JP2009288623A - Electrophotographic photoreceptor, and process cartridge and electrophotographic apparatus including the electrophotographic photoreceptor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electrophotographic photoreceptor which has suppressed variation in the sensitivity due to environment and has excellent endurance potential variation. <P>SOLUTION: The electrophotographic photoreceptor includes a conductive support, an intermediate layer disposed over the conductive support, and a photosensitive layer disposed in contact with the intermediate layer, wherein the intermediate layer contains a polyolefin resin containing a compound having at least one of a carboxylic acid group and a carboxylic acid anhydride group and an acrylic compound of a specific structure as constituents, and a mass ratio (%) of the compound having at least one of a carboxylic acid group and a carboxylic acid anhydride group contained as a constituent in the polyolefin resin is 0.01-30 mass%. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an electrophotographic photosensitive member, and also relates to an electrophotographic process cartridge having the electrophotographic photosensitive member and an electrophotographic apparatus.

An electrophotographic photoreceptor basically comprises a photosensitive layer that forms a latent image by exposure using charging and light, and a conductive substrate as a support for providing the photosensitive layer.
Semiconductor lasers are the main light source currently used in electrophotographic devices, and the charge generation material used for the charge generation layer in the photoreceptor is also a material having a sensitivity at a relatively long wavelength of about 790 nm of the oscillation wavelength of the semiconductor laser. Is being considered.
Among them, organic pigments such as aluminum chlorophthalocyanine, chloroindium phthalocyanine, oxyvanadyl phthalocyanine, chlorogallium phthalocyanine, magnesium phthalocyanine and oxytitanium phthalocyanine, which are sensitive to long wavelength light, are often used. It has been.
These organic pigments are dispersed in a solvent such as tetrahydrofuran, cyclohexanone, methyl ethyl ketone, and ethyl acetate to form a coating liquid for producing a charge generation layer.
In many cases, the coating solution for the charge generation layer is of an organic pigment dispersion system, the thickness of the charge generation layer is generally as thin as about 0.01 to 1 μm, and the solid content concentration is low. Since the fluidity is high, unevenness is likely to occur in the film.

  When the photosensitive layer is directly formed on the support, stains on the support surface, uneven shape and properties, and roughness appear as film formation unevenness of the photosensitive layer as they are, and the resulting image is blank. There arises a problem that black spots and density unevenness occur. Furthermore, rather than immediately coating and forming a photosensitive layer for securing adhesion to the support, protecting electrical breakdown of the photosensitive layer, improving carrier injection into the photosensitive layer, etc., the gap between the support and the photosensitive layer is increased. An intermediate layer has been provided.

As a material for forming the intermediate layer, for example, polyamide (patent documents 1, 2 and 3), polyester (patent documents 4 and 5), vinyl acetate-ethylene copolymer (patent documents 6 and 7), chlorinated ethylene (patent Document 7), maleic anhydride ester polymer (Patent Document 8), polyvinyl butyral (Patent Document 9), quaternary ammonium salt-containing polymer (Patent Document 10), etc. are known, and these resins are dissolved in a solvent. The intermediate layer is produced by applying and heating the intermediate layer coating solution.
However, in many cases, these resins have high polar functional groups in their molecular chains and thus have high hygroscopicity, and the resistance value varies greatly depending on the humidity of the outside world. Therefore, when the intermediate layer is formed of these resins alone, the residual potential is increased, and the electrical characteristics of the photoreceptor are changed in the environment of low temperature and low humidity and high temperature and high humidity, and the image defects are not sufficiently improved.

Patent Documents 11 and 12 clearly show that by drying a polyolefin resin dispersion excellent in liquid stability, a film having good water resistance, transparency, and adhesion to a base film can be obtained. . However, none of the problems specific to the electrophotographic photosensitive member, such as sensitivity of the electrophotographic photosensitive member, environmental change of potential, and durability change, is stated.
JP-A-46-47344 JP-A-52-25638 JP 58-95351 A JP-A-52-20836 JP 54-26738 A JP-A-48-261141 JP 2005-10591 A JP 52-10138 A JP-A-57-90639 JP 51-126149 A Japanese Patent Publication No. 3699935 JP 2003-268164 A

  SUMMARY OF THE INVENTION An object of the present invention is to provide an electrophotographic photosensitive member in which fluctuations in environmental sensitivity are suppressed and fluctuations in endurance potential are good.

  As a result of intensive studies on the above-described conventional techniques and problems, the present inventors have completed the present invention described below. That is, the gist of the present invention is as follows.

An electrophotographic photosensitive member having a conductive support, an intermediate layer provided on the conductive support, and a photosensitive layer provided in contact with the intermediate layer,
The polyolefin in which the intermediate layer contains, as a constituent component, a compound having at least one of a carboxylic acid group and a carboxylic acid anhydride group, and at least one compound selected from the group represented by the following formulas (1) to (4) The mass ratio (%) of the compound containing a resin and having at least one of a carboxylic acid group and a carboxylic anhydride group contained as the constituent component in the polyolefin resin is 0.01% by mass to 30% by mass. An electrophotographic photoreceptor.

（式中、Ｒ_１は水素またはメチル基であり、Ｒ_２は炭素数１０以下のアルキル基であり、Ｒ_３は水素または炭素数１０以下のアルキル基である。）

(In the formula, R ₁ is hydrogen or a methyl group, R ₂ is an alkyl group having 10 or less carbon atoms, and R ₃ is hydrogen or an alkyl group having 10 or less carbon atoms.)

  According to the present invention, it is possible to provide an electrophotographic photosensitive member in which environmental fluctuations in sensitivity are suppressed and fluctuations in endurance potential are good.

Hereinafter, the electrophotographic photoreceptor of the present invention will be described in detail.
The electrophotographic photosensitive member of the present invention is an electrophotographic photosensitive member having a conductive support, an intermediate layer provided on the conductive support, and a photosensitive layer provided in contact with the intermediate layer. Contains a polyolefin resin containing as a constituent component a compound having at least one of a carboxylic acid group and a carboxylic acid anhydride group, and at least one compound selected from the group represented by the following formulas (1) to (4) In the polyolefin resin, the mass ratio (%) of the compound having at least one of a carboxylic acid group and a carboxylic anhydride group contained as a constituent component is 0.01% by mass or more and 30% by mass or less. To do.

