses and irradiation times were determined such that the ratio of the hardness of a second portion (high hardness portion) to the hardness of a first portion (low hardness portion) was approximately 30 and that the hardness of the first portion (low hardness portion) was approximately 0.15 GPa. The coating film was then dried at 90° C. for 2 minutes. The dried surface layer (film) had a thickness of 5 μm.
In a 1 mm×1 mm square region disposed on an arbitrary position of the surface of the surface layer (film), a second surface region formed of the second portion (high hardness portion) accounted for 50% by area of the square region, and a first surface region formed of the first portion (low hardness portion) and the second surface region accounted for 100% by area of the square region. The ratio of the hardness of the second portion (high hardness portion) to the hardness of the first portion (low hardness portion) was 27.3, and the hardness of the first portion (low hardness portion) was 0.15 GPa. Both the first portion (low hardness portion) and the second portion (high hardness portion) passed through the film.
A film was prepared in the same manner as in Example 1-1 except that the ultraviolet irradiances and irradiation times were determined such that the ratio of the hardness of the second portion (high hardness portion) to the hardness of the first portion (low hardness portion) was approximately 1.5 and that the hardness of the first portion (low hardness portion) was approximately 0.05 GPa. The dried film had a thickness of 15 μm.
In a 1 mm×1 mm square region disposed on an arbitrary position of the surface of the film, a second surface region formed of the second portion (high hardness portion) accounted for 50% by area of the square region, and a first surface region formed of the first portion (low hardness portion) and the second surface region accounted for 100% by area of the square region. The ratio of the hardness of the second portion (high hardness portion) to the hardness of the first portion (low hardness portion) was 1.5, and the hardness of the first portion (low hardness portion) was 0.05 GPa. Both the first portion (low hardness portion) and the second portion (high hardness portion) passed through the film.
A film was prepared in the same manner as in Example 1-1 except that the ultraviolet irradiances and irradiation times were determined such that the ratio of the hardness of the second portion (high hardness portion) to the hardness of the first portion (low hardness portion) was approximately 1.7 and that the hardness of the first portion (low hardness portion) was approximately 0.50 GPa. The dried film had a thickness of 16 μm.
In a 1 mm×1 mm square region disposed on an arbitrary position of the surface of the film, a second surface region formed of the second portion (high hardness portion) accounted for 49% by area of the square region, and a first surface region formed of the first portion (low hardness portion) and the second surface region accounted for 100% by area of the square region. The ratio of the hardness of the second portion (high hardness portion) to the hardness of the first portion (low hardness portion) was 1.7, and the hardness of the first portion (low hardness portion) was 0.51 GPa. Both the first portion (low hardness portion) and the second portion (high hardness portion) passed through the film.
A film was prepared in the same manner as in Example 1-1 except that a photomask having a line width of 20 μm and a space width of 20 μm was used in the second ultraviolet irradiation. The dried film had a thickness of 17 μm.
In a 1 mm×1 mm square region disposed on an arbitrary position of the surface of the film, a second surface region formed of the second portion (high hardness portion) accounted for 51% by area of the square region, and a first surface region formed of the first portion (low hardness portion) and the second surface region accounted for 100% by area of the square region. The ratio of the hardness of the second portion (high hardness portion) to the hardness of the first portion (low hardness portion) was 1.6, and the hardness of the first portion (low hardness portion) was 0.13 GPa. Both the first portion (low hardness portion) and the second portion (high hardness portion) passed through the film.
A film was prepared in the same manner as in Example 1-1 except that a photomask having a line width of 4 μm and a space width of 22.7 μm was used in the second ultraviolet irradiation. The dried film had a thickness of 16 μm.
In a 1 mm×1 mm square region disposed on an arbitrary position of the surface of the film, a second surface region formed of the second portion (high hardness portion) accounted for 16% by area of the square region, and a first surface region formed of the first portion (low hardness portion) and the second surface region accounted for 100% by area of the square region. The ratio of the hardness of the second portion (high hardness portion) to the hardness of the first portion (low hardness portion) was 1.7, and the hardness of the first portion (low hardness portion) was 0.14 GPa. Both the first portion (low hardness portion) and the second portion (high hardness portion) passed through the film.
A film was prepared in the same manner as in Example 1-1 except that a photomask having a line width of 4 μm and a space width of 1.3 μm was used in the second ultraviolet irradiation. The dried film had a thickness of 17 μm.
In a 1 mm×1 mm square region disposed on an arbitrary position of the surface of the film, a second surface region formed of the second portion (high hardness portion) accounted for 77% by area of the square region, and a first surface region formed of the first portion (low hardness portion) and the second surface region accounted for 100% by area of the square region. The ratio of the hardness of the second portion (high hardness portion) to the hardness of the first portion (low hardness portion) was 1.7, and the hardness of the first portion (low hardness portion) was 0.14 GPa. Both the first portion (low hardness portion) and the second portion (high hardness portion) passed through the film.
A film was prepared in the same manner as in Example 1-3 except that the amount of photopolymerization initiator in the coating liquid for the surface layer was 3 parts by mass and that the ultraviolet irradiances and irradiation times were determined such that the ratio of the hardness of the second portion (high hardness portion) to the hardness of the first portion (low hardness portion) was approximately 1.5, the hardness of the first portion (low hardness portion) was approximately 0.15 GPa, and the length of the second portion (high hardness portion) extending in the thickness direction of the film was approximately 4 μm. The dried film had a thickness of 5 μm.
In a 1 mm×1 mm square region disposed on an arbitrary position of the surface of the film, a second surface region formed of the second portion (high hardness portion) accounted for 50% by area of the square region, and a first surface region formed of the first portion (low hardness portion) and the second surface region accounted for 100% by area of the square region. The ratio of the hardness of the second portion (high hardness portion) to the hardness of the first portion (low hardness portion) was 1.6, and the hardness of the first portion (low hardness portion) was 0.14 GPa. The first portion (low hardness portion) passed through the film, and the second portion (high hardness portion) extended to a depth of 75% of the thickness of the film.
A film was prepared in the same manner as in Example 1-1 except that the ultraviolet irradiances and irradiation times were determined such that the hardness of the surface of the film after the first ultraviolet irradiation was approximately 0.22 GPa, and the second ultraviolet irradiation was not performed. The dried film had a thickness of 17 μm.
The first portion and the second portion had the same hardness in the resulting film. The surface of the film had hardness of 0.22 GPa.
A film was prepared in the same manner as in Example 1-1 except that the ultraviolet irradiances and irradiation times were determined such that the hardness of the surface of the film after the first ultraviolet irradiation was approximately 0.15 GPa, and the second ultraviolet irradiation was not performed. The dried film had a thickness of 17 μm.
The first portion and the second portion had the same hardness in the resulting film. The surface of the film had hardness of 0.15 GPa.
A polycarbonate substrate that has a diameter of 81 mm and a thickness of 1 mm and has a circular opening having a diameter of 51 mm at the center of the substrate was heated to 100° C. with a 85 mm×85 mm×0.8 mm nickel stamper mold that has a pattern having a line width of 4 μm, a space width of 4 μm, and a height difference between the line and the space of 2 μm, which was heated to 190° C. The pattern of the stamper mold was transferred to the polycarbonate substrate at a load of 6500 N for 5 minutes.
The first portion and the second portion had the same hardness in the resulting film. The surface of the film had hardness of 0.18 GPa.
A film was prepared in the same manner as in Example 1-1 except that a photomask having a line width of 500 μm and a space width of 2000 μm (2 mm) was used in the second ultraviolet irradiation. The dried film had a thickness of 19 μm.
In some 1 mm×1 mm square regions on the surface of the film, a second surface region formed of the second portion (high hardness portion) accounted for 100% by area of the square region. The ratio of the hardness of the second portion (high hardness portion) to the hardness of the first portion (low hardness portion) was 1.5, and the hardness of the first portion (low hardness portion) was 0.19 GPa. Both the first portion (low hardness portion) and the second portion (high hardness portion) passed through the film.
A film was prepared in the same manner as in Example 1-1 except that the ultraviolet irradiances and irradiation times were determined such that the ratio of the hardness of the second portion (high hardness portion) to the hardness of the first portion (low hardness portion) was approximately 1.1 and that the hardness of the first portion (low hardness portion) was approximately 0.15 GPa. The dried film had a thickness of 16 μm.
In a 1 mm×1 mm square region disposed on an arbitrary position of the surface of the film, a second surface region formed of the second portion (high hardness portion) accounted for 51% by area of the square region, and a first surface region formed of the first portion (low hardness portion) and the second surface region accounted for 100% by area of the square region. The ratio of the hardness of the second portion (high hardness portion) to the hardness of the first portion (low hardness portion) was 1.1, and the hardness of the first portion (low hardness portion) was 0.15 GPa. Both the first portion (low hardness portion) and the second portion (high hardness portion) passed through the film.
A film was prepared in the same manner as in Example 1-1 except that the ultraviolet irradiances and irradiation times were determined such that the ratio of the hardness of the second portion (high hardness portion) to the hardness of the first portion (low hardness portion) was approximately 35 and that the hardness of the first portion (low hardness portion) was approximately 0.15 GPa. The dried film had a thickness of 15 μm.
In a 1 mm×1 mm square region disposed on an arbitrary position of the surface of the film, a second surface region formed of the second portion (high hardness portion) accounted for 51% by area of the square region, and a first surface region formed of the first portion (low hardness portion) and the second surface region accounted for 100% by area of the square region. The ratio of the hardness of the second portion (high hardness portion) to the hardness of the first portion (low hardness portion) was 34.5, and the hardness of the first portion (low hardness portion) was 0.15 GPa. Both the first portion (low hardness portion) and the second portion (high hardness portion) passed through the film.
A film was prepared in the same manner as in Example 1-1 except that a photomask having a line width of 4 μm and a space width of 76 μm was used in the second ultraviolet irradiation. The dried film had a thickness of 17 μm.
In a 1 mm×1 mm square region disposed on an arbitrary position of the surface of the film, a second surface region formed of the second portion (high hardness portion) accounted for 6% by area of the square region, and a first surface region formed of the first portion (low hardness portion) and the second surface region accounted for 100% by area of the square region. The ratio of the hardness of the second portion (high hardness portion) to the hardness of the first portion (low hardness portion) was 1.6, and the hardness of the first portion (low hardness portion) was 0.15 GPa. Both the first portion (low hardness portion) and the second portion (high hardness portion) passed through the film.
A film was prepared in the same manner as in Example 1-1 except that a photomask having a line width of 4 μm and a space width of 0.7 μm was used in the second ultraviolet irradiation. The dried film had a thickness of 17 μm.
In a 1 mm×1 mm square region disposed on an arbitrary position of the surface of the film, a second surface region formed of the second portion (high hardness portion) accounted for 85% by area of the square region, and a first surface region formed of the first portion (low hardness portion) and the second surface region accounted for 100% by area of the square region. The ratio of the hardness of the second portion (high hardness portion) to the hardness of the first portion (low hardness portion) was 1.6, and the hardness of the first portion (low hardness portion) was 0.15 GPa. Both the first portion (low hardness portion) and the second portion (high hardness portion) passed through the film.
A film was prepared in the same manner as in Example 1-3 except that the amount of photopolymerization initiator in the coating liquid for the surface layer was 5 parts by mass and that the ultraviolet irradiances and irradiation times were determined such that the ratio of the hardness of the second portion (high hardness portion) to the hardness of the first portion (low hardness portion) was approximately 1.5, the hardness of the first portion (low hardness portion) was approximately 0.15 GPa, and the length of the second portion (high hardness portion) extending in the thickness direction of the film was approximately 0.2 μm. The dried film had a thickness of 5 μm.
In a 1 mm×1 mm square region disposed on an arbitrary position of the surface of the film, a second surface region formed of the second portion (high hardness portion) accounted for 50% by area of the square region, and a first surface region formed of the first portion (low hardness portion) and the second surface region accounted for 100% by area of the square region. The ratio of the hardness of the second portion (high hardness portion) to the hardness of the first portion (low hardness portion) was 1.7, and the hardness of the first portion (low hardness portion) was 0.14 GPa. The first portion (low hardness portion) passed through the film, and the second portion (high hardness portion) extended to a depth of 4% of the thickness of the film.
The following solution 1 and solution 2 were separately charged in two solution tanks of an ink jet applicator (trade name: PixelJet 128, manufactured by Trident). This ink jet applicator has two liquid ejection units, each of which has a plurality of nozzles.
The solution 1 contained the following components.
Fluorocarbon siloxane rubber composition (trade name: Sifel 610, manufactured by Shin-Etsu Chemical Co., Ltd.): 75% by mass
Fluorinated solvent (trade name: X-70-580, manufactured by Shin-Etsu Chemical Co., Ltd.): 25% by mass
—Solution 2—
The solution 2 contained the following components.
Fluorocarbon siloxane rubber composition (trade name: Sifel 650, manufactured by Shin-Etsu Chemical Co., Ltd.): 75% by mass
Fluorinated solvent (trade name: X-70-580, manufactured by Shin-Etsu Chemical Co., Ltd.): 25% by mass
Twenty nozzles of each of the two liquid ejection units were used. A square polyimide sheet (100 mm×100 mm×1 mm) was placed 10 mm apart from the nozzle ejection surface. The solution 1 and the solution 2 of the two liquid ejection units were ejected onto the polyimide sheet from one side to the opposite side of the polyimide sheet at a driving frequency of 2.6 kHz and a liquid ejection unit traveling speed of 450 mm/min such that each of the solution 1 and the solution 2 formed a line having a width of 4 μm on the polyimide sheet, the line of the solution 1 was contiguous to the line of the solution 2, and the line of the solution 1 and the line of the solution 2 were parallel to a side of the polyimide sheet. This process was repeatedly performed to form lines of the solution 1 and lines of the solution 2 each having a width of 4 μm disposed contiguous to and parallel to each other, forming a coating film on the polyimide sheet as illustrated in
In a 1 mm×1 mm square region disposed on an arbitrary position of the surface of the film, a second surface region formed of the second portion (high hardness portion) accounted for 50% by area of the square region, and a first surface region formed of the first portion (low hardness portion) and the second surface region accounted for 100% by area of the square region. The ratio of the hardness of the second portion (high hardness portion) to the hardness of the first portion (low hardness portion) was 2.8, and the hardness of the first portion (low hardness portion) was 0.00038 GPa. Both the first portion (low hardness portion) and the second portion (high hardness portion) passed through the film.
