WO2017072972A1 - 電子写真用感光体、その製造方法および電子写真装置 - Google Patents
電子写真用感光体、その製造方法および電子写真装置 Download PDFInfo
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
- G03G5/02—Charge-receiving layers
- G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
- G03G5/043—Photoconductive layers characterised by having two or more layers or characterised by their composite structure
- G03G5/047—Photoconductive layers characterised by having two or more layers or characterised by their composite structure characterised by the charge-generation layers or charge transport layers
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- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G15/00—Apparatus for electrographic processes using a charge pattern
- G03G15/75—Details relating to xerographic drum, band or plate, e.g. replacing, testing
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- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G15/00—Apparatus for electrographic processes using a charge pattern
- G03G15/75—Details relating to xerographic drum, band or plate, e.g. replacing, testing
- G03G15/751—Details relating to xerographic drum, band or plate, e.g. replacing, testing relating to drum
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
- G03G5/02—Charge-receiving layers
- G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
- G03G5/05—Organic bonding materials; Methods for coating a substrate with a photoconductive layer; Inert supplements for use in photoconductive layers
- G03G5/0525—Coating methods
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
- G03G5/02—Charge-receiving layers
- G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
- G03G5/05—Organic bonding materials; Methods for coating a substrate with a photoconductive layer; Inert supplements for use in photoconductive layers
- G03G5/0528—Macromolecular bonding materials
- G03G5/0557—Macromolecular bonding materials obtained otherwise than by reactions only involving carbon-to-carbon unsatured bonds
- G03G5/056—Polyesters
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- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
- G03G5/02—Charge-receiving layers
- G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
- G03G5/05—Organic bonding materials; Methods for coating a substrate with a photoconductive layer; Inert supplements for use in photoconductive layers
- G03G5/0528—Macromolecular bonding materials
- G03G5/0557—Macromolecular bonding materials obtained otherwise than by reactions only involving carbon-to-carbon unsatured bonds
- G03G5/0578—Polycondensates comprising silicon atoms in the main chain
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- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
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- G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
- G03G5/05—Organic bonding materials; Methods for coating a substrate with a photoconductive layer; Inert supplements for use in photoconductive layers
- G03G5/0528—Macromolecular bonding materials
- G03G5/0589—Macromolecular compounds characterised by specific side-chain substituents or end groups
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- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
- G03G5/02—Charge-receiving layers
- G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
- G03G5/06—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic
- G03G5/0601—Acyclic or carbocyclic compounds
- G03G5/0603—Acyclic or carbocyclic compounds containing halogens
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
- G03G5/02—Charge-receiving layers
- G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
- G03G5/06—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic
- G03G5/0601—Acyclic or carbocyclic compounds
- G03G5/0605—Carbocyclic compounds
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
- G03G5/02—Charge-receiving layers
- G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
- G03G5/06—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic
- G03G5/0601—Acyclic or carbocyclic compounds
- G03G5/0609—Acyclic or carbocyclic compounds containing oxygen
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
- G03G5/02—Charge-receiving layers
- G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
- G03G5/06—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic
- G03G5/0601—Acyclic or carbocyclic compounds
- G03G5/0612—Acyclic or carbocyclic compounds containing nitrogen
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
- G03G5/02—Charge-receiving layers
- G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
- G03G5/06—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic
- G03G5/0622—Heterocyclic compounds
- G03G5/0624—Heterocyclic compounds containing one hetero ring
- G03G5/0627—Heterocyclic compounds containing one hetero ring being five-membered
- G03G5/0631—Heterocyclic compounds containing one hetero ring being five-membered containing two hetero atoms
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
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- G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
- G03G5/06—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic
- G03G5/0664—Dyes
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- G03G5/0677—Monoazo dyes
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- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
- G03G5/14—Inert intermediate or cover layers for charge-receiving layers
- G03G5/147—Cover layers
Definitions
- the present invention relates to an electrophotographic photosensitive member (hereinafter, also simply referred to as a “photosensitive member”) used in an electrophotographic printer, a copier, a facsimile, etc., a method of manufacturing the same, and an electrophotographic apparatus.
- the present invention relates to a photosensitive member for electrophotography having high sensitivity, low residual potential, no light fatigue, and excellent contamination resistance, a method for producing the same, and an electrophotographic apparatus, by combining the above with a specific electron transport material.
- An electrophotographic photoreceptor is required to have a function of holding surface charge in a dark place, a function of receiving light to generate a charge, and a function of receiving light and transporting a charge as well.
- the layer is functionally separated into a so-called single-layer type photoreceptor that combines these functions and a layer that mainly contributes to charge generation and a layer that contributes to the retention of surface charge in the dark and charge transport at the time of light reception.
- the Carlson method is applied to image formation by electrophotography using these electrophotographic photoreceptors.
- image formation charging of the photoreceptor in a dark place, formation of an electrostatic image such as characters and pictures of a document on the charged photoreceptor surface, and development of the formed electrostatic image by toner And transfer fixing of the developed toner image to a support such as paper.
- the photoreceptor after transferring the toner image is reused after removal of residual toner and charge removal.
- materials for the above-mentioned electrophotographic photosensitive member materials in which inorganic photoconductive materials such as selenium, selenium alloy, zinc oxide or cadmium sulfide are dispersed in a resin binder, poly-N-vinylcarbazole, 9 10, Anthracenediol polyester, pyrazoline, hydrazone, stilbene, butadiene, benzidine, phthalocyanine or bisazo compound dispersed in resin binder, or vacuum evaporated or sublimated, etc. Is used.
- a photosensitive member composed of poly-N-vinylcarbazole and 2,4,7-trinitolulor-9-one (described in Patent Document 1)
- a photosensitive member composed mainly of an organic pigment (described in Patent Document 2)
- a functionally separated multi-layer type photosensitive member in which a photosensitive layer is formed by laminating a charge generation layer containing a charge generation material and a charge transport layer containing a charge transport material has become mainstream.
- a negatively charged type in which a charge transport layer is formed by using an organic pigment as a charge generation material, a deposited layer or a layer dispersed in a resin as a charge generation layer, and using an organic low molecular weight compound as a charge transport material.
- organic photoreceptors have been proposed.
- organic materials have many advantages that inorganic materials do not, at present there is no material that fully satisfies all the properties required for electrophotographic photoreceptors. That is, the deterioration of the image quality is caused by the decrease of the charging potential due to the repeated use, the increase of the residual potential, the change of sensitivity and the like. Although the cause of this deterioration is not completely understood, one of the factors is that the resin is repeatedly exposed to image exposure and discharge lamp light, and exposed to external light during maintenance. It is conceivable that the material may be photodegraded or the charge transport material may be decomposed.
- Patent Document 4 describes that in the surface protective layer, a dye or an ultraviolet absorber having an absorption property including the absorption wavelength range of the charge transport layer is added.
- Patent Document 5 describes that a yellow dye is added to the charge transport layer.
- the contamination resistance of the photoreceptor surface is also strictly required.
- polycarbonate resin is mainly used as a binder resin, but polyarylate resin is also used. Since the photosensitive member always contacts the charging roller and the transfer roller, the components of the roller component contaminate the surface of the photosensitive member, and there is a problem that black streaks occur in a halftone image.
- the transfer roller mainly contains rubber.
- a method using a rubber composition having an epichlorohydrin rubber as a component and containing a filler has been proposed.
- the conductive roller has a sea-island structure in which an island phase of rubber component B mainly composed of epichlorohydrin rubber is dispersed in a sea phase of rubber component A mainly composed of acrylonitrile butadiene rubber.
- a method of using a rubber composition having the same has been proposed.
- the rubber material of the rubber layer is made of a polymer containing acrylonitrile butadiene rubber as a main component
- a method is proposed in which sulfur and chlorine-free subs are contained in an amount of 20 parts by mass or more with respect to 100 parts by mass of acrylonitrile butadiene rubber.
- these methods have not been able to sufficiently respond to contamination resistance.
- the polyarylate resin shows a good stain resistance result as compared with the polycarbonate resin, but on the other hand, there is a concern that deterioration by light may occur. That is, the polyarylate resin has a high ability to absorb ultraviolet light, absorbs ultraviolet energy, causes a fleece transfer reaction, and produces a benzophenone structure in the surface layer portion of the resin, so it is weak to light resistance.
- an object of the present invention is to provide a photosensitive member for electrophotography having high sensitivity, low residual potential, no light fatigue, and sufficient stain resistance, in order to solve the above problems.
- An electrophotographic apparatus is provided.
- the present inventors have used polyarylate resin in the outermost surface layer of the photoreceptor and added specific electron transport materials to achieve high sensitivity and residual potential. Low light fatigue, light penetration from components of the charging roller and the transfer roller to the photosensitive member surface is suppressed, and a photosensitive member with improved contamination resistance can be obtained.
- the present invention has been completed.
- the electrophotographic photoreceptor of the present invention is an electrophotographic photoreceptor having at least a photosensitive layer on a conductive substrate,
- the outermost surface layer contains at least a resin binder and an electron transport material
- the resin binder contains a polyarylate resin having a structural unit represented by the following chemical structural formula 1
- the electron transport material has the following general formula (ET2) It is characterized by containing the compound which has a structure represented by these.
- W 1 and W 2 are a single bond, —O—, —S—, —SO—, —CO—, —SO 2 —, —CR 22 R 23 — (R 22 and R 23 may be the same. It may be different, and a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a halogenated alkyl group, or 6 carbon atoms 12 substituted or unsubstituted aryl groups), substituted or unsubstituted cycloalkylidene groups having 5 to 12 carbon atoms, substituted or unsubstituted ⁇ , ⁇ alkylene groups having 2 to 12 carbon atoms, -9, 9- Two different types selected from the group consisting of a fluorenylidene group, a substituted or unsubstituted arylene group having 6 to 12 carbon atoms, and a divalent group containing an aryl group or an arylene group having 6 to 12 carbon atoms.
- R 20 which may be the same or different, each represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a fluorine atom, a chlorine atom or a bromine atom
- R 21 represents a hydrogen atom having 1 to 20 carbon atoms
- An alkyl group, an aryl group which may have a substituent, a cycloalkyl group which may have a substituent, a fluorine atom, a chlorine atom or a bromine atom is shown, and s and t each represents an integer of 1 or more.