（式中、Ｒ_１は水素またはメチル基であり、Ｒ_２は炭素数１０以下のアルキル基であり、Ｒ_３は水素または炭素数１０以下のアルキル基である。）

(In the formula, R ₁ is hydrogen or a methyl group, R ₂ is an alkyl group having 10 or less carbon atoms, and R ₃ is hydrogen or an alkyl group having 10 or less carbon atoms.)

The intermediate layer used in the present invention constitutes a compound having at least one of a carboxylic acid group and a carboxylic acid anhydride group, and at least one compound selected from the group represented by the above formulas (1) to (4). The mass ratio (%) of the compound containing a polyolefin resin contained as a component and having at least one of a carboxylic acid group and a carboxylic anhydride group contained as a constituent component in the polyolefin resin is 0.01% by mass to 30% by mass. It is characterized by the following.
Further, the intermediate layer used in the present invention may contain metal oxide particles, an organic electron transport material, and carbon black as necessary. The mass ratio (%) of the polyolefin resin in the intermediate layer is 25%. It is preferably ˜100%.

In the polyolefin resin, the mass ratio (%) of the compound having at least one of a carboxylic acid group and a carboxylic anhydride group contained as a constituent component is preferably 0.01% by mass or more and 10% by mass or less. More preferably, it is 0.01 mass% or more and 5 mass% or less.
When the mass ratio (%) of the compound having at least one of a carboxylic acid group and a carboxylic acid anhydride group contained as a constituent component is less than 0.01% by mass, endurance fluctuation tends to increase, and the mass ratio (%) However, when it exceeds 30% by mass, the sensitivity and the environmental fluctuation increase.

The compound having at least one of a carboxylic acid group and a carboxylic acid anhydride group contained as a constituent component in the polyolefin resin refers to either one or both of the carboxylic acid group and the carboxylic acid anhydride group within the compound molecule (monomer A compound having at least in the unit).
The compound having at least one of the carboxylic acid group and the carboxylic acid anhydride group is preferably an unsaturated carboxylic acid and / or an anhydride thereof. Specific examples include acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, fumaric acid, crotonic acid and the like, as well as unsaturated dicarboxylic acid half esters and half amides.
Among these, acrylic acid, methacrylic acid, maleic acid, and maleic anhydride are preferable, and acrylic acid and maleic anhydride are particularly preferable.
The compound having at least one of the carboxylic acid group and the carboxylic acid anhydride group is preferably contained as a copolymer in the polyolefin resin. Moreover, the form of the said copolymer is not specifically limited, A random copolymer, a block copolymer, a graft copolymer, etc. are mentioned.
The unsaturated carboxylic acid anhydride such as maleic anhydride forms an acid anhydride structure in which the adjacent carboxyl groups are dehydration-cyclized in the dry state of the resin. However, for example, in an aqueous medium containing a basic compound, part or all of the ring is opened, and the structure of a carboxylic acid or a salt thereof is easily formed.
In the present invention, when the amount of the compound having a carboxylic acid group or a carboxylic acid anhydride group is defined based on the amount of the carboxyl group of the resin, all the carboxylic acid anhydride groups in the resin are ring-opened. It is calculated assuming that it is based.

Examples of the compounds described in the groups represented by the above formulas (1) to (4), which are contained as constituent components in the polyolefin resin, include the following compounds.
(Meth) acrylic acid esters represented by the formula (1), such as methyl (meth) acrylate, ethyl (meth) acrylate, and butyl (meth) acrylate.
Maleate esters such as dimethyl maleate, diethyl maleate, and dibutyl maleate represented by formula (2).
(Meth) acrylic acid amides represented by the formula (3).
Vinyl alcohol obtained by saponifying alkyl vinyl ethers such as methyl vinyl ether and ethyl vinyl ether represented by formula (4) and vinyl esters with a basic compound or the like.
In addition, these compounds can also be used individually or as a mixture.
In this, the (meth) acrylic acid ester shown by Formula (1) is preferable, and methyl acrylate or ethyl acrylate is more preferable.
The mass ratio (%) of the total amount of the compounds described in the groups represented by the formulas (1) to (4) in the polyolefin resin is preferably 1% to 39%, and preferably 10% to 39. % Is more preferable, and 10% to 18% is most preferable.

Further, the polyolefin resin is represented by any one or both of an unsaturated carboxylic acid and its anhydride (A1), an alkene component (A2) having 2 to 6 carbon atoms, and the above formulas (1) to (4). A polyolefin resin containing a copolymer that contains at least one compound (A3) selected from the group as a constituent component of the copolymer, wherein the constituent components (A1), (A2), and ( It is preferable that the mass ratio (%) of A3) satisfies the following formulas (I) and (II).
Formula (I) 0.01 ≦ (A1) / {(A1) + (A2) + (A3)} × 100 ≦ 10
Formula (II) (A2) / (A3) = 55 / 45-99 / 1

In particular, it is more preferable that the mass ratio (%) of the constituent components (A1), (A2), and (A3) in the polyolefin resin satisfies the following formula (III).
Formula (III) 0.01 ≦ (A1) / {(A1) + (A2) + (A3)} × 100 ≦ 5

In the mass ratio (%) of the structural components (A2) and (A3) in the polyolefin resin, when the ratio of the component (A2) is too low, durability fluctuation and environmental fluctuation tend to be reduced.
The above (A2) / (A3) more preferably satisfies 60/39 to 93/1, and most preferably satisfies 60/39 to 87/10.

Examples of the alkene component (A2) having 2 to 6 carbon atoms include alkenes having 2 to 6 carbon atoms such as ethylene, propylene, isobutylene, 1-butene, 1-pentene and 1-hexene. These can be used alone or as a mixture.
Among these, alkenes having 2 to 4 carbon atoms such as ethylene, propylene, isobutylene and 1-butene are more preferable, and ethylene is particularly preferable.

The polyolefin resin used in the present invention particularly preferably contains a terpolymer comprising ethylene, methyl (meth) acrylate or ethyl (meth) acrylate, and maleic anhydride.
Specific examples of the terpolymer include ethylene-acrylic acid ester-maleic anhydride terpolymer or ethylene-methacrylic acid ester-maleic anhydride terpolymer.

