JP2005275367A - Electrophotographic photoreceptor, its manufacturing method, electrophotographic process cartridge, and image forming apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electrographic photoreceptor which reduces occurrence of oxide deterioration caused by electification stress even during long-term use and has a high image quality and a long service life, and to provide its manufacturing method, an electrophotographic process cartridge and an image forming apparatus. <P>SOLUTION: In the electrophotographic photoreceptor including a photosensitive layer on a conductive substrate, a top layer contains one or more kinds of resins including a bridged structure and oxygen permeability on the top layer at 25°C is 1500 fm/sPa or less. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an electrophotographic photosensitive member and a manufacturing method thereof, an electrophotographic process cartridge, and an image forming apparatus.

  In recent years, so-called xerographic image forming apparatuses having a charging unit, an exposure unit, a developing unit, a transfer unit, and a fixing unit have been further increased in speed and life due to technical development of each member and system. . As a result, the demand for high-speed compatibility and high reliability of each subsystem is increasing. In particular, the electrophotographic photosensitive member used for image writing and the cleaner for cleaning the electrophotographic photosensitive member are subject to a lot of stress due to sliding with the electrophotographic photosensitive member, and are liable to cause image defects due to scratches, wear, chipping, etc. Demand for high-speed compatibility and high reliability is even stronger. On the other hand, there is a strong demand for higher image quality, and it is possible to reduce the particle size of the toner, make the particle size distribution uniform, and make it spherical. Toners, so-called chemical toners, have been actively developed. As a result, recently, so-called photographic image quality has been obtained.

In order to extend the life of the electrophotographic photosensitive member, it is extremely important to increase the mechanical strength in order to reduce the wear of the outermost surface layer. For example, Patent Document 1 reports that an electrophotographic photosensitive member having a cross-linked structure and a structural unit having a charge transporting capability has a very long lifetime.
Japanese Patent No. 3264218

  The electrophotographic photosensitive member of the above-mentioned Japanese Patent No. 3264128 has another problem because it does not wear although the mechanical strength of the outermost surface layer is high and wear does not occur.

  That is, the phenomenon of adhesion to the outermost surface, such as oxidative degradation caused by charging stress, is no longer negligible. Such an adhesion phenomenon causes a decrease in image quality such as white spots and density unevenness depending on the type and degree of adhesion.

  In the conventional photoconductor, the outermost surface is mechanically worn by the cleaning stress, but at that time, the above-mentioned deposits are scraped off and can be removed. However, since the mechanical strength of the outermost surface layer is increased and the amount of mechanical wear is reduced, the deposits cannot be sufficiently removed. On the other hand, there may be a phenomenon in which the cleaning blade presses the adhered material against the outermost surface of the photoconductor to increase the strength of the adhesion.

  Accordingly, an object of the present invention is to produce an electrophotographic photosensitive member having a high image quality and a long life, and an electrophotographic process cartridge, an electrophotographic process cartridge, and an image with little occurrence of oxidative degradation due to charging stress or the like even during long-term use. It is to provide a forming apparatus.

  As a result of diligent efforts, the present inventors have found that the following electrophotographic photosensitive member, process cartridge and electrophotographic apparatus are high-quality and long-life electrophotographic photosensitive members, process cartridge and image forming apparatus. . That is, the present invention

  (1) In an electrophotographic photosensitive member having a photosensitive layer on a conductive substrate, the outermost surface layer contains a resin having at least one kind of cross-linked structure, and the oxygen permeability at 25 ° C. of the outermost surface layer is 1500 fm. An electrophotographic photosensitive member characterized by being not more than / s · Pa.

  (2) The electrophotographic photosensitive member according to (1), wherein the oxygen permeability of the outermost surface layer at 25 ° C. is 250 fm / s · Pa or more and 1500 fm / s · Pa or less.

  (3) The electrophotographic photosensitive member according to (1) or (2), comprising at least a charge generation layer and a plurality of layers having different compositions on the charge generation layer.

(4) When the oxygen permeability at 25 ° C. of the resin having a plurality of groups having active hydrogen in the photosensitive layer and having the crosslinked structure is O ₂ GTR1, the oxygen permeability O at 25 ° C. _{2. The} electrophotographic photosensitive member according to any one of (1) to (3), wherein GTR2 contains a resin having a relationship represented by the following formula (1) in the outermost surface layer.
Formula (1): O ₂ GTR2 <O ₂ GTR1

  (5) The electrophotographic photosensitive member according to any one of (1) to (4), wherein the outermost surface layer has a crosslinked structure and contains a structural unit having a charge transporting ability.

  (6) The electrophotographic photosensitive member according to any one of (1) to (4), wherein the outermost surface layer contains a resin having a plurality of groups having active hydrogen.

(7) The electrophotographic photosensitive member according to any one of (4) to (6), wherein the oxygen permeability O ₂ GTR1 is 1500 fm / s · Pa or more and 5000 fm / s · Pa or less.

(8) The oxygen transmission rate O ₂ GTR2 is 1 × 10 ⁻¹⁵ fm / s · Pa or more and 500 fm / s · Pa or less, according to any one of (4) to (7), Electrophotographic photoreceptor.

(9) The resin having the oxygen permeability O ₂ GTR2 is at least one kind in a resin group consisting of copolymerized polyamide, polyvinyl alcohol, polyethylene-polyvinyl alcohol copolymer, polyvinylidene chloride, and unsaturated polyester. The electrophotographic photosensitive member according to any one of (4) to (8), wherein:

(10) and a resin having a crosslinked structure by the oxygen permeability O ₂ GTR1, a resin having the oxygen permeability O ₂ GTR2, but characterized by having a site which is chemically bonded (4) to The electrophotographic photosensitive member according to any one of (9).

  (11) formed using a coating liquid containing two or more types of organic solvents having different boiling points, and after forming a coating film with the coating liquid, the boiling point of the solvent species showing the lowest boiling point contained in the coating liquid; (1) to (10), wherein at least one layer of the photosensitive layer is formed by drying at a temperature between the boiling point of the solvent species exhibiting the highest boiling point. Electrophotographic photoreceptor.

  (12) The electrophotographic photosensitive member according to (11), wherein at least one of the photosensitive layers is a charge transport layer.

  (13) The electrophotographic photosensitive member according to any one of (11) to (12), wherein the organic solvent is selected from tetrahydrofuran and aromatic hydrocarbons.

  (14) The electrophotographic photosensitive member according to any one of (11) to (13), wherein the drying temperature is from 70 ° C to 120 ° C.

  (15) The electrophotography according to any one of (11) to (14), wherein the mass of the solvent species exhibiting the lowest boiling point is at least twice the mass of the solvent species exhibiting the highest boiling point. Photoconductor.

  (16) The electrophotographic photosensitive member according to any one of (1) to (15), and having at least one of at least charging means, exposure means, transfer means, fixing means, and cleaning means. And an electrophotographic process cartridge which is removable from the main body of the image forming apparatus.

(17) The electrophotographic process cartridge according to (16), wherein the charging unit is a contact-type charging unit that contacts the electrophotographic photosensitive member to charge the photosensitive member.

  (18) The electrophotographic photosensitive member according to any one of (1) to (15), and at least one of at least charging means, exposure means, transfer means, fixing means, and cleaning means. An image forming apparatus.

  (19) The image forming apparatus according to (18), wherein the charging unit is a contact-type charging unit that contacts the electrophotographic photosensitive member to charge the photosensitive member.

(20) A method for producing the electrophotographic photosensitive member according to (1),
Using a coating liquid containing two or more organic solvents having different boiling points, and forming a coating film with the coating liquid, the boiling point of the solvent type showing the lowest boiling point and the solvent type showing the highest boiling point contained in the coating liquid And producing at least one layer of the photosensitive layer by drying at a temperature between the boiling point of the electrophotographic photosensitive member.

  (21) The method for producing an electrophotographic photosensitive member according to (20), wherein a charge transport layer is formed as at least one layer of the photosensitive layer.

  (22) The method for producing an electrophotographic photosensitive member according to any one of (20) to (21), wherein the organic solvent is selected from tetrahydrofuran and aromatic hydrocarbons.

  (23) The method for producing an electrophotographic photosensitive member according to any one of (20) to (22), wherein the drying temperature is 70 ° C to 120 ° C.

  (24) The electrophotographic apparatus according to any one of (20) to (23), wherein the mass of the solvent species exhibiting the lowest boiling point is set to be twice or more the mass of the solvent species exhibiting the highest boiling point. A method for producing a photoreceptor.

  According to the electrophotographic photosensitive member of the present invention, surface adhesion does not remain even during long-term use, and high image quality and long life can be realized. In addition, according to the electrophotographic process cartridge and the image forming apparatus of the present invention, high image quality and long life can be realized without causing image quality defects even during long-term use.

  Hereinafter, the electrophotographic photosensitive member, the manufacturing method thereof, the electrophotographic process cartridge, and the image forming apparatus of the present invention will be described in detail.

<Electrophotographic photoreceptor>
The electrophotographic photosensitive member of the present invention has a photosensitive layer on a conductive substrate, the outermost surface layer contains at least one resin having a crosslinked structure, and the outermost surface layer has an oxygen transmission rate at 25 ° C. of 1500 fm / The electrophotographic photosensitive member is characterized by having an s · Pa or less (preferably 1200 fm / s · Pa or less).

  The oxygen permeability represents the ease of oxygen gas permeation of the layer. In addition, if the gas changes, the absolute value of the transmittance changes, but there is almost no reversal of the magnitude relationship between the layers serving as the specimens. Therefore, it may be interpreted as a general scale for expressing the ease of gas permeation. Since the oxygen permeability is a measure of the ease of gas permeation, it can be regarded as a substitute characteristic of the physical void ratio of the layer if the view is changed. In the present invention, the oxygen permeability is a value obtained as follows. A sample film is set between the sealed cells, both cells are evacuated, oxygen at a constant pressure (eg, 100 kPa) is sealed in one cell, and the amount of oxygen passing through the sample film is measured in the other cell. With the pressure sensor set to, read as pressure value and convert to oxygen amount.

Oxidation degradation products, etc., which adhere to the surface of a long-life photoconductor, are considered to be caused by, for example, NO _x or ozone gas penetrating into the photosensitive layer and chemical degradation of a part of the photosensitive layer. . Therefore, as the gas permeation of the outermost surface layer hardly occurs, that is, as the oxygen permeability is lower, oxidation degradation products and the like are less likely to occur, which is advantageous for high image quality and long life.

  The present inventors include at least one type of resin having a crosslinked structure in the outermost surface layer of the photoreceptor so that the outermost surface layer has high mechanical strength and excellent wear resistance, and the outermost surface layer has a temperature of 25 ° C. It has been found that when the oxygen permeability in is 1500 fm / s · Pa or less (preferably 1200 fm / s · Pa or less), high image quality and long life can be realized without causing the above problems.

  On the other hand, in the case where oxidative degradation products or the like have been generated, the image quality is adversely affected if they remain attached to the outermost surface of the electrophotographic photosensitive member. Therefore, it is necessary to remove these oxidation degradation products by some method such as a cleaning blade or brush. However, if the outermost surface of the photoconductor is in a dense state with no gaps, the contact area with the oxidation degradation products is large and attached. Since the adhesion becomes strong, it becomes difficult to remove, and sometimes it is pressed by blade stress and the adhesion becomes stronger. Therefore, if the gap ratio is too small, that is, if the oxygen permeability is too low, it may be disadvantageous for high image quality and long life.

  From the above, the oxygen transmission rate at 25 ° C. of the outermost surface layer of the electrophotographic photosensitive member of the present invention is preferably 250 fm / s · Pa or more and 1500 fm / s · Pa or less, more preferably 500 fm / s · Pa or more. 1500 fm / s · Pa or less, more preferably 780 fm / s · Pa or more and 1500 fm / s · Pa, particularly preferably 780 fm / s · Pa or more and 1200 fm / s · Pa or less.

When the oxygen transmission rate at 25 ° C. of the outermost surface layer of the photoreceptor exceeds 1500 fm / s · Pa, gas such as NO _x and ozone can be easily transmitted, and the generation of oxidation degradation products and the like increases rapidly. On the other hand, if it is less than 250 fm / s · Pa, it may be extremely difficult to remove the oxidized degradation product.

  The layer structure of the electrophotographic photoreceptor of the present invention is not particularly limited as long as it has a photosensitive layer. However, the layer contains at least a charge generation layer and a plurality of layers having different compositions on the charge generation layer. A configuration is preferred. For example, when a stacked structure such as a charge generation layer, a charge transport layer, and a surface protective layer (outermost surface layer) is used, higher functions can be realized because functional separation is possible as long as the respective layers satisfy their respective functions. In addition, even if it is a laminated structure or a single layer structure, the layer functioning as the outermost surface layer needs to satisfy the requirements of the present invention.

  The material constituting the outermost surface layer of the electrophotographic photosensitive member of the present invention is not particularly limited as long as it has an oxygen transmission rate within the range of the present invention, but is preferable when the material composition is as follows. .

That is, the photosensitive layer has a plurality of groups having active hydrogen, the outermost surface layer contains a resin having a crosslinked structure, and the oxygen permeability at 25 ° C. of the resin having the crosslinked structure alone is defined as O ₂ GTR1. At this time, it is preferable that the oxygen permeability O ₂ GTR2 at 25 ° C. is a material structure containing a resin having the relationship of the following formula (1) (hereinafter sometimes referred to as a filling resin).
Formula (1): O ₂ GTR2 <O ₂ GTR1

  With such a material structure, the oxygen permeability can be controlled relatively easily while maintaining the mechanical strength of the outermost surface layer high. Here, in order to have a plurality of groups having active hydrogen in the photosensitive layer, for example, materials such as diol, triol, dicarboxylic acid, tetracarboxylic acid, diamine, triamine, and epoxy compound are preferably used.

  In addition, it is preferable that the outermost surface layer has a cross-linked structure and the outermost surface layer includes a structural unit having a charge transporting ability, which hardly causes a picture flow due to insufficient mobility of the outermost surface layer.

  In addition, if the material structure contains a resin having a plurality of active hydrogen-containing groups on the outermost surface layer, chemical bonds can be formed in the crosslinked structure, so that these resins are easily dispersed uniformly in the film. The above effects can be sustained over a long period of time, and effects such as reduction of defects during coating can be obtained. The mechanical strength is increased and the wear is less likely to occur. . Here, examples of the resin having a plurality of groups having active hydrogen include diol, triol, dicarboxylic acid, tetracarboxylic acid, diamine, triamine, and epoxy compound.