- R 32 to R 37 are the same or different and are a hydrogen atom, a halogen atom, a cyano group, a nitro group, a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms
- an acyl group an alkenyl group, an alkynyl group, a carboxyl group, a carbonyl group, a carboxylic acid group and a halogenated alkyl group, and the substituent is a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy having 1 to 6 carbon atoms.
- the electron transporting material preferably further contains one or both of the compounds having a structure represented by the following general formula (ET1) or (ET3).
- R 24 and R 25 are the same or different and each represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or an aryl group which may have a substituent
- R 26 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a substituent, a cycloalkyl group, an aralkyl group which may have a substituent, or a halogenated alkyl group
- R 27 to R 31 are the same or different and each represents a hydrogen atom, a halogen atom, a carbon atom, or an aryl group which may have a cycloalkyl group, a cycloalkyl group, an aral
- R 38 and R 39 are the same or different and are a hydrogen atom, a halogen atom, a cyano group, a nitro group, a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms
- An aryl group which may have a substituent, a heterocyclic group which may have a substituent, an ester group, a cycloalkyl group, an aralkyl group which may have a substituent, an allyl group, an amide group, an amino group
- an acyl group an alkenyl group, an alkynyl group, a carboxyl group, a carbonyl group, a carboxylic acid group and a halogenated alkyl group, and the substitu
- the photosensitive layer is preferably the outermost surface layer, and a surface protective layer is preferably provided on the photosensitive layer, and the surface protective layer is preferably the outermost surface layer.
- the photosensitive layer preferably comprises a charge generation layer and a charge transport layer, the charge transport layer is preferably the outermost surface layer, and the photosensitive layer is a positively charged single layer type. It is also preferable that the photosensitive layer be composed of a charge transport layer and a charge generation layer, and the charge generation layer be the outermost surface layer.
- the outermost surface layer preferably contains 10 parts by mass or less of the electron transport material with respect to 100 parts by mass of the resin binder.
- a method of manufacturing a photosensitive member according to the present invention is a method of manufacturing a photosensitive member for electrophotography, including the step of applying a coating solution on a conductive substrate to form an outermost surface layer,
- the coating solution is characterized by containing a polyarylate resin having a structural unit represented by the chemical structural formula 1 and a compound having a structure represented by the general formula (ET2).
- An electrophotographic apparatus is characterized in that the electrophotographic photosensitive member according to the present invention is mounted.
- the high sensitivity, low residual potential, and no light fatigue are suppressed, and the penetration of the component that exudes from the components of the charging roller and the transfer roller onto the photosensitive member surface is suppressed, and the contamination resistance is improved. It has become possible to realize the electrophotographic photoreceptor, the method for producing the same, and the electrophotographic apparatus.
- FIG. 6C is a schematic cross-sectional view showing an example of the positive charge function separation type laminate type electrophotographic photoreceptor according to the present invention.
- FIG. 1 is a schematic configuration view showing one configuration example of an electrophotographic apparatus of the present invention.
- the electrophotographic photoreceptor comprises a negatively charged laminate type photoreceptor and a positively charged laminate type photoreceptor as a function separation type laminate type photoreceptor, and a single-layer type photoreceptor mainly composed of a positive charge type. It is divided roughly.
- FIG. 1 is a schematic cross-sectional view showing an electrophotographic photoreceptor according to an embodiment of the present invention, wherein (a) shows an example of a negatively charged type functionally separated laminated electrophotographic photoreceptor, and (b) shows a positive. An example of a charged single layer type electrophotographic photosensitive member is shown, and (c) is an example of a positively charged type function separation laminated type electrophotographic photosensitive member.
- a photosensitive layer is formed on an electroconductive substrate 1 comprising an undercoat layer 2, a charge generation layer 4 having a charge generation function and a charge transport layer 5 having a charge transport function. Layers 3 are sequentially stacked.
- an undercoat layer 2 and a single photosensitive layer 3 having both functions of charge generation and charge transport are sequentially laminated on the conductive substrate 1. ing.
- a photosensitive layer 3 comprising an undercoat layer 2, a charge transport layer 5 having a charge transport function, and a charge generation layer 4 having a charge generation function on a conductive substrate 1 Are sequentially stacked.
- the undercoat layer 2 may be provided as necessary, and a surface protective layer 6 may be further provided on the photosensitive layer 3.
- the term "photosensitive layer” is a concept including both a laminated photosensitive layer in which a charge generation layer and a charge transport layer are laminated, and a single layer photosensitive layer.
- the present invention it is important to use a polyarylate resin and a specific electron transport material in combination in any of the photosensitive layer constituting the outermost surface layer of the photosensitive member, the surface protective layer and the like. That is, when the outermost surface layer is a photosensitive member having a photosensitive layer, the desired effect of the present invention can be obtained by containing a polyarylate resin and a specific electron transport material in the photosensitive layer. it can.
- the photosensitive layer is a negatively charged multi-layered photosensitive member comprising a charge generation layer and a charge transport layer
- the outermost surface layer is a charge transport layer
- the charge transport layer comprises a polyarylate resin and specific electrons.
- the intended effect of the present invention can be obtained.
- the photosensitive layer is a positively charged single layer type photosensitive member in which the photosensitive layer is a positively charged single layer type
- the present invention can be achieved by containing a polyarylate resin and a specific electron transport material in the single layer type photosensitive layer.
- the desired effect of can be obtained.
- the photosensitive layer is a positively charged laminated type photoreceptor comprising a charge transport layer and a charge generation layer, and the outermost surface layer is a charge generation layer
- the charge generation layer is charged with a polyarylate resin and a specific electron transport.
- the surface protective layer contains a polyarylate resin and a specific electron transport material. The intended effect of the present invention can be obtained.
- the addition amount of the specific electron transport material in the outermost surface layer is preferably 10 parts by mass or less with respect to 100 parts by mass of the resin binder contained in the layer.
- the range of 1 to 10 parts by mass is more preferable, and the range of 3 to 5 parts by mass is particularly preferable. If the amount of the compound used exceeds 10 parts by mass, precipitation occurs, which is not preferable.
- the conductive substrate 1 serves as an electrode of the photosensitive member and simultaneously serves as a support of each layer constituting the photosensitive member, and may have any shape such as a cylindrical shape, a plate shape, or a film shape.
- a material of the conductive substrate metals such as aluminum, stainless steel, nickel and the like, or a material such as glass, resin or the like subjected to a conductive treatment can be used.
- the undercoat layer 2 is composed of a layer containing a resin as a main component and a metal oxide film such as alumite.
- the undercoat layer 2 controls the injection of charges from the conductive substrate 1 to the photosensitive layer, or covers the defects on the surface of the conductive substrate, improves the adhesion between the photosensitive layer and the conductive substrate 1, etc.
- the resin material used for the undercoat layer 2 include insulating polymers such as casein, polyvinyl alcohol, polyamide, melamine and cellulose, and conductive polymers such as polythiophene, polypyrrole and polyaniline. These resins may be used alone or in combination. Alternatively, they can be used in combination as appropriate. In addition, metal oxides such as titanium dioxide and zinc oxide may be contained in these resins and used.
- the charge generation layer 4 is formed by a method such as applying a coating solution in which particles of a charge generation material are dispersed in a resin binder, and receives light to generate charge.
- the charge generation efficiency is high and the chargeability of the generated charge to the charge transport layer 5 is important, and the dependence on the electric field is small, and it is desirable that the injection be good even in a low electric field.
- Charge generation materials include X-type metal-free phthalocyanine, ⁇ -type metal-free phthalocyanine, ⁇ -type titanyl phthalocyanine, ⁇ -type titanyl phthalocyanine, Y-type titanyl phthalocyanine, ⁇ -type titanyl phthalocyanine, amorphous-type titanyl phthalocyanine, and ⁇ -type copper phthalocyanine Compounds, various azo pigments, anthanthrone pigments, thiapyrilium pigments, perylene pigments, perinone pigments, squarylium pigments, quinacridone pigments, etc.
- a resin binder polycarbonate resin, polyester resin, polyamide resin, polyurethane resin, vinyl chloride resin, vinyl acetate resin, phenoxy resin, phenoxy resin, polyvinyl acetal resin, polyvinyl butyral resin, polystyrene resin, polysulfone resin, diallyl phthalate resin, methacrylic acid ester resin It is possible to use a combination of polymers and copolymers of the following.
- the content of the resin binder in the charge generation layer 4 is preferably 20 to 80% by mass, more preferably 30 to 70% by mass, with respect to the solid content of the charge generation layer 4. Further, the content of the charge generation material in the charge generation layer 4 is preferably 20 to 80% by mass, more preferably 30 to 70% by mass with respect to the solid content in the charge generation layer 4.
- the charge generation layer 4 Since the charge generation layer 4 only needs to have a charge generation function, its film thickness is determined by the light absorption coefficient of the charge generation material, and is generally 1 ⁇ m or less, preferably 0.5 ⁇ m or less.
- the charge generation layer 4 may be mainly composed of a charge generation material, to which a charge transport material or the like may be added.
- the charge transport layer 5 is mainly composed of a charge transport material and a resin binder.
- a polyarylate resin having a structural unit represented by the chemical structural formula 1 as a resin binder of the charge transport layer 5.
- such polyarylate resin may have other structural units.
- the blending ratio of the structural unit represented by the chemical structural formula 1 is preferably 10 to 100 mol%, and more preferably 50 to 100 mol%.
- the photoreceptor of the present invention when the total amount of the structural unit represented by the chemical structural formula 1 (a 1 + a 2 + b 1 + b 2 + c + d + e + f) and 100 mol%, as the amount of the siloxane component (c + d + e + f ) is It is 0 to 10 mol%. Furthermore, in the photosensitive member of the present invention, in the chemical structural formula 1, c and d are preferably 0 mol%, or e and f are preferably 0 mol%.
- s and t are integers of 1 or more and 400 or less, preferably 1 or more and 400 or less, more preferably 8 or more and 250 or less.