  The polyolefin resin used in the present invention may contain other components other than those described above as constituent components of the copolymer to the extent that the effects of the present invention are not impaired. Specific examples of other monomers include dienes, (meth) acrylonitrile, vinyl halides, halogenated vinylidenes, carbon monoxide, sulfur disulfide and the like. The mass ratio (%) of the total amount of the constituent components (A1), (A2), and (A3) in the polyolefin resin is preferably 90% to 100%.

The molecular weight of the polyolefin resin used in the present invention is not particularly limited, and the synthesis method is not particularly limited. The polyolefin resin can be obtained, for example, by high-pressure radical copolymerization of a monomer constituting the polyolefin resin in the presence of a radical generator.
As specific methods for synthesizing polyolefin resins, Chapter 4 (Kyoritsu Shuppan Co., Ltd.), “2003-105145,” and “2003” in “New Polymer Experiments 2 Polymer Synthesis and Reaction (1)”. It is possible to use a known method described in the publication 147028.

In the present invention, the properties of the resin were measured or evaluated by the following methods.
(1) Content of unsaturated carboxylic acid component in olefin resin The acid value of the olefin resin was measured according to JIS K5407, and the content (graft ratio) of the unsaturated carboxylic acid was determined from the following equation.
Content of unsaturated carboxylic acid component (mass%) = (mass of grafted unsaturated carboxylic acid) / (mass of raw material olefin resin) × 100
(2) Composition of resin other than unsaturated carboxylic acid component In orthodichlorobenzene (d4), 1H-NMR, 13C-NMR analysis (manufactured by Varian Technologies Japan Limited, 300 MHz) is performed at 120 ° C. It was. In 13C-NMR analysis, measurement was performed using a gated decoupling method in consideration of quantitativeness.

The coating solution for the intermediate layer is prepared by dissolving the polyolefin resin in a suitable solvent, by preparing it in a molten state by maintaining it at a temperature higher than the softening point of the polyolefin resin, in a suitable solvent. There is a method of producing by making a dispersion by heating and stirring.
In addition, an intermediate layer is formed by depositing these coating solutions by dip coating, roll coating, spray coating, curtain coating, spin coating, etc. From the viewpoint of efficiency / productivity Is preferably a dip coating method.

As the conductive support used in the present invention, a metal or alloy such as aluminum, nickel, copper, gold, or iron, a metal such as aluminum, silver, or gold on an insulating support such as polyester, polycarbonate, polyimide, or glass. Or what formed the thin film of electrically conductive materials, such as an indium oxide and a tin oxide, what disperse | distributed carbon and a conductive filler in resin, and provided the electroconductivity etc. can be illustrated.
The shape of the conductive support is not particularly limited, and a plate, drum, or belt shape is used as necessary.
These conductive support surfaces have an electrochemical treatment such as anodic oxidation or an acidic aqueous solution mainly composed of alkali phosphate or phosphoric acid or tannic acid for improving electrical characteristics or adhesion. Further, chemical treatment using a solution obtained by dissolving a metal salt compound or a fluorine compound metal salt may be performed.

In addition, when the photoconductor is used in a printer using a single wavelength laser beam, the surface of the conductive support is preferably moderately roughened in order to suppress interference fringes.
That is, as the conductive support, a conductive support whose surface is treated by honing, blasting, cutting, electropolishing, or the like, or a conductive metal oxide and a binder resin on a support of aluminum or an aluminum alloy. A conductive support having a conductive coating made of

As the honing treatment, there are dry and wet treatment methods, and any of them may be used. The wet honing treatment is a method in which a powdery abrasive is suspended in a liquid such as water and sprayed onto the surface of the support at a high speed to roughen the surface. The surface roughness is the spray pressure, speed, and amount of abrasive. It can be controlled by the type, shape, size, hardness, specific gravity, suspension temperature and the like.
On the other hand, the dry honing treatment is a method in which an abrasive is sprayed onto the support surface at a high speed with air to roughen the surface, and the surface roughness can be controlled by the same method as the wet honing treatment. Examples of the abrasive used for the wet or dry honing treatment include particles of silicon carbide, alumina, iron, glass beads, and the like.

In the method of applying a conductive film composed of the conductive metal oxide and the binder resin on a support of aluminum or aluminum alloy to form a conductive support, the conductive film is composed of conductive fine particles as a filler. It is preferable to contain a powder.
This method has the effect of dispersing the conductive fine particles in the film to diffusely reflect the laser beam to prevent interference fringes and to conceal the scratches and protrusions on the support before coating.
Examples of the conductive fine particles include zinc oxide, titanium oxide, and barium sulfate. Further, if necessary, it is possible to provide an appropriate specific resistance as a filler by providing a conductive coating layer with tin oxide or the like on the conductive fine particles.

The specific resistance of the conductive fine particles is preferably 0.1 to 1000 Ωcm, more preferably 1 to 1000 Ωcm.
In the present invention, the specific resistance of the conductive fine particles was measured using a resistance measuring apparatus Loresta AP (Loresta Ap) manufactured by Mitsubishi Chemical Corporation. The conductive fine particles to be measured were hardened at a pressure of 500 kg / cm ² and attached to the measuring device as a coin-like sample.

  The average particle size of the conductive fine particles is preferably 0.05 to 1.0 μm, and more preferably 0.07 to 0.7 μm. In the present invention, the average particle diameter of the conductive fine particles is a value measured by a centrifugal sedimentation method.

  Furthermore, the content of the conductive fine particles as a filler is preferably 1.0 to 90% by mass and more preferably 5.0 to 80% by mass with respect to the conductive film. The conductive film may contain fluorine or antimony as necessary.

Examples of the binder resin used for the conductive film include phenol resin, polyurethane, polyamide, polyimide, polyamideimide, polyamic acid, polyvinyl acetal, epoxy resin, acrylic resin, melamine resin, and polyester.
These resins may be used alone or in combination of two or more. When these resins are used, the adhesiveness of the conductive film to the support is good, the dispersibility of the conductive fine particles is improved, and the solvent resistance after film formation is preferable. Among the above resins, phenol resin, polyurethane and polyamic acid are particularly preferable.