Table 1 summarizes Examples 1-1 to 1-10 and Comparative Examples 1-1 to 1-10.
A photosensitive silicone polymer serving as a negative photoresist material manufactured by Shin-Etsu Chemical Co., Ltd. (trade name: SINR-3170PX) was applied to a silicon wafer by spinner coating to form a coating film. The coating film was then irradiated twice with ultraviolet rays. The first ultraviolet irradiation was performed over the entire surface of the coating film. The second ultraviolet irradiation was performed using a honeycomb photomask in which each of the regular hexagons had a side length of 10 μm and a wall thickness of 2 μm. The first and second ultraviolet irradiances and irradiation times were determined such that the ratio of the hardness of a second portion (high hardness portion) to the hardness of a first portion (low hardness portion) was approximately 1.6 and that the hardness of the second portion (high hardness portion) was approximately 0.22 GPa. The coating film was then dried at 90° C. for 2 minutes. The dried film had a thickness of 17 μm.
In a 1 mm×1 mm square region disposed on an arbitrary position of the surface of the film, a second surface region formed of the second portion (high hardness portion) accounted for 23% by area of the square region, and a first surface region formed of the first portion (low hardness portion) and the second surface region accounted for 100% by area of the square region. The ratio of the hardness of the second portion (high hardness portion) to the hardness of the first portion (low hardness portion) was 1.6, the hardness of the first portion (low hardness portion) was 0.14 GPa, and the hardness of the second portion (high hardness portion) was 0.22 GPa. Both the first portion (low hardness portion) and the second portion (high hardness portion) passed through the film.
A film was prepared in the same manner as in Example 2-1 except that a honeycomb photomask in which each of the regular hexagons had a side length of 10 μm and a wall thickness of 1 μm was used in the second ultraviolet irradiation. The dried film had a thickness of 18 μm.
In a 1 mm×1 mm square region disposed on an arbitrary position of the surface of the film, a second surface region formed of the second portion (high hardness portion) accounted for 12% by area of the square region, and a first surface region formed of the first portion (low hardness portion) and the second surface region accounted for 100% by area of the square region. The ratio of the hardness of the second portion (high hardness portion) to the hardness of the first portion (low hardness portion) was 1.7, the hardness of the first portion (low hardness portion) was 0.14 (0.135) GPa, and the hardness of the second portion (high hardness portion) was 0.23 GPa. Both the first portion (low hardness portion) and the second portion (high hardness portion) passed through the film.
A film was prepared in the same manner as in Example 2-1 except that a honeycomb photomask in which each of the regular hexagons had a side length of 10 μm and a wall thickness of 6 μm was used in the second ultraviolet irradiation. The dried film had a thickness of 17 μm.
In a 1 mm×1 mm square region disposed on an arbitrary position of the surface of the film, a second surface region formed of the second portion (high hardness portion) accounted for 69% by area of the square region, and a first surface region formed of the first portion (low hardness portion) and the second surface region accounted for 100% by area of the square region. The ratio of the hardness of the second portion (high hardness portion) to the hardness of the first portion (low hardness portion) was 1.6, the hardness of the first portion (low hardness portion) was 0.14 GPa, and the hardness of the second portion (high hardness portion) was 0.23 GPa. Both the first portion (low hardness portion) and the second portion (high hardness portion) passed through the film.
A film was prepared in the same manner as in Example 2-1 except that the first and second ultraviolet irradiances and irradiation times were determined such that the ratio of the hardness of the second portion (high hardness portion) to the hardness of the first portion (low hardness portion) was approximately 1.2 and that the hardness of the second portion (high hardness portion) was approximately 0.19 GPa. The dried film had a thickness of 16 μm.
In a 1 mm×1 mm square region disposed on an arbitrary position of the surface of the film, a second surface region formed of the second portion (high hardness portion) accounted for 23% by area of the square region, and a first surface region formed of the first portion (low hardness portion) and the second surface region accounted for 100% by area of the square region. The ratio of the hardness of the second portion (high hardness portion) to the hardness of the first portion (low hardness portion) was 1.2, the hardness of the first portion (low hardness portion) was 0.15 GPa, and the hardness of the second portion (high hardness portion) was 0.18 GPa. Both the first portion (low hardness portion) and the second portion (high hardness portion) passed through the film.
A coating liquid for a charge-transport layer having the following composition was applied to a 100 mm×100 mm×0.75 mm aluminum sheet by Mayer bar coating and was dried to form the charge-transport layer having a thickness of 20 μm.
Bisphenol Z polycarbonate: 10 parts by mass
Compound having the structural formula (101) (charge-transport substance): 9 parts by mass
Chlorobenzene: 100 parts by mass
A coating liquid for a surface layer having the following composition was applied to the charge-transport layer by spray coating to form a coating film having a thickness of 5 μm.
Coating Liquid for the Surface Layer
Compound having the structural formula (14) (radical polymerizable compound having a charge-transport structure): 10 parts by mass
Trimethylolpropane triacrylate: 10 parts by mass
Photopolymerization initiator: 1 part by mass
Chlorobenzene: 100 parts by mass
The coating film was then irradiated twice with ultraviolet rays. The first ultraviolet irradiation was performed over the entire surface of the coating film. The second ultraviolet irradiation was performed using a honeycomb photomask in which each of the regular hexagons had a side length of 10 μm and a wall thickness of 2 μm. The first and second ultraviolet irradiances and irradiation times were determined such that the ratio of the hardness of a second portion (high hardness portion) to the hardness of a first portion (low hardness portion) was approximately 30 and that the hardness of the second portion (high hardness portion) was approximately 0.30 GPa. The coating film was then dried at 90° C. for 2 minutes. The dried surface layer (film) had a thickness of 5 μm.
In a 1 mm×1 mm square region disposed on an arbitrary position of the surface of the surface layer (film), a second surface region formed of the second portion (high hardness portion) accounted for 23% by area of the square region, and a first surface region formed of the first portion (low hardness portion) and the second surface region accounted for 100% by area of the square region. The ratio of the hardness of the second portion (high hardness portion) to the hardness of the first portion (low hardness portion) was 26.8, the hardness of the first portion (low hardness portion) was 0.01 (0.01044) GPa, and the hardness of the second portion (high hardness portion) was 0.28 GPa. Both the first portion (low hardness portion) and the second portion (high hardness portion) passed through the film.
A film was prepared in the same manner as in Example 2-1 except that the first and second ultraviolet irradiances and irradiation times were determined such that the ratio of the hardness of the second portion (high hardness portion) to the hardness of the first portion (low hardness portion) was approximately 1.4 and that the hardness of the second portion (high hardness portion) was approximately 0.02 GPa. The dried film had a thickness of 17 μm.
In a 1 mm×1 mm square region disposed on an arbitrary position of the surface of the film, a second surface region formed of the second portion (high hardness portion) accounted for 23% by area of the square region, and a first surface region formed of the first portion (low hardness portion) and the second surface region accounted for 100% by area of the square region. The ratio of the hardness of the second portion (high hardness portion) to the hardness of the first portion (low hardness portion) was 1.4, the hardness of the first portion (low hardness portion) was 0.01 (0.014) GPa, and the hardness of the second portion (high hardness portion) was 0.02 GPa. Both the first portion (low hardness portion) and the second portion (high hardness portion) passed through the film.
A coating liquid for a charge-transport layer having the following composition was applied to a 100 mm×100 mm×0.75 mm aluminum sheet by Mayer bar coating and was dried to form the charge-transport layer having a thickness of 20 μm.
Bisphenol Z polycarbonate: 10 parts by mass
Compound having the structural formula (101) (charge-transport substance): 10 parts by mass
Chlorobenzene: 100 parts by mass
A coating liquid for a surface layer having the following composition was applied to the charge-transport layer by spray coating to form a coating film having a thickness of 5 μm.
Radical polymerizable compound having a charge-transport structure (exemplary compound No. 9 (Compound having the structural formula (9))): 10 parts by mass
Methyl ethyl ketone: 100 parts by mass
The coating film was then irradiated twice with an electron beam. The first electron beam irradiation was performed over the entire surface of the coating film. The second electron beam irradiation was performed using a honeycomb electron beam mask in which each of the regular hexagons had a side length of 10 μm and a wall thickness of 2 μm. The electron beam irradiation was performed at an accelerating voltage of 30 kV under nitrogen purge. The first and second electron beam doses and irradiation times were determined such that the ratio of the hardness of a second portion (high hardness portion) to the hardness of a first portion (low hardness portion) was approximately 1.6 and that the hardness of the second portion (high hardness portion) was approximately 5.00 GPa. The coating film was then dried at 90° C. for 2 minutes. The dried surface layer (film) had a thickness of 5 μm.
In a 1 mm×1 mm square region disposed on an arbitrary position of the surface of the surface layer (film), a second surface region formed of the second portion (high hardness portion) accounted for 23% by area of the square region, and a first surface region formed of the first portion (low hardness portion) and the second surface region accounted for 100% by area of the square region. The ratio of the hardness of the second portion (high hardness portion) to the hardness of the first portion (low hardness portion) was 1.8, the hardness of the first portion (low hardness portion) was 2.69 GPa, and the hardness of the second portion (high hardness portion) was 4.84 GPa.
A film was prepared in the same manner as in Example 2-1 except that a photomask having a hole form in which each of the holes had a diameter of 0.2 μm and a center-to-center distance of 0.4 μm was used in the second ultraviolet irradiation. The dried film had a thickness of 17 μm.
In a 1 mm×1 mm square region disposed on an arbitrary position of the surface of the film, a second surface region formed of the second portion (high hardness portion) accounted for 21% by area of the square region, and a first surface region formed of the first portion (low hardness portion) and the second surface region accounted for 100% by area of the square region. The ratio of the hardness of the second portion (high hardness portion) to the hardness of the first portion (low hardness portion) was 1.7, the hardness of the first portion (low hardness portion) was 0.13 GPa, and the hardness of the second portion (high hardness portion) was 0.22 GPa. Both the first portion (low hardness portion) and the second portion (high hardness portion) passed through the film.
A film was prepared in the same manner as in Example 2-1 except that a honeycomb photomask in which each of the regular hexagons had a side length of 50 μm and a wall thickness of 10 μm was used in the second ultraviolet irradiation. The dried film had a thickness of 18 μm.
In a 1 mm×1 mm square region disposed on an arbitrary position of the surface of the film, a second surface region formed of the second portion (high hardness portion) accounted for 23% by area of the square region, and a first surface region formed of the first portion (low hardness portion) and the second surface region accounted for 100% by area of the square region. The ratio of the hardness of the second portion (high hardness portion) to the hardness of the first portion (low hardness portion) was 1.6, the hardness of the first portion (low hardness portion) was 0.14 GPa, and the hardness of the second portion (high hardness portion) was 0.23 GPa. Both the first portion (low hardness portion) and the second portion (high hardness portion) passed through the film.
A film was prepared in the same manner as in Example 2-1 except that the first ultraviolet irradiation over the entire surface of the coating film was not performed and that, after ultraviolet irradiation was performed using a honeycomb photomask in which each of the regular hexagons had a side length of 10 μm and a wall thickness of 2 μm, a non-irradiated area was etched. The dried film had a thickness of 17 μm.
The first portion and the second portion had the same hardness in the resulting film. The surface of the film had hardness of 0.24 GPa. The film had asperities having a height of 17 μm.
A film was prepared in the same manner as in Example 2-1 except that a honeycomb photomask in which each of the regular hexagons had a side length of 10 μm and a wall thickness of 0.5 μm was used in the second ultraviolet irradiation. The dried film had a thickness of 17 μm.
In a 1 mm×1 mm square region disposed on an arbitrary position of the surface of the film, a second surface region formed of the second portion (high hardness portion) accounted for 6% by area of the square region, and a first surface region formed of the first portion (low hardness portion) and the second surface region accounted for 100% by area of the square region. The ratio of the hardness of the second portion (high hardness portion) to the hardness of the first portion (low hardness portion) was 1.6, the hardness of the first portion (low hardness portion) was 0.14 GPa, and the hardness of the second portion (high hardness portion) was 0.23 GPa. Both the first portion (low hardness portion) and the second portion (high hardness portion) passed through the film.
A film was prepared in the same manner as in Example 2-1 except that a honeycomb photomask in which each of the regular hexagons had a side length of 10 μm and a wall thickness of 8 μm was used in the second ultraviolet irradiation. The dried film had a thickness of 17 μm.
In a 1 mm×1 mm square region disposed on an arbitrary position of the surface of the film, a second surface region formed of the second portion (high hardness portion) accounted for 92% by area of the square region, and a first surface region formed of the first portion (low hardness portion) and the second surface region accounted for 100% by area of the square region. The ratio of the hardness of the second portion (high hardness portion) to the hardness of the first portion (low hardness portion) was 1.5, the hardness of the first portion (low hardness portion) was 0.15 GPa, and the hardness of the second portion (high hardness portion) was 0.22 GPa. Both the first portion (low hardness portion) and the second portion (high hardness portion) passed through the film.
A film was prepared in the same manner as in Example 2-1 except that the first and second ultraviolet irradiances and irradiation times were determined such that the ratio of the hardness of the second portion (high hardness portion) to the hardness of the first portion (low hardness portion) was approximately 40.0 and that the hardness of the second portion (high hardness portion) was approximately 5.00 GPa. The dried film had a thickness of 16 μm.
In a 1 mm×1 mm square region disposed on an arbitrary position of the surface of the film, a second surface region formed of the second portion (high hardness portion) accounted for 23% by area of the square region, and a first surface region formed of the first portion (low hardness portion) and the second surface region accounted for 100% by area of the square region. The ratio of the hardness of the second portion (high hardness portion) to the hardness of the first portion (low hardness portion) was 37.3, the hardness of the first portion (low hardness portion) was 0.13 GPa, and the hardness of the second portion (high hardness portion) was 4.85 GPa. Both the first portion (low hardness portion) and the second portion (high hardness portion) passed through the film.