- W 2 is a single bond, —O— or —CR 22 R 23 — (R 22 and R 23 are each may be the same or different and is preferably a hydrogen atom, a methyl group or an ethyl group), also, W 1 is, -CR 22 R 23 - (R 22 and R 23 are the same Which may be different or different and is preferably a hydrogen atom, a methyl group or an ethyl group). More preferably, W 1 is a methylene group, W 2 is a single bond, R 1 and R 6 are methyl groups, and R 2 to R 5 and R 7 to R 20 are hydrogen atoms.
- siloxane structure of the polyarylate resin of the above-mentioned chemical structural formula 1 for example, the following molecular formula (2) (Reactive silicone Silaplain FM4411 (weight average molecular weight 1000) manufactured by Chisso Corporation, FM 4421 (weight average molecular weight 5000), FM 4425 (Weight average molecular weight 15000)) Component monomers such as the following molecular formula (3) (Reactive silicone Cylaplane FMDA 11 (weight average molecular weight 1000), FMDA 21 (weight average molecular weight 5000), FMDA 26 (weight average molecular weight 15000)) Can be mentioned.
- molecular formula (3) Reactive silicone Cylaplane FMDA 11 (weight average molecular weight 1000), FMDA 21 (weight average molecular weight 5000), FMDA 26 (weight average molecular weight 15000)
- R 21 represents an n-butyl group.
- the polyarylate resin represented by the above-mentioned chemical structural formula 1 may be used alone or in combination with other resins.
- Such other resins include other polyarylate resins, and further various polycarbonate resins such as bisphenol A type, bisphenol Z type, bisphenol A type-biphenyl copolymer, bisphenol Z type-biphenyl copolymer, polyphenylene resin polyphenylene resin , Polyester resin, polyvinyl acetal resin, polyvinyl butyral resin, polyvinyl alcohol resin, vinyl chloride resin, vinyl acetate resin, polyethylene resin, polypropylene resin, polypropylene resin, acrylic resin, polyurethane resin, epoxy resin, melamine resin, silicone resin, polyamide resin, polystyrene resin Polyacetal resin, polysulfone resin, polymers of methacrylic acid ester, copolymers of these, and the like can be used. Furthermore, the same kind of resins having different molecular weights may be mixed and used.
- the content of the resin binder is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, with respect to the solid content of the charge transport layer 5. Further, the content of the polyarylate resin with respect to the resin binder is preferably in the range of 1% by mass to 100% by mass, and more preferably 5% by mass to 80% by mass.
- the weight average molecular weight of these polyarylate resins is preferably 5,000 to 250,000, and more preferably 10,000 to 150,000.
- R 21 represents an n-butyl group.
- the charge transport layer 5 When the charge transport layer 5 is the outermost surface layer, it is necessary to contain a compound having a structure represented by the above general formula (ET2) as the electron transport material constituting the charge transport layer.
- a compound having a structure represented by the above general formula (ET2) as the electron transport material constituting the charge transport layer.
- an electron transporting material having an electron attractive substituent such as chloro group (-Cl)
- HOMO / LUMO becomes deeper, electron acceptability is improved and mobility is improved as compared with the case of no substitution. It is preferable because the speed is increased, the electron transporting ability is increased, and the resistance to light fatigue is improved in a photoreceptor using the same.
- the electron transport material constituting the charge transport layer preferably further contains one or both of the compounds having the structure represented by the above general formula (ET1) or (ET3), and in addition, it is anhydrous Succinic acid, maleic anhydride, dibromosuccinic anhydride, phthalic anhydride, 3-nitrophthalic anhydride, 4-nitrophthalic anhydride, pyromellitic anhydride, pyromellitic acid, trimellitic acid, trimellitic anhydride, phthalimide, 4-nitrophthalimide, tetracyanoethylene, tetracyanoquinodimethane, chloranil, bromanyl, o-nitrobenzoic acid, malononitrile, trinitrofluorenone, trinitrothioxanthone, dinitrobenzene, dinitroanthracene, dinitroacridine, nitroanthraquinone, dinitroanthraquinone, Thiopi 1 type of electron transport materials (acceptor compounds) such as quinone compounds, quin
- charge transport material of the charge transport layer 5 various hydrazone compounds, styryl compounds, diamine compounds, butadiene compounds, indole compounds and the like can be used singly or in combination as appropriate.
- charge transport materials include, but are not limited to, those shown in the following (II-1) to (II-14).
- the content of the resin binder in the charge transport layer 5 is preferably 20 to 90% by mass, more preferably 30 to 80% by mass, with respect to the solid content of the charge transport layer 5.
- the content of the hole transport material in the charge transport layer 5 is preferably 9.8 to 71% by mass, more preferably 19.4 to 65.5% by mass with respect to the solid content of the charge transport layer 5. %.
- the content of the electron transport material in the charge transport layer 5 is preferably 0.2 to 9% by mass, more preferably 0.6 to 4.5% by mass with respect to the solid content of the charge transport layer 5 .
- the thickness of the charge transport layer 5 is preferably in the range of 3 to 50 ⁇ m, and more preferably in the range of 15 to 40 ⁇ m, in order to maintain a practically effective surface potential.
- the photosensitive layer 3 in the case of the single layer type mainly comprises a charge generating material, a hole transporting material, an electron transporting material (acceptor compound) and a resin binder.
- charge generating material for example, phthalocyanine pigments, azo pigments, anthrone pigments, perylene pigments, perinone pigments, polycyclic quinone pigments, squarylium pigments, thiapyrylium pigments, quinacridone pigments and the like can be used.
- these charge generation materials can be used alone or in combination of two or more.
- Preferred examples of -perylene-bis (carboximide) and phthalocyanine pigments are metal free phthalocyanine, copper phthalocyanine and titanyl phthalocyanine.
- titanyl phthalocyanine having a Bragg angle 2 ⁇ of 9.6 ° as the maximum peak in the CuK ⁇ : X-ray diffraction spectrum described in US Pat. No. 5,736,282 and US Pat. No. 5,874,570 sensitivity, durability and image quality are improved It shows a significantly improved effect in point.
- the content of the charge generation material is preferably 0.1 to 20% by mass, and more preferably 0.5 to 10% by mass, with respect to the solid content of the single layer type photosensitive layer 3.
- the hole transport material for example, hydrazone compounds, pyrazoline compounds, pyrazolone compounds, oxadiazole compounds, oxazole compounds, arylamine compounds, benzidine compounds, stilbene compounds, styryl compounds, poly-N-vinylcarbazole, polysilane, etc. are used. can do. In addition, these hole transport materials can be used alone or in combination of two or more.
- the hole transport material used in the present invention is preferably one that is excellent in the ability to transport holes generated upon irradiation with light and that it is suitable for combination with a charge generation material.
- the content of the hole transport material is preferably 3 to 80% by mass, and more preferably 5 to 60% by mass, with respect to the solid content of the single-layer type photosensitive layer 3.
- the electron transport material of the single-layer type photosensitive layer 3 when the single-layer type photosensitive layer 3 is the outermost surface layer, a compound having a structure represented by the above general formula (ET2) is contained as the electron transport material of the single-layer type photosensitive layer 3. is necessary.
- the electron transport material of the single-layer type photosensitive layer 3 preferably further contains one or both of the compounds having a structure represented by the above general formula (ET1) or (ET3), and in addition, Succinic anhydride, maleic anhydride, dibromosuccinic anhydride, phthalic anhydride, 3-nitrophthalic anhydride, 4-nitrophthalic anhydride, pyromellitic anhydride, pyromellitic acid, trimellitic acid, trimellitic anhydride, phthalimide , 4-nitrophthalimide, tetracyanoethylene, tetracyanoquinodimethane, chloranil, bromanyl, o-nitrobenzoic acid, malononitrile, trinitrofluorenone,
- a polyarylate resin having a structural unit represented by the above-mentioned chemical structural formula 1 should be used as a resin binder of the single layer type photosensitive layer 3 is necessary.
- Such polyarylate resin may have other structural units.
- the blending ratio of the structural unit represented by the chemical structural formula 1 is preferably 10 to 100 mol%, particularly preferably 50 to 100 mol%.
- the polyarylate resin represented by the above-mentioned chemical structural formula 1 may be used alone, or may be used by mixing with other resins.
- Such other resins include various polycarbonate resins such as bisphenol A type, bisphenol Z type, bisphenol A type-biphenyl copolymer, bisphenol Z type-biphenyl copolymer, polyphenylene resin, polyester resin, polyvinyl acetal resin, polyvinyl butyral Resin, polyvinyl alcohol resin, vinyl chloride resin, vinyl acetate resin, polyethylene resin, polypropylene resin, acrylic resin, polyurethane resin, epoxy resin, epoxy resin, melamine resin, silicone resin, polyamide resin, polystyrene resin, polyacetal resin, other polyarylate resin, A polysulfone resin, a polymer of methacrylic acid ester, a copolymer of these, and the like can be used.
- the content of the resin binder is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, with respect to the solid content of the single layer type photosensitive layer 3. Further, the content of the polyarylate resin with respect to the resin binder is preferably in the range of 1% by mass to 100% by mass, and more preferably 5% by mass to 80% by mass.
- the thickness of the single layer type photosensitive layer 3 is preferably in the range of 3 to 100 ⁇ m, and more preferably in the range of 5 to 40 ⁇ m, in order to maintain a practically effective surface potential.
- the charge transport layer 5 is mainly composed of a charge transport material and a resin binder.
- the charge transport material and the resin binder used for the charge transport layer 5 in the positively chargeable laminate type photoreceptor the same materials as those described in the embodiment of the charge transport layer 5 in the negatively chargeable laminate type photoreceptor can be used.
- the content of each material and the film thickness of the charge transport layer 5 can also be the same as in the case of the negatively charged laminate type photosensitive member.
- a polyarylate resin having a structural unit represented by the above-mentioned chemical structural formula 1 can be optionally used as a resin binder.
- the charge generation layer 4 mainly comprises a charge generation material, a hole transport material, an electron transport material and a resin binder.
- the charge generation material, the hole transport material, the electron transport material, and the resin binder the same materials as those described as the embodiment of the single layer type photosensitive layer 3 in the single layer type photoreceptor can be used.
- the content of each material and the film thickness of the charge generation layer 4 can be the same as those of the single layer type photosensitive layer 3 in the single layer type photosensitive member.