The conductive film can be formed by, for example, immersion or solvent application using a Meyer bar or the like. The thickness of the conductive film is preferably 0.1 to 30 μm, and more preferably 0.5 to 20 μm. The volume resistivity of the conductive film is preferably 1.0 × 10 ⁵ Ωcm or more 1.0 × ^{10 13} Ωcm or less, at 1.0 × 10 ⁵ Ωcm or more 1.0 × ^{10 12} Ωcm or less More preferably.
In the present invention, the volume resistivity is determined by applying a conductive film to be measured on an aluminum plate, further forming a gold thin film on the film, and determining a current value flowing between both the aluminum plate and the gold thin film electrode. , Measured using a pA meter. Furthermore, a leveling agent may be added to the conductive film in order to improve surface properties.

The electrophotographic photoreceptor of the present invention has a conductive support, an intermediate layer provided on the conductive support, and a photosensitive layer provided in contact with the intermediate layer.
In the electrophotographic photosensitive member of the present invention, it is preferable that an intermediate layer and a photosensitive layer are formed in this order on the conductive support.
As the photosensitive layer, those having a single layer structure and a laminated structure are known. The laminated photosensitive layer preferably comprises at least a charge generation layer and a charge transport layer.

  The charge generation layer is preferably formed containing a charge generation material and other components such as a binder resin. For example, the charge generation layer is obtained by dissolving a binder resin in a solvent, adding a charge generation material thereto, applying a charge generation layer coating solution obtained by dispersing the charge generation material, and drying the solution. Can be formed. When dispersing the charge generation material, a media type disperser such as a sand mill or a ball mill, or a disperser such as a liquid collision type disperser can be used.

Examples of the charge generating material include pyrylium dyes, thiopyrylium dyes, phthalocyanine pigments, anthanthrone pigments, dibenzpyrenequinone pigments, pyratron pigments, azo pigments, indigo pigments, quinacridone pigments, and quinocyanine dyes. Can be mentioned.
Examples of the phthalocyanine pigment include metal-free phthalocyanine, oxytitanium phthalocyanine, hydroxyphthalocyanine, and gallium halide phthalocyanine such as chlorogallium. These charge generation materials can be used alone or as a mixture.

  In the charge generation layer, when a charge generation material other than the phthalocyanine pigment and the phthalocyanine pigment is mixed and used, the charge generation material other than the phthalocyanine pigment may be contained up to 50% by mass with respect to the total charge generation material. Is possible. In this case, as a charge generation material other than the phthalocyanine pigment, for example, selenium-tellurium, pyrylium, thiapyrylium dye, anthanthrone, dibenzpyrenequinone, trisazo, cyanine, disazo, monoazo, indigo, quinacridone, and asymmetric quinocyanine And pigments.

The charge generation layer is composed of the charge generation material in a mass ratio of 0.3 to 4 times the binder resin and solvent, a homogenizer, an ultrasonic dispersion, a ball mill, a vibration ball mill, a sand mill, an attritor, a roll mill, or a liquid collision type. It is formed by applying and drying a sufficiently dispersed solution using a high-speed disperser or the like.
Examples of the binder resin include butyral resin, polyester resin, polycarbonate resin, polyarylate resin, polystyrene resin, polyvinyl methacrylate resin, polyvinyl acrylate resin, polyvinyl acetate resin, polyvinyl chloride resin, polyamide resin, polyurethane resin, silicone resin, Examples include, but are not limited to, alkyd resins, epoxy resins, cellulose resins, and melamine resins. Of these, a butyral resin is particularly preferred.

The charge transport layer contains a charge transporting substance in a molecular dispersion state and a binder resin, and is applied with a solution in which a binder resin having a film-forming property and the following charge transporting substance is dissolved and dried. It is preferable to form by doing.
Examples of charge transport materials include polycyclic aromatic compounds, heterocyclic compounds, hydrazone compounds, styryl compounds, benzidine compounds, triarylamine compounds, triphenylamine, or a group comprising these compounds as a main chain or a side chain. However, the present invention is not limited to these.

  Examples of the binder resin used for the charge transport layer include, but are not limited to, polyester, polycarbonate, polymethacrylic acid ester, polyarylate, polysulfone, and polystyrene. Of these, polycarbonate and polyarylate are particularly preferred.

  The process cartridge of the present invention integrally supports the electrophotographic photosensitive member of the present invention and at least one means selected from the group consisting of a charging means, a developing means, a transfer means, and a cleaning means. The process cartridge is detachable.

  The electrophotographic apparatus of the present invention is an electrophotographic apparatus having the electrophotographic photosensitive member of the present invention, a charging unit, an exposing unit, a developing unit and a transfer unit.

Next, FIG. 1 shows an example of a schematic configuration of a process cartridge including the electrophotographic photosensitive member of the present invention and an electrophotographic apparatus including the process cartridge.
In FIG. 1, reference numeral 1 denotes a drum-shaped electrophotographic photosensitive member, which is driven to rotate about a shaft 2 in a direction indicated by an arrow at a predetermined peripheral speed.
The peripheral surface of the electrophotographic photosensitive member 1 to be rotationally driven is uniformly charged to a predetermined negative potential by a charging means 3 (primary charging means), and then exposure means (not shown) such as slit exposure or laser beam scanning exposure. ) From the exposure light (image exposure light) 4 output. In this way, electrostatic latent images corresponding to the target image are sequentially formed on the peripheral surface of the electrophotographic photosensitive member 1. The voltage applied to the charging means 3 may be either a voltage obtained by superimposing an AC component on a DC component or a voltage containing only a DC component. In the present invention, a charging means that applies only a DC component is used.

The electrostatic latent image formed on the peripheral surface of the electrophotographic photosensitive member 1 is developed with toner of the developing unit 5 to become a toner image. Next, the toner images formed and supported on the peripheral surface of the electrophotographic photoreceptor 1 are sequentially transferred by a transfer bias from the transfer unit 6 (transfer roller). The transfer material P (paper or the like) is taken out from the transfer material supply means (not shown) between the electrophotographic photoreceptor 1 and the transfer means 6 (contact portion) in synchronization with the rotation of the electrophotographic photoreceptor 1. Be fed.
The transfer material P that has received the transfer of the toner image is separated from the peripheral surface of the electrophotographic photosensitive member 1 and is introduced into the fixing means 8 to undergo image fixing, and is printed out of the apparatus as an image formed product (print, copy). Out.