A film was prepared in the same manner as in Example 2-5 except that the amount of photopolymerization initiator in the coating liquid for the surface layer was 5 parts by mass and that the first and second ultraviolet irradiances and irradiation times were determined such that the ratio of the hardness of the second portion (high hardness portion) to the hardness of the first portion (low hardness portion) was approximately 1.6, the hardness of the second portion (high hardness portion) was approximately 0.22 GPa, and the length of the second portion (high hardness portion) extending in the thickness direction of the film was approximately 1 μm. The dried film had a thickness of 5 μm.
In a 1 mm×1 mm square region disposed on an arbitrary position of the surface of the film, a second surface region formed of the second portion (high hardness portion) accounted for 23% by area of the square region, and a first surface region formed of the first portion (low hardness portion) and the second surface region accounted for 100% by area of the square region. The ratio of the hardness of the second portion (high hardness portion) to the hardness of the first portion (low hardness portion) was 1.5, the hardness of the first portion (low hardness portion) was 0.13 GPa, and the hardness of the second portion (high hardness portion) was 0.20 GPa. The first portion (low hardness portion) passed through the film, and the second portion (high hardness portion) extended to a depth of 20% of the thickness of the film.
Polytetrafluoroethylene (PTFE) particles having an average particle size of 0.5 μm serving as a lubricant manufactured by Daikin Industries, Ltd. (trade name: Lubron L-2) and a surfactant manufactured by Toagosei Co., Ltd. (trade name: GF-300) were added to a photosensitive silicone polymer serving as a negative photoresist material manufactured by Shin-Etsu Chemical Co., Ltd. (trade name: SINR-3170PX) to prepare a liquid mixture. The amount of polytetrafluoroethylene particles (dispersion concentration) was 10% by volume of the liquid mixture. The liquid mixture was applied to a silicon wafer by spinner coating and was dried at 90° C. for 2 minutes (pre-drying).
The coating film was then irradiated twice with ultraviolet rays. The first ultraviolet irradiation was performed over the entire surface of the coating film. The second ultraviolet irradiation was performed using a photomask having a line width of 4.0 μm and a space width of 4.0 μm. The first and second ultraviolet irradiances and irradiation times were determined such that the ratio of the hardness of a second portion (high hardness portion) to the hardness of a first portion (low hardness portion) was approximately 1.6 and that the hardness of the first portion (low hardness portion) was approximately 0.14 GPa. The coating film was then dried at 90° C. for 2 minutes (post-drying). The dried film had a thickness of 17 μm.
In a 1 mm×1 mm square region disposed on an arbitrary position of the surface of the film, a second surface region formed of the second portion (high hardness portion) accounted for 51% by area of the square region, and a first surface region formed of the first portion (low hardness portion) and the second surface region accounted for 100% by area of the square region. The ratio of the hardness of the second portion (high hardness portion) to the hardness of the first portion (low hardness portion) was 1.6, and the hardness of the first portion (low hardness portion) was 0.14 GPa. Both the first portion (low hardness portion) and the second portion (high hardness portion) passed through the film.
A film was prepared in the same manner as in Example 3-1 except that polytetrafluoroethylene particles having an average particle size of 1.0 μm was used as a lubricant. The dried film had a thickness of 16 μm.
In a 1 mm×1 mm square region disposed on an arbitrary position of the surface of the film, a second surface region formed of the second portion (high hardness portion) accounted for 53% by area of the square region, and a first surface region formed of the first portion (low hardness portion) and the second surface region accounted for 100% by area of the square region. The ratio of the hardness of the second portion (high hardness portion) to the hardness of the first portion (low hardness portion) was 1.6, and the hardness of the first portion (low hardness portion) was 0.15 GPa. Both the first portion (low hardness portion) and the second portion (high hardness portion) passed through the film.
A film was prepared in the same manner as in Example 3-1 except that polytetrafluoroethylene particles having an average particle size of 4.0 μm was used as a lubricant. The dried film had a thickness of 17 μm.
In a 1 mm×1 mm square region disposed on an arbitrary position of the surface of the film, a second surface region formed of the second portion (high hardness portion) accounted for 40% by area of the square region, and a first surface region formed of the first portion (low hardness portion) and the second surface region accounted for 100% by area of the square region. The ratio of the hardness of the second portion (high hardness portion) to the hardness of the first portion (low hardness portion) was 1.6, and the hardness of the first portion (low hardness portion) was 0.14 GPa. Both the first portion (low hardness portion) and the second portion (high hardness portion) passed through the film.
A film was prepared in the same manner as in Example 3-1 except that polytetrafluoroethylene particles having an average particle size of 10 μm was used as a lubricant. The dried film had a thickness of 17 μm.
In a 1 mm×1 mm square region disposed on an arbitrary position of the surface of the film, a second surface region formed of the second portion (high hardness portion) accounted for 20% by area of the square region, and a first surface region formed of the first portion (low hardness portion) and the second surface region accounted for 100% by area of the square region. The ratio of the hardness of the second portion (high hardness portion) to the hardness of the first portion (low hardness portion) was 1.6, and the hardness of the first portion (low hardness portion) was 0.14 GPa. Both the first portion (low hardness portion) and the second portion (high hardness portion) passed through the film.
A film was prepared in the same manner as in Example 3-1 except that the dispersion concentration of the polytetrafluoroethylene particles was 1% by volume. The dried film had a thickness of 17 μm.
In a 1 mm×1 mm square region disposed on an arbitrary position of the surface of the film, a second surface region formed of the second portion (high hardness portion) accounted for 55% by area of the square region, and a first surface region formed of the first portion (low hardness portion) and the second surface region accounted for 100% by area of the square region. The ratio of the hardness of the second portion (high hardness portion) to the hardness of the first portion (low hardness portion) was 1.6, and the hardness of the first portion (low hardness portion) was 0.14 GPa. Both the first portion (low hardness portion) and the second portion (high hardness portion) passed through the film.
A film was prepared in the same manner as in Example 3-1 except that the dispersion concentration of the polytetrafluoroethylene particles was 5% by volume. The dried film had a thickness of 17 μm.
In a 1 mm×1 mm square region disposed on an arbitrary position of the surface of the film, a second surface region formed of the second portion (high hardness portion) accounted for 50% by area of the square region, and a first surface region formed of the first portion (low hardness portion) and the second surface region accounted for 100% by area of the square region. The ratio of the hardness of the second portion (high hardness portion) to the hardness of the first portion (low hardness portion) was 1.6, and the hardness of the first portion (low hardness portion) was 0.14 GPa. Both the first portion (low hardness portion) and the second portion (high hardness portion) passed through the film.
A film was prepared in the same manner as in Example 3-1 except that the dispersion concentration of the polytetrafluoroethylene particles was 20% by volume. The dried film had a thickness of 17 μm.
In a 1 mm×1 mm square region disposed on an arbitrary position of the surface of the film, a second surface region formed of the second portion (high hardness portion) accounted for 30% by area of the square region, and a first surface region formed of the first portion (low hardness portion) and the second surface region accounted for 100% by area of the square region. The ratio of the hardness of the second portion (high hardness portion) to the hardness of the first portion (low hardness portion) was 1.6, and the hardness of the first portion (low hardness portion) was 0.14 GPa. Both the first portion (low hardness portion) and the second portion (high hardness portion) passed through the film.
A film was prepared in the same manner as in Example 3-2 except that a photomask having a hole form in which each of the holes had a diameter of 4.0 μm was used. The dried film had a thickness of 17 μm.
In a 1 mm×1 mm square region disposed on an arbitrary position of the surface of the film, a second surface region formed of the second portion (high hardness portion) accounted for 52% by area of the square region, and a first surface region formed of the first portion (low hardness portion) and the second surface region accounted for 100% by area of the square region. The ratio of the hardness of the second portion (high hardness portion) to the hardness of the first portion (low hardness portion) was 1.6, and the hardness of the first portion (low hardness portion) was 0.13 GPa. Both the first portion (low hardness portion) and the second portion (high hardness portion) passed through the film.
A film was prepared in the same manner as in Example 3-2 except that a photomask having a honeycomb form in which the maximum distance between opposite apexes was 4.0 μm was used. The dried film had a thickness of 16 μm.
In a 1 mm×1 mm square region disposed on an arbitrary position of the surface of the film, a second surface region formed of the second portion (high hardness portion) accounted for 51% by area of the square region, and a first surface region formed of the first portion (low hardness portion) and the second surface region accounted for 100% by area of the square region. The ratio of the hardness of the second portion (high hardness portion) to the hardness of the first portion (low hardness portion) was 1.6, and the hardness of the first portion (low hardness portion) was 0.14 GPa. Both the first portion (low hardness portion) and the second portion (high hardness portion) passed through the film.
A film was prepared in the same manner as in Example 3-1 except that mica particles having an average particle size of 0.5 μm manufactured by Co-op Chemical Co., Ltd. (trade name: MK-100) was used as a lubricant. The dried film had a thickness of 16 μm.
In a 1 mm×1 mm square region disposed on an arbitrary position of the surface of the film, a second surface region formed of the second portion (high hardness portion) accounted for 50% by area of the square region, and a first surface region formed of the first portion (low hardness portion) and the second surface region accounted for 100% by area of the square region. The ratio of the hardness of the second portion (high hardness portion) to the hardness of the first portion (low hardness portion) was 1.7, and the hardness of the first portion (low hardness portion) was 0.14 GPa. Both the first portion (low hardness portion) and the second portion (high hardness portion) passed through the film.
A film was prepared in the same manner as in Example 3-1 except that boron nitride (BN) particles having an average particle size of 0.5 μm manufactured by Maruka Corp. (trade name: AP-20S) was used as a lubricant. The dried film had a thickness of 17 μm.
In a 1 mm×1 mm square region disposed on an arbitrary position of the surface of the film, a second surface region formed of the second portion (high hardness portion) accounted for 50% by area of the square region, and a first surface region formed of the first portion (low hardness portion) and the second surface region accounted for 100% by area of the square region. The ratio of the hardness of the second portion (high hardness portion) to the hardness of the first portion (low hardness portion) was 1.7, and the hardness of the first portion (low hardness portion) was 0.14 GPa. Both the first portion (low hardness portion) and the second portion (high hardness portion) passed through the film.
A film was prepared in the same manner as in Example 3-1 except that melamine cyanurate (MCN) particles having an average particle size of 0.5 μm manufactured by Sakai Chemical Industry Co., Ltd. (trade name: MC-5F) was used as a lubricant. The dried film had a thickness of 17 μm.
In a 1 mm×1 mm square region disposed on an arbitrary position of the surface of the film, a second surface region formed of the second portion (high hardness portion) accounted for 50% by area of the square region, and a first surface region formed of the first portion (low hardness portion) and the second surface region accounted for 100% by area of the square region. The ratio of the hardness of the second portion (high hardness portion) to the hardness of the first portion (low hardness portion) was 1.6, and the hardness of the first portion (low hardness portion) was 0.14 GPa. Both the first portion (low hardness portion) and the second portion (high hardness portion) passed through the film.
A film was prepared in the same manner as in Example 3-1 except that silica particles having an average particle size of 0.5 μm manufactured by Ube-Nitto Kasei Co., Ltd. (trade name: Hipresica) was used as a lubricant. The dried film had a thickness of 17 μm.
In a 1 mm×1 mm square region disposed on an arbitrary position of the surface of the film, a second surface region formed of the second portion (high hardness portion) accounted for 50% by area of the square region, and a first surface region formed of the first portion (low hardness portion) and the second surface region accounted for 100% by area of the square region. The ratio of the hardness of the second portion (high hardness portion) to the hardness of the first portion (low hardness portion) was 1.6, and the hardness of the first portion (low hardness portion) was 0.14 GPa. Both the first portion (low hardness portion) and the second portion (high hardness portion) passed through the film.
A coating liquid for a charge-transport layer having the following composition was applied to a 100 mm×100 mm×0.75 mm aluminum sheet by Mayer bar coating and was dried to form the charge-transport layer having a thickness of 20 μm.
Coating Liquid for the Charge-Transport Layer
Bisphenol Z polycarbonate: 10 parts by mass
Compound having the structural formula (101) (charge-transport substance): 9 parts by mass
Chlorobenzene: 100 parts by mass
A coating liquid for a surface layer having the following composition was applied to the charge-transport layer by spray coating to form a coating film having a thickness of 5 μm.
Coating Liquid for a Surface Layer
Compound having the structural formula (28) (radical polymerizable compound having a charge-transport structure): 10 parts by mass
Trimethylolpropane triacrylate: 10 parts by mass
Polytetrafluoroethylene particles (average particle size 1.0 μm): 1 part by mass (corresponding to 10% by volume)
Surfactant manufactured by Toagosei Co., Ltd. (trade name: GF-300): 0.05 parts by mass
2,2-dimethoxy-1,2-diphenylethane-1-one (photopolymerization initiator, trade name: IRGACURE 651, manufactured by BASF): 1 part by mass
Chlorobenzene: 100 parts by mass
The coating film was then irradiated twice with ultraviolet rays. The first ultraviolet irradiation was performed over the entire surface of the coating film. The second ultraviolet irradiation was performed using a photomask having a line width of 4.0 μm and a space width of 4.0 μm. The first and second ultraviolet irradiances and irradiation times were determined such that the ratio of the hardness of a second portion (high hardness portion) to the hardness of a first portion (low hardness portion) was approximately 1.5 and that the hardness of the first portion (low hardness portion) was approximately 0.15 GPa. The coating film was then dried at 90° C. for 2 minutes. The dried surface layer (film) had a thickness of 5 μm.
In a 1 mm×1 mm square region disposed on an arbitrary position of the surface of the surface layer (film), a second surface region formed of the second portion (high hardness portion) accounted for 51% by area of the square region, and a first surface region formed of the first portion (low hardness portion) and the second surface region accounted for 100% by area of the square region. The ratio of the hardness of the second portion (high hardness portion) to the hardness of the first portion (low hardness portion) was 1.6, and the hardness of the first portion (low hardness portion) was 0.14 GPa. Both the first portion (low hardness portion) and the second portion (high hardness portion) passed through the film.
A coating liquid for a charge-transport layer having the following composition was applied to a 100 mm×100 mm×0.75 mm aluminum sheet by Mayer bar coating and was dried to form the charge-transport layer having a thickness of 20 μm.
Bisphenol Z polycarbonate: 10 parts by mass
Compound having the structural formula (101) (charge-transport substance): 10 parts by mass
Chlorobenzene: 100 parts by mass
A coating liquid for a surface layer having the following composition was applied to the charge-transport layer by spray coating to form a coating film having a thickness of 5 μm.