- a polyarylate resin having a structural unit represented by the above-mentioned chemical structural formula 1 is used as a resin binder of the charge generation layer 4
- a compound having a structure represented by the above general formula (ET2) is used as the electron transport material of the charge generation layer 4
- Compounds having a structure are also used.
- any laminated or single-layered photosensitive layer contains an antidegradant such as an antioxidant or a light stabilizer for the purpose of improving the environmental resistance and the stability to harmful light.
- an antidegradant such as an antioxidant or a light stabilizer for the purpose of improving the environmental resistance and the stability to harmful light.
- Compounds used for such purpose include chromanol derivatives such as tocopherol and esterified compounds, polyarylalkane compounds, hydroquinone derivatives, etherified compounds, dietherified compounds, benzophenone derivatives, benzotriazole derivatives, thioether compounds, phenylenediamine derivatives And phosphonic acid ester, phosphorous acid ester, phenol compound, hindered phenol compound, linear amine compound, cyclic amine compound, hindered amine compound and the like.
- the photosensitive layer can also contain a leveling agent such as silicone oil or fluorine-based oil for the purpose of improving the leveling properties of the formed film and imparting lubricity.
- a leveling agent such as silicone oil or fluorine-based oil for the purpose of improving the leveling properties of the formed film and imparting lubricity.
- metal oxides such as silicon oxide (silica), titanium oxide, zinc oxide, calcium oxide, aluminum oxide (alumina), zirconium oxide, etc. for the purpose of adjusting film hardness, reducing friction coefficient, imparting lubricity, etc. Containing metal sulfides such as barium sulfate and calcium sulfate, fine particles of metal nitrides such as silicon nitride and aluminum nitride, or fluorocarbon resin particles such as tetrafluorinated ethylene resin, fluorocarbon type graft polymerization resin, etc. It is also good.
- other known additives can also be contained within a range that does not significantly
- a surface protective layer 6 can be provided on the surface of the photosensitive layer as necessary for the purpose of further improving the environmental resistance and the mechanical strength. It is desirable that the surface protective layer 6 be made of a material excellent in mechanical stress resistance and environmental resistance, and have the ability to transmit light to which the charge generation layer is sensitive with as low loss as possible.
- the surface protective layer 6 is a layer containing a resin binder as a main component, and in the resin binder, silicon oxide (silica), oxide for the purpose of improving the conductivity, reducing the friction coefficient, imparting lubricity, etc.
- silicon oxide silicon oxide
- Metal oxides such as titanium, zinc oxide, calcium oxide, aluminum oxide (alumina) zirconium oxide, metal sulfides such as barium sulfate and calcium sulfate, fine particles of metal nitrides such as silicon nitride and aluminum nitride, or tetrafluoroethylene Particles of a fluorine-based resin such as a resin or a fluorine-based double graft polymerization resin may be contained.
- silicone oil or fluorine is contained for the purpose of improving the leveling property of the formed film or imparting lubricity, or containing the charge transport material or electron receptive material used in the photosensitive layer. It is also possible to contain a leveling agent such as a system oil.
- a compound having a structure represented by the above general formula (ET2) as an electron transporting material is contained.
- the content of the resin binder in the surface protective layer 6 is preferably 50 to 90% by mass, more preferably 70 to 90% by mass, with respect to the solid content of the surface protective layer 6.
- the content of fine particles of metal oxide or metal nitride is preferably 0 to 60% by mass, more preferably 10 to 50% by mass, with respect to the solid content of the surface protective layer 6.
- the content of the charge transport material or the electron transport material in the surface protective layer 6 is preferably 0 to 30% by mass, more preferably 10 to 20% by mass, with respect to the solid content of the surface protective layer 6.
- the coating solution for forming the outermost layer is a coating solution for forming the charge transporting layer in the case of the photosensitive layer, in particular, the charge transporting layer in the outermost layer, and for the charge generating layer in the case of the charge generating layer.
- the coating solution is a coating solution for forming a single layer type photosensitive layer in the case of a single layer type photosensitive layer, and is a coating solution for forming a surface protective layer in the case where the outermost surface layer is a surface protective layer.
- the coating solution can be applied to various coating methods such as a dip coating method or a spray coating method, and is not limited to any coating method.
- the electrophotographic apparatus of the present invention comprises at least a photosensitive layer on a conductive substrate, and the outermost surface layer comprises the photosensitive member of the present invention containing the predetermined polyarylate resin and the compound described above.
- the desired effect can be obtained by applying to a machine process. Specifically, a charging process such as a contact charging method using a charging member such as a roller or a brush, a non-contact charging method using corotron, scorotron or the like, and one nonmagnetic component, one magnetic component, two components, etc. Sufficient effects can be obtained also in development processes such as contact development and non-contact development using a development system (developer) of
- FIG. 2 shows a schematic configuration diagram of an electrophotographic apparatus according to the present invention.
- the illustrated electrophotographic apparatus 60 mounts the electrophotographic photoreceptor 7 of the present invention including the conductive substrate 1, the undercoat layer 2 coated on the outer peripheral surface thereof, and the photosensitive layer 300. More specifically, the illustrated electrophotographic apparatus 60 includes a roller charging member 21 disposed at the outer peripheral edge of the photosensitive member 7, a high voltage power supply 22 for supplying an applied voltage to the roller charging member 21, and an image exposing member 23.
- a developing device 24 having a developing roller 241, a sheet feeding member 25 having a sheet feeding roller 251 and a sheet feeding guide 252, a transfer charger (directly charged type) 26, and a cleaning device having a cleaning blade 271 27 and the charge removing member 28, it may be a color printer.
- Example 1 5 parts by mass of alcohol-soluble nylon (trade name "CM 8000” manufactured by Toray Industries, Inc.) and 5 parts by mass of aminosilane-treated titanium oxide fine particles are dissolved and dispersed in 90 parts by mass of methanol to prepare a coating solution 1 did.
- the coating solution 1 was dip coated on the outer periphery of an aluminum cylinder having an outer diameter of 30 mm as the conductive substrate 1 and dried at a temperature of 100 ° C. for 30 minutes to form an undercoat layer 2 having a thickness of 3 ⁇ m.
- the coating liquid 2 was prepared by dissolving and dispersing. The coating liquid 2 was dip-coated on the undercoat layer 2 and dried at a temperature of 80 ° C. for 30 minutes to form a charge generation layer 4 with a thickness of 0.3 ⁇ m.
- the coating solution 3 was prepared by dissolving 5 parts by mass of the compound to be dissolved in 1000 parts by mass of dichloromethane.
- the coating liquid 3 was dip-coated on the charge generation layer 4 and dried at a temperature of 90 ° C. for 60 minutes to form a charge transport layer 5 having a thickness of 25 ⁇ m.
- the produced photosensitive member was brought into contact with a charging roller and a transfer roller mounted on a printer LJ4250 manufactured by HP, and left to stand in a 90% humidity environment at a temperature of 60 ° C. for 30 days.
- Example 1 Example 1 except that the polyarylate resin represented by Structural Formula (I-1) used in Example 1 was replaced with the polyarylate resin represented by Structural Formulas (I-2) to (I-32), respectively A photoconductor was produced in the same manner as in the above. The prepared photoreceptor was left to stand for 30 days in the same manner as in Example 1.
- Example 33 A photoconductor was produced in the same manner as in Example 1 except that the Y-type titanyl phthalocyanine used in Example 1 was replaced with ⁇ -type titanyl phthalocyanine. The prepared photoreceptor was left to stand for 30 days in the same manner as in Example 1.
- Example 34 Example except that the compound represented by Structural Formula (ET2-3) as electron transport material and silicone oil were removed from the coating liquid for charge transport layer used in Example 1 and the charge transport layer was formed to a film thickness of 20 ⁇ m The charge transport layer was formed in the same manner as 1). Thereafter, 80 parts by mass of a compound represented by Structural Formula (II-1) as a charge transport material and 120 parts by mass of polyarylate resin represented by Structural Formula (I-1) as a resin binder are further provided on the upper layer thereof.
- a compound represented by Structural Formula (II-1) as a charge transport material and 120 parts by mass of polyarylate resin represented by Structural Formula (I-1) as a resin binder are further provided on the upper layer thereof.
- Example 2 The polyarylate resin represented by Structural Formula (I-1) used in Example 1 is changed to a polycarbonate resin (PCZ-500 manufactured by Mitsubishi Gas Chemical Co., Ltd.), and structural formula (ET2-3) as an electron transport material A photoconductor was produced in the same manner as in Example 1 except that the charge transport layer was provided without adding the compound shown in 1. The prepared photoreceptor was left to stand for 30 days in the same manner as in Example 1.
- Example 3 Example 1 and Example 1 except that the polyarylate resin represented by the structural formula (I-1) used in Example 1 is changed to a polycarbonate resin (PCZ-500 manufactured by Mitsubishi Gas Chemical Co., Ltd.) and a charge transport layer is provided. A photoreceptor was produced in the same manner. The prepared photoreceptor was left to stand for 30 days in the same manner as in Example 1.
- PCZ-500 manufactured by Mitsubishi Gas Chemical Co., Ltd.
- Example 4 110 parts by mass of the polyarylate resin represented by the structural formula (I-1) used in Example 1, 100 parts by mass of the polyarylate resin represented by the structural formula (I-1), and a polycarbonate resin (Mitsubishi Gas Chemical )
- the charge transport layer is provided without adding the compound represented by the structural formula (ET2-3) as an electron transport material, instead of 10 parts by mass of PCZ-500 manufactured by A photoreceptor was produced.
- the prepared photoreceptor was left to stand for 30 days in the same manner as in Example 1.
- Example 5 110 parts by mass of the polyarylate resin represented by the structural formula (I-1) used in Example 1, 55 parts by mass of the polyarylate resin represented by the structural formula (I-1), and a polycarbonate resin (Mitsubishi Gas Chemical )
- the charge transport layer is provided without adding a compound represented by the structural formula (ET2-3) as an electron transport material, instead of 55 parts by mass of PCZ-500 manufactured by A photoreceptor was produced.
- the prepared photoreceptor was left to stand for 30 days in the same manner as in Example 1.