The surface of the electrophotographic photosensitive member 1 after the transfer of the toner image is cleaned by removing the developer (toner) remaining after transfer by a cleaning means 7 (cleaning blade), and further from a pre-exposure means (not shown). After being neutralized by the pre-exposure light 11, it is repeatedly used for image formation.
As the transfer means, for example, an intermediate transfer type transfer means using an intermediate transfer body such as a belt shape or a drum shape may be employed.
In FIG. 1, an electrophotographic photosensitive member 1, a charging unit 3, a developing unit 5 and a cleaning unit 7 are integrally supported to form a cartridge, and an electrophotographic apparatus is used using a guide unit 10 such as a rail of the electrophotographic apparatus main body. The process cartridge 9 is detachable from the main body.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In addition, the number of parts in the following composition is part by mass unless otherwise specified.

  An electrophotographic photosensitive member is produced by the method described below using a polyolefin resin containing (A1) type, (A2) type, and (A3) type with the constituent components and mass ratio (%) shown in Table 1 below. did.

<Example 1>
75.0 g of resin (B-1), 60.0 g of 2-propanol (hereinafter referred to as IPA), 5.1 g of triethylamine in a hermetically sealed 1 liter glass container equipped with a heater and equipped with a heater. (Hereinafter referred to as TEA) and 159.9 g of distilled water were added and stirred at a stirring blade rotation speed of 300 rpm. No sedimentation of resin particles was observed at the bottom of the vessel, and the suspension was in a floating state. Was confirmed. Therefore, while maintaining this state, the heater was turned on and heated after 10 minutes. Then, the system temperature was kept at 140 to 145 ° C. and further stirred for 20 minutes. Then, after putting in a water bath and cooling to room temperature (about 25 ° C.) while stirring at a rotational speed of 300 rpm, pressure filtration (air pressure 0.2 MPa) with a 300 mesh stainless steel filter (wire diameter 0.035 mm, plain weave) Then, an aqueous dispersion (C-1) containing milky white uniform polyolefin resin particles was obtained.

On the other hand, 0.2 mol of stannic chloride pentahydrate was dissolved in 200 ml of water to make a 0.5 M aqueous solution, and 28% ammonia water was added with stirring to increase the pH of white tin oxide exceeding 1.5. A slurry containing fine particles was obtained. The obtained tin oxide ultrafine particle-containing slurry is heated to 70 ° C. and then naturally cooled to around 50 ° C., and then pure water is added to obtain a 1 L tin oxide ultrafine particle-containing slurry, and solid-liquid separation is performed using a centrifuge. went. After adding 800 ml of pure water to this water-containing solid content, stirring and dispersing with a homogenizer, washing was performed by solid-liquid separation using a centrifuge. 75 ml of pure water was added to the water-containing solid content after washing to prepare a tin oxide ultrafine particle-containing slurry. To the obtained tin oxide ultrafine particle-containing slurry, 3.0 ml of triethylamine was added and stirred. After the transparency was raised, the temperature was raised to 70 ° C., and then the heating was stopped and the mixture was naturally cooled to obtain a solid content concentration of 20% by mass. A tin oxide sol solution containing an organic amine as a dispersion stabilizer was obtained.
99 parts by mass of the aqueous dispersion (C-1), 875 parts by mass of the tin oxide sol solution, and 350 parts by mass of IPA were mixed to obtain a coating solution for an intermediate layer.

An aluminum base pipe (ED pipe: JIS-A3003) having an outer diameter of 30.5 mm, an inner diameter of 28.5 mm, and a length of 260.5 mm obtained by hot extrusion was prepared.
120 parts by mass of a powder composed of fine particles of barium sulfate having a coating layer formed of tin oxide (coverage: 50 mass%, powder specific resistance: 700 Ω · cm) and a resol type phenol resin (trade name: Bryofen J-325, Prepare a solution consisting of 70 parts by mass of Dainippon Ink & Chemicals, Inc., solid content 70%) and 100 parts by mass of 2-methoxy-1-propanol, and disperse the powder for about 20 hours using a ball mill. Then, a coating liquid for conductive particle resin dispersion layer was prepared (the average particle size of the powder contained in this coating liquid was 0.22 μm).
This liquid was applied on the aluminum base tube by a dip coating method and heated and cured at 140 ° C. for 30 minutes to form a conductive particle resin dispersion layer having a thickness of 15 μm, which was used as a conductive support. .
The intermediate layer coating solution was applied onto the conductive support by a dip coating method and dried at 120 ° C. for 10 minutes to form an intermediate layer having a thickness of 0.8 μm.

  Next, 10 parts by mass of polyvinyl butyral resin (trade name: BX-1, manufactured by Sekisui Chemical Co., Ltd.) and 350 parts by mass of cyclohexanone are added to 20 parts by mass of hydroxygallium phthalocyanine crystal as a charge generation material, and 1 mmφ glass beads The mixture was dispersed for 3 hours using a sand mill, and 1200 parts by mass of ethyl acetate was added thereto and diluted to obtain a dispersion. At this time, the dispersed particle diameter of the charge generation material in the dispersion measured using a natural / centrifugal sedimentation particle size distribution analyzer (CAPA-700, manufactured by Horiba, Ltd.) was 0.15 μm. On the intermediate layer, this charge generation layer coating solution was applied by dip coating and dried at 100 ° C. for 10 minutes to form a charge generation layer having a thickness of 0.2 μm.

  Next, 7 parts by mass of a compound represented by the following structural formula (7), 1 part by mass of a compound represented by the following structural formula (8), and a bisphenol C type having a structural unit represented by the following structural formula (9) 10 parts by mass of a polyarylate resin (weight average molecular weight [Mw] 110000) was dissolved in a mixed solvent consisting of 50 parts by mass of monochlorobenzene and 10 parts by mass of dichloromethane to prepare a coating solution for the charge transport layer. This coating solution was applied onto the charge generation layer by a dip coating method and dried at 110 ° C. for 1 hour to form a charge transport layer having a thickness of 18 μm. Thus, an electrophotographic photosensitive member was produced.