Coating Liquid for the Surface Layer
Compound having the structural formula (28) (radical polymerizable compound having a charge-transport structure): 10 parts by mass
Polytetrafluoroethylene particles (average particle size 1.0 μm): 1 part by mass (corresponding to 10% by volume)
Surfactant manufactured by Toagosei Co., Ltd. (trade name: GF-300): 0.05 parts by mass
Methyl ethyl ketone: 100 parts by mass
The coating film was then irradiated twice with an electron beam. The first electron beam irradiation was performed over the entire surface of the coating film. The second electron beam irradiation was performed using an electron beam mask (metal mask) having a line width of 4.0 μm and a space width of 4.0 μm. The electron beam irradiation was performed at an accelerating voltage of 30 kV under nitrogen purge. The first and second electron beam doses were determined such that the ratio of the hardness of a second portion (high hardness portion) to the hardness of a first portion (low hardness portion) was approximately 1.6 and that the hardness of the first portion (low hardness portion) was approximately 0.15 GPa. The coating film was then dried at 90° C. for 2 minutes. The dried surface layer (film) had a thickness of 5 μm.
In a 1 mm×1 mm square region disposed on an arbitrary position of the surface of the surface layer (film), a second surface region formed of the second portion (high hardness portion) accounted for 50% by area of the square region, and a first surface region formed of the first portion (low hardness portion) and the second surface region accounted for 100% by area of the square region. The ratio of the hardness of the second portion (high hardness portion) to the hardness of the first portion (low hardness portion) was 1.6, and the hardness of the first portion (low hardness portion) was 0.15 GPa. Both the first portion (low hardness portion) and the second portion (high hardness portion) passed through the film.
Polytetrafluoroethylene particles having an average particle size of 0.5 μm serving as a lubricant manufactured by Daikin Industries, Ltd. (trade name: Lubron L-2) and a surfactant manufactured by Toagosei Co., Ltd. (trade name: GF-300) were added to a photosensitive polyimide silicone serving as a negative photoresist material manufactured by Shin-Etsu Chemical Co., Ltd. (trade name: SPS-7750) to prepare a liquid mixture. The amount of polytetrafluoroethylene particles (dispersion concentration) was 10% by volume of the liquid mixture. The liquid mixture was applied to a silicon wafer by spinner coating and was dried at 90° C. for 2 minutes (pre-drying). The dried film had a thickness of 17 μm.
The first portion and the second portion had the same hardness in the resulting film. The surface of the film had hardness of 0.14 GPa.
A film was prepared in the same manner as in Comparative Example 3-1 except that mica particles having an average particle size of 0.50 μm manufactured by Co-op Chemical Co., Ltd. (trade name: MK-100) was used as a lubricant. The dried film had a thickness of 17 μm.
The first portion and the second portion had the same hardness in the resulting film. The surface of the film had hardness of 0.14 GPa.
Table 2 summarizes Examples 3-1 to 3-15 and Comparative Examples 3-1 and 3-2.
The friction coefficient of the surface of a film was measured with a torque type friction and wear tester (trade name: Type: 20) manufactured by Shinto Scientific Co., Ltd. A film to be measured was placed on a turntable (diameter 12.7 mm) of the tester. A urethane rubber member (JIS-A hardness: 70) 3 mm in thickness×1 cm in width×1 cm in length was made to abut against the circumference of the film at an angle of 24 degrees (0 degrees indicates that the rubber member is parallel to the film) in the driven direction (the same direction as the rotation). The film (radius 33 mm) on the turntable was rotated under a load of 30 gf at a number of revolutions of 47.8 rpm. The friction coefficient (the coefficient of kinetic friction) was determined from the force generated between the film and the urethane rubber member.
For Examples 1-1 to 1-10 and Comparative Examples 1-1 to 1-10, the friction coefficient (the coefficient of kinetic friction) was measured after the film was rotated for 10 or 30 hours while the urethane rubber member abutted against the film. For Examples 2-1 to 2-9, Comparative Examples 2-1 to 2-5, Examples 3-1 to 3-15, and Comparative Examples 3-1 and 3-2, the friction coefficient (the coefficient of kinetic friction) was measured after the film was rotated for 1 or 20 hours while the urethane rubber member abutted against the film.
The surface asperities of a film were measured with a surface profiler (trade name: Tencor P-10) manufactured by KLA-Tencor Corp. The widths of the raised portion formed of the second portion and the depressed portion formed of the first portion and the height difference between the raised portion and the depressed portion were measured.
For Examples 1-1 to 1-10 and Comparative Examples 1-1 to 1-9, stick and slip was evaluated with a torque type friction and wear tester (trade name: Type: 20) manufactured by Shinto Scientific Co., Ltd. After a film was rotated for 30 hours while the urethane rubber member abutted against the film, the urethane rubber member was made to abut against the circumference of the film at an angle of 24 degrees (0 degrees indicates that the rubber member is parallel to the film) in the reverse direction (counter direction). The film (radius 33 mm) on the turntable was then rotated under a load of 30 gf at a number of revolutions of 23.9 rpm (slow rotation) or 47.8 rpm (fast rotation). The stick and slip was evaluated on the basis of the behavior of the urethane rubber member in accordance with the following three criteria.
A: The film rotated without problems at numbers of revolutions of 23.9 and 47.8 rpm.
B: The urethane rubber member continuously bounded at a number of revolutions of 23.9 rpm, but the film rotated without problems at a number of revolutions of 47.8 rpm.
C: The urethane rubber member continuously bounded at numbers of revolutions of 23.9 and 47.8 rpm.
The frequency of stick and slip tends to increase with the friction coefficient.
For Examples 1-1 to 1-10, Comparative Examples 1-1 to 1-10, Examples 2-1 to 2-9, and Comparative Examples 2-1 to 2-5, the destruction of the raised portion formed of the second portion was evaluated with an ultra-high depth shape measurement microscope (trade name: VK-9510) manufactured by Keyence Corp. and an image processor (trade name: Luzex AP) manufactured by Nireco Corp.
For Examples 1-1 to 1-10 and Comparative Examples 1-1 to 1-10, after the film was rotated for 30 hours while the urethane rubber member abutted against the film, the destruction of the raised portion was evaluated in accordance with the following two criteria.
A: In each 1 mm×1 mm square, a broken area of the raised portion was less than 20% of the total area of the raised portion.
C: In each 1 mm×1 mm square, a broken area of the raised portion was 30% or more of the total area of the raised portion.
For Examples 2-1 to 2-9 and Comparative Examples 2-1 to 2-5, after the film was rotated for 20 hours while the urethane rubber member abutted against the film, the destruction of the raised portion was evaluated in accordance with the following three criteria.
A: In each 1 mm×1 mm square, a broken area of the raised portion was less than 10% of the total area of the raised portion.
B: In each 1 mm×1 mm square, a broken area of the raised portion was 10% or more and less than 20% of the total area of the raised portion.
C: In each 1 mm×1 mm square, a broken area of the raised portion was 20% or more of the total area of the raised portion.
After the film was rotated for 10 hours while the urethane rubber member abutted against the film, the first portion formed a depressed portion having a width of 4 μm, the second portion formed a raised portion having a width of 4 μm, the height difference between the raised portion and the depressed portion was 0.25 μm, and the friction coefficient of the surface of the film was 0.44.
After the film was rotated for 30 hours while the urethane rubber member abutted against the film, the first portion formed a depressed portion having a width of 4 μm, the second portion formed a raised portion having a width of 4 μm, the height difference between the raised portion and the depressed portion was 0.24 μm, and the friction coefficient of the surface of the film was 0.42. Stick and slip was not observed for both the slow rotation and the fast rotation, and the raised portion was not broken. Thus, it was shown that even after the film was rotated for 30 hours while the urethane rubber member abutted against the film, the film retained its surface shape and a low friction coefficient.
After the film was rotated for 10 hours while the urethane rubber member abutted against the film, the first portion formed a depressed portion having a width of 4 μm, the second portion formed a raised portion having a width of 4 μm, the height difference between the raised portion and the depressed portion was 0.18 μm, and the friction coefficient of the surface of the film was 0.56.
After the film was rotated for 30 hours while the urethane rubber member abutted against the film, the first portion formed a depressed portion having a width of 4 μm, the second portion formed a raised portion having a width of 4 μm, the height difference between the raised portion and the depressed portion was 0.19 μm, and the friction coefficient of the surface of the film was 0.50. Stick and slip was not observed for both the slow rotation and the fast rotation, and the raised portion was not broken. Thus, it was shown that even after the film was rotated for 30 hours while the urethane rubber member abutted against the film, the film retained its surface shape and a low friction coefficient. However, the friction coefficient was higher than the friction coefficient in Example 1-1.
After the film was rotated for 10 hours while the urethane rubber member abutted against the film, the first portion formed a depressed portion having a width of 4 μm, the second portion formed a raised portion having a width of 4 μm, the height difference between the raised portion and the depressed portion was 0.30 μm, and the friction coefficient of the surface of the film was 0.49.
After the film was rotated for 30 hours while the urethane rubber member abutted against the film, the first portion formed a depressed portion having a width of 4 μm, the second portion formed a raised portion having a width of 4 μm, the height difference between the raised portion and the depressed portion was 0.31 μm, and the friction coefficient of the surface of the film was 0.52. Stick and slip was not observed for both the slow rotation and the fast rotation, and the raised portion was not broken. Thus, it was shown that even after the film was rotated for 30 hours while the urethane rubber member abutted against the film, the film retained its surface shape and a low friction coefficient.
After the film was rotated for 10 hours while the urethane rubber member abutted against the film, the first portion formed a depressed portion having a width of 4 μm, the second portion formed a raised portion having a width of 4 μm, the height difference between the raised portion and the depressed portion was 0.38 μm, and the friction coefficient of the surface of the film was 0.68.
After the film was rotated for 30 hours while the urethane rubber member abutted against the film, the first portion formed a depressed portion having a width of 4 μm, the second portion formed a raised portion having a width of 4 μm, the height difference between the raised portion and the depressed portion was 0.39 μm, and the friction coefficient of the surface of the film was 0.73. Stick and slip was observed for the slow rotation but was not observed for the fast rotation. The raised portion was not broken. After the film was rotated for 10 hours and 30 hours while the urethane rubber member abutted against the film, the friction coefficient of the surface of the film was higher than the friction coefficient in Example 1-1.
After the film was rotated for 10 hours while the urethane rubber member abutted against the film, the first portion formed a depressed portion having a width of 4 μm, the second portion formed a raised portion having a width of 4 μm, the height difference between the raised portion and the depressed portion was 0.36 μm, and the friction coefficient of the surface of the film was 0.62.
After the film was rotated for 30 hours while the urethane rubber member abutted against the film, the first portion formed a depressed portion having a width of 4 μm, the second portion formed a raised portion having a width of 4 μm, the height difference between the raised portion and the depressed portion was 0.36 μm, and the friction coefficient of the surface of the film was 0.68. Stick and slip was observed for the slow rotation but was not observed for the fast rotation. The raised portion was not broken. After the film was rotated for 10 hours and 30 hours while the urethane rubber member abutted against the film, the friction coefficient of the surface of the film was higher than the friction coefficient in Example 1-1.
After the film was rotated for 10 hours while the urethane rubber member abutted against the film, the first portion formed a depressed portion having a width of 4 μm, the second portion formed a raised portion having a width of 4 μm, the height difference between the raised portion and the depressed portion was 0.27 μm, and the friction coefficient of the surface of the film was 0.61.
After the film was rotated for 30 hours while the urethane rubber member abutted against the film, the first portion formed a depressed portion having a width of 4 μm, the second portion formed a raised portion having a width of 4 μm, the height difference between the raised portion and the depressed portion was 0.28 μm, and the friction coefficient of the surface of the film was 0.66. Stick and slip was observed for the slow rotation but was not observed for the fast rotation. The raised portion was not broken. After the film was rotated for 10 hours and 30 hours while the urethane rubber member abutted against the film, the friction coefficient of the surface of the film was higher than the friction coefficient in Example 1-1.
After the film was rotated for 10 hours while the urethane rubber member abutted against the film, the first portion formed a depressed portion having a width of 20 μm, the second portion formed a raised portion having a width of 20 μm, the height difference between the raised portion and the depressed portion was 0.51 μm, and the friction coefficient of the surface of the film was 0.71.
After the film was rotated for 30 hours while the urethane rubber member abutted against the film, the first portion formed a depressed portion having a width of 20 μm, the second portion formed a raised portion having a width of 20 μm, the height difference between the raised portion and the depressed portion was 0.51 μm, and the friction coefficient of the surface of the film was 0.70. Stick and slip was observed for the slow rotation but was not observed for the fast rotation. The raised portion was not broken. After the film was rotated for 10 hours and 30 hours while the urethane rubber member abutted against the film, the friction coefficient of the surface of the film was higher than the friction coefficient in Example 1-1.
After the film was rotated for 10 hours while the urethane rubber member abutted against the film, the first portion formed a depressed portion having a width of 22.7 μm, the second portion formed a raised portion having a width of 4 μm, the height difference between the raised portion and the depressed portion was 0.57 μm, and the friction coefficient of the surface of the film was 0.53.
After the film was rotated for 30 hours while the urethane rubber member abutted against the film, the first portion formed a depressed portion having a width of 22.7 μm, the second portion formed a raised portion having a width of 4 μm, the height difference between the raised portion and the depressed portion was 0.58 μm, and the friction coefficient of the surface of the film was 0.54. Stick and slip was not observed for both the slow rotation and the fast rotation, and the raised portion was not broken. Thus, it was shown that even after the film was rotated for 30 hours while the urethane rubber member abutted against the film, the film retained its surface shape and a low friction coefficient.
After the film was rotated for 10 hours while the urethane rubber member abutted against the film, the first portion formed a depressed portion having a width of 1.3 μm, the second portion formed a raised portion having a width of 4 μm, the height difference between the raised portion and the depressed portion was 0.15 μm, and the friction coefficient of the surface of the film was 0.75.