- Example 6 110 parts by mass of the polyarylate resin represented by the structural formula (I-1) used in Example 1, 10 parts by mass of the polyarylate resin represented by the structural formula (I-1), and a polycarbonate resin (Mitsubishi Gas Chemical )
- the charge transport layer is provided without adding the compound represented by the structural formula (ET2-3) as an electron transport material, instead of 100 parts by mass of PCZ-500 manufactured by A photoreceptor was produced.
- the prepared photoreceptor was left to stand for 30 days in the same manner as in Example 1.
- a halogen lamp is used as a light source, and the exposure light, which has been dispersed at 780 nm using a filter, is irradiated for 5 seconds to the photosensitive member from the time when the surface potential becomes -600 V, and light decays until the surface potential becomes -300 V.
- the exposure amount required for the image formation was determined as E1 / 2 (.mu.Jcm.sup.- 2 ), and the residual potential on the surface of the photosensitive member 5 seconds after the exposure was determined as Vr5 (-V).
- the photosensitive member was left to stand for 10 minutes under a fluorescent lamp of 1500 (lx ⁇ s), and the potential after leaving was measured using a photosensitive drum electrical characteristic evaluation apparatus.
- the potential in the light fatigue characteristic is charged so that the charge potential V0 becomes about -600 V while rotating the drum, and the charge potential V0 is measured, and then light of 780 nm, 2 ⁇ W / cm 2 is irradiated for 0.25 seconds.
- the light portion potential VL was measured.
- Example 35 Manufacture of positively charged single layer type photoreceptor (Example 35) A vinyl chloride-vinyl acetate-vinyl alcohol copolymer (Nisshin Chemical Industry Co., Ltd., trade name "Solvain TA5R") as an undercoat layer on the outer periphery of an aluminum cylinder having an outer diameter of 24 mm as the conductive substrate 1 A coating solution prepared by stirring and dissolving 0.2 parts by mass in 99 parts by mass of methyl ethyl ketone was dip-coated and dried for 30 minutes at a temperature of 100 ° C. to form an undercoat layer 2 with a film thickness of 0.1 ⁇ m.
- the following formula as a charge generating material 1 part by mass of metal-free phthalocyanine represented by the following formula, and the following formula as a hole transport material, 30 parts by mass of a stilbene compound represented by And 15 parts by mass of a stilbene compound represented by the following formula: 30 parts by mass of a compound represented by the following formula, 55 parts by mass of a polyarylate resin represented by the structural formula (I-1) as a resin binder, and 3 parts by mass of a compound represented by the structural formula (ET2-3) as an electron transporting material
- a coating solution prepared by dissolving and dispersing in 350 parts by mass of tetrahydrofuran was dip coated and dried at a temperature of 100 ° C. for 60 minutes to form a photosensitive layer having a film thickness of 25 ⁇ m. .
- the prepared photoreceptor was left to stand for 30 days in the same manner as in Example 1.
- Example 36 A photoconductor was produced in the same manner as in Example 35 except that the metal-free phthalocyanine used in Example 35 was changed to Y-type titanyl phthalocyanine. The prepared photoreceptor was left to stand for 30 days in the same manner as in Example 1.
- Example 37 A photoconductor was produced in the same manner as in Example 35 except that the metal-free phthalocyanine used in Example 35 was changed to ⁇ -type titanyl phthalocyanine. The prepared photoreceptor was left to stand for 30 days in the same manner as in Example 1.
- Example 7 A photoreceptor was produced in the same manner as in Example 35 except that the polyarylate resin represented by Structural Formula (I-1) used in Example 35 was used and the electron transporting material was not added. The prepared photoreceptor was left to stand for 30 days in the same manner as in Example 1.
- Example 35 Example 35 and Example 35 except that the polyarylate resin represented by the structural formula (I-1) used in Example 35 is changed to a polycarbonate resin (PCZ-500 manufactured by Mitsubishi Gas Chemical Co., Ltd.) and the electron transport material is not added.
- a photoreceptor was produced in the same manner. The prepared photoreceptor was left to stand for 30 days in the same manner as in Example 1.
- Example 9 A photoconductor in the same manner as in Example 35 except that the polyarylate resin represented by Structural Formula (I-1) used in Example 35 is changed to a polycarbonate resin (PCZ-500 manufactured by Mitsubishi Gas Chemical Co., Ltd.) was produced. The prepared photoreceptor was left to stand for 30 days in the same manner as in Example 1.
- Example 10 55 parts by mass of the polyarylate resin represented by the structural formula (I-1) used in Example 35, 50 parts by mass of the polyarylate resin represented by the structural formula (I-1) and a polycarbonate resin (Mitsubishi Gas Chemical Co., Ltd.)
- a photoconductor was produced by the same method as that of Example 35 except that 5 parts by mass of PCZ-500 (manufactured by PCZ-500) was used and no electron transport material was added.
- the prepared photoreceptor was left to stand for 30 days in the same manner as in Example 1.
- Example 11 55 parts by mass of the polyarylate resin represented by the structural formula (I-1) used in Example 35, 30 parts by mass of the polyarylate resin represented by the structural formula (I-1) and a polycarbonate resin (Mitsubishi Gas Chemical Co., Ltd.)
- a photoconductor was produced by the same method as that of Example 35 except that 25 parts by mass of PCZ-500 (manufactured by Mr. PCZ-500) was used and no electron transporting material was added.
- the prepared photoreceptor was left to stand for 30 days in the same manner as in Example 1.
- Example 12 55 parts by mass of the polyarylate resin represented by the structural formula (I-1) used in Example 35, 5 parts by mass of the polyarylate resin represented by the structural formula (I-1) and a polycarbonate resin (Mitsubishi Gas Chemical Co., Ltd.)
- a photoconductor was produced by the same method as that of Example 35 except that 50 parts by mass of PCZ-500 (manufactured by PCZ-500) was used and no electron transport material was added.
- the prepared photoreceptor was left to stand for 30 days in the same manner as in Example 1.
- a halogen lamp is used as a light source, and exposure light of 1.0 ⁇ W / cm 2 dispersed at 780 nm using a filter is applied to the photosensitive member for 5 seconds after the surface potential reaches +600 V.
- the exposure amount required for light attenuation until the light intensity reaches +300 V was determined as E 1/2 ( ⁇ J cm ⁇ 2 ), and the residual potential of the photosensitive member surface 5 seconds after the exposure was determined as Vr 5 (V).
- the photosensitive member was left to stand for 10 minutes under a fluorescent lamp of 1500 (lx ⁇ s), and the potential after leaving was measured using a photosensitive drum electrical characteristic evaluation apparatus.
- the potential in the light fatigue characteristic is charged so that the charging potential V0 becomes approximately +650 V while rotating the drum, and the charging potential V0 is measured, and then light of 780 nm, 2 ⁇ W / cm 2 is irradiated for 0.25 seconds.
- the bright part potential VL was measured.
- a coating solution was prepared by dissolving 50 parts by mass of the compound represented by and 50 parts by mass of a polycarbonate resin (PCZ-500 manufactured by Mitsubishi Gas Chemical Co., Ltd.) as a resin binder in 800 parts by mass of dichloromethane.
- This coating solution was dip coated on the outer periphery of an aluminum cylinder with an outer diameter of 24 mm as a conductive substrate, and dried at a temperature of 120 ° C. for 60 minutes to form a charge transport layer with a film thickness of 15 ⁇ m.
- the following formula as a charge generating material On this charge transport layer, the following formula as a charge generating material, And 1.5 parts by mass of metal-free phthalocyanine represented by the following formula, and the following formula as a hole transport material, 10 parts by mass of a stilbene compound represented by the following formula: 25 parts by mass of a compound represented by the formula, 60 parts by mass of a polyarylate resin represented by the structural formula (I-1) as a resin binder, and 3 parts by mass of a compound represented by the structural formula (ET2-3) as an electron transporting material And a coating solution prepared by dissolving and dispersing in 800 parts by mass of 1,2-dichloroethane by dip coating, and drying for 60 minutes at a temperature of 100.degree. C. to form a photosensitive layer having a film thickness of 15 .mu.m. Type photosensitive member was produced. The prepared photoreceptor was left to stand for 30 days in the same manner as in Example 1.
- Example 13 A photoreceptor was produced in the same manner as in Example 38 except that the polyarylate resin represented by Structural Formula (I-1) used in Example 38 was used and the electron transporting material was not added. The prepared photoreceptor was left to stand for 30 days in the same manner as in Example 1.
- Example 38 and Example 38 except that the polyarylate resin represented by the structural formula (I-1) used in Example 38 is changed to a polycarbonate resin (PCZ-500 manufactured by Mitsubishi Gas Chemical Co., Ltd.) and the electron transport material is not added.
- a photoreceptor was produced in the same manner. The prepared photoreceptor was left to stand for 30 days in the same manner as in Example 1.
- the photosensitive resin was prepared in the same manner as in Example 38 except that the polyarylate resin represented by Structural Formula (I-1) used in Example 38 was changed to a polycarbonate resin (PCZ-500 manufactured by Mitsubishi Gas Chemical Co., Ltd.) The body was made. The prepared photoreceptor was left to stand for 30 days in the same manner as in Example 1.
- Comparative example 16 60 parts by mass of polyarylate resin represented by Structural Formula (I-1) used in Example 38, 50 parts by mass of polyarylate resin represented by Structural Formula (I-1) and polycarbonate resin (Mitsubishi Gas Chemical Company, Ltd.
- a photoconductor was manufactured by the same method as that of Example 38 except that the amount was changed to 10 parts by mass of PCZ-500, and no electron transport material was added. The prepared photoreceptor was left to stand for 30 days in the same manner as in Example 1.
- Example 17 60 parts by mass of the polyarylate resin represented by the structural formula (I-1) used in Example 38, 30 parts by mass of the polyarylate resin represented by the structural formula (I-1), and a polycarbonate resin (Mitsubishi Gas Chemical Co., Ltd.) A photoconductor was manufactured by the same method as that of Example 38 except that the amount was changed to 30 parts by mass of PCZ-500, and no electron transport material was added. The prepared photoreceptor was left to stand for 30 days in the same manner as in Example 1.