The evaluation method of the electrophotographic photosensitive member is as follows. The electrophotographic photosensitive member produced above was converted into a color laser printer manufactured by Hewlett-Packard Co., Ltd., a laser jet 4600 remodeling machine (primary charging: roller contact DC charging, dark part potential −500 V, process speed 100 mm / second, laser exposure, light intensity 0 .3 uJ / cm ² ), the light potential at 23 ° C./50% RH at normal temperature and humidity was measured and used as the sensitivity. Further, after measuring the bright part potential at low temperature and low humidity of 15 ° C./10% RH, 3000 images were output at an image density of 4%, and the bright part potential was measured again. The difference in bright part potential between the normal temperature and normal humidity environment and the low temperature and low humidity environment was defined as the environmental fluctuation value, and the bright part potential difference before and after the image output was defined as the durable potential fluctuation value. The results are shown in Table 2.
The sensitivity is preferably less than 130V, and the environmental fluctuation value and the endurance potential fluctuation value are preferably less than 20V and less than 35V, respectively. When the environmental fluctuation and the endurance potential fluctuation value are large, the obtained image density change is also large, more preferably 15 V or less and 22 V or less, respectively, and when image density stability is required, 10 V or less and 15 V or less, respectively. It is.

<Example 2>
To 100 parts by mass of titanium oxide (TTO55N, manufactured by Ishihara Sangyo Co., Ltd.), 750 parts by mass of methanol, and 50 parts by mass of distilled water, 1000 parts by mass of 1 mmφ glass beads are added and dispersed for 15 hours by a paint shaker. Obtained. An intermediate layer and an electrophotographic photosensitive member were produced in the same manner as in Example 1 except that the tin oxide sol solution of the intermediate layer coating solution was changed to 900 parts by mass of the titanium oxide dispersion. The obtained electrophotographic photoreceptor was evaluated in the same manner as in Example 1. The results are shown in Table 2.

<Example 3>
In Example 2, titanium oxide (titanium oxide, PT401M, manufactured by Ishihara Sangyo Co., Ltd.)
An intermediate layer and an electrophotographic photosensitive member were produced in the same manner as in Example 2 except that: The obtained electrophotographic photoreceptor was evaluated in the same manner as in Example 1. The results are shown in Table 2.

<Example 4>
In Example 2, an intermediate layer and an electrophotographic photoreceptor were prepared in the same manner as in Example 2 except that the titanium oxide was changed to (titanium oxide, PT301M, manufactured by Ishihara Sangyo Co., Ltd.). The obtained electrophotographic photoreceptor was evaluated in the same manner as in Example 1. The results are shown in Table 2.

<Example 5>
25 parts by mass of a compound represented by the following structural formula (10) was dissolved in a solvent of 350 parts by mass of cyclohexanone and 350 parts by mass of methanol. In Example 1, the intermediate layer and the electrophotography were the same as Example 1 except that the tin oxide sol solution of the intermediate layer coating solution was changed to 725 parts by mass of the compound solution represented by the structural formula (10). A photoconductor was prepared. The obtained electrophotographic photoreceptor was evaluated in the same manner as in Example 1. The results are shown in Table 2.
The compound represented by the structural formula (10) can be synthesized by using a known synthesis method described in US Pat. No. 4,442,193, US Pat. No. 4,992,349 and US Pat. No. 5,468,583. It was synthesized by the following method. Under a nitrogen stream, 20 parts by mass of 1,4,5,8-naphthalenetetracarboxylic dianhydride and 1 part by mass of imidazole are mixed, and 50 parts by mass of 2-methyl-6-ethylaniline and 2-amino-1-butanol are mixed. 7.3 parts by mass were added, and the mixture was stirred with heating at 170 ° C. for 3 hours. After completion of the reaction, 500 ml of toluene was added and separation and purification were performed by silica gel column chromatography. The obtained brown liquid was heated and cooled to obtain 10 parts by mass of yellowish white crystals.
(MALDI-TOF MS: ultraflex manufactured by Bruker Daltonics Co., Ltd.) (acceleration voltage: 20 kV, mode: Reflector, molecular weight standard product: fullerene C ₆₀ ), when the molecular weight was measured by mass spectrometry, 456 was the peak top value. Obtained. Moreover, it confirmed that it was a compound shown by Structural formula (10) from an infrared absorption spectrum and proton NMR.
Infrared absorption spectrum was measured by a KBr tablet method using a Fourier transform infrared spectrophotometer (trade name: Paragon 1000) manufactured by PerkinElmer Japan Co., Ltd., with a resolution of 4 cm ⁻¹ , and NMR was R-1100 manufactured by Hitachi, Ltd. : CDCl3, concentration 10%, internal standard TMS

<Example 6>
The compound represented by the following structural formula (11) is replaced with 2-methyl-6-ethylaniline and 2-amino-1-butanol used in the synthesis of the structural formula (10). The synthesis was performed in the same manner except that 2-methyl-4nitroaniline was used. An intermediate layer and an electrophotographic photoreceptor were prepared in the same manner as in Example 5 except that the compound represented by the structural formula (11) was used instead of the compound represented by the structural formula (10). The obtained electrophotographic photoreceptor was evaluated in the same manner as in Example 1. The results are shown in Table 2.

<Example 7>
The compound represented by the following structural formula (12) was synthesized in the same manner except that 2-6-diethyl-3chloroaniline was used instead of 2-methyl-6-ethylaniline used in the synthesis of structural formula (10). . An intermediate layer and an electrophotographic photosensitive member were produced in the same manner as in Example 5 except that the compound represented by the structural formula (12) was used instead of the compound represented by the structural formula (10). The obtained electrophotographic photoreceptor was evaluated in the same manner as in Example 1. The results are shown in Table 2.

<Example 8>
In Example 1, the aqueous dispersion (C-13) containing polyolefin resin particles was used in the same manner as in Example 1 except that the resin (B-1) was changed to the resin (B-13) shown in Table 1. Produced. 99 parts by weight of the aqueous dispersion (C-13), 700 parts by weight of distilled water, and 200 parts by weight of IPA were mixed to obtain the intermediate layer and the intermediate layer in the same manner as in Example 1 except that a coating liquid for the intermediate layer was obtained. An electrophotographic photosensitive member was produced. The obtained electrophotographic photoreceptor was evaluated in the same manner as in Example 1. The results are shown in Table 2.