After the film was rotated for 30 hours while the urethane rubber member abutted against the film, the first portion formed a depressed portion having a width of 1.3 μm, the second portion formed a raised portion having a width of 4 μm, the height difference between the raised portion and the depressed portion was 0.16 μm, and the friction coefficient of the surface of the film was 0.73. Stick and slip was observed for the slow rotation but was not observed for the fast rotation. The raised portion was not broken. After the film was rotated for 10 hours and 30 hours while the urethane rubber member abutted against the film, the friction coefficient of the surface of the film was higher than the friction coefficient in Example 1-1.
After the film was rotated for 10 hours while the urethane rubber member abutted against the film, the first portion formed a depressed portion having a width of 4 μm, the second portion formed a raised portion having a width of 4 μm, the height difference between the raised portion and the depressed portion was 0.26 μm, and the friction coefficient of the surface of the film was 0.45.
After the film was rotated for 30 hours while the urethane rubber member abutted against the film, each of the depressed portion and the raised portion had a width of 4.0 μm, the height difference between the raised portion and the depressed portion was 0.26 μm, and the friction coefficient of the surface of the film was 0.43. Stick and slip was not observed for both the slow rotation and the fast rotation, and the raised portion was not broken. Thus, it was shown that even after the film was rotated for 30 hours while the urethane rubber member abutted against the film, the film retained its surface shape and a low friction coefficient.
After the film was rotated for 10 hours while the urethane rubber member abutted against the film, no asperity was observed, and the friction coefficient of the surface of the film was 1.77.
After the film was rotated for 30 hours while the urethane rubber member abutted against the film, no asperity was observed, and the friction coefficient of the surface of the film was 1.74. Stick and slip occurred in both the slow rotation and the fast rotation, and unstable friction behavior was observed.
After the film was rotated for 10 hours while the urethane rubber member abutted against the film, no asperity was observed, and the friction coefficient of the surface of the film was 0.95.
After the film was rotated for 30 hours while the urethane rubber member abutted against the film, no asperity was observed, and the friction coefficient of the surface of the film was 0.91. Stick and slip occurred in both the slow rotation and the fast rotation, and unstable friction behavior was observed.
After the film was rotated for 10 hours while the urethane rubber member abutted against the film, the first portion formed a depressed portion having a width of 4 μm, the second portion formed a raised portion having a width of 4 μm, the height difference between the raised portion and the depressed portion was 1.68 μm, and the friction coefficient of the surface of the film was 0.99.
After the film was rotated for 30 hours while the urethane rubber member abutted against the film, the first portion formed a depressed portion having a width of 4 μm, the second portion formed a raised portion having a width of 4 μm, the height difference between the raised portion and the depressed portion was 1.05 μm. This shows that the rotation of the film for 30 hours while the urethane rubber member abutted against the film resulted in the wearing of the raised portion and the gradual disappearance of the asperities. The friction coefficient of the surface of the film was 1.24. Stick and slip occurred in both the slow rotation and the fast rotation, unstable friction behavior was observed, and a broken area of the raised portion accounted for 41% of the total area of the raised portion.
After the film was rotated for 10 hours while the urethane rubber member abutted against the film, the first portion formed a depressed portion having a width of 2000 μm, the second portion formed a raised portion having a width of 500 μm, the height difference between the raised portion and the depressed portion was 1.89 μm, and the friction coefficient of the surface of the film was 1.88.
After the film was rotated for 30 hours while the urethane rubber member abutted against the film, the first portion formed a depressed portion having a width of 2000 μm, the second portion formed a raised portion having a width of 500 μm, the height difference between the raised portion and the depressed portion was 1.93 μm, and the friction coefficient of the surface of the film was 1.86. Stick and slip occurred in both the slow rotation and the fast rotation, and unstable friction behavior was observed. The raised portion was not broken.
After the film was rotated for 10 hours while the urethane rubber member abutted against the film, the first portion formed a depressed portion having a width of 4 μm, the second portion formed a raised portion having a width of 4 μm, the height difference between the raised portion and the depressed portion was 0.11 μm, and the friction coefficient of the surface of the film was 0.97.
After the film was rotated for 30 hours while the urethane rubber member abutted against the film, the first portion formed a depressed portion having a width of 4 μm, the second portion formed a raised portion having a width of 4 μm, the height difference between the raised portion and the depressed portion was 0.10 μm, and the friction coefficient of the surface of the film was 0.97. Stick and slip occurred in both the slow rotation and the fast rotation, and unstable friction behavior was observed. The raised portion was not broken.
After the film was rotated for 10 hours while the urethane rubber member abutted against the film, the first portion formed a depressed portion having a width of 4 μm, the second portion formed a raised portion having a width of 4 μm, the height difference between the raised portion and the depressed portion was 0.66 μm, and the friction coefficient of the surface of the film was 0.99.
After the film was rotated for 30 hours while the urethane rubber member abutted against the film, the first portion formed a depressed portion having a width of 4 μm, the second portion formed a raised portion having a width of 4 μm, the height difference between the raised portion and the depressed portion was 0.64 μm, and the friction coefficient of the surface of the film was 0.92. Stick and slip occurred in both the slow rotation and the fast rotation, and unstable friction behavior was observed. The raised portion was not broken.
After the film was rotated for 10 hours while the urethane rubber member abutted against the film, the first portion formed a depressed portion having a width of 76 μm, the second portion formed a raised portion having a width of 4 μm, the height difference between the raised portion and the depressed portion was 0.77 μm, and the friction coefficient of the surface of the film was 0.95.
After the film was rotated for 30 hours while the urethane rubber member abutted against the film, the first portion formed a depressed portion having a width of 76 μm, the second portion formed a raised portion having a width of 4 μm, the height difference between the raised portion and the depressed portion was 0.75 μm, and the friction coefficient of the surface of the film was 1.23. Stick and slip occurred in both the slow rotation and the fast rotation, unstable friction behavior was observed, and a broken area of the raised portion accounted for 36% of the total area of the raised portion.
After the film was rotated for 10 hours while the urethane rubber member abutted against the film, the first portion formed a depressed portion having a width of 0.7 μm, the second portion formed a raised portion having a width of 4 μm, the height difference between the raised portion and the depressed portion was 0.11 μm, and the friction coefficient of the surface of the film was 1.05.
After the film was rotated for 30 hours while the urethane rubber member abutted against the film, the first portion formed a depressed portion having a width of 0.7 μm, the second portion formed a raised portion having a width of 4 μm, the height difference between the raised portion and the depressed portion was 0.13 μm, and the friction coefficient of the surface of the film was 1.03. Stick and slip occurred in both the slow rotation and the fast rotation, and unstable friction behavior was observed. The raised portion was not broken.
After the film was rotated for 10 hours while the urethane rubber member abutted against the film, no asperity was observed, and the friction coefficient of the surface of the film was 1.06.
After the film was rotated for 30 hours while the urethane rubber member abutted against the film, no asperity was observed, and the friction coefficient of the surface of the film was 1.02. Stick and slip occurred in both the slow rotation and the fast rotation, and unstable friction behavior was observed.
After the film was rotated for 10 hours while the urethane rubber member abutted against the film, no asperity was observed, and the friction coefficient of the surface of the film was 1.90.
After the film was rotated for 30 hours while the urethane rubber member abutted against the film, no asperity was observed, and the friction coefficient of the surface of the film was 1.88. Stick and slip occurred in both the slow rotation and the fast rotation, and unstable friction behavior was observed.
After the film was rotated for one hour while the urethane rubber member abutted against the film, honeycomb asperities each having a regular hexagonal depressed portion surrounded by a raised portion were observed on the surface of the film, the side length of the regular hexagon was 10 μm, the wall thickness was 2 μm, the height difference between the raised portion and the depressed portion was 0.22 μm, and the friction coefficient of the surface of the film was 0.44.
After the film was rotated for 20 hours while the urethane rubber member abutted against the film, honeycomb asperities were observed, the height difference between the raised portion and the depressed portion was 0.25 μm, and the friction coefficient of the surface of the film was 0.43. In each 1 mm×1 mm square, a broken area of the raised portion was less than 10% of the total area of the raised portion.
After the film was rotated for one hour while the urethane rubber member abutted against the film, honeycomb asperities each having a regular hexagonal depressed portion surrounded by a raised portion were observed on the surface of the film, the side length of the regular hexagon was 10 μm, the wall thickness was 1 μm, the height difference between the raised portion and the depressed portion was 0.33 μm, and the friction coefficient of the surface of the film was 0.48.
After the film was rotated for 20 hours while the urethane rubber member abutted against the film, honeycomb asperities were observed, the height difference between the raised portion and the depressed portion was 0.34 μm, and the friction coefficient of the surface of the film was 0.52. In each 1 mm×1 mm square, a broken area of the raised portion was 14% of the total area of the raised portion.
After the film was rotated for one hour while the urethane rubber member abutted against the film, honeycomb asperities each having a regular hexagonal depressed portion surrounded by a raised portion were observed on the surface of the film, the side length of the regular hexagon was 10 μm, the wall thickness was 6 μm, the height difference between the raised portion and the depressed portion was 0.11 μm, and the friction coefficient of the surface of the film was 0.75.
After the film was rotated for 20 hours while the urethane rubber member abutted against the film, honeycomb asperities were observed, the height difference between the raised portion and the depressed portion was 0.12 μm, and the friction coefficient of the surface of the film was 0.72. In each 1 mm×1 mm square, a broken area of the raised portion was less than 10% of the total area of the raised portion.
After the film was rotated for one hour while the urethane rubber member abutted against the film, honeycomb asperities each having a regular hexagonal depressed portion surrounded by a raised portion were observed on the surface of the film, the side length of the regular hexagon was 10 μm, the wall thickness was 2 μm, the height difference between the raised portion and the depressed portion was 0.16 μm, and the friction coefficient of the surface of the film was 0.81.
After the film was rotated for 20 hours while the urethane rubber member abutted against the film, honeycomb asperities were observed, the height difference between the raised portion and the depressed portion was 0.17 μm, and the friction coefficient of the surface of the film was 0.81. In each 1 mm×1 mm square, a broken area of the raised portion was 12% of the total area of the raised portion.
After the film was rotated for one hour while the urethane rubber member abutted against the film, honeycomb asperities each having a regular hexagonal depressed portion surrounded by a raised portion were observed on the surface of the film, the side length of the regular hexagon was 10 μm, the wall thickness was 2 μm, the height difference between the raised portion and the depressed portion was 0.24 μm, and the friction coefficient of the surface of the film was 0.45.
After the film was rotated for 20 hours while the urethane rubber member abutted against the film, honeycomb asperities were observed, the height difference between the raised portion and the depressed portion was 0.34 μm, and the friction coefficient of the surface of the film was 0.85. In each 1 mm×1 mm square, a broken area of the raised portion was less than 10% of the total area of the raised portion.
After the film was rotated for one hour while the urethane rubber member abutted against the film, honeycomb asperities each having a regular hexagonal depressed portion surrounded by a raised portion were observed on the surface of the film, the side length of the regular hexagon was 10 μm, the wall thickness was 2 μm, the height difference between the raised portion and the depressed portion was 0.16 μm, and the friction coefficient of the surface of the film was 0.81.
After the film was rotated for 20 hours while the urethane rubber member abutted against the film, honeycomb asperities were observed, the height difference between the raised portion and the depressed portion was 0.16 μm, and the friction coefficient of the surface of the film was 0.86. In each 1 mm×1 mm square, a broken area of the raised portion was 15% of the total area of the raised portion.
After the film was rotated for one hour while the urethane rubber member abutted against the film, honeycomb asperities each having a regular hexagonal depressed portion surrounded by a raised portion were observed on the surface of the film, the side length of the regular hexagon was 10 μm, the wall thickness was 2 μm, the height difference between the raised portion and the depressed portion was 0.27 μm, and the friction coefficient of the surface of the film was 0.53.
After the film was rotated for 20 hours while the urethane rubber member abutted against the film, honeycomb asperities were observed, the height difference between the raised portion and the depressed portion was 0.35 μm, and the friction coefficient of the surface of the film was 0.88. In each 1 mm×1 mm square, a broken area of the raised portion was less than 10% of the total area of the raised portion.
After the film was rotated for one hour while the urethane rubber member abutted against the film, asperities having a circular hole form were observed on the surface of the film, in which each of the holes had a diameter of 0.2 μm and a center-to-center distance of 0.4 μm, the height difference between the raised portion and the depressed portion was 0.03 μm, and the friction coefficient of the surface of the film was 0.85.
After the film was rotated for 20 hours while the urethane rubber member abutted against the film, asperities having a hole form were observed, the height difference between the raised portion and the depressed portion was 0.03 μm, and the friction coefficient of the surface of the film was 0.84. In each 1 mm×1 mm square, a broken area of the raised portion was less than 10% of the total area of the raised portion.
After the film was rotated for one hour while the urethane rubber member abutted against the film, honeycomb asperities each having a regular hexagonal depressed portion surrounded by a raised portion were observed on the surface of the film, the side length of the regular hexagon was 50 μm, the wall thickness was 10 μm, the height difference between the raised portion and the depressed portion was 0.84 μm, and the friction coefficient of the surface of the film was 0.83.
After the film was rotated for 20 hours while the urethane rubber member abutted against the film, honeycomb asperities were observed, the height difference between the raised portion and the depressed portion was 0.89 μm, and the friction coefficient of the surface of the film was 0.86. In each 1 mm×1 mm square, a broken area of the raised portion was 15% of the total area of the raised portion.
After the film was rotated for one hour while the urethane rubber member abutted against the film, honeycomb asperities each having a regular hexagonal depressed portion surrounded by a raised portion were observed on the surface of the film, the side length of the regular hexagon was 10 μm, the wall thickness was 2 μm, the height difference between the raised portion and the depressed portion was 17 μm, and the friction coefficient of the surface of the film was 0.78.
After the film was rotated for 20 hours while the urethane rubber member abutted against the film, honeycomb asperities were observed, the height difference between the raised portion and the depressed portion was 16 μm, and the friction coefficient of the surface of the film was 0.92. In each 1 mm×1 mm square, a broken area of the raised portion was 23% of the total area of the raised portion.
After the film was rotated for one hour while the urethane rubber member abutted against the film, honeycomb asperities each having a regular hexagonal depressed portion surrounded by a raised portion were observed on the surface of the film, the side length of the regular hexagon was 10 μm, the wall thickness was 0.5 μm, the height difference between the raised portion and the depressed portion was 0.35 μm, and the friction coefficient of the surface of the film was 0.54.