In the present invention, the value of O ₂ GTR1 of the resin having the above crosslinked structure is not particularly limited, but it is preferable when the value is 1500 fm / s · Pa or more and 5000 fm / s · Pa or less. When this value exceeds 5000 fm / s · Pa, the oxygen permeability at 25 ° C. as a layer may not be controlled to 1500 fm / s · Pa or less even when other resins are mixed. On the other hand, if it is less than 1500 fm / s · Pa, the gap is small and it may be difficult to fill with other resin.

Further, the oxygen permeability O ₂ GTR2 at 25 ° C. of the filled resin is not particularly limited, but is preferably 1 × 10 ⁻¹⁵ fm / s · Pa or more and 500 fm / s · Pa or less. If O ₂ GTR2 exceeds 500 fm / s · Pa, the oxygen transmission rate at 25 ° C. as the layer may not be controlled to 1500 fm / s · Pa or less. On the other hand, if it is less than 1 × 10 ⁻¹⁵ fm / s · Pa, the oxygen permeability at 25 ° C. as the layer cannot be controlled to 250 fm / s · Pa or more, and the removal of deposits may be insufficient. .

The type of the resin having the oxygen permeability O ₂ GTR2 alone at 25 ° C., that is, the resin to be filled in the resin having a crosslinked structure is not particularly limited, but is not limited to copolymer polyamide, polyvinyl alcohol, polyethylene-polyvinyl. When it is at least one kind in the resin group consisting of an alcohol copolymer, polyvinylidene chloride, and unsaturated polyester, it is preferable in terms of balance between oxygen permeability control at 25 ° C. and mechanical strength as a layer.

Furthermore, when having a site where the resin having a crosslinked structure of the oxygen permeability O ₂ GTR1 in the 25 ° C., the oxygen permeability resin O ₂ GTR2 at 25 ° C. are chemically bound, at 25 ° C. as a layer It is preferable because the positional variation in the surface direction and depth direction of the oxygen permeability is small and the mechanical strength is high. Here, in order to give the bonded site, for example, a combination of a hydroxyl group and a carboxylic acid, a combination of a hydroxyl group and an epoxy group, a combination of a hydroxyl group and an amino group, a combination of a hydroxyl group and a phenolic hydroxyl group, etc. You can select the material.

Further, the ratio of the resin having a cross-linked structure of oxygen permeability O ₂ GTR1 at 25 ° C. to the resin having oxygen permeability O ₂ GTR2 at 25 ° C. filled therein is not particularly limited, but the mass ratio The range of 30/70 to 95/5 is preferable.

Next, the electrophotographic photoreceptor of the present invention will be briefly described for each layer.
Examples of the conductive support include a metal plate, a metal drum, a metal belt, or a conductive material using a metal or an alloy such as aluminum, copper, zinc, stainless steel, chromium, nickel, molybdenum, vanadium, indium, gold, or platinum. Examples thereof include paper, a plastic film, a belt, and the like on which a conductive compound such as a polymer or indium oxide, or a metal or alloy such as aluminum, palladium, or gold is applied, vapor-deposited, or laminated. When the photosensitive drum is used in a laser printer, the laser oscillation wavelength is preferably from 350 nm to 850 nm, and the shorter wavelength is preferable because the resolution is excellent.

  In order to prevent interference fringes generated when laser light is irradiated, the surface of the support is preferably roughened to a center line average roughness Ra of 0.04 μm to 0.5 μm. As a roughening method, wet honing is performed by suspending an abrasive in water and spraying it on the support, or centerless grinding in which the support is pressed against a rotating grindstone and grinding is performed continuously, an anode Oxidation is preferred. If Ra is smaller than 0.04 μm, it becomes close to a mirror surface, so that the effect of preventing interference cannot be obtained. When non-interfering light is used for the light source, it is not particularly necessary to roughen the interference fringes, and it is possible to prevent the occurrence of defects due to the unevenness of the surface of the base material, which is suitable for longer life.

  The anodizing treatment is to form an oxide film on the aluminum surface by anodizing in an electrolyte solution using aluminum as an anode. Examples of the electrolyte solution include a sulfuric acid solution and an oxalic acid solution. However, the intact porous anodic oxide film is chemically active, easily contaminated, and has a large resistance fluctuation due to the environment. Therefore, the pores of the anodic oxide film are sealed with pressurized water vapor or boiling water (a metal salt such as nickel may be added) by volume expansion due to a hydration reaction, and a sealing process is performed to change to a more stable hydrated oxide. .

The thickness of the anodic oxide film is preferably 0.3 to 15 μm. When it is thinner than 0.3 μm, the barrier property against injection is poor and the effect is not sufficient. On the other hand, if it is thicker than 15 μm, the residual potential increases due to repeated use.
The treatment with an acidic treatment solution comprising phosphoric acid, chromic acid and hydrofluoric acid is carried out as follows. The mixing ratio of phosphoric acid, chromic acid and hydrofluoric acid in the acidic treatment liquid is such that phosphoric acid is in the range of 10 to 11% by mass, chromic acid is in the range of 3 to 5% by mass, and hydrofluoric acid is in the range of 0.5 to 2% by mass. The concentration of these acids as a whole is preferably in the range of 13.5 to 18% by mass. The processing temperature is 42 to 48 ° C., but by keeping the processing temperature high, a thicker film can be formed faster. About the film thickness of a film, 0.3-15 micrometers is preferable. When it is thinner than 0.3 μm, the barrier property against injection is poor and the effect is not sufficient. On the other hand, if it is thicker than 15 μm, the residual potential increases due to repeated use.

  The boehmite treatment can be performed by immersing in pure water at 90 to 100 ° C. for 5 to 60 minutes or by contacting with heated steam at 90 to 120 ° C. for 5 to 60 minutes. About the film thickness of a film, 0.1-5 micrometers is preferable. This can be further anodized using an electrolyte solution with low film solubility such as adipic acid, boric acid, borate, phosphate, phthalate, maleate, benzoate, tartrate, citrate. Good.

  If desired, an undercoat layer can be formed between the substrate and the photosensitive layer. The undercoat layer prevents the leakage of electric charges from the conductive support to the photosensitive layer, and also holds the photosensitive layer integrally bonded to the conductive support, so that the conductive support and the photosensitive layer are bonded together. It can be provided in between. Materials used include zirconium chelate compounds, zirconium alkoxide compounds, organic zirconium compounds such as zirconium coupling agents, titanium chelate compounds, titanium alkoxide compounds, organic titanium compounds such as titanate coupling agents, aluminum chelate compounds, aluminum coupling agents, etc. In addition to organoaluminum compounds, antimony alkoxide compounds, germanium alkoxide compounds, indium alkoxide compounds, indium chelate compounds, manganese alkoxide compounds, manganese chelate compounds, tin alkoxide compounds, tin chelate compounds, aluminum silicon alkoxide compounds, aluminum titanium alkoxide compounds, aluminum Zirconium alkoxide compounds, etc. Machine metal compounds, especially organic zirconium compound, an organic titanyl compound, an organic aluminum compound residual potential to show the good electrophotographic properties lower, are preferably used. Among these, the undercoat layer formed using at least a zirconium alkoxide compound has a high ability to prevent charge leakage from the conductive support to the photosensitive layer, and the residual potential is also kept low, and further accompanying environmental changes. It is preferable because the variation in characteristics is small. A layer formed using a material capable of transporting only a charge having the same polarity as the charge polarity can also be used as the undercoat layer. Also, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris-2-methoxyethoxysilane, vinyltriacetoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-aminopropyl Triethoxysilane, γ-chloropropyltrimethoxysilane, γ-2-aminoethylaminopropyltrimethoxysilane, γ-mercapropropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, β-3,4-epoxycyclohexyltri It can be used by containing a silane coupling agent such as methoxysilane. Furthermore, polyvinyl alcohol, polyvinyl methyl ether, poly-N-vinyl imidazole, polyethylene oxide, ethyl cellulose, methyl cellulose, ethylene-acrylic acid copolymer, polyamide, polyimide, casein, gelatin, polyethylene, conventionally used for the undercoat layer Known binder resins such as polyester, phenol resin, vinyl chloride-vinyl acetate copolymer, epoxy resin, polyvinyl pyrrolidone, polyvinyl pyridine, polyurethane, polyglutamic acid, and polyacrylic acid can also be used.

  These mixing ratios can be appropriately set as necessary. Further, an electron transporting pigment may be mixed / dispersed in the undercoat layer. Examples of the electron transport pigment include organic pigments such as perylene pigment, bisbenzimidazole perylene pigment, polycyclic quinone pigment, indigo pigment, and quinacridone pigment described in JP-A-47-30330, cyano group, nitro group, Examples thereof include organic pigments such as bisazo pigments and phthalocyanine pigments having electron-withdrawing substituents such as nitroso groups and halogen atoms, and inorganic pigments such as zinc oxide and titanium oxide. Among these pigments, perylene pigments, bisbenzimidazole perylene pigments and polycyclic quinone pigments, zinc oxide, and titanium oxide are preferably used because of their high electron mobility. Further, the surface of these pigments may be surface-treated with the above-mentioned coupling agent or binder for the purpose of controlling dispersibility and charge transport property. If the amount of the electron transporting pigment is too large, the strength of the undercoat layer is lowered and a coating film defect is caused. As the mixing / dispersing method, a conventional method using a ball mill, a roll mill, a sand mill, an attritor, an ultrasonic wave, or the like is applied. Mixing / dispersing is performed in an organic solvent. As an organic solvent, a fixed metal compound or resin is dissolved,

  Further, any material can be used as long as it does not cause gelation or aggregation when the electron transport pigment is mixed / dispersed. For example, methanol, ethanol, n-propanol, n-butanol, benzyl alcohol, methyl cellosolve, ethyl cellosolve, acetone, methyl ethyl ketone, cyclohexanone, methyl acetate, n-butyl acetate, dioxane, tetrahydrofuran, methylene chloride, chloroform, chlorobenzene Ordinary organic solvents such as toluene can be used alone or in admixture of two or more. The thickness of the undercoat layer is generally 0.1 to 30 μm, preferably 0.2 to 25 μm. In addition, as the coating method used when the undercoat layer is provided, conventional methods such as a blade coating method, a Meyer bar coating method, a spray coating method, a dip coating method, a bead coating method, an air knife coating method, and a curtain coating method are used. Can be used. The coated layer is dried to obtain an undercoat layer. Usually, the drying is performed at a temperature at which the solvent can be evaporated to form a film. In particular, the base material subjected to the acidic solution treatment and the boehmite treatment is preferably formed with an intermediate layer because the defect concealing power of the base material tends to be insufficient.

  In the undercoat layer, fine powders of various organic compounds or fine powders of inorganic compounds can be added for the purpose of improving electrical characteristics and light scattering properties. In particular, white pigments such as titanium oxide, zinc oxide, zinc white, zinc sulfide, lead white and lithopone, inorganic pigments as extender pigments such as alumina, calcium carbonate and barium sulfate, Teflon resin particles, and benzoguanamine resin particles In addition, styrene resin particles are effective. The added fine powder has a particle size of 0.01 to 2 μm. The fine powder is added as necessary, but the addition amount is preferably 10 to 90% by mass, and 30 to 80% by mass with respect to the total mass of the solid content of the undercoat layer. It is more preferable.

  In addition, it is also effective from the viewpoint of lower residual potential and environmental stability to contain the electron transporting substance, the electron transporting pigment and the like described above in the undercoat layer. Furthermore, the thickness of the undercoat layer is 0.01 to 30 μm, preferably 0.05 to 25 μm. In addition, when preparing a coating liquid for forming the undercoat layer, when a fine powder substance is added, it is added to a solution in which the resin component is dissolved and dispersed. As the dispersion treatment method, methods such as a roll mill, a ball mill, a vibrating ball mill, an attritor, a sand mill, a colloid mill, and a paint shaker can be used. Further, the undercoat layer can be formed by applying a coating solution for forming the undercoat layer on the conductive support and drying it. As a coating method at this time, usual methods such as a blade coating method, a wire bar coating method, a spray coating method, a dip coating method, a bead coating method, an air knife coating method, a curtain coating method, and the like can be used.

Next, the charge generation layer will be described.
Known charge generation materials include azo pigments such as bisazo and trisazo, condensed aromatic pigments such as dibromoanthanthrone, organic pigments such as perylene pigments, pyrrolopyrrole pigments, and phthalocyanine pigments, and inorganic pigments such as trigonal selenium and zinc oxide. In particular, when an exposure wavelength of 380 to 500 nm is used, metal and metal-free phthalocyanine pigments are preferable. Among these, hydroxygallium phthalocyanine disclosed in JP-A-5-263007 and JP-A-5-279591, chlorogallium phthalocyanine disclosed in JP-A-5-98181, JP-A-5-140472, and JP-A-5-140473 Particularly preferred are the dichlorotin phthalocyanines prepared, JP-A-4-189873 and titanyl phthalocyanine disclosed in JP-A-5-43813.

  The binder resin can be selected from a wide range of insulating resins, and can also be selected from organic photoconductive polymers such as poly-N-vinylcarbazole, polyvinylanthracene, polyvinylpyrene, and polysilane. Preferred binder resins include polyvinyl butyral resin, polyarylate resin (polycondensate of bisphenol A and phthalic acid, etc.), polycarbonate resin, polyester resin, phenoxy resin, vinyl chloride-vinyl acetate copolymer, polyamide resin, acrylic resin. Insulating resin such as polyacrylamide resin, polyvinyl pyridine resin, cellulose resin, urethane resin, epoxy resin, casein, polyvinyl alcohol resin, polyvinyl pyrrolidone resin can be used, but is not limited thereto. These binder resins can be used alone or in admixture of two or more.

  The mixing ratio of the charge generation material and the binder resin (mass ratio) is preferably in the range of 10: 1 to 1:10. In addition, as a method for dispersing these, a usual method such as a ball mill dispersion method, an attritor dispersion method, a sand mill dispersion method, or the like can be used. . Incidentally, it has been confirmed that the crystal form is not changed before dispersion in any of the dispersion methods implemented in the present invention. Further, at the time of this dispersion, it is effective to make the particles have a particle size of 0.5 μm or less, preferably 0.3 μm or less, more preferably 0.15 μm or less. Moreover, as a solvent used for these dispersions, methanol, ethanol, n-propanol, n-butanol, benzyl alcohol, methyl cellosolve, ethyl cellosolve, acetone, methyl ethyl ketone, cyclohexanone, methyl acetate, n-butyl acetate, dioxane, tetrahydrofuran Ordinary organic solvents such as methylene chloride, chloroform, chlorobenzene and toluene can be used alone or in admixture of two or more. The thickness of the charge generation layer used in the present invention is generally 0.1 to 5 μm, preferably 0.2 to 2.0 μm. In addition, as a coating method used when the charge generation layer is provided, usual methods such as a blade coating method, a Meyer bar coating method, a spray coating method, a dip coating method, a bead coating method, an air knife coating method, and a curtain coating method are used. Can be used.