<Example 9>
In Example 1, 80 parts by mass of the aqueous dispersion (C-1), 875 parts by mass of a tin oxide sol solution, 5 parts by mass of N-methoxymethylated 6 nylon, and 350 parts by mass of IPA were mixed, and coating for an intermediate layer was performed. An intermediate layer and an electrophotographic photosensitive member were produced in the same manner as in Example 1 except that the solution was used. The obtained electrophotographic photoreceptor was evaluated in the same manner as in Example 1. The results are shown in Table 2.

<Example 10>
In Example 1, the aqueous dispersion (C-14) containing polyolefin resin particles was used in the same manner as in Example 1 except that the resin (B-1) was changed to the resin (B-14) shown in Table 1. Produced. 99 parts by weight of the aqueous dispersion (C-14), 700 parts by weight of distilled water, and 200 parts by weight of IPA were mixed to obtain a coating solution for the intermediate layer, and the film thickness of the intermediate layer was 0.3 μm. An intermediate layer and an electrophotographic photosensitive member were produced in the same manner as in Example 1 except that. The obtained electrophotographic photoreceptor was evaluated in the same manner as in Example 1. The results are shown in Table 3.

<Example 11>
In Example 1, resin (B-2) was used instead of resin (B-1), and an aqueous dispersion (
C-2) was obtained, and 99 parts by mass of the aqueous dispersion (C-2), 835 parts by mass of distilled water, and 65 parts by mass of IPA were mixed as an intermediate layer coating liquid to obtain an intermediate layer coating liquid. Then, an intermediate layer and an electrophotographic photosensitive member were produced in the same manner as in Example 1 except that the intermediate layer coating solution was used and the thickness of the intermediate layer was 0.3 μm. The obtained electrophotographic photoreceptor was evaluated in the same manner as in Example 1. The results are shown in Table 3.

<Example 12>
In Example 1, 99 parts by weight of the aqueous dispersion (C-1), 645 parts by weight of distilled water, and 280 parts by weight of IPA were mixed into the intermediate layer coating liquid as the intermediate layer coating liquid. An intermediate layer and an electrophotographic photosensitive member were produced in the same manner as in Example 1 except that the intermediate layer coating solution was used and the thickness of the intermediate layer was 0.3 μm. The obtained electrophotographic photoreceptor was evaluated in the same manner as in Example 1. The results are shown in Table 3.

<Example 13>
In the same manner as in Example 10, except that the resin (B-3) shown in Table 1 was used instead of the resin (B-14) used in Example 10 to obtain an aqueous dispersion (C-3) containing resin particles. An intermediate layer and an electrophotographic photosensitive member were produced. The obtained electrophotographic photoreceptor was evaluated in the same manner as in Example 1. The results are shown in Table 3.

<Example 14>
60 parts by mass of aqueous dispersion (C-1), 700 parts by mass of distilled water, 200 parts by mass of IPA, N-
10 parts by mass of methoxymethylated 6 nylon was mixed to obtain a coating solution for the intermediate layer. An intermediate layer and an electrophotographic photosensitive member were produced in the same manner as in Example 1 except that the intermediate layer coating solution was used and the thickness of the intermediate layer was 0.3 μm. The obtained electrophotographic photoreceptor was evaluated in the same manner as in Example 1. The results are shown in Table 3.

<Example 15>
In the same manner as in Example 10, except that the resin (B-4) shown in Table 1 was used instead of the resin (B-14) used in Example 10 to obtain an aqueous dispersion (C-4) containing resin particles. An intermediate layer and an electrophotographic photosensitive member were produced. The obtained electrophotographic photoreceptor was evaluated in the same manner as in Example 1. The results are shown in Table 3.

<Example 16>
In the same manner as in Example 10, except that the resin (B-5) shown in Table 1 was used instead of the resin (B-14) used in Example 10 to obtain an aqueous dispersion (C-5) containing resin particles. An intermediate layer and an electrophotographic photosensitive member were produced. The obtained electrophotographic photoreceptor was evaluated in the same manner as in Example 1. The results are shown in Table 3.

<Example 17>
The same procedure as in Example 10 was conducted except that the resin (B-6) shown in Table 1 was used instead of the resin (B-14) used in Example 10 to obtain an aqueous dispersion (C-6) containing resin particles. An intermediate layer and an electrophotographic photosensitive member were produced. The obtained electrophotographic photoreceptor was evaluated in the same manner as in Example 1. The results are shown in Table 3.

<Example 18>
In the same manner as in Example 10, except that the resin (B-7) shown in Table 1 was used instead of the resin (B-14) used in Example 10 to obtain an aqueous dispersion (C-7) containing resin particles. An intermediate layer and an electrophotographic photosensitive member were produced. The obtained electrophotographic photoreceptor was evaluated in the same manner as in Example 1. The results are shown in Table 3.

<Example 19>
In the same manner as in Example 10, except that the resin (B-8) shown in Table 1 was used instead of the resin (B-14) used in Example 10 to obtain an aqueous dispersion (C-8) containing resin particles. An intermediate layer and an electrophotographic photosensitive member were produced. The obtained electrophotographic photoreceptor was evaluated in the same manner as in Example 1. The results are shown in Table 3.

<Example 20>
In the same manner as in Example 10, except that the resin (B-9) shown in Table 1 was used instead of the resin (B-14) used in Example 10, and the resin particle-containing aqueous dispersion (C-9) was used. An intermediate layer and an electrophotographic photosensitive member were produced. The obtained electrophotographic photoreceptor was evaluated in the same manner as in Example 1. The results are shown in Table 3.

<Example 21>
In the same manner as in Example 10, except that the resin (B-10) shown in Table 1 was used instead of the resin (B-14) used in Example 10 to obtain an aqueous dispersion (C-10) containing resin particles. An intermediate layer and an electrophotographic photosensitive member were produced. The obtained electrophotographic photoreceptor was evaluated in the same manner as in Example 1. The results are shown in Table 3.