After the film was rotated for 20 hours while the urethane rubber member abutted against the film, honeycomb asperities were observed, the height difference between the raised portion and the depressed portion was 0.39 μm, and the friction coefficient of the surface of the film was 0.94. In each 1 mm×1 mm square, a broken area of the raised portion was 27% of the total area of the raised portion.
After the film was rotated for one hour while the urethane rubber member abutted against the film, honeycomb asperities each having a regular hexagonal depressed portion surrounded by a raised portion were observed on the surface of the film, the side length of the regular hexagon was 10 μm, the wall thickness was 8 μm, the height difference between the raised portion and the depressed portion was 0.07 μm, and the friction coefficient of the surface of the film was 0.96.
After the film was rotated for 20 hours while the urethane rubber member abutted against the film, honeycomb asperities were observed, the height difference between the raised portion and the depressed portion was 0.07 μm, and the friction coefficient of the surface of the film was 0.95. In each 1 mm×1 mm square, a broken area of the raised portion was less than 10% of the total area of the raised portion.
After the film was rotated for one hour while the urethane rubber member abutted against the film, honeycomb asperities each having a regular hexagonal depressed portion surrounded by a raised portion were observed on the surface of the film, the side length of the regular hexagon was 10 μm, the wall thickness was 2 μm, the height difference between the raised portion and the depressed portion was 0.27 μm, and the friction coefficient of the surface of the film was 0.49.
After the film was rotated for 20 hours while the urethane rubber member abutted against the film, honeycomb asperities were observed, the height difference between the raised portion and the depressed portion was 0.42 μm, and the friction coefficient of the surface of the film was 0.99. In each 1 mm×1 mm square, a broken area of the raised portion was less than 10% of the total area of the raised portion.
After the film was rotated for one hour while the urethane rubber member abutted against the film, honeycomb asperities each having a regular hexagonal depressed portion surrounded by a raised portion were observed on the surface of the film, the side length of the regular hexagon was 10 μm, the wall thickness was 2 μm, the height difference between the raised portion and the depressed portion was 0.22 μm, and the friction coefficient of the surface of the film was 0.47.
After the film was rotated for 20 hours while the urethane rubber member abutted against the film, no asperity was observed, and the friction coefficient of the surface of the film was 1.61.
For Examples 1-1 to 1-10 and Comparative Examples 1-1 to 1-9, the friction coefficient was evaluated in accordance with the following three criteria.
A: After the film was rotated for 10 or 30 hours while the urethane rubber member abutted against the film, the friction coefficient of the surface of the film was 0.60 or less.
B: After the film was rotated for 10 or 30 hours while the urethane rubber member abutted against the film, the friction coefficient of the surface of the film was 0.61 or more and 0.80 or less.
C: After the film was rotated for 10 or 30 hours while the urethane rubber member abutted against the film, the friction coefficient of the surface of the film was 0.81 or more.
For Examples 2-1 to 2-9 and Comparative Examples 2-1 to 2-5, the friction coefficient was evaluated in accordance with the following three criteria.
A: After the film was rotated for 1 or 20 hours while the urethane rubber member abutted against the film, the friction coefficient of the surface of the film was 0.60 or less.
B: After the film was rotated for 1 or 20 hours while the urethane rubber member abutted against the film, the friction coefficient of the surface of the film was 0.61 or more and 0.90 or less.
C: After the film was rotated for 1 or 20 hours while the urethane rubber member abutted against the film, the friction coefficient of the surface of the film was 0.91 or more.
Table 3 summarizes the results.
After the film was rotated for one hour while the urethane rubber member abutted against the film, the first portion formed a depressed portion having a width of 4.0 μm, the second portion formed a raised portion having a width of 4.0 μm, the height difference between the raised portion and the depressed portion was 0.25 μm, and the friction coefficient of the surface of the film was 0.33.
After the film was rotated for 20 hours while the urethane rubber member abutted against the film, the first portion formed a depressed portion having a width of 4.0 μm, the second portion formed a raised portion having a width of 4.0 μm, the height difference between the raised portion and the depressed portion was 0.24 μm, and the friction coefficient of the surface of the film was 0.33. Optical microscope observation showed the accumulation of a lubricant abrasion powder produced by the wearing of the film containing the lubricant (hereinafter referred to as an abrasion powder) in the depressed portion.
After the film was rotated for one hour while the urethane rubber member abutted against the film, the first portion formed a depressed portion having a width of 4.0 μm, the second portion formed a raised portion having a width of 4.0 μm, the height difference between the raised portion and the depressed portion was 0.22 μm, and the friction coefficient of the surface of the film was 0.32.
After the film was rotated for 20 hours while the urethane rubber member abutted against the film, the first portion formed a depressed portion having a width of 4.0 μm, the second portion formed a raised portion having a width of 4.0 μm, the height difference between the raised portion and the depressed portion was 0.21 μm, and the friction coefficient of the surface of the film was 0.27. Optical microscope observation showed the accumulation of an abrasion powder in the depressed portion.
After the film was rotated for one hour while the urethane rubber member abutted against the film, the first portion formed a depressed portion having a width of 4.0 μm, the second portion formed a raised portion having a width of 4.0 μm, the height difference between the raised portion and the depressed portion was 0.28 μm, and the friction coefficient of the surface of the film was 0.37.
After the film was rotated for 20 hours while the urethane rubber member abutted against the film, the first portion formed a depressed portion having a width of 4.0 μm, the second portion formed a raised portion having a width of 4.0 μm, the height difference between the raised portion and the depressed portion was 0.24 μm, and the friction coefficient of the surface of the film was 0.35. Optical microscope observation showed the accumulation of an abrasion powder in the depressed portion.
After the film was rotated for one hour while the urethane rubber member abutted against the film, the first portion formed a depressed portion having a width of 4.0 μm, the second portion formed a raised portion having a width of 4.0 μm, the height difference between the raised portion and the depressed portion was 0.23 μm, and the friction coefficient of the surface of the film was 0.35.
After the film was rotated for 20 hours while the urethane rubber member abutted against the film, the first portion formed a depressed portion having a width of 4.0 μm, the second portion formed a raised portion having a width of 4.0 μm, the height difference between the raised portion and the depressed portion was 0.23 μm, and the friction coefficient of the surface of the film was 0.35. Optical microscope observation showed the accumulation of an abrasion powder in the depressed portion.
After the film was rotated for one hour while the urethane rubber member abutted against the film, the first portion formed a depressed portion having a width of 4.0 μm, the second portion formed a raised portion having a width of 4.0 μm, the height difference between the raised portion and the depressed portion was 0.27 μm, and the friction coefficient of the surface of the film was 0.65.
After the film was rotated for 20 hours while the urethane rubber member abutted against the film, the first portion formed a depressed portion having a width of 4.0 μm, the second portion formed a raised portion having a width of 4.0 μm, the height difference between the raised portion and the depressed portion was 0.26 μm, and the friction coefficient of the surface of the film was 0.64. Optical microscope observation showed the accumulation of an abrasion powder in the depressed portion.
After the film was rotated for one hour while the urethane rubber member abutted against the film, the first portion formed a depressed portion having a width of 4.0 μm, the second portion formed a raised portion having a width of 4.0 μm, the height difference between the raised portion and the depressed portion was 0.25 μm, and the friction coefficient of the surface of the film was 0.53.
After the film was rotated for 20 hours while the urethane rubber member abutted against the film, the first portion formed a depressed portion having a width of 4.0 μm, the second portion formed a raised portion having a width of 4.0 μm, the height difference between the raised portion and the depressed portion was 0.25 μm, and the friction coefficient of the surface of the film was 0.50. Optical microscope observation showed the accumulation of an abrasion powder in the depressed portion.
After the film was rotated for one hour while the urethane rubber member abutted against the film, the first portion formed a depressed portion having a width of 4.0 μm, the second portion formed a raised portion having a width of 4.0 μm, the height difference between the raised portion and the depressed portion was 0.26 μm, and the friction coefficient of the surface of the film was 0.26.
After the film was rotated for 20 hours while the urethane rubber member abutted against the film, the first portion formed a depressed portion having a width of 4.0 μm, the second portion formed a raised portion having a width of 4.0 μm, the height difference between the raised portion and the depressed portion was 0.25 μm, and the friction coefficient of the surface of the film was 0.26. Optical microscope observation showed the accumulation of an abrasion powder in the depressed portion.
After the film was rotated for one hour while the urethane rubber member abutted against the film, a hole form was observed on the film in which each of the holes had a diameter of 4.0 μm, the height difference between the raised portion and the depressed portion was 0.25 μm, and the friction coefficient of the surface of the film was 0.32.
After the film was rotated for 20 hours while the urethane rubber member abutted against the film, a hole form was observed on the film in which each of the holes had a diameter of 4.0 μm, the height difference between the raised portion and the depressed portion was 0.25 μm, and the friction coefficient of the surface of the film was 0.22. Optical microscope observation showed the accumulation of an abrasion powder in the depressed portion.
After the film was rotated for one hour while the urethane rubber member abutted against the film, a honeycomb form was observed on the film in which the maximum distance between opposite apexes was 4.0 μm, the height difference between the raised portion and the depressed portion was 0.24 μm, and the friction coefficient of the surface of the film was 0.32.
After the film was rotated for 20 hours while the urethane rubber member abutted against the film, a honeycomb form was observed on the film in which the maximum distance between opposite apexes was 3.9 μm, the height difference between the raised portion and the depressed portion was 0.24 μm, and the friction coefficient of the surface of the film was 0.20. Optical microscope observation showed the accumulation of an abrasion powder in the depressed portion.
After the film was rotated for one hour while the urethane rubber member abutted against the film, the first portion formed a depressed portion having a width of 4.0 μm, the second portion formed a raised portion having a width of 4.0 μm, the height difference between the raised portion and the depressed portion was 0.26 μm, and the friction coefficient of the surface of the film was 0.35.
After the film was rotated for 20 hours while the urethane rubber member abutted against the film, the first portion formed a depressed portion having a width of 4.2 μm, the second portion formed a raised portion having a width of 3.8 μm, the height difference between the raised portion and the depressed portion was 0.26 μm, and the friction coefficient of the surface of the film was 0.31. Optical microscope observation showed the accumulation of an abrasion powder in the depressed portion.
After the film was rotated for one hour while the urethane rubber member abutted against the film, the first portion formed a depressed portion having a width of 4.0 μm, the second portion formed a raised portion having a width of 4.0 μm, the height difference between the raised portion and the depressed portion was 0.26 μm, and the friction coefficient of the surface of the film was 0.52.
After the film was rotated for 20 hours while the urethane rubber member abutted against the film, the first portion formed a depressed portion having a width of 4.1 μm, the second portion formed a raised portion having a width of 3.9 μm, the height difference between the raised portion and the depressed portion was 0.25 μm, and the friction coefficient of the surface of the film was 0.47. Optical microscope observation showed the accumulation of an abrasion powder in the depressed portion.
After the film was rotated for one hour while the urethane rubber member abutted against the film, the first portion formed a depressed portion having a width of 4.0 μm, the second portion formed a raised portion having a width of 4.0 μm, the height difference between the raised portion and the depressed portion was 0.25 μm, and the friction coefficient of the surface of the film was 0.32.
After the film was rotated for 20 hours while the urethane rubber member abutted against the film, the first portion formed a depressed portion having a width of 4.0 μm, the second portion formed a raised portion having a width of 4.0 μm, the height difference between the raised portion and the depressed portion was 0.25 μm, and the friction coefficient of the surface of the film was 0.28. Optical microscope observation showed the accumulation of an abrasion powder in the depressed portion.
After the film was rotated for one hour while the urethane rubber member abutted against the film, the first portion formed a depressed portion having a width of 4.0 μm, the second portion formed a raised portion having a width of 4.0 μm, the height difference between the raised portion and the depressed portion was 0.25 μm, and the friction coefficient of the surface of the film was 0.42.
After the film was rotated for 20 hours while the urethane rubber member abutted against the film, the first portion formed a depressed portion having a width of 4.0 μm, the second portion formed a raised portion having a width of 4.0 μm, the height difference between the raised portion and the depressed portion was 0.25 μm, and the friction coefficient of the surface of the film was 0.38. Optical microscope observation showed the accumulation of an abrasion powder in the depressed portion.
After the film was rotated for one hour while the urethane rubber member abutted against the film, the first portion formed a depressed portion having a width of 4.0 μm, the second portion formed a raised portion having a width of 4.0 μm, the height difference between the raised portion and the depressed portion was 0.25 μm, and the friction coefficient of the surface of the film was 0.32.
After the film was rotated for 20 hours while the urethane rubber member abutted against the film, the first portion formed a depressed portion having a width of 4.0 μm, the second portion formed a raised portion having a width of 4.0 μm, the height difference between the raised portion and the depressed portion was 0.25 μm, and the friction coefficient of the surface of the film was 0.27. Optical microscope observation showed the accumulation of an abrasion powder in the depressed portion.
After the film was rotated for one hour while the urethane rubber member abutted against the film, the first portion formed a depressed portion having a width of 4.0 μm, the second portion formed a raised portion having a width of 4.0 μm, the height difference between the raised portion and the depressed portion was 0.25 μm, and the friction coefficient of the surface of the film was 0.32.
After the film was rotated for 20 hours while the urethane rubber member abutted against the film, the first portion formed a depressed portion having a width of 4.0 μm, the second portion formed a raised portion having a width of 4.0 μm, the height difference between the raised portion and the depressed portion was 0.25 μm, and the friction coefficient of the surface of the film was 0.28. Optical microscope observation showed the accumulation of an abrasion powder in the depressed portion.
After the film was rotated for one hour while the urethane rubber member abutted against the film, no asperity was observed, and the friction coefficient of the surface of the film was 0.33.
After the film was rotated for 20 hours while the urethane rubber member abutted against the film, no asperity was observed, and the friction coefficient of the surface of the film was 0.52. An abrasion powder was produced by friction but was immediately removed from the friction surface.
After the film was rotated for one hour while the urethane rubber member abutted against the film, no asperity was observed, and the friction coefficient of the surface of the film was 0.35.
After the film was rotated for 20 hours while the urethane rubber member abutted against the film, no asperity was observed, and the friction coefficient of the surface of the film was 0.53. An abrasion powder was produced by friction but was immediately removed from the friction surface.