Next, the charge transport layer will be described.
As the charge transport layer, a layer formed by a known technique can be used. These charge transport layers are formed containing a charge transport material and a binder resin, or are formed containing a polymer charge transport material.

  Examples of charge transport materials include quinone compounds such as p-benzoquinone, chloranil, bromanyl, anthraquinone, tetracyanoquinodimethane compounds, fluorenone compounds such as 2,4,7-trinitrofluorenone, xanthone compounds, benzophenone compounds , Electron transport compounds such as cyanovinyl compounds and ethylene compounds, triarylamine compounds, benzidine compounds, arylalkane compounds, aryl-substituted ethylene compounds, stilbene compounds, anthracene compounds, hydrazone compounds, etc. Examples thereof include pore-transporting compounds. These charge transport materials may be used alone or in combination of two or more, but are not limited thereto. In addition, these charge transport materials can be used alone or in combination of two or more, but those having the following structure are preferred from the viewpoint of mobility.

(In the formula, R ¹⁴ represents a hydrogen atom or a methyl group, and n represents 1 or 2. Ar ₆ and Ar ₇ are substituted or unsubstituted aryl groups, or —C (R ¹⁸ ) ═C (R ¹⁹ ) (R ²⁰ ), —CH═CH—CH═C (Ar) ₂ , the substituent being a halogen atom, an alkyl group having 1 to 5 carbon atoms, or a carbon number of 1 to 5 A substituted amino group substituted with an alkoxy group in the range or an alkyl group having 1 to 3 carbon atoms, Ar represents a substituted or unsubstituted aryl group, and R ¹⁸ , R ¹⁹ and R ²⁰ are hydrogen. Represents an atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group.)

Wherein R ¹⁵ and R ¹⁵同一 may be the same or different and each represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms. R ¹⁶ , R ^{16 ′} , R ¹⁷ and R ¹⁷て も may be the same or different and are substituted with a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an alkyl group having 1 to 2 carbon atoms. Represents an amino group, a substituted or unsubstituted aryl group, or —C (R ¹⁸ ) ═C (R ¹⁹ ) (R ²⁰ ), —CH═CH—CH═C (Ar) _2. Or an unsubstituted aryl group, R ¹⁸ , R ¹⁹ and R ^{20 each} represent a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, and m and n are integers of 0 to 2. .)

(In the formula, R ₂₁ represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a substituted or unsubstituted aryl group, or —CH═CH—CH═C (Ar) ₂ . Ar represents a substituted or unsubstituted aryl group, and R ₂₂ and R ₂₃ may be the same or different, and may be a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms. Group, an amino group substituted with an alkyl group having 1 to 2 carbon atoms, or a substituted or unsubstituted aryl group.)

  Further, the binder resin used for the charge transport layer is polycarbonate resin, polyester resin, methacrylic resin, acrylic resin, polyvinyl chloride resin, polyvinylidene chloride resin, polystyrene resin, polyvinyl acetate resin, styrene-butadiene copolymer, vinylidene chloride- Acrylonitrile copolymer, vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate-maleic anhydride copolymer, silicone resin, silicone-alkyd resin, phenol-formaldehyde resin, styrene-alkyd resin, poly-N- Vinyl carbazole, polysilane, and polymer charge transport materials such as polyester polymer charge transport materials disclosed in JP-A-8-176293 and JP-A-8-208820 can also be used. These binder resins can be used alone or in admixture of two or more. The blending ratio (mass ratio) between the charge transport material and the binder resin is preferably 10: 1 to 1: 5.

  A polymer charge transport material can also be used alone. As the polymer charge transporting material, known materials having charge transporting properties such as poly-N-vinylcarbazole and polysilane can be used. In particular, polyester polymer charge transport materials disclosed in JP-A-8-176293 and JP-A-8-208820 have a high charge transporting property and are particularly preferable. The polymer charge transport material alone can be used as the charge transport layer, but it may be formed by mixing with the binder resin.

The thickness of the charge transport layer is generally 5 to 50 μm, preferably 10 to 30 μm. As a coating method, a normal method such as a blade coating method, a Meyer bar coating method, a spray coating method, a dip coating method, a bead coating method, an air knife coating method, or a curtain coating method can be used. Furthermore, as a solvent used when providing a charge transport layer, aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene, ketones such as acetone and 2-butanone, and halogenation such as methylene chloride, chloroform and ethylene chloride Ordinary organic solvents such as aliphatic hydrocarbons, cyclic ethers such as tetrahydrofuran and ethyl ether and linear ethers can be used alone or in admixture of two or more. Additives such as antioxidants, light stabilizers, and heat stabilizers are added to the photosensitive layer to prevent photoconductor deterioration caused by ozone, oxidizing gas, or light or heat generated in the copying machine. can do. For example, examples of the antioxidant include hindered phenol, hindered amine, paraphenylenediamine, arylalkane, hydroquinone, spirochroman, spiroidanone and derivatives thereof, organic sulfur compounds, and organic phosphorus compounds. Examples of the light stabilizer include derivatives such as benzophenone, benzotriazole, dithiocarbamate, and tetramethylpiperidine. In addition, at least one kind of electron accepting substance can be contained for the purpose of improving sensitivity, reducing residual potential, and reducing fatigue during repeated use. Examples of the electron acceptor usable in the photoreceptor of the present invention include succinic anhydride, maleic anhydride, dibromomaleic anhydride, phthalic anhydride, tetrabromophthalic anhydride, tetracyanoethylene, tetracyanoquinodimethane, o -Dinitrobenzene, m-dinitrobenzene, chloranil, dinitroanthraquinone, trinitrofluorenone, picric acid, o-nitrobenzoic acid, p-nitrobenzoic acid, phthalic acid and the like, and compounds represented by the general formula (I) Can do. Of these, benzene derivatives having electron-withdrawing substituents such as fluorenone, quinone and Cl, CN, NO ₂ are particularly preferred.

Next, the outermost surface layer will be described.
First, the resin component containing a crosslinked structure is preferably provided with a high-strength surface layer in order to give the surface layer resistance to abrasion, scratches, and the like and to increase the transfer efficiency of the toner. As this high-strength surface layer, conductive fine particles dispersed in a binder resin, lubricating fine particles such as fluororesin and acrylic resin dispersed in an ordinary charge transport layer material, silicon and acrylic hard A coating agent can be used, but from the viewpoints of strength, electrical characteristics, image quality maintenance, etc., those having a crosslinked structure are preferred, and those containing a charge transporting material are more preferred.

  Various materials can be used for forming the crosslinked structure, but phenolic resins, urethane resins, siloxane resins, and the like are preferable in view of characteristics, and those made of siloxane resins are particularly preferable. Of these, those having a structure derived from the compounds represented by the general formulas (I) and (II) are particularly preferred because of their excellent strength and stability.

(Wherein F is an organic group derived from a compound having a hole transporting ability, D is a flexible subunit, R ² is hydrogen, an alkyl group, a substituted or unsubstituted aryl group, and Q is a hydrolyzable group. A represents an integer of 1 to 3, and b represents an integer of 1 to 4.)

  Here, the crosslinked product having a structure derived from the compound represented by the general formula (I) includes a plurality of photofunctional organosilicon compounds (compounds represented by the general formula (I)) having the same or different molecular structures. A molecule reacts with water in the hydrolyzable group Q portion to hydrolyze, and then adjacent molecules dehydrate and condense using the hydrolyzable group Q portion after hydrolysis. The cross-linked product is cross-linked by the siloxane bond (O-Si-O bond) to be formed. Two or more silicon atoms are bonded to an organic group having carbon and fluorine atoms, and oxygen atoms are further bonded to these silicon atoms. (Hereinafter referred to as “photofunctional organic silicate skeleton”).

  The photofunctional organosilicon compound (the compound represented by the general formula (I)) and water for causing a hydrolysis reaction are previously contained in, for example, a coating solution for forming the outermost surface layer of the photosensitive layer. However, it may not be included when hydrolysis proceeds sufficiently using moisture in the air. Moreover, you may further add the organosilicon compound which has a hydrolysable group which has a molecular structure different from a photofunctional organosilicon compound (compound shown by general formula (I)).

  By including such a crosslinked product having a photofunctional organic silicate skeleton in the photosensitive film, the anti-adhesion property to contaminants such as water, discharge products, and toners can be sufficiently enhanced, and the contaminants adhere. In addition, since contaminants can be removed without damaging the surface, it is possible to obtain sufficiently good image quality over a long period of time in the electrophotographic process.

In general formula (I), the flexible subunit represented by D (a divalent group having flexibility) is preferably —C _n H _2n —, —C _n H _2n-2 —, _{-C n H 2n-4 - (} n is an integer from 1 to 15, preferably an integer of _{2~10), - CH 2 -C 6} H 4 - or -C ₆ H ₄ -C ₆ H ₄ A divalent hydrocarbon group represented by-, an oxycarbonyl group (-COO-), a thio group (-S-), an oxy group (-O-), an isocyano group (-N = CH-), or these 2 It is a divalent group by a combination of species or more. Note that these divalent groups may have a substituent such as an alkyl group, a phenyl group, an alkoxy group, or an amino group in the side chain. When D is the above-mentioned preferable divalent group, moderate flexibility is imparted to the photofunctional organic silicate skeleton, and the strength of the layer tends to be improved.

  Moreover, b is more preferably an integer of 2 to 4. If b is an integer of 2 to 4, the photofunctional organic silicon compound (compound represented by the general formula (I)) contains two or more Si atoms, and a photofunctional organic silicate skeleton is easily formed. Thus, the mechanical strength can be further improved.

  An organic group (photofunctional organic group) derived from a compound having a hole transporting ability represented by F is photoisomerization (structure change), photochromism, photoionization, light emission (color change) by absorption of light energy. An organic group exhibiting a physical change or a physicochemical change such as a nonlinear optical effect, a photoelectrochemical effect, and a refractive index change.

  The photofunctional organic group represented by F is not particularly limited as long as it exhibits photofunctionality, but is preferably a group having an aromatic ring, and includes a phthalocyanine structure, a porphyrin structure, an azobenzene structure, and a stilbene structure. , Tris (bipyridyl) -rhodium structure, azulene structure, polyene structure, nitroaniline structure, triarylamine structure, benzidine structure, arylalkane structure, aryl-substituted ethylene structure, anthracene structure, hydrazone structure, quinone structure and fluorenone structure It is more preferable that it is a group having one more selected.

(In the formula, F is an organic group derived from a compound having a hole transport function, R ₁ is an alkylene group, Z is an oxygen atom, a sulfur atom or NH, CO ₂ , and m is an integer of 1 to 4. X is an integer. Oxygen or sulfur, n represents 0 or 1)

  More preferable compounds represented by the general formula (I) include compounds represented by the following general formula (III).

(In the formula, Ar _{1 to} Ar ₄ each independently represents a substituted or unsubstituted aryl group, Ar ₅ represents a substituted or unsubstituted aryl group or an arylene group, and 2 to 4 of Ar _{1 to} Ar ₅ ) Each has a bond represented by -D-Si (R ² ) _(3-a) Q _a , D is a flexible subunit, R ² is hydrogen, an alkyl group, a substituted or unsubstituted aryl group, Q represents a hydrolyzable group, a represents an integer of 1 to 3. k is 0 or 1.)

Ar _{1 to} Ar ₄ in the general formula (III) each independently represent a substituted or unsubstituted aryl group, and specifically, those shown in the following structural group 1 are preferable.

  Ar in the structure group 1 is preferably selected from the following structure group 2.

  Z ′ in the structure group 1 is preferably selected from the following structure group 3.

  W in the structure group 3 is preferably that represented by the following structure group 4. Here, in the structure group 4, s ′ represents an integer of 0 to 3.

(In Structure Groups 1 to 4, R ⁶ is hydrogen, a phenyl group substituted with an alkyl group having 1 to 4 carbon atoms, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, or unsubstituted. R ^{7 to} R ¹³ are each selected from hydrogen, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or 1 to 4 carbon atoms. Selected from a phenyl group substituted by an alkoxy group, or an unsubstituted phenyl group, an aralkyl group having 7 to 10 carbon atoms, and halogen, m and s represent 0 or 1, and q and r are 1 to 10 An integer, t is an integer of 1 to 3, and s ′ is an integer of 0 to 3. Here, X is —D—Si (R ² ) _(3-a) already shown in the definition of the general formula (I _). The substituent represented by Q _a is shown.)

The specific structure of Ar ₅ in the general formula (III) is as follows. When k = 0, the structure of Ar _{1 to} Ar ₄ shown in the structural group 1 is m = 1, and when k = 1, And the structure of Ar _{1 to} Ar ₄ represented by the structure group 1 where m = 0.

  Specific examples of the general formula (I) (general formula (III)) include those shown in Tables 1 to 7 below, but the present invention is not limited thereto.

  Specific examples of the general formula (II) include those shown below, but the present invention is not limited to these.

  In addition, in order to control various physical properties such as strength and film resistance, a compound represented by the following general formula (VI) can also be added.

(Wherein R ² represents hydrogen, an alkyl group, a substituted or unsubstituted aryl group, Q represents a hydrolyzable group, and c represents an integer of 1 to 4)

  Specific examples of the compound represented by the general formula (VI) include the following silane coupling agents.

  Tetrafunctional alkoxysilane such as tetramethoxysilane and tetraethoxysilane (c = 4); methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, methyltrimethoxyethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane , Phenyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltri Methoxysilane, γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, (tridecafluoro-1,1,2,2-tetrahydrooctyl) triethoxysilane, (3 3,3-trifluoropropyl) trimethoxysilane, 3- (heptafluoroisopropoxy) propyltriethoxysilane, 1H, 1H, 2H, 2H-perfluoroalkyltriethoxysilane, 1H, 1H, 2H, 2H-perfluoro Trifunctional alkoxysilanes such as decyltriethoxysilane, 1H, 1H, 2H, 2H-perfluorooctyltriethoxysilane (c = 3); bifunctional alkoxy such as dimethyldimethoxysilane, diphenyldimethoxysilane, methylphenyldimethoxysilane Silane (c = 2); monofunctional alkoxysilane such as trimethylmethoxysilane (c = 1) and the like can be mentioned. Trifunctional and tetrafunctional alkoxysilanes are preferable for improving the strength of the film, and bifunctional and monofunctional alkoxysilanes are preferable for improving the flexibility and film forming property.