- Example 18 60 parts by mass of the polyarylate resin represented by the structural formula (I-1) used in Example 38, 10 parts by mass of the polyarylate resin represented by the structural formula (I-1) and a polycarbonate resin (Mitsubishi Gas Chemical Co., Ltd.) A photoconductor was manufactured by the same method as that of Example 38 except that the amount was 50 parts by mass of PCZ-500, and no electron transport material was added. The prepared photoreceptor was left to stand for 30 days in the same manner as in Example 1.
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Abstract
Description
最表面層が樹脂バインダおよび電子輸送材料を少なくとも含み、該樹脂バインダが下記化学構造式1で表される構造単位を有するポリアリレート樹脂を含有するとともに、該電子輸送材料が下記一般式(ET2)で表される構造を有する化合物を含有することを特徴とするものである。
(化学構造式1)
(ここで、化学構造式1中、部分構造式(A1)、(A2)、(B1)、(B2)、(C)、(D)、(E)および(F)は樹脂バインダを構成する構造単位を示す。a1、a2、b1、b2、c、d、eおよびfはそれぞれ各構造単位(A1)、(A2)、(B1)、(B2)、(C)、(D)、(E)および(F)のmol%を示し、a1+a2+b1+b2+c+d+e+fが100mol%であり、c+d+e+fが0~10mol%である。また、W1およびW2は、単結合、‐O‐、‐S‐、‐SO‐、‐CO‐、‐SO2‐、‐CR22R23‐(R22およびR23は、同一であっても異なっていてもよく、水素原子、炭素数1~12のアルキル基、ハロゲン化アルキル基、または、炭素数6~12の置換若しくは無置換のアリール基である)、炭素数5~12の置換若しくは無置換のシクロアルキリデン基、炭素数2~12の置換若しくは無置換のα,ωアルキレン基、‐9,9‐フルオレニリデン基、炭素数6~12の置換若しくは無置換のアリーレン基、および、炭素数6~12のアリール基もしくはアリーレン基を含有する2価の基からなる群から選ばれる異なる2種である。R1~R20は、同一でも異なっていてもよく、水素原子、炭素数1~8のアルキル基、フッ素原子、塩素原子、または臭素原子を示す。R21は水素原子、炭素数1~20のアルキル基、置換基を有してもよいアリール基あるいは置換基を有してもよいシクロアルキル基、フッ素原子、塩素原子、または臭素原子を示す。s、tは1以上の整数を示す。)
(式(ET2)中、R32~R37は、同一または異なって、水素原子、ハロゲン原子、シアノ基、ニトロ基、水酸基、炭素数1~12のアルキル基、炭素数1~12のアルコキシ基、置換基を有してもよいアリール基、置換基を有してもよい複素環基、エステル基、シクロアルキル基、置換基を有してもよいアラルキル基、アリル基、アミド基、アミノ基、アシル基、アルケニル基、アルキニル基、カルボキシル基、カルボニル基、カルボン酸基、ハロゲン化アルキル基を表す。置換基は、ハロゲン原子、炭素数1~6のアルキル基、炭素数1~6のアルコキシ基、水酸基、シアノ基、アミノ基、ニトロ基、ハロゲン化アルキル基を表す。)
(式(ET1)中、R24、R25は、同一または異なって、水素原子、炭素数1~12のアルキル基、炭素数1~12のアルコキシ基、置換基を有してもよいアリール基、シクロアルキル基、置換基を有してもよいアラルキル基、ハロゲン化アルキル基を表す。R26は、水素原子、炭素数1~6のアルキル基、炭素数1~6のアルコキシ基、置換基を有してもよいアリール基、シクロアルキル基、置換基を有してもよいアラルキル基、ハロゲン化アルキル基を表す。R27~R31は、同一または異なって、水素原子、ハロゲン原子、炭素数1~12のアルキル基、炭素数1~12のアルコキシ基、置換基を有してもよいアリール基、置換基を有してもよいアラルキル基、置換基を有してもよいフェノキシ基、ハロゲン化アルキル基、シアノ基、ニトロ基を表し、また、2つ以上の基が結合して環を形成してもよい。置換基は、ハロゲン原子、炭素数1~6のアルキル基、炭素数1~6のアルコキシ基、水酸基、シアノ基、アミノ基、ニトロ基、ハロゲン化アルキル基を表す。)
(式(ET3)中、R38、R39は、同一または異なって、水素原子、ハロゲン原子、シアノ基、ニトロ基、水酸基、炭素数1~12のアルキル基、炭素数1~12のアルコキシ基、置換基を有してもよいアリール基、置換基を有してもよい複素環基、エステル基、シクロアルキル基、置換基を有してもよいアラルキル基、アリル基、アミド基、アミノ基、アシル基、アルケニル基、アルキニル基、カルボキシル基、カルボニル基、カルボン酸基、ハロゲン化アルキル基を表す。置換基は、ハロゲン原子、炭素数1~6のアルキル基、炭素数1~6のアルコキシ基、水酸基、シアノ基、アミノ基、ニトロ基、ハロゲン化アルキル基を表す。)
前記塗布液に、前記化学構造式1で表される構造単位を有するポリアリレート樹脂と、前記一般式(ET2)で表される構造を有する化合物とを含有させることを特徴とするものである。
上述のように、電子写真用感光体は、機能分離型積層型感光体としての、負帯電積層型感光体および正帯電積層型感光体と、主として正帯電型である単層型感光体とに大別される。図1は、本発明の一例の電子写真用感光体を示す模式的断面図であり、(a)は負帯電型の機能分離積層型電子写真用感光体の一例を示し、(b)は正帯電単層型電子写真用感光体の一例を示し、(c)は正帯電型の機能分離積層型電子写真用感光体の一例を示す。
負帯電積層型感光体において、電荷発生層4は、電荷発生材料の粒子を樹脂バインダ中に分散させた塗布液を塗布するなどの方法により形成され、光を受容して電荷を発生する。また、その電荷発生効率が高いことと同時に発生した電荷の電荷輸送層5への注入性が重要であり、電場依存性が少なく、低電場でも注入の良いことが望ましい。
本発明において、単層型の場合の感光層3は、主として電荷発生材料、正孔輸送材料、電子輸送材料(アクセプター性化合物)および樹脂バインダからなる。
正帯電積層型感光体において、電荷輸送層5は、主として電荷輸送材料と樹脂バインダとにより構成される。正帯電積層型感光体における電荷輸送層5に用いる電荷輸送材料および樹脂バインダとしては、負帯電積層型感光体における電荷輸送層5の実施の形態に挙げたものと同じ材料を用いることができる。各材料の含有量や、電荷輸送層5の膜厚についても、負帯電積層型感光体の場合と同様とすることができる。なお、正帯電積層型感光体における電荷輸送層5については、樹脂バインダとして上記化学構造式1で示される構造単位を有するポリアリレート樹脂を任意に用いることができる。
本発明の感光体を製造するに際しては、導電性基体上に塗布液を塗布して最表面層を形成するにあたり、この塗布液中に、上記化学構造式1で表される構造単位を有するポリアリレート樹脂と、上記式(ET2)で表される構造を有する化合物とを含有させる点が重要であり、これにより、本発明の所期の効果が得られる感光体を得ることができる。この最表面層の形成用の塗布液とは、最表面層が感光層、特には、電荷輸送層の場合は電荷輸送層形成用塗布液であり、電荷発生層の場合は電荷発生層形成用塗布液であり、単層型感光層の場合は単層型感光層形成用塗布液であり、最表面層が表面保護層の場合は表面保護層形成用塗布液である。かかる塗布液は、浸漬塗布法または噴霧塗布法等の種々の塗布方法に適用することが可能であり、いずれかの塗布方法に限定されるものではない。
本発明の電子写真装置は、導電性基体上に少なくとも感光層を有し、最表面層が上記所定のポリアリレート樹脂および化合物を含有する本発明の感光体を搭載してなるものであり、各種マシンプロセスに適用することにより所期の効果が得られるものである。具体的には、ローラや、ブラシなどの帯電部材を用いた接触帯電方式、コロトロン、スコロトロンなどを用いた非接触帯電方式等の帯電プロセス、および、非磁性一成分、磁性一成分、二成分などの現像方式(現像剤)を用いた接触現像および非接触現像方式などの現像プロセスにおいても十分な効果を得ることができる。
(実施例1)
アルコール可溶性ナイロン(東レ(株)製、商品名「CM8000」)5質量部と、アミノシラン処理された酸化チタン微粒子5質量部とを、メタノール90質量部に溶解、分散させて、塗布液1を調製した。導電性基体1としての外径30mmのアルミニウム製円筒の外周に、この塗布液1を浸漬塗工し、温度100℃で30分間乾燥して、膜厚3μmの下引き層2を形成した。
で示される化合物90質量部と、前記表1に示す樹脂バインダとしての構造式(I-1)で示されるポリアリレート樹脂110質量部と、電子輸送材料としての構造式(ET2-3)で示される化合物5質量部とを、ジクロロメタン1000質量部に溶解して、塗布液3を調製した。上記電荷発生層4上に、塗布液3を浸漬塗工し、温度90℃で60分間乾燥して、膜厚25μmの電荷輸送層5を形成し、負帯電積層型感光体を作製した。作製した感光体を、HP社製のプリンタLJ4250に搭載した帯電ローラおよび転写ローラに当接させ、温度60℃で湿度90%環境に30日間放置を行った。
実施例1で使用した構造式(I-1)で示されるポリアリレート樹脂を、それぞれ構造式(I-2)~(I-32)で示されるポリアリレート樹脂に代えた以外は、実施例1と同様の方法で感光体を作製した。作製した感光体について、実施例1と同様に30日間放置を行った。
実施例1で使用したY型チタニルフタロシアニンを、α型チタニルフタロシアニンに代えた以外は、実施例1と同様の方法で感光体を作製した。作製した感光体について、実施例1と同様に30日間放置を行った。