A reduction rate defined as described below was used as a measure of an effect of preventing an increase in the friction coefficient resulting from the abrasion powder flowing out of the wearing surface. A reduction rate of less than 0% indicates an increase in the friction coefficient with use.
Reduction rate=(the friction coefficient of a film after the film was rotated for one hour while a urethane rubber member abutted against the film−the friction coefficient of the film after the film was rotated for 20 hours while the urethane rubber member abutted against the film)/(the friction coefficient of the film after the film was rotated for one hour while the urethane rubber member abutted against the film)×100
Table 4 summarizes the results.
A photomask for use in the fabrication of an electrophotographic photosensitive member was prepared as described below.
A square nickel mesh having a line width of 10 μm, an opening size of 6 μm, and an opening ratio 14% (trade name: #1500, manufactured by Clever Co., Ltd.) was used as a photomask 1 for use in the fabrication of an electrophotographic photosensitive member.
Square nickel meshes having the line width, the opening size, and the opening ratio listed in Table 5 were used as photomasks 2 to 5 for use in the fabrication of an electrophotographic photosensitive member.
Honeycomb nickel meshes having the line width, the opening size, and the opening ratio listed in Table 5 were used as photomasks 6 to 8 for use in the fabrication of an electrophotographic photosensitive member.
A surface of a transparent polymer film having a thickness of 40 μm (trade name: Zeonor film ZF14-040, manufactured by Optes Inc.) was subjected to corona treatment for hydrophilization. Gold was deposited on the transparent polymer film to a thickness of 100 nm while the photomask 1 was placed on the transparent polymer film, forming a square pattern (the area percentage of the deposited gold pattern: 64%). The polymer film was used as a photomask 9 for use in the fabrication of an electrophotographic photosensitive member. The area percentage of the deposited gold pattern of the photomask 9 was 64%. The photomask 9 had a square pattern size (corresponding to the opening size in
Square patterns were formed in the same manner as in the photomask 9 for use in the fabrication of an electrophotographic photosensitive member except that photomasks 2 to 8 were placed on the transparent polymer film in gold vapor deposition. These polymer films were used as photomasks 10 to 16 for use in the fabrication of an electrophotographic photosensitive member. The area percentage of the deposited gold pattern of the photomask 10 was 36%. The area percentage of the deposited gold pattern of the photomask 11 was 46%. The area percentage of the deposited gold pattern of the photomask 12 was 64%. The area percentage of the deposited gold pattern of the photomask 13 was 78%. The area percentage of the deposited gold pattern of the photomask 14 was 34%. The area percentage of the deposited gold pattern of the photomask 15 was 23%. The area percentage of the deposited gold pattern of the photomask 16 was 62%. The photomask 10 had a square pattern size (corresponding to the opening size in
A square plain-woven stainless steel mesh having a line width of 1000 μm, an opening size of 1500 μm, and an opening ratio 36% was used as a photomask 101 for use in the fabrication of an electrophotographic photosensitive member.
A square nickel mesh having a line width of 18 μm, an opening size of 7 μm, and an opening ratio 8% (trade name: #1000, manufactured by Clever Co., Ltd.) was used as a photomask 102 for use in the fabrication of an electrophotographic photosensitive member.
A square nickel mesh having a line width of 4.5 μm, an opening size of 46.5 μm, and an opening ratio 83% (trade name: #500, manufactured by Clever Co., Ltd.) was used as a photomask 103 for use in the fabrication of an electrophotographic photosensitive member.
Square patterns were prepared in the same manner as in the photomask 9 for use in the fabrication of an electrophotographic photosensitive member except that photomasks 101 to 103 were placed on the transparent polymer film in gold vapor deposition. These polymer films were used as photomasks 104 to 106 for use in the fabrication of an electrophotographic photosensitive member. The area percentage of the deposited gold pattern of the photomask 104 was 22%. The area percentage of the deposited gold pattern of the photomask 105 was 8%. The area percentage of the deposited gold pattern of the photomask 106 was 83%. The photomask 104 had a square pattern size (corresponding to the opening size in
An aluminum cylinder having a diameter of 30 mm, a length of 357.5 mm, and a thickness of 0.75 mm was used as a support (electroconductive support).
A polyamide (trade name: Amilan CM8000, manufactured by Toray Industries, Inc.) was dissolved in methanol to prepare a coating liquid for an undercoat layer (the polyamide content was 5% by mass). The coating liquid for an undercoat layer was applied to the support by dip coating and was dried to form an undercoat layer having a thickness of 0.5 μm.
3.5 parts by mass of hydroxy gallium phthalocyanine crystals (a charge-generating substance), which have strong peaks at Bragg angles (2θ±0.2 degrees) of 7.4 and 28.2 degrees in CuKα characteristic X-ray diffraction, 1 part by mass of poly(vinyl butyral) (trade name: S-Lec BX-1, manufactured by Sekisui Chemical Co., Ltd.), and 120 parts by mass of cyclohexanone were dispersed in a sand mill with glass beads having a diameter of 1 mm for three hours. 120 parts by mass of ethyl acetate was added to the mixture to prepare a coating liquid for a charge-generating layer. The coating liquid for a charge-generating layer was applied to an undercoat layer by dip coating and was dried at 100° C. for 10 minutes to form the charge-generating layer having a thickness of 0.15 μm.
A coating liquid for a charge-transport layer prepared in the same manner as in Example 1-3 was applied to the charge-generating layer by dip coating and was dried at 125° C. for 80 minutes to form the charge-transport layer having a thickness of 20 μm. Through these processes, a plurality of electrophotographic photosensitive members 1 were fabricated.
Sixty parts by mass of dipentaerythritol hexaacrylate (trade name: Kayarad DPHA, manufactured by Nippon Kayaku Co., Ltd.), 60 parts by mass of tin oxide particles having an average particle size of 0.03 μm before dispersion, 20 parts by mass of 2,2-dimethoxy-1,2-diphenylethane-1-one (trade name: IRGACURE 651, manufactured by BASF) serving as a photopolymerization initiator, and 400 parts by mass of methanol were dispersed in a sand mill for 66 hours to prepare a coating liquid for a surface layer. The coating liquid for a surface layer was applied to the charge-transport layer of one of the electrophotographic photosensitive members 1 by dip coating and was irradiated with ultraviolet rays of a high-pressure mercury lamp such that the coating film had hardness of approximately 0.14 GPa, thus forming the surface layer. Through these processes, a plurality of electrophotographic photosensitive members 2 were fabricated. The electrophotographic photosensitive members 2 had a surface hardness of 0.14 GPa and a surface layer thickness of 3 μm.
One of the electrophotographic photosensitive members 2 was again irradiated with ultraviolet rays of the high-pressure mercury lamp for photo-curing and was subjected to post-baking at 130° C. for one hour to fabricate an electrophotographic photosensitive member 3. The electrophotographic photosensitive member 3 had a surface hardness of 0.52 GPa and a surface layer thickness of 3 μm.
The photomask 1 for use in the fabrication of an electrophotographic photosensitive member was cut into a piece having a width of 5 cm, which was then placed around one of the electrophotographic photosensitive members 2 as illustrated in
Electrophotographic photosensitive members 5 to 9 and 101 to 105 were fabricated in the same manner as in the electrophotographic photosensitive member 4 except that the photomask 1 for use in the fabrication of an electrophotographic photosensitive member was replaced by a photomask listed in Table 6. Table 6 summarizes the area percentage of a second surface region formed of the second portion (high hardness portion) in a 1 mm×1 mm square region disposed on an arbitrary position of the surface of the surface layer of the electrophotographic photosensitive members 5 to 9 and 101 to 105, as well as the hardness of the first portion (low hardness portion), the hardness of the second portion (high hardness portion), and the ratio of the hardness of the second portion (high hardness portion) to the hardness of the first portion (low hardness portion) of the electrophotographic photosensitive members 5 to 9 and 101 to 105. In the electrophotographic photosensitive members 5 to 9 and 101 to 105, both the first portion (low hardness portion) and the second portion (high hardness portion) of the surface layer passed through the surface layer. In the electrophotographic photosensitive members 5 to 9 and 101 to 105, a first surface region formed of the first portion (low hardness portion) and the second surface region accounted for 100% by area of the square region.
Sixty parts by mass of dipentaerythritol hexaacrylate (trade name: Kayarad DPHA, manufactured by Nippon Kayaku Co., Ltd.), 60 parts by mass of tin oxide particles having an average particle size of 0.03 μm before dispersion, 20 parts by mass of 2,2-dimethoxy-1,2-diphenylethane-1-one (trade name: IRGACURE 651, manufactured by BASF) serving as a photopolymerization initiator, and 400 parts by mass of methanol were dispersed in a sand mill for 66 hours to prepare a coating liquid for a surface layer. The coating liquid for a surface layer was applied to the charge-transport layer of one of the electrophotographic photosensitive members 1 by dip coating and was irradiated with ultraviolet rays of a high-pressure mercury lamp such that the coating film had hardness of approximately 0.31 GPa, forming the surface layer having a thickness of 3 μm. Thus, an electrophotographic photosensitive member was fabricated.
The photomask 12 for use in the fabrication of an electrophotographic photosensitive member was cut into a piece having a width of 5 cm, which was then placed around the electrophotographic photosensitive member as illustrated in
A plurality of electrophotographic photosensitive members 11 were fabricated in the same manner as in the electrophotographic photosensitive member 2 except that the coating liquid for a surface layer was changed as described below.
Sixty parts by mass of dipentaerythritol hexaacrylate (trade name: Kayarad DPHA, manufactured by Nippon Kayaku Co., Ltd.), 60 parts by mass of tin oxide particles having an average particle size of 0.04 μm before dispersion, 50 parts by mass of polytetrafluoroethylene particles (average particle size 0.18 μm), 20 parts by mass of 2,2-dimethoxy-1,2-diphenylethane-1-one (trade name: IRGACURE 651, manufactured by BASF) serving as a photopolymerization initiator, and 400 parts by mass of methanol were dispersed in a sand mill for 66 hours to prepare a coating liquid for a surface layer. The electrophotographic photosensitive members 11 had a surface hardness of 0.14 GPa and a surface layer thickness of 3 μm.
An electrophotographic photosensitive member 12 was fabricated in the same manner as in the electrophotographic photosensitive member 3 except that the coating liquid for a surface layer was changed as described below. The electrophotographic photosensitive member 12 had a surface hardness of 0.52 GPa and a surface layer thickness of 3 μm.
Sixty parts by mass of dipentaerythritol hexaacrylate (trade name: Kayarad DPHA, manufactured by Nippon Kayaku Co., Ltd.), 60 parts by mass of tin oxide particles having an average particle size of 0.04 μm before dispersion, 50 parts by mass of polytetrafluoroethylene particles (average particle size 0.18 μm), 20 parts by mass of 2,2-dimethoxy-1,2-diphenylethane-1-one (trade name: IRGACURE 651, manufactured by BASF) serving as a photopolymerization initiator, and 400 parts by mass of methanol were dispersed in a sand mill for 66 hours to prepare a coating liquid for a surface layer.
The photomask 1 for use in the fabrication of an electrophotographic photosensitive member was cut into a piece having a width of 5 cm, which was then placed around one of the electrophotographic photosensitive members 11 as illustrated in
Electrophotographic photosensitive members 14 to 27 were fabricated in the same manner as in the electrophotographic photosensitive member 13 except that the photomask 1 for use in the fabrication of an electrophotographic photosensitive member was replaced by a photomask listed in Table 7. Table 7 summarizes the area percentage of a second surface region formed of the second portion (high hardness portion) in a 1 mm×1 mm square region disposed on an arbitrary position of the surface of the surface layer of the electrophotographic photosensitive members 14 to 27, as well as the hardness of the first portion (low hardness portion), the hardness of the second portion (high hardness portion), and the ratio of the hardness of the second portion (high hardness portion) to the hardness of the first portion (low hardness portion) of the electrophotographic photosensitive members 14 to 27. In the electrophotographic photosensitive members 14 to 27, both the first portion (low hardness portion) and the second portion (high hardness portion) of the surface layer passed through the surface layer. In the electrophotographic photosensitive members 14 to 27, a first surface region formed of the first portion (low hardness portion) and the second surface region accounted for 100% by area of the square region.
Electrophotographic photosensitive members 28 and 29 were fabricated in the same manner as in the electrophotographic photosensitive member 24 except that the irradiation intensity of ultraviolet rays after the photomask was placed around the electrophotographic photosensitive member was increased such that the hardness of the first portion (low hardness portion), the hardness of the second portion (high hardness portion), and the ratio of the hardness of the second portion (high hardness portion) to the hardness of the first portion (low hardness portion) were changed as listed in Table 7. Table 7 summarizes the area percentage of a second surface region formed of the second portion (high hardness portion) in a 1 mm×1 mm square region disposed on an arbitrary position of the surface of the surface layer of the electrophotographic photosensitive members 28 and 29, as well as the hardness of the first portion (low hardness portion), the hardness of the second portion (high hardness portion), and the ratio of the hardness of the second portion (high hardness portion) to the hardness of the first portion (low hardness portion) of the electrophotographic photosensitive members 28 and 29. In the electrophotographic photosensitive members 28 and 29, both the first portion (low hardness portion) and the second portion (high hardness portion) of the surface layer passed through the surface layer. In the electrophotographic photosensitive members 28 and 29, a first surface region formed of the first portion (low hardness portion) and the second surface region accounted for 100% by area of the square region.
Five parts by mass of dipentaerythritol hexaacrylate (trade name: Kayarad DPHA, manufactured by Nippon Kayaku Co., Ltd.) and 20 parts by mass of an exemplary compound No. 14 (a compound having the structural formula (14)) were dissolved in a mixed solvent of 60 parts by mass of ethanol and 15 parts by mass of methyl ethyl ketone to prepare a coating liquid for a surface layer. The coating liquid for a surface layer was applied to the charge-transport layer of one of the electrophotographic photosensitive members 1 by dip coating and was irradiated with an electron beam such that the coating film had hardness of approximately 0.20 GPa, thus forming the surface layer. Through these processes, a plurality of electrophotographic photosensitive members 30 were fabricated. The electrophotographic photosensitive members 30 had a surface hardness of 0.20 GPa and a surface layer thickness of 3 μm.