  In addition, a silicon-based hard coat agent mainly produced from these coupling materials can also be used. Commercially available hard coat agents include KP-85, X-40-9740, X-40-2239 (manufactured by Shin-Etsu Silicone), and AY42-440, AY42-441, AY49-208 (manufactured by Toray Dow Corning). Can be used.

  In order to increase the strength, it is also preferable to use a compound having two or more silicon atoms as shown in the general formula (IV).

(In the formula, B represents a divalent organic group, R ² represents hydrogen, an alkyl group, a substituted or unsubstituted aryl group, Q represents a hydrolyzable group, and a represents an integer of 1 to 3)

  Specific examples of the compound having two or more silicon atoms as shown in the general formula (IV) include those shown in the following Table 8, but the present invention is not limited thereto. Is not to be done.

Moreover, you may use the fluorine-containing organosilicon compound represented with the following general formula (A).
Formula (A): W ′ [— SiR ′ _{3-a ′} Q ′ _{a ′} ] _{b ′}
Here, in the general formula (A), W ′ represents an organic group containing a carbon atom and a fluorine atom. R ′ represents a hydrogen atom, an alkyl group, or a substituted or unsubstituted aryl group exemplified in the description of R ^{2 in} the general formula (I). Further, Q ′ represents a hydrolyzable group having the same meaning as the hydrolyzable group Q exemplified in the description in the general formula (I), a ′ represents an integer of 1 to 3, and b ′ represents an integer of 2 or more. Represents.

In the general formula (A), the organic group containing a carbon atom and a fluorine atom represented by W ′ is preferably a divalent or trivalent fluorinated hydrocarbon group. The fluorinated hydrocarbon group here includes an aliphatic fluorinated hydrocarbon group such as a fluorinated alkylene group and an aromatic fluorinated hydrocarbon group such as a fluorinated arylene group. In the case of an aliphatic fluorinated hydrocarbon group, the carbon number is preferably 2 to 20, and in the case of an aromatic fluorinated hydrocarbon group, the carbon number is preferably 6 to 20. Among such fluorinated hydrocarbon groups, any of the groups represented by the following formulas (30) to (46) is particularly preferable.
− (CF ₂ ) ₂ − (30)
− (CF ₂ ) ₄ − (31)
− (CF ₂ ) ₈ − (32)
_{- (CH 2) 2 - (} CF 2) 2 - (CH 2) 2 - (33)
— (CH ₂ ) ₂ — (CF ₂ ) ₄ — (CH ₂ ) ₂ — (34)
— (CH ₂ ) ₂ — (CF ₂ ) ₆ — (CH ₂ ) ₂ — (35)
_{- (CH 2) 2 - (} CF 2) 8 - (CH 2) 2 - (36)

Specific examples of preferable combinations of W ′ of the fluorine-containing organosilicon compound represented by the general formula (A) and —SiR ′ _{3-a ′} Q ′ _{a ′} include those shown in Table 9 below. However, it is not limited to these. In Table 9, the number in the column of W ′ means that W ′ is any one of the above formulas (30) to (46).

Further, for the purpose of prolonging pot life, controlling film characteristics, and reducing torque, a cyclic compound having a repeating structural unit represented by the following general formula (V) or a derivative thereof can be contained. Here, in the following general formula (V), A ¹ and A ² each independently represent a monovalent organic group.

  A commercially available cyclic siloxane can be mentioned as a cyclic compound having a repeating structural unit represented by the general formula (V). Specifically, cyclic dimethylcyclosiloxanes such as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, 1,3,5-trimethyl-1,3,5- Triphenylcyclotrisiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetraphenylcyclotetrasiloxane, 1,3,5,7,9-pentamethyl-1,3,5,7 , 9-pentaphenylcyclopentasiloxane and other cyclic methylphenylcyclosiloxanes, hexaphenylcyclotrisiloxane and other cyclic phenylcyclosiloxanes, and 3- (3,3,3-trifluoropropyl) methylcyclotrisiloxane and other fluorine Contain cyclosiloxanes and methylhydrosiloxane Things, pentamethylcyclopentasiloxane include a phenyl hydrosilyl group-containing cyclosiloxanes such hydrocyclosiloxane, cyclic siloxanes and vinyl group-containing cyclosiloxanes, such as penta vinyl pentamethylcyclopentasiloxane like.

  These cyclic siloxane compounds may be used alone or as a mixture thereof.

  Further, various fine particles can be added in order to control the antifouling substance adhesion, lubricity, hardness and the like on the surface of the electrophotographic photosensitive member. They can be used alone or in combination. Examples of the fine particles include silicon-containing fine particles. The silicon-containing fine particles are fine particles containing silicon as a constituent element, and specific examples include colloidal silica and silicone fine particles. The colloidal silica used as the silicon-containing fine particles is selected from those having an average particle diameter of 1 to 100 nm, preferably 10 to 30 dispersed in an acidic or alkaline aqueous dispersion, or an organic solvent such as alcohol, ketone or ester. A commercially available product can be used. The solid content of colloidal silica in the outermost surface layer is not particularly limited, but is 0.1 to 50% by mass in the total solid content of the outermost surface layer in terms of film forming properties, electrical characteristics, and strength. Is used, preferably in the range of 0.1 to 30% by mass.

  Silicone fine particles used as silicon-containing fine particles are spherical and have an average particle diameter of 1 to 500 nm, preferably 10 to 100 nm, and are selected from silicone resin particles, silicone rubber particles, and silicone surface-treated silica particles, and are generally commercially available. Can be used. Silicone fine particles are small particles that are chemically inert and excellent in dispersibility in resin, and since the content required to obtain sufficient characteristics is low, the electron does not hinder the crosslinking reaction, The surface properties of the photographic photoreceptor can be improved. In other words, it is possible to improve the lubricity and water repellency of the surface of the electrophotographic photosensitive member while being uniformly incorporated into a strong cross-linked structure, and to maintain good wear resistance and adherence to contaminants over a long period of time. it can. The content of the silicone fine particles in the outermost surface layer in the electrophotographic photoreceptor of the present invention is in the range of 0.1 to 30% by mass, preferably 0.5 to 10% by mass in the total solid content of the outermost surface layer. Range.

Other fine particles include fluorine-based fine particles such as tetrafluoroethylene, trifluoride ethylene, propylene hexafluoride, vinyl fluoride, and vinylidene fluoride, and “8th Polymer Material Forum Lecture Proceedings p89”. Fine particles made of a resin obtained by copolymerizing the fluororesin and a monomer having a hydroxyl group, ZnO—Al ₂ O ₃ , SnO ₂ —Sb ₂ O ₃ , In ₂ O ₃ —SnO ₂ , ZnO—TiO ₂ , Examples thereof include semiconductive metal oxides such as ZnO—TiO ₂ , MgO—Al ₂ O ₃ , FeO—TiO ₂ , TiO ₂ , SnO ₂ , In ₂ O ₃ , ZnO, and MgO. For the same purpose, an oil such as silicone oil can be added. Examples of silicone oil include silicone oil such as dimethylpolysiloxane, diphenylpolysiloxane, and phenylmethylsiloxane, amino-modified polysiloxane, epoxy-modified polysiloxane, carboxyl-modified polysiloxane, carbinol-modified polysiloxane, methacryl-modified polysiloxane, and mercapto. Examples thereof include reactive silicone oils such as modified polysiloxane and phenol-modified polysiloxane. These may be added in advance to the coating solution, or may be impregnated under reduced pressure or increased pressure after producing the photoreceptor.

  In addition, additives such as plasticizers, surface modifiers, antioxidants, and photodegradation inhibitors can also be used. Examples of the plasticizer include biphenyl, biphenyl chloride, terphenyl, dibutyl phthalate, diethylene glycol phthalate, dioctyl phthalate, triphenyl phosphate, methyl naphthalene, benzophenone, chlorinated paraffin, polypropylene, polystyrene, and various fluorohydrocarbons. An antioxidant having a hindered phenol, hindered amine, thioether or phosphite partial structure can be added to the resin layer in the present invention, which is effective in improving the potential stability and image quality when the environment changes. . Antioxidants include the following compounds, such as “Sumizer BHT-R”, “Sumizer MDP-S”, “Sumizer BBM-S”, “Sumizer WX-R”, “Sumizer NW” as hindered phenols, "Sumilizer BP-76", "Sumilizer BP-101", "Sumilizer GA-80", "Sumizer GM", "Sumizer GS" or more manufactured by Sumitomo Chemical Co., Ltd., "IRGANOX1010", "IRGANOX1035", "IRGANOX10X", "98" ”,“ IRGANOX1135 ”,“ IRGANOX1141 ”,“ IRGANOX1222 ”,“ IRGANOX1330 ”,“ IRGANOX1 25WL ”,“ IRGANOX1520L ”,“ IRGANOX245 ”,“ IRGANOX259 ”,“ IRGANOX3114 ”,“ IRGANOX3790 ”,“ IRGANOX5057 ”,“ IRGANOX565 ”or more manufactured by Ciba Specialty Chemicals, Inc.,“ Adekastab AO-20 ”,“ Adekastab A ” "ADK STAB AO-40", "ADK STAB AO-50", "ADK STAB AO-60", "ADK STAB AO-70", "ADK STAB AO-80", "ADK STAB AO-330" or more, manufactured by Asahi Denka. As the hindered amine series, “Sanol LS2626”, “Sanol LS765”, “Sanol LS770”, “Sanol LS744”, “Tinuvin 144”, “Tinuvin 622LD”, “Mark LA57”, “Mark LA67”, “Mark LA62”, “Mark LA68”, “Mark LA63”, “Smilizer TPS”, “Smilizer TP-D” as thioether system, “Mark 2112”, “Mark PEP / 8”, “Mark PEP / 8G”, “Mark” as phosphite system PEP · 36 ”,“ Mark 329K ”,“ Mark HP · 10 ”, and hindered phenols and hindered amine antioxidants are particularly preferable. Further, they may be modified with a substituent such as an alkoxysilyl group capable of undergoing a crosslinking reaction with the material forming the crosslinked film.

It is preferable to add or use a catalyst when preparing the coating liquid or coating liquid. Catalysts used include inorganic acids such as hydrochloric acid, acetic acid, phosphoric acid and sulfuric acid, organic acids such as formic acid, propionic acid, oxalic acid, p-toluenesulfonic acid, benzoic acid, phthalic acid and maleic acid, potassium hydroxide and hydroxide An alkali catalyst such as sodium, calcium hydroxide, ammonia, triethylamine, or a solid catalyst insoluble in the system can be used. Amberlite 15, Amberlite 200C, Amberlist 15E (above, manufactured by Rohm and Haas); Dowex MWC-1-H, Dowex 88, Dowex HCR-W2 (above, Dow Chemical Co.); Levacit SPC-108, Levacit SPC-118 (manufactured by Bayer); Diaion RCP-150H (Mitsubishi Kasei); Sumikaion KC-470, Duolite C26-C, Duolite C-433, Duolite-464 (Above, manufactured by Sumitomo Chemical Co., Ltd.); cation exchange resins such as Nafion-H (manufactured by DuPont); shades such as Amberlite IRA-400 and Amberlite IRA-45 (above, manufactured by Rohm and Haas) ion exchange _{resins; Zr (O 3 PCH 2 CH} 2 SO 3 H) 2, Th (O 3 PC Polyorganosiloxanes containing protonic acid group, such as polyorganosiloxane having sulfonic acid groups;; ₂ CH ₂ COOH) groups containing protonic acid group, such as ₂ inorganic solid that is bound to the surface cobalt tungstate, phosphorus Heteropolyacids such as molybdic acid; isopolyacids such as niobic acid, tantalum acid and molybdic acid; monometallic oxides such as silica gel, alumina, chromia, zirconia, CaO, MgO; silica-alumina, silica-magnesia, silica-zirconia And composite metal oxides such as zeolites; clay minerals such as acid clay, activated clay, montmorillonite and kaolinite; metal sulfates such as LiSO ₄ and MgSO ₄ ; metal phosphates such as zirconia phosphate and lanthanum phosphate; LiNO _3, Mn (NO ₃₎ metal nitrate such as _2; Inorganic solids in which amino group-containing groups such as solids obtained by reacting aminopropyltriethoxysilane on licagel are bonded to the surface; polyorganosiloxanes containing amino groups such as amino-modified silicone resins, etc. Can be mentioned. Moreover, it is preferable to use a solid catalyst that is insoluble in a photofunctional compound, reaction product, water, solvent, or the like when preparing the coating liquid because the stability of the coating liquid tends to be improved.

  A solid catalyst that is insoluble in the system is particularly if the catalyst component is insoluble in the compound represented by the general formula (I), the material for forming the general formula (II), other additives, water, solvent, etc. It is not limited. Although the usage-amount of these solid catalysts is not restrict | limited in particular, 0.1-100 mass parts is preferable with respect to a total of 100 mass parts of the compound which has a hydrolysable group. Further, as described above, these solid catalysts are insoluble in raw material compounds, reaction products, solvents and the like, and therefore can be easily removed after the reaction according to a conventional method. The reaction temperature and reaction time are appropriately selected according to the type and amount of the raw material compound or solid catalyst, but the reaction temperature is usually 0 to 100 ° C, preferably 10 to 70 ° C, more preferably 15 to 50. The reaction time is preferably 10 minutes to 100 hours. If the reaction time exceeds the upper limit, gelation tends to occur.

  When a catalyst that is insoluble in the system is used in the coating liquid preparation step, it is preferable to use a catalyst that is further dissolved in the system for the purpose of improving strength, liquid storage stability, and the like. Such catalysts include, in addition to those described above, aluminum triethylate, aluminum triisopropylate, aluminum tri (sec-butyrate), mono (sec-butoxy) aluminum diisopropylate, diisopropoxyaluminum (ethyl acetoacetate). ), Aluminum tris (ethyl acetoacetate), aluminum bis (ethyl acetoacetate) monoacetylacetonate, aluminum tris (acetylacetonate), aluminum diisopropoxy (acetylacetonate), aluminum isopropoxy-bis (acetylacetonate) Organic aluminum compounds such as aluminum tris (trifluoroacetylacetonate) and aluminum tris (hexafluoroacetylacetonate) It is possible to use.