<Example 22>
In the same manner as in Example 10, except that the resin (B-11) shown in Table 1 was used instead of the resin (B-14) used in Example 10, and an aqueous dispersion (C-11) containing resin particles was used. An intermediate layer and an electrophotographic photosensitive member were produced. The obtained electrophotographic photoreceptor was evaluated in the same manner as in Example 1. The results are shown in Table 3.

<Comparative Example 1>
In the same manner as in Example 10, except that the resin (B-12) shown in Table 1 was used instead of the resin (B-14) used in Example 10 to obtain an aqueous dispersion (C-12) containing resin particles. An intermediate layer and an electrophotographic photosensitive member were produced. The obtained electrophotographic photoreceptor was evaluated in the same manner as in Example 1. The results are shown in Table 3.

<Comparative Example 2>
In the same manner as in Example 10, except that the resin (B-15) shown in Table 1 was used instead of the resin (B-14) used in Example 10 to obtain an aqueous dispersion (C-15) containing resin particles. An intermediate layer and an electrophotographic photosensitive member were produced. The obtained electrophotographic photoreceptor was evaluated in the same manner as in Example 1. The results are shown in Table 3.

<Comparative Example 3>
In the same manner as in Example 10, except that the resin (B-16) shown in Table 1 was used instead of the resin (B-14) used in Example 10, and the resin particle-containing aqueous dispersion (C-16) was used. An intermediate layer and an electrophotographic photosensitive member were produced. The obtained electrophotographic photoreceptor was evaluated in the same manner as in Example 1. The results are shown in Table 3.

<Comparative example 4>
In the same manner as in Example 10, except that the resin (B-17) shown in Table 1 was used instead of the resin (B-14) used in Example 10 to obtain an aqueous dispersion (C-17) containing resin particles. An intermediate layer and an electrophotographic photosensitive member were produced. The obtained electrophotographic photoreceptor was evaluated in the same manner as in Example 1. The results are shown in Table 3.

<Comparative Example 5>
SG2000 (ethylene and acrylic acid copolymer resin aqueous solution as the intermediate layer coating solution)
An intermediate layer and an electrophotographic photosensitive member were produced in the same manner as in Example 10 except that the product manufactured by Lead City Corporation was used. The obtained electrophotographic photoreceptor was evaluated in the same manner as in Example 1. The results are shown in Table 3.

<Comparative Example 6>
The intermediate layer and the electron as in Example 10 except that 10 parts by mass of ELVAX 4260 (manufactured by DuPont), which is a copolymer resin of ethylene and vinyl acetate, was dissolved in 200 parts by mass of toluene as the coating liquid for the intermediate layer. A photographic photoreceptor was prepared. The obtained electrophotographic photoreceptor was evaluated in the same manner as in Example 1. The results are shown in Table 3.

<Comparative Example 7>
The intermediate layer and the electrophotographic photosensitive member were the same as in Example 10 except that 10 parts by mass of Superchloron (manufactured by Nippon Paper Industries Co., Ltd.) and 200 parts by mass of toluene were used as the coating liquid for the intermediate layer. Produced. The obtained electrophotographic photoreceptor was evaluated in the same manner as in Example 1. The results are shown in Table 3.

FIG. 2 is a diagram illustrating an example of a schematic configuration of a process cartridge on which the electrophotographic photosensitive member of the present invention is mounted and an electrophotographic apparatus including the process cartridge.

Explanation of symbols

1 Electrophotographic photosensitive member 2 Axis 3 Charging means (primary charging means)
4 exposure light (image exposure light)
5 Developing means 6 Transfer means (transfer roller)
7 Cleaning means (cleaning blade)
8 Fixing means 9 Process cartridge 10 Guide means 11 Pre-exposure light P Transfer material (paper, etc.)

Claims (6)

An electrophotographic photosensitive member having a conductive support, an intermediate layer provided on the conductive support, and a photosensitive layer provided in contact with the intermediate layer,
The polyolefin in which the intermediate layer contains, as a constituent component, a compound having at least one of a carboxylic acid group and a carboxylic acid anhydride group, and at least one compound selected from the group represented by the following formulas (1) to (4) The mass ratio (%) of the compound containing a resin and having at least one of a carboxylic acid group and a carboxylic anhydride group contained as the constituent component in the polyolefin resin is 0.01% by mass to 30% by mass. An electrophotographic photoreceptor.

(In the formula, R ₁ is hydrogen or a methyl group, R ₂ is an alkyl group having 10 or less carbon atoms, and R ₃ is hydrogen or an alkyl group having 10 or less carbon atoms.) The polyolefin resin is one or both of an unsaturated carboxylic acid and its anhydride (A1), an alkene component having 2 to 6 carbon atoms (A2), and a group represented by the following formulas (1) to (4) A polyolefin resin containing a copolymer containing at least one compound (A3) selected from as a constituent component of the copolymer, wherein the constituent components (A1), (A2) and ( The electrophotographic photosensitive member according to claim 1, wherein the mass ratio (%) of A3) satisfies the following formulas (I) and (II).
Formula (I) 0.01 ≦ (A1) / {(A1) + (A2) + (A3)} × 100 ≦ 10
Formula (II) (A2) / (A3) = 55 / 45-99 / 1

(In the formula, R ₁ is hydrogen or a methyl group, R ₂ is an alkyl group having 10 or less carbon atoms, and R ₃ is hydrogen or an alkyl group having 10 or less carbon atoms.) The electrophotographic photosensitive member according to claim 2, wherein a mass ratio (%) of the constituent components (A1), (A2), and (A3) in the polyolefin resin satisfies the following formula (III).
Formula (III) 0.01 ≦ (A1) / {(A1) + (A2) + (A3)} × 100 ≦ 5   The said polyolefin resin contains an ethylene-acrylic acid ester-maleic anhydride terpolymer or an ethylene-methacrylic ester-maleic anhydride terpolymer. The electrophotographic photosensitive member according to item 1.   An electrophotographic photosensitive member according to any one of claims 1 to 4, and at least one means selected from the group consisting of a charging means, a developing means, a transfer means, and a cleaning means, are integrally supported, and electrophotographic A process cartridge that is detachable from the main unit. An electrophotographic apparatus comprising the electrophotographic photosensitive member according to claim 1, a charging unit, an exposure unit, a developing unit, and a transfer unit.

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