An electrophotographic photosensitive member 31 was fabricated in the same manner as in the electrophotographic photosensitive member 30 except that the coating liquid for a surface layer was irradiated with a higher dose of electron beam and was then subjected to post-baking at 120° C. for one hour. The electrophotographic photosensitive member 31 had a surface hardness of 0.75 GPa and a surface layer thickness of 3 μm.
The photomask 1 for use in the fabrication of an electrophotographic photosensitive member was cut into a piece having a width of 5 cm, which was then placed around one of the electrophotographic photosensitive members 30 as illustrated in
Electrophotographic photosensitive members 33 to 39 and 201 to 203 were fabricated in the same manner as in the electrophotographic photosensitive member 32 except that the photomask 1 for use in the fabrication of an electrophotographic photosensitive member was replaced by a photomask listed in Table 8. Table 8 summarizes the area percentage of a second surface region formed of the second portion (high hardness portion) in a 1 mm×1 mm square region disposed on an arbitrary position of the surface of the surface layer of the electrophotographic photosensitive members 33 to 39 and 201 to 203, as well as the hardness of the first portion (low hardness portion), the hardness of the second portion (high hardness portion), and the ratio of the hardness of the second portion (high hardness portion) to the hardness of the first portion (low hardness portion) of the electrophotographic photosensitive members 33 to 39 and 201 to 203. In the electrophotographic photosensitive members 33 to 39 and 201 to 203, both the first portion (low hardness portion) and the second portion (high hardness portion) of the surface layer passed through the surface layer. In the electrophotographic photosensitive members 33 to 39 and 201 to 203, a first surface region formed of the first portion (low hardness portion) and the second surface region accounted for 100% by area of the square region.
An electrophotographic photosensitive member 40 was fabricated in the same manner as in the electrophotographic photosensitive member 34 except that the electron beam dose after the photomask was placed around the electrophotographic photosensitive member was increased such that the hardness of the first portion (low hardness portion), the hardness of the second portion (high hardness portion), and the ratio of the hardness of the second portion (high hardness portion) to the hardness of the first portion (low hardness portion) were changed as listed in Table 8. Table 8 summarizes the area percentage of a second surface region formed of the second portion (high hardness portion) in a 1 mm×1 mm square region disposed on an arbitrary position of the surface of the surface layer of the electrophotographic photosensitive member 40, as well as the hardness of the first portion (low hardness portion), the hardness of the second portion (high hardness portion), and the ratio of the hardness of the second portion (high hardness portion) to the hardness of the first portion (low hardness portion) of the electrophotographic photosensitive member 40. Both the first portion (low hardness portion) and the second portion (high hardness portion) of the electrophotographic photosensitive member 40 passed through the surface layer. A surface region formed of the first portion (low hardness portion) and the second surface region of the electrophotographic photosensitive member 40 accounted for 100% by area of the square region.
1.25 parts by mass of a fluorine-containing resin (trade name: GF-300, manufactured by Toagosei Co., Ltd.) was dissolved in a mixed solvent of 37.5 parts by mass of 1,1,2,2,3,3,4-heptafluorocyclopentane (trade name: Zeorora H, manufactured by Zeon Corp.) and 37.5 parts by mass of 1-propanol. 25 parts by mass of polytetrafluoroethylene particles (trade name: Lubron L-2, manufactured by Daikin Industries, Ltd.) were added as a lubricant to the solution. The mixture was dispersed three times in a high-pressure dispersing apparatus (trade name: Microfluidizer M-110EH, manufactured by Microfluidics) at a pressure of 58.8 MPa (600 kgf/cm2) to prepare a lubricant dispersion liquid.
20 parts by mass of dipentaerythritol hexaacrylate (trade name: Kayarad DPHA, manufactured by Nippon Kayaku Co., Ltd.), 80 parts by mass of the exemplary compound No. 14 (the compound having the structural formula (14)), 45 parts by mass of the lubricant dispersion liquid, 66.7 parts by mass of 1,1,2,2,3,3,4-heptafluorocyclopentane, and 66.7 parts by mass of 1-propanol were agitated and subjected to pressure filtration through a 5-μm polytetrafluoroethylene (PTFE) membrane filter to prepare a coating liquid for a surface layer. The coating liquid for a surface layer was applied to the charge-transport layer of one of the electrophotographic photosensitive members 1 by dip coating and was irradiated with an electron beam such that the coating film had hardness of approximately 0.19 GPa, thus forming the surface layer. Through these processes, a plurality of electrophotographic photosensitive members 41 were fabricated. The electrophotographic photosensitive members 41 had a surface hardness of 0.19 GPa and a surface layer thickness of 3 μm.
An electrophotographic photosensitive member 42 was fabricated in the same manner as in the electrophotographic photosensitive member 41 except that the coating liquid for a surface layer was irradiated with a higher dose of electron beam and was then subjected to post-baking at 120° C. for one hour. The electrophotographic photosensitive member 42 had a surface hardness of 0.74 GPa and a surface layer thickness of 3 μm.
The photomask 1 for use in the fabrication of an electrophotographic photosensitive member was cut into a piece having a width of 5 cm, which was then placed around one of the electrophotographic photosensitive members 41 as illustrated in
Electrophotographic photosensitive members 44 to 58, 62, and 301 to 303 were fabricated in the same manner as in the electrophotographic photosensitive member 43 except that the photomask for use in the fabrication of an electrophotographic photosensitive member was replaced by a photomask listed in Table 9. Table 9 summarizes the area percentage of a second surface region formed of the second portion (high hardness portion) in a 1 mm×1 mm square region disposed on an arbitrary position of the surface of the surface layer of the electrophotographic photosensitive members 44 to 58, 62, and 301 to 303, as well as the hardness of the first portion (low hardness portion), the hardness of the second portion (high hardness portion), and the ratio of the hardness of the second portion (high hardness portion) to the hardness of the first portion (low hardness portion) of the electrophotographic photosensitive members 44 to 58, 62, and 301 to 303. In the electrophotographic photosensitive members 44 to 58, 62, and 301 to 303, both the first portion (low hardness portion) and the second portion (high hardness portion) of the surface layer passed through the surface layer. In the electrophotographic photosensitive members 44 to 58, 62, and 301 to 303, a first surface region formed of the first portion (low hardness portion) and the second surface region accounted for 100% by area of the square region.
Ten parts by mass of dipentaerythritol hexaacrylate (trade name: Kayarad DPHA, manufactured by Nippon Kayaku Co., Ltd.) and 10 parts by mass of an exemplary compound No. 27 (a compound having the structural formula (27)) were dissolved in a mixed solvent of 60 parts by mass of ethanol and 15 parts by mass of methyl ethyl ketone to prepare a coating liquid for a surface layer. The coating liquid for a surface layer was applied to the charge-transport layer of one of the electrophotographic photosensitive members 1 by dip coating and was irradiated with an electron beam such that the coating film had hardness of approximately 0.10 GPa, thus forming the surface layer. Through these processes, a plurality of electrophotographic photosensitive members 41-2 were fabricated. The electrophotographic photosensitive members 41-2 had a surface hardness of 0.10 GPa and a surface layer thickness of 3 μm.
The photomask 3 for use in the fabrication of an electrophotographic photosensitive member was cut into a piece having a width of 5 cm, which was then placed around one of the electrophotographic photosensitive members 41-2 as illustrated in
Electrophotographic photosensitive members 60, 61, and 63 were fabricated in the same manner as in the electrophotographic photosensitive member 59 except that the electron beam dose after the photomask was placed around the electrophotographic photosensitive member was increased such that the hardness of the first portion (low hardness portion), the hardness of the second portion (high hardness portion), and the ratio of the hardness of the second portion (high hardness portion) to the hardness of the first portion (low hardness portion) were changed as listed in Table 9. Table 9 summarizes the area percentage of a second surface region formed of the second portion (high hardness portion) in a 1 mm×1 mm square region disposed on an arbitrary position of the surface of the surface layer of the electrophotographic photosensitive members 60, 61, and 63, as well as the hardness of the first portion (low hardness portion), the hardness of the second portion (high hardness portion), and the ratio of the hardness of the second portion (high hardness portion) to the hardness of the first portion (low hardness portion) of the electrophotographic photosensitive members 60, 61, and 63. In the electrophotographic photosensitive members 60, 61, and 63, both the first portion (low hardness portion) and the second portion (high hardness portion) of the surface layer passed through the surface layer. In the electrophotographic photosensitive members 60, 61, and 63, a first surface region formed of the first portion (low hardness portion) and the second surface region accounted for 100% by area of the square region.
A surface of the electrophotographic photosensitive member 3 was polished with a lapping tape to Rz=0.5 μm, thus fabricating an electrophotographic photosensitive member 64.
A surface of the electrophotographic photosensitive member 31 was polished with a lapping tape to Rz=0.5 μm, thus fabricating an electrophotographic photosensitive member 65.
One of the electrophotographic photosensitive members 1 was rotated while the electrophotographic photosensitive member 1 was pressed against a metal mold having a depressed portion to form a quadrangular prism raised portion on the surface of the electrophotographic photosensitive member 1 (the quadrangular prism had a 6 μm×6 μm bottom and a height of 0.2 μm and accounted for 14% by area of a 1 mm×1 mm square region). Through these processes, an electrophotographic photosensitive member 66 was fabricated.
Electrophotographic photosensitive members 2 to 10 and 101 to 105 were evaluated.
The electrophotographic photosensitive members 2 to 10 and 101 to 105 were installed in a monochrome copying machine GP-215 (trade name) manufactured by CANON KABUSHIKI KAISHA. 10,000 sheets of an image were output at a temperature of 30° C. and a humidity of 80% RH. The status (blade curling and blade chattering) of a cleaning blade (urethane rubber blade) in contact with (abutting against) an electrophotographic photosensitive member was evaluated. The monochrome copying machine GP-215 (trade name) includes a cleaning unit configured to clean the surface of an electrophotographic photosensitive member. The cleaning unit includes a cleaning blade configured to come into contact with the surface of the electrophotographic photosensitive member.
In Tables 10 to 13, the occurrence of blade curling or blade chattering during the output of 10,000 sheets of an image was indicated by B, and the nonoccurrence of blade curling or blade chattering was indicated by A.
After 10,000 sheets of an image were output, a urethane rubber blade (urethane blade) was made to abut against the electrophotographic photosensitive member at an angle of 26 degrees under a vertical load of 30 g at a friction speed of 100 mm/min as illustrated in
After 10,000 sheets of an image were output, the abrasion loss of the surface of the electrophotographic photosensitive member was measured with an ultra-high depth shape measurement microscope (trade name: VK-9510) manufactured by Keyence Corp. and an image processor (trade name: Luzex AP) manufactured by Nireco Corp.
Table 10 summarizes the results of Examples 4-1 to 4-6 and Comparative Examples 4-1 to 4-8.
Examples 4-1 to 4-6, in which the ratio of the hardness of the second portion to the hardness of the first portion was in the range of 1.2 to 30 and the second surface region accounted for 10% to 80% by area, had a low friction coefficient even after the 10,000 sheets of an image were output.
In Comparative Examples 4-1 and 4-2, which included no first portion and no second portion, the friction decreasing effect due to the difference in height between the first portion and the second portion could not be obtained.
Comparative Example 4-3, in which the ratio of the hardness of the second portion to the hardness of the first portion was less than 1.2, had an insufficient difference in height between the first portion and the second portion and an insufficient friction decreasing effect.
In Comparative Example 4-5, in which the second surface region accounted for less than 10% by area, the contact area between the second surface region and the cleaning blade was small. Thus, the raised second portion was easily broken under the load, and the friction decreasing effect was insufficient.
In Comparative Examples 4-6 and 4-8, in which the second surface region accounted for more than 80% by area, the contact area between the second surface region and the cleaning blade was large. Thus, the friction decreasing effect was insufficient.
In Comparative Examples 4-4 and 4-7, in which the second surface region accounted for less than 10% by area in one area and more than 80% by area in the other area. Thus, the friction decreasing effect was insufficient.
The electrophotographic photosensitive members 11 to 29 were evaluated in the same manner as in Examples 4-1 to 4-6 and Comparative Examples 4-1 to 4-8.
Table 11 summarizes the results of Examples 4-7 to 4-23 and Comparative Examples 4-9 and 4-10.
Examples 4-24 to 4-32 and Comparative Examples 4-11 to 4-15
The electrophotographic photosensitive members 30 to 40 and 201 to 203 were evaluated in the same manner as in Examples 4-1 to 4-6 and Comparative Examples 4-1 to 4-8 except that the electrophotographic apparatus was changed from the monochrome copying machine GP-215 (trade name) manufactured by CANON KABUSHIKI KAISHA to a monochrome copying machine GP-405 (trade name) manufactured by CANON KABUSHIKI KAISHA and that the number of output sheets was changed from 10,000 to 20,000. The monochrome copying machine GP-405 (trade name) also includes a cleaning unit configured to clean the surface of an electrophotographic photosensitive member. The cleaning unit includes a cleaning blade configured to come into contact with the surface of the electrophotographic photosensitive member.
Table 12 summarizes the results of Examples 4-24 to 4-32 and Comparative Examples 4-11 to 4-15.
The electrophotographic photosensitive members 41 to 63 and 301 to 303 were evaluated in the same manner as in Examples 4-24 to 4-32 and Comparative Examples 4-11 to 4-15. Table 13 summarizes the results of Examples 4-33 to 4-51 and Comparative Examples 4-16 to 4-25.
While the present invention has been described with reference to exemplary embodiments, it is to be understood that the invention is not limited to the disclosed exemplary embodiments. The scope of the following claims is to be accorded the broadest interpretation so as to encompass all such modifications and equivalent structures and functions.
This application claims the benefit of Japanese Patent Applications No. 2011-088442, filed Apr. 12, 2011, No. 2011-094158, filed Apr. 20, 2011, No. 2011-110620, filed May 17, 2011, No. 2012-053581, filed Mar. 9, 2012, and No. 2012-085035, filed Apr. 3, 2012, which are hereby incorporated by reference herein in their entirety.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2011-088442 | Apr 2011 | JP | national |
| 2011-094158 | Apr 2011 | JP | national |
| 2011-110620 | May 2011 | JP | national |
| 2012-053581 | Mar 2012 | JP | national |
| 2012-085035 | Apr 2012 | JP | national |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/JP2012/059953 | 4/5/2012 | WO | 00 | 9/25/2013 |