  Besides organic aluminum compounds, organic compounds such as dibutyltin dilaurate, dibutyltin dioctiate, and dibutyltin diacetate; titanium tetrakis (acetylacetonate), titanium bis (butoxy) bis (acetylacetonate), titanium bis Organic titanium compounds such as (isopropoxy) bis (acetylacetonate); zirconium tetrakis (acetylacetonate), zirconium bis (butoxy) bis (acetylacetonate), zirconium bis (isopropoxy) bis (acetylacetonate), etc. Zirconium compounds; etc. can also be used, but from the viewpoints of safety, low cost, and pot life length, it is preferable to use an organoaluminum compound, particularly an aluminum chelate compound. It is more preferable. Although the usage-amount in particular of these catalysts is not restrict | limited, 0.1-20 mass parts is preferable with respect to a total of 100 mass parts of the compound which has a hydrolysable group, and 0.3-10 mass parts is especially preferable.

  In the present invention, when an organometallic compound is used as a catalyst, it is preferable to add a multidentate ligand from the viewpoint of pot life and curing efficiency. Examples of such multidentate ligands include those shown below and those derived therefrom, but the present invention is not limited to these.

Specifically, β-diketones such as acetylacetone, trifluoroacetylacetone, hexafluoroacetylacetone, and dipivaloylmethylacetone; acetoacetate esters such as methyl acetoacetate and ethyl acetoacetate; bipyridine and derivatives thereof; glycine and its Derivatives; ethylenediamine and derivatives thereof; 8-oxyquinoline and derivatives thereof; salicylaldehyde and derivatives thereof; catechol and derivatives thereof; bidentate ligands such as 2-oxyazo compounds; diethyltriamine and derivatives thereof; nitrilotriacetic acid and derivatives thereof And tridentate ligands such as ethylenediaminetetraacetic acid (EDTA) and derivatives thereof. In addition to the organic ligands as described above, inorganic ligands such as pyrophosphoric acid and triphosphoric acid can be exemplified. As the multidentate ligand, a bidentate ligand is particularly preferable, and specific examples include a bidentate ligand represented by the following general formula (VII) in addition to the above. Among them, a bidentate ligand represented by the following general formula (VII) is more preferable, and R ⁵ and R ⁶ in the following general formula (VII) are particularly preferable. By making R ⁵ and R ^{6 the} same, the coordination power of the ligand near room temperature becomes strong, and the coating agent can be further stabilized.

(In the formula, R ⁵ and R ⁶ each independently represent an alkyl group having 1 to 10 carbon atoms, a fluorinated alkyl group, or an alkoxy group having 1 to 10 carbon atoms.)

  The compounding amount of the polydentate ligand can be arbitrarily set, but is 0.01 mol or more, preferably 0.1 mol or more, more preferably 1 mol or more, with respect to 1 mol of the organometallic compound used. It is preferable to do this. The production of the silicon-containing coating agent of the present invention can be carried out in the absence of a solvent, but if necessary, alcohols such as methanol, ethanol, propanol and butanol; ketones such as acetone and methyl ethyl ketone; tetrahydrofuran; diethyl ether; In addition to ethers such as dioxane; and the like, various solvents can be used. As such a solvent, those having a boiling point of 100 ° C. or less are preferable, and they can be arbitrarily mixed and used. The amount of the solvent can be arbitrarily set, but if it is too small, the organosilicon compound is likely to be precipitated, so that it is 0.5 to 30 parts by mass, preferably 1 to 20 parts by mass with respect to 1 part by mass of the organosilicon compound. preferable.

In the present invention, the resin on the side filled with the resin having a crosslinked structure, that is, the resin having an oxygen gas permeability at 25 ° C. represented by O ₂ GTR2 is added in the form of a resin to the coating liquid of the resin having the crosslinked structure. , Can be introduced by a method of dissolution. In the case of a resin that takes time to dissolve in the coating solution, the resin may be dissolved in a suitable organic solvent in advance, and the solution may be added to the coating solution of the resin having the crosslinked structure. At this time, the coating solution may be heated or a compatibilizing agent may be added as necessary.

  The reaction temperature and reaction time for curing the coating solution are not particularly limited, but the reaction temperature is preferably 60 ° C. or higher, more preferably 80 to 80 ° C. from the viewpoint of mechanical strength and chemical stability of the resulting silicon resin. It is 200 ° C., and the reaction time is preferably 10 minutes to 5 hours. In addition, maintaining the organic layer obtained by curing the coating liquid in a high humidity state is effective in stabilizing the characteristics of the organic layer. Furthermore, depending on the application, the organic layer can be subjected to surface treatment using hexamethyldisilazane, trimethylchlorosilane, or the like to make it hydrophobic.

  A siloxane-based resin having a charge transporting property and having a cross-linked structure has excellent mechanical strength and sufficient photoelectric characteristics. Therefore, it can be used as it is as a charge transport layer of a multilayer photoreceptor. In that case, a usual method such as a blade coating method, a Meyer bar coating method, a spray coating method, a dip coating method, a bead coating method, an air knife coating method, or a curtain coating method can be used. However, when a required film thickness cannot be obtained by a single application, the necessary film thickness can be obtained by applying a plurality of times. When performing multiple times of repeated application, the heat treatment may be performed every time of application, or after multiple times of repeated application.

  In the case of a single-layer type photosensitive layer, it is formed containing the charge generating material and a binder resin. As the binder resin, the same binder resins as those used for the charge generation layer and the charge transport layer can be used. The content of the charge generating substance in the single-layer type photosensitive layer is about 10 to 85% by mass, preferably 20 to 50% by mass. A charge transport material or a polymer charge transport material may be added to the single-layer type photosensitive layer for the purpose of improving photoelectric characteristics. The addition amount is preferably 5 to 50% by mass. Moreover, you may add the compound shown by general formula (I). The solvent and coating method used for coating can be the same as described above. The film thickness is preferably about 5 to 50 μm, more preferably 10 to 40 μm.

  By the way, in the present invention, in order to obtain the characteristics of a photosensitive layer (coating film) required as an electrophotographic photosensitive member, a drying step when forming the layer is one of important steps. For example, depending on the drying temperature and the drying time, the amount of residual solvent in the coating film and the degree of cure of the binder resin are affected. In addition, temperature unevenness and temperature rise characteristics in the drying furnace also affect the curing of the residual solvent and the binder resin, and affect the photoreceptor quality. Thus, for example, the degree of cure of the resin constituting the coating film affects the generation and movement of charges important as electrophotographic characteristics, and this is determined by the drying temperature and drying time of the coating film. At this time, even if the coating film is excessively cured or insufficient, the movement of electric charges is hindered, and good electrophotographic characteristics cannot be obtained. Therefore, it is necessary to control the curing of the coating film within a certain range, and this requires precise setting and control of drying conditions.

  In particular, when a state where the coating film is hardened is desirable as the photoreceptor characteristics, it is necessary to control the drying temperature to be low or to shorten the drying time. However, when the drying conditions are relaxed in this way, the residual solvent may adversely affect the photoreceptor characteristics and other contact members such as a charging member.

  Therefore, in order to enable drying of the coating film under a wide range of drying conditions, particularly at a low temperature, the photosensitive layer (coating film) may be formed as follows. The coating liquid constituting at least one layer of the photosensitive layer (coating film) of the electrophotographic photosensitive member contains at least two kinds of organic solvents having different boiling points, and is formed in the coating liquid after the coating film is formed by the coating liquid. The coating film is dried at a temperature between the boiling point of the solvent species exhibiting the lowest boiling point and the boiling point of the solvent species exhibiting the highest boiling point. Then, the outermost surface layer (surface protective layer) is formed on the photosensitive layer (coating film). Here, the solvent species exhibiting the highest boiling point is the organic solvent having the highest boiling point among the organic solvents contained in the coating liquid, and the solvent species exhibiting the lowest boiling point is the solvent having the lowest boiling point.

  This makes it possible to dry the coating film under a wider range of drying conditions, especially at a low temperature. This enables a wide range of control of the photoreceptor characteristics, and further penetration of the residual solvent into the member in contact with the electrophotographic photoreceptor. Thus, an excellent electrophotographic photoreceptor having a reduced surface potential of the photoreceptor can be obtained without secondary obstructions such as the above. The reason for this is that even if some solvent remains in the coating film by drying at a relatively low temperature, an additional outermost surface layer (surface protective layer) having a low oxygen transmission rate is provided so that the residual solvent is removed from the photoreceptor surface. It is presumed that it can be prevented from penetrating into the water.

  Therefore, even in this case, if the oxygen permeability of the surface protective layer is as large as 1500 fm / Pa · s as described above, the residual solvent penetrates the surface of the photoreceptor, leaving contact marks on other contact members, and image quality defects. May be.

  In addition, as another reason, by constituting the coating liquid from two or more kinds of organic solvents having different boiling points, a solvent having a high boiling point azeotropes with a solvent having a low boiling point. Therefore, even in drying at a relatively low temperature condition, It is expected that the amount of residual solvent will decrease.

  Conventionally, in the case of a thick film such as a charge transport layer, a solvent having a relatively high boiling point has been often used for the purpose of ensuring film formability, so it is necessary to remove the residual solvent by drying at a high temperature above a certain level. was there. On the other hand, according to the present invention, it is possible to dry the coating film in a lower temperature region than in the past without secondary obstacles such as residual solvent.

  In addition, the photosensitive layer (coating film) formed from a coating solution containing two or more organic solvents having different boiling points may be any layer of the photosensitive layer (charge generation layer, charge transport layer), It is suitable for a charge transport layer.

  The solvent used as at least two kinds of organic solvents having different boiling points can be selected from those exemplified above, but is most preferably selected from tetrahydrofuran and aromatic hydrocarbons.

  At this time, in order to sufficiently remove the solvent in the drying step and to obtain better photoreceptor characteristics, when forming a coating film from a coating solution containing two or more organic solvents having different boiling points, 70 to It is preferable to dry at 120 ° C., preferably 80 to 110 ° C., more preferably 90 to 100 ° C.

  If the drying temperature is lower than this, the coating film will not be cured sufficiently, and good photoreceptor characteristics will not be obtained, and even if a large amount of solvent remains in the coating film and a surface protective layer is provided, it will return to the photoreceptor surface May not be able to inhibit the penetration of On the other hand, at a drying temperature higher than this, curing of the coating film proceeds excessively, and there may be a problem such as deterioration of electrical characteristics.

  In the coating solution, the mass of the solvent species exhibiting the lowest boiling point is preferably at least twice the mass of the solvent species exhibiting the highest boiling point. When the solvent ratio is smaller than this, it is expected that the residual solvent amount of the solvent species having a particularly high boiling point will increase and affect the photoreceptor characteristics.

Next, the toner will be described.
The toner used in the present invention is not particularly limited by the production method as long as it satisfies the above shape index and particle size. For example, the binder resin, the colorant, the release agent, and the like as necessary. Kneading and pulverizing method for kneading, pulverizing and classifying charge control agent, etc., a method for changing the shape of particles obtained by kneading and pulverizing method by mechanical impact force or thermal energy, polymerizable monomer for binder resin Emulsion polymerization and agglomeration, and a dispersion of the formed dispersion and a dispersion of a colorant, a release agent and, if necessary, a charge control agent are agglomerated and heat-fused to obtain toner particles. A suspension polymerization method in which a polymerizable monomer, a colorant, a release agent, and a charge control agent, if necessary, are suspended in an aqueous solvent for polymerization to obtain a binder resin; a binder resin; Suspend a solution of colorant, mold release agent, charge control agent, etc. in an aqueous solvent and granulate. Dissolution suspension method or the like can be used.

In addition, a known method such as a production method in which the toner obtained by the above method is used as a core, and agglomerated particles are further adhered and heat-fused to give a core-shell structure can be used, but from the viewpoint of shape control and particle size distribution control Suspension polymerization method, emulsion polymerization aggregation method, and dissolution suspension method, which are produced from an aqueous solvent, are preferred, and emulsion polymerization aggregation method is particularly preferred. The toner base material includes a binder resin, a colorant, and a release agent. If necessary, silica or a charge control agent may be used. A toner having an average particle diameter of 2 to 12 μm, preferably a toner base material of 3 to 9 μm can be used. A toner having an average shape index (ML ² / A == [(absolute maximum length of toner particles) ² ] / [(projected area of toner particles) × π × 1/4 × 100]) of 115 to 140 is used. As a result, an image with high development, transferability and high image quality can be obtained.

  Binder resins include styrenes such as styrene and chlorostyrene, monoolefins such as ethylene, propylene, butylene and isoprene, vinyl esters such as vinyl acetate, vinyl propionate, vinyl benzoate and vinyl butyrate, and methyl acrylate. , Α-methylene aliphatic monocarboxylic esters such as ethyl acrylate, butyl acrylate, dodecyl acrylate, octyl acrylate, phenyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, dodecyl methacrylate, vinyl Homopolymers and copolymers of vinyl ethers such as methyl ether, vinyl ethyl ether, and vinyl butyl ether, vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone, and vinyl isopropenyl ketone can be exemplified. Typical binder resins include polystyrene, styrene-alkyl acrylate copolymer, styrene-alkyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, styrene-maleic anhydride copolymer. , Polyethylene, polypropylene and the like. Further examples include polyester, polyurethane, epoxy resin, silicone resin, polyamide, modified rosin, paraffin wax and the like.

  Coloring agents include magnetic powders such as magnetite and ferrite, carbon black, aniline blue, caryl blue, chrome yellow, ultramarine blue, duPont oil red, quinoline yellow, methylene blue chloride, phthalocyanine blue, malachite green oxalate, and lamp black. Rose Bengal, C.I. I. Pigment red 48: 1, C.I. I. Pigment red 122, C.I. I. Pigment red 57: 1, C.I. I. Pigment yellow 97, C.I. I. Pigment yellow 17, C.I. I. Pigment blue 15: 1, C.I. I. Pigment Blue 15: 3 can be exemplified as a representative one.

Typical examples of the release agent include low molecular weight polyethylene, low molecular weight polypropylene, Fischer tropic wax, montan wax, carnauba wax, rice wax, and candelilla wax.
In addition, a charge control agent may be added to the toner as necessary. Known charge control agents can be used, but azo metal complex compounds, metal complex compounds of salicylic acid, and resin type charge control agents containing polar groups can be used. When the toner is manufactured by a wet manufacturing method, it is preferable to use a material that is difficult to dissolve in water in terms of controlling ionic strength and reducing wastewater contamination. The toner in the present invention may be either a magnetic toner containing a magnetic material or a non-magnetic toner containing no magnetic material.