実施例1で用いた電荷輸送層用塗布液から電子輸送材料としての構造式(ET2-3)で示される化合物およびシリコーンオイルを除いて、電荷輸送層を膜厚20μmで形成した以外は実施例1と同様にして電荷輸送層を形成した。その後、さらにその上層に、電荷輸送材料としての構造式(II-1)で示される化合物80質量部と、樹脂バインダとしての構造式(I-1)で示されるポリアリレート樹脂120質量部とを、ジクロロメタン900質量部に溶解した後、シリコーンオイル(KP-340,信越ポリマー(株)製)を0.1質量部加え、さらに、電子輸送材料としての構造式(ET2-3)で示される化合物を12質量部加えて調製した塗布液を塗布成膜し、温度90℃で60分間乾燥して、膜厚約10μmの表面保護層を形成し、電子写真用感光体を作製した。作製した感光体について、実施例1と同様に30日間放置を行った。
実施例1で使用した構造式(I-1)で示されるポリアリレート樹脂を用い、電子輸送材料としての構造式(ET2-3)で示される化合物を添加せずに電荷輸送層を設けた以外は実施例1と同様の方法で感光体を作製した。作製した感光体について、実施例1と同様に30日間放置を行った。
実施例1で使用した構造式(I-1)で示されるポリアリレート樹脂を、ポリカーボネート樹脂(三菱ガス化学(株)製 PCZ-500)に変え、電子輸送材料としての構造式(ET2-3)で示される化合物を添加せずに電荷輸送層を設けた以外は実施例1と同様の方法で感光体を作製した。作製した感光体について、実施例1と同様に30日間放置を行った。
実施例1で使用した構造式(I-1)で示されるポリアリレート樹脂を、ポリカーボネート樹脂(三菱ガス化学(株)製 PCZ-500)に変えて電荷輸送層を設けた以外は実施例1と同様の方法で感光体を作製した。作製した感光体について、実施例1と同様に30日間放置を行った。
実施例1で使用した構造式(I-1)で示されるポリアリレート樹脂110質量部を、構造式(I-1)で示されるポリアリレート樹脂100質量部と、ポリカーボネート樹脂(三菱ガス化学(株)製 PCZ-500)10質量部とに変え、電子輸送材料としての構造式(ET2-3)で示される化合物を添加せずに電荷輸送層を設けた以外は実施例1と同様の方法で感光体を作製した。作製した感光体について、実施例1と同様に30日間放置を行った。
実施例1で使用した構造式(I-1)で示されるポリアリレート樹脂110質量部を、構造式(I-1)で示されるポリアリレート樹脂55質量部と、ポリカーボネート樹脂(三菱ガス化学(株)製 PCZ-500)55質量部とに変え、電子輸送材料としての構造式(ET2-3)で示される化合物を添加せずに電荷輸送層を設けた以外は実施例1と同様の方法で感光体を作製した。作製した感光体について、実施例1と同様に30日間放置を行った。
実施例1で使用した構造式(I-1)で示されるポリアリレート樹脂110質量部を、構造式(I-1)で示されるポリアリレート樹脂10質量部と、ポリカーボネート樹脂(三菱ガス化学(株)製 PCZ-500)100質量部とに変え、電子輸送材料としての構造式(ET2-3)で示される化合物を添加せずに電荷輸送層を設けた以外は実施例1と同様の方法で感光体を作製した。作製した感光体について、実施例1と同様に30日間放置を行った。
上記実施例1~34および比較例1~6において作製した感光体について、温度60℃で湿度90%環境に30日間放置した後、ハーフトーン画像の画像出しを行い、以下に従い評価した。
○:ハーフトーン画像で黒スジ発生無し。
×:ハーフトーン画像で黒スジ発生有り。
上記実施例1~34および比較例1~6において作製した感光体を、帯電ローラおよび転写ローラを備えるHP社製のプリンタLJ4250に搭載し、下記の方法で評価した。すなわち、感光体表面を暗所にてコロナ放電により-650Vに帯電せしめた後、帯電直後の表面電位V0を測定した。続いて、コロナ放電を暗所で5秒間放置後、表面電位V5を測定し、下記式(1)に従って、帯電後5秒後における電位保持率Vk5(%)を求めた。
Vk5=V5/V0×100 (1)
(実施例35)
導電性基体1としての外径24mmのアルミニウム製円筒の外周に、下引き層として、塩化ビニル-酢酸ビニル-ビニルアルコール共重合体(日信化学工業(株)製、商品名「ソルバインTA5R」)0.2質量部をメチルエチルケトン99質量部に攪拌溶解させて調製した塗布液を浸漬塗工し、温度100℃で30分間乾燥して、膜厚0.1μmの下引き層2を形成した。
で示される無金属フタロシアニン1質量部と、正孔輸送材料としての下記式、
で示されるスチルベン化合物30質量部および下記式、
で示されるスチルベン化合物15質量部と、電子輸送材料としての下記式、
で示される化合物30質量部と、樹脂バインダとしての構造式(I-1)で示されるポリアリレート樹脂55質量部と、電子輸送材料としての構造式(ET2-3)で示される化合物3質量部を、テトラヒドロフラン350質量部に溶解、分散させて調製した塗布液を浸漬塗工し、温度100℃で60分間乾燥して、膜厚25μmの感光層を形成し、単層型感光体を作製した。作製した感光体について、実施例1と同様に30日間放置を行った。
実施例35で使用した無金属フタロシアニンをY型チタニルフタロシアニンに変えた以外は実施例35と同様の方法で感光体を作製した。作製した感光体について、実施例1と同様に30日間放置を行った。
実施例35で使用した無金属フタロシアニンをα型チタニルフタロシアニンに変えた以外は実施例35と同様の方法で感光体を作製した。作製した感光体について、実施例1と同様に30日間放置を行った。
実施例35で使用した構造式(I-1)で示されるポリアリレート樹脂を用い、電子輸送材料を添加しない以外は実施例35と同様の方法で感光体を作製した。作製した感光体について、実施例1と同様に30日間放置を行った。
実施例35で使用した構造式(I-1)で示されるポリアリレート樹脂を、ポリカーボネート樹脂(三菱ガス化学(株)製 PCZ-500)に変え、電子輸送材料を添加しない以外は実施例35と同様の方法で感光体を作製した。作製した感光体について、実施例1と同様に30日間放置を行った。
実施例35で使用した構造式(I-1)で示されるポリアリレート樹脂を、ポリカーボネート樹脂(三菱ガス化学(株)製 PCZ-500)に変えた以外は実施例35と同様の方法で感光体を作製した。作製した感光体について、実施例1と同様に30日間放置を行った。
実施例35で使用した構造式(I-1)で示されるポリアリレート樹脂55質量部を、構造式(I-1)で示されるポリアリレート樹脂50質量部およびポリカーボネート樹脂(三菱ガス化学(株)製 PCZ-500)5質量部に代え、電子輸送材料を添加しない以外は実施例35と同様の方法で感光体を作製した。作製した感光体について、実施例1と同様に30日間放置を行った。
実施例35で使用した構造式(I-1)で示されるポリアリレート樹脂55質量部を、構造式(I-1)で示されるポリアリレート樹脂30質量部およびポリカーボネート樹脂(三菱ガス化学(株)製 PCZ-500)25質量部に代え、電子輸送材料を添加しない以外は実施例35と同様の方法で感光体を作製した。作製した感光体について、実施例1と同様に30日間放置を行った。
実施例35で使用した構造式(I-1)で示されるポリアリレート樹脂55質量部を、構造式(I-1)で示されるポリアリレート樹脂5質量部およびポリカーボネート樹脂(三菱ガス化学(株)製 PCZ-500)50質量部に代え、電子輸送材料を添加しない以外は実施例35と同様の方法で感光体を作製した。作製した感光体について、実施例1と同様に30日間放置を行った。
上記実施例35~37および比較例7~12において作製した感光体について、温度60℃で湿度90%環境に30日間放置した後、ハーフトーン画像の画像出しを行い、以下に従い評価した。
○:ハーフトーン画像で黒スジ発生無し。
×:ハーフトーン画像で黒スジ発生有り。
上記実施例35~37および比較例7~12において作製した感光体を、帯電ローラおよび転写ローラを備えるブラザー社製のプリンターHL‐2040に搭載し、下記の方法で評価した。すなわち、まず、感光体表面を暗所にてコロナ放電により+650Vに帯電せしめた後、帯電直後の表面電位V0を測定した。続いて、この感光体を、暗所で5秒間放置した後、表面電位V5を測定し、下記式(1)に従って帯電後5秒後における電位保持率Vk5(%)を求めた。
Vk5=V5/V0×100 (1)
(実施例38)
電荷輸送材料としての下記式、
で示される化合物50質量部と、樹脂バインダとしてのポリカーボネート樹脂(三菱ガス化学(株)製 PCZ-500)50質量部とを、ジクロロメタン800質量部に溶解して、塗布液を調製した。導電性基体としての外径24mmのアルミニウム製円筒の外周に、この塗布液を浸漬塗工し、温度120℃で60分間乾燥して、膜厚15μmの電荷輸送層を形成した。
で示される無金属フタロシアニン1.5質量部と、正孔輸送材料としての下記式、
で示されるスチルベン化合物10質量部と、電子輸送材料としての下記式、
で示される化合物25質量部と、樹脂バインダとしての構造式(I-1)で示されるポリアリレート樹脂60質量部と、電子輸送材料としての構造式(ET2-3)で示される化合物3質量部とを、1、2-ジクロロエタン800質量部に溶解、分散させて調製した塗布液を浸漬塗工し、温度100℃で60分間乾燥して、膜厚15μmの感光層を形成し、正帯電積層型感光体を作製した。作製した感光体について、実施例1と同様に30日間放置を行った。
実施例38で使用した構造式(I-1)で示されるポリアリレート樹脂を用い、電子輸送材料を添加しない以外は実施例38と同様の方法で感光体を作製した。作製した感光体について、実施例1と同様に30日間放置を行った。
実施例38で使用した構造式(I-1)で示されるポリアリレート樹脂を、ポリカーボネート樹脂(三菱ガス化学(株)製 PCZ-500)に変え、電子輸送材料を添加しない以外は実施例38と同様の方法で感光体を作製した。作製した感光体について、実施例1と同様に30日間放置を行った。
実施例38で使用した構造式(I-1)で示されるポリアリレート樹脂を、ポリカーボネート樹脂(三菱ガス化学(株)製 PCZ-500)に変えた以外は、実施例38と同様の方法で感光体を作製した。作製した感光体について、実施例1と同様に30日間放置を行った。