  The toner can be produced by mixing the toner particles and the external additive with a Henschel mixer or a V blender. In addition, when the toner particles are produced by a wet method, external addition can be performed by a wet method.

  Lubricating particles added to the toner include solid lubricants such as graphite, molybdenum disulfide, talc, fatty acids, fatty acid metal salts, low molecular weight polyolefins such as polypropylene, polyethylene, polybutene, and silicones that have a softening point when heated. , Fatty acid amides such as oleic amide, erucic acid amide, ricinoleic acid amide, stearic acid amide, etc., plant waxes such as carnauba wax, rice wax, candelilla wax, tree wax, jojoba oil, beeswax Can use mineral waxes such as animal wax, montan wax, ozokerite, ceresin, paraffin wax, microcrystalline wax, Fischer-Tropsch wax, etc., and their modified products. Or It may be use. However, the average particle size may be in the range of 0.1 to 10 μm, and the particles having the above chemical structure may be pulverized to have the same particle size. The amount added to the toner is preferably in the range of 0.05 to 2.0 mass%, more preferably 0.1 to 1.5 mass%.

To the toner, inorganic fine particles, organic fine particles, composite fine particles obtained by adhering inorganic fine particles to the organic fine particles, and the like can be added for the purpose of removing deposits and deteriorated substances on the surface of the electrophotographic photosensitive member. Inorganic fine particles include silica, alumina, titania, zirconia, barium titanate, aluminum titanate, strontium titanate, magnesium titanate, zinc oxide, chromium oxide, cerium oxide, antimony oxide, tungsten oxide, tin oxide, tellurium oxide, Various inorganic oxides such as manganese oxide, boron oxide, silicon carbide, boron carbide, titanium carbide, silicon nitride, titanium nitride, and boron nitride, nitrides, borides, and the like are preferably used. Titanium coupling agents such as tetrabutyl titanate, tetraoctyl titanate, isopropyl triisostearoyl titanate, isopropyl tridecylbenzenesulfonyl titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, γ- (2-aminoethyl) Aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, N-β- (N-vinylbenzylaminoethyl) γ-aminopropyltrimethoxysilane hydrochloride , Hexamethyldisilazane, methyltrimethoxysilane, butyltrimethoxysilane, isobutyltrimethoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane Alternatively, the treatment may be performed with a silane coupling agent such as decyltrimethoxysilane, dodecyltrimethoxysilane, phenyltrimethoxysilane, o-methylphenyltrimethoxysilane, p-methylphenyltrimethoxysilane, or the like. In addition, hydrophobic treatment with a higher fatty acid metal salt such as silicone oil, aluminum stearate, zinc stearate or calcium stearate is also preferably used.
Examples of the organic fine particles include styrene resin particles, styrene acrylic resin particles, polyester resin particles, and urethane resin particles.

  As the particle size of these particles, if the particle size is too small, the polishing ability is insufficient, and if the particle size is too large, the surface of the electrophotographic photosensitive member is likely to be scratched. More preferably, the one at 5 nm to 700 nm is used. Moreover, it is preferable that the sum with the addition amount of slippery particles is 0.6 mass% or more.

Other inorganic oxides added to the toner are small-diameter inorganic oxides with a primary particle size of 40 nm or less for powder flowability, charge control, etc. It is preferable to add a large-diameter inorganic oxide. These inorganic oxide fine particles may be known ones, but it is preferable to use silica and titanium oxide in combination for precise charge control. Further, the surface treatment of the small-diameter inorganic fine particles increases the dispersibility and increases the effect of increasing the powder fluidity.
The color toner for electrophotography is used by mixing with a carrier. As the carrier, iron powder, glass beads, ferrite powder, nickel powder, or those having a surface coated with resin coating are used. The mixing ratio with the carrier can be set as appropriate.

<Process cartridge>
FIG. 1 is a schematic configuration diagram showing a basic configuration of a preferred embodiment of a process cartridge according to the present invention. The process cartridge 100 includes a charging unit 8, a developing unit 11, a cleaning unit 13, an opening 18 for exposure, and a static eliminator 14 together with the electrophotographic photosensitive member 7. It is. The process cartridge 100 is detachably attached to an image forming apparatus main body including transfer means 12, fixing means 15, and other components not shown. The image forming apparatus together with the electrophotographic apparatus main body. It constitutes.

<Image forming apparatus>
FIG. 2 is a schematic configuration diagram of a basic configuration of a preferred embodiment of the image forming apparatus of the present invention. An image forming apparatus 200 shown in FIG. 2 includes an electrophotographic photosensitive member 7, a charging unit that charges the electrophotographic photosensitive member 7 by a corona discharge method, a power source 9 connected to the charging unit 8, and charging by the charging unit 8. Exposure means 10 for exposing the electrophotographic photosensitive member 7 to be developed, developing means 11 for developing a portion exposed by the exposure means 10, and transfer means for transferring the image developed on the electrophotographic photosensitive member 7 by the developing means 11 12, a cleaning unit 13, a static eliminator 14, and a fixing unit 15.

  FIG. 3 is a schematic outline of the basic configuration of another embodiment of the image forming apparatus of the present invention. The image forming apparatus 210 shown in FIG. 3 has the same configuration as the image forming apparatus 200 shown in FIG. 2 except that the image forming apparatus 210 includes a charging unit 8 that charges the electrophotographic photoreceptor 7 by a contact method. In particular, an image forming apparatus that employs a contact-type charging unit in which an AC voltage is superimposed on a DC voltage can be preferably used because it has excellent wear resistance. In this case, the static eliminator 14 may not be provided.

  In the process cartridge and the image forming apparatus described above, main members will be described.

  First, the charging method of the charging means is not particularly limited, and any of a known corotron, non-contact charging method using scorotron, or contact charging method may be used, but a contact charging method that generates less ozone is preferable. The contact charging method is a method of charging the surface by applying a voltage to a conductive member brought into contact with the surface of the photoreceptor. As the charging means, since the electrophotographic photosensitive member has a strong mechanical strength, it exhibits particularly excellent durability even when a contact charging method in which stress on the electrophotographic photosensitive member is large is used. be able to.

  The shape of the conductive member may be any of a brush shape, a blade shape, a pin electrode shape, a roller shape, or the like, but it is particularly preferable to use a roller-shaped member from the viewpoint of charging uniformity.

  As a method for charging the photosensitive member using these conductive members, either a method in which the applied voltage when applying a voltage to the conductive member is a DC voltage or a method in which an AC voltage is superimposed on the DC voltage is used. preferable. The magnitude of the applied voltage is preferably positive or negative 50 to 2000 V, more preferably 100 to 1500 V, depending on the required photoreceptor charging potential when a DC voltage is applied. When the AC voltage is superimposed, the peak-to-peak voltage is preferably 400 to 1800 V, more preferably 800 to 1600 V, and still more preferably 1200 to 1600 V. Moreover, it is preferable that the frequency of an alternating voltage is 50-20000 Hz, and it is more preferable that it is 100-5000 Hz.

  Hereinafter, the case where a roller-shaped member is used as the conductive member will be described. Usually, the roller-shaped member is composed of a resistance layer in contact with the photoreceptor, an elastic layer therein, and a core material. Furthermore, a protective layer can be provided outside the resistance layer as necessary. The roller-like member rotates at the same peripheral speed as that of the photoreceptor without contacting the photoreceptor, and functions as a charging means. However, some driving means may be attached to the roller member, and the roller member may be charged by being rotated at a peripheral speed different from that of the photosensitive member.

  The core material is not particularly limited as long as it has conductivity, but generally iron, copper, brass, stainless steel, aluminum, nickel, or the like is used. In addition, a resin molded product in which conductive particles are dispersed can be used.

The constituent material of the elastic layer is not particularly limited as long as it has conductivity or semiconductivity, but generally a material in which conductive particles or semiconductive particles are dispersed in a rubber material is used. As this rubber material, EPDM, polybutadiene, natural rubber, polyisobutylene, SBR, CR, NBR, silicon rubber, urethane rubber, epichlorohydrin rubber, SBS, thermoplastic elastomer, norbornene rubber, fluorosilicone rubber, ethylene oxide rubber, etc. are used. . Conductive particles or semiconductive particles dispersed in the rubber material include metals such as carbon black, zinc, aluminum, copper, iron, nickel, chromium, and titanium, ZnO—Al ₂ O ₃ , SnO ₂ —Sb ₂ O. ₃ , metal oxides such as In ₂ O ₃ —SnO ₂ , ZnO—TiO ₂ , MgO—Al ₂ O ₃ , FeO—TiO ₂ , TiO ₂ , SnO ₂ , Sb ₂ O ₃ , In ₂ O ₃ , ZnO, MgO Can be used. In addition, said material may be used independently and may mix and use 2 or more types.

The low efficiency of the resistance layer and the protective layer can be controlled by dispersing conductive particles or semiconductive particles in the binder resin. The resistivity of the resistance layer and the protective layer is generally in the range of 10 ³ to 10 ¹⁴ Ωcm, preferably 10 ⁵ to 10 ¹² Ωcm, and preferably 10 ⁷ to 10 ¹² Ωcm. More preferred. Moreover, generally as thickness of a resistance layer and a protective layer, it may be 0.01-1000 micrometers, it is preferable that it is 0.1-500 micrometers, and it is more preferable that it is 0.5-100 micrometers.

  As the above binder resin, acrylic resin, cellulose resin, polyamide resin, methoxymethylated nylon, ethoxymethylated nylon, polyurethane resin, polycarbonate resin, polyester resin, polyethylene resin, polyvinyl resin, polyarylate resin, polythiophene resin, PFA Polyolefin resins such as FEP and PET, styrene butadiene resins, and the like are used.

  In addition, as the conductive particles or semiconductive particles, carbon black, metal, and metal oxide similar to the elastic layer are used. If necessary, an antioxidant such as hindered phenol and hindered amine, a filler such as clay and kaolin, and a lubricant such as silicone oil can be added.

  As a means for forming these layers, a blade coating method, a wire bar coating method, a spray coating method, a dip coating method, a bead coating method, an air knife coating method, a curtain coating method, or the like can be used.

  The exposure means (image input device) is a device that functions to form an electrostatic latent image by exposing a charged photoreceptor. The light source is not specifically limited, For example, well-known light sources, such as LED light and liquid-crystal shutter light other than a semiconductor laser beam, can be used. As an image input device serving as an exposure unit, for example, an optical device that can be exposed in a desired image-like manner with light from a light source such as the semiconductor laser light, LED light, or liquid crystal shutter light can be used.

  The developing unit is an apparatus that develops an electrostatic latent image with toner to form a toner image. In particular, in the case where the exposure means uses a known light source such as a semiconductor laser beam, LED light, or liquid crystal shutter light, the reversal development method that develops the exposed portion is used as the developing means. It is preferable. As such a developing means, for example, one having a function of attaching a magnetic or non-magnetic one-component developer or two-component developer to an electrophotographic photosensitive member by using a brush, a roller, or the like is used. Can do.

  The transfer unit is a member that transfers the toner image to a transfer target such as paper. As the transfer member, for example, a known transfer charger such as a contact charger using a roller, a scorotron transfer charger using corona discharge, or a corotron transfer charger can be used.

  EXAMPLES Hereinafter, although this invention is demonstrated using an Example, this invention is not limited at all by these Examples. In this example, “part” means “part by mass”.

[Example A]
(Photoreceptor 1)
The cylindrical Al substrate was polished by a centerless polishing apparatus, and the surface roughness was Rz = 0.6 μm. As a cleaning step, this cylinder was degreased, etched with a 2 wt% sodium hydroxide solution for 1 minute, neutralized, and further washed with pure water. Next, as an anodizing treatment step, an anodized film (current density 1.0 A / dm ² ) was formed on the cylinder surface by a 10 wt% sulfuric acid solution. After washing with water, a 1 wt% nickel acetate solution was immersed in 80 ° C. for 20 minutes for sealing treatment. Furthermore, pure water washing | cleaning and the drying process were performed. In this way, a 7 μm anodic oxide film was formed on the surface of the aluminum cylinder.

  Chlorogallium having strong diffraction peaks on this aluminum substrate with Bragg angles (2θ ± 0.2 °) of 7.4 °, 16.6 °, 25.5 ° and 28.3 ° in the X-ray diffraction spectrum 1 part of phthalocyanine is mixed with 1 part of polyvinyl butyral (ESREC BM-S, Sekisui Chemical Co., Ltd.) and 100 parts of n-butyl acetate. Was dip coated on the undercoat layer and dried by heating at 100 ° C. for 10 minutes to form a charge generation layer having a thickness of about 0.15 μm.

  A coating solution in which 2 parts of a benzidine compound having the following structure and 3 parts of the following polymer compound (viscosity average molecular weight 39,000) were dissolved in 20 parts of chlorobenzene was applied onto the charge generation layer by a dip coating method, For 20 minutes to form a charge transport layer having a thickness of 20 μm. This is a photoreceptor 1.

(Photoreceptor 2)
The constituent materials shown below on the photoreceptor 1 are dissolved in 5 parts of isopropyl alcohol, 3 parts of tetrahydrofuran and 0.3 part of distilled water, 0.5 parts of ion exchange resin (Amberlyst 15E) is added, and the mixture is stirred at room temperature. For 24 hours.

―Constituent materials―
・ Compound 1 2 parts ・ Methyltrimethoxysilane 2 parts ・ Tetramethoxysilane 0.5 part ・ Colloidal silica 0.3 part

  Then, 0.1 parts of aluminum trisacetylacetonate (Al (aqaq) 3) and 3,5-di-t-butyl-4-hydroxytoluene are obtained by filtering and separating the ion exchange resin from the hydrolyzed product. (BHT) 0.4 part is added, this coating liquid is applied on the charge transport layer by a ring-type dip coating method, air-dried at room temperature for 30 minutes, and then cured by heat treatment at 170 ° C. for 1 hour, A surface protective layer (outermost surface layer) having a thickness of about 5 μm was formed. This is a photoreceptor 2.

(Photoconductor 3-6)
In the coating solution in Photoreceptor 2, 0.3 parts of polyvinyl alcohol (Nippon Gosei Co., Ltd., Gohsenol), polyethylene-polyvinyl alcohol copolymer (Kuraray Co., Eval E105B) 0.3 for Photoreceptors 3 to 6, respectively. A surface protective layer having a film thickness of 5 μm was formed in the same manner as the photosensitive member 2 except that 0.3 part of copolymer polyamide (manufactured by TORAY, CM4001) and 0.3 part (manufactured by TORAY, CM8000) were added. . This is designated as photoreceptors 3-6.

(Photoreceptor 7)
An anodic oxide film was formed on the cylindrical Al substrate in the same manner as the photoreceptor 1. One part of titanyl phthalocyanine having a strong diffraction peak at a Bragg angle (2θ ± 0.2 °) of X-ray diffraction spectrum on this aluminum substrate of 27.2 ° is polyvinyl butyral (ESREC BM-S, Sekisui Chemical). After mixing with 1 part and 100 parts of n-butyl acetate and treating with glass beads for 1 hour with a paint shaker to disperse, the resulting coating solution was dip coated on the undercoat layer at 100 ° C. for 10 minutes. A heat generation layer having a film thickness of about 0.15 μm was formed by heating and drying. Otherwise, the photoreceptor 7 was obtained in the same manner as the photoreceptor 6.

(Photoreceptor 8)
On a cylindrical Al substrate subjected to a honing treatment, 100 parts of a zirconium compound (trade name: Orgatics ZC540, manufactured by Matsumoto Pharmaceutical Co., Ltd.), 10 parts of a silane compound (trade name: A1100, manufactured by Nippon Unicar Co., Ltd.), 400 parts of isopropanol, A solution comprising 200 parts of butanol was dipped and applied, and dried by heating at 150 ° C. for 10 minutes to form an undercoat layer of 0.1 μm.

  On this aluminum substrate, the Bragg angles (2θ ± 0.2 °) in the X-ray diffraction spectrum are 7.5 °, 9.9 °, 12.5 °, 16.3 °, 18.6 °, 25. 1 part of hydroxygallium phthalocyanine with strong diffraction peaks at 1 ° and 28.3 ° is mixed with 1 part of polyvinyl butyral (Esreck BM-S, Sekisui Chemical) and 100 parts of n-butyl acetate, and paint shaker with glass beads Then, the resulting coating solution was dip-coated on the undercoat layer and dried by heating at 100 ° C. for 10 minutes to form a charge generation layer having a thickness of about 0.15 μm.

  Next, a coating solution prepared by dissolving 2 parts of a charge transporting compound having the following structure and 3 parts of a polymer compound (viscosity average molecular weight 39,000) in 20 parts of chlorobenzene was applied onto the charge generation layer by a dip coating method. A charge transport layer having a thickness of 20 μm was formed by heating at 40 ° C. for 40 minutes. A surface protective layer similar to that of the photoreceptor 6 was formed thereon, whereby a photoreceptor 8 was obtained.

(Photoreceptor 9)
100 parts of zinc oxide (SMZ-017N: manufactured by Teika) was stirred and mixed with 500 parts of toluene, and 2 parts of a silane coupling agent (A1100: manufactured by Nihon Unicar) was added and stirred for 5 hours. Thereafter, toluene was distilled off under reduced pressure and baked at 120 ° C. for 2 hours. As a result of analyzing the obtained surface-treated zinc oxide by fluorescent X-ray, the Si element strength was 1.8 × 10 ⁻⁴ of the zinc element strength.

  35 parts of the surface-treated zinc oxide and hardener-blocked isocyanate sumijoule 3175) (manufactured by Sumitomo Bayern Urethane): 15 parts, butyral resin BM-1 (manufactured by Sekisui Chemical Co., Ltd.): 6 parts and methyl ethyl ketone: 44 parts Were mixed and dispersed for 2 hours in a sand mill using 1 mmφ glass beads to obtain a dispersion. Dioctyltin dilaurate: 0.005 parts and Tospearl 130 (manufactured by GE Toshiba Silicon Corporation): 17 parts were added as catalysts to the resulting dispersion to obtain an undercoat layer coating solution. This coating solution was applied onto an Al base material by a dip coating method, followed by drying and curing at 160 ° C. for 100 minutes to obtain an undercoat layer having a thickness of 20 μm. The surface roughness was measured using a surface roughness profile measuring device Surfcom 570A manufactured by Tokyo Seimitsu Co., Ltd., at a measurement distance of 2.5 mm and a scanning speed of 0.3 mm / sec, and had an Rz value of 0.24.

  Next, a charge generation layer having a film thickness of about 0.15 μm was formed in the same manner as the photoreceptor 3. Next, a charge transport layer having a thickness of 20 μm was formed in the same manner as the photoreceptor 1. Then, a surface protective layer similar to that of the photoreceptor 6 was formed, and a photoreceptor 9 was obtained.

(Photoreceptor 10)
A photoconductor 10 was obtained in the same manner as the photoconductor 6 except that the following compound 2 was used instead of the compound 1.

((Developer 1))
Each physical property value was measured by the following method.

-Toner, composite particle size distribution-
Using a multisizer (manufactured by Nikka Machine Co., Ltd.), measurement was performed with an aperture diameter of 100 μm.

- toner, the composite particles having an average shape factor ML ² / A-
It means a value calculated by the following formula. In the case of a true sphere, ML ² / A = 100.
ML ² / A = (maximum length) ² × π × 100 / (area × 4)
As a specific method for obtaining the average shape factor, a toner image is taken from an optical microscope into an image analyzer (LUZEX III, manufactured by Nireco), an equivalent circle diameter is measured, and individual particles are determined from the maximum length and area. The value of ML ² / A in the above formula was obtained.

[Manufacture of toner base particles]
(Adjustment of resin fine particle dispersion)
A mixture of 370 g of styrene, 30 g of n-butyl acrylate, 8 g of acrylic acid, 24 g of dodecanethiol and 4 g of carbon tetrabromide was dissolved in 6 g of a nonionic surfactant (Nonipol 400: manufactured by Sanyo Chemical Co., Ltd.) and anion Ion exchange in which 10 g of a surfactant (Neogen SC: manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) is emulsion-polymerized in a flask in which 550 g of ion-exchanged water is dissolved, and 4 g of ammonium persulfate is dissolved in the flask while slowly mixing for 10 minutes. 50 g of water was added. After carrying out nitrogen substitution, the inside of the flask was stirred and heated in an oil bath until the contents reached 70 ° C., and emulsion polymerization was continued for 5 hours. As a result, a resin fine particle dispersion in which resin particles of 150 nm, Tg = 58 ° C., and weight average molecular weight Mw = 11500 were dispersed was obtained. The solid content concentration of this dispersion was 40% by mass.

(Adjustment of colorant dispersion (1))
・ Carbon black (Mogal L: Cabot) 60g
・ Nonionic surfactant (Nonipol 400: manufactured by Sanyo Chemical Co., Ltd.) 6g
・ Ion-exchanged water 240g

  The above components are mixed, dissolved, stirred for 10 minutes using a homogenizer (Ultra Turrax T50: manufactured by IKA), then dispersed with an optimizer (colorant (carbon) having an average particle size of 250 nm. Black) A colorant dispersant (1) in which particles were dispersed was prepared.

(Adjustment of colorant dispersion (2))
・ Cyan Pigment B15: 3 60g
・ Nonionic surfactant (Nonipol 400: Sanyo Chemical Co., Ltd.) 5g
・ Ion-exchanged water 240g

  The above components are mixed, dissolved, stirred for 10 minutes using a homogenizer (Ultra Turrax T50: manufactured by IKA), and then dispersed with an optimizer to give a colorant (Cyan having an average particle size of 250 nm) Pigment) A colorant dispersant (2) in which particles were dispersed was prepared.

(Adjustment of colorant dispersion (3))
・ Magenta pigment R122 60g
・ Nonionic surfactant (Nonipol 400: Sanyo Chemical Co., Ltd.) 5g
・ Ion-exchanged water 240g

  The above components are mixed, dissolved, stirred for 10 minutes using a homogenizer (Ultra Turrax T50: manufactured by IKA), then dispersed with an optimizer and a colorant (Magenta) having an average particle size of 250 nm. Pigment) A colorant dispersant (3) in which particles were dispersed was prepared.

(Adjustment of colored dispersion (4))
・ Yellow pigment Y180 90g
・ Nonionic surfactant (Nonipol 400: Sanyo Chemical Co., Ltd.) 5g
・ Ion-exchanged water 240g

  The above components are mixed, dissolved, stirred for 10 minutes using a homogenizer (Ultra Turrax T50: manufactured by IKA), then dispersed with an optimizer and a colorant having an average particle size of 250 nm (Yellow) Pigment) A colorant dispersant (4) in which particles were dispersed was prepared.

(Release agent dispersion)
・ 100 g paraffin wax
(HNP0190: Nippon Seiwa Co., Ltd., melting point 85 ° C.)
・ Cationic surfactant 5g
(Sanisol B50: manufactured by Kao Corporation)
・ Ion-exchanged water 240g

  The above components were dispersed in a round stainless steel flask using a homogenizer (Ultra Turrax T50: manufactured by IKA) for 10 minutes, and then dispersed with a pressure discharge type homogenizer, and the average particle size was 550 nm. A release agent dispersion in which the mold agent particles were dispersed was prepared.

<Adjustment of toner mother particle K1>
-Resin fine particle dispersion (prepared at the time of preparing composite fine particles) 234 parts-Colorant dispersion (1) 30 parts-Release agent dispersion 40 parts-Polyaluminum hydroxide (Pho2S manufactured by Asada Chemical Co., Ltd.) 0. 5 parts, 600 parts of ion exchange water

The above ingredients were mixed and dispersed in a round stainless steel flask using a homogenizer (Ultra Turrax T50: manufactured by IKA), and then heated to 40 ° C. while stirring the flask in a heating oil bath. . After maintaining at 40 ° C. for 30 minutes, it was confirmed that aggregated particles having a D50 of 4.5 μm were produced. Further, the temperature of the heating oil bath was raised and maintained at 56 ° C. for 1 hour, and D50 was 5.3 μm. Thereafter, 26 parts of the resin fine particle dispersion was added to the dispersion containing the aggregate particles, and then the temperature of the heating oil bath was raised to 50 ° C. and held for 30 minutes. The dispersion containing the aggregated particles was added with 1N sodium hydroxide to adjust the pH of the system to 7.0, and then the stainless steel flask was sealed and heated to 80 ° C. while continuing stirring using a magnetic seal. And held for 4 hours. After cooling, the toner base particles were separated by filtration, washed four times with ion exchange water, and then lyophilized to obtain toner base particles K1. The toner base particle K1 had a D50 of 5.9 μm and an average shape factor ML ² / A of 132.

<Adjustment of toner base particle C1>
Toner mother particles C1 were obtained in the same manner as K1 except that the colored particle dispersion (2) was used instead of the colored particle dispersion (1). The toner base particle C1 had a D50 of 5.8 μm and an average shape factor ML ² / A of 131.

<Adjustment of toner mother particle M1>
Toner mother particles M1 were obtained in the same manner as K1 except that the colored particle dispersion (3) was used instead of the colored particle dispersion (1). The toner base particles M1 had a D50 of 5.5 μm and an average shape factor ML ² / A of 135.

<Adjustment of toner base particle Y1>
Toner mother particles Y1 were obtained in the same manner as K1 except that the colored particle dispersion (4) was used instead of the colored particle dispersion (1). D50 of the toner mother particles Y1 was 5.9 μm, and the average shape factor ML2 / A was 130.

[Manufacture of carriers]
・ Ferrite particles (average particle size: 50 μm) 100 parts ・ Toluene 14 parts ・ Styrene / methacrylate copolymer (component ratio: 90/10) 2 parts ・ Carbon black (R330: manufactured by Cabot Corporation) 0.2 part

  First, the above components excluding ferrite particles are stirred with a stirrer for 10 minutes to prepare a dispersed coating solution. Next, the coating solution and ferrite particles are placed in a vacuum degassing kneader and stirred at 60 ° C. for 30 minutes. After that, the carrier was obtained by further degassing by depressurization while heating and drying. This carrier had a volume resistivity of 1011 Ωcm when an applied electric field of 1000 V / cm.

  100 parts of each of the toner base particles K1, C1, M1, Y1 is 1 part of rutile type titanium oxide (particle diameter 20 nm, n-decyltrimethoxysilane treatment), silica (particle diameter 40 nm, silicone oil treatment, gas phase oxidation method). ) 2.0 parts, 1 part of cerium oxide (average particle size 0.7 μm), higher fatty acid alcohol (higher fatty acid alcohol having a molecular weight of 700) and zinc stearate in a ratio of 5: 1 by mass with a jet mill, average After blending 0.3 parts with a 5 L Henschel mixer at a peripheral speed of 30 m / s × 15 minutes, coarse particles were removed using a 45 μm mesh sieve and toner 1 was prepared. Obtained. Further, 100 parts of the carrier and 5 parts of the toner were stirred with a V-blender at 40 rpm × 20 minutes, and sieved with a sieve having an opening of 212 μm to obtain developer 1.

((Developer 2))
<Adjustment of toner mother particles K2>
-Resin fine particle dispersion (prepared at the time of preparing composite fine particles) 234 parts-Colorant dispersion (1) 30 parts-Release agent dispersion 40 parts-Polyaluminum hydroxide (Pho2S manufactured by Asada Chemical Co., Ltd.) 0. 5 parts, 600 parts of ion exchange water

The above ingredients were mixed and dispersed in a round stainless steel flask using a homogenizer (Ultra Turrax T50: manufactured by IKA), and then heated to 40 ° C. while stirring the flask in a heating oil bath. . After maintaining at 40 ° C. for 30 minutes, it was confirmed that aggregated particles having a D50 of 4.5 μm were produced. Further, the temperature of the heating oil bath was raised and maintained at 56 ° C. for 1 hour, and D50 was 5.3 μm. Thereafter, 26 parts of the resin fine particle dispersion was added to the dispersion containing the aggregate particles, and then the temperature of the heating oil bath was raised to 50 ° C. and held for 30 minutes. The dispersion containing the aggregated particles is added with 1N sodium hydroxide to adjust the pH of the system to 5.0, and then the stainless steel flask is sealed and heated to 95 ° C. while stirring with a magnetic seal. And held for 4 hours. After cooling, the toner base particles were filtered off, washed four times with ion exchange water, and then freeze-dried to obtain toner base particles K2. The toner base particle K2 had a D50 of 5.8 μm and an average shape factor ML ² / A of 109.

<Adjustment of toner base particle C2>
Toner base particles C2 were obtained in the same manner as K2 except that the colored particle dispersion (2) was used instead of the colored particle dispersion (1). D50 of the toner mother particles C2 was 5.7 μm, and the average shape factor ML ² / A was 110.