実施例38で使用した構造式(I-1)で示されるポリアリレート樹脂60質量部を、構造式(I-1)で示されるポリアリレート樹脂50質量部およびポリカーボネート樹脂(三菱ガス化学(株)製 PCZ-500)10質量部に変え、電子輸送材料を添加しない以外は実施例38と同様の方法で感光体を作製した。作製した感光体について、実施例1と同様に30日間放置を行った。
実施例38で使用した構造式(I-1)で示されるポリアリレート樹脂60質量部を、構造式(I-1)で示されるポリアリレート樹脂30質量部およびポリカーボネート樹脂(三菱ガス化学(株)製 PCZ-500)30質量部に変え、電子輸送材料を添加しない以外は実施例38と同様の方法で感光体を作製した。作製した感光体について、実施例1と同様に30日間放置を行った。
実施例38で使用した構造式(I-1)で示されるポリアリレート樹脂60質量部を、構造式(I-1)で示されるポリアリレート樹脂10質量部およびポリカーボネート樹脂(三菱ガス化学(株)製 PCZ-500)50質量部に変え、電子輸送材料を添加しない以外は実施例38と同様の方法で感光体を作製した。作製した感光体について、実施例1と同様に30日間放置を行った。
2 下引き層
3 感光層
4 電荷発生層
5 電荷輸送層
6 表面保護層
7 電子写真用感光体
21 ローラ帯電部材
22 高圧電源
23 像露光部材
24 現像器
241 現像ローラ
25 給紙部材
251 給紙ローラ
252 給紙ガイド
26 転写帯電器(直接帯電型)
27 クリーニング装置
271 クリーニングブレード
28 除電部材
60 電子写真装置
300 感光層
Claims (10)
- 導電性基体上に、少なくとも感光層を有する電子写真用感光体において、
最表面層が樹脂バインダおよび電子輸送材料を少なくとも含み、該樹脂バインダが下記化学構造式1で表される構造単位を有するポリアリレート樹脂を含有するとともに、該電子輸送材料が下記一般式(ET2)で表される構造を有する化合物を含有することを特徴とする電子写真用感光体。
(化学構造式1)
(ここで、化学構造式1中、部分構造式(A1)、(A2)、(B1)、(B2)、(C)、(D)、(E)および(F)は樹脂バインダを構成する構造単位を示す。a1、a2、b1、b2、c、d、eおよびfはそれぞれ各構造単位(A1)、(A2)、(B1)、(B2)、(C)、(D)、(E)および(F)のmol%を示し、a1+a2+b1+b2+c+d+e+fが100mol%であり、c+d+e+fが0~10mol%である。また、W1およびW2は、単結合、‐O‐、‐S‐、‐SO‐、‐CO‐、‐SO2‐、‐CR22R23‐(R22およびR23は、同一であっても異なっていてもよく、水素原子、炭素数1~12のアルキル基、ハロゲン化アルキル基、または、炭素数6~12の置換若しくは無置換のアリール基である)、炭素数5~12の置換若しくは無置換のシクロアルキリデン基、炭素数2~12の置換若しくは無置換のα,ωアルキレン基、‐9,9‐フルオレニリデン基、炭素数6~12の置換若しくは無置換のアリーレン基、および、炭素数6~12のアリール基もしくはアリーレン基を含有する2価の基からなる群から選ばれる異なる2種である。R1~R20は、同一でも異なっていてもよく、水素原子、炭素数1~8のアルキル基、フッ素原子、塩素原子、または臭素原子を示す。R21は水素原子、炭素数1~20のアルキル基、置換基を有してもよいアリール基あるいは置換基を有してもよいシクロアルキル基、フッ素原子、塩素原子、または臭素原子を示す。s、tは1以上の整数を示す。)
(式(ET2)中、R32~R37は、同一または異なって、水素原子、ハロゲン原子、シアノ基、ニトロ基、水酸基、炭素数1~12のアルキル基、炭素数1~12のアルコキシ基、置換基を有してもよいアリール基、置換基を有してもよい複素環基、エステル基、シクロアルキル基、置換基を有してもよいアラルキル基、アリル基、アミド基、アミノ基、アシル基、アルケニル基、アルキニル基、カルボキシル基、カルボニル基、カルボン酸基、ハロゲン化アルキル基を表す。置換基は、ハロゲン原子、炭素数1~6のアルキル基、炭素数1~6のアルコキシ基、水酸基、シアノ基、アミノ基、ニトロ基、ハロゲン化アルキル基を表す。) - 前記電子輸送材料が、さらに、下記一般式(ET1)または(ET3)で表される構造を有する化合物のいずれか一方または双方を含有する請求項1記載の電子写真用感光体。
(式(ET1)中、R24、R25は、同一または異なって、水素原子、炭素数1~12のアルキル基、炭素数1~12のアルコキシ基、置換基を有してもよいアリール基、シクロアルキル基、置換基を有してもよいアラルキル基、ハロゲン化アルキル基を表す。R26は、水素原子、炭素数1~6のアルキル基、炭素数1~6のアルコキシ基、置換基を有してもよいアリール基、シクロアルキル基、置換基を有してもよいアラルキル基、ハロゲン化アルキル基を表す。R27~R31は、同一または異なって、水素原子、ハロゲン原子、炭素数1~12のアルキル基、炭素数1~12のアルコキシ基、置換基を有してもよいアリール基、置換基を有してもよいアラルキル基、置換基を有してもよいフェノキシ基、ハロゲン化アルキル基、シアノ基、ニトロ基を表し、また、2つ以上の基が結合して環を形成してもよい。置換基は、ハロゲン原子、炭素数1~6のアルキル基、炭素数1~6のアルコキシ基、水酸基、シアノ基、アミノ基、ニトロ基、ハロゲン化アルキル基を表す。)
(式(ET3)中、R38、R39は、同一または異なって、水素原子、ハロゲン原子、シアノ基、ニトロ基、水酸基、炭素数1~12のアルキル基、炭素数1~12のアルコキシ基、置換基を有してもよいアリール基、置換基を有してもよい複素環基、エステル基、シクロアルキル基、置換基を有してもよいアラルキル基、アリル基、アミド基、アミノ基、アシル基、アルケニル基、アルキニル基、カルボキシル基、カルボニル基、カルボン酸基、ハロゲン化アルキル基を表す。置換基は、ハロゲン原子、炭素数1~6のアルキル基、炭素数1~6のアルコキシ基、水酸基、シアノ基、アミノ基、ニトロ基、ハロゲン化アルキル基を表す。) - 前記感光層が、前記最表面層である請求項1記載の電子写真用感光体。
- 前記感光層が電荷発生層と電荷輸送層とからなり、該電荷輸送層が前記最表面層である請求項3記載の電子写真用感光体。
- 前記感光層上に表面保護層を備え、該表面保護層が前記最表面層である請求項1記載の電子写真用感光体。
- 前記感光層が正帯電単層型である請求項3記載の電子写真用感光体。
- 前記感光層が電荷輸送層と電荷発生層とからなり、該電荷発生層が前記最表面層である請求項3記載の電子写真用感光体。
- 前記最表面層が、前記樹脂バインダ100質量部に対し、前記電子輸送材料を10質量部以下で含む請求項1記載の電子写真用感光体。
- 導電性基体上に塗布液を塗布して最表面層を形成する工程を包含する電子写真用感光体の製造方法において、
前記塗布液に、下記化学構造式1で表される構造単位を有するポリアリレート樹脂と、下記一般式(ET2)で表される構造を有する化合物とを含有させることを特徴とする電子写真用感光体の製造方法。
(化学構造式1)
(ここで、化学構造式1中、部分構造式(A1)、(A2)、(B1)、(B2)、(C)、(D)、(E)および(F)は樹脂バインダを構成する構造単位を示す。a1、a2、b1、b2、c、d、eおよびfはそれぞれ各構造単位(A1)、(A2)、(B1)、(B2)、(C)、(D)、(E)および(F)のmol%を示し、a1+a2+b1+b2+c+d+e+fが100mol%であり、c+d+e+fが0~10mol%である。また、W1およびW2は、単結合、‐O‐、‐S‐、‐SO‐、‐CO‐、‐SO2‐、‐CR22R23‐(R22およびR23は、同一であっても異なっていてもよく、水素原子、炭素数1~12のアルキル基、ハロゲン化アルキル基、または、炭素数6~12の置換若しくは無置換のアリール基である)、炭素数5~12の置換若しくは無置換のシクロアルキリデン基、炭素数2~12の置換若しくは無置換のα,ωアルキレン基、‐9,9‐フルオレニリデン基、炭素数6~12の置換若しくは無置換のアリーレン基、および、炭素数6~12のアリール基もしくはアリーレン基を含有する2価の基からなる群から選ばれる異なる2種である。R1~R20は、同一でも異なっていてもよく、水素原子、炭素数1~8のアルキル基、フッ素原子、塩素原子、または臭素原子を示す。R21は水素原子、炭素数1~20のアルキル基、置換基を有してもよいアリール基あるいは置換基を有してもよいシクロアルキル基、フッ素原子、塩素原子、または臭素原子を示す。s、tは1以上の整数を示す。)
(式(ET2)中、R32~R37は、同一または異なって、水素原子、ハロゲン原子、シアノ基、ニトロ基、水酸基、炭素数1~12のアルキル基、炭素数1~12のアルコキシ基、置換基を有してもよいアリール基、置換基を有してもよい複素環基、エステル基、シクロアルキル基、置換基を有してもよいアラルキル基、アリル基、アミド基、アミノ基、アシル基、アルケニル基、アルキニル基、カルボキシル基、カルボニル基、カルボン酸基、ハロゲン化アルキル基を表す。置換基は、ハロゲン原子、炭素数1~6のアルキル基、炭素数1~6のアルコキシ基、水酸基、シアノ基、アミノ基、ニトロ基、ハロゲン化アルキル基を表す。) - 請求項1記載の電子写真用感光体を搭載してなることを特徴とする電子写真装置。
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Also Published As
Publication number | Publication date |
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JP6432694B2 (ja) | 2018-12-05 |
TW201733990A (zh) | 2017-10-01 |
US10782622B2 (en) | 2020-09-22 |
JPWO2017072972A1 (ja) | 2018-02-01 |
CN107533304A (zh) | 2018-01-02 |
KR20180077097A (ko) | 2018-07-06 |
US20180024449A1 (en) | 2018-01-25 |
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