<Adjustment of toner mother particle M2>
Toner mother particles M2 were obtained in the same manner as K2 except that the colored particle dispersion (3) was used instead of the colored particle dispersion (1). D50 of the toner mother particles M2 was 5.6 μm, and the average shape factor ML ² / A was 114.

<Adjustment of toner base particle Y2>
Toner base particles Y2 were obtained in the same manner as above except that the colored particle dispersion (4) was used instead of the colored particle dispersion (1). D50 of the toner base particle Y2 was 5.8 μm, and the average shape factor ML ² / A was 108.

  Toner 1 and developer 1 except that K2, C2, M2, Y2 are used as toner base particles, and aluminum oxide (average particle size 0.1 μm) is used instead of 1 part of cerium oxide (average particle size 0.7 μm). In the same manner as above, Developer 2 was obtained.

((Developer 3))
<Adjustment of toner mother particles K3>
-Polyester resin 100 parts (Tg: 62 ° C., Mn 12000, Mw: 32000, a linear polyester obtained from terephthalic acid-bisphenol A ethylene oxide adduct-cyclohexanedimethanol)
・ Carbon black 4 parts ・ Carnauba wax 5 parts

The above mixture was kneaded with an extruder, pulverized with a jet mill, and then classified with an air classifier to obtain toner base particles K3 having an average particle size of 5.9 μm and a shape factor (ML ² / A) of 145.

<Adjustment of toner mother particle C3>
Toner base particles C3 having an average particle size of 5.6 μm and a shape factor (ML ² / A) of 141 are obtained in the same manner as K3, except that a cyan colorant (CI pigment blue 15: 3) is used instead of carbon black. Obtained.

<Adjustment of toner mother particles M3>
Toner mother particles M3 having an average particle diameter of 5.9 μm and a shape factor (ML ² / A) of 149 were obtained in the same manner as K3 except that magenta colorant (R122) was used instead of carbon black.

<Adjustment of toner mother particle Y3>
A toner base particle Y3 having an average particle size of 5.8 μm and a shape factor (ML ² / A) of 144 was obtained in the same manner as K3 except that a yellow colorant (Y180) was used instead of carbon black.

  Developer 3 was obtained in exactly the same manner as toner 2 and developer 2, except that K3, C3, M3, and Y3 were used as toner base particles.

(Examples A1 to A16, Comparative Examples A1 to A3)
A combination of the photoreceptor and developer shown in Table 10 was used to test the image formation of 10,000 sheets in a high-temperature, high-humidity (28 ° C, 75% RH) environment using a printer (Fuji Xerox Co., Ltd., DocuCenter Color 400CP). Subsequently, the degree of deposits on the photoconductor after a 10,000-sheet image formation test in an environment of low temperature and low humidity (10 ° C., 20% RH) was visually evaluated. The presence or absence of defects in print image quality was evaluated visually. Further, as a constituent material of the surface protective layer (outermost surface layer), a resin single film containing a crosslinked structure as a base, a resin single film to be filled, and a film as a surface protective layer (outermost surface layer) are separately added to a spin coater. Then, the oxygen permeability O ₂ GTR1, O ₂ GTR2, and O ₂ GTRt at 25 ° C. are measured with a gas permeability measuring device (MC-3, manufactured by Toyo Seiki Co., Ltd.), and the results are shown. This is also shown in Table 10.

  As is apparent from Table 10, the electrophotographic photosensitive member of the present invention shown in Examples A1 to A16 did not remain attached to the surface of the photosensitive member, and the print image quality was good. On the other hand, the electrophotographic photoreceptors outside the scope of the present invention shown in Comparative Examples A1 to A3 were adhered to the surface of the photoreceptor, and the print image quality was also defective.

[Example B]
(Preparation of coating solution for undercoat layer)
15 parts by mass of polyvinyl butyral resin (ESREC BM-S, manufactured by Sekisui Chemical Co., Ltd.) and 20 parts by mass of a curing agent (BL3475, Sumitomo Bayer Urethane) are dissolved in 80 parts by mass of 2-butanone to obtain zinc oxide powder (SMZ-017N10, The product was mixed and stirred with 90 parts by mass of Taika Co., Ltd., and dispersed for 20 hours using a Dinomill disperser (Shinmaru Enterprises Co., Ltd.). Silicon fine particles (R935: average particle size 5.0 μm, Toray Fine Chemical) were added to the resulting solution so that the volume ratio was 5% with respect to the total solid content of the solution.

(Preparation of coating solution for charge generation layer)
7.5 °, 9.9 °, 12.5 °, 16.3 °, 18.6 °, 25.1 at the Bragg angle (2θ ± 0.2 °) of the X-ray diffraction spectrum using Cukα rays. A mixture of 3 parts by mass of hydroxygallium phthalocyanine having a diffraction peak at a position of °, 28.1 °, 2 parts by mass of vinyl chloride-vinyl acetate copolymer (VMCH, manufactured by Nihon Unicar) and 180 parts by mass of butyl acetate was sand milled. For 4 hours.

(Preparation of coating solution for charge transport layer)
As a charge transport material, 4 parts by mass of N, N′-bis (3,4-dimethylphenyl) biphenyl-4-amine, 6 parts by mass of bisphenol Z-type polycarbonate resin (Mitsubishi Chemical Corporation: Iupilon Z400), 2,6- 0.2 parts by mass of di-t-butyl-4-methylphenol was added to 60 parts by mass of a mixed solvent of tetrahydrofuran (THF) and monochlorobenzene (MCB) and dissolved. Table 11 shows the mass ratio of tetrahydrofuran and monochlorobenzene in each Example and Comparative Example. Tetrahydrofuran has a boiling point of 66 ° C. and monochlorobenzene has a boiling point of 132 ° C.

(Preparation of coating solution for surface protective layer (outermost surface layer))
Compound represented by the following formula (49); 2 parts by mass, compound represented by the following formula (50); 2 parts by mass, isopropyl alcohol; 5 parts by mass, tetrahydrofuran; 3 parts by mass, distilled water; It is represented by the formula (49) by dissolving in 3 parts by mass, adding an ion exchange resin (Rohm and Haas, trade name: Amberlyst 15E); 0.05 parts by mass and stirring at room temperature. Hydrolysis of the compound and the compound represented by Formula (50) was performed for 24 hours. Next, a liquid obtained by filtering and separating the ion exchange resin from the hydrolyzed compound represented by the formula (49) and the compound represented by the formula (50); 0.2 parts by mass of aluminum trisacetylacetonate; 04 parts by mass were added to prepare a coating solution for forming the surface protective layer.

(Example B1)
As the conductive support, ED tube aluminum (30 mmφ) was used. The undercoat layer coating solution was dip-coated on the aluminum support so as to have a film thickness of 30 μm. The lower end 20 mm was pulled up at a low speed to form a thin film portion having a film thickness of about 10 μm.
Further, an undercoat layer was formed by drying at 150 ° C. for 60 minutes.
Next, the charge generation layer coating solution was dip coated on the undercoat layer to a thickness of 0.2 μm to form a charge generation layer.
Next, the charge transport layer coating solution was applied on the charge generation layer in the same manner, and then dried at 70 ° C. for 30 minutes to form a charge transport layer having a thickness of 20 μm.
Finally, a coating solution for the surface protective layer (outermost surface layer) is applied on the photoreceptor by a ring-type dip coating method, air-dried at room temperature for 30 minutes, and then heat-treated at 120 ° C. for 20 minutes to be cured. A surface protective layer (outermost surface layer) having a thickness of about 3 μm was formed.

(Example B2)
An electrophotographic photosensitive member was produced in the same manner as in Example B1, except that the charge transport layer was dried at 100 ° C. for 30 minutes.

(Example B3)
An electrophotographic photosensitive member was produced in the same manner as in Example B1, except that the charge transport layer was dried at 130 ° C. for 30 minutes.

(Example B4)
The solvent of the coating liquid constituting the charge transport layer was changed to 30 parts by mass of tetrahydrofuran and 30 parts by mass of monochlorobenzene, and the charge transport layer was dried at 100 ° C. for 30 minutes. A photographic photoreceptor was prepared.

(Example B5)
An electrophotographic photosensitive member was produced in the same manner as in Example B1, except that the charge transport layer was dried at 60 ° C. for 30 minutes.

(Example B6)
An electrophotographic photosensitive member was produced in the same manner as in Example B1, except that the charge transport layer was dried at 150 ° C. for 30 minutes.

(Comparative Example B1)
The electrophotographic photosensitive member was prepared in the same manner as in Example B1, except that the compound constituting the surface protective layer (outermost surface layer) was replaced with the compound shown in III-13 of Table 8 instead of (50). Was made.

(Comparative Example B2)
An electrophotographic photosensitive member was produced in the same manner as in Example B1, except that the surface protective layer (outermost surface layer) was not provided.

(Evaluation)
Table 11 shows the results of evaluation of the photoreceptor obtained as follows.
The electrophotographic photoreceptors in Examples and Comparative Examples were mounted on a Fuji Xerox full color printer DocuCenter Color 400CP modified machine (contact charging system, tandem system), and the surface potential of the photoreceptor in the machine after charging and exposure was measured. The DocuCentre Color 400CP remodeling machine is remodeled so that the surface potential of the photoreceptor can be measured in the machine.

  Further, the oxygen transmission rate of the surface protective layer was measured as follows. Each surface protective layer coating solution was applied on a polypropylene film having a known oxygen permeability and dried to obtain a sample having a thickness of 10 μm. Using this sample, measurement was performed in accordance with ASTM D-1434 method with a gas permeability measuring device BT-3 type (manufactured by Toyo Seiki).

  In these Examples B, the same results as in Example A above were obtained, and two solvents were used at a temperature between the boiling point of the solvent species showing the lowest boiling point and the boiling point of the solvent species showing the highest boiling point. In Example B1 to Example B4 in which the charge transport layer was formed by drying, it was found that the photoreceptor surface potential could be reduced as compared with the comparative example.

  On the other hand, in Example B5 in which the drying temperature of the charge transport layer was not more than the lowest boiling point of the solvent, there was no effect of reducing the surface potential of the photoreceptor, and if the electrophotographic photoreceptor was left in the electrophotographic apparatus for 1 month, the photoreceptor and Solvent erosion marks were generated on the contact charging member, and the image quality defect occurred at the site. In Example B6 in which the drying temperature was higher than the maximum boiling point of the solvent, the surface potential was increased.

  Further, in Comparative Example 1 in which the oxygen transmission rate is larger than that in the claims and Comparative Example 2 in which the surface protective layer is not provided, when the electrophotographic photosensitive member is left in the electrophotographic apparatus for one month, the photosensitive member and the charging member Solvent erosion traces remained, resulting in image quality defects.

  As a result, it becomes clear that the coating film can be dried under a wider range of drying conditions than in the past, in particular, at a low temperature, and thereby the photoreceptor characteristics can be controlled over a wide range. It can also be seen that the surface potential of the photoconductor can be reduced without secondary obstacles such as penetration of residual solvent into the member in contact with the electrophotographic photoconductor.

1 is a schematic configuration diagram of a basic configuration of a preferred embodiment of a process cartridge according to the present invention. 1 is a schematic configuration diagram of a basic configuration of a preferred embodiment of an image forming apparatus of the present invention. 2 is a schematic outline of a basic configuration of another embodiment of the image forming apparatus of the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Conductive base material 2 Undercoat layer 3 Photosensitive layer 4 Intermediate layer 5 Protective layer 6 Photosensitive layer 7 Electrophotographic photosensitive member 8 Charging means 9 Power supply 10 Exposure means 11 Developing means 12 Transfer means 13 Cleaning device 14 Static eliminator 15 Fixing means 16 Mounting rail

Claims (12)

  In an electrophotographic photosensitive member having a photosensitive layer on a conductive substrate, the outermost surface layer contains at least one resin having a cross-linked structure, and the outermost surface layer has an oxygen permeability of 1500 fm / s · at 25 ° C. An electrophotographic photoreceptor having a Pa or less.   The electrophotographic photosensitive member according to claim 1, comprising at least a charge generation layer and a plurality of layers having different compositions on the charge generation layer. When the oxygen permeability at 25 ° C. of the resin alone having a plurality of groups having active hydrogen in the photosensitive layer and having the crosslinked structure is O ₂ GTR1, the oxygen permeability O ₂ GTR2 at 25 ° C. alone is The electrophotographic photosensitive member according to claim 1, wherein the outermost surface layer contains a resin having a relationship represented by the following formula (1).
Formula (1): O ₂ GTR2 <O ₂ GTR1   The electrophotographic photosensitive member according to claim 1, wherein the outermost surface layer has a cross-linked structure and contains a structural unit having a charge transporting ability.   The electrophotographic photosensitive member according to claim 1, wherein the outermost surface layer contains a resin having a plurality of groups having active hydrogen. The electrophotographic photosensitive member according to any one of claims 3 to 5, wherein the oxygen permeability O ₂ GTR1 is 1500 fm / s · Pa or more and 5000 fm / s · Pa or less. The electrophotographic photoreceptor according to claim 3, wherein the oxygen permeability O ₂ GTR2 is 1 × 10 ⁻¹⁵ fm / s · Pa or more and 500 fm / s · Pa or less. The resin having the oxygen permeability O ₂ GTR2 is at least one or more of a resin group consisting of copolymerized polyamide, polyvinyl alcohol, polyethylene-polyvinyl alcohol copolymer, polyvinylidene chloride, and unsaturated polyester. The electrophotographic photosensitive member according to any one of claims 3 to 7. A resin having a crosslinked structure by the oxygen permeability O ₂ GTR1, a resin having the oxygen permeability O ₂ GTR2, but any of claims 3-8, characterized in that it has a site which is chemically bonded 2. The electrophotographic photosensitive member according to item 1.   An image forming apparatus comprising: the electrophotographic photosensitive member according to claim 1; and at least one of charging means, exposure means, transfer means, fixing means, and cleaning means. An electrophotographic process cartridge which is detachable from a main body.   The electrophotographic photosensitive member according to claim 1, comprising at least one of charging means, exposure means, transfer means, fixing means, and cleaning means. Image forming apparatus. A method for producing an electrophotographic photosensitive member according to claim 1,
Using a coating liquid containing two or more organic solvents having different boiling points, and forming a coating film with the coating liquid, the boiling point of the solvent type showing the lowest boiling point and the solvent type showing the highest boiling point contained in the coating liquid And producing at least one layer of the photosensitive layer by drying at a temperature between the boiling point of the electrophotographic photosensitive member.